+

WO2010112395A1 - S-perfluoroalkyl substituted hydroxybenzylthioethers and derivatives as surface modifiers - Google Patents

S-perfluoroalkyl substituted hydroxybenzylthioethers and derivatives as surface modifiers Download PDF

Info

Publication number
WO2010112395A1
WO2010112395A1 PCT/EP2010/053900 EP2010053900W WO2010112395A1 WO 2010112395 A1 WO2010112395 A1 WO 2010112395A1 EP 2010053900 W EP2010053900 W EP 2010053900W WO 2010112395 A1 WO2010112395 A1 WO 2010112395A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
hydrogen
unsubstituted
crc
alkylene
Prior art date
Application number
PCT/EP2010/053900
Other languages
French (fr)
Inventor
Michèle Gerster
Manuel Mihalic
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2010112395A1 publication Critical patent/WO2010112395A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C08K5/375—Thiols containing six-membered aromatic rings

Definitions

  • the present invention relates to compositions comprising an organic material, for example a synthetic polymer, which is susceptible to oxidative, thermal or light-induced degradation and S-perfluoroalkyl substituted hydroxybenzylthioethers and derivatives thereof.
  • the present invention relates also to a process for reducing the surface energy of organic materials which comprises treating the organic material with at least a S-perfluoroalkyl substituted hydroxybenzylthioether and derivative thereof.
  • S-perfluoroalkyl substituted hydroxybenzylthioethers are described, which are useful for various technical applications such as for example for increasing the oil and water repellency of organic materials like for example synthetic polymers. Furthermore, S-perfluoroalkyl substituted hydroxybenzylthioethers are also useful for various technical applications such as for example the making of improved electret articles.
  • perfluorinated compounds possessing one or more perfluorinated substituents based on only 6 perfluorinated carbon atoms surprisingly still provide beneficial water and oil repellency properties known from perfluorinated compounds respectively mixtures of these compounds possessing substituents based on 8 or more perfluorinated carbon atoms. These beneficial water and oil repellency properties are provided despite the absence of perfluorinated compounds possessing substituents based on 8 perfluorinated carbon atoms.
  • the present invention relates to a composition
  • a composition comprising a) an organic material which is susceptible to oxidative, thermal or light-induced degradation, and b) a compound of the formula I
  • Ri is hydrogen, Ci-C 25 alkyl, C 2 -C 25 alkenyl, -CO-R 5 , -CH(R 10 )CO-R 5 , -C(Ri ⁇ ) 2 CO-R 5 ,
  • R 1 is unsubstituted or with CrC 4 alkyl, benzyl or phenyl substituted CrC 24 alkylene; with oxygen or sulfur interrupted C 2 -C 24 alkylene; -CO-R 8 -CO-, -CH(R 10 )CO-R 8 -CO-CH(R 10 )-, -C(R 10 ) 2 CO-R 8 -CO-C(R 10 ) 2 -, -CO-N(R 6 )-R 9 -N(R 6 )-CO-,
  • R 2 , R 3 and R 4 independently of each other are hydrogen, CrC 25 alkyl, C 2 -C 25 alkenyl, or
  • R 4 Is -CH(Rn)-S(O) P -R 12 ;
  • R 5 is CrC 25 alkyl, C 2 -C 25 alkenyl, unsubstituted or with CrC 4 alkyl or halogen substituted phenyl; or C 7 -C 12 phenylalkyl,
  • R 6 is hydrogen or Ci-C 4 alkyl
  • R 7 is hydrogen, CrC 25 alkyl, unsubstituted or with CrC 4 alkyl or halogen substituted phenyl,
  • R 8 is phenylene, unsubstituted or with Ci-C 4 alkyl, benzyl or phenyl substituted
  • R 9 is a direct bond, unsubstituted or with Ci-C 4 alkyl, benzyl or phenyl substituted C 2 -
  • R 10 is hydrogen or CrC 8 alkyl
  • R 11 is hydrogen, CrC 8 alkyl, unsubstituted or with CrC 4 alkyl substituted phenyl,
  • R 12 is a monovalent linear or branched organic radical containing a perfluorinated alkyl having 6 fully fluorinated carbon atoms
  • R 13 is hydrogen, C r C 25 alkyl, C 2 -C 25 alkenyl, -CO-R 5 , -CO-N(R 6 )-R 7 or
  • R 14 is hydrogen, C r C 25 alkyl, C 2 -C 25 alkenyl Or -CH(Rn)-S(O) P -R 12 ,
  • R 15 is hydrogen, C r C 25 alkyl, C 2 -C 25 alkenyl Or -CH(Rn)-S(O) P -R 12 ,
  • R 16 is unsubstituted or with CrC 4 alkyl substituted methylene, -S-, -S(O)-, -S(O) 2 - or
  • R 17 is Ci-C 4 alkyl, n is 1 , 2 or 3, and p is O, 1 or 2; with the proviso that the compounds of the formula A and B - A -
  • composition does not contain a compound with a perfluorinated substituent other than that of formula (I).
  • Alkyl having up to 25 carbon atoms is a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3- tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl
  • Alkenyl having 2 to 25 carbon atoms is a branched or unbranched radical such as, for example, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n- 2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl.
  • Ci-C 24 alkylene is a branched or unbranched radical such as, for example methylene, ethylene, propylene, butylene, penty- lene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecy- lene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, methyl- methylene, ethylmethylene, 2-methylpropylene, 2-phenylpropylene, 2-benzylpropylene, ben- zylmethylene or phenylmethylene (benzylidene).
  • C 2 -C 24 Alkylene interrupted by oxygen or sulfur is, for example, -CH 2 -O-CH 2 -, -CH 2 -S-CH 2 -, -CH 2 -O-CH 2 CH 2 -, -CH 2 CH 2 -O-CH 2 CH 2 -, -CH 2 CH 2 -O-CH 2 CH 2 -O-CH 2 CH 2 - , -CH 2 CH 2 -(O-CH 2 CH 2 -) 2 O-CH 2 CH 2 -, -CH 2 CH 2 -(O-CH 2 CH 2 -) 3 O-CH 2 CH 2 -, -CH 2 CH 2 -(O-CH 2 CH 2 -) 4 O-CH 2 CH 2 - or -CH 2 CH 2 -S-CH 2 CH 2 -.
  • Ci-C 4 Alkyl or halogen substituted phenyl which contains preferably from 1 to 3, especially 1 or 2, alkyl or halogen groups, is, for example, o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-di- methylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2- chlorophenyl, 4-chlorophenyl or 2-methyl-4-chlorophenyl.
  • Ci-C 4 alkyl unsubstituted or substituted on the phenyl radical by from 1 to 3 Ci-C 4 alkyl groups is, for example, benzyl, ⁇ -methylbenzyl, ⁇ , ⁇ -dimethylbenzyl, 2-phenylethyl, 2-methyl- benzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzyl or 4-tert- butylbenzyl. Preference is given to benzyl.
  • a monovalent linear or branched organic radical containing a perfluorinated alkyl having 6 fully fluorinated carbon atoms is for example -CI-I 2 CI-I 2 (CF 2 )SCF 3 .
  • An interesting composition comprises a compound of the formula I wherein, when n is 1 , R 1 is hydrogen, d-Ci 8 alkyl, C 2 -Ci 8 alkenyl, -CO-R 5 , -CO-N(R 6 )-R 7 or -CH 2 -CO-N(R 6 )-R 7 ;
  • Ri is unsubstituted or with Ci-C 4 alkyl, benzyl or phenyl substituted Ci-C- ⁇ 8 alkylene; with oxygen or sulfur interrupted C 2 -d 8 alkylene; -CO-R 8 -CO-, -CO-N(R 6 )-R 9 -N(R 6 )-CO- or -CH(R 10 )-CO-N(R 6 )-R 9 -N(R 6 )-CO-CH(R 10 )-;
  • R 2 , R 3 and R 4 independently of each other are hydrogen, Ci-Ci 8 alkyl, C 2 -Ci 8 alkenyl,
  • R 5 is Ci-Ci 8 alkyl, C 2 -Ci 8 alkenyl, unsubstituted or with d-C 4 alkyl or halogen substituted phenyl; or C 7 -Ci 2 phenylalkyl,
  • R 6 is hydrogen or CrC 4 alkyl
  • R 7 is hydrogen, Ci-Ci 8 alkyl, unsubstituted or with Ci-C 4 alkyl or halogen substituted phenyl
  • R 8 is phenylene, unsubstituted or with Ci-C 4 alkyl, benzyl or phenyl substituted Ci-C 24 alky- lene; with oxygen or sulfur interrupted C 2 -C 24 alkylene,
  • Rg is a direct bond or unsubstituted or with Ci-C 4 alkyl, benzyl or phenyl substituted C 2 -C 18 al- kylene,
  • Rio is hydrogen or Ci-C 8 alkyl
  • Rn is hydrogen, Ci-C 8 alkyl, unsubstituted or with Ci-C 4 alkyl substituted phenyl
  • Ri 2 is a monovalent linear or branched organic radical containing a perfluorinated alkyl having 6 fully fluorinated carbon atoms
  • Ri3 is hydrogen, C r Ci 8 alkyl, C 2 -Ci 8 alkenyl, -CO-R 5 , -CO-N(R 6 )-R 7 or -CH 2 -CO-N(R 6 )-R 7 ,
  • R i4 is hydrogen, C r Ci 8 alkyl, C 2 -C 18 alkenyl or -CH(Rn)-S(O ) P -R i2
  • Ris is hydrogen, C r Ci 8 alkyl, C 2 -C 18 alkenyl or -CH(Rn)-S(O ) P -R i2 ,
  • Ri6 is unsubstituted or with Ci-C 4 alkyl substituted methylene, -S-, -S(O)-, -S(O) 2 - or -CO-,
  • R i7 is Ci-C 4 alkyl, n is 1 , 2 or 3, and p is O, 1 or 2.
  • a preferred composition comprises a compound of the formula I wherein R 12 is saturated and contains 6 - 15 carbon atoms, of which 6 are fully fluorinated and contains at least one terminal perfluoromethyl group.
  • composition comprising a compound of the formula I wherein R 2 , R 3 and R 4 independently of each other are hydrogen, Ci-C 4 alkyl, -CH(Rn)-S(0) p -Ri 2 or ith the proviso that at least one of the radicals R 2 , R 3 or R 4 is
  • R 11 is hydrogen, CrC 8 alkyl, unsubstituted or with CrC 4 alkyl substituted phenyl
  • R 12 is a monovalent linear or branched organic radical containing a perfluorinated alkyl having 6 fully fluorinated carbon atoms
  • R 13 is hydrogen, CrC 18 alkyl, C 2 -C 18 alkenyl or acetyl
  • Ri4 is hydrogen, Ci-Ci 8 alkyl, C 2 -Ci 8 alkenyl or -CH(Rn)-S(O ) P -Ri 2
  • Ri5 is hydrogen, d-Ci 8 alkyl, C 2 -Ci 8 alkenyl or -CH(Rn)-S(O ) P -Ri 2 ,
  • Ri6 is unsubstituted or with d-C 4 alkyl substituted methylene, -S-, -S(O)-, -S(O) 2 - or -CO-, and p is O, 1 or 2.
  • composition comprising a compound of the formula I wherein, when n is 1 , R 1 is hydrogen, C r Ci 8 alkyl, -CO-R 5 , -CO-N(R 6 )-R 7 or -CH 2 -CO-N(R 6 )-R 7 ;
  • Ri is unsubstituted or with d-C 4 alkyl substituted Ci-C 8 alkylene; -CO-R 8 -CO-, -CO-N(R 6 )-R 9 -N(R 6 )-CO- or -CH(R 1 O)-CO-N(Re)-R 9 -N(Re)-CO-CH(R 10 )-;
  • R 2 , R 3 and R 4 independently of each other are hydrogen, CrC 8 alkyl, -CH(Rn)-S(0) p -R 12 ,
  • R 2 , R 3 or R 4 is -CH(Rn)-S(0) p -R 12 ;
  • R 5 is CrC 18 alkyl, unsubstituted or with CrC 4 alkyl substituted phenyl; or C 7 -C 12 phenylalkyl, R 6 is hydrogen or CrC 4 alkyl,
  • R 7 is hydrogen, CrC 8 alkyl, unsubstituted or with CrC 4 alkyl substituted phenyl
  • R 8 is phenylene, unsubstituted or with CrC 4 alkyl substituted CrC 18 alkylene
  • R 9 is unsubstituted or with CrC 4 alkyl substituted C 2 -C 18 alkylene
  • R 10 is hydrogen or CrC 8 alkyl
  • R 11 is hydrogen, CrC 8 alkyl, unsubstituted or with CrC 4 alkyl substituted phenyl
  • Ri 2 is saturated and contains 6 - 15 carbon atoms, of which 6 carbon atoms are fully fluorinated and contains at least one terminal perfluoromethyl group
  • Ri3 is hydrogen, d-Ci 2 alkyl, -CO-R 5 , -CO-N(R 6 )-R 7 or -CH 2 -CO-N(R 6 )-R 7
  • Ru is hydrogen, C r Ci 2 alkyl or
  • Ri6 is unsubstituted or with d-C 4 alkyl substituted methylene, n is 1 , 2 or 3, and p is O.
  • composition comprising a compound of the formula I wherein Ri2 is -CH 2 CH 2 (CF 2 ) 5 CF 3 .
  • composition comprising a compound of the formula I wherein when n is 1 R 1 is hydrogen, d-Ci 8 alkyl, -CO-R 5 , -CO-N(R 6 )-R 7 or -CH 2 -CO-N(R 6 )-R 7 ;
  • Ri is Ci-C 8 alkylene, -CO-R 8 -CO-, -CO-N(R 6 )-R 9 -N(R 6 )-CO- or -CH(R 10 )-CO-N(R 6 )-R 9 -N(R 6 )-CO-CH(R 10 )-;
  • R 2 , R 3 and R 4 independently of each other are hydrogen, Ci-C 8 alkyl, -CH(Rn)-S(0) p -Ri 2 ,
  • R 2 , R 3 or R 4 is -CH(Rn)-S(0) p -Ri 2 ;
  • R 5 is Ci-Ci 8 alkyl, unsubstituted or with d-C 4 alkyl substituted phenyl; or benzyl,
  • R 6 is hydrogen
  • R 7 is hydrogen, Ci-C 8 alkyl, unsubstituted or with d-C 4 alkyl substituted phenyl, R 8 is phenylene or Ci-Ci 8 alkylene, R 9 is C 2 -Ci 8 alkylene, Rio is Ci-C 4 alkyl,
  • Rn is hydrogen, Ci-C 8 alkyl, unsubstituted or with d-C 4 alkyl substituted phenyl
  • Ri2 is -CH 2 CH 2 (CF 2 )SCF 3
  • Ri3 is hydrogen Or -CO-R 5
  • Ri 4 is hydrogen or Ci-C 8 alkyl
  • Ri5 is Ci-C 4 alkyl or -CH(Rn)-S(O ) P -Ri 2
  • Ri6 is methylene
  • n is 1 , 2 or 3, and p is 0.
  • composition comprising a compound of the formula I, wherein when n is 1 , R 1 is hydrogen, C r Ci 2 alkyl, -CO-R 5 , -CO-N(R 6 )-R 7 or -CH 2 -CO-N(R 6 )-R 7 ;
  • R 1 is methylene, -CO-R 8 -CO- or -CH(R 10 )-CO-N(R 6 )-R 9 -N(R 6 )-CO-CH(R 10 )-;
  • R 2 , R 3 and R 4 independently of each other are hydrogen, Ci-C 4 alkyl, -CH(Rn)-S(0) p -Ri 2 or
  • R 5 is C r C 18 alkyl
  • R 6 is hydrogen
  • R 7 is hydrogen, CrC 6 alkyl, unsubstituted or with CrC 4 alkyl substituted phenyl
  • R 8 is phenylene
  • R 9 is ethylene
  • Rio is methyl
  • Rn is hydrogen, d-C 8 alkyl, unsubstituted or with methyl substituted phenyl
  • Ri2 is -CH 2 CH 2 (CF 2 ) 5 CF 3
  • Ri 3 is hydrogen or acetyl
  • Ru is Ci-C 4 alkyl
  • R 15 Is -CH(Rn)-S(O) P -R 12
  • R 16 is methylene
  • n is 1 , 2 or 3
  • p is O.
  • composition comprising a compound of the formula I, wherein when n is 2, R 1 is -CO-R 8 -CO-; R 2 , R 3 and R 4 independently of each other are hydrogen, Ci-C 4 alkyl, -CH(Rn)-S(O) P -R 12 or
  • R 8 is phenylene
  • R 11 is hydrogen, CrC 8 alkyl, unsubstituted or with methyl substituted phenyl
  • R 12 is -CH 2 CH 2 (CF 2 ) 5 CF 3 ,
  • R 13 is hydrogen or acetyl
  • R 14 is Ci-C 4 alkyl
  • R 16 is methylene, n is 2, and p is O.
  • composition comprising a compound of the formula I, wherein when n is 2, R 1 is -CO-R 8 -CO-;
  • R 2 , R 3 and R 4 independently of each other are hydrogen, CrC 4 alkyl or -CH(Rn)-S(0) p -R 12 ; with the proviso that at least one of the radicals R 2 , R 3 or R 4 is -CH(Rn)-S(O ) P -R 12 ; R 8 is phenylene,
  • Rn is hydrogen, CrC 8 alkyl, unsubstituted or with methyl substituted phenyl,
  • Ri2 is -CH 2 CH 2 (CF 2 ) 5 CF 3 , n is 2, and p is 0.
  • compositions which comprise as component (b) one of the compounds 101 to 142.
  • the compounds of the formula I can be prepared by methods known in the art, in analogy to the process disclosed in WO 2007/144283 or in analogy to the process disclosed for example in U.S. Patent 4,874,885.
  • the compounds of the formula I are suitable as oil and water repellency agents for organic materials. Examples of organic materials which may be present in the compositions of the invention are following materials:
  • Polymers of monoolefins and diolefins for example polypropylene, polyisobutylene, po- lybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
  • HDPE high density polyethylene
  • HDPE-HMW high density and high molecular weight polyethylene
  • HDPE-UHMW high density and ultrahigh molecular weight polyethylene
  • MDPE medium density polyethylene
  • Polyolefins i.e. the polymers of monoolefins exemplified in the preceding paragraph, prefe- rably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
  • a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table.
  • These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either ⁇ - or ⁇ -coordinated.
  • These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide.
  • These catalysts may be soluble or insoluble in the polymerisation medium.
  • the catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, Na and/or Ilia of the Periodic Table.
  • the activators may be modified conveniently with further ester, ether, amine or silyl ether groups.
  • These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC). 2.
  • Mixtures of the polymers mentioned under 1 for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
  • Copolymers of monoolefins and diolefins with each other or with other vinyl monomers for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g.
  • ethylene/norbornene like COC ethylene/1 -olefins copolymers, where the 1 -olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vi- nylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1 ) above, for example polypropylene/ethy- lene-propylene copolymers, LD
  • Hydrocarbon resins for example C 5 -Cg
  • hydrogenated modifications thereof e.g. tackifiers
  • mixtures of polyalkylenes and starch
  • Homopolymers and copolymers from 1.) - 4.) may have any stereostructure including syndio- tactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Polystyrene poly(p-methylstyrene), poly( ⁇ -methylstyrene).
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Ste- reoblock polymers are also included.
  • Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/bu- tadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhy- dride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/pro- pylene/diene terpoly
  • Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6. especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
  • PCHE polycyclohexylethylene
  • PVCH polyvinylcyclohexane
  • Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
  • Graft copolymers of vinyl aromatic monomers such as styrene or ⁇ -methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acry- lonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpoly
  • Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
  • Polymers derived from ⁇ , ⁇ -unsatu rated acids and derivatives thereof such as polyacry- lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni- triles, impact-modified with butyl acrylate.
  • Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
  • Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace- tals thereof for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1 ) above.
  • Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
  • Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11 , polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly- m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetram
  • Polyureas Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
  • Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones for example polyethylene terephthalate, polybutylene tereph- thalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
  • Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
  • Crosslinkable acrylic resins derived from substituted acrylates for example epoxy acry- lates, urethane acrylates or polyester acrylates.
  • Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
  • Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
  • Blends of the aforementioned polymers for example PP/EPDM, PoIy- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
  • polyblends for example PP/EPDM, PoIy- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/
  • Naturally occurring and synthetic organic materials which are pure monomeric com- pounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.
  • synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
  • synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
  • synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
  • synthetic esters e.g. phthalates, adipates, phosphates or trimellitates
  • synthetic esters e.g. phthalates, adipates, phosphates
  • Preferred organic materials are natural, semi-synthetic or, preferably, synthetic polymers.
  • organic materials are synthetic polymers, most preferably thermoplastic polymers.
  • organic materials are polyacetals, polyolefins such as polypropylene or polyethylene, polyether/polyurethanes, polyesters such as polybutylene tereph- thalate, polycarbonates or polyamides.
  • Organic materials with low surface energy have intrinsically better properties like for example water and oil repellency, hydrophobicity, barrier properties, easy to clean, self cleaning, antigraffiti or solvent resistance.
  • the compounds of the formula I will preferably be added to the organic material in concentrations of 0.01 to 10 %, preferably 0.01 to 2 %, typically 0.1 to 2 %, based on the weight of said material.
  • the present invention also relates to a composition in the form of a masterbatch or concentrate comprising component (a) in an amount of from 5 to 90 % and component (b) in an amount of from 5 to 80 % by weight.
  • composition of the invention may comprise further additives, such as for example the following:
  • Alkylated monophenols for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-( ⁇ -methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methylunde
  • Alkylthiomethylphenols for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl- thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4- nonylphenol.
  • Hydroquinones and alkylated hydroquinones for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu- tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy- droxyphenyl) adipate.
  • 2,6-di-tert-butyl-4-methoxy- phenol 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amyl
  • Tocopherols for example ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol, ⁇ -tocopherol and mixtures thereof (vitamin E).
  • Hydroxylated thiodiphenyl ethers for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)- disulfide.
  • 2,2'-thiobis(6-tert-butyl-4-methylphenol 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6
  • Alkylidenebisphenols for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-( ⁇ -methylcyclohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4- methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl- phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-( ⁇ -methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-( ⁇ , ⁇ -dimethyl
  • Hydroxybenzylated malonates for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di- dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 ,1 ,3,3-te- tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
  • dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate di-octadecyl-2-(3-tert-butyl-4-
  • Aromatic hydroxybenzyl compounds for example 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
  • Triazine compounds for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy- anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5-tri- azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxyben- zyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl
  • Benzylphosphonat.es for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl- ⁇ -tert-butyM-hydroxy-S-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
  • Acylaminophenols for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
  • esters of ⁇ -(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol- propane, 4-hydroxy
  • esters of ⁇ -(5-tert-butyl-4-hvdroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl- olpropane, 4-hydroxymethyl-1 -phos
  • esters of ⁇ -(3,5-dicvclohexyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1 -phospha ⁇ j-trioxabi
  • esters of 3,5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alcohols e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[
  • Aminic antioxidants for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-bu- tyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3- methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicy- clohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p- phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl
  • UV absorbers and light stabilizers 2.1.
  • 2-(2'-Hvdroxyphenyl)benzotriazoles for example 2-(2'-hydroxy-5'-methylphenyl)-benzo- triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe- nyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di- tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphe- nyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphen
  • 2-Hvdroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl- oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
  • Esters of substituted and unsubstituted benzoic acids for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben- zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
  • Acrylates for example ethyl ⁇ -cyano- ⁇ , ⁇ -diphenylacrylate, isooctyl ⁇ -cyano- ⁇ , ⁇ -diphe- nylacrylate, methyl ⁇ -carbomethoxycinnamate, methyl ⁇ -cyano- ⁇ -methyl-p-methoxycinna- mate, butyl ⁇ -cyano- ⁇ -methyl-p-methoxy-cinnamate, methyl ⁇ -carbomethoxy-p-methoxycin- namate, N-( ⁇ -carbomethoxy- ⁇ -cyanovinyl)-2-methylindoline, neopentyl tetra( ⁇ -cyano- ⁇ , ⁇ -di- phenylacrylate.
  • Nickel compounds for example nickel complexes of 2,2'-thio-bis[4-(1 ,1 ,3,3-tetramethyl- butyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert- butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphe- nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or with- out additional ligands.
  • additional ligands such as n- butylamine, triethanolamine or N-cyclohexyl
  • Sterically hindered amines for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1 -octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1 ,2,2,6,6-pentamethyl-4- piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2- hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert- oc
  • Oxamides for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
  • Metal deactivators for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl- oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
  • Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di- cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphos
  • Hvdroxylamines for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N- dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N- dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydrox- ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
  • Nitrones for example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl- alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnnitrone, N- hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al- pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta- decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N
  • Thiosynergists for example dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate or distearyl disulfide.
  • Peroxide scavengers for example esters of ⁇ -thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis( ⁇ - dodecylmercapto)propionate.
  • esters of ⁇ -thiodipropionic acid for example the lauryl, stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole zinc dibutyldithiocarbamate
  • dioctadecyl disulfide pentaerythritol tetrakis( ⁇ - dodecyl
  • Polvamide stabilizers for example copper salts in combination with iodides and/or phos- phorus compounds and salts of divalent manganese.
  • Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
  • Basic co-stabilizers for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ric
  • Nucleating agents for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers).
  • inorganic substances such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals
  • organic compounds such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate
  • polymeric compounds such as ionic copolymers (
  • Fillers and reinforcing agents for example calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
  • additives for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
  • the further additives are typically used in concentrations of 0.01 to 10 %, based on the total weight of the material to be treated.
  • a preferred composition of the invention comprises, as other additives phenolic antioxidants, light stabilizers and/or processing stabilizers.
  • a further embodiment of the present invention is a process for reducing the surface energy of organic materials which comprises treating the organic material with at least a compound of the formula I
  • Ri is hydrogen, Ci-C 25 alkyl, C 2 -C 25 alkenyl, -CO-R 5 , -CH(R 10 )CO-R 5 , -C(Ri ⁇ ) 2 CO-R 5 ,
  • R 1 is unsubstituted or with CrC 4 alkyl, benzyl or phenyl substituted CrC 24 alkylene; with oxygen or sulfur interrupted C 2 -C 24 alkylene, -CO-R 8 -CO-, -CH(R 10 )CO-R 8 -CO-CH(R 10 )-, -C(R 10 ) 2 CO-R 8 -CO-C(R 10 ) 2 -, -CO-N(R 6 )-R 9 -N(R 6 )-CO-,
  • R 2 , R 3 and R 4 independently of each other are hydrogen, CrC 25 alkyl, C 2 -C 25 alkenyl,
  • R 5 is Ci-C 25 alkyl, C 2 -C 25 alkenyl, unsubstituted or with d-C 4 alkyl or halogen substituted phenyl; or C 7 -Ci 2 phenylalkyl, R 6 is hydrogen or Ci-C 4 alkyl,
  • R 7 is hydrogen, Ci-C 25 alkyl, unsubstituted or with Ci-C 4 alkyl or halogen substituted phenyl,
  • Rs is phenylene, unsubstituted or with Ci-C 4 alkyl, benzyl or phenyl substituted
  • Ci-C 24 alkylene with oxygen or sulfur interrupted C 2 -C 24 alkylene
  • Rg is a direct bond, unsubstituted or with Ci-C 4 alkyl, benzyl or phenyl substituted C 2 -C 24 alkylene; or with oxygen or sulfur interrupted C 2 -C 24 alkylene,
  • R 1 0 is hydrogen or d-C 8 alkyl
  • R 11 is hydrogen, d-C 8 alkyl, unsubstituted or with Ci-C 4 alkyl substituted phenyl,
  • Ri 2 is a monovalent linear or branched organic radical containing a perfluorinated alkyl having 6 fully fluorinated carbon atoms
  • Ri3 is hydrogen, C r C 25 alkyl, C 2 -C 25 alkenyl, -CO-R 5 , -CO-N(R 6 )-R 7 or -CH 2 -CO-N(R 6 )-R 7 ,
  • R i4 is hydrogen, C r C 25 alkyl, C 2 -C 25 alkenyl or -CH(Rn)-S(O ) P -R i2 ,
  • Ris is hydrogen, C r C 25 alkyl, C 2 -C 25 alkenyl or -CH(Rn)-S(O ) P -R i2 ,
  • R 1 6 is unsubstituted or with Ci-C 4 alkyl substituted methylene, -S-, -S(O)-, -S(O) 2 - or -CO-,
  • R i7 is Ci-C 4 alkyl, n is 1 , 2 or 3, p is O, 1 or 2; and wherein the treatment is carried out in the absence of a compound with a perfluorinated substituent other than that of formula (I).
  • Preferred is a process for imparting oil and water repellency to the organic material.
  • Preferred is a process for imparting oil repellency. Preferred is a process with a compound of the formula I wherein, when n is 1 ,
  • Ri is hydrogen, d-Ci 2 alkyl, -CO-R 5 , -CO-N(R 6 )-R 7 or -CH 2 -CO-N(R 6 )-R 7 ;
  • R 1 is methylene, -CO-R 8 -CO- or -CH(R 10 )-CO-N(R 6 )-R 9 -N(R 6 )-CO-CH(R 10 )-;
  • R 2 , R 3 and R 4 independently of each other are hydrogen, d-C 4 alkyl, -CH(Rn)-S(0) p -Ri 2 or ith the proviso that at least one of the radicals R 2 , R 3 or R 4 is
  • R 5 is C r C 18 alkyl
  • R 6 is hydrogen
  • R 7 is hydrogen, CrC 6 alkyl, unsubstituted or with CrC 4 alkyl substituted phenyl,
  • R 8 is phenylene
  • R 9 is ethylene
  • R 10 is methyl
  • R 11 is hydrogen, CrC 8 alkyl, unsubstituted or with methyl substituted phenyl,
  • R 12 is -CH 2 CH 2 (CF 2 ) 5 CF 3 ,
  • R 13 is hydrogen or acetyl
  • R 14 is C r C 4 alkyl, R 15 Js -CH(Rn)-S(O) P -R 12 ,
  • R 16 is methylene, n is 1 , 2 or 3, and p is 0.
  • Component (b) and, if desired, further additives, can also be added before or during polymerisation or before crosslinking.
  • Component (b), with or without further additives, can be incorporated in pure form or encap- sulated in waxes, oils or polymers into the synthetic polymer.
  • Component (b), with or without further additives, can also be sprayed onto the synthetic polymer. It is able to dilute other additives (for example the conventional additives indicated above) or their melts so that they too can be sprayed together with these additives onto the polymer. Addition by spraying on during the deactivation of the polymerization catalysts is particularly advantageous, it being possible to carry out spraying using, for example, the steam used for deactivation.
  • component (b), with or without other additives may, for example, be advantageous to apply component (b), with or without other additives, by spraying.
  • the synthetic polymers prepared in this way can be employed in a wide variety of forms, for example as foams, films, fibres, tapes, moulding compositions, as profiles or as binders for coating materials, especially powder coatings, adhesives, putties or especially as thick-layer polyolefin mouldings which are in long-term contact with extractive media, such as, for example, pipes for liquids or gases, films, fibres, geomembranes, tapes, profiles or tanks.
  • extractive media such as, for example, pipes for liquids or gases, films, fibres, geomembranes, tapes, profiles or tanks.
  • the preferred thick-layer polyolefin mouldings have a layer thickness of from 1 to 50 mm, in particular from 1 to 30 mm, for example from 2 to 10 mm.
  • compositions according to the invention can be advantageously used for the preparation of various shaped articles. Examples are:
  • Floating devices Floating devices, marine applications, pontoons, buoys, plastic lumber for decks, piers, boats, kayaks, oars, and beach reinforcements.
  • I-2) Automotive applications in particular bumpers, dashboards, battery, rear and front linings, moldings parts under the hood, hat shelf, trunk linings, interior linings, air bag covers, electronic moldings for fittings (lights), panes for dashboards, headlamp glass, instrument panel, exterior linings, upholstery, automotive lights, head lights, parking lights, rear lights, stop lights, interior and exterior trims; door panels; gas tank; glazing front side; rear windows; seat backing, exterior panels, wire insulation, profile extrusion for sealing, cladding, pillar covers, chassis parts, exhaust systems, fuel filter / filler, fuel pumps, fuel tank, body side mouldings, convertible tops, exterior mirrors, exterior trim, fasteners / fixings, front end module, glass, hinges, lock systems, luggage / roof racks, pressed/stamped parts, seals, side impact protection, sound deadener / insulator and sunroof.
  • Road traffic devices in particular sign postings, posts for road marking, car accessories, warning triangles, medical cases, helmets, tires.
  • I-5) Devices for space applications in particular rockets and satellites, e.g. reentry shields.
  • I-6) Devices for architecture and design, mining applications, acoustic quietized systems, street refuges, and shelters.
  • Appliances, cases and coverings in general and electric/electronic devices personal computer, telephone, portable phone, printer, television-sets, audio and video devices), flower pots, satellite TV bowl, and panel devices.
  • Electric appliances in particular washing machines, tumblers, ovens (microwave oven), dish-washers, mixers, and irons.
  • shutters e.g. roller shutters
  • Hygienic articles in particular diapers (babies, adult incontinence), feminine hygiene articles, shower curtains, brushes, mats, tubs, mobile toilets, tooth brushes, and bed pans.
  • Pipes cross-linked or not for water, waste water and chemicals, pipes for wire and cable protection, pipes for gas, oil and sewage, guttering, down pipes, and drainage sy- stems.
  • Glass substitutes in particular extruded plates, glazing for buildings (monolithic, twin or multiwall), aircraft, schools, extruded sheets, window film for architectural glazing, train, transportation, sanitary articles, and greenhouse.
  • Plates (walls, cutting board), extrusion-coating (photographic paper, tetrapack and pipe coating), silos, wood substitute, plastic lumber, wood composites, walls, surfaces, furniture, decorative foil, floor coverings (interior and exterior applications), flooring, duck boards, and tiles.
  • III-9) Intake and outlet manifolds.
  • 111-10) Cement-, concrete-, composite-applications and covers, siding and cladding, hand rails, banisters, kitchen work tops, roofing, roofing sheets, tiles, and tarpaulins.
  • IV-1 Plates (walls and cutting board), trays, artificial grass, astroturf, artificial covering for stadium rings (athletics), artificial floor for stadium rings (athletics), and tapes.
  • V) Films (packaging, dump, laminating, agriculture and horticulture, greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, waste bags, wallpaper, stretch film, raffia, desalination film, batteries, and connectors.
  • VI-2) Storage systems such as boxes (crates), luggage, chest, household boxes, pallets, shelves, tracks, screw boxes, packs, and cans.
  • Vl 1-1 Extrusion coating (photo paper, tetrapack, pipe coating), household articles of any kind (e.g. appliances, thermos bottle / clothes hanger), fastening systems such as plugs, wire and cable clamps, zippers, closures, locks, and snap-closures.
  • Support devices articles for the leisure time such as sports and fitness devices, gymnastics mats, ski-boots, inline-skates, skis, big foot, athletic surfaces (e.g. tennis grounds); screw tops, tops and stoppers for bottles, and cans.
  • sports and fitness devices gymnastics mats, ski-boots, inline-skates, skis, big foot, athletic surfaces (e.g. tennis grounds); screw tops, tops and stoppers for bottles, and cans.
  • Footwear (shoes / shoe-soles), insoles, spats, adhesives, structural adhesives, food boxes (fruit, vegetables, meat, fish), synthetic paper, labels for bottles, couches, artificial joints (human), printing plates (flexographic), printed circuit boards, and display technologies.
  • compositions comprising as component (a) fibers and fabrics used in nonwo- ven medical fabric and related apparel (surgical gowns, drapes, bandages), construction fabrics (house wrapping, roofing, swimming-pool wrapping) and home furnishing (carpets, table linens, shower curtains).
  • compositions comprising as component (a) fibers and nonwovens.
  • a further embodiment of the present invention relates to a shaped article, in particular a film, pipe, profile, bottle, tank or container, fiber containing a composition as described above.
  • a shaped article in particular a film, pipe, profile, bottle, tank or container, fiber containing a composition as described above.
  • fibers and nonwovens are preferred.
  • a further embodiment of the present invention relates to a molded article containing a composition as described above.
  • the molding is in particular effected by injection, blow, com- pression, roto-molding or slush-molding or extrusion.
  • a preferred embodiment of the present invention is also the use of a compound of the formula I as reducer of surface energy [e.g. as oil and water repellency agent] for an organic material.
  • reducer of surface energy e.g. as oil and water repellency agent
  • Example 1 Preparation of compound 101 (2-methyl-4,6-bis-(3,3,4,4,5,5,6,6,7,7,8,8,8- tridecafluoro-octylsulfanylmethyl)-phenol)
  • Example 5 Preparation of compound 105 (terephthalic acid bis-[2,4,6-tris- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octylsulfanylmethyl)-phenyl] ester)
  • Example 6 Preparation of compound 106 (acetic acid 2,4, 6-tris-(3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8,8,8- tridecafluoro-octylsulfanylmethyl)-phenyl ester)
  • Example 7 Water and oil repellency in polypropylene
  • the sample preparation is a combination of polypropylene nonwovens and a thermal treatment (e.g. 130 0 C for 10 minutes), which increases the migration of the additive to the surface and a proper surface rearrangement of the chemical groups. This extra heat cycle is recommended to melt the compounds of the formula I in order to obtain a homogeneous redistribution over the surface of the substrate.
  • An industrial sample of polypropylene nonwoven, fabric weight: 40 g/m 2 is dipped into a 1 % isopropanol solution of the test compound, simultaneously applying ultrasonic energy for one minute. After that, the sample is dried overnight at room temperature and then two hours at 90°C in an oven. A part of the sample is afterwards annealed for 10 minutes at 130 0 C.
  • the treated nonwoven samples are evaluated in the water repellency test similar to INDA test method 80.8 (99).
  • the wetting behavior of the nonwovens is tested with a series of water/isopropanol mixtures. The observation of the wetting behavior is rated from 0 (water wetting, no repellency) to 10 (optimum water repellency). The results are summarized in Table 1.
  • the treated nonwoven samples are evaluated in the oil repellency test similar to AATCC test method 118-1997 / ISO 14419. This test follows the same concepts of the already described for water repellency test method, but using, as test solvents, a series of hydrocarbons. The observation of the wetting behavior is rated from 0 (no repellency) to 8 (optimum repellency). The results are summarized in Table 2. Table 1:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention describes a composition of comprising an organic material which is susceptible to oxidative, thermal or light-induced degradation, and a compound of the formula (I) wherein the general symbols are as defined in claim 1; especially wherein at least one of the radicals R2, R3 or R4 is -CH(R11)-S(O)p-R12; R11 is hydrogen, C1-C8alkyl, unsubstituted or with d-C1-C4 alkyl substituted phenyl, R12 is a monovalent linear or branched organic radical containing a perfluorinated alkyl having 6 fully fluorinated carbon atoms, n is 1, 2 or 3, and p is 0, 1 or 2. The invention describes further a process for reducing the surface energy of organic materials such as for example increasing the oil and water repellency and stain release of organic materials, which comprises treating the organic material with at least a compound of the formula I.

Description

S-Perfluoroalkyl substituted hydroxybenzylthioethers and derivatives as surface modifiers
The present invention relates to compositions comprising an organic material, for example a synthetic polymer, which is susceptible to oxidative, thermal or light-induced degradation and S-perfluoroalkyl substituted hydroxybenzylthioethers and derivatives thereof. The present invention relates also to a process for reducing the surface energy of organic materials which comprises treating the organic material with at least a S-perfluoroalkyl substituted hydroxybenzylthioether and derivative thereof.
The use of various fluorochemical compositions on fibers and fibrous substrates, such as for example textiles, carpets, paper, leather and non-woven webs to impart oil and water repel- lency is known for example in U.S. 6,127,485. This reference discloses hydrophobic and oleophobic fibers, films and molded articles comprising synthetic organic polymer wherein dispersed within the fiber, fabric or molded article and present at the surface of the fiber, fabric or molded article are fluorochemical compounds.
In WO 2007/144283, S-perfluoroalkyl substituted hydroxybenzylthioethers are described, which are useful for various technical applications such as for example for increasing the oil and water repellency of organic materials like for example synthetic polymers. Furthermore, S-perfluoroalkyl substituted hydroxybenzylthioethers are also useful for various technical applications such as for example the making of improved electret articles.
There are trends to replace perfluorinated compounds possessing substituents with 8 perfluorinated carbon atoms due to various reasons.
It has now been found that certain perfluorinated compounds possessing one or more perfluorinated substituents based on only 6 perfluorinated carbon atoms surprisingly still provide beneficial water and oil repellency properties known from perfluorinated compounds respectively mixtures of these compounds possessing substituents based on 8 or more perfluorinated carbon atoms. These beneficial water and oil repellency properties are provided despite the absence of perfluorinated compounds possessing substituents based on 8 perfluorinated carbon atoms.
The present invention relates to a composition comprising a) an organic material which is susceptible to oxidative, thermal or light-induced degradation, and b) a compound of the formula I
Figure imgf000003_0001
wherein, when n is 1 ,
Ri is hydrogen, Ci-C25alkyl, C2-C25alkenyl, -CO-R5, -CH(R10)CO-R5, -C(Riθ)2CO-R5,
-CO-N(R6)-R7, -CH(R10)CO-N(R6)-R7, -C(R10)2CO-N(R6)-R7, -CH(R10)COOR5 or
Figure imgf000003_0002
when n is 2,
R1 is unsubstituted or with CrC4alkyl, benzyl or phenyl substituted CrC24alkylene; with oxygen or sulfur interrupted C2-C24alkylene; -CO-R8-CO-, -CH(R10)CO-R8-CO-CH(R10)-, -C(R10)2CO-R8-CO-C(R10)2-, -CO-N(R6)-R9-N(R6)-CO-,
-CH(R10)CO-N(Re)-R9-N(Re)-CO-CH(R10)-, -C(R1O)2CO-N(Re)-R9-N(Re)-CO-C(R1O)2-, -CH(R10)CO-O-R9-O-CO-CH(R10)- or -C(R10)2CO-O-R9-O-CO-C(R10)2-;
when n is 3,
Figure imgf000003_0003
R2, R3 and R4 independently of each other are hydrogen, CrC25alkyl, C2-C25alkenyl, or
Figure imgf000004_0001
with the proviso that at least one of the radicals R2, R3 or
Figure imgf000004_0002
R4 Is -CH(Rn)-S(O)P-R12;
R5 is CrC25alkyl, C2-C25alkenyl, unsubstituted or with CrC4alkyl or halogen substituted phenyl; or C7-C12phenylalkyl,
R6 is hydrogen or Ci-C4alkyl,
R7 is hydrogen, CrC25alkyl, unsubstituted or with CrC4alkyl or halogen substituted phenyl,
R8 is phenylene, unsubstituted or with Ci-C4alkyl, benzyl or phenyl substituted
C-i-C24alkylene; with oxygen or sulfur interrupted C2-C24alkylene,
R9 is a direct bond, unsubstituted or with Ci-C4alkyl, benzyl or phenyl substituted C2-
C24alkylene; or with oxygen or sulfur interrupted C2-C24alkylene,
R10 is hydrogen or CrC8alkyl,
R11 is hydrogen, CrC8alkyl, unsubstituted or with CrC4alkyl substituted phenyl,
R12 is a monovalent linear or branched organic radical containing a perfluorinated alkyl having 6 fully fluorinated carbon atoms,
R13 is hydrogen, CrC25alkyl, C2-C25alkenyl, -CO-R5, -CO-N(R6)-R7 or
-CH2-CO-N(R6)-R7,
R14 is hydrogen, CrC25alkyl, C2-C25alkenyl Or -CH(Rn)-S(O)P-R12,
R15 is hydrogen, CrC25alkyl, C2-C25alkenyl Or -CH(Rn)-S(O)P-R12,
R16 is unsubstituted or with CrC4alkyl substituted methylene, -S-, -S(O)-, -S(O)2- or
-CO-,
R17 is Ci-C4alkyl, n is 1 , 2 or 3, and p is O, 1 or 2; with the proviso that the compounds of the formula A and B - A -
Figure imgf000005_0001
are excluded; and wherein the composition does not contain a compound with a perfluorinated substituent other than that of formula (I).
Alkyl having up to 25 carbon atoms is a branched or unbranched radical, for example methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl, 1 ,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1 ,1 ,3,3- tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1 ,1 ,3-trimethylhexyl, 1 ,1 ,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1 ,1 ,3,3,5,5- hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl or docosyl.
Alkenyl having 2 to 25 carbon atoms is a branched or unbranched radical such as, for example, propenyl, 2-butenyl, 3-butenyl, isobutenyl, n-2,4-pentadienyl, 3-methyl-2-butenyl, n- 2-octenyl, n-2-dodecenyl, iso-dodecenyl, oleyl, n-2-octadecenyl or n-4-octadecenyl.
Unsubstituted or with d-C4alkyl, benzyl or phenyl substituted Ci-C24alkylene is a branched or unbranched radical such as, for example methylene, ethylene, propylene, butylene, penty- lene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecy- lene, tetradecylene, pentadecylene, hexadecylene, heptadecylene, octadecylene, methyl- methylene, ethylmethylene, 2-methylpropylene, 2-phenylpropylene, 2-benzylpropylene, ben- zylmethylene or phenylmethylene (benzylidene).
C2-C24Alkylene interrupted by oxygen or sulfur is, for example, -CH2-O-CH2-, -CH2-S-CH2-, -CH2-O-CH2CH2-, -CH2CH2-O-CH2CH2-, -CH2CH2-O-CH2CH2-O-CH2CH2- , -CH2CH2-(O-CH2CH2-)2O-CH2CH2-, -CH2CH2-(O-CH2CH2-)3O-CH2CH2-, -CH2CH2-(O-CH2CH2-)4O-CH2CH2- or -CH2CH2-S-CH2CH2-.
Ci-C4Alkyl or halogen substituted phenyl which contains preferably from 1 to 3, especially 1 or 2, alkyl or halogen groups, is, for example, o-, m- or p-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-di- methylphenyl, 2-methyl-6-ethylphenyl, 4-tert-butylphenyl, 2-ethylphenyl, 2,6-diethylphenyl, 2- chlorophenyl, 4-chlorophenyl or 2-methyl-4-chlorophenyl.
C7-Ci2Phenylalkyl unsubstituted or substituted on the phenyl radical by from 1 to 3 Ci-C4alkyl groups is, for example, benzyl, α-methylbenzyl, α,α-dimethylbenzyl, 2-phenylethyl, 2-methyl- benzyl, 3-methylbenzyl, 4-methylbenzyl, 2,4-dimethylbenzyl, 2,6-dimethylbenzyl or 4-tert- butylbenzyl. Preference is given to benzyl.
A monovalent linear or branched organic radical containing a perfluorinated alkyl having 6 fully fluorinated carbon atoms is for example -CI-I2CI-I2(CF2)SCF3.
An interesting composition comprises a compound of the formula I wherein, when n is 1 , R1 is hydrogen, d-Ci8alkyl, C2-Ci8alkenyl, -CO-R5, -CO-N(R6)-R7 or -CH2-CO-N(R6)-R7;
when n is 2,
Ri is unsubstituted or with Ci-C4alkyl, benzyl or phenyl substituted Ci-C-ι8alkylene; with oxygen or sulfur interrupted C2-d8alkylene; -CO-R8-CO-, -CO-N(R6)-R9-N(R6)-CO- or -CH(R10)-CO-N(R6)-R9-N(R6)-CO-CH(R10)-;
when n is 3,
Figure imgf000006_0001
R2, R3 and R4 independently of each other are hydrogen, Ci-Ci8alkyl, C2-Ci8alkenyl,
-CH(Rn)-S(OVR12,
Figure imgf000006_0002
with the proviso that at least one of the radicals R2, R3 or R4 is -CH(Rn)-S(O )P-Ri2; R5 is Ci-Ci8alkyl, C2-Ci8alkenyl, unsubstituted or with d-C4alkyl or halogen substituted phenyl; or C7-Ci2phenylalkyl,
R6 is hydrogen or CrC4alkyl,
R7 is hydrogen, Ci-Ci8alkyl, unsubstituted or with Ci-C4alkyl or halogen substituted phenyl, R8 is phenylene, unsubstituted or with Ci-C4alkyl, benzyl or phenyl substituted Ci-C24alky- lene; with oxygen or sulfur interrupted C2-C24alkylene,
Rg is a direct bond or unsubstituted or with Ci-C4alkyl, benzyl or phenyl substituted C2-C18al- kylene,
Rio is hydrogen or Ci-C8alkyl, Rn is hydrogen, Ci-C8alkyl, unsubstituted or with Ci-C4alkyl substituted phenyl,
Ri2 is a monovalent linear or branched organic radical containing a perfluorinated alkyl having 6 fully fluorinated carbon atoms,
Ri3 is hydrogen, CrCi8alkyl, C2-Ci8alkenyl, -CO-R5, -CO-N(R6)-R7 or -CH2-CO-N(R6)-R7,
Ri4 is hydrogen, CrCi8alkyl, C2-C18alkenyl or -CH(Rn)-S(O )P-Ri2, Ris is hydrogen, CrCi8alkyl, C2-C18alkenyl or -CH(Rn)-S(O )P-Ri2,
Ri6 is unsubstituted or with Ci-C4alkyl substituted methylene, -S-, -S(O)-, -S(O)2- or -CO-,
Ri7 is Ci-C4alkyl, n is 1 , 2 or 3, and p is O, 1 or 2.
A preferred composition comprises a compound of the formula I wherein R12 is saturated and contains 6 - 15 carbon atoms, of which 6 are fully fluorinated and contains at least one terminal perfluoromethyl group.
Preference is also given to a composition comprising a compound of the formula I wherein R2, R3 and R4 independently of each other are hydrogen, Ci-C4alkyl, -CH(Rn)-S(0)p-Ri2 or ith the proviso that at least one of the radicals R2, R3 or R4 is
Figure imgf000007_0001
R11 is hydrogen, CrC8alkyl, unsubstituted or with CrC4alkyl substituted phenyl, R12 is a monovalent linear or branched organic radical containing a perfluorinated alkyl having 6 fully fluorinated carbon atoms, R13 is hydrogen, CrC18alkyl, C2-C18alkenyl or acetyl, Ri4 is hydrogen, Ci-Ci8alkyl, C2-Ci8alkenyl or -CH(Rn)-S(O )P-Ri2, Ri5 is hydrogen, d-Ci8alkyl, C2-Ci8alkenyl or -CH(Rn)-S(O )P-Ri2,
Ri6 is unsubstituted or with d-C4alkyl substituted methylene, -S-, -S(O)-, -S(O)2- or -CO-, and p is O, 1 or 2.
Particular preference is given to a composition comprising a compound of the formula I wherein, when n is 1 , R1 is hydrogen, CrCi8alkyl, -CO-R5, -CO-N(R6)-R7 or -CH2-CO-N(R6)-R7;
when n is 2,
Ri is unsubstituted or with d-C4alkyl substituted Ci-C8alkylene; -CO-R8-CO-, -CO-N(R6)-R9-N(R6)-CO- or -CH(R1O)-CO-N(Re)-R9-N(Re)-CO-CH(R10)-;
when n is 3,
Figure imgf000008_0001
R2, R3 and R4 independently of each other are hydrogen, CrC8alkyl, -CH(Rn)-S(0)p-R12,
; with the proviso that at least one of the radicals
Figure imgf000008_0002
R2, R3 or R4 is -CH(Rn)-S(0)p-R12;
R5 is CrC18alkyl, unsubstituted or with CrC4alkyl substituted phenyl; or C7-C12phenylalkyl, R6 is hydrogen or CrC4alkyl,
R7 is hydrogen, CrC8alkyl, unsubstituted or with CrC4alkyl substituted phenyl, R8 is phenylene, unsubstituted or with CrC4alkyl substituted CrC18alkylene, R9 is unsubstituted or with CrC4alkyl substituted C2-C18alkylene, R10 is hydrogen or CrC8alkyl, R11 is hydrogen, CrC8alkyl, unsubstituted or with CrC4alkyl substituted phenyl, Ri2 is saturated and contains 6 - 15 carbon atoms, of which 6 carbon atoms are fully fluorinated and contains at least one terminal perfluoromethyl group, Ri3 is hydrogen, d-Ci2alkyl, -CO-R5, -CO-N(R6)-R7 or -CH2-CO-N(R6)-R7, Ru is hydrogen, CrCi2alkyl or -CH(Rn)-S(O )P-Ri2, Ri5 is Ci-Ci8alkyl or -CH(Rn)-S(O )p-Ri2,
Ri6 is unsubstituted or with d-C4alkyl substituted methylene, n is 1 , 2 or 3, and p is O.
Of interest is a composition comprising a compound of the formula I wherein Ri2 is -CH2CH2(CF2)5CF3.
Of interest is a composition comprising a compound of the formula I wherein when n is 1 R1 is hydrogen, d-Ci8alkyl, -CO-R5, -CO-N(R6)-R7 or -CH2-CO-N(R6)-R7;
when n is 2,
Ri is Ci-C8alkylene, -CO-R8-CO-, -CO-N(R6)-R9-N(R6)-CO- or -CH(R10)-CO-N(R6)-R9-N(R6)-CO-CH(R10)-;
when n is 3,
Figure imgf000009_0001
R2, R3 and R4 independently of each other are hydrogen, Ci-C8alkyl, -CH(Rn)-S(0)p-Ri2,
; with the proviso that at least one of the radicals
Figure imgf000009_0002
R2, R3 or R4 is -CH(Rn)-S(0)p-Ri2;
R5 is Ci-Ci8alkyl, unsubstituted or with d-C4alkyl substituted phenyl; or benzyl,
R6 is hydrogen,
R7 is hydrogen, Ci-C8alkyl, unsubstituted or with d-C4alkyl substituted phenyl, R8 is phenylene or Ci-Ci8alkylene, R9 is C2-Ci8alkylene, Rio is Ci-C4alkyl,
Rn is hydrogen, Ci-C8alkyl, unsubstituted or with d-C4alkyl substituted phenyl, Ri2 is -CH2CH2(CF2)SCF3, Ri3 is hydrogen Or -CO-R5, Ri4 is hydrogen or Ci-C8alkyl, Ri5 is Ci-C4alkyl or -CH(Rn)-S(O )P-Ri2, Ri6 is methylene, n is 1 , 2 or 3, and p is 0.
Also of interest is a composition comprising a compound of the formula I, wherein when n is 1 , R1 is hydrogen, CrCi2alkyl, -CO-R5, -CO-N(R6)-R7 or -CH2-CO-N(R6)-R7;
when n is 2,
R1 is methylene, -CO-R8-CO- or -CH(R10)-CO-N(R6)-R9-N(R6)-CO-CH(R10)-;
when n is 3,
Figure imgf000010_0001
R2, R3 and R4 independently of each other are hydrogen, Ci-C4alkyl, -CH(Rn)-S(0)p-Ri2 or
— R X 11-T6 — <f y-H ; with the proviso that at least one of the radicals R2, R3 or R4 is
H R
Figure imgf000010_0002
R5 is CrC18alkyl, R6 is hydrogen,
R7 is hydrogen, CrC6alkyl, unsubstituted or with CrC4alkyl substituted phenyl, R8 is phenylene, R9 is ethylene, Rio is methyl,
Rn is hydrogen, d-C8alkyl, unsubstituted or with methyl substituted phenyl, Ri2 is -CH2CH2(CF2)5CF3, Ri3 is hydrogen or acetyl, Ru is Ci-C4alkyl, R15 Is -CH(Rn)-S(O)P-R12, R16 is methylene, n is 1 , 2 or 3, and p is O.
Also of particular interest is a composition comprising a compound of the formula I, wherein when n is 2, R1 is -CO-R8-CO-; R2, R3 and R4 independently of each other are hydrogen, Ci-C4alkyl, -CH(Rn)-S(O)P-R12 or
■ w'tn tne Prov'so tnat at 'east one °f tne radicals R2, R3 or R4 is
Figure imgf000011_0001
-CH(Rn)-S(O)P-R12;
R8 is phenylene,
R11 is hydrogen, CrC8alkyl, unsubstituted or with methyl substituted phenyl, R12 is -CH2CH2(CF2)5CF3,
R13 is hydrogen or acetyl,
R14 is Ci-C4alkyl,
R15 JS -CH(Rn)-S(O)P-R12,
R16 is methylene, n is 2, and p is O.
Further of special interest is a composition comprising a compound of the formula I, wherein when n is 2, R1 is -CO-R8-CO-;
R2, R3 and R4 independently of each other are hydrogen, CrC4alkyl or -CH(Rn)-S(0)p-R12; with the proviso that at least one of the radicals R2, R3 or R4 is -CH(Rn)-S(O )P-R12; R8 is phenylene,
Rn is hydrogen, CrC8alkyl, unsubstituted or with methyl substituted phenyl,
Ri2 is -CH2CH2(CF2)5CF3, n is 2, and p is 0.
Of very special interest are compositions, which comprise as component (b) one of the compounds 101 to 142.
Figure imgf000012_0001
Figure imgf000012_0003
Figure imgf000013_0001
Figure imgf000013_0002
Figure imgf000013_0003
Figure imgf000013_0004
Figure imgf000014_0001
Figure imgf000014_0002
Figure imgf000014_0003
Figure imgf000014_0004
Figure imgf000014_0005
Figure imgf000015_0001
Figure imgf000015_0002
Figure imgf000015_0003
Figure imgf000015_0004
Figure imgf000015_0005
Figure imgf000016_0001
Figure imgf000016_0002
Figure imgf000016_0003
Figure imgf000016_0004
Figure imgf000016_0005
Figure imgf000017_0001
Figure imgf000017_0002
Figure imgf000017_0003
Figure imgf000017_0004
Figure imgf000018_0001
Figure imgf000018_0002
Figure imgf000018_0003
Figure imgf000018_0004
Figure imgf000018_0005
10
Figure imgf000019_0001
Figure imgf000019_0002
Figure imgf000019_0003
Figure imgf000019_0004
Figure imgf000020_0001
Figure imgf000020_0002
Figure imgf000020_0003
Figure imgf000021_0001
Figure imgf000021_0002
Figure imgf000021_0003
Of very particular interest are compounds 104 and 105.
The compounds of the formula I can be prepared by methods known in the art, in analogy to the process disclosed in WO 2007/144283 or in analogy to the process disclosed for example in U.S. Patent 4,874,885. The compounds of the formula I are suitable as oil and water repellency agents for organic materials. Examples of organic materials which may be present in the compositions of the invention are following materials:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, po- lybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, prefe- rably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
a) radical polymerisation (normally under high pressure and at elevated temperature.
b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either π- or σ-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(lll) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, Na and/or Ilia of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC). 2. Mixtures of the polymers mentioned under 1 ), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g. ethylene/norbornene like COC), ethylene/1 -olefins copolymers, where the 1 -olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vi- nylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1 ) above, for example polypropylene/ethy- lene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene- acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyal- kylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-Cg) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
Homopolymers and copolymers from 1.) - 4.) may have any stereostructure including syndio- tactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).
6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including styrene, α-methylstyrene, all isomers of vinyl toluene, especially p-vinyltoluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, and mixtures thereof. Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Ste- reoblock polymers are also included.
6a. Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/bu- tadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhy- dride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/pro- pylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/sty- rene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propy- lene/styrene.
6b. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6.), especially including polycyclohexylethylene (PCHE) prepared by hydrogenating atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).
6c. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6a.).
Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
7. Graft copolymers of vinyl aromatic monomers such as styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acry- lonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo- chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from α,β-unsatu rated acids and derivatives thereof such as polyacry- lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni- triles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
1 1. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace- tals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1 ) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides. 15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadi- enes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11 , polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly- m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene tereph- thalate, poly-1 ,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins. 22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acry- lates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, PoIy- amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
29. Naturally occurring and synthetic organic materials which are pure monomeric com- pounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials. 30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carbo- xylated styrene/butadiene copolymers.
Preferred organic materials are natural, semi-synthetic or, preferably, synthetic polymers.
Particularly referred organic materials are synthetic polymers, most preferably thermoplastic polymers. Especially preferred organic materials are polyacetals, polyolefins such as polypropylene or polyethylene, polyether/polyurethanes, polyesters such as polybutylene tereph- thalate, polycarbonates or polyamides.
To be singled out for special mention is the efficacy of the compounds of the formula I as reducers of surface energy of the organic materials. Organic materials with low surface energy have intrinsically better properties like for example water and oil repellency, hydrophobicity, barrier properties, easy to clean, self cleaning, antigraffiti or solvent resistance.
The compounds of the formula I will preferably be added to the organic material in concentrations of 0.01 to 10 %, preferably 0.01 to 2 %, typically 0.1 to 2 %, based on the weight of said material.
The present invention also relates to a composition in the form of a masterbatch or concentrate comprising component (a) in an amount of from 5 to 90 % and component (b) in an amount of from 5 to 80 % by weight.
In addition to the compounds of the formula I, the composition of the invention may comprise further additives, such as for example the following:
1. Antioxidants
1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-di- methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-bu- tyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethyl- phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth- oxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6-(1 '-methylundec-1 '-yl)phenol, 2,4-dimethyl-6-(1 '- methylheptadec-1 '-yl)phenol, 2,4-dimethyl-6-(1 '-methyltridec-1'-yl)phenol and mixtures thereof.
1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl- thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4- nonylphenol.
1.3. Hydroquinones and alkylated hydroquinones, for example 2,6-di-tert-butyl-4-methoxy- phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade- cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu- tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy- droxyphenyl) adipate.
1.4. Tocopherols, for example α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).
1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tert-butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2- methylphenol), 4,4'-thiobis(3,6-di-sec-amylphenol), 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)- disulfide.
1.6. Alkylidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)- phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4- methylphenol), 2,2'-methylenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4,6-di-tert-butyl- phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(α-methylben- zyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methy- lenebis(2,6-di-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylphenol), 1 ,1-bis(5-tert- butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4- methylphenol, 1 , 1 ,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1 , 1 -bis(5-tert-butyl-4- hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert- butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopenta- diene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephtha- late, 1 ,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphe- nyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1 ,1 ,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
1.7. Q-, N- and S-benzyl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi- benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy- 3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4- tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxy- benzyl)sulfide, isooctyl-S^-di-tert-butyM-hydroxybenzylmercaptoacetate.
1.8. Hydroxybenzylated malonates, for example dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hy- droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di- dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-(1 ,1 ,3,3-te- tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
1.9. Aromatic hydroxybenzyl compounds, for example 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxy- benzyl)-2,4,6-trimethylbenzene, 1 ,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame- thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10. Triazine compounds, for example 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy- anilino)-1 ,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1 ,3,5-tri- azine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,3,5-triazine, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenoxy)-1 ,2,3-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxyben- zyl)isocyanurate, 1 ,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-tris- (3,5-di-tert-butyl-4-hydroxyphenylethyl)-1 ,3,5-triazine, 1 ,3,5-tris(3,5-di-tert-butyl-4-hydroxy- phenylpropionyl)-hexahydro-1 ,3,5-triazine, 1 ,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)iso- cyanurate.
1.1 1. Benzylphosphonat.es, for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho- nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy- droxybenzylphosphonate, dioctadecyl-δ-tert-butyM-hydroxy-S-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid. 1.12. Acylaminophenols, for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.13. Esters of β-(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9- nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethy- lene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hy- droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol- propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14. Esters of β-(5-tert-butyl-4-hvdroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis- (hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl- olpropane, 4-hydroxymethyl-1 -phospha-2,6,7-trioxabicyclo[2.2.2]octane; 3,9-bis[2-{3-(3-tert- butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1 ,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]- undecane.
1.15. Esters of β-(3,5-dicvclohexyl-4-hvdroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1 -phospha^θj-trioxabicyclop^^octane.
1.16. Esters of 3,5-di-tert-butyl-4-hvdroxyphenyl acetic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1 ,6-hexanediol, 1 ,9-nonanediol, ethylene glycol, 1 ,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox- amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy- droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1.17. Amides of β-(3,5-di-tert-butyl-4-hvdroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert- butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxy- phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hy- drazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Nau- gard®XL-1 , supplied by Uniroyal).
1.18. Ascorbic acid (vitamin C)
1.19. Aminic antioxidants, for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-bu- tyl-p-phenylenediamine, N,N'-bis(1 ,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3- methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicy- clohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p- phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1 ,3-dimethylbutyl)-N'-phe- nyl-p-phenylenediamine, N-(1 -methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'- phenyl-p-phenylenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di- sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenyl- amine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naph- thylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butyl- aminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4- octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylamino- methylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetra- methyl-4,4'-diaminodiphenylmethane, 1 ,2-bis[(2-methylphenyl)amino]ethane, 1 ,2-bis(phenyl- amino)propane, (o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N- phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenyl- amines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyl- diphenylamines, a mixture of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro- 3,3-dimethyl-4H-1 ,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert- butyl/tert-octylphenothiazines, a mixture of mono- and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1 ,4-diaminobut-2-ene.
2. UV absorbers and light stabilizers 2.1. 2-(2'-Hvdroxyphenyl)benzotriazoles, for example 2-(2'-hydroxy-5'-methylphenyl)-benzo- triazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphe- nyl)benzotriazole, 2-(2'-hydroxy-5'-(1 ,1 ,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di- tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphe- nyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'- hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy- 5'-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyl- oxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2- methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-meth- oxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonyl- ethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxy- phenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis[4-(1 , 1 ,3,3- tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3'-tert-bu- tyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol
300; [ R - CH2CH2 - COO - CH2CH2 -J^ , where R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-
2-ylphenyl, 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1 ,1 ,3,3-tetramethylbutyl)-phenyl]- benzotriazole; 2-[2'-hydroxy-3'-(1 ,1 ,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)-phenyl]ben- zotriazole.
2.2. 2-Hvdroxybenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyl- oxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4-tert-butylben- zoyl)resorcinol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzo- ate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxyben- zoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrylates, for example ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphe- nylacrylate, methyl α-carbomethoxycinnamate, methyl α-cyano-β-methyl-p-methoxycinna- mate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p-methoxycin- namate, N-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline, neopentyl tetra(α-cyano-β,β-di- phenylacrylate.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis[4-(1 ,1 ,3,3-tetramethyl- butyl)phenol], such as the 1 :1 or 1 :2 complex, with or without additional ligands such as n- butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert- butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphe- nylundecylketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or with- out additional ligands.
2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1 -octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1 ,2,2,6,6-pentamethyl-4- piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-(2- hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert- octylamino-2,6-dichloro-1 ,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1 ,2,3,4-butanetetracarboxylate, 1 ,1'-(1 ,2-ethanediyl)- bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy- 2,2,6,6-tetramethylpiperidine, bis(1 ,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5- di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1 ,3,8-triazaspiro[4.5]decane-2,4- dione, bis(1 -octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1 -octyloxy-2,2,6,6- tetramethylpiperidyl)succinate, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4- piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1 ,3,5-triazine, the condensate of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1 ,3,5-triazine and 1 ,2-bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino- 1 ,2, 2, 6, 6-pentamethylpiperidyl)-1 ,3,5-triazine and 1 ,2-bis(3-aminopropylamino)ethane, 8- acetyl-3-dodecyl-7,7,9,9-tetramethyl-1 ,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1 - (2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 3-dodecyl-1 -(1 ,2,2,6,6-pentamethyl-4- piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6- tetramethylpiperidine, a condensate of N,N'-bis(2,2,6,6-tetramethyl-4- piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1 ,3,5-triazine, a condensate of 1 ,2-bis(3-aminopropylamino)ethane and 2, 4, 6-trichloro-1 ,3,5-triazine as well as 4-butylamino-2!2!6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); a condensate of 1 ,6-hexanediamine and 2,4,6-trichloro-1 ,3,5-triazine as well as N,N-dibutylamine and 4- butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [192268-64-7]); N-(2,2,6,6- tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-(1 , 2,2,6, 6-pentamethyl-4-piperidyl)-n- dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro- [4,5]decane and epichlorohydrin, 1 ,1-bis(1 ,2,2,6, 6-pentamethyl-4-piperidyloxycarbonyl)-2-(4- methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexa- methylenediamine, a diester of 4-methoxymethylenemalonic acid with 1 ,2,2,6,6-pentamethyl- 4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, a reaction product of maleic acid anhydride-α-olefin copolymer with 2,2,6,6-tetramethyl-4-ami- nopiperidine or 1 ,2,2,6,6-pentamethyl-4-aminopiperidine, 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6- tetramethylpiperidine-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1 ,3,5-triazine, 1 -(2-hydr- oxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 5-(2-ethylhexanoyl)- oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor (Clariant; CAS Reg. No. 106917-31-1], 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, the reaction product of 2,4-bis- [(i-cyclohexyloxy^^θ.θ-piperidine^-yObutylaminoJ-θ-chloro-s-triazine with N,N'-bis(3-ami- nopropyl)ethylenediamine), 1 ,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazine-3-one-4- yl)amino)-s-triazine, 1 ,3,5-tris(N-cyclohexyl-N-(1 ,2,2,6,6-pentamethylpiperazine-3-one-4-yl)- amino)-s-triazine.
2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy- 5,5'-di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and p-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hydroxyphenyl)-1 ,3,5-triazines, for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2- (2, 4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2,4-bis(2-hydroxy-4-propyl- oxyphenyl)-6-(2,4-dimethylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4- methylphenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine, 2- [2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1 ,3,5-triazine, 2-[2- hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1 ,3,5-triazine, 2-[4- (dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)- 1 ,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl- phenyl)-1 ,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1 ,3,5-triazine, 2-(2-hydr- oxy-4-methoxyphenyl)-4,6-diphenyl-1 ,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2- hydroxypropoxy)phenyl]-1 ,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl- 1 ,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4- dimethylphenyl)-1 ,3,5-triazine, 2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4- methoxyphenyl)-1 ,3,5-triazine.
3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1 ,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl- oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
4. Phosphites and phosphonites, for example triphenyl phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di- cumylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)- pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristea- ryl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6- isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1 ,3,2-dioxaphosphocin, bis(2,4-di-tert- butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1 ,3,2-dioxaphosphocin, 2,2',2"-nitrilo- [triethyltris(3,3',5,5'-tetra-tert-butyl-1 ,1 '-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-te- tra-tert-butyl-1 ,1 '-biphenyl-2,2'-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)- 1 ,3,2-dioxaphosphirane.
5. Hvdroxylamines, for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N- dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N- dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydrox- ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
6. Nitrones, for example, N-benzyl-alpha-phenylnitrone, N-ethyl-alpha-methylnitrone, N-octyl- alpha-heptylnitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnnitrone, N- hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-al- pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta- decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxyl- amine derived from hydrogenated tallow amine.
7. Thiosynergists, for example dilauryl thiodipropionate, dimistryl thiodipropionate, distearyl thiodipropionate or distearyl disulfide.
8. Peroxide scavengers, for example esters of β-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto- benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(β- dodecylmercapto)propionate.
9. Polvamide stabilizers, for example copper salts in combination with iodides and/or phos- phorus compounds and salts of divalent manganese.
10. Basic co-stabilizers, for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
1 1. Nucleating agents, for example inorganic substances, such as talcum, metal oxides, such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds, such as mono- or polycarboxylic acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Especially preferred are 1 ,3:2,4-bis(3',4'-dimethylbenzylidene)sorbitol, 1 ,3:2,4-di(paramethyl- dibenzylidene)sorbitol, 1 ,3:2,4-di(benzylidene)sorbitol, and Irgaclear XT 386 (RTM, Ciba Inc.).
12. Fillers and reinforcing agents, for example calcium carbonate, silicates, glass fibres, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
13. Other additives, for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
14. Benzofuranones and indolinones, for example those disclosed in U.S. 4,325,863; U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-431661 1 ; DE-A-4316622; DE-A-4316876; EP-A-0589839, EP-A-0591102; EP-A-1291384 or 3-[4-(2- acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxy- ethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)ben- zofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-di- methylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di- tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3- dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2-acetyl-5-isooctylphenyl)-5-isooctyl- benzofuran-2-one.
The further additives are typically used in concentrations of 0.01 to 10 %, based on the total weight of the material to be treated.
A preferred composition of the invention comprises, as other additives phenolic antioxidants, light stabilizers and/or processing stabilizers.
Incorporation of the compounds of the formula I and, if desired, further additives into the syn- thetic polymers is carried out by known methods, for example before or during moulding or else by applying the dissolved or dispersed compounds to the synthetic polymer, if appropriate with subsequent slow evaporation of the solvent. A further embodiment of the present invention is a process for reducing the surface energy of organic materials which comprises treating the organic material with at least a compound of the formula I
Figure imgf000039_0001
wherein, when n is 1 ,
Ri is hydrogen, Ci-C25alkyl, C2-C25alkenyl, -CO-R5, -CH(R10)CO-R5, -C(Riθ)2CO-R5,
-CO-N(R6)-R7, -CH(R10)CO-N(R6)-R7, -C(R10)2CO-N(R6)-R7, -CH(R10)COOR5 or
Figure imgf000039_0002
when n is 2,
R1 is unsubstituted or with CrC4alkyl, benzyl or phenyl substituted CrC24alkylene; with oxygen or sulfur interrupted C2-C24alkylene, -CO-R8-CO-, -CH(R10)CO-R8-CO-CH(R10)-, -C(R10)2CO-R8-CO-C(R10)2-, -CO-N(R6)-R9-N(R6)-CO-,
-CH(R10)CO-N(Re)-R9-N(Re)-CO-CH(R10)-, -C(R1O)2CO-N(Re)-R9-N(Re)-CO-C(R1O)2-, -CH(R10)CO-O-R9-O-CO-CH(R10)- or -C(R10)2CO-O-R9-O-CO-C(R10)2-;
when n is 3,
Figure imgf000039_0003
R2, R3 and R4 independently of each other are hydrogen, CrC25alkyl, C2-C25alkenyl,
Figure imgf000039_0004
with the proviso that at least one of the radicals R2, R3 or R4 is
Figure imgf000040_0001
-CH(RH)-S(OVR12;
R5 is Ci-C25alkyl, C2-C25alkenyl, unsubstituted or with d-C4alkyl or halogen substituted phenyl; or C7-Ci2phenylalkyl, R6 is hydrogen or Ci-C4alkyl,
R7 is hydrogen, Ci-C25alkyl, unsubstituted or with Ci-C4alkyl or halogen substituted phenyl,
Rs is phenylene, unsubstituted or with Ci-C4alkyl, benzyl or phenyl substituted
Ci-C24alkylene; with oxygen or sulfur interrupted C2-C24alkylene,
Rg is a direct bond, unsubstituted or with Ci-C4alkyl, benzyl or phenyl substituted C2-C24alkylene; or with oxygen or sulfur interrupted C2-C24alkylene,
R10 is hydrogen or d-C8alkyl,
R11 is hydrogen, d-C8alkyl, unsubstituted or with Ci-C4alkyl substituted phenyl,
Ri2 is a monovalent linear or branched organic radical containing a perfluorinated alkyl having 6 fully fluorinated carbon atoms, Ri3 is hydrogen, CrC25alkyl, C2-C25alkenyl, -CO-R5, -CO-N(R6)-R7 or -CH2-CO-N(R6)-R7,
Ri4 is hydrogen, CrC25alkyl, C2-C25alkenyl or -CH(Rn)-S(O )P-Ri2,
Ris is hydrogen, CrC25alkyl, C2-C25alkenyl or -CH(Rn)-S(O )P-Ri2,
R16 is unsubstituted or with Ci-C4alkyl substituted methylene, -S-, -S(O)-, -S(O)2- or -CO-,
Ri7 is Ci-C4alkyl, n is 1 , 2 or 3, p is O, 1 or 2; and wherein the treatment is carried out in the absence of a compound with a perfluorinated substituent other than that of formula (I).
The preferred compounds of the formula I in the process are identical to those of the inventive composition.
Preferred is a process for imparting oil and water repellency to the organic material.
Preferred is a process for imparting oil repellency. Preferred is a process with a compound of the formula I wherein, when n is 1 ,
Ri is hydrogen, d-Ci2alkyl, -CO-R5, -CO-N(R6)-R7 or -CH2-CO-N(R6)-R7;
when n is 2,
R1 is methylene, -CO-R8-CO- or -CH(R10)-CO-N(R6)-R9-N(R6)-CO-CH(R10)-;
when n is 3,
Figure imgf000041_0001
R2, R3 and R4 independently of each other are hydrogen, d-C4alkyl, -CH(Rn)-S(0)p-Ri2 or ith the proviso that at least one of the radicals R2, R3 or R4 is
Figure imgf000041_0002
R5 is CrC18alkyl,
R6 is hydrogen,
R7 is hydrogen, CrC6alkyl, unsubstituted or with CrC4alkyl substituted phenyl,
R8 is phenylene,
R9 is ethylene, R10 is methyl,
R11 is hydrogen, CrC8alkyl, unsubstituted or with methyl substituted phenyl,
R12 is -CH2CH2(CF2)5CF3,
R13 is hydrogen or acetyl,
R14 is CrC4alkyl, R15 Js -CH(Rn)-S(O)P-R12,
R16 is methylene, n is 1 , 2 or 3, and p is 0. Component (b) and, if desired, further additives, can also be added before or during polymerisation or before crosslinking.
Component (b), with or without further additives, can be incorporated in pure form or encap- sulated in waxes, oils or polymers into the synthetic polymer.
Component (b), with or without further additives, can also be sprayed onto the synthetic polymer. It is able to dilute other additives (for example the conventional additives indicated above) or their melts so that they too can be sprayed together with these additives onto the polymer. Addition by spraying on during the deactivation of the polymerization catalysts is particularly advantageous, it being possible to carry out spraying using, for example, the steam used for deactivation.
In the case of spherically polymerized polyolefins it may, for example, be advantageous to apply component (b), with or without other additives, by spraying.
The synthetic polymers prepared in this way can be employed in a wide variety of forms, for example as foams, films, fibres, tapes, moulding compositions, as profiles or as binders for coating materials, especially powder coatings, adhesives, putties or especially as thick-layer polyolefin mouldings which are in long-term contact with extractive media, such as, for example, pipes for liquids or gases, films, fibres, geomembranes, tapes, profiles or tanks.
The preferred thick-layer polyolefin mouldings have a layer thickness of from 1 to 50 mm, in particular from 1 to 30 mm, for example from 2 to 10 mm.
The compositions according to the invention can be advantageously used for the preparation of various shaped articles. Examples are:
1-1 ) Floating devices, marine applications, pontoons, buoys, plastic lumber for decks, piers, boats, kayaks, oars, and beach reinforcements.
I-2) Automotive applications, in particular bumpers, dashboards, battery, rear and front linings, moldings parts under the hood, hat shelf, trunk linings, interior linings, air bag covers, electronic moldings for fittings (lights), panes for dashboards, headlamp glass, instrument panel, exterior linings, upholstery, automotive lights, head lights, parking lights, rear lights, stop lights, interior and exterior trims; door panels; gas tank; glazing front side; rear windows; seat backing, exterior panels, wire insulation, profile extrusion for sealing, cladding, pillar covers, chassis parts, exhaust systems, fuel filter / filler, fuel pumps, fuel tank, body side mouldings, convertible tops, exterior mirrors, exterior trim, fasteners / fixings, front end module, glass, hinges, lock systems, luggage / roof racks, pressed/stamped parts, seals, side impact protection, sound deadener / insulator and sunroof.
1-3) Road traffic devices, in particular sign postings, posts for road marking, car accessories, warning triangles, medical cases, helmets, tires.
I-4) Devices for plane, railway, motor car (car, motorbike) including furnishings.
I-5) Devices for space applications, in particular rockets and satellites, e.g. reentry shields.
I-6) Devices for architecture and design, mining applications, acoustic quietized systems, street refuges, and shelters.
11-1 ) Appliances, cases and coverings in general and electric/electronic devices (personal computer, telephone, portable phone, printer, television-sets, audio and video devices), flower pots, satellite TV bowl, and panel devices.
II-2) Jacketing for other materials such as steel or textiles.
II-3) Devices for the electronic industry, in particular insulation for plugs, especially computer plugs, cases for electric and electronic parts, printed boards, and materials for electronic data storage such as chips, check cards or credit cards.
II-4) Electric appliances, in particular washing machines, tumblers, ovens (microwave oven), dish-washers, mixers, and irons.
II-5) Covers for lights (e.g. street-lights, lamp-shades).
II-6) Applications in wire and cable (semi-conductor, insulation and cable-jacketing). 11-7) Foils for condensers, refrigerators, heating devices, air conditioners, encapsulating of electronics, semi-conductors, coffee machines, and vacuum cleaners.
111-1 ) Technical articles such as cogwheel (gear), slide fittings, spacers, screws, bolts, handles, and knobs.
III-2) Rotor blades, ventilators and windmill vanes, solar devices, swimming pools, swimming pool covers, pool liners, pond liners, closets, wardrobes, dividing walls, slat walls, folding walls, roofs, shutters (e.g. roller shutters), fittings, connections between pipes, sleeves, and conveyor belts.
III-3) Sanitary articles, in particular shower cubicles, lavatory seats, covers, and sinks.
III-4) Hygienic articles, in particular diapers (babies, adult incontinence), feminine hygiene articles, shower curtains, brushes, mats, tubs, mobile toilets, tooth brushes, and bed pans.
III-5) Pipes (cross-linked or not) for water, waste water and chemicals, pipes for wire and cable protection, pipes for gas, oil and sewage, guttering, down pipes, and drainage sy- stems.
III-6) Profiles of any geometry (window panes) and siding.
III-7) Glass substitutes, in particular extruded plates, glazing for buildings (monolithic, twin or multiwall), aircraft, schools, extruded sheets, window film for architectural glazing, train, transportation, sanitary articles, and greenhouse.
III-8) Plates (walls, cutting board), extrusion-coating (photographic paper, tetrapack and pipe coating), silos, wood substitute, plastic lumber, wood composites, walls, surfaces, furniture, decorative foil, floor coverings (interior and exterior applications), flooring, duck boards, and tiles.
III-9) Intake and outlet manifolds. 111-10) Cement-, concrete-, composite-applications and covers, siding and cladding, hand rails, banisters, kitchen work tops, roofing, roofing sheets, tiles, and tarpaulins.
IV-1 ) Plates (walls and cutting board), trays, artificial grass, astroturf, artificial covering for stadium rings (athletics), artificial floor for stadium rings (athletics), and tapes.
IV-2) Woven fabrics continuous and staple, fibers (carpets / hygienic articles / geotextiles / monofilaments; filters; wipes / curtains (shades) / medical applications), bulk fibers (applications such as gown / protection clothes), nets, ropes, cables, strings, cords, threads, safety seat-belts, clothes, underwear, gloves; boots; rubber boots, intimate apparel, garments, swimwear, sportswear, umbrellas (parasol, sunshade), parachutes, paraglides, sails, "balloon-silk", camping articles, tents, airbeds, sun beds, bulk bags, and bags.
IV-3) Membranes, insulation, covers and seals for roofs, tunnels, dumps, ponds, dumps, walls roofing membranes, geomembranes, swimming pools, curtains (shades) / sun-shields, awnings, canopies, wallpaper, food packing and wrapping (flexible and solid), medical packaging (flexible & solid), airbags/safety belts, arm- and head rests, carpets, centre console, dashboard, cockpits, door, overhead console module, door trim, headliners, interior lighting, interior mirrors, parcel shelf, rear luggage cover, seats, steering column, steering wheel, textiles, and trunk trim.
V) Films (packaging, dump, laminating, agriculture and horticulture, greenhouse, mulch, tunnel, silage), bale wrap, swimming pools, waste bags, wallpaper, stretch film, raffia, desalination film, batteries, and connectors.
VI-1 ) Food packing and wrapping (flexible and solid), bottles.
VI-2) Storage systems such as boxes (crates), luggage, chest, household boxes, pallets, shelves, tracks, screw boxes, packs, and cans.
VI-3) Cartridges, syringes, medical applications, containers for any transportation, waste baskets and waste bins, waste bags, bins, dust bins, bin liners, wheely bins, container in general, tanks for water / used water / chemistry / gas / oil / gasoline / diesel; tank liners, boxes, crates, battery cases, troughs, medical devices such as piston, ophthalmic applications, diagnostic devices, and packing for pharmaceuticals blister.
Vl 1-1 ) Extrusion coating (photo paper, tetrapack, pipe coating), household articles of any kind (e.g. appliances, thermos bottle / clothes hanger), fastening systems such as plugs, wire and cable clamps, zippers, closures, locks, and snap-closures.
VII-2) Support devices, articles for the leisure time such as sports and fitness devices, gymnastics mats, ski-boots, inline-skates, skis, big foot, athletic surfaces (e.g. tennis grounds); screw tops, tops and stoppers for bottles, and cans.
VII-3) Furniture in general, foamed articles (cushions, impact absorbers), foams, sponges, dish clothes, mats, garden chairs, stadium seats, tables, couches, toys, building kits (boards / figures / balls), playhouses, slides, and play vehicles.
VII-4) Materials for optical and magnetic data storage.
VII-5) Kitchen ware (eating, drinking, cooking, storing).
VII-6) Boxes for CD's, cassettes and video tapes; DVD electronic articles, office supplies of any kind (ball-point pens, stamps and ink-pads, mouse, shelves, tracks), bottles of any volume and content (drinks, detergents, cosmetics including perfumes), and adhesive tapes.
VII-7) Footwear (shoes / shoe-soles), insoles, spats, adhesives, structural adhesives, food boxes (fruit, vegetables, meat, fish), synthetic paper, labels for bottles, couches, artificial joints (human), printing plates (flexographic), printed circuit boards, and display technologies.
VII-8) Devices of filled polymers (talc, chalk, china clay (kaolin), wollastonite, pigments, carbon black, TiO2, mica, nanocomposites, dolomite, silicates, glass, asbestos).
Of interest are compositions comprising as component (a) fibers and fabrics used in nonwo- ven medical fabric and related apparel (surgical gowns, drapes, bandages), construction fabrics (house wrapping, roofing, swimming-pool wrapping) and home furnishing (carpets, table linens, shower curtains). Of special interest are compositions comprising as component (a) fibers and nonwovens.
Thus, a further embodiment of the present invention relates to a shaped article, in particular a film, pipe, profile, bottle, tank or container, fiber containing a composition as described above. Of special interest are fibers and nonwovens.
A further embodiment of the present invention relates to a molded article containing a composition as described above. The molding is in particular effected by injection, blow, com- pression, roto-molding or slush-molding or extrusion.
A preferred embodiment of the present invention is also the use of a compound of the formula I as reducer of surface energy [e.g. as oil and water repellency agent] for an organic material.
The preferred compounds of the formula I or component (b) respectively, and optionally further additives, in the use as reducer of surface energy [e.g. increasing the oil and water repellency] of organic materials are the same as those described for the process and composition.
The following examples illustrate the invention further. Parts or percentages relate to weight.
Example 1 : Preparation of compound 101 (2-methyl-4,6-bis-(3,3,4,4,5,5,6,6,7,7,8,8,8- tridecafluoro-octylsulfanylmethyl)-phenol)
)
Figure imgf000047_0001
10.6 g (98.0 mmol) of o-cresol, 74.6 g (196 mmol) of 1 H,1 H,2H,2H-perfluorooctane-1-thiol, 2.70 g (19.6 mmol) of dimethylamine (33% in EtOH), 11.8 g (392 mmol) of paraformaldehyde and 1.0 ml of N,N-dimethylformamide (DMF) are mixed and heated under reflux for 4 hours under nitrogen atmosphere. Ethyl acetate is added and the organic phase is washed repeatedly with water and brine until pH neutral. The organic phase is dried over magnesium sulfate, filtered and concentrated using a vacuum rotary evaporator to give 89.1 g of the compound 101 , yellow liquid with a 96% GC-purity. 1H NMR: (400 MHz, CDCI3): δ = 7.06 (d, J = 1.6 Hz, ArH, 1 H); 6.92 (d, J = 1.6 Hz, ArH, 1 H); 6.06 (s, OH, 1 H); 3.83 (s, ArCH2, 2H); 3.66 (s, ArCH2, 2H); 2.70 - 2.55 (m, CH2CH2CF2, 4H); 2.40-2.20 (m, CH2CH2CF2, 4H); 2.27 (s, CH3, 3H).
Example 2: Preparation of compound 102 (2-tert-butyl-4,6-bis-(3,3,4,4,5,5,6,6,7,7,8,8,8- tridecafluoro-octylsulfanylmethyl)-phenol)
Figure imgf000048_0001
0.80 g (5.35 mmol) of 2-tert-butyl-phenol, 6.51 g (17.1 mmol) of 1 H,1 H,2H,2H- perfluorooctane-1 -thiol, 0.22 g (1.61 mmol) of dimethylamine (33% in EtOH), 0.96 g (32.1 mmol) of paraformaldehyde and 1.0 ml of N,N-dimethylformamide (DMF) are mixed and heated under reflux for 12 hours under nitrogen atmosphere. Ethyl acetate is added and the organic phase is washed repeatedly with water and brine until pH neutral. The organic phase is dried over magnesium sulfate, filtered and concentrated using a vacuum rotary evaporator to give 7.19 g of a yellow liquid. The crude product is purified by flash chromatography (cyclohexane/ethyl acetate: 40 : 1 ) to give 3.91 g of compound 102, pale yellow solid, m.p. 47-49°C. 1H NMR: (400 MHz, CDCI3): δ = 7.18 (d, J = 2.0 Hz1 ArH, 1 H); 6.95 (d, J = 2.0 Hz, ArH, 1 H); 6.58 (s, OH, 1 H); 3.87 (s, ArCH2, 2H); 3.68 (s, ArCH2, 2H); 2.65 - 2.55 (m, CH2CH2CF2, 4H); 2.40-2.15 (m, CH2CH2CF2, 4H); 1.43 (s, CH3, 9H).
Example 3: Preparation of compound 103 (2,4, 6-tris-(3, 3,4,4, 5,5,6,6, 7, 7,8,8, 8-tridecafluoro- octylsulfanylmethyl)-phenol)
Figure imgf000048_0002
0.37 g (3.93 mmol) of phenol, 4.79 g (12.6 mmol) of 1 H,1 H,2H,2H-perfluorooctane-1-thiol, 0.16 g (1.18 mmol) of dimethylamine (33% in EtOH), 0.71 g (23.6 mmol) of paraformaldehyde and 1.0 ml of N,N-dimethylformamide (DMF) are mixed and heated under reflux for 12 hours under nitrogen atmosphere. Ethyl acetate is added and the organic phase is washed repeatedly with water and brine until pH neutral. The organic phase is dried over magnesium sulfate, filtered and concentrated using a vacuum rotary evaporator to give 5.61 g of a yellow liquid. The crude product is purified by flash chromatography (cyclohexane/ethyl acetate: 19 : 1 ) to give 3.85 g of compound 103, pale yellow solid, m.p. 36-400C. 1H NMR: (300 MHz, CDCI3): δ = 7.10 (s, ArH, 2H); 6.82 (s, OH, 1 H); 3.84 (s, ArCH2, 4H); 3.67 (s, ArCH2, 2H); 2.70-2.55 (m, CH2CH2CF2, 6H); 2.50-2.15 (m, CH2CH2CF2, 6H).
Example 4: Preparation of compound 104 (terephthalic acid bis-[2-methyl-4,6-bis- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octylsulfanylmethyl)-phenyl] ester)
Figure imgf000049_0001
87.5 g (98.0 mmol) of compound 101 and 1 1.9 g (118 mmol) of triethylamine are dissolved in 200 ml of tetrahydrofuran. 9.95 g (49.0 mmol) of terephthaloyl chloride is added portionwise to the reaction mixture at room temperature under nitrogen atmosphere. The reaction mixture is stirred at room temperature for 12 hours. Ethyl acetate (200 ml) is added and the organic phase is washed repeatedly with water until pH neutral. The organic phase is dried over magnesium sulfate, filtered and concentrated using a vacuum rotary evaporator to give 93.2 g of a pale yellow wax. The crude product is suspended in methanol (200 ml), heated to reflux and filtered. Then the filtered solid is crystallized in hexane (400 ml) to give 50.1 g of compound 104, white solid, m.p. 83-87°C. 1H NMR: (400 MHz, CDCI3): δ = 8.40 (s, ArH, 4H); 7.25-7.15 (m, ArH, 4H); 3.76 (s, ArCH2, 4H); 3.69 (s, ArCH2, 4H); 2.75-2.60 (m, CH2CH2CF2, 8H); 2.45-2.15 (m, CH2CH2CF2, 8H); 2.23 (s, CH3, 6H).
Example 5: Preparation of compound 105 (terephthalic acid bis-[2,4,6-tris- (3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoro-octylsulfanylmethyl)-phenyl] ester)
Figure imgf000050_0001
4.80 g (3.78 mmol) of compound 103 and 0.42 g (4.16 mmol) of triethylamine are dissolved in 100 ml of tetrahydrofuran. 0.38 g (1.89 mmol) of terephthaloyl chloride is added portionwise to the reaction mixture at 500C under nitrogen atmosphere. The reaction mixture is stirred at 500C for 12 hours. Ethyl acetate (100 ml) is added and the organic phase is washed repeatedly with water until pH neutral. The organic phase is dried over magnesium sulfate, filtered and concentrated using a vacuum rotary evaporator to give 4.50 g of a pale yellow wax. The crude product is crystallized in acetonitrile (50 ml) under vigorous stirring to give 3.70 g of compound 105, white solid, m.p. 92-96°C. 1H NMR: (400 MHz, CDCI3): δ = 8.31 (s, ArH, 4H); 7.30 (s, ArH, 4H); 3.70 (s, ArCH2, 4H); 3.60 (s, ArCH2, 8H); 2.70-2.50 (m, CH2CH2CF2, 12H); 2.40-2.05 (m, CH2CH2CF2, 12H).
Example 6: Preparation of compound 106 (acetic acid 2,4, 6-tris-(3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8,8,8- tridecafluoro-octylsulfanylmethyl)-phenyl ester)
Figure imgf000050_0002
1.50 g (1.18 mmol) of compound 103 and 0.14 g (1.42 mmol) of triethylamine are dissolved in 20 ml of tetrahydrofuran. 0.09 g (1.18 mmol) of acetyl chloride is added to the reaction mixture at room temperature under nitrogen atmosphere. The reaction mixture is stirred at room temperature for 4 hours. Ethyl acetate (50 ml) is added and the organic phase is washed repeatedly with water until pH neutral. The organic phase is dried over magnesium sulfate, filtered and concentrated using a vacuum rotary evaporator to give 1.50 g of a pale brown wax. The crude product is crystallized in acetonitrile/water (20 ml/60 ml) under vigorous stirring at 00C to give 1.30 g of compound 106, white solid, m.p. 40-430C. 1H NMR: (300 MHz, CDCI3): δ = 7.30 (s, ArH, 2H); 3.73 (s, ArCH2, 2H); 3.65 (s, ArCH2, 4H); 2.70-2.55 (m, CH2CH2CF2, 6H); 2.45-2.15 (m, CH2CH2CF2, 6H); 2.38 (s, COCH3, 3H).
Example 7: Water and oil repellency in polypropylene In order to determine the repellency properties of the compounds of the formula I, they are tested according to the following procedure. The sample preparation is a combination of polypropylene nonwovens and a thermal treatment (e.g. 1300C for 10 minutes), which increases the migration of the additive to the surface and a proper surface rearrangement of the chemical groups. This extra heat cycle is recommended to melt the compounds of the formula I in order to obtain a homogeneous redistribution over the surface of the substrate. An industrial sample of polypropylene nonwoven, fabric weight: 40 g/m2, is dipped into a 1 % isopropanol solution of the test compound, simultaneously applying ultrasonic energy for one minute. After that, the sample is dried overnight at room temperature and then two hours at 90°C in an oven. A part of the sample is afterwards annealed for 10 minutes at 1300C.
The treated nonwoven samples are evaluated in the water repellency test similar to INDA test method 80.8 (99). The wetting behavior of the nonwovens is tested with a series of water/isopropanol mixtures. The observation of the wetting behavior is rated from 0 (water wetting, no repellency) to 10 (optimum water repellency). The results are summarized in Table 1.
The treated nonwoven samples are evaluated in the oil repellency test similar to AATCC test method 118-1997 / ISO 14419. This test follows the same concepts of the already described for water repellency test method, but using, as test solvents, a series of hydrocarbons. The observation of the wetting behavior is rated from 0 (no repellency) to 8 (optimum repellency). The results are summarized in Table 2. Table 1:
Figure imgf000052_0001

Claims

What is claimed is:
1. A composition comprising a) an organic material which is susceptible to oxidative, thermal or light-induced degradation, and b) a compound of the formula I
Figure imgf000053_0001
wherein, when n is 1 ,
Ri is hydrogen, Ci-C25alkyl, C2-C25alkenyl, -CO-R5, -CH(R10)CO-R5, -C(Riθ)2CO-R5,
-CO-N(R6)-R7, -CH(R10)CO-N(R6)-R7, -C(R10)2CO-N(R6)-R7, -CH(R10)COOR5 or
Figure imgf000053_0002
when n is 2,
R1 is unsubstituted or with CrC4alkyl, benzyl or phenyl substituted CrC24alkylene; with oxygen or sulfur interrupted C2-C24alkylene, -CO-R8-CO-, -CH(R10)CO-R8-CO-CH(R10)-, -C(R10)2CO-R8-CO-C(R10)2-, -CO-N(R6)-R9-N(R6)-CO-,
-CH(R10)CO-N(Re)-R9-N(Re)-CO-CH(R10)-, -C(R1O)2CO-N(Re)-R9-N(Re)-CO-C(R1O)2-, -CH(R10)CO-O-R9-O-CO-CH(R10)- or -C(R10)2CO-O-R9-O-CO-C(R10)2-;
when n is 3,
Figure imgf000053_0003
R2, R3 and R4 independently of each other are hydrogen, CrC25alkyl, C2-C25alkenyl, or
Figure imgf000054_0001
with the proviso that at least one of the radicals R2, R3 or
Figure imgf000054_0002
R4 is -CH(Rn)-S(O)P-Ri2;
R5 is Ci-C25alkyl, C2-C25alkenyl, unsubstituted or with d-C4alkyl or halogen substituted phenyl; or C7-Ci2phenylalkyl,
R6 is hydrogen or Ci-C4alkyl,
R7 is hydrogen, Ci-C25alkyl, unsubstituted or with Ci-C4alkyl or halogen substituted phenyl,
R8 is phenylene, unsubstituted or with Ci-C4alkyl, benzyl or phenyl substituted
Ci-C24alkylene; with oxygen or sulfur interrupted C2-C24alkylene,
R9 is a direct bond; unsubstituted or with Ci-C4alkyl, benzyl or phenyl substituted C2-
C24alkylene; or with oxygen or sulfur interrupted C2-C24alkylene,
R10 is hydrogen or d-C8alkyl,
R11 is hydrogen, d-C8alkyl, unsubstituted or with Ci-C4alkyl substituted phenyl,
Ri2 is a monovalent linear or branched organic radical containing a perfluorinated alkyl having 6 fully fluorinated carbon atoms,
Ri3 is hydrogen, CrC25alkyl, C2-C25alkenyl, -CO-R5, -CO-N(R6)-R7 or
-CH2-CO-N(R6)-R7,
Ri4 is hydrogen, CrC25alkyl, C2-C25alkenyl or -CH(Rn)-S(O )P-Ri2,
Ris is hydrogen, CrC25alkyl, C2-C25alkenyl or -CH(Rn)-S(O )P-Ri2,
R16 is unsubstituted or with Ci-C4alkyl substituted methylene, -S-, -S(O)-, -S(O)2- or
-CO-,
Ri7 is Ci-C4alkyl, n is 1 , 2 or 3, and p is O, 1 or 2; with the proviso that the compounds of the formula A and B
Figure imgf000055_0001
are excluded; and wherein the composition does not contain a compound with a perfluorinated substituent other than that of formula (I).
2. A composition according to claim 1 , wherein, when n is 1 ,
Ri is hydrogen, d-Ci8alkyl, C2-Ci8alkenyl, -CO-R5, -CO-N(R6)-R7 or -CH2-CO-N(R6)-R7;
when n is 2,
Ri is unsubstituted or with d-C4alkyl, benzyl or phenyl substituted Ci-Ci8alkylene; with oxygen or sulfur interrupted C2-Ci8alkylene, -CO-R8-CO-, -CO-N(R6)-R9-N(R6)-CO- or
-CH(R10)-CO-N(R6)-R9-N(R6)-CO-CH(R10)-;
when n is 3,
Figure imgf000055_0002
R2, R3 and R4 independently of each other are hydrogen, Ci-Ci8alkyl, C2-Ci8alkenyl,
Figure imgf000055_0003
with the proviso that at least one of the radicals R2, R3 or R4 is -CH(Rn)-S(O )P-Ri2;
R5 is Ci-Ci8alkyl, C2-Ci8alkenyl, unsubstituted or with d-C4alkyl or halogen substituted phenyl; or C7-Ci2phenylalkyl,
R6 is hydrogen or d-C4alkyl,
R7 is hydrogen, Ci-Ci8alkyl, unsubstituted or with d-C4alkyl or halogen substituted phenyl, R8 is phenylene, unsubstituted or with CrC4alkyl, benzyl or phenyl substituted Ci-C24alky- lene; with oxygen or sulfur interrupted C2-C24alkylene,
R9 is a direct bond or unsubstituted or with CrC4alkyl, benzyl or phenyl substituted C2-Ci8al- kylene, Rio is hydrogen or CrC8alkyl,
Rn is hydrogen, Ci-C8alkyl, unsubstituted or with d-C4alkyl substituted phenyl,
R-I2 is a monovalent linear or branched organic radical containing a perfluorinated alkyl having 6 fully fluorinated carbon atoms,
Ri3 is hydrogen, CrCi8alkyl, C2-Ci8alkenyl, -CO-R5, -CO-N(R6)-R7 or -CH2-CO-N(R6)-R7, Ru is hydrogen, CrCi8alkyl, C2-Ci8alkenyl or -CH(Rn)-S(O )P-Ri2,
Ri5 is hydrogen, CrCi8alkyl, C2-C18alkenyl or -CH(Rn)-S(O )P-Ri2,
Ri6 is unsubstituted or with d-C4alkyl substituted methylene, -S-, -S(O)-, -S(O)2- or -CO-,
Ri7 is Ci-C4alkyl, n is 1 , 2 or 3, and p is O, 1 or 2.
3. A composition according to claims 1 or 2, wherein R12 is saturated and contains 6 - 15 carbon atoms, of which 6 carbon atoms are fully fluorinated and contains at least one terminal perfluoromethyl group.
4. A composition according to claims 1 to 3, wherein Ri2 is -CH2CH2(CF2)5CF3.
5. A composition according to claims 1 to 4, wherein, when n is 1 ,
Ri is hydrogen, CrCi8alkyl, -CO-R5, -CO-N(R6)-R7 or -CH2-CO-N(R6)-R7;
when n is 2,
Ri is Ci-C8alkylene, -CO-R8-CO-, -CO-N(R6)-R9-N(R6)-CO- or -CH(R10)-CO-N(R6)-R9-N(R6)-CO-CH(R10)-;
when n is 3,
Figure imgf000057_0001
R2, R3 and R4 independently of each other are hydrogen, d-C8alkyl, -CH(Rn)-S(0)p-Ri2,
; with the proviso that at least one of the radicals
Figure imgf000057_0002
R2, R3 or R4 is -CH(Rn)-S(0)p-Ri2;
R5 is Ci-Ci8alkyl, unsubstituted or with Ci-C4alkyl substituted phenyl; or benzyl,
R6 is hydrogen,
R7 is hydrogen, d-C8alkyl, unsubstituted or with Ci-C4alkyl substituted phenyl,
R8 is phenylene or Ci-Ci8alkylene, R9 is C2-Ci8alkylene,
R10 is Ci-C4alkyl,
R11 is hydrogen, Ci-C8alkyl, unsubstituted or with Ci-C4alkyl substituted phenyl,
Ri2 is -CH2CH2(CF2)5CF3,
Ri3 is hydrogen Or -CO-R5, Ri4 is hydrogen or Ci-C8alkyl,
Ris is Ci-C4alkyl or -CH(Rn)-S(O )P-Ri2,
R16 is methylene, n is 1 , 2 or 3, and p is O.
6. A composition according to claims 1 to 5, wherein the organic material is a natural, semisynthetic or synthetic polymer.
7. A composition according to claims 1 to 6, wherein the organic material is a synthetic polymer.
8. A composition according to claims 1 to 7, wherein the organic material is a fiber or nonwoven.
9. A composition according to claims 1 to 8, wherein the compound of the formula I is present in an amount of from 0.01 to 10 %, based on the weight of the organic material.
10. A composition according to claims 1 to 9, comprising in addition, besides the organic material and the compound of the formula I, further additives.
11. A composition according to claims 1 to 10, comprising as further additives phenolic antioxidants, light-stabilizers and/or processing stabilizers.
12. A process for reducing the surface energy of organic materials which comprises treating the organic material with at least a compound of the formula I
Figure imgf000058_0001
wherein, when n is 1 ,
Ri is hydrogen, Ci-C25alkyl, C2-C25alkenyl, -CO-R5, -CH(R10)CO-R5, -C(Riθ)2CO-R5,
-CO-N(R6)-R7, -CH(R10)CO-N(R6)-R7, -C(R10)2CO-N(R6)-R7, -CH(R10)COOR5 or
-C(R10)2CO-OR5;
when n is 2,
R1 is unsubstituted or with Ci-C4alkyl, benzyl or phenyl substituted CrC24alkylene; with oxygen or sulfur interrupted C2-C24alkylene, -CO-R8-CO-, -CH(R10)CO-R8-CO-CH(R10)-,
-C(R10)2CO-R8-CO-C(R10)2-, -CO-N(R6)-R9-N(R6)-CO-, -CH(R10)CO-N(Re)-R9-N(Re)-CO-CH(R10)-, -C(R1O)2CO-N(Re)-R9-N(Re)-CO-C(R1O)2-,
-CH(R10)CO-O-R9-O-CO-CH(R10)- or -C(R10)2CO-O-R9-O-CO-C(R10)2-;
when n is 3,
Figure imgf000059_0001
R2, R3 and R4 independently of each other are hydrogen, CrC25alkyl, C2-C25alkenyl,
or
Figure imgf000059_0002
with the proviso that at least one of the radicals R2, R3 or R4 is
Figure imgf000059_0003
-CH(RH)-S(OVR12;
R5 is CrC25alkyl, C2-C25alkenyl, unsubstituted or with CrC4alkyl or halogen substituted phenyl; or C7-C12phenylalkyl,
R6 is hydrogen or Ci-C4alkyl, R7 is hydrogen, CrC25alkyl, unsubstituted or with CrC4alkyl or halogen substituted phenyl,
Rs is phenylene, unsubstituted or with Ci-C4alkyl, benzyl or phenyl substituted
CrC24alkylene; with oxygen or sulfur interrupted C2-C24alkylene,
Rg is a direct bond, unsubstituted or with Ci-C4alkyl, benzyl or phenyl substituted
C2-C24alkylene; or with oxygen or sulfur interrupted C2-C24alkylene, R10 is hydrogen or CrC8alkyl,
R11 is hydrogen, CrC8alkyl, unsubstituted or with CrC4alkyl substituted phenyl,
R12 is a monovalent linear or branched organic radical containing a perfluorinated alkyl having 6 fully fluorinated carbon atoms,
R13 is hydrogen, CrC25alkyl, C2-C25alkenyl, -CO-R5, -CO-N(R6)-R7 or -CH2-CO-N(R6)-R7, R14 is hydrogen, CrC25alkyl, C2-C25alkenyl Or -CH(Rn)-S(O)P-R12,
R15 is hydrogen, CrC25alkyl, C2-C25alkenyl Or -CH(Rn)-S(O)P-R12,
R16 is unsubstituted or with CrC4alkyl substituted methylene, -S-, -S(O)-, -S(O)2- or -CO-,
R17 is Ci-C4alkyl, n is 1 , 2 or 3, p is O, 1 or 2; and wherein the treatment is carried out in the absence of a compound with a perfluorinated substituent other than that of formula (I).
13. A process according to claim 12, wherein, when n is 1 ,
Ri is hydrogen, d-Ci2alkyl, -CO-R5, -CO-N(R6)-R7 or -CH2-CO-N(R6)-R7;
when n is 2,
R1 is methylene, -CO-R8-CO- or -CH(R10)-CO-N(R6)-R9-N(R6)-CO-CH(R10)-;
when n is 3,
Figure imgf000060_0001
R2, R3 and R4 independently of each other are hydrogen, d-C4alkyl, -CH(Rn)-S(0)p-Ri2 or ith the proviso that at least one of the radicals R2, R3 or R4 is
Figure imgf000060_0002
R5 is CrC18alkyl,
R6 is hydrogen,
R7 is hydrogen, CrC6alkyl, unsubstituted or with CrC4alkyl substituted phenyl, R8 is phenylene,
R9 is ethylene,
R10 is methyl,
R11 is hydrogen, CrC8alkyl, unsubstituted or with methyl substituted phenyl,
R12 is -CH2CH2(CF2)5CF3, R13 is hydrogen or acetyl,
R14 is CrC4alkyl,
R15 Js -CH(R1O-S(O)P-R12,
R16 is methylene, n is 1 , 2 or 3, and p is 0.
14. A process according to claims 12 or 13 for imparting oil and water repellency to the organic material.
15. Use of the compounds of the formula I according to claim 1 as reducers of surface energy for organic materials.
PCT/EP2010/053900 2009-04-02 2010-03-25 S-perfluoroalkyl substituted hydroxybenzylthioethers and derivatives as surface modifiers WO2010112395A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP09157216 2009-04-02
EP09157216.4 2009-04-02

Publications (1)

Publication Number Publication Date
WO2010112395A1 true WO2010112395A1 (en) 2010-10-07

Family

ID=40935726

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/053900 WO2010112395A1 (en) 2009-04-02 2010-03-25 S-perfluoroalkyl substituted hydroxybenzylthioethers and derivatives as surface modifiers

Country Status (2)

Country Link
TW (1) TW201100477A (en)
WO (1) WO2010112395A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013210787A1 (en) 2013-06-10 2014-12-11 Basf Se Spherical particles and their use

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4325863A (en) 1979-02-05 1982-04-20 Sandoz Ltd. Benzofuranone or indolinone compounds useful as stabilizers for organic materials
US4874885A (en) 1986-12-24 1989-10-17 Ciba-Geigy Corporation Process for the preparation of mercaptomethylphenols
US5068397A (en) * 1990-08-15 1991-11-26 Ciba-Geigy Corporation Tris-perfluoroalkyl terminated neopentyl alcohols and derivatives therefrom
US5175312A (en) 1989-08-31 1992-12-29 Ciba-Geigy Corporation 3-phenylbenzofuran-2-ones
US5216052A (en) 1991-07-01 1993-06-01 Ciba-Geigy Corporation Bisbenzofuran-2-ones
US5252643A (en) 1991-07-01 1993-10-12 Ciba-Geigy Corporation Thiomethylated benzofuran-2-ones
DE4316622A1 (en) 1992-05-22 1993-11-25 Ciba Geigy 3- (carboxymethoxyphenyl) benzofuran-2-ones as stabilizers
DE4316611A1 (en) 1992-05-22 1993-11-25 Ciba Geigy 3- (acyloxyphenyl) benzofuran-2-ones as stabilizers
DE4316876A1 (en) 1992-05-22 1993-11-25 Ciba Geigy 3- (alkoxyphenyl) benzofuran-2-ones as stabilizers
EP0589839A1 (en) 1992-09-23 1994-03-30 Ciba-Geigy Ag 3-(Dihydrobenzofuran-5-yl)benzofuran-2-ones as stabilizers
EP0591102A1 (en) 1992-09-23 1994-04-06 Ciba-Geigy Ag 3-(2-Acyloxyethoxyphenyl)benzofuran-2-ones as stabilizers
US5310773A (en) * 1992-06-04 1994-05-10 Ciba-Geigy Corporation Perfluoroalkyl substituted hydroxyphenylalkanoic ester antioxidants and stabilized compositions
US6127485A (en) 1997-07-28 2000-10-03 3M Innovative Properties Company High temperature-stable fluorochemicals as hydrophobic and oleophobic additives to synthetic organic polymers
EP1291384A1 (en) 2001-09-11 2003-03-12 Ciba SC Holding AG Benzofuran-2-one compounds as stabilizers of synthetic polymers
WO2007144283A1 (en) 2006-06-14 2007-12-21 Ciba Holding Inc. S-perfluoroalkyl substituted hydroxybenzylthioethers and derivatives as surface modifiers

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4325863A (en) 1979-02-05 1982-04-20 Sandoz Ltd. Benzofuranone or indolinone compounds useful as stabilizers for organic materials
US4338244A (en) 1979-02-05 1982-07-06 Sandoz Ltd. Benzofuran(2)one or indolin(2)one compounds useful as stabilizers for organic materials
US4874885A (en) 1986-12-24 1989-10-17 Ciba-Geigy Corporation Process for the preparation of mercaptomethylphenols
US5175312A (en) 1989-08-31 1992-12-29 Ciba-Geigy Corporation 3-phenylbenzofuran-2-ones
US5068397A (en) * 1990-08-15 1991-11-26 Ciba-Geigy Corporation Tris-perfluoroalkyl terminated neopentyl alcohols and derivatives therefrom
US5216052A (en) 1991-07-01 1993-06-01 Ciba-Geigy Corporation Bisbenzofuran-2-ones
US5252643A (en) 1991-07-01 1993-10-12 Ciba-Geigy Corporation Thiomethylated benzofuran-2-ones
DE4316611A1 (en) 1992-05-22 1993-11-25 Ciba Geigy 3- (acyloxyphenyl) benzofuran-2-ones as stabilizers
DE4316622A1 (en) 1992-05-22 1993-11-25 Ciba Geigy 3- (carboxymethoxyphenyl) benzofuran-2-ones as stabilizers
DE4316876A1 (en) 1992-05-22 1993-11-25 Ciba Geigy 3- (alkoxyphenyl) benzofuran-2-ones as stabilizers
US5310773A (en) * 1992-06-04 1994-05-10 Ciba-Geigy Corporation Perfluoroalkyl substituted hydroxyphenylalkanoic ester antioxidants and stabilized compositions
EP0589839A1 (en) 1992-09-23 1994-03-30 Ciba-Geigy Ag 3-(Dihydrobenzofuran-5-yl)benzofuran-2-ones as stabilizers
EP0591102A1 (en) 1992-09-23 1994-04-06 Ciba-Geigy Ag 3-(2-Acyloxyethoxyphenyl)benzofuran-2-ones as stabilizers
US6127485A (en) 1997-07-28 2000-10-03 3M Innovative Properties Company High temperature-stable fluorochemicals as hydrophobic and oleophobic additives to synthetic organic polymers
EP1291384A1 (en) 2001-09-11 2003-03-12 Ciba SC Holding AG Benzofuran-2-one compounds as stabilizers of synthetic polymers
WO2007144283A1 (en) 2006-06-14 2007-12-21 Ciba Holding Inc. S-perfluoroalkyl substituted hydroxybenzylthioethers and derivatives as surface modifiers

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102013210787A1 (en) 2013-06-10 2014-12-11 Basf Se Spherical particles and their use

Also Published As

Publication number Publication date
TW201100477A (en) 2011-01-01

Similar Documents

Publication Publication Date Title
CA2425095C (en) Stabilizer mixtures
WO2009007265A1 (en) Stabilizer compositions
EP1749037A1 (en) Perfluorinated esters, polyester, ethers and carbonates
WO2006063957A1 (en) Stabilized organic materials containing fillers
WO2008028858A1 (en) Liquid polymeric phosphites and phosphonites as stabilizers
EP2276754A1 (en) Stabilization and surface modification of organic materials
EP1891142A1 (en) Oligo- and poly-carbonates terminated with silicon containing groups as surface modifiers
EP2300525A1 (en) Storage-stable aqueous emulsions and liquid blends with low viscosity as stabilizers
WO2007054446A1 (en) Photolatent systems
EP2069279A1 (en) Perfluoroalkyl substituted phenol derivatives as surface modifiers
WO2007144283A1 (en) S-perfluoroalkyl substituted hydroxybenzylthioethers and derivatives as surface modifiers
CA2549146C (en) Fluorocarbon terminated oligo- and poly-carbonates as surface modifiers
WO2007134997A1 (en) N-substituted perfluoroalkylated pyrrolidines as surface modifiers
WO2006082166A1 (en) Functionalized esters, amides or urethanes of perfluorinated alcohols or amines as surface modifiers
WO2012052376A1 (en) Oligomeric light stabilizers with a specific functionalization
KR20130016250A (en) Sterically hindered amines
WO2006021529A1 (en) Surface modifiers
WO2009095328A1 (en) Additive mixtures for styrenic polymers
WO2010112395A1 (en) S-perfluoroalkyl substituted hydroxybenzylthioethers and derivatives as surface modifiers
WO2006089851A1 (en) Fluorinated compounds
WO2010076278A1 (en) Phosphorus based dispersants for inorganic particles in polymer matrices

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10711208

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10711208

Country of ref document: EP

Kind code of ref document: A1

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载