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WO2008065039A1 - Copolymères siloxane/urée - Google Patents

Copolymères siloxane/urée Download PDF

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Publication number
WO2008065039A1
WO2008065039A1 PCT/EP2007/062695 EP2007062695W WO2008065039A1 WO 2008065039 A1 WO2008065039 A1 WO 2008065039A1 EP 2007062695 W EP2007062695 W EP 2007062695W WO 2008065039 A1 WO2008065039 A1 WO 2008065039A1
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Prior art keywords
formula
different
optionally
sime
radical
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PCT/EP2007/062695
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German (de)
English (en)
Inventor
Wolfgang Ziche
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Wacker Chemie Ag
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Publication of WO2008065039A1 publication Critical patent/WO2008065039A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0895—Manufacture of polymers by continuous processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/458—Block-or graft-polymers containing polysiloxane sequences containing polyurethane sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
    • C09J183/10—Block or graft copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups

Definitions

  • the invention relates to organopolysiloxane-urea copolymers, processes for preparing the organopolysiloxane-urea copolymers, compositions containing the organopolysiloxane-urea copolymers and their preparation.
  • these copolymers can be thermoplastic elastomers.
  • such copolymers are plastic above the softening point, while having elastic properties below.
  • they can be used, for example, as a structural polymer for components such as gaskets.
  • a disadvantage of the use of such copolymers as structural polymer is that deformation can occur due to temperature increase and pressure, as in the case of all thermoplastic elastomers, ie the compression set is large, since hydrogen bonds can constantly dissolve and re-bond even below the softening point , Thus, the range of application is limited to applications in which no elevated temperatures or forces act on the thermoplastic elastomer.
  • the invention relates to copolymers of the general formula
  • X may be identical or different and is an alkylene radical optionally substituted by fluorine, chlorine, C 1 -C 6 -alkyl or C 1 -C 6 -alkyl ester having 1 to 10 000 carbon atoms, in which non-adjacent methylene units are represented by groups -O-, - COO, -OCO- or -OCOO- may be replaced, or an optionally substituted arylene radical having 6 to 22 carbon atoms, Y may be the same or different and a divalent hydrocarbon radical having 1 to 30 carbon atoms, in the non-adjacent methylene units by Groups -O- may be replaced, or the radical is - (CH 2 ) 3 -NH- SiR 2 - (CH 2 ) 3 -NH-,
  • Z may be identical or different and is a bivalent hydrocarbon radical optionally substituted by fluorine or chlorine and having from 1 to 30 carbon atoms,
  • D may be the same or different and represents hydrogen or a monovalent, optionally substituted hydrocarbon radical
  • E may be the same or different and represents an oxygen atom or an amino group -ND-
  • R can be identical or different and denotes a monovalent hydrocarbon radical with 1 to 20 carbon atoms which is optionally substituted by fluorine or chlorine,
  • R 'in the case of R''is a hydrogen atom is a radical HND-Y-Si (OR 1) 0 R2 0 - (0-SiR 2) n -O-Si (OR 1) o R 2 _ o -Y-ND -, HNR 4 -G-NR 4 - or HE-XE- and in the case of R '' is equal to -CO-NH- (Z-NH-CO-NHJh-Z-NCO the meaning of OCN- ⁇ Z-NH-CO-NHJh-Z-NH-CO-ND-Y-Si (OR 1) 0 R2 0 - (0-SiR 2) n "0- Si (OR 1 J 0 R 2 - O -Y-ND-, OCN-iZ-NH-CO-NHJ h -Z-NH-CO-NR ⁇ G-NR 4 - or OCN- ⁇ Z-NH-CO-NHJ h -Z-NH-CO- EXE-, n
  • the copolymer of formula (I) has at least one unit with h different 0 and the individual blocks (A), (B) and (C) may be randomly distributed in the polymer.
  • organopolysiloxanes is intended to encompass both polymeric, oligomeric and dimeric siloxanes.
  • divalent radicals Z are alkylene radicals, such as the methylene, ethylene, n-propylene, iso-propylene, n-butylene, iso-butylene, tert. Butylene, n-pentylene, iso-pentylene, neo-pentylene, tert.
  • Pentylene radical hexylene radicals, such as the n-hexylene radical, heptylene radicals, such as the n-heptylene radical, octylene radicals, such as the n-octylene radical and isooctylene radicals, such as the 2,2,4-trimethylpentylene radical, nonylene radicals, such as n -Nonyl radical, decyl radicals, such as the n-decylene radical, dodecylene radicals, such as the n-dodecylene radical; Alkenylene radicals, such as the vinylene and allylene radicals; Cycloalkylene radicals, such as cyclopentylene, cyclohexylene, cycloheptylene radicals and methylcyclohexylene radicals; Arylene radicals, such as the phenylene and the naphthylene radical; Alkarylene radicals, such as o-, m
  • Radical Z is preferably alkylene groups having 1 to 24 carbon atoms, more preferably hexylene,
  • Examples of the bivalent radicals G are the examples listed for Z.
  • Radicals G are preferably alkylene radicals having 1 to 6 carbon atoms, arylene radicals, such as the o-, m- or p-phenylene radical, and aralkylene radicals, such as the phenylene radical, with the radical -CH 2 CH 2 - being particularly preferred ,
  • Z ⁇ examples are all examples given for Z.
  • it is at rest Z ⁇ alkylene groups having 1 to 24 carbon atoms, more preferably alkylene groups having 1 or 3 carbon atoms.
  • radicals Y are preferably alkylene radicals having 1 to 30 carbon atoms, in which non-adjacent methylene units may be replaced by groups -O-, or arylene radicals having 6 to 22 carbon atoms.
  • Particularly preferred radical Y is alkylene groups having 1 to 3 carbon atoms, in particular the methylene or propylene radical.
  • radical X examples are the butylene radical, ethylene radical, hexylene radical, - (CH 2 ) 3 - (O-CH (CH 3 ) -CH 2 ) 2 - 3 ooo-O- (CH 2 ) 3 -, -CH ( CH 3) -CH 2 - (O-CH (CH 3) -CH 2) 2 - 3O oo-, - (CH 2) 3 - (0-CH 2 -CH 2) 2 _ 300 -O- (CH 2 ) 3 - and -CH 2 -CH 2 - (OCH 2 -CH 2 ) 2-300- •
  • the radicals X are preferably polyether radicals, particularly preferably polypropylene glycol radicals, in particular those having 2 to 600 carbon atoms.
  • radical R examples include alkyl radicals, such as the methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert. Butyl, n-pentyl, iso-pentyl, neo-pentyl, tert.
  • -Pentyl hexyl, such as the n-hexyl, heptyl, such as the n-heptyl, octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2, 2, 4-trimethylpentyl, nonyl, such as the n Nonyl radical, decyl radicals, such as the n-decyl radical, dodecyl radicals, such as the n-dodecyl radical; Alkenyl radicals, such as the vinyl and allyl radicals; Cycloalkyl radicals, such as cyclopentyl, cyclohexyl, cycloheptyl radicals and methylcyclohexyl radicals; Aryl radicals, such as the phenyl and the naphthyl radical; Alkaryl radicals, such as o-, m-, p-tolyl radicals, xy
  • Radical R is preferably a hydrocarbon radical having 1 to 6 carbon atoms, more preferably an alkyl radical having 1 to 4 carbon atoms, in particular the methyl radical.
  • Radicals R 1 are preferably linear or branched alkyl radicals having 1 to 12 carbon atoms and alkoxyalkyl radicals such as 2-methoxyethyl, 2-ethoxyethyl and 2- (2'-methoxyethyl) ethyl, particularly preferably alkyl radicals 1 to 12 carbon atoms, in particular the methyl and ethyl radical.
  • radical R 4 are the radicals specified for R, hydrogen atom and the radicals - (CH 2 ) 4 Si (OCH 3 ) 3 ,
  • Radical R 4 is preferably hydrogen and the abovementioned silyl-substituted alkyl radicals, more preferably hydrogen and the radicals - (CH 2 ) 3 Si (OCH 3 ) 3 ,
  • hydrocarbon radicals D are the radicals given above for R.
  • the radical D is preferably an alkyl radical or hydrogen atom, particularly preferably an alkyl radical having 1 to 12 carbon atoms or hydrogen atom, in particular hydrogen atom.
  • the radical E is preferably an oxygen atom.
  • A preferably has the meaning of an integer from 1 to 1000, particularly preferably from 5 to 1000, in particular from 5 to 100.
  • B preferably has the meaning of an integer from 1 to 1000, particularly preferably from 5 to 1000, in particular from 5 to 100.
  • c has the meaning of 0 or an integer of 1 to 100, more preferably of 0 or an integer of 1 to 10, especially 0.
  • H has the meaning of an integer from 1 to 4, particularly preferably from 1 to 2, in particular 1.
  • radicals R ' in the case where R "is hydrogen, are radicals which result from the unreacted end groups from the educts used, such as H 2 N- (CH 2 ) 3-Si (CH 3 ) 2 - (O-Si (CH 3 ) 2 ) 40 -O-Si (CH 3 ) 2 - (CH 2 ) 3 -NH-, H 2 N-CH 2 -CH 2 -N- (CH 2 ) 3 Si ( OCH 3 ) 3 ,
  • radicals R ' in the event that R "is equal to -CO-NH- (Z-NH-CO-NHJh-Z-NCO, radicals which arise from the unreacted end groups from the starting materials used, such as OCN- ⁇ (CH 2 ) 6 -NH-CO-HNj 2 - (CH 2 ) 3 -Si (CH 3 ) 2 - (O-Si (CH 3 ) 2 ) 4 o-O-Si (CH 3 ) 2 - (CH 2) 3 -NH-, OCN- (C 6 H 1O -CH 2 -C 6 H 10 -NH-CO-HNH-CH 2 -CH 2 -N- (CH 2) 3 Si (OCH 3) 3 ,
  • the radical R ' is in the case of R''is a hydrogen atom preferably a radical HND-Y-Si (OR 1) 0 R 2 - 0 - (0-SiR 2) n -O- Si (OR 1 J 0 R 2 - O -Y-ND- or HNR 4 -G-NR 4 - and in the case of R ", equal -CO-NH- (Z-NH-CO-NHJh-Z-NCO, preferably at OCN- (Z-) NH-CO-NHJh-Z-NH-CO-ND-Y-Si (OR 1 J 0 R 2 - O - (0-SiR 2) n -0-Si (OR 1 J 0 R 2 - o -Y ND or OCN- ⁇ Z-NH-CO-NH ⁇ h -Z-NH-CO-NR 4 -G-NR 4 -.
  • radicals R are hydrogen atom, -CO-NH- (CH 2 ) 6 -NH-CO-NH- (CH 2 ) 6 -NCO, -CO-NH-C 6 H 1 O -CH 2 -C 6 H 10 -NCO and -CO-NH-C 6 H 3 (CH 3 ) -NCO, with hydrogen being preferred.
  • N is preferably an integer from 10 to 4000, more preferably from 30 to 1000.
  • Copolymers of the invention comprising units (C) can give a harder material compared to copolymers according to the invention which contain no unit (C), since there are more hydrogen bonds in them.
  • Polyether units as units (C) can be used, e.g. in US 20060014916 A can be used to keep the processing temperatures of the material below the decomposition temperatures of the material, if necessary.
  • the properties such as, for example, peel and peel strength, printability, tensile and tear propagation resistance or water vapor permeability, can be set in a targeted manner.
  • Copolymers of the formula (I) with c are preferably 0, since thus exclusively siloxane chains are present and thus the polymers have advantages such as, for example, high transparency and UV stability with simultaneously low surface energies.
  • copolymers of the formula (I) according to the invention are H [NH (CH 2) 3SiMe 2 O (SiMe 2 O) 35SiMe 2 (CH2) 3-NH-CO-NH- (CH 2) 6 -NH-CO-NH- (CH 2) 6 -NH-CO -NH-CH 2 CH 2 -NH-CO-NH- (CH 2 ) 6 -NH-CO-NH- (CH 2 ) 6 -NH-CO] 10 -NH (CH 2 ) 3 SiMe 2 O (SiMe 2 O 35SiMe 2 (CH 2 ) 3-NH 2 ,
  • copolymers of the formula (I) according to the invention have a content of units A of the formula (II) of preferably greater than 70% by weight, particularly preferably greater than 80% by weight, in each case based on the total weight of the copolymer.
  • novel copolymers of the formula (I) are preferably rubber-elastic solids at room temperature with tensile strengths of preferably between about 0.5 and 20 MPa and elongation at break of between about 50 and 1000%. They soften at temperatures between preferably 60 and 240 0 C and thereby lose their rubber-elastic properties.
  • the hydrolyzable radical -OR 1 can react to form OH groups, which in turn can condense with further OR 1 or OH groups to form siloxane bonds.
  • copolymers according to the invention also have the advantage that they have very good mechanical properties without having to add fillers.
  • copolymers according to the invention are distinguished by excellent physical properties, as are known from polyorganosiloxanes, such as, for example, lower
  • copolymers according to the invention are the high thermal and oxidative stability, good resistance to swelling and decomposition by hydrocarbons containing solvents.
  • copolymers according to the invention can be prepared analogously to any process which is already known to the person skilled in the art and is carried out, for example, for the synthesis of (prep) polymers for polyurethanes.
  • X, Y, Z, D, E, G, R, R 1 , R 4 , and o have one of the meanings mentioned above and h 'is an integer of at least 1.
  • Examples of the compounds of the formula (V) used in accordance with the invention are CCCO-aminopropyldimethylsilyl-terminated polydimethylsiloxanes, CC, CO-aminopropyldimethoxysilyl-terminated polydimethylsiloxanes, CC, CO-aminomethyldimethylsilyl-terminated polydimethylsiloxanes and CC, CO-aminomethyldimethoxysilyl-terminated polydimethylsiloxanes.
  • Preferred compounds of the formula (VI) which can be used in the process according to the invention are 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropyldimethylmethoxysilane, 3- (2-aminoethyl) aminopropylmethyldiethoxysilane, N, N'-bis (3-trimethoxysilylpropyl) ethylenediamine, N, N'-bis- (3-triethoxysilylpropyl) - ethylenediamine, N, N'-bis- (3-dimethoxymethylsilylpropyl) ethylenediamine and N, N'-bis (3-diethoxymethylsilylpropyl) ethylenediamine, N-trimethoxysilylmethyl
  • isocyanates of the formula (IX) used in accordance with the invention are hexylene diisocyanate, 4,4'-methylenedicyclohexyl-1-diisocyanate, 4,4'-methylenediphenylene diisocyanate, 1,3-diazotidine-2,4-dione bis (4,4 '). -methylenedicyclohexyl) diisocyanate, 1, 3-diazetidine-2,4-dione bis (4,4'-methylenediphenyl) diisocyanate,
  • Tetramethylenexylylene diisocyanate and isophorone diisocyanate, hexylene diisocyanate, 4,4'-methylenedicyclohexylene diisocyanate, 4,4'-methylenediphenylene diisocyanate, tetramethylenexylylene diisocyanate, cyanate and isophorone diisocyanate are preferred as well as Hexylendiisocy- anat, 4, 4 '-Methylendicyclohexylendiisocyanat and isophorone diisocyanate are particularly preferred.
  • Examples of the isocyanates of the formula (VII) used according to the invention are OCN-Z-NH-CO-NH-Z-NCO, OCN-Z-NH-CO-NH-Z-NH-CO-NH-Z-NCO, with Z is hexylene, 4, 4 '-methylenedicyclohexylene, 4, 4' -methylenediphenylene, tetramethylenxylylene and isophorone lenrest, wherein OCN-Z-NH-CO-NH-Z-NCO with Z is hexylene, 4, 4 'Methylenedicyclohexylen-, 4, 4' -Methylendiphenylen-, Tetramethylenxylylen- and Isophoronylenrest preferred and OCN-Z-NH-CO-NH-Z-NCO with Z equal to 4, 4 '-Methylendicyclohexylen- and isophoronylene are particularly preferred.
  • the isocyanates of the formula (VII) used according to the invention can be prepared by reacting diisocyanates of the formula (IX) and water, preferably in the presence of catalysts, such as, for example, N, N-dimethylethanolamine, bis (2-dimethylaminoethyl) ether, N, N, N ', N', N'-pentamethyldiethylenetriamine, N, N'-trimethylaminoethylethanolamine, triethylenediamine, dibutyltin dilaurate, tin (II ) octoate and synergistic mixtures of triethylenediamine and dibutyltin dilaurate are prepared or formed in situ in carrying out the method according to the invention.
  • the catalysts used to prepare the diisocyanates of the formula (VII) do not interfere with the reaction according to the invention of (a) with (b) and optionally (c), (d) and (e).
  • the isocyanates of formulas (VII) and / or (IX) may each be wholly or partly in the form of the corresponding blocked diisocyanates, but this is not preferred. These may be, in particular, thermally unstable reaction products of isocyanates with, for example, phenols, ketoximes, lonestern and nitrogen-containing heterocycles, which are known in the art. In the reaction of the blocked isocyanate with the other educts then the necessary temperature for deblocking must be achieved, the then freed blocking molecules remain in the reaction mixture.
  • Examples of the compounds of the formula (VIII) used according to the invention are compounds known from polyurethane chemistry, such as diols, e.g. Ethylene glycol, 1,4-butanediol, polyethylene glycols, polypropylene glycols and polyester polyols, diamines, e.g.
  • the compounds of the formula (VIII) are preferably 1,4-butanediol, polyethylene glycols, polypropylene glycols, 2-methyl-1,5-pentanediamine and amino-terminated polyethers (ATPE), 1,4-butanediol, polypropylene glycols, Methyl-1,5-pentanediamine are particularly preferred.
  • the stoichiometry of the reactants for the preparation of the copolymers according to the invention is preferably selected such that the molar ratio of the isocyanate groups from the compounds of the formulas (VII) and (IX) to the sum of the isocyanate-reactive EH and NH groups from the compounds of the formulas (V), (VI) and (VIII) is in the range of preferably 0.7 to 1.3, particularly preferably 0.95 to 1.05, in particular 1. At a ratio of the isocyanate groups to the reactive
  • R " -CO-NH- (Z-NH-CO-NH-NH-Z-NCO and the resulting R 'radicals as defined above at the other end of the polymer chains.
  • the process according to the invention can be carried out in the presence of catalysts (f).
  • the catalysts which may be used may be all known catalysts which comprise the addition of the isocyanate groups of the compounds of the general formulas (VII) and (IX) to the active groups of the compounds of the formulas (V), (VI) and ( VIII) promote, are used.
  • catalysts (f) are diorganotin compounds such as stannous octoate, dibutyltin dilaurate and dibutyltin diacectate, bismuth compounds such as bismuth (2-ethylhexanoate), bismuth neodecanoate and bismuth tetramethylheptanedionate, and zinc compounds such as zinc acetylacetonate, zinc 2-ethylhexanoate and zinc neodecanoate.
  • diorganotin compounds such as stannous octoate, dibutyltin dilaurate and dibutyltin diacectate
  • bismuth compounds such as bismuth (2-ethylhexanoate), bismuth neodecanoate and bismuth tetramethylheptanedionate
  • zinc compounds such as zinc acetylacetonate, zinc 2-ethylhexanoate and zinc n
  • Examples of commercially available catalysts are Borchi® Kat 22, Borchi® Kat VP 0243 and Borchi® Kat VP 0244 from Borchers GmbH, Germany, the BICAT® grades from The Shepherd Chemical Company, USA and K-Kat® K-348 from KING INDUSTRIES, INC., USA.
  • catalysts are used in the process according to the invention, these are amounts of preferably 0.0001 to 1 part by weight, particularly preferably 0.001 to 0.1 part by weight, in each case based on 100 parts by weight of the total mixture.
  • the process according to the invention can be carried out in the presence of solvents (g), with orga- nische solvents, in particular non-protic, polar solvents, are preferred.
  • solvents are used in the process according to the invention, these are amounts of preferably 10 to 200 parts by weight, more preferably 10 to 100 parts by weight, in each case based on 100 parts by weight of the total mixture.
  • the reaction according to the invention can be carried out in solution or in substance, a reaction in substance being preferred.
  • temperatures of from 0 to 100 ° C. are preferred and from 20 to 80 ° C. are particularly preferred.
  • temperatures above the softening point of the copolymer produced of the formula (I) are preferred.
  • the process according to the invention can be carried out by methods known to the person skilled in the art, for example by means of extruders, kneaders, roll mills, dynamic or static mixers.
  • the process according to the invention is carried out, in particular in the presence of organyloxysilyl groups, preferably with the exclusion of moisture.
  • siloxane-urea copolymers prepared according to the invention can now be freed of any starting materials still present or of any solvents or catalysts used, if appropriate, by any desired methods known hitherto. by distillation or extraction.
  • the components used in the process according to the invention are commercially available products or can be prepared by methods customary in chemistry.
  • the components used in the process according to the invention may each be a type of such a component as well as a mixture of at least two types of a respective component.
  • the process according to the invention has the advantage that it is simple to carry out and many possible copolymers with great variability can be prepared.
  • the process according to the invention has the advantage that copolymers can be prepared in a well-defined manner.
  • the copolymers according to the invention or those produced according to the invention can be used everywhere where organopolysiloxane-urea copolymers have hitherto been used.
  • copolymers of the formula (I) according to the invention or prepared according to the invention can be processed by the customary processing methods for polymers or thermoplastic elastomers, for example by means of extrusion, injection molding, blow molding, vacuum thermoforming. Processing as a solution or emulsion or suspension is also possible.
  • Preferred applications of the copolymers of the formula (I) according to the invention or inventively prepared are uses as a base material for thermoplastic elastomers, such as cable sheaths, hoses, gaskets, keyboard mats, for membranes, such as selectively gas-permeable membranes, paintable and recoatable components for the automotive industry, film for Laminated safety glass, as additives in polymer blends, such as impact modifiers or flame retardants, or as a material for the modification of fibers or for coating applications, for example in anti-adhesive coatings, fabric-compatible coatings, flame-retardant coatings or as a coating material for wood, paper or cardboard, such as as a release coating for adhesive tapes and labels.
  • thermoplastic elastomers such as cable sheaths, hoses, gaskets, keyboard mats
  • membranes such as selectively gas-permeable membranes, paintable and recoatable components for the automotive industry
  • film for Laminated safety glass as additives in
  • Preferred applications are furthermore coatings for textile fibers or textile fabrics, as a coating material for natural materials, such as leather and furs.
  • Further possible applications include sealants and adhesives, such as, for example, hot melt adhesives or adhesives to be applied as a solution, primers for improving the adhesion of sealants and adhesives on various substrates, additives for polymer processing, such as extrusion aids for thermoplastic processing, Cleaning, cleaning or care preparations, anti-fouling coatings, cosmetics, body care preparations, paint additives, PSA coatings, detergent additives and textile processing, defoamer formulations, modifiers for resins or bitumen modification, as mold release agents, as biocompatible materials in medical applications, such as contact lenses, as material for membranes and as material for photoactive systems, for example for lithographic processes, optical data backup or optical data transmission.
  • sealants and adhesives such as, for example, hot melt adhesives or adhesives to be applied as a solution
  • copolymers of the formula (I) according to the invention or those prepared according to the invention are suitable for use in crosslinkable compositions, such as room-temperature crosslinkable compositions.
  • Another object of the present invention are crosslinkable compositions containing inventive or inventively prepared copolymers of the formula (I).
  • condensation reaction implies that, if appropriate, a hydrolysis step of hydrolyzable radicals takes place before the condensation reaction.
  • crosslinkable compositions according to the invention are preferably one-component compositions.
  • the constituents used in each case can be mixed with one another in any desired and hitherto known manner. This mixing preferably takes place at room temperature or at a temperature which occurs when the components are added together at room temperature without additional heating or cooling, and the pressure of the surrounding atmosphere, ie about 900 to 1100 hPa. If desired, however, this mixing can take place even at higher or lower pressures, for example at low pressures to avoid gas inclusions.
  • the preparation of the compositions according to the invention and their storage are preferably carried out under substantially anhydrous conditions in order to avoid premature reaction of the compositions.
  • the component (i) used according to the invention is preferably copolymers of the formula (I) which have at least two radicals -OR 1 , where R 1 has the meaning given above.
  • crosslinkers (ii) are preferably organyloxysilanes and also their partial hydrolysates, such as tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, methyltrimethoxysilane, methyltriethoxysilane, n-butyltrimethoxysilane, n-octyltrimethoxysilane, i-octyltrimethoxysilane, vinyltrimethoxysilane and Vi - nyltriethoxysilane and their Generalhydrolysate, with methyl and vinyltrimethoxysilane are particularly preferred.
  • crosslinkable compositions according to the invention contain crosslinkers (ii), these are amounts of preferably 0.05 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based in each case on 100 parts by weight of crosslinkable composition.
  • condensation catalysts (iii) are butyl titanates and organic tin compounds, such as di-n-butyltin dilaurate and di-n-butyltin diacetate, and also the reaction products thereof with the alkoxysilanes which are mentioned as crosslinkers or adhesion promoters.
  • NEN dialkyltin oxide in the mentioned as crosslinkers or adhesion promoters alkoxysilanes, with di-n-butyltin dilaurate and dibutyltin oxide in tetraethoxysilane is preferred and di-n-butyltin dilaurate is particularly preferred.
  • crosslinkable compositions according to the invention comprise catalyst (iii), these are amounts of preferably 0.01 to 3 parts by weight, preferably 0.05 to 2 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
  • Filler (iv) is preferably pyrogenic kiesiklaren or carbon blacks or mixtures thereof, with carbon black having a BET surface area of at least 30 m 2 / g is particularly preferred. If the compositions according to the invention comprise fillers (iv), these are amounts of preferably 1 to 50 parts by weight, preferably 2 to 30 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
  • adhesion promoter (s) optionally used it is possible to use all adhesion promoters which have hitherto been used in compositions which can be crosslinked by condensation.
  • adhesion promoters (v) are silanes with hydrolyzable groups and SiC-bonded vinyl, acryloxy, methacryloxy, epoxy, acid anhydride, acid, ester or ether groups and their partial and mixed hydrolysates.
  • compositions according to the invention comprise adhesion promoters (v), these are amounts of preferably 0.01 to 5 parts by weight, preferably 0.5 to 4 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
  • component (vi) are amounts of preferably 0.01 to 30 parts by weight, particularly preferably 0.05 to 25 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
  • crosslinkable compositions according to the invention can contain crosslinkable polymers (vii), such as organopolysiloxanes having reactive end groups.
  • crosslinkable siloxanes are CCCO-dihydroxypolydimethylsiloxanes and OC, CO-bis (dimethoxymethylsilyl) -terminated polydimethylsiloxanes.
  • the component (vii) optionally used in the crosslinkable compositions according to the invention is preferably polydiorganosiloxanes having at least one OH group or a hydrolyzable group at the chain ends, more preferably polydimethylsiloxanes having at least one OH group or a hydrolyzable group at the chain ends , in particular ⁇ , ⁇ -dihydroxypolydimethylsiloxanes or ⁇ , ⁇ -bis (di-methoxymethylsilyl) terminated polydimethylsiloxanes having a viscosity of 100 to 500,000 mPas.
  • the crosslinkable compositions according to the invention preferably contain component (vii).
  • This component is preferably used to adjust the processing properties, such as viscosity or pot life. If component (vii) is used, these are amounts of preferably 1 to 50 parts by weight, more preferably 2 to 25 parts by weight, in each case based on 100 parts by weight of crosslinkable composition.
  • the individual constituents of the crosslinkable compositions according to the invention may each be one type of such constituent as well as a mixture of at least two different types of such constituents.
  • compositions according to the invention contain no further constituents apart from component (i), if appropriate (ii), (iii), (iv), (v), (vi) and (vii).
  • the preparation of the crosslinkable compositions according to the invention can be carried out by simple mixing.
  • Vulcanizates of the compositions according to the invention can be obtained by optionally necessary hydrolysis of hydrolyzable radicals and subsequent condensation of the resulting silanol groups.
  • the hydrolysis can be carried out by atmospheric moisture or by steam, water baths or aqueous solutions in contact with the copolymer of the invention according to the general formula (I).
  • the usual water content of the air is preferably sufficient.
  • the crosslinking of the compositions of the invention is preferably carried out at room temperature. If desired, it can also be used at higher or lower Ren temperatures as room temperature, such as at -5 to 15 ° C or at 30 to 50 0 C, for example, by means of the normal water content of the air excess concentrations of water are performed.
  • the crosslinking is carried out at a pressure of 100 to 1100 hPa, in particular at the pressure of the surrounding atmosphere, that is about 900 to 1100 hPa.
  • the vulcanizates of the copolymers according to the invention have, after moisture crosslinking, a lower dependence of the mechanical properties on the temperature.
  • the vulcanizates of the copolymers according to the invention no longer become plastic when the temperature increases, so they can no longer flow and are thus more dimensionally stable.
  • the vulcanizates according to the invention generally have better mechanical properties over a wider temperature range, so that they can be used in more diverse fields of application.
  • crosslinkable compositions of the invention are preferably used as hot melt adhesive, adhesive, PSA (Pressure Sensitive Adhesive), sealant, coating for example paper, textile, fibers or silicate surfaces, impregnating agent, paint, Component used in composites, additive for polymers, molding and component for medical purposes as well as for use in automotive or laminated glass.
  • PSA Pressure Sensitive Adhesive
  • sealant coating for example paper, textile, fibers or silicate surfaces
  • impregnating agent paint
  • Component used in composites additive for polymers, molding and component for medical purposes as well as for use in automotive or laminated glass.
  • compositions of the invention have the advantage that they possess all of the abovementioned advantages of the copolymers according to the invention used.
  • compositions of the invention have the advantage that they have very good mechanical properties.
  • compositions according to the invention are the high thermal and oxidative stability, good resistance to swelling and decomposition by solvents containing hydrocarbons.
  • compositions of the invention have the advantage that the properties, such as peel and peel strength, printability, tensile and tear propagation resistance or water vapor permeability, can be adjusted in a targeted manner.
  • the shaped bodies according to the invention have the advantage that they have a lower dependence of the mechanical properties on the temperature, in particular at higher temperatures.
  • the shaped bodies according to the invention furthermore have the advantage that they have a very good adhesion to substrates.
  • all viscosity data refer to a temperature of 25 ° C. Unless indicated otherwise, the following examples are at a pressure of the surrounding atmosphere, that is about 1000 hPa, and at room temperature, ie at about 23 ° C, or at a temperature that occurs when combining the reactants at room temperature without additional heating or cooling, and carried out at a relative humidity of about 50%. Furthermore, all parts and percentages are by weight unless otherwise specified.
  • the Shore A hardness is determined according to DIN (German Industrial Standard) 53505 (March 2000 edition).
  • the compression set (DVR) was determined according to ISO 815 at 70 0 C.
  • Example 1 17.1 g of isophorone diisocyanate are heated to 70 ° C. for 2 hours with 0.7 g of water and 10 mg of dibutyltin dilaurate in 100 ml of tetrahydrofuran. For this purpose, 99.3 g of a CC, CO-aminopropyl-terminated polydimethylsiloxane having a molecular weight M w of 2890 g / mol and a viscosity of 50 mPas are added. The viscous solution was poured into PTFE molds and the solvent removed by evaporation.
  • thermoplastic material was obtained.
  • test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 82 Shore A, tensile strength 7.8 MPa, elongation at break 461%, stress at 100% elongation 4.07 MPa. The DVR is 88%. Comparative Example 1
  • 20.0 g of 4, 4 '-Methylendicyclohexylendiisocyanat be with 0.7 g of water and 10 mg of dibutyltin dilaurate in 100 ml of tetrahydrofuran for 2 hours at 70 0 C heated.
  • 99.3 g of a CC, C0-amino-propyl-terminated polydimethylsiloxane having a molecular weight M w of 2890 g / mol and a viscosity of 50 mPas are added.
  • the viscous solution was poured into PTFE molds and the solvent removed by evaporation.
  • thermoplastic material was obtained.
  • test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 81 Shore A, tensile strength 8.4 MPa, elongation at break 301%, stress at 100% elongation 5.49 MPa.
  • the DVR is 90%.
  • thermoplastic material was obtained.
  • test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 55 Shore A, tensile strength 5.3 MPa, elongation at break 450%, stress at 100% elongation 1.6 MPa. The DVR is 98%.
  • 1700.0 g of an ⁇ , ⁇ -aminopropyl-terminated polydimethylsiloxane having a molecular weight M w of 2890 g / mol and a viscosity of 50 mPas are vigorously stirred with 300 g of water and then allowed to stand for 14 days and separated from the water.
  • the polydimethylsiloxane then contains 3032 ppm of water.
  • 100 g of the hydrous polydimethylsiloxane were dissolved in 340 ml of tetrahydrofuran (THF) and admixed with 11.5 g of isophorone diisocyanate and 10 mg of di-butyltin dilaurate. Subsequently, the mixture was heated to 70 0 C for 1 hour. The viscous solution was poured into PTFE molds and the solvent removed by evaporation.
  • THF tetrahydrofuran
  • thermoplastic material was obtained.
  • test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 61 Shore A, tensile strength 6.1 MPa, elongation at break 557%, stress at 100% elongation 2.25 MPa.
  • Example 4 4.4 g of isophorone diisocyanate are heated to 70 ° C. with 0.18 g of water and 10 mg of dibutyltin dilaurate in 100 ml of tetrahydrofuran for 2 hours.
  • the viscous solution was poured into PTFE molds and the solvent removed by evaporation.
  • thermoplastic material was obtained.
  • test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 31 Shore A, tensile strength 3.4 MPa, elongation at break 601%, stress at 100% elongation 0.81 MPa.
  • the DVR is 51%.
  • thermoplastic material was obtained.
  • test specimens of the form S2 according to DIN 53504 were punched. The following mechanical properties were determined: hardness 15 Shore A, tensile strength 1.2 MPa, elongation at break 650%, stress at 100% elongation 0.45 MPa.
  • the DVR is 97%.
  • the temperature of the extruder was 170 ° C at this point. The remaining sectors were kept at 180 ° C. At the end of the extruder emerged a crystal clear colorless thermoplastic extrudate strand which was comminuted in a subsequent granulator. The granules thus obtained were pressed in a press at 180 0 C to a 2 mm thick plate and punched therefrom mold S2 according to DIN 53504. The following mechanical properties were determined: hardness 66 Shore A, tensile strength 6.8 MPa, elongation at break 543%, stress at 100% elongation 2.3 MPa.

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Abstract

L'invention concerne des copolymères de polyorganosiloxane et d'urée, un procédé de production de ces copolymères de polyorganosiloxane et d'urée, des compositions contenant des copolymères de polyorganosiloxane et d'urée, ainsi que leur préparation.
PCT/EP2007/062695 2006-11-29 2007-11-22 Copolymères siloxane/urée WO2008065039A1 (fr)

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CN108610466A (zh) * 2018-05-17 2018-10-02 山东大学 一种以聚硅氧烷完全替代聚醚的聚脲弹性体及其制备方法
CN116478525A (zh) * 2023-03-09 2023-07-25 山东大学 一种新型三组分共混型聚脲热塑性弹性体及其制备方法

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DE102010036107A1 (de) * 2010-09-01 2012-03-01 Scheu-Dental Gmbh Dentales Tiefziehmaterial
PL2778267T3 (pl) * 2013-03-11 2020-02-28 Parabeam b.v. Materiał wyścielający do sprężynującego, izolującego lub wyściełającego pokrycia przedmiotów lub elementów konstrukcyjnych
US20210284840A1 (en) * 2016-09-19 2021-09-16 Dow Silicones Corporation Copolymer composition for coating and adhesive applications

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EP1496079A1 (fr) * 2003-07-10 2005-01-12 Wacker-Chemie GmbH Copolymères polysiloxane-urée durcissables.

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EP1496079A1 (fr) * 2003-07-10 2005-01-12 Wacker-Chemie GmbH Copolymères polysiloxane-urée durcissables.

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108610466A (zh) * 2018-05-17 2018-10-02 山东大学 一种以聚硅氧烷完全替代聚醚的聚脲弹性体及其制备方法
CN108610466B (zh) * 2018-05-17 2021-04-06 山东大学 一种以聚硅氧烷完全替代聚醚的聚脲弹性体及其制备方法
CN116478525A (zh) * 2023-03-09 2023-07-25 山东大学 一种新型三组分共混型聚脲热塑性弹性体及其制备方法

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