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WO1999048965A1 - Compositions de matiere plastique presentant une resistance amelioree aux intemperies - Google Patents

Compositions de matiere plastique presentant une resistance amelioree aux intemperies Download PDF

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Publication number
WO1999048965A1
WO1999048965A1 PCT/NL1999/000160 NL9900160W WO9948965A1 WO 1999048965 A1 WO1999048965 A1 WO 1999048965A1 NL 9900160 W NL9900160 W NL 9900160W WO 9948965 A1 WO9948965 A1 WO 9948965A1
Authority
WO
WIPO (PCT)
Prior art keywords
tetramethyl
piperidinyl
bis
plastics composition
beta
Prior art date
Application number
PCT/NL1999/000160
Other languages
English (en)
Inventor
Pieter Gijsman
Arnoldus Egbertus Joannes Schaafsma
Original Assignee
Dsm N.V.
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 Dsm N.V. filed Critical Dsm N.V.
Priority to AU29644/99A priority Critical patent/AU2964499A/en
Publication of WO1999048965A1 publication Critical patent/WO1999048965A1/fr

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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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/549—Silicon-containing compounds containing silicon in a ring

Definitions

  • the invention relates to a plastics composition containing a polymer and at least one hindered-amine light stabilizer.
  • HALS compound a hindered-amine light stabilizer
  • a plastics composition containing a polymer and at least one HALS compound is known from US-A- 3,904,581.
  • the patent specification US-A-3 , 904 , 581 describes a plastics composition which contains a polymer and a 4-aminopiperidine compound, which is a HALS compound, as a result of which the plastics composition is stabilized against degradation under the influence of heat and light. It is commonly known that stabilizing a plastics composition against degradation under the influence of heat and light, in particular against degradation under the influence of UV radiation, improves the plastics composition's weather resistance, as a result of which the plastics composition becomes suitable for certain applications, for example for outdoor applications.
  • the aim of the invention is to provide a plastics composition having such improved weather resistance.
  • the plastics composition according to the invention also contains at least one bridged amine compound which contains one N atom in a bridge, according to the following general formula I,
  • X and Y are bridgeheads and the individual bridge heads are independently of one another chosen from the group comprizing carbon, silicon and phosphorus, it being understood that carbon and silicon may be substituted;
  • D x and D m each stand for a chain having a length of 1 to 20 atoms, the number of atoms of which the chains are composed being equal to 1 and m, it being possible to choose each number and type of atoms independently of one another and it being possible for the chains to have different lengths and to be composed of different types of atoms .
  • the chains may also contain side groups, the number of atoms in the side groups not being included in the number of atoms of the chain. Suitable choices for the atoms of - 3 -
  • the chains are composed are carbon, nitrogen, oxygen, silicon and phosphorus. Preferably the chains are composed of carbon atoms .
  • the substituent R is a hydrogen, ether, ester, amine, amide, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl or aryl group, which substituents may in turn also contain functional groups; examples of these functional groups are alcohols, ketones, anhydrides, imines, siloxanes, ethers, carboxyl groups, aldehydes, esters, amides, imides, amines, nitriles, ethers, urethanes and any combination thereof. R may moreover connect several of the compounds of Formula I to one another.
  • a plastics composition containing a polymer, at least one HALS compound and at least one bridged amine compound which one N atom in a bridge shows a weather resistance that is substantially better than that of the known plastics composition not containing the bridged amine compound which one N atom in a bridge . It has also been found that in a plastics composition containing a polymer, at least one HALS compound and at least one bridged amine compound which one N atom in a bridge has a weather resistance that is better than the sum of the contributions of the HALS compounds and the bridged amine compound suggests. This is all the more surprizing because it has also been found that a plastics composition containing a polymer and only a bridged amine compound is virtually not stabilized against degradation under the influence of heat and light.
  • a xenon test is used as a measure of the weather resistance.
  • the xenon test determines a plastics composition's resistance to degradation under the influence of light from a filtered (borosilicate glass) xenon lamp at a black-panel temperature of 62 °C and an intensity of 0.35 W.m “ .nm “1 , at a wavelength of 340 nm and at a relative humidity of 55 vol . % in a wet/dry cycle of 18 minutes wet and 102 minutes dry.
  • the degradation of the plastics composition is measured as the increase in the difference between the absorption of carbonyl at 1713 cm “ and the absorption at 1860 cm “1 after the plastics composition has been exposed to said combination of light, temperature and humidity for a certain time. Said increase in the difference between the absorptions of carbonyl at 1713 cm “1 and 1860 cm “1 will here and hereafter be called the 'carbonyl increase'. It was thus found that the weather resistance of the plastics composition according to the invention may show a weather resistance whose carbonyl increase is less than half of that of known plastics compositions .
  • a HALS compound is understood to be compounds having the following general formulas : Ri (II)
  • R_ up to and including R 5 are here independent substituents
  • suitable substituents are hydrogen, ether, ester, amine, amide, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl and aryl groups, which substituents may in turn also contain functional groups; examples of functional groups are alcohols, ketones, anhydrides, imines, siloxanes, ethers, carboxyl groups, aldehydes, esters, amides, imides, amines, nitriles, ethers, urethanes and any combination thereof.
  • a hindered-amine light stabilizer may also form part of a polymer.
  • a compound derived from a substituted piperidine compound in particular any compound derived from an alkyl-substituted piperidyl, piperidinyl or piperazinone compound, and substituted alkoxypiperidinyl compounds are chosen as the HALS compound. Examples of such compounds are:
  • HALS 7 D-glucitol, 1, 3 :2,4-bis-0- (2,2, 6, 6-tetramethyl-4- piperidinylidene) (HALS 7) ; - oligomer of 7-oxa-3 , 20-diazadispiro [5.1.11.2] - heneicosan-21-one,2, 2,4, 4 -tetramethyl-20 -
  • - di- (2,2,6,6- tetramethyl-4 -piperidyl) sebacate also known under the tradename Tinuvin R 770
  • - oligomer of N-(2- hydroxyethyl) -2 , 2 , 6, 6-tetramethyl-4 -piperidinol and succinic acid (Tinuvin ® 622); - bis- (1-octyloxy-
  • the bridged amine compound which one N atom in a bridge is used with a HALS compound in a ratio, relative to the amount of HALS compound, of approximately 1:20 (m:m) to approximately 20:1 (m:m) , more preferably in a ratio of approximately 1:10 (m:m) to approximately 10:1 (m:m) , most preferably in a ratio of approximately 1:5 (m:m) to approximately 5:1 (m:m) .
  • the weather resistance is better than expected on the basis of the amounts of the bridged amine compound which one N atom in a bridge and the HALS compound present .
  • the amount of bridged amine compound which one N atom in a bridge that can be used in the plastics composition may vary within a wide range, which is easy - 12 -
  • the range may vary depending on for example the type of polymer, the type of HALS compound, the other additives in the additives package, the weather resistance to be obtained or, in general, the type of plastics composition, its properties and its specific application.
  • the bridged amine compound which one N atom in a bridge to be present in the plastics composition in an amount, relative to the amount of polymer in the plastics composition, of preferably approximately 0.01 wt . % to approximately 10.0 wt.%, more preferably in an amount of 0.05 wt.% to 5 wt.%, most preferably in an amount of 0.1 wt . % to 2.5 wt . % .
  • the bridged amine compound which one N atom in a bridge is chosen so that a plastics composition is obtained having a weather resistance measured with the xenon test of which the carbonyl increase after 1750 hours' exposure to light is less than 0.1, more preferably less than 0.005.
  • Suitable choices for the bridged amine compound which one N atom in a bridge are: tropinol, tropinone, tropane or derivatives of any of these compounds.
  • the bridged amine compound which one N atom in a bridge is substituted with at least one substituent having a molecular weight preferably of at least 50, more preferably of at least 100. - 13 -
  • the plastics composition according to the invention preferably contains a thermoplastic polymer chosen from the group comprizing polyolefins and styrene polymers .
  • a thermoplastic polymer chosen from the group comprizing polyolefins and styrene polymers .
  • Suitable choices are for example : - propylene polymers, such as propylene homopolymer, ethylene-propylene random copolymer, ethylene-propylene block copolymer and mixtures hereof.
  • propylene polymers in the context of this invention are mixtures containing at least 50 wt.% of one of the aforementioned propylene polymers with for example polyethene or ethylene-propylene-diene copolymers;
  • ethylene polymers such as low-density polyethylene (LDPE) , high-density polyethylene (HDPE) , very-low- density polyethylene (VLDPE) , linear-low-density polyethylene (LLDPE) or ultra-high-molecular-weight polyethylene (UHMWPE) ;
  • LDPE low-density polyethylene
  • HDPE high-density polyethylene
  • VLDPE very-low- density polyethylene
  • LLDPE linear-low-density polyethylene
  • UHMWPE ultra-high-molecular-weight polyethylene
  • styrene polymers such as polybutylene-1.
  • styrene polymers are for example polystyrene, high-impact polystyrene (HIPS) , styrene- acrylonitrile copolymer (SAN) , acrylonitrile-butadiene- styrene copolymer (ABS) , styrene-maleic anhydride copolymer (SMA) and styrene-maleimide copolymer (SMI) .
  • HIPS high-impact polystyrene
  • SAN styrene- acrylonitrile copolymer
  • ABS acrylonitrile-butadiene- styrene copolymer
  • SMA styrene-maleic anhydride copolymer
  • SMI styrene-maleimide copolymer
  • the polymer is a propylene polymer or an ABS, even more
  • the bridged amine compound which one N atom in a bridge can easily, and at any desired time before a plastic article, for example a moulded part, foil, film, fibre, coating, foam, tape, latex or powder, is produced from the plastics composition, be introduced - 14 -
  • the bridged amine compound which one N atom in a bridge is mixed with the other components of the plastics composition, which are for example in the form of a powder or a melt .
  • the bridged amine compound which one N atom in a bridge is first mixed with at least one HALS compound and optionally other additives in a so-called additives package, for example in the form of a powder, solution, emulsion or suspension, and this package is subsequently added to the plastic, for example in the form of powder or as a melt .
  • the plastics composition containing a polymer, at least one HALS compound and at least one bridged amine compound which one N atom in a bridge may also contain other additives, such as antioxidants, thermal and UV stabilizers, metal deactivators, fillers, pigments, flame retardants, optical bleaching agents and similar additives that are used in plastics compositions.
  • additives such as antioxidants, thermal and UV stabilizers, metal deactivators, fillers, pigments, flame retardants, optical bleaching agents and similar additives that are used in plastics compositions.
  • a polymer powder (PP) was mixed with a solution containing an amount of a HALS compound. This mixture was dried in an oven (Hereaus Vacutherm) for 24 hours at a temperature of 28°C and a pressure of approximately 20 mm Hg. Next, a solution of the bridged amine compound which one N atom in a bridge was added to the plastics composition. This plastics composition was also dried in the same way as described above . This process was also used to prepare plastics compositions (blanks) in which the amount of HALS compound and/or bridged amine compound which one N atom in a bridge in the solution was nil.
  • the PP composition was compressed to form a film using a Fontijne press (type TP200, 5 minutes pressureless preheating at 190°C, after which the pressure was raized to 100-120 kNewton, followed by 10 minutes' cooling at said pressure) .
  • the thickness was checked with the aid of a Heidenhain electronic meter. On average a thickness of 120 -150 ⁇ m was for the films . - 16 -
  • a plastics composition's weather resistance was determined in a weather resistance test, carried out in an Atlas Material Testing Technology Weather-0 meter (type Ci65) according to the method described above. The degradation was measured with the aid of FT- IR. The weather resistance is then expressed as the carbonyl increase after the plastics composition has been exposed to said combination of light, temperature and humidity for 1750 hours.
  • Example I and Comparative Experiments A-C Weather resistance of various plastics compositions.
  • a series of plastics compositions was prepared using the process described above, in which the composition of the plastics composition was varied.
  • Di- (2,2, 6, 6-tetramethyl-4 -piperidyl) sebacate (tradename: Tinuvin R 770, Ciba-Geigy, Basel) was chosen as the HALS compound.
  • Tropinol was chosen as the bridged amine compound which one N atom in a bridge.
  • PP Stamylan R , grade P83ml8, DSM, the Netherlands
  • Films were produced from the plastics compositions using the process described above. The films were subjected to a weather resistance - 17 -

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une composition de matière plastique contenant un polymère, au moins un stabilisant à la lumière, à amine encombrée (composé HALS) ainsi qu'au moins un composé amine ponté dont l'atome d'azote est présent dans le pont. De préférence le composé d'amine ponté est tropinol, tropinone ou tropane ou un dérivé de l'un quelconque de ces composés. De préférence le polymère est un polymère de propylène. La composition de matière plastique de l'invention présente une résistance améliorée aux intempéries.
PCT/NL1999/000160 1998-03-23 1999-03-22 Compositions de matiere plastique presentant une resistance amelioree aux intemperies WO1999048965A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU29644/99A AU2964499A (en) 1998-03-23 1999-03-22 Plastics composition with improved weather resistance

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL1008680 1998-03-23
NL1008680A NL1008680C2 (nl) 1998-03-23 1998-03-23 Kunststofsamenstelling met een verbeterde weersbestendigheid.

Publications (1)

Publication Number Publication Date
WO1999048965A1 true WO1999048965A1 (fr) 1999-09-30

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PCT/NL1999/000160 WO1999048965A1 (fr) 1998-03-23 1999-03-22 Compositions de matiere plastique presentant une resistance amelioree aux intemperies

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AU (1) AU2964499A (fr)
NL (1) NL1008680C2 (fr)
WO (1) WO1999048965A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1338622A2 (fr) * 2003-03-14 2003-08-27 Ciba SC Holding AG Mélanges stabilisants
EP1571177A1 (fr) * 2004-03-03 2005-09-07 DSM IP Assets B.V. Elastomeres avec résistance aux intempéries ameliorée

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2076569A6 (en) * 1970-01-20 1971-10-15 Commissariat Energie Atomique Tropine nitroxide radicals - useful as initiators, inhibitors of polymerization, antioxidants
US4000113A (en) * 1974-01-14 1976-12-28 Ciba-Geigy Corporation Acylated derivatives of 2,6-dihydroxy-9-azabicyclo[3.3.1]nonane and stabilized compositions
JPS62297847A (ja) * 1986-06-17 1987-12-25 Konica Corp ハロゲン化銀写真感光材料
EP0313941A1 (fr) * 1987-10-16 1989-05-03 Nissan Motor Co., Ltd. Produit photochrome
JPH0299323A (ja) * 1988-10-06 1990-04-11 Mitsubishi Kasei Corp 積層体
US5759727A (en) * 1997-01-21 1998-06-02 Xerox Corporation Method of generating simulated photographic quality images on luminescent, mirror coated, melt-formed backing substrates

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2076569A6 (en) * 1970-01-20 1971-10-15 Commissariat Energie Atomique Tropine nitroxide radicals - useful as initiators, inhibitors of polymerization, antioxidants
US4000113A (en) * 1974-01-14 1976-12-28 Ciba-Geigy Corporation Acylated derivatives of 2,6-dihydroxy-9-azabicyclo[3.3.1]nonane and stabilized compositions
JPS62297847A (ja) * 1986-06-17 1987-12-25 Konica Corp ハロゲン化銀写真感光材料
EP0313941A1 (fr) * 1987-10-16 1989-05-03 Nissan Motor Co., Ltd. Produit photochrome
JPH0299323A (ja) * 1988-10-06 1990-04-11 Mitsubishi Kasei Corp 積層体
US5759727A (en) * 1997-01-21 1998-06-02 Xerox Corporation Method of generating simulated photographic quality images on luminescent, mirror coated, melt-formed backing substrates

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 8806, Derwent World Patents Index; AN 88-039434, XP002085977, "Silver halide photographic material-" *
PATENT ABSTRACTS OF JAPAN vol. 012, no. 192 (P - 712) 4 June 1988 (1988-06-04) *
PATENT ABSTRACTS OF JAPAN vol. 014, no. 305 (M - 0992) 29 June 1990 (1990-06-29) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1338622A2 (fr) * 2003-03-14 2003-08-27 Ciba SC Holding AG Mélanges stabilisants
EP1338622A3 (fr) * 2003-03-14 2003-09-10 Ciba SC Holding AG Melanges stabilisants
EP1571177A1 (fr) * 2004-03-03 2005-09-07 DSM IP Assets B.V. Elastomeres avec résistance aux intempéries ameliorée

Also Published As

Publication number Publication date
NL1008680C2 (nl) 1999-09-24
AU2964499A (en) 1999-10-18

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