CA2280158A1 - Plastics composition having improved weather resistance - Google Patents
Plastics composition having improved weather resistance Download PDFInfo
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- CA2280158A1 CA2280158A1 CA002280158A CA2280158A CA2280158A1 CA 2280158 A1 CA2280158 A1 CA 2280158A1 CA 002280158 A CA002280158 A CA 002280158A CA 2280158 A CA2280158 A CA 2280158A CA 2280158 A1 CA2280158 A1 CA 2280158A1
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- tetramethyl
- plastics composition
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- piperidinyl
- bridgehead
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- 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
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
-
- 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
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention relates to a plastics composition which contains a polymer, at least one hindered-amine light stabilizer (HALS compound) and at least one bridged amine compound having at least one N-bridgehead. Preferably the bridged amine compound is hexamethylenetetramine or diazabicyclo[2.2.2]octane or a derivative of either compound. Preferably the polymer is a propylene polymer or an acrylonitrile-butadiene-styrene copolymer (ABS). The plastics composition according to the invention has improved weather resistance.
Description
PLASTICS COMPOSITION HAVING IMPROVED
WEATHER RES T S'T'ANCE
The invention relates to a plastics composition containing a polymer and at least one hindered-amine light stabilizer.
In what follows below, a hindered-amine light stabilizer will be referred tc as a HALS
compound.
A plastics composition containing a polymer and at least one HALS compound ,is disclosed in US-A-3,904,581. Patent Specif,ycation 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 resu'_t of which the plastics composition is stabilized against degradation caused by heat and light. It is generally known that the stabilization of a plastics composition against degradation caused by heat and light, in particular against degradation caused by UV radiation, improves the weather resistance of the plastics composition, as a result of which the plastics composition becomes suitable for particular applications, for example for outdoor applications.
Although a plastics composition which contains a polymer and at least one HA.LS compound already has a good weather resistance, there is a need for a plastics composition which has improved weather resistance.
The object of the invention is to provide a plastics composition which has such improved weather resistance.
This object is achieved, according to the invention, in that the plastics composition according to the invention contains a polymer, at least one HALS
compound and at least one bridged amine compound having at least one N-bridgehead.
Surprisingly, it has in fact been tound that a plastics composition which contains a polymer, at least one HALS compound and at least one bridged amine compound having at least one N-bridgehead has a weather resistance which is appreciably better than that cf the known plastics composition which does not contain the bridged amine compound having at least one N-bridgehead. It has also been found t:~at a plastics composition which contains a polymer, at least one F-iALS
compound and at least one bridged amine compound having at least one N-bridgehead has a weather resistance that is better than would be expected on the basis of the sum of the contributions of the HALS compound and the bridged amine compound. This is all the more surprising because it has also been found that a plastics composition which contains a polymer and only one bridged amine compound is hardly stabilized against degradation caused by heat and light. Thus, with certain choices of the components of the plastics composition according to the invention, it was found that the weather resistance of the plastics composition according to the invention could have a weather resistance which was more than double the weather resistance of the known plastics compositions.
DE 2637193 describes that compounds having the general formula N=C- F
,w ~ , N
tI~
protect organic polymers against the influence of sight. In Formula I, if n = 1, R is an alkyl or isoalkyl group having 1-17 C atoms, a phenylalkyl group having 1-4 C atoms in the alkyl chain, a phenyl or a naphthyl group, which may be substituted by 2 chlorine atoms, a hydroxyl group or by at most 3 alkoxy or alkyl l0 groups having 1-4 C atoms, or represents a heterocyclic 5- or 6-ring with an N or 0 atom, while, if n = 2, R
stands for an alkylene group having 2 to 6 C atoms or a phenylene group. DE 2637193 describes that the aforementioned compounds (I) are also effective in the presence of the usual stabilizers such as antioxidants, W absorbers, light stabilizers, phosphate stabilizers, metal compounds, epoxy stabilizers, polyhydric alcohols, antistatic agents, flame retardants and pigments. Sterically hindered piperidine compounds are mentioned as examples of the W absorbers and/or light stabilizers. It is nowhere apparent from DE 2637193 that compounds having the general formula (I) would improve the effect of the usual stabilizers, let alone that there would be a synergistic effect between compounds having the general formula (I) and HALS
stabilizers. Compounds having the general formula (I) are excluded from the plastics composition according to the invention.
Within the scope of this invention, a xenon test is employed as a measure of the weather resistance. The xenon test determines a plastics composition's resistance to degradation when e:~posed to light from a filtered (borosilicate glass) xenon lamp at a black panel temperature of 62°C having an intensity of 0.35 W~m-'~nm-1, at a wavelength of 340 nm and a 1C relative humidity of 55% by volume in a wet/dry cycle of 18 minutes wet and 102 minutes dry. The degradation of the plastics composition is measured as the difference in the carbonyl absorption at 1713 cm-1 and the absorption at 1860 cm-1 as a function of the time for which the plastics composition is subjected to said combination of light, temperature and humidity. The weather resistance is expressed as the time for which a plastics composition is subjected to said combination of light, temperature and humidity and at which the difference between the measured carbonyl absorptions is less than a certain value to be chosen beforehand. In the xenon test employed here, this value is 0.10 for the films and 0.50 for plates.
'Hindered-amine light stabilizers' are understood to be compounds having the following general formulas:
~I
3a ~- \ ~\Rz F~-O-~- N\ - F'~s ~a and combinations hereof.
R1 up to and including RS are herein independent substituents; examples of suitable substituents are hydrogen, ether, ester, amine, amide, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl and aryl groups, which substituents may in turn 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.
Preferably, the HATS compound chosen is a compound derived from a substituted piperidine compound, in particular any compound which is derived from an alkyl-substituted piperidyl, piperidinyl or piperazinone compound and substituted alkoxypiperidinyl compounds. Examples of such compounds are:
- 2,2,6,6-tetramethyl-4-piperidone;
- 2,2,6,6-tetramethyl-4-piperidinol;
- bis-(1,2,2,6,6-pentamethylpiperidyl',-(3',5'-di-tert-l0 butyl-4'-hydroxybenzyl) butylmalonate;
- di-(2,2,6,6-tetramethyl-4-piperid~rl) sebacate (Tinuvin~ 770 ) ;
- oligomer of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid (Tinuvin9 622);
- oligomer of cyanic acid and N,N-di(2,2,6,6-tetramethyl-4-piperidyl) hexamethylene diamine;
- bis-(2,2,6,6-tetramethyl-4-piperidinyl) succinate;
- bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin~ 123);
- bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (TinuvinD 765 ) ;
- tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate;
- N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl) hexane-1,6-diamine (Chimassorb~ T5);
- N-butyl-2,2,6,6-tetramethyl-4-piperidinamine;
- 2,2'-[(2,2,6,6-tetramethylpiperidinyl)imino]-bis-[ethanol] ;
- poly((6-morpholine-S-triazine-2,4-diyl)(2,2,6,6-tetramethyl-4-piperidinyl)-iminohexamethylene-(2,2,6,6-tetramethyl-4-piperidinyl)-imino) (Cyasorb~ UV 3346);
WEATHER RES T S'T'ANCE
The invention relates to a plastics composition containing a polymer and at least one hindered-amine light stabilizer.
In what follows below, a hindered-amine light stabilizer will be referred tc as a HALS
compound.
A plastics composition containing a polymer and at least one HALS compound ,is disclosed in US-A-3,904,581. Patent Specif,ycation 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 resu'_t of which the plastics composition is stabilized against degradation caused by heat and light. It is generally known that the stabilization of a plastics composition against degradation caused by heat and light, in particular against degradation caused by UV radiation, improves the weather resistance of the plastics composition, as a result of which the plastics composition becomes suitable for particular applications, for example for outdoor applications.
Although a plastics composition which contains a polymer and at least one HA.LS compound already has a good weather resistance, there is a need for a plastics composition which has improved weather resistance.
The object of the invention is to provide a plastics composition which has such improved weather resistance.
This object is achieved, according to the invention, in that the plastics composition according to the invention contains a polymer, at least one HALS
compound and at least one bridged amine compound having at least one N-bridgehead.
Surprisingly, it has in fact been tound that a plastics composition which contains a polymer, at least one HALS compound and at least one bridged amine compound having at least one N-bridgehead has a weather resistance which is appreciably better than that cf the known plastics composition which does not contain the bridged amine compound having at least one N-bridgehead. It has also been found t:~at a plastics composition which contains a polymer, at least one F-iALS
compound and at least one bridged amine compound having at least one N-bridgehead has a weather resistance that is better than would be expected on the basis of the sum of the contributions of the HALS compound and the bridged amine compound. This is all the more surprising because it has also been found that a plastics composition which contains a polymer and only one bridged amine compound is hardly stabilized against degradation caused by heat and light. Thus, with certain choices of the components of the plastics composition according to the invention, it was found that the weather resistance of the plastics composition according to the invention could have a weather resistance which was more than double the weather resistance of the known plastics compositions.
DE 2637193 describes that compounds having the general formula N=C- F
,w ~ , N
tI~
protect organic polymers against the influence of sight. In Formula I, if n = 1, R is an alkyl or isoalkyl group having 1-17 C atoms, a phenylalkyl group having 1-4 C atoms in the alkyl chain, a phenyl or a naphthyl group, which may be substituted by 2 chlorine atoms, a hydroxyl group or by at most 3 alkoxy or alkyl l0 groups having 1-4 C atoms, or represents a heterocyclic 5- or 6-ring with an N or 0 atom, while, if n = 2, R
stands for an alkylene group having 2 to 6 C atoms or a phenylene group. DE 2637193 describes that the aforementioned compounds (I) are also effective in the presence of the usual stabilizers such as antioxidants, W absorbers, light stabilizers, phosphate stabilizers, metal compounds, epoxy stabilizers, polyhydric alcohols, antistatic agents, flame retardants and pigments. Sterically hindered piperidine compounds are mentioned as examples of the W absorbers and/or light stabilizers. It is nowhere apparent from DE 2637193 that compounds having the general formula (I) would improve the effect of the usual stabilizers, let alone that there would be a synergistic effect between compounds having the general formula (I) and HALS
stabilizers. Compounds having the general formula (I) are excluded from the plastics composition according to the invention.
Within the scope of this invention, a xenon test is employed as a measure of the weather resistance. The xenon test determines a plastics composition's resistance to degradation when e:~posed to light from a filtered (borosilicate glass) xenon lamp at a black panel temperature of 62°C having an intensity of 0.35 W~m-'~nm-1, at a wavelength of 340 nm and a 1C relative humidity of 55% by volume in a wet/dry cycle of 18 minutes wet and 102 minutes dry. The degradation of the plastics composition is measured as the difference in the carbonyl absorption at 1713 cm-1 and the absorption at 1860 cm-1 as a function of the time for which the plastics composition is subjected to said combination of light, temperature and humidity. The weather resistance is expressed as the time for which a plastics composition is subjected to said combination of light, temperature and humidity and at which the difference between the measured carbonyl absorptions is less than a certain value to be chosen beforehand. In the xenon test employed here, this value is 0.10 for the films and 0.50 for plates.
'Hindered-amine light stabilizers' are understood to be compounds having the following general formulas:
~I
3a ~- \ ~\Rz F~-O-~- N\ - F'~s ~a and combinations hereof.
R1 up to and including RS are herein independent substituents; examples of suitable substituents are hydrogen, ether, ester, amine, amide, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl and aryl groups, which substituents may in turn 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.
Preferably, the HATS compound chosen is a compound derived from a substituted piperidine compound, in particular any compound which is derived from an alkyl-substituted piperidyl, piperidinyl or piperazinone compound and substituted alkoxypiperidinyl compounds. Examples of such compounds are:
- 2,2,6,6-tetramethyl-4-piperidone;
- 2,2,6,6-tetramethyl-4-piperidinol;
- bis-(1,2,2,6,6-pentamethylpiperidyl',-(3',5'-di-tert-l0 butyl-4'-hydroxybenzyl) butylmalonate;
- di-(2,2,6,6-tetramethyl-4-piperid~rl) sebacate (Tinuvin~ 770 ) ;
- oligomer of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid (Tinuvin9 622);
- oligomer of cyanic acid and N,N-di(2,2,6,6-tetramethyl-4-piperidyl) hexamethylene diamine;
- bis-(2,2,6,6-tetramethyl-4-piperidinyl) succinate;
- bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin~ 123);
- bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (TinuvinD 765 ) ;
- tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate;
- N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl) hexane-1,6-diamine (Chimassorb~ T5);
- N-butyl-2,2,6,6-tetramethyl-4-piperidinamine;
- 2,2'-[(2,2,6,6-tetramethylpiperidinyl)imino]-bis-[ethanol] ;
- poly((6-morpholine-S-triazine-2,4-diyl)(2,2,6,6-tetramethyl-4-piperidinyl)-iminohexamethylene-(2,2,6,6-tetramethyl-4-piperidinyl)-imino) (Cyasorb~ UV 3346);
- 5-(2,2,6,6-tetramethyl-4-piperidinyl)-2-cyclo-undecyloxazole) (Hostaviri N2o);
-- 1,1'-(1,2-ethanediyl)-bis-(3,3',5,5'-tetramethyl-piperazinone);
- e-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro(4,5)decane-2,4-dione;
- polymethylpropyl-3-oxy[4(2,2,6,6-tetramethyl)-piperidinyl)siloxane (Uvasil~ 299);
- 1,2,3,4-butanetetracarboxylic acid-1,2,3-tris(1,2,2,6,6-pentamethyl-4-piperidinyl)-4-tridecyl ester;
l0 - copolymer of a-methylstyrene-T3-(2,2,6,6-tetramethyl-4-piperidinyl)maleimide and N-stearylmaleirnide;
- 1,2,3,4-butanetetracarboxylic acid, polymer w,.~th beta, beta, beta',beta'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, 1,2,2,6,6-pentamethyl-4-piperidinyl ester (Mark LA63) - 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol,beta,beta,beta',beta'-tetramethyl-, polymer with 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinyl ester (MarkR LA68) - D-glucitol, 1,3:2,4-bis-O-(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-(oxiranylmethyl) (Hostavina N30) - propanedioic acid, [(4-methoxyphenyl)methylene] -bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester ( Sanduvor~ PR 31 ) - formamide, N,N'-1,6-hexanediylbis[N-(2,2,6,6-tetramethyl-4-piperidinyl (Uvinul~ 4050H).
- 1,3,5-triazine-2,4,6-triamine, N,N~~ -[1,2-ethanediylbis [[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-iperidinyl)amino]-1,3,5-triazine-2-yl]imino]-3,1-propanediyl]]-bis[N',N' -dibutyl-N~,N' -bis(1,2,2,6,6-pentamethyl-4-piperidinyl) (Chimassorby 119) - 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (2,2,6,6-tetramethyl-4-peridinyl) ester (Cyasorb~~~
UV-500) - 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (1,2,2,6,6-pentamethyl-4-peridinyl) ester (CyasorbR
UV-516) - N-2,2,6,6-tetramethyl-4-piperidinyl-N-amino-oxamide;
- 4-acryloyloxy-1,2,2,6,6-pentamethyl-4-piperidine;
- 1,5,8,12-tetrakis[2',4'-bis(1",2",2",6",6"-pentamethyl-4"-piperidinyl(butyl)amino)-1',3',5'-triazin-6'-yl]-1,5,8,12-tetrazadodecane.
HALS PB-41 (Clariant Huningue S.A.) Nylostab~ S-EED (Clariant Huningue S.A.) 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-pyrrolidin-2,5-dione Uvasorb« HA88 1,1'-(1,2-ethane-di-yl)-bis-(3,3',5,5'-tetra-methyl-piperazinone) (Good-rite° 3034) 1,1~,1~ -(1,3,5-triazine-2,4,6-triyltris ((cyclohexylimino)-2,1-ethanediyl)tris(3,3,5,5-tetramethylpiperazinone); (Good-rite' 3150) 1,1~,1~ -(1,3,5-triazine-2,4,6-triyltris((cyclohexylimino)-2,1-ethanediyl)tris(3,3,4,5,5-tetramethylpiperazinone) (Good-rite° 3159) Preferably use is made of di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate, (also known under the tradename of TinuvinR 770), oligomer of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid (Tinuvin° 622); bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin° 123);
bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate - g _ (Tinuvin'"~ 765); N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexane-1,6-diamine (Chimassorb'"-~ TS);
poly((6-morpholine-S-triazine-2,4-diyl)(2,2,6,6-tetramethyl-4-piperidinyl)-iminohexamethylene-(2,2,6,6-tetramethyl-4-piperidinyl)-imino) (Cyasorb°' UV 3346);
5-(2,2,6,6-tetramethyl-4-piperidinyl)-2-cyclo-undecyi-oxazoi) (HostavinG N20);
polymethylpropyl-3-oxy-[4(2,2,6,6-tetramethyl)-piperidinyl)-siloxane (Uvasil~' 299), l0 - 1,2,3,4-butanetetracarboxylic acid, polymer ~~ri~h beta,beta,beta',beta'-tetrameth~.~l-2,4,8,10-tetraoxaspiro(5.5]undecane-3,9-diethanol, 1,2,2,6,6-pentamethyl-4-piperidinyl ester (Marl:"' LA63) - 2,4,8,10-tetraoxaspiro(5.5]undecane-3,9-diethanol,beta,beta,beta',beta'-tetramethyl-, polymer with 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinyl ester (Marks LA68) - D-glucitol, 1,3:2,4-bis-O-(2,2,6,6-tetramethi~l-4-piperidinylidene) (HALS 7) - oligomer of 7-oxa-3,20-diazadispiro(5.1.11.2]heneicosan-21-one,2,2,4,4-tetramethyl-20-(oxiranylmethyl) (Hostavin~' N30) - propanedioic acid, [(4-methoxyphenyl)methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester (Sanduvor° PR 31) - formamide, N,N'-1,6-hexanediylbis(N-(2,2,6,6-tetramethyl-4-piperidinyl (Uvinul° 4o50H).
- 1,3,5-triazine-2,4,6-triamine, N,N~~ -[1,2-ethanediylbis (((4,6-bis(butyl(1,2,2,6,6-pentamethyl-4-iperidinyl)amino]-1,3,5-triazine-2-yl] imino] -3 , 1-propanediyl] ] -bis [N' ,N" -dibutyl-N~ , N' -bis(1,2,2,6,6-pentamethyl-4-piperidinyl) (Chimassorb°
119 ) - 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (2,2,6,6-tetramethyl-4-peridinyl) ester (Cyasorb°
UV-500) - 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (1,2,2,6,6-pentamethyl-4-peridinyl) ester (Cyasorb~"' UV516) - mixtures of esters of 2,2,6,6-tetramethyl-4-piperidinol and fatty acids (Cyasorbv UV 3853);
HALS PB-41 (Clariant Huningue S.A.) Nylostab'J S-EED (Clariant Huningue S.A.) 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-pyrrolidine-2,5-dione Uvasorb~~ HA88 1,1'-(1,2-ethane-di-yl)-bis-(3,3',5,5'-tetra-methyl-piperazinone) (Good-rites' 3034) 1,1~,1~ -(1,3,5-triazine-2,4,6-triyltris ((cyclohexylimino)-2,1-ethanediyl)tris(3,3,5,5-tetramethylpiperazinone); (Good-rite' 3150) 1,1~,1~ -(1,3,5-triazine-2,4,6-triyltris((cyclohexylimino)-2,1-ethanediyl)tris(3,3,4,5,5-tetramethylpiperazinone) (Good-rites 3159).
The bridged amine compound having at least one N-bridgehead that can be used within the scope of this invention is preferably a compound derived from a compound having the general formula 1 or 2 (see formula sheet), where M1 to M4 are bridgeheads and each bridgehead is chosen independently of one another from carbon, nitrogen, silicon or phosphorus, with the 3o proviso that at least one bridgehead should always be a nitrogen atom and carbon and silicon may be substituted; an N-bridgehead is defined as a bridgehead which is a nitrogen atom; D1, Dm, Dn, Do, Dp and Dq here each stand for a chain having a length of 1 to 20 atoms, the number of atoms of which the chains are made up being equal to 1, m, n, o, p and q, each number of atoms and type of atom to be chosen independently of one another, and the chains being capable of having different lengths and being capable of being made up of different types of atoms. The c:-wins may also contain side groups, the number cf atoms in tre side groups not being included in the number of atoms of the chain.
Suitable choices for the atoms cf which the chairs are made up are carbon, nitrogen, cxygen, silicon and phosphorus. Preferably the chains are made up of 1 to 3 carbon atoms.
Preferably the bridged amine compound having at least one N-bridgehead is used with a HALS
compound in a ratio, relative to the amount of ziALS
compound, of between approximately 1:20 (m:m) and approximately 20:1 (m:m), more preferably in a ratio of between approximately 1:10 (m: m) and approximately 1C:1 (m: m), most preferably in a ratio of between approximately 1:5 (m: m) and approximately 5:1 (m: m).
Within the limits of the latter ratios the weather resistance is better than is expected on the basis of the amounts of the bridged amine compound having at least one N-bridgehead and the HALS compound present.
The amount of bridged amine compound having at least one N-bridgehead that can be used in the plastics composition may vary within a wide range, which can be easily determined by an average person skilled in the art. The range may vary depending on for example the type of polymer, the type of FiALS compound, the other additives in the additives package, the weather resistance to be realized or in general the type of plastics composition, its properties and its specific application.
It is for example possible for the bridged amine compound having at least one N-bridgehead to be S present in the plastics composition in an amount, relative to the amount of polymer in the plastics composition, of, preferably, between approximately 0.01% by weight and approximately 10.0% by weight, more preferably in an amount of between 0.05% by weight and l0 5% by weight, most preferably in an amount of between 0.1% by weight and 2.5% by weight.
Preferably the bridged amine compound having at least one N-bridgehead is chosen so that a plastics composition is obtained having a weather 15 resistance measured with the aid of the xenon test which is higher than approximately 500 hours, more preferably higher than approximately 750 hours, and most preferably higher than approximately 1000 hours.
Suitable choices for the bridged amine 20 compound having at least one N-bridgehead are:
- derivatives of 7-nitro-1,3,5-triazadamantane and 7-amino-1,3,5-triazadamantane, - derivatives of 7-amino-1,3,5-triazadamantane having the general structure II or III:
R
N~ ~N
N
(II) ~R
N- G
S 'R
I
,N'~ ~.N
i ~/ N', (III) where R and R' are independent substituents; examples of suitable substituents are hydrogen, ether, ester, amine, amide, alkyl, alkenyl) alkynyl, aralkyl, cycloalkyl and aryl groups, which substituents may in turn 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.
The substituent may moreover connect several of the I and/or II compounds to one another.
- derivatives obtained in a reaction of 7-amino-1,3,5-triazadamantane with compounds containing one or more functional groups. Examples of these functional groups are: aldehydes, acids, esters, amides, ketones, anhydrides and isocyanates.
- triazadamantane derivatives that are bound to a polymer (preferably a polyolefin) with the aid of an imide functionality;
- polymer-bound compounds obtained by the reaction of 7-amino-1,3,5-triazadamantane with a polymer (preferably a polyolefin) functionalized with malefic anhydride;
- hexamethylenetetramine (HMTA), diazabicyclo[2.2.2]octane (DABC01 or derivatives thereof. HMTA and DABCO are easy to obtain comme~:cially or are easy to prepare using generally known processes.
HMTA, for example, can easily be prepared from the cheap and easily obtainable basic raw materials ammonia and formaldehyde.
The bridged amine compound having at least one N-bridgehead is preferably used as a salt, more preferably as an ammonium salt. Preferably a carboxylic acid is chosen as the salt-forming agent. Examples of suitable carboxylic acids are aliphatic carboxylic acids, aliphatic dicarboxylic acids and aromatic carboxylic acids. Suitable choices are stearic acid, sebacic acid, cyclohexanedicarboxylic acid and benzenetricarboxylic acid. Preferably the bridged amine compound having at least one N-bridgehead is not used as a salt if the salt-forming agent contains a halogen or sulphur, for it is generally known that halogen-containing or sulphur-containing compounds can reduce the effect of the HALS stabilizer.
The bridged amine compound having at least one N-bridgehead is preferably substituted with at least one substituent having a molecular weight of preferably at least 50, more preferably at least 100.
Surprisingly, it has been found that, as a result of using the bridged amine compound having at least one N-bridgehead either in its salt form, or substituted with at least one substituent having a molecular weight greater than approximately 50, or in its salt form and substituted with at least one substituent having a molecular weight greater than approximately 50, a plastics composition is obtained which has still better weather resistance.
The plastics composition according to the invention preferably contains a thermoplastic polymer chosen from the group of 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. Also defined as propylene polymers within the scope of this invention are mixtures containing at least 50% by weight of one of the aforementioned propylene polymers with, for example, polyethylene or ethylene-propylene-dime 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);
- butylene polymers, such as poly(1-butylene).
Suitable choices of styrene polymers are, for example, polystyrene, high-impact-resistant polystyrene (HIPS), styrene-acrylonitrile copolymer (SAN), acrylonitrile-butadiene-styrene copolymer (ABS), styrene-malefic anhydride copolymer (SMA) and styrene-maleimide copolymer (SMI).
More preferably, the polymer is a propylene polymer or an AHS, still more preferably a propylene polymer.
The bridged amine compound having at least one N-bridgehead can be introduced into the plastics composition with the aid of one of the many standard methods known to a person skilled in the art at any desired time before making a plastic article, for example a moulded part, sheet, film, fibre, coating, foam, tape, latex or powder, from the plastics composition.
According to a first method, the bridged amine compound having at least one N-bridgehead is mixed, for example in the form of a powder, solution, emulsion or suspension, with the other components of the plastics composition which are in the form of, for example, a powder or a melt.
According to a second method, the bridged amine compound having at least one N-bridgehead is first mixed with at least one HALS compound and optionally with other additives in a so-called additives package, for example in the form of a powder, solution, emulsion or suspension, and said package is then added to the plastic, for example in the form of a powder or as a melt.
The plastics composition containing a polymer, at least one HALS compound and at least one bridged amine compound having at least one N-bridgehead may also contain other additives, for example antioxidants, thermal and UV stabilizers, metal deactivators, fillers, pigments, flame retardants, optical whiteners and similar additives which are used in plastics compositions.
The invention will be explained further by reference to the examples without being limited hereto.
Exa~les In the examples, the following general processes were followed.
Dreparar;on of the various bridq-ed amines DABCO stearate:
A solution of 28.45 grams (0.1 mol) of stearic acid in ethanol was added, drop by drop, at room temperature, with stirring, to a solution o~ 11.2 grams (0.1 mol) of DAHCO in ethancl. The mixture was evaporated with the aid of a Rotavap.
HMTA stearate:
A solution of 28.45 grams (0.1 mol) of stearic acid in ethanol was added, drop by drep, with stirring, to a solution of 14 grams (0.1 mol) c~ DABCO
in ethanol. The mixture was evaporated with the aid of a Rotavap.
DABCO sebacate:
A solution of 20.2 grams (0.1 mol) of sebacic acid in methanol was added, drop by drop, at room temperature, with stirring, to a solution of 22.4 grams (0.2 mol) of DABCO in methanol. The mixture was evaporated with the aid of a Rotavap.
DABCO benzene tricarboxylate:
A solution of 21 grams (0.1 mol) of benzene tricarboxylic acid in absolute ethanol was added, drop by drop, at room temperature, with stirring, to a solution of 33.6 grams (0.3 mol) of DABCO in absolute ethanol. The salt was precipitated from the solution.
The mixture was evaporated with the aid of a Rotavap and dried in a vacuum drying stove.
DABCO distearate:
A solution of 56.9 grams (0.2 mol) of stearic acid in ethanol was added, drop by drop, at room temperature, with stirring, to a solution of 11.2 grams (0.1 mol) of DABCO in ethanol. The mixture was evaporated with the aid of a Rotavap and dried in a vacuum drying stove.
7-Nitro-1,3,5-triazadamantane:
A mixture of 56.8 ml (1.0 mol) of nitromethane and 45 ml (1.2 mol) of formic acid was added, drop by drop, to a solution of 140.2 grams (1.0 mol) of hexamethylenetetramine in 500 ml of ethanol (80%), with constant stirring and refluxing. The mixture was refluxed for 4 hours and set aside for one night. The separated crystalline product was washed a few times with water and ethanol. After recrystallization in water, the product (white needles) was dried in the vacuum drying stove. (Literature:
Czechoslov. Chem. Commun Collection [vol. 40J, 1975, pp. 2179-82).
7-Amino-1,3,5-triazadamantane:
15.0 grams of 7-nitro-1,3,5-triazadamantane, 100 ml of methanol and 1.5 grams of wet Raney cobalt as a catalyst were introduced into a Parr autoclave (volume 160 ml) fitted with a stirrer and baffles. The hydrogenation was carried out for an hour at maximum speed, beneath hydrogen at 80 bar pressure and 80°C. After removal of the catalyst through filtration, the methanol was removed by means of the rotavapor. The crystalline product was dried in a vacuum drying stove.
7-Dodecylideneamino-1,3,5-triazadamantane:
8.4 grams of 7-amino-1,3,5-triazadamantane, 10.0 grams of dodecanal, 85 ml of methanol, 10 ml of toluene and 2.0 grams of wet Raney cobalt as a catalyst were introduced into a Parr autoclave (volume 160 ml) fitted with a stirrer and baffles. The reaction was carried out for an hour in a nitrogen atmosphere (2 bar) at maximum speed and 80°C. After removal of the catalyst through filtration, the filtrate was evaporated witr. the aid of a Rotavapc~ and dried in a vacuum drying stove.
PP-MA-7-amino-1,3,5-triazadamantane:
0.8 grams of 7-amino-1,3,5-triazadamantane in 75 ml of solvent was added, drop by drop, with constant stirring, at 160-165°C, to a solution of 10.0 grams of PP-MA (Hostaprime~HCS) (PP grafted with approximately 2.8% malefic anhydride) in 150 ml of inert solvent.
After cooling to approx. 90°C, the product was precipitated using 100 ml of acetone. The separated product was dried in a vacuum drying stove, after which it was compressed to form a plate at 210°C. The latter was cryogenically ground to a powder.
p~paration of a plastics composition A polymer powder (PP or ABS) 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. Then a solution of the bridged amine compound having at least one N-bridgehead was added to the plastics composition. This plastics composition was also dried in the same way as described above. Plastics compositions (blanks) in which the amount of HALS compound and/or bridged amine compound S having at least one N-bridgehead in the solution was zero were also prepared using this process.
production of PP f~lms and g~a s The PP composition was compressed to form a film using a Fontijne press (type TP200, 5 minutes pressureless preheating at 190°C, followed by the application of a pressure of 100 - 120 kNewton, followed by 10 minutes cooling at said pressure). The thickness was checked using a Heidenhain electronic meter. On average, thicknesses of 120 - 150 ~Zm were obtained for the films and 1 mm for the plates.
Production of ABS films and plates The ABS composition was compressed to form a film using a Fontijne press (type TP200, 5 minutes preheating at a pressure of 50 kNewton and 210°C, followed by the application of a pressure of 100-120 kNewton, followed by l0 minutes cooling at said pressure). The thickness was checked using a Heidenhain electronic meter. On average, thicknesses of 120 - 150 ~m were obtained for the films and 1 mm for the plates.
Production of PE films The PE compositions were produced by means of compounding at 160°C. Next, films with a thickness of 150 ~m were blown at the same temperature.
DerPrmination of the weather resistance The weather resistance of a plastics composition was determined in a weather-resistance test performed in an Atlas Material Testing Technology Weather-O meter (type Ci65) according to the method described in the preceding description. The degradation was measured with the aid of F'='-IR. The weather resistance is then expressed as the amount of time (the number of hours) for which a plastics composition is l0 subjected to said combinatio~: of light, tempera:.ure and humidity and at which the difference between the measured carbonyl absorptions is less than 0.10 before and after ageing in the case of the films and less than 0.5 in the case of the plates.
In some cases the change in colour as a result of ageing was characterized with the aid of a calorimeter according to ASTM standard 1925.
In the examples, the following abbreviations and tradenames were used:
PE: polyethylene PP: polypropylene ABS: acrylonitrile-butadiene-styrene copolymer Tinuvin 770: di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate Tinuvin~622: oligomer of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid Tinuviri 123: bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate Chimassorb~ 944: oligomer of cyanic acid and N,N
di(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylene diamine Chimassorb~ 119: 1,3,5-triazine-2,4,6-triamine, N,N~~ -[1,2-ethane-diylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-iperidinyl)amino]-1,3,5-triazine-2-yl] imino) -3 , 1-propanediyl] ] -bis (N~ , 2d~ -dibutyl-N~ , N~ -bis(1,2,2,6,6-pentamethyl-4-piperidinyl) Hostavin9 N30: oligomer of 7-oxa-3,20-diazadispiro 15.1.11.2]-heneicosan-21-one,2,2,4,4-tetramethyl-20-(oxiranylmethyl) DABCO: diazabicyclol2.2.2]octane HMTA: hexamethylenetetramine DABCO stearate: monosalt of stearic acid and DABCO
DABCO distearate: salt of DABCO containing two stearic acid molecules DABCO sebacate: salt of sebacic acid (diacid) containing two DABCO molecules DABCO benzenetricarboxylate: salt of benzenetricarboxylic acid containing three DABCO
molecules HMTA stearate: monosalt of stearic acid and DABCO
Atade: 7-amino-1,3,5-triazadamantane Dodecylidene-atade: 7-dodecylideneamino-1,3,5-triazadamantane.
PP-MA-atade: MA-grafted polypropylene modified with atade, synthesized according to the above specification.
Examples I-II and Comparative Experiments A-D: Weather resistance of various plastics compositions A series of plastics compositions was prepared using the process described above. In this process, the composition of the plastics composition was varied. Di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate (tradename: Tinuvin 770, Ciba-Geigy, Basel) was chosen as the HALS compound.
PP (Stamylanm, type P83m18, DSM, the Netherlands) was chosen as the polymer. Films were produced from the plastics compositions using the process described above. The films were subjected to a weather-resistance test and the weather resistance was determined as described above. The results are summarized in Table 1.
a~
U
.,-i cn u1 u1 tn o 0 V1 ~-I I~ t~ t~ tI1 o I~
w r~, o ~ o v rt a~
p I v N
p b t~ ~ rd ?-~rd p ~ b ~ ~ ~r v b ~ it p a~ ~ y v ~ cn ~ ~n O N
O ~ O x U t~
a~ a x a b 3 3 3 3 O' b ~
N ~
p aw aw ow ow m o m o w O
2s .- 3 3 3 U ~ O ~ i i i ~7 ow ow ow p ~ rl rl r-1 U o o O
N
H H H H H H
W W L1 ~ G1~ G3~
v r~ C4 ~ W C4 W W
O
3 p, v ri '~' ~(,'(.T~U A H H
,La W H
H
Examt~les III VII and Comparative Experiments E and F:
Weather resistance of Mastics comn~~itions having various concentrations of HALS compound and bridged amine compound Example I was repeated, the concentrations of the HALS stabilizer chosen and the bridged amine compound having at least one N-bridgehead being varied.
The results are summarized in Table 2. From this it can be concluded that a plastics composition containing amounts of 0.1% by weight to 0.5% by weight of a bridged amine compound exhibits improved weather resistance, which increases as more bridged amine compound is used. It was thus possible to more than double the weather resistance (Example F versus ViI).
H
t-~ CrJ C C5' c c H H x H H 'T1 C
H Q N
..
ro a ro ro ro ro ro ro ro Q G r~
ro ro ro ro ro ro ro H H H H H H H (D
(D
H H H H H H H ~"~ ~fj a.
ri O O O O O O O
n n N N N F~ I-' N H' W O 1-~-I d o\ d ~ d a\ d N.
d O 'C7 'C 'G "G "G "G ~ ~ ~ ~ lD
'G tL
rt G
- a a.
rr c~ rr rr rT rr 7 rr n ~~
O
I G
j O O O ~ ~ ~ ~ O f1~
N V-' ~ N 1-~ ~ 1-'-d U1 d O O
tr' d tr' t~' tT G ~D G n "G 'G tr'~C '~G ~ Q.
~G ~n n n C ~c3 O O O O N-O O
-- ~
~n cn ~n m N-U~ O
c-t (-t c-r rr w fD (D rr fD (D G rr tv W (D tv N p O
rt f-S W n ft , G
iv H ~ s~ I--' rr ~t W rr c"r m (D fD n fD (D (D
fD W G' ~ C
~.
O G
G
fD
z w n m n o f.,_ G
rr . cn w ~n n n x o c~
o n ~ n 0o N o o J .~ a, G (D a fD
N W N W 00 ~7 O ~'t UI
0 0 0 0 0 0 0 0111-' H
N
rr W
W rr n o m rn Examples IX-XII : Trleather rebsistance of Mastics compositions containing various bridged amine compounds having at least one N-bridgehead Example I was repeated using a plastics composition containing 0.2% of a HATS (Tinuvir.~ 770), the type of bridged amine compound having at least one N-bridgehead being varied. The results are summarized in Table 3.
H
x x H
H H x x ~ rn n ~ ro ro ro ro 0 o c~
ro G
ro ro ro ro H H H H fD
H H H H
H H H H
n _ n r- m N N N N W O
do prodo pro O 'L7 ~-' fD
E G
V . (D
rt rr rr rt o w i U7 M
ro w ca m m o t7 t~ co z n d d ~ o ~
m n n o n ~ '~ r-r, O
O r, C7 O O w ~ Q.
fn cn rr O n ~ 'b N- O cT lD N- G 1-~-G' O
a, n m tr' o ~ A.
n~ ~ ~ ~ a. Cl. tY
1~- nt ~i n (D
m a' w w i p., O
rt p fT t'r ~
m x cn m w o n rt rt ~ ~ O
c~
w f.,.
W
C
w w rr n m O
v G' ~-i G
O
N G ni N J U1 ~D ~"~fD
O O O O '-'h'-O
W
,7 O
(y M
fD
n !~-.
l~
(D
WO 98/36023 PCTlNL98/00088 Example XIII and Comparative Experiment G: Weather ~PSistance of PE films Example I was repeated using two plastics compositions, both composed of PE (LDPE, type 2304 AN00, DSM, the Netherlands) and 0.05% by weight of HALS
compound (Tinuvin~ 770), with 0 and 0.06% by weight, respectively, of DABCO added thereto. The plastics compositions were processed tc form blown films 150 Ecm thick. The films were exposed to light in a Suntester.
The weather-resistance treatment was performed in a borosilicate glass vessel according to a method described in Po~ytn Deq_ & Stab., 39, 225-233 (i993).
The weather resistance was determined as described above; however, in this case, a change in the carbonyl absorption of 0.05 units was employed as deterr,:ir.ing the weather resistance. The weather resistance of the film without DABCO (Comparative Experiment G) was 2700 hours and the degradation increased considerably from 2400 hours onwards; the weather resistance of the film containing DP.BCO was more than 3500 hours and the degradation showed a constant profile at 0.03 units.
Example XIV and Comparative Experiments H and I:
WPatheY resistance of ABS films Example I was repeated using three plastics compositions composed of ABS (Ronfaliri , type 356**, DSM, the Netherlands), ABS and 0.5% by weight of HALS
compound (Tinuvin~ 770) and ABS, 0.5% by weight of HALS
compound and 0.5% by weight of DABCO stearate, respectively. The degradation was measured as a colour change using a colorimeter and the weather resistance was determined according to ASTM standard 1925 as the amount of time (the number of hours) for which a plastics composition is subjected to said weather-resistance test and at which the measured colour change is less than 5 units. The results are summarized in Table 4.
I
x x H H x c ro c~
H H H f'S ~-j ~i O O
n tn tn N O fT
d d O ~
c o r G ~
..-I
o ~~ ~ ~ rd d ~ w ~ o cr .C i ~ rr n m w b m r-rr O
G
m O N
G ~"T
n ?
U1 fD
n fi N fD
H J J N
wn o N-N
rr G
n m Examples XV XVII and Comrarat-ive Experiment. J:
Weather resistance of ABS films A series of plastics compositions was prepared using the process described above. In this process the composition of the plastics composition was varied. Di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate (tradename: TinuvinD 770, Ciba-Geigy, Basel) was chosen as the HALS compound. ABS (Ronfalin~, type 356**, DSM, the Netherlands) was chosen as the polymer. Elates were to produced from the plastics compositions using the process described above. The degradation was measured as a change in colour using a colorimeter and the weather resistance was determined according to ASTM
standard 1925 as the amount of time (the number of hours) for which a plastics composition is subjected to said weather-resistance test and at which the measured change in colour is less than 5 units. The results are summarized in Table S.
WO 98/36023 PC'T/NL98/00088 H
w rr H C C ~-i >C (D
fD
w O
t!~ (l Wl1(O E"' lD
H H H H
H H H H
N
N.
fT
w O O O H G
cn v, u, o d d d d ~ ~ 'x O n7 ~ O
CJ' CJ' t~ L3' C O C r"h "G 'G 'G ': C C U~
rr G
-' C1 (-r rt r t'r b I
_ O 3 H c-r f"f m ~y ~ ~ ~ m f'T w U1 ~ ~ M O
~ rr w ~ m w ~ ~ O
cn n. ly ~ b N.
fD w ~~ ~ a. rr Ct C. C lLl (D fD ~ ~ ~ y i N
_ (D
V V V ~
H H O ~, w O O O ll1 C ~ f"r O O O ~ r't n '~
Examples XVIII - XXIII and Comparative E~cperiments K -Weather resistance of ~lasti~-s comz~ositions ~ontaininq various bridged amine compounds having at least one r1-bridgehead Examples III - VIII were repeated, the type o~ bridged amine compound having at least one N-bridgehead being varied. The results are summarized in Table 6.
x x H ~ ~r o z .~ r x x DC H
H
b ro ro b ro ~o ro ro ro w b o E
ro ro ro ro ro ro ro ro ro 0 a C C C C C C C C C n n w n ' C
( J
H..
0 0 0 ~ ~ o o b m 0 I o r ~
E.-~N N 0 0 ~ m d d d ~ N d ~ (~ rr o\ o\ d N d tr' ~ ~ '~ d ,~ ,~ ~ ro f'f ~ "',.J
E r~r r~r ~ E rT C
n rr rr rr rr rr ~ m i rr ~ m ' a ~
O
Cn rn rr w I
tr' 3 ~ rr 3 p rr J ~ n m cn \: ~- ~ ~ O ~"t N- ~ ~ hj p ~ ~
m ~ ~' cn n ~ w rr B
0 0 ~ ~ ~ ~' r-r ~ ~ ~ 0 0 _ ~u _ o a o w ~ ~ ~ ~ ~ O ~
fD ~ (D ~ F-~ (D fD (D ~ G ~ r~
r~-~a' ri r~-~~ W Q, ~ N
w v w w ~ 1-, ~ rt , n a. Q' ~T ~ ~,.~ rT ~ ~ o w rr fD fD (D N ~. .
~ ~
tn ~ i n O
fr d cD p) N.
'.~
fr.
~ W
C
'D N F-~ ~t J f'' W 01 J (,~,. N
fD
o op ~''~o m m J o O N W G
0 tn ui o G ~ rr r-S p~ m ~' N (~7 ~
fD rr (D
N
O
M
r3' ~i N.
Q.
W
fD
x x x H x x x H H H ' H H
ro ro ro ro ro o ro b ro ro H H H H
C C C C
O O O
O
o\ N N N W
e\ o\ \
O n b rr '~ G
rr rr ~T
n H
n cn 3 3 ~ N- ~ O
w n ~ n O ~ ~
CT
cn ~n a. ~ rt 3 N o b N.
rr rr iv N.
(D (D ~ ~ N O G C1 ~
w n~ w - ~ ~
~, r u w w n ~ ~"' ~' n p.
o N f-'-d~ (D
N N 1-~p 1-'' J W W W
T
W O O~ W ~- ~
OD ~P 01 j n (D
E~camples XXIV - XXIX~ Weath r resistance of Mastics compositions containina various bridaed amine compounds havina at least one t1-bridgehead Examples III - VIII were repeated, the concentration of 7-amino-1,3,5-triazadamantane being varied. The results are summarized in Table 7.
H
x x x r tr x c x ~ x ~ x '~
x H H H C C n H .'~
~1 ~, ..
b i fD
ro ro ro ro b ro W
rr ro ro ro ro b ro C C C C C C ~p O
n m w M
~
o 0 0 0 0 0 N N N N I~ N w n d d d o\ o\ d O n Er CT CT' b' CT CT'CT G ~ N
.C ~ "C 'G 'G "G rGr 'C G.
~ ~ I
~ ~ rb rr r' ~ rt rT G
rr I) G m G
I r r ~
rn ~
r' ~1 O
0 0 ~ 0 0 0 ~ ~~ ~ b Ut N Ui N N W ~ N UI
do d N o\ d I ~ Er.
do d O t~. O rr N
N
'-' ~ w U1 c~r rr rr ~r rr c-r yn C
W
C
w n O
_ ~ ~ G
m ~ cn 'a ~,",~ .a m ~ N.
O ~ ~ n a o o tn a~ J G
o o ~ ~ ~ O
- G H n n (D
iD G
rr fi N.
O
m O
rn Examples XXX LXXXV and Comparative E~tneriments R -A7 Weather resistance of various plastics ~~mpositions.
A series of plastics compositions was prepared using the process described above. In this process the composition of the plastics composition was varied. Di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin"' 770), oligomer of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid (Tinuvir.~' l0 622), bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin''-' ~.23) , oligomer of cyanic acid and N,N-di(2,2,6,6-tetramethyl-4-piperidyl) hexamethylene diamine (ChimassorbU 944), 1,3,5-triazine-2,4,6-triamine, N,N~~ -[1,2-ethane-diylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-iperidinl~1) amino] -1, 3, 5-triazine-2-yll iminol -3, 1-propanediyll]-bis[N~,N~ -dibutyl-N~,N~ -bis(1,2,2,6,6-pentamethyl-4-piperidinyl) (Chimassorb~ 119) and oligomer of 7-oxa-3,20-diazadispiro [5.1.11.21-heneicosan-21-one,2,2,4,4-tetramethyl-20-(oxiranylmethyl)- (Hostavin N30) were chosen as the HAhS compounds. HMTA stearate, 7-dodecylideneamino-1,3,5-triazadamantane and PP-MA-7-amino-1,3,5-triazadamantane were chosen as the bridged amines.
PP (Stamylan9, type P83m18, batch VI DSM, the Netherlands) was chosen as the polymer. Films were produced from the plastics compositions using the process described above. The films were subjected to a weather-resistance test and the weather resistance was determined as described above. The results are summarized in Tables 8 - 20.
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rn arative ~'xperiments AK - ~.R~ Weather resistance of , various M astics compositions A series of plastics compositions was prepared using the process described above. In this process the composition of the plastics composition was varied using various non-HAZS stabilizers. 2-hydroxy-4-n-octoxy-benzophenone (ChimassorbT 81), 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chloro-benzotriazol (Tinuvin~ 327) and octadecyl-3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-propionate (Irganoxc 1076) were chosen as the non-HALS stabilizers. DABCO stearate and HMTA
stearate were chosen as the bridged amines having an N-bridgehead.
PP (Stamylanp, type P83m18, DSM, the Netherlands) was chosen as the polymer. Films were produced from the plastics compositions using the process descr'_bed above. The films were subjected to a weather-resistance test and the weather resistance was determined as described above. The results are summarized ir. Table 21.
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-- 1,1'-(1,2-ethanediyl)-bis-(3,3',5,5'-tetramethyl-piperazinone);
- e-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro(4,5)decane-2,4-dione;
- polymethylpropyl-3-oxy[4(2,2,6,6-tetramethyl)-piperidinyl)siloxane (Uvasil~ 299);
- 1,2,3,4-butanetetracarboxylic acid-1,2,3-tris(1,2,2,6,6-pentamethyl-4-piperidinyl)-4-tridecyl ester;
l0 - copolymer of a-methylstyrene-T3-(2,2,6,6-tetramethyl-4-piperidinyl)maleimide and N-stearylmaleirnide;
- 1,2,3,4-butanetetracarboxylic acid, polymer w,.~th beta, beta, beta',beta'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, 1,2,2,6,6-pentamethyl-4-piperidinyl ester (Mark LA63) - 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol,beta,beta,beta',beta'-tetramethyl-, polymer with 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinyl ester (MarkR LA68) - D-glucitol, 1,3:2,4-bis-O-(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-(oxiranylmethyl) (Hostavina N30) - propanedioic acid, [(4-methoxyphenyl)methylene] -bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester ( Sanduvor~ PR 31 ) - formamide, N,N'-1,6-hexanediylbis[N-(2,2,6,6-tetramethyl-4-piperidinyl (Uvinul~ 4050H).
- 1,3,5-triazine-2,4,6-triamine, N,N~~ -[1,2-ethanediylbis [[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-iperidinyl)amino]-1,3,5-triazine-2-yl]imino]-3,1-propanediyl]]-bis[N',N' -dibutyl-N~,N' -bis(1,2,2,6,6-pentamethyl-4-piperidinyl) (Chimassorby 119) - 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (2,2,6,6-tetramethyl-4-peridinyl) ester (Cyasorb~~~
UV-500) - 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (1,2,2,6,6-pentamethyl-4-peridinyl) ester (CyasorbR
UV-516) - N-2,2,6,6-tetramethyl-4-piperidinyl-N-amino-oxamide;
- 4-acryloyloxy-1,2,2,6,6-pentamethyl-4-piperidine;
- 1,5,8,12-tetrakis[2',4'-bis(1",2",2",6",6"-pentamethyl-4"-piperidinyl(butyl)amino)-1',3',5'-triazin-6'-yl]-1,5,8,12-tetrazadodecane.
HALS PB-41 (Clariant Huningue S.A.) Nylostab~ S-EED (Clariant Huningue S.A.) 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-pyrrolidin-2,5-dione Uvasorb« HA88 1,1'-(1,2-ethane-di-yl)-bis-(3,3',5,5'-tetra-methyl-piperazinone) (Good-rite° 3034) 1,1~,1~ -(1,3,5-triazine-2,4,6-triyltris ((cyclohexylimino)-2,1-ethanediyl)tris(3,3,5,5-tetramethylpiperazinone); (Good-rite' 3150) 1,1~,1~ -(1,3,5-triazine-2,4,6-triyltris((cyclohexylimino)-2,1-ethanediyl)tris(3,3,4,5,5-tetramethylpiperazinone) (Good-rite° 3159) Preferably use is made of di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate, (also known under the tradename of TinuvinR 770), oligomer of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid (Tinuvin° 622); bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin° 123);
bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate - g _ (Tinuvin'"~ 765); N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexane-1,6-diamine (Chimassorb'"-~ TS);
poly((6-morpholine-S-triazine-2,4-diyl)(2,2,6,6-tetramethyl-4-piperidinyl)-iminohexamethylene-(2,2,6,6-tetramethyl-4-piperidinyl)-imino) (Cyasorb°' UV 3346);
5-(2,2,6,6-tetramethyl-4-piperidinyl)-2-cyclo-undecyi-oxazoi) (HostavinG N20);
polymethylpropyl-3-oxy-[4(2,2,6,6-tetramethyl)-piperidinyl)-siloxane (Uvasil~' 299), l0 - 1,2,3,4-butanetetracarboxylic acid, polymer ~~ri~h beta,beta,beta',beta'-tetrameth~.~l-2,4,8,10-tetraoxaspiro(5.5]undecane-3,9-diethanol, 1,2,2,6,6-pentamethyl-4-piperidinyl ester (Marl:"' LA63) - 2,4,8,10-tetraoxaspiro(5.5]undecane-3,9-diethanol,beta,beta,beta',beta'-tetramethyl-, polymer with 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinyl ester (Marks LA68) - D-glucitol, 1,3:2,4-bis-O-(2,2,6,6-tetramethi~l-4-piperidinylidene) (HALS 7) - oligomer of 7-oxa-3,20-diazadispiro(5.1.11.2]heneicosan-21-one,2,2,4,4-tetramethyl-20-(oxiranylmethyl) (Hostavin~' N30) - propanedioic acid, [(4-methoxyphenyl)methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester (Sanduvor° PR 31) - formamide, N,N'-1,6-hexanediylbis(N-(2,2,6,6-tetramethyl-4-piperidinyl (Uvinul° 4o50H).
- 1,3,5-triazine-2,4,6-triamine, N,N~~ -[1,2-ethanediylbis (((4,6-bis(butyl(1,2,2,6,6-pentamethyl-4-iperidinyl)amino]-1,3,5-triazine-2-yl] imino] -3 , 1-propanediyl] ] -bis [N' ,N" -dibutyl-N~ , N' -bis(1,2,2,6,6-pentamethyl-4-piperidinyl) (Chimassorb°
119 ) - 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (2,2,6,6-tetramethyl-4-peridinyl) ester (Cyasorb°
UV-500) - 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (1,2,2,6,6-pentamethyl-4-peridinyl) ester (Cyasorb~"' UV516) - mixtures of esters of 2,2,6,6-tetramethyl-4-piperidinol and fatty acids (Cyasorbv UV 3853);
HALS PB-41 (Clariant Huningue S.A.) Nylostab'J S-EED (Clariant Huningue S.A.) 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-pyrrolidine-2,5-dione Uvasorb~~ HA88 1,1'-(1,2-ethane-di-yl)-bis-(3,3',5,5'-tetra-methyl-piperazinone) (Good-rites' 3034) 1,1~,1~ -(1,3,5-triazine-2,4,6-triyltris ((cyclohexylimino)-2,1-ethanediyl)tris(3,3,5,5-tetramethylpiperazinone); (Good-rite' 3150) 1,1~,1~ -(1,3,5-triazine-2,4,6-triyltris((cyclohexylimino)-2,1-ethanediyl)tris(3,3,4,5,5-tetramethylpiperazinone) (Good-rites 3159).
The bridged amine compound having at least one N-bridgehead that can be used within the scope of this invention is preferably a compound derived from a compound having the general formula 1 or 2 (see formula sheet), where M1 to M4 are bridgeheads and each bridgehead is chosen independently of one another from carbon, nitrogen, silicon or phosphorus, with the 3o proviso that at least one bridgehead should always be a nitrogen atom and carbon and silicon may be substituted; an N-bridgehead is defined as a bridgehead which is a nitrogen atom; D1, Dm, Dn, Do, Dp and Dq here each stand for a chain having a length of 1 to 20 atoms, the number of atoms of which the chains are made up being equal to 1, m, n, o, p and q, each number of atoms and type of atom to be chosen independently of one another, and the chains being capable of having different lengths and being capable of being made up of different types of atoms. The c:-wins may also contain side groups, the number cf atoms in tre side groups not being included in the number of atoms of the chain.
Suitable choices for the atoms cf which the chairs are made up are carbon, nitrogen, cxygen, silicon and phosphorus. Preferably the chains are made up of 1 to 3 carbon atoms.
Preferably the bridged amine compound having at least one N-bridgehead is used with a HALS
compound in a ratio, relative to the amount of ziALS
compound, of between approximately 1:20 (m:m) and approximately 20:1 (m:m), more preferably in a ratio of between approximately 1:10 (m: m) and approximately 1C:1 (m: m), most preferably in a ratio of between approximately 1:5 (m: m) and approximately 5:1 (m: m).
Within the limits of the latter ratios the weather resistance is better than is expected on the basis of the amounts of the bridged amine compound having at least one N-bridgehead and the HALS compound present.
The amount of bridged amine compound having at least one N-bridgehead that can be used in the plastics composition may vary within a wide range, which can be easily determined by an average person skilled in the art. The range may vary depending on for example the type of polymer, the type of FiALS compound, the other additives in the additives package, the weather resistance to be realized or in general the type of plastics composition, its properties and its specific application.
It is for example possible for the bridged amine compound having at least one N-bridgehead to be S present in the plastics composition in an amount, relative to the amount of polymer in the plastics composition, of, preferably, between approximately 0.01% by weight and approximately 10.0% by weight, more preferably in an amount of between 0.05% by weight and l0 5% by weight, most preferably in an amount of between 0.1% by weight and 2.5% by weight.
Preferably the bridged amine compound having at least one N-bridgehead is chosen so that a plastics composition is obtained having a weather 15 resistance measured with the aid of the xenon test which is higher than approximately 500 hours, more preferably higher than approximately 750 hours, and most preferably higher than approximately 1000 hours.
Suitable choices for the bridged amine 20 compound having at least one N-bridgehead are:
- derivatives of 7-nitro-1,3,5-triazadamantane and 7-amino-1,3,5-triazadamantane, - derivatives of 7-amino-1,3,5-triazadamantane having the general structure II or III:
R
N~ ~N
N
(II) ~R
N- G
S 'R
I
,N'~ ~.N
i ~/ N', (III) where R and R' are independent substituents; examples of suitable substituents are hydrogen, ether, ester, amine, amide, alkyl, alkenyl) alkynyl, aralkyl, cycloalkyl and aryl groups, which substituents may in turn 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.
The substituent may moreover connect several of the I and/or II compounds to one another.
- derivatives obtained in a reaction of 7-amino-1,3,5-triazadamantane with compounds containing one or more functional groups. Examples of these functional groups are: aldehydes, acids, esters, amides, ketones, anhydrides and isocyanates.
- triazadamantane derivatives that are bound to a polymer (preferably a polyolefin) with the aid of an imide functionality;
- polymer-bound compounds obtained by the reaction of 7-amino-1,3,5-triazadamantane with a polymer (preferably a polyolefin) functionalized with malefic anhydride;
- hexamethylenetetramine (HMTA), diazabicyclo[2.2.2]octane (DABC01 or derivatives thereof. HMTA and DABCO are easy to obtain comme~:cially or are easy to prepare using generally known processes.
HMTA, for example, can easily be prepared from the cheap and easily obtainable basic raw materials ammonia and formaldehyde.
The bridged amine compound having at least one N-bridgehead is preferably used as a salt, more preferably as an ammonium salt. Preferably a carboxylic acid is chosen as the salt-forming agent. Examples of suitable carboxylic acids are aliphatic carboxylic acids, aliphatic dicarboxylic acids and aromatic carboxylic acids. Suitable choices are stearic acid, sebacic acid, cyclohexanedicarboxylic acid and benzenetricarboxylic acid. Preferably the bridged amine compound having at least one N-bridgehead is not used as a salt if the salt-forming agent contains a halogen or sulphur, for it is generally known that halogen-containing or sulphur-containing compounds can reduce the effect of the HALS stabilizer.
The bridged amine compound having at least one N-bridgehead is preferably substituted with at least one substituent having a molecular weight of preferably at least 50, more preferably at least 100.
Surprisingly, it has been found that, as a result of using the bridged amine compound having at least one N-bridgehead either in its salt form, or substituted with at least one substituent having a molecular weight greater than approximately 50, or in its salt form and substituted with at least one substituent having a molecular weight greater than approximately 50, a plastics composition is obtained which has still better weather resistance.
The plastics composition according to the invention preferably contains a thermoplastic polymer chosen from the group of 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. Also defined as propylene polymers within the scope of this invention are mixtures containing at least 50% by weight of one of the aforementioned propylene polymers with, for example, polyethylene or ethylene-propylene-dime 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);
- butylene polymers, such as poly(1-butylene).
Suitable choices of styrene polymers are, for example, polystyrene, high-impact-resistant polystyrene (HIPS), styrene-acrylonitrile copolymer (SAN), acrylonitrile-butadiene-styrene copolymer (ABS), styrene-malefic anhydride copolymer (SMA) and styrene-maleimide copolymer (SMI).
More preferably, the polymer is a propylene polymer or an AHS, still more preferably a propylene polymer.
The bridged amine compound having at least one N-bridgehead can be introduced into the plastics composition with the aid of one of the many standard methods known to a person skilled in the art at any desired time before making a plastic article, for example a moulded part, sheet, film, fibre, coating, foam, tape, latex or powder, from the plastics composition.
According to a first method, the bridged amine compound having at least one N-bridgehead is mixed, for example in the form of a powder, solution, emulsion or suspension, with the other components of the plastics composition which are in the form of, for example, a powder or a melt.
According to a second method, the bridged amine compound having at least one N-bridgehead is first mixed with at least one HALS compound and optionally with other additives in a so-called additives package, for example in the form of a powder, solution, emulsion or suspension, and said package is then added to the plastic, for example in the form of a powder or as a melt.
The plastics composition containing a polymer, at least one HALS compound and at least one bridged amine compound having at least one N-bridgehead may also contain other additives, for example antioxidants, thermal and UV stabilizers, metal deactivators, fillers, pigments, flame retardants, optical whiteners and similar additives which are used in plastics compositions.
The invention will be explained further by reference to the examples without being limited hereto.
Exa~les In the examples, the following general processes were followed.
Dreparar;on of the various bridq-ed amines DABCO stearate:
A solution of 28.45 grams (0.1 mol) of stearic acid in ethanol was added, drop by drop, at room temperature, with stirring, to a solution o~ 11.2 grams (0.1 mol) of DAHCO in ethancl. The mixture was evaporated with the aid of a Rotavap.
HMTA stearate:
A solution of 28.45 grams (0.1 mol) of stearic acid in ethanol was added, drop by drep, with stirring, to a solution of 14 grams (0.1 mol) c~ DABCO
in ethanol. The mixture was evaporated with the aid of a Rotavap.
DABCO sebacate:
A solution of 20.2 grams (0.1 mol) of sebacic acid in methanol was added, drop by drop, at room temperature, with stirring, to a solution of 22.4 grams (0.2 mol) of DABCO in methanol. The mixture was evaporated with the aid of a Rotavap.
DABCO benzene tricarboxylate:
A solution of 21 grams (0.1 mol) of benzene tricarboxylic acid in absolute ethanol was added, drop by drop, at room temperature, with stirring, to a solution of 33.6 grams (0.3 mol) of DABCO in absolute ethanol. The salt was precipitated from the solution.
The mixture was evaporated with the aid of a Rotavap and dried in a vacuum drying stove.
DABCO distearate:
A solution of 56.9 grams (0.2 mol) of stearic acid in ethanol was added, drop by drop, at room temperature, with stirring, to a solution of 11.2 grams (0.1 mol) of DABCO in ethanol. The mixture was evaporated with the aid of a Rotavap and dried in a vacuum drying stove.
7-Nitro-1,3,5-triazadamantane:
A mixture of 56.8 ml (1.0 mol) of nitromethane and 45 ml (1.2 mol) of formic acid was added, drop by drop, to a solution of 140.2 grams (1.0 mol) of hexamethylenetetramine in 500 ml of ethanol (80%), with constant stirring and refluxing. The mixture was refluxed for 4 hours and set aside for one night. The separated crystalline product was washed a few times with water and ethanol. After recrystallization in water, the product (white needles) was dried in the vacuum drying stove. (Literature:
Czechoslov. Chem. Commun Collection [vol. 40J, 1975, pp. 2179-82).
7-Amino-1,3,5-triazadamantane:
15.0 grams of 7-nitro-1,3,5-triazadamantane, 100 ml of methanol and 1.5 grams of wet Raney cobalt as a catalyst were introduced into a Parr autoclave (volume 160 ml) fitted with a stirrer and baffles. The hydrogenation was carried out for an hour at maximum speed, beneath hydrogen at 80 bar pressure and 80°C. After removal of the catalyst through filtration, the methanol was removed by means of the rotavapor. The crystalline product was dried in a vacuum drying stove.
7-Dodecylideneamino-1,3,5-triazadamantane:
8.4 grams of 7-amino-1,3,5-triazadamantane, 10.0 grams of dodecanal, 85 ml of methanol, 10 ml of toluene and 2.0 grams of wet Raney cobalt as a catalyst were introduced into a Parr autoclave (volume 160 ml) fitted with a stirrer and baffles. The reaction was carried out for an hour in a nitrogen atmosphere (2 bar) at maximum speed and 80°C. After removal of the catalyst through filtration, the filtrate was evaporated witr. the aid of a Rotavapc~ and dried in a vacuum drying stove.
PP-MA-7-amino-1,3,5-triazadamantane:
0.8 grams of 7-amino-1,3,5-triazadamantane in 75 ml of solvent was added, drop by drop, with constant stirring, at 160-165°C, to a solution of 10.0 grams of PP-MA (Hostaprime~HCS) (PP grafted with approximately 2.8% malefic anhydride) in 150 ml of inert solvent.
After cooling to approx. 90°C, the product was precipitated using 100 ml of acetone. The separated product was dried in a vacuum drying stove, after which it was compressed to form a plate at 210°C. The latter was cryogenically ground to a powder.
p~paration of a plastics composition A polymer powder (PP or ABS) 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. Then a solution of the bridged amine compound having at least one N-bridgehead was added to the plastics composition. This plastics composition was also dried in the same way as described above. Plastics compositions (blanks) in which the amount of HALS compound and/or bridged amine compound S having at least one N-bridgehead in the solution was zero were also prepared using this process.
production of PP f~lms and g~a s The PP composition was compressed to form a film using a Fontijne press (type TP200, 5 minutes pressureless preheating at 190°C, followed by the application of a pressure of 100 - 120 kNewton, followed by 10 minutes cooling at said pressure). The thickness was checked using a Heidenhain electronic meter. On average, thicknesses of 120 - 150 ~Zm were obtained for the films and 1 mm for the plates.
Production of ABS films and plates The ABS composition was compressed to form a film using a Fontijne press (type TP200, 5 minutes preheating at a pressure of 50 kNewton and 210°C, followed by the application of a pressure of 100-120 kNewton, followed by l0 minutes cooling at said pressure). The thickness was checked using a Heidenhain electronic meter. On average, thicknesses of 120 - 150 ~m were obtained for the films and 1 mm for the plates.
Production of PE films The PE compositions were produced by means of compounding at 160°C. Next, films with a thickness of 150 ~m were blown at the same temperature.
DerPrmination of the weather resistance The weather resistance of a plastics composition was determined in a weather-resistance test performed in an Atlas Material Testing Technology Weather-O meter (type Ci65) according to the method described in the preceding description. The degradation was measured with the aid of F'='-IR. The weather resistance is then expressed as the amount of time (the number of hours) for which a plastics composition is l0 subjected to said combinatio~: of light, tempera:.ure and humidity and at which the difference between the measured carbonyl absorptions is less than 0.10 before and after ageing in the case of the films and less than 0.5 in the case of the plates.
In some cases the change in colour as a result of ageing was characterized with the aid of a calorimeter according to ASTM standard 1925.
In the examples, the following abbreviations and tradenames were used:
PE: polyethylene PP: polypropylene ABS: acrylonitrile-butadiene-styrene copolymer Tinuvin 770: di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate Tinuvin~622: oligomer of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid Tinuviri 123: bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate Chimassorb~ 944: oligomer of cyanic acid and N,N
di(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylene diamine Chimassorb~ 119: 1,3,5-triazine-2,4,6-triamine, N,N~~ -[1,2-ethane-diylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-iperidinyl)amino]-1,3,5-triazine-2-yl] imino) -3 , 1-propanediyl] ] -bis (N~ , 2d~ -dibutyl-N~ , N~ -bis(1,2,2,6,6-pentamethyl-4-piperidinyl) Hostavin9 N30: oligomer of 7-oxa-3,20-diazadispiro 15.1.11.2]-heneicosan-21-one,2,2,4,4-tetramethyl-20-(oxiranylmethyl) DABCO: diazabicyclol2.2.2]octane HMTA: hexamethylenetetramine DABCO stearate: monosalt of stearic acid and DABCO
DABCO distearate: salt of DABCO containing two stearic acid molecules DABCO sebacate: salt of sebacic acid (diacid) containing two DABCO molecules DABCO benzenetricarboxylate: salt of benzenetricarboxylic acid containing three DABCO
molecules HMTA stearate: monosalt of stearic acid and DABCO
Atade: 7-amino-1,3,5-triazadamantane Dodecylidene-atade: 7-dodecylideneamino-1,3,5-triazadamantane.
PP-MA-atade: MA-grafted polypropylene modified with atade, synthesized according to the above specification.
Examples I-II and Comparative Experiments A-D: Weather resistance of various plastics compositions A series of plastics compositions was prepared using the process described above. In this process, the composition of the plastics composition was varied. Di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate (tradename: Tinuvin 770, Ciba-Geigy, Basel) was chosen as the HALS compound.
PP (Stamylanm, type P83m18, DSM, the Netherlands) was chosen as the polymer. Films were produced from the plastics compositions using the process described above. The films were subjected to a weather-resistance test and the weather resistance was determined as described above. The results are summarized in Table 1.
a~
U
.,-i cn u1 u1 tn o 0 V1 ~-I I~ t~ t~ tI1 o I~
w r~, o ~ o v rt a~
p I v N
p b t~ ~ rd ?-~rd p ~ b ~ ~ ~r v b ~ it p a~ ~ y v ~ cn ~ ~n O N
O ~ O x U t~
a~ a x a b 3 3 3 3 O' b ~
N ~
p aw aw ow ow m o m o w O
2s .- 3 3 3 U ~ O ~ i i i ~7 ow ow ow p ~ rl rl r-1 U o o O
N
H H H H H H
W W L1 ~ G1~ G3~
v r~ C4 ~ W C4 W W
O
3 p, v ri '~' ~(,'(.T~U A H H
,La W H
H
Examt~les III VII and Comparative Experiments E and F:
Weather resistance of Mastics comn~~itions having various concentrations of HALS compound and bridged amine compound Example I was repeated, the concentrations of the HALS stabilizer chosen and the bridged amine compound having at least one N-bridgehead being varied.
The results are summarized in Table 2. From this it can be concluded that a plastics composition containing amounts of 0.1% by weight to 0.5% by weight of a bridged amine compound exhibits improved weather resistance, which increases as more bridged amine compound is used. It was thus possible to more than double the weather resistance (Example F versus ViI).
H
t-~ CrJ C C5' c c H H x H H 'T1 C
H Q N
..
ro a ro ro ro ro ro ro ro Q G r~
ro ro ro ro ro ro ro H H H H H H H (D
(D
H H H H H H H ~"~ ~fj a.
ri O O O O O O O
n n N N N F~ I-' N H' W O 1-~-I d o\ d ~ d a\ d N.
d O 'C7 'C 'G "G "G "G ~ ~ ~ ~ lD
'G tL
rt G
- a a.
rr c~ rr rr rT rr 7 rr n ~~
O
I G
j O O O ~ ~ ~ ~ O f1~
N V-' ~ N 1-~ ~ 1-'-d U1 d O O
tr' d tr' t~' tT G ~D G n "G 'G tr'~C '~G ~ Q.
~G ~n n n C ~c3 O O O O N-O O
-- ~
~n cn ~n m N-U~ O
c-t (-t c-r rr w fD (D rr fD (D G rr tv W (D tv N p O
rt f-S W n ft , G
iv H ~ s~ I--' rr ~t W rr c"r m (D fD n fD (D (D
fD W G' ~ C
~.
O G
G
fD
z w n m n o f.,_ G
rr . cn w ~n n n x o c~
o n ~ n 0o N o o J .~ a, G (D a fD
N W N W 00 ~7 O ~'t UI
0 0 0 0 0 0 0 0111-' H
N
rr W
W rr n o m rn Examples IX-XII : Trleather rebsistance of Mastics compositions containing various bridged amine compounds having at least one N-bridgehead Example I was repeated using a plastics composition containing 0.2% of a HATS (Tinuvir.~ 770), the type of bridged amine compound having at least one N-bridgehead being varied. The results are summarized in Table 3.
H
x x H
H H x x ~ rn n ~ ro ro ro ro 0 o c~
ro G
ro ro ro ro H H H H fD
H H H H
H H H H
n _ n r- m N N N N W O
do prodo pro O 'L7 ~-' fD
E G
V . (D
rt rr rr rt o w i U7 M
ro w ca m m o t7 t~ co z n d d ~ o ~
m n n o n ~ '~ r-r, O
O r, C7 O O w ~ Q.
fn cn rr O n ~ 'b N- O cT lD N- G 1-~-G' O
a, n m tr' o ~ A.
n~ ~ ~ ~ a. Cl. tY
1~- nt ~i n (D
m a' w w i p., O
rt p fT t'r ~
m x cn m w o n rt rt ~ ~ O
c~
w f.,.
W
C
w w rr n m O
v G' ~-i G
O
N G ni N J U1 ~D ~"~fD
O O O O '-'h'-O
W
,7 O
(y M
fD
n !~-.
l~
(D
WO 98/36023 PCTlNL98/00088 Example XIII and Comparative Experiment G: Weather ~PSistance of PE films Example I was repeated using two plastics compositions, both composed of PE (LDPE, type 2304 AN00, DSM, the Netherlands) and 0.05% by weight of HALS
compound (Tinuvin~ 770), with 0 and 0.06% by weight, respectively, of DABCO added thereto. The plastics compositions were processed tc form blown films 150 Ecm thick. The films were exposed to light in a Suntester.
The weather-resistance treatment was performed in a borosilicate glass vessel according to a method described in Po~ytn Deq_ & Stab., 39, 225-233 (i993).
The weather resistance was determined as described above; however, in this case, a change in the carbonyl absorption of 0.05 units was employed as deterr,:ir.ing the weather resistance. The weather resistance of the film without DABCO (Comparative Experiment G) was 2700 hours and the degradation increased considerably from 2400 hours onwards; the weather resistance of the film containing DP.BCO was more than 3500 hours and the degradation showed a constant profile at 0.03 units.
Example XIV and Comparative Experiments H and I:
WPatheY resistance of ABS films Example I was repeated using three plastics compositions composed of ABS (Ronfaliri , type 356**, DSM, the Netherlands), ABS and 0.5% by weight of HALS
compound (Tinuvin~ 770) and ABS, 0.5% by weight of HALS
compound and 0.5% by weight of DABCO stearate, respectively. The degradation was measured as a colour change using a colorimeter and the weather resistance was determined according to ASTM standard 1925 as the amount of time (the number of hours) for which a plastics composition is subjected to said weather-resistance test and at which the measured colour change is less than 5 units. The results are summarized in Table 4.
I
x x H H x c ro c~
H H H f'S ~-j ~i O O
n tn tn N O fT
d d O ~
c o r G ~
..-I
o ~~ ~ ~ rd d ~ w ~ o cr .C i ~ rr n m w b m r-rr O
G
m O N
G ~"T
n ?
U1 fD
n fi N fD
H J J N
wn o N-N
rr G
n m Examples XV XVII and Comrarat-ive Experiment. J:
Weather resistance of ABS films A series of plastics compositions was prepared using the process described above. In this process the composition of the plastics composition was varied. Di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate (tradename: TinuvinD 770, Ciba-Geigy, Basel) was chosen as the HALS compound. ABS (Ronfalin~, type 356**, DSM, the Netherlands) was chosen as the polymer. Elates were to produced from the plastics compositions using the process described above. The degradation was measured as a change in colour using a colorimeter and the weather resistance was determined according to ASTM
standard 1925 as the amount of time (the number of hours) for which a plastics composition is subjected to said weather-resistance test and at which the measured change in colour is less than 5 units. The results are summarized in Table S.
WO 98/36023 PC'T/NL98/00088 H
w rr H C C ~-i >C (D
fD
w O
t!~ (l Wl1(O E"' lD
H H H H
H H H H
N
N.
fT
w O O O H G
cn v, u, o d d d d ~ ~ 'x O n7 ~ O
CJ' CJ' t~ L3' C O C r"h "G 'G 'G ': C C U~
rr G
-' C1 (-r rt r t'r b I
_ O 3 H c-r f"f m ~y ~ ~ ~ m f'T w U1 ~ ~ M O
~ rr w ~ m w ~ ~ O
cn n. ly ~ b N.
fD w ~~ ~ a. rr Ct C. C lLl (D fD ~ ~ ~ y i N
_ (D
V V V ~
H H O ~, w O O O ll1 C ~ f"r O O O ~ r't n '~
Examples XVIII - XXIII and Comparative E~cperiments K -Weather resistance of ~lasti~-s comz~ositions ~ontaininq various bridged amine compounds having at least one r1-bridgehead Examples III - VIII were repeated, the type o~ bridged amine compound having at least one N-bridgehead being varied. The results are summarized in Table 6.
x x H ~ ~r o z .~ r x x DC H
H
b ro ro b ro ~o ro ro ro w b o E
ro ro ro ro ro ro ro ro ro 0 a C C C C C C C C C n n w n ' C
( J
H..
0 0 0 ~ ~ o o b m 0 I o r ~
E.-~N N 0 0 ~ m d d d ~ N d ~ (~ rr o\ o\ d N d tr' ~ ~ '~ d ,~ ,~ ~ ro f'f ~ "',.J
E r~r r~r ~ E rT C
n rr rr rr rr rr ~ m i rr ~ m ' a ~
O
Cn rn rr w I
tr' 3 ~ rr 3 p rr J ~ n m cn \: ~- ~ ~ O ~"t N- ~ ~ hj p ~ ~
m ~ ~' cn n ~ w rr B
0 0 ~ ~ ~ ~' r-r ~ ~ ~ 0 0 _ ~u _ o a o w ~ ~ ~ ~ ~ O ~
fD ~ (D ~ F-~ (D fD (D ~ G ~ r~
r~-~a' ri r~-~~ W Q, ~ N
w v w w ~ 1-, ~ rt , n a. Q' ~T ~ ~,.~ rT ~ ~ o w rr fD fD (D N ~. .
~ ~
tn ~ i n O
fr d cD p) N.
'.~
fr.
~ W
C
'D N F-~ ~t J f'' W 01 J (,~,. N
fD
o op ~''~o m m J o O N W G
0 tn ui o G ~ rr r-S p~ m ~' N (~7 ~
fD rr (D
N
O
M
r3' ~i N.
Q.
W
fD
x x x H x x x H H H ' H H
ro ro ro ro ro o ro b ro ro H H H H
C C C C
O O O
O
o\ N N N W
e\ o\ \
O n b rr '~ G
rr rr ~T
n H
n cn 3 3 ~ N- ~ O
w n ~ n O ~ ~
CT
cn ~n a. ~ rt 3 N o b N.
rr rr iv N.
(D (D ~ ~ N O G C1 ~
w n~ w - ~ ~
~, r u w w n ~ ~"' ~' n p.
o N f-'-d~ (D
N N 1-~p 1-'' J W W W
T
W O O~ W ~- ~
OD ~P 01 j n (D
E~camples XXIV - XXIX~ Weath r resistance of Mastics compositions containina various bridaed amine compounds havina at least one t1-bridgehead Examples III - VIII were repeated, the concentration of 7-amino-1,3,5-triazadamantane being varied. The results are summarized in Table 7.
H
x x x r tr x c x ~ x ~ x '~
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rn Examples XXX LXXXV and Comparative E~tneriments R -A7 Weather resistance of various plastics ~~mpositions.
A series of plastics compositions was prepared using the process described above. In this process the composition of the plastics composition was varied. Di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin"' 770), oligomer of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid (Tinuvir.~' l0 622), bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin''-' ~.23) , oligomer of cyanic acid and N,N-di(2,2,6,6-tetramethyl-4-piperidyl) hexamethylene diamine (ChimassorbU 944), 1,3,5-triazine-2,4,6-triamine, N,N~~ -[1,2-ethane-diylbis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-iperidinl~1) amino] -1, 3, 5-triazine-2-yll iminol -3, 1-propanediyll]-bis[N~,N~ -dibutyl-N~,N~ -bis(1,2,2,6,6-pentamethyl-4-piperidinyl) (Chimassorb~ 119) and oligomer of 7-oxa-3,20-diazadispiro [5.1.11.21-heneicosan-21-one,2,2,4,4-tetramethyl-20-(oxiranylmethyl)- (Hostavin N30) were chosen as the HAhS compounds. HMTA stearate, 7-dodecylideneamino-1,3,5-triazadamantane and PP-MA-7-amino-1,3,5-triazadamantane were chosen as the bridged amines.
PP (Stamylan9, type P83m18, batch VI DSM, the Netherlands) was chosen as the polymer. Films were produced from the plastics compositions using the process described above. The films were subjected to a weather-resistance test and the weather resistance was determined as described above. The results are summarized in Tables 8 - 20.
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rn arative ~'xperiments AK - ~.R~ Weather resistance of , various M astics compositions A series of plastics compositions was prepared using the process described above. In this process the composition of the plastics composition was varied using various non-HAZS stabilizers. 2-hydroxy-4-n-octoxy-benzophenone (ChimassorbT 81), 2-(2'-hydroxy-3',5'-di-tert-butyl-phenyl)-5-chloro-benzotriazol (Tinuvin~ 327) and octadecyl-3-(3,5-di-tert-butyl-4-hydroxy-phenyl)-propionate (Irganoxc 1076) were chosen as the non-HALS stabilizers. DABCO stearate and HMTA
stearate were chosen as the bridged amines having an N-bridgehead.
PP (Stamylanp, type P83m18, DSM, the Netherlands) was chosen as the polymer. Films were produced from the plastics compositions using the process descr'_bed above. The films were subjected to a weather-resistance test and the weather resistance was determined as described above. The results are summarized ir. Table 21.
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Claims
1. Plastics composition containing a polymer and at least one hindered-amine light stabilizer (HALS), and a bridged amine compound having at least one N-bridgehead, characterized in that the bridged amine compound having at least one N-bridged amine compound is a salt.
2. Plastics composition according to Claim 1, wherein the ratio of the bridged amine compound having at least one N-bridgehead and the HALS lies between 1:5 (m:m) and 5:1 (m:m).
3. Plastics composition according to Claim 1 or Claim 2 in which the amine compound having at least one N-bridgehead is present in an amount, relative to the total amount of polymer in the plastics composition, of between 0.1 and 2.5% by weight.
4. Plastics composition according to any one of Claims 1-3, in which the HALS is:
- di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate, (also known under the tradename of Tinuvin R 770);
- oligomer of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid (Tinuvin R 622);
- bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin R 123);
bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (Tinuvin R 765);
- N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexane-1,6-diamine (Chimassorb R T5);
- poly((6-morpholine-S-triazine-2,4-diyl)(2,2,6,6-tetramethyl-4-piperidinyl)-iminohexamethylene-(2,2,6,6-tetramethyl-4-piperidinyl)-imino) (Cyasorb R UV 3346);
- 5-(2,2,6,6-tetramethyl-4-piperidinyl)-2-cyclo-undecyl-oxazol) (Hostavin R
N20) ;
- polymethylpropyl-3-oxy-[4(2,2,6,6-tetramethyl)-piperidinyl) siloxane (Uvasil R 299);
- 1,2,3,4-butanetetracarboxylic acid, polymer with beta,beta,beta',beta'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, 1,2,2,6,6-pentamethyl-4-piperidinyl ester (Mark LA63);
- 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol,beta,beta,beta',beta'-tetramethyl-, polymer with 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinyl ester (Mark LA68);
- D-glucitol, 1,3:2,4-bis-O-(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-(oxiranylmethyl)- (Hostavin N30);
- propanedioic acid, [(4-methoxyphenyl)methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester (Sanduvor PR 31);
- formamide, N,N'-1,6-hexanediylbis[N-(2,2,6,6-tetramethyl-4-piperidinyl (Uvinul 4050H) - 1,3,5-triazine-2,4,6-triamine, N,N'''-[1,2-ethanediylbis [[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-iperidinyl)amino]-1,3,5-triazine-2-yl] imino]-3,1-propanediyl]]-bis[N',N''-dibutyl-N',N''-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) (Chimassorb 119);
- 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (2,2,6,6-tetramethyl-4-peridinyl) ester (Cyasorb UV-500);
- 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (1,2,2,6,6-pentamethyl-4-peridinyl) ester (Cyasorb R UV516);
- mixtures of esters of 2,2,6,6-tetramethyl-4-piperidinol and fatty acids (Cyasorb R UV 3853);
- HALS PB-41 (Clariant Huningue S.A.);
- Nylostab S-EED (Clariant Huningue S.A.);
- 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-pyrrolidine-2,5-dione;
- Uvasorb HA88;
- 1,1'-(1,2-ethane-di-yl)-bis-(3,3',5,5'-tetra-methyl-piperazinone) (Good-rite R 3034);
- 1,1',1''-(1,3,5-triazine-2,4,6-triyltris ((cyclohexylimino)-2,1-ethanediyl)tris(3,3,5,5-tetramethylpiperazinone) (Good-rite R 3150); or - 1,1',1''-(1,3,5-triazine-2,4,6-triyltris((cyclohexylimino)-2,1-ethanediyl)tris(3,3,4,5,5-tetramethylpiperazinone) (Good-rite R 3159).
5. Plastics composition according to any one of Claims 2-4, characterized in that the weather resistance, measured in a xenon test, is higher than 500 hours.
6. Plastics composition according to any one of Claims 1-5, characterized in that the bridged amine compound having at least one N-bridgehead is hexamethylenetetramine, diazabicyclo[2.2.2]octane or a derivative of either compound.
7. Plastics composition according to any one of Claims 1-6, characterized in that the salt is an ammonium salt.
8. Plastics composition according to any one of Claims 1-6, characterized in that the salt is a carbonate.
9. Plastics composition according to any one of Claims 1-8, characterized in that the bridged amine compound having at least one N-bridgehead is substituted with at least one aliphatic or aromatic substituent having a molecular weight of at least 50.
10. Plastics composition according to any one of Claims 1-9, characterized in that the polymer is chosen from the group comprising propylene polymers and acrylonitrile-butadiene-styrene copolymer (ABS).
11. Use of a salt of a bridged amine compound having at least one N-bridgehead in combination with a hindered-amine light stabilizer as a stabilizer for a plastics composition having improved weather resistance.
12. Use of a salt of a bridged amine compound having at least one N-bridgehead according to Claim 11, characterized in that salt of the bridged amine compound having at least one N-bridgehead is hexamethylenetetramine, diazabicyclo[2.2.2]octane or a derivative of either compound.
14. Articles produced from the plastics composition according to any one of Claims 1-10.
15. Plastics composition having improved weather resistance as described and explained by reference to the examples.
2. Plastics composition according to Claim 1, wherein the ratio of the bridged amine compound having at least one N-bridgehead and the HALS lies between 1:5 (m:m) and 5:1 (m:m).
3. Plastics composition according to Claim 1 or Claim 2 in which the amine compound having at least one N-bridgehead is present in an amount, relative to the total amount of polymer in the plastics composition, of between 0.1 and 2.5% by weight.
4. Plastics composition according to any one of Claims 1-3, in which the HALS is:
- di-(2,2,6,6-tetramethyl-4-piperidyl) sebacate, (also known under the tradename of Tinuvin R 770);
- oligomer of N-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol and succinic acid (Tinuvin R 622);
- bis-(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin R 123);
bis-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (Tinuvin R 765);
- N,N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)-hexane-1,6-diamine (Chimassorb R T5);
- poly((6-morpholine-S-triazine-2,4-diyl)(2,2,6,6-tetramethyl-4-piperidinyl)-iminohexamethylene-(2,2,6,6-tetramethyl-4-piperidinyl)-imino) (Cyasorb R UV 3346);
- 5-(2,2,6,6-tetramethyl-4-piperidinyl)-2-cyclo-undecyl-oxazol) (Hostavin R
N20) ;
- polymethylpropyl-3-oxy-[4(2,2,6,6-tetramethyl)-piperidinyl) siloxane (Uvasil R 299);
- 1,2,3,4-butanetetracarboxylic acid, polymer with beta,beta,beta',beta'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol, 1,2,2,6,6-pentamethyl-4-piperidinyl ester (Mark LA63);
- 2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diethanol,beta,beta,beta',beta'-tetramethyl-, polymer with 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinyl ester (Mark LA68);
- D-glucitol, 1,3:2,4-bis-O-(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-(oxiranylmethyl)- (Hostavin N30);
- propanedioic acid, [(4-methoxyphenyl)methylene]-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester (Sanduvor PR 31);
- formamide, N,N'-1,6-hexanediylbis[N-(2,2,6,6-tetramethyl-4-piperidinyl (Uvinul 4050H) - 1,3,5-triazine-2,4,6-triamine, N,N'''-[1,2-ethanediylbis [[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-iperidinyl)amino]-1,3,5-triazine-2-yl] imino]-3,1-propanediyl]]-bis[N',N''-dibutyl-N',N''-bis(1,2,2,6,6-pentamethyl-4-piperidinyl) (Chimassorb 119);
- 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (2,2,6,6-tetramethyl-4-peridinyl) ester (Cyasorb UV-500);
- 1,5-dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (1,2,2,6,6-pentamethyl-4-peridinyl) ester (Cyasorb R UV516);
- mixtures of esters of 2,2,6,6-tetramethyl-4-piperidinol and fatty acids (Cyasorb R UV 3853);
- HALS PB-41 (Clariant Huningue S.A.);
- Nylostab S-EED (Clariant Huningue S.A.);
- 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)-pyrrolidine-2,5-dione;
- Uvasorb HA88;
- 1,1'-(1,2-ethane-di-yl)-bis-(3,3',5,5'-tetra-methyl-piperazinone) (Good-rite R 3034);
- 1,1',1''-(1,3,5-triazine-2,4,6-triyltris ((cyclohexylimino)-2,1-ethanediyl)tris(3,3,5,5-tetramethylpiperazinone) (Good-rite R 3150); or - 1,1',1''-(1,3,5-triazine-2,4,6-triyltris((cyclohexylimino)-2,1-ethanediyl)tris(3,3,4,5,5-tetramethylpiperazinone) (Good-rite R 3159).
5. Plastics composition according to any one of Claims 2-4, characterized in that the weather resistance, measured in a xenon test, is higher than 500 hours.
6. Plastics composition according to any one of Claims 1-5, characterized in that the bridged amine compound having at least one N-bridgehead is hexamethylenetetramine, diazabicyclo[2.2.2]octane or a derivative of either compound.
7. Plastics composition according to any one of Claims 1-6, characterized in that the salt is an ammonium salt.
8. Plastics composition according to any one of Claims 1-6, characterized in that the salt is a carbonate.
9. Plastics composition according to any one of Claims 1-8, characterized in that the bridged amine compound having at least one N-bridgehead is substituted with at least one aliphatic or aromatic substituent having a molecular weight of at least 50.
10. Plastics composition according to any one of Claims 1-9, characterized in that the polymer is chosen from the group comprising propylene polymers and acrylonitrile-butadiene-styrene copolymer (ABS).
11. Use of a salt of a bridged amine compound having at least one N-bridgehead in combination with a hindered-amine light stabilizer as a stabilizer for a plastics composition having improved weather resistance.
12. Use of a salt of a bridged amine compound having at least one N-bridgehead according to Claim 11, characterized in that salt of the bridged amine compound having at least one N-bridgehead is hexamethylenetetramine, diazabicyclo[2.2.2]octane or a derivative of either compound.
14. Articles produced from the plastics composition according to any one of Claims 1-10.
15. Plastics composition having improved weather resistance as described and explained by reference to the examples.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1005254A NL1005254C2 (en) | 1997-02-12 | 1997-02-12 | Plastic composition with improved weather resistance. |
| NL1005254 | 1997-02-12 | ||
| PCT/NL1998/000088 WO1998036023A1 (en) | 1997-02-12 | 1998-02-12 | Plastics composition having improved weather resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2280158A1 true CA2280158A1 (en) | 1998-08-20 |
Family
ID=19764404
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002280158A Abandoned CA2280158A1 (en) | 1997-02-12 | 1998-02-12 | Plastics composition having improved weather resistance |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0960160A1 (en) |
| JP (1) | JP2001511834A (en) |
| KR (1) | KR20000071031A (en) |
| CN (1) | CN1252081A (en) |
| AU (1) | AU6123198A (en) |
| BR (1) | BR9807679A (en) |
| CA (1) | CA2280158A1 (en) |
| IL (1) | IL131325A0 (en) |
| NL (1) | NL1005254C2 (en) |
| TR (1) | TR199901924T2 (en) |
| WO (1) | WO1998036023A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL1009844C2 (en) * | 1998-08-12 | 2000-02-15 | Dsm Nv | Plastic composition with improved weather resistance. |
| JP2001288360A (en) * | 2000-04-04 | 2001-10-16 | Unitika Ltd | Polyamide resin composition and method for producing the same |
| EP1571177A1 (en) * | 2004-03-03 | 2005-09-07 | DSM IP Assets B.V. | Elastomer with improved weather resistance |
| KR20070036069A (en) * | 2004-06-22 | 2007-04-02 | 인비스타 테크놀러지스 에스.에이.알.엘 | Solubilized additive composition comprising acidic and basic constituents |
| US7790077B2 (en) | 2006-09-15 | 2010-09-07 | The Coca-Cola Company | Pressurized tooling for injection molding and method of using |
| CN110028784B (en) * | 2018-01-12 | 2022-03-08 | 天津利安隆新材料股份有限公司 | Light stabilizer composition for nylon |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2545292C3 (en) * | 1975-10-09 | 1980-05-29 | Hoechst Ag, 6000 Frankfurt | Azaadamantane compounds as stabilizers for organic polymer compositions |
| DE2702205A1 (en) * | 1977-01-20 | 1978-07-27 | Hoechst Ag | N-SUBSTITUTED TRIAZAADAMANTANYL URNENTS AS STABILIZERS FOR THERMOPLASTICS |
| JPH0613539B2 (en) * | 1984-07-04 | 1994-02-23 | 旭電化工業株式会社 | Organic phosphite composition |
| IT1243719B (en) * | 1990-09-18 | 1994-06-21 | Enichem Sintesi | STABILIZING MIXTURE FOR PHOTOCROMATIC ACTIVITY COMPOUNDS |
-
1997
- 1997-02-12 NL NL1005254A patent/NL1005254C2/en not_active IP Right Cessation
-
1998
- 1998-02-12 BR BR9807679-5A patent/BR9807679A/en not_active Application Discontinuation
- 1998-02-12 KR KR1019997007298A patent/KR20000071031A/en not_active Application Discontinuation
- 1998-02-12 CA CA002280158A patent/CA2280158A1/en not_active Abandoned
- 1998-02-12 TR TR1999/01924T patent/TR199901924T2/en unknown
- 1998-02-12 WO PCT/NL1998/000088 patent/WO1998036023A1/en not_active Application Discontinuation
- 1998-02-12 CN CN98804096A patent/CN1252081A/en active Pending
- 1998-02-12 IL IL13132598A patent/IL131325A0/en unknown
- 1998-02-12 JP JP53561198A patent/JP2001511834A/en active Pending
- 1998-02-12 AU AU61231/98A patent/AU6123198A/en not_active Abandoned
- 1998-02-12 EP EP98905864A patent/EP0960160A1/en not_active Ceased
Also Published As
| Publication number | Publication date |
|---|---|
| KR20000071031A (en) | 2000-11-25 |
| WO1998036023A1 (en) | 1998-08-20 |
| IL131325A0 (en) | 2001-01-28 |
| TR199901924T2 (en) | 1999-12-21 |
| CN1252081A (en) | 2000-05-03 |
| BR9807679A (en) | 2000-02-15 |
| EP0960160A1 (en) | 1999-12-01 |
| NL1005254C2 (en) | 1998-08-13 |
| AU6123198A (en) | 1998-09-08 |
| JP2001511834A (en) | 2001-08-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |