Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
A-19795/AlCGM 438 21 3 7 8 7 0
Stabiliær for chlorine-containing polymers
The invention relates to a novel stabilizer combination for chlorine-cont~ -g polymers,
to a process for the stabilization of chlorine-cont~ining polymers, to the
chlorine-containing polymers obtainable in this way, and to the use of the stabilized
polymers.
Organotin compounds, such as organotin aL~coxides, carboxylates, mercaptides, oxides and
sulfides, have been proposed a number of times as stabilizers for clorine-c~ g
polymers.
Organotin oxides are principally employed in combination with other compounds.
US-A-3 196 129 and 3 919 165 disclose combinations with thiophosphates, acetals or
phenols. Combinations with organotin mercaptides are described, for example, in
DE-A-l 806 494.
The known stabiliærs and stabiliær mixtures cannot meet all the dem~n(ls made in the
polymers. Thus, the very widely used organotin maleates, as preferred organotin
carboxylates, cause a considerable tendency of the polymer melt to stick to the metal parts
of the processing machines, which must be compensated by increased addition of
lubricant. Other sulfur-free organotin compounds have a si~nifi~ntly worse
thermostabilizing action than the maleates. Organotin oxides also exhibit this
disadvantage, which becomes particularly noticeable during extrusion and injection
moulding at elevated le"ll)el~ul~,s. Sulfur-containing organotin compounds frequently
have an adverse effect on the light stability of the m~teri~l~, which hinders use in outside
applic~tion~
The object was therefore to find a stabiliær system which enables the pr~ccssillg of
chlorine-containing polymers at high tempe~a~ul~s and with high frictional stress. This
preferably relates to processes such as extrusion and injection moulding of cl~lorin~te~
PVC.
Surprisingly, a stabilizer combination comprising an organotin oxide compound and a
compound from the series consisting of crystalline alkali/~lk~line earth metal
alumosilicates meets the requirements to a large extent. In addition to good thermal
stability, high heat distortion resistance and light stability are also achieved.
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The invention therefore relates to a stabiliær composition compri~ing
a) at least one organotin oxide compound of the formula
(RaSnOb)c (I),
where R is Cl-Cl8aLkyl; a is the number 1 or 2; b = (4-a)/2; and c is greater than or equal
to l; and
b) at least one compound from the series consisting of crystalline aL~ali/~lk~line earth
metal alumo~ilic~tes
Components a) and b) can also be in the form of mixtures.
The novel stabilizer compositions may comprise further components. However, the novel
stabilizer compositions preferably contain no further organotin compounds.
Suitable aL~yl substituents having up to 18 carbon atoms are radicals such as methyl,
ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hex~ecyl and
octadecyl, and corresponding branched isomers.
The chlorine-cont~ining polymers can be those listed below: polymers of vinyl chloride,
vinyl resins cont~ining vinyl chloride units in the* structure, such as copolymers of vinyl
chloride and vinyl esters of aliphatic acids, in particular vinyl acetate, copolymers of vinyl
chloride with esters of acrylic and methacrylic acid and with acrylonitrile, copolymers of
vinyl chloride with diene compounds and unsaturated dicarboxylic acids or anhydrides
thereof, such as copolymers of vinyl chloride with diethyl m~ te, diethyl fumarate or
maleic anhydride, post-chlorinated polymers and copolymers of vinyl r~hlori~
copolymers of vinyl chloride and vinylidene çhloridt' with unsa~ ,d aldehydes, kçtonçs
and others, such as acrolein, crotonaldehyde, vinyl methyl ketone, vinyl methyl ether,
vinyl isobutyl ether and similar, polymers of vinylidene chloride and copolymers thereof
with vinyl chlonde and other polymerizable compou~lds; polymers of vinyl chloro~ cet~tes
and dichlorodivinyl ether; chlorinated polymers of vinyl acetate, chlrlrin~t~l polymeric
esters of acrylic acid and alpha-substituted acrylic acid; polymers of çhl~nn~t~l slyl~,nes,
for example dichlorostyrene; chlorinated rubbers; çhlorin~te~ polymers of ethylene;
polymers and post-chlorin~tecl polymers of chlorobutadiene and copolymers thereof with
vinyl chlonde, rubber hydrochloride and chlorinated rubber hydrochloride; and mixtures
of said polymers with one another or with other polymerizable compounds.
Also suitable are graft polymers of PVC with EVA, ABS and MBS. Plerelled substrates
are also mixtures of the abovementioned homopolymers and copolymers, in particular
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vinyl chloride homopolymers, with other therrnoplastic and/or elastomeric polymers, in
particular blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM
and polylactones.
Also ~lcre,led are suspension, bulk and emulsion polymers.
Particularly prerell~,d chlorine-containing polymers are post-chlorinated polyvinyl
ch1Ori~1e, polyvinyl chloride and also polymers of vinylidene çhloricle and copolymers
thereof with vinyl chloride and other polymerizable compounds.
Preference is given to stabiliær compositions as described above wherein a) is acompound of formula (RaSnOb)c (I), where R is C4-Cl2aLcyl; a is the number l or 2;
b = (4-a)/2, and c is greater than or equal to l. R is particularly preferably C4- or C8alkyl.
Preference is also given to mixtures of compounds of the formulae R2SnO (II) and(RSnO)20 (III), where R is Cl-Cl8alkyl, preferably C4-Cl2alkyl. In the plefell~,d mixtures
of compounds of the forrnulae (II) and (III), the proportion of the compound of the
formula (III) in the mixture does not exceed 50 % by weight.
Expedient stabiliær compositions are those as described above wherein b) is at least one
compound from the series consisting of crystalline aLkali/~lk~linç earth metal
alumoçi1icates, where Li, Na and K may be mentioned as aLkali metals and Mg, Ca, Sr and
Ba may be mentioned as alkaline earth metals.
The term aLcali/~1k~1inç earth metal alumosilic~tes covers both aLkali metal alumoçi1i~tçs
and ~1k~1inç earth metal alumo~ilic~tes and also alumosi1i~t~os cont~ining aLkali metals
and ~lk~line earth metals. The alkali/~lk~linç earth metal alumo~ tçs can be of natural
or synthetic origin.
Component b) is preferably a compound from the series con.,i~,ling of the zeolites. 7~o1ite~
can be described by the general formula (X)
MX~n[(Alo2)x(sio2)y]-wH2o (X)
in which n is the charge on the cation M;
M is an element from the first or second main group, such as Li, Na, K, Mg, Ca, Sr or Ba;
y:x is a number between 0.8 and 15, preferably 0.8 and 1.2; and
w is a number between 0 and 300, preferably between 0.5 and lO.
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Furthermore, zeolites which can be used according to the invention are ~ close~l in "Atlas
of Zeolite Structure Types", W.M. Meier and D.H. Olson, Butterworths, 3rd F(lition,
1992.
The preferred zeolites, known per se, of the NaA type which have a mean effective pore
diameter of 4 A, and are thus also known as æolite 4A, can be prepared by known
methods.
Suitable synthetic methods are described, inter alia, in DE-A 2 412 837. Further details on
the properties and preparation of these sodium alumosilicates are given, for example, in
the following references: DE-A 2 651 485, DE-A 2 651 445, DE-A 2 651 436,
DE-A 2 651 419, DE-A 2 651 420, DE-A 2 651 437 and US Patent 3 112 176.
It is also possible to use, according to the invention, finely divided water-insoluble sodium
alumo~ilic~tes which have been precipitated in the presence of water-soluble, inorganic or
organic dispersants and crystallized. Suitable water-soluble organic dispersants are
surfactants, non-surfactant aromatic sulfonic acids and compounds having a complexing
capacity for calcium. Said dispersants can be introduced into the reaction mixture in any
desired manner before or during the precipitation; they can, for example, be introduced as
a solution before the precipitation or dissolved in the ~lnmin~te and/or silicate solution.
The amount of dispersant should be at least 0.05 per cent by weight, preferably 0.1-5 per
cent by weight, based on the entire precipitation batch. For cryst~lli7~tion, the precipi~al~d
product is heated at from 50 to 200C for 1/2 to 24 hours. From the large number of
dis~el~allls which can be used, examples which may be mention~A are sodium lauryl ether
sulfate, sodium polyacrylate and the sodium salts of 1-hyd~o~yelllane-1,1-diphosphonic
acid.
The alkali metaV~lk~line earth metal alumosilis~tes which are suitable according to the
invention cont~in, for example, from 13 to 25 per cent by weight of bound water; plcfell~,d
products are those whose water content is in the range from 18 to 25 per cent by weight.
Preference is given to stabilizer compositions as described above wherein b) is at least one
of the compounds of the formulae
Nal2AIl2sil248 27 H2O [zeolite A],
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Na6Al6Si6O24 2NaX 7,5 H20, X = OH, Cl, C104, l/2CO3 tso~l~lite]
Na6Al6Si30O72 24 H2O,
Na8Al8Si40Og6 24 H2O,
Nal6All6si24o8o 16 H2O,
Nal6All6si32o96 16 H2O,
Na56Als6Sil36O384 250 H2O, [æolite Y]
Na86Al86Sil06O384 264 H20 [zeolite Xl
or the æolites which can be formed by replacement of some or all of the Na atoms by Li,
K, Mg, Ca, Sr, Ba or Zn atoms, such as
(Na,K)l0All0Si22O64 20 H2O -
Ca4 5Na3[(AlO2)l2(SiO2)l2] 30 H2O
KgNa3[(Alo2)l2(sio2)l2] 27 H2O
The above zeolites can also have a lower water content or contain no water at all.
Components a) and b) are present in the stabilizer ~ s in a weight rado of, for
example, from 1:1 to 1:10.
The present invention rullhellnore relates to stabilized c.hlorin~-co~ ing polymer
composition~ comprising a chlorine-cont~ining polymer,
a) at least one compound of the formula (I) and
b) at least one compound from the series con~isting of crystalline alkali/~lk~linç earth
metal alumosilicates.
E!re~e~nce is given to stabiliæd chlorine-cont~ining polymer compositions comprising
a) from 0.1 to 4 parts by weight of a compound of the formula (I),
b) from 0.2 to 10 parts by weight of a compound from the series consistdng of crystalline
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aLkali/~lk~line earth metal alumosilir~t~s, and
100 parts by weight of chlorine-containing polymer.
The plc;rell~ d amount range for the compound of the formula a) in the polymer
composition is from 0.4 to 2 parts by weight, based on 100 parts by weight of
chlorine-containing polymer. The pl~efelled amount range for a ~ Lure of the colllpounds
of the formulae (II) and (III) in the polymer composition is from 0.4 to 1.5 parts by weight
of a compound of the formula (II) and from 0 to 0.2 part by weight of a compound of the
formula (III), in each case based on 100 parts by weight of chlorine-cont~ining polymer.
The ~lerell~d amount range for the compound from the series consisting of crystalline
aL~ali/~lk~line earth metal alumosilicates in the polymer composition is from 0.4 to 6 parts
by weight, based on 100 parts by weight of chlorine-containing polymer. The particularly
preferred range is from 0.8 to 4 parts by weight.
The preferred stabilizer composition thus comprises, for example, 25 parts of
(CBHl7)2SnO, 0.75 part of (C8Hl7SnO)2O and 75 parts of sodium zeolite type 4A.
Preference is also given to stabilizer and polymer compositions which, in addition to a
compound of the formula (I) and a compound from the series con~i~ting of crystalline
aL~cali/~lk~line earth metal alumosilicates, also comprises a perchlorate of a monovalent or
divalent metal, where the perchlorate compound can also be a n~ Lul~; of dirr~ le.1t
perchlorates.
If further stabilizers from the series consisting of the organic and inorganic zinc, c~lcillm,
barium, m~gnesium and lead compounds, for example fatty acid salts, are used, it is
possible to use, for example, from 0 to 10 parts by weight, based on the polymercomposition. From 0.05 to 5 parts by weight, preferably from 0.1 to 5 parts by weight, are
expedient.
The compositions according to the invention may also contain further stabilizing addidves
which are conventional for chlorine-containing thermoplastics. Thus, they contain, for
example, 0-3 parts, in particular 0-1.5 parts, especially 0-1 part, based on the polymer
composition, of one or more phosphites. Such phosphites can be used, for example, in an
amount of 0.01-3 parts, in particular 0.01-1.5 parts, for example 0.01-1 part, preferably
0.1-0.6 part, for example 0.2-0.5 part. Examples of such phosphites are, for example, those
of the formulae
~1~7~70
R1"O\ /
R2"O ~P and R1nO--P X P--OR2"
in which Rl, R2 and R3 are identical or dirrclcnt and are C6-Cl8alkyl, C6-Cl8alkenyl,
substituted or unsubstituted phenyl or C5-C7cycloalkyl.
C6-Cl8alkyl Rl, R2 and R3 are, for example, n-hexyl, n-octyl, n-nonyl, decyl, dodecyl,
tetradecyl, hexadecyl or octadecyl. Preference is given to alkyl groups having 8 to
18 carbon atoms.
Substituted phenyl Rl, R2 and R3 are, for example, tolyl, ethylphenyl, xylyl, cumyl,
cymyl, cresyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, ethoxyphenyl, butoxyphenyl,p-n-octylphenyl, p-n-nonylphenyl or p-n-dodecylphenyl.
Particularly suitable phosphites are trioctyl, tridecyl, tridodecyl, tritetradecyl, tristearyl,
trioleyl, triphenyl, tricresyl, tris-p-nonylphenyl and tricyclohexyl phosphites, and
particular ~lefGlGIlce is given to aryl dialkyl phosphites and alkyl diaryl phosphites, for
example phenyl didecyl, 2,4-di-tert-butylphenyl didodecyl and 2,6-di-tert-but~lphellyl
(1i~1O~3ecyl phosphites and dialkyl and diaryl pentaerythrityl diphosphites, such as distearyl
pentaerythrityl diphosphite.
Preferred organic phosphites are distearyl pent~ylhlilyl diphosphite, trisnonylphenyl
phosphite and phenyl didecyl phosphite.
The compositions according to the invention may furthermore contain further known
costabilizers, for example 0-2 parts, in particular 0-1.5 parts, based on the polymer
composition. They are then preferably present in an amount of 0.01-2 parts, in particular
0.05-1.5 parts, for example 0.1-1 part, especially 0.1-0.5 part. Examples of these
costabiliærs which may be mentioned are 1,3-diketones, epoxy compounds,
aminocrotonic esters, dehydracetic acid, 2,4-dihydroxybenzophtonone,
2,4-dihydroxy-4'-tert-butylbenzophenone, dihydropyridine derivatives and pyrrolederivatives.
Expedient compounds are 1,3-diketone of the formula (IV) or (IVa),
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o o
R a C--CHR--C - R
R b~ X
(IVa)
-- -- 2
where
Ra is alkyl having 1 to 22 carbon atoms, C5-Cl0hydroxyalkyl, alkenyl having 2 to 22
carbon atoms, phenyl, phenyl which is substituted by 1 to 3 groups in the series con~isting
of -OH, Cl-C4alkyl, Cl-C4alkoxy and halogen, or is phenyl-Cl-C4alkyl, a group of the
formula O ~, cycloaL~yl having S to 12 ring carbon atoms, or cycloalkyl
CH2--O
having S to 12 ring carbon atoms which is substituted by 1 to 3 Cl-C4alkyl groups,
Rc is alkyl having 1 to 22 carbon atoms, Cs-ClOhydroxyalkyl, aL~enyl having 2 to 22
carbon atoms, phenyl, phenyl which is substituted by 1 to 3 groups in the series con~isting
of -OH, Cl-C4alkyl, Cl-C4alkoxy and halogen, or is phenyl-Cl-C4aL~yl, a group of the
formula O ~, cycloalkyl having S to 12 ring carbon atoms, or cycloaLkyl
CH2--O
having S to 12 ring carbon atoms which is substituted by 1 to 3 Cl-C4alkyl groups,
Rb is -H, alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 12 carbon atoms, phenyl,
Cl-C4alkyl-substituted phenyl, phenyl-Cl-C4alkyl, or a group of the formula - ICI-Rd,
where Rd is -CH3, -C2Hs or phenyl, or in which
Ra and Rb together are a tetramethylene radical or a tetramethylene radical which is fused
to a benzene radical, or
Ra and Rc together are a trimethylene radical or a trimethylene radical which is sub~ t~d
by 1 to 3 Cl-C4alkyl groups, and X is aL~ylene having 1-4 carbon atoms.
Ra and Rc as aL~cyl having 1 to 22 carbon atoms may be, for example, methyl, ethyl,
propyl, n-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl,
tridecyl, octadecyl or eicosyl, and Rb as aLkyl having 1 to 18 carbon atoms may be, for
example, as de~med above, apart from eicosyl.
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Examples of C5-ClOhydroxyalkyl Ra and Rc are 5-hydroxypentyl, 6-hy~Lo~yelhyl and7-hydroxyheptyl.
Examples of Ra and Rc as alkenyl having 2 to 22 carbon atoms are vinyl, pl~enyl, allyl,
butenyl, methallyl, hexenyl, decenyl and heptadecenyl. Corresponding examples of Rb as
aLkenyl having 2 to 12 carbon atoms can be taken correspondingly from the above list.
The phenyl groups which are preferably substituted by one to three groups from the series
consisting of -OH, C1-C4alkyl, Cl-C4alkoxy and halogen, as mentioned for Ra and RC,
may be 4-hydroxyphenyl, 4-hydroxy-3,5-di-C1-C4alkylphenyl where C1-C4alkyl is, for
example, methyl or t-butyl, or methylphenyl, dimethylphenyl, ethylphenyl, n-butylphenyl,
tert-butylphenyl, methyl-tert-butylphenyl, di-tert-butylphenyl, methoxy, ethoxyphenyl or
monochlorophenyl .
C1-C4alkyl-substituted phenyl Rb is thus, for example, methylphenyl, ethylphenyl or
tert-butylphenyl .
Phenyl-Cl-C4alkyl Ra, Rb and Rc are, for example, benzyl or methylbenzyl.
Ra and Rc may also be cycloalkyl having S to 12 ring carbon atoms or cycloaLkyl having S
to 12 ring carbon atoms which is substituted by 1 to 3 C1-C4aL~cyl groups. Examples are
cyclopentyl, cyclohexyl, cycloheptyl, cyclobutyL cyclononyl, cyclodof~e~yl, etc., and
methylcyclohexyl,- dimethylcyclohexyl, trimethylcyclohexyl and tert-butylcyclohexyl.
Examples of 1,3--likPtones are: dehydracetic acid, dehydr~ionylacetic acid,
dehydrobenzoylacetic acid, cyclohexane-1,3-dione, dimedone,
2,2'-methylenebiscyclohexane-1,3-dione, 2-benzyleyclohexane-1,3-dione, acetyltetralone,
palmitoyltetralone, stearoyltetralone, benzoyltetralone, 2-acetylcyclohexanone,
2-benzoylcyclohexanone, 2-acetylcyclohexane-1,3-dione,
benzoyl-p-chlorobenzoylmethane, bis(4-methylbenzoyl)methane,
bis(2-hydroxybenzoyl)methane, benzoylacetone, tribenzoylmethane,
diacetylbenzoylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane,
lauroylbenzoylmethane, dibenzoylmethane, 4-methoxybenzoylbenzoylmethane,
bis(4-methoxybenzoyl)methane, bis(4-chlorobenzoyl)methane,
bis(3,4-methylenedioxybenzoyl)methane, benzoylacetyloctylmethane,
benzoylacetylphenylmethane, stearoyl-4-methoxybenzoylmethane,
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- 10-
bis(4-t-butylbenzoyl)methane, butanoylacetone, heptanoylacetone, distearoylmeth~n~,
acetylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, benzoylfol-l-ylmethane,
benzoylphenylacetylmethane, bis(cyclohexane-1,3-dionyl)methane and
dipivaloylmethane.
1,3-Diketo compounds which can be used as costabilizers are in particular those described
in DE-B 2 600 516 and EP-A 35 268, for exarnple those of the formula given in the claim
of DE-B 2 600 516. ~c;fe-l-,d 1,3-diketo compounds are benzoylstearoylmethane,
aLkyl(for example ethyl) 2-benzoylacetoacetates and triacylmethanes.
The epoxide compounds which can be used for the purposes of the invention can have an
aliphatic, aromatic, cycloaliphatic, araliphatic or heterocyclic structure; they contain
epoxide groups as side groups. The epoxide groups are preferably bonded to the rem~in-ler
of the molecule as glycidyl groups via ether or ester bonds, or they are N-glycidyl
derivatives of heterocyclic amines, amides or imides. Epoxide compounds of these types
are known in general terrns and are commercially available.
The epoxide compounds contain at least one epoxy radical, in particular of the formula A
--CH- (CH2)--C--CH (A)
R, R2 R3
which is bonded directly to carbon, oxygen, nitrogen or sulfur atoms, where Rl and R3 are
both hydrogen, R2 is hydrogen or methyl, and n is 0, or in which Rl and R3 together are
-CH2-CH2- or -CH2-CH2-CH2-, R2 is then hydrogen, and n is 0 or 1.
Examples which may be mentioned of epoxide compounds are:
I) Glycidyl and ,~-methylglycidyl esters obtainable by reacting a compound c- nt~ining at
least one carboxyl group in the molecule and epichlorohydrin or glycerol dichlorohydrin
or ~-methylepichlorohydrin. The reaction is preferably carried out in the presence of
bases.
The compounds containing at least one carboxyl group in the molecule can be aliphatic
carboxylic acids. Examples of these carboxylic acids are glutaric acid, adipic acid, pimelic
acid, suberic acid, azelaic acid, sebacic acid or dimerized or trimeriæd linoleic acid,
213787~
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acrylic acid, methacrylic acid, caproic acid, caprylic acid, lauric acid, myristic acid,
palmitic acid, stearic acid and pelargonic acid.
However, it is also possible to employ cycloaliphatic carboxylic acids, for example
cyclohexanecarboxylic acid, tetrahydrophthalic acid, 4-methyltetrahydrophthalic acid,
hexahydrophthalic acid or 4-methylhexahydrophthalic acid.
It is also possible to use aromatic carboxylic acids, for example benzoic acid, phthalic
acid, isophthalic acid, trimellitic acid or pyromellitic acid.
It is likewise possible to use carboxyl-terminated adducts, for example of trimellitic acid
and polyols, for example glycerol or 2,2-bis(4-hydroxycyclohexyl)propane.
Other epoxide compounds which can be used for the purposes of the present invention are
given in EP 0 506 617.
II) Glycidyl or ,~-methylglycidyl ethers obtainable by reacting a compound cont~ining at
least one free alcoholic hydroxyl group andJor phenolic hydroxyl group and a suitably
substituted epichlorohydrin under alkaline conditions, or in the presence of an acid
catalyst followed by aL~cali treatment.
Ethers of this type are derived, for example, from acyclic ~lcohol~, such as ethylene
glycol, diethylene glycol and higher poly(oxyethylene) glycols, pr~alle-1,2-diol or
poly(oxypropylene) glycols, propane-1,3-diol, butane-1,4-diol, poly(o~y~ll~nethylene)
glycols, pentane-1,5-diol, hexane-1,6-diol, hexane-2,4,6-triol, glycerol,
1,1,1-trimethylolpropane, bistrimethylolpropane, pentaely~ ol, sorbitol, and from
polyepichlorohydrins, butanol, amyl alcohol, pentanol and from monofnn~tion~l ~lcohol~
such as isooctanol, 2-ethylhexanol, isodecanol and C7-C9aL~anol and Cg-Cllalkanol
mixtures.
However, they are also derived, for example, from cycloaliphatic ~lcohols, such as 1,3- or
1,4-dihydroxycyclohexane, bis(4-hydroxycyclohexyl)methane,
2,2-bis(4-hydroxycyclohexyl)propane or 1,1-bis(hydroxymethyl)cyclohex-3-ene, or they
contain aromatic rings, such as N,N-bis(2-hydroxyethyl)aniline or
p,p '-bis(2-hydroxyethylamino)diphenylmethane.
The epoxide compounds can also be derived from monocyclic phenols, for example from
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phenol, resorcinol or hydroquinone; or they are based on polycyclic phenols, for example
on bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)~ pane,
2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 4,4'-dihyd~ ydiphenyl sulfone or oncondensation products of phenols with formaldehyde obtained under acid con~ on~, such
as phenol novolaks.
Examples of other possible terminal epoxides are: glycidyl l-naphthyl ether, glycidyl
2-phenylphenyl ether, 2-biphenyl glycidyl ether, N-(2,3-epo~y~r~yl)phth~limi(le and
2,3-epoxypropyl 4-methoxyphenyl ether.
III) N-Glycidyl compounds obtainable by dehydrochlorinating the products of the reaction
of epichlorohydrin with amines, which contain at least one amino hydrogen atom. These
amines are, for example, aniline, N-methylaniline, toluidine, n-butylamine,
bis(4-aminophenyl)methane, m-xylylene~ mine or bis(4-methylaminophenyl)methane,
but also N,N,O-triglycidyl-m-aminophenol or N,N,O-triglycidyl-p-aminophenol.
However, the N-glycidyl compounds also include N,N'-di-, N,N',N"-tri- and
N,N',N",N"'-tetraglycidyl derivatives of cycloalkyleneureas, such as ethyleneurea or
1,3-propyleneurea, and N,N'-diglycidyl derivatives of hydantoins, such as of
5,5-dimethylhydantoin or glycol uril and triglycidyl isocyanurate.
IV) S-Glycidyl compounds, for example di-S-glycidyl derivatives derived from llithir~
for example ethane-1,2-dithiol or bis(4-mercaplolllethylphenyl) ether.
V) Epoxide compounds containing a radical of the formula A in which Rl and R3 together
are -CH2-CH2-, and n is 0, are bis(2,3-epoxycyclopentyl) ether, 2,3-epoxycyclopentyl
glycidyl ether or 1,2-bis(2,3-epoxycyclopentoxy)ethane. An example of an epoxy resin
containing a radical of the formula A in which Rl and R3 together are -CH2-CH2- and n is
1 is (3,4'-epoxy-6'-methylcyclohexyl)methyl 3,4-epoxy-6-methylcyclohex~nec~rboxylate.
Other epoxy compounds which can be used, such as epoxidized soybean oil, are described,
for example, in "Plastics Additives", editors H. Gachter and H. Muller, Hanser Verlag,
3rd edition, 1990, pages 303/4, and US 3 928 267.
Suitable aminocrotonic esters are, in particular, the esters with monohydric, straight-chain
C8-C20-, in particular Cl2-Cl8alcohols, and/or with 1,3- or 1,4-butanediols and/or
1,2-dipropylene glycol and/or thiodiethylene glycol.
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- 13 -
Pyrrole costabilizers which may be mentioned in particular are those described in
EP-A 22 087 and GB-A 2 078 761, for example of the formula I given therein, preferably
the pyrrole derivatives defined in Claims 2-9 of EP-A 22 087. An example which may be
mentioned is 2-methyl-3-cyclohexyloxycarbonyl-4-phenyl-lH-pyrrole.
Other stabilizers which may be used in the compositions according to the invention are
polyols. The amounts to be used are, for example, up to 3 parts by weight, expediently up
to 2 parts by weight and preferably from 0.01 to 1 part by weight, based on 100 parts by
weight of polymer composition. Typical examples of polyols are pentaerythritol,
dipentaerythritol, trimethylolpropane, ditrimethylolpropane, tris(2-hydroxyethyl)
isocyanula~e (THEIC), the latter being preferred, sorbitol, m~nnitol and inositol.
The compositions according to the invention rr,ay furthermore contain conventional
antioxidants, pigments, light stabilizers and UV absorbers.
The present invention furthermore relates to a process for the stabili7~ion of
chlorine-cont~ining polymers. To this end, in general the stabilizer compositioncomprising components a) and b) and, if desired, further additives is incorporated into the
polymer, for which purpose equipment known per se, such as c~l~n-l~rs, mixers,
compounders and the like, can be used. Components a) and b) of the novel stabiliær
composition and optional additives can also be added individually or in the form of a
masterbatch to- the polymers to be stabilized. Plefcl~Gd colllpol e.lts a) and b), plef~
proportions and the other possible additives are evident from the above dcscliplions of the
novel stabilizer and polymer compositions.
The compositions stabilized in accordance with the present invention can be conlr~L~d
into the desired shape in a known manner. Such methods are, for example, c~ n-lerin~,
extrusion, injection moulding, sintering and extrusion blow moulding. The compositions
can also be converted into foams.
Preferred stabiliæd chlorine-containing polymer compositions are unpl~ti~i7e~ orplasticiær-free or essentially plasticizer-free compositions.
The present invention furthermore relates to the use of the stabilized polymer
compositions in particular, in the form of rigid formulations, for hollow articles (bottles),
packaging films (thermoforming films), blown films, tubes, foams, heavy profiles
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(window frames), light-wall profiles, building profiles, sidings, fittings and equipment
housings (computers and domestic appliances).
The above-described polymer compositions are preferably used as rigid profiles for
external applications and as rigid films.
The examples below illustrate the invention in greater detail. Parts and ~rcent~ges are all
by weight, unless stated otherwise.
Example 1: Various CPVC compositions are prepared by mixing the individual
components as shown in the table below (amounts in parts by weight).
Table 1:
Example: Comparison
Chlorinated PVC (CPVC) 100.0 100.0
Impact modifier (acrylate) 8.5 8.5
Polymethyl methacrylate 1.5 l.S
Partially oxidized PE wax 1.3 1.3
ChaLk 2.0 2.0
Tit~nillm dioxide 4.0 4.0
Di-n-butyltin oxide 0.8 0.8
Zeolite A (Wessalith P) --- 4.0
In each case, 57 g of the CPVC composition are subjected to therm~l and mction~l stress
at 190C and 35 rpm in the compounding chamber of a Brabender pl~tocorder. At
5 minute intervals, samples (about 5 g) are taken from the pl~tic~tGcl CPVC co~ )osilion
and subsequently pressed at 180C for l.S minutes to give test specimen~. The colour
dirÇelel ce value (~ E) of the test specimens is determined colorimetrically in accordance
with DIN 6174 (CIE-LAB 1976). The results shown in Table 2 below illustrate the
si~nific~nt improvement in the stability for the sample according to the invention. A
higher colour difference value indicates greater discoloration.
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Table 2: ~E of the test specimens after heating at 190C
5 10 15 20 25 30 [min]
Comparison 27.3 35.8 43.5 51.0 Decomposition
Example 1 24.1 31.5 34.6 37.9 41.4 46.8
