CA2037676A1 - Stabilised chlorine-containing polymer compositions - Google Patents

Abstract

Stabilised chlorine-containing polymer compositions Abstract Chlorine-containing polymers are stabilised by addition of a stabiliser mixture comprising:

a) at least one sterically hindered amine, b) at least one organic or inorganic zinc compound, c) at least one organotin compound of the formulae A to D and d) at least one 1,3-dicarbonyl compound of the formula E.

Such polymer compositions can be employed, for example, for hollow articles and as packaging films.

Description

2~3~7~

Stabilised chlorine-containing polvmer comPositions The invention relates to stabilised chlorine-containing polymer compositions comprising a sterically hindered amine in combination with a zinc compound, an organotin carboxylate and a 1,3-dicarbonyl compound.

Heat-stabilised halogen-containing plastics compositions comprising 2,~,6,6-tetrasubstituted piperidines are known from JP-A-86/163 965. The Zn, alkali metal and alkaline earth metal salts of organic acids are mentioned as further stabilisers.

The stabilisation of rigid PVC using 2,2,6,6-tetraalkylpiperidines and organotincarbo~ylates is described in EP-A-237 485. These compositions comprise no zinc compounds.

Stabilised chlorine-containing plastics compositions comprising metal salts, including zinc salts, and cyclic 1,3-diketones of the general formula ~c~, in which R can be, for exarnple, alkyl, alkenyl, aryl, aralkyl, cycloalkyl and the like, are known from JP-A-84/86647. Epoxide compounds are used as costabilisers.

The known stabilisers and stabiliser mixtures cannot meet all the requirements imposed in the polymers, in particular in respect of the initial colour, colour retention and long-term stability.

It has now been found that the chlorine-containing polymer compositions stabilised according to the present invention have properties which have been improved further in rcspect of stability to heat and light.

' `:

.
. -. . , ,, --.

.

2 ~ 7 33 -According to the invention, this is achieved by a polymer composition comprising a chlorine-containing polymer and a stabiliser mixture comprising:

a) at least one sterically hindered amine, b) at least one organic or inorganic zinc compound, c) at least one organotin compound of the forrnulae A, B, C or/and D

(z)msn(ooc-zl)4-m A

(Z)mSn(OOC-CH=CH)COOZ~ )4 m B

OOC- CH
(Z)2Sn 11 c OOC- CH

Zl-COO-Sn--O--Sn-OOC-ZI D

in which m is 1, 2 or 3, Z is Cl-C20alkyl and Zl is hydrogen, Cl-C20alkyl, C3-C20alkenyl, C5-C8cycloalkyl, phenyl, C7-CI8alkylphenyl or C7-Cgphenylalkyl, and d) at least one 1,3-dicarbonyl compound of the formula E

o o Il 11 Rl--C--CHR2--C--R3 E

in which Rl is Cl-C22alkyl, Cs-CI0hydroxyalkyl, C2-CI8alkenyl, phenyl, phenyl which is substituted by OH, Cl-C4alkyl, Cl-C4alkoxy or halogen, C7-CI0phenylalkyl, C5-CI2cycloalkyl, Cs-C~2cycloalkyl which is substituted by Cl-C4alkyl, or a group -R5-S-R6 or -R5-O-E~6, R2 is hydrogen, Cl-C8alkyl, C2-CI2alkenyl, phenyl, C7-CI2alkylphenyl, C7-CI0phenylalkyl or a group -CO-R4, R3 has one of the meanings ' - - ' 2 ~ 7 ~3 defined for Rl or is Cl-CI8allcoxy, R4 is Cl-C4alkyl or phenyl, Rs is Cl-CIOalkylene and R6 is Cl-C~2alkyl, phenyl, C7-CI8alkylphenyl or C7-CIOphenylalkyl The chlorine-containing polymer can be, for example, a homo- or copolymer of vinyl chloride or of vinylidene chloride, or a post-chlorinated polymer or copolymer of vinyl chloride or of vinylidene chloride, a chlorinated polyolefin, for example a chlorinated polyethylene, a chlorinated polymer or copolymer of styrene or of butadiene or achlorillated rubber or a rubber hydrochloride, as well as a mixture of such a chlorine-containing polymer with another chlorine-containing or chlorine-free polymer.
The chlorine-containing polyme' is preferably a polyvinyl chloride or a copolymer comprising at least 80 % of vinyl chloride, or a mixture (polyblend) of such a polymer with other chlorine-containing or chlorine-free polymers. The polyvinyl chloride can be an emulsion, suspension or bulk polymer.

The sterically hindered amine is preferably a polyalkylpiperidine derivative, and preferably contains at least one group of the forrnula I

-N~<

in which R is hydrogen or methyl, and is, in particular, a derivative of 2,2,6,6-tetramethylpiperidine of the formula I, in which R is hydrogen. These compounds are preferably substituted by one or two polar groups or a spiro ring system in the ~I-position of the piperidine ring. These compounds can be low molecular weight or oligomeric or polymeric compounds.

The following classes of polyaLkylpiperidines are of importance in particular.

2 ~3 ~ iJ

a) Compounds of the formula II

RCH2~R
Rll-N~ 0----Rl2 II

RCH2 CH3 n in ~vllich n is a number from 1 to 4, preferably 1 or 2, R is llydrogen or methyl, Rl I is hydro~en, oxyl, hydroxyl, Cl-Cl2alkyl, C3-C8alkenyl, C3-C8alkynyl, C7-C~2aralkyl, Cl-CI8alkoxy, Cs-C8cycloalkoxy, C7-C9phenylalkoxy, Cl-C8alkanoyl, C3-Csalkenoyl,Cl-CI~alkanoyloxy, benzyloxy, glyeidyl or a group -CH2CH(OH)-Z, in which Z is hydrogen, methyl or phenyl, Rll preferably being H, Cl-C4alkyl, allyl, benzyl, acetyl or acryloyl, and Rl2, if n is 1, is hydrogen, Cl-Cl8alkyl, whieh may be interrupted by one or more oxygen atoms, cyanoethyl~ benzyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, araliphatie, unsaturated or aromatic carboxylic acid, carbamic acid or acid eontaining phosphorus, or a monovalent silyl radical, preferably a radical of an aliphatic earboxylie aeid having 2 to 18 C atoms, a eycloaliphatic carboxylic acid having 7 to 15 C
atoms, an o~"B-unsaturated carboxylic aeid having 3 to 5 C atoms or an aromatic carboxylie aeid having 7 to 15 C atoms, or, if n is 2, is Cl-C12alkylene, C4-CI2alkenylene, xylylene, a divalent radical of an aliphatie, eyeloaliphatie, araliphatie or aromatie dicarboxylic aeid, diearbamie aeid or aeid eontaining phosphorus, or a divalent silyl radieal, preferably a radieal of an aliphatie diearboxylie aeid having 2 to 36 C atoms, a eyeloaliphatic or aromatie diearboxylie aeid having 8-14 C atoms or an aliphatie, eyeloaliphatie or aromatie diearbamie aeid having 8-14 C atoms, or, if n is 3, is a trivalent radieal of an aliphatie, eyeloaliphatie or aromatie triearboxylie aeid, an aromatie triearbamie aeid or an aeid eontaining phosphorus, or a trivalent silyl radieal, or if n is 4, is a tetravalent radieal of an aliphatie, eyeloaliphatie or aromatie tetraearboxylie aeid.

Any Cl-Cl2aL~yl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undeeyl or n-dodecyl.

Cl-CI8Alkyl Rll or R12 can be, for example, the abovementioned groups, and in addition also, for example, n-tridecyl, n-tetradecyl, n-hexadeeyl or n-octadecyL

., , .

~3 ~r~ ''' C3-CsAlkenyl Rl1 can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, ~-hexenyl, 2-octenyl or 4-tert-butyl-2-butenyl.

C3-C8Alkynyl Rll is preferably propargyl.

C7-Cl2Aralkyl Rll is, in particular, phenethyl, and especially benzyl.

Cl-C8Alkanoyl Rll is, for example, formyl, propionyl, butyryl or octanoyl, but preferably acetyl, and C3-C5alkenoyl Rl I is, in particular, acryloyl.

A monovalent radical Rl I of a carboxylic acid is, for example, an acetic acid, caproic acid, stearic acid, acrytic acid, methacrylic acid, benzoic acid or ~-(3,~-di-tert-butyl-4-hydroxyphenyl)-propionic acid radical.

A divalent radical Rl2 of a dicarboxylic acid is, for example, a malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, sebacic acid, maleic acid, itaconic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)-malonic acid or bicycloheptenedicarboxylic acid radical.

.~ trivalent radical R12 of a tricarboxylic acid is, for example, a trimellitic acid, citric acid or nitrilotriacetic acid radical.

A tetravalent radical Rl2 Of a tetracarboxylic acid is, for example, the tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.

A divalent radical E~12 of a dicarbamic acid is, for example, a hexamethylenedicarbamic acid or a 2,4-toluylene-dicarbamic acid radical.

Preferred compounds of the formula II are those in which R is hydrogen, Rll is hydrogen or methyl, n is 2 and Rl2 is the diacyl radical of an aliphatic dicarboxylic acid having 4-12 C atoms.

Examples of polyalkylpiperidine compounds of this class are the following compounds:

1) 4-hydroxy-2,2,6,6-tetramethylpiperidine 2 ~ '~ r~l ~ rr~ ,~

2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine 3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine 4) 1-(4-tert-butyl-2-butenyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine S) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine 6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine 7) 4-methacryloyloxy-1,2,2,6,S-pentamethylpiperidine ~) 1,2,2,6,6-pentamethylpiperidin-4-yl-~-~3,5-di-tert-butyl-4-hydroxyphenyl)-propionate 9) di-(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) maleate 10) di-(2,2,6,6-tetramethylpiperidin-4-yl) succinate I l) di-(2,2,6,6-tetramethylpiperidin-4-yl) glutarate 12) di-(2,2,6,6-tetramethylpiperidin-4-yl) adipate 13) di-(2,2,6,6-tetramethylpiperidin-4-yl) sebacate 14) di-(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate IS) di-(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) sebacate 16) di-(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate 17) 1-hydroxy-4-~-cyanoethyloxy-2,2,6,6-tetramethylpiperidine t~) l-acetyl-2,2,6,6-tetramethylpiperidin-4-yl acetate 19) tri-(2,2,6,6-tetramethylpiperidin-4-yl) trimellitate 20) 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine 21) di-(2,2,6,6-tetramethylpiperidin-4-yl) diethylmalonate ~2) di-(1,2,2,6,6-pentamethylpiperidin-4-yl) dibutylmalonate 23) di-(1,2,2,6,6-pentamethylpiperidin-4-yl) butyl-(3,5-di-tert-butyl-4-hydroxybenzyl) malonate 24) di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate 2~) di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate 26) hexane- 1 ',6'-bis(4-carbamoyloxy- 1 -n-butyl-2,2,6,6-tetramethylpiperidine)27) toluene-2',4'-bis(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine) 28) tetra-t2,2,6,6-tetramethylpiperidin-4-yl) butanetetracarboxylate 29) tetra-(1,2,2,6,6-pentamethylpiperidin-4-yl) butanetetracarboxylate 30) tris(l-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite 31 ) tris( 1 -propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate 32) phenyl [bis-(1,2,2,6,6-pentamethylpiperidin-4-yl)] phosphonate 33) 4-hydroxy-1,2,2,6,6-pentamethylpiperidine 34) 4-hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine 3S) 4-hydroxy-N-(2-hydroxypropyl)-2,2,6,6-tetramethylpiperidine 36) 1-glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine ---` 2 ~ 3 1 ~ ~ 13 b) Compounds of the formiula III

RCH2,~,R
R~l-N )--N- --R14 III

RCH2 CH3 _ n in which n is the number 1 or 2, R and Rll are as defined under a), Rl3 is hydrogen, Cl-CI2alkyl, C2-Cshydroxyalkyl, C5-C7cycloalkyl, C7-C8aralkyl, C2-CI8alkanoyl, C3-C5alkenoyl, benzoyl or a jgroup of the forrnula ~. >~
R~-N ~--RCH2 cH3 and Rl4, if n is l, is hydrogen, Cl-Cl8alkyl, C3-C8alkenyl, Cs-C7cycloalkyl, Cl-C4alkyl which is substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group, glycidyl or a jgroup of the formula -CH2-CH(OH)-Z or of the formula -CONH-Z, in which Z is hydrogen, methyl or phenyl; or, if n is 2, is C2-CI2aLlcylene, C6-CI2arylene, xylylene, a -CH2-CH(OH)-CH2 jgroup or a group -CH2-CH(OH)-CH2-O-D-O-, in which D is C2-CIOalkylene, C6-CI5arylene or C6-CI2cycloalkylene, or, provided that Rl3 is not ~Ikanoyl, alkenoyl or benzoyl, Rl4 can also be a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or the group -CO-, or Rl3 and Rl4 together, if n is 1, can be the divalent radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

Any Cl-CI2 or Cl-CI8alkyl substituents are as already defined above under a).

Any C5-C7cycloalkyl substi~uents aro, in particular, cyclohexyl.

C7-C~Aralkyl R13 is, in particular, phenethyl or especially benzyl. C2-C5Hydroxyalkyl Rl3 is, in particular, 2-hydroxyethyl or 2-hydroxypropyl.

.

:. ~
. .
- ~ .

., . .. j . , .

C~-Cl~AL~anoyl R13 is, for example, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl or octadecanoyl, but preferably acetyl, and C3-Csalkenoyl Rl3 is, in particular, acryloyl.

C2-C~Alkenyl Rl4 is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or ~-octenyl.

Cl-C~Alkyl Rl4 substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group can be, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2-(dimethylaminocarbonyl)-ethyl.
Any C2-Cl2alkylene substituents are, for example, ethylene, propylene, dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

Any C6-CI5arylene substituents are, for example, o-, m- or p-phenylene, I ,4-naphthylene or 4,4'-diphenylene.

C6-Cl2Cycloalkylene D is, in particular, cyclohexylene.

Preferred compounds of the formula III are those in which n is 1 or 2, ~ is hydrogen, R
is hydrogen or methyl, Rl3 is hydrogen, Cl-Cl2alkyl or a group of the formula Rll-N~' and Rl4, if n = 1, is hydrogen or Cl-CI2alkyl or, if n = 2, is C2-C~alkylene.

Examples of polyalkylpiperidine compounds of this class are the following compounds:

37) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-hexamethylene-1,6-diamine 38) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-hexamethylene-1,6-diacetamide 39) bis(2,2,6,6-tetramethylpiperidin-4-yl)-amine '. . ' , - : .: . ., . ~ ~ ' ' ' .
' : ' _ 9 _ 40) 4-benzoylamino-2,2,6,6-tetramethylpiperidine 41) N,N'-bis~2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dibutyl-adipamide 42) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dicyclohexyl-2-hydroxypropylene-1,3-diamine 43) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylene-diamine 44) N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)succindiamide 45) di-(2,2,6,6-tetramethylpiperidin-4-yl) N-(2,2,6,6-tetramethylpiperidin-4-yl)-~-aminodipropionate 46) the compound of the formula ~ IC4H9 CH3-N ~ N--CH2--CH(OH~ CH2--O

'` CH3 CH3 ¢~

CH3 CH3 ~
~ I
CH3-N ~ N--CH2--CH(OH~ CH2--O
~ C4H9 47) 4-tbis-2-hydroxyethyl-arnino)-1,2,2,6,6-pentarnethylpipendine 48) 4-(3-methyl-4-hydroxy-5-tert-butyl-benzamido)-2,2,6,6-tetramethylpiperidine 49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine c) Compounds of the formula IV
RCH2~,R

Rl1--N~< ~ R15 IV
RCH2 CH3 n ~ :
in which n is the number 1 or 2, R and Rl1 are~ as defined under a) and RIS, if n is 1, is . ~ : . :~ . , :
- . ~ . : .
,;....

~ ~ ~y~ ~ v) l~ ~

- lo -C2-C8alkylene or -hydroxyalkylene or C4-C22acyloxyalkylene, or, if n is 2, is the group (-CH2)2C(CH2-)2-C2-CsAlkylene or -hydroxyaLtcylene Rl5 is, for example, ethylene, 1-methyl-ethylene, propylene, 2-ethyl-propylene or 2-ethyl-2-hydroxymethylpropylene.

C~-C22Acyloxyalkylene R15 is, for example, 2-ethyl-2-acetoxymethylpropylene.

Examples of polyalkylpiperidine compounds of this class are the following compounds:

S0) 9-aza-8,8,10,10-tetrarnethyl-1,5-dioxaspiro[5.5]undecane S1) 9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]undecane 52) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro[4.5]decane 53) 9-aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro[5.5]undecane ~4) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-l,S-dioxaspiro[S.S]-undecane 55) 2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3'-dioxane)-S'-spiro-5"-(1",3"-dioxane)-2"-spiro-4"'-(2"',2"',6"',6"'-tetrarnethylpiperidine).

d) Compounds of the forrnulae VA, VB and VC
R R16 ~

~n --R17 VA

RCH2 CH3 _ n RCH2 CH3 R Tl .k--f--T2 VB
N--C=O

R~l-N~ ¦ K17 VC

RCH2 CH3 n '.' ' ,.

2 ~ c~ t~ V

in ~vhich n is the number 1 or 2, R and Rll are as defined under a), Rl6 is hydrogen, Cl-CI2alkyl, allyl, benzyl, glycidyl or C2-C6allcoxyalkyl and Rl7, if n is 1, is hydrogen, Cl-CI2alkyl, C3-C5alkenyl, C7-Cgaralkyl, Cs-C7cycloalkyl, C2-C4hydroxyalkyl, C2-C6alkoxyalkyl, C6-CIOaryl, glycidyl or a group of the fonnula -(CH2)p-COO-Q or of the formula -(CH2)p-O-CO-Q, in which p is 1 or 2 and Q is Cl-C4alkyl or phenyl, or, if n is 2, is C2-CI2alkylene, C4-CI2aLkenylene, C6-C12arylene, a group -CH2-CH(OH)-CH2-O-D-O-CH2-CH(OH)-CH2-, in which D is C2-CIOalkylene, C6-CI5~rylene or C6-CI2cycloalkylene, or a group -C~l,C~l(OZ')CH2-(OCH2-cH(Oz')cH2)2-, in which Z' is hydrogen, Cl-Cl~alkyl, allyl, benzyl, C2-CI2alkanoyl or benzoyl, Tl and T2 independently of one another are hydrogen, Cl-Cl8alkyl, C6-CIOaryl which is unsubstituted or substituted by halogen or Cl-C~alkyl, or C7-Cgaralkyl~ or Tl and T2, together with the C atom joining them, fonn a Cs-Cl,cycloalkane ring.

Any Cl-CI2alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Ally Cl-CI~alkyl substituents can be, for example, the abovementioned groups, and in addition also, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Any C2-C6alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl,propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, t~rt-butoxyethyl, isopropoxyethyl or propoxypropyl.

C3-CsAlkenyl Rl7 is, for example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.

C7-CgAralkyl R17, Tl and T2 are, in particular, phenethyl or especially benzyl. A
cycloalkane ring formed by Tl and T2, together with the C atom, can be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.

C2-C4Hydroxyalkyl Rl7 is, for example~ 2-hydroxyethyl, 2-hydroxypropyl,'~-hydroxybutyl or 4-hydroxybutyl. -C6-CIOAryl Rl7, Tl and T2 are, in particular, phenyl or a- or ~-naphthyl, which are unsubstituted or substituted by halogen or C1-C4alkyl.

r~ ir~ r~

C2-CI2Alkylene Rl7 is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

C4-CI2Alkenylene Rl7 is, in particular, 2-butenylene, 2-pentenylene or 3-hexenylene.

C6-CI2Arylene Rl7 is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

C2-CI2Alkanoyl Z' is, for example, propionyl, butyryl, octanoyl or dodecanoyl, but pret`erably acetyh C2-CIOalkylene, C6-C15arylene or S~6-CI2cycloalkylene D is as defined under b).

Examples of polyalkylpiperidine compounds of this class are the following compounds:

56) 3-benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-Z,4-dione 57) 3-n-octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione 58) 3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro[4.5]decane-2,4-dione 59) 3-glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro[4.5]decane-2,4-dione 60) 1,3,7,7,8,9,9-heptamethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione 61) 2-iso-propyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5]decane 62) 2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro-[4.5]decane 63) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane 64) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxo-spiro-[4.5]decane 65) 8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione or the compounds of the following formulae:

2~ r~ ~J

2 1 ~r V~Z yV
~ ~V
~r U = O
V--~
o ~ ~, z 3 V Z V ~
3>~ ? V_Z
o ~VI
V Z
. o I

Q ~ 1l l=o ~ v=o z u=o (~ 1=
v>~<v ~ ~<3 u.>~<

v I ~ v I u . v v v u - -. . :, .

, . ... .

.. . .
,,~ .
. .
. . . .
.

r~J ~

e) Compounds of the forrnula VI

NJ~N
RlgJ~N~ n R20 VI

in which n is the number 1 or 2 and Rl8 is a group of the formula ~ `.
--E--(A).~ N--R I I
'` ~7< ' in which R and Rll is as defined under a), E is -O- or -NR2l-, A is C2-C6alkylene or -(CH2)3-O- and x is the number O or 1, Rlg is Rl8 or one of the groups -NR2,R22, -OR23, -NHCH20R23 or -N(CH20R23)2. R20. if n is 1, is Rlg or Rlg, or, if n is 2, is a group -E-B-E-, in which B is C2-C6alkylene which may be interrupted by -N(R21)-, R21 is Cl-Cl2alkyl, cyclohexyl, benzyl or Cl-C4hydroxyalkyl, or a group of the formula --~ N--R~1 R22 is Cl-Cl2alkyl, cyclohexyl, benzyl or Cl-C4hydroxyalkyl and R23 is hydrogen,Cl-CI2alkyl or phenyl, or R21 and R22 together are C4-Csalkylene or -oxaalkylene, for -CH2CH2~ -CH2CH2 example / ~ or a group of the formula jN--Rl I

or R21 and R22 in each case are a group of ~the~forrnula ' :

:
., \ /
~ C4Hg HN~ N ~ NH--A--N ~,N
CH3 CH3 `r CH3 ~< CH3 Any Cl-Cl2alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Any Cl-C4hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl F 4-hydroxybutyl.

C2-C6Alkylene A is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.

C4-C5Alkylene or -oxaalkylene forrned by R2, and R22 toge~her is, for example, tetramethylene, pentarnethylene or 3-oxapentarnethylene.

Preferred compounds of the formula VI are those in which n is 4, Rl8 and Rl9 are a group ~CH3 --N--~, N--RlI

in which Rll is hydrogen or methyl and R21 is hydrogen or Cl-C6alkyl, and R20 is the pentavalent radical of an aliphatic tetramine.

Examples of polyalkylpiperidine compounds of this class are the compounds of thefollowing formulae:

:

, .~- , i, . .
~.

y~

H3C yN ~ CH3 H3C ~CH3 70) N--C4H9 N~N
(CH3CH2)2N N N(CH2CH3)2 ~ ~C4H9)2 C,~CH3 71 ) C2H5 - N~ N ~N ~--N ~N - C2H5 . ~ .
R H~CH3 7~) N~N whereR=-NU-CU2CU2CU2-O~N--CU3 .: . ".:. ., , ~ , :, - : . : .
,: ..

rl ,~

u ~ u ~u u~--z: u u u Z~
` rz '7<

U U
O~ U U

~<a~

a~ z ~ a a Z=( U U
~ _z y .' ~ U U
3~ u a~u~
2~ U

:

:

~ ' " ' , . ' . . ' . ' .; . . . ,' .

',3 R . R
7 ,) R-NH-(CH2)3 - N - (cH2)2- N - (CH2)3-NH-R
C,~CH3 where R = ,N~N~NH
N;~ N
~ CH3 CH3 CH3 >[~ CH3 R R
76) R-NH-(CH2)3 -N- (cH2)2--N- (CH2)3-NH-R

~ 4 9 ~<
where R = --~ ~ N ~ N - CH3 N~, N 7~
~ CH3 CH3 CH3 ~ CH3 C~ H3 R R CH3 77) R - N -(CH2)3 - N - (cH2)2- N - (CH2)3- N - R

C4H9 C~<CH3 where R = "' `il N_< N-CH3 N,~ N 7( ~ CH3 CH3 C4Hg - N
CH3 ~ CH3 ' :
., . .: ., , :
. . . .' :.
- ~' '- ' ' ' ' ' : ~ ' .
.
.
. .
. .

~ CH3 C8H~7 N--< NH
N ~ N - CH3 CH3 78) C8H17 N N NH(CH2)3 _ CH3 ~ CH3 H
_ 2 CH3~_" N CH3 - CH3 ~CH3 N-C4Hg V N ~ N CH3 CH3 H~CH2CH2 - N ~ N ~ N ~ 1 ~ N - CH2CHr OH
~ C4Hg C4Hg ~

CH2- CH= CH2 H3C ~ N ~ CH3 H3C l J CH3 ~3C ~ N N ~ CH3~

H2C=HC-H2C - N ~ N N N ~ N - CH2-CH= cH2 ~ C4Hg C4Hg ~

f) Oligomeric or polymeric compounds, the recumng structural unit of which contains a polyalkylpiperidine radical of the forrnula (T), in particular polyesters, polyethers, polyamides, polyamines, polyurethanos, poiyureas, polyamlnotriazines, : ~ :
:~

:, - ~:: : , , . . ~ , : . , . ~
, , :. :

.. : . . . . . .
: . . . . .
:: . . . , :, ;. , . . ~ . .

~ ~ 3 ~

poly(meth)acrylates, poly(meth)acrylamides and copolymers thereof which contain such radicals. Amongst these, the polyesters and polyaminotriazines are prefcrred.

E~camples of 2,2,6,6-polyalkylpiperidine light stabilisers of this class are the compounds of the following formulae, in which p is a number from 2 to about 200.

~1) O O ~
C--CH2 -CH2--C - O CH2 -CH2--N~

~) ~CH2 -CH2 - N~ O--C--(CH2)4- C - {~N--CH2--CH2--O--C--(CH2)4--C

S3) ~ O O ~ O O
~NH -(CH2)3~ NH- C ~ CH;~ (CH2)3- NH--C ~ C

~) C, H3 C, H3 JJ--N (CH2)6 N 3p CH3 ~<CH3 CH3 >~CH3 `: , ' :

~5) [ N -- CH2-CH(OH) CH3 ~ CH3 86) O ~ N - CH2- CH= CH- CH2- N ~ O C4Hg O

~7) ,~ N ~ N - (CH2)6 C~3 CH3 CH3 ~ ~ CH3 b CH3 N CH3 CH3 N CH3 Sg) j O ~ N - CH2 ~ CH _ N ~ O - - ~CHz)j-89) O C2H5 0 )~\
C2H5 C ~ O -CH2-CH2-N ~ O

90) ,CH3 ¦ CH3 CH3 O = C
O ~ N - CH3`

` ~ ~ - : : : . `

: ., : , ,,, ' 2 ~ 3 i~ ~ rj) r~

9~) C~H3 E f CH2 ~
¦ CH3 CH3 O=C ,y C6H13--N _~ N--CH3 9~) ~0~

N~N
~N~ (CH2)6 N ]

CH3 ~ CH3 CH3 ~ ¦, CH3 CH3 N CH3 CH3 N~`CH3 H H

[ -N (CH2)6 ~ CH2-CH

CH3 ~ ~ CH3 CH3 ~ ~ CH3 H H
9~) O O
[ N--(CH2)6--N--C--CH2--C

CH3 ~ CH3 CH3 ~ CH3 H H

Of these classes, classes a), d), e) and f~ are particularly preferred, especially the compounds 10, 13, 14, 23, 24, 28, 29, 63, 65, 75, 77, 81, 84 and 92.

These sterically hindered amines are known compounds, and many of them are commercially obtainable. It is also possible to use two different sterically hindered amines, for example one of low and one of higher molecular weight, as is described in US-A-4 692486. ~ :

.
,, .
.
- : , , , : ~

.

J '7 3 The zinc compound used as component b) can be an organic zinc compound, for example the zinc salt of a carboxylic acid, sulfonic acid, phosphonic acid or phosphinic acid, or the zinc salt of a phenol or a zinc chelate, for example the enolate of a 1,3-diketo compound.
Component b) can also be an inorganic zinc compound, for example an oxide, hydroxide, carbonate, phosphate, phosphite, sulfate, chloride, fluoride7 tetrafluoborate orhypophosphite.

b) is preferably the zinc salt of a Cl-C22carboxylic acid, a C6-CI8phenol or a C~-Cr,6 1,3-diketone. The carboxylic acid can be a saturated or unsaturated aliphatic or cycloaliphatic carboxylic acid or an aromatic or aromatic-aliphatic carboxylic acid.

Examples of these acids are formic acid, acetic acid, propionic acid, butyric acid, caproic acid, 2-ethylhexanoic acid, caprylic acid, lauric acid, myristic acid, oenanthic acid, neodecanoic acid, palmitic acid, stearic acid, isostearic acid, 12-hydroxystearic acid, oleic acid, behenic acid, montanic acid, benzoic acid, chlorobenzoic acid, p-tert-butylbenzoic acid, p-dodecylbenzoic acid, salicylic acid, 3,4-di-tert-butyl-4-hydroxybenzoic acid, tolylic acid, dimethylbenzoic acid, p-dimethylaminobenzoic acid, thioglycolic acid, lactic acid, abietic acid, ~-mercaptopropionic acid, ~-dodecylmercaptopropionic acid, phenylacetic acid or the half-ester or the half-amide of a dicarboxylic acid. Zinc salts of long-chain a-aminocarboxylic acids or N-acylaminocarboxylic acids are also suitable for this purpose.

Examples of C6-CI8phenols are phenol, cresol, xylenol, 4-tert-butylphenol, 4-nonylphenol, 4-dodecylphenol, 4-chlorophenol or 2-hydroxydiphenyl.

E~amples of Cs-C26 1,3-diketones are acetylacetone, butanoylacetone, stearoylacetone, la~lroylacetone, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, benzoyl-6-hydroxyhexanoyl-methane, stearoyl-benzoylmethane or ~ ~-bis(4-methylbenzoyl)-methane.
b) is preferably the zinc salt of acetylacetone or of benzoyl-6-hydroxyhexanoyl-methane.

b) is preferably the zinc salt of a Cl-C20carboxylic acid. Mixtures of zinc compounds can also be used, for example the zinc salts of industrial carboxylic acid mixtures or industrial alkylphenol mixtures. The zinc carboxylate can also be a basic zinc carboxylate. Zinc :. . ,. ; - . . ~
` ' ' ' '' ' ~ . ~ ' r~

stearate, zinc-2-ethylhexanoate, zinc neodecanoate, zinc laurate and zinc oleate are particularly preferred.

Cl-C20Alkyl Z or Zl in the organotin compounds of component c) are straight-chain or branched alkyl groups Examples of these are: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-amyl, neopentyl, isoamyl, n-hexyl, isohexyl, heptyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and eicosyl.

C~-C,O~lkenyl Zl can be, for example, 2-propenyl, 3-propenyl, 2-butenyl, 1-hexenyl, I-octenyl, 1 I-undecenyl or oleyl. Cs-C8Cycloalkyl Zl is preferably cyclohexyl.
C7-CI8Alkylphenyl Zl is, for example, p-tolyl, 2,4-dimethylphenyl, 4-tert-butylphenyl, ~-isopropylphenyl, 4-hexylphenyl, 4-nonylphenyl or 4-dodecylphenyl. C7-CgPhenyl-alkyl Zl is preferably benzyl or 2-phenethyl.

Z is preferably Cl-Cl2alkyl, in particular methyl, butyl, octyl or dodecyl. Zl is preferably C~-CI~alkyl, oleyl or phenyl.

The index m is preferably ~.

Specific examples of the organotin compounds which can be employed according to the invention are:
dibutyltin dilaurate, dioctyltin dilaurate, dimethyltin bis(2-ethylhexanoate), dibutyltin di-isooctadecylate, butyltin trioctanoate, diphenyltin dilaurate, dibutyltin bis(isooctylmaleate), dibutyltin dipelargonate, dibutyltin distearate, dihexyltin dioleate, ciioctyltin tallate, dioctyltin diundecylenate, dibutyltin bis(neodecanoate), dioctyltin bis(neotridecanoate), dibutyltin maleate, dibutyltin bis(monomethylmaleate), dihexyltin bis(mnnohexylmaieate), dihexyltin bis(mono-isooctylmaleate), dibutyltin bis(monocetylmaleate), dibutyltin bis~monooctadecylmaleate), dibutyltin bis(mono-2-ethoxyethylmaleate), dioctyltin bis(monocyclohexylmaleate), dihexyltin bis(monobenzyl-maleate), butylhexyltin bis(mono-tert-butylbenzyl-maleate) and dioctyltin maleate.

Component c) is preferably a compound of the formula A, B or C, in particular a compound of the formula A or B, in which m is 2, especially a compound of the forrnula A in which m is ~, Z is butyl or octyl and Zl is C8-CI2alkyl.

J

The org~notin compounds of component c) are known compounds, and are known as stabilisers for chlorine-containing polymers. Some of them are commercially obtainable.
Component c) can also be a mixture of two or more organotin compounds of the formulae A-D. For example, there are commercial products of the formula A and B which aremixtures where m = 1 and m = 2. ~lixtu~es with different radicals Z are also known, these being formed when industrial carboxylic acid mixtures are used for the esteTification.

The 1,3-dicarbonyl compounds of the formula E which can be used as component d) can be 1,3-diketones or ~-ketocarboxylic acid esters. Rl and R3 in formula E can be Cl-C22alkyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, dodecyl, octadecyl or eicosyl. Alkyl Rl and R3 are preferably Cl-CIO,alkyl, in particular Cl-CIOalkyl.

C~-CIOHydroxyalkyl Rl and R3 are, in particular, a group -(CH2)n-OH, in which n is 5, 6 or7.

C2-CI~,Alkenyl Rl and R3 can be, for example, vinyl, allyl, methallyl, butenyl, hexenyl or oleyl, preferably allyl.

Phenyl Rl and R3 which is substituted by OH, alkyl, alkoxy or halogen can be, for example, tolyl, xylyl, tert-butylphenyl, methoxyphenyl, ethoxyphenyl, hydroxyphenyl, chlorophenyl or dichlorophenyl. Phenylalkyl Rl and R3 are, in particular, benzyl.
Cycloalkyl or alkyl-cycloalkyl Rl and R3 are, in particular, cyclohexyl or methylcyclohexyl.

Alkyl R2 can be, in particular, Cl-C4alkyl.
C .-CI2Alkenyl R2 can be, in particular, allyl. Alkylphenyl R2 is, in particular, tolyl.
Phenylalkyl R2 can be, in particular, benzyl. R2 is preferably hydrogen.
Alkoxy R3 can be, for example, methoxy, ethoxy, butoxy, hexyloxy, octyloxy, dodecyloxy, tridecyloxy, tetradecyloxy or octadecyloxy.
Cl-CIOAlkylene Rs is, in particular, C2-C4alkylene.
Alkyl R6 is, in particular, C4-C12alkyl, for example butyl, hexyl, octyl, decyl or dodecyl.
Alkylphenyl R6 can be, in particular, tolyl.
Phenylalkyl R6 is, in particular, benzyl.

Examples of 1,3-dicarbonyl compounds of the forrnula E are acetylacetone, but~noylacetone, heptanoylacetone, stearoylacetone, palmitoylacetone, lauroylacetone, 7-tert-nonylthio-heptane-2,4-dione, benzoylacetone, dibenzoylmethane, lauroylbenzoylmethane, palmitoyl-benzoylmethane, stearoyl-benzoylmethane, 6-hydroxyhexanoyl-benzoylmethane, tribenzoylmethane, bis(4-methylbenzoyl)methane.
benzoyl-p-chlorobenzoylmethane, bis(2-hydroxybenzoyl)methane, 4-methoxybenzoyl-benzoylmethane, bis(4-methoxybenzoyl)methane.
I-benzoyl-1-acetylnonane, benzoyl-acetyl-phenylmethane, stearoyl-4-methoxybenzoylmethane, bis(4-tert-butylbenzoyl)methane, benzoyl-formylmethane, benzoyl-phenylacetylmethane, bis(cyclohexanoyl)methane, di(pivaloyl)methane, methyl, ethyl, hexyl, octyl, dodecyl or octadecyl acetoacetate, ethyl, butyl, 2-ethylhexyl, dodecyl or octadecyl benzoylacetate and ethyl, propyl, butyl, hexyl or octyl stearoylacetate.

Preferred compounds of the formula E are those in which Rl is Cl-CIgalkyl, phenyl, phenyl which is substituted by OH, methyl or methoxy, C7-Cl~)phenylalkyl or cyclohexyl, R, is hydrogen and R3 has one of the meanings defined for Rl.

The compounds of the formula E are known compounds. Many of them are commercially obtainable.

The polymer compositions according to the invention preferably comprise, per 100 parts by weight of chlorine-containing polymer, 0.01 to 3 parts by weight of component a), 0.01 to 3 parts by weight of component b), 0.1 to 5 parts by weight of component c) and 0.01 to ~ parts by weight of component d). 100 parts by weight of the chlorine-containing polymer particularly preferably comprise 0.1 to 1 part by weight of component a), 0.5 to 2 parts by weight of component b), 1 to 4 parts by weight of component c) and 0.05 to 1 part by weight of component d).

The composition can moreover comprise further additives, such as are known and customary for processing and stabilising chlorine-containing polymers. These are, for example, plasticisers, phosphites, compounds of calcium, magnesium, sodium, barium, lead and cadmium, hydrotalcites, metal-free PVC stabilisers, impact strength modifiers, agents for improving the heat distortion point, epoxide compounds, antioxidants, UV
absorbers and light stabilisers, pigments, dyes, fillers, lubricants or flameproofing agents.

Examples of plasticisers are the esters of phthalic acid and adipic, azelaic, sebacic or .

~ ~ 3 ~ J~

trimellitic acid, polyesters of aliphatic diols and dicarboxylic acids, phosphoric acid esters, cllloroparaffins or epoxidised fatty acid esters. Further examples can be found in "Taschenbuch der Kunststoff-Additive (Handbook of Plastics Additives)", R. Gachter, H. ~luller, Hanser-Verlag 1983, pages 280-307. The plasticisers can be used in an amount of 1~ to 100 parts by weight per 100 parts by weight of the chlorine-containing polymer.

Organic phosphites are known costabilisers for chlorine-containing polymers stabilised with metal stabilisers, in particular in combination with stabilisers of the zinc, barium or ~admi~ l type~ Examples of such phosphites are trioctyl, tridecyl and tridodecylphosphite, decyl diphenyl phosphite, triphenyl phosphite, phenyl didecyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerytllritol diphosphite, 2,4-di-tert-butylphenyl di(dodecyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite,bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tristearylsorbitol triphosphite and 3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[S.S]undecane.

The compounds of Ca, Mg, Na, Ba, Cd and Pb can be organic compounds, for example the metal salts of carboxylic acids, sulfonic acids or phosphonic acids, of phenols or of 1,3-dicarbonyl compounds. They can also be inorganic compounds, for example the o~ides, hydroxides, carbonates, phosphates, phosphites or hypophosphites of these metals.
The metal carboxylates, for example the stearates, laurates or oleates of these metals, and the enolates of 1,3-dicarbonyl compounds of the metals calcium, magnesium, sodium and barium are preferred. The acetylacetonates of calcium, magnesium and barium are particularly preferred.

~nother important class of metal compounds which have a stabilising action in PV(~ are the hydrotalcites. These can be naturally occurring, synthetic or semi-synthetic (modified) hydrotalcites. These are a particular type of basic magnesium aluminium carbonates, which can also contain further cations.

~letal-free stabilisers for chlorine-consaining polymers are, for example, aliphatic polyols, such as pentaerythritol, dipentaerythritol, trimethylolpropane, tris(2-hydroxyethyl) isocyanurate, sorbitol or mannitol; aminocrotonic acid esters; dehydroacetic acid;
2,4-dihydroxybenzophenone; enol carbonates, such as are described in EP-A-224 438;
aromatic amides, such as are described in EP-A-122 228 and 174 412; and nitrogen-containing heterocyclic compounds, such as are descnbed in EP-A-2007, 22087, .

~ ~3 22749, 41479, 65934, 260 226 and 354 179, DE-A-3 048 659 and 3 124 853, GB-A-2 170 203 and US-A-4 908 398.

Other examples of metal-containing or metal-free stabilisers can be found in the"Taschenbuch der Kunststoff-Additive (Handbook of Plastics Additives)", R. Gachter, H. Muller, Hanser-Verlag 1983, pages 227-232.

Impact strength modifiers are, for example, polyacrylates, ethylene-vinylacetatecopolymers or chlorinated polyethylene. Agents for improving the heat resistance are, for e~ample, poly(meth)acrylates, acrylate-maleimide copolymers or acrylonitrile-methylstyrene copolymers.

Epoxide compounds are also known stabilisers for chlorine-containing polymers. If they have a suitable structure, they can also act as plasticisers at the same time. Examples of epoxide stabilisers are epoxidised polybutadiene, epoxidised soya oil, epoxidised linseed oil, epoxidised fish oil, epoxidised tallow, methylbutyl or 2-ethylhexyl epoxystearate, tris(epoxypropyl) isocyanurate, epoxidised castor oil, epoxidised sunflower oil, epoxidised butyloleate, 3-(2-phenoxy)-1,2-epoxypropane, bisphenol A diglycidyl e~her, vinylcyclohexene diepoxide, dicyclopentadiene diepoxide or 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.

Examples of antioxidants are:
1~ Alkvlated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-~ert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol~ 2,6-di-tert-butyl-4-i-butylphenol, 2,6-di-cyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tri-cyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol and 2,6-dl-nonyl-4-methylphenoh 2~ Alkvlated hvdroquinones, for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amyl-hydroquinone and 2,6-diphenyl-4-octadecyloxyphenoh 3~ Hvdroxylated diphenvl thioethers, for example 2,2'-thio-bis(6-tert-butyl-4-methylphenol), 2,2'-thio-bis(4-octylphenol), 4,1'-thio-bis(6-tert-butyl-3-methylphenol) and 4,4'-thio-bis(6-tert-butyl-2-methylphenol)~

: .

..
, .

4. Alkylidene bisphenols, for example 2~2umethylene-bis(6-tert-butyl-4-methylphenol)~
2,2'-methylene-bis(6-tert-butyl-4-ethylphenol), 2,2'-methylene-bis[4-methyl-6-(a-methylcyclohexyl)-phenol], 2,2'-methylene-bis(4-methyl-6-cyclohexylphenol), 2,2'-methylene-bis(6-nonyl-4-methylphenol), 2,2'-methylene-bis(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 2,2'-ethylidene-bis(6-tert-butyl-4-isobutylphenol), 2,2'-methylene-bis[6-(ol-methylbenzyl)-4-nonylphenol], 2,2'-methylene-bis[6-(c~,(x-dimethylbenzyl)-4-nonylphenol], 4,4'-methylene-bis(2,6-di-tert-butylphenol), ~,4'-methylene-bis(6-tert-butyl-2-methylphenol), I, I -bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane, ~,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylpheno 1, I, I ,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane, 1,1-bis(S-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylme rcaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)-butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene and bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-buty 1-4-methyl-phenyl]
terephthalate.

5. Benzvl compounds, for example I ,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzyl-mercaptoacetate, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol-terephthalate, 1,3,S-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,S-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate, the Ca salt of 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonic acid monoethyl ester and 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl) isocyanurate.

6. Acylaminophenols, for example 4-hydroxy-lauroylanilide, 4-hydroxy-stearoylanilide, 2,4-bis(octylmercapto)-6-(3,S-di-tert-butyl-4-hydroxyanilino)-s-triazine and octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.

. .
.

2 ~

7. Esters of ,B-(3~5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with mono- orpolyhydric alcohols, for example with methanol, octadecanol, 1,6-hexanediol, neopentylglycol, diethylene thioglycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate or N,N'-bis(hydroxyethyl)-oxalic acid diamide.

~ Esters of ~-(S-tert-butvl-4-hvdroxy-3-methylphenvl)-propionic acid with mono- or polyhydric alcohols, for exarnple with methanol, octadecanol~ 1,6-hexanediol.
neor)entylglycol, diethylene thioglycol, diethylene glycol, triethylene glycol, pent.lerythritol, tris(hydroxy)ethyl isocyanurate or N,N'-bis(hydroxyethyl)-oxalic acid dialllide.

9~ Esters of ~-(3.5-dicvclohexvl-4-hvdroxvphenvl)-propionic acid with mono- or polyhydric alcohols, for example with methanol, octadecanol, 1,6-hexanediol, neopentylglycol, diethylene thioglycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxy)ethyl isocyanurate or N,N'-bis(hydroxyethyl)-oxalic acid diamide.

I(). Amides of ~-(3.5-di-tert-butvl-4-hvdroxvphenvl)-propionic acid, for exampleN,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine and N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

Examples of UV absorbers and light stabilisers are:

E 2-(2'-Hvdroxvphenyl)-benzotriazoles, for example the S'-methyl, 3',5'-di-tert-butyl, S'-tert-butyl, 5'-(1,1,3,3-tetramethylbutyl), S-chloro-3',5'-di-tert-butyl, S-chloro-3'-tert-butyl-5'-methyl, 3'-sec-butyl-S'-tert-butyl, 4'-octoxy, 3',5'-di-tert-amyl and 3',5'-bis~a,a-dimethylbenzyl) derivative.

2. 2-Hvdroxvbenzophenones, for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivative.

3~ Esters of unsubstituted or substituted benzoic acids, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, - , ~ .
.
. ' .

,. ' ' ': ~ ' .

bis(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate.

4. Acrylates, for exarnple ethyl and isooctyl cc-cyano-,~,~-diphenylacrylate, methyl c~-carbomethoxycinnamate, methyl and butyl a-cyano-~-methyl-p-methoxycinnamate, methyl c~-carbomethoxy-p-methoxycinnamate and N-(~-carbomethoxy-,~-cyanovinyl)-2-methyl-indoline.

Nickel compounds, for example nickel complexes of `-thio-bis[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the 1:1 or 1:2 complex, if appropriate with additional ligands, such as N-butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyl-dithiocarbamate, nickel salts of ~-hydroxy-3,5-di-tert-butylbenzylphosphonate acid monoalkyl esters, such as of the methyl or ethyl ester, nickel complexes of ketoximes, such as of ~-hydroxy-4-methyl-phenyl-undecylketoxime and nickel complexes of l-phenyl-4-lauroyl-5-hydroxy-pyrazole, if appropriate with additional ligands.

fi. Oxalic acid diamides, for example 4,4'-di-octyloxy-oxanilide, '-di-octyloxy-5,5'-di-tert-butyl-oxanilide, ~,~'-di-dodecyloxy-5,5'-di-tert-butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, ~,N'-bist3-dimethylaminopropyl)-oxalamide, 2-ethoxy-S-tert-butyl-2'-ethyloxanilide and a mixture thereof with 2-ethoxy-~'-ethyl-5,4'-di-tert-butyl-oxanilide and mixtures of o- and p-methoxy- and of o- and p-ethoxy-disubstituted oxanilides.

The pigments used can be inorganic or organic pigments, and they can also be metallic pigments. Fillers are, for example, chalk, carbon black, graphite, talc, kaolin or silicatic minerals.

Lllbricants are, in particular, fatty acids and their salts, esters and amides, fatty alcohols, paraffins and polyethylene waxes. Flameproofing agents are, in particular, antimony oxide, aromatic bromine compounds and phosphoric acid esters.

A review of the use of impact strength modifiers, colouring agents, fillers, hlbricants and flameproofing agents in chlorine-containing polymers, specifically in PVC, is to be found in "Taschenbuch der Kunststoff-Additive (Handbook of Plastics Additives)", R. Gachter, H. Muller, Hanser-Verlag 1983.

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The compositions according to the invention can be prepared in a manner which is known per se. As a rule, the stabiliser system is incorporated into the polymer, for which a number of known devices, such as calenders, mixers, kneaders, extruders and the like, exist.

The compositions stabilised according to the present invention can be brought into the desired fonn in a known manner. Such processes are, for example, calendering, ex~rusion, inJectiotl moulding, sintering or spinning, and furthermore extmsion blow moulding or prncessing by the plastisol process.

The compositions according to the invention are particularly suitable in the form of rigid recipes for hollow articles (bottles), packaging films (thermoforming films), blown films, crashpad films (cars), pipes, heavy profiles (window frames), luminous wall profiles, construction profiles, sidings, fittings, office films and apparatus housings (computers, domestic appliances).

Other compositions in the form of flexible recipes are suitable for wire sheathings, cable insulations, decorative films, roofing films, agricultural films, hoses, sealing profiles, office films and films for air-inflated structures.

Examples of the use of the compositions according to the invention as plastisols are imitation leather, tloorings, textile coatings, wallpapers, coil coatings and undersealing for motor vehicles.

Examples of sintered PVC uses of the compositions according to the invention are slush, slush mould and coil coatings.

The following examples illustrate the invention in more detail. All the data in parts and percentages relate to the weight, unless stated otherwise.

Examples 1-15: Various PVC compositions are prepared by mixing the individual components according to the following Table I (numerical data are parts by weight).

The heating test is carried out by rolling the PVC composition at l80C on a mixing roll mill for S rninutes. Film samples from the approximately 0.3 mm thick rolled sheet forrned 2 ~ 3 ~ ~ 7 ~

are exposed to heat in a test oven ((~)Mathis Thermotaker type LTF-ST) at 180C. The Yellowness Index (YI) is determined in accordance with ASTM D 1925-70 on a test sample taken after each of the intervals of time stated in the following Table 2 (high YI
values mean severe discolouration and therefore low stability).

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Table 2: Yellowness Index (YI) in accordance with ASTM D 1925-70 \ime 5 10 15 20 25 30 35 Example minutes 1 11.1 11.9 13.5 15.3 17.7 20.3 23.3 2 7.69.0 9 9 11.6 13.7 16.3 20.0 3 3.25.8 7.8 13.4 20.0 32.6 52.6 4 4.84.5 10.9 16.3 25.1 45.2 63.7 3.55.1 7.8 12.9 21.2 36.0 50.4 6 2.12.7 3.1 4.2 7.4 13.7 25.8 . 7 2.42.4 2.3 2.4 6.4 10.7 18.9 8 10.211.214.1 16.7 19.7 9 8.810.312.3 14.9 17.4 10 9.310.412.8 15.6 18 8 ..._ 11 7.79.6 9.7 11.1 13.4 12 11.3 15.3 23.1 37.0 59.4 13 6.67.4 8.6 9.1 10.8 13.6 16.2 14 5.56.7 7.8 9.4 11.7 13.6 17.0 15 9.1 10.3 11.4 13.4 15.0 18.0 22.6 CH3 C, H3 ~1~ CH3 CH3 [ ~N ~L N (cH2)6 N

CH3 >~<CH3 CH3 ~h<CH3 CH3 NH _ CH3 CH3 N CH3 Mn ~ 2500 , J~

~) .
H3C~ CH3 HN~ OOC--(CH2)8--COO ~NH

(~) H3 C~N - CH3 ~ / H3C CH3 HO~' `~CH2--C
)=/ / \ H3C CH3 C(CH3)3 C4Hg \ ~
COO~N - CH3 H3C~ H,,~CH3 HNk~--N (CH2)6 N ~ NH

H3C CH3 ¦ ¦ H3C CH3 CH3CH3 N ~ ~ N CH3 C, H3 H3C- C ^CH2 - C - HN </ N N \)- NH- C ^ CH2^ Cl - CH2 CH3 CH3 N =~ N CH3 CH3 H3C~ CH3 HNk~--N (CH2)6----N ~NH

Example 16: Plasticiser^free PVC films are produced by mixing 100 parts of PVC of K
value 64, 1.~ parts of dibutyltin dilaurate,;0.3~part of the sterically hlndered amine (~) and the costabilisers mentioned in Table 3.

The films are produced and tested as described in Example 1. Table 3 shows the Yellowness Index after exposure to heat at 1 80C.

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Table 3:

Costabilisers$) Yellowness Index after 10 20 30 40 S0 minutes none 34 94 >100 0.3 Zn neodecanoate 23 40 S3 65 90 n.3 Zn neodecanoate + 0.3 benzoyl-stearoylmethane9 13 19 28 43 ~) Parts per 100 parts of PVC

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Claims (22)

1. WHAT IS CLAIMED IS:
   
   l. A stabilised chlorine-containing polymer composition comprising a chlorine-containing polymer and a stabiliser mixture comprising:
   
   a) at least one sterically hindered amine, b) at least one organic or inorganic zinc compound, c) at least one organotin compound of the formulae A, B, C or/and D
   (Z)mSn(OOC-Z1)4-m A
   
   (Z)mSn(OOC-CH=CH)COOZ1)4-m B
   C
   D
   in which m is 1, 2 or 3, Z is C1-C20alkyl and Z1 is hydrogen, C1-C20alkyl, C3-C20alkenyl, C5-C8cycloalkyl, phenyl, C7-C18alkylphenyl or C7-C9phenylalkyl, and d) at least one 1,3-dicarbonyl compound of the formula E
   E
   in which R1 is C1-C22alkyl, C5-C10hydroxyalkyl, C2-C18alkenyl, phenyl, phenyl which is substituted by OH, C1-C4alkyl, C1-C4alkoxy or halogen, C7-C10phenylalkyl, C5-C12cycloalkyl, C5-C12cycloalkyl which is substituted by C1-C4alkyl, or a group -R5-S-R6 or -R5-O-R6, R2 is hydrogen, C1-C8alkyl, C2-C12alkenyl, phenyl, C7-C12alkylphenyl, C7-C10phenylalkyl or a group -CO-R4, R3 has one of the meanings defined for R1 or is C1-C18alkoxy, R4 is C1-C4alkyl or phenyl, R5 is C1-C10alkylene and R6 is C1-C12alkyl, phenyl, C7-C18alkylphenyl or C7-C10phenylalkyl.
2. 2. A polymer composition according to claim 1, in which component a) is a polyvinyl chloride or a copolymer comprising at least 80 % of vinyl chloride or a mixture (polyblend) of such a polymer with other chlorine-containing or chlorine-free polymers.
3. 3. A polymer composition according to claim 1 comprising as component a) at least one compound from the series of polyalkylpiperidine derivatives which contains at least one group of the formula I
   I
   in which R is hydrogen or methyl.
4. 4. A polymer composition according to claim 3, in which R in formula I is hydrogen.
5. 5 A polymer composition according to claim 3, in which component b) is a polyalkylpiperidine derivative of the formula II
   II
   in which R is hydrogen, R11 is hydrogen or methyl, n is 2 and R12 is the diacyl radical of an aliphatic dicarboxylic acid having 4-12 C atoms.
6. 6. A polymer composition according to claim 3, comprising as the polyalkylpiperidine derivative the compound of the formula
7. 7. A polymer composition according to claim 3, in which component b) is a polyalkylpiperidine compound of the formula VI
   VI
   in which n is 4, R18 and R19 are a group in which R11 is hydrogen or methyl and R21 is hydrogen or C1-C6alkyl, and R20 is the tetravalent radical of an aliphatic tetramine.
8. 8. A polymer composition according to claim 3, in which component b) is an oligomeric or polymeric polyalkylpiperidine compound from the series comprising polyesters and polyaminotriazines.
9. 9. A polymer composition according to claim 8, in which component b) is a compound of the formula in which p is 3-20.
10. 10. A polymer composition according to claim 8, comprising as the polyalkylpiperidine compound one of the compounds of the formulae in which p is a value from 2 to 20, or
11. 11. A polymer composition according to claim 1, in which component b) is the zinc salt of a C1-C22carboxylic acid, of a C6-C18phenol or of a C5-C26 1,3-diketone.
12. 12. A polymer composition according to claim 11, in which b) is the zinc salt of a saturated aliphatic C1-C20carboxylic acid.
13. 13. A polymer composition according to claim 11, in which b) is the zinc salt ofacetylacetone or of benzoyl-6-hydroxyhexanoylmethane.
14. 14. A polymer composition according to claim 1, in which component c) is a compound of the formula A, B or C.
15. 15. A polymer composition according to claim 1, in which component c) is a compound of the formula A or B in which m is 2.
16. 16. A polymer composition according to claim 1, in which component c) is a compound of the formula A to D in which Z is C1-C12alkyl and Z1 is C4-C18alkyl, oleyl or phenyl.
17. 17. A polymer composition according to claim 15, in which component c) is a compound of the formula A in which m is 2, Z is butyl or octyl and Z1 is C8-C12alkyl.
18. 18. A polymer composition according to claim 1, in which component d) is a compound of the formula E in which R1 is C1-C18alkyl, phenyl, phenyl which is substituted by OH, methyl or methoxy, C7-C10phenylalkyl or cyclohexyl, R2 is hydrogen and R3 has one of the meanings defined for R1.
19. 19. A polymer composition according to claim 1, comprising 0.01 to 3 parts by weight of component a), 0.01 to 3 parts by weight of component b), 0.1 to 5 parts by weight of component c) and 0.01 to 2 parts by weight of component d) per 100 parts by weight of the chlorine-containing polymer.
20. 20. A polymer composition according to claim 1, comprising 0.1 to 1 part by weight of component a), 0.5 to 2 parts by weight of component b), 1 to 4 parts by weight of component c) and 0.05 to 1 part by weight of component d) per 100 parts by weight of the chlorine-containing polymer.
21. 21. A polymer composition according to claim 1, comprising, in addition to components (a) to (d), one or more additives from the series comprising plasticisers, phosphites, compounds of calcium, magnesium, sodium, barium, lead and cadmium, hydrotalcites, metal-free PVC stabilisers, impact strength modifiers, agents for improving the heat resistance, epoxide compounds, antioxidants, UV absorbers and light stabilisers, pigments, dyes, fillers, lubricants and flameproofing agents.
22. 22. A process for stabilising a chlorine-containing polymer against damage by heat and light by addition of a) at least one sterically hindered amine, b) at least one organic or inorganic zinc compound, c) at least one organotin compound of the formulae A, B, C or/and D
    
    (Z)mSn(OOC-Z1)4-m A
    
    (Z)mSn(OOC-CH=CH)COOZ1)4-m B
    C
    D
    
    in which m is 1, 2 or 3, Z is C1-C20alkyl and Z1 is hydrogen, C1-C20alkyl, C3-C20alkenyl, C5-C8cycloalkyl, phenyl, C7-C18alkylphenyl or C7-C9phenylalkyl, and d) at least one 1,3-dicarbonyl compound of the formula E
    E
    
    in which R1 is C1-C22alkyl, C5-C10hydroxyalkyl, C2-C18alkenyl, phenyl, phenyl which is substituted by OH, C1-C4alkyl, C1-C4alkoxy or halogen, C7-C10phenylalkyl, C5-C12cycloalkyl, C5-C12cycloalkyl which is substituted by C1-C4alkyl, or a group -R5-S-R6 or-R5-O-R6, R2 is hydrogen, C1-C8alkyl, C2-C12alkenyl, phenyl, C7-C12alkylphenyl, C7-C10phenylalkyl or a group -CO-R4, R3 has one of the meanings defined for R1 or is C1-C18alkoxy, R4 is C1-C4alkyl or phenyl, R5 is C1-C10alkylene and R6 is C1-C12alkyl, phenyl, C7-C18alkylphenyl or C7-C10phenylalkyl.
    
    FD 4.3/SA/ms*