POLYMER STABILISING COMPOSITIONS, POLYMERS STABILISED THEREWITH, SHAPED ARTICLES FORMED FROM SUCH POLYMERS AND A PROCESS FOR POLYMER STABILISATION

Abstract: This invention relates to stabilizer compositions for polymers containing 1) an organotin compound, or mixture of organotin compounds, 2) a mercaptan-containing organic compound or mixture of mercaptan-containing organic compounds, and optionally, 3) a halogen-containing tin compound or mixture of halogen-containing tin compounds, said stabilizers having a total halogen content of about 0.1% to about 10% by weight based on the weight of the stabilizer composition. This invention also relates to compositions containing said stabilizers, to a process for stabilizing polymer by adding thereto said stabilizers, and to articles of manufacture, e.g. pipe, comprising a polymer and said stabilizers.

Description: "POLYMER STABILISING COMPOSITIONS, POLYI4ERS STABILISED THEREWITH, SHAPED ARTICLES FORMED FROM SUCH POLYMERS AND A PROCESS FOR POLYMER STABILISATION" This invention relates to stabilizer compositions containing an organotin compound or mixture of organotin compounds, a mercaptan-containing organic compound or mixture of mercaptan-containing organic compounds, and, optionally, a halogen-containing tin compound or mixture of halogen-containing tin compounds. This invention also relates to polymer compositions containing said stabilizer compositions, to methods for stabilizing polymers by adding thereto said stabiliser compositions and to articles of manufacture, e.g. pipe, made from polymers stabilized with said stabilizer compositions. Organotin compounds, particularly useful as stabilizers for halogen containing polymers, are well known in the art. These organotin compounds can provide stabilization of such polymers when used alone or in admixture with various compounds. For example, U.S. Patent No. 3,715,333 to W.A. Larkin discloses stabilizers for halogen-containing polymers which contain; as a first stabilizer, an organotin halide having the formula: RSnX3 where R is a hydrocarbon and X is chlorine, bromine, or iodine; and, as a second stabilizer, a sulfur-containing organotin compound exhibiting two direct carbon to tin bonds and a direct bond from tin to each of two sulfur atoms. Likewise, U.S. Patent No. 3,503,924 to M.W. Pollock discloses stabilizers for polyvinyl chloride resins which are mixtures containing a diorganotin mercaptide and a minor amount of an alpha-mercapto acid. Pollock also discloses, in U.S. Patent No. 3,507,827, stabilizer mixtures for decreasing early discoloration of polyvinyl chloride resins which contain (1) a dialkyl, dicycloalkyl or alkylcycloalkyl tin mercapto carboxylic acid ester, and (2) an alpha- or beta-mercapto acid having at least three carbon atoms, or an alpha- or betamercapto alcohol having at least two carbon atoms. In accordance with this invention there are proved compositions for stabilizing halogen-containing organic polymers which comprise an organotin compound or mixture of organotin compounds, a mercaptan-containing organic compound or mixture of mercaptan-containing organic compounds, and, optionally, a halogen-containing tin compound or mixture of halogen-containing tin compounds. The invention is also directed to polymer compositions containing a stabilizing composition comprising an organotin compound or mixture of organotin compounds, a mercaptancontaining organic compound or mixture of mercaptancontaining organic compounds, and, optionally, a halogencontaining tin compound or mixture of halogen-containing tin compounds; to a process for stabilizing polymers by adding thereto a stabilizing composition comprising an organotin compound or mixture of organotin compounds, a mercaptan-containing organic compound or mixture of mercaptan containing organic compounds, and, optionally, a halogencontaining tin compound or mixture of halogen-containing tin compounds; and to articles of manufacture, e.g. pipe, made .from polymers stabilized with a stabilizing composition comprising an organotin compound or mixture of organotin compounds, a mercaptan-containing organic compound or mixture of mercaptan-containing compounds, and, optionally, a halogen-containing tin compound or mixture of halogencontaining tin compounds. The stabilizer compositions of this invention have quite unexpectedly been found to impart stabilization against the deteriorative effects of heat to halogencontaining organic polymers which is superior to those stabilizer compositions previously known in the art. The term halogen-containing organic polymers as used herein refers to halogen-containing vinyl and vinylidene polymers or resins in which the halogen is attached directly to the carbon atoms. Preferably, the polymer is a vinyl halide polymer, more particularly a vinyl chloride polymer. Usually, the vinyl chloride polymer is made from monomers consisting of vinyl chloride alone or a mixture of monomers eomprising; preferably, at least about 70geo by weight based on the total monomer weight of vinyl chloride. The halogen-containing polymers which can be stabilized according to this invention include chlorinated polyethylene having 14 to 75%, e.g. 27%, chloride by weight, chlorinated natural and synthetic rubber, rubber hydrochloride, chlorinated polystyrene, chlorinated polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, copolymers of vinyl chloride with 1 to 90geo, preferably 1 to 30%, of a copolymerizable ethylenically unsaturated material such as, for example, vinyl acetate, vinyl butyrate, vinyl benzoate, vinylidene chloride, diethyl fumarate, diethyl maleate, other alkyl fumarates and maleates, vinyl propionate, methyl acrylate, 2-ethylhexyl acrylate, butyl acrylate and other alkyl acrylates, methyl methacrylate, ethyl methacrylate, butyl methacrylate and other alkyl methacrylates, methyl alpha-chloroacrylate, styrene, trichloroethylene, vinyl ethers such as vinyl ethyl ether, vinyl chloroethyl ether and vinyl phenyl ether, vinyl ketones such as vinyl methyl ketone and vinyl phenyl ketone, 1-fluoro-2-chloroethylene, acrylonitrile, chloroacrylonitrile, allylidene diacetate and chloroallylidene diacetate. Typical copolymers include vinyl chloride-vinyl acetate (96:4 sold commercially as VYNW), a vinyl chloride-vinyl acetate (87:13), vinyl chloride-vinyl acetate-maleic anhydride (86:13:1), vinyl chloride-vinylidene chloride (95:5); vinyl chloride-diethyl fumarate (95:5), and vinyl chloride-2-ethylhexyl acrylate (80:20). In addition to the stabilizer compositions of this invention, there can also be incorporated into the halogencontaining organic polymer conventional additives such as plasticizers, pigments, fillers, dyes, ultraviolet light absorbing agents, densifying agents and the like. The stabilizer compositions of this invention comprise an organotin compound or mixture of organotin compounds, a mercaptan-containing organic compound or mixture of mercaptancontaining organic compounds, and, optionally, a halogencontaining tin compound or mixture of halogen-containing tin compounds. The organotin compounds usetul in this invention contain one or more tetravalent tin atoms which each have at least one direct tin to carbon bond and have structures selected from the following formulae: EMI4.1 EMI5.1 and EMI5.2 wherein X and X1 are the same or different and are selected from -SR2, Cl, Br, I, EMI5.3 and 0-R8 with the proviso that in formula (II) when t = 1, in formula (V) when z = 1 and in formulae (III) and (IV) at least one X or X1 is -SR2; Y is EMI5.4 Z is EMI5.5 EMI5.6 W and W1 are the same or different and are oxygen or sulfur; R and R1 are the same or different and are selected from alkyl, aryl, alkenyl, aralkyl, alkaryl, cycloalkyl, cycloalkenyl, EMI6.1 -R9-O-R12, and -R9-CN; ; R2 is alkyl, alkenyl, aryl, aralkyl, cycloalkyl, cycloalkenyl, EMI6.2 EMI6.3 or R3 0 R8; R3 is alkylene of at least 2 carbon atoms, arylene, alkenylene of at least 2 carbon atoms, cycloalkylene, or cycloalkenylene; R4 is alkylene, arylene,- alkenylene pf at least 2 carbon atoms, cycloalkylene, or cycloalkenylene; R5 is R3; R6 is a carbon to carbon single bond or R4; R7 is -H or R8; R8 is alkyl, alkenyl, aryl, aralkyl, alkaryl, cycloalkyl, or cycloalkenyl; R9 is C1 to C4 alkylene; R12 is -E or a monovalent C1 to C20 hydrocarbon radical; R13 and R21 are the same or different and are each C1 to C20 alkyl or C1 to C20 alkoxy; R24 is EMI7.1 -H; -OH, -SH, aryl, C1 to C18 alkyl or/ 8 R16 is -H or i = O or an integer from 1 to 6 inclusive; ; m = 1 or 2 and t = O or 1 with the proviso that m + t = 2; n = 0, 1 or 2, n' = 0, 1 or 2 and p = 1 or 2 with the proviso that n + n' = 1 or 2 and n + n1 + p = 3; inclusive a = 0, 1 or 2, b - O, 1 or 2, q = an integer from 1 to 5/ c = 1, 2 or 3 and d = 0, 1 or 2 with the proviso that a + b = 2 and c + d = 3; v = an integer from 1 to 8 inclusive; and w = 0, 1 or 2, x = O or 1, y = l or 2, z = O or 1 with the proviso that when x = 0 and w = 1 or 2 then y = 1 and z = 1, when x = 1 then y = 1, z = O and w = 1, when w = 2 then x = O, y = 1 and z = 1 and-when w = 0 then x = O, y = 1, z = 1 and Y is -W-R3-W1- or EMI7.2 As used herein the term alkyl represents monovalent straight or branched chain hydrocarbon radicals containing, for example, 1 to 20 carbon atoms. The term aryl refers to monovalentC6-C10 aromatic rings such as benzene and naphthalene. The term alkenyl refers to monovalent straight or branched chain C2 to C20 hydrocarbon radicals containing at least one double bond. The term aralkyl represents a monovalent C1 to C20 hydrocarbon radical having attached thereto an aryl radical. The term alkaryl refers to monovalent aryl radicals having attached thereto at least one C1-C20 alkyl radical. The term cycloalkyl represents monovalent C3-C8 saturated cycloaliphatic radicals, and the term cycloalkenyl represents Cs-Cg cycloaliphatic radicals containing at least one double bond. The organotin compounds useful in this invention are prepared by methods well known in the art. For example, methods of preparing these organotin compounds are disclosed in U.S. Patents 3,565,930, 3,869,487, 3,979,359, 4,118,371, 4,134,878 and 4,183,846. The preferred organotin compounds useful in this invention are those compounds according to formula (I) where R is methyl, butyl or octyl and W is sulfur; those compounds according to formula (II) where R1 is methyl or butyl, W is sulfur, X is -SR2 where R2 is EMI8.1 m = 1 and t = 1:; those compounds according to formula (IIa) where R and R1 are methyl, butyl, octyl or EMI8.2 W and W1 are oxygen or sulfur; and Z is EMI8.3 EMI8.4 those compounds according to formula (III) where R is methyl or butyl, R1 is methyl or butyl, X is -SR2 where R2 is EMI9.1 X1is -SR2 where R2 is EMI9.2 n = O or 1, n' = O or 1, n + n' = 1 and p = 2; those compounds according to formula (IV) where R is methyl, X is -SR2 where R2 is EMI9.3 R1is methyl, X1 is -SR2 where R2 is EMI9.4 Y is -S-, a = O, b = 2, c = 1, d = 2 and g = 1; and those compounds according to formula (V) where R is methyl, R1 is methyl, Y is -S-, w = 1, x = 1, y = 1 and z = 0. Examples of organotin compounds which are useful in this invention include, but are not limited to those illustrated in Tables I-IV below. Thus, representative of the organotin compounds described by formulas (I) and (II) are those illustrated in Table I below. Representative of the organotin compounds described by formula (IIa) are'those illustrated in Table Ia below. Examples of the organotin compounds represented by formula (III) are illustrated in Table II below. The oranctin compounds illustrated in Table III below are representative of compounds described by formula (TV). The organotin compound illustrated in Table IV below is representative of compounds described by ormul2 (V). TABLE I EMI10.1 EMI10.2 <tb> <SEP> Organotin <tb> <SEP> Compound <SEP> I <tb> <SEP> No. <SEP> R <SEP> R <SEP> W <SEP> X <SEP> m <SEP> t <tb> <SEP> 1 <SEP> -c <SEP> H <tb> 1 <SEP> -C4B9 <SEP> ¯ <SEP> S <SEP> ¯ <SEP> ¯ <SEP> . <tb> 2 <SEP> -c <SEP> B317 <SEP> 0 <SEP> - <SEP> - <SEP> <tb> <SEP> 0 <tb> <SEP> 3 <SEP> - <SEP> -CH3 <SEP> S <SEP> -SCH2CH2OCC17-H33 <SEP> 1 <SEP> 1 <tb> <SEP> .0 <tb> <SEP> II <tb> <SEP> 4 <SEP> - <SEP> .-CH3 <SEP> S <SEP> -SCH2COC8H17 <SEP> 1 <SEP> 1 <tb> <SEP> 0 <SEP> 0 <tb> <SEP> II <SEP> II <tb> <SEP> 5 <SEP> - <SEP> -ci2ci2coc4H9 <SEP> S <SEP> -SCH2CH2COCl8B37. <SEP> 1 <SEP> 1 <tb> <SEP> 6 <SEP> - <SEP> -C4H9 <SEP> S <SEP> - <SEP> 2 <SEP> 0 <tb> <SEP> 7 <SEP> - <SEP> -C8H17 <SEP> 0 <SEP> - <SEP> 2 <SEP> 0 <tb> TABLE Ia EMI11.1 EMI11.2 <tb> <SEP> Organotin <tb> <SEP> Compound <SEP> R <SEP> and <SEP> R1 <SEP> W <SEP> z <tb> <SEP> No. <SEP> owl <tb> <SEP> ia <SEP> -CH3 <SEP> S <SEP> S <SEP> -SCH2CH2O(CH2)4OCH2CH2-s <tb> <SEP> 7b <SEP> -c <SEP> 4H9 <SEP> S <SEP> S <SEP> -SCH2CH208CH2CH2S <tb> <SEP> 7c <SEP> C8 <SEP> 17 <SEP> 0 <SEP> O <SEP> S <SEP> -SCH2cOcHçcH208cRH2s <tb> <SEP> -CH2CH2COC4H9 <SEP> S <SEP> S <SEP> -SCH2CH20 <SEP> CH=CHCOCH2CH2S <tb> <SEP> -CH3 <SEP> S <SEP> S <SEP> -SCH,CH-o <tb> <SEP> C9H19 <SEP> C9H19 <tb> C4H9 <SEP> 7f <SEP> -C4Hg <SEP> | <SEP> S <SEP> t <SEP> S <SEP> -SCH$H\ <SEP> s <tb> <SEP> 7g <SEP> -C4H9 <SEP> 0 <SEP> O <SEP> <SEP> -SCHCoCH2CH2CH2 <tb> <SEP> OClCH=CHCOCH3 <tb> <SEP> II <tb> <SEP> 0 <SEP> 0 <tb> <SEP> -CH3 <SEP> <SEP> S <SEP> S <SEP> . <SEP> II <tb> <SEP> SCH2tt0CH2CCH2OCCH2S <tb> <SEP> (CH2 <SEP> )2 <tb> <SEP> (CH2OH)2 <tb> <SEP> 7i <SEP> -CH3 <SEP> S <SEP> S <SEP> -SCX2 <SEP> OCHzCCH20 <SEP> CH7c <tb> <SEP> 3 <SEP> 222 <tb> <SEP> 1 <SEP> (CHZO <tb> TABLE II EMI12.1 EMI12.2 <tb> Organotin <tb> ComDound <SEP> 1 <SEP> 1 <tb> No. <SEP> R <SEP> and <SEP> R <SEP> X <SEP> and <SEP> X <SEP> n <SEP> n <SEP> p <tb> <SEP> 0 <tb> <SEP> II <tb> <SEP> 8 <SEP> -CH3 <SEP> SCfl,COC <SEP> 17 <SEP> 1 <SEP> 0 <SEP> 2 <tb> <SEP> O <tb> <SEP> II <tb> <SEP> 9 <SEP> -C4H9 <SEP> -. <SEP> -SCH2CH2OCC7H15 <SEP> 1 <SEP> 0 <SEP> 2 <tb> <SEP> 0 <SEP> -o <tb> <SEP> It <SEP> I) <tb> <SEP> 10 <SEP> -CH2CH2COC4H9 <SEP> SCH2CH20CCH3 <SEP> 2 <SEP> 0 <tb> <SEP> 0 <tb> <SEP> II <tb> <SEP> 11 <SEP> -CH3 <SEP> -SCH2CH2OCC17H35 <SEP> 2 <SEP> 0 <tb> EMI13.1 EMI13.2 <tb> <SEP> U <SEP> H <SEP> H <SEP> H <SEP> H <SEP> es <SEP> H <SEP> H <SEP> H <SEP> H <SEP> H <tb> Organo <SEP> Lin <tb> C0poUfld <SEP> No. <SEP> R <SEP> and <SEP> I <SEP> N <SEP> N <SEP> abcdq <tb> <SEP> ¯ <SEP> , <SEP> .. <SEP> ¯ <tb> <SEP> 12 <SEP> -C113 <SEP> -ClI2CN20CC11H23 <SEP> Same <SEP> -S- <SEP> c <SEP> 2 <SEP> 1 <SEP> 2 <SEP> 1 <tb> <SEP> rJ <SEP> o <SEP> rl <SEP> o <SEP> 6 <SEP> c' <SEP> d <SEP> oi <SEP> o <tb> <SEP> U <SEP> -C8!117 <SEP> -SCII20C'0C13H27 <SEP> fax <SEP> -S- <SEP> 1 <SEP> 1 <SEP> 2 <SEP> O <tb> <SEP> to <tb> <SEP> 2N <tb> <SEP> U <tb> <SEP> O=U <tb> <SEP> 0 <tb> <SEP> I <SEP> co <SEP> 0 <tb> <SEP> 15 <SEP> -Ci!2CH2C0C4I[9 <SEP> -SCII2C1J2C10Cti17 <SEP> do <SEP> '-S-s- <SEP> Q <SEP> I <SEP> 1 <SEP> 2 <SEP> 1 <tb> <SEP> O <SEP> O <SEP> n <SEP> V <SEP> O=U <SEP> 0 <tb> <SEP> I <SEP> I <SEP> U <SEP> v) <SEP> O=U <SEP> 1 <SEP> I <SEP> -cu <SEP> I <tb> <SEP> N <SEP> ) <SEP> N <SEP> Z <tb> <SEP> 16 <SEP> -Cu3 <SEP> -cIi2 <SEP> CII2OC'C <SEP> 17H33 <SEP> do <SEP> -SCJ!2C0C4H8OCCH2S- <SEP> 0. <SEP> 2 <SEP> 1 <SEP> 2 <tb> <SEP> U <SEP> U <SEP> I <tb> <SEP> tn <SEP> a <tb> <SEP> II <SEP> ii <tb> <SEP> 17 <SEP> -C!3 <SEP> -c!i2C[I20CcH=C}iC0CH3 <SEP> do <SEP> -S- <SEP> 0. <SEP> 2 <SEP> 1 <SEP> 2 <SEP> 1 <tb> <SEP> 0 <tb> <SEP> 18 <SEP> -C4l49 <SEP> I <SEP> -S'CIi2C!120CC171133 <SEP> . <SEP> Cl <SEP> -S- <SEP> 1 <SEP> 1 <SEP> 2 <SEP> 1 <SEP> 1 <tb> <SEP> ' <SEP> X <SEP> F <tb> <SEP> o <SEP> f <tb> <SEP> =e <SEP> -C4119 <SEP> V <tb> <SEP> u <SEP> as <SEP> X <tb> <SEP> C) <tb> <SEP> . <SEP> n <SEP> ' <SEP> n <SEP> O- <SEP> n <SEP> q <tb> <SEP> 20 <SEP> -C113 <SEP> -SCII2Ci120CC11H23 <SEP> do <SEP> -S- <SEP> m <SEP> 2 <SEP> n <SEP> 1 < <SEP> 2 <SEP> 1 <tb> <SEP> ri <SEP> ri <SEP> U <SEP> "I <SEP> ri <SEP> . <SEP> g <tb> <SEP> rv., <tb> <SEP> V <SEP> m <SEP> 03 <SEP> r( <SEP> I <SEP> I <tb> <SEP> U <SEP> v <SEP> O <SEP> C) <SEP> U <SEP> U <SEP> . <tb> <SEP> 21 <SEP> m <SEP> 119 <SEP> O <SEP> 0= <SEP> 0 <SEP> O= <SEP> CII <SEP> C=U) <SEP> C=U <SEP> C=J <SEP> <tb> <SEP> > : <SEP> O <SEP> = <SEP> O <SEP> C=t) <SEP> O <SEP> O <SEP> O <SEP> C <SEP> O <SEP> O <tb> <SEP> rs <SEP> U <SEP> r <tb> <SEP> cJ <SEP> Ow <SEP> r <tb> <SEP> f <tb> <SEP> S <tb> <SEP> U <SEP> rD <SEP> U <SEP> V <SEP> U <SEP> U <SEP> ¯ <SEP> r <SEP> } <SEP> ¯a <SEP> U <tb> <SEP> tr <SEP> rJ <SEP> > <SEP> v^ <SEP> U) <SEP> vJ <SEP> J <tb> <SEP> or <tb> <SEP> t <SEP> N <tb> <SEP> = <SEP> b <SEP> v <tb> <SEP> X <SEP> H <SEP> > <SEP> U <SEP> > <SEP> <tb> <SEP> n <SEP> 3: <SEP> X <SEP> fS <SEP> n <SEP> X <SEP> v <SEP> ¯ <SEP> n <SEP> ¯ <tb> <SEP> P: <SEP> X <SEP> GD <SEP> v <SEP> X <SEP> ¯ <SEP> v <SEP> v <SEP> z <SEP> er <tb> <SEP> . <SEP> U <SEP> U <SEP> U <SEP> U <SEP> U <SEP> U <SEP> U <SEP> U <SEP> U <SEP> U <tb> <SEP> . <SEP> mB <tb> <SEP> O <SEP> N <SEP> n <SEP> v <SEP> tO <SEP> t9 <SEP> F <SEP> m <SEP> cs <SEP> o <SEP> t <tb> <SEP> E <SEP> g <SEP> H <SEP> ., <SEP> H <SEP> H <SEP> H <SEP> H <SEP> H <SEP> vI <SEP> rs <SEP> N <tb> <SEP> gg <tb> TABLE IV EMI14.1 EMI14.2 <tb> Orcanotin <SEP> x <tb> Compound <SEP> a"djnd <tb> No. <SEP> R1 <SEP> and <SEP> B <SEP> Y <SEP> O <SEP> w <SEP> x <SEP> y <SEP> z <tb> <SEP> 0 <SEP> 0 <tb> <SEP> -SCN2CN20C11C"0CN2C2S <SEP> 22 <SEP> -CR3 <SEP> - <SEP> 1 <SEP> 1 <SEP> 1 <SEP> 0 <tb> As used in Tables I-III above, and throughout this specification, the radicals -C4H9, -C8H17, -Cl2H2s, -CgHl9 and -C10H21 represent n-butyl, n-octyl, n-dodecyl, n-nonyl and n-decyl respectively. The carboxyl radicals EMI15.1 EMI15.2 are derived from oleic acid, stearic acid, n-octanoic acid, lauric acid, and pelargonic acid respectively. Likewise, the radicals -OC13H27, -OCl8H37, and -OC8Hl7 are derived from tridecanol, stearyl alcohol and iso-octanol respectively. The mercaptan-containing organic compounds useful in this invention include hydrocarbyl mercaptans, mercapto esters, mercapto alcohols, and mercapto acids. These mercaptancontaining organic compounds have structures illustrated by the following formulas: EMI15.3 EMI16.1 RIO is cycloalkyl, cycloalkenyl or phenyl; R14 is H, aryl or C1 to C18 alkyl; R24 is as previously defined, R15 is EMI16.2 -OH, -SH, aryl, C1 to C18 alkyl, or -H; R16 is as previously defined; R17 is EMI16.3 R18 is arylene, C1 to C8 alkylene, or EMI16.4 Rl9 is -H or a divalent group which may contain halogen, hydroxy, mercapto or alkyl substituents and which combines with R10 when R10 is phenyl to form a naphthalene ring; ; R20 is -CR3, -CH2-CH3, or EMI17.1 R23 is EMI17.2 -SH, aryl, C1 to C18 alkyl, -OH or -H; with the proviso that in formula (VII) when RIU is phenyl, R23 is -OH and i = 0, then the -OH and. ,-SH groups are on non-adjacent carbon atoms; R200 and 20.1 are the same or different and are alkylene, alkenylene, arylene, cycloalkylene or cycloalkenylene; or alkylene, alkenylene, arylene, cycloalkylene or cycloalkenylene each substituted with one or two -R, -OR7, EMI17.3 groups; R, R4, R7, and R8 are as previously defined; i is as previously defined; j = 0, 1, 2 or 3; and f = 1 or 2. The mercaptan-containing organic compounds useful in this invention are well known compounds (see, for example, ü. S. Patents o. 3,503,924 and 3,507,827). The preferfed mercaptan-containing organic compounds useful in this invention are those compounds according to formula (VI) where R14 is -H, R24 is -H, R15 is EMI17.4 and i = 1; those compounds according to formula (VII) where RlU is phenyl, R14 is -H, R23 is -H, R19 is -H, i = 1 and j = 1; those compounds according to formula (VIII) where R14 is -H, R17 is EMI18.1 and i = 1; those compounds according to formula (IX) there R14 is -E and i = 1; those compounds according to formula (X) where R20 is -C2H5 or EMI18.2 Rl4 is -H and i = 1; and those compounds according to formula (XI) where R14 is -H and i = 1; and those compounds according to formula (XIa) where R200 is -CH2CH2- or EMI18.3 Of the foregoing, the mercaptan-containing organic compounds. according to formula (VI) are more preferred. Examples of the mercaptan-containing organic compounds described by formula (VI) include, but are not limited to, the following compounds: HSC12H25 EMI19.1 EMI20.1 HSCH2CH2OH HSCH2CH2CH2OH EMI20.2 EMI21.1 Examples of the mercaptan-containing organic compounds described by formula (VII) include, but are not limited to, the following compounds: EMI21.2 Examples of mercaptan-containing organic compounds represented by formula (VIII) include, but are not limited to, the following compounds: EMI22.1 An example of the mercaptan-containing organic compounds described by formula (IX) includes, but is not limited to, the following: EMI22.2 The mercaptan-containing organic compounds represented by formula (X) are exemplified by, but are not limited to, the following: : EMI23.1 The mercaptan-containing organic compounds represented by formula (XI) are exemplified by, but are not limited to, the following: EMI23.2 The mercaptan-containing organic compounds represented by formula (XIa) are exemplified by, but are not limited to, the following: EMI23.3 The halogen-containing tin compounds useful in this invention contain a tetravalent tin atom having bonded directly thereto at least one halogen atom, and are selected from compounds having the formula: EMI24.1 where Q is Cl, r, or I; R11 and R22 are the same or different and are selected from EMI24.2 where R, R1, R8 R9, R12, R13 and R21 are as previously defined; and g = 0, 1, 2 or 3, r = 0, 1, 2, or 3 and h = 1, 2, 3 or 4 with the proviso that g + r +'h = 4. The preferred halogen-containing tin compounds useful in this invention are those compounds according to formula (XII) where R11 is methyl, R22 is -Cl, Q is Cl, g=1, h=2 and r=1. Examples of halogen-containing tin compounds which are useful in this invention include, but are not limited to, the compounds illustrated below. CH3SnCl3 (CH3)2SnCl2 C4H9SnCl3 C8H17SnCl3 SnCl4 EMI25.1 (C8H17)3SnCl EMI25.2 CH3SnBr3 EMI25.3 CH3SnI3, EMI25.4 (C4H9)2SnCl2 EMI26.1 (C12H25)2SnBr2 (NCCH2CH2)2SnCl2 EMI26.2 (HOCH2CH2CH2)2SnCl2 EMI26.3 The halogen-containing tin compounds useful in this invention are conveniently prepared by methods well known in te art. For example, methods for preparing these halogen-containing tin compounds are disclosed in U. S. Patents No. 3,745,183, 3,857,868 and 4,l34,878. It should be noted that, in an effort to simplify the foregoing formulas I-XII and render them as clear and concise as possible, some letters are used more than once in the same formula and/or in more than one formula. Thus, for example, R1 appears twice in formula IV and also in formulas II, IIa, III, V and XII. It is intended that, in those instances where the same letter is used either more than once in the same formula or in more than one formula, that letter represents at each independent occurence any group contained in the set of groups encompassed by its definition, or any and all subsets thereof. It is further intended that any modification or limitation in the definition of a particular letter at one occurence does not necessarily affect its definition at any other occur EMI27.1 <tb> ence. <SEP> For <SEP> example, <SEP> should <SEP> the <SEP> definition <SEP> of <SEP> X <SEP> in <SEP> formula <tb> II <SEP> be <SEP> limited <SEP> from <SEP> -SR2 <SEP> Cl,Br, <SEP> 1,-OR8 <SEP> or <SEP> -OR <SEP> to <SEP> Cl, <tb> Br or I, then X in each. of formulae III, IV and V may still EMI27.2 <tb> represent <SEP> at <SEP> each <SEP> independent <SEP> occrence <SEP> the <SEP> set <SEP> of <SEP> groups <tb> h <SEP> or <SEP> -SR2 <SEP> 8 <SEP> 8 <tb> consisting <SEP> of <SEP> -SR2, <SEP> Cl, <SEP> Br, <SEP> I, <SEP> -OCR <SEP> and <SEP> -OR <SEP> , <SEP> or <SEP> bny <SEP> and <tb> ail <SEP> substs <SEP> thereof <SEP> such <SEP> as, <SEP> for <SEP> example; <SEP> -SR21 <SEP> &num; <SEP> 8 <tb> all <SEP> subsets <SEP> thereof <SEP> such <SEP> as, <SEP> for <SEP> example, <SEP> -SR2, <SEP> -o8R8 <SEP> and <tb> -OR8 or Cl, Br, I and -OR8 In one embodiment, the stabilizer compositions, of this invention comprise A) an organotin compound or mixture of organotin compounds selected from organotin conipounds according to formulas (I), (it), (IIa), (III) (IV) and/or (V) B) a mercaptan-containing organic compound or mixture of mercaptan-containing organic compounds selected from compounds according to formulas (VI), (VII), (VIII), (IX), (X), (XI) and/or (XIa); and, optionally, C) a halogencontaining tin compound or mixture of halogen-containing tin compounds selected from compounds according to formula (XII), with the proviso that when no halogen-containing tin compound according to formula XII is employed, then at least one of the organotin compounds of component A is selected from compounds according to formulas (II), (III), (IV) or (V) wherein at least one X or X is Cl, Br, or I. In another embodiment, the stabilizer compositions of this invention comprise A) organotin compounds comprising an organotin compound or mixture of organotin compounds according to formula (IIa) either alone or in admixture with any or all the organotin compounds according to formulas (I), (II), (III), (IV) and/or (V); B) a mercaptan-containing organic compound or mixture of mercaptan-containing organic compounds according to formulas (VI), (VII), (VIII), (IX), (X) and (XI); and C) a halogen-containing tin compound or mixture of halogen-containing tin compounds according to formula XII and/or according to formulaes (II), (III), (IV) and (V) where at least one X or X1 is Cl, Br or I. In a further embodiment, the stabilizer compositions of this invention comprise A) an organotin compound or mixture of organotin compounds accroding to formulas (I), (II), (IIa), (III), (IV) and/or (V);, B) a mercaptan-containing organic compound or mixture of mercaptan-containing organic compounds according to formula (XIa) either alone or in admixture with the mercaptan-containing organic compounds according to formulas (VI.), (VII), (VIII), llX) x (X) and/or (XI); ; and, optionally, C) a halogen-containing tin compound or mixture of halogen-containing tin compounds according to formula XII, with the proviso that when no halogencontaining tin co ipound according to formula XII is employed, then at least one of the organotin compounds of component A is selected from compounds according to formulas (II), (III), (,IV) or (Y) wherein at least one X or X is Cl, Br or I. The stabilizer compositions of this invention may be prepared by blending the components thereof in any convenient manner which produces a homogeneous mixture, such as by shaking or stirring in a container. Likewise, the stabilizer compositions of this invention can be incorporated into the halogen-containing organic polymer by admixlng the stabilizer composition and polymer, such as, for example, in an appropriate mill or mixer or by any other of the wellknown methods which provide uniform distribution of the stabilizer throughout the polymer. As previously stated, the stabilizer compositions of the present invention comprise an organotin compound or mixture of organotin compounds, a mercaptan-containing organic compound or mixture of mercaptan-containing organic compounds, and, optionally, a halogen-containing tin compound or mixture of halogen-containing compounds. It should be emphasized that all of the stabilizer compositions of this invention contain a weight percent of halogen, based on the total weight of the stabilizer composition, of about 0.1 to about 1, preferably about 0.5% to about 2%. A weight percent or halogen of about 0.1% has been found to be effective in providing the stabilizers of the invention with improved performance, while weight percents of halogen in excess or 10 tend to decrease the effectiveness of the stabilizer compositions. This required weight percent of halogen may come from the halogencontaining tin compounds alone; from a combination of the halogen-containing tin compounds and organotin compounds according to formulae (II), ills), (IV) and (V) wherein at least one X or X1 is Cl, Br or I; or solely from organotin compounds according to formulae ill), (III), (IV) and (V) wherein at least one X or X1 is Cl, Br or I. For example, when no halogen-containing tin compound according to formula (XII) is present in the stabilizer composition, i.e. when the weight percent or halogen containing tin compound is 0, then the organotin compound is selected from those represented by formulae (II), (III), (IV) and (V) wherein at least one X or X1 is Cl, Br or I, and said organotin compound or mixture of said organotin compounds is employed in an amount sufficient to provide the required weight percent of halogen. The stabilizer compositions of this invention contain about l0'% to about 60io preferably about 20% to about 4010 by weight based on the total weight of the stabilizer composition of mercaptan-containing organic compound or mixtures of mercaptan-containing organic compounds. The remainder of the stabilizer composition is comprised of organotin compound or mixture of organotin compounds, and, optionally, halogen-containing tin compound or mixture of halogencontaining tin compounds, said compounds being selected to provide the required weight percent of halogen in the stabilizer composition. While the precise amount of organotin compounds and optional halogen-containing tin compounds employed in the stabilizer compositions of this invention will be determined by the halogen content of the particular compounds utilized, in general the stabilizer compositions of this invention contain about 40% to about 90%0, preferably about 50geo to about 70% organotin compound or mixture of organotin compounds, and 0% to about 33""o, preferably about 0.1% to about 15% halogen-containing tin compound or mixture of halogen-containing tin compounds, all percentages being by weight based on the total weight of the stabilizer composition. The stabilizer compositions of this invention are employed in an amount sufficient to impart the desired resistance to heat deterioration to halogen-containing organic polymers. It will be readily apparent to one of ordinary skill in the art, that the precise amount of stabilizer composition used will depend upon several factors, including, but not limited to, the particular halogen-containing organic polymer employed, the temperature to which the polymer will be subjected, and the possible presence of other stabilizing compounds In general, the more severe the conditions to which the halogen-containing organic polymer is subjected, and the longer the term required for resisting degradation, the greater will be the amount of stabilizer composition required. Generally, as little as about 0.40 parts by weight of the stabilizer composition per hundred parts by weight of halogen-containing organic polymer will be stabilizingly effective. While there is no critical upper limit to the amount of stabilizer composition which can be employed, amounts in excess of about 10 parts by weight of stabilizer composition per hundred parts by weight of halogen-containing organic polymer do not give an increase in effectiveness commensurate with the additional amount of stabilizer employed. The stabilized halogen-containing organic polymer compositions of this invention may be used to form articles of manufacture, e.g. pipe. A variety of conventional molding techniques may be employed to form the stabilized compositions into any desired shape. The following examples illustrate this invention. Unless otherwise indicated, all parts and percentages in the examples and throughout this specification are by weight. EXAMPLES 1-6 Several mixtures are prepared by dry blending to llO0C in a Henschel high intensity mixer (Model 2JSS ) 100.0 parts of polyvinyl chloride (Geon 103EP-F-76 available commercially from B. F. Goodrich Chemical Company) with 3.0 parts of fine particle size calcium carbonate coated with calcium stearate, l.0 part titÅanium dioxide, 1.2 parts paraffin wax (ADVAWAX@ 165 paraffin wax available commercially from Car stab Corporation), 0.60 part calcium stearate, 0.15 part of an oxidized low molecular weight ethylene homopolymer (AC629A available consmercially from Allied Chemical Corporation), and each in turn of the stabilizer compositions listed in Table A in the amounts indicated in Table A, said amounts being parts by weight of stabilizer per hundred parts polyvinyl chloride. The resulting mixture is masticated on a tworoll mill at about 193 C. Samples are taken at one minute intervals beginning after the first introduction of the mix to the mill. The appearance of each sample taken from the mill is evaluated using the following scale: 10 9 8 7 6 5 4 :3 2 1 0 White EMI32.1 Tan-Orcnge EMI32.2 Blrn The results of these tests are indicated in Table A. TABLE A EMI33.1 <tb> <SEP> lu <tb> <SEP> o <SEP> o <SEP> o <SEP> o <tb> <SEP> o <tb> <SEP> H <SEP> H <SEP> N <SEP> H <tb> <SEP> Parts <SEP> Minutes <SEP> of <SEP> N <SEP> rl <tb> <SEP> w <SEP> By' <SEP> c <SEP> 2 <SEP> 3 <SEP> 4 <SEP> 5 <SEP> 6 <SEP> 7 <SEP> 8 <SEP> 9 <SEP> 10 <tb> No. <SEP> Stabilizer <SEP> Coiiiosi <SEP> N <SEP> Weight <SEP> COLOR <tb> <SEP> I <tb> w <SEP> Organotin <SEP> Cmpd. <SEP> No. <SEP> 3 <SEP> fron <SEP> Table <SEP> v <SEP> 0.40 <tb> <SEP> 44 <SEP> W <SEP> <tb> <SEP> vi <SEP> 0.08 <SEP> 10+ <SEP> -O <SEP> 10 <SEP> 9 <SEP> 7 <SEP> 6 <SEP> 4 <SEP> 2 <SEP> 1 <SEP> I;D <tb> <SEP> lnU <tb> <SEP> D <SEP> ¯ <SEP> . <SEP> . <SEP> ¯ <SEP> I <tb> <SEP> z <SEP> o <SEP> a <SEP> co <SEP> I <SEP> o <tb> ------¯ <SEP> rl <SEP> . <SEP> I <SEP> H <SEP> <tb> <SEP> 0 <tb> <SEP> < <SEP> 0.20 <SEP> 1,0+' <SEP> 10+ <SEP> 10 <SEP> 9 <SEP> 8 <SEP> 6 <SEP> 4' <SEP> 2, <SEP> 1 <SEP> 1-H <SEP> <tb> <SEP> I <SEP> -t- <SEP> + <tb> <SEP> o <SEP> o <SEP> o <SEP> o <tb> <SEP> ¯¯ <SEP> ' <SEP> ¯ <SEP> <tb> 2b <SEP> Organotin <SEP> 9mpd. <SEP> No. <SEP> 9 <SEP> from <SEP> Table <SEP> II <SEP> 0.40 <tb> <SEP> 4 <SEP> > <SEP> O' <SEP> c0 <SEP> H <SEP> O' <SEP> O <SEP> O <SEP> O <SEP> O <SEP> O <SEP> LN <SEP> O <SEP> n <tb> <SEP> k <SEP> oo <SEP> NO <SEP> m <SEP> o <tb> <SEP> n <SEP> - <SEP> g) <SEP> d <SEP> d <SEP> d. <SEP> d <SEP> o <tb> <SEP> C <SEP> (CII2OCCll2SH) <SEP> P4 <SEP> P <SEP> B <SEP> O <SEP> O <SEP> O <SEP> O <SEP> 9 <SEP> 8 <SEP> O <SEP> O <SEP> O <SEP> 3 <SEP> 2 <SEP> O <tb> <SEP> . <SEP> 2SnCl2 <SEP> H <SEP> H <SEP> 1d <tb> <SEP> C <tb> 3 <SEP> OrganoLin <SEP> Cinpd'. <SEP> No. <SEP> It <SEP> H <tb> <SEP> C <tb> <SEP> 0 <SEP> C <tb> <SEP> C <SEP> f-l <tb> <SEP> O <SEP> 0.10 <SEP> 10+ <SEP> 10+ <SEP> 10+ <SEP> 10 <SEP> 9 <SEP> 8 <SEP> 5 <SEP> 3 <SEP> 1 <SEP> 0 <tb> <SEP> E <SEP> E <SEP> E <SEP> E <tb> <SEP> 0 <SEP> 0 <SEP> 0 <SEP> 0 <tb> <SEP> rl <SEP> k <SEP> k <SEP> k <tb> <SEP> n <SEP> n <SEP> C <SEP> CE <SEP> fs <tb> <SEP> t) <SEP> O <SEP> O <SEP> z <SEP> LN <tb> <SEP> N <SEP> t <SEP> ¯{ <SEP> 55 <SEP> ¯ <SEP> X <SEP> G <SEP> t <SEP> ¯ <tb> <SEP> sol' <SEP> z <SEP> t <SEP> ffi <SEP> > <SEP> z <SEP> ¯ <SEP> X <SEP> > <tb> <SEP> H <SEP> E <SEP> co <SEP> E <SEP> H <SEP> E <SEP> w <SEP> ¯ <SEP> < <tb> <SEP> .d <SEP> U <SEP> U <SEP> U <SEP> U <SEP> U <SEP> X <SEP> N <SEP> U <SEP> U <tb> <SEP> 5) <SEP> o <SEP> o <SEP> ¯ <SEP> U <SEP> cs <SEP> < <SEP> o=u <tb> <SEP> tJ <SEP> s: <SEP> 0=O <SEP> < <SEP> O <SEP> < <SEP> ¯ <SEP> U <SEP> 5 <SEP> O <SEP> N <tb> <SEP> U) <SEP> 4 <SEP> w <SEP> H <SEP> ,$ <SEP> ¯ <SEP> X <SEP> O <SEP> =C,) <SEP> U) <SEP> sJ <tb> <SEP> O <SEP> C) <SEP> O <SEP> O <SEP> O <SEP> O <SEP> O <SEP> N <SEP> O <SEP> U <SEP> v <tb> <SEP> < <SEP> N <SEP> < <SEP> < <SEP> N <SEP> v <SEP> = <SEP> N <SEP> = <SEP> N <SEP> % <tb> <SEP> U <SEP> ' <SEP> < <SEP> = <SEP> H <SEP> U <SEP> = <SEP> n <SEP> U <SEP> L <SEP> N <tb> <SEP> b <SEP> U <SEP> n <SEP> > <SEP> U <SEP> U <SEP> t <SEP> r <SEP> U <SEP> oR <tb> <SEP> v <SEP> s <SEP> R <SEP> U <SEP> k <SEP> X <SEP> W <tb> <SEP> O <SEP> ,- <SEP> U <SEP> 0 <SEP> 5 <SEP> U) <SEP> O <SEP> U <SEP> ¯ <SEP> O <SEP> = <SEP> w <tb> <SEP> H <tb> <SEP> E <SEP> O <SEP> U <SEP> Q <tb> <SEP> X <SEP> z <SEP> < <SEP> fS <SEP> (S <SEP> n <tb> <SEP> X <tb> TABLE A (Continued) EMI34.1 <tb> <SEP> Parts <SEP> W <SEP> i <SEP> of <SEP> Milling <tb> 'Xamp1e <SEP> By <SEP> 1 <SEP> 2 <SEP> 3 <SEP> 4 <SEP> 5 <SEP> 6 <SEP> 7 <SEP> 8 <SEP> 9 <SEP> 10 <tb> <SEP> C: <SEP> cO <SEP> e <SEP> N <SEP> n <SEP> n <tb> <SEP> -rl <tb> <SEP> 0 <SEP> 0 <tb> <SEP> No <SEP> &commat; <SEP> Ï <SEP> O <SEP> t <SEP> in <tb> <SEP> HS'CH20C <SEP> (Cu2) <SEP> 4COC!!25I! <tb> <SEP> m <SEP> U <SEP> . <SEP> rs <tb> <SEP> or <SEP> Organotin <SEP> Cmpd. <SEP> No. <SEP> o <SEP> from <SEP> Table <SEP> III <SEP> 0.50 <tb> <SEP> 0 <SEP> 0 <tb> <SEP> II <tb> <SEP> n <SEP> &verbar; <SEP> T <SEP> &verbar; <tb> <SEP> O <SEP> O <SEP> 08 <tb> <SEP> 0 <tb> <SEP> c^q <SEP> H <SEP> ' <SEP> + <SEP> 0.20 <tb> <SEP> H <SEP> <SEP> <SEP> of <SEP> egual <SEP> weighL' <SEP> proportions <SEP> of <tb> <SEP> ¯ <SEP> Cmpd. <SEP> No. <SEP> L <SEP> < <SEP> Table <SEP> H <SEP> an <SEP> 0.30 <tb> <SEP> tq <SEP> < <SEP> . <SEP> n <tb> <SEP> 4 <SEP> 10+ <SEP> O <SEP> 9 <SEP> 8 <SEP> 7 <SEP> 5 <SEP> o <SEP> o <SEP> m <SEP> n <tb> <SEP> k <SEP> m <SEP> m <SEP> oo <tb> <SEP> < <SEP> > &commat; <SEP> .- <SEP> 0.03 <tb> <SEP> z <SEP> m <SEP> 3 <SEP> o <SEP> o <SEP> o <SEP> o <SEP> o <SEP> o <SEP> o <SEP> o <SEP> o <tb> <SEP> SnC14 <SEP> 0.003 <SEP> C <tb> <SEP> C <tb> <SEP> Q <SEP> 0 <tb> <SEP> as <SEP> Q) <SEP> o <tb> <SEP> H <SEP> < <SEP> F <SEP> &commat; <SEP> O <tb> <SEP> Q <SEP> Q <SEP> Q <SEP> 4 <SEP> < <SEP> H <tb> <SEP> U <SEP> < <SEP> R <SEP> Q <SEP> .Q <tb> <SEP> = <SEP> B <SEP> B <SEP> XPs <tb> <SEP> 3 <SEP> c <SEP> E <SEP> t <SEP> O <SEP> <tb> <SEP> ,1 <SEP> qq <SEP> w <SEP> rs <SEP> m <SEP> R <tb> <SEP> to <SEP> z <SEP> X <SEP> W <SEP> W <tb> <SEP> O <SEP> v: > <SEP> o <SEP> U <SEP> H <tb> <SEP> z <SEP> - <SEP> z <SEP> o¯u <SEP> z <SEP> z <SEP> <tb> <SEP> {-1 <SEP> U <SEP> er <SEP> < <SEP> = <tb> <SEP> N <SEP> -O <SEP> 0¯0 <SEP> r <SEP> N <SEP> n <SEP> : <SEP> t <SEP> U <tb> <SEP> . <SEP> Qt <SEP> v <SEP> ffi <SEP> 3: <SEP> <SEP> U <SEP> z <SEP> ffi <SEP> O=V <tb> <SEP> .i <SEP> ¯ <SEP> ¯ <SEP> N <SEP> E <SEP> U <SEP> u <SEP> &commat; <SEP> E <SEP> E <SEP> o <tb> <SEP> ,1 <SEP> U <SEP> rs <SEP> . <SEP> U <SEP> ¯ <SEP> < <SEP> U <SEP> U <SEP> N <tb> <SEP> n <SEP> .¯ <SEP> U <SEP> o <SEP> =O <SEP> tn <SEP> eq <SEP> w <tb> <SEP> U <SEP> < <SEP> U <SEP> U <SEP> o <SEP> o <SEP> w <SEP> o <SEP> A <SEP> < <SEP> U <tb> <SEP> : <SEP> ,{ <SEP> tn <SEP> d <SEP> c9 <SEP> U <SEP> ,4 <tb> <SEP> U) <SEP> <SEP> O=U <SEP> N <SEP> 4 <SEP> N <SEP> ) <SEP> X <SEP> U <SEP> : <tb> <SEP> O <SEP> -O <SEP> O <SEP> U <SEP> z <SEP> o4 <SEP> 0 <SEP> 0 <SEP> t) <tb> <SEP> a <SEP> < <SEP> N <SEP> 0 <SEP> t <SEP> D <tb> <SEP> e <SEP> = <SEP> =. <SEP> U <SEP> x <SEP> n <SEP> <SEP> U <tb> <SEP> ex <SEP> U <SEP> v <SEP> D} <SEP> X <SEP> > <SEP> > <SEP> U <SEP> U <tb> <SEP> 54 <SEP> tn <SEP> U <SEP> R <SEP> U) <SEP> U <SEP> ,{ <tb> <SEP> O <SEP> n <SEP> ¯ <SEP> O <SEP> ; <SEP> ¯ <SEP> E:00 <SEP> :o <SEP> tq <tb> <SEP> n. <SEP> v <SEP> Q <SEP> U} <tb> <SEP> U <SEP> O <tb> TABLE A (Continued) EMI35.1 <tb> <SEP> o <tb> <SEP> Parts <SEP> Minutes <SEP> of <SEP> Milling <tb> Fxample <SEP> By <SEP> 1 <SEP> 2 <SEP> 3 <SEP> 4 <SEP> 5 <SEP> 6 <SEP> 7 <SEP> '8 <SEP> 9 <SEP> 10 <tb> <SEP> H <SEP> > <SEP> . <SEP> n <SEP> v <SEP> sr <tb> <SEP> m <SEP> r <tb> <SEP> Sb <SEP> ' <SEP> Mixture <SEP> of <SEP> equal <SEP> weIjht <SEP> z <SEP> of <tb> <SEP> c <SEP> Cmpd <SEP> No.1 <SEP> from <SEP> Table <SEP> I <SEP> m <tb> <SEP> Organotin <SEP> Cmpd <SEP> No.11 <SEP> from <SEP> Table <SEP> UN <tb> <SEP> 0 <tb> <SEP> ut <SEP> o <tb> <SEP> m <SEP> 10 <SEP> 9 <SEP> co <SEP> 5 <SEP> 3 <SEP> 2 <SEP> 1 <SEP> 0 <tb> <SEP> D <SEP> I'117 <SEP> 0.03 <tb> <SEP> (CH3) <SEP> 25nC12 <SEP> 0.10 <tb> <SEP> m <SEP> o <SEP> o <SEP> o <tb> <SEP> H <SEP> l <SEP> H <SEP> S <SEP> H <tb> <SEP> Sc <SEP> Mixture <SEP> of <SEP> l <SEP> + <SEP> +s <tb> <SEP> rs <SEP> o <SEP> o <SEP> &commat;.* <SEP> o <SEP> o <SEP> o <tb> <SEP> rl <SEP> Cinpd <SEP> rl. <SEP> Hv <SEP> H <tb> <SEP> 1- <SEP> <tb> <SEP> o <SEP> o <SEP> 17 <SEP> 0.10 <tb> <SEP> (C3)2Snnr2 <SEP> < <tb> <SEP> o <SEP> oo <SEP> O <SEP> 0 <SEP> 0 <SEP> 0 <tb> <SEP> F1 <SEP> .rl <SEP> m <SEP> o <SEP> rl <SEP> m <SEP> r( <SEP> o <SEP> u <SEP> N <SEP> O <tb> <SEP> 6 <SEP> o <SEP> o <SEP> o <SEP> o <SEP> o <SEP> o <SEP> of <SEP> equal <SEP> wel(,;hL <SEP> proportions <SEP> of <tb> <SEP> -- <SEP> Cmpd <SEP> No.19 <SEP> from <SEP> Table <SEP> III <SEP> 0.20 <tb> <SEP> and <SEP> 0rganoLin <SEP> Cmpd <SEP> No. <SEP> 5: <SEP> D) <SEP> H <tb> <SEP> O <SEP> U <SEP> H <SEP> < <SEP> 12 <SEP> 8 <SEP> H <SEP> OH <tb> <SEP> H <SEP> rl <SEP> H <tb> <SEP> 1 <SEP> H <SEP> d <SEP> H <SEP> H <SEP> H <tb> <SEP> JJ <SEP> Q) <SEP> Q <SEP> O <SEP> 4 <SEP> O <SEP> Q <tb> <SEP> k <SEP> 01 <SEP> k <SEP> O' <SEP> krl <SEP> rJ. <tb> <SEP> 0 <SEP> rl <SEP> a <SEP> O <SEP> n <SEP> E-1 <tb> <SEP> (C113) <SEP> n, <SEP> Q <SEP> rb <SEP> Q <SEP> Q <SEP> U <SEP> Q <SEP> 0.01 <tb> <SEP> 0 <SEP> 0 <SEP> rJ <SEP> E <SEP> OE <SEP> s <tb> <SEP> a <SEP> E <SEP> a <SEP> E <SEP> aE. <tb> <SEP> 4S <SEP> SL <SEP> F <SEP> Ï <SEP> E <SEP> O <SEP> O <SEP> X <tb> <SEP> U) <SEP> a) <SEP> O <SEP> St <SEP> s <SEP> O <SEP> R <SEP> X <SEP> t¯ <SEP> N <tb> <SEP> O <SEP> z <SEP> SW <SEP> o <SEP> RN <SEP> oW <SEP> <tb> <SEP> & <SEP> mN <SEP> W <SEP> ¯ <tb> <SEP> o <SEP> a) <SEP> 1 <SEP> OSH <SEP> Ow <tb> <SEP> V <SEP> 3 <SEP> > <SEP> 3 <SEP> . <SEP> . <SEP> 3 <SEP> ^ <tb> <SEP> O <SEP> O <SEP> H <SEP> O <SEP> o <SEP> O <SEP> z <tb> <SEP> S <SEP> < <SEP> Z <SEP> Z <SEP> v <SEP> H <SEP> Z <SEP> Z <SEP> < <SEP> Z <SEP> c:; <tb> <SEP> O <SEP> U <SEP> = <SEP> U <SEP> U <SEP> U <tb> <SEP> N <SEP> D <SEP> XS <SEP> t <SEP> V <SEP> n <SEP> S:5 <SEP> t <SEP> D <SEP> r <tb> <SEP> ,l <SEP> a <SEP> Q <SEP> P <SEP> 0U <SEP> a <SEP> Qa <SEP> m <SEP> r <SEP> z <SEP> < <SEP> m <SEP> m <tb> <SEP> r1 <SEP> a) <SEP> E <SEP> E <SEP> o <SEP> O <SEP> E <SEP> E <SEP> > <SEP> U <tb> <SEP> -,{ <SEP> U <SEP> U <SEP> CS <SEP> cS <SEP> V <SEP> U <SEP> H <SEP> fS <SEP> U <SEP> $ <SEP> Ú <SEP> sr <tb> <SEP> Q <SEP> W <SEP> 5: <SEP> H <SEP> W <SEP> = <SEP> z <SEP> t4 <SEP> 0 <SEP> O=V <SEP> CJ <tb> <SEP> nJ <SEP> O <SEP> < <SEP> :: <SEP> U <SEP> O <SEP> O <SEP> r <SEP> n <SEP> O <SEP> < <SEP> C <SEP> O <SEP> O <tb> <SEP> U) <SEP> G <SEP> $ <SEP> s <SEP> X <SEP> U) <SEP> Q) <SEP> Q <SEP> 2 <SEP> O <SEP> u) <SEP> Q) <SEP> X <SEP> tn <SEP> ¯ <SEP> U)U <tb> <SEP> 54 <SEP> 0 <SEP> 0 <SEP> U <SEP> N <SEP> R <SEP> O <SEP> O <SEP> O=V <SEP> N <SEP> k <SEP> O <SEP> v <SEP> V <SEP> N <tb> <SEP> 2 <SEP> = <SEP> t: <SEP> N <SEP> 2 <SEP> r <SEP> o <SEP> rs <SEP> <tb> <SEP> 4M <SEP> n <SEP> 4 <SEP> U <SEP> U <SEP> ^ <SEP> n <SEP> X <SEP> U <SEP> w <SEP> m <tb> <SEP> X <SEP> r <SEP> r <SEP> U <SEP> e <SEP> X <SEP> b <SEP> r <SEP> U <SEP> w <SEP> X <SEP> me <SEP> U <SEP> ¯ <tb> <SEP> ,l <SEP> tn <SEP> U <SEP> ,{ <SEP> k <SEP> R <SEP> W <SEP> U <SEP> d <tb> <SEP> E:00 <SEP> :2: <SEP> - <SEP> 200 <SEP> v <SEP> ¯ <SEP> E:0 <SEP> U <SEP> b <SEP> ¯ <tb> <SEP> O <tb> <SEP> H <tb> <SEP> Qa <SEP> . <SEP> Q <SEP> t) <SEP> W <tb> <SEP> U <SEP> O <SEP> Ln <SEP> ur <tb> <SEP> X <SEP> Z <tb> EXAMPLES 7-26 The stabilizer compositions indicated in Table B below are tested in the same manner and with substantially equivalent results as the stabilizer compositions of Examples 1-6. TABLE B EMI37.1 <tb> <SEP> Parts <tb> Example <SEP> By <tb> <SEP> No. <SEP> Stabilizer <SEP> Composition <SEP> height <tb> <SEP> 7 <SEP> Organotin <SEP> Cmpd <SEP> No.5 <SEP> from <SEP> Table <SEP> I <SEP> 0.40 <tb> <SEP> 0 <tb> <SEP> HsCH2CH2COC8 <SEP> 17 <SEP> 0.15. <tb> <SEP> C}33SnBr3 <SEP> 0.05 <SEP> CH3SnBr3 <tb> <SEP> 8 <SEP> Organotin <SEP> Cmpd <SEP> No.9 <SEP> from <SEP> Table <SEP> II <SEP> 0.40 <tb> <SEP> 0 <tb> <SEP> HSCH2CH2 <SEP> 0CC17R33 <SEP> 0.20 <tb> <SEP> C8H17SnC13, <SEP> 0.05 <tb> <SEP> 9 <SEP> Organotin <SEP> Cmpd <SEP> No.9 <SEP> from <SEP> Table <SEP> II <SEP> 0.40 <tb> <SEP> 0 <SEP> 0 <tb> <SEP> 'I <tb> <SEP> (HSCH <SEP> CH <SEP> OCCH <SEP> ' <SEP> C-COCH <SEP> CH <SEP> SS <SEP> 0.40 <tb> <SEP> OH <tb> <SEP> (C8R17) <SEP> 3S,nCl <SEP> 0.05 <tb> <SEP> 10 <SEP> Organotin <SEP> Cmpd <SEP> No.l2 <SEP> from <SEP> Table <SEP> III <SEP> 0.35 <tb> <SEP> 0 <tb> <SEP> II <tb> <SEP> H5CH2C-20CCl7B35 <SEP> 0.10 <tb> <SEP> (9CH2 <SEP> ,2SnC12 <SEP> 0.10 <tb> <SEP> . <SEP> ¯ <SEP> ¯ <tb> <SEP> ila <SEP> Organotin <SEP> Cinpd <SEP> No.18 <SEP> from <SEP> Table <SEP> III <tb> <SEP> 0 <tb> <SEP> -HSCHCHOCC8-il7 <SEP> 0.60 <tb> <SEP> 21 <SEP> 8'17 <tb> <SEP> CH3 <tb> <SEP> (C12R25)2 <SEP> SnBr2 <SEP> 0.10 <tb> TABLE B (Continued) EMI38.1 <tb> <SEP> Parts <tb> Example <SEP> By <tb> <SEP> No. <SEP> Stabilizer <SEP> Composition <SEP> Weight <tb> <SEP> llb <SEP> Organotin <SEP> Cmpd <SEP> No.18 <SEP> from <SEP> Table <SEP> III <SEP> 0.40 <tb> <SEP> 0 <tb> <SEP> ti <tb> <SEP> HSCH2CIHOCC8Hl7 <SEP> 0.60 <tb> <SEP> CR3 <tb> <SEP> 0 <tb> <SEP> rf <tb> <SEP> (CdH,OCCHZCH2 <SEP> 2SnC1 <SEP> 0.005- <SEP> 1 <tb> <SEP> HSCH2CH20CCH=CHCOCH2CH2SH <SEP> 0.1.0 <tb> <SEP> (ROCR2CR2CH2) <SEP> 2SnCl,2 <SEP> 0.10 <tb> <SEP> lld <SEP> Organotin <SEP> Cmpd <SEP> No.18 <SEP> from <SEP> Table <SEP> III <SEP> 0.40 <tb> <SEP> It <tb> <SEP> HSCH2CH20CCP,=CHCOCH2CH2SR <SEP> 0.10 <tb> <SEP> (NCCH2CR2) <SEP> 25nC12 <SEP> 0.10 <tb> <SEP> 12 <SEP> Mixture <SEP> of <SEP> equal <SEP> weight <SEP> proportions <SEP> of <tb> <SEP> Organotin <SEP> Cmpd <SEP> No.l <SEP> from <SEP> Table <SEP> I <SEP> and <tb> <SEP> Organotin <SEP> Cis.pd <SEP> No.11 <SEP> from <SEP> Table <SEP> II <SEP> 0.30 <tb> <SEP> 0 <tb> <SEP> II <tb> <SEP> HSCH2CH20CCH3 <SEP> o.o's <tb> <SEP> CH3SnCl3 <SEP> 0.10 <tb> <SEP> 13a <SEP> Mixture <SEP> of <SEP> equal <SEP> weight <SEP> proportions <SEP> of <tb> <SEP> Organotin <SEP> Cmpd <SEP> No.19 <SEP> from <SEP> Table <SEP> IlIand <tb> <SEP> Organotin <SEP> Cmpd <SEP> No.2 <SEP> from <SEP> Table <SEP> I <SEP> 0.20 <tb> <SEP> 0 <tb> <SEP> II <tb> <SEP> HSCH2C,,H2OCCH3 <SEP> 0.20 <tb> <SEP> ( <SEP> t <SEP> ,2SnCl2 <SEP> 0.005 <tb> TABLE B (Continued) EMI39.1 <tb> <SEP> Parts <tb> <SEP> Exampl <SEP> . <SEP> By <tb> <SEP> N9. <SEP> Stabilizer <SEP> Composition <SEP> Weight <tb> <SEP> 13b <SEP> Mixture <SEP> of <SEP> equal <SEP> weight <SEP> proportions <SEP> of <tb> <SEP> Organotin <SEP> Cmpd <SEP> No.l9 <SEP> from <SEP> Table <SEP> Ill <SEP> and <tb> <SEP> Organotin <SEP> Cmpd <SEP> No.2 <SEP> from <SEP> Table <SEP> I <SEP> ' <SEP> 0.20 <tb> <SEP> O <tb> <SEP> ii <tb> <SEP> HSCH2CH20CCH3 <SEP> 0.20 <tb> <SEP> SnCl4 <SEP> 0.20 <tb> <SEP> 13c <SEP> Mixture <SEP> of <SEP> equal <SEP> weight <SEP> proportions <SEP> of <tb> <SEP> Organotin <SEP> Cmpd <SEP> No.19 <SEP> from <SEP> Table <SEP> IlIand <tb> <SEP> Organotin <SEP> Cmpd <SEP> No. <SEP> 2 <SEP> from <SEP> Table <SEP> I <SEP> 0.20 <tb> <SEP> 0 <tb> <SEP> II <tb> <SEP> HSCH2CH2OCCH3 <SEP> 0.20 <tb> <SEP> . <SEP> (CH3)2lnOC4H9 <SEP> 0.01 <tb> <SEP> Cl <tb> <SEP> 13d <SEP> Mixture <SEP> of <SEP> equal <SEP> weight <SEP> proportions <SEP> of <tb> <SEP> Organotin <SEP> Cmpd <SEP> No.19 <SEP> from <SEP> Table <SEP> Island <tb> <SEP> Organotin <SEP> Cmpd <SEP> No. <SEP> 2 <SEP> from <SEP> Table <SEP> I <SEP> 0.20 <tb> <SEP> . <SEP> 104 <tb> <SEP> I' <tb> <SEP> RSCR2CH2OCCR'30 <SEP> 0.20 <tb> <SEP> CH3Sn(SCH2CR2OCC11R23)2 <SEP> 0.05 <tb> <SEP> 3I <SEP> L <tb> <SEP> C <tb> <SEP> 13e <SEP> Mixture <SEP> of <SEP> equal <SEP> weight <SEP> proportions <SEP> of <tb> <SEP> Organotin <SEP> Cmpd <SEP> No. <SEP> 19 <SEP> from <SEP> Table <SEP> III <SEP> an" <tb> Organotin <SEP> Cmpd <SEP> No. <SEP> 2 <SEP> from <SEP> Table <SEP> I <SEP> 0.20 <tb> <SEP> HSCH2CH2OH <SEP> 0.20 <tb> <SEP> CH3S1n <SEP> (SCH2C11OC8R17) <SEP> 2 <SEP> 0;08 <tb> <SEP> Cl <tb> TABLE B (Continued) EMI40.1 <tb> <SEP> Parts <tb> <SEP> Example <SEP> : <SEP> Parts <tb> <SEP> No. <SEP> Stabilizer <SEP> Cornposition <SEP> Weight <tb> <SEP> 13f <SEP> Mixture <SEP> of <SEP> equal <SEP> weight <SEP> proportions <SEP> of <tb> <SEP> Organotin <SEP> Cmpd <SEP> No.19 <SEP> from <SEP> Table <SEP> IIIand <tb> <SEP> Organotin <SEP> Cmpd <SEP> No.2 <SEP> from <SEP> Table <SEP> I <SEP> ' <SEP> 0.20 <tb> <SEP> HSCH2COOH <SEP> 0.10 <tb> <SEP> 0 <tb> <SEP> CR3S1n <SEP> (SCH2COC8H,17)2 <SEP> 0.08 <tb> <SEP> Cl <tb> <SEP> 13g <SEP> Mixture <SEP> of <SEP> equal <SEP> weight <SEP> proportions <SEP> of, <tb> Organotin <SEP> Cmpd <SEP> No.19 <SEP> from <SEP> Table' <SEP> Ill <SEP> and, <tb> <SEP> Organotin <SEP> Cmpd <SEP> No. <SEP> 2 <SEP> from <SEP> Table <SEP> I <SEP> 0.20 <tb> <SEP> 0 <tb> <SEP> HSCH2CH2OCCH3 <SEP> ' <SEP> 0.20 <tb> <SEP> 9 <tb> <SEP> Cl2Sn <SEP> (0CC17H33) <SEP> 2 <SEP> 0.10 <tb> <SEP> 14 <SEP> Organotin <SEP> Cmpd <SEP> No. <SEP> 20 <SEP> from <SEP> Table <SEP> III <SEP> 0.25 <tb> <SEP> 0 <SEP> 0 <tb> <SEP> II <tb> <SEP> ESCH2CoCE(CEOCCH2SH)2 <SEP> 0.10 <tb> <SEP> CH3SnCl3 <SEP> 0.02 <tb> <SEP> ¯ <SEP> . <tb> <SEP> 15 <SEP> Mixture <SEP> of <SEP> equal <SEP> weight <SEP> proportions <SEP> of <tb> <SEP> Org=notin <SEP> Cmpd <SEP> No.6 <SEP> from <SEP> Table <SEP> I <SEP> and <tb> <SEP> Organotin <SEP> Cmpd <SEP> No.11 <SEP> from <SEP> Table <SEP> II <SEP> 0.30 <tb> <SEP> 0 <tb> <SEP> HSCE2CH2OCCl7B33 <SEP> 0.17 <tb> <SEP> H <SEP> 3 <tb> <SEP> C8 <SEP> 3 <SEP> O <SEP> 3 <SEP> 0.05 <tb> <SEP> 16 <SEP> 1:2 <SEP> weight <SEP> ratio <SEP> mixture <SEP> of <SEP> Organotin <tb> <SEP> ,Cmpd <SEP> No. <SEP> 7 <SEP> from <SEP> Table <SEP> I <SEP> and <SEP> Organotin <tb> <SEP> Cmpd <SEP> Indo. <SEP> 19 <SEP> from <SEP> Table <SEP> III <SEP> 0.40 <tb> <SEP> 0 <tb> <SEP> H <SEP> 0.10 <tb> <SEP> HSCH <SEP> COC8H, <SEP> 0.l0 <tb> <SEP> (CH3) <SEP> 2SnC12 <SEP> 0.04 <tb> TABLE B (Continued) EMI41.1 <SEP> <tb> <SEP> Parts <tb> Example <SEP> By <tb> <SEP> No. <SEP> Stabilizer <SEP> Composition <SEP> Weight <tb> <SEP> 17 <SEP> Organotin <SEP> Cmpd <SEP> No. <SEP> 21 <SEP> from <SEP> Table <SEP> III <SEP> 0.30 <tb> <SEP> 0 <tb> <SEP> HSCH2CH2OCCl7E33 <SEP> 0.-08 <tb> <SEP> CH3SnCl3 <SEP> ¯ <SEP> ¯ <SEP> 0.03 <tb> <SEP> 18 <SEP> Organotin <SEP> Cmpd <SEP> No. <SEP> 18 <SEP> from <SEP> Table <SEP> III <SEP> 0.40 <tb> <SEP> 0 <SEP> 0 <tb> <SEP> ti <SEP> It <tb> <SEP> ESCH2CH2OCCH=CHCOCH2CH2SH <SEP> .- <SEP> 0.10 <tb> <SEP> 19 <SEP> ' <SEP> Organotin <SEP> Cmpd <SEP> No. <SEP> 18 <SEP> from <SEP> Table <SEP> III <SEP> - <SEP> : <SEP> 0.40 <tb> <SEP> 0 <tb> <SEP> If <tb> <SEP> RSCH2C1HOCC8H17. <SEP> 0.60 <tb> <SEP> CH3 <tb> <SEP> 20 <SEP> Organotin <SEP> cmpd. <SEP> No. <SEP> 7a <SEP> from <SEP> Table <SEP> Ia <SEP> 0.325 <tb> <SEP> RSC <SEP> C12H25 <SEP> H <SEP> 0.075 <tb> <SEP> 12 <SEP> 25 <tb> <SEP> CH,3SnCl3 <SEP> . <SEP> 0.025 <tb> <SEP> 3 <tb> <SEP> 21 <SEP> Organotin <SEP> cmpd. <SEP> No. <SEP> 7d <SEP> from <SEP> 'Table <SEP> la <SEP> : <SEP> 0.45 <tb> I <SEP> HSCK' <SEP> 0.10 <tb> <SEP> SnC14 <SEP> 0.01 <tb> <SEP> 22 <SEP> Organotin <SEP> cmpd. <SEP> No. <SEP> 8 <SEP> from <SEP> Table <SEP> II <SEP> 0.275 <tb> <SEP> 0 <tb> <SEP> n <tb> <SEP> HSCH2CH2OCCH2SH <SEP> 0.10 <tb> <SEP> (cur3) <SEP> 2SnCl2 <SEP> . <SEP> 0.05 <tb> TABLE B (Continued) EMI42.1 <tb> <SEP> C <SEP> s <SEP> s <tb> <SEP> Parts <tb> Example <SEP> . <SEP> By <tb> <SEP> No. <SEP> Stabilizer <SEP> Composition <SEP> Weight <tb> <SEP> 23 <SEP> Organotin <SEP> cmpd. <SEP> No. <SEP> 18 <SEP> from <SEP> Table <SEP> III <SEP> 0.225 <tb> <SEP> 0 <tb> <SEP> II <tb> <SEP> HSCH2CH2OCCHSB <SEP> 0.125 <tb> <SEP> OH <tb> <SEP> 24 <SEP> Organotin <SEP> cmpd. <SEP> No. <SEP> 7h <SEP> from <SEP> Table <SEP> -Ia <SEP> 0.15 <tb> <SEP> S <SEP> S <tb> <SEP> C8El7 <SEP> Sn¯S¯Sn <SEP> C8Hl7 <SEP> 0.lS0.15 <tb> <SEP> 0 <tb> <SEP> II <tb> <SEP> HSCH2C0C,8H17 <SEP> 0.10 <tb> <SEP> 'C4H9SnC13 <SEP> 0.03 <tb> <SEP> 25 <SEP> Organotin <SEP> cmpd. <SEP> No. <SEP> 7i <SEP> from <SEP> Table <SEP> Ia <SEP> 0.15 <tb> <SEP> organotin <SEP> cmpd. <SEP> No. <SEP> 11 <SEP> from <SEP> Table <SEP> II <SEP> 0.20 <tb> <SEP> 0 <tb> <SEP> II <tb> <SEP> HSCH2CECH20CCH2 <SEP> SH <SEP> 0.15 <tb> <SEP> OoCH3 <tb> <SEP> 0 <tb> <SEP> 0 <tb> <SEP> II <tb> <SEP> (R'9C4OCCH2CR2)2SnCl2 <SEP> 0.05 <tb> <SEP> 26 <SEP> Organotin <SEP> cmpd. <SEP> No. <SEP> 7e <SEP> rom <SEP> Table <SEP> Ia <SEP> 0.25 <SEP> 1 <tb> <SEP> 0 <tb> <SEP> 1 <tb> <SEP> C4Hg¯sn4SCH2CH2OCCl7H33)2 <SEP> 0.20 <tb> <SEP> Cl <tb> <SEP> 0 <tb> <SEP> HSCR2CH2OCCH2SH <SEP> 0.20 <tb>

Claims: CLAIMS 1. A composition for stabilizing halogen-containing polymers against the deteriorative effects of heat characterised in that it comprises: (A) 40% to 90% of an organotin compound or mixture of organotin compounds having one or more tetravalent tin atoms which each have at least one direct tin to carbon bond selected from compounds having the general formulae: : EMI43.1 EMI44.1 EMI44.2 and EMI44.3 wherein and X' are the same or different and are selected from -Sr2, Cl, Br, I, EMI44.4 and 0-R8 with the proviso that-in formula (II) when t = 1, in formula (V) when x = 1 and in formulae (III) and (IV) at least one X or X1 is -SR2; EMI44.5 EMI45.1 W and W1 are the same or different and are oxygen or sulfur; R and R1 are the same or different and are selected from alkyl, aryl, alkenyl, aralkyl, alkaryl, cycloalkyl, cycloalkenyl, EMI45.2 -R9-0-R12, and -R9-CN; R is alkyl, alkenyl, aryl, aralkyl, cycloalkyl, cycloalkenyl, EMI45.3 EMI45.4 or R3-o-R8; R3 is alkylene of at least 2 carbon atoms, arylene, alkenylene of at least 2 carbon atoms, cycloalkylene, or cycloalkenylene; ; 'R4 is alkylene, arylene, alkenylene of at least 2 carbon atoms cycloalkylene, or cycloalkenylene; R5 is R3; R6 is a carbon to carbon single bond or R4; R7 is -H or R8; R8 is alkyl, alkenyl, aryl, aralkyl, alkaryl, cycloalkyl, or cycloalkenyl; R9 is C1 to C4 alkylene; R12 is -H or a monovalent C1 to C20 hydrocarbon radical R13 and R21 are the same or different and are each C1 to C20 alkyl or C1 to C20 alkoxy; R24 is EMI46.1 -OH, -SH, aryl, C1 to C18 alkyl or -H; R16 is -H or R8; i = 0 or an integer from 1 to 6 inclusive; m = 1 or 2 and t = 0 or 1 with the proviso that m + t = 2; n = 0, 1 or 2, n' = 0, 1 or 2 and p = 1 or 2 with the proviso that n. + n' = 1 or 2 and n + n' + p = 3; a = 0, 1 or 2, b = 0, 1 or 2, q = an integer from 1 to 5 inclusive; c = 1, 2 or 3 and d = 0, 1 or 2 with the proviso that a + b = 2 and c + d = 3; v = an integer from 1 to 8 inclusive; and w = 0, 1 or 2, x = 0 or 1, y = 1 or 2, z = 0 or 1 with the proviso that when x = 0 and w = 1 or 2 then y = 1 and z = 1, when x = 1 then y = 1, z = 0 and w = 1, when w = 2 then z = O,y = 1 and z = 1 gnd when w = 0 then x = 0, y = 1, z = 1 and Y is -W-R3-W1- or EMI46.2 (B) 10% to 60% of a mercaptan-containing organic compound or mixture of mercaptan-containing organic compounds having the general formula selected from: : EMI46.3 EMI47.1 EMI47.2 and EMI47.3 where (XIa) EMI47.4 where R10 is cycloalkyl, cycloalkenyl or phenyl; R14 is H, aryl or C1 to C18 alkyl R24 is as previously defined; R15 is EMI47.5 -OH, -SH, aryl, C1 to C18 alkyl, or H; R16 is as previously defined; R17 is EMI47.6 EMI47.7 or R18 is arylene, C1 to C8 alkylene, or EMI48.1 R19 is -H or a divalent group which may contain halogen, hydroxy, mercapto or alkyl substituents and which combines with R10 when R10 is phenyl to form a naphthalene ring; R20 is -CH3, -CH2CH3, or EMI49.1 R23 ;s EMI49.2 -SH, aryl, C1 to C18 alkyl, -OR or -H; with the proviso that in formula (VII) when R@@ is phenyl, R23 is -OH and i = 0, then the -OH and -SR groups are on non-adjacent carbon atoms; R200 and R21 are the same or different and are alkylene, alkenylene, arylene, cycloalkylene or cycloalkenylene; or alkylene, alkenylene, arylene, cycloalkylene or cycloalkenylene each substituted with one or two -R, -OR7, EMI49.3 groups; R, R4, R7 and R8 are as previously defined; i is as previously defined; j = 0, l, 2 or 3; and f l or 2; and (C.) Up to 33% of a halogen-containing tin compound or mixture of halogen-containing tin compounds wherein the tin atom is tetravalent and has at least one halogen atom bonded directly to it, said halogen-containing tin compound or compounds being selected from -compounds having the general formula: 9 (XII) EMI50.1 where Q is Cl, Br, or I; R11 and R22 are the same or different and are selected from -R, -R1, EMI50.2 EMI50.3 where R, R1, R8, R9, R12, R13 and H21 are as previously defined; and g = 0, 1, 2 or 3, r = 0, 1, 2, or 3 and h = 1, 2, 3 or 4 with the proviso that g + r + h = 4. all percentages being by weight based on the total weight of the stabilizer composition, with the proviso that when the weight percent of the halogen-containing tin compound is 0 then at least one of the organotin compounds of Component A is selected from compounds having the general formulae (II), (III), (IV) and (V) wherein at least one X or X1 is Cl, Br or I. 2. A composition as claimed in claim 1 further characterised in that in general formula (I) R is methyl, butyl or octyl and W is sulfur. 3. A composition as claimed in claim 1 further characterised in that in general formula (II) R1 is methyl or butyl, W is sulfur, X is -SR2 where R2 is EMI51.1 m = 1 and t = 1. 4. A composition as claimed in claim 1 further characterised in that in general formula (IIa) R and R1 are methyl, butyl, octyl or EMI51.2 W and W1 are oxygen or sulfur; and Z is EMI51.3 5. A composition as claimed in claim 1 further characterised in that in general formula (III) R is methyl or butyl, R1 is methyl or butyl, X is -SR2 where R2 is EMI51.4 X1 is SR2 where R2 is EMI51.5 n = O or 1, n' = O or 1, n + n = 1 and p = 2. 6. A composition as claimed in claim 1 further characterised in that in general formula (IV) R is methyl, X is -SR2 where R2 is EMI51.6 R1 is methyl, X1 is -SR2 where R2 is EMI51.7 Y is -S-, a = O, b = 2, c = 1, d = 2 and q = 1. 7. A composition as claimed in claim 1 further characterised in that in general formula (V) R is methyl, R1 is methyl, Y is -S-, w = 1, x = 1, y = 1 and z = 0. 8. A composition as claimed in claim 1 further characterised in that in general formula (VI) R14 is -H, R24 is -H, R15 EMI52.1 and i = 1. 9. A composition as claimed in claim 1 further characterised in that in general formula (VII) R10 is phenyl, R14 is -H, R23 is -H, R19 is -H, i = 1 and j = 1. 10. A composition as claimed in claim 1 further characterised in that in general formula (VIII) R14 is -H, R17 EMI52.2 and i = 1. 11. A composition as claimed in claim 1 further characterised in that in general formula (IX) R14 is -H and i = 1. 12. A composition as claimed in claim 1 'further characterised in that in general formula (X) R20 is -C2H5 or EMI52.3 R14 is -H and i = 1. 13. A composition as claimed in claim 1 further characterised in that in general formula (XI) R14 is -H and i = 1. 14. A composition as claimed in claim 1 further characterised in that in general formula (XIa) R200 is -CF CH2 or CH2CH-, C9H19 EMI52.4 -CH-, OH 15. A composition as claimed in any one of claims 2 to 7 further characterised in that the mercaptan-containing organic compound or mixture of mercaptan-containing organic compounds is according to general formula (VI). 16. A composition as claimed in claim 15 further characterised in that in general formula (VI) R14 is -H, R24 is -H, R15 is EMI52.5 and i = 1. 17. A composition as claimed in any one of the preceding claims further characterised in that the weight percent of halogen-containing tin compound (C) -is 0. 18. A composition as claimed in any one of claims 1-16 further characterised in that the weight percent of halogen-containing tin compound or mixture of halogen containing tin compounds according to formula (XII) is 0.1% to 15%. 19. A composition as claimed in claim 18 further characterised in that in formula (XII) R11 is methyl, R22 is -Cl, Q is Cl, g = 1, h = 2 and r = 1. 20. A composition as claimed in any one of claims 17-19 further characterised in that the mercaptan-containing organic compound or mixture of mercaptan-containing organic compounds (B) is according to general formula (VI). 21. A polymer composition stabilized against the deteriorative effects of heat comprising a halogen-containing organic polymer and characterised in that it contains a stabilizing amount of the composition claimed in any of claims 1 to 20. 22. A process for stabilizing a halogen-cDntaining organic polymer against the deteriorative effects of heat characterised in that it comprises admixing said polymer with a stabilizing amount of the composition claimed in any one of claims 1 to 20. 23. A shaped article of manufacture such as a pipe comprising a halogen-containing organic polymer and characterised in that it contains a stabilizing amount of the composition according to any one of claims 1 to 20. 24. A composition as claimed in any of claims 1 to 20 further characterised in that the weight percent of halogen in the stabilizing composition is 0.1% to 10%, preferably 0.5% to 2%, based upon the total weight of the composition.

Inventors: KUGELE, THOMAS G., MESCH, KEITH A., WURSTHORN, KARL R.
Applicants: MORTON THIOKOL, INC.
Application year: 1982
Main classification: C08K5
IPC codes: C08K5