NL8101857A - STABILIZER FOR HALOGENATED RESINS. - Google Patents

Description

- 1 - * A "i

Stabilizer for halogenated resins.

The invention relates to a composition comprising a mixture of a tintetrakis (mercaptide) and a sulfur-containing organotin compound.

It is well known in the industry that halogenated resins tend to degrade when heated in the absence of a heat stabilizer. When the halogenated resin shows such degradation, it normally discolors from white to yellow to orange to red to purple and finally to black. Stabilizers are incorporated into halogenated resins to prevent this discoloration, especially at the initial stage, for example when the resin is extruded or injection molded. Some stabilizers do not allow the halogenated resin to decompose, but do allow discoloration faster than others.

The use of sulfur-containing organotin compounds as heat stabilizers for halogenated resins is well known. U.S. Patent No. 1,115,352 describes the sulfur-containing organotin compounds and their use as stabilizers for halogenated resins. Although the organotin compounds have been recognized as one of the most effective stabilizers for inhibiting the degradation of halogenated resins at the high temperatures that occur during processing, many of these compounds unfortunately do not entirely prevent the early discoloration of the resins. It would therefore have commercial significance to provide substances which can enhance the early color inhibiting effect of these stabilizers.

Tintetrakis (mercaptides) have been proposed as stabilizers for halogen resins, also to protect them from heat degradation during processing of the resin into valuable articles. Older patents, which describe tintetrakis (mereaptides) and their use as stabilizers, 8101857 t * 2 - 2 - (are U.S. Pat. Nos. 2T26.2TT and 2,888. 35. Also pending U.S. Patent Application No. 828703, which filed on August 29, 1979, teaches about the tintrakis (mercaptides) as stabilizers, however, in commercial practice 5, however, the tetrakis (mercaptides) have not been used as stabilizers only, because their activity lags far behind that of the above organotin mercaptides (characterized by at least 1 C Sn bonding In some cases, it has actually been found that the tintetrakis (mercaptides) only catalyze the decomposition of the halogenated resin itself.

With the present invention, the problem of early color syndrome is now overcome as will be further demonstrated.

The present invention relates to a composition comprising a mixture of (a) 99 to 20 wt% sulfur containing organotin compound with a -C-Sn-S group and (b ·) 1 to 80 wt% tetrakis (mercaptide) with four Sn-S bonds. This preparation may contain a third and / or fourth optional component, namely an alkali or alkaline earth salt of a mercaptan or mercaptoic acid and / or an overbased organic complex of an alkali or alkaline earth base. These additional components further improve the stabilizing effect, especially long-term stability.

The sulfur-containing organotin compounds used in the present invention are generally characterized by a sulfur-containing radical or an atom attached to it. tin is bonded via the sulfur atom and a hydrocarbon group or substituted hydrocarbon group which is bonded directly to the tin via a carbon atom, ie compounds with a -C-Sn-S group. The bondings are usually derived from polyvalent tin with at least one valence for bonding to the sulfur atom, while the remaining valence or valencies serve for bonding to a hydrocarbon radical.

35 Organotin compounds, which for use with the 81018 5 7 λ - 3 -

V I

are derived from tetravalent tin. The types of organotin compounds contemplated are those mentioned in U.S. Pat. Nos. 3-764,571, column 3, line 1 through column 5, line 55, 2,641,588, column 1, lines 32-53, and column 2, lines 13-46, 2,641,596, column 1, lines 10-44, 2,726,254, column 1, line 63 to column 2, line 19 »2,789,963, column 2, lines 35-60, 2,914,504, column 1, line 59 to column 4, line 8, 2,870,119, column 1, lines 27-53 and 3,126,400, column 1, lines 21-61. Other patents that give examples of sulfur-containing organotin compounds include U.S. Patents 3,069,447, 3,478,071, 2,998,441, 2,809,956, 3,293,273, 3,396,185, 3,485,794, 2,830,067 and 2,855,417.

Other sulfur-containing sulfur-containing organotin compounds, which are included in the invention, are characterized by the formula 1, wherein the meaning is below and n is an integer from 2 to 1000. These polymers are described in the patent literature, for example, in U.S. Pat. Nos. 3,021,302, column 1, line 60 through column 2, line 17, 3,424,712, column 3, line 34 through column 4, line 2, and 3,424,717, column 3, line 13 to column 4, line 21. For more details, reference is made to these patents and the passages specifically mentioned therefrom. Other tin mercaptide polymeric compounds having the -C-Sn-S bonds characteristic of the sulfur-containing organotin compounds suitable for use in the invention are given, for example, in U.S. Pat. Nos. 2,809,956, 3,293,273, 3,396,185 and 3,485-794.

Preferred organotin stabilizers are of the formula 2, wherein 30 is 1 or 2, RJ represents a hydrocarbon radical of 1-18 carbon atoms, which is an alkyl, cycloalkyl, aryl, mixed alkyl-aryl radical or the like hydrocarbon radical with one of the substituents -CN, -OR ^, - (CO) R2 oi> - ^ 2 ^ 3 * of which 35 R ^ is an alkyl, alkenyl or mixed alkylaryl group with 1-20 carbon- 81 01 857 * ·

V

- u - represents material atoms,

Rg represents a hydrocarbon radical (e.g., alkyl, cycloalkyl, aryl, or mixed alkyl-aryl) with 1-22 carbon atoms, optionally substituted with halogen, -XH, -XR ^, 5- (CXjR ^, -X (CY) R2) or - (CY) XR ^, where R ^ has the above meaning and X and Y independently represent oxygen or sulfur, Z has the meaning 0, S, R ^, -SRg or -SSn (R ^) (SRg) ^, where b is 1 or 2.

10 The nature of R- | in most cases has only a minor impact on the performance of the final product. Examples of group R 1 are methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, lauryl, allyl, benzyl, phenyl, tolyl, naphthyl and cyclohexyl or a substituted hydrocarbon radical such as 2-carbomethoxyethyl, cyanoethyl (of the United States U.S. Pat. No. 3. ^ + 71338 type described), etc.

The group SR ^ of formula 2 can be derived from a. mercaptan or a mercapto alcohol or an ester of a mer-captoalkolhol or mercapto acid. Aliphatic and aromatic mercaptans can be used to form the group SRg. In the case of aliphatic mercaptans, those with 8-18 carbon atoms, for example decyl and dodecyl mercaptan, are usually preferred, because the lower mercaptans are unsuitable for the preparation and use of the stabilizers due to their offensive odor.

Suitable aromatic mercaptans are, for example, thionaphthol, thiobenzyl alcohol, phenoxymethyl mercaptan, phenoxyethoxyethyl mercaptan and others. Examples of suitable mercapto alcohols include monothioethylene glycol, monothiopropylene glycol, thioglycerol, thiodiethylene glycol and others.

The esters of the mercapto alcohols in which the hydroxyl groups are esterified with an aliphatic, aromatic or acyclic saturated or unsaturated monocarboxylic acid are particularly suitable. Readily available mereaptoic acid esters are the esters of thioglycolic acid, such as ethyl thioglycolate, isooctyl thioglycolate 35, and generally the esters of monobasic and dibasic aliphatic 81 018 & 7 * * - 5 - and aromatic mercapto acids as esters of g-thiopropic acid, thiobolic acid, thiobolic acid, .

Of course, the present invention does not relate to organomercaptides, organotin mercapto acids, organotin mercapto acid esters, etc. as such, and the said patents and the passages cited therefrom provide information about these compounds themselves and about the methods of their preparation thereby again to prepare the compositions of the invention.

Particularly preferred examples of organotin stabilizers are: (CH3) 2Sn (SCH2C02CqH1 γ) g) ^ (SCH ^ C ^ γ) g 15 (CH3) 2Sn (SCH2CH2C02C8H1 γ) 2 (C ^ H) ^ (SC ^ CH ^ C ^?) 2 20 CH3Sn (SCH2C02C8H1T) 3 C ^ SiaiSCE ^ O ^^) ^ CH3Sn (SCH2CH2C02C8H1 T) 3 C ^ SniSCE ^ CO ^ E ^) 3 25 (CH3) 2Sn (SCHC02CuH9) 2 () gSn (SCHCOgC ^) 2 CH2CO2C ^ 9 CH2CO2c, H9 30 1 81018 5 7 '* * * -Ji * *' *. · - - - β -, (CH3) 2Sn: H2C02C8Hi7- (C4H9) 2 | nCH2C02C8H17 J s CH2Sn {CH2C02CgH ^ 7) 2 · C4H9Sn (CH2G02CgH ^ 7) 2 (CH3) 2 SxfiCH2CH202CuH35. (C4H9) 2 SnC ^ CH ^ CC ^ gss CH3sn (SCH2CH202C17H35l2 ^ HgSniCHjCHjOjCC ) 2 CH3Sn (SCH2C02G13H27) 3 C4HgSn (SCH2C02C13H27) 3 (C8Hi7) 2Sn (SCH2C02C8H17) 2 (CH3) 2Sn (SC12H25} 2 (C8 ^ 1?) 2Sn (SCH2CH2C02Cn ^ 7g) 2 (^ Hg) 2) ) 2

CgH17Sn (SCH2C02CgH17) 3 (CH3) 2Sn (SCH2CH202CC17H3g) 2

CgH17Sn (SCH2CH2C02CgH17) 3 (CHg) 2Sn (SCH2CH202CC17H33) 2 (C8H17} 2Sn {s ^ HC02C4H9) 2 CH3Sn (SCH2CH202CC17.H35) 2 '' CH2C02C4H9 CH3Sn (SCH2CH202CC02) 2CH3C2H2) 2 CH2C02C4Hg (C4H9) 2Sn (SCH2CH202CC17H33) 2 "C4HgSn (SCHjCH ^ CC ^ Hgg) 3 C4H9Sn (SCH2CH202CC17H33) 3 8101857 - 7 -

Alkali and alkaline earth salt and of mercaptans and mer-capto acids, which can be included in the composition of the invention, are described in U.S. Patent No. 1,115-352. This reference describes the metal salts 5 of formulas III, IV and V, wherein M is a Group IA metal (an alkali metal, in which case n = 1) or a Group IIA metal (an alkaline earth metal, in which case n = 2) M1 represents a Group IIA metal, R1 represents a hydrocarbon radical (eg, alkyl, cycloalkyl, aryl, or mixed alkylaryl) having 1-22 carbon atoms, which is optionally substituted with halogen, -XH, -XR ^, -X (CY) E ^, or - (CY) XR3, wherein the above meaning has X and Y independently represent 0 or S and H_ represents a linking hydrocarbon group having 5 to 1 to 5 carbon atoms (part of a cyclic structure and is optionally substituted with halogen, -XH, -XR ^, -XiCYjR ^ or - (CY) XR3, wherein R ^, X and Y have the above meanings.

In the preparation of compounds of the formula 206, "polymeric" linear salts of the same empirical formula could be formed and these mixtures are useful and are within the scope of the invention.

Compositions containing more than one metal and mixed group R formulations are also useful and are within the scope of the invention.

The preferred salts of mercaptans or mercapto acids optionally used in the invention are the alkaline earth metal salts: 30 Ca (SCH 2 CO 2 C 8 H 17) 2 CatSC ^ K, ^

Ca (SCH2CH2C02CgH17) 2 salt of the formula 8 35 81 01 857 -8-

Ba (SC12Hg ^) 2 salt of the formula 9

Ba (SCH2C02C8H17) 2 CaiSCHCO ^ H ^

Ba (SCEgCHgCOgCgH1?) G Ba (SCHgCH ^ CC1 ^) g 10 salt with the formula 10 BaiSCHgCiïgOgCC ^ ^ H ^ ig salt with the formula 11 CaiSCHgCHgOgCC ^^ H ^ Jg 15

Ba (SCHC02C ^ H9) 2 CaiSC ^ CffgOgCC ^^ g ch2co2cuh9 20

Due to their superior action, the following barium and calcium salts are particularly preferred: 25 Ba (SCH2C02C8H17) 2 BaiSCHgCHgCO ^ gH ^ g

Ba (SCH2CH202CC17H33) 2 BaiSC ^ CH ^ CC ^^

Ca (SCH2C02C8H1T) 2 ... Ca (SCH2CH2C02C8H1T) 2 30

Ca (SCHgCHgOgCC 1 ^ £ Ca (SCHgCH ^ CC 1 ^?) G

The tintetrakis (mercaptides) useful in the invention are characterized by four Sn-S bonds and 3 ^ have the formula 6 wherein 8101857 - 9 - R-, R, Rq and R_ represent hydrocarbon radicals-0 (0 y len (for example, alkyl, cycloalkyl, aryl, or mixed alkyl-aryl) of 1-22 carbon atoms, which are optionally substituted with halogen, -XE, -XR e - (CY) R3, -X (C1) R3, or - (cDXR ^ wherein R3 represents an alkyl, alkenyl, cycloalkyl, aryl, or mixed alkylaryl group having 1-20 carbon atoms and X and Y independently represent 0 or S.

Examples of these tintetrakis (mercaptides) are: 10

Sn (SCH ^ Sn (SCH2CHC1 + H9) 1; c2h5 15 Sn (SCuH Sn (SCH2C02C8H1T) u

Sn (SC12H25) h Sn (SC ^ CH ^ CgH1γ) k 20 compound with the SniSCHCO ^^ H ^) ^ formula 12 | CH2CW9 compound with the SniSCHCOgCgH2) formula 13 | 30 C02 ° 2H5 35 8101857 * r t -10 "'.

O

Sn (SC6H4-p-CH3) 4 SnCSCK ^ CCgH ^ t

Sn (SCgH4-p-Cl) 4 Sn {SCgH5) ^ (SCHCO ^ Hg) 2 g ch2co2c4h9

O

Sn (SCH2C6H5) 4 Sn (SC3H7SCCH3) 4

Sn (SCH2CH2OH) 4 Sn (SCH3) 3 (SCH2CO2C20H41)

Sn (SCH2CHCH2) 4 Sn (SCH2CH2SC10H21) 4

OHOH

i

Sn (SC2H402CC6H5) 4 Sn (SCH2CHCH2-Cl) 4 oc2H5

Sn (SC3H602CC17H33) 4 Sn (SCH2C02C4H9) (SCHC02C4Hg) 3 • ch2co2c4h9.

.. Sn (SC2H402CC17H35) 4 compound of the formula ^

Sn (SCH2CHCH202CCH3) 4 Sn (SC4H9) {SCR ^ O ^^ S. ^) 3 o2cch3

Sn (SC8H17) 2 (SCH2C02C8H17) 2 Sn (SC2H5) 2 (SC4Hg) 2

Sn (SCH2C02C3H7) 2> 5 (SCH2CH2C02C8H17)

Sn (SC12H25) 2 (SCH2C02C4H9) 2 Sn (SC ^ Hg) 2 (SCH2C02CgH17) 2

Sn (SCH2CH2S2CCH3) 4 Sn (SC4H9) 3 (SCH2C02CgH17)

Sn (SC2H402CC17H33) 4! 8101857 -11-

Particularly preferred tintetrakis (mercaptides) are:

SniSCHgCOgCgV ^ Sn (SC12H25) 2 (SCH2C02C8H1T) 2 5

SniSC ^ JfSCHgCOgCgH ^ Jg SniSCHgCHgCOgCgE ^) ^ 10 3η (3 ^ Η9) 2 (30Η200208Η1τ) 2 Sn (SC12H25) (SCH2CH2C02C8H17) 3

Sn (3CuH9) 3 (SCH2002C8Hn) SnfSC ^ ysCH ^ OOjCgH, ^ 15 M3CKR25) k Sn (SCHCOgC ^ H ^) ^ 20 Sn (SC12H25) (SCH2C02 ° 8H17) 3 SntSC ^ ysCHCO ^)., Ο2 »2ν,

Sn (S012H25) iSCBC02CllS) 3 S ^ SC ^ CCj ^ lj 25

The tintetrakis (mercaptides) of the invention can be conveniently prepared by reacting selected mercaptans with anhydrous stannic chloride, optionally in the presence of an HCl acceptor as an inorganic or organic base.

The overbased organic complexes of alkali or alkaline earth bases, which are also included in the composition of the invention y. can be included, described in the current 8101857 <* -12-

U.S. Patent Application No. 828703, filed August 29, 1977 and in the U.S. Patents cited therein. This application 828703 describes the overbased organic complex of an alkali or alkaline earth alkali of formula 7, wherein R | 0 represents the residue of an organic acid, namely of a carboxylic acid, thiocarboxylic acid, sulfonic acid, sulfinic acid, phosphonic acid, phosphophic acid, thiophosphonic acid, thiophosphinic acid , phenolic acid or thiophenolic acid, 10 n and n 'are 1 or 2, M and MJ represent the same or different alkali or alkaline earth metals (metals from group I and Ha of the periodic table) X is a positive number greater than 0 and A represents the anionic part of the basic substance, OH ", CO 3", O 2 ", SO 2", SO 2 ", HCO 3" or S2 ".

The organic complex is generally dispersed in a low volatile liquid, for example, hydrocarbon oil, a plasticizer, an epoxy ester, or a combination thereof.

The basic method of preparing such overbased complexes involves the preparation of a soap or salt of an organic acid in the presence of an amount of neutralizing agent, for example, a metal oxide or hydroxide, resulting in the formation of a stable product containing an amount of metal, which is a significant excess of the amount theoretically required to replace the acidic hydrogen atoms of the organic acid, for example, the carboxylic acid, phenolic acid, sulfonic acid, sulfinic acid, etc. used as the starting material. In general, the stoichiometric excess of metal for the overbased complexes is at least one. equivalent, as is currently preferred, but may range from 0.1 to 30 equivalents. The reaction product can also be treated with an acid gas (eg CO 2) in order to reduce the free basicity of the complex. (Free basicity is considered to be the amount of metal base that is titratable to a pH of 8, while the total basicity of the complex is titratable to a pH of 3). As set forth in U.S. Pat. wherein the acid is a phosphoric acid, a thiophosphoric acid, phosphoric acid-sulfur combination or sulfuric acid and are prepared from polyolefins described in U.S. Pat. Nos. 2,883,340, 2,915 * 517 * 3-001,981, 10 3,108,960 and 3,232,883. Overbased phenolates are described in U.S. Patent 2,959,551, while overbased ketones are described in U.S. Patent 2,798,852. A number of different overbases prepared from oil-soluble, metal-free, non-tautomeric, neutral and basic organic polar compounds such as esters, amines, amides, alcohols, ethers, sulfides, sulfoxides, etc., are described in U.S. Pat. Nos. 2,968. 642, 2,971,014, and 2,989,463. Another group of substances that can be overbased are the oil-soluble nitro-substituted aliphatic hydrocarbons, especially nitro-substituted polyolefins such as polyethylene, polypropylene, polyisobutylene, etc. Substances of this type are given in the US patent 2,959,551. The oil-soluble reaction product of alkylene polyamines such as propylene diamine or N-alkylated propylene diamine with formaldehyde or a formaldehyde-providing compound (for example paraformaldehyde) can also be made overbased. Other suitable compounds are described in the above-cited patents or are otherwise well known.

A group of particularly suitable organic substances, the remainder of which may form the group of the above-mentioned formula for the overbased organic complex, are oil-soluble organic acids, preferably those with at least 12 aliphatic carbon atoms, although the acids can have only 8 aliphatic carbon atoms When the acid molecule contains an 8101857 "aromatic ring", for example phenyl, naphthyl, etc. Good examples of organic acids are discussed and disclosed in detail in the above patents. In particular, U.S. Pat. Nos. 2,616. 9CA and 2,777.87 ^ 5 describe a number of different highly suitable organic acids For economic reasons and because of their action, oil-soluble carboxylic acids, sulfonic acids and phenolic acids are particularly suitable.

Within the group of overbased carboxylic acids, sulfonic acids and phenolic acids, the barium and calcium overbasic mono-, di- and trialkylbenzene and naphthalene (including hydrogenated forms thereof) petrosulfonic acids, higher fatty acids and alkylated phenols are particularly suitable. The petroleum sulfonic acids are a well-known group of substances used as starting materials in the preparation of overbased products since the beginning of overbasing as shown by the above patents.

The overbased organic complexes used in the stabilizer systems of the invention usually contain 10-70% by weight of metal-containing components. The exact nature of these metal-containing components is not known. In addition, the overbased organic complexes may be in colloidal non-Newtonian form as described in U.S. Patent 3,38U,586 as opposed to single phase homogeneous systems. However, this depends on the reaction conditions and the choice of the reagents in the preparation of the overbased substances. Sometimes insoluble impurities are present in the product. These impurities are normally unreacted basic substances such as calcium oxide, barium oxide, calcium hydroxide, containing hydroxide and other metal bases, which are used as a reaction with the overbased material. It should be noted, however, that the removal of these impurities is not absolutely essential to the operation of the invention.

The metal compounds used in the preparation of the organic overbased complexes are the basic salts of metals of group I and Ila of the periodic table such as sodium, potassium, calcium, barium, magnesium and strontium.

The anionic part of the salt can be hydroxyl, oxide, carbonate, bicarbonate, sulfite, sulfide or sulfate as described in the above patents.

Preferred overbased organic complexes are those which have been overbased with CaCO2 and BaCO2, with BaCO2 particularly preferred.

The stabilizer composition of the invention can be used in an amount of 0.05-10% by weight of halogenated resin. The preferred amount is 0.2-5.0 wt.%.

The four components are generally combined in the following weight percentages: 15% by weight. % pt-8O # tintetrakis (mercaptide) 99-20% sulfur-containing organotin compound 20-OQ # alkali or alkaline earth salt of a mercaptan or a mereaptoic acid.

0-%% overbased organic complex of an alkali or alkaline earth as e.

100 25

Preferred weight amounts are the following: wt. % 1- 50% tintetrakis (mercaptide) 99-% 0% sulfur-containing organotin compound 0-hO% alkali or alkaline earth metal salt of a mercaptan or a mereaptoic acid.

35-40% overbased organic complex of an alkali or dalkalibas e.

100

The new stabilizer compositions of the invention can be used in halogen containing vinyl and vinylidene. resins in which the halogen is directly bonded to the carbon atoms.

As the halogen resin, one can use polyethylene with 14-75, for example. 27% by weight of chlorine, polyvinyl chloride, poly-10-vinylidene chloride, polyvinyl bromide, polyvinyl fluoride, poly-vinylidene fluoride, copolymers of vinyl chloride with 1-90, preferably 1-30% copolymerizable ethylenically unsaturated material, for example vinyl acetate, vinyl butyrate, vinylidene chloride , diethyl fumarate, diethyl maleate, 15 other alkly fumarates and maleates, vinyl propionate, methyl acrylate, 2-ethylhexyl acrylate, butyl acrylate and other alkyl acrylates, methyl methacrylate, ethyl metacrylate, butyl methacrylate, methyl-ethyl-chloroethyl acrylate as vinyl ethyl ether, vinyl chlorethyl ether and vinyl phenyl ether, vinyl ketones such as vinyl methyl ketone and vinyl phenyl ketone, 1-fluoro-1-chloroethene, acrylic acid nitrile, chloroacrylic nitrile, allylidene diacetate and chlorallylidene diacetate .. Good examples of copolymers sold as vinyl chloride 96 VlIW), 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), vinyl chloride trichlorethylene (95: 5) and vinyl cmcride-2-ethylhexyl acrylate (80:20).

Preferably, the resin is a vinyl halide resin, especially a vinyl chloride resin.

The stabilizer composition of the invention can be incorporated into the resin by mixing in an appropriate mill or mixer or in some other well known manner that provides an even distribution throughout the resin compositions. Thus, mixing can be accomplished by milling or rolling at 100-160 ° C.

In addition to the new stabilizers, the resin may also contain the usual additives such as plasticizers, conventional stabilizers, antioxidants, pigments, fillers, dyes, ultraviolet light absorbers, densifiers, etc., as shown and in the amounts specified in the U.S. U.S. Patent 3,925,309.

The following examples illustrate the invention.

10

Example 1

Preparation of tintetrakis (isooctyl thioglycolate).

A mixture of 10.5 g or 0.1 mol of triethylamine in 100 is added to a mixture of 8, 1.7 g of 0.1 mol of isooctylthio-15-glycolate and 26.1 g or 0.1 mol of anhydrous stannic chloride dissolved in 250 ml of hexane. ml of hexane. The mixture is stirred at room temperature for 3 hours and then filtered. The filtrate is concentrated under reduced pressure to 81.0 g of product or 87.0% yield. The infrared data correspond to the assigned structure.

Anal. Ber. for C 1 H 25 gS 2 Sn: C, 51.6; H, 8.22; S, 13.8; Sn, 12.7

Found: C, 52.6; H, 8.37; S, 13.6; Sn, 11, U

25 Example 2.

Preparation of tintetrakis (2-mercaptoethyl stearate).

7.0 g or 0.11 mole of ammonia is bubbled through a solution of 137.8 g or 0.1 mole of 2-mercaptoethyl stearate and 26.1 g or 0.1 mole of anhydrous stannic chloride in 10 ml of toluene.

The reaction mixture is then heated to reflux for 3 hours, cooled and filtered. The filtrate is concentrated under reduced pressure to 123.6 g of product or 82.0% yield. The infrared data correspond to the assigned structure.

81018 57 i -18-

Anal. Ber. for C80H156SU ° 8Sni C "61 +" ^ H "" 10s5; S »8.59;

Sn, 7.95

Found: C, 65.5; H, 10.6; S, 7.79;

Sn, 6.82 5

Example 3.

Preparation "of barium carbonate dispersion (overbased organic complex.).

In a three-necked round bottom flask equipped with a mechanical stirrer, Dean-Stark trap and a plug, a mixture of 57 g of nitrated polyisobutylene, 133 g of light paraffin oil, 50 g of isooctyl alcohol, 60.8 g or 0.28 equivalent is heated with stirring. p-nonylphenol and 138.7 g or 1.6 equivalence barium hydroxide monohydrate at 150 ° C and maintain this temperature for 5 hours to displace the water. The reaction mixture is then treated with carbon dioxide gas at 150 DEG C. for 3 hours at an hour. Isooctyl alcohol and excess water are then stripped in vacuo and the product is filtered. The yield of product, a dark, viscous solution, is 3 * 11.3 g or 8 µl.

Theory: Ba, 27.7% CO 2, 10.0 t Found: Ba, 23.1%; C0 ^, 8, * 5 $ 25 Examples * 1 - 17

In the following examples, a standard single screw pipe preparation containing 100 parts by weight of polyvinyl chloride homopolymer (VC 100 PM, Borden Chemical Co.), 30 3.0 parts by weight of processing aid, which is an acrylic acid polymer, consisting of 90% methyl methacrylate and 10% ethyl acrylate is used. late (K-120N, Rohm. and Haas Co.), 0.5 parts by weight of paraffin wax (Rosswax 165, FB Ross Co.), 0.2 parts by weight of partially saponified ester wax (Wax OP, American Hoechst Co.), 1, U contains 35 parts by weight of calcium stearate, 2.0 parts by weight of titanium dioxide, and stabilizer as indicated.

The bar blends are blended dry in a Waring Commercial Blender and dynamic heat stability is determined on a Brabender Plastograph using a batch of 67.5 g stock temperature of 213 ° C and a mixing head speed of 10 revolutions per minute. Samples are taken from the Brabender at 3 minute intervals. The discoloration of the mixture is visually estimated and recorded using the following abbreviations: 10

Color Grade G = gray L = light

Pk = pink P = pale W = white V = severe 15 Y = yellow

The stabilizers used are abbreviated as follows: DMTG - Dimethyltiribis (isooctylthioglycolate) 20 MTMS - Methyltintris (2-mercaptoethyl stearate) TTTG - Tintetrakis (isooctylthioglycolate) TTMS - Tintetrakis (2-mercaptoethylstearium) barstoethyl stearate)

25 Table A

Example Parts Stabilizers Time (Minutes) no. _ _ 3 6 9 12 15 2Q IV - no Pk G -

V 1.5 DMTG W W VPY VPY PY

VI 1.5 TTTG G -

VII 1.35 DMTG www VPY PY

0.15 TTTG

35 VIII 1.20 DMTG W W W W PY

8101857 5

rg V.

-20-

(continued) Table A

Example Parts Stabilizers Time (Minutes) no. _ _ 3 6 9 12 15

.30 TTTG W W W W PY

IX 1.20 DMTG W VPY VPY VPY PY

0.30 With BaCQ, overbased. made complete ·

X 0.90 DMTG W W W W VPY

10 0.30 Complex made basic with BaCO

.30 TTTG

XI 1.5 MTMS W W W Y G

XII 1.5 TTMS Y G

15 XIII 1.35 MTMS W W W PY G

0.15 TTMS

XIV 1.2 MTMS W W PY Y Y

0.3 With BaCO., Made overbased

2Q XV 0.90 MTMS W W PY PY Y

0.30 With BaCO. basic made complex

0.30 TTMS

XVI 1.25 MTMS W W W W PY

0.10 Complex made with BaCO overbased

0.15 BBMS

XVII 1.10 MTMS W W W W W

0.10 Complex made basic with BaC0_

30 0.15 BBMS

0.15 TTMS 1 8101857

Claims (16)

A composition, characterized in that it comprises a mixture of (a) 99-20% by weight sulfur-containing organotin compound with a -C-Sn-S group and (b) 1 - 80% by weight tintetrakis (mercaptide) with four Sn-S bindings. Preparation according to claim 1, characterized in that it additionally comprises 1 - 60% by weight, based on the weight of the preparation, of an alkali or alkaline earth metal salt of a mercaptan or a mercapto acid. 3. A composition according to claim 1, characterized in that it additionally comprises 1 - 60% by weight, based on the weight of the preparation, of an overbased organic complex of an alkali or alkaline earth base. U. A composition according to claim 2, characterized in that it additionally comprises 1 - 60 wt. %, based on the weight of the composition, includes an overbased organic complex of an alkali or alkaline earth base. Preparation according to claim 1, characterized in that the tintetrakis (mercaptide) has the formula 6, wherein Rg, Rj, Rq and R18 represent hydrocarbon radicals having 1 to 22 carbon atoms, which independently of one another represent an alkyl, cyclo- alkyl, aryl or mixed alkylaryl radical, which hydrocarbon radicals have a substituent in the form of halogen, -XH, -XR ^, - (CY) R ^. -X (CY) R ^ and - (ΟΥ) ΧΗ ^, where R represents a hydrocarbon radical of 1-20 carbon atoms, an alkyl, alkenyl, cycloalkyl, aryl or mixed alkylaryl radical and X and Y independently of one another oxygen or sulfur. 6. Preparation according to claim 5, characterized in that the sulfur-containing organotin compound has the formula 2, wherein Rj represents a hydrocarbon radical of 1 to 18 carbon atoms, an alkyl, cycloalkyl, aryl or mixed arylalkyl radical, which hydrocarbon radicals have a substituent in the form of -CN, -OR ^, - (COjR ^ or -CO ^ R ^ and 35 81 01 857 V -22- Rg represents a hydrocarbon radical, which is an alkyl, cycloalkyl, aryl or mixed arylalkyl radical of 1 to 22 carbon atoms, optionally substituted with halogen, -XH, -XR ^, - ( CXjR ^ s -X (C1) R2 or - (CYjXR ^, where R ^ has the above meaning and X and Y independently represent oxygen or sulfur, while Z represents oxygen, sulfur, R ^ or -SR ^ - Represents SSn (R- ') (SR ^), where b is 1 or 2. 7. Preparation according to claim 6, characterized in that it additionally contains 1 - 60%, based on the weight of the preparation, of an alkali or alkaline earth metal salt of a mercaptan or marcaptoic acid of one of the formulas 3, 4 or 5, wherein M alkali or alkaline earth metal represents an alkaline earth metal, n = 1, when M represents an alkali metal, and n = 2, when M represents an alkaline earth metal, R 1 represents a hydrocarbon radical of 1 to 22 carbon atoms, which is an alkyl, cycloalkyl, aryl or mixed alkylary radical, which hydrocarbon radical has a substituent in the form of halogen, -XH, -XR ^, - (CYjR ^, -XtCY ^^ 20 or - (CYjXR ^, where R ^ has the above meaning, X and Y independently oxygen or sulfur and R ^ represents a divalent linking hydrocarbon group having 1 to 5 carbon atoms, which linking hydrocarbon group may have a substituent in the form of halogen, -XH, -XR ^, -X (CY) R ^ or - ( CY) XR ^, where R ^ X and Y bov and have said meaning. 8. A composition according to claim 6, characterized in that it additionally contains 1-6%, based on the weight of the composition, of the overbased organic complex of an alkaline earth metal carbonate. Preparation according to claim 7, characterized in that it additionally contains 1 - 60%, based on the weight of the preparation, of an overbased organic complex of an alkaline earth metal carbonate. 8101857 -23- Preparation according to claim 5, characterized in that the tintetrakis (mercaptide) "belongs to one of the following compounds: 5 sn (sca2co2c8H17) 1 (, SatSOHgOHgOOgOgH ^) ^, SniSC, ^) ^, 10 Sn (SCH2C0203I1T) 3 ( SC12H25), Sn (SCH2C02C3H17) 2 {SC12H25) 2, 15 SntSCHCO ^ H -) ^ CH2C0AV SntSCH ^ CC ^) ,,, and ΡΠ Sn (SCH2CH202CC17H35) 1 ;. 1 81 01 857 A preparation according to claim 6, characterized in that the sulfur-containing organotin compound belongs to one of the 2 ^ following compounds: CH3Sn (SCH2C02CgH1) 3, CH3Sn (SCI ^ CH ^ CC ^ 33) 3, CH3Sn (SCH2CH302CC1TH35) 3, ( CgH ^ JgSniSCHgCOgCgH ^) ^ (CH3) 2Sn (SCH2C02C8H1T) 2, C ^ SniSCH ^ CgH ^^, 3Q (CH3) 2Sn (SCH2CÏÏ202CC1TH33) 2S CgH ^ nCSCHgCOgCgC ^) (SC3) ^ n (SC3) ^ n (SC3) ^ n () a ^ SnCSO ^ BC ^^, (CH3) 2Sn SCHOOR, (C ^ SnlSC ^ CC ^^, CHjCOgC ^, C! 1H9Sn (SC2H902C017H33) 3> and 35 (C ^ SniSCHgCO ^ gH,. ^, 0,, Η98η (802Η9020017Η35) 3. -2U-r 12. A composition according to claim 9, characterized in that the overbased organic complex is overbased with BaCO 4 or GaCO 4 and the alkali salt of a mercaptan or mercaptoic acid is one of the following: 5 Ba (SCH2C02C8H17) 2, Ba {SCH2CH2C02C8H17) 2, Ba (SCH2CH202CC17H33) 2, Ba (SCH2CH202CC17H35) 2, 10 Ca (SCH2C02C8H17) 2, Ca (SCH2CH2C02C8H17) 2i Ca (SCH2CH202CC17H33) 2? and 15 Ca (SCH2CH202CC17H35) 2. The formulation of claim 1 dispersed in a halogenated resin. 1U. Preparation according to claim 2 dispersed in a halogenated resin. 2g 15. A composition according to claim 3 dispersed in a halogenated resin. A composition according to claim dispersed in a halogenated resin. 25 / Λ / fjj 81 01 857 ^ I \ ---------