NO813227L - HALOGEN-CONTAINING POLYMER COMPOSITION CONTAINING SULFID-CONTAINING TIN STABILIZERS FOR HEAT STABILIZATION OF THE POLYMER - Google Patents

Description

The present invention relates to halogen-containing polymer compositions containing new organotinmercaptoalkyl-carboxylic acid ester sulphides which can be used as stabilizers in said composition.

In the present description, the term lower apto-alkylcarboxylic acid ester is understood to mean that the alcohol group is esterified with the carboxylic acid group. The compounds can also be called mercapto-■ alkanolcarboxylic acid esters (or mercaptoalkylcarboxylates). A typical starting ester for the production of organotin compounds according to the present invention is thus e.g. mercaptoethyl caprylate with the following formula:

H^which-is different from the starting ester, i.e. e.g. isoethyl thioglycolate having the following formula:

and as e.g. used in J^ud«?r U.S. Patent No. 3.S65.9/30 and.Brecker U.S. patent no. 3«565-931• * d©g ng compounds used in the present invention are thus the free mercapto group which

reacts with a tin compound in the formation of compounds according to the present invention, is bound to the alcohol part of the ester., while in the esters mentioned in the above-mentioned patents, it is bound to the acid part of the ester. This is very important because the compounds according to the present invention have significantly better effects than those described by Kauder or Brecker. Firstly, it has far better stabilizing properties for vinyl chloride polymers and other halogen-containing polymers. You can do this

note aXlered in dynamic grinding tests in the laboratory, but the advantage is even more marked during real expulsion tests. Furthermore, compounds according to the present invention have far better storage stability than the corresponding alkylthioalkanoates.

The organotin mercaptoalkylcarboxylates described here also have a major advantage over organotin alkylmercaptocarboxylates in that the stabilizers both have a longer lifetime and resistance to precipitation. Although the theoretical application is uncertain, one assumes

that the instability of alkyl mercaptocarboxylates is due to a hydrolysis of the ester function whereby an organotin mercaptocarboxylate ring or polymeric material is formed, after which this is precipitated. This is again due to the carboxylate ion having strong tin nucleophilicity. With mercaptoalkyl carboxylates, however, the nucleophilicity of the alcohol oxygenator is not sufficient to promote a rearrangement of the mercaptoalkyl carboxylate so that an insoluble ring or a polymeric type product is formed.

'■Samples exposed to air saturated with water vapor at 37°C showed only very weak formation of cloudy products when organotin alkyl mercaptocarboxylates were present, while storage under the same conditions with the corresponding alkylthioalkanoates created voluminous precipitates.

Details regarding the ls^ring stability test are as follows: jiiv^ii.J : v 50 gram samples were stored in open 50 cm^ narrow-necked bottles in a closed chamber that contained a 1.25 cm layer of water at the bottom. The chamber was placed in an oven and the temperature was varied, 5 days at 3°C and 2 days at room temperature from 10 to 21°C. This variation was carried out for a total of 60 days. After this one trial period was approx. 50% of the alkylthioalkanoate present precipitated, while in contrast only

cai 1 # of the mercaptoalkyl alkanoate present.

The alkylthioalkanoate and raercaptoalkylalkanoate used in this test had the following formula:

Compounds according to the present invention furthermore have far less odor compared to the compounds described by Brecker or Kauder.

It is important to have a sulphide group to achieve unique stabilizing properties. Thus, products according to the present invention are far better stabilizers than e.g. organotin compounds which are prepared by reacting methyltin trichloride (or dimethyltin dichloride) with 2-mercaptoethyl caprylate, i.e. tin compounds of the type described in patent no. 2,731,482,4B*s4 U.S. U.S. Patent No. 2,731,484V&ei»**e*f Patent No. 2.87O.H9 ogrteistne^ U.S. patent no.. 2.87O.I82.

Compounds according to the present invention can be described as monoorganotin and/or diorg-snotin mercaptoalkyl-carboxylate monosulfides and/or polysulfides which can be used as ..• stabilizers to improve the resistance to degradation in vinyl chloride polymers (e.g. vinyl chloride resins) when these are heated to 175 °C The compounds are characterized by the fact that they contain at least two tin atoms bound together exclusively through sulphide-sulfur and where to said tin atoms L?^n"^~^'rhQn^^fly is bound one to two hydroxy groups (e.g. alkyl, aryl , cycloalkyl, aralkyl or alkenyl with from 1 to 20 carbon atoms), and • where at least one mercaptoalkylcarboxylic acid ester group is bound to the tin through the sulfur atom in the mercaptoalkyl group, and where the compounds contain tin in amounts from 10 to 4% by weight,

and sulfur in amounts .varying from 8 to 42 percent by weight.

The mercaptoalkyl or ptohydroxyalkyl group usually has at least two carbon atoms and usually no more than 6 carbon atoms. Preferably, the group has 2 to 3 carbon atoms, and preferably lacks hydroxy groups, i.e. it is mercaptoethyl or mercptopropyl. However, you can also use hydroxyl-containing ones

compounds, e.g. derivatives of monothioglyoerol such as monothioglycerin monoacetate, monothioglycerin monostearate as well as compounds such as monothipglycerindistearate, monothiopentaerythritol triacetate, monothipentaerythritol tristearate, and monothiopentaerythritol diacetate.

The sulfides can be mono- or polysulfides, e.g. they may contain 1, 2, 3-4»5-6, 1° or more sulfur atoms bound together, but are preferably mono- to tetrasulphides, most preferred are mono- to disulphides.

The preferred hydrocarbon radical attached to the tin atoms is methyl.

As stabilizers, men preferably use a mixture of monoorganotin compounds and diorganotin compounds according to the present invention, especially mixtures containing from 96 to 50% of a monoorganotin compound and correspondingly .4 to 50% of the diorganotin compound. The individual

compounds according to the present invention can also be mixed mono-diorganotin compounds, which will be apparent from the following specific examples.

Compounds according to the present invention can have the following formula:

where R is hydrocarbyl, e.g. alkyl. aryl, cycloalkyl, aralkyl or alkenyl and where R usually has from 1 to 20 carbon atoms, R^g is R or<1>

where Z is a polyvalent?alkylene or

hydroxyalkylene radical with at least 2 carbon atoms and usually no

over 20 carbon atoms, and where Z's valency is ni+1, R-^q is as defined above, m is the number of OOCR^Q groups, m is a number from 1

to 3» n is a number from .1 to 2 while x varies from 1 to 10,

usually .from 1 to 4.

In a more specific form, compounds according to the present invention can have this formula:

where x is 1 to 10, usually 1 to 4»preferably 1 to 3»most preferably 1 to 2, y is at least 1, Z is 0 or a number and where y+z is at least 2 and can be up to 18 or 20 or higher, R^, Rg. R^»R^ and R^ are hydrocarbyl. e.g. alkyl, aryl, cycloalkyl, aralkyl or alkenyl having from 1 to 20 carbon atoms.

halogen, flex. Cl, Br or J or OH, R,- are as de-

refined above for R^, R,, R.^ and R^, but is preferably not

hydrocarbyl as a presence of a trihydrocarbyl moiety tends to lower the efficiency and increase the compound's

toxicity,

Rg and<R>^g are hydrogen, hydroxyl,

alkyl,

eg..with from 1 to 18 carbon atoms.

Ry and R^ej are hydrogen or alkyl, with e.g. 1 to 18 carbon atoms,

R^q is hydrogen, alkyl, aryl, aralkyl, cycloalkyl, aralkenyl, alkenyl with up to 3 ethylenic double bonds, hydroxy-alkyl, hydroxyalkenyl or -R-j^COOR,,^» where R^ is (CHg)p, phenylene or -CH ^CH- where p is 0 or a number up to 8 and Rjj^ is alkyl group with from 1 to 20 carbon atoms, cycloalkyl with from 5 to 6 carbon atoms, alkenyl with from 2 to 20 carbon atoms, aryl, e.g. phenyl or tolyl or benzyl. R^q may have from 1 to 19 carbon atoms or more when the group is a hydrocarbon or hydroxyhydrocarbon group. Preferably, the group has from 7 to 17 carbon atoms. Rg is alkylene (this includes alkylidene) with from 1 to 20 carbon atoms, or such an alkylene group with a halogen or hydroxy substituent, or an ethylenically unsaturated divalent aliphatic hydrocarbon group or hydroxyhydrocarbon group with from 2 to 19 carbon atoms, R^ and R^0 are hydrocarbyl , e.g. alkyl, aryl, cycloalkyl, aralkyl or alkenyl with from 1 to 20 carbon atoms, R is alkylene with from 2 to 20 carbon atoms. At least one of the groups R₁, R₂, R₂ and R₂ must be a hydrocarbyl group, and preferably at least one of the groups R₂ and R₂ is hydrocarbyl.

In addition to the compounds indicated above, one can also use so-called "overbased" tin compounds by reacting in •-«an a compound with the following formula:

where or is defined as R^, in quantities of up to 2 mol per available carboxyl group with a tin sulphide according to the present invention. The "overbased" product can be produced simply by e.g. that one dissolves the dihydrocarbyl tin oxide in the tin mercaptoalkyl carboxylic acid ester sulphide. The overbased product has the same application area as other products according to the present invention. It is particularly surprising that overbased

products can be prepared with dimethyltin oxide, as this compound is usually not soluble in other compounds,

then it is soluble in the present compounds.

The overbase reaction is further shown in Weisfeld U.S. patent No. 3,478,071 and Stapfer et al, J. Organometallic Chemistry Vol. 24 (1970) pp. 355-338. The description in the aforementioned Weisfeld patent and Staffer's article are thus included as a reference in the present invention.

With the term "overbased with dihydrocarbyl tin oxide

(or

is understood to be the reaction product between such

organotin oxide and a mono- or diorganotin mercaptoalkyl compound (or mercapto-hydroxyalkylcarboxylic acid ester sulphide).

Without being bound by one or more specific theories, it is assumed that the above overbase reaction proceeds in the following way:

When preparing compounds according to the present invention, the R^, R^, R^fR^ and R^ groups when they are hydrocarbyl and bound to tin, e.g. be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, amyl, hexyl, octyl, isobctyl, 2-ethylhexyl, benzyl, phenyl. p-tolyl, dodecyl, allyl, eicosanyl, octadecyl, oleyl, vinyl, cyclopentyl or cyclohexyl.

Compounds according to the present invention can be prepared in various ways, e.g. as shown below. You can thus use the method from Kauder U.S. Patent No. 3,565,930 or in Brecker U.S. Pat. patent no. 3,565,93I by using alkali metal, alkaline earth metal or ammonium sulphides or polysulphides, e.g. NaP<S>x.<K25>x'CaSx»BaSxor ^NH4^2Sx where x is as defined above, instead of the alkali metal or alkaline earth metal monosulphides mentioned in Kauder or Brecker, and further use a compound of the following formula:

instead of isoocatylthioglycolate or similar compounds of the type mentioned in Brecker or Kauder. If one or more of the groups R^, R^,, R^, R^ and R^ are: -SRg, -^Ri40R<q>or then a compound with the formula HSRg, HSR^ORg, or Man can thus react 1 mol of a compound of the formula with 1 mol of a compound of the formula: after which one neutralizes with an alkali or alkaline earth metal hydroxide in an amount corresponding to the mercaptoalkanol ester of the carboxylic acid, after which one carries out a reaction with ammonium or an alkali or alkaline earth metal sulfide . If the connection

is replaced by a compound with the formula R^-SnX^, so

must one use 2 mol of the mercaptoalkanol ester. X can be a halogen atom with an atomic weight from 35 to 127. As starting material, methyltin trichloride, methyltin tribromide, methyltin triiodide, ethyltin trichloride, butyltin trichloride, butyltin bromide, butyltin triiodide, sec-butyltin trichloride, octyltin trichloride, benzyltin trichloride, dimethyltin dichloride, dimethyltin- dibromide, diethyltin diiodide, dipropyltin dichloride, butylmethyl-

tin dichloride, dibutyltin dichloride, dibutyltin dibromide, dioctyltin diiodide, dioctyltin dichloride, dibenzyltin dichloride, phenyltin trichloride, p-tolyltin trichloride, diphenyltin dichloride, di-p-tolyltin dichloride, cyclohexyltin trichloride, dicyclohexyltin dichloride,

cyclopentyltin trichloride, oleyltin trichloride, dioleyltin dichloride, vinyltin trichloride, diallyltin dichloride, allyltin trichloride, eicosanyltin trichloride.

As the mercaptoalkanol ester, one can e.g. use esters of mercaptoethanol, 2-thioglycerin, 3-thioglycerin, 3-thiopropanol, 2-thiopropanol, 4-thiobutsnol, 18-thiooctadecanol, 9-thiononanol, 8-thiooctsnol, 6-thiohexanol with acids such as raauric acid, acetic acid, propionic acid , butyric acid, pivo.linic acid, V9leric acid, caprylic acid, caproic acid, decanoic acid, lauric acid, rayristic acid, palmitic acid, 2-ethylhexanoic acid, stearic acid, eicosanoic acid, oleic acid, linoleic acid, linolenic acid, crotonic acid, methacrylic acid, acrylic acid, cinnamic acid, benzoic acid, p-toluene acid, o -toluene acid, p-t-butylbenzoic acid, enanthic acid, p-n-butylbenzoic acid, cyclohexanonecarboxylic acid, phenylacetic acid, ricinolenic acid, hydrogenated ricinolenic acid, phenylpropionic acid. Of course, you can also use mixtures of acids, e.g. tallow oleic acids, palmitic acid-stearic acid mixtures varying from 60:40 to 40:60, soya oleic acids, cotton seed oleic acids, hydrogenated borax seed oleic acids, peanut oleic acids, coconut oleic acids, corn oil acids, castor oleic acids, hydrogenated castor oleic acids, tallow acid etc. ' Examples of half-esters of polycarboxylic acids which can <g>trees

with the mercaptoalkanol are monomethyl maleate, monoethyl maleate, mono-propyl maleate, monobutyl maleate, monooctyl maleate, mono-2-ethylhexyl maleate, monostearyl maleate, monoethyl fumarate, monomethyl.oxa.late, mono-ethyl oxalate, monoethyl malonate, monobutyl malonate, monoisopropyl succinate, monomethyl succinate, monomethyl glutarate, monoethyl adipate , monomethyl azelate, monomethyl phthalate, monoethyl phthalate, monoisooctyl phthalate, monoethyl terephthalate.

Illustrative examples of mercaptoesters that can be used in the reaction with the tin compound are the following:

2-mercaptoethyl acetate,

2-mercaptoethyl propionate,

2-mercaptoethyl butyrate,

2-mercaptoethyl valerate,

2^-mercaptoetyipivs la t,

2-mecaptoethyl caproate, 2-mercaptoethyl caprylate,

2-Mercaptoethyl Pelargonate, 2-Mercaptoethyl Decanoet, 2-Mercaptoethyl Laurst, 2-Eercaptoethyl Stearate, 2-fBiercaptoethyl Eicosanoate, 2-Mercaptoethyl Palmitate, 2-Mercaptoethyl Oleate, 2-Mercaptoethyl Recinoleate, 2-Mercaptoethyl Linoleate, 2-Mercaptoethyl Linolenate, 2-Mercaptoethyl Tallate, 2-Mercaptoethyl Ester of Boreseed Oil, 2-mercaptoethyl ester of tallow acids, 2-mercaptoethyl ester of cooking oleic acids, 2-mercaptoethyl ester of soya oleic acids, 2-mercaptoethyl benzoate,

2-mercaptoethyl p-toluate, 2-mercaptoethyl crotonate. 2-mercaptoethylcinnamate, 2-mercaptoethylphenylacetate,

2-mercaptoethylphenylpropionate, 2-mercaptoethylmethylraaleate,

2-mercaptoethylethyl fumarate, 2-mercaptoethylbutyloxalate, 2-mercaptoethylmethyloxalate, 2-mercaptoethylethylmalonate, 2-mercaptoethylmethylsuccinate, 2«mercaptoethylmethylazelate, 2-mercaptoethylhexylazelate, 2- merca<p>toet<y>lmet<y>lphthalate, 3- mercaptopropyl pelargonate, 3- mercaptopropylene ananthate, 3-mercaptopropyl stearate, 3-mercaptopropyl oleate, 3-niercaptopropyl ricinoleate, 3-mercaptopropyl ethyl maleate,

3-mercaptopropylbenzoate,

2-thlyoglyceryl pelargonate,

3- thio<g>l<y>cer<y>l<p>elar<g>onate,

6-mercaptohexyl acetate

7- mercaptoheptyl acetate»

7- mercaptoheptyl propionate,

8- ærcaptooctylacetate,

8-mercaptooctylenanthate,

18-mercaptooctadecyl acetate,

18 -raercaptooctadecylenanthate, When a compound of the formula HSRg, HSR^ORq or

can you e.g. use

esters of mercaptoacetic acid, a-mercaptopropionic acid, 3-mercaptopropionic acid, a-mercaptobutyric acid, B-mercaptobutyric acid, gamma-roercapto-butyric acid, gamma-mercaptovaleric acid, a-mercaptovaleric acid, 6-mercaptovaleric acid. Thus, you can use methyl mercaptoacetate (methyl thioglycolate), 6-ethylmercaptoacetate, propylmercaptoacetate, butylmercaptoacetate, isobutylmercaptoacetate, sec.-butylmercaptoacetate, t-butylmercaptoacetate, amylmercaptoacetate, hexylmercaptoacetate, octylmercaptoacetate, isooctylmercaptoacetate, 2-ethylhexylmercaptoacetate, decylmercaptoacetate, isodecylmercaptoacetate, laurylmercaptoacetate. myristyl mercaptoacetate, hexadecyl mercapto-acetate, stearyl mercaptoacetate, allyl mercaptoacetate, metallyl mercaptoacetate, crotyl mercaptoacetate, oleyl mercaptoacetate, cyclo-pentyl mercaptoacetate, cyclohexyl mercaptoacetate, 2-methylcyclohexyl mercaptoacetate, benzyl mercaptoacetate, methyl-B-mercaptopropionate, ethyl-8-mercaptopropionate/ isopropyl-B-mercaptopropionate, octyl-8-mercaptopropionate., isooctyl-B-mercaptopropionate, 2-ethylhexyl-B-mercaptopropionate, decyl-B-mercaptopropionate, octadecyl-3-mercaptopropionate, allyl-B-mercaptopropionate, oleyl-B-mercaptopropionate, benzyl-8-mercaptopropionate , cyclohexyl-S-marcaptopropion at, methyl-α-mercaptopropionate, hexyl-α-mercaptopropionate, nonyl-α-mercaptopropionate, octyl-α-mernaptopropionate, isooctyl-α-mercaptopropionate, stearyl-α-mercaptopropionate, oleyl-α-mercaptopropionate, raethyl-α-mercaptobutyrate . ^-mercsptobutyrate, benzyl-ε-mercaptobutyrate,

cyclopentyl-7-mercaptobutyrate, oleyl-Z-mercsptobutyrate, isbpropyl-<$-mercaptovalerate, octyl-<5-mercaptovaléra t, isooctyl-4-mercaptovalerate, octadecyl-rf-mercaptovcilerate, oleyl-i-mercaptovalerate, cyclohexyl-5-mercaptovalerate and benzyl 6-mercaptovalerate, methyl mercaptan, ethyl mercaptan, butyl mercaptan, octyl mercaptan, dodecyl mercaptan, stearyl mercaptan, oleyl mercaptan, methoxyethyl mercaptan, ethoxyethyl mercaptan, octoxyethyl mercaptan, ethoxypropyl mercaptan, acetic acid, stearic acid, benzoic acid, caprolic acid, caprylic acid, decanoic acid, enanthic acid and oleic acid*

When preparing compounds according to the present invention, numerous methods can be used as described in the following. Regardless of the method used, however, the reaction should be carried out at temperatures varying from room temperature to 100°C, usually at 25 - 50°C. The reaction can usually be carried out with water as a solvent regardless of the method used. You can also use water-immiscible organic solvents, e.g. aliphatic and aromatic hydrocarbons such as hexane, octane, benzene, toluene, xylene, aliphatic carboxylic acid esters etc., e.g. butyl acetate, propyl propionate,

and methyl valerate. The amount of solvent is not critical and can be varied within a large range.

If nothing else is stated, all parts and percentages are per weight in the following examples.

In the examples, the refractive index (R.I.) is measured at 25°C, unless otherwise stated. Illustrative methods include the following:

FRI METHOD 1:

This is the general procedure of Kauder and Brecker except that sodium monosulfide, sodium disulfide, sodium urate trisulfide, sodium urate tetrasulfide, ammonium monosulfide, ammonium disulfide, ammonium trisulfide or ammonium tetrasulfide are reacted with an appropriate tin compound and appropriate -5H-containing compound or compounds as indicated above. .

FORWARD PATH 2:

In this method, the sodium mono- or polysulfide (or potassium mono or polysulfide), water, mercaptc-containing esters, hydrocarbon if this is desired and ammonium hydroxide are added to a reactor after which an aqueous solution of an alkyl tin halide is slowly added..e.g. at temperatures from 25-35°_C. The mixture was then heated .f. e.g. to 50°C, the layers were separated after which the product was washed and dried.

PROGRESS METHOD 3:

In this process, the mercapto-containing ester, water, an organic solvent and ammonium hydroxide added to a flask, after which two solutions are simultaneously added,

ie (A) an alkyltin chloride and (B) an alkali metal mono or polysulfide. The product is then separated, washed and distilled.

PROCEDURE 4:

This is the same method as method 3, except that NaHCO 3 is used in the same raolar quantity as said ammonium hydroxide.

FRE M WAY S:

In this method, alkyltin chloride, water and ammonium hydroxide are added to a flask, after which the mercapto-containing ester and an alkali metal mono- or polysulphide are simultaneously added.

PROCEDURE 6:

This method involves adding the mercapto-containing ester, water and ammonium hydroxide to a reactor, after which an alkyl tin chloride is added and then an alkali metal polysulphide or monosulphide at 30°C. After heating to 45°C, the product is separated, washed and distilled.

These methods are described in more detail in Kugele et al, U.S. Pat. patent no. 3.869.4^7• The entire method described there is thus included as a reference. The working examples in the aforementioned patent can be followed by completely or partially replacing the mercapto compounds used by Kugele with mercaptophor compounds with the following formula:

Stabilizers according to the present invention can be used with halogen-containing vinyl and vinylidene polytners, e.g.

resins .where the halogenatora is attached directly to the carbon atoms. Preferably, the polymer is a vinyl halide polymer, in particular

a vinyl chloride polymer..Usually the vinyl chloride polymer is made from monomers consisting of either vinyl chloride alone or

one mixture of monomers where vinyl chloride makes up at least 70% by weight. When vinyl chloride copolymers are stabilized, preferably the saropolymer of vinyl chloride with an ethylenic unsaturated compound copolymerizable with vinyl chloride should contain at least 10% polymerized vinyl chloride.

As the chlorinated polymer, chlorinated polyethylene can be used with from 14 to 75 e.g. 27% by weight chloride, chlorinated natural and synthetic rubber, rubber hydrochloride, chlorinated polystyrene, vchlorinated polyvinyl chloride, polyvinyl chloride, polyvinylidene chloride, polyvinyl bromide, polyvinyl fluoride, copolymers of vinyl chloride with from 1 to 90%, preferably from 1 to 30 °h of a copolymerizable ethylenic unsaturated compound such as vinyl acetate, vinyl butyrate, vinyl benzoate, vinylidene chloride, diethyl fumarate, diethyl maleate, other alkyl funra rates and maleates, vinyl propionate, methyl acrylate, 2-ethyl hexyl acrylate, butyl acrylate and other alkyl acrylates, raethyl raethacrylate, ethyl methacrylate, butyl rnetacrylate and other alkyl methacrylates, methyl-a -chloroacrylate, styrene, trichloroethylene, vinyl ethers such as vinyl ethyl ether, vinyl chloroethyl ether and vinyl phenyl ether, yinyl ketones such as<y>ynyl methyl ketone and vinyl phenyl-

1'ketone, 1-fluoro-2-chloroethylene, acrylonitrile, chloroacrylonitrile, allylidene diacetate and chlorallylidene diacetate. Typical copolymers include vinyl chloride-vinyl acetate (96:4 sold commercially as VTNW), 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-trichloroethylene (95:5), vinyl chloride-2-ethylhexyl acrylate (80:20).

The stabilizers according to the present invention can be added to the polymer by mixing the polymer and the stabilizer in a suitable mill egg or by mixing or by means of other well-known methods which give uniform distribution throughout the polymer composition. The mixture can thus be carried out by rolling at 100-160°C. ;

In addition to the new stabilizers, the resin can also be supplemented with common additives such as softeners, pigments, fillers, dyes, ultraviolet absorbents, thickening agents and the like. One can. also add common and well-known tin stabilizers, e.g. of the type described in Kauder or Kugele et al or in V/e is fe ld U.S. Patent No. 3,640,950, Leistner U.S. Patents Nos. 2,870,II9 and 2,870,I82, Best U.S. Patent No. 2,731,484, Stefl U.S. patent No. •2,731,482. and Måck U.S. patent no. 2,914*50^»eg. These patents are thus included as a reference here.

If softening agents are used, these are used in normal amounts, e.g. from 10 to 150 parts per 100 parts polymer. Typical plasticizers are di-2-ethylhexyl phthalate, dibutyl sebacate, dioctyl sebacate, tricresyl phosphate.

The tin-containing stabilizers according to the present invention are usually used in amounts of from 0.01 to 10 percent by weight of the polymer, more preferably 0.2 to 5 percent by weight of the polymer.

As mentioned earlier, you can also add from 0.1 to 10 parts of a methol salt stabilizer per 100 parts of the halogen-containing polymer. You can thus use barium, strontium, calcium, cadmium, zinc, lead, tin, magnesium, cobalt, nickel, titanium and aluminum salts of phenols. aromatic carboxylic acids, fatty acids or epoxy fatty acids.

Examples of suitable salts include barium di-^(nonylphenolate), strontium di(nonylphenolate), strontium di(amylphenolate), barium di(octylphenolate), strontium di(octylphenolate), barium di(nonylphenolate o-cresolate), lead di(octylphenolate), cadmium-2-ethylhexoate, cadmium laurate, cadmium stearate, zinc caprylate, cadmium caprate, barium stearate, barium ?-ethylhexoate, barium laurate, barium ricinoleate, lead stearate, aluminum stearate, cadmium naphthenate, cadmium benzoate, cadmium p-tert.butyl benzoate, barium octyl salicylate, cadmium epoxy stearate, strontium epoxy stearate, cadmium salt of epoxidized acids of soybean oil and lead epoxy stearate.

In plaster sol preparations, it is also preferred to add from 0.1 to 10 parts of an epoxy vegetable oil per

100 parts of the polymer. One can e.g. use an epoxidized soybean oil or epoxidized tall oil, epoxy esters of fatty acids, e.g. isooctylepoxystearate.

In the following examples, monoalkyltin-tris(mercaptoalkanyl)alkanoates and dialkyltin-bis(mercaptoalkanyl)-alkanoates and the like are mentioned, because even if they are not part of the present invention, their use in a mixture with compounds according to the present invention be part of the present invention. Mono- and polysulfides according to the present invention can also be prepared by reacting ammonium and/or alkali metal mono- or polysulfide with such mono- and dialkyltin mercaptp-alkanyl alkanoates.

EKS EMPEL 1

. In a ? 204 g (1.0 mol) of 2-mercaptoethyl caprylate, 200 ml of water, 84 g (1.0 mol) of sodium bicarbonate and 300 ml of heptane were added to a 3 liter flask. At 30-40°C, 110 g (0.5 mol) of dimethyltin dichloride dissolved in 200 ml of water were added dropwise to the mixture. The mixture was stirred for one hour at 30-40°C and two layers were obtained.

The organic layer was washed with 200 ml of water and then distilled

under vacuum at approx. 100°C. A yield of 273 g of dimethyltin bis(2-mercaptoethyl caprylate) was obtained. n^7 1.5060.

OAK SAMPLE 2

A 2 liter flask was charged with 306 g (1.5 mol) of 2-mercaptoethyl caprylate, 200 ml of water, 126 g (1.5 mol) of sodium bicarbonate and 3.0 ml of heptane. The mixture was added at 40°C

120 g (0.5 mol) of monomethyltin trichloride dissolved in 150 ml of water.

After the addition, the mixture was stirred for one hour at 30-40°C. The layers were separated, and the organic phase was washed with 200 ml of water. The heptane was removed under vacuum to give 363 g of monomethyltin-tris(2-mercaptoethyl caprylate) as a clear. colorless liquid,

n^<>>1.5041.

EXAMPLE EL 3

A 2 liter flask was charged with 516 g (1.5 mol) of 2-mercaptoethyl stearate, 200 ml of water, 12b g of sodium bicarbonate and 500 ml of heptane. At 40-50°C, 120 g (0.5

mol) monomethyltin trichloride dissolved in 150 ml of water. The mixture was then stirred for one hour at 40-50°G and two layers were obtained. The organic layer was separated and washed with 200 ml of water and then distilled under vacuum at 106°C. A yield of 560 g of monomethyltin tris(2-aminoaptoethyl)stearate was obtained as a white solid, melting point 44-47 °C

EXAMPLE 4

To a 2 liter flask was added 430 g (1.25 mol) of 2-raercaptoethyl stearate, 200 ml of water. 69 g (0.65 mol) sodium carbonate and 300 ml heptane. The mixture was added at 30-40°C

55 g (0.25 mol) dimethyltin dichloride and 60 g (0.25 mol) raonomethyl tin trichloride dissolved in 150 ml water. The mixture was then stirred in

one hour at the aforementioned reaction temperature, and two layers were separated. The organic phase was washed with 200 ml of water and then distilled under vacuum at c. 100°C, and this gave 493 S of a colorless oil. The product was a mixture of monomethyl-dimethyltin-tris,bis-(2-mercaptoethylstearate). Melting point jf>-^ 0°C .

EXAMPLE 5

A 2 liter flask was added. 18? g (1.5 mol) of 2-mercaptoethyl acetate, 200 ml of water, 300 ml of heptane and 120 g (0.5 mol) of monomethyltin trichloride. 126 g (1.5 mol) of sodium bicarbonate were added portionwise to the mixture and the temperature was maintained at 25-40°C during the addition. The mixture was then stirred for one hour at 25-40°C. The layers were separated and the organic phase washed with 200 ml of water. The heptane was then removed under vacuum. A yield of 240 g of monomethyltin tris(2-mercaptoethyl acetate) was obtained as a colorless oil. n^ 1.5575.

EXAMPLE 6

To a 2 liter flask was added 513 g (1.5 mol) of 2-mercaptoethyl oleate, 200 ml of water, 126 g of sodium bicarbonate and

500 ml of heptane. The mixture was then at 25-35°C added 120 g

(0.5 mol) of monomethyltin trichloride dissolved in 150 ml of water. The mixture was then stirred for one hour at 25-35°C and two layers were separated on standing. The organic layer was washed with 200 ml and then distilled under vacuum at 100°C. Monomethyltin-tris(2-mercaptoethyl oleate) was prepared in a yield of 9^.5% as a pale yellow oil* n|<5 >1.5008

EXAMPLE 7

The procedure from example 2 was repeated using 142 g (0.50 mol) of monobutyltin trichloride instead of the mentioned monomethyltin trichloride<.>The yield was 3&3 S of a colorless oil

• which consisted of monobutyltin-tris(2-mercaptoethyl caprylate).

njp 1.5061.

EXAMPLE Q

The procedure from Example 1 was repeated using 52 g (0.125 mol) dioctyltin dichloride and 85 g (0.25 mol) monooctyltin trichloride instead of dimethyltin dichloride. The yield was 297 g of a pale yellow oil consisting of dioctyltin bis(2-mercaptoethyl caprylate) and monooctyltin tris(2-mercaptoethyl caprylate).

lip 1.5001

EXAMPLE Q

To a 2 liter flask was added 204 g (1.0 mol) of 2-mercaptoethyl caprylate, 200 ml of water, 300 ml of heptane and 120 g (0.5 mol) of monomethyltin trichloride. To the mixture was then added 80 g (1.0 mol) of a 50% aqueous NaOH solution at 25-35°C. Stirring was continued for one hour under the conditions mentioned and two layers were separated, and the organic layer was distilled under reduced pressure and 273% of a pale yellow oil was obtained. The product essentially consisted of monomethyl monochlorotin bis(2-mercaptoethyl caprylate). njp 1.5244.

EXAMPLE 10

A 2 liter flask was charged with 286 g (1.5 mol) of mono-thioglycerin diacetate ester, 200 ml of water, 126 g of sodium bicarbonate and 500 ml of heptane. At 40-50°C, 120 g (0.5 mol) of monomethyltin trichloride dissolved in 150 ml of water were added to the mixture. The mixture was stirred for one hour at 40°C and the layers were separated. The organic layer was washed with 200 ml of water and distilled under vacuum at 100°C. A yield of 328 g was obtained consisting essentially of monomethyltin tris(monothioglycerin diacetate) as a thick oil. n£5 1.5310.

EXAMPLE 11

A 2 liter flask was added with 120 g (0.5 mol) of monomethyltin trichloride dissolved in 200 ml of water. The whole was heated to 30°C and 1204 g (1.0 mol) of 2-mercaptoethyl caprylate was added.

Then 80 g (1.0 mol) of a 50% aqueous sodium hydroxide solution was added dropwise at 30-40°C. The mixture was stirred for one hour. After this, a solution prepared by heating 32.5 g (0.25 mol) of 60.% aqueous Na^S and 8.0 g (0.25 mol) of sulfur in 100 ml of water was added dropwise. The addition was carried out at 25-35°C. After stirring for one hour at 35°C, the product layer was separated and washed with 200 ml of water. The product was then distilled to 100°C under vacuum, and a 100% yield of a pale yellow oil was obtained. The product is essentially bis(methyltin-di-"-mercvptoethylc.?.prylate Jdisulf id.<ng>5 1.5279.

Eczema PEL 12

The procedure from example 11 was repeated using 3?t5g (0.25 mol) of 60% aqueous sodium sulphide instead of the formed (0.25 noi) sodium disulphide, and the corresponding monosulphide was produced. The yield was 277 g of a pale yellow oil, ng5 1.5269.

EXAMPLE 13

The procedure from example 11 was repeated using 96 g (0.4 mol) methyltin trichloride, 33 g (0.15 mol) dimethyltin dichloride instead of the mentioned methyltin trichloride. The yield was 285 g of a pale yellow oil consisting essentially of (monomethyltin-di(2-mercaptoethylcaprylate)) (dimethyltin mono(2-mercaptoethylcaprylate)) disulfide. njp 1.5258.

EXAMPLE 14

120 g (0.50 mol) of monomethyltin trichloride in 200 ml of water were heated to 30°G and 204 g (1.00 mol) of 2-mercaptoethyl caprylate were added, after which 3 g (0.5 mol) of 28% ammonium hydroxide was slowly added. The mixture was stirred for one hour. Man added

then 125 g (0.25 mol) of 20%, aqueous ammonium disulfide solution" over 30 minutes at 25-35°^. The mixture was heated

to 50°C and the lower product layer was separated from the aqueous phase. The product was washed with 200 ml of water and dried at 100°C at 2 mm Hg absolute pressure. A quantitative yield of a pale yellow oil was obtained. The product is essentially bis{monomethyltin-bis(2-mercaptoethylcaprylate)] disulfide. nj^ .1.5288.

EXAMPLE 15 i

A 2 liter flask was added 32.5 g (0.25 mol)

60% aqueous sodium sulfide and 8.0 g (0.25 mL) of sulfur dissolved in

100 ml of water, 300 ml of heptane, 150 ml of water, 218 g (1.0 mol) of 2-mercaptoethyl pelargonate and 61 g (1.0 mol) of 26% aqueous ammonium hydroxide. Mari then added a mixture of 96 g (0.4 mol) methyltin trichloride and 33 g (0.15 mol) dimethyltin dichloride dissolved in 150 ml of water. The mixture was then held at 50°C for 30 minutes, the layers were separated and the product layer was washed and dried to

100°C under vacuum. The product (99%) essentially consisted of

bisfmethyl/dimethyl-tin-mono/dilP-mercsptoethylpelargonate)) disulphide.

n^ 1.5245-

EXE MPEL 16

The procedure from Example 15 was repeated using 32.5 g (0.25 mol) of 60% aqueous sodium sulphide instead of the formed sodium disulphide, whereby msn obtained the corresponding

OK

monosulphide. Yield 296 g of a pale yellow oil. n^ 1.5222.

EXAMPLE 17

To a 2 liter flask was added 300 ml of heptane, 91 g (1.5 mol) of 28% aqueous ammonium hydroxide, 200 ml of water, and 218 g (1.0 mol) of 2-mercaptoethyl pyrrolgonate. A mixture of 120 g (0.5 mol) of methyltin trichloride dissolved in 150 ml of water was then added. The mixture was heated to 35°C and held at this temperature for 30 minutes, the layers were then separated after which the product layer was washed and dried at 100°C under reduced pressure. The product of 206 g was bis(monoraethyltin-bis(2-mercaptoethyl pelargonate)'j oxide.-n*5 1.5197.

EXAMPLE 18

A 2 liter flask was added with 120 g (0.5 mol) of methyltin trichloride dissolved in 200 ml of water. The mixture was heated

to 30°C and 163.5 g (°>75 mol) of 2-mercaptoethyl pelargonate were added. 60 g (0.75 mol) of 50% aqueous sodium hydroxide solution was then added dropwise at 30-40°C. The mixture was then stirred for one hour. A solution prepared by heating 32.5 g (0.25 mol) of 60% aqueous Na0S and 100 ml of water at 25-35°C was then added, the mixture was stirred for one hour, the layers were separated and the product layer was washed with 200 ral water. The organic layer was distilled at 100° C. under vacuum, and 240 g of a pale yellow oil was obtained which contained fmonomethylmcnchlorotin-2-mercaptoethyl-polargonate) (mohomethyltin-bis(2-merc3ptoethylpenrirgonate)] sulphide. njp 1.5293. !

in

EKS EMPEL 19 . ' ,

To a 2 liter flask was added 120 g (0.5 mol) of methyltin trichloride in 200 ml of venn. The mixture was heated to 30°C

and added 153 g (0.75 mol) of 2-mercaptoethylc2pryl:t and 50.5 g (0.25.mol) laurylmercaptan. Then wood was added dropwise.

30-40°C 6l g (1.0 mol) 28 # aqueous ammonium hydroxide. The mixture was then stirred for one hour. A solution of 32.5 g (0.25 mol) of 60% aqueous sodium sulphide in 100 ml of water at 35°C was then added. Stirring was then carried out for an hour, the layers were separated and that

organic layers washed with 200 ml of water. The organic phase was distilled to 100°C under vacuum, and mrtn obtained 269 g of a yellow oil which substantially contained (monomethyltin-bis(2-mercaptc~ et yles pryla t)) (monoethyltin—mono( ?-mer~:ptoethylcaprylate )mono-lauryl mercaptide} sulfide. n£- 1.5267.

EXAMPLE 20

The same procedure as in example 19 was used, but 1 g (0.25 mol) of isooctylthioglycolate was used instead of lauryl mercaptide. The yield was 27? g of a pale yellow oil. i.e. [raono-methyltin-bis(2-mercaptoethylcaprylate)) ( monomethyltin-raono(2-mercaptoethylcaprylate)monoisooctylthioglycolrLtJ sulfide, n^ 1.5278.

EXAMPLE 21

The same procedure as in example 19 was used, but 54.5 g (0.25 mol) isooctyl mercaptopropionate and 0.25 ml sodium disulfide were used instead of the aforementioned lauryl meroaptan and sodium sulfide, respectively. A yield of 274 g of a yellow oil was obtained which consisted of (monomethyltin-bis(2-mercaptoethyl caprylate)) (monomethyltin-mono(2-merca<p>toet<y>lca<p>r<y>late)monoisooct <y>lmerca<p>to<p>ro<p>ionate) disulfide. n^5 1.5266.

EKS EMPEL 22

The same procedure as in example 19 was used, but 3 g (0.25 ml) of 2-ethylhexoic acid was used instead of lauryl mercaptan. The yield is 251 g of a yellow oil containing (monomethyltin-bis(2-mercaptoethylcaprylate)J | monomethyltin-mono(2-mercaptoethylcaprylate)mono(2-ethylhexoate)J sulphide, n'^ 1.5214.

EXAMPLE EL 23

The procedure from Example 15 was repeated, using 258 g (0.75 mol) of 2-mercaptoethyl stearate and 57 g (0.25 mol) of isooctyl maleate instead of said (1.0 mol) 2-mercaptoethyl pelorgonate. A low-melting white solid, melting point 38-43°C, weighing 370 g was obtained, and the product essentially consisted of '(raonomethyltin-bis(2-mercaptoethylstearate)] imonomethyltin-mono(2~mercaptoethylstearate)monoisooctylmaleate)disulfide, ri^ P 1.5193'

EXAMPLE 24

To a 2 liter flask was added 204 g (1.0 mol) of 2-mercaptoethyl caprylate. 102 g (0.5 mol) isooctylthioglycolate, 200 ml water, 300 ml heptane and 126 g (1.5 mol) sodium bicarbonate.

To the mixture was added dropwise at 25~30°C a solution of

120 g (0.5 mol) methyltin trichloride in 150 ml water. After addition, the mixture was stirred for one hour at 40°C and two layers were separated. The organic phase was washed with 200 ml of water and distilled under vacuum at 100°G. A yield of 366 g was obtained which essentially consisted of monomethyltin bis(2-mercaptoethyl caprylate) monoisooctylthioglycolate as a pale yellow oil,

n£<5>1.5103.

EXAMPLE 25

A 2 liter flask was added with 120 g (0.5 mol) of monomethyltin trichloride dissolved in 200 ral of water. The mixture was heated to 30°C and at this temperature 80 g (1.0 mol) of 50# aqueous sodium hydroxide solution was added dropwise. The mixture was then stirred for one hour, after which a solution of a-v'32.5 S (0.25 mol) 60 # aqueous sodium sulphide in 100 ml of water was added dropwise at 25-35°C. After stirring for one hour at 35°C, the product layer was separated and washed with 200 ml of water. The product was distilled to 100°C under vacuum, and a 100% yield of a yellow oil was obtained. The product is essentially bis(methyltin-di(2-mercaptoethyl tallate)) sulphide, ng<5>1.5168.

EXAMPLE 26

A 2 liter flask was charged with 785 g (1.0 mol) methyltin tris(2-mercaptoethyl pelargonate) and 120 g (0.5 mol) methyltin trichloride. The mixture was stirred at 50°C for one hour. The resulting product, a clear and colorless oil (905 g) • is essentially monomethyl morioclprtlnn-bis(2-mercaptoethyl pelargonate).

rff 1.5248. ,

EXAMPLE 27

To a 3-necked flask was added 785 g (1.0 mol) raonomethyltin-tris(2-merco.ptoethylpelargonate), 248 g (1.0 mol) dibutyltin oxide and 75 ml toluene. The mixture was stirred and kept at 100°C

for 2 hours, and a clear solution was obtained. The solvent was removed under vacuum to give 1016 g of a pale yellow oil.

Monoethyltin bis(2-mercaptoethyl pelargonate)raono(2-mercaptoethyl oxydibutyltin pelargonate) has a refractive index at 25°C of 1.5069.

OAK SAMPLE 28

A 2 liter flask was added with 120 g (0.5 mol) of monomethyltin trichloride dissolved in 200 ml of water. The solution was heated to 30°C and 197 g (1.0 mol) of 2-mercaptoethylphenylacetate was added. It was then added dropwise at J0-/\. 0°C approx. 80 g (1.0 mol) 5° aqueous sodium hydroxide. The mixture was then stirred

for one hour. A solution of 32.5 g (0.25 mol) of 60% sodium sulphide dissolved in 100 ml of water was then added dropwise at 30-35°C. After stirring for one hour, a product layer was separated which • was washed with 200 ml of water. The product was distilled under vacuum, and a 100% yield of a yellow oil was obtained. 270 g of bis(raonomethyltin-bis(2-mercaptoethylphenylacetate)] sulphide. nQ- 1.6122.

E XAMPLE 2q

To a 3-neck flask was added 83 g (0.5 mol) of methylstannoic acid. 273 K (1.5 m°l) 2-mercaptoethyl benzoate and 500 ml toluene. The mixture was refluxed for 3 hours, cooled to 3°C and filtered. The organic layer was removed by vacuum distillation at 100°C, and 322 g of a white solid was obtained. The solid consists essentially of monomethyltin-tris(2-mercaptoethylbenzoate), melting point 263-2o7<c>C.

EXAMPLE 30

A 2 liter flask was added with 28 l g (1.0 mol) of monobutyltin trichloride dissolved in 400 ml of water. The solution was heated to 30°C and 436 g (2.0 mol) of 2-mercaptoethyl pelargonate was added. 169 g (2.0 mol) of 50% aqueous sodium hydroxide were then added dropwise at 30-35°C. The mixture was stirred for one hour, and 65 g (0.5 mol) of sodium sulphide (60 #) dissolved in 100 ml of water was added dropwise at 40°C. After stirring for one hour at this temperature, a product layer separated which was washed with 400 ml of water. The product was then vacuum distilled to 100°G and 617 g of a pale yellow oil was obtained, bis(monobutyltin-bis(2-mercaptoethylpelargonate))-sulphide, ng<5>1.5?19•

EXAMPLE 31

A 2 liter flask was added with 28 l g (1.0 mol) of butyl trichloride dissolved in 400 ml of water. The solution was heated to 30°C and 101.5 g (0.5 mol) of isooctylthioglycolate and 327 g (1.5 mol) of 2-mercaptoethyl pelargonate were added. Then, 122 g (2.0 mol) of ammonium hydroxide (28%) were added dropwise at 35-40°C. The mixture was stirred for one hour at 35-40°C. 64 g (0.5 mol) of ammonium sulphide (40%) were then added; and stirred the mixture for an hour. Kan then had a product layer separated which was washed with 400 ml of water and dried under vacuum at 100°C. A total of 596 g of one yellow oil (^monobutyltin-bis(2-mercaptoethyl geragonate)) was obtained -

(monobutyltin(isooctylthioglycolate) (2-mercaptoethyl pelargonate)) - sulfide, nj<p>1.5211.

EXAMPLE 32

A 2 liter flask was added with 28 l g (1.0 mol) of butyltin trichloride dissolved in 400 ml of water. The solution was heated to 30°C and then 305 g (1.5 mol) of 2-mercaptoethyl caprylate was added. 120 g (1.5 mol) of 50% aqueous sodium hydroxide were then added dropwise at 30-40°C and the mixture was stirred for one hour at the said temperature. 65.0 g (0.5 mol) were then added

60% Na^S dissolved in 100 ml of water, and stirred the mixture for one hour

at 30-40°C. The layers were separated and the product layer was washed with 400 ml of water distilled under vacuum to 100°G. The product (monobutyltin bis(2-mercaptoethylcaprylate)) sulfide was obtained in 98% yield as a yellow oil. 1.5276.

EXAMPLE 33

To a 2 liter flask was added 240 g (1.0 mol) monomethyltin trichloride dissolved in 400 mlVc:nn. The solution was heated to 3°C and 218 g (1.0 mol) of 2-mercaptoethyl pelargonate and 109 g (0.51 mol) of isooctyl mercaptopropionate were added. 120 g (1.5 mol) of 50% aqueous sodium hydroxide solution was then added dropwise at 25-30°C and the whole was stirred for one hour. Then 65.0 g (0.5 mol) of 60# sodium sulphide dissolved in 100 ml of water was added and the mixture was stirred for one hour at 30-40°C. The layers were separated, the organic layer was then washed with 400 ml of water and purified by vacuum distillation at 100°C. The product sorn was 474 g of a pale yellow oil essentially a mixture of methyltin-bis(2-mercaptoethylpelargonate)J (.monoraethylmonochlorotinnf isooctylmercaptopropionate)J sulphide and (monomethyltin(isooctylraercaptopropionate)-

(2-mercaptoethyl pelargonate)} fmonomethyl monochlorotin(2-mercaptoethyl pelargonate ))sulph id. np l,<t>3288.

EXAMPLE 34

To a 2 liter flask was added 240 g (1.0 mol) of monomethyltin trichloride dissolved in 400 ml of water. The solution was heated to 30°C and 218 g (1.0 mol) of 2-mercaptoethyl pelargonate was added. Then 80 g (1.0 mol) of 50% aqueous sodium hydroxide was added dropwise and stirred for one hour at 25-35°C. Then 65 g (0.5 mol) of 60% sodium sulphide dissolved in 150 ral of water was added and the blank was stirred in one hour at 35°C The layers were separated, the organic phase was then washed with 400 ml of water and distilled under vacuum to 100°G. The product, bis[monomethyltin(2-mercaptoethylpelargonate)) bis-3ulfide was obtained in a yield of $96.5 as a pale yellow oil. njy<>>1.5630.

example 35

To a 2 liter flask was added 240 g (1.0 mol) of monomethyltin trichloride dissolved in 400 ml of water. The solution was heated to 35°C and 660 g (2.0 mol) of 2-mercaptoethyl oleate was added.

160 g (2.0 mol) 50% were then added dropwise at 35°C

aqueous sodium hydroxide. The mixture was then stirred for one hour. 65 g (0.5 mol) of sodium sulphide dissolved at 60 °C were then added

in 150 ml of water at 30-35°C After stirring for one hour, the product layer was separated and washed with 400 ral of water, distilled to 100°C

under vacuum, and 788 g of a pale amber oil was obtained. The product consisted essentially of bisfmonomethyltin bis(2-mer~captoethyloleate) sulphide, nj^ 1.5118.

EXAMPLE 36

To a 3-necked flask was added 120 g (0.5 mol) of methyltin trichloride in 15O! ml of water, 109 g (0.5 mol) of 2-mercaptoethyl pelargonate and 200 ml of toluene. The mixture was heated to 30°C and then 40 g (0.5 mol) of 50% aqueous sodium hydroxide were added dropwise and. then portionwise added 43 g (0.33 mol) 60% Na dissolved in 75 ml of water. The mixture was stirred at 30-40°C for one hour. The teams

was separated and the organic phase distilled, to 100°C below

vacuum, and 190 g of a colorless oil was obtained. n^ 1.5336. It is assumed that the product has the following structure:

118.5 g (0.1 mol) of the above compound was added to 200 ml of water and 43.5 g (0.2 mol) of 2-mercaptoethyl pelargonate. At 25°C, 16 g (0.2 mol) of 50# aqueous sodium hydroxide was then added dropwise to the mixture. The reaction mixture was stirred for one hour at 25-30°C and two layers were separated. The organic layer was separated and washed with 100 ml of water and distilled at 100°C under vacuum. The resulting product, which was 142 g of a colorless oil, had a refractive index n^ of 1.5266. The structure is assumed to be as follows:

EXAMPLE 37

To a 3-neck flask was added 150.5 g (0.5 mol) of phenyltin trichloride, 300 ml of water, 400 ml of benzene and 218 g (1.0 mol) of 2-mercaptoethyl plargonate. The mixture was added dropwise at 40°C with 80 g (1.0 mol) of 50% aqueous sodium hydroxide. After stirring for one hour at 40°C, 32.5 g (0.25 aeol) of sodium sulphide dissolved in 75 ml of water were added dropwise. After stirring for one hour at 40°C, two layers were separated, and the organic layer was dried and purified under vacuum to 100°C. The resulting product bisfmono-phenyl-bis(2-mercaptoethylpelargonate)) sulfide was obtained in an ex-

in pc

exchange on ^ 12 g as a pale yellow oil. n^v 1.5517.

EXAMPLE 38 I

A 2 liter flask was added with 120 g (0.5 mol) of monomethyltin trichloride dissolved in 200 ml of water. The solution was heated to 30°C and 218 g (1.0 mol) of 2-mercaptoethyl pelargonate was added. 80 g (1.0 mol) of a 50% aqueous sodium hydroxide solution were then added dropwise at 30-40°C. The mixture was then stirred for one hour. A solution prepared by heating 32.5 g (0.2.5 mol) of 60% sodium sulphide and 16 g (0.5 mol) of sulfur in 150 ml of water was then added. The addition took place in portions at 30-40°C. Stirring was continued for one hour, and a separated layer was obtained, after which the product layer was washed with 200 ml of water. The organic phase was distilled to 100°C under vacuum and 296 g of a pale yellow oil was obtained which contained bis(monomethylt.inn-bis(2~merc«pto-ethyl pélargonate)) trisulfide. n'^ 1.5,790

Eczema PEL 39

To a 3-neck flask was added 169 g (0.5 mol) of monooctyltin trichloride, 300 ml of water, 400 ml of benzene and 204 g (1.0 mol) of 2-mercaptoethyl caprylate. The mixture was kept at 30-40°C and then 80 g (1.0 mol) of 50% aqueous sodium hydroxide was added dropwise. Stirring was continued for one hour and a solution of 3.5 g (0.25 mol) of 60% aqueous sodium sulphide dissolved in 100 ml of water was added dropwise. Stirring was continued for a further hour and the layers were separated and the organic layer distilled at 100°C under vacuum. The resulting pale yellow oil weighing 320 g is bis(mono-octyltin-bis(2-mercaptoethyl caprylate)) sulphide, n'^ 1.5144.

EXAMPLE 40

To one 3-necked flask was added 79-5 g (0.33 mol) of monomethyltin trichloride, 147.5 g (0.67 mol) of dimethyltin dichloride dissolved in 250 ml of water, and 454 g (1.33 mol) of 2-mercaptoethyl oleate. The solution was heated to 3°C°S added dropwise at 30°C

106 g (1.33 mol) of 50$ aqueous sodium hydroxide during the entirae. The reaction mixture was then stirred for an additional hour. To it was then added dropwise 65 g (0.5 mol) of 60% sodium sulfide dissolved in 100 ml of water and the mixture was stirred for one hour. The layers were separated and the organic layer washed with 200 ml of water and distilled at 100°C under vacuum. The resulting product of 577 g is a yellow oil, probably a mixture of bis(mpnomethyltin-bis(2-mercaptoethyl oleate)) sulfide, bis(dimethyltin-mono(2-mercaptoethyl oleate)) sulfide and (monoroethyltin-bis(2-mercaptoethyl oleate) ) (dimethyltin mono(2-mercaptbutyloleate)) sulfide, n^ 1.5070.

EXAMPLE L 41

To a 3-necked flask was added 120 g (0.5 mmol) of monomethyltin trichloride dissolved in 200 ml of water. The make-up was heated to 30°C and 218 g (1.0 mol) of 1-methyl-2-mercaptoethyl caprylate was added. Then 80 g (0.5

mol) of $50 aqueous sodium hydroxide and stirred the mixture for one hour. Then, inan added dropwise 32.5 g (0.25 mol) of 60 # aqueous sodium sulfide in 100 ml of water at 25-35°C, stirred the mixture for one hour, and separated the formed layers. The organic layer was washed with 200 ml of water and distilled under reduced pressure, whereby 283 g of an almost colorless oil was obtained. n^ 1 1.5256. The product essentially consists of bis(monomethyltin-bis(1-methyl-2-mercaptoethyl caprylate)) sulphide.

EXAMPLE 42

To a 3-necked flask was added 120 g (0.5 mol) of methyltin trichloride dissolved in 200 ml of water, 121 g (1.0 mol) of 2-recapto-ethyl acetate, after which 1 g (0.5 mol) of 28 "jo aqueous ammonium hydroxide. The mixture was stirred for one hour at 30-35°C, whereupon 125 g (0.25 mol) of 20% aqueous ammonium disulfide was added over 60 minutes at said temperature. The mixture was heated to 50°C "and the lower product layer was separated from the aqueous phase. The product was washed with 200 ml of water and dried at 100°C under reduced pressure. A 96% yield of a pale yellow oil was obtained with a refractive index at 25°C of 1, 5697. The product is essentially bis(^monomethyltin-bis(2-mercaptoethyl acetate)3-disulfide.

^ EXAMPLE 43

To a 3-neck flask was added 131 g (0.6 mol) of 2-mercaptoethyl caprylate, 61.5 g (0.3 mol) of isooctylthioglycolate, 400 ml of toluene, 200 ml of water and 216 g (0.9 mol) of monomethyltin trichloride. The solution was cooled to 10°C and 64 g (0.8 mol) of 50% aqueous sodium hydroxide at 10-20°C were added. The reaction mixture was stirred for 15 minutes and 17 g (0.9 mol) of 60% Na 2 S in 150 ml of water was added over 30 minutes. The mixture was then stirred for 15 minutes and then 8.0 g (0.1 mol) of aqueous NaOH was added and then stirred at 50°C. The organic layer was separated and distilled under vacuum at 100°C. The yield was 315 g of a viscous, yellow oil, and it was assumed that this was the following compound:

r<ff>1.5388.

EXAMPLE 44

To a 3-neck flask was added 181.5 g (0.5 mol) of methyl thiostannoic acid and 371.5 g (0.5 mol) of methyltin tris(2-mercaptoethyl caprylate). The mixture was stirred and heated under nitrogen for 1.5 hours at 120°C. The product, which was a clear, amber-colored oil, was obtained in a yield of 96. It is assumed that the product has the following structure:

n^ 1.5<3>48.

EXAMPLE EL 45

To a 3-necked flask was added 120 g (0.5 mol) of methyltin trichloride dissolved in 200 ml of water. The solution was heated to 30°C and 260 g (1.0 mol) of 6-mercaptohexyl caprylate was added. 80 g (1.0 mol) of 50% aqueous NaOH solution were then added dropwise at 30-40°C. The mixture was then stirred for one hour. Mari then added a solution of 32.5 g (0.25 mol) p0% aqueous sodium sulfide in 100 ml of water at 25-35°C. After stirring for one hour at 35°C, the product layer was separated and washed with 200 ml of water. The product was then distilled at 100°C under vacuum, and a yield of 99% of pale yellow oil was obtained. n^-' '1.5345. It is assumed that the oil is bislmethyltin-bis(6-merc3ptohexylcaprylate)J sulphide.

EKS EMPEL 46

To a 2 liter flask was added 120 g (0.5 mol) of methyltin trichloride in 200 ml of water. The solution was heated to 30°C

and added 1536 (0.75 mol) of 2-mercaptoethyl caprylate and 19.5 g (0.25 mol) of mercaptoethanol and 400 ml of toluene. Then added

one dropwise at 30-40°C 84 g (1.0 mol) sodium bicarbonate dissolved

in 250 u ml of water. The mixture was then stirred for 2 hours. A solution of 3?5& (0.25 mol) was then added dropwise at 35°

$60 > aqueous sodium sulphide in 100 ml of water. The reaction mixture

was stirred for 2 hours, the organic layer was separated and this was distilled to 90°C under vacuum, and 204 g of a pale, yellow

pc

oil. nD" 1.5292. It is assumed that the product is essentially (monomethyltin(2-mercaptoethylcaprylot)(2-mercaptoethanol)] (monomethyltin-bis(2-mercaptoethylcaprylvit)) sulphide.

EXAMPLE 47

To a 3-neck flask was added 122.5 g (°.5 mol) of butyl chlorotin dihydroxide, 165 g (0.5 mol) of 2-mercaptoethyl oleate and 75O

ml of toluene. The mixture was boiled under reflux until m~n had removed 8.5 ml of water. The organic layer was distilled, and 260 g of a pale yellow oil with a refractive index of

njp 1.5320. It is assumed that the product is bis[monobutylmonochlorotin-(2-mercaptoethyloleate)oxide.

OAK SAMPLE 48

To a 3-necked flask was added 181.5 g (0.5 mol) of methylthiostannoic acid and 408 g (2.0 mol) of 2-mernaptoethyl caprylate, and the mixture was stirred and heated at 90-110°C for 1.5 hours under slightly reduced pressure. The liquid was then cooled and filtered at 40°C. The product of 571 g of a pale yellow oil had a refractive index at 25°C of 1.5248.

E XAMPLE 49 !

To a 3-necked flask was added 36<0>g (1.5 mol) of monomethyltin trichloride dissolved in 500 ml of water. The solution was heated to 30°C and 817 g (4<.>0 mol) of 2-mercaptoethyl caprylate was added. 320 g (4.0 mol) of 50% aqueous sodium hydroxide was then added dropwise at 30-40°C and the mixture was stirred for one hour at the said temperature. A solution of 32.5 µl (0.25 mol) of 60% sodium sulphide dissolved in 100 ml of water was then added. After stirring for 1 hour at the aforementioned temperature, the product layer was separated and washed with 400 ml of water. The product was then distilled to 100°C under vacuum, and 999 g of an almost colorless oil was obtained,

n<jp>is 1.5113.

EXAMPLE 50

To a 3-neck flask was added 555 g (0.5 mol) bis-(methyltin-bis(2-merca<p>toet<y>lc;:prylate)) sulfide, 97 g (0.5 mol) dimethyltin oxide and 4Q0 ml of toluene. The mixture was stirred and refluxed for 2 hours, and a clear solution was obtained. The solvent was removed under vacuum to give 650 g of a pale yellow oil. The reaction product contains [monomethyltin bis(2-mercaptoethyl caprylate )J ^monomethyltin mono(2rraercaptoethyl caprylate)mono(2-mercaptoethyloxydimethyltin caprylate f) sulphide.

ng5 1.5289.

EXAMPLE 51

A 3-necked flask was added with 180 g (0.75 mol) of monomethyltin trichloride dissolved in 100 ml of water and the whole was heated to 30°C and 306.5 g (1.5 mol) of 2-mercaptoethylcaprylyl was added. Subsequently, 120 g (1.5 mol) of 50% aqueous NaOH solution were added dropwise at temperatures from 30-40 0. The mixture was stirred for a

hour. A solution of 16.3 g (0.125 mol) SO% sodium sulphide dissolved in 75 ml of water at 30-40°C was then added. After

stirring for one hour at the mentioned temperature, the product layer was separated and washed with 250 ml of water. The product was distilled to 100°C under vacuum, and 430 g of a pale yellow oil was obtained. The reaction product contains two compounds with the following formulas:

The refractive index of the flash is 1.5151 at 25°C.

EXAMPLE 52

To a 3-necked flask was added 216 g (0.9 mol) of methyltin trichloride, 22 g (0.1 mol) of dimethyltin dichloride dissolved in 300 ml of water. The solution was warmed to 3°C and 511 g (2.5 mol) of 2-mercaptpetylcapryllacAt was added. 200 g (2.5 mol) of 5% aqueous sodium hydroxide was then added dropwise at 30-40°C. The mixture was stirred for one hour. A solvent was then added. ning of 26 g (0.20 mol) of 60% aqueous sodium sulphide dissolved in 75 ml of water at ^ 0~^. 0°C, After stirring for one hour, the product layer was separated and washed with 250 ml of water. The product was then vacuum distilled to 100°C, and 631 g of a colorless oil was obtained. njp 1.5153.

EXAMPLE 53

To a 3-necked flask was added 120 g (0.5 mol) of methyltin trichloride dissolved in 200 ml of water. The solution was heated to 30°C and 360 g (1.0 mol) monothioglycerin dicaprylate ester was added. 80 g (1.0 mol) of 50 # aqueous sodium hydroxide solution were then added dropwise at temperatures from 30-40°C. The mixture was stirred for one hour. A solution prepared by heating 32.5 g (0.25 mol) of 60% aqueous Na₂S and 8.0 g (0.25 mol) of sulfur in 100 ml of water was then added. The solution was added dropwise at 30-4°C. After stirring for one hour, the product layer was separated and washed with 200 ml of water. The product was then distilled to 100°C under vacuum, and a yield of 325 g was obtained

pc

of a yellow oil. nn-J 1.5143' The product is essentially bis-(monomethyltin bis(thioglycerin dicaprylate) disulfide).

' OAK SAMPLE 54

A 3-necked flask was added with 110 g (0.5 mol) of dimethyltin dichloride dissolved in 200 ml of water. The solution was heated to 30°C and 100 g (0.5 mol) of 2-mercaptoethyl pelargonate was added. 40 g (0.5 mol) of a 50 # aqueous sodium hydroxide solution was then added dropwise at 30-40°C. The mixture was then stirred

for one hour. A solution of 32.5 g (0.25 mol) of 60% aqueous Na2S dissolved in 75 ml of water at 25-35°C was then added. After stirring for one hour at 35°C, the product layer was separated and washed with 2.00 ml of water. The product was distilled to 100°C under vacuum,

and a yield of 95»5$ was obtained from a pale yellow oil.

nj^ 1.5319' The product is essentially bis(dimethyltin mono-(2-mercaptoethyl pelargonate) sulphide.

EXAMPLE 55

A 2 liter flask was added with 60 g (0.25 mol) of monomethyltin trichloride, 55 g (0.25 mol) of dimethyltin dichloride dissolved in 200 ral of water. The solution was heated to 0°C and 162 g (0.75 ml)-2-mercaptoethyl pelargonate was added, then 60 g (0.75 mol) of 50 µl aqueous sodium hydroxide was slowly added. The mixture was stirred for one hour, and. 32.5 g (0.25 mol) of 60% aqueous sodium sulfide dissolved in 75 ml of water were added. After stirring for one hour at 35°C, the layers were separated, the organic phase was washed with 200 ml of water and dried under vacuum at 100°C. A total of 229 g was obtained

TC

a pale yellow oil n^ 1.5296. The product is a mixture of mono-methyldimethyltin-mono/di-2-mercaptoethyl pelargonate sulphide.

EXAMPLE MPEL 56 .. Bis(monomethyltin-bis(2-mercaptoethyl pelargonate)-sulfide was mixed 'with Y^^dimej^-ltiri jgonal^sjiWidl in a. ratio "of 2/1, "n^ is 1.5301.

Products according to the present invention, i.e. mercaptoalkylalkanoates have an ability to react with greater efficiency than the corresponding alkylthioalkanoates, with dialkyl tin oxide and alkylstannoic acids. Under conditions where methyltin-tris(alkyl merc3ptdacetate or propion.;t) does not react at all with BugSnO or Me^SnO, then the corresponding methyltin-tris(2-mercaptoethylalkanoate) will react completely after 'a treatment in a couple of hours at 80-120°n. It is assumed that the products have the following formula:

1

In order to illustrate the beneficial effects that can be achieved with stabilized compositions according to the present invention, the following experiments were carried out. All stabilizers

was judged on a 'basis' with regard to equal costs and unequal weight shares. This means that certain stabilizers

.were used in larger quantities because of all their unit costs are lower. The tables are also set up in essentially the same way

tin base. The composition of the PVC resins in Tables I-VI

are the following:

COMPOSITION I

The resins from several major PVC factories were used to show that compounds according to the present invention can be used in different PVC resins.

Stability test (Dynamic nine-hole stability) The stabilizer was mixed with the PVC resin on a • two-roll mill at 195°C. a temperature at which the mixture is liquid and a good and light mixture is obtained, the mixture was then crushed at the same temperature and tested at one minute intervals after it was first added to the mill.

The appearance of the samples after the dynamic paint stability test is indicated in tables I to IV, and the sample numbers are the same in all tables, r 1

in

in •

In a tube extrusion test, compounds of the present invention proved to be far better stabilizers than commercially available tin stabilizers, producing a white tube with excellent production rate. Both dynamic mill stability (IMS) and residual furnace stability tests were carried out on the products.

The products were the same as those used in Tables I to IV using Allied SR 414-3 as the vinyl chloride resin. The amounts of stabilizer are indicated in Tables V and VI. The amounts were chosen so that the moon had approximately the same amount of tin in each of the compositions^ The sample numbers are the same as in tables I to IV and further numbers are indicated under table V.

Mixtures of monoalkyltin compounds and dialkyltin compounds according to the present invention prove to be more effective than individual components, and this applies whether they are prepared together from chlorides or simply mixed afterwards, and this is evident from table VII..

Claims (17)

1. Halogen-containing polymer composition containing a heat-stabilizing amount of monoorganotin or diorganotin mercaptoalkyl ester of a carboxylic acid or mercaptohydroxyalkyl ester of a carboxylic acid mono- or polysulfide, characterized in that the heat-stabilizing compound contains at least one tin atom having one or two hydrocarbyl groups with 1-20 carbon atoms and selected from the group consisting of alkyl, aryl, cycloalkyl, aralkyl and alkenyl and is bonded to the tin atom through carbon, at least one mercaptoalkyl ester of a carboxylic acid group bonded to tin through the sulfur in the mercaptoalkyl group and at least one mono- or polysulfide sulfur group bonded exclusively to tin, in that the organotin compound contains an amount of tin in the range 10-4 2% by weight and an amount of sulfur in the range 8-42% by weight, provided that if there is only one tin atom in the compound, then this is directly bonded only to carbon or sulphur, and if there is more than one tin atom in the compound, then one tin atom is bonded only to carbon or sulfur and the remaining tin atoms are directly bonded ku-h to carbon or sulfur or the remaining tin atoms is directly bound only to carbon, sulfur and oxygen. 2. Composition according to claim 1, characterized in that the organic compound has the formula: where x is a number from l Lii 10, R1, R2, R3 and R4 are alkyl, aryl, cycloalkyl, aralkyl or alkenyl with 1-20 carbon atoms, <R> 9'. <R> 17' <f>^ g and R19 are alkyl, cycloalkyl, aralkyl or alkenyl with 1-20 carbon atoms, Rg, R-^g/ R26 and R3 are hydrogen, hydroxyl, or alkyl with 1-20 carbon atoms, R^ , R-^ir/ R2y 0<3 ^35 is hydrogen or alkyl with 1-18 carbon atoms, y is at least 1,2 is 0 or an integer and the sum of y and z i is 2-20, R-j^r R2g and R^ q is hydrogen, hydrocarbyl with 1-19 carbon atoms where hydrocarbyl groups are alkyl, aryl, aralkyl, cycloalkyl, aralkenyl, or alkenyl with up to 3 ethylenic double bonds, hydroxyalkyl with up to 19 carbon atoms or hydroxyalkenyl with up to 19 carbon atoms, Rg is the alkylene with 1-20 carbon atoms or such a group with a halogen or hydroxy substituent or an ethylenic unsaturated divalent aliphatic hydrocarbon-yl-hydroxyl-hydrocarbon group with 2-19 carbon atoms, R... and is alkyl, aryl, cycloalkyl, aralkyl or alkenyl with 1-20 carbon atoms and R 14 is the alkylene of 2-20 carbon atoms provided that at least one of R 1 , R 1 , R 1 and R 1 is hydrocarbyl. 3. Composition according to claim 2, characterized in that when R^ , R2 , R3 , R^ , R1? , R 1 g and R 19 are hydrocarbyl, the hydrocarbyl group is methyl. 4. Composition according to claim 1, characterized is the alkylene having from 2 to 3 carbon atoms. 5. Composition according to claim 4, characterized in that R1Q is alkyl with from 6 to 19 carbon atoms, alkenyl with 17 carbon atoms or hydroxyalkenyl with 17 carbon atoms. 6. Composition according to claim 5, characterized in that when R^' R2 , R3 , R4, R17, R^ Q and R 1 g is hydrocarbyl, then they are methyl groups. 7. Composition according to claim 6, characterized in that x is 1 or 2. 8. Composition according to claim 7, characterized in that x. is 1. 9. Composition according to claim 1, characterized in that it contains a bis-monoalkyltin-di(mercapto-alkylalkanoate)-mono to disulfide where the merca <p>toalkyl group has from 2 to 3 carbon atoms and the alkanoate has from 6 to 20 carbon atoms. . 10.. Composition according to claim 9, characterized in that said monoalkyltin is monomethyltin. 11. Composition according to claim 1, characterized in that it contains a bis-monoalkyltin-di(mercapto-alkylalkanoate) mono- to disulphide where the mercaptoalkyl group contains from 2 to 3 double bonds. 12. Composition according to claim 11, characterized in that said monoalkyltin group is monomethyltin. 13. Composition according to claim 1, characterized in that it contains monoalkyltin-di[(mercaptoalkylalkanoate)]-[dialkyltin-mono(mercaptoalkylalkanoate)] mono- to disulfide where the mercaptoalkyl group has from 2 to 3 carbon atoms and the alkanoate group has from 2 to 20 carbon atoms. 14. Composition according to claim 13, characterized in that said monoalkyltin group is monomethyltin and said dialkyltin groups are dimethyltin. 15. Composition according to claim 1, characterized in that it contains a [monoalkyltin-bis (mercapto 2 to 3 carbon atoms alkylalkanoate or alkenoate)][monoalkyltin-mono(mercapto 2 to 3 carbon atoms. alkylalkanoate or alkenoate)mono-alkyl mercaptide] mono- to disulfide where the alkanoate group has from 2 to 20 carbon atoms and the alkenoate has 18 carbon atoms and 1 to 3 double bonds. 16. Composition according to claim 1, characterized in that it contains a compound selected from the group consisting of (1.) bis [monoalkyltin-bis (mercapto 2 to 3 carbon atom alkyl alkanoate, alkenoate. or ricinoleate)] sulphide or disulphide, (2) bis-[dialkyltin mono(mercapto 2 to 3 carbon atom alkylalkanoate, alkenoate or ricinoleate)] sulfide or disulfide and (3) [monoalkyltin bis-(mercapto 2 to 3 carbon atom alkylalkanoate, alkenoate or ricinoleate)] [dialkyltin mono( mercapto 2 to 3 carbon atom alkylalkanoate, alkenoate or ricinoleate)]sulfide or disulfide. 17. Composition according to claim 1, characterized in that it contains a compound with the formula: where R, Rn and R, are alkyl, aryl, cycloalkyl, aralkyl or alkenyl having from 1 to 20 carbon atoms and Z is or where n is 2 or 3, R 2 Q is alkyl, alkenyl, aryl or aralkyl having from 1 to 19 carbon atoms and R21 is alkyl or alkenyl with from 1 to 20 carbon atoms provided that at least one Z group is