CH619961A5 - Process for the preparation of organotin mercaptides. - Google Patents

Description

The invention relates to a new process for the preparation of organotin mercaptides by reacting organotin sulfides with reactive organic halides in the presence of specific aprotic solvents or even better in the presence of water. Moist freshly prepared organotin sulfides are preferably used. The implementations follow the following equations:

(1)

(RSn) 2S + 2RiX-

SRi SRi

I I

RSn -S-SnR

20th

O

Ri = -CH2OC-R12

means.

27. The method according to claim 18, characterized in that R is an alkyl group having 1 to 8 carbon atoms and Ri is the allyl or methallyl group.

28. The method according to claim 18, characterized in that R is an alkyl group having 1 to 8 carbon atoms and Ri is the benzyl group.

29. The method according to claim 1, characterized in that compounds of the general formula

SRi SRi

I I

RSn-S-SnR

I I

X X

produces in which R and X have the meaning given in claim 1 and

O O R14

II II I

Rl - (CH2) nC - OR7, - (CH2) mOCRl2, - CH2 - C = CH,

or represents the benzyl group, where n, R7, R12 and Rw have the meaning given in claim 1 and m is the number 3.

30. The method according to claim 29, characterized in that one produces compounds in which

O

II

Rl = - (CH2) nC — OR7,

wherein R7 is an alkyl, cycloalkyl, alkenyl or aralkyl group and n = 1 or 2.

31. The method according to claim 29, characterized in that compounds are prepared in which Ri is the allyl or methallyl group.

32. The method according to claim 29, characterized in that compounds are prepared in which Ri is the benzyl group.

(2)

(3) RO

R2

R3

SnS + RiX-

Rs

X

R2 \

/ r3

R4

X

, SRi

Sn

R4

R4 - Sn —S — Sn - R4 + RiX-> Rs - Sn - SRi + Rs - SnX Rs ^^ RÖ Rfi ^^ RÖ

S X

II I

30 (4) (RSn) 2S + 3RiX-> RSn (SRi) 2 + RSn —SRi

I I

X X

35

(5)

RSn — SR11 + RiX- ^ RSn

SRi

SR11

in which R, R2, R3, R4, Rs and Rö are alkyl groups with usually 1 to 20 carbon atoms, cycloalkyl groups with usually 5 or 6 carbon atoms in the ring, alkenyl groups with usually 2 to 20 or more, preferably 3 4s to 18 carbon atoms, aryl groups , usually phenyl or alkylphenyl groups with 1 to 4 carbon atoms in the alkyl group or aralkyl groups with usually 7 carbon atoms (R, R2, R3, R4, Rs and Rö are preferably the methyl group);

50

O

II

Rl = - (CH2) —nC - OR7,

55 O

II

- (CH2) - m -OC — R12, benzyl,

Rl4

60 I.

CH2 = C-CH2-

O

II

65 or —CH (CH3) C— OR ?,

wherein Rw is hydrogen or the methyl group;

R11 has the same meaning as Ri;

R.7 is an alkyl group of usually 1 to 20 carbon atoms, a cycloalkyl group of usually 5 or 6 carbon atoms in the ring, an alkenyl group of usually 2 to 20 carbon atoms and especially 3 to 18 carbon atoms or an aralkyl group of usually 7 carbon atoms;

Ri2 is an alkyl group usually having 1 to 19 carbon atoms or an alkenyl group usually having 2 to 17 carbon atoms;

X is a halogen atom with an atomic weight of 35 to 80, ie chlorine or bromine;

n = 1 or 2 and m = 2 or 3.

The aprotic solvents used as catalysts are the following:

O Rg

II X

(d) N-methyl-2-pyrrolidone,

where Rs represents a hydrogen atom or the methyl group and R9 and Rio represent methyl or ethyl groups. The preferred aprotic solvent is dimethylformamide. The amount of the aprotic solvent (if used) can vary, for example from 0.1 to 10 moles per mole of organotin sulfide, preferably from 0.8 to mole per mole of organotin sulfide.

The use of the catalyst or water is critical because, in the absence of the catalyst or water, decomposition reactions predominate and little or no product is formed.

If aprotic solvents are used as catalysts, this can be, for example, dimethylformamide, dimethylacetamide, diethylformamide, diethylacetamide, dimethyl sulfoxide, diethyl sulfoxide, tris (dimethylamino) phosphine oxide, tris (diethylamino) phosphine oxide or N-methyl-2- be pyrrolidone.

It has also been found that wet, preferably freshly prepared, moist organotin sulfides are much more reactive than dried organotin sulfides and, in the absence of catalysts such as dimethylformamide or the others mentioned above, react with isooctyl chloroacetate or other reactive organic halides. It is most advantageous to use a slurry of the organotin sulfide in water.

Organotin sulfides are usually made by reacting aqueous sodium sulfide with organotin chlorides. The insoluble organotin sulfides precipitate out and are filtered off. The wet sulphides become by heating

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removes moisture at elevated temperatures. It is possible that the sulfides may become less reactive during this drying process. A catalyst, for example dimethylformamide, is necessary for these dried and less reactive sulfides in order to effect the reaction with the reactive organic halides.

Surprisingly, on the other hand, the moist, freshly prepared organotin sulfides react easily in the absence of a catalyst.

According to the invention, the following can be used as compounds of the general formula RiX:

Methyl chloroacetate, methyl bromoacetate, Äthylchloracetat, Propylchloracetat, Propylbromacetat, butyl chloroacetate, bromoacetate, Hexylchloracetat, Hexylbromacetat, Octylchloracetat, Octylbromacetat, Isooctylchloracetat, Isooctylbromacetat, 2-Äthylhexylchloracetat, 2-Äthylhexylbromacetat, Isodecylchloracetat, Isodecylbromacetat, Decylchloracetat, Decylbromacetat, Dodecylchloracetat, Dodecylbromacetat, Hexadecylchlorace-tat, Hexadecyl bromoacetate, octadecyl chloroacetate, octadecyl bromoacetate, eicosanyl chloroacetate, eicosanyl bromoacetate, cyclopentyl chloroacetate, cyclopentyl bromoacetate, cyclohexylchloroacetate, cyclohexylbromacetate, benzylchloroacetate, benzylbromacetate, vinylchloromethacyl acetate, vinylchloromethacyl acetate, vinylchloroacetate

Crotyl chloroacetate, crotyl bromoacetate, 3-bromopropyl octoate,

2-bromoethyl pelargonate, 3-bromopropyl acetate,

3-bromopropyl stearate, 2-chloroethyllinoleate, 2-chloroethyllinolenoleate, oleyl chloroacetate,

Oleyl bromoacetate, 2-chloroethyl acetate,

2-bromoethyl acetate, 2-chloroethyl propionate, 2-bromoethyl propionate, 2-chloroethyl butyrate, 2-bromoethyl butyrate, 2-chloroethyl valerate,

2-bromoethyl valerate, 2-chloroethyl pivalate,

2-bromoethyl pivalate, 2-chloroethyl caproate,

2-bromoethyl caproate, 2-chloroethyl octoate,

2-bromoethyl octoate, 2-chloroethyl deconoate, 2-bromoethyl decanoate, 2-chloroethyl laurate,

2-bromoethyl laurate, 2-chloroethyl palmitate,

2-bromoethyl palmitate, 2-chloroethyl stearate,

2-bromoethyl stearate, 2-chloroethyl icosanate, 2-bromoethyl icosanate, 2-chloroethyl acrylate,

2-bromoethyl acrylate, 2-chloroethyl methacrylate, 2-bromoethyl methacrylate, 2-chloroethyl crotonate, 2-bromoethyl crotonate, 2-chloroethyl oleate, 2-bromoethyl oleate, allyl chloride, allyl bromide, methallyl chloride, methallyl bromide, benzyl chloride, methyl 2-chloro-methyl-bromide, bromopropionate, methyl 3-chloropropionate, methyl 3-bromopropionate, ethyl 2-chloropropionate, ethyl 2-bromopropionate, ethyl 3-chloropropionate, ethyl 3-bromopropionate, propyl 2-chloropropionate, propyl 3-bromopropionate, Butyl-2-bromopropionate, butyl-3-chloropropionate, octyl-2-chloropropionate, octyl-3-chloropropionate, octyl-2-bromopropionate, octyl-3-bromopropionate, isooctyl-2-chloropropionate, isooctyl-2-bromopropionate, isooctyl- 3-bromopropionate, isodecyl-2-chloropropionate, isodecyl-2-bromopropionate, isodecyl-3-chloropropionate, n-decyl-3-bromopropionate, dodecyl-2-chloropropionate, tetradecyl-3-chloropropionate, hexadecyl-2-chloropropionate 3-chloropropionate, octadecyl-2-chloropropionate, octadecyl-3-chloropropionate, octadecyl-2-bromopropionate, Octadecyl-3-bromopropionate, 2-ethylhexyl-3-chloropropionate, 2-ethylhexyl-2-chloropropionate, eicosanyl-3-chloropropionate, cyclohexyl-2-chloropropionate, cyclohexyl-3-bromopropionate, cyclohexyl-3-chloropropyl 2-chloropropionate, benzyl 3-chloropropionate,

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619961

Benzyl 2-bromopropionate, vinyl 2-chloropropionate, vinyl 3-bromopropionate, allyl-2-chloropropionate, allyl-3-chloropropionate, allyl-2-bromopropionate, allyl-3-bromopropionate, methallyl-3-chloropropionate, crotyl- 2-chloropropionate, oleyl 2-chloropropionate, oleyl 3-chloropropionate, oleyl 2-bromopropionate and oleyl 3-bromopropionate.

Examples of starting materials of the general formula

S

(RSn) 2S

are Monomethylzinnsulfid, Monoäthylzinnsulfid, monobutyltin sulfide, Monooctylzinnsulfid, Monododecyl-tin sulfide, Monooctadecylzinnsulfid, Monoeicosanylzinnsulfid, Monocyclohexylzinnsulfid, Monocyclopentylzinnsulfid, Monovinylzinnsulfid, mono-2-äthylhexylzinnsulfid, Monoallylzinnsulfid, Monomethallylzinnsulfid, Monooleylzinnsulfid, Monophenylzinnsulfid, mono-p-tolylzinnsulfid, mono-p-butylphenylzinnsulfid and Monobenzylzinnsulfid .

Examples of starting materials of the general formula

R2

Rs are dimethyltin sulfide, diethyltin sulfide, methylbutyltin sulfide, dipropyltin sulfide,

Dibutyltin sulfide, Dihexylzinnsulfid, dioctyltin sulfide, di-2-äthylhexyIzinnsulfid, Diisooctylzinnsulfid, di-dodecylzinnsulfid, di-octadecylzinnsulfid, di-eicosanylzinnsulfid, di-cyclohexylzinnsulfid, Divinylzinnsulfid, Diallylzinnsulfid, Dimethallylzinnsulfid, Dicrotylzinnsulfid, Dioleylzinnsulfid,

Diphenyltin sulfide, mono-methyl-mono-phenyltin sulfide, di-p-tolyltin sulfide, di-p-butylphenyltin sulfide xmd dibenzyltin sulfide.

Examples of starting materials of the general formula

R4 R4

R ^ - ^ Sn - S - Rs

Re ^ Re are bis (trimethyltin) sulfide, bis (triethyltin) sulfide, bis (tributyltin) sulfide, bis (trioctyltin) sulfide, bis (trioctadecyltin) sulfide, bis (trivinyltin) - sulfide, bis (triallyltin) sulfide, bis (trimethyltin) sulfide, bis (trioleyltin) sulfide, bis (triphenyltin) sulfide, bis (tri-p-tolyltin) sulfide and bis (tribenzyltin) )-sulfide.

Many of the products produced according to the invention are known. For example, US Pat. No. 2,641,596 describes some of the non-chlorine-containing compounds obtainable by reaction (3). US Pat. No. 3,565,931 explains many compounds that can be prepared by reaction (1). Many of the compounds obtainable through reactions (2) and (4) are in U.S. Patent 3,542,825 and British Patent 1,117,652

described. Furthermore, US Pat. No. 3,665,025 and British Pat. No. 1,297,550 show some of the compounds obtainable by reaction (4) and compounds which are approximately similar to those prepared by reaction (1).

The organotin mercaptides obtainable by reactions (1), (2), (3) and (4) can be used for the same purposes as described in US Pat. Nos. 3,565,931 and 3,630,992 and in British Patents 1 117 652 and 1 297 550. They are particularly suitable not only as stabilizers but also as starting materials for the preparation of stabilizers for polyvinyl chloride resins by replacing the halogen atom (s) with oxygen, carboxyl, mercaptyl or ester mercaptyl groups. They are also less expensive than organotin mercaptides made from mercaptans and organotin oxides or halogens.

The organotin mercaptide stabilizing agents obtainable by the reactions (1), (2) and (3) according to the invention can be used for halogen-containing vinyl and vinylidene resins in which the halogen is bonded directly to carbon atoms. Preferably the resin is a vinyl halide resin and especially a vinyl chloride resin. Usually the vinyl chloride resin is made from monomers consisting of vinyl chloride alone or mixtures with monomers containing at least 70% by weight vinyl chloride. When vinyl chloride copolymers are stabilized, preferably the copolymers of vinyl chloride with copolymerizable ethylenically unsaturated compounds, they contain at least 10% polymerized vinyl chloride.

Halogenated resins can be chlorinated polyethylene with 14 to 75, for example 27% by weight of chlorine, polyvinyl chloride, polyvinylidene chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene fluoride, copolymers of vinyl chloride and 1 to 90%, preferably 1 to 30%, of a copolymerizable ethylenically unsaturated Materials such as vinyl acetate, vinyl butyrate, vinyl benzoate, vinylidene chloride, diethyl fumarate, diethyl maleate, other alkyl fumarates and maleates, vinyl propionate, methyl acrylate, 2-ethylhexyl acrylate, butyl acrylate and other alkyl acrylates, methyl methacrylate, ethyl methacrylate, and other methyl methacrylate, and other methyl methacrylate, and other methyl methacrylate, butyl methacrylate, and other methyl methacrylate, butyl methacrylate, and other methyl methacrylate, butyl methacrylate -chloroacrylate, styrene, trichlorethylene, vinyl ethers, such as vinyl ethyl ether, vinyl chloroethyl ether and vinylphenyl ether, vinyl ketones, such as vinyl methyl ketone and vinylphenyl ketone, 1-fluoro-l-chloroethylene, acrylonitrile, chloroacrylonitrile, allylidene diacetate and chloroallylidene diacetate. Typical copolymers include vinyl chloride-vinyl acetate (96: 4, commercially available as VYNW), 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 chloride-2-ethylhexyl acrylate (80:20).

The stabilizers made in accordance with the present invention can be incorporated into the resin in a suitable grinder or mixer or in any other known manner which results in an even distribution in the resin composition. For example, the mixing can be effected by grinding on rolls at 100 to 160 ° C.

In addition to the new stabilizing agents produced according to the invention, customary additives such as plasticizers, pigments, fillers, dyes, absorbents for ultraviolet light, densifying agents and the like can be added to the resin.

If a plasticizer is used, it is used in the usual amounts, for example 30 to 150 parts per 100 parts of resin. Typical plasticizers are Di-2-

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ethylhexyl phthalate, dibutyl sebacate, dioctyl sebacate and tricresyl phosphate.

The tin-containing stabilizers are normally used in an amount of 0.01 to 10% by weight of the resin, preferably in an amount of 0.1 to 5% by weight of the resin. The organotin mercaptides according to reactions (1), (2) and (3) are clear, mobile liquids which are soluble in hydrocarbons and polar solvents such as benzene, toluene, acetone and ethyl acetate. The mono- and diorganotin sulfides used as starting materials for the reactions (1) and (2) are high-melting solids which are insoluble in the reaction products and in most of the solvents which dissolve the reaction products. This shows that the reaction products are not simply solutions of the organotin sulfides.

Specific combinations for the reaction of organotin sulfides with RiX compounds other than those given in the examples are listed below. The numbers indicate the number of moles of the catalyst (and in reaction (1) also the moles of the other reactants) per mole of the starting sulfide.

Reaction (1)

1. Monomethyltin sulfide + 2 methyl chloroacetate

2. Monooctyltin sulfide + 2 methyl bromoacetate

3. Monooctadecyltin sulfide + 2 isodecylchloroacetate

4. Monobenzyltin sulfide + 2 butyl chloroacetate

5. Monophenyltin sulfide + 2 cyclohexyl chloroacetate

6. Monoallyl tin sulfide + 2 benzyl chloroacetate

7. Monomethyltin sulfide + 2 2-chloroethyl stearate

8. Monobutyltin sulfide + 2 2-chloroethyl oleate

9. Monocyclohexyltin sulfide + 2 2-chloroethyl acetate

10. Monomethyltin sulfide + 2 2-chloroethyl methacrylate

11. Monomethyltin sulfide + 2 dodecyl-3-chloropropionate

12. Monobutyltin sulfide + 2 allyl chloride

Reaction (2)

13. Dimethyltin sulfide + ethyl chloroacetate

14. Dibenzyltin sulfide + propyl bromoacetate

15. Dioctyltin sulfide + decylchloroacetate

16. dibutyltin sulfide + sec. Butyl chloroacetate

17. Di-p-tolyltin sulfide + cyclohexylbromoacetate

18. Dioleyltin sulfide + phenylethyl chloroacetate

19. Dimethyltin sulfide + 2-chloroethyl palmitate

20. Dibutyltin sulfide + 2-bromoethyl crotonate

21. Dicyclohexyltin sulfide + 2-chloroethyl pivalate

22. Dimethyltin sulfide + 2-chloroethyl acrylate

23. Dimethyltin sulfide + isooctyl-3-bromopropionate

24. Dibutyltin sulfide + methallyl bromide

Reaction (3)

25. bis (trimethyltin) sulfide + isopropyl chloroacetate

26. bis (tribenzyltin) sulfide + 2-ethylhexyl chloroacetate

27. Bis- (trioctyltin) sulfide + nonylbromoacetate

28. bis (tributyltin) sulfide + hexylchloroacetate

29. bis (triphenyltin) sulfide + isooctylchloroacetate

30. bis (triallyltin) sulfide + benzyl chloroacetate

31. bis (trimethyltin) sulfide + 2-chloroethylicosanate

32. bis (tributyltin) sulfide + bromoethyl methacrylate

33. bis (tricyclohexyltin) sulfide + 2-chloroethyl myristate

34. bis (trimethyltin) sulfide + 2-bromoethyl oleate

35. bis (trimethyltin) sulfide + dodecyl-3-chloropropionate

36. bis (tributyltin) sulfide + allyl chloride

Reaction (4)

37. Monomethyltin sulfide + 3 methyl chloroacetate

38. Monooctyltin sulfide + 3 methyl bromoacetate

39. Monooctadecyltin sulfide + 3 isodecylchloroacetate

40. Monobenzyltin sulfide + 3 butyl chloroacetate

41. Monophenyltin sulfide + 3 cyclohexylchloroacetate

42. Monoallyl tin sulfide + 3 benzyl chloroacetate

43. Monomethyltin sulfide + 3 2-chloroethyl stearate

44. Monobutyltin sulfide + 3 2-chloroethyl oleate

45. Monocyclohexyltin sulfide + 3 2-chloroethyl butyrate

46. Monomethyltin sulfide + 3 2-chloroethyl methacrylate

47. Monomethyltin sulfide + 3 hexyl-3-chloropropionate

48. Monobutyltin sulfide + 3 allyl bromide

The temperature is not critical, but is usually heated, preferably to 130 to 155 ° C. The temperature is usually at least 90 ° C and can be, for example, up to 200 ° C.

Unless otherwise indicated, all parts and percentages are by weight.

Example 1 shows that the use of a dried sulfide does not lead to a reaction in the absence of an aprotic solvent.

Example 1 (comparative example)

1/10 mole of dried dimethyltin sulfide was mixed with 1/10 mole of isooctyl chloroacetate and heated under nitrogen. The solid dimethyltin sulfide was completely dissolved at 90 ° C. and a clear, almost colorless liquid was obtained. After two hours of reaction at 135 to 145 ° C, the reaction mixture was cooled. At 90 ° C the unreacted dimethyltin sulfide started to precipitate. The precipitation was completed by cooling to 20 ° C. The unreacted dimethyltin sulfide was filtered off and the isooctyl chloroacetate was removed by washing with heptane. 97% of the dimethyltin sulfide used as the starting material was recovered unchanged. The reactivity of wet, freshly prepared sulfides can be seen from the following examples:

Example 2

0.4 mol of aqueous (50%) dimethyltin dichloride was added to 0.4 mol of sodium sulfide in 100 g of water at 50 to 70 ° C. in the course of 30 minutes. The resulting slurry of dimethyltin sulfide was heated to 90 ° C and then mixed with 0.4 mole of isooctyl chloroacetate. After heating at 95-105 ° C for 15 minutes, two clear layers formed. The lower organic layer was separated and reacted at 135 to 140 ° C under nitrogen for two hours. After cooling to 25 ° C, the reaction mixture was filtered to remove traces of salt which had been entrained with the moist sulfide. The product is soluble in benzene in all proportions. It is believed to have the following structure.

O

II

CH3 S - CH2C - OCsHn

CH3 Cl

Yield: 151 g (calculated 155)

Cl: 9.0% (calculated 9.16%) S: 8.3% (calculated 8.26%)

Use of the product produced according to the invention:

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0.2 mol of the above product was reacted with 0.2 mol of isooctyl thioglycolate and 0.2 mol of aqueous ammonia in good yield to give dimethyltin bis (isooctylthioglycolate). This compound was examined as a stabilizing agent for polyvinyl chloride and compared with dimethyltin bis (isooctylthio-glycolate), which had been prepared in a conventional manner from dimethyltin di-chloride and isooctylthioglycolate. The two stabilizers turned out to be equally good.

Example 3

0.2 mol of aqueous dimethyltin dichloride was added to 0.2 mol of sodium sulfide in 50 g of water at 50 to 70 ° C. in the course of 30 minutes. The resulting slurry of dimethyltin sulfide was heated to 90 ° C and then mixed with 0.2 mol of 2-chloroethyl octanoate. After mixing and heating at 95 to 105 ° C. for 15 minutes, the dimethyltin sulfide dissolved in the organic phase and two clear layers formed on standing. The lower organic phase was separated and reacted under nitrogen at 145 to 155 ° C for two hours. After cooling to 25 ° C, no dimethyltin sulfide precipitated, indicating complete conversion

(CH3) 2SnCl2 + Na2S- ^ (CH3) 2SnS

Example 4

To a mixture of 50 g of water, 0.2 mol of methyltin tri-chloride and 0.2 mol of isooctylthioglycolate, 0.2 mol of dilute aqueous sodium hydroxide and then 0.2 mol of dilute aqueous sodium sulfide were added. The mixture was heated to 80 ° C and then left to stand. The lower organic phase was separated off with 0.2 mol of isooctyl chloroacetate to give the product of the formula (CHî) 2Sn-SCH2CH2OCOC7H15

I.

CI

displays. The product obtained according to the invention was reacted with 0.2 mol of 2-mercaptoethyl octanoate and 0.2 mol of aqueous ammonia to give dimethyltin bis (2-thioethyl octanoate).

Yield: 94.8% (based on the dimethyltin dichloride) Appearance: colorless oil

15

When stabilizing polyvinyl chloride, it showed the same effect as the same compound but made from dimethyltin dichloride and 2-mercaptoethyl octanoate.

20 It is assumed that the above implementations proceed according to the following scheme:

(I)

mixed and heated to 145 to 155 ° C under nitrogen for two hours. According to the invention, the product of the formula II was formed.

After cooling, the product of the formula II obtained according to the invention was reacted further by treatment with 0.1 mol of aqueous sodium sulfide. It is assumed that the implementations proceed as follows:

O

II

O S-CH2CH2O-C-C7H15

II /

(CH3) 2SnS + CICH2CH2OCC7H15 - »(CH3) 2Sn

^^ Cl

O O

II II

(I) + HSCH2CH2OCC7H15 -> (CH3) 2Sn (S-CH2CH2OC-C7Hi5) 2

4 «

O SO

II II II

CHsSnCb + HSCH2C-OC8H17 + NaOH + Na2S- ClftSn-SCIfcC-OCgHn

O

O 11

o C1CH2C-OC8H17 CH3Sn (SCH2C-OC8Hn) 2 4

Cl

(II)

O

II

CH3Sn (SCH2C-OC8Hi7) 2

S O Na2S I II>, CH3Sn (SCH2C-OCsHi7) 2

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Yield: 105 g (94.4%)

Appearance: colorless oil

The action as a stabilizer for polyvinyl chloride was as good as that of the same compound made from methyltin trichloride, isooctylthioglycolate and sodium sulfide.

The compound of formula II obtained according to Example 4 can also be used for the following preparation:

After cooling, the methyltin tris-isooctylthioglycolate is obtained as a colorless oil in an amount of 146 g from the compound of the formula II with 0.2 mol of isooctylthioglycolate and 0.2 mol of aqueous ammonia.

The effect as a stabilizer for polyvinyl chloride was as good as that of the same compound made from methyltin trichloride, isooctylthioglycolate and aqueous ammonia.

Reaction process:

O

«

CH3Sn (S € H200CsHi7) 2

a <n> °

HSCttC-OOH.,> CH, S "(SCH J-OC.H ,,),

NH40H

Example 5

The procedure of Example 4 was repeated except that 2-mercaptoethyl octanoate was used instead of isooctyl thioglycolate and 2-chloroethyl octanoate instead of isooctyl chloroacetate in the same molar amounts. According to the invention, the product of the formula III was formed. The product was then with sodium sulfide

Thio-bis- [methyltin-bis- (2-thioethyloctanoate)], which is a light yellow oil.

The effect as a stabilizer for polyvinyl chloride was as good as that of the same compound prepared from methyltin trichloride, 2-mercaptoethyl octanoate and sodium sulfide.

Reaction process:

O S o

11 I! II

CH3SnCh + HSCH2CH2O-CC7H15 + NaOH + Na2S - »CH3Sn-S-CH2CH2-OCC7Hi5

O

O CICH2CH2-O-CC7H15

CH3Sn (S-CH2CH2-0-CC7His) 2 <

Cl (III)

Na2S

O

CH3Sn (SCH2CH20-C-C7Hi5) 2 S?

CH3Sn (SCH2CH20-C-C7Hi5) 2

The compound of formula III can also be used for the reaction with 2-mercaptoethyl octanoate. Methyl tin tris (2-thioethyl octanoate)

which is a colorless oil.

Reaction process:

Its PVC stabilizing effect is as good as that of the 55 same compound made from methyltin trichloride and 2-mercaptoethyl octanoate.

CH3Sn (SCH2CH20C-C7Hi5) 2

I (HI) O °

HSCH2CH2OC-OH15 CH "S" (SCH2CH20-C & H, s) l

J.

NH40H

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Example 6

0.2 mol of aqueous dimethyltin dichloride was added to 0.2 mol of sodium sulfide in 50 g of water at 50 to 70 ° C. in the course of 30 minutes. The resulting slurry of dimethyltin sulfide was heated to 90 ° C and then mixed with 0.2 mol of benzyl chloride. After mixing and heating at 95 to 100 ° C for 10 minutes, the dimethyltin sulfide dissolves in the organic phase, and two clear layers are formed on standing. The bottom organic

Phase was separated and reacted under nitrogen at 145 to 155 ° C for two hours. The product of the formula IV was formed according to the invention. After cooling to 30 ° C., the product thus obtained was converted into dimethyl-tin-isooctylthioglycolate-benzyl-mercaptide (yellow oil ) implemented.

The compound obtained proved to be an effective stabilizing agent for polyvinyl chloride.

Reaction process:

(CH3) 2SnCl2 + Na2S ^ (CH3) 2SnS SCH2C6H5

(CH3) 2Sn

(IV)

"" Cl

NH4OH

O

HSCH2C — OCsHi7

C6H5CH2CI «

S-CH2C6H5 (CH3) 2Sn // 'O

\ II

SCH2C-OC8H17

To a mixture of 50 g of water, 0.2 mol of methyltin trichloride and 0.2 mol of isooctylthioglycolate, 0.2 mol of dilute aqueous sodium hydroxide and then 0.2 mol of dilute aqueous sodium sulfide were added. The mixture was heated to 80 ° C and then left to stand. The lower product phase was separated, mixed with 0.2 mol of benzyl bromide and heated to 145 to 155 ° C. under nitrogen for two hours.

Example 7

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According to the invention, the product of formula V was formed

After cooling, the product thus obtained was mixed with 0.2 mol of isooctylthioglycolate and 0.2 mol of aqueous ammonia. Methyltin bis (isooctylthioglyco-lat) benzyl mercaptide (yellow oil) was obtained in good yield.

The compound obtained proved to be an effective stabilizing agent for polyvinyl chloride.

Reaction process:

O

O

CHbSnCb + HSCH2C-OCsHn + NaOH + Na2S CHsSn-SCTfcC-OCsHn O

S-CH2C-OC8H17

CH3Sn-S-CH2-C6H5, \ r (V)

O

II

HSCH2C-OC8H17

CôHsCthBr <

NH4OH

O

II

CH3Sn (SCH2C-OCsHi7) 2

II

S-CH2C6H5

Example 8

0.2 mol of aqueous dimethyltin dichloride was added to 0.2 mol of sodium sulfide in 50 g of water at 50 to 70 ° C. in the course of 30 minutes. The resulting slurry of dimethyltin sulfide was heated to 90 ° C and then mixed with 0.2 mole of isooctyl-3-chloropropionate. After mixing and heating at 95 to 105 ° C. for 15 minutes, the dimethyltin sulfide dissolved in the organic phase and two clear layers formed on standing. The lower one

60 organic phase was separated and reacted under nitrogen at 145 to 155 ° C for two hours. According to the invention, the product of the formula VI was formed.

After cooling, the product thus obtained was reacted with 0.2 mol of isooctyl-3-mercaptopropionate and 0.2 mol of aqueous 65% sodium hydroxide in good yield to give dimethyltin bis-isooctyl-thiopropionate (colorless oil).

The investigation in polyvinyl chloride showed a good stabilizing effect.

11

Reaction process:

619 961

(CHs) 2SnCl2 + Na2S -> (CH3) 2SnS

O

O

(CH3) 2Sn

^ SCHiCHiCOCsHiv CICH2CH2C-OC8H17

<-

Cl

(VI)

O

? !

HSCH2CH2C-OC8Hi7 (CH3) 2Sn (SCH2CH2C-OCsHi7) 2>

NaOH

Example 9

A slurry of 0.5 mol of monomethyltin sulfide in water, which had been obtained by reacting aqueous sodium sulfide with methyltin trichloride, was mixed with 1.0 mol of isooctylchloroacetate and heated and further treated in the manner described in Example 2. The product obtained is believed to have the following structure:

Cl Cl

II II

CH3Sn-S-SnCH3 O

I II

SCH2-COC8H17

O

II

SCH2C-OC8H17

Example 13

Example 2 was repeated with the difference that the same molar amount of isooctyl bromoacetate was used instead of the isooctyl chloroacetate. You got:

CH3

Br

30th

Sn O

X \ II

CH3 SCH2COC8H17

Example 14

Example 6 was repeated with the exception that the same molar amount of benzyl bromide was used instead of the benzyl chloride. The product was obtained:

CH3

Br

Example 10

Example 2 was repeated with the difference that instead of the isooctyl chloroacetate the same molar amount of isooctyl-3-chloropropionate was used. You got:

CH3

CH3

Cl

Sn

O

SCH2CH2COC8H17

Sn

CH3

CH2-C6H5

Example 15

The procedure of Example 9 was repeated except that 1.5 moles of isooctyl chloroacetate were used. It is believed that the product obtained from a mixture of equal molar amounts of

Cl

O

Example 11

Example 2 was repeated with the difference that the dimethyltin dichloride was replaced by the same molar amount of dibutyltin dichloride. You got:

C4H9

, C1

Sri O

/ \ II

CiH'j SCH2COC8H17

Example 12

Example 9 was repeated with the difference that the same molar amount of butyltin trichloride was used instead of the methyltin trichloride. The butyl analog of Example 9 was obtained.

65

CH3Sn (SCH2COC8Hn) 2 and Cl O

I II

CH3Sn-SCH2COCsHi7 Cl existed.

To prepare the starting compounds for the reaction (5), a compound of the general formula RSnCb can be reacted with a compound of the general formula HSRi and alkali metal (for example sodium or potassium) or ammonium sulfide in water. The HSRi connection can be any HSRi analogue to the above-mentioned RiX connections.

619961

12

In the process according to the invention explained by Examples 4, 5 and 7, the organic phase for the reaction with the isooctyl chloroacetate, the 2-chloroethyl octoate or the benzyl bromide was not dried and therefore contained water.

As already mentioned, the temperature is not critical, but is preferably kept between 130 and 155 ° C. Usually it is between 100 ° C and the boiling point of the catalyst when a catalyst is used. All catalysts are liquids at the reaction temperatures.

Example 16

0.5 mol of dimethyltin sulfide was mixed with 0.5 mol of isooctyl chloroacetate and 75.0 g of dimethylformamide and heated to 130 to 135 ° C. for two hours. The dimethylformamide was distilled off from the reaction mixture by heating to a final temperature of the reaction vessel of 110 ° C. at 10 mm Hg. The residue (the product) was clarified by filtration. Yield: 188.5 g (97.3% of theory) of a light yellow oil. It is soluble in heptane and acetone. The NMR spectrum of the product was in agreement with the expected structure:

CHs

CH3

Cl: S:

O

S-CH2C-OC8H17

25th

Sn

Cl

9.2% (calculated 9.16%) 8.4% (calculated 8.26%)

Example 17

0.5 mol of monomethyltin sulfide (CH3SnS) 2S was mixed with 1.0 mol of isooctyl chloroacetate and 150 g of dimethylformamide. The mixture was then heated to 130 to 135 ° C for two hours. The dimethylformamide was removed in vacuo at 110 ° C and 10 mm Hg. The residue was filtered. 370.0 g of yellow oil (95.0% of theory) were obtained. The product is soluble in benzene and acetone. It is believed to have the following structure:

Cl

I.

CHsSn S-

O

Cl

SnCHs O

SCH2COC8H17 SCH2COC8H17

Cl: 9.4% (calculated 9.12%)

S: 11.9% (calculated 12.3%)

Example 18

A mixture of 0.1 mol of dimethyltin sulfide, 0.1 mol of benzyl chloride and 40 g of dimethylformamide was heated to 130 to 135 ° C. for two hours. After removal of the dimethylformamide at 110 ° C and 10 mm Hg, 30.5 g of light yellow oil remained. The theoretical yield was 30.7 g for:

55

CH3

CHs

S: Cl:

Cl

SCH2C6H5

65

10.2% (calculated 10.4%) 11.6% (calculated 11.5%)

Example 19

A mixture of 0.1 mol of dimethyltin sulfide, 0.1 mol of 2-chloroethyloctoate and 40 g of dimethylformamide was heated at 150 ° C. for four hours under a nitrogen atmosphere. After removing the dimethylformamide at 120 ° C and 10 mm Hg and filtering, 34.2 g of a yellow oil were obtained. The theoretical yield was 39.7 g for:

CH3 ^, C1 Sn

O

15

CHs s - cm - CH2 - oc - C7H15

Cl: 8.6% (calculated 8.94%) s: 8.3% (calculated 8.06%)

Example 20

0.5 mol of dimethyltin sulfide was mixed with 0.5 mol of isooctyl-3-chloropropionate and 75 g of dimethylacetamide and heated at 145 to 155 ° C for four hours. After removing the dimethylacetamide at 120 ° C and 10 mm Hg and filtering, 194.6 g of a yellow oil was obtained. The theoretical yield was 200.7 g for

CH3

Cl

30th

.Sn

O

CH3

Cl: S:

S - ch2 - ch2c - OCsHn

8.5% (calculated 8.84%) 8.1% (calculated 7.98%)

Example 21

A mixture of 0.1 mol of dimethyltin sulfide, 0.1 mol of isooctyl chloroacetate and 40 g of dimethyl sulfoxide was heated to 130 ° C. under nitrogen for 1/2 hour. After removal of the dimethyl sulfoxide at 110 ° C and 10 mm Hg, 32.0 g of a red oil remained.

45 cm

, C1

^ Sn O

/ \ i

CHs S-CmCOCsHn

S: 8.5% (calculated 8.26%)

Example 22

A mixture of 0.1 mol of dimethyltin sulfide, 0.1 mol of isooctyl chloroacetate and 30 g of tris (dimethylamino) phosphino-oxide was heated to 130 ° C. for two hours. After removing the solvent at 120 ° C and 10 mm Hg, 37.1 g of a yellow oil remained.

60

cm

Cl

.Sn O

/ \ 1

Cm S-CH2COC8H17

Cl: 9.3% (calculated 9.16%)

13

619 961

Example 23

A mixture of 0.2 mol of dibutyltin sulfide, 0.2 mol of isooctyl chloroacetate and 40.0 g of dimethylformamide was heated to 130 to 135 ° C. under nitrogen for two hours. After removing the solvent and filtering, 93.8 g of a yellow liquid was obtained. The theoretical yield was 94.3 g for:

C4H9, Cl v °

/ \ »

C4Ü9 S-CH2C-OC8H17

10th

Cl: 7.2% (calculated 7.51%) S: 6.5% (calculated 6.77%)

Example 24

A mixture of 0.1 moles of monobutyltin sulfide

S

(C4H9Sn) 2S,

0.2 mol of isooctyl chloroacetate and 40.0 g of dimethylformamide were heated at 130 to 135 ° C. under nitrogen for two hours. Removal of the solvent at 120 ° C and 10 mm Hg gave 83.7 g of a viscous amber oil. The theoretical yield was 86.1 g for:

Cl

C4H9-Sn-

O

Cl

- Sn-C4H9 O

SCH2COC8H17 SCH2COC8H17

Cl: 8.0% (calculated 8.22%)

S: 10.7% (calculated 11.10%)

Example 25

A mixture of 0.1 mol of bis (tributyltin) sulfide, 0.1 mol of isooctyl chloroacetate and 20 g of dimethylformamide was two

Heated to 130 to 135 ° C for hours. After removing the solvent and filtering, 91.3 g of yellow oil remained.

Cl: 4.1% (calculated 4.32%)

Example 26 ■

A mixture of 0.1 mol of dimethyltin sulfide, 0.1 mol of isooctyl bromoacetate and 20.0 g of dimethylformamide was heated at 130 to 135 ° C. under nitrogen for two hours. After removing the solvent at 110 ° C and 10 mm Hg, 37.8 g of yellow oil remained. The theoretical yield was 43.2 g for

CHs

Br

IS

Sn O

/ \ I

CHs S-CH2-C-OC8H17

Br:

17.9% (calculated 18.5%)

Example 27

A mixture of 0.1 mol of dimethyltin sulfide, 0.1 mol of benzyl bromide and 30 g of dimethylformamide was heated to 130 ° C. for two hours. After removal of the solvent, 33.8 g of yellow oil remained. The theoretical yield was 35.2 g for:

CHs

Br

30th

Sn

35

40

CH3 CH2-C6H5

Br: 21.9% (calculated 22.7%)

Example 28

0.5 mol of monomethyltin sulfide (CH3SnS) 2S was mixed with 1.5 mol of isooctyl chloroacetate and 150 g of N-methyl-2-pyrrolidone and heated to 130 to 135 ° C. for two hours. The N-methyl-2-pyrrolidone was recovered in vacuo at 120 ° C and 10 mm Hg. The residue obtained was filtered and gave 465 g of an amber oil (94.6% of theory).

S: 9.6% (calculated 9.76%)

Cl: 10.9% (calculated 10.82%)

Assumed reaction course:

O Cl O

II Cat. I II

(CH3SnS) 2S + 3CICH2C-O-C8H17 »CH3Sn (S-CH2 C-OC8Hn) 2 +

Cl O

CH3Sn-S-CH2C-OCsHi7

Cl

Example 28 shows that by varying the molar ratio of monoorganotin sulfide to RiX compound from 1: 2 to 1: 3, the products obtained are changed. Instead of

®> (CHiSnS) 2S in Example 28 can be any other compound of the general formula

(RSn) 2S

and any other compound of the general formula RiX can be used instead of the isooctyl chloroacetate.

B

Claims (26)

619 961 (1) S II (RSn) 2S, 2. The method according to claim 1, characterized in that one carries out the reaction with a slurry of the Orga-nocin sulfide in water. (2) 2nd PATENT CLAIMS 1. Process for the preparation of organotin mercaptides of the formulas SRi I. RSn-S- ! x R2 \ R4 Rs R Ris' R Sn V Sn , Sn SRi i Sn R I. X SRi / \ X R6 "SRi SRi / X, SRi X or characterized in that an organotin sulfide of the general formulas 3. The method according to claim 1, characterized in that one carries out the reaction at 130 to 155 ° C. 3rd 619 961 (3) R2 R3 R4 Rs Rf / SnS, R4 Sn — S —Sn - Rs or 4th R.4 R4 Rs Sn - S - Sn ^^ Rs Ro ^ R6 with 1 mole of a compound of the general formula RiX. 4. The method according to claim 1, characterized in that one carries out the reaction at 90 to 200 ° C with compounds in which R, R2, R3, R <t, Rs and Re alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 5 or 6 carbon atoms in the ring, alkenyl groups with 2 to 40 carbon atoms, phenyl groups and alkylphenyl groups with up to 4 carbon atoms in the alkyl group, R7 is an alkyl group with 1 to 20 carbon atoms, a cycloalkyl group with 5 or 6 carbon atoms in the ring, an alkenyl group with 2 to 20 Carbon atoms or the benzyl group and R12 is an alkyl group with 1 to 19 carbon atoms or an alkenyl group with 2 to 17 carbon atoms. (4) S II Reacts RSn — SR il with a compound of the general formula RiX, where R, R2, R3, R4, Rs and R6 represent alkyl, cycloalkyl, alkenyl, aryl or aralkyl groups, Ri and Rn represent the radicals s O II - (CH2) nC-OR7, O 5. The method according to claim 4, characterized in that X is chlorine. 6. The method according to claim 5, characterized in that R is an alkyl group having 1 to 8 carbon atoms. 7. The method according to claim 1, characterized in that one mole of a compound of the general formula R2 ^ SnS R3 with 1 mole of a compound of the general formula RiX. 8. The method according to claim 7, characterized in that that one carries out the reaction with an aqueous slurry of the organotin sulfide. 9. The method according to claim 8, characterized in that R2 and R3 are methyl groups. 10th 10. The method according to claim 9, characterized in that O O II II Ri = - (CH2) nCOR7, - (CH2) mOCRi2 or the benzyl group. 10 II - (CH2) mOCRl2, Rl4 1S CH2 = C-CH2- O II -CH (CH3) C-OR7 11. The method according to claim 10, characterized in that R7 is an alkyl group with 6 to 18 carbon atoms and R12 is an alkyl group with 5 to 17 carbon atoms. 12. The method according to claim 10, characterized in that m = 2. 13. The method according to claim 1, characterized in that 1 mol of a compound of the general formula S II RSnSRn with 1 mole of a compound of the general formula RiX. 14. The method according to claim 13, characterized in that O O II II Ri = - (CH2) nCOR7 or - (CH2) mOCRi2. 15 15. The method according to claim 14, characterized in that R7 is an alkyl group having 6 to 18 carbon atoms, R12 is an alkyl group with 5 to 17 carbon atoms and O O II II R11 = - (CH2) nCOR7, - (CH2) mOCRi2 or the benzyl radical. 16. The method according to claim 15, characterized in that R is the methyl group and m = 2. 17. The method according to claim 1, characterized in that R, R2, R3, R4, Rs and Ró alkyl groups having 1 to 8 carbon atoms and Ri and R11 the radicals O O II II - (CH2) nCOR7, - (CH2) mOCRl2 or benzyl groups, R7 is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 3 to 18 carbon atoms or the benzyl group and R12 is an alkyl group having 1 to 17 carbon atoms or an alkenyl group having 17 carbon atoms. 18. The method according to claim 1, characterized in that one carries out the reaction in the presence of an aprotic solvent as a catalyst at a temperature up to the boiling point of the catalyst. 19. The method according to claim 18, characterized in that the catalyst is used in an amount of 0.8 to 8 moles per mole of organotin sulfide. 20th 20. The method according to claim 19, characterized in that dimethylformamide is used as solvent. 20th or the benzyl group, R7 is an alkyl, cycloalkyl, alkenyl or aralkyl group, R12 is an alkyl or alkenyl group, X is a halogen atom with an atomic weight of 35 to 80, 25 n = 1 or 2, m = 2 or 3 and Rh is a hydrogen atom or the methyl group, this reaction either with water-moist organotin sulfide or in the presence of an aprotic solvent as a catalyst with the general formula 30th O R9 (a) RsC-N < SR.10 35 (b) 40 Rs Rio S = O, 45 (c) R9 Rio - P = O or 50 55 (d) CH2 CH: I I CH2 c = o \ / N I. CH3 is carried out, wherein Rs is a hydrogen atom or the methyl group and Rs and Rio represent alkyl groups having 1 or 2 6s carbon atoms. 21. The method according to claim 18, characterized in that 1 mole of a compound of the general formula S II (RSn) 2S with 2 moles of a compound of the general formula RiX. 22. The method according to claim 18, characterized in that 1 mol of a compound of the general formula S (RSn): S reacted with 3 moles of a compound of the general formula RiX. 23. The method according to claim 18, characterized in that 1 mole of a compound of the general formula R2 Rs reacted with 1 mole of a compound of the general formula RiX. 24. The method according to claim 18, characterized in that 1 mol of a compound of the general formula s 25. The method according to claim 18, characterized in that R is an alkyl group having 1 to 8 carbon atoms and O II Rl- (CH2) nC-OR7 where R7 represents an alkyl group having 6 to 18 carbon atoms. 25th 30th 35 40 45 SO SS 60 6S 619 961 26. The method according to claim 18, characterized in that R is an alkyl group having 1 to 8 carbon atoms and