DE2559531A1 - ORGANO TIN MERCAPTIDE HALOGENIDE - Google Patents

Description

UEXKÜLL & STOLBERG PATENTANWÄLTE

BESELERSTRASSE 4

DR. J.-D. FRHR. by UEXKÜLL

DR. ULRICH GRAF STOLBERG DIPL.-ING. JÜRGEN SUCHANTKE

Cincinnati Milacron

Chemicals, Inc. M

Reading, Ohio / V.St.A. Hamburg, August 19, 1976

TELEPHONE OK-TO | 893O81 TELEX 02 14 204 TELEGRAMS UEXPAT

Organotin mercaptide halides

The invention relates to organotin mercaptide halides the general formula

I I

RSn S SnR

I I

X X

in which R is an alkyl, cycloalkyl, alkenyl, aryl or

0 · O

Il Il

Represents aralkyl group, R ₁ = - (CH ₉ ) C-OR ₇ , - (CH ₉ ) OCR ₁₉ ,

I ^ * Xl ■ / ■ £ * .III I ^

CH ₉ = C-CH ₉ - or the benzyl group, R _{7 is} an alkyl, cycloalkyl, alkenyl or aralkyl group, R _{19 is} an alkyl or alkenyl group, X is chlorine or bromine, η = 1, m = 2 or 3 and R _{14 is} a hydrogen atom or the methyl group.

The inventive method for producing these Compounds consists in making an organotin sulfide the general formula

709809/1127 originally inspected

RJSn) j _r in which R has the meaning given, in the water-moist state or in the presence of an aprotic solvent of the general formulas

(a)

II

R ₈ C

> * 9

- N '

: R

10

Rc

(b)

(C)

(d)

S = O,

10

R ₉ ^R 10

CH ₂ CH ₂

P = O

CH ₂

C = O

or

CH ₃

where Rg is a hydrogen atom or the methyl group and Rg and R ^ represent alkyl groups with 1 or 2 carbon atoms, reacts as a catalyst in a molar ratio of 1: 2 with a compound of the general formula R ₁ X, in which RJ has the meaning given.

The above-mentioned alkyl groups usually contain 1 to 20 carbon atoms, and the alkeny groups usually contain 2 to

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20 or more, preferably 3 to 18 carbon atoms, and the cycloalkyl groups usually 5 or 6 carbon atoms in the ring. The aryl groups are phenyl or alkylphenyl groups having 1 to 4 carbon atoms in the alkyl group, and the aralkyl groups are usually those having 7 carbon atoms. When R _{12 is} an alkyl group it usually contains 1 to 19 carbon atoms, when it is an alkenyl group it usually contains 2 to 17 carbon atoms. The compounds according to the invention are suitable as stabilizers for halogen-containing polymers, in particular for 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 of vinyl chloride. If vinyl chloride copolymers are stabilized, preferably the copolymers of vinyl chloride with copolymerizable ethylenically unsaturated compounds, these contain at least 10% polymerized vinyl chloride. The stabilizers according to the invention are superior to known stabilizers. To demonstrate the superior mode of action, the compound of Example 2 and the known one were used

Dimethyl tin bis-isooctyl thioglycolate into the following Formulation incorporated:

7 0 9 8 0 9/1127 ORIGINAL INSPECTED

PVC resin (Geon 103 EP) Omya 90 T

TiO ₂

Calcium stearate paraffin wax

Ac 629 A

Stabilizers

100 parts
2.5 parts 1.5 parts O ₇ 8 parts 1 / O parts 0.15 parts O ₇ 4 parts.

Both formulations were run at a roller temperature of 190 ° C, a front roller speed of 30 rpm and the rear roller at 40 rpm for 10 minutes. Samples were taken at 2 minute intervals. While the formulation produced with the stabilizing agent according to the invention still retains its original color 4 minutes of grinding, this only applied to the formulation prepared with the known stabilizing agent after 2 minutes to. After grinding for 10 minutes, that was produced with the stabilizing agent according to the invention Formulation much less colored than that made with the known stabilizer:

As halogen-containing resins, chlorinated polyethylene with 14 to 75, e.g. 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 3O% of a copolymerizable, ethylenically unsaturated material, such as vinyl acetate, vinyl butyrate, Vinyl benzoate, vinylidene chloride / diethyl fumarate, diethyl maleate,

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other alkyl fumarates and maleates, vinyl propionate, methyl acrylate, 2-ethylhexyl acrylate, butyl acrylate and other alkyl acrylates, methyl methacrylate, ethyl methacrylate, butyl methacrylate and other alkyl methacrylates, methyl-OL ~ ^{cll oracr} Yl ^at styrene, trichlorethylene, such as vinyl ether, vinyl ether and vinyl ether , Vinyl ketones such as vinyl methyl ketone and vinyl phenyl ketone, 1-fluoro-i-chloroethylene, acrylonitrile, chloroacrylonitrile, allylidene diacetate and chloroallylidene diacetate can be used. Typical copolymers are e.g. 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 of the present invention can be incorporated into the resin in a suitable milling machine or mixer, or in any other known manner which results in an even distribution throughout the resin composition. For example, the mixing can be effected by grinding on rolls at 100 to 160 ⁰ C.

Except for the new stabilizers according to the invention You can add the usual additives to the resin, such as plasticizers, pigments, fillers, dyes, and ultraviolet absorbers Light, densifying agents and similar additives can be added.

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The tin-containing stabilizers are normally used in an amount of from 0.01 to 10% by weight of the resin, preferably in an amount of 0.1 to 5 percent by weight of the resin. The preferred aprotic solvent in the invention Process is dimethylformamide. The amount of aprotic solvent can vary, for example from 0.1 to 10 moles per mole of organotin sulfide, preferably from 0.8 up to 8 moles per mole of organotin sulfide.

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

When using aprotic solvents as catalysts these can be e.g. dimethylformamide, dimethylacetamide, Diethylformamide, diethylacetamide, dimethyl sulfoxide, diethyl sulfoxide, Tris (dimethylamine) phosphine oxide, tris (diethylamino) phosphine oxide or N-methyl-2-pyrrolidone.

It has been found that water-wet, preferably freshly prepared moist organotin sulfides are much more reactive are as dried organotin sulfides and in the absence of catalysts such as dimethylformamide or the others above mentioned, react with isooctyl chloroacetate or other reactive organic halides. Most beneficial

7 0 9809/1127

is, a slurry of the organotin sulfide in water to use.

Organotin sulfides are usually made by reacting aqueous sodium sulfide with organotin chlorides. The insoluble organotin sulfides precipitate and are filtered off. It is believed that when wet sulfides are heated to elevated temperatures, the moisture is removed During the drying process, the polymeric sulfides will continue to polymerize and become less reactive. For those dried and less reactive sulfides a catalyst, e.g. dimethylformamide, is necessary in order to react with the reactive organic halides cause.

Surprisingly, on the other hand, the moist ones react fresh organotin sulfides easily produced in the absence of a catalyst.

As compounds of the general formula R ,. X can be used be: methyl chloroacetate, methyl bromoacetate, ethyl chloroacetate, propyl chloroacetate, propyl bromoacetate, butyl chloroacetate, butyl bromoacetate, Hexyl chloroacetate, hexyl bromoacetate, octyl chloroacetate, Octyl bromoacetate, isooctyl chloroacetate, isooctyl bromoacetate, 2-ethylhexyl

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chloroacetate, 2-ethylhexyl bromoacetate, isodecyl chloroacetate, Isodecyl bromoacetate, decyl chloroacetate, decyl bromoacetate, dodecyl chloroacetate, Dodecyl bromoacetate, hexadecyl chloroacetate, hexadecyl bromoacetate, Octadecyl chloroacetate, octadecyl bromoacetate, eicosanyl chloroacetate, eicosanyl bromoacetate, cyclopentyl chloroacetate, Cyclopentyl bromoacetate, cyclohexyl chloroacetate, cyclohexyl bromoacetate, Benzyl chloroacetate, benzyl bromoacetate, vinyl chloroacetate, vinyl bromoacetate, allyl chloroacetate, allyl bromoacetate, Methallyl chloroacetate, methallyl bromoacetate, crotyl chloroacetate, Crotyl bromoacetate, 3-bromopropyl octoate, 2-bromoethyl pelargonate, 3-bromopropyl acetate, 3-bromopropyl stearate, 2-chloroethyl linoleate, 2-Chloräthyllinoleno et, OleyIchloracetat, 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 decanoate, 2-bromo ethyl decanoate, 2-chloroethyl laurate, 2-bromoethyl laurate, 2-chloroethyl palmitate, 2-bromoethyl palmitate, 2-chloroethyl stearate, 2-bromoethyl stearate, 2-chloroethyleicosanate, 2-bromoethyleicosanate, 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, benzyl bromide,

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Methyl 2-chloropropionate, methyl 2-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 _f 3- tetradecyl chloropropionate, hexadecyl 2-chloropropionate, hexydecyl 3-chloropropionate, octadecyl 2-chloropropionate, octadecyl 3-chloropropionate, octadecyl 2-bromopropionate, octadecyl 3-bromopropionate, 2-ethylhexyl-3-chloropropionate, 2-hexyl-3-chloropropionate -chlorpropionate, eicosanyl-3-chloropropionate, cyclohexyl-2-chloropropionate , cyclohexyl-3-bromopropionate, cyclohexyl-S-chloropropionate, benzyl-2-chloropropionate, benzyl-3-ch loropropionate, benzyl-2-bromopropionate, vinyl-2-chloropropionate, vinyl-3-bromopropionate, allyl-2-chloropropionate, allyl-3-chloropropionate, allyl-2-bromopropionate, allyl-3-brorapropionate, methallyl-3-chloropropionate, Crotyl-2-chloropropionate, oleyl-2-chloropropionate, oleyl-3-chloropropionate, oleyl-2-bromopropionate and oleyl-3-bromopropionate

the
Examples of / starting materials of the general formula

(RSn) ₂ p

709809/1 127

are monomethyl tin sulfide, monoethyl tin sulfide, monobutyl tin sulfide, Monooctyl tin sulfide, monododecyl tin sulfide, Monooctadecyl tin sulfide, monoeicosanyl tin sulfide, monogyclohexyl tin sulfide, Monocyclopentyl tin sulfide, monovinyl tin sulfide, Mono-2-ethylhexyl tin sulfide, monoallyl tin sulfide, Monometalyl tin sulfide, monooleyl tin sulfide, monophenyl tin sulfide, Mono-p-tolylz innsulfid ", Mono-p-butylphenylz innsulf id and monobenzyltin sulfide.

The organotin mercaptide halides according to the invention are clear mobile liquids that are contained in hydrocarbons and polar solvents such as benzene, toluene, acetone and ethyl acetate are soluble. The ones used as raw materials Monotin sulfides are polymeric high-melting solids which are insoluble in the reaction products and in most solvents which dissolve the reaction products. It follows that the reaction products are not simply solutions of the organotin sulfides.

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

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1. Monomethyl tin sulfide + 2 methyl chloroacetate

2. Monooctyl tin sulfide + 2 methyl bromoacetate

3. Monooctadecyl tin sulfide + 2 isodecyl chloroacetate

4. Monobenzyl tin sulfide + 2 butyl chloroacetate

5. Monophenyltin sulfide + 2 cyclohexyl chloroacetate

6. Monoallyl tin sulfide + 2 benzyl chloroacetate

7. Monomethyl tin sulfide + 2 2-chloroethyl stearate

8. Monobutyltin sulfide + 2 2-chloroethyl oleate

9. Monocyclohexyltin sulfide + 2 2-chloroethyl acetate

10. Monomethyl tin sulfide + 2 2-chloroethyl methacrylate

11. Monomethyl tin sulfide + 2 dodecyl S-chloropropionate

12. Monobutyl tin sulfide + 2 allyl chloride

The temperature is not in the process according to the invention critical, but is usually heated, preferably to 130 to 155 C. The temperature is usually at least

and can be, for example, up to 200 ° C.

Unless stated otherwise, all parts and percentages are based on weight.

¹ that the use does not result in a dried sulfide in the absence of an aprotic solvent to a reaction, it is apparent from Example. 1

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example 1

1/10 mole of dried dimethyltin sulfide was 1/10 mole Isooctyl chloroacetate mixed and heated under nitrogen. At 90 ° C. the solid dimethyltin sulfide was completely dissolved and a clear, almost colorless liquid was obtained. After two hours of reaction at 135 to 145 ° C, the Reaction mixture cooled. At 90 ° C., the unreacted dimethyltin sulfide began to precipitate. The precipitation was caused by Cooling to 20 ° C completed. The unreacted dimethyltin sulfide was filtered off and washed with heptane from Isooctyl chloroacetate freed. 97% of the dimethyltin sulfide used as the starting material was recovered unchanged. The reactivity of wet, freshly prepared sulfides is shown in the following example:

Example 2

A slurry of 0.5 mol of monomethyltin sulfide in water, which can be obtained by reacting aqueous sodium sulfide with methyltin trichloride was mixed with 1.0 mole of isooctyl chloroacetate. After heating to 95 bis for 15 minutes 105 ° C two clear layers formed. The lower organic layer was separated and kept at 135-140 ° C for 2 hours implemented under nitrogen. After cooling to 25 ° C., the reaction mixture was filtered to remove any traces of salt that came with the moist sulphide had been introduced. The product is soluble in benzene in all proportions. It is believed to have the following structure:

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Cl Cl

CH-jSn-τ-S SnCH.

3.0,:

Example 3

0.5 mole of monomethyl _{tin sulfide (CH 3} SnS) ₂ S was mixed with 1.0 mole of isooctyl chloroacetate and 150 g of dimethylformamide. The mixture was then heated to 130 to 135 ° C. for 2 hours. The dimethylformamide was removed in vacuo at 110 ^° C. and 10 mmHg. 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

CH ₃ Sn

Cl I SnCH

Il

SCH ₂ COCgH ₁₇ SCH ₂ COCgH ₁₇

Cl: 9.4% (calculated 9.12%)
S: 11.9% (calculated 12.3%)

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Example 4 p

Il

A mixture of 0.1 mole of monobutyltin sulfide (C.HgSn) -S 0.2 mol of isooctyl chloroacetate and 40.0 g of dimethylformamide were heated to 130 to 135 ° C. under nitrogen for 2 hours. After removing the solvent at 120 ° C and 10 mmHg 83.7 of a viscous amber oil was obtained. The theoretical yield was 86.1 g for:

Cl Cl

I I

C ₄ H ₉ - Sn S Sn - C ₄ H ₉

0} 0

Cl: 8.0% (calculated 8.22%)
S: 10.7% (calculated 11.1%).

709809/1127

Claims (3)

Claims 1. Organotin mercaptide halides of the general formula I I RSn S SnR t ι X X in which R is an alkyl, cycloalkyl, alkenyl, aryl or 0 ti Il cWräaHCh I
döSndertI Represents aralkyl group, R ₁ = - (CH ₃ ) _n C-OR _? , R CH ₂ = C-CH ₂ - or the benzyl group, R _{7 is} an alkyl, cycloalkyl, alkenyl or aralkyl group, R _{12 is} an alkyl or alkenyl group, X is chlorine or bromine, η = 1, m = 2 or and R _{14 is} a hydrogen atom or the methyl group. 2. Process for the preparation of the compounds according to claim 1, characterized in that an organotin sulfide of the general formula S. I » ^ RjSn) ₂ , in which R has the meaning given, in the water-moist state or in the presence of an aprotic solvent of the general formulas 709809/1127 (a) O - ν ' ι I » R ₈ C , R ₉ R < (b) (c) (d) S = O, 10 Rc P = or CH ₂ CH ₂ CH- C = O N t CH ₃ where Rg is a hydrogen atom or the methyl group and Rg and R _{10 represent} alkyl groups with 1 or 2 carbon atoms, reacts as a catalyst in a molar ratio of 1: 2 with a compound of the general formula R ₁ X, in which R ^ has the meaning given. 3. The use of the compounds according to claim 1 as stabilizers for halogen-containing polymers. sch: cm / 1 3343 709809/1127