DE2559531B2 - Organotin mercaptide chloride - Google Patents

Description

in which R is a C ₁ -C ₈ alkyl radical and R is a Ci-Cis alkyl radical.

can be prepared by using an organotin sulfide of the formula

Il

RSn / ₂ S

in which R has the meaning given, in the water-moist state or in the presence of an aprotic κι solvent of the formulas

(a)

Ii

Il

R ₈ CN

R,

(b)

20th

The compounds forming the subject of the invention according to the claim, which are obtainable by the process of DE-PS 25 03 554 and 25 59 446, are suitable as stabilizers for halogen-containing polymers, in particular for vinyl chloride and 2, vinylidene chloride resins and their copolymers ethylenically unsaturated compounds. The polymers can be produced from vinyl chloride or from monomer mixtures which preferably contain 70% by weight of vinyl chloride. In the stabilization of j _(l polymers of vinyl chloride and copolymerizable ethylenically unsaturated compounds, these at least 10% polymerized vinyl chloride should contain.

The stabilizers according to the invention are superior to known stabilizers. To the after- j-, Because of the superior effect, the compounds of Examples 1 and 3, i. H. Connections with

R = -CH ₃ or -C ₈ H ₁₇ and R ₁ CH ₁ , -C ₄ H ₄ ,

-CsHi ₇ , - C ₁₂ H ₂ S or C ₁ SHj ₇ and the known dimethyltin bis-isooctylthioglycolate each incorporated into 41) the following formulation:

PVC resin (Geon103EP) 100 parts coated with calcium stearate finely divided calcium carbonate (Omya90T) 2.5 parts TiO ₂ 1.5 parts Calcium stearate 0.8 parts Paraffin wax (150 wax) 1.0 parts oxidized ethylene homopolymer low molecular weight (Ac 629 A) 0.15 parts Stabilizers 0.4 parts.

All formulations were made at a roller temperature of 190 ° C, a speed of Grind the front roller at 30 rpm and the rear roller at 40 rpm for 10 minutes. At time intervals Samples were taken from 2 minutes. While those with the stabilizers according to the invention produced formulations still had their original color after grinding for 4 minutes this only increases after 2 minutes for the formulation produced with the known stabilizer. After grinding for 10 minutes, those produced with the stabilizers according to the invention were obtained Formulations much less colored than the composition made with the known stabilizer. The compounds according to the invention

R ₁ ,

N-P = O

or

(d)

CH, CH,

I "I"

CH, _{/ C} -O

as a catalyst, where R «is a hydrogen atom or the methyl group and Rt and R _{1n represent} alkyl groups having 1-4 or 2 carbon atoms, in a molar ratio of 1: 2 with a compound of the formula CICH ₂ (O) ORi, in which R ₁ has the meaning given.

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

If aprotic solvents are used as catalysts, these can, for. B. off

Dimethylformamide, dimethylacetamide,
ν-, diethylformamide, diethylacetamide,
Dimethyl sulfoxide, diethyl sulfoxide,
Tris (dimethylamino) phosphine oxide,
Tris (diethylamino) phosphine oxide or
N-methyl-2-pyrrolidone

ω exist. The preferred aprotic solvent is Dimethylformamide.

The amount of aprotic solvent can vary, e.g. B. from 0.1 to 10 moles per mole of organotin sulfide, preferably from 0.8 to 8 moles per mole of organotin sulfide.

It has been found that water-wet, preferably freshly prepared, moist organotin sulfides are high are more reactive than dried organotin sulfides

and in the absence of catalysts such as dimethylformamide or the others mentioned above with Isooctyl chloroacetate or other reactive organic halides react. Most beneficial is 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 and are filtered off. It is believed that when the moisture is removed from wet sulphides by heating to elevated temperatures, while During the drying process, the polymeric sulfides continue to polymerize and thus become less reactive. For these dried and less reactive sulfides a catalyst, e.g. B. dimethylformamide necessary to effect the reaction with the reactive organic halides.

Surprisingly, however, the moist, freshly prepared organotin sulfides react slightly in Absence of a catalyst.

Suitable vinyl chloride copolymers are those composed of vinyl chloride and 1 to 90%, preferably 1 to 30% copolymerizable ethylenically unsaturated compounds, 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, butyl methacrylate and
other alkyl methacrylates,
Methyl a-chloroacrylate,
Styrene, trichlorethylene,
Vinyl ether, such as vinyl ethyl ether,
Vinyl chloroethyl ether and vinyl phenyl ether,
Vinyl ketones such as vinyl methyl ketone and
Vinyl phenyl ketone, 1-fluoro-1-choräthyIen,
Acrylonitrile, chloroacrylonitrile,
Allylidene diacetate and chlorallylidene diacetate.
Typical copolymers are e.g. B.
Vinyl chloride-vinyl acetate

(96/4, commercially available as VYNVV),
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 ^ 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 in the resin composition. For example, the mixing can be effected by grinding on rolls at 100 to 160 ⁰ C.

In addition to the new stabilizers according to the invention, conventional additives such as Plasticizers, pigments, fillers, dyes, ultraviolet light absorbers, densifying agents and like additives are added.

The tin-containing stabilizers are normally used in an amount of from 0.01 to 10% by weight of the Resin used, preferably in an amount of 0.1 to 5% by weight of the resin,

Suitable starting materials of the formula
ClCH ₂ C (O) OR ₁

for the preparation of the compounds according to the invention

Methyl chloroacetate, ethyl chloroacetate,

Propyl chloroacetate, butyl chloroacetate,

Hexyl chloroacetate, octyl chloroacetate,

Isooctyl chloroacetate.
ίο 2-ethylhexyl chloroacetate,

Isodecyl chloroacetate, decyl chloroacetate,

Dodecyl chloroacetate,

Hexadecyl chloroacetate and

Octadecyl chloroacetate.

Examples of the organotin sulfides of the general formula used as starting materials

RSn

are

Monomethyltin sulfide,
Monoethyltin sulfide,
Monobutyl tin sulfide,
>") Monooctyltin sulfide and

Mono-2-ethylhexyltin sulfide.

The organotin mercaptide halides according to the invention represent clear, mobile liquids that reside in hydrocarbons and polar solvents, such as »Ι Benzene, toluene, acetone and ethyl acetate are soluble. The monoalkyltin sulfides used as starting materials polymeric high melting point solids that are present in the reaction products and in most of the reaction products Solvent solvents are insoluble, ji It follows that the reaction products are not simply represent solutions of the organotin sulfides used as starting materials.

The temperature is in the process of the invention

not critical, but is generally heated, preferably to 130 to 155 ° C. Usually the temperature is at least 9O ⁰ C. It can be increased but also up to 200 ° C.

Unless stated otherwise, all parts and percentages are based on weight. 4 ^r > The following examples illustrate the invention.

Example 1 a)

A slurry of 0.5 moles of monomethyl tin sulfide

CH ₃ -Sn-S / ₂

in water, which had been obtained by reacting aqueous sodium sulfide with methyltin trichloride, was mixed with 1.0 mol of isooctyl chloroacetate. After heating at 95 to 105 ^° C. for 15 minutes, two clear layers formed. The lower organic layer was separated off and ^{reacted for 2 hours at 135 to 140 °} C. under nitrogen. After cooling to 25 ° C., the reaction mixture was filtered in order to remove traces of salt which had been entrained with the moist sulfide. The product is in benzo in all proportions! soluble.

It has the following structure: Cl Cl

I I

CH ₃ Sn S SnCH ₃

amide was heated to 130 to 135 ° C. under nitrogen for 2 hours heated. After removal of the solvent at 120 ° C. and 10 mm Hg, 83.7 of a viscous one was obtained amber colored ois. The theoretical yield was 86.1 g for:

10

15th

SCH ₂ COC ₈ Hi ₇ SCH ₂ COQH ₁₇

Example 1 b) 0.5 mol of monomethyl tin sulfide

S \
, CH ₃ SnJ ₂ S

were mixed with 1.0 mole of isooctyl chloroacetate and 150 g of dimethylformamide. Then it became 2 hours heated to 130 to 135 ° C. The dimethylformamide was removed in vacuo at 110 ° C and 10 mm Hg. The residue was filtered. 370.0 g of a yellow oil were obtained (95.0% of theory). The product is soluble in benzene and acetone. It has the structure:

Cl

C ₄ H ₉ -Sn-

Cl

Sn-C ₄ H ₉ O

SCH ₂ COQH ₁₇ SCH ₂ COQH ₁₇

Ci: 8.0% (calculated 8.22 ° / o)
S: 10.7% (calculated 11.1%).

Example 3 A mixture of 0.1 mole of monooctyl tin sulfide

D ₈ H ₁₇ Sn / ₂ S

Cl
CH ₃ Sn-

Cl

-SnCH ₃

30 0.2 mol of methyl chloroacetate and 40.0 g of dimethylformamide were heated ^{to 130 to 135 ° C. under nitrogen for 2 hours.} After removal of the solvent by heating at 12O ⁰ C at a pressure of 10 mm Hg to give 75.9 g of product. The theoretical yield was 77.6 g for

SCH ₂ COQH ₁₇ SCH ₂ -COC ₈ H ₁₇

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

Example A mixture of 0.1 mol of monobutyltin sulfide Cl

Cl

40

1, C ₄ H ₉ SnJ ₂ S
0.2 moles of isooctyl chloroacetate and 40.0 g of dimethylform-C ₈ H ₁₇ Sn-S-Sn-C 1-H ₁₇

SCH ₂ COCH ₃ SCH ₂ COCH, OO

Cl: 9.04% (calculated 9.14%) S: 12.1% (calculated 12.36%)

Similarly, the following organotin mercaptide halides were made manufactured:

link Yield, g% S

found ber.

ber.

% Cl found

Cl Cl

I I

QH ₁₇ Sn-S-Sn _{QH n} C ₄ H ₉ OC-CH ₂ S SCH ₂ -COC ₄ H ₉

O

Cl Cl

I I

QH ₁₇ Sn-S-Sn-C ₈ H ₁₇ C ₁₂ H ₂₅ OC-CH ₂ S SCH ₂ -COC ₁₂ H ₂₅

85.7 86.0 11.3

11.2

8.1

108.0 108.4 8.7 8.8 6.3 6.5

link

(Ί (Ί

i C "H ₁₇ Sn S Sn C _x II ₁ -

C, _H H, ₇ () CC! I, S SCH, COC _1n II ₁₇

'Ρ Il

ο ο

Yield, μ

ι: el Ιηί

"" S

ι; ι · Ι her.

"" (Ί lid

123.7 125.2 7. (ι 7.7 5.7 5.7

Claims (1)

Claim: Organotin mercaptide chlorides of the formula
R ₁ O (O) CCH ₂ -S S-CH ₂ C (O) -OR ₁ RSn-S-SnR I I CI CI