JPS5949229B2 - Sulfur-containing organotin compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to novel sulfur-containing organotin compounds useful as stabilizers for polyvinyl chloride and other halogen-containing polymers.

In the broadest sense, these compounds include (a) at least two tin atoms bonded by a bridge through sulfur, and said bridge also contains at least two carbon atoms. and (b) 1 to 2 carbon atoms containing 1 to 8 carbon atoms and directly bonded to the tin atom.
and (c) a mercaptoalkanol or a derivative thereof directly bonded to at least one of the tin atoms through a sulfur atom.

It can be said that the bridge consists of -S--S-, and that no other functional groups are present in the bridge, such as, for example, bisoxide, alcoholade or phenate groups.

The nature of the bridge is irrelevant as long as it contains at least 2 carbon atoms in the chain. The required chain carbon atoms contain one or more carboxylate carbon atoms. The structure of the compounds of the invention is thus: where Q is -S-, Z together with Q is any divalent organic group containing at least 2 carbon atoms, and R is alkyl having 1 to 8 carbon atoms, and x is 1
or 2, and the two x may be the same or different, R1 may be alkylene, arylene, or substituted alkylene or substituted arylene (preferably R1 is unsubstituted alkylene or arylene), Y is hydrogen, acyl (e.g. acyl of carboxylic acid)
or any other thing.

In a further particular embodiment of the invention, said compound has the formula [
In this formula, R is an alkyl group having 1 to 8 carbon atoms, and A is S
Y (0\dDR'', or a halogen with an atomic weight of 35 to 127, the A groups may be the same or different, provided that at least one of the A's on each SO atom is: d is O or 1: each k is alkylene of 1 to 10 carbon atoms when d is O; and alkylene of 2 to 10 carbon atoms when d is 1: each Rf is an alkylene of 1 to 10 carbon atoms when d is 1; alkyl of 1 to 20 carbon atoms or 1 to 3 ethylenic double bonds and 2 to 19 carbon atoms
an ethylenically unsaturated aliphatic hydrocarbyl having , each bi is hydrogen, 1 to 2 carbon atoms when d is O;
0 alkyl, ethylenically unsaturated aliphatic hydrocarbyl having 1 to 3 ethylenic double bonds and 2 to 19 carbon atoms; x is 1 or 2; y
is 1 or 2: z is 1; and the sum of x+y+z is 4; Z
is -5 or: R4 is -CH:1CH- or alkylene of 2 to 10 carbon atoms; R5 is alkylene of 1 to 8 carbon atoms, phenylene or ~CH2CH-: R
6 is alkylene of 1 to 10 carbon atoms, -CH:ri:CH- or arylene; Rl3 is 2 carbon atoms
to 8 alkylene or -CH=CH-]
It is indicated by.

Group -SCH2CH2OCCH2CHCO(CH2),S
One can be produced by reacting 2 moles of mercaptol with 1 mole of maleic acid.

Group -S(CH2). COR6OC(CH,)S- (where n is 1 or 2) is thioglycolic acid or β-
2 moles of thiopropionic acid and e.g. ethylene glycol, diethylene glycol, propylene glycol,
It can be produced by reacting with 1 mole of a diol such as decamethylene glycol. The above compounds are useful for stabilizing halogen-containing vinyl resins and vinylidene resins, such as polyvinyl chloride.

Examples of R groups are methyl, ethyl, propyl, isopropyl,
n-butyl, isobutyl, sec-butyl, tert-butyl, amyl, hexyl, octyl, 2-ethylhexyl and isooctyl, most preferably R is methyl.

Examples of a group of R groups (SubgrOup) are (a) methyl and butyl and (b) methyl, butyl and octyl.

When A is halogen it is preferably chlorine. Examples of k groups (and R6 groups) are methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, octamethylene, hexamethylene, decamethylene, p-phenylene and m-phenylene.

Examples of R4 are the same as those described for k above, except for methylene. Examples of R5 are methylene, ethylene, trimethylene, propylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, 1CH=
CH- (both cis and trans).

The compounds of the present invention can be produced by various methods, such as those described below.

Tin is, for example, a monoalkyltin trihalide such as methyltin trichloride, methyltin tripromide, methyltin triiodide, ethyltin trichloride, sec-butyltin trichloride, butyltin tripromide or octyltin trichloride, e.g. Conveniently it is added as a dialkyl dihalide, such as tin dichloride, dimethyltin dipromide, dimethyltin diiodide, dipropyltin dichloride.

When using monomethyltin halide and dimethyltin halide or other monomethyltin halide or dimethyltin halide starting materials to ensure low toxicity, the amount of tin present as impurity trimethyltin compound is 0. Must be less than .5%.

DR! ' The group can be attached to tin by reaction of the mono- or dialkyl tin halides mentioned above with a compound having the formula HST(0CC]DR'', i.e. an ester of a methylcaptoalkanol such as mercaptoethanol. , 2-thioglycerin, 3-thioglycerin, 3-thiopropanol, 2
-thiopropanol, 4-thiobutanol, 18-thiooctadecanol, 9-thiononanol, 8-thiooctanol, 6-thiohexanol, and formic acid, acetic acid, propionic acid, butyric acid, pivalic acid, valeric acid, hydrofuric acid, caproic acid, decanoic acid, lauric acid, myristic 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-toluic acid, o-toluic acid, p-tertiary
Esters with acids such as butylbenzoic acid, natonic acid, p-n-butylbenzoic acid, cyclohexanecarboxylic acid, phenyl acetic acid, ricinoleic acid, hydrogenated ricinoleic acid, phenylpropionic acid can be used. Of course, for example, 60% of tall oil acid, palmitic acid and stearic acid.
:40 to 40:60 mixture, acid mixtures such as soybean oil acid, cottonseed oil acid, hydrogenated cottonseed oil acid, peanut oil acid, coconut oil acid, corn oil acid, castor oil acid, hydrogenated castor oil acid, lard acid, etc. can be used. Examples of half esters of polycarboxylic acids that can be esterified with mercaptoalkanols are monomethyl maleate, monoethyl maleate, monopropyl maleate, monobutyl maleate, monooctyl maleate, mono-2-ethylhexyl maleate. , monostearyl maleate, monoethyl fumarate, monomethyl oxalate, monoethyl oxalate, monoethyl malonate, monobutyl malonate, monoisopropyl succinate, monomethyl succinate, monomethyl glutarate, monoethyl adipate , monomethyl azelate, monomethyl phthalate, monoethyl phthalate, monoisooctyl phthalate, and monoethyl terephthalate.
Examples of mercaptoesters that can be used for reaction with tin compounds include 2-mercaptoethyl acetate, 2-mercaptoethylpropionate, 2-mercaptoethylbutyrate, 2-methicaptoethylvalerate, -Mercaptoethyl pivalate, 2-mercaptoethyl caproate, 2-mercaptoethyl caprylate, 2-mercaptoethyl pelargonate, 2-mercaptoethyl decanoate, 2-mercaptoethyl laurate, 2-mercaptoethyl stearate , 2-mercaptoethyl eicosanate, 2-mercaptoethyl palmitate, 2-mercaptoethyl oleate, 2-mercaptoethyl ricinolate, 2-mercaptoethyl linoleate, 2-mercaptoethyl linolenate, 2-mercaptoethyl to 2-mercaptoethyl ester of cottonseed oil acid, 2-mercaptoethyl ester of lard acid, 2-mercaptoethyl ester of coconut oil acid,
Mercaptoethyl ester, 2-mercaptoethyl ester of soybean oil acid, 2-mercaptoethyl benzoate,
2-mercaptoethyl p-toluate, 2-mercaptoethyl crotonate, 2-mercaptoethyl cinnamate, 2-mercaptoethyl phenyl acetate, 2-mercaptoethyl phenyl propionate, 2-mercaptoethyl methyl maleate, 2- Mercaptoethyl ethyl fumarate, 2-mercaptoethylbutyl oxalate,
2-mercaptoethyl methyl oxalate, 2-mercaptoethyl ethyl malonate, 2-mercaptoethyl methyl succinate, 2-mercaptoethyl methyl azelate, 2-mercaptoethylhexyl azelate, 2-
Mercaptoethyl methyl phthalate, 2-mercaptopropyl pelargonate, 2-mercaptopropyl enanthate, 2-mercaptopropyl stearate, 2-mercaptopropyl oleate, 2-mercaptopropyl ricinolate, 2-mercaptopropylethyl maleate, 2 -Mercaptopropyl benzoate, 2-thioglyceryl pelargonate, 3-thioglyceryl pelargonate, 2-mercaptoethyl bromoacetate, 6-mercaptohexyl acetate, 2-mercaptoethyl-3'-fluorobenzoate, 7-mercaptohebutyl acetate , 2-mercaptoethyl-2'-bromobenzoate, 7-mercaptohebutylpropionate, 2-mercaptoethyl-l
-chlorobenzoate, 8-mercaptooctyl acetate, 2-mercaptoethyl-2'-chloropropionate, 8-mercaptooctyl enanthate, 2-mercaptoethyl chloroacetate, 18-mercaptooctadecyl acetate, 2-mercaptoethyl trichloro Acetate, 18-mercaptoogtadecyl enanthate, 2-mercaptoethylcyclohexanoate, 2-
Mercabutethylcyclopentanoate.

Sulfur compounds used when d is zero include 2-mercaptoethanol, 3-mercaptopropanol, 4-mercaptobutanol, 3-mercaptobutanol, and 5-mercaptobutanol.
Included are thioalkanols such as mercaptopentanol, 10-mercaptodecanol.

Other formulas HSR'0CR! The starting compounds for '' include monothioglycerol dicaprylate, monothioglycerol diacetate, monothioglycerol distearate, monothioglycerol dioleate, and monothioglycerol dilinoleate.

The Z-bridge of the compound is produced by reacting a compound of the formula HZH with a compound of the formula: can do.

Examples of compounds having the formula HZH include mercaptoethyl mercaptopropionate, mercaptoethylthioglycolate, 3-mercaptopropylthioglycolate,
3-mercaptopropyl mercaptopropionate, mercaptoethyl mercaptobutyrate, mercaptoethyl mercaptodecanoate, 10-mercaptodecyl thioglycolate, 4-mercaptobutyl mercaptopropionate, mercaptoethyl thioglycolic acid mercaptoethyl ester, mercaptoethyl Kabutopropyl thioglycolic acid mercaptoethyl ester, mercaptoethyl thioglycolic acid mercaptopropyl ester, mercaptoethyl mercaptopropionate mercaptoethyl ester, mercaptopropyl mercaptopropionate mercaptopropyl ester, bis(2-mercaptoethyl)
Adipate, bis(3-mercaptopropyl)adipate, bis(4-mercaptobutyl)adipate, bis(
10-mercaptodecyl) adipate, bis(2-mercaptoethyl) maleate, bis(3-mercaptopropyl) maleate, bis(2-mercaptopropyl) adipate, bis(4-mercaptobutyl) maleate,
Bis(2-mercaptoethyl) fumarate, bis(3-
mercaptopropyl) fumarate, bis(2-mercaptoethyl) oxalate, bis(3-mercaptopropyl) malonate, bis(2-mercaptoethyl) succinate, bis(3-mercaptopropyl) succinate, bis(2-mercaptoethyl) glutarate ,Screw(
3-mercaptopropyl) azelate, bis(2-mercaptoethyl) suberate, bis(2-mercaptoethyl) sebacate, bis(2-mercaptoethyl) terephthalate, ethanedithiol, propanedithiol-1
,3,butanedithiol-1,4,butanedithiol-
1,3, hexanedithiol-1,6, decanedithiol-1,10, bis(2-mercaptoethyl) maleate, tetramethylene glycol bis(mercaptoacetate), and propylene glycol bis(3-mercaptopropionate).

A variety of methods can be used to prepare the compounds of the invention, some of which are illustrated in the Examples.

However, irrespective of the method used, the reaction can be carried out over a wide temperature range, for example from room temperature to 10[sigma]<0>C, usually from 25 to 50<0>C. The reaction is usually carried out using water as solvent, regardless of the procedure used. Also suitable as solvents are aqueous solvents such as aliphatic and aromatic hydrocarbons (e.g. hexane, octane, benzene, toluene, xylene), aliphatic carboxylic acid esters (e.g. butyl acetate, propyl propionate, methyl valerate). It is also possible to use miscible organic solvents. The proportions of solvent used are not critical and can vary widely.
→( In the following, all parts and percentages are by weight unless otherwise indicated. In the examples below, the refractive index (R.I.) was measured at a temperature of 25° C. unless otherwise indicated.

Example 1 Methyltin trichloride 120 dissolved in 200a water
9 (0.5 mol) in a 3-necked flask, and the mixture was
The mixture was warmed to a temperature of 0° C. and 2-mercaptoethyl caprylate 2049 (1.0 mol) was added.

Next, 80 g of 50% aqueous solution of sodium hydroxide (1.0
mol) was added dropwise at a temperature of 30°C and the mixture was
Stirring was carried out for 1 hour at a temperature of 0 to 40°C.
After this reaction time, 66.59 ml of bis(2-mercaptoethyl)adipate (0.25 mono(h)) was added in portions, followed by 50% NaOH4O9 (0.5 mol) and the mixture was stirred at 30-40°C. The product layer was separated and washed with 200 ml of water. The product was then stripped under vacuum to a temperature of 100° C., yielding 3189 as an almost colorless oil. The product was mainly bis(methyltinbis[2-mercaptoethylcaprylate]-mercaptotin(he)adipate) with an ND of 1.5283. The main product was represented by the following formula: Elemental analysis: % Sn calculated value: 8.8 Actual value: 9.3 Example 2 The procedure of Example 1 was followed except that bis(2-mercaptoethyl)adipate was replaced with mercaptoethylmercaptopropionate 429 (0.25 mol).

Pale yellow oil bis(methyltinbis[2-mercaptoethylcaprylate]) mercaptoethylmercaptopropionate 295f! I got it. nD was 1.5352. The product has the following formula: Elemental analysis: %Sn calculated 9.5 Found 9.9 Example 3 Bis(2-mercaptoethyl)adipate was converted to bis(2-
Mercaptoethyl) maleate 599 (0.25 mol)
The procedure of Example 1 was followed instead.

Pale yellow oil bis(methyl-tin bis[2-mercaptoethyl caprylate] mercaptoethinolimaleate 3
029 was obtained. ND was 1.5389. The product has the following formula: Elemental Analysis: %Sn Calculated 9.0 Found 9.3 Example 4 Bis(2-mercaptoethyl)adipate was converted to glycol bis(thioglycolate) 529 (0.25 The procedure of Example 1 above was followed except that the amount of mol) was changed.

An almost colorless oil 2999 was obtained. NO is 1.519
It was 3. The product has the following formula: Elemental analysis: %Sn calculated 9.2 Found 9.2 Example 5 Methyltin trichloride 12 dissolved in 200 TLI of water
0 g (0.5 mol) is placed in a 3-necked flask, the mixture is warmed to a temperature of 30° C. and 2-mercaptoethyl caprylate 1539 (0.75 mol) is added.

Next, 60f1 (0.
75 mol) was added dropwise at a temperature of 30°C, and the mixture was
Stir for 1 hour at a temperature of 40°C to 40°C. After this reaction time, 66.59% of bis(2-mercaptoethyl)adipate (0.25 mono(to)) was added little by little,
Then 40f of 50% NaOH aqueous solution! (0.50 mmol) is added and the mixture is stirred for 1 hour at a temperature of 30-40°C. The product layer is separated and washed with 200 d of water. The product is then stripped under reduced pressure. to obtain colorless oil 2639.n sweetness is 1.539
It was 6.

The product contained.

Example 6 110 dimethyltin dichloride dissolved in 200 ml of water
9 (0.5 mol) in a 3-necked flask, and the mixture was
It was warmed to a temperature of 0°C and then 2-mercabutethyl oleate 1709 (0.5 mol) was added.

Then a 50% aqueous solution of sodium hydroxide 409 (0.5
mol) was added dropwise at a temperature of 30° C. and the mixture was stirred and vigorously mixed for 1 hour at a temperature of 30 to 40° C. After this reaction time, bis(2-mercaptoethyl)adipate 66.59
(0.25 mol) and then immediately 5 mol of NaOH.
Add 40 g (0.5 mol) of 0q6 aqueous solution, then add 3
The mixture was stirred for 1 hour at a temperature of 0°C to 40°C. The product layer was separated, washed with 200 ml of water and dried under vacuum for 10
Stripping to a temperature of 00C gave 2969 as a yellow oil. NO was 1.5106. The reaction contained. Example 7 Dimethyltin dichloride 559 dissolved in 200 ml of water
(0.25 mol) and methyltin trichloride 609
(0.25 mol) in a 3-necked flask, and the mixture was
0. C. and 255 fI (0.75 mol) of 2-mercaptoethyl oleate were added.

Next, 60 g of a 50% aqueous solution of sodium hydroxide (0.7
5 mol) were added dropwise at a temperature of 30°C and the mixture was
Stirring was carried out for 1 hour at a temperature of 0 to 40°C.
After this reaction time, 66.5 g (0.25 mol) of bis(2-mercaptoethyl)adipate were added, followed immediately by the addition of NaOH aqueous solution 409 (0.50 mol), and then at a temperature of 30 to 40°C. I stirred it for an hour. The product layer was separated, washed with 200 ml of water and then stripped under vacuum to a temperature of 100° C. to give 3839 as a yellow oil. NO was 1.5080.

The reaction product contained.

Example 8 The procedure of Example 1 was followed except that 2-mercaptoethyl caprylate was replaced with 2-mercaptoethyl octadecyl ether 3309 (1.0 mol).

It is an almost colorless oily substance containing bis(methyltinbis).
441 g of 2-mercaptoethyl octadecyl ether (mercaptoethyl) adipate was obtained.
was 1.5149. Example 9 The procedure of Example 1 was followed except that 2-mercaptoethyl caprylate was replaced with monothioglycerol dicaprylate ester 3609 (1.0 mol).

A yellow oil 4589 containing bis(methyltinbis[thioglycerol dicaprylate]-2-mercaptoethino(he)adiperot) was obtained. N25OD was 1.516.
It was 0.

Example 10 The procedure of Example 1 was followed except that 260 g (1.0 mol) of 6-mercaptohexyl caprylate was used instead of 2-mercaptoethyl caprylate.

Pale yellow oil 366 which is mainly bis(methyltinbis[6-mercaptohexylcaprylate]-2-mercaptoethyl)adipate and has an ND of 1.5202.
I got a 9. Example 11 The procedure of Example 7 was repeated, substituting mercaptoethylthioglycolate 389 (0.25 mol) for bis(2-mercaptoethynolyadipate).

pale yellow oil with NO of 1.5161 34
I got 21. Example 12 Dimethyltin dichloride 559 dissolved in 200 ml of water
(0.25 mol) and methyltin trichloride 609
(0.25 mol) in a 3-necked flask, and the mixture was
It was warmed to a temperature of 0° C. and 2-mercaptoethyl caprylate 1029 (0.50 mol) was added.

Then a 50% aqueous solution of sodium hydroxide 409 (0.5
mol) was added dropwise at a temperature of 30° C. and the mixture was stirred at a temperature of 30 to 40° C. for 1 hour. After this reaction time, mercaptoethyl mercaptopropionate 4
29 (0.25 mol) and then immediately NaOH
Aqueous solution (50%) 409 (0.5 mon) was added and then stirred for 1 hour at a temperature of 30-40°C. The product layer was separated, washed with 200 d of water and placed under vacuum for 1 h.
It was stripped to a temperature of 00°C. 92 g of a yellow oil having a N25 of 1.5428 was obtained.

Example 13 The procedure of Example 1 was followed except that monomethyltin trichloride was replaced with butyltin trichloride 1419 (0.5 mol).

A pale yellow oil 3309 was obtained. The product is primarily bis(butyltinbis[2-mercaptoethylcaprylate]-2-mercaptoethyl)adipate, ND
was 1.5210. The main product is represented by the formula: Example 14 Methyltin trichloride converted to butyltin trichloride 14
19 (0.5 mol) and replacing bis(2-mercaptoethyl) adipate with bis(2-mercaptoethyl) maleate 599 (0.25 mol), the procedure of Example 5 was followed.

Almost colorless も containing U and n=1.5420
D° oil 2809 was obtained.

Example 15 Dimethyltin dichloride and dibutyltin cyclooctopus 7
5.59 (0.25 mol), methyltin trichloride and butyltin trichloride 70.59 (0.25 mol)
The procedure of Example 7 was followed instead.

and n is 1.5077 D
4O29 was obtained.

The compounds of the invention can be used as stabilizers with halogen-containing vinyl polymers and halogen-containing vinylidene polymers, such as resins in which the halogen is bonded directly to the carbon atom.

Preferably the polymer is a halogenated vinyl polymer, especially a vinyl chloride polymer. Typically, the vinyl chloride polymer is prepared from a monomer consisting solely of vinyl chloride or from a mixture of monomers containing at least 70% by weight vinyl chloride. When stabilizing vinyl chloride copolymers, it is preferred that the copolymer of vinyl chloride and the ethylenically unsaturated compound that can be copolymerized therewith contains at least 10% polymerized vinyl chloride. . Possible chlorinated polymers include chlorinated polyethylene (containing 14 to 75% chlorine, for example 27% by weight), chlorinated natural rubber and chlorinated synthetic rubber, hydrochloric acid rubber, chlorinated polystyrene, and chlorinated polyethylene. vinyl chloride, polyvinyl chloride, polyvinylidene chloride, polyvinyl bromide, polyvinyl fluoride, 1 to 90%, preferably 1 to 30% of copolymerizable ethylenically unsaturated compounds (e.g. vinyl acetate, vinyl butylene vinyl benzoate, vinylidene chloride, diethyl fumarate, diethyl maleate, other alkyl fumarates and alkyl 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 α-chloroacrylate, styrene,
copolymers of vinyl chloride (such as trichlorethylene) and vinyl chloride; vinyl ethers (such as vinyl ethyl ether, vinyl chloroethyl ether and vinyl phenyl ether); vinyl ketones (such as vinyl methyl ketone and vinyl phenyl ketone); like),
1-fluoro-2-chloro-ethylene, acrylonitrile, chloroacrylonitrile, allylidene diacetate and chloroallylidene diacetate.

A typical copolymer is vinyl chloride monovinyl acetate (9
6:4VYNW), vinyl chloride monovinyl acetate (87:13), vinyl chloride monovinyl acetate monomaleic anhydride WR (86:13:1), vinyl chloride monovinylidene chloride (95:5), vinyl chloride -diethyl fumarate (95:5), vinyl chloride-trichloroethylene (95:5),
5:5), vinyl chloride-2-ethylhexyl acrylate (90:20). The stabilizers of this invention can be incorporated with the polymer by mixing with the polymer in a suitable mill or mixer, or by any other known method of dispersing the stabilizer thoroughly and uniformly throughout the polymer composition. That is, it can be mixed by grinding on rolls at a temperature of 100 to 160°C. In addition to the novel stabilizers, customary additives such as plasticizers, pigments, fillers, dyes, UV absorbers, densifying agents, etc. can also be mixed with the resin.

Also, for example, by Kauder or Kugel, or Weisfeld CW.
Eisfeld, U.S. Pat. No. 3,640,950; Leistner, U.S. Pat. No. 28,701.
No. 19 and No. 2870182, Best
U.S. Pat. No. 2,731,484, Stefl
), US Pat. No. 2,731,482 and Mac
It is also possible to add the customary and known tin stabilizers disclosed in US Pat. No. 2,914,506 (k). The disclosures of all patent specifications mentioned in this section are incorporated herein by reference. If plasticizers are used, they are used in conventional amounts, such as from 10 to 150 parts per 100 parts of polymer.

Typical plasticizers are di-2-ethylhexyl phthalate,
These are dibutyl sebacate, dioctyl sebacate, and tricresyl phosphate. The tin-containing stabilizer of the present invention is usually used in an amount of 0.01 to 10% by weight based on the polymer, more preferably 0.2 to 5% by weight based on the polymer. do.

As mentioned above, 0.1 to 10 parts of metal salt stabilizer per 100 parts of halogen content can also be co-admixed.

For example, phenols, aromatic carboxylic acids, fatty acids or epoxy fatty acids barium, strontium,
Calcium, cadmium, zinc, lead, tin, magnesium, cobalt, nickel, titanium, and aluminum salts can be used. Examples of suitable salts include barium di(nonyl phenolate), strontium di(
nonyl phenolate), strontium di(amyl phenolate), barium di(octyl phenolate), strontium di(octyl phenolate), barium di(nonyl-0-cresolate) lead di(octyl phenolate), cadmium di(2-ethyl) Xoate, cadmium laurate, cadmium stearate, zinc caprylate, cadmium caprate, barium stearate, barium-2-ethylhexoate, barium laurate, barium ricinolate, lead stearate, aluminum stearate, magnesium stearate Calcium octoate, calcium stearate, cadmium naphthenate, cadmium benzoate, cadmium p-tertiary butyl benzoate, barium octyl salicylate, cadmium epoxy stearate, strontium epoxy stearate, cadmium in soybean oil epoxidation acid Includes salts and lead epoxy stearates.

In plastisol formulations, an epoxy vegetable oil, such as epoxidized soybean oil or epoxidized tall oil, and a fatty acid epoxy ester, such as isooctyl epoxy stearate, are added at 0.1 parts per 100 parts of polymer.
It is also preferable that 10 to 10 parts are included.

Chuuyuyu 111ba .

100 parts of polyvinyl chloride commercially available under the trade name GeOn 103EP and 90 parts of Omya
T (fine powder of CacO3 coated with calcium stearate) 1.0 part, trade name: Advawax
) Paraffin wax 1.0 commercially available under 165
1 part, 0.1 part of AC629A (oxide of low molecular weight ethylene homopolymer) and a stabilizer as shown in Table 1 below. The composition was heated to a temperature of 3800 F' and then milled and samples were taken at one minute intervals after the initial introduction of the mixture into the mill. The test results are shown below.
Shown in the table. Overall, as can be seen from Table 1 above, the products of the present invention compare favorably with the commercially available control stabilizers C symbol *
) shows better dynamic mill stability.

Claims (1)

[Claims] 1 Formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In the formula, R is an alkyl group having 1 to 8 carbon atoms, and A is SR'
O▲There are mathematical formulas, chemical formulas, tables, etc.▼_dR'', or a halogen with an atomic weight of 35 to 127, and the A groups may be the same or different, provided that at least one on each Sn atom is -SR'O ▲There are mathematical formulas, chemical formulas, tables, etc.▼_dR''; d is 0 or 1; each R' is alkylene with 1 to 10 carbon atoms when d is 0; each R'' is alkyl of 1 to 20 carbon atoms or 1 to 3 ethylenic double bonds and 2 to 1 carbon atoms when d is 1;
9 ethylenically unsaturated aliphatic hydrocarbyls, each R'', when d is 0, hydrogen, alkyl of 1 to 20 carbon atoms, 1 to 3 ethylenic double bonds and 2 to 2 carbon atoms; is an ethylenically unsaturated aliphatic hydrocarbyl having 19 atoms; X is 1 or 2; y is 1 or 2; z is 1; and the sum of x+y+z is 4;
is ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼; R_4 is -
CH=CH- or alkylene of 2 to 10 carbon atoms; R_5 is alkylene of 1 to 8 carbon atoms, phenylene or -CH=CH-; R_6 is alkylene of 1 to 10 carbon atoms, -CH =CH- or arylene; R_1_3 is alkylene having 2 to 8 carbon atoms or -CH=CH-. 2 the first wherein x and z are 1 and y is 2;
Compounds described in Section. 3. The compound according to item 2 above, wherein one of the A's bonded to each tin atom is a halogen with an atomic weight of 35 to 127, and the other A's are ▲a numerical formula, a chemical formula, a table, etc.▼. 4 The compound according to the above item 2, wherein all A groups are -SR'OCR''. 5 The compound according to the above item 1, where d is 0. 6 The compound according to the above item 1, where x and z are 1, and y is 2 The said fifth
Compounds described in Section. 7. The compound according to item 1 above, wherein Z is 1 and the A group is ▲a mathematical formula, a chemical formula, a table, etc.▼ or a halogen having an atomic weight of 35 to 127. 8. The compound according to item 7 above, wherein Z is ▲There are mathematical formulas, chemical formulas, tables, etc.▼. 9 The compound according to item 8 above, wherein R'' is alkyl or ethylenically unsaturated aliphatic hydrocarbyl. 10 The compound according to item 9 above, wherein R_4 is alkylene. 11 The compound according to item 9, wherein R_4 is -CH=CH-. The compound according to Item 9. 12 The compound according to Item 7, wherein Z is ▲ ▲ A mathematical formula, chemical formula, table, etc. Compounds described in Section. 14 Z is ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (
(provided that n is 2) The compound according to item 7 above. 15 Formulas ▲ Numerical formulas, chemical formulas, tables, etc. alkyl having 1 to 20 carbon atoms, ethylenically unsaturated aliphatic hydrocarbyl having 1 to 3 ethylenic double bonds and having 2 to 19 carbon atoms; x is 1 or 2; y is 1 or 2; and the sum of x+y is 3; R_8 is alkylene or cyclohexaline methylene having 2 to 10 carbon atoms; n is 1 or 2] according to item 1 above. 16 The compound according to the above item 15, wherein n is 1. 17 The compound according to the above item 15, wherein R_8 is alkylene having 2 to 10 carbon atoms.