FI63944C - ORGANOTENN-MERKAPTOALKYLKARBOXYLSYRAESTERSULFIDER ANVAENDBARA SOM STABILISATORER FOER HALOGEN-INNEHAOLLANDE POLYMERER - Google Patents

Description

! i! Ι - "^“ ·· Ι Γβ, / 44, KU RELEASE PUBLICATION, -, η Α λ W (11) UTLÄGGNINGSSKRIFT 6 3 9 4 4 CW '' ”^ ~ 3 ^ --- ^ (5ΐ) Kv.ik. Va3 C 07 F 7/22 // C 08 Κ 5/58 FINLAND — FINLAND (21) PK ^ »ttih« k * mti * -p «« ot «t» ek «» «* 753033 (22) Hakvmiapthrt - AnaMcntofttfac 30.10.75 (23) Alkuptivt — GlMghmdaf 30.10.75 (41) Tullut JulkiMkil - BIMt offmcMg 01.05.77 ^ Btentd- Jb rekirterthallfatt / 44) NIhtivIJulpanon jt kuL | ullctitun date - ratnit- och r * gift * rat * l 'Amfiku utlagd odi utUkrtftM puMicwad 31.05.63 (32) (33) (31) Pyy * · »*« «» © Ikeu * - «« fird priority (71) Carstab Corporation, Delaware, USA (US) (72) Thomas Gordon Kugele, Cincinnati, Ohio, USA (71) Berggren Oy Ab (5 * 0 Organotina mercaptoalkylcarboxylic acid ester sulfides useful as stabilizers for halogenated polymers -Organotenn mercaptoalkylcarboxylsyraesterulfider

The present invention relates to novel organotin mercaptoalkyl carboxylic acid ester sulfides useful as stabilizers for halogenated polymers such as polyvinyl chloride.

The organotin compounds of the invention have the formula R-0 | 1 1

R 1 -Sn-SR-OC-R 2 ^ S 0, xe R, -Sn-SR-OC-R 11 5 x 10 wherein R is a number from 1 to 4, R 1, R 2, R 1 and R 2 are alkyl or aryl groups having 1 to 8 carbon atoms, or R 1 and / or R 2 may also be R 1 n 0 0

3 ° II II

-Sx-Sn-R31, -S-R-OC-R10, -S-R-C-OR10, -SR10, -S-R-OR10, 0 R, -O 0

»32 il N

-OC-R 10, -OC-RC-OR 10 or chlorine, wherein R 1 q, R 31 and R 2 are 2 63944 alkyl or aryl groups having 1 to 8 carbon atoms or O 0 -SR-OC-R 10, - SRC-OR1q, -SR1Q, -SR-OR10, -OC-R1Q, 0 0

II II

-OC-RC-OR ^ q, or chlorine, wherein R is alkylene or hydroxyalkylene which may be substituted with 0 -10-R-Q, and R ^ q is hydrogen, a hydrocarbon group having 1 to 19 carbon atoms, wherein the hydrocarbon group is alkyl, aryl, aralkyl, cycloalkyl, aralkenyl or alkenyl having 1 to 3 ethylene double bonds, hydroxyalkyl having 1 to 19 carbon atoms or hydroxyalkenyl having 2 to 19 carbon atoms; except thio-bis- / methyltin-bis- (2-thioethyl octanoate) _7.

DE-A-2 503 55 ^ (Example 6) discloses the compound thio-bis- / methyltin-bis- (2-thioethyloctanoate) 7, which is therefore not within the scope of the invention.

The group R is preferably alkylene having 2 or 3 carbon atoms.

X is preferably 1 or 2, i.e. the compounds are preferably mono- or disulfides. The most preferred alkyl group attached to tin atoms is methyl. The group R 10 is preferably alkyl of 6 to 19 carbon atoms, alkenyl of 17 carbon atoms or hydroxyalkoxyalkyl of 17 carbon atoms.

The compounds of the invention are particularly useful as stabilizers to improve the degradation resistance of vinyl chloride polymers when heated to 177 ° C.

The term "mercaptoalkylcarboxylic acid ester" as used in the name of the compounds of the invention means that the alcohol group is esterified with the carboxyl group. is a mercaptoethyl caprylate of formula 3,33944 HSCH2CH2OOC (CH2) 6CH3 which is different from the starting ester, isooctyl thioglycolate of formula HSCH2COOCgH17 used e.g. according to U.S. Patents 3,565,930 and 3,565,931. the starting compounds used according to the invention have the free mercapto group which reacts with the tin compound to form the compounds according to the invention in the alcohol part of the ester, while according to the above-mentioned U.S. patents it is in the acid part of the ester.

This is a considerable difference because the compounds of the invention have significant advantages over the compounds disclosed in the aforementioned U.S. patents. First, they have superior stabilizing properties in vinyl chloride polymers and other halogen-containing polymers.

This has been found both in laboratory tests and even more so on a factory scale. These compounds have greater storage stability than the corresponding alkylthioalkanoates. The organotin mercaptoalkyl carboxylates disclosed have the great advantage over organotin alkyl mercaptocarboxylates in that the stabilizers have a higher storage stability and resistance to precipitation. Although not wishing to be bound by any theory, we believe that the instability of alkyl mercaptocarboxylates is due to hydrolysis of the ester, resulting in the formation of an organotin mercaptocarboxylate ring or polymeric material that precipitates. This in turn is due to the nucleophilicity of the unbound carboxylate anion with respect to tin. However, in the case of mercaptoalkyl carboxylates, the nucleophilicity of the alcohol oxygen is not sufficient to cause the mercaptoalkyl alkanoate to flourish and form an insoluble annular or polymeric product.

Samples exposed to steam-saturated air at 38 ° C have shown very little turbidity when organotin alkyl mercaptocarboxylates are used, while when stored under the same conditions the corresponding alkyl thioalkanoates form large fines.

The details of the storage resistance test are as follows: 50 g samples were stored in open 56 g narrow bottles in a closed desiccator with a 1.27 cm aqueous layer at the bottom. The desiccator was placed in an oven and used for 5 days at 38 ° C and and 2 days at room temperature (10-21 ° C). The duration of the experiment was 60 days. At the end of this time, about 50% of the alkylthioalkanoate had precipitated while only about 1% of the mercaptoalkyl alkanoate had precipitated.

The structures of the alkylthioalkanoate and mercaptoalkyl alkanoate used in the experiment were as follows:

ti II

MeSn (SCH2COCgH17) 2 iso MeSn (SCH2CH2OCCgH17) 2 S2 S2 | o | o

Il I

MeSn (SCH2COCgH17) 2 large MeSn (SCH2CH2OCC8H17) 2 alkylthioalkanoate mercaptoalkylalkanoate

The compounds of the invention also have a more dilute odor compared to the compounds mentioned in the aforementioned U.S. patents.

It is important that a sulfide group be present so as to provide excellent stabilization properties. Thus, the compounds of the invention are superior stabilizers to, e.g., organotin compounds prepared by reacting methyltin trichloride (or dimethyltin dichloride) with 2-mercaptoethyl caprylate, the latter types of tin compounds being described in U.S. Pat. W, 2,870,119 and 2,870,182.

5,63944

The organotin compounds of the invention, which are diorganotin compounds, can be used as stabilizers alone or in admixture with mono-organotin compounds. Mixtures containing 96-50% of a mono-organotin compound and H-50% of a diorganotin compound of the invention are preferred.

The compounds of the invention may be prepared in various ways, e.g. as set out below. Thus, the methods disclosed in U.S. Patent Nos. 3,565,930 or 3,565,931 can be used using alkali metal, alkaline earth metal, or ammonium sulfides or polysulfides, e.g., Na 2 Sx, K 2 Sx,

BaSx or (NH 2) 2 Sx, where x is as defined above, in place of the alkali metal or alkaline earth metal monosulfide used in the aforementioned U.S. patents, and also using a compound of formula 0 * HS-R-OCR10 used in the aforementioned U.S. patents. instead of isooctyl thioglycolate or the like. In the case that the group and / or R 1 (in formula I is O--C-R-C-OR 10, -SR 10, -S-R-OR 10, -OC-R 10 or

0 0 Il II

-OC-R-C-OR 2 q, a compound of formula 0 0 0 0 should also be present

II II I HS-R-C-OR10, HSR1q, HS-R-OR1q, HOC-R10 or HOC-R-C-OR10.

Thus, 1 mole of a compound of formula R 1 may be reacted with 1 mole of a compound of formula:

II

HS-R-OCR10 followed by neutralization with an alkali or alkaline earth metal hydroxide using an amount corresponding to the carboxylic acid content.

6,63944 Captoalkanol ester followed by reaction with ammonium or alkali or alkaline earth metal sulfide. If the compound ^ SnX2 R2 then has the formula R ^ -SnX- ^, then 2 moles of mercaptoalkanol ester must be used. X may be halogen having an atomic weight of 35 to 127. Thus, methyltin trichloride, methyltin tribromide, methyltin triiodide, ethyltin trichloride, butyltin trichloride, butyltin tribromide, butyltin triiodide, sec. butyltin trichloride, octyltin trichloride, benzyltin trichloride, dimethyltin dichloride, dimethyltin dibromodia, dimethyltin diiodide, dipropyltin di-dichloride, butylmethyltin dichloride, butyltin dichloride, dibutyl dichloride, dibenzyltin dichloride, phenyltin trichloride, p-tolytithin trichloride, diphenyltin dichloride and di-p-tolyltin dichloride.

0

II

Examples of mercapto esters of the formula HS-R-OCR 2 Q which can be used in the reaction with a tin compound are: 2-mercaptoethyl acetate, 2-mercaptoethyl propionate, 2-mercaptoethyl butyrate, 2-mercaptoethyl valerate, 2-mercaptoethylaphthalate, 2-mercaptoethyl pala 2-merkaptoetyylikaprylaatti, 2-merkaptoetyylipelargonaatti, 2-merkaptoetyylidekanoaatti, 2-merkaptoetyylilauraatti, 2-merkaptoetyylistearaatti, 2-merkaptoetyylieikosanaatti, 2-merkaptoetyylipalmitaatti, 2-mercaptoethyl, 2-merkaptoetyylirisiinioleaatti, 2-merkaptoetyylilinoleaatti, 2-merkaptoetyylilinolenaatti, 2-merkaptoetyylitallaatti, puuvillansiemenöljyhapon 2-mercaptoethyl ester, 2-mercaptoethyl ester of lardic acids, 2-mercaptoethyl ester of coconut oil acids, 2-mercaptoethyl ester of soybean oil acids, 2-mercaptoethyl benzoate, 2-mercaptoethyl 2-meroate, 2-mercaptoethyl, 2-mercaptoate, 2-mercaptoate 2-merkaptoetyy] ifenyyliasetaatt i, 7 63944 2-mercaptoethylphenylpropionate, 3-mercaptopropyl pelargonate, 3-mercaptopropyl enanthate, 3-mercaptopropyl stearate, 3-mercaptopropyl oleate, 3-mercaptopropyl ricinoleate, 3-thiophile a-oleacyl, 3-mercaptopropylethyl maleate, 3-mercaptopropylethyl maleate, 3 mercaptohexyl acetate, 7-mercaptoheptyl acetate, 7-mercaptoheptyl propionate, 8-mercaptooctyl acetate, 8-mercaptooctyl enanthate, 18-mercapto octadecyl acetate and 18-mercapto octadecyl enanthate.

Examples of compounds of formula 0 0

H II

HSRqC-OR9, HSRg, HSR14OR9 or HOC-R10 are the following, methyl mercaptoacetate, (methyl thioglycolate), ethyl mercaptoacetate, propyl mercaptoacetate, butyl mercaptoacetate, isobutyl limercaptoacetate, sec-butyl mercapto iso oktyylimerkaptoase-acetate, 2-etyylihaksyylimerkaptoasetaatti, dekyylimerkapto acetate, isodekyylimerkaptoasetaatti, lauryylimerkaptoase-acetate, myristyylimerkaptoasetaatti, heksadekyylimerkapto acetate, stearyylimerkaptoasetaatti, allyylimerkaptoasetaat-acetate, metallyylimerkaptoasetaatti, krotyylimerkaptoasetaatti, oleyylimerkaptoasetaatti, syklopentyylimerkaptoasetaatti, sykloheksyylimerkaptoasetaatti, 2-metyylisykloheksyylimerkap-orthoacetate, bentsyylimerkaptoasetaatti, methyl beta-mercaptopropionate, ethyl beta-mercaptopropionate, isopropyl beta-mercaptopropionate, octyl beta-mercaptopropionate, iso-octyl beta-mercaptopropion ionaatti, 2-etyyliheksyylibetamerkapto-propionate, dekyylibetamerkaptopropionaatti, octadecyl-betamerkaptopropionaatti, allyylibetamerkaptopropionaatti, oleyylibetamerkaptopropionaatti, bentsyylibetamerkaptopropio carbonate, sykloheksyylibetamerkaptopropionaatti, metyylialfa-mercaptopropionate, heksyylialfamerkaptopropionaatti, nonyy-lialfamerkaptopropionaatti, oktyylialfamerkaptopropionaatti, iso oktyylialfamerkaptopropionaatti, stearyylialfamerkapto-propionate, oleyylialfamerkaptopropionaatti, metyylialfa- 8 63944 merkaptobutyraatti, oktyylialfamerkaptobutyraatti, iso oktyylialfamerkaptobutyraatti, oktadekyylialfamerkaptobutyraatti, oleyylialfamerkaptobutyraatti, etyyligammamerkaptobutyraatti, oktyyligammamerkaptobutyraatti, 2-etyyliheksyyligammamerkapto-butyrate, iso-oktyyligammamerkaptobutyraatti, bentsyyligamma-merkaptobutyraatti, Cyclopentyl-ligammamerkaptobutyraatti, oleyyligammamerkaptobutyraatti, isopropyylideltamerkaptovale stearate, oktyylideltamerkaptovaleraatti, iso oktyylideltamer-kaptovaleraatti, oktadekyylideltamerkaptovaleraatti, oleyl deltamerkaptovaleraatti, syklohekyylideltamerkaptovaleraatti and bentsyylideltamerkaptovaleraatti, methyl mercaptan, ethyl mercaptan, butyl mercaptan, octyl mercaptan, dodeca-kyylimerkaptaani, stearyylimerkaptaani, oleyylimerkaptaani, metoksietyylimerkaptaanij etoksietyylimerkaptaani, octoxy, ethyl mercaptan, etoksipropyylimerkaptaani, acetic acid, stearic acid, benzoic acid, kaproehappo, caprylic , decanoic acid, enanthic acid and oleic acid.

Several methods can be used to prepare the compounds of the invention, as set forth below. Regardless of the method used, however, the reaction can be carried out over a wide range of temperatures, e.g. from room temperature to 100 ° C, usually between 25 ° C and 50 ° C. The reaction is usually carried out using water as the solvent, regardless of the method used. Water-immiscible organic solvents can also be used, e.g. aliphatic and aromatic hydrocarbons such as hexane, octane, benzene, toluene, xylene, aliphatic carboxylic acid esters, e.g. butyl acetate, propyl propionate and methyl valerate. Solvent levels are not critical and can vary widely.

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

In the examples, refractive indices (R.I.) are measured at 25 ° C unless otherwise stated. Typical methods are as follows: 9,63944

Method 1: This method follows the general procedure set forth in the aforementioned U.S. Patents, except that sodium monosulfide, sodium disulfide, sodium trisulfide, sodium tetrasulfide, ammonium monosulfide, ammonium disulfide, ammonium trisulfide, or ammonium tetrasulfide are reacted with an anti-compound or with compounds as described above.

Method 2: In this method, sodium mono- or polysulfide (or potassium mono- or polysulfide), water, mercapto-containing ester, hydrocarbon, if necessary, and ammonium hydroxide are introduced into the reactor and an alkyltin halide solution is slowly added, e.g. at 25-35 ° C. The mixture is then heated to e.g. 50 ° C, the layers are separated and the product is washed and dried.

Method 3 · In this method, the mercaptopic ester, water, organic solvent and ammonium hydroxide are introduced into a flask and then two solutions of (A) alkyltin chloride and (B) alkali metal mono- or polysulfide are added simultaneously. The product is then separated, washed and dried.

Method * 4: This is the same method as Method 3 except that the same molar amount is used instead of ammonium hydroxide.

NaHCOj: a.

_ - r ίο 6 3 94 4

Method 5 · In this method, alkyltin chloride, water and ammonium hydroxide are introduced into a flask and then a mercapto-containing ester and an alkali metal mono- or polysulfide are added simultaneously.

Method 6: This method involves introducing a mercaptopic ester, water and ammonium hydroxide into the reactor and then adding alkyltin chloride, followed by slow addition of an alkali metal polysulfide or monosulfide at 30 ° C. After heating to 55 ° C, the product is separated, washed and dried.

These basic methods are further described in detail in U.S. Patent 3,869-87, which is incorporated herein by reference. The preparation examples presented in this patent publication can be followed by replacing the mercapto compounds used in whole or in part with mercapto compounds of the formula:

O

il HS-R-OCR10

The stabilizers according to the invention can be used in connection with halogen-containing vinyl and vinylidene polymers, e.g. in the case of resins in which halogen is attached directly to carbon atoms. The polymer is preferably a vinyl halide polymer, especially a vinyl chloride polymer. The vinyl chloride polymer is usually prepared from monomers containing vinyl chloride alone or from a mixture of monomers containing at least 70% by weight of vinyl chloride. When stabilizing vinyl chloride copolymers, the copolymer of vinyl chloride with an ethylenically unsaturated compound which copolymerizes with the former preferably contains at least 10% of polymerized vinyl chloride.

11 63944

As the chlorinated polymer, chlorinated polyethylene having 14-75% »e.g. 27% by weight of chloride, chlorinated natural or synthetic rubber, rubber hydrochloride, chlorinated polystyrene, chlorinated polyvinyl chloride polyvinyl chloride, polyvinyl chloride, polyvinyl chloride, polyvinyl chloride, polyvinyl chloride a copolymer of an ethylenically unsaturated material copolymerizable with 1 to 90, preferably 1 to 30, such as vinyl acetate, vinyl butyrate, vinyl benzoate, vinylidene chloride, diethyl fumarate, diethyl maleate, ethyl maleate or other alkyl fumarates, or other alkyl fumarates, acrylate, butyl acrylate or other alkyl acrylates, methyl methacrylate, ethyl methacrylate, butyl methacrylate and other alkyl methacrylates, methyl alphachloroacrylate, styrene, trichlorethylene, vinyl ethyl and vinyl ethers such as vinyl ethyl vinyl phenyl ether, vinyl ketone such as vinyl methyl ketone and vinyl phenyl ketone, 1-fluoro-2-chloroethylene, acrylonitrile, chloroacrylonitrile, allylidene diacetate and chloroallylidene diacetate. Typical copolymers are vinyl chloride-vinyl acetate (96: 4, sold under the name VYNW), vinyl chloride-vinyl acetate (87:13) »vinyl chloride-vinyl acetate-maleic anhydride (86: 13: 1)» vinyl chloride-chloride-vinylidene , vinyl chloride diethyl fumarate (95: 5) »vinyl chloride-trichlorethylene (95: 5)» vinyl chloride-2-ethylhexyl acrylate (80:20).

The stabilizers of the invention may be combined with the polymer by mixing in a suitable mill or mixer or by any other well known method which provides uniform distribution throughout the polymer blend. Thus, the mixing can be carried out in a rolling mill at a temperature of 100-160 ° C.

In addition to these new stabilizers, conventional additives such as plasticizers, pigments, fillers, dyes, ultraviolet light absorbers, sealants, etc. can also be added to the resin. Conventional and known tin stabilizers, e.g., those described in U.S. Pat. : ot 3,869,487, 3,565,930, 3,640,950,? 870,119, 2,870,182, 2,731,484, 2,731,482 and 2,914,506, which are incorporated herein by reference.

When a plasticizer is used, it is used in an ordinary amount, e.g. 10 to 150 parts per 100 parts of polymer. Typical plasticizers include di-2-ethylhexyl phthalate, dibutyl sebacate, dioctyl sebacate and tricresyl phosphate.

The tin-containing stabilizers according to the invention are usually used in an amount of 0.01 to 10% by weight of polymer, in particular 0.2 to 5% of tin compound, based on the weight of the polymer.

As mentioned, 0.1 to 10 parts of a metal salt stabilizer per 100 parts of halogen-containing polymer can also be used. Thus, barium, strontium, calcium, cadmium, zinc, lead, tin, magnesium, cobalt, nickel, titanium and aluminum salts of phenols, aromatic carboxylic acids, fatty acids or epoxy fatty acids can be used.

Examples of suitable salts are barium di (nonylphenolate), strontiumdi (nonylphenolate), strontiumdi (amylphenolate), bariumdi (octylphenolate), strontiumdi (octylphenolate), bariumdi (nonyl-o-cresolate), ethyloxyene, lead (octylate) , kadmiumlauraatti, cadmium stearate, sinkkikaprylaatti, kadmiumkapraatti, barium stearate, barium-2-ethylhexoate, bariumlauraatti, bariumrisiinioleaatti, lead stearate, aluminum stearate, magnesium stearate, calcium siumoktoaatti, calcium stearate, kadmiumnaftenaatti, kadmiumbentsoaatti, cadmium p-tert.butyylibentsoaatti, bariumoktyylisalisylaatti, kadmiumepoksi stearate , strontium epoxy stearate, cadmium salt of epoxidised acids of soybean oil and lead epoxy stearate.

The plastisol mixtures also preferably use 0.1 to 10 parts of an epoxy vegetable oil per 100 parts of polymer, such as epoxidized soybean oil or epoxidized tallow oil, epoxy esters of fatty acids, e.g. isooctyl epoxystearate.

comparison Tests

In order to illustrate the beneficial effects of the stabilizing compositions of the invention, the following experiments were performed. All stabilizers used were evaluated on the basis of their cost and not the corresponding amounts. In other words, certain stabilizers were used more because of their lower unit costs. The tables are also based on substantially the corresponding teaspoons of 13,63944 tin. The composition of the PVC resin mixtures in the tables is as follows:

Seos I

Coalition Weight section

Polyvinyl chloride (PVC) 100.0 "Omya 90T" (finely divided CaCO, coated with CaSt) ^ 1.0

Titanium dioxide 1.0

Calcium stearate (CaSt) 0.6

Paraffin wax ("Advawax 165") 1.0 "AC 629A" (oxidized low molecular weight ethylene homopolymer) 0.1

Stabilizer as shown Resins obtained from several PVC manufacturers were used to determine the overall effect of the compounds of the invention in various PVC resins.

PVC Resin Manufacturer PVC 450 (K = 64.3) Diamond Shamrock

Geon 103 EP (K = 62.2-64.3) B.F. Goodrich Q-SAN-7 (K = 65.8) Union Carbide

Allied SR 414-3 (K = 64.7) Universal PVC Resin

Stability test (dynamic grinding stability)

The stabilizer is mixed with the PVC resin mixture in a twin roller powder apparatus at 193 ° C, at a temperature where the mixture is fluid and promotes thorough mixing, the mixture is kneaded at 193 ° C and a sample is taken at 1 minute intervals, after which the mixture is fed to a mill.

The appearance of the samples obtained from the dynamic grinding stability test is shown in Tables 1-4, whereby the sample numbers are the same in all tables.

Samples 1, 4, 5, 8, 10-12, 14-17, 20, 22 and 23 shown in the tables are not organotin compounds according to the invention, but are reference samples.

r “14 63944

Table I

Resin "Allied SR-414-3"

Dynamic grinding stability 193 C 30/40 rpm (minutes) Sample Tin - 1 2 3 4 5 6 7 8 9 ^ n concentration (mg) 7 28.0 10+ 10 9 8+ 8 6 5 4 2 1 2 30.7 10 9 8+ 8.7 6 5 4 2 1 1 33.5 10 9 8+ 8 7 6+ 5+ 4 2 1 9 28, ¾ 10+ 10 9 9 8+ 7 6 5 3 1 17 32.5 10 9 8+ '8. 7 6+ '5+ 4 2 1 18 28.4 10+ 10 9 9 8+ 7 6 5 3 1 4 36.0 9 + 876 + 654 3 1 1 19 35.0 10+ 10 9 9 8+ 7 6 5 2 1 Color scale: 10 (white) to 5 (brown-orange) to 0 (burnt) (intensity, no hue) Sample: 17. "Thermoite 136" Butyltin, 85% mono / 15% di in part to isooctylthioglycolate in part - S-bond to partially unreacted chloride diluted to 12.8% tin content 18. 2/3 monomethyltin tris (2-mercaptoethyl oleate) and 1/3 bis / monomethyltin bis (2-mercaptoethyl oleate) sulfide.

19. Bis / methyltin di (2-mercaptoethyl pelargonate) 7 sulfide.

Table II

Resin "B.F. Goodrich Geon 103 E?"

Dynamic grinding stability 193 ° C 30/40 'rpm (minutes) Sample Tin-12 3456 7 89 10 No. (mg) 1 33.5 10 9+ 9876 5 32 2 3 34.0 10+ 10+ 10 9+ 8 5 2 10 0 4 36.0 9 + 8 7 6+ 5+ 5 4 3 2 2 6 33.6 10+ 10+ 10+ 10 9+ 8 6 5 3 1 2 30.7 10 9 8765 4 32 1 7 28.0 10+ 10 9+ 9 7 6 5 3 1 1 5 · 26.3 98 6+ 5+ 54 2 21 1 8 25.8 10 9+ 9 7 5+ 4 2 2 1 l 15 63944 Color scale: 10 (white) - 5 (brown-orange) - 0 (burnt) Sample: 1 "Cardinal AC-78" Butyltin, 85% ir.ono / 15% di into isooctylthioglycolate into -S- bonds diluted 13 .4% tin dioctyl. with phthalate 2 2/3 monomethyltin tris-isooctyl thioglycolate and 1/3 bis / monomethyltin bis (isooctyl thioglycolate27 disulphide (70%) + mineral oil (30%) 3 bis / methyltin di (2-mercaptoethylate)) 7sulfide 4 "Mark 1905” methyltin, 50% mono / 50% di to iso-octylthioglycolate S-bond plus diluent, 14.4% tin 5 Butyltin tris-isooctylthioglycolate 6 Bi 2/3 monomethyltin tris (2-mercaptoethyl pelargonate and 1/3 bis / monomethyltin bis (2-mercaptoethyl pelargonate) 27 sulphide (70%) and mineral oil (30%).

8 Butyltin tri.s (2-mercaptoethyl pelargonate).

Table III

Resin "Union Carbide Q-SAN-7"

Dynamic grinding stability 193 ° 0 30/40 rpm (minutes) Sample Tin 1 1 23 ^ 56789 10 No. (mg) 9 28.4 10 10 9 8 7+ 6 5+ 4 3 2 10 25.3 9 8+ 8765 ^ 32 1 11 31.0 9 8 7.5 4 3 3 2 2 2 12 29.0 10 9 + 9876531 1 13 35.0 10+ 10+ 10 9 8 7+ 6 5 3 2 14 35.8 9 87655422 2 15 35.0 10 10 9 7 5+ 5 4 2 2 2 16 33.0 8 76543322 2 Color scale: 10 (white) - 5 (brown-orange) - 0 (burnt) 16 63944 Sample: 9 2/3 monomethyltin tris (2-mercaptoethyl stearate) and 1/3 bis-nonomethyltin bis (2-mercaptoethyl list) 7sulfidia 10 Methyltin tris (2-mercaptoethyl pelargonate) 11 '' Mark 1909 '(same as No 4 without diluent), 20% tin 12 Same composition as No. 10 13 bis / monomethyltin-bis-mercaptoethyl stearate and sulfide 14 Dimethyltin-bis (isooctyltic glycolate) 15 Dimethyltin-bis (2-mercaptoethyl-gelatin) gelatin octyl thioglycolate).

Table IV

Resin "Diamond Shamrock PVC 450"

Dynamic grinding stability 193 ° C 30/40 rpm (minutes) Sample Tin-1234567 8 9 10 No. (mg) 13 3 5.0 10+ 10+ 1056 10? 10 9 8 7 4 2 20 36.7 10 988764 3 2 1 21 35.0 10+ 10+ 10+ 10 9 8 7 6 4 3 7 28.0 10+ 10+ 10+ 10 9 7 6 4 2 1 2 30.7 10 987654 3 2 1 1 33.5 10987654 3 2 1 9 28.4 10+ 10+ 10 9+ 9 8 7 4 2 l 17 32.5 10 9+ 8+ 7 6 5 4 3 2 1 Color scale : 10 (white) - 5 (brown-orange) - 0 (burnt) (intensity, no hue) Sample: 20 bis / methyltin-bis (isooctyl thioglycolate / Zdisulphide.

21 bis / monomethyltin bis (2-mercaptoethyl oleate 27 sulfide.

In a factory-scale tube extrusion test, the compounds of the invention had superior stabilizing properties over commercial tin stabilizers and produced a very white tube at corresponding production rates. Both the dynamic grinding stability test (DMS) and the oven stability test were performed on the mixtures used.

63944 17

The composition was the same as that used in Tables I-IV using "Allied SR 414-3" as the vinyl chloride resin. · The stabilization amounts are shown in Tables V and VI. The amounts chosen are such that the mixtures contain approximately the same amount of tin. The sample numbers are the same in Tables I- IV with the added values shown in Table V.

Table V

1. Residual stability of the tube, 190 ° C

Mixture- Part / 0 '2' 4 '6' 8 '10' 12 '14' 16 '18' 20 'sample 100 parts of resin 2 0.25 10 10 10 9+ 9 8 7 7 6 5 4 17 0.25 9+ 9+ 9+ 9 9 7+ 6 6 5 5 4 22 0.25 10 10 10 10 10 8 7 7 6 5 4 23 0.175 10 10 10 9+ 9+ 8 7 7 6 5 4 4 0.25 9 + 9+ 9 8+ 8 7+ 7 6+ 6 5 .4 11 0.15 99988 766544 1 0.25 9 + 9 + 9 + 98 7 7 7 6 5 ~ 5 7 0.25 10+ 10+ 10+ 10 + 10 987765 24 0,175 10+ 10+ 10+ 10+ 10+ 10 9 8 7 6+ 5 19 0,175 10+ 10+ 10+ 10+ 10+ 10 9 7+ 7+ 6+ 6 25 0,175 10+ 10+ 10+ 10+ 10 10 8 7 7 6 5+: Color scale: 10 (white - 5 (orange) - 0 (burnt) Sample: 22 "Thermolite 138" is a commercial methyltin product 23 "Thermolite 148" is a commercial methyltin product 24 2/3 monomethyltin tris (2-mercaptoethyl pelargonate) and 1/3 bis / monomethyltin bis (2-mercaptoethyl pelargonate27-sulphide 25 2/3 monomethyltin tris (2-mercaptoethyl laurate) and 1/3 bis / monomethyltin-bis (2-mercaptoethyl laurate)) yyl Fragile ti) 7sulf idia.

'' '18 63944

Table VI

2. Grinding stability of pipe mixtures 193 ° C 30/40 rpm Sample Part / 1 '2 »3' 4» 5 '' 6 '7' 8 'S' mixture 100 parts resin 2 0.25 10 9 8 7 6 5 ^ 21 17 0.25 10 8+ 7 6 5 4 + 311 22x 0.25 10 9 8. 7 6 5 4 2 1 23 0.175 10 99876431 4 0.25 9 8 7 6 5 + 4 3 2 1 11 0, 15 "9 7 6 5+ 5 4 2.1 1 1 0.25 1098765411 7 0.25 10+ 9+ 8 7 6 5 421 24 0.175 10+ 9 8 6+ 5+ 5 4 1 1 19 0.175 10+ 9+ 9 8 7 5+ 4 2 1 25 0,175 10+ 8 6+ 5+ 4 3 1 1 1 Color scale: 10 (white) - 5 (orange) - 0 (burnt) x22 - slightly gray impurities

Mixtures of the dialkyltin compounds of the invention with monoalkyltin compounds appear to be more effective than the individual components when prepared together from chlorides or simply mixed together as shown in Table VII.

Table VII

Mixture II Resin M3.F. Goodrich Geon 103 EP "

Dynamic grinding stability 193 ° C

30/40 rpm (minutes) Sample Tin - 123 4 56789 10 No. Concentration (mg) 19 150 10 + 10 9 8 7 7 6 4+ 3 1+ 26 150 9+ 9 9 7+ 6+ 6 5 4 3 2 27 150 10+ 10 10 9+ 9 8+ 8 6+ 5+ 3 27 * 150 10+ 10 10 9+ 9 8+ 8 6 5 3 28 150 10+ 10 9 8+ 8 6+ 5+ 3 + 2 1 29 150 10+ 10 9+ 8+ 8+ 7 6 5 4 3 30 150 10+ 10 9 8+ 7+ 7 5+ 4 4 3 31 · 150 9+ 9 8+ 8 7 5+ 4 3+ 3 2 19 63944 Color scale: 10 (white) to 5 (brown to orange) to 0 (burnt) Sample: 26 bis.Zclimethyltin mono (2-mercaptoethyl pelargonate) 7 sulphide 27 2/3 bis / monomethyltin bis (2 -mercaptoethyl pelargonate) sulfide and 1/3 bis (N-dimethyltin-mono 2-mercaptoethyl pelargonate) sulfide. Prepared according to Example 45.

27 Prepared according to Example 44.

28 1/3 bis / monomethyltin bis (2-mercaptoethyl pelargonate) 7 sulfide and 2/3 bis 2Hmethyltin mono 2-mercaptoethyl pelargonate) 7 sulfide.

29 1/3 dimethyltin bis (2-mercaptoethyl pelargonate) and 2/3 bis / monomethyltin bis (2-mercaptoethyl pelargonate) 7 sulfides.

30 2/3 monomethyltin tris (2-mercaptoethyl pelargonate) and 1/3 bis / dimethyltin mono (2-mercaptoethyl pelargonate) 7 sulphides.

31 1/3 dimethyltin bis (2-mercaptoethyl pelargonate) and 2/3 monomethyltin tris (2-mercaptoethyl pelargonate).

Table VIII

Dynamic grinding stability Sample No. Tin content 193 ° C 30/40 rpm

Example * _ (mg) _ α 2 3 putts 6? 8 g 1Q

25 31.7 10+ 10 9+ 9 8 7 6 5 4 2 32 30.2 10+ 10+ 10 9 6 3 2 1 0 0 33 29.9 10+ 10 9+ 8+ 7 6 4 3 2 1 37 34.1 10 9 8+ 8 7 6 5 4 2 1 38 32.5 98 6+ 543210 0 42 28.1 10 9 7+ 654 321 0 Color scale 10 (white) - 5 (brown-orange) - 0 (burnt) Composition

Geon 103 EP 100 parts OMYA 90T 1.0 parts

TiO2 1.0 parts

Ca stearate? »* J 03aa 165 Wax l> ° parts AC62QA 0.1 parts

Stabilizer such as *

The numbers in this column refer to the stabilizer prepared in these examples.

6 3 94 4 20

The following examples describe the preparation of monoalkyltin tris- (mercaptoalkanyl) alkanoates and dialkyltin bis (mercaptoalkanyl) alkanoates and the like (Examples 1-10), and although not within the scope of the invention, may be used in admixture with the compounds of the invention. The mono- and polysulfides of the invention can also be formed by reacting ammonium and / or alkali metal mono- or polysulfide with such mono- and dialkyltin mercaptoalkanyl alkanoate.

Example 1 To a 2 liter flask are added 204 g (1.0 mole) of 2-mercaptoethyl caprylate, 200 ml of water, 84 g (1.0 mole) of sodium bicarbonate and 300 ml of heptane. 110 g (0.5 mol) of dimethyltin dichloride dissolved in 200 ml of water are added dropwise to the above mixture at a temperature of 30-40 ° C. It is then stirred for 1 hour at 30-40 ° C and the layers are allowed to separate. The organic layer is washed with 200 ml of water and then evaporated in vacuo at a temperature in the region of 100 ° C. 273 g of dimethyltin-bi's (2-mercaptoethyl caprylate) are obtained, njp 1.5060.

Example 2 306 g (1.5 moles) of 2-mercaptoethyl caprylate, 200 ml of water, 126 g (1.5 moles) of sodium bicarbonate and 300 ml of heptane are introduced into a 2-liter flask. To the above stirred mixture is added at 40 ° C 120 g (0.5 mol) of monomethyltin trichloride dissolved in 150 ml of water. After the addition is complete, stir for 1 hour at 30-40 ° C. The layers are separated and the organic phase is washed with 200 ml of water. The heptane is then separated in vacuo. 363 g of monomethyltin tris (2-mercaptoethyl caprylate) are obtained in the form of a clear, colorless liquid, m.p. 1.5041.

Example 3 516 g (1.5 moles) of 2-mercaptoethyl stearate, 200 ml of water, 126 g of sodium bicarbonate and 500 ml of heptane are introduced into a 2-liter flask. 120 g (0.5 moles) of monomethyltin trichloride dissolved in 150 ml of water are added to the above stirred mixture at 40-50 ° C. After the addition is complete, stir for 1 hour at 40-50 ° C and then allow the layers to separate. The organic phase is washed with .200 ml of water and then evaporated in vacuo at a temperature in the region of 100 ° C. This gives, in a yield of 560 g, monomethyltin tris (2-mercaptoethyl stearate) as a white solid, m.p. 44-47 ° C.

li 21 6 3 9 4 4

Example 4 A 2-liter flask is charged with 430 δ (1.25 moles) of 2-mercaptoethyl stearate, 200 ml of water, 69 g (0.65 moles) of sodium carbonate and 300 ml of heptane. To the above-mentioned stirred mixture are added at a temperature of 30 to 40 ° C 55 g (0.25 mol) of dimethyltin dichloride and 60 g (0.25 mol) of non-ethyltin trichloride dissolved in 150 ml of water. After the addition is complete, stir for 1 hour at the reaction temperature and allow the precipitate to separate. The organic phase is washed with 200 ml of water and then evaporated in vacuo at a temperature in the region of 100 [deg.] C. to give 493 g of a colorless oil. The product is a mixture containing ronomethyl-dimethyltin-tris, bis (2-mercaptoethyl stearate). Sp. 36-40 ° C.

Example 5 182 g (1.5 moles) of * 2-mercaptoethyl acetate, 200 ml of water, 300 ml of heptane and 120 g of 0.5 (0.5 moles) of monomethyltin trichloride are introduced into a 2-liter flask. 126 g (1.5 moles) of sodium bicarbonate are added portionwise to the above stirred mixture, keeping the temperature of the vessel at 25-40 ° C by adjusting the addition rate. When the addition is complete, stir for 1 hour at 25-40 ° C. The layers are separated and the organic phase is washed with 200 ml of water. The heptane is removed in vacuo. 240 g of monomethyltin tris (2-mercaptoethyl acetate) are obtained in the form of a colorless oil, mp 1.5575-

Example 6 A 2 liter flask is charged with 513 g (1.5 moles) of 2-mercaptoethyl oleate, 200 ml of water, 126 g of sodium bicarbonate and 500 ml of heptane. 120 g (0.5 mol) of monomethyltin trichloride dissolved in 150 ml of water are added to the above stirred mixture at 25-35 ° C. After the addition is complete, stir for 1 hour at 25-35 ° C and then allow the layers to separate. The organic layer is washed with 200 ml of water and then evaporated in vacuo at 100 ° C. Morphomethyltin tris (2-mercaptoethyl oleate) is obtained in 98.5% yield as a pale yellow oil, n = 1.5008.

Example 7

The procedure of Example 2 is repeated using 142 g (0.50 moles) of monobutyltin trichloride instead of monomethyltin trichloride. The yield is 383 g of a colorless oil formed by monobutyltin tris (2-mercaptoethyl caprylate). nj * 5 1.5061.

_ 1

Example 6 22 3 O 4 4

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

n £ 5 1,5001.

%

Example 9 20 g (1.0 mol) of 2-mercaptoethyl caprylate, 200 ml of water, 300 ml of heptane and 120 g (0.5 mol) of monomethyltin trichloride were charged to a 2-liter flask. To the above stirred mixture was added 80 g (1.0 mol) of 50 5N aqueous NaOH at 25-35 ° C. The mixture was then stirred for 1 hour under these conditions until the layers separated and the organic phase was evaporated under reduced pressure to give 273 g of a pale yellow oil. The product consisted mainly of monomethyl monochlorotin-bis (2-mercaptoethyl, icaprylate). Πρ5 1.52 * »1ΐ.

Example 10 286 g (1.5 moles) of monothioglycerol diacetate ester, 200 ml of water, 126 g of sodium bicarbonate and 500 ml of heptane were charged to a 2 liter flask. To the above stirred mixture was added 120 g (0.5 moles) of monomethyltin trichloride dissolved in 150 ml of water at a temperature of 0 ° C to 50 ° C. After the addition was complete, the mixture was stirred for 1 hour at * 10 ° C and the layers were allowed to separate. The organic phase was washed with 200 ml of water and then evaporated in vacuo at a temperature of about 100 ° C. The yield was 328 g and consisted mainly of monomethyltin tris (monothioglycerol diacetate) as a thick oil. n ^ 5 1.5310.

Example 11 A 2 liter flask was charged with 120 g (0.5 moles) of monomethyltin trichloride dissolved in 200 ml of water. The mixture was warmed to 30 ° C and 2 g (1.0 mole) of 2-mercaptoethyl caprylate was added. 80 g (1.0 mol) of 50 ml of aqueous sodium hydroxide solution were then added dropwise at 30 DEG C. The mixture was stirred for one hour. After the addition was complete, a solution was formed by heating 32.5 g (0.25 moles) of a 60 * aqueous solution of Na 2 S and 8.0 g '(0.25 moles) of sulfur in 100 ml of water was added dropwise at 25-35 ° C. After stirring for 1 hour at 35 ° C, the product layer was separated and washed with 200 ml of water. The product was then evaporated at 100 ° C in vacuo to give 23,63944 light yellow oil in 100 h yield. The product consisted mainly of bisimethyl (> 25 tin di-2-mercaptoethyl caprylate) disulfide. 1.5279.

Example 12

The procedure of Example 11 was repeated using 32.5 g (0.25 moles) of a 60% aqueous solution of sodium sulfide instead of 0.25 niol of sodium disulfide to form the corresponding monosulfide.

2 * 5

The yield was 277 g of a pale yellow oil. nD 1.5269.

Example 13

The procedure of Example 11 was repeated using 96 g (0.1 mol) of methyltin trichloride and 33 g (0.15 mol) of dimethyltin dichloride instead of 0.5 mol of methyltin trichloride. The yield was 285 g of a pale yellow oil and consisted mainly of N-monomethyltin di (2-mercaptoethyl caprylate) 7 / dimethyltin mono- (2- to 25-mercaptoethyl caprylate) disulfide. n ^ 1.5258.

Example 1 To 120 g (0.50 moles) of monomethyltin trichloride in 200 ml of water heated to 30 ° C was added 20 g (1.00 moles) of 2-mercaptoethyl caprylate, followed slowly by 31 g (0 , 50 moles) of 28 l of ammonium hydroxide. The mixture was stirred for 1 hour. Then, 125 g (0.25 moles) of a 20 L aqueous solution of ammonium disulfide was added over 30 minutes at 25-35 ° C. The mixture was heated to 50 ° C and the lower product layer was separated from the aqueous phase. The product was washed with 200 ml of water and dried at 100 ° C under 2 mm Hg. A pale yellow oil was obtained in quantitative yield. The product was mainly bis / inonomethyltin-bis (2-mercaptoethyl caprylate27 disulfide. 1.5288.

Example 15 A 2 liter flask was charged with 32.5 g (0.25 moles) of 60 5% aqueous sodium sulfide and 8.0 g (0.25 moles) of sulfur dissolved in 100 mL of water, 300 mL of heptane, 150 mL water, 218 g (1.0 mol) of 2-mercaptic ethyl pelargonate and 6 g (1.0 mol) of 28 * aqueous ammonium hydroxide solution. A mixture of 96 g (0.1 mol) of methyltin trichloride and 33 g (0.15 mol) of dimethyltin dichloride dissolved in 150 ml of water was then added. The mixture was then heated to 50 ° C for 30 minutes, the layers separated and the product layer washed and dried at 100 ° C under vacuum. The product (99%) consisted mainly of bis / methyl / dimethyltin-methyl / di (2-mercapto-2S ethyl ethyl argonate) / disulphide. n ^ 1.5 * 2 ^ 5- 63944 __ - 1 2k

Example 16

The procedure of Example 15 was repeated using 32.5 g (0.25 moles) of 60 # aqueous sodium sulfide instead of sodium disulfide to form the corresponding monosulfide. Yield 296 g of a pale yellow oil. n ^ 5 1.5222.

Example 17 A 2 liter flask was charged with 120 g (0.5 moles) of methyltin trichloride dissolved in 200 ml of water. The mixture was heated to 30 ° C and 16 g (0.75 moles) of 2-mercaptoethyl pelargonate was added. 60 g (0.75 mol) of a 50% aqueous sodium hydroxide solution were then added dropwise at 30 [deg.] C. The mixture was stirred for 1 hour. After this addition, a solution was formed by heating 32.5 g (0.25 moles) of 60 5 N aqueous solution of Nap. 100 ml of water were then added portionwise at 25-35 ° C, stirred for 1 hour after the addition was complete, the layers were separated and the product layer was washed with 200 ml of water. The organic layer was evaporated at 100 ° C in vacuo to give 240 g of a pale yellow oil containing (monomethyl monochlorotin-2-mercaptoethyl pelargonate) / monomethyltin bis (2-mercaptoethyl pelargonate) 7 sulfide. nD 1.5293.

Example 18 120 g (0.5 moles) of methyltin trichloride in 200 ml of water were introduced into a 2 liter flask. The mixture was warmed to 30 ° C and 153 g (0.75 moles) of 2-mercaptoethyl caprylate and 50.5 g (0.25 moles) of lauryl mercaptan were added. Then, 6 g (1.0 mol) of an aqueous solution of ammonium hydroxide was added dropwise at 30 DEG-0 DEG C. The mixture was stirred for 1 hour. At the end of this time, a solution of 32.5 g (0.25 moles) of a 60% aqueous solution of sodium sulfide in 100 ml of water was added dropwise at 35 ° C. After stirring for 1 hour after the addition was complete, the layers were separated and the organic layer was washed with 200 ml of water. The organic phase was evaporated at 100 ° C in vacuo to give 269 g of a yellow oil, containing mainly N-mononethyltin bis (2-niercaptoethyl caprylate) 7-monomethyltin mono (2-mercaptecetylcapyridyl) sulphurolate . 1.5267.

Example 19

The procedure of Example 18 was repeated using 51 g (0.25 moles of isooctyl thioglycolate instead of lauryl mercaptide) to give 272 g of a pale yellow oil, / monomethyltin bis (2-mercaptoethyl caprylate) 7 / monomethyltin mono (2-mercaptoethyl) caprylate octyl thioglycolate7 sulfide 1.5278.

Example 20

The treatment of Example 18 was repeated using 54.5 g (0.25 moles) of isooctyl mercaptopropionate and 0.25 moles of sodium disulfide instead of lauryl mercaptan and sodium sulfide, respectively. The yellow oil, consisting mainly of monomethyltin bis (2-mercaptoethyl caprylate27 / monomethyltin mono (2-mercaptoethyl caprylate) monoisooctyl mercaptopropionate) disulfide, weighed 274 g-n 1.55266.

Example 21

The procedure of Example 18 was repeated using 36 g (0.25 moles) of 2-ethylhexanoic acid instead of lauryl mercaptan. The yield was 251 g of a yellow oil containing Ancnomethyltin bis (2-mercaptoethyl caprylate) -N-ionionyltin mono (2-mercaptoethyl caprylate) -mono (2-ethylhexoate ^ / sulfide. N. 1.5214.

Example 22

The treatment of Example 15 was repeated using 253 g (0.75 moles) of 2-mercaptoethyl stearate and 57 g (0.25 moles) of isooctyl maleate instead of 2-mercaptoethyl pelargonate (1.0 mole). A low melting white solid (370 g) was obtained at 33-43 ° C and consisted predominantly of monomethyltin bis (2-mercaphthyl ethyl stearate) / anonomethyltin mono (2-mercaptoethyl stearate) -minoisooctyl maleate disulfide. n ^ p 1.5193.

* 3944 26

Example 23 A 2 liter flask was charged with 120 g (0.5 moles) of monomethyltin trichloride dissolved in 200 ml of water. The mixture was warmed to 30 ° C and 80 g (1.0 mol) of a 50% aqueous solution of sodium hydroxide was added dropwise at 30-40 ° C. The mixture was stirred for 1 hour. After this addition, a solution of 32.5 g (0.25 mol) of a 60% aqueous solution of sodium sulfide in 100 ml of water was added dropwise at 25-35 ° C. After stirring for 1 hour at 35 ° C, the product layer was separated and washed with 200 ml of water. The product was then evaporated at 100 ° C in vacuo to give a yellow oil in $ 100 yield. The product consisted mainly of bisZmethyltin di (2-25 mercaptoethyl talalate) sulfide. ηβ 1.5168.

Example 24 A 2 liter flask was charged with 120 g (0.5 moles) of monomethyltin trichloride dissolved in 200 ml of water. The mixture was warmed to 30 ° C and added to 197 g (1.0 mol) of 2-mercaptoethylphenyl acetate. 80 g (1.0 mol) of a 50% aqueous sodium hydroxide solution were then added dropwise at 30-40 ° C. The mixture was stirred for 1 hour. After this reaction time, a solution of 32.5 g (0.25 mol) of 60 5S sodium sulfide dissolved in 100 ml of water was added dropwise at 30-35 ° C. After stirring for 1 hour, the product layer was separated and washed with 200 ml of water. The product was then evaporated in vacuo to give a yellow oil of 270 g of bis-monomomethyltin-bis (2-mercaptoethylphenyl acetate) 7 sulfide. n ^ 5 1.6122.

Example 25 28 g (1.0 mol) of monobutyltin trichloride dissolved in 400 ml of water were introduced into a 2 liter flask. The mixture was warmed to 30 ° C and then 436 g (2.0 moles) of 2-mercaptoethyl pelargonate was added. 169 g (2.0 moles) of 50% aqueous sodium hydroxide solution were then added dropwise at 30-35 ° C. The mixture was stirred for 1 hour. After this reaction time, 65 g (0.5 mol) of sodium sulfide (60%) dissolved in 100 ml of water were added dropwise at 40 ° C. After stirring for 1 hour at this temperature, the product layer was separated and washed with 400 ml of water. The product was then evaporated in vacuo at 100 ° C to give 617 g of a pale yellow oil, bis / monobutyltin. # p 5 'bis (2-mercar * ethyl ethyl argonate)' su 'fidia. n 1.5219 · 27,63944

Example 26 A 2 liter flask was charged with 28 g (1.0 mole) of butyltin trichloride dissolved in 400 ml of water. It was then warmed to 30 ° C and 101.5 g (0.5 moles) of isooctylthioglycolate and 327 g (1.5 moles) of 2-mercaptoethyl pelargonate were added.

122 g (2.0 moles) of ammonium hydroxide (28%) were then added dropwise at 35-40 ° C. The mixture was stirred for 1 hour at 35-40 ° C. After this reaction time, 64 g (0.50 mol) of ammonium sulfide (40%) were added and stirred for 1 hour before separating the layers. The product layer was washed with 400 ml of water and dried in vacuo at 100 ° C. 596 g of a yellow oil / monobutyltin bis (2-mercaptoethyl pelargonate) 7 Zmono-butyltin (isooctyl thioglycolate) (2-mercaptoethyl pelargonate) 7 sulfide were obtained. njip 1.5211.

Example 27 28 g (1.0 mol) of butyltin trichloride dissolved in 400 ml of water were introduced into a 2 liter flask. It was then warmed to 30 ° C and 305 g (1.5 moles) of 2-mercaptoethyl caprylate was added. Then 120 g (1.5 moles) of 50% were added dropwise at 30-40 ° C. aqueous sodium hydroxide solution and stirred for 1 hour at this temperature. After this reaction time, 65.0 g (0.50 moles) of 60 N Na 2 S dissolved in 100 ml of water were added and stirred for 1 hour at 30-40 ° C. The layers were separated and the product layer was washed with 400 ml of water and thus evaporated in vacuo at 100 ° C. The product / monobutyl monochlorotin (2-mercaptoethyl caprylate) 7 / monobutyltin bis (2-mercaptoethyl caprylate) 7 sulfide was obtained in 93% yield as a yellow oil, n ^ 1.5276.

Example 28 240 g (1.0 mol) of monomethyltin trichloride dissolved in 400 ml of water were introduced into a 2 liter flask. The mixture was warmed to 30 ° C and 218 g (1.0 mol) of 2-mercaptoethyl pelargonate and 109 g (0.5 mol) of isooctyl mercaptopropionate were added. Then, 120 g (1.5 moles) of a 50% aqueous solution of sodium hydroxide was added dropwise and stirred for 1 hour at 25-30 ° C. After this reaction time, 65.0 g (0.50 mol) of a 60 μl solution of sodium sulfide in 100 ml of water were added and stirred for 1 hour at 30-40 ° C. The layers were separated, the organic layer was washed with 400 ml of water and evaporated in vacuo at 100 ° C. The product, 474 g of a pale yellow oil, consists essentially of a mixture of (methyltin-bis (2-mercaptoethyl-pelargonate)) / monomethyl monochlorite (isooctyl mercaptopropropionate) 7 sulfide and / ) J Monomethyl monochlorotinate (2-mercaptoethyl pelargonate) 7 sulphide.

_ - 1 έ8 pc 63944 1.5288.

Example 29.

240 g (1.0 mol) of monomethyltin trichloride dissolved in 400 g of water were placed in a 2 liter flask. The mixture was warmed to 30 ° C and 218 g (1.0 mol) of 2-mercaptoethyl pelargonate was added. Then, 80 g (1.0 mole) of an aqueous solution of sodium hydroxide 50 was added dropwise, and the mixture was stirred for 1 hour at 25 to 35 ° C. After this reaction time, 65 g (0.50 moles) of 60 μl of sodium sulfide dissolved in 150 water and stirred for 1 hour at 35 [deg.] C. The layers were separated, the organic phase was washed with 400 ml of water and evaporated in vacuo at 10 [deg.] C. The product, bis / monomethyltin (2-mercaptoethyl pelargonate) 27-bisulphide, was obtained in 96.5% yield as a pale yellow oil. ^ 1.5630.

Example 30 240 g (1.0 mol) of monomethyltin trichloride dissolved in 400 g of water were introduced into a 2 liter flask. The mixture was warmed to 35 ° C and 660 g (2.0 moles) of 2-mercaptoethyl oleate was added. 160 g (2.0 moles) of a 50 £ aqueous solution of sodium hydroxide were then added dropwise at 35 ° C. The mixture was stirred for 1 hour. After this reaction time, a solution of 65 g (0.5 moles) of 60% sodium sulfide dissolved in 150 g of water was added dropwise at 30-35 ° C. After stirring for 1 hour, the product layer was separated and washed with 400 ml of water, then evaporated at 100 ° C in vacuo to give 788 g of a light brown oil. The product consisted mainly of bis / monomethyltin bis (2-mercaptoethyl oleate) Jfilfide. n ^ 1.5118.

Example 31

120 g (0.5 moles) of methyltin trichloride in 150 ml of water, 109 g (0.5 moles) of 2-mercaptoethyl pergonate and 200 ml of toluene were placed in a three-necked flask. The mixture was heated to 30 ° C and 40 g (0.5 moles) of a 50% aqueous solution of sodium hydroxide was added dropwise, kept at 30 ° C, and then 43 g (0.33 moles) of 60 55 dissolved in 75 ml were added portionwise. no water. It was then stirred at 30-40 ° C for 1 hour after the addition was complete. The layers were separated and the organic phase was evaporated at 100 ° C in vacuo to give 190 g of a colorless oil, n = 1.5336. The structure of the product was assumed to be as follows: 29 ch, ch, ch, 6 3 9 4 4 1 ·> I> \ j CISn - S - Sn -S - SnCl 0 0 0 Π Μ r 11 SCH2CH2OCCgH17. SCH2CH2CO2H17 SCH2CH2OCCl217 To 118 g (0.1 mol) of the above product were added 200 ml of water and 43.5 g (0.2 mol) of 2-mercaptoethyl pelargonate. 16 g (0.2 mol) of a 50 l aqueous solution of sodium hydroxide were then added dropwise at 25 ° C. After stirring for 1 hour at 25-30 ° C, the layers were separated. The organic layer was washed with 100 ml of water and evaporated at 100 ° C in vacuo. The resulting product, consisting of 142 g of a colorless oil, had a refractive index of 1.5286. The structure is assumed to be as follows: CH, CH, CH, »3 i 3 t 3

Sn - S - Sn - S -Sn 0 0 0 n n n (H17CgCOCH2CH2S) 2 SCH2CH2OCCgH17 (SCH2CH2OCCgH17) 2

Example 32

150.5 g (0.5 mol) of phenyltin trichloride, 300 ml of water, 400 ml of benzene and 218 g (1.0 mol) of 2-mercapto ethyl pelargonate were introduced into a three-necked flask. To the stirred mixture was then added dropwise at 40 ° C 80 g (1.0 mol) of a 50 μl aqueous solution of sodium hydroxide. After stirring for 1 hour at 40 ° C, 32.5 g (0.25 moles) of 60 3> sodium sulfide dissolved in 75 ml of water were added dropwise. After stirring for 1 hour at 40 ° C, the layers were separated and the organic phase was dried and evaporated in vacuo at 100 ° C. The product obtained, bis / inonophenyl bis (2-mercaptoethyl pelargonate VT sulfide), formed 312 g of a pale yellow oil, n ^ 1.5517.

Example 33 A 2 liter flask was charged with 120 g (0.5 moles) of monomethyltin trichloride dissolved in 200 ml of water. The mixture was warmed to 30 ° C and 218 g (1.0 mol) of 2-mercaptoethyl pelargonate was added. Then, 80 g (1.0 mol - -130 6394 4 l) of a 50 μl aqueous solution of sodium hydroxide was added dropwise at 30 to 40 ° C. The mixture was stirred for 1 hour. After this addition, a solution was formed by heating 32.5 g (0.25 moles) of 60> E sodium sulfide and 16 g (0.5 moles) of sulfur in 150 mL of water and added portionwise at 30-40 ° C. Stirring was continued for 1 hour after the addition was complete, the layers were separated and the product layer was washed with 200 ml of water.

The organic phase was evaporated at 100 ° C in vacuo to give 296 g of a pale yellow oil of bis / monomethyl-tin-bis (2-mercaptoethyl pelargonate p / trisulfide. ND 1.5290. Example 3 * 1

169 g (0.5 mol) of monooctyltin trichloride, 300 ml of water, * 100 ml of benzene and 204 g (1.0 mol) of 2-mercaptoethyl caprylate were introduced into a three-necked flask. The mixture was heated to 30-40 ° C and then 80 g (1.0 mol) of a 50 μl aqueous solution of sodium hydroxide was added dropwise. After stirring for 1 hour under these conditions, a solution of 32.5 g (0.25 mol) of a 60% aqueous solution of NagSt dissolved in 100 ml of water was added dropwise.

After stirring for one hour, the layers were separated, the layers were separated and the organic phase was evaporated at 100 ° C in vacuo. 320 g of a pale yellow oil were obtained, bis / monooctyltin-pc bis (2-mercaptoethyl caprylate2 / sulfide).

Example 35

79 * 5 g (0.33 moles) of monomethyltin trichloride, 147.5 g (0.67 moles) of dimethyltin dichloride dissolved in 250 ml of water and 454 g (1.33 moles) of 2-mercaptoethyl oleate were introduced into a three-necked flask.

The mixture was warmed to 30 ° C and 106 g (1.33 moles) of a 50% aqueous solution of sodium hydroxide was added dropwise over 1 hour at 30 ° C. It was then stirred for another hour at this temperature. 65 g (0.5 mol) of 60 [mu] M sodium sulphide dissolved in 100 ml of water were then added dropwise and the mixture was stirred for a further hour after the addition was complete. The layers were separated and the organic layer was washed with 200 ml of water and evaporated at 100 ° C in vacuo. The product obtained, 577 g, was a yellow oil, presumably a mixture of bis / monomethyltin bis (2-mercaptoethyl oleate) sulfide, bis / dimethyl mono (2-nercaptoethyl oleate) sulfide and monomethyltin ethyl 2 bis ) / '- - 25 / dime styles ma-mono (2-mercaptoethyl cleate) _ / sulfide 1.5070.

63944 31

Example 36

120 g (0.5 moles) of monomethyltin trichloride dissolved in 200 ml of water were introduced into a three-necked flask. The mixture was warmed to 30 ° C and 218 g (1.0 mol) of 1-methyl-2-mercaphthyl ethyl caprylate was added. 80 g of a 50% aqueous solution of sodium hydroxide at 30 DEG-0 DEG C. were then added dropwise and stirred for 1 hour after the addition was complete. 32.5 g (0.25 mol) of a 60% aqueous solution of sodium sulphide in 100 ml of water at 25 DEG-35 DEG C. were then added dropwise, the mixture was stirred for 1 hour and the layers were separated. The organic layer was washed with 200 ml of water and evaporated under reduced pressure. 283 g of an almost colorless oil, n = 1.5256, were obtained, the product consisting mainly of bis / monomethyltin bis (1-methyl-2-mercaptoethyl caprylate) 7 sulfide.

Example 37

120 g (0.5 moles) of methyltin trichloride dissolved in 200 ml of water, 121 g (1.0 moles) of 2-mercaptoethyl acetate were introduced into a three-necked flask, followed by the slow addition of 31 g (0.50 moles) of a 28% solution of ammonium hydroxide. . The mixture was stirred for 1 hour at a reaction temperature of 30-35 ° C. 125 g (0.25 moles) of a 20% aqueous solution of ammonium disulfide were then added over 60 minutes at 25-35 ° C. The mixture was heated to 50 ° C and the lower product layer was separated from the aqueous phase. The product was washed with 200 ml of water and dried at 100 ° C under reduced pressure. A pale yellow oil was obtained in 96% yield with a refractive index of 25697 at 25 ° C. The product was mainly bis / monomethyltin bis (2-mercaptoethyl acetate) 7 disulfide.

Example 38

120 g (0.5 mol) of methyltin trichloride dissolved in 200 ml of water were introduced into a three-necked flask. The mixture was warmed to 30 ° C and 260 g (1.0 mol) of 6-mercaptohexyl caprylate was added. 80 g (1.0 mol) of a 50% aqueous solution of NaOH were then added dropwise at 30 DEG-0 DEG C. The mixture was stirred for 1 hour. After this addition, a solution of 32.5 g (0.25 mol) of a 60% aqueous solution of sodium sulfide in 100 ml of water was added dropwise at 25-35 ° C. After __-ι 32 63944 was stirred for 1 hour at 35 ° C, the product layer was separated and washed with 200 ml of water. The product was then evaporated at 100 ° C in vacuo to give a pale yellow oil in 99% yield, n-1.5345- This oil was assumed to be bis / methyltin-bis (6-mercaptohexyl caprylate) .7 sulfide.

Example 39 To a 2 liter flask was charged 120 g (0.5 moles) of methyltin trichloride in 200 ml of water. The mixture was warmed to 30 ° C and 153 g (0.75 moles) of 2-mercaptoethyl caprylate and 19.5 g (0.25 moles) of mercaptoethanol and 400 ml of toluene were added. 84 g (1.0 mol) of sodium bicarbonate dissolved in 250 ml of water were then added dropwise at 30-40 ° C. The mixture was stirred for 2 hours. A solution of 32.5 g (0.25 mol) of a 60% aqueous solution of sodium sulfide in 100 ml of water was then added dropwise at 35 ° C. After stirring for 2 hours after the addition was complete, the layers were separated and the organic layer was evaporated at 90 ° C in vacuo to give 204 g of a pale yellow oil, n = 1.5292. The product was assumed to be predominantly / monomethyltin (2-mercaptoethyl caprylate) (2-mercaptoethanol) -7 / monomethyltin bis (2-mercaptoethyl caprylate) 7 sulfide.

Example 40

360 g (1.5 moles) of monomethyltin sodium chloride dissolved in 500 ml of water were placed in a three-necked flask. The mixture was warmed to 30 ° C and 817 g (4.0 moles) of 2-mercaptoethyl caprylate was added. 320 g (4.0 moles) of a 50% aqueous solution of sodium hydroxide at 30-40 ° C were then added dropwise. The mixture was stirred for 1 hour. After this addition, a solution of 32.5 g (0.25 mol) of 60% sodium sulfide dissolved in 100 ml of water was added dropwise at 30-40 ° C. After stirring for 1 hour at this temperature, the product layer was separated and washed with 400 ml of water. The product was then evaporated at 100 ° C in vacuo to give 999 g of an almost colorless oil. nD 1.5113- 63944 33

Example 4l

180 g (0.75 mol) of monomethyltin trichloride dissolved in 300 ml of water heated to 30 [deg.] C. are added to a three-necked flask and 306.5 g (1.5 mol) of 2-mercaptoethyl caprylate are added. 120 g (1.5 moles) of a 50% aqueous solution of NaOH at 30-40 ° C are then added dropwise.

The mixture is stirred for 1 hour. After this addition, a solution of 16.3 g (0.125 mol) of 60% sodium sulfide dissolved in 75 ml of water is added dropwise at 30-40 ° C. After stirring for 1 hour at this temperature, the product layer is separated and washed with 250 ml of water. The product is then evaporated at 100 ° C in vacuo to give 430 g of a pale yellow oil. The reaction product has the following structures / C1

Me S-CH „CH„ OCOC „H, c Me-Sn \ / 2 2 7 15 \ \ / S xSCH2CH2OCOC7H15

Sn and Me-Sn-SCHoCHo0C0C7H.c I, 2 2 7 15

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

Example 42

120 g (0.5 moles) of methyltin trichloride dissolved in 200 ml of water are placed in a three-necked flask. The mixture is warmed to 30 ° C and 360 g (1.0 mol) of mono-thioglycerol dicaprylate ester are added. 80 g (1.0 mol) of a 50% aqueous solution of sodium hydroxide are then added dropwise at 30-40 ° C. The mixture is stirred for 1 hour. After this addition, a solution formed by heating 32.5 g (0.25 mol) of a 60% aqueous Na 2 S solution and 8.0 g (0.25 mol) of sulfur in 100 ml of water was added dropwise at 30-40 ° C. . After stirring for 1 hour at this temperature, the product layer was separated and washed with 200 ml of water. The product was then evaporated at 100 ° C in vacuo to give 325 g of a yellow oil. nD 1.5143. The product consisted mainly of bis / monomethyltin-bis (thioglycerol dicaprylate) sulfide.

63944 34

Example 43

A three-necked flask was charged with 110 g (0.5 moles) of dimethyltin dichloride dissolved in 200 mL of water. The mixture was warmed to 30 ° C and 109 g (0.5 moles) of 2-mercaptoethyl pelargonate was added. 40 g (0.5 mol) of a 50% aqueous solution of sodium hydroxide were then added dropwise at 30-40 ° C. The mixture was stirred for 1 hour. After this addition, a solution of 32.5 g (0.25 mol) of a 60% aqueous Na 2 Sm solution dissolved in 75 ml of water was added dropwise at 25-35 ° C. After stirring for 1 hour at 35 °, the product layer was separated and washed with 200 ml of water. The product was then evaporated at 100 ° C in vacuo to give a pale yellow solid in 95.5% yield.

p C

ta oil n ^ 1.5319. The product was mainly bis (dimethyltin monoZ2-mercaptoethyl pelargonate7) sulfide.

Example 44 A 2 liter flask was charged with 60 g (0.25 moles) of monomethyltin trichloride and 55 g (0.25 moles) of dimethyltin dichloride dissolved in 200 ml of water. The mixture was warmed to 30 ° C and 162 g (0.75 moles) of 2-mercaptoethyl pelargonate was added, followed by the slow addition of 60 g (0.75 moles) of 50% aqueous sodium hydroxide solution. The mixture was stirred for 1 hour. 32.5 g (0.25 mol) of a 60% aqueous solution of sodium sulphif dissolved in 75 ml of water were then added. After stirring for 1 hour at 35 ° C, the layers were separated, the organic phase was washed with 200 ml of water and dried in vacuo at 100 ° C. 229 g of pale 25. .

yellow oil, nQ 1.5296. The product consisted of a mixture of monomethyldimethyltin monono (di-2-mercaptoethyl pelargonate sulfide).

Example 45

BisZmonomethyltin bis- (2-mercaptoethyl pelargonate) J sulfide was mixed according to Example 43 with the product, bisZdimethyltin mono (2-mercaptoethyl pelargonate) 7 sulfide in a ratio of 2/1, n ^ 5 1.5301.

j

Claims (8)

1. Organotin mercaptoalkyl carboxylic acid ester sulfides useful as stabilizers for halogen-containing polymers, characterized in that they have the formula R, 9 in 1 in R 2 -Sn-S-R-OC-R. n _ £ I 1U 1 S 0 IX II R, -Sn-S-R-OC-R..n 3 | -LU wherein x is a tai 1-4, R 2, R p, R 2 and R 2 are alkyl or aryl groups of 1-8 carbon atoms, or R 2 and / or R 2 may also be R, n u ll | l -Sx-Sn-R31, -SR-OC-R10, -SRC-OR1q, -SR1 (), -SR-OR1q, Or R 2 are chloro, wherein R 2, R 2 and R 2 are 0 II alkyl or aryl groups of 1-8 carbon atoms or - SR-OC-R 10, 0 0 0 0 II II II II II SRC-OR 10, -SR 10, -SR-OR 10, -OC-R 10, -OC-RC-OR 10, or chlorine in which formulas R is alkylene or the hydroxyalkyl, which may be substituted with the group -OC-R ^ q, and R ^ q is hydrogen, a hydrocarbon group having 1-19 carbon atoms, the hydrocarbon group being alkyl, aryl, aralkyl, cycloalkyl, aralkenyl or alkenyl having 1-3 ethylene double bonds, hydroxyalkyl of 1-19 carbon atoms or hydroxyalkylene of 2-19 carbon atoms; with the exception of the compound thio-bis-Zmethyl-tin-bis- (2-thioethyl octanoate) J.