JPS647099B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel organic antimony-sulfur compound that can be used as a heat stabilizer for chlorine-containing thermoplastic resins, particularly polyvinyl chloride, and to a stabilizer for chlorine-containing thermoplastic resins comprising the compound. Thermal decomposition of chlorine-containing thermoplastics such as polyvinyl chloride (PVC) has become a very important industrial problem in the molding of this type of plastic. Rational processing is essentially only possible with the addition of stabilizers. Additives used for this purpose include, inter alia, metal carboxylates, organotin compounds and aminocrotonates. It happens that antimony mercaptide, for example the following formula: Sb
(SR) ₃ (wherein R represents an alkyl group, an aryl group, or an aralkyl group) (US Pat. No. 2,684,956) or the following formula: Sb(SR′COOR″) ₃ (formula Among them, R′ is an alkylene group,
represents an arylene group or an aralkylene group,
R″ represents a substituted or unsubstituted alkyl group, aryl group, or arylalkyl group (U.S. Pat.
2680726) has been proposed. A typical example of the latter type is “Irgastab”.
Sb(S
It is a compound represented by CH ₂ COO-i-C ₈ H ₁₇ ) ₃ . The disadvantage of this kind of antimony mercaptide is that
It has lower storage stability and light stability than organic tin compounds. There has therefore been commercial interest in antimony stabilizers with high storage stability and high stability against the action of light. The inventors have demonstrated that certain antimony carcaptides, in which the antimony atom is bonded to only one or two mercapto groups, exhibit increased storage stability and improved optical stability compared to known tris-mercaptides. It has been found that it has stability and is equivalent to or superior to known tris-mercaptide in its action as a polyvinyl chloride stabilizer. Furthermore, compared to these tris-mercaptides, the compounds of the invention are also characterized by the fact that when added to chlorine-containing polymers, they facilitate the thermoplastic processing of these polymers. The specific antimony mercaptide is a new compound. Therefore, the present invention provides the following formula, or:

【formula】 【formula】

【formula】

[Formula] (wherein, X is a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, -OR ¹ group, -OOCR ² groups,
-OOC-R ⁴ -COOR ³ groups, or -N (R ⁵ ) (R ⁶ )
represents a group or formed by two X groups together -O-R ⁹ -O- group or -OCO-R ⁹
-COO- group, Y is one of the groups defined as X or -
NHR ⁵ group, -NHNH ₂ group or -NHNH- phenyl group, Z represents one of the groups defined as X or SR group, R is hydroxyl group, -OCOR ⁷ group, -OR ⁸ group,
represents an alkyl group having 1 to 6 carbon atoms substituted with one or two of -SR ⁸ groups or -COOR ⁸ groups, R' represents -CH ₂ - or -CH ₂ CH ₂ -, and R ¹ is an alkyl group having 1 to 18 carbon atoms, -
represents an alkyl group having 1 to 6 carbon atoms substituted with OR ⁸ group, -SR ⁸ group or -OCOR ⁷ group,
or R ¹ is an aryl group having 6 to 10 carbon atoms;
represents a phenylalkyl group having 7 to 9 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, R ² is an alkyl group having 1 to 18 carbon atoms,
Alkenyl group having 2 to 18 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, 6 carbon atoms
represents a phenyl group or a phenyl alkyl group having 7 to 9 carbon atoms substituted with an aryl group having 1 to 10 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group and/or a halogen atom, and R ³ is a carbon represents an alkyl group, allyl group, cyclohexyl group, or phenyl group having 1 to 12 atoms; R ⁴ is an alkylene group having 2 to 12 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or an alkenylene group having 5 to 12 carbon atoms; represents a cycloalkylene or cycloalkenylene group, a phenylene group or a halophenylene group, and R ⁵ and R ⁶ may be the same or different and each represents an alkyl group having 1 to 12 carbon atoms, a benzyl group or a cyclohexyl group, or R ⁵ and R ⁶ represent a pyrrolidine, piperidine or morpholine group formed together with a nitrogen atom, R ⁷ is an alkyl group having 1 to 18 carbon atoms, a CH ₃ COCH ₂ - group,
cyclohexyl group, benzyl group, aryl group having 6 to 10 carbon atoms or 1 to 4 carbon atoms
represents a phenyl group substituted with an alkyl group, a hydroxyl group and/or a halogen atom, or a phenyl alkyl group having 7 to 9 carbon atoms, R ⁸ is an alkyl group having 1 to 18 carbon atoms,
allyl, cyclohexyl or phenyl, and R ⁹ represents C 2 -C 6 alkylene, C 3 -C 6 alkylene interrupted by O, S or (R ⁵ )N; or represents a propylene group interrupted by an --OR ⁸ group or --OCOR ⁷ group. ) and a stabilizer for chlorine-containing thermoplastic resins comprising the antimony-sulfur compound. The radical R represents a mono- or di-substituted alkyl group. In the case of di-substituted alkyl groups, the substituents may be the same or different. The alkyl group itself can be straight chain or branched. Examples of the group R include 2-hydroxyethyl group, 2-hydroxypropyl group, 2,3-dihydroxypropyl group, 2-hydroxybutyl group, 2-hydroxy-
3-butoxypropyl group, 2-octyloxyethyl group, 2-phenoxypropyl group, 2-acetoxybutyl group, 2-(dodecylmercapto)-ethyl group, 2-hydroxy-3-isopropoxypropyl group, 2- Hydroxy-3-caproyl-oxypropyl group, 2-lauroyloxyethyl group, 2,3-dibutyroylpropyl group, 2,3-
Bis-[4-hydroxy-3,5-di-tert-butylbenzoyloxy]-propyl group, 2,3-bis-[2-(4-hydroxy-3,5-di-tert-butyl phenyl)-propionyloxy ]-propyl group, 2-benzoyloxybutyl group, 2,3
-Bis-(acetoacetoxy)-propyl group or 2-acetoxy-3-phenoxypropyl group. R is preferably, for example, an octyloxycarbonylmethyl group, a dodecyloxycarbonylmethyl group, or 2-(decyclooxycarbonyl)
-Ethyl group, 2-(butyloxycarbonyl)-
Propyl group, 1,3-bis-(octadecyloxycarbonyl)-2-propyl group or 2,3-
Bis-(2-ethylhexyloxycarbonyl)
-Represents a lower alkyl group substituted by one or two of the COOR ⁸ groups, such as a propyl group. Particularly preferably, R is of the formula: -CH ₂ COOR ⁸
(In the formula, R ⁸ represents an alkyl group having 8 to 14 carbon atoms.) When R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ or R ⁸ represent an alkyl group, they represent straight-chain or branched alkyl groups such as methyl, ethyl, isopropyl, It can be a tertiary butyl group, a secondary amyl group, an n-hexyl group, a 2-ethylhexyl group, an n-decyl group or an n-dodecyl group. R ¹ , R ² , R ⁷ and R ⁸ as alkyl groups can further be long-chain alkyl groups such as tetradecyl, hexadecyl or octadecyl and have 8 carbon atoms.
to 14 alkyl groups are preferred. R ¹ as an alkyl group substituted with -OR ⁸ , -SR ⁸ or -OCOR ⁷ is, for example, 2-butoxyethyl group, 3-octyloxypropyl group, 2-iso-proboxypropyl group, 2-(dodecylmercapto )-ethyl group, 2-(tert-butylmercapto)-propyl group, 2-acetoxyethyl group, 2
- can be a lauroyloxypropyl group or a 3-stearoyloxyethyl group. R ¹ or R ² as a cycloalkyl group can be, for example, a cyclopentyl group, a cyclohexyl group or a cyclooctyl group. ^R2 as an alkenyl group is, for example, a vinyl group, a propenyl group,
It can be a pentadienyl, hexenyl, decenyl or heptadecenyl group. R ¹ , R ² or R ⁷ as an aryl group can be a phenyl group or a naphthyl group: R ² and R ⁷
Also, for example, 4-tolyl group, 2-tolyl group, 4-
tert-butylphenyl group, 3-chlorophenyl group,
2,4-dichlorophenyl group, 4-ethyl-2-
Chlorophenyl group, 3-hydroxyphenyl group,
4-chloro-2-hydroxyphenyl group, 2-methyl-4-hydroxyphenyl group or 3,5-
It can be a phenyl group substituted by a lower alkyl group, a hydroxyl group and/or a halogen atom, such as a di-tert-butyl-4-hydroxyphenyl group. R ¹ as phenylalkyl can be, for example, benzyl, 2-phenylethyl, 1-phenylethyl or 2-phenylpropyl. R ² and R ⁷ as lower alkyl groups, hydroxyl groups and/or phenylalkyl groups substituted with halogen atoms are, for example, 4-butylbenzyl group, 3-chlorobenzyl group, 2-methyl-4-
Hydroxybenzyl group or 2-(3,5-di-
It can be a tert-butyl-4-hydroxyphenyl)-ethyl group. R ⁴ represents a divalent carboxylic acid group, such as 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, 1,2-octylene group, 1 , 2-vinylene group, 1-propene-2,3-diyl group, cyclopentane-1,2-diyl group, cyclohexane-
1,2-diyl group, cyclooctane-1,2-diyl group, 1-cyclohexane-4,5-diyl group, 2-norbornene-5,6-diyl group, 1,
It can be a 2-phenylene group or a 4-chloro-1,2-phenylene group. R ⁹ represents a divalent group of diol or dicarboxylic acid, and for example a 1,2-ethylene group,
1,2-propylene group, 1,3-propylene group,
1,2-butylene group, 1,4-butylene group, 2,
2-dimethyl-1,3-propylene group, 3-oxa-1,3-propylene group, 3-oxa-1,5
-pentylene group, 3-methyl-aza-1,5-pentylene group, 3-phenylaza-1,5-pentylene group, 3-octyloxy-1,2-propylene group, 3-dodecyl-oxy-1,2- propylene group, 2-stearoyloxy-1,3-propylene group, 3-phenyloxy-1,2-propylene group, 3-lauroyloxy-1,2-propylene group, 3-stearyloxy-1,2-propylene group, 3-acetoacetyloxy-1,2-propylene group or 2-stearoyloxy-1,3
-Can be a propylene group. Preferred are compounds represented by the formula or formula in which X, Y or Z represents a chlorine atom. X or Y is -OR ¹ group, -OOC-R ⁴ -COOR ³ group or -
Also preferred are compounds of the formula or which represent one of the ^two OOCR groups. Examples of the compound represented by the formula include compounds represented by the following formula. Cl ₂ Sb―SCH ₂ COO―iso―C ₈ H ₁₇ Cl ₂ Sb―SCH ₂ CH ₂ COOC ₄ H ₉ Cl 2 Sb―SCH ₂ CH ₂ OH Cl ₂ Sb― _{SCH 2 CH 2} OOC―C ₁₁ H ₂₃ Cl ₂ Sb―SCH ₂ CH(OH)CH ₂ OOC―C ₁₇ H ₃₅ (HO) ₂ Sb―SCH ₂ CH ₂ OC ₆ H ₅ (C ₄ H ₉ O) ₂ Sb―SCH ₂ COOC ₁₂ H ₂₅ (C ₁₂ H ₂₅ O) ₂ Sb―SCH ₂ CH ₂ COOC ₁₂ H ₂₅ (C ₄ H ₉ OCH ₂ CH ₂ O) ₂ Sb―SCH ₂ CH ₂ OOC―
C ₁₁ H ₂₃ (C ₁₂ H ₂₅ SCH ₂ COO) ₂ Sb―SCH ₂ COOCH ₃ (C ₈ H ₁₇ CH＝CHC ₇ H ₁₄ COO) ₂ Sb―S―CH ₂ ―
CH ₍ OH) _―CH2 ― _SC4H9 Examples of compounds represented by the formula include the following compounds: BrSb(SCH ₂ CH ₂ OC ₈ H ₁₇ ) ₂ ClSb(SCH ₂ COOC ₁₂ H ₂₅ ) ₂ ClSb(SCH ₂ CH(OH)CH ₂ O-sec ―C ₄ H ₉ ) ₂ HO―Sb (SCH ₂ COOC ₁₈ H ₃₇ ) ₂ isoC ₈ H ₁₇ O―Sb (SCH ₂ COO―isoC ₈ H ₁₇ ―) ₂ C ₁₈ H ₃₇ O―Sb (SCH ₂ COOC ₄ H ₉ ) ₂ C ₁₂ H ₂₅ O―Sb (SCH ₂ CH ₂ COOC ₂ H ₅ ) ₂ C ₄ H ₉ SCH ₂ CH ₂ O―Sb
(SCH ₂ CH ₂ COOC ₁₂ H ₂₅ ) ₂ C ₆ H ₅ CH ₂ O―Sb (SCH ₂ CH ₂ OOC―C ₁₇ H ₃₅ ) ₂ C ₁₁ H ₂₃ COOCH ₂ CH ₂ O―Sb (SCH ₂ CH (OH )
CH ₂ OC ₄ H ₉ ) ₂ C ₆ H ₅ CH ₂ COO―Sb (SCH ₂ COOisoC ₈ H ₁₇ ) ₂ C ₁₈ H ₃₇ COO―Sb (SCH ₂ COOCH ₃ ) ₂ C ₄ H ₉ OOC―CH ₂ CH ₂ ―COO―Sb
(SCH ₂ CH ₂ COOC ₁₈ H ₃₇ ) ₂ (C ₄ H ₉ ) ₂ N―Sb (SCH ₂ CH ₂ COOC ₄ H ₉ ) ₂ C ₆ H ₁₁ NH―Sb (SCH ₂ CH ₂ CH O―iso―
Examples of _the compound represented by _{the formula C8H17 )} 2C6H5NHNH-Sb _{( SCH2CHCH2OC12H25 ) 2} include the following compounds _: (C ₁₂ H ₂₅ OOCCH ₂ S) ₂ Sb―O―Sb
(SCH ₂ COOC ₁₂ H ₂₅ ) ₂ Examples of the compound represented by the formula include the following compounds:

【formula】

[Formula] Compounds represented by formula and are often combined with antimony tris mercaptide and SbX ₃ or
It can be produced by comproportionation with a compound represented by SbY ₃ : Sb(SR) ₃ +2SbX ₃ →3RS−SbX ₂ () 2Sb(SR) ₃ +SbY ₃ →3 (RS) ₂ SbY () Compounds SbX ₃ and SbY ₃ suitable for this purpose include in particular antimony halides (SbCl ₃ ,
SbBr ₃ , SbI ₃ ), antimony alcoholates e.g.
Mention may be made _of Sb( _OC2H5 ) ₃ or Sb( _OC6H13 ) ₃ and antimony carboxylates such as Sb( _OOCCH3 ) _{3 .} These composition reactions can be carried out without a solvent or in an inert solvent.
The temperature required for the reaction is 100°C to 200°C. Suitable solvents include, for example, toluene, xylene or tetrahydrofuran. Tris mercaptide Sb(SR) ₃ is described, for example, in the aforementioned U.S. Pat.
It is a known compound as described in Specifications No. 2684956 and No. 2680726. Compounds of the formula and in which X and Y represent halogen atoms are used as intermediates for other compounds of the formula and. The corresponding chlorine compounds of the formula and: RS—SbCl ₂ () (RS) ₂ SbCl () are particularly suitable for this purpose. Therefore, by reacting a compound of the formula and with R ¹ OH in the presence or absence of a hydrogen chloride acceptor, a compound of the formula and in which X or Y represents R ¹ O- is formed. be done.
X or Y is R ² COO—or R ³ OOC—R ⁴ —
A compound represented by the formula or COO- represents a chlorine compound represented by the formula or
It is formed by reacting a half ester of a monocarboxylic or dicarboxylic acid in the presence of an equivalent amount of base, preferably a tertiary amine, or by reacting with an alkali metal salt of such acid. By hydrolyzing the compounds of the formula, compounds of the formula where X represents a hydroxyl group and compounds of the formula where Z represents a hydroxyl group are obtained. By hydrolyzing the compound represented by the formula, a compound represented by the formula in which Y represents a hydroxyl group and a compound represented by the formula in which Z represents an SR group are obtained. Compounds of the formula or in which X and Y each represent a (R ⁵ )(R ⁶ )N- group can be obtained by reacting a chlorine compound of the formula V or with a secondary amine, in which case The hydrogen chloride acceptor used can be either an excess of the amine or an equivalent amount of the other base. In a similar manner, a compound of the formula can be reacted with a primary amine, hydrazine or phenylhydrazine so that Y is -NHR ⁵ , -
A compound of the formula NHNH ₂ or -NHNH-phenyl group is obtained. Both X groups together form -O-R ²
The compound represented by the formula representing -O- is one equivalent of the compound represented by the following formula: HO-R ⁹ -
It can be produced by reacting a compound represented by OH in the presence of 2 equivalents of a hydrogen chloride acceptor. Both X groups together form -O-CO
-R ⁹ -CO-O- The compound represented by the formula and the following formula: HOOC
It can be produced by reacting a dicarboxylic acid represented by -R ⁹ -COOH with an alkali metal salt. The compound represented by the formula is the following formula: (In the formula, R ⁸ represents the above-mentioned meaning.) It can be produced by hydrolyzing the compound represented by alkaline. Compounds represented by the formula and can also be produced by reacting antimony trichloride with the corresponding mercapto compound (RSH). SbCl ₃ +RSH−HCl ―――――→ RS―SbCl ₂ () SbCl ₃ +2RSH−2HCl ――――――――→ (RS) ₂ SbCl () These reactions are performed in an organic solvent such as methylene chloride. is preferable. Suitable hydrogen chloride acceptors are organic or inorganic bases, especially solid alkali metal carbonates (eg NaHCO ₃ or K ₂ CO _{3 )} . Mixtures of compounds can also be formed by the synthetic method described here. In the preparation of a compound of the formula, for example by the composition method, some amount of the compound of the formula may also be produced as a by-product; or in the case of hydrolysis of a compound of the formula:
In addition to the products of the formula, products of the formula may also be formed. For many applications, mixtures of this type can be used in the same way as pure compounds. However, if pure compounds are desired, they can be obtained by conventional purification methods such as fractional distillation, recrystallization or chromatographic methods. Antimony mercaptides of the formula, and are used as stabilizers for polymers and copolymers of chlorine-containing thermoplastics such as vinyl chloride or vinylidene chloride, chlorinated polyolefins, post-chlorinated polyvinyl chloride or chlorinated rubber. be able to. Stabilization of polyvinyl chloride (PVC) is particularly important. The material of interest can be a suspension polyvinyl chloride, an emulsion polyvinyl chloride or a polymer made by bulk polymerization. The compounds represented by the formulas, and are added to the chlorine-containing thermoplastic resin in an amount of 0.1 to 5% by weight based on the thermoplastic resin. Preferably
Amounts of 0.5 to 3% by weight are used. formula,,
It is also possible to use a mixture of two or more of the compounds represented by and. Precursors of stabilizers according to the invention can also be added to thermoplastic resins. For example, instead of the compound of the formula, a mixture of Sb(SR) ₃ and SbX ₃ (preferably in a molar ratio of 1:2) can be added, from which the compound of the formula can be heated under thermoplastic molding conditions. Can be formed in plastic resin. However, direct addition of compounds of formulas, and is preferred. Incorporation of the stabilizer into the polymeric matrix can be achieved by mixing the ingredients together in powder form and subsequently molding, or by adding the stabilizer into the thermoplastic resin on a roll mill or in a kneader. This can be carried out by a conventional method of mixing. Common in the chlorine-containing thermoplastics industry, such as lubricants, plasticizers, fillers, additives increasing impact strength, pigments, light stabilizers and antioxidants or even heat stabilizers such as metal carboxylates or organic phosphites. Other known additives can be mixed in at the same time. Of particular importance is the addition of costabilizers, especially from the series of pyrocatechol derivatives. For example, US Pat. No. 4,029,618 shows that pyrocatechol and its derivatives have a synergistic effect with organic antimony compounds as stabilizers for chlorine-containing thermoplastic resins.
No. 4,158,640.
Co-stabilizers of this type that synergistically enhance the action of basic stabilizers are also called boosters. This type of boosting effect of pyrocatechol and pyrocatechol derivatives is also observed when used in combination with compounds of the formulas, and. Pyrocatechols with this kind of synergistic action are, for example, represented by the following formula:

[Formula] (R=H, alkyl group, alkenyl group, alkoxycarbonyl group)

[Formula] (R″=alkyl group, haloalkyl group, aryl group, aralkyl group) Compounds of the formula as well as antimony and tin phenolates of such pyrocatechol, such as the following formula: (X′=alkylene, oxaalkylene, thioalkylene, phenylene)

【formula】

【formula】 (R' = alkyl, aryl, aralkyl)

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

It is a compound represented by the formula: Furthermore, as a pyrocatechol derivative having a synergistic effect, the following formula:

[Formula] and

Examples include cyclic borates or phosphites of pyrocatechol, such as the compound represented by the formula: (wherein R and X have the meanings given above). Other synergistic pyrocatechol derivatives include halogenated pyrocatechols such as 3-chloro-, 3,4-dibromo-, 3-bromo-4-
Tertiary butyl or 3,4,5,6-tetrabromopyrocatechol can be mentioned. These co-stabilizers are used in an amount of 2 to 50% by weight based on the amount of the compound, or, so that the weight ratio of stabilizer:co-stabilizer is 2:1 to 98:2. The optimum amount ratio must be determined experimentally for each stabilizer/co-stabilizer combination. The stabilized chlorine-containing thermoplastic resin according to the invention comprises:
They can be shaped into shaped articles by conventional application methods such as extrusion, injection molding or calendering, or by being processed as plastisols. Next, the production and use of the compounds represented by the formulas, and are further explained with reference to Examples. In the examples, "parts" represent "parts by weight." Example 1: Composition of SbCl ₃ in solution 114.2 g (0.5 mol) of antimony trichloride and 731 g (1 mol) of antimony trichloride-thioglycolic acid isooctyl ester in 200 ml of toluene were mixed into 20
Refluxed for an hour. After cooling, it was filtered to remove trace impurities, and the solvent was distilled off under reduced pressure. Sb：S：
A colorless viscous oil with an H-NMR signal of thiomethylene proton at δ=3.90 ppm with an elemental ratio of Cl=1:1.924:0.996 was obtained in virtually quantitative yield. This is the following formula: ClSb(SCH ₂ COO-isoC ₈ H ₁₇ ) ₂ (Compound No. 1)
It corresponds to the compound represented by Similar results were obtained by conducting the test in ethylene chloride instead of toluene. Similarly, 228.2 g (1 mol) of SbCl ₃ and Sb
From 365.4 g (0.5 mol) of (SCH ₂ COO-isoC ₈ H ₁₇ ), a crystalline solid with a melting point of 48 to 49°C, represented by the following formula: Cl ₂ SbSCH ₂ COO-isoC ₈ H ₁₇ (compound No. 2) A compound of the form was obtained. The elemental ratio according to elemental analysis is 1:0.92:2.1, and the H-NMR spectrum shows a singlet for thiomethylene proton at δ=4.17. Example 2: Composition of SbCl ₃ without solvent 45.6 g of antimony trichloride and Sb[SCH ₂ CH
78 _g of (OH) _CH2O -iso- _C8H17 ] ₃ was shaken at room temperature for 12 hours. During this time, the initially undissolved SbCl ₃ dissolved. The slightly yellowish oil obtained is a crude monomercaptide having the following formula: Cl ₂ SbSCH ₂ CH(OH)CH ₂ O-isoC ₈ H ₁₇ (Compound No. 3). Similarly, from 11.4 g of SbCl ₃ and 78 g of the above tris-mercaptide, a compound represented by the following formula: ClSb[SCH ₂ CH(OH)CH ₂ O-isoC ₈ H ₁₇ ] ₂ (compound No. 4) was prepared. , obtained as a pale yellow liquid. Example 3: Alcoholysis of antimony chloromercaptide ClSb(SCH ₂ COO-isoC ₈ H ₁₇ ) ₂ (Compound No. 1)
113 g was dissolved in 200 ml of diethyl ether. 2-ethylhexanol in 100ml of diethyl ether
A solution containing 26 g of triethylamine and 20 g of triethylamine was slowly added dropwise with stirring, and the mixture was then refluxed for 1 hour. After cooling, the precipitated amine hydrochloride was filtered off, and the solution was concentrated by distilling off the solvent. 121 g of a product of the following formula: isoC ₈ H ₁₇ OSb (SCH ₂ COO-isoC ₈ H ₁₇ ) ₂ (compound No. 5) was obtained as a transparent oily liquid. The H-NMR spectrum was consistent with the above formula. Elemental analysis value Sb S Measured value 18.3% 9.6% Calculated value 18.5% 9.9% From 113 g of ClSb (SCH ₂ COO-isoC ₈ H ₁₇ ) ₂ , 54 g of octadecanol (stearyl alcohol) and 20 g of triethylamine, the following formula is similarly calculated. : C ₁₈ H ₃₇ OSb (SCH ₂ COO-isoC ₈ H ₁₇ ) ₂ (compound
133 g of the compound represented by No. 6) was obtained as a colorless waxy substance with a melting point of 48 to 49°C. Elemental analysis value Sb S Measured value 15.5% 8.3% Calculated value 15.9% 8.4% Cl ₂ SbSCH ₂ COO-isoC ₈ H ₁₇ (Compound No. 2) 99
Similarly, from 135 g of octadecanol and 51 g of triethylamine, the following formula: (C ₁₈ H ₃₇ O) ₂ SbSCH ₂ COO-isoC ₈ H ₁₇ (compound
No. 7) 215g of the compound represented by
It was obtained as a colorless waxy substance. Elemental analysis value Sb S Measured value 12.6% 6.6% Calculated value 13.0% 6.9% Example 4: Reaction of antimony chloromercaptide with carboxylic acid 11.2 g of ClSb (SCH ₂ COO-isoC ₈ H ₁₇ ) ₂ was dissolved in 20 ml of diethyl ether It was dissolved in A solution of 2 g of triethylamine dissolved in 10 ml of ether and 4.8 g of endomethylenetetrahydrophthalic acid monobutyl ester in 20 ml of ether were simultaneously added dropwise with stirring, and the whole was refluxed for 1 hour. The precipitated amine hydrochloride was filtered off, and the filtrate was concentrated by distilling off the solvent. The following formula: 13.6 g of the product were obtained in the form of a colorless wax. Elemental analysis value Sb S Actual value 15.8% 8.2% Calculated value 16.1% 8.5% The following compound was obtained in the same manner. C ₁₇ H ₃₅ COOSb (SCH ₂ COO-isoC ₈ H ₁₇ ) ₂ (Compound No. 12) Wax-like, melting point 47-48℃; (C ₁₇ H ₃₅ COO) ₂ SbSCH ₂ COO-isoC ₈ H ₁₇ (Compound No. .13) Wax-like, melting point 61-63℃; C ₉ H ₁₉ COOSb (SCH ₂ COO-isoC ₈ H ₁₇ ) ₂ (compound
No. 14) Viscous oil [from “Versatic acid 10” (mixture of branched chain monocarboxylic acids with 10 carbon atoms, commercial product)] Example 5: SbCl ₃ and thioglycolic acid ester Reaction of SbCl ₃ 4.56g, HSCH ₂ COO-isoC ₈ H ₁₇ 4.08g
and 1.85 g of NaHCO ₃ were reacted in 50 ml of methylene chloride at reflux temperature. After the gas evolution had ended, the reaction mixture was filtered off and the filtrate was concentrated under reduced pressure. A colorless oil consisting mainly of Compound No. 2 was obtained. crude product
The NMR spectrum shows that as a by-product in an amount of about 10 mol%, the following formula: C ₈ H ₁₇ OOCH ₂ S—Sb(Cl)—O—Sb(Cl)—
Indicates the presence of a compound represented by SCH ₂ COOC ₈ H ₁₇ . Similarly, from 4.56 g of antimony trichloride, 8.16 g of thioglycolic acid isooctyl ester, and 3.69 g of NaHCO ₃ , compound No. 1 was prepared mainly with the following formula as a by-product: (C ₈ H ₁₇ OOC CH ₂ S) ₂ Sb—O -Sb
A crude product in the form of a colorless oil consisting of about 10 mol % of the compound represented by (SCH ₂ COOC ₈ H ₂₇ ) ₂ was obtained. Example 6: Stabilization of polyvinyl chloride The following formulation suitable for the manufacture of water pipes was used. Suspended polyvinyl chloride (K value 68) 100 parts Chiyoke 1.0 parts Titanium dioxide (rutile) 1.0 parts Paraffin wax 0.8 parts Calcium stearate 0.8 parts Stabilizer 0.4 parts 104 parts The above components were dry mixed and the mixture was heated at 200℃. Long-term roll tests were conducted on a chamber roll mill. The resulting discoloration was confirmed by measuring the yellowness index of test pieces taken from the 0.3 mm thick rolled sheet after 3.6 and 12 minutes, respectively. “Irgastab” was used for comparison with the conventional technology.
511” [Antimony trimercaptoester represented by the following formula: Sb(CH ₂ COO-isoC ₈ H ₁₇ ) ₃ ]
It was used. The results are summarized in the table below.

[Table] Example 7: Stabilization of polyvinyl chloride by adding costabilizer Example except that 0.35 part of stabilizer is used instead of 0.4 part of stabilizer and 0.05 part of tetrabromopyrocatechol is used as costabilizer. A mixture was prepared in the same manner as in 6.

【table】

Claims (1)

[Claims] Primary formula, or: [Formula] [Formula] [Formula] [Formula] (wherein, X is a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, -OR ¹ group, -OOCR ² groups,
-OOC-R ⁴ -COOR represents ^three groups or -N(R ⁵ ) (R ⁶ ) group, or formed by two X groups together -O-R ⁹ -O- or -OCO- R ⁹ -
represents a COO- group, Y is one of the groups defined as X or-
NHR ⁵ group, -NHNH ₂ group or -NHNH- phenyl group, Z represents one of the groups defined as X or SR group, R is hydroxyl group, -OCOR ⁷ group, -OR ⁸ group,
represents an alkyl group having 1 to 6 carbon atoms substituted with one or two of -SR ⁸ groups or -COOR ⁸ groups, R' represents -CH ₂ - or -CH ₂ CH ₂ -, and R ¹ is an alkyl group having 1 to 18 carbon atoms, -
represents an alkyl group having 1 to 6 carbon atoms substituted with OR ⁸ group, -SR ⁸ group or -OCOR ⁷ group,
or R ¹ is an aryl group having 6 to 10 carbon atoms;
represents a phenylalkyl group having 7 to 9 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, R ² is an alkyl group having 1 to 18 carbon atoms,
Alkenyl group having 2 to 18 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, 6 carbon atoms
R 3 represents a phenyl group or a phenyl alkyl group having 7 to 9 carbon atoms substituted with an aryl group having 1 to 10 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group and/or a ^halogen atom; represents an alkyl group, allyl group, cyclohexyl group, or phenyl group having 1 to 12 carbon atoms; R ⁴ is an alkylene group having 2 to 12 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or an alkenylene group having 5 to 12 carbon atoms; represents a cycloalkylene or cycloalkenylene group, a phenylene group or a halophenylene group, and R ⁵ and R ⁶ may be the same or different and each has 1 carbon atom.
to 12 alkyl, benzyl, or cyclohexyl groups, or R ⁵ and R ⁶ together with a nitrogen atom to form a pyrrolidine, piperidine, or morpholine group, and R ⁷ has 1 to 1 carbon atoms; 18 alkyl groups, CH ₃ COCH ₂
-, cyclohexyl, benzyl, C6 -C10 aryl or C1 -C4 alkyl, phenyl substituted by hydroxyl and/or halogen or C7 -C9 represents a phenyl alkyl group having 1 to 18 carbon atoms, R ⁸ represents an alkyl group having 1 to 18 carbon atoms, an allyl group, a cyclohexyl group or a phenyl group, and R ⁹ represents an alkylene group having 2 to 6 carbon atoms, O, S or (R ⁵ ) represents an alkylene group having 3 to 6 carbon atoms interrupted by N, or -OR ⁸ group or -
OCOR represents a propylene group interrupted by ^{a 7} group. ) antimony-sulfur compound. 2 In formula, or, X, Y or Z
The compound according to claim 1, wherein represents a chlorine atom. 3 In the formula or, X or Y is -OR ¹
2. The compound according to claim 1, which represents any one of the following groups: -OOC-R ⁴ -COOR ³ or -OOCR ² . 4 In the formula, , or, R represents an alkyl group having 1 to 6 carbon atoms substituted with one or two -COOR ⁸ groups, and R ⁸ represents the meaning described in claim 1. A compound according to claim 1. 5 In formula, , or, R is -
5. A compound according to claim 4, which represents CH ₂ COOR ⁸ and R ⁸ represents an alkyl group having 8 to 14 carbon atoms. 6 The following formula,, or: [Formula] [Formula] [Formula] [Formula] (wherein, X is a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, -OR ¹ group, -OOCR ² groups,
-OOC-R ⁴ -COOR represents ^three groups or -N(R ⁵ ) (R ⁶ ) group, or formed by two X groups together -O-R ⁹ -O- or -OCO- R ⁹ -
represents a COO- group, Y is one of the groups defined as X or-
NHR ⁵ group, -NHNH ₂ group or -NHNH- phenyl group, Z represents one of the groups defined as X or SR group, R is hydroxyl group, -OCOR ⁷ group, -OR ⁸ group,
represents an alkyl group having 1 to 6 carbon atoms substituted with one or two of -SR ⁸ groups or -COOR ⁸ groups, R' represents -CH ₂ - or -CH ₂ CH ₂ -, and R ¹ is an alkyl group having 1 to 18 carbon atoms, -
represents an alkyl group having 1 to 6 carbon atoms substituted with OR ⁸ group, -SR ⁸ group or -OCOR ⁷ group,
or R ¹ is an aryl group having 6 to 10 carbon atoms;
represents a phenylalkyl group having 7 to 9 carbon atoms or a cycloalkyl group having 5 to 8 carbon atoms, R ² is an alkyl group having 1 to 18 carbon atoms,
Alkenyl group having 2 to 18 carbon atoms, cycloalkyl group having 5 to 8 carbon atoms, 6 carbon atoms
R 3 represents a phenyl group or a phenyl alkyl group having 7 to 9 carbon atoms substituted with an aryl group having 1 to 10 carbon atoms, an alkyl group having 1 to 4 carbon atoms, a hydroxyl group and/or a ^halogen atom; represents an alkyl group, allyl group, cyclohexyl group, or phenyl group having 1 to 12 carbon atoms; R ⁴ is an alkylene group having 2 to 12 carbon atoms, an alkenylene group having 2 to 6 carbon atoms, or an alkenylene group having 5 to 12 carbon atoms; represents a cycloalkylene or cycloalkenylene group, a phenylene group or a halophenylene group, and R ⁵ and R ⁶ may be the same or different and each has 1 carbon atom.
to 12 alkyl, benzyl, or cyclohexyl groups, or R ⁵ and R ⁶ together with a nitrogen atom to form a pyrrolidine, piperidine, or morpholine group, and R ⁷ has 1 to 1 carbon atoms; 18 alkyl groups, CH ₃ COCH ₂
-, cyclohexyl, benzyl, C6 -C10 aryl or C1 -C4 alkyl, phenyl substituted by hydroxyl and/or halogen or C7 -C9 represents a phenyl alkyl group having 1 to 18 carbon atoms, R ⁸ represents an alkyl group having 1 to 18 carbon atoms, an allyl group, a cyclohexyl group or a phenyl group, and R ⁹ represents an alkylene group having 2 to 6 carbon atoms, O, S or (R ⁵ ) represents an alkylene group having 3 to 6 carbon atoms interrupted by N, or -OR ⁸ group or -
OCOR represents a propylene group interrupted by ^{a 7} group. ) A stabilizer for chlorine-containing thermoplastic resins comprising an antimony-sulfur compound represented by: 7. The stabilizer according to claim 6, wherein the thermoplastic resin is polyvinyl chloride. 8. A stabilizer as claimed in claim 6 in combination with a co-stabilizer made from a pyrocatechol derivative. 9 Claim No. 6 for thermoplastic resin
7. The stabilizer according to claim 6, wherein the antimony-sulfur compound represented by the formula, or is contained in an amount of 0.1 to 5% by weight. 10. The stabilizer according to claim 9, wherein the thermoplastic resin is polyvinyl chloride. 11. The stabilizer of claim 9, wherein the thermoplastic further contains other additives commonly known in the chlorine-containing thermoplastic industry. 12. The stabilizer according to claim 11, wherein the thermoplastic resin contains pyrocatechol or a pyrocatechol derivative as a co-stabilizer. 13. The stabilizer of claim 12, wherein the weight ratio of stabilizer to co-stabilizer is from 2:1 to 98:2. 14. The stabilizer according to claim 11, wherein the thermoplastic resin contains a calcium or zinc salt of a carboxylic acid as a co-stabilizer.