JPH08143582A - Odorless sulfur-containing organic tin compound for chlorine-containing resin stabilizer and deodorization method using the compound - Google Patents

Abstract

PURPOSE: To provide a sulfur-containing organic tin compound free from odorous component and having excellent stabilizer performance and odorlessness and low volatile loss and accordingly giving a void-free molded article of a chlorine- containing resin. CONSTITUTION: This odorless sulfur-containing organic tin compound for a chlorine-containing resin stabilizer is free from odorous component. The compound can be produced by distilling a sulfur-containing organic compound such as dimethyltin bis(isooctylmercaptoacetate), dipropyltin sulfide and di-n-octyltin bis(laurylmercaptide) under 0.1-30mmHg pressure at 80-150 deg.C, thereby deodorizing the tin compound. The compounding ratio of the compound is preferably 0.1-3 pts.wt. based on 100 pts.wt. of the chlorine-containing resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an odorless sulfur-containing organotin compound for a chlorine-containing resin stabilizer and a deodorizing method thereof.

[0002]

2. Description of the Related Art Conventionally, sulfur-containing organotin compounds have been used as stabilizers for chlorine-containing resins. However, since this compound contains a small amount of a by-product, unreacted raw material and the like during production, it has an odor. Therefore, when the compound is used as it is as a stabilizer for a chlorine-containing resin, it produces a bad odor during handling and is not preferable in terms of hygiene during work, and also has a bad influence on the performance as a stabilizer for a chlorine-containing resin.

[0003]

SUMMARY OF THE INVENTION In view of the above, it is an object of the present invention to provide an odorless sulfur-containing organotin compound which is odorless and has excellent stabilizer performance, and a deodorizing method thereof.

[0004]

The present invention provides (1) an odorless sulfur-containing organotin compound for a chlorine-containing resin stabilizer, which is substantially free of odorous components. (2) 0.1 mmHg to 30 mm of sulfur-containing organotin compound
A method for deodorizing an odorless sulfur-containing organotin compound for a chlorine-containing resin stabilizer, which comprises performing distillation at 80 ° C to 150 ° C under a pressure of Hg.

The odorous component is a compound by-produced during the production of a sulfur-containing compound or an unreacted raw material, and examples thereof include thioglycolic acid, thioglycolic anhydride, 2-mercaptoethanol, 2-mercaptoethanol dimer and isooctyl. Examples thereof include thioglycolate and low molecular weight mercapto compounds having a structure similar to the above. The substantial absence of odorous components is usually 1% by weight or less. If the odorous component is 1% by weight or more, an odor is emitted when handling the sulfur-containing organic tin compound or when processing a vinyl chloride resin, which is not preferable in the working environment. Further, if the odor remains in the processed product, the value of the product is reduced, which is not preferable. Also, in injection molding, voids are generated in the product, which is not preferable.

The deodorizing method for removing odorous components is as described above. If the distillation is performed at 30 mmHg or more, the odorous components cannot be distilled off efficiently. 0.1 mmHg
The following conditions are not realistic because they are difficult to process. 80
If the temperature is lower than 0 ° C, the odorous component cannot be efficiently distilled off, and if the temperature is higher than 150 ° C, the sulfur-containing organotin compound is deteriorated by decomposition due to the heat when the odorous component is distilled off, which is not preferable.

The organotin mercapto compound is not particularly limited, and examples thereof include the following. Dimethyltin bis (isooctyl mercaptoacetate), dimethyltin bis (2-ethylhexyl mercaptoacetate), dimethyltin bis (lauryl mercaptide), dimethyltin bis (stearyl mercaptide),
Dimethyltin bis (mercaptoethyl tall oil fatty acid ester), dimethyltin bis (mercaptoethyl butyl succinate), dimethyltin bis (2-mercaptoethyl caprylate), dimethyltin bis (2-mercaptoethyl stearate), dimethyltin bis (2-mercaptoethyl oleate), dimethyltin bis _(2-hydroxy-C 10 _{-C 14} mixed alkyl mercaptan Tide), dimethyltin bis (2-octanoyloxy-dodecyl mercaptan Tide), dimethyltin bis (2 -Lauryl oxide decyl mercaptide), dimethyltin bis (isooctyl mercaptopropionate), dimethyltin bis (monothioglycol octylate), bis [dimethyltin dis (2-mercaptoethyl oleate)] sulfide,
Bis [dimethyltin dis (2-mercaptoethyl tall oil fatty acid ester)] sulfide.

Monomethyl tin tris (isooctyl mercaptoacetate), monomethyl tin tris (2-ethylhexyl mercapto acetate), monomethyl tin tris (lauryl mercaptide), monomethyl tin tris (stearyl mercaptide), monomethyl tin tris (mercaptoethyl) -Tall oil fatty acid ester), monomethyltin tris (mercaptoethyl butyl succinate), monomethyltin tris (2-mercaptoethyl caprylate), monomethyltin tris (2-mercaptoethyl stearate), monomethyltin tris (2- mercaptoethyl oleate), monomethyl tin tris _(2-hydroxy-C 10 _{-C 14} mixed alkyl mercaptan Tide), monomethyl tin tris (2-octanoyloxy-dodecyl mercaptan Tide), Mo Methyltin tris (2-lauryl oxide decyl mercaptide), monomethyltin tris (isooctyl mercaptopropionate), monomethyltin tris (monothioglycol octylate), monomethyltin sulfide (adamantane structure), dimethyltin sulfide, Dimethyltin-β-mercaptopropionate, bis [monomethyltindi (isooctylmercaptoacetate)] sulfide, bis [monomethyltindi (isooctylmercaptopropionate)] sulfide, bis [monomethyltindi (monothioglycoloctyl) Acid ester)] sulfide, bis [monomethyltin di (2-mercaptoethyloleate)] sulfide, poly (thiobis-methyltin sulfide).

Dibutyltin bis (isooctyl mercaptoacetate), dibutyltin bis (2-ethylhexylmercaptoacetate), dibutyltin bis (laurylmercaptide), dibutyltin bis (stearyl mercaptide), dibutyltin bis (mercaptoethyl) -Tall oil fatty acid ester), dibutyltin bis (mercaptoethyl butyl succinate), dibutyltin bis (2-mercaptoethyl caprylate), dibutyltin bis (2-
Mercaptoethyl stearate), dibutyltin bis (2
-Mercaptoethyl oleate), dibutyltin bis (2-
Hydroxy C ₁₀ -C ₁₄ mixed alkyl mercaptan Tide), dibutyltin bis (2-octanoyloxy-dodecyl mercaptan Tide), dibutyltin bis (2-lauryloxy-dodecyl mercaptan Tide), dibutyltin bis (isooctyl mercaptopropionate Pionate), dibutyltin bis (monothioglycol octylate).

Monobutyltin tris (isooctyl mercaptoacetate), monobutyltin tris (2-ethylhexylmercaptoacetate), monobutyltin tris (lauryl mercaptide), monobutyltin tris (stearyl mercaptide), monobutyltin tris (mercaptoethyl) -Tall oil fatty acid ester), monobutyltin tris (mercaptoethyl butyl succinate), monobutyltin tris (2-mercaptoethyl caprylate), monobutyltin tris (2-mercaptoethyl stearate), monobutyltin tris (2- mercaptoethyl oleate), monobutyltin tris _(2-hydroxy-C 10 _{-C 14} mixed alkyl mercaptan Tide), monobutyltin tris (2-octanoyloxy-dodecyl mercaptan Tide), Mo Butyltin tris (2-lauryloxy-dodecyl mercaptan Tide), monobutyltin tris (isooctyl mercaptopropionate), monobutyltin tris (mono thioglycolic octyl ester), poly (thiobis -n- butyl tin sulfide).

Di-n-octyltin bis (isooctylmercaptoacetate), di-n-octyltin bis (2-
Ethylhexyl mercaptoacetate), di-n-octyltin bis (lauryl mercaptide), di-n-octyltin bis (stearyl mercaptide), di-n-octyltin bis (mercaptoethyl tall oil fatty acid ester), Di-n-octyltin bis (mercaptoethyl
Butyl succinate), di-n-octyltin bis (2-mercaptoethyl caprylate), di-n-octyltin bis (2-mercaptoethyl stearate), di-n-octyltin bis (2-mercaptoethyl) Oleate), di-n-octyltin bis (2-hydroxy C ₁₀
To C ₁₄ mixed alkyl mercaptide), di-n-octyltin bis (2-octanoyl oxide decyl mercaptide), di-n-octyl tin bis (2-lauryl oxide decyl mercaptide), di-n -Octyltin bis (isooctyl mercaptopropionate), di-n-
Octyl tin bis (monothioglycol octyl ester).

Mono-n-octyltin tris (isooctylmercaptoacetate), mono-n-octyltin tris (2-ethylhexylmercaptoacetate), mono-n-octyltin tris (laurylmercaptide),
Mono-n-octyltin tris (stearyl mercaptide), mono-n-octyltin tris (mercaptoethyl tall oil fatty acid ester), mono-n-octyltin tris (mercaptoethyl butyl succinate),
Mono-n-octyltin tris (2-mercaptoethyl caprylate), mono-n-octyltin tris (2-mercaptoethyl stearate), mono-n-octyltin tris (2-mercaptoethyloleate), mono-n - octyl tin tris _(2-hydroxy-C 10 _{-C 14} mixed alkyl mercaptan Tide), mono -n- octyl tin tris (2-octanoyloxy-dodecyl mercaptan Tide),
Mono-n-octyltin tris (2-lauryl oxide decyl mercaptide), mono-n-octyltin tris (isooctyl mercaptopropionate), mono-n
Octyl tin tris (monothioglycol octyl ester).

Poly (thiobis-n-octyltin sulfide), dipropyltin sulfide, dibutyltin sulfide, dibenzyltin sulfide, dihexyltin sulfide, di-2-ethylhexyltin sulfide, di (isobutyl) tin sulfide, di (isoamyl) tin. Sulfide, di (isohexyl) tin sulfide, 2-
Ethylbutyltin sulfide, butyltin sesquisulfide, hexyltin sesquisulfide, isooctyltin sesquisulfide, heptyltin sesquisulfide,
n-octyltin sesquisulfide, S-butyltin sesquisulfide, propyltin sesquisulfide, isoamyltin sesquisulfide, 2-ethylhexyltin sesquisulfide.

The above organic tin mercapto compounds can be used alone or as a mixture of two or more. Most of these are liquids, but some are solid.

The organotin mercapto compound is contained in an amount of 0.01 to 5.0 parts by weight based on 100 parts by weight of the chlorine-containing resin. If it is less than 0.01 parts by weight, thermal stability will be insufficient, and if it exceeds 5.0 parts by weight, it will not be suitable for the purpose of the present invention. Preferably 0.1 to
3.0 parts by weight.

The chlorine-containing resin composition of the present invention is constituted by incorporating the above-mentioned components into a chlorine-containing resin. The chlorine-containing resin is not particularly limited, and examples thereof include polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, post-chlorinated polyvinyl chloride, and post-chlorinated polyodor. Vinyl chloride, post-chlorinated polyvinyl fluoride, brominated polyethylene,
Rubber chloride, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer Polymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer Polymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-
Halogen-containing synthetic resins such as methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, internally plasticized polyvinyl chloride, and the above halogen-containing synthetic resins and α-such as polyethylene, polypropylene, polypten, poly-3-methylputin, etc. Olefin polymer, or ethylene-
Polyolefin such as vinyl acetate copolymer, ethylene-propylene copolymer and copolymers thereof, polystyrene, acrylic resin, copolymerization of styrene with other monomer (eg, maleic anhydride, butadiene, acrylonitrile, etc.) Examples thereof include a blend, an acrylonitrile-butadiene-styrene copolymer, and a blended product with a methacrylic acid ester-butadiene-styrene copolymer.

In the chlorine-containing resin composition of the present invention, if necessary, for example, a crosslinking agent, a pigment, a filler, a foaming agent, an antistatic agent, an antifogging agent, a plateout preventing agent, a surface treatment agent, Lubricants, flame retardants, fluorescent agents, preservatives, antibacterial agents, metal deactivators, photodegradants, processing aids, mold release agents, reinforcing agents, etc. can be contained.

[0018]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. Comparative Example 1 A 300 ml four-necked flask equipped with a stirrer, a thermometer and a cooling tube was charged with di-n-octyltin oxide 93.6.
g (0.25 ml) and 102.6 g (0.5 ml) of thioglycolic acid isooctyl ester were charged and stirred.
Then, it heated up at 90 degreeC. Start depressurization from 50 ° C,
After almost no by-products were distilled out at 90 ° C. × 30 mmHg, the same conditions were maintained for 60 minutes. Thereafter, the reduced pressure was released, the temperature was cooled to room temperature, and the amount of the organotin compound having a unique odor obtained by filtration was 188 g.
n-octyltin bis (isooctyl thioglycolate)
Met. (Comparative Compound 1) Example 1 The organotin compound obtained by the following method was used in a film distillation apparatus (manufactured by Shinko Pantech Co., Ltd .: Wiprene 6-1 type) to give 130
As a result of high-vacuum distillation under the conditions of ° C x 0.2 mmHg, 165.4 g of an organotin compound having a very low odor was obtained. (Invention Compound 1)

2 parts by weight each of the sulfur-containing organotin compound obtained in Example 1 (invention compound 1) and the compound obtained in Comparative Example 1 (comparative compound 1) per 100 parts by weight of a vinyl chloride resin having a rating ,
0.5 parts by weight of stearic acid was added to produce a vinyl chloride resin sheet. (Sheet 1, Sheet 2)

The sheet is cut into small pieces of 2 to 3 mm square. 10 g of the shredded pieces are put in a glass container of about 100 cm ³ and sealed tightly, and heated in a warm water tank at 80 ° C. for 30 minutes. The container is taken out of the warm water tank, cooled to room temperature and opened. Evaluated by mourning the odor immediately after opening the bottle,
For comparison, the same sulfur-containing organotin compound that has not been deodorized is used. The conventional sulfur-containing organotin compounds that had not been subjected to deodorization emitted an odor, but those that had been subjected to deodorization had almost no odor. The results are shown in Table 1.

[0021]

[Table 1]

Example 2 and Comparative Example 2 Di-n-octyltin bisisooctylthioglycolate (containing 3% of mono-n-octyltin trisisooctylthioglycolate) (Comparative Compound 2) and the odor of the compound. 120 ° C, 5 mmHg to remove low volatile components
Vacuum distillation was carried out for 7 hours. (Invention Compound 2) The odors of Invention Compound 2 and Comparative Compound 2 and the volatilization loss after 180 ° C. for 1 hour were measured. Also, with the following composition, the thickness is 15m.
A flange having a diameter of m and a diameter of 150 mm was injection-molded, and a molding test was performed using Comparative Compound 2 and Invention Compound 2 to examine the presence or absence of voids at the center of the molded product. The results are shown in Table 2.

[0023]

[Table 2]

Injection molding formulation Tin stabilizer 3 parts by weight Lubricant 2 parts by weight

[0025]

EFFECTS OF THE INVENTION As a result, the compound 2 of the present invention had no odor, the amount of volatilization loss was small, and as a result, the voids of the molded product were eliminated. It was found to be superior to Comparative Compound 2.

Claims (2)

[Claims] 1. An odorless sulfur-containing organotin compound for a chlorine-containing resin stabilizer, which is substantially free of odorous components. 2. A sulfur-containing organotin compound in an amount of 0.1 mmHg to 3
A method for deodorizing an odorless sulfur-containing organotin compound for a chlorine-containing resin stabilizer, which comprises performing distillation at 80 ° C to 150 ° C under a pressure of 0 mmHg.