JPS60156695A - Preparation of stabilizer of organotin mercaptocarboxylic acid ester salt for halogen-containing resin - Google Patents

Abstract

PURPOSE:To obtain the titled stabilizer with a weak smell of mercaptan, by treating a thioglycolic ester under specific conditions to remove low-boiling compounds, reacting it with an organotin oxide, removing water prepared as a by- product at low temperature under reduced pressure. CONSTITUTION:A compound (e.g. thioglycolic acid isooctyl ester, etc.) shown by the formula HS(CH2)nCOOR (R is 6-18C alkyl, alkenyl, or alkoxyalkyl; n is 1 or 2) is heat-treated at a degree of reduced pressure (preferably <=100mm.Hg at <=80 deg.C) not to distill the compound, or a nitrogen gas is introduced so that the compound will not flow, and low-boiling compounds are removed. The compound is then reacted with one or more compounds (e.g., dimethyltin oxide, etc.) shown by the formula I - formula III (R' is 1-8C alkyl), and water prepared as a by- product is removed at <=60 deg.C at <=100mm.Hg, to give the desired stabilizer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to a method 1i11 of an organic tin mercapto stabilizer for halogenated invertebrates with low odor. When halogen-containing resins are heated and processed, thermal deterioration is likely to occur due to the dehydrohalogenation reaction. etc. will occur. In order to improve these drawbacks, metal salts such as lead stearate, cadmium stearate, calcium stearate, barium stearate, zinc stearate and other metal salts/system stabilizers such as alkaline tin compounds, etc. are generally used. The first method is to add a tin-based stabilizer.

□ Among the stabilizers, organic tin mercaptocarboxylic ester salt stabilizers such as dialkyltin bis(isooctylthioglycolate) and monoalkyltintris(inoctylthioglycolate) are particularly effective in improving thermal stability and transparency. To!
It is widely used because it is excellent in A-. Such stabilizers are produced by a method in which a thioglycol ester and an alkyl tin oxide are reacted in the presence of a t-solvent or in the absence of a bath agent, and the resulting water is removed by vacuum treatment.

However, such organic tin mercaptocarboxylic acid ester salts usually contain violet impurities in the thioglycolic acid ester that is the raw material, so after the synthesis, υ alkyltin mercapto compounds such as alkyltin sulfides are produced as a side reaction product. Alternatively, it contains substances with strong toxic properties such as alkyl tin mercaptocarboxylate, which are difficult to handle, and the improvement is 1! desired.

As a result of extensive research on rubonic acid ester salts, infrared...62. ~3 Oyu: btll*15.60tx
-'l 1740-IL ゛ absorbance ratio (1560aIL
We have focused on the fact that alkyltin mercapto compounds in which Ha( CR) ncOOEL (However, R is an alkyl group or alkenyl group with a disaster prime number of 6 to 18,
It is an alkoxyalkyl group and is an integer of 1,100 or 2. ) is heat-treated at a reduced pressure such that the compound does not distill out, or low-boiling point compounds are removed by introducing KM elementary gas so that the compound does not flow out (however, R' is an alkyl having a carbon number of 1 to 8). Add at least -at selected from 2.
Provided is a method for loading a tin-tin mercaptocarboxylic ester salt-based stabilizer for halogen-containing resins, which is removed under conditions of MR1 or less.

)111□1, the H8(C4,)ncOOlt used in the present invention
contains impurities generated during the manufacture or storage of the compound up to an extent of 2Xm. Of course, such a compound may be used as long as it absorbs more than 2fi% of impurities.

Specific compounds of Ha(CR,)ncQOR include:
Thioglycol octyl ester, thioglycol #2, ethylhexyl, thioglyny. Acid Ithecyleth, Chil, Thioglycolic acid lauryl ester, Thioglycolic acid tridecyl ester, Thioglyte,
- Lucetyl S f pw, thioglycolic acid stearyl ester, thioglycolic acid cyclohemidyl ester,
β-me, lucatoprobionic acid inoctyl ester,
β-mercagtoglobion 2-ethylhexyl, β-
Examples include mercaptoglobionic tridecyl ester, β-mercaptoglobionic acid cetyl ester, β-mercaptopropionic acid stearyl ester, β-mercaptopropionic acid P hexyl ester, etc.]aB
7 parts of LCH*)ncOOR, dehydrated maleic acid, maleic monoalcohol (C1-C1,) ester and charcoal l
A fatty monocarboxylic acid having an A number of 6 to 18 and an aromatic monocarboxylic acid may be used in combination with a filter that does not impair heat resistance and transparency.

Tin oxide, di-n-7tyltin oxide, diisobutyltin oxide 1. Examples include di-n-octyltin oxide, diisulfur, and cutyltin oxide. Further, examples include rutin oxide, monobutyltin hydroxide, monooctyltin oxide, and monooctyltin hydroxide.

The means for removing low boiling point compounds from H8(Cam)ncOOR containing impurities of the present invention is H8(Cam)ncOOR
The treatment is carried out at a degree of reduced pressure that does not cause OR distillation, for example, 200aH# or less, preferably 1001H or less, and at a temperature of 100'C or less, preferably 80C or less, or Ha(C
This is carried out by flowing the pixel gas at a temperature of 100° C. or lower, preferably 80'C or lower, while preventing the H,)ncOOR from flowing out. In the darning process, if it is carried out at a temperature exceeding 100°C, the components that cause odor will increase due to the decomposition of Ha (Cam) ncOOR, which is not preferable. Although the processing time varies depending on the conditions, it is generally 1
Approximately 20 minutes is appropriate.

The treated Ha(CH,)ncOOR was then heated to 40°C
Reacts with at least one compound selected from the following to produce a normal product (symbols in the formula are as above). At this time, water is produced as a by-product, but it is preferable to remove this water at the lowest possible temperature and under reduced pressure, that is, below 60° C. and below 109 amHp. In particular, pressure reduction start temperature 50-60℃, pressure reduction degree 10011a R
Remove by-products (water) under conditions of 1 or less, then 10mHp
More preferably, the maximum temperature under reduced pressure is ioo°C. If by-products are not removed promptly, Ha
(Cam)ncOOR is hydrolyzed with water, thereby containing the strong-smelling reaction product of)sm-8(CL)ncOO8n(), and the resulting compound □ has an absorbance ratio of (156031-”/1 , 4o, -t) is 0.2
That's all I'm confused about.

The obtained alkyltin mercapto compounds have a small 1560 cm-"tD absorbance observed in the infrared absorption spectrum of alkyltin sulfides and alkyltin mercapto carboxylates that emit a strong odor, and 1 found in tin-cut compounds
Absorbance ratio of 140cm-” (1560aa”A740
(+ll-") is 0.2 or less. As such a compound, one having an absorbance ratio of 1560α-Z7□40csc-' of 0.15 or less is more preferable.

The organic tin mercaptocarboxylic acid ester salt used in the present invention is usually α1-5 based on 100 parts by weight of the halogen-containing resin.
Parts by weight are used.

Examples of halogen-containing resins that cause heat include polyvinyl chloride, poly, vinylidene chloride, chlorinated polyethylene, chlorinated polyglobin/, chlorinated rubber, polyvinyl bromide, polyvinyl fluoride, vinyl chloride-vinyl acetate copolymer, chlorinated Vinyl-butadiene copolymer, vinyl chloride-maleic ester copolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-styrene-7crylonitrile copolymer, etc. can give.

The stabilizer of the present invention may also include other stabilizers, such as calcium stearate, barium stearate, dialkyl tin malate poly ff Soybean oil, organic phosphites, and antioxidants can be used in combination.

Next, the present invention will be explained in more detail with reference to Examples.

Example l A fourth flask of 11 equipped with a stirrer, a thermometer and a condenser was charged with 99.0% pure thioglycolic acid inoctyl ester 408,9 (2 mol), and after stirring, 15-25M )lt vacuum. 'After that, the temperature was raised to 70°C under the reduced pressure, and 15~25cm H7X60
It was kept at ~70°C for 2 hours to remove compounds with low boiling points.

Thereafter, the voltage was returned to normal, and after cooling to below 40°C, 56,111 mol of dioctyltin oxide was added, the temperature was raised to 50°C, and pressure reduction was started. After almost no by-products were distilled out at 50° C. and 15 g Hf, the temperature was raised to 98° C. while maintaining the condition of 10 to 20 m H#. After the by-products distilled out under the conditions of 95-b are gone, return to normal pressure 7
It was cooled to 0°C and passed through the mouth.゛Dioctyltinbis (isooctylthioglycolate)
was obtained, and the infrared absorption spectrum was measured using an infrared spectrophotometer. The results are shown in Figure 1. In addition, the wavelength is 1560 cw
Absorbance ratio of L-' and 1740 cm- (1560aa'
7', 74o, -0 was 0.09. This organotin compound has very little mercapto odor, and is prepared in a 1) 4-bottle flask equipped with a stirrer, thermometer, and cooling tube, with 412.9 ml of 2-ethylhexyl thioglycolate (2, 01 mol) was added and stirred. Next, the temperature was raised to 70°C while blowing N gas, and the temperature was increased to 60-70°C.
Low boilers were removed by bubbling N1 gas at ℃ for 2 hours.

Thereafter, the mixture was cooled to 40° C., and dioctyltin bis(2-ethylhexylthioglycolate) was obtained in the same manner as in Example 1. Figure 2 shows the infrared absorption spectrum of the obtained tin compound measured with an infrared spectrophotometer. From Figure-2, the absorbance ratio (1560tx71740CII-ri is 0,1
The compound No. 1 had very little mercaptobenety.・Comparative example I.

Triol 200i9.0 was placed in a 2104-hole flask equipped with a stirrer, temperature control, and condensing tube. The same thioglycol acid inoctyl a12i2 as in Example 1. o1 mol) and stirred, then leoctyltin oxide 561.9
(1 mol) was added, the temperature was raised to 90°C, and the distilled water was removed using a decanter, and the doluol distilled out at this time was allowed to return to the flask. After no more water was distilled out, the temperature was raised to 130°C to remove most of the drol. - After most of the doruol was gone, it was cooled to below 100°C, and the doruol was completely removed at 90 to 100°C under a reduced pressure of 15HH7. '□... The infrared absorption spectrum and torque of the obtained dioctyltinbis(isooctylthioglycolate) are shown in Figure 6. The absorbance ratio (/1740;→) of this compound was 0.46. This compound had a much stronger mercapto odor than that of Example 1.

Comparative Example ■ 1114 KN flasks equipped with a stirrer, temperature needle, and cooling tube The same thioglycol soap 2-ethylhexyl 412i (2.01 mol) as in Example 2 was charged and stirred, and then dioctyltin ocypoid 361 (1 mol) was added. In addition, the temperature was raised to 70°C, and the distillate was treated under reduced pressure (15MH) or less to eliminate any distillate, and then the temperature was raised to 98°C.
When there are no more by-products distilled under the conditions of 0MH7, always
The mixture was returned to pressure, cooled to 70°C, and passed through the mouth.

Figure 4 shows the infrared absorption spectrum of the obtained dioctyltin bis(2-ethylhexylthioglycolate) measured with an infrared spectrophotometer. From Figure 4, the absorbance ratio (156
0txn7174DcIL-') was 0.6. It should be noted that the mercapto odor was stronger compared to this Example (1) and Example (2).

Example 2 In Example I, thioglycolic acid isooctyl ester 408.9 (2 mol) was synthesized from 612 J (3 mol) and dioctyltin oxide 361# (1 mol) was synthesized from monobutyltin high ctyl thioglycolate. The compound had almost no odor.The absorbance ratio (1560α) according to the infrared absorption spectrum of this compound was
71740tx −1) was 0.001.

Application Example: Vinyl chloride resin Lp = 700) 100 parts of violet, stearin #11 part, and stabilizer 21 part of each Example and each Comparative Example were used to prepare each formulation f'F-, and its odor was investigated. . Thereafter, each formulation was subjected to rotational speeds of 21 and 19 r, plm,
A sheet was obtained by kneading for 5 minutes at a temperature of 170° C. using two 6-inch rolls with a roll interval of 0.5 m, and this sheet had a thickness of 2JIjI.

After pressing for 5 minutes at a press temperature of 180° C., a total pressure of 200 Kg, and a temperature of 180° C. using a metal wire having a width of 15 CIL and a length of 20 cm, the sheet was cooled to room temperature to obtain a °C pressed sheet. We compared and examined their transparency. The results are shown in the table.

The odor of the combination of symbols in the table is as follows: ○: Almost no mercapto odor - 1X: Very strong mercapto odor to 9 Resist sheet gateposts 0: Transparency is as good as transparent glass □ ×: Transparency bad

[Brief explanation of drawings]

◆The figure is an infrared absorption spectrum diagram of each → compound of Example 1 and ■ and Comparative Example 1 and ■ below. 1. ．． 1 Figure-1 = Example 1 Figure-2 °・ Figure-6: Comparative inversion □ □ Figure-4: 〃 ■ Agent Patent attorney Katsutoshi Takahashi

Claims (1)

[Claims] 1s(Cut)ncOOR (where R is 6 to 18 carbon atoms
is an alkyl group, alkenyl group, or tercoxoalkyl group, and n is an integer of 1 or 2. ) is heat-treated at a reduced pressure such that compound i does not distill out, or nitrous gas is introduced to remove the low-boiling point compounds so that the compound does not pass away, and then 1111 11] 1 R' ( However, R' is an alkyl group having 1' to 8 carbon atoms.)
Selected from 1.11 Halogen-containing - oil-use tin mercaptocarbon - which is characterized by adding at least two electrodes and removing the resulting water under conditions of 60° C. or lower and 100 aa + H7 or lower. Mether salt pregnancy stabilizer packaging method.