CN1064686C - PVC resin preparing process using mixture of methyl tin and thiolate as thermal stabilizer - Google Patents
PVC resin preparing process using mixture of methyl tin and thiolate as thermal stabilizer Download PDFInfo
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- CN1064686C CN1064686C CN 95106159 CN95106159A CN1064686C CN 1064686 C CN1064686 C CN 1064686C CN 95106159 CN95106159 CN 95106159 CN 95106159 A CN95106159 A CN 95106159A CN 1064686 C CN1064686 C CN 1064686C
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Abstract
The present invention relates to a method for esterifying methyl tin mercaptan as a polyvinyl chloride (PVC) heat stabilizer. The present invention has the method that the purification and the esterification of raw materials are merged to be completed by one step, a midbody is dissolved by a solvent and is filtrated to remove impurities, sulfhydryl ester is added, and lye is dripped to carry out esterification reaction. Post treatment is carried out on reacting substances, and colorless oily liquid products are obtained.
Description
The present invention relates to the chemical industry technology, be specifically related to a kind of preparation polyvinyl chloride (PVC) thermo-stabilizer methyl tin thiol ester preparation process of mixture.
At present, organo-tin compound is used in polyvinyl chloride resin early has patent report as thermo-stabilizer, as United States Patent (USP) 3222317,3396185 etc., mainly is that the cost of butyl tin and tin octylate etc. is higher, and in addition because of propyl group tin scent of, and ethyl tin is poisonous and be substituted.
The methyl tin mercapto alcohol ester of the seventies U.S. MORTON company exploitation, its commodity are called AOVATABT TM-181FS, it is the efficient stable agent of a kind of PVC of being widely used in and PVC copolymer resin, AOVATABT TM-181FS has multifrequency nature, it and PVC and other auxiliary agents have good consistency, can improve the transparency of goods, can be used for blow molding, under the lower situation of consumption, also has good heat-resisting and light stability, improved processing stability man-hour adding, and improve and improved initial painted, the methyl tin thiol ester stabilizer is when PVC powder batch mixing, can reduce melt viscosity, increase mobile, consumption is between 0.1-0.5% (weight), methyl tin thiol ester stabilizer processing characteristics, be applicable to strict PVC processing, single screw rod or twin-screw extrusion, injection moulding, blowing, working methods such as calendering, and the methyl tin thiol ester stabilizer that is used for PVC is divided into three classes by tin content: coventional type (tin content 16-18% (weight)), high-content type (tin content is 23-25% (weight)) and low levels type (tin content is 7-8% (weight)), wherein the coventional type effect is ideal.
Toxicity problem about the methyl tin thiol ester stabilizer, according to Barnes and Stoner data report, and the tin methide dichloride is done intravenous injection to rabbit, its toxicity is littler than other dialkyl tin dichloride, carry out oral toxicity and the test of skin eye irritation with the methyl tin thiol ester stabilizer, oral toxicity (LD50) is littler than dibutyl tin two (isooctyl mercaptoacetate) toxicity, belongs to low toxicity.
The preparation method of methyl tin thiol ester, the seventies just has the patent report, as United States Patent (USP) 3810868,3887519 etc., its method is that raw material midbody isooctyl mercaptoacetate, water, sodium bicarbonate, heptane (solvent) are added in the reactor, drips tin methide dichloride solution and reacts, the reaction output object is through aftertreatment, obtain product, this method more complicated is though add a large amount of solvents, but raw material can not get purifying, and quality product is undesirable.
Another kind method is to be that the reaction of raw material and isooctyl mercaptoacetate makes stablizer with the tin methide oxide compound, though method is simpler than above-mentioned synthetic method, but raw material midbody tin methide oxide compound costs an arm and a leg, its production process is complicated, to just can obtain through a few step reactions, improve production cost.
The oxide compound reaction formula:
The objective of the invention is to, intermediate purification and one step of esterification are carried out, this method is specially adapted to synthesize the measured product of matter under the intermediate situation off quality, and the product purity that makes is higher, and yield can reach more than 98%.
The objective of the invention is to be achieved through the following technical solutions, raw material midbody (comprising intermediate off quality) methyl tin chloride is dissolved in the trichloromethane and dissolves, solution removes by filter impurity and catalyzer, and filtrate adds thiol esters, dripping alkali liquid, the concentration of dripping alkali liquid is in 5-30% (weight), optimum concn is 15%, and temperature of reaction 10-60 ℃, optimum temps is 20-25 ℃, reaction times 1-5 hour, Best Times 2 hours.
Stablizer of the present invention comprises following structural: (1) compound 65-95% (weight)
(2) compound 5-35% (weight) CH
3-Sn-S (CH
2)
nCOOR]
3(c) compound is no more than 0.6%
Here R represents C
1-20 hydrocarbon, n are 1 to 3 integers.
The positively effect that stablizer of the present invention produced is: methyl tin thiol ester (TM-118) and dibutyl tin two (isooctyl mercaptoacetate) (TM-180) carry out the performance comparison test, its as a result TM-118 show good processing stability.Key is that the inventive method is that technology is fairly simple, has overcome the problem that exists in the past, has improved the quality and the yield of product, has reduced production cost.
The technology of the present invention content and application are described in detail as follows by following most preferred embodiment:
The preparation example 1 of methyl tin thiol ester: reaction formula
Taking by weighing 100 gram intermediate (tin methide dichloride and methyl trichloride) mixtures is added in the 500ml there-necked flask, add the 200ml trichloromethane again, stirring is warmed up to 50-55 ℃ dissolves intermediate fully, insulation removes by filter insoluble impurity, filtrate adds thiol esters 178 grams and mixes, simultaneously temperature is reduced to 20-25 ℃, dripping alkali liquid (3 gram sodium hydroxide add the alkali lye that 200ml water is mixed with concentration 15%) dripped about 40-50 minute, standing demix is removed water layer, organic layer with the 200ml water washing once, leave standstill and removed water layer in 20 minutes, organic layer carries out vacuum distilling at 100 ℃, filters to obtain 232 gram colorless oil products, yield reaches 98% (weight), tin content 19.5% (weight), refractive index 1.5108 (25 ℃), proportion 1.17 (25 ℃).Example 2: reaction formula
204 gram (1.0 mol) isooctyl mercaptoacetates and 82 gram (0.5 mol) tin methide oxide compounds are added in the there-necked flask, heat to 100 ℃, under this temperature, keep reaction 1 hour, the reaction solution standing demix is removed water layer, organic layer washes with water, and product is the distillation dehydration drying under vacuum, obtains transparent oily liquid product 251.1 grams (yield 99%).
The product analysis result
At part by weight, tin content 20.3%, sulphur content 11.6%, refractive index (25 ℃) 1.5110, proportion (25 ℃) is 1.15.Example 3 reaction formula:
Taking by weighing 100 gram intermediate (tin methide dichloride and methyl tin trichloride) mixtures is added in the 500ml there-necked flask, add the 200ml trichloromethane again, stirring is warmed up to 50-55 ℃ dissolves intermediate fully, insulation removes by filter insoluble impurity, adding different monooctyl ester 214 grams of thiohydracrylic acid in the filtrate mixes, simultaneously temperature is reduced to 20-25 ℃, dripping alkali liquid (35 gram sodium hydroxide, add water 200ml and be mixed with 15% alkali lye) dripped about 40-50 minute, standing demix is removed water layer, and organic layer with the 200ml water washing once leaves standstill and removed water layer in 20 minutes, organic layer filters and obtains 242 gram colorless transparent oil liquid (yield 98%) 100 ℃ of vacuum distillings
The product analysis result:
Tin content: 20.1% (weight), sulphur content: 10.9% (weight), refractive index are (25 ℃) 1.5106.Example 4
Stabilizer T M-118 and TM-180 performance comparison test prescription:
100 parts of PVC
0.5 part of calcium stearate
Stablizer adds in accordance with regulations
Time (in minute)
Umber 0 15 30 45 60 75 90TM-180 1.0 144446 9TM-118 1.0 122235 8TM-118 0.8 122359 10
Even TM-118 is under the lower situation of consumption as seen from the above table, its initial coloration is also outstanding than TM-180.
The processing stability test
Prescription:
100 parts of PVC
0.5 part of calcium stearate
Stablizer sees Table stablizer umber fusion time peak torque minimal torque steady time
(minute) (minute) low amount TM-180 0.40 2.1 2,750 3.6 1900
Amount TM-180 0.60 3.7 2,400 6.0 1575 among the TM-118 0.36 1.9 3,433 5.7 1700
TM-118 0.53 1.6 3,920 6.7 1715 low amount TM-180 0.80 1.4 3,200 8.5 1600
TM-118 0．72 1．3 3840 8．8 1600
As seen from the above table, aspect the colour stability of the processing stability and the course of processing, all obviously surpass TM-180, also like this when consumption is low.No matter TM-118 is at twin-screw extrusion, and still single screw rod extrusion molding is even at its few 20% o'clock of amount ratio TM-180, all show good processing properties.
Annotate: TM-180-dibutyl tin two (isooctyl mercaptoacetate)
TM-118-product methyl tin thiol ester of the present invention.
Claims (5)
1, a kind of methyl tin thiol ester preparation process of mixture, it is characterized in that: the raw material methyl tin chloride is dissolved with trichloromethane, remove by filter impurity, add thiol esters, dropping concentration is that the alkali lye of 5%～30% weight makes pH value between 6.5-7, wherein, reaction times 1-5 hour, temperature of reaction 10-60 ℃, its reactant was through aftertreatment, building-up process be feedstock purification and esterification be combined into one the step finish, yield reaches 98%.
2, according to the described methyl tin thiol ester preparation process of mixture of claim 1, it is characterized in that: described mixture comprises following structural formula: (a) structural formula: by 65-95% (weight)
(b) structural formula: by 5-35% (weight) CH
3-Sn-[S (CH
2) nCOOR]
3(c) structural formula: be no more than 0.6% (weight)
R in (a) and (b), (c) structural formula is alkyl-cycloalkyl or the phenyl that contains 1 to 20 carbon atom, and n is 1 to 3 a integer in the formula.
3, according to claim 1 or 2 described methyl tin thiol ester preparation process of mixture, it is characterized in that: the R in above-mentioned (a) and (b), (c) structural formula is alkyl-cycloalkyl or phenyl, and this stablizer Lethal Dose 50 LD50 is not less than 1000.
4, according to claim 1 or 3 described methyl tin thiol ester preparation method of mixture, it is characterized in that: the R in the above-mentioned chemical structural formula is the alkyl of 4 to 12 carbon atoms, and n is 1 to 2 integer.
5, according to the described methyl tin thiol ester preparation method of mixture of claim 1, it is characterized in that, said mixture contains compound (a) structural formula 71-81% (weight), and (b) the formula compound is no more than 29-19% (weight), and (c) the formula compound is no more than 0.6% (weight).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95106159 CN1064686C (en) | 1995-05-27 | 1995-05-27 | PVC resin preparing process using mixture of methyl tin and thiolate as thermal stabilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 95106159 CN1064686C (en) | 1995-05-27 | 1995-05-27 | PVC resin preparing process using mixture of methyl tin and thiolate as thermal stabilizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1137048A CN1137048A (en) | 1996-12-04 |
| CN1064686C true CN1064686C (en) | 2001-04-18 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 95106159 Expired - Fee Related CN1064686C (en) | 1995-05-27 | 1995-05-27 | PVC resin preparing process using mixture of methyl tin and thiolate as thermal stabilizer |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100503716C (en) * | 2004-08-20 | 2009-06-24 | 江从宇 | Preparation process of thermal stabilizer of tin methyl thio hydroacetate tin isooctoate for PVC |
| CN101402651B (en) * | 2008-11-20 | 2011-11-23 | 杭州盛创实业有限公司 | Method for preparing methyl tin thiol ester heat stabilizer |
| CN106243146B (en) * | 2016-07-28 | 2018-02-23 | 邹平县星宇塑料助剂有限公司 | Two oleic acid mercaptoethyl alcohol ester dimethoxycarbonyl ethyl tin compounds and preparation method thereof |
| CN107033183B (en) * | 2017-05-08 | 2019-04-12 | 南通艾德旺化工有限公司 | The preparation process and its product of Methyl stannum mercaptide, application |
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1995
- 1995-05-27 CN CN 95106159 patent/CN1064686C/en not_active Expired - Fee Related
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