CN100503716C - Preparation process of thermal stabilizer of tin methyl thio hydroacetate tin isooctoate for PVC - Google Patents
Preparation process of thermal stabilizer of tin methyl thio hydroacetate tin isooctoate for PVC Download PDFInfo
- Publication number
- CN100503716C CN100503716C CNB2004100607720A CN200410060772A CN100503716C CN 100503716 C CN100503716 C CN 100503716C CN B2004100607720 A CNB2004100607720 A CN B2004100607720A CN 200410060772 A CN200410060772 A CN 200410060772A CN 100503716 C CN100503716 C CN 100503716C
- Authority
- CN
- China
- Prior art keywords
- tin
- preparation
- ethyl hexyl
- chloride
- thermo
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a method of preparing PVC heat stabilizer methyl tin-mercapto 2-ethyl hexyl ethanoate-based tin, adding methyl tin chloride to equimolar mercapto 2-ethyl hexyl ethanoate, reacting for 1-6 hours at 0 deg.C-50 deg.C, then during mixing at a speed of 60-300 rpm, adding in organic alkali 0.02%-0.1% and inorganic alkali 10%-30% to react for 0.5-1 hour at 0 deg.C-50 deg.C, and filtering to obtain the product. It has simple process low energy source consumption, and needs no solvent and after-treatment.
Description
Technical field
The present invention relates to the preparation method of a kind of PVC with thermo-stabilizer methyl mercapto 2-ethyl hexyl ethanoate base tin.
Background technology
Methyl mercapto 2-ethyl hexyl ethanoate base tin (mixture of monomethyl tri-thiol 2-ethyl hexyl ethanoate base tin and dimethyl dimercapto 2-ethyl hexyl ethanoate base tin) be a kind of application very extensively and the PVC plastic heat stabilizer of excellent property, the synthetic method that prior art provides, as Chinese patent CN1117495A, CN1137048A, normally adopt raw material isooctyl mercaptoacetate, water, sodium bicarbonate, solvent are added in the reactor, react at the aqueous solution that drips methyl tin chloride, reactant obtains product through strict aftertreatment behind the removal low-boiling-point substance.Make technological process and condition more complicated in this way, also will add a large amount of solvents, reclaim solvent, need the investment solvent recovery unit, increased production cost of products.The latest domestic report is to adopt the direct reaction method as Chinese patent CN1439670A at present, though this method has overcome above-mentioned disadvantage, but its desired processing unit condition is relative with energy consumption higher, under the really degree of wearing and temperature condition of this method, the raw material isooctyl mercaptoacetate also has loss to a certain degree.If its used former roasting mesosome methyl tin chloride carries out purification processes without certain method, the product of gained has certain color and smell, can not really reach the purpose of improving the quality of products.
Summary of the invention
Purpose of the present invention is exactly that a kind of PVC will be provided the preparation method with thermo-stabilizer methyl mercapto 2-ethyl hexyl ethanoate base tin, and it adopts simple production technique, need not complicated product aftertreatment and other intermediate reaction process, has improved product yield.
The object of the present invention is achieved like this: a kind of PVC preparation method of thermo-stabilizer methyl mercapto 2-ethyl hexyl ethanoate base tin, it is that the methyl tin chloride is added in the isooctyl mercaptoacetate of equimolar amount, being 0 ℃-50 ℃ in temperature reacted 1-6 hour down, then under agitation condition, mixing speed is 60-300 rev/min, add the ethylamine of 0.02%-0.1% or the mineral alkali of methylamine and 10%-30%, be 0 ℃-50 ℃ in temperature and reacted 0.5-1 hour down, filter and obtain product.Described methyl tin chloride is pure product, or the crude product of industrial preparation.The methyl tin chloride crude product of described industrial preparation without purification in vacuum tightness is-0.092MPa---under the condition of 0.08MPa, add thermal distillation with 120 ℃-150 ℃ temperature, overhead product directly absorbs with the isooctyl mercaptoacetate of equimolar amount.Described methyl tin chloride is the monomethyl tin trichloride, or is dimethyltin chloride, or is the mixture of monomethyl tin trichloride and dimethyltin chloride.In the mixture of described monomethyl tin trichloride and dimethyltin chloride, monomethyl tin trichloride proportion is 10%-50%.Described mineral alkali is any in yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, lime carbonate, Calcium hydrogen carbonate, sodium hydroxide, potassium hydroxide, the calcium hydroxide, or wantonly two kinds mixture.
Optimum process condition of the present invention is: purification vacuum tightness is-0.085MPa, and distillation temperature is 125 ℃-130 ℃, and the absorption reaction temperature is 35 ℃-40 ℃, and ethylamine or methylamine consumption are 0.05%, and mineral alkali adds by the equivalent that generates hydrochloric acid.
Advantage of the present invention is: simplified production technique, need not complicated product aftertreatment and other intermediate reaction process, improved product yield, yield is more than 99%; Low to the production unit requirement, need not the high-air-tightness requirement of high vacuum unit and equipment, shortened the reaction times, reduced energy consumption effectively, reduced manufacturing cost; The raw material midbody of having purified has been removed the influence to quality product of the impurity that produces in the intermediate building-up process effectively, and the foreign matter content of the finished product is no more than 0.3%.
Embodiment
A kind of PVC preparation method of thermo-stabilizer methyl mercapto 2-ethyl hexyl ethanoate base tin, it is that the methyl tin chloride is added in the isooctyl mercaptoacetate of equimolar amount, being 0 ℃-50 ℃ in temperature reacted 1-6 hour down, then under agitation condition, mixing speed is 60-300 rev/min, add the ethylamine of 0.02%-0.1% or the mineral alkali of methylamine and 10%-30%, be 0 ℃-50 ℃ in temperature and reacted 0.5-1 hour down, filter and obtain product.Described methyl tin chloride is pure product, or the crude product of industrial preparation.The methyl tin chloride crude product of described industrial preparation is without purification, in vacuum tightness be-0.092MPa--condition of 0.08MPa under, add thermal distillation with 120 ℃-150 ℃ temperature, overhead product directly absorbs with the isooctyl mercaptoacetate of equimolar amount.Described methyl tin chloride is the monomethyl tin trichloride, or is dimethyltin chloride, or is the mixture of monomethyl tin trichloride and dimethyltin chloride.In the mixture of described and dimethyltin chloride, monomethyl tin trichloride proportion is 10%-50%.Described mineral alkali is any in yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, lime carbonate, Calcium hydrogen carbonate, sodium hydroxide, potassium hydroxide, the calcium hydroxide, or wantonly two kinds mixture.
Embodiment 1:
The mixture (dimethyltin chloride: monomethyl tin trichloride=80:20) change in the 500ml matrass of 250 gram methyl tin chlorides, and be connected with the 2000ml reaction flask that induction stirring is housed with airway, in reaction flask, add 450 gram isooctyl mercaptoacetates and 0.2 gram triethylamine, reaction flask and vacuum pump link, open vacuum pump and induction stirring and heat matrass and begin intermediate purification absorption, keep the absorption liquid temperature between 35 ℃-40 ℃ with water-bath, when reaction flask weight is increased to 220 grams-223 grams, stopping distillation purifying, remove water distilling apparatus, change magnetic agitation into powerful the stirring, and the powdery yellow soda ash that adding 120 restrains in reaction flask several times in 1 hour, adding the alkali reaction temperature is 35 ℃-40 ℃, adding the alkali back that finishes continue to stir 1 hour, filter, get colourless transparent oil liquid product 666.5 grams, yield is 99.2%.
Reaction formula is as follows:
(CH
3)
2SnCl
2+2HSCH
2COOC
8H
17→(CH
3)
2Sn(SCH
2COOC
8H
17)
2+2HCl
CH
3SnCl
3+3HSCH
2COOC
8H
17→CH
3Sn(SCH
2COOC
8H
17)
3+3HCl
The product analysis result:
Tin content: 19.24%, sulphur content: 11.71%, refractive index (25 ℃): 1.508, proportion (25 ℃): 1.171.
Embodiment 2:
In the powerful 2000ml reaction flask that stirs is housed, add 450 gram isooctyl mercaptoacetates and 0.2 gram triethylamine, start and stir and maintain the temperature between 35 ℃-40 ℃, the mixture of the methyl tin chloride that adding 223 grams have been purified (dimethyltin chloride: the monomethyl tin trichloride=80:20), after treating that institute adds intermediate and dissolves fully, the powdery yellow soda ash that in 1 hour, in reaction flask, adds 120 grams several times, adding the alkali reaction temperature is 40 ℃-45 ℃, adding the alkali back that finishes continue to stir 0.5 hour, filter, get colourless transparent oil liquid product 668.0 grams, yield is 99.2%.
Reaction as follows:
(CH
3)
2SnCl
2+2HSCH
2COOC
8H
17→(CH
3)
2Sn(SCH
2COOC
8H
17)
2+2HCl
CH
3SnCl
3+3HSCH
2COOC
8H
17→CH
3Sn(SCH
2COOC
8H
17)
3+3HCl
The product analysis result:
Tin content: 19.45%, sulphur content: 11.58%, refractive index (25 ℃): 1.509, proportion (25 ℃): 1.174.
Embodiment 3: thermo-stabilizer performance comparison test
Prescription: 100 parts of poly-hydrogen ethene
2 parts of the different monooctyl esters of phthalic acid
5 parts of anti-buffering improving agents
Organotin adds in accordance with regulations
Operation: setting double roller plastic-making device roller temperature is 165 ℃, after treating that intensification is stable, adding just mixed material on roll gap top plasticates, it is even to observe the material color and luster, do not show card nailing neps on the cross section, smooth surface and when certain intensity is arranged, the roll-in end of processing is got the square print base of one-inch rapidly, and filling of flat board machine press bolster is heated to 180 ℃, set suitable pressure, the print that cuts is placed between the stainless steel template, puts into the press bed central position, start press, in the mold closing pressurization after about 10 minutes of mould and die preheating slab, about 30 minutes of heat-insulation pressure keeping, pressure relief when being cooled to about 80 ℃ of mould temperature is taken out mould and demoulding deburring and is got the PVC goods.
Using the same method, produce the PVC print of organotin (code name ss-218) each is some for the PVC print of producing this experiment gained organotin and Hubei Southern Star chemical general factory, print is put into air dry oven, the temperature inside the box is set at 180 ℃, observes print color and record every sampling in 10 minutes.(seeing Table 1)
Table 1:
Even under the lower situation of consumption, its initial coloring has certain advantage than home brands organotin ss-218 by the visible present method gained methyl mercapto 2-ethyl hexyl ethanoate base tin of last table 1.
Claims (6)
1, a kind of PVC preparation method of thermo-stabilizer methyl mercapto 2-ethyl hexyl ethanoate base tin, it is characterized in that: the methyl tin chloride is added in the isooctyl mercaptoacetate of equimolar amount, being 0 ℃-50 ℃ in temperature reacted 1-6 hour down, then under agitation condition, mixing speed is 60-300 rev/min, add the ethylamine of 0.02%-0.1% or the mineral alkali of methylamine and 10%-30%, be 0 ℃-50 ℃ in temperature and reacted 0.5-1 hour down, filter and obtain product.
2, a kind of PVC according to claim 1 preparation method of thermo-stabilizer methyl mercapto 2-ethyl hexyl ethanoate base tin, it is characterized in that: described methyl tin chloride is pure product, or the crude product of industrial preparation.
3, a kind of PVC according to claim 2 preparation method of thermo-stabilizer methyl mercapto 2-ethyl hexyl ethanoate base tin, it is characterized in that: the methyl tin chloride crude product of described industrial preparation is without purification, in vacuum tightness be-0.092MPa---under the condition of 0.08MPa, temperature with 120 ℃-150 ℃ adds thermal distillation, and overhead product directly absorbs with the isooctyl mercaptoacetate of equimolar amount.
4, a kind of PVC according to claim 1 preparation method of thermo-stabilizer methyl mercapto 2-ethyl hexyl ethanoate base tin, it is characterized in that: described methyl tin chloride is the monomethyl tin trichloride, or be dimethyltin chloride, or be the mixture of monomethyl tin trichloride and dimethyltin chloride.
5, a kind of PVC according to claim 4 preparation method of thermo-stabilizer methyl mercapto 2-ethyl hexyl ethanoate base tin, it is characterized in that: in the mixture of described monomethyl tin trichloride and dimethyltin chloride, monomethyl tin trichloride proportion is 10%-50%.
6, a kind of PVC according to claim 1 preparation method of thermo-stabilizer methyl mercapto 2-ethyl hexyl ethanoate base tin, it is characterized in that: described mineral alkali is any in yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, lime carbonate, Calcium hydrogen carbonate, sodium hydroxide, potassium hydroxide, the calcium hydroxide, or wantonly two kinds mixture.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100607720A CN100503716C (en) | 2004-08-20 | 2004-08-20 | Preparation process of thermal stabilizer of tin methyl thio hydroacetate tin isooctoate for PVC |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100607720A CN100503716C (en) | 2004-08-20 | 2004-08-20 | Preparation process of thermal stabilizer of tin methyl thio hydroacetate tin isooctoate for PVC |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1597764A CN1597764A (en) | 2005-03-23 |
| CN100503716C true CN100503716C (en) | 2009-06-24 |
Family
ID=34666332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100607720A Expired - Fee Related CN100503716C (en) | 2004-08-20 | 2004-08-20 | Preparation process of thermal stabilizer of tin methyl thio hydroacetate tin isooctoate for PVC |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100503716C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101768184B (en) * | 2010-01-29 | 2012-08-29 | 湖北犇星化工有限责任公司 | Coordination methyl tin mercaptide compound, preparation method and application thereof |
| CN102061010A (en) * | 2010-11-29 | 2011-05-18 | 杭州天道实业有限公司 | Tin methyl heat stabilizer |
| CN106243147A (en) * | 2016-07-28 | 2016-12-21 | 邹平县星宇塑料助剂有限公司 | Methyl mercaptan tin compound and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4104292A (en) * | 1976-11-02 | 1978-08-01 | M&T Chemicals Inc. | Method for preparing organotin compounds |
| US4496490A (en) * | 1973-03-22 | 1985-01-29 | M&T Chemicals Inc. | Non-toxic organotin stabilizers for vinyl chloride polymers |
| CN1088930A (en) * | 1993-10-12 | 1994-07-06 | 泰安市精细化工总厂 | Stable organotin compound and its production and application |
| CN1117495A (en) * | 1994-08-24 | 1996-02-28 | 深圳泛胜塑胶助剂有限公司 | Tin methide Stabilizer, the prepn. thereof |
| CN1137048A (en) * | 1995-05-27 | 1996-12-04 | 深圳泛胜塑胶助剂有限公司 | PVC resin preparing process using mixture of methyl tin and thiolate as thermal stabilizer |
| CN1270961A (en) * | 1999-04-19 | 2000-10-25 | 张麟 | Preparation of tin methyl mercaptide |
| WO2002042370A2 (en) * | 2000-11-27 | 2002-05-30 | Akzo Nobel N.V. | Carboxylate-containing alkyltin heat stabilizer |
-
2004
- 2004-08-20 CN CNB2004100607720A patent/CN100503716C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4496490A (en) * | 1973-03-22 | 1985-01-29 | M&T Chemicals Inc. | Non-toxic organotin stabilizers for vinyl chloride polymers |
| US4104292A (en) * | 1976-11-02 | 1978-08-01 | M&T Chemicals Inc. | Method for preparing organotin compounds |
| CN1088930A (en) * | 1993-10-12 | 1994-07-06 | 泰安市精细化工总厂 | Stable organotin compound and its production and application |
| CN1117495A (en) * | 1994-08-24 | 1996-02-28 | 深圳泛胜塑胶助剂有限公司 | Tin methide Stabilizer, the prepn. thereof |
| CN1137048A (en) * | 1995-05-27 | 1996-12-04 | 深圳泛胜塑胶助剂有限公司 | PVC resin preparing process using mixture of methyl tin and thiolate as thermal stabilizer |
| CN1270961A (en) * | 1999-04-19 | 2000-10-25 | 张麟 | Preparation of tin methyl mercaptide |
| WO2002042370A2 (en) * | 2000-11-27 | 2002-05-30 | Akzo Nobel N.V. | Carboxylate-containing alkyltin heat stabilizer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1597764A (en) | 2005-03-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100475809C (en) | Method for synthesizing 1,3-propane sultone | |
| CN101434970A (en) | Double decomposition precipitation transformation production method of potassium citrate | |
| CN101284772B (en) | Synthetic method of D-(+)-2-chloro-propanoyl chloride | |
| CN102633689A (en) | Method for preparing taurine by adopting sulfonation of ammonium sulfite | |
| CN104817588A (en) | Preparation method of ethyl chloride | |
| CN100503716C (en) | Preparation process of thermal stabilizer of tin methyl thio hydroacetate tin isooctoate for PVC | |
| CN103113197B (en) | Method for comprehensively utilizing trichlorosucrose production waste gas | |
| CN105085303A (en) | Quaternary ammonium salt compound, preparation method therefor and use thereof as catalyst in acyl chloride preparation | |
| CN106397353A (en) | A preparing method of a rubber vulcanization accelerator 2-mercaptobenzothiazole | |
| CN106350870B (en) | A kind for the treatment of and use method of sulfuric acid waste | |
| CN101704746B (en) | Method for synthesizing levo formyl mandelic acid chloride | |
| CN104529779A (en) | Synthesis method of D-dibenzoyl tartaric acid | |
| CN104496820A (en) | Preparation method of light stabilizer 2, 4-di-tert-butylphenyl 3, 5-di-tert-butyl-4-hydroxybenzoate | |
| CN102863402A (en) | Preparation method of accelerator CBS | |
| CN102627668A (en) | Preparation method of triphenylphosphine | |
| WO2013076969A1 (en) | METHOD FOR PRODUCING β-MERCAPTOCARBOXYLIC ACID | |
| CN102250136A (en) | Preparation method of methyltin mercaptide | |
| CN1113887C (en) | Preparation of tin methyl mercaptide | |
| CN102303879B (en) | Method for preparing magnesium hydroxide by utilizing light calcined dolomite | |
| CN110117234B (en) | Synthesis method of N-fatty acyl glutamic acid alkali metal salt | |
| CN103880635A (en) | Preparation method of modified zinc stearate | |
| CN106883259A (en) | A kind of preparation method of oleic acid methyl tin | |
| CN111793082A (en) | Preparation method of methyl tin neodecanoate | |
| CN1166453A (en) | Combiend production process of potassium carbonate and light magnesium carbonate | |
| CN106892849A (en) | A kind of preparation method of lauric acid methyl tin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090624 |