CN102516290B - Method for preparing mixture of methyl tin chloride - Google Patents
Method for preparing mixture of methyl tin chloride Download PDFInfo
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- CN102516290B CN102516290B CN201110393532.2A CN201110393532A CN102516290B CN 102516290 B CN102516290 B CN 102516290B CN 201110393532 A CN201110393532 A CN 201110393532A CN 102516290 B CN102516290 B CN 102516290B
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Abstract
The invention discloses a method for preparing a mixture of methyl tin chloride, which comprises the following steps of: heating tin and catalyst in a reaction vessel; injecting chloromethane when the temperature in the reaction vessel reaches 180 DEG C; keeping temperature between 250 and 280 DEG C when the temperature in the reaction vessel reaches 250 DEG C; and then injecting stannic chloride; stopping injecting the stannic chloride when the ratio of the molar weight of the stannic chloride to the molar weight of the tin is more than 0.9; sealing the reaction vessel, keeping the temperature, and reacting for one hour; transferring the materials in the reaction vessel into a distilling container; distilling the materials in the reaction vessel under the state of 130-160 DEG C temperature and 6-10 KPa pressure; and absorbing the material steam by water, thereby obtaining an aqueous solution of the mixture of methyl tin chloride, wherein the content of methyl trichlorosilane is high. According to the method provided by the invention, the waste residues in the synthetic reaction are efficiently reduced, the conversion rate of raw material tin is increased, and meanwhile, the decomposition of the methyl trichlorosilane is efficiently reduced.
Description
Technical field
The invention belongs to fine chemistry industry production field, relate to a kind of preparation method of mixture of methyl tin chloride, the monomethyl tin trichloride content in the mixture of methyl tin chloride utilizing this preparation method to obtain is high.
Background technology
Organic tin compound uses the history of existing 6 or seven years as PVC plastic stablizer, describe butyl tin, the production of tin octylate thermo-stabilizer and use in american documentation literature US3222317, US3396185, american documentation literature US3810868, US3887519, US4129584 etc. describe production technique and the use case of thiol methyl tin.Through the development of nearly 30 years, thiol methyl tin becomes the main product of organotin stabilizer industry gradually, now general thiol methyl tin is the mixture of Methyl disulfide alcohol tin and monomethyl three tin mercaptides, and wherein, the ratio shared by monomethyl three tin mercaptides is 20 ~ 30%.
Along with continuing to optimize of device of plastic processing, the complete processing of high-level efficiency, high extruded velocity continues to bring out, and industry finds gradually, improve the ratio of monomethyl three tin mercaptides, be conducive to the steady speed improving thiol methyl tin, in the complete processing of high extruded velocity, stabilising effect is fine.In order to improve the ratio of monomethyl three tin mercaptides in thiol methyl tin, common way is, before production thiol methyl tin, walk intermediate---time " methyl chloride tin ", improve the ratio of monomethyl tin trichloride in mixture of methyl tin chloride.The present invention, just for this demand, have studied a kind of preparation method of mixture of methyl tin chloride, and wherein, in the mixture of methyl tin chloride utilizing this preparation method to obtain, the ratio shared by monomethyl tin trichloride can up to more than 90%.
The chemical equation preparing mixture of methyl tin chloride is as follows:
Sn+CH
3CL→(CH
3)
2SnCL
2
(CH
3)
2SnCL
2+SnCL
4→CH
3SnCL
3
As can be seen from above-mentioned reaction formula, the preparation of mixture of methyl tin chloride through two step chemical reactions, will adopt two-step approach abroad more, and namely two step chemical reactions carry out respectively in two reaction vessels, as described in american documentation literature US4269782 etc.And domesticly adopt one kettle way more, namely two step chemical reactions progressively carry out in same reaction vessel, as described in Chinese patent literature CN101318974A, CN102079755A.
In two-step approach, loss of material can be caused during transfer dimethyltin chloride, and a large amount of methyl chloride tin vaporizers must be had in its pressure reduction to enter follow-up water absorption system, and a certain amount of highly toxic substance will be made like this---" trimethyltin chloride " enters water absorption system.Its reason is, in the first step reaction of two-step approach, certainly exist the disproportionation reaction of dimethyltin chloride, namely, sub-fraction dimethyltin chloride can be converted into monomethyl tin trichloride and trimethyltin chloride, and the molten boiling point of trimethyltin chloride is all lower than the molten boiling point of monomethyl tin trichloride and dimethyltin chloride, so can conclude, when the first step reaction terminates and carries out material transfer, trimethyltin chloride evaporates at first and enters water absorption system.If the trimethyltin chloride in the aqueous solution exceeds standard, this is that subsequent production methyl tin stabilizer institute is unacceptable.In order to address this problem, industrially often inject a certain amount of tin tetrachloride in a first step, to restrain the generation of trimethyltin chloride simultaneously.
One kettle way is adopted to produce dimethyltin chloride content when being greater than the mixture of methyl tin chloride of 70%, temperature of reaction between 130 ~ 220 DEG C, reaction pressure is between 0.3 ~ 1.5MPa, effect is fine, the tin tetrachloride injecting reaction vessel rapidly and dimethyltin chloride reaction, generation monomethyl tin trichloride.Due in reaction system, the concentration of dimethyltin chloride is far above monomethyl tin trichloride, so reaction preference is obvious, second step chemical reaction is easy to carry out.But, when the product needing production monomethyl tin trichloride content very high, must continue to inject tin tetrachloride, along with the concentration of the monomethyl tin trichloride in reaction system raises, second step reaction becomes more and more difficult, at this moment two side reactions may occur, and one is that tin tetrachloride decomposes, and its reaction formula is: SnCL4 → SnCL2+CL2.Another is when there is trace water in reaction system, and tin tetrachloride and glass putty react and generate tindichloride, and its reaction formula is: SnCL4+Sn → SnCL2; And, under above-mentioned temperature of reaction, the tindichloride generated can form a skim at glass putty or tin sheet surface, glass putty and methyl chloride is stoped to continue to react, such meeting generates a large amount of waste residue at the bottom of reaction vessel, and these waste residues cannot continue to use, thus greatly reduce the transformation efficiency of raw material tin, add production cost.
Summary of the invention
The object of the invention is to the preparation method proposing a kind of mixture of methyl tin chloride, it can overcome the above-mentioned defect existed in prior art.
For this reason, the present invention improves in the production technique of the intermediate of the thiol methyl tin of routine, and improving one's methods is all improve and optimizate middle summary from actual production.
According to the preparation method of mixture of methyl tin chloride of the present invention, comprise the following steps:
A) in reaction vessel, tin is added and as the dimethyl sulphide of catalyzer or tetramethyl-ammonia chloride;
B) with the air in methyl chloride replacement(metathesis)reaction container;
C) sealed reaction vessel;
D) reaction vessel is heated, when the temperature in reaction vessel reaches 180 DEG C, in reaction vessel, inject methyl chloride, when the pressure in reaction vessel reaches 2.5MPa, stop injecting methyl chloride; When the temperature in reaction vessel reaches 250 DEG C, the temperature in reaction vessel is made to remain between 250 ~ 280 DEG C;
E) inject tin tetrachloride subsequently in reaction vessel, when the molar weight of the tin tetrachloride in reaction vessel is greater than 0.9 with the ratio of the molar weight of tin, stops injecting tin tetrachloride, and make reaction vessel sealed thermal insulating, to react one hour;
F) material in reaction vessel is transferred to distil container;
G) temperature be 130 ~ 160 DEG C, pressure be 6 ~ 10KPa state under the material in distil container is distilled, absorb material steam with water and obtain the aqueous solution of mixture of methyl tin chloride, and the temperature of this aqueous solution is controlled below 25 DEG C.
Take above-mentioned preparation method, improve the temperature of reaction of reaction vessel aborning, when temperature of reaction reaches more than 250 DEG C, tin and tindichloride are liquid state, and tindichloride can not form the film of the reaction intercepting tin and methyl chloride again.
In addition, monomethyl tin trichloride compared with dimethyltin chloride, in temperature higher (it is generally acknowledged more than 40 DEG C) and vacuum tightness is higher, the former tends to decompose, that is, monomethyl tin trichloride likely resolves into tindichloride and methyl chloride.If tindichloride enters the aqueous solution, then can be unfavorable for the subsequent production of thiol methyl tin, cause product to occur gonorrhoea.The present invention by controlling to carry out distilling the temperature and pressure absorbed to methyl chloride tin, thus efficiently solves this problem.
Preferably, can high speed agitator be provided with in reaction vessel, to stir the material in reaction vessel, make it fully mix and react.Time more than 250 DEG C, raw material tin liquefy tin and be sunken to the bottom of reaction vessel, if at this moment adopt high speed agitator to carry out high-speed stirring, effectively can improve the transformation efficiency of tin, decrease the generation of waste residue in reaction vessel.
Preferably, in step e) in, inject tin tetrachloride in reaction vessel before, can first to nitrogen injection in reaction vessel, to fill the upper space in reaction vessel.
Preferably, after reaction vessel sealed thermal insulating reacts one hour, when the material in reaction vessel is transferred to distil container, a part of material can be left in reaction vessel, using as the solvent reacted next time.
Beneficial effect of the present invention is, the monomethyl tin trichloride content in the mixture of methyl tin chloride utilizing this preparation method to obtain is high, and this preparation method effectively reduces the waste residue amount in building-up reactions, improves the transformation efficiency of raw material tin; Meanwhile, by the control of the temperature to distillation, pressure and absorption water temperature, the decomposition of monomethyl tin trichloride is significantly reduced.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but these embodiments do not form limitation of the invention.
Embodiment 1
In the 10L stainless steel pressure-resistant reaction vessel that high speed agitator is housed, add metallic tin powder 1800g, as the tetramethyl-ammonia chloride of catalyzer or dimethyl sulphide 8g, pass into the upper layer of air in methyl chloride replacement(metathesis)reaction container; Then, sealed reaction vessel, start heating unit and high speed agitator, when the temperature in reaction vessel reaches 180 DEG C, inject methyl chloride from the bottom of reaction vessel, glass putty and methyl chloride start to react, when the pressure in reaction vessel reaches 2.5MPa, stop injecting methyl chloride, when the temperature in reaction vessel reaches 250 DEG C, regulate heating unit, remain between 250 ~ 280 DEG C to make the temperature in reaction vessel.In reaction vessel, inject a certain amount of nitrogen, to fill the upper space in reaction vessel, then start to inject tin tetrachloride, after being filled with 3400g tin tetrachloride, stopping injecting tin tetrachloride, make reaction vessel sealed thermal insulating react one hour subsequently.After reaction terminates, material is transferred to distil container.
Temperature be 130 ~ 160 DEG C, pressure be 6 ~ 10KPa state under the material in distil container is distilled, material steam is absorbed with the water of 6500g, the temperature of the aqueous solution produced controls below 25 DEG C, thus obtains the aqueous solution of mixture of methyl tin chloride.
Through detecting, mixture of methyl tin chloride content is in aqueous 49.9%, and the content of monomethyl tin trichloride in mixture of methyl tin chloride is 94.2%.
Embodiment 2
In the 800L stainless steel pressure-resistant reaction vessel that high speed agitator is housed, add metallic tin powder 150kg, as the tetramethyl-ammonia chloride of catalyzer or dimethyl sulphide 1.5kg, pass into the upper layer of air in methyl chloride replacement(metathesis)reaction container; Then, sealed reaction vessel, start heating unit and high speed agitator, when the temperature in reaction vessel reaches 180 DEG C, inject methyl chloride from the bottom of reaction vessel, glass putty and methyl chloride start to react, when the pressure in reaction vessel reaches 2.5MPa, stop injecting methyl chloride, when the temperature in reaction vessel reaches 250 DEG C, regulate heating unit, remain between 250 ~ 280 DEG C to make the temperature in reaction vessel.In reaction vessel, inject a certain amount of nitrogen, to fill the upper space in described reaction vessel, then start to inject tin tetrachloride, when being filled with 275kg tin tetrachloride, stopping injecting tin tetrachloride, making reaction vessel insulation reaction subsequently one hour.After reaction terminates, material is transferred to distil container.
Temperature be 130 ~ 160 DEG C, pressure be 6 ~ 10KPa state under the material in distil container is distilled, material steam is absorbed with 600kg water, the temperature of the aqueous solution produced controls below 25 DEG C, thus obtains the aqueous solution of mixture of methyl tin chloride.
Through detecting, mixture of methyl tin chloride content is in aqueous 48.03%, and the content of monomethyl tin trichloride in mixture of methyl tin chloride is 91.4%.
Aforesaid embodiment and advantage are only exemplary, and can not be considered as limitation of the present invention.Description is herein intended to example, instead of the scope of restriction claim.For a person skilled in the art, multiple alternative, remodeling and amendment are all apparent.The feature of exemplary embodiment described herein, method and other characteristic can combine in many ways, thus obtain other and/or interchangeable exemplary embodiment.
Due to when not deviating from characteristic of the present invention, feature of the present invention can be embodied in a variety of forms, so it should also be understood that, above-described embodiment is not limited to any details described above, unless otherwise noted, and should broadly be interpreted as being in the scope of claims restriction, therefore, fall into all modifications in the scope of claim and the equivalents of boundary or this scope and boundary and retrofit and all should contain for claims.
Claims (4)
1. a preparation method for mixture of methyl tin chloride, described preparation method comprises the following steps:
A) in reaction vessel, tin is added and as the dimethyl sulphide of catalyzer or tetramethyl-ammonia chloride;
B) air in described reaction vessel is replaced with methyl chloride;
C) described reaction vessel is sealed;
D) described reaction vessel is heated, when the temperature in described reaction vessel reaches 180 DEG C, in described reaction vessel, inject methyl chloride, when the pressure in described reaction vessel reaches 2.5MPa, stop injecting methyl chloride; When the temperature in described reaction vessel reaches 250 DEG C, the temperature in described reaction vessel is made to remain between 250 ~ 280 DEG C;
E) inject tin tetrachloride subsequently in described reaction vessel, when the molar weight of the tin tetrachloride in described reaction vessel is greater than 0.9 with the ratio of the molar weight of tin, stops injecting tin tetrachloride, and make described reaction vessel sealed thermal insulating, to react one hour;
F) react after one hour, the material in described reaction vessel is transferred to distil container;
G) temperature be 130 ~ 160 DEG C, pressure be 6 ~ 10KPa state under the material in described distil container is distilled, obtain the aqueous solution of mixture of methyl tin chloride with the steam of water absorption material, and the temperature of this aqueous solution is controlled below 25 DEG C.
2. preparation method according to claim 1, is characterized in that, is provided with high speed agitator, in steps d in described reaction vessel) and step e) in, start described high speed agitator, to stir the material in described reaction vessel.
3. preparation method according to claim 1, is characterized in that, in step e) in, inject tin tetrachloride in described reaction vessel before, first to nitrogen injection in described reaction vessel, to fill the upper space in described reaction vessel.
4. preparation method according to claim 1, is characterized in that, in step f) in, in described reaction vessel, leave a part of material, using as the solvent reacted next time.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110393532.2A CN102516290B (en) | 2011-11-22 | 2011-11-22 | Method for preparing mixture of methyl tin chloride |
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|---|---|---|---|
| CN201110393532.2A CN102516290B (en) | 2011-11-22 | 2011-11-22 | Method for preparing mixture of methyl tin chloride |
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| CN102516290A CN102516290A (en) | 2012-06-27 |
| CN102516290B true CN102516290B (en) | 2015-04-08 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4658046A (en) * | 1985-07-08 | 1987-04-14 | Zemex Corporation | Process for the preparation of methyltin chlorides |
| CN1270961A (en) * | 1999-04-19 | 2000-10-25 | 张麟 | Preparation of tin methyl mercaptide |
| CN102079755A (en) * | 2010-11-29 | 2011-06-01 | 杭州天道实业有限公司 | Preparation method of methyl tin heat stabilizer |
-
2011
- 2011-11-22 CN CN201110393532.2A patent/CN102516290B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4658046A (en) * | 1985-07-08 | 1987-04-14 | Zemex Corporation | Process for the preparation of methyltin chlorides |
| CN1270961A (en) * | 1999-04-19 | 2000-10-25 | 张麟 | Preparation of tin methyl mercaptide |
| CN102079755A (en) * | 2010-11-29 | 2011-06-01 | 杭州天道实业有限公司 | Preparation method of methyl tin heat stabilizer |
Non-Patent Citations (2)
| Title |
|---|
| PVC-U管材用热稳定剂--甲基锡巯基乙酸异辛酯的研制;许爱东 等;《化学建材》;19980815(第4期);第34-36页 * |
| 甲基硫醇锡的生产合成工艺;阮文响;《塑料助剂》;20011015(第5期);第11-12页 * |
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Inventor after: Li Jianfeng Inventor after: Han Yonghe Inventor after: Li Jian Inventor after: Wang You Inventor after: Wang Aihong Inventor after: Long Shoukui Inventor after: Zhong Xinle Inventor after: Gao Yong Inventor before: Li Jianfeng Inventor before: Li Jian Inventor before: Wang You Inventor before: Wang Aihong Inventor before: Long Shoukui Inventor before: Zhong Xinle Inventor before: Gao Yong |
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Free format text: CORRECT: INVENTOR; FROM: LI JIANFENG LI JIAN WANG YOU WANG AIHONG LONG SHOUKUI ZHONG XINLE GAO YONG TO: LI JIANFENG HAN YONGHE LI JIAN WANG YOU WANG AIHONG LONG SHOUKUI ZHONG XINLE GAO YONG |
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