CN102516290A - Method for preparing mixture of methyl tin chloride - Google Patents
Method for preparing mixture of methyl tin chloride Download PDFInfo
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- CN102516290A CN102516290A CN2011103935322A CN201110393532A CN102516290A CN 102516290 A CN102516290 A CN 102516290A CN 2011103935322 A CN2011103935322 A CN 2011103935322A CN 201110393532 A CN201110393532 A CN 201110393532A CN 102516290 A CN102516290 A CN 102516290A
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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 the fine chemistry industry production field, relate to a kind of preparation method of methyl chloride tin mixture, utilize the monomethyl tin trichloride content in the methyl chloride tin mixture that this preparation method obtains high.
Background technology
The organic tin compound uses the history in existing 6 or seven years as the PVC stabilizer for plastics; Described the production and the use of butyl tin, tin octylate thermo-stabilizer among american documentation literature US3222317, the US3396185, american documentation literature US3810868, US3887519, US4129584 etc. have introduced the production technique and the use case of thiol methyl tin.Through nearly 30 years development; Thiol methyl tin becomes the main product of organotin stabilizer industry gradually; Now general thiol methyl tin is the mixture of DMDS alcohol tin and monomethyl three tin mercaptides, and wherein, the shared ratio of 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 is found gradually; Improve the ratio of monomethyl three tin mercaptides; Help improving the steady speed of 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 the thiol methyl tin, common way is, at the preceding step midbody of producing thiol methyl tin---when " methyl chloride tin ", improve the ratio of monomethyl tin trichloride in the methyl chloride tin mixture.The present invention has studied a kind of preparation method of methyl chloride tin mixture just to this demand, and wherein, in the methyl chloride tin mixture that utilizes this preparation method to obtain, the shared ratio of monomethyl tin trichloride can be up to more than 90%.
The reaction formula of preparation methyl chloride tin mixture is following:
Sn+CH
3CL→(CH
3)
2SnCL
2
(CH
3)
2SnCL
2+SnCL
4→CH
3SnCL
3
Can find out that from above-mentioned reaction formula the preparation of methyl chloride tin mixture will be through two step chemical reactions, the much more external two-step approachs that adopt, promptly two step chemical reactions carry out in two reaction vessels respectively, and are of american documentation literature US4269782 etc.And the domestic one kettle way that adopts, promptly two step chemical reactions progressively carry out in same reaction vessel, and are of Chinese patent document CN101318974A, CN102079755A. more
In two-step approach; Can cause loss of material when shifting dimethyltin chloride; And in its step-down process, must have a large amount of methyl chloride tin vaporizers to get into follow-up water absorption system, will make that so a certain amount of highly toxic substance---" trimethyltin chloride " gets into the water absorption system.Its reason is in the first step reaction of two-step approach, to certainly exist the disproportionation reaction of dimethyltin chloride; Promptly; The 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 carrying out the material transfer when the first step reaction end, trimethyltin chloride evaporates the entry absorption system of going forward side by side at first.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, often in the first step, inject a certain amount of tin tetrachloride in the industry simultaneously, to restrain the generation of trimethyltin chloride.
When adopting one kettle way to produce dimethyltin chloride content greater than 70% methyl chloride tin mixture; Temperature of reaction between 130～220 ℃, reaction pressure is between 0.3～1.5MPa; Effect is fine; Inject the rapid and dimethyltin chloride reaction of tin tetrachloride of reaction vessel, generate the monomethyl tin trichloride.Because in reaction system, the concentration of dimethyltin chloride is far above the monomethyl tin trichloride, so reaction preference is obvious, the second step chemical reaction is easy to carry out.But; When needs are produced the very high product of monomethyl tin trichloride content, must continue to inject tin tetrachloride, along with the concentration of the monomethyl tin trichloride in the reaction system raises; Second step was reacted the more and more difficult that becomes; At this moment two side reactions possibly take place, and one is that tin tetrachloride decomposes, and its reaction formula is: SnCL4 → SnCL2+CL2.Another is when having trace water in the reaction system, and tin tetrachloride and glass putty reaction generate tindichloride, and its reaction formula is: SnCL4+Sn → SnCL2; And; Under above-mentioned temperature of reaction, the tindichloride of generation can form a skim at glass putty or tin sheet surface, stops glass putty and methyl chloride to continue reaction; Can at the bottom of reaction vessel, generate a large amount of waste residues like this; And these waste residues can't continue to use, thereby greatly reduce the transformation efficiency of raw material tin, have increased production cost.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of methyl chloride tin mixture, it can overcome the above-mentioned defective that exists in the prior art.
For this reason, the present invention improves on the production technique of the midbody of the thiol methyl tin of routine, and improving one's methods all is from the improving and optimizating of actual production, to sum up.
Preparing method according to methyl chloride tin mixture of the present invention may further comprise the steps:
A) in reaction vessel, add tin and as the dimethyl sulphide or the tetramethyl-ammonia chloride of catalyzer;
B) with the air in the methyl chloride replacement(metathesis)reaction container;
C) sealed reaction vessel;
D) reaction vessel is heated, when the temperature in the reaction vessel reaches 180 ℃, in reaction vessel, inject methyl chloride, when the pressure in the reaction vessel reaches 2.5MPa, stop to inject methyl chloride; When the temperature in the reaction vessel reaches 250 ℃, the temperature in the reaction vessel is remained between 250～280 ℃;
E) in reaction vessel, inject tin tetrachloride subsequently, when the ratio of the molar weight of the tin tetrachloride in the reaction vessel and the molar weight of tin greater than 0.9 the time, stop to inject tin tetrachloride, and make the airtight insulation of reaction vessel, to react one hour;
F) material in the reaction vessel is transferred to distil container;
G) be that 130～160 ℃, pressure are under the state of 6～10KPa the material in the distil container to be distilled in temperature, water absorbs material steam and obtains the aqueous solution of methyl chloride tin mixture, and the temperature of this aqueous solution is controlled at below 25 ℃.
Take above-mentioned preparation method, improved the temperature of reaction of reaction vessel aborning, when temperature of reaction reached more than 250 ℃, tin and tindichloride were liquid state, and tindichloride can not form the film of the reaction that intercepts tin and methyl chloride again.
In addition, the monomethyl tin trichloride is compared with dimethyltin chloride, and under temperature higher (it is generally acknowledged more than 40 ℃) and vacuum tightness condition with higher, the former tends to decompose, that is, the monomethyl tin trichloride might resolve into tindichloride and methyl chloride.If tindichloride gets into the aqueous solution, then can be unfavorable for the subsequent production of thiol methyl tin, cause product gonorrhoea to occur.The present invention distills the temperature and pressure of absorption through control to methyl chloride tin, thereby has solved this problem effectively.
Preferably, in reaction vessel, high speed agitator be can be provided with,, its thorough mixing and reaction made so that the material in the reaction vessel is stirred.More than 250 ℃ the time, 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, can effectively improve the transformation efficiency of tin, has reduced the generation of waste residue in the reaction vessel.
Preferably, in step e), in reaction vessel, inject before the tin tetrachloride, nitrogen injection in reaction vessel earlier is to fill the upper space in the reaction vessel.
Preferably, the airtight insulation reaction of reaction vessel when the material in the reaction vessel is transferred to distil container, can stay a part of material after one hour in reaction vessel, with as next time the reaction solvent.
Beneficial effect of the present invention is, utilizes the monomethyl tin trichloride content in the methyl chloride tin mixture that this preparation method obtains high, and this preparation method reduced the waste residue amount in the building-up reactions effectively, improved the transformation efficiency of raw material tin; Simultaneously, through control, reduced the decomposition of monomethyl tin trichloride effectively to distillatory temperature, pressure and absorption water temperature.
Embodiment
Below in conjunction with embodiment the present invention is further described, but these embodiment do not constitute qualification of the present 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 or the dimethyl sulphide 8g of catalyzer, feed the last layer of air in the methyl chloride replacement(metathesis)reaction container; Then, sealed reaction vessel starts heating unit and high speed agitator; When the temperature in the reaction vessel reaches 180 ℃, inject methyl chloride from the bottom of reaction vessel, glass putty and methyl chloride begin reaction; When the pressure in the reaction vessel reaches 2.5MPa, stop to inject methyl chloride, when the temperature in the reaction vessel reaches 250 ℃; Regulate heating unit, so that the temperature in the reaction vessel remains between 250～280 ℃.In reaction vessel, inject a certain amount of nitrogen,, then begin to inject tin tetrachloride, after having injected the 3400g tin tetrachloride, stop to inject tin tetrachloride, make the airtight insulation reaction of reaction vessel one hour subsequently to fill the upper space in the reaction vessel.Reaction is transferred to distil container with material after finishing.
In temperature is that 130～160 ℃, pressure are under the state of 6～10KPa the material in the distil container to be distilled; Water with 6500g absorbs material steam; The temperature of the aqueous solution that is produced is controlled at below 25 ℃, thereby obtains the aqueous solution of methyl chloride tin mixture.
Through detecting, the content of methyl chloride tin mixture in the aqueous solution is 49.9%, and the content of monomethyl tin trichloride in the methyl chloride tin mixture 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 or the dimethyl sulphide 1.5kg of catalyzer, feed the last layer of air in the methyl chloride replacement(metathesis)reaction container; Then, sealed reaction vessel starts heating unit and high speed agitator; When the temperature in the reaction vessel reaches 180 ℃, inject methyl chloride from the bottom of reaction vessel, glass putty and methyl chloride begin reaction; When the pressure in the reaction vessel reaches 2.5MPa, stop to inject methyl chloride, when the temperature in the reaction vessel reaches 250 ℃; Regulate heating unit, so that the temperature in the reaction vessel remains between 250～280 ℃.In reaction vessel, inject a certain amount of nitrogen,, then begin to inject tin tetrachloride, when having injected the 275kg tin tetrachloride, stop to inject tin tetrachloride, made the reaction vessel insulation reaction subsequently one hour to fill the upper space in the said reaction vessel.Reaction is transferred to distil container with material after finishing.
In temperature is that 130～160 ℃, pressure are under the state of 6～10KPa the material in the distil container to be distilled; Absorb material steam with 600kg water; The temperature of the aqueous solution that is produced is controlled at below 25 ℃, thereby obtains the aqueous solution of methyl chloride tin mixture.
Through detecting, the content of methyl chloride tin mixture in the aqueous solution is 48.03%, and the content of monomethyl tin trichloride in the methyl chloride tin mixture is 91.4%.
Aforesaid embodiment and advantage only are exemplary, and can not be regarded as limitation of the present invention.The description of this paper is intended to example, rather than the scope of restriction claim.For a person skilled in the art, multiple alternative, remodeling and modification all are conspicuous.The characteristic of exemplary embodiment described herein, method and other characteristic can make up in many ways, thus that obtain other and/or interchangeable exemplary embodiment.
Because under the situation that does not deviate from characteristic of the present invention; Can embody characteristic of the present invention in a variety of forms, be not limited to any details of above description so should also be understood that the foregoing description; Only if indicate in addition; Be in the accompanying claims restricted portion and should broadly be interpreted as, therefore, fall into the scope of claim and the interior all modifications of equivalents of boundary or this scope and boundary and all should contain for accompanying claims with remodeling.
Claims (4)
1. the preparation method of a methyl chloride tin mixture, said preparation method may further comprise the steps:
A) in reaction vessel, add tin and as the dimethyl sulphide or the tetramethyl-ammonia chloride of catalyzer;
B) replace the air in the said reaction vessel with methyl chloride;
C) seal said reaction vessel;
D) said reaction vessel is heated, when the temperature in the said reaction vessel reaches 180 ℃, in said reaction vessel, inject methyl chloride, when the pressure in the said reaction vessel reaches 2.5MPa, stop to inject methyl chloride; When the temperature in the said reaction vessel reaches 250 ℃, the temperature in the said reaction vessel is remained between 250～280 ℃;
E) in said reaction vessel, inject tin tetrachloride subsequently, when the ratio of the molar weight of the tin tetrachloride in the said reaction vessel and the molar weight of tin greater than 0.9 the time, stop to inject tin tetrachloride, and make the airtight insulation of said reaction vessel, to react one hour;
F) reaction was transferred to distil container with the material in the said reaction vessel after one hour;
G) be that 130～160 ℃, pressure are under the state of 6～10KPa the material in the said distil container to be distilled in temperature, water absorbs the steam of material and obtains the aqueous solution of methyl chloride tin mixture, and the temperature of this aqueous solution is controlled at below 25 ℃.
2. preparation method according to claim 1 is characterized in that, is provided with high speed agitator in the said reaction vessel, in step d) and step e), starts said high speed agitator, so that the material in the said reaction vessel is stirred.
3. preparation method according to claim 1 is characterized in that, in step e), in said reaction vessel, injects before the tin tetrachloride, and elder generation's nitrogen injection in said reaction vessel is to fill the upper space in the said reaction vessel.
4. preparation method according to claim 1 is characterized in that, in step f), in said reaction vessel, stays a part of material, with as next time the reaction solvent.
Priority Applications (1)
| 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 true CN102516290A (en) | 2012-06-27 |
| CN102516290B CN102516290B (en) | 2015-04-08 |
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Cited By (1)
| 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 |
|---|
| 许爱东 等: "PVC-U管材用热稳定剂--甲基锡巯基乙酸异辛酯的研制", 《化学建材》 * |
| 阮文响: "甲基硫醇锡的生产合成工艺", 《塑料助剂》 * |
Cited By (1)
| 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 |
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| CN102516290B (en) | 2015-04-08 |
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| C53 | Correction of patent of invention or patent application | ||
| CB03 | Change of inventor or designer information |
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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Granted publication date: 20150408 Termination date: 20201122 |