CN101838283B - Production method of high-purity dimethyltin dichloride crystal - Google Patents
Production method of high-purity dimethyltin dichloride crystal Download PDFInfo
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- CN101838283B CN101838283B CN2009101566190A CN200910156619A CN101838283B CN 101838283 B CN101838283 B CN 101838283B CN 2009101566190 A CN2009101566190 A CN 2009101566190A CN 200910156619 A CN200910156619 A CN 200910156619A CN 101838283 B CN101838283 B CN 101838283B
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Abstract
The invention relaters to a production method of a high-purity dimethyltin dichloride crystal, belonging to the technical field of production methods of chemical products. The method comprises following steps of: (1) putting a chlorinated methyltin mixture as the raw material in a distilling still, distilling at the temperature of 120-150 DEG C and after being vacuumized to 300-600 mmHg, and distilling over light constituents to be collected for later use; and (2) rectifying when continuously heating the distilling still to 140-190 DEG C and making the vacuum control to 75-300 mmHg, and receiving effluence when the content of dimethyltin dichloride is larger than 98 percent so as to obtain the high-purity dimethyltin dichloride finished production. The production method has simple processing steps; and the dimethyltin dichloride prepared by the method has high purity and safe use and is an ideal raw material for producing catalyst, drier and organic synthesis catalyst and the like of high-performance coating glass, polyurethane plastics, polyurethane coating and organic silicon rubber.
Description
Technical field
The invention belongs to the working method technical field of Chemicals, be specially the working method of high-purity dimethyltin dichloride crystal.
Background technology
Dimethyltin chloride molecular formula: C
2H
6CI
2Sn, structural formula: (CH
3)
2SnCI
2, be a kind of chemical that is used for glass coating and synthetic catalyst field.Chinese patent CN92109309.8 and CN99105326.5 have all reported the method for a kind of PVC of preparation thermo-stabilizer midbody dimethyltin chloride and methyl tin trichloride mixture; Be to make in pressure reactor by tin, tin tetrachloride, solvent, catalyzer, methyl chloride to be used for dimethyltin chloride and the methyl tin trichloride mixture that thiol methyl tin is produced; Though control the proportionlity of dimethyltin chloride and methyl tin trichloride and eliminate the stronger trimethyltin chloride of toxicity with the method that adds tin tetrachloride in the report; But the tin tetrachloride and the trimethyltin chloride of inevitable remained unreacted; The purity of dimethyltin chloride is less than 80%, and quality can not satisfy the needs of glass coating and synthetic catalyst.
Summary of the invention
To the problems referred to above that exist in the prior art; The objective of the invention is to design the technical scheme that a kind of high-purity dimethyltin dichloride crystal working method is provided; Adopt the method for rectifying to make high-purity dimethyltin dichloride crystal; The product purity that makes is high, and quality satisfies the needs of glass coating and synthetic catalyst.
The working method of described high-purity dimethyltin dichloride crystal is characterized in that by following method preparation:
1) method of employing rectifying; The methyl chloride tin mixture that will contain 7-37% monomethyl tin trichloride, 62-92% dimethyltin chloride, 0.1-0.5% trimethylammonium monochlor(in)ate tin, 0.2-0.8% tin tetrachloride and small amount of solid impurity is put in the still kettle as raw material; 120-150 ℃, be evacuated under the 300-600mmHg condition and distill; Steam light constituent monomethyl tin trichloride, trimethylammonium monochlor(in)ate tin and a spot of dimethyltin chloride, and collect the light constituent storage tank, subsequent use;
2) still kettle is continued to be warming up to 140-190 ℃, vacuum control is carried out rectifying at 75-300mmHg; The dimethyltin chloride content of sample examination elute is greater than 98% o'clock, elute switched to the product Receiving bin do not steam till logistics goes out to having, and what make steams in the thing dimethyltin chloride content greater than 98%; Monomethyl tin trichloride content is less than 1.8%; Trimethylammonium monochlor(in)ate tin content is less than 0.2%, and tin tetrachloride content is high purity dimethyl tindichloride finished product less than 0.1%.
The working method of described high-purity dimethyltin dichloride crystal is characterized in that the light constituent distillation temperature is controlled at 125-145 ℃ in the step 1), and vacuum tightness is 350-550mmHg.
The working method of described high-purity dimethyltin dichloride crystal is characterized in that the light constituent distillation temperature is controlled at 130-140 ℃ in the step 1); Vacuum tightness is 400-450mmHg.
The working method of described high-purity dimethyltin dichloride crystal is characterized in that step 2) in rectification temperature be controlled at 150-180 ℃, vacuum tightness is 100-250mmHg.
The working method of described high-purity dimethyltin dichloride crystal is characterized in that step 2) in rectification temperature be controlled at 160-170 ℃, vacuum tightness is 150-200mmHg.
The working method of described high-purity dimethyltin dichloride crystal; The working method that it is characterized in that methyl chloride tin mixture raw material in the step 1) is: in withstand voltage reaction kettle, add dimethyltin chloride, metallic tin grain and tetramethyl ammonium chloride catalyzer; The add-on of metallic tin grain is 0.4-0.6 a times of dimethyltin chloride weight; Catalyst consumption is 0.005-0.015 a times of dimethyltin chloride weight; Be warming up to 190-200 ℃ and feed the chloromethylation that methyl chloride gas is carried out tin, temperature of reaction is 190-230 ℃, pressure 0.8-1.2Mpa; Treat to add when methyl chloride no longer reacts anhydrous stannic chloride; The add-on of anhydrous stannic chloride is 1/15-7/15 a times of metallic tin grain weight, and temperature of reaction is 190-210 ℃, sample examination; Finish less than reaction in 0.5% o'clock to trimethylammonium monochlor(in)ate tin content, promptly get the methyl chloride tin mixture of the methyl chloride tin mixture that contains 7-37% monomethyl tin trichloride, 62-92% dimethyltin chloride, 0.1-0.5% trimethylammonium monochlor(in)ate tin, 0.2-0.8% tin tetrachloride and small amount of solid impurity.
The working method of described high-purity dimethyltin dichloride crystal; It is characterized in that the light constituent that steams in the step 1) puts in the withstand voltage reaction kettle; The tin tetrachloride of adding and trimethylammonium monochlor(in)ate tin, dimethyltin chloride mole number sum 70-90% carries out disproportionation reaction under 190-210 ℃; Reaction times is 2-6 hour; After disproportionation reaction finishes this material is carried out underpressure distillation under temperature 120-150 ℃, vacuum tightness 75-600mmHg condition, overhead product is monomethyl tin trichloride content greater than 90% methyl chloride tin.
The working method of described high-purity dimethyltin dichloride crystal is characterized in that treating adding when methyl chloride no longer reacts anhydrous stannic chloride, and the add-on of anhydrous stannic chloride is 3/15-6/15 a times of metallic tin grain weight, and temperature of reaction is 195-200 ℃.
The working method of described high-purity dimethyltin dichloride crystal; The consumption that it is characterized in that tin tetrachloride is trimethylammonium monochlor(in)ate tin, dimethyltin chloride mole number sum 75-80%; The temperature of disproportionation reaction is 195-200 ℃, and the reaction times is 3-4 hour.
The working method of described high-purity dimethyltin dichloride crystal, the reaction conditions that it is characterized in that underpressure distillation are temperature 130-145 ℃, vacuum tightness 90-500mmHg.
The working method of described high-purity dimethyltin dichloride crystal, the reaction conditions that it is characterized in that underpressure distillation are temperature 135-140 ℃, vacuum tightness 150-300mmHg.
Aforementioned production method as raw materials for production, adopt the method for rectifying to prepare high-purity dimethyltin dichloride crystal, and coproduction monomethyl tin trichloride content is higher than 90% methyl chloride tin with the methyl chloride tin mixture.
At first under catalyst action, carry out the chloromethylation of tin with methyl chloride through tin, reaction conditions is temperature 190-230 ℃, pressure 0.8-1.2Mpa, and reaction formula is:
Sn+CH3CI→(CH
3)
xSnCI
(4-x)(x＝1、2、3)
Catalyzer is elected tetramethyl ammonium chloride as; Reactant is the mixture of monomethyl tin trichloride, dimethyltin chloride, trimethylammonium monochlor(in)ate tin; For eliminating the bigger trimethylammonium monochlor(in)ate tin of toxicity, need to add tin tetrachloride and carry out disproportionation reaction, the disproportionation reaction condition is 200 ± 10 ℃; Reaction times 2-6 hour, the reaction formula that trimethylammonium monochlor(in)ate tin and tin tetrachloride carry out disproportionation reaction was:
(CH
3)
3SnCI+SnCI
4＝(CH3)
2SnCI
2+(CH
3)SnCI
3
Contain monomethyl tin trichloride 7-37%, dimethyltin chloride 62-92%, trimethylammonium monochlor(in)ate tin 0.1-0.5%, tin tetrachloride 0.2-0.8% and small amount of solid impurity in the reaction product, contain tin protoxide, White tin oxide, oxychlorination tin and organic carbide in the solid impurity.
In the aforementioned production method, the light constituent of collecting can be used to prepare monomethyl tin trichloride content greater than 90% methyl chloride tin, and the reaction formula that dimethyltin chloride and tin tetrachloride carry out disproportionation reaction is:
(CH
3)
2SnCI
2+SnCI
4＝2(CH3)SnCI
3
Monomethyl tin trichloride content is the main raw material of preparation mercaptan monomethyl tin heat stabilizer greater than 90% methyl chloride tin, and mercaptan monomethyl tin is the splendid PVC thermo-stabilizer of tint permanence in early stage.
In the present patent application, unless otherwise indicated, the content that relates to is weight percentage.
This working method; Process step is simple, and in the high purity dimethyl tindichloride finished product that makes, dimethyltin chloride content is greater than 98%; Monomethyl tin trichloride content is less than 1.8%; Trimethylammonium monochlor(in)ate tin content is less than 0.2%, and tin tetrachloride content is less than 0.1%, and product purity is high and safe in utilization; Be the desirable feedstock of producing high-performance coating glass and producing the fields such as catalyzer, siccative and organic catalyst compound of urethane plastic, polyurethane coating, organo-silicone rubber, quality satisfies the needs of glass coating and organic catalyst compound.
Embodiment
Below through specific embodiment the present invention is described further.
Embodiment 1:
With withstand voltage reaction kettle with nitrogen replacement to oxygen level less than 0.5%, add 300kg dimethyltin chloride (, recycling) as reaction media; Add 150kg metallic tin grain, 3.0kg tetramethyl ammonium chloride catalyzer; Begin when being warming up to 190 ℃ to feed the chloromethylation that methyl chloride gas is carried out tin, carry out attemperation and pressure through the input speed of control methyl chloride in the reaction process, temperature is controlled at 190-230 ℃; Pressure 0.8-1.2Mpa; When treating that methyl chloride no longer reacts, add the 20kg anhydrous stannic chloride, 200 ℃ are reacted to trimethylammonium monochlor(in)ate tin content and finished less than 0.5% o'clock; Promptly get methyl chloride tin mixture 291.6kg, contain 12.6% monomethyl tin trichloride, 86.5% dimethyltin chloride, 0.3% trimethylammonium monochlor(in)ate tin, 0.3% tin tetrachloride, 0.3% other component in this mixture.
And then above-mentioned methyl chloride tin mixture 300kg put in the still kettle, still kettle is warming up to 135 ℃, vacuum 300mmHg carries out light constituent and deviates from, and light constituent weight is 58kg, collects the light constituent storage tank, and is subsequent use; Still kettle is continued to be warming up to 145 ℃; Vacuum is increased to 150mmHg, carries out dimethyltin chloride rectifying, and the dimethyltin chloride content of waiting to steam thing was greater than 98% o'clock; Elute is switched to the product Receiving bin; Product weight is 240kg, and dimethyltin chloride content is 98.53%, and once through yield is 92.5%.
Table one: different tin tetrachloride consumption product change of component situation embodiment data sheet
Table two: differing temps and vacuum tightness influence the embodiment data sheet to quality and once through yield
| Sequence number | Light constituent is deviate from condition | The dimethyltin chloride purification condition | Light constituent is deviate from amount (kg) | Dimethyltin chloride output (kg) | Dimethyltin chloride content (%) | Dimethyltin chloride once through yield (%) |
| 1 | Temperature: 120 ℃, vacuum: 600mmHg | Temperature: 140 ℃, vacuum: 300mmHg | 10 | 80 | 70.8 | 26.67 |
| 2 | Temperature: 120 ℃, vacuum: 450mmHg | Temperature: 140 ℃, vacuum: 150mmHg | 15 | 169 | 88.2 | 56.33 |
| 3 | Temperature: 120 ℃, vacuum: 300mmHg | Temperature: 140 ℃, vacuum: 75mmHg | 22 | 245 | 93.6 | 81.67 |
| 4 | Temperature: 135 ℃, vacuum: 600mmHg | Temperature: 150 ℃, vacuum: 300mmHg | 18 | 58 | 65.2 | 19.33 |
| 5 | Temperature: 135 ℃, vacuum: 450mmHg | Temperature: 150 ℃, vacuum: 150mmHg | 35 | 235 | 96.5 | 78.33 |
| 6 | Temperature: 135 ℃, vacuum: 300mmHg | Temperature: 150 ℃, vacuum: 75mmHg | 58 | 240 | 98.5 | 80.00 |
| 7 | Temperature: 150 ℃, vacuum: 600mmHg | Temperature: 170 ℃, vacuum: 300mmHg | 32 | 215 | 93.2 | 71.67 |
| 8 | Temperature: 150 ℃, vacuum: 450mmHg | Temperature: 170 ℃, vacuum: 150mmHg | 45 | 250 | 97.8 | 83.33 |
| 9 | Temperature: 150 ℃, vacuum: 300mmHg | Temperature: 170 ℃, vacuum: 75mmHg | 66 | 229 | 98.8 | 76.33 |
Table two data show, reach more than 98% for guaranteeing dimethyltin chloride content, when proposing front-end volatiles, approximately need the dimethyltin chloride distillation with about 10% to get into light constituent.
Embodiment 2:
Other is with embodiment 1; The light constituent of embodiment 1 is taken by weighing 300kg to be put in the withstand voltage reaction kettle; Wherein: monomethyl tin trichloride content is 63.87%, dimethyltin chloride content is 35.38%, trimethylammonium monochlor(in)ate tin content is 0.75%; Drop into the 100kg anhydrous stannic chloride, temperature control 180-200 ℃ was carried out disproportionation reaction 3 hours, and trimethylammonium monochlor(in)ate tin in the light constituent and part dimethyltin chloride are converted into the monomethyl tin trichloride; Disproportionation reaction finishes the back and under 150 ℃ of temperature, vacuum tightness 75mmHg condition, carries out underpressure distillation, and it is 92.0% methyl chloride tin mixture 392kg that overhead product is monomethyl tin trichloride content, and yield is 98.0%.
Table three: the influence that tin tetrachloride input amount, disproportionation time are formed methyl chloride tin
| Sequence number | Light constituent is formed | SnCI 4Input amount (kg) | The disproportionation time (hour) | Product is formed (%) |
| 1 | (CH3)SnCI 3：63.87％ (CH 3) 2SnCI 2：35.38％ (CH 3) 3SnCI：0.75％ SnCI 4: do not measure | 100 | 2 | (CH3)SnCI 3：88.5％ (CH 3) 2SnCI 2：8.7％ (CH 3) 3SnCI：0.5％ SnCI 4：2.3％ |
| 2 | (CH3)SnCI 3：63.87％ (CH 3) 2SnCI 2：35.38％ (CH 3) 3SnCI：0.75％ SnCI 4: do not measure | 100 | 4 | (CH3)SnCI 3：92.1％ (CH 3) 2SnCI 2：7.3％ (CH 3) 3SnCI：0.3％ SnCI 4：0.3 |
| 3 | (CH3)SnCI 3：63.87％ (CH 3) 2SnCI 2：35.38％ (CH 3) 3SnCI：0.75％ SnCI 4: do not measure | 100 | 6 | (CH3)SnCI 3：92.6％ (CH 3) 2SnCI 2：7.2％ (CH 3) 3SnCI：0.2％ SnCI 4: do not measure |
In the specific embodiment of present patent application, the variation of each processing parameter in said scope all can obtain the technique effect that the present invention describes.
Claims (11)
1. the working method of high-purity dimethyltin dichloride crystal is characterized in that by following method preparation:
1) method of employing rectifying; The methyl chloride tin mixture that will contain 7-37% monomethyl tin trichloride, 62-92% dimethyltin chloride, 0.1-0.5% trimethylammonium monochlor(in)ate tin, 0.2-0.8% tin tetrachloride and small amount of solid impurity is put in the still kettle as raw material; 120-150 ℃, be evacuated under the 300-600mmHg condition and distill; Steam light constituent monomethyl tin trichloride, trimethylammonium monochlor(in)ate tin and a spot of dimethyltin chloride, and collect the light constituent storage tank, subsequent use;
2) still kettle is continued to be warming up to 140-190 ℃, vacuum control is carried out rectifying at 75-300mmHg; The dimethyltin chloride content of sample examination elute is greater than 98% o'clock, elute switched to the product Receiving bin do not steam till logistics goes out to having, and what make steams in the thing dimethyltin chloride content greater than 98%; Monomethyl tin trichloride content is less than 1.8%; Trimethylammonium monochlor(in)ate tin content is less than 0.2%, and tin tetrachloride content is high purity dimethyl tindichloride finished product less than 0.1%.
2. the working method of high-purity dimethyltin dichloride crystal as claimed in claim 1 is characterized in that the light constituent distillation temperature is controlled at 125-145 ℃ in the step 1), and vacuum tightness is 350-550mmHg.
3. the working method of high-purity dimethyltin dichloride crystal as claimed in claim 1 is characterized in that the light constituent distillation temperature is controlled at 130-140 ℃ in the step 1); Vacuum tightness is 400-450mmHg.
4. the working method of high-purity dimethyltin dichloride crystal as claimed in claim 1 is characterized in that step 2) in rectification temperature be controlled at 150-180 ℃, vacuum tightness is 100-250mmHg.
5. the working method of high-purity dimethyltin dichloride crystal as claimed in claim 1 is characterized in that step 2) in rectification temperature be controlled at 160-170 ℃, vacuum tightness is 150-200mmHg.
6. the working method of high-purity dimethyltin dichloride crystal as claimed in claim 1; The working method that it is characterized in that methyl chloride tin mixture raw material in the step 1) is: in withstand voltage reaction kettle, add dimethyltin chloride, metallic tin grain and tetramethyl ammonium chloride catalyzer; The add-on of metallic tin grain is 0.4-0.6 a times of dimethyltin chloride weight; Catalyst consumption is 0.005-0.015 a times of dimethyltin chloride weight; Be warming up to 190-200 ℃ and feed the chloromethylation that methyl chloride gas is carried out tin, temperature of reaction is 190-230 ℃, pressure 0.8-1.2MPa; Treat to add when methyl chloride no longer reacts anhydrous stannic chloride; The add-on of anhydrous stannic chloride is 1/15-7/15 a times of metallic tin grain weight, and temperature of reaction is 190-210 ℃, sample examination; Finish less than reaction in 0.5% o'clock to trimethylammonium monochlor(in)ate tin content, promptly get the methyl chloride tin mixture that contains 7-37% monomethyl tin trichloride, 62-92% dimethyltin chloride, 0.1-0.5% trimethylammonium monochlor(in)ate tin, 0.2-0.8% tin tetrachloride and small amount of solid impurity.
7. the working method of high-purity dimethyltin dichloride crystal as claimed in claim 1; It is characterized in that the light constituent that steams in the step 1) puts in the withstand voltage reaction kettle; The tin tetrachloride of adding and trimethylammonium monochlor(in)ate tin, dimethyltin chloride mole number sum 70-90% carries out disproportionation reaction under 190-210 ℃; Reaction times is 2-6 hour; After disproportionation reaction finishes this material is carried out underpressure distillation under temperature 120-150 ℃, vacuum tightness 75-600mmHg condition, overhead product is monomethyl tin trichloride content greater than 90% methyl chloride tin.
8. the working method of high-purity dimethyltin dichloride crystal as claimed in claim 6; It is characterized in that treating adding when methyl chloride no longer reacts anhydrous stannic chloride; The add-on of anhydrous stannic chloride is 3/15-6/15 a times of metallic tin grain weight, and temperature of reaction is 195-200 ℃.
9. the working method of high-purity dimethyltin dichloride crystal as claimed in claim 7; The consumption that it is characterized in that tin tetrachloride is trimethylammonium monochlor(in)ate tin, dimethyltin chloride mole number sum 75-80%; The temperature of disproportionation reaction is 195-200 ℃, and the reaction times is 3-4 hour.
10. the working method of high-purity dimethyltin dichloride crystal as claimed in claim 7, the reaction conditions that it is characterized in that underpressure distillation is temperature 130-145 ℃, vacuum tightness 90-500mmHg.
11. the working method of high-purity dimethyltin dichloride crystal as claimed in claim 7, the reaction conditions that it is characterized in that underpressure distillation are temperature 135-140 ℃, vacuum tightness 150-300mmHg.
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| CN102516288B (en) * | 2011-11-22 | 2015-09-02 | 南通艾德旺化工有限公司 | The synthesis technique of dimethyltin chloride |
| CN113717216B (en) * | 2021-10-15 | 2024-05-10 | 上海沃凯生物技术有限公司 | Preparation method of trimethyltin chloride |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077196A (en) * | 1992-08-13 | 1993-10-13 | 北京科技协作中心精细化学分部 | Preparation of a mixture of dimethyltin dichloride and methyltrichlorotin |
| CN101263149A (en) * | 2005-07-12 | 2008-09-10 | 阿肯马弗利辛恩公司 | Process for the preparation of monoalkyl tin trihalides and dialkyl tin dihalides |
| CN101318974A (en) * | 2008-07-18 | 2008-12-10 | 湖北犇星化工有限责任公司 | Process for synthesizing methyl tin chloride |
-
2009
- 2009-12-29 CN CN2009101566190A patent/CN101838283B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1077196A (en) * | 1992-08-13 | 1993-10-13 | 北京科技协作中心精细化学分部 | Preparation of a mixture of dimethyltin dichloride and methyltrichlorotin |
| CN101263149A (en) * | 2005-07-12 | 2008-09-10 | 阿肯马弗利辛恩公司 | Process for the preparation of monoalkyl tin trihalides and dialkyl tin dihalides |
| CN101318974A (en) * | 2008-07-18 | 2008-12-10 | 湖北犇星化工有限责任公司 | Process for synthesizing methyl tin chloride |
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