CN102002064A - Preparation method of trimethyl borate - Google Patents
Preparation method of trimethyl borate Download PDFInfo
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- CN102002064A CN102002064A CN 201010576438 CN201010576438A CN102002064A CN 102002064 A CN102002064 A CN 102002064A CN 201010576438 CN201010576438 CN 201010576438 CN 201010576438 A CN201010576438 A CN 201010576438A CN 102002064 A CN102002064 A CN 102002064A
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- trimethyl borate
- acid
- methyl alcohol
- boric acid
- preparation
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Abstract
The invention discloses a preparation method of trimethyl borate. The method comprises the following steps of: (1) heating and dehydrating a boric acid solid to prepare metaboric acid and pyroboric acid solids; (2) adding the metaboric acid and pyroboric acid solids which are obtained in the step (1) to methanol to make the mixture react under a stirring state; (3) heating and distilling the reaction solution obtained in the step (2) to obtain an azeotrope solution of the methanol and the trimethyl borate, distilling and cooling raffinate to obtain boric acid; and (4) separating the azeotrope solution of the methanol and the trimethyl borate, which is obtained in the step (3), to obtain a trimethyl borate product. In the invention, by firstly heating and dewatering the boric acid to prepare the metaboric acid and the pyroboric acid and then making the metaboric acid and the pyroboric acid react with the methanol to prepare trimethyl borate, the reaction speed is accelerated, the conversion per pass is improved, the reaction conditions are mild and no risks exist.
Description
Technical field
The present invention relates to the preparing technical field of boric acid ester, relate in particular to a kind of preparation method of trimethyl borate.
Background technology
Trimethyl borate is a kind of important organic boric acid ester, is mainly used in the preparation of the synthetic and high purity boron of organic boride, also can be used as the stablizer of organic solvent, softening agent, catalyzer, welding fusing assistant, fire retardant and polymkeric substance etc.
Trimethyl borate is a kind of main raw material of synthetic boron-containing compound, can be used for producing sodium borohydride and senior ester; Secondly also be widely used in fields such as olefinic polymerization, wood preservation, oil and lubricant additive.In addition, trimethyl borate also is used for the preparation of Optical devices special glass and the preparation of boronic acid intermediate class material etc.
The preparation method of trimethyl borate mainly contains following three kinds:
1, boric acid and methyl alcohol direct reaction, its reaction formula is: 3CH
3OH+H
3BO
3-B (OCH
3)
3+ 3H
2O
Usually the trimethyl borate that generates in the reaction is distilled out with excessive methyl alcohol formation azeotrope, obtains trimethyl borate by separating azeotrope again.
2, boron oxide and methyl alcohol direct reaction, its reaction formula is: B
2O
3+ 6CH
3OH-2B (OCH
3)
3+ 3H
2O
3, borax, methyl alcohol and direct reaction of sulfuric acid, its reaction formula is:
Na
2B
4O
7·10H
2O+12CH
3OH+2H
2SO
4-4B(OCH
3)
3+2NaHSO
4+17H
2O
Usually the trimethyl borate that generates in the reaction is distilled out with excessive methyl alcohol formation azeotrope, azeotrope is separated obtaining trimethyl borate again.
Wherein in first method, owing to adopt boric acid and methyl alcohol direct reaction, reaction generates a large amount of water, can influence speed of response and transformation efficiency, removes these moisture and consumes lot of energy and distill.Second method, defective at first method, the water of boric acid removed in advance make boron oxide, make speed of response and transformation efficiency improve a lot, reflux ratio also only is 3: 1 in the rectifying, but this method has two shortcomings: (1) prepares boron oxide by boric acid, very difficulty, boric acid dewaters when being heated to 70～100 ℃ gradually, loses an one's share of expenses for a joint undertaking water and generates metaboric acid (HBO
2), when being heated to 150～160 ℃, lose 0.25 molecular water again, generate pyroboric acid (H
2B
4O
7), when being heated to more than 300 ℃, lose 0.25 molecular water again, generate boron oxide (B
2O
3).Hence one can see that, prepares boron oxide by boric acid, and processing condition are very harsh; Vigorous reaction at room temperature just takes place in (2) methyl alcohol and boron oxide reaction, has very big security risk.And the third method, advantage is that raw materials cost is lower, but still has two shortcomings: just there is a large amount of water in (1) raw material itself, and along with reaction is carried out, the water of whole reaction system constantly increases, and also can run into the drawback of method one; (2) produced the inorganic salt sodium pyrosulfate in the reaction process, the water intractable in the system of feasible reaction back is brought environmental issue.
Summary of the invention
Technical problem to be solved by this invention is: at the deficiency that prior art exists, provide the preparation method of the trimethyl borate that a kind of technology is controlled easily, speed of response is fast, reaction conversion ratio is high.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of preparation method of trimethyl borate may further comprise the steps:
(1), makes metaboric acid and pyroboric acid solid with boric acid solid thermal dehydration;
(2) under the whipped state, the metaboric acid of step (1) gained and pyroboric acid solid joined in the methyl alcohol react;
(3) reaction soln with step (2) gained adds thermal distillation, obtains the azeotropic liquid of methyl alcohol and trimethyl borate, obtains boric acid after the vinasse cooling;
(4) methyl alcohol with step (3) gained separates with the azeotropic liquid of trimethyl borate, obtains the product trimethyl borate.
The temperature of described boric acid thermal dehydration is 100～200 ℃.
Preferably, the temperature of described boric acid thermal dehydration is 120～160 ℃.
The adding mol ratio of described metaboric acid and pyroboric acid and methyl alcohol is 1: 4～1: 10.
Preferably, the adding mol ratio of described metaboric acid and pyroboric acid and methyl alcohol is 1: 8.
In the step (3), described when adding thermal distillation the distillation tower head temperature be 53～57 ℃.
The boric acid recycling that step (3) obtains.
Per pass conversion 〉=80% of reaction.
Owing to adopted technique scheme, the invention has the beneficial effects as follows:
The present invention is when using boric acid and methyl alcohol prepared in reaction trimethyl borate, earlier the boric acid thermal dehydration is prepared into metaboric acid and pyroboric acid, use metaboric acid and pyroboric acid and methyl alcohol prepared in reaction trimethyl borate, because boric acid prepares metaboric acid and the pyroboric acid ratio is easier to realize, the processing condition ratio is easier to control, and use metaboric acid and pyroboric acid and methyl alcohol prepared in reaction trimethyl borate, because the water that reaction generates reduces in a large number, therefore accelerated the carrying out of reaction to the positive reaction direction, accelerated speed of response, improved per pass conversion, and reaction conditions is relatively gentleer, does not have security risk.
The boric acid that the present invention obtains when distilling after metaboric acid and methyl alcohol reaction is recycled, and has improved raw material availability, has reduced production cost.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.
Embodiment 1
The boric acid solid is heated to 120 ℃ of dehydrations, obtain the metaboric acid solid, 256g methyl alcohol is joined in the 500ml four-hole boiling flask, heat temperature raising to 40 ℃, under whipped state, adding 44g metaboric acid solid reacts, use distillation tower to add thermal distillation reacted solution, collecting the distillation tower head temperature is 53～57 ℃ the methyl alcohol and the azeotropic liquid 126g of trimethyl borate, the vinasse heating steams the methyl alcohol postcooling and filters and obtains boric acid, the boric acid recycle that obtains separates 126g methyl alcohol with the azeotropic liquid of trimethyl borate, obtain product trimethyl borate 89g.
Embodiment 2
The boric acid solid is heated to 115 ℃ of dehydrations, obtain the metaboric acid solid, 192g methyl alcohol is joined in the 500ml four-hole boiling flask, heat temperature raising to 40 ℃, under whipped state, adding 44g metaboric acid solid reacts, use distillation tower to add thermal distillation reacted solution, collecting the distillation tower head temperature is 53～57 ℃ the methyl alcohol and the azeotropic liquid 118g of trimethyl borate, the vinasse heating steams the methyl alcohol postcooling and filters and obtains boric acid, the boric acid recycle that obtains separates 118g methyl alcohol with the azeotropic liquid of trimethyl borate, obtain product trimethyl borate 85g.
Embodiment 3
The boric acid solid is heated to 125 ℃ of dehydrations, obtain the metaboric acid solid, 128g methyl alcohol is joined in the 500ml four-hole boiling flask, heat temperature raising to 40 ℃, under whipped state, adding 44g metaboric acid solid reacts, use distillation tower to add thermal distillation reacted solution, collecting the distillation tower head temperature is 53～57 ℃ the methyl alcohol and the azeotropic liquid 117g of trimethyl borate, the vinasse heating steams the methyl alcohol postcooling and filters and obtains boric acid, the boric acid recycle that obtains separates 117g methyl alcohol with the azeotropic liquid of trimethyl borate, obtain product trimethyl borate 83g.
Embodiment 4
The boric acid solid is heated to 130 ℃ of dehydrations, obtain the metaboric acid solid, 320g methyl alcohol is joined in the 500ml four-hole boiling flask, heat temperature raising to 40 ℃, under whipped state, adding 44g metaboric acid solid reacts, use distillation tower to add thermal distillation reacted solution, collecting the distillation tower head temperature is 53～57 ℃ the methyl alcohol and the azeotropic liquid 128g of trimethyl borate, the vinasse heating steams the methyl alcohol postcooling and filters and obtains boric acid, the boric acid recycle that obtains separates 128g methyl alcohol with the azeotropic liquid of trimethyl borate, obtain product trimethyl borate 88g.
Embodiment 5
The boric acid solid is heated to 126 ℃ of dehydrations, obtain the metaboric acid solid, 160g methyl alcohol is joined in the 500ml four-hole boiling flask, heat temperature raising to 40 ℃, under whipped state, adding 44g metaboric acid solid reacts, use distillation tower to add thermal distillation reacted solution, collecting the distillation tower head temperature is 53～57 ℃ the methyl alcohol and the azeotropic liquid 120g of trimethyl borate, the vinasse heating steams the methyl alcohol postcooling and filters and obtains boric acid, the boric acid recycle that obtains separates 120g methyl alcohol with the azeotropic liquid of trimethyl borate, obtain product trimethyl borate 85g.
Embodiment 6
The boric acid solid is heated to 145 ℃ of dehydrations, obtain metaboric acid and pyroboric acid solid, 224g methyl alcohol is joined in the 500ml four-hole boiling flask, heat temperature raising to 40 ℃, under whipped state, adding 44g metaboric acid and pyroboric acid solid reacts, use distillation tower to add thermal distillation reacted solution, collecting the distillation tower head temperature is 53～57 ℃ the methyl alcohol and the azeotropic liquid 121g of trimethyl borate, the vinasse heating steams the methyl alcohol postcooling and filters and obtains boric acid, the boric acid recycle that obtains separates 121g methyl alcohol with the azeotropic liquid of trimethyl borate, obtain product trimethyl borate 87g.
Embodiment 7
The boric acid solid is heated to 170 ℃ of dehydrations, obtain metaboric acid and pyroboric acid solid, 288g methyl alcohol is joined in the 500ml four-hole boiling flask, heat temperature raising to 40 ℃, under whipped state, adding 44g metaboric acid and pyroboric acid solid reacts, use distillation tower to add thermal distillation reacted solution, collecting the distillation tower head temperature is 53～57 ℃ the methyl alcohol and the azeotropic liquid 127g of trimethyl borate, the vinasse heating steams the methyl alcohol postcooling and filters and obtains boric acid, the boric acid recycle that obtains separates 127g methyl alcohol with the azeotropic liquid of trimethyl borate, obtain product trimethyl borate 89g.
Claims (8)
1. the preparation method of a trimethyl borate is characterized in that may further comprise the steps:
(1), makes metaboric acid and pyroboric acid solid with boric acid solid thermal dehydration;
(2) under the whipped state, the metaboric acid of step (1) gained and pyroboric acid solid joined in the methyl alcohol react;
(3) reaction soln with step (2) gained adds thermal distillation, obtains the azeotropic liquid of methyl alcohol and trimethyl borate, obtains boric acid after the vinasse cooling;
(4) methyl alcohol with step (3) gained separates with the azeotropic liquid of trimethyl borate, obtains the product trimethyl borate.
2. the preparation method of trimethyl borate as claimed in claim 1, it is characterized in that: the temperature of described boric acid thermal dehydration is 100～200 ℃.
3. the preparation method of trimethyl borate as claimed in claim 2, it is characterized in that: the temperature of described boric acid thermal dehydration is 120～160 ℃.
4. the preparation method of trimethyl borate as claimed in claim 1, it is characterized in that: the adding mol ratio of described metaboric acid and pyroboric acid and methyl alcohol is 1: 4～1: 10.
5. the preparation method of trimethyl borate as claimed in claim 4, it is characterized in that: the adding mol ratio of described metaboric acid and pyroboric acid and methyl alcohol is 1: 8.
6. the preparation method of trimethyl borate as claimed in claim 1 is characterized in that: in the step (3), described when adding thermal distillation the distillation tower head temperature be 53～57 ℃.
7. the preparation method of trimethyl borate as claimed in claim 1 is characterized in that: the boric acid recycling that step (3) obtains.
8. as the preparation method of described any trimethyl borate of claim 1 to 7, it is characterized in that: the per pass conversion of reaction 〉=80%.
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| CN 201010576438 CN102002064A (en) | 2010-11-25 | 2010-11-25 | Preparation method of trimethyl borate |
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|---|---|---|---|
| CN 201010576438 CN102002064A (en) | 2010-11-25 | 2010-11-25 | Preparation method of trimethyl borate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816178A (en) * | 2012-09-14 | 2012-12-12 | 南通鸿志化工有限公司 | Method and special device for separating trimethyl borate from carbinol mixture |
| CN104478916A (en) * | 2014-11-26 | 2015-04-01 | 大连理工大学 | Method for preparing trimethyl borate at high conversion rate |
| CN107778323A (en) * | 2016-08-31 | 2018-03-09 | 南通鸿志化工有限公司 | A kind of preparation method of trimethylborate |
| CN110862406A (en) * | 2018-08-28 | 2020-03-06 | 宁夏佰斯特医药化工有限公司 | Preparation method of trimethyl borate |
| CN111233912A (en) * | 2019-12-24 | 2020-06-05 | 大连理工大学 | Method for semi-continuously synthesizing trimethyl borate-methanol azeotrope |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050014656A1 (en) * | 2003-07-16 | 2005-01-20 | The Lubrizol Corporation | Transmission lubricating compositions with improved performance, containing acid/polyamine condensation product |
-
2010
- 2010-11-25 CN CN 201010576438 patent/CN102002064A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050014656A1 (en) * | 2003-07-16 | 2005-01-20 | The Lubrizol Corporation | Transmission lubricating compositions with improved performance, containing acid/polyamine condensation product |
Non-Patent Citations (2)
| Title |
|---|
| 《上海化工》 19981231 白力英等 硼酸三甲酯制备中的分离新方法 第37-38页 1-8 第23卷, 第13期 * |
| 《化学世界》 19641231 苏裕光 硼酸三甲酯的制备 第125-126页 1-8 , 第3期 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102816178A (en) * | 2012-09-14 | 2012-12-12 | 南通鸿志化工有限公司 | Method and special device for separating trimethyl borate from carbinol mixture |
| CN102816178B (en) * | 2012-09-14 | 2015-10-28 | 南通鸿志化工有限公司 | A kind of method and special purpose device thereof being separated trimethyl borate and carbinol mixture |
| CN104478916A (en) * | 2014-11-26 | 2015-04-01 | 大连理工大学 | Method for preparing trimethyl borate at high conversion rate |
| CN107778323A (en) * | 2016-08-31 | 2018-03-09 | 南通鸿志化工有限公司 | A kind of preparation method of trimethylborate |
| CN110862406A (en) * | 2018-08-28 | 2020-03-06 | 宁夏佰斯特医药化工有限公司 | Preparation method of trimethyl borate |
| CN111233912A (en) * | 2019-12-24 | 2020-06-05 | 大连理工大学 | Method for semi-continuously synthesizing trimethyl borate-methanol azeotrope |
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Application publication date: 20110406 |