CN101613364B - Preparation method for heptamethyldisilazane - Google Patents
Preparation method for heptamethyldisilazane Download PDFInfo
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- CN101613364B CN101613364B CN2009101647751A CN200910164775A CN101613364B CN 101613364 B CN101613364 B CN 101613364B CN 2009101647751 A CN2009101647751 A CN 2009101647751A CN 200910164775 A CN200910164775 A CN 200910164775A CN 101613364 B CN101613364 B CN 101613364B
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- heptamethyldisilazane
- reaction
- monomethyl
- temperature
- product
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- ZSMNRKGGHXLZEC-UHFFFAOYSA-N n,n-bis(trimethylsilyl)methanamine Chemical compound C[Si](C)(C)N(C)[Si](C)(C)C ZSMNRKGGHXLZEC-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 27
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- -1 monomethylamino Chemical group 0.000 claims abstract description 14
- 239000005051 trimethylchlorosilane Substances 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 4
- BRUZZEMTHTULBO-UHFFFAOYSA-N potassium;methylazanide Chemical compound [K+].[NH-]C BRUZZEMTHTULBO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- KXDHHKIAGHRLRO-UHFFFAOYSA-N sodium methylazanide Chemical compound [Na+].[NH-]C KXDHHKIAGHRLRO-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 17
- 150000003839 salts Chemical class 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000007040 multi-step synthesis reaction Methods 0.000 abstract description 2
- 238000013459 approach Methods 0.000 abstract 2
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 abstract 1
- 150000001339 alkali metal compounds Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000010008 shearing Methods 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000011814 protection agent Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
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Abstract
The invention discloses a preparation method for heptamethyldisilazane, which comprises the following steps: (1) adding trimethyl chlorosilane and alkali metal compounds of monomethylamine and monomethylamino or monomethyl ethanolamine into a reaction kettle according to the molar mass ratio of 2:3.03-3.3, and performing high-shearing type reaction at the temperature of less than or equal to 120 DEG C and the pressure of less than or equal to 0.2 MPa; (2) when the reaction temperature approaches 120 DEG C, and the pressure approaches 0.2 MPa, maintaining the temperature and the pressure unchanged for more than 20 minutes, and ending the reaction; and (3) adding water into the reaction kettle, stirring the mixture, and standing and layering, wherein the upper layer is a product of the heptamethyldisilazane. The method provides a one-step synthesis method. The method has the advantages that: firstly, compared with the multi-step synthesis method, the method has simpler process, lower material cost, less equipment investment and lower production cost; secondly, the method adopts a non-solvent process method so as to improve the production capability and greatly reduce the energy consumption, and the product quality is better; and thirdly, water soluble salt technology is adopted, so the method simplifies the process, is easy to operate, and greatly improves the product yield.
Description
Technical field
The present invention relates to a kind of preparation method of disilazane substituent, particularly relate to a kind of preparation method of heptamethyldisilazane.
Background technology
Heptamethyldisilazane, colourless transparent liquid, water insoluble, be dissolved with the machine solvent, meet acid and be combined into salt compounds.As a radical protection agent, be widely used in the medicine production such as agricultural chemicals, veterinary drug.Yet the production of relevant heptamethyldisilazane product, internal and international on all less than corresponding report.
And with the hexamethyldisilazane of heptamethyldisilazane similar, generally at present adopt conventional solvent method to prepare, promptly need a large amount of solvents, guarantee that the salt product that generates can leach in solvent deposition, impel reaction to carry out to generating target product.If adopt the method for producing hexamethyldisilazane to prepare the heptamethyldisilazane product, then have following shortcoming: technical process is long, complicated operation, and throughput is low, the energy consumption height, yield is low, poor product quality, product cost height.
Summary of the invention
Be directed to this, the objective of the invention is to, a kind of preparation method of heptamethyldisilazane is provided, this preparation method's operational path is simple, and operational condition is easy.
For achieving the above object, technical scheme provided by the present invention is: a kind of preparation method of heptamethyldisilazane is made of following steps:
(1), in reactor, adds trimethylchlorosilane, add Monomethylamine, monomethyl alkali amide compound or monomethyl thanomin again, before and after both molar mass ratio be 2: 3.03～3.3, in temperature≤120 ℃, high-shear formula stirring reaction under pressure≤0.2MPa;
(2), when temperature of reaction near 120 ℃, pressure is near 0.2MPa, and both keep no change more than 20 minutes, reaction finishes;
(3), in reactor, add entry, stir, standing demix, the upper strata is the heptamethyldisilazane product.
Monomethyl alkali amide compound in the described step (1) is monomethyl sodium amide or monomethyl potassium amide.
Stirring in the described step (1) is pusher the stirring or the stirring of slurry formula.
A kind of preparation method of heptamethyldisilazane is made of following steps:
(1), in reactor, adds trimethylchlorosilane, add Monomethylamine, monomethyl alkali amide compound or monomethyl thanomin again, before and after both molar mass ratio be 2: 3.03～3.3, in temperature≤120 ℃, high-shear formula stirring reaction under pressure≤0.2MPa;
(2), when temperature of reaction near 120 ℃, pressure is near 0.2MPa, and both keep no change more than 20 minutes, reaction finishes;
(3), in reactor, add entry, stir, standing demix, the upper strata is the heptamethyldisilazane product;
(4), to the rectifying of heptamethyldisilazane product, the theoretical plate number of described rectifying tower 〉=12 block plate.
Compared with prior art, the present invention just can finish reaction for single stage method is synthetic, compares with adopting the multistep synthesis method, and technology is simpler, and raw materials cost is lower, and facility investment and production cost are all lower; Secondly, adopt solvent-free processing method, improved throughput, greatly reduce energy consumption, and product quality is better; The 3rd, adopt the water-soluble salt technology, simplified technology more, be easier to operation, and improved product yield widely.
Description of drawings
Fig. 1 is a reaction process synoptic diagram of the present invention.
Embodiment
Describe the present invention below in conjunction with accompanying drawing, the description of this part only is exemplary and explanatory, should any restriction not arranged to protection scope of the present invention.
The method of raw material trimethylchlorosilane and Monomethylamine direct reaction is adopted in the production of this product more.Reaction equation is as follows:
2(CH
3)
3SiCl+3CH
3NH
2→[(CH
3)
3Si]
2NCH
3+2CH
3NH
3Cl+Q
Two moles of trimethylchlorosilanes and three moles of Monomethylamines reactions only generate one mole of product in being reacted as can be seen by reaction equation, generate two moles of monomethyl chlorination amine salt and precipitate, and emit heat simultaneously.
(1) reaction process
Reaction process as shown in Figure 1 originally is reflected under trimethylchlorosilane and the Monomethylamine direct reaction and finishes (need not solvent), generates a large amount of salt in the reaction, is under strong mixing,＞8 kilojoules/m
3, guarantee to carry out under the flow state preferably.Temperature of reaction≤120 ℃, pressure≤0.2MPa, speed of response is to control with the speed that feeds Monomethylamine.The heat that reaction generates is to take out of with the water coolant that reacting kettle jacketing feeds.Reaction end is excessive with Monomethylamine, be the molar mass theoretical amount 1.01-1.1 doubly, and be aided with temperature and pressure is determined.After reaction is finished, add an amount of water (or salt solution, buck), static layering after the stirred for several minute, lower floor is salt solution (or supersaturated brine or mixed solution), the upper strata is thick product, two-layer natural separation.Crude product after the separation is taken rectifying tower and is carried out rectifying.In rectifying, small part by product hexamethyldisiloxane boiling point is lower, at first by extraction.The most of product of extraction then, purity is all more than 99%, and a little still raffinate of residue is emitted after repeatedly accumulating rectifying in the last still.Above byproduct and still raffinate all can be used as byproduct and sell.
(2) equipment requirements
1. synthesis reactor is answered acid and alkali-resistance, is furnished with stirring, intensity＞8 kilojoules/m
3Agitator; Is furnished with the logical Monomethylamine pipe in bottom; Thermometric, pressure tap; Add dissolved salt agent hole; Is furnished with the outer heat exchange jacket of equipment.
2. rectifying tower should be alkaline-resisting; Theoretical plate number 〉=12 block plate.
(3) operational condition
Feed intake: trimethylchlorosilane 500kg; Monomethylamine is 1.01-1.1 a times of molar mass theoretical amount; Dissolved salt agent add-on is 200-700kg.
Reaction: alternating temperature degree operation requires temperature≤120 ℃; Pressure≤0.2MPa; Feed a first ammonia speed, in preceding 2 hours, feed 99%; Adding the dissolved salt agent stirred 5-30 minute; 5-30 minute static layering time.
Reaction end is judged: when temperature of reaction near 120 ℃ of jacket temperatures, reaction pressure near operation upper limit 0.2MPa after, keep not having more than 20 minutes and become, think that reaction finishes.Crude product synthesizes content 〉=85%.
Distillation operation: adopt the batch operation mode; The varying reflux ratio operation; Cat head extraction product temperature is 147 ℃, product content 〉=99%.
The present invention first is that the employing Monomethylamine is a raw material, and a step is finished the operational path of building-up reactions, has avoided the methylated again complicated technology of employing hexamethyldisilazane; The secondth, adopt the solventless method processing method, under the strong mixing condition, guarantee system is finished reaction smoothly under (and not having the dead angle) state that flows preferably; The 3rd adopts the water-soluble salt technology, and its precondition is almost not have former trimethylchlorosilane raw material in the system of reaction back to exist, and a first ammonia is excessive, and system is alkalescence.
Wherein,, also can adopt monomethyl ammonobase compound,, or adopt monomethyl thanomin etc. as monomethyl sodium amide, monomethyl potassium amide etc. for use raw material Monomethylamine.
For the solventless method production method, can adopt different whipped forms, stir as push type, the stirring of slurry formula, the stirring of high-shear formula etc., all can reach the whipped form of higher stirring intensity.
Can adopt basic aqueous solution, salt brine solution, saline and alkaline mixed aqueous solution and and immiscible neutrality of product or alkaline aqueous solution etc. for the water-soluble salt technology.
It below only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (4)
1. the preparation method of a heptamethyldisilazane is made of following steps:
(1), in reactor, adds trimethylchlorosilane, add Monomethylamine, monomethyl alkali amide compound or monomethyl thanomin again, before and after both molar mass ratio be 2: 3.03～3.3, in temperature≤120 ℃, high-shear formula stirring reaction under pressure≤0.2MPa;
(2), when temperature of reaction near 120 ℃, pressure is near 0.2MPa, and both keep no change more than 20 minutes, reaction finishes;
(3), in reactor, add entry, stir, standing demix, the upper strata is the heptamethyldisilazane product.
2. the preparation method of heptamethyldisilazane according to claim 1, it is characterized in that: the monomethyl alkali amide compound in the described step (1) is monomethyl sodium amide or monomethyl potassium amide.
3. the preparation method of heptamethyldisilazane according to claim 1 is characterized in that: the stirring in the described step (1) is stirred or the slurry formula stirs for pusher.
4. the preparation method of a heptamethyldisilazane is made of following steps:
(1), in reactor, adds trimethylchlorosilane, add Monomethylamine, monomethyl alkali amide compound or monomethyl thanomin again, before and after both molar mass ratio be 2: 3.03～3.3, in temperature≤120 ℃, high-shear formula stirring reaction under pressure≤0.2MPa;
(2), when temperature of reaction near 120 ℃, pressure is near 0.2MPa, and both keep no change more than 20 minutes, reaction finishes;
(3), in reactor, add entry, stir, standing demix, the upper strata is the heptamethyldisilazane product;
(4), to the rectifying of heptamethyldisilazane product, the theoretical plate number of described rectifying tower 〉=12 block plate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101647751A CN101613364B (en) | 2009-07-22 | 2009-07-22 | Preparation method for heptamethyldisilazane |
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| CN2009101647751A CN101613364B (en) | 2009-07-22 | 2009-07-22 | Preparation method for heptamethyldisilazane |
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| CN101613364A CN101613364A (en) | 2009-12-30 |
| CN101613364B true CN101613364B (en) | 2011-10-19 |
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| CN111732602A (en) * | 2020-05-26 | 2020-10-02 | 浙江新安化工集团股份有限公司 | Preparation method of silazane |
| CN112409398A (en) * | 2020-12-08 | 2021-02-26 | 江西贝特利新材料有限公司 | Synthesis method of tetramethyl divinyl disilazane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4644076A (en) * | 1985-04-11 | 1987-02-17 | Far Research, Inc. | Continuous process for the synthesis of hexamethyldisilazane |
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2009
- 2009-07-22 CN CN2009101647751A patent/CN101613364B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4644076A (en) * | 1985-04-11 | 1987-02-17 | Far Research, Inc. | Continuous process for the synthesis of hexamethyldisilazane |
Non-Patent Citations (1)
| Title |
|---|
| 逯凯霄等."七甲基二硅氮烷的合成".《河北化工》.2005,(第2期),35. |
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Assignee: Xinyaqiang Silicon Chemistry Jiangsu Co.,Ltd. Assignor: Jilin Xinyaqiang Biochem Co., Ltd. Contract record no.: 2012320000371 Denomination of invention: Preparation method for heptamethyldisilazane Granted publication date: 20111019 License type: Exclusive License Open date: 20091230 Record date: 20120401 |
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Effective date of registration: 20151111 Address after: 223800 eco chemical science and Technology Industrial Park, Jiangsu, Suqian Province, No. five, No. 3 Patentee after: Jilin Xinyaqiang Biochem Co., Ltd. Address before: 132200 No. 20, Shanghai street, Yongji Economic Development Zone, Jilin, Jilin Patentee before: Jilin Xinyaqiang Biochem Co., Ltd. |