CN114181243B - Preparation method of methyldimethoxy hydrosilane - Google Patents
Preparation method of methyldimethoxy hydrosilane Download PDFInfo
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- CN114181243B CN114181243B CN202111455959.0A CN202111455959A CN114181243B CN 114181243 B CN114181243 B CN 114181243B CN 202111455959 A CN202111455959 A CN 202111455959A CN 114181243 B CN114181243 B CN 114181243B
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- butyl ether
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims abstract description 39
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000005048 methyldichlorosilane Substances 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 14
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000004321 preservation Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003377 acid catalyst Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- WCYAALZQFZMMOM-UHFFFAOYSA-N methanol;sulfuric acid Chemical compound OC.OS(O)(=O)=O WCYAALZQFZMMOM-UHFFFAOYSA-N 0.000 abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 17
- 238000004587 chromatography analysis Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000010198 maturation time Effects 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- FDCBKHMYMQKXGF-UHFFFAOYSA-N chloro-methoxy-methylsilane Chemical compound CO[SiH](C)Cl FDCBKHMYMQKXGF-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- -1 silylmethoxy groups Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/188—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-O linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention provides a preparation method of methyldimethoxy hydrosilane, which takes methyl tertiary butyl ether and methyldichloro silane as raw materials and obtains methyldimethoxy hydrosilane by reaction under the strong acid condition; the reaction equation involved is: CH (CH) 3 SiCl 2 H+2CH 3 OC(CH 3 ) 3 →CH 3 Si(OCH 3 ) 2 H+2(CH 3 ) 3 CCl. According to the invention, methyl dichlorosilane and methyl tertiary butyl ether are reacted under the catalysis of concentrated sulfuric acid methanol solution to generate methyl dimethoxysilane, so that hydrogen chloride generation is avoided, the acidity of a product is controlled, and the method has the advantages of mild reaction conditions, low-cost and easily obtained reaction raw materials, stable reaction result, high product yield and good industrial mass production prospect.
Description
Technical Field
The invention belongs to the technical field of synthesis of fine chemical products, and particularly relates to a preparation method of methyldimethoxy hydrosilane.
Background
The methyldimethoxyhydrosilane contains both hydrolyzable silylmethoxy groups and active silicon hydrogen bonds. The silicon hydrogen bond can be subjected to hydrosilylation reaction with a series of alkene, alkyne and other unsaturated group compounds, and different functional groups are introduced to obtain various silane coupling agents; the epoxy resin can also be used as a blocking group of polyether to obtain a base adhesive of the organosilicon modified polyether sealant, and meanwhile, the methyldimethoxy hydrosilane has proper hydrolysis speed, can realize deep curing, is a blocking group with excellent performance, and has wide application in the organosilicon industry, and is an important intermediate.
The foreign methyldimethoxyhydrosilane has been industrially produced and widely used, and the synthesis methods currently reported in domestic literature mainly comprise an ester exchange method and a group exchange method. The transesterification method mainly uses methanol and methyldichlorosilane as raw materials, and the esterification reaction is carried out under a single solvent or a mixed solvent to generate methyldimethoxysilane, but a large amount of hydrogen chloride is generated in the reaction process, which is difficult to remove, and even the methyl dichlorosilane and the methanol can generate monochloro substances if the conditions are improperly controlled, so that the subsequent separation and purification difficulty is increased. The manner of treating hydrogen chloride in the transesterification process has been an important impediment to the industrialization of the process. The method for synthesizing the methyldimethoxysilane by adopting the methyltrimethoxysilane and the methyldichlorosilane through the radical exchange has certain advantages in industrial production compared with the transesterification method, but the finished product must contain the methylmonomethoxyhydrosilane, the difficulty of purifying the subsequent product is increased, and the acidity of the product is also influenced.
Aiming at a plurality of problems in the existing synthesis process of the methyldimethoxyhydrosilane, a simple and effective synthesis process is necessary to be researched, so that the existing technical problems can be solved, and the industrial production can be realized.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a preparation method of methyldimethoxy hydrosilane, which is simple, efficient, economical and practical. The technical scheme of the invention is as follows:
a process for preparing methyldimethoxy hydrosilane from methyl tert-butyl ether and methyldichloro hydrosilane includes such steps as preparing solvent, stirring, and adding strong acidReacting under a sexual condition to obtain methyldimethoxy hydrosilane; the reaction equation involved is: CH (CH) 3 SiCl 2 H+2CH 3 OC(CH 3 ) 3 →CH 3 Si(OCH 3 ) 2 H+2(CH 3 ) 3 CCl。
Further, the preparation method comprises the following steps:
(1) Firstly, mixing a strong acid catalyst and methyl tertiary butyl ether, adding the methyl tertiary butyl ether into methyl dichlorosilane in a continuous feeding mode under the stirring condition, controlling the temperature of a reaction system to be not more than 40 ℃, and keeping the temperature for curing after the feeding is completed;
(2) After the reaction is finished, the mixture is subjected to vacuum rectification and purification to obtain the methyldimethoxy hydrosilane.
Further, the strong acid catalyst in the step (1) is a methanol solution of 98% concentrated sulfuric acid, and the mass fraction of the 98% concentrated sulfuric acid in the methanol is 10% -30%.
Preferably, in the step (1), the mass fraction of the 98% concentrated sulfuric acid in the methanol is 15% -20%.
Further, the addition amount of the methanol solution of the 98% concentrated sulfuric acid is 3% -5% of the mass of the methyl tertiary butyl ether.
Preferably, the addition amount of the methanol solution of the 98% concentrated sulfuric acid is 3% of the mass of the methyl tertiary butyl ether.
Further, the molar ratio of the methyldichlorosilane to the methyl tertiary butyl ether in the step (1) is (1.01-1.07): 2.
Preferably, the feeding mole ratio of the methyldichlorosilane to the methyl tertiary butyl ether in the step (1) is (1.03-1.05): 2.
Further, the control conditions of the thermal insulation curing in the step (1) are as follows: the temperature is controlled to be between 35 and 40 ℃, and the heat preservation and curing time is 30 to 50 minutes.
Preferably, the control conditions of the thermal insulation curing in the step (1) are as follows: the temperature is controlled to be 39-40 ℃, and the heat preservation and curing time is 30-40 min.
Further, the pressure of the reduced pressure rectification in the step (2) is minus 0.05MPa, and the temperature of the extracted target product in the reduced pressure rectification is 37-38 ℃.
The invention has the technical effects that: according to the invention, methyl dichlorosilane and methyl tertiary butyl ether are reacted under the catalysis of concentrated sulfuric acid methanol solution to generate methyl dimethoxysilane, so that hydrogen chloride generation is avoided, the acidity of a product is controlled, and the method has the advantages of mild reaction conditions, low-cost and easily obtained reaction raw materials, stable reaction result, high product yield and good industrial mass production prospect.
Detailed Description
In the description of the present invention, it is to be noted that the specific conditions are not specified in the examples, and the description is performed under the conventional conditions or the conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The present invention will be described in further detail with reference to the following specific embodiments, so as to assist those skilled in the art in a more complete, accurate and thorough understanding of the inventive concept and technical solution of the present invention, and the scope of the present invention includes, but is not limited to, the following examples, any modifications made in the details and form of the technical solution of the present invention falling within the scope of the present invention without departing from the spirit and scope of the present application.
The specific embodiment of the invention provides a preparation method of methyldimethoxy hydrosilane, which takes methyl tertiary butyl ether and methyldichloro hydrosilane as raw materials and obtains methyldimethoxy hydrosilane by reaction under the strong acid condition; the reaction equation involved is:
CH 3 SiCl 2 H+2CH 3 OC(CH 3 ) 3 →CH 3 Si(OCH 3 ) 2 H+2(CH 3 ) 3 CCl。
example 1
Influence of catalysts with different proportions on reaction results
17.6g of methyl tertiary butyl ether and 0.8g of concentrated sulfuric acid methanol solution with different concentrations are mixed and poured into a constant pressure dropping funnel, 12g of methyl dichlorosilane is added into a 100mL three-neck flask, magnetic stirring is started, the temperature is increased, when the temperature is increased to above 35 ℃, the methyl tertiary butyl ether mixed solution starts to be dropped, the reaction temperature is controlled to be not higher than 40 ℃, and after three hours of dropping, the temperature is kept for curing for 45 minutes. And (3) transferring the reacted liquid to a rectifying tower for reduced pressure rectification, wherein the rectifying pressure is-0.05 MPa, collecting components with the temperature of 37-38 ℃ to obtain a product, and carrying out gas chromatographic analysis.
TABLE 1 reaction Effect of catalysts in different proportions
| Sequence number | Concentrated sulfuric acid mass fraction/% | Yield/% | Purity/% |
| 1 | 10 | 83.78 | 93.48 |
| 2 | 15 | 88.95 | 97.05 |
| 3 | 20 | 89.77 | 96.62 |
| 4 | 25 | 85.02 | 96.53 |
| 5 | 30 | 83.12 | 95.51 |
| 6 | 35 | 80.53 | 93.89 |
The experimental results show that: under the same conditions, the yield and the product purity can be improved by properly increasing the mass fraction of the concentrated sulfuric acid in the catalyst, but the product yield is reduced along with the increase of the mass fraction of the concentrated sulfuric acid in the catalyst, which proves that the methanol is favorable for mixing methyl tertiary butyl ether and protonic acid under a certain proportion and promotes the bond breaking reaction of ether bonds. Therefore, the mass fraction of 98% concentrated sulfuric acid in methanol is preferably controlled to be 10% -30%, and the yield and purity are controlled to be 15% -20% relatively high.
Example 2
Influence of different catalyst addition amounts on reaction results
17.6g of methyl tertiary butyl ether and 98% concentrated sulfuric acid methanol solution with the mass fraction of 15% are mixed and poured into a constant pressure dropping funnel, 12g of methyl dichlorosilane is added into a 100mL three-neck flask, magnetic stirring is started, the temperature is increased, when the isothermal temperature is increased to above 35 ℃, the methyl tertiary butyl ether mixed solution starts to be dropped, the reaction temperature is controlled to be not higher than 40 ℃, and after three hours of dropping, the mixture is kept warm and cured for 45 minutes. And (3) transferring the reacted liquid to a rectifying tower for reduced pressure rectification, wherein the rectifying pressure is-0.05 MPa, collecting components with the temperature of 37-38 ℃ to obtain a product, and carrying out gas chromatographic analysis.
TABLE 2 reaction Effect of different catalyst addition amounts
| Sequence number | 15% of 98% of concentrated sulfuric acid methanol solution added per gram | Yield/% | Purity/% |
| 1 | 0.18(1％) | 82.56 | 93.51 |
| 2 | 0.53(3％) | 89.95 | 97.14 |
| 3 | 0.88(5％) | 90.25 | 96.02 |
| 4 | 1.06(7％) | 88.30 | 92.59 |
The experimental results show that: under the same conditions, the product yield increased with increasing catalyst addition, but was not significant. The excessive catalyst results in increased methanol, which has similar boiling point to the target product and may react to form methyltrimethoxysilane, resulting in lowered product purity. Therefore, the amount of 98% concentrated sulfuric acid methanol is controlled to 3-5% by mass, preferably 3% by mass, of methyl tertiary butyl ether.
Example 3
Influence of different reaction temperatures on the reaction results
17.6g of methyl tertiary butyl ether and 0.53g of 15% 98% concentrated sulfuric acid methanol solution are mixed and poured into a constant pressure dropping funnel, 12g of methyl dichlorosilane is added into a 100mL three-neck flask, magnetic stirring is started, the temperature is increased, the reaction temperature is controlled to be 30-45 ℃, and heat preservation and curing are continued for 45min after three hours of dropping are completed. And (3) transferring the reacted liquid to a rectifying tower for reduced pressure rectification, wherein the rectifying pressure is-0.05 MPa, collecting components with the temperature of 37-38 ℃ to obtain a product, and carrying out gas chromatographic analysis.
TABLE 3 reaction Effect at different reaction temperatures
| Sequence number | Reaction temperature/. Degree.C | Yield/% | Purity/% |
| 1 | 30 | 68.41 | 87.39 |
| 2 | 35 | 87.48 | 95.36 |
| 3 | 40 | 90.95 | 97.57 |
| 4 | 45 | 59.24 | 80.01 |
The experimental results show that: the lower temperature is unfavorable for the conversion of the reaction, and unreacted raw materials are difficult to remove in the subsequent separation and purification, so that the purity is affected. When the temperature is raised to 45 ℃, the raw materials start to gasify, so that the two raw materials react incompletely, and the yield and purity are seriously affected. Therefore, the reaction temperature is controlled to be in the range of 35 to 40℃and preferably 39 to 40 ℃.
Example 4
Influence of different feed ratios on reaction results
17.6g of methyl tertiary butyl ether and 0.53g of 15% of 98% concentrated sulfuric acid methanol solution are mixed and poured into a constant pressure dropping funnel, methyl dichlorosilane with different mass is added into a 100mL three-neck flask, magnetic stirring is started, the temperature is increased, when the temperature is increased to above 35 ℃, methyl tertiary butyl ether mixed solution is dripped, the reaction temperature is controlled to be 39-40 ℃, and after three hours of dripping, heat preservation and curing are continued for 45 minutes. And (3) transferring the reacted liquid to a rectifying tower for reduced pressure rectification, wherein the rectifying pressure is-0.05 MPa, collecting components with the temperature of 37-38 ℃ to obtain a product, and carrying out gas chromatographic analysis.
TABLE 4 reaction Effect of different feed ratios
| Sequence number | The mass/g of methyl dichlorosilane is added | Feed ratio | Yield/% | Purity/% |
| 1 | 10.93 | 0.95:2 | 83.29 | 95.32 |
| 2 | 11.62 | 1.01:2 | 88.89 | 97.49 |
| 3 | 11.96 | 1.04:2 | 92.95 | 97.57 |
| 4 | 12.32 | 1.07:2 | 89.63 | 95.13 |
| 5 | 12.67 | 1.1:2 | 85.12 | 90.76 |
The experimental results show that: since methyldichlorosilane is volatile and is partially lost in the reaction, the reaction yield is lower when the amount of feed is less than 1:2 of the reaction weight. When methyldichlorosilane is in excess of 5% or more, the volatilization loss is removed, and methyldichlorosilane is still in excess, resulting in a decrease in purity. Therefore, the molar ratio of methyldichlorosilane to methyl t-butyl ether is preferably controlled to be about 1.04:2, and is preferably controlled to be about 1.03 to 1.05:2, with the molar ratio being controlled to be (1.01 to 1.07): 2.
Example 5
Influence of different maturation times on the reaction results
17.6g of methyl tertiary butyl ether and 0.53g of 15% concentrated sulfuric acid methanol solution are mixed and poured into a constant pressure dropping funnel, 12g of methyl dichlorosilane is added into a 100mL three-neck flask, magnetic stirring is started, the temperature is raised, when the isothermal temperature is raised to above 35 ℃, the methyl tertiary butyl ether mixed solution starts to be dropped, the reaction temperature is controlled to be 39-40 ℃, and after three hours of dropping, the mixture is continuously kept at the temperature for curing for different times. And (3) transferring the reacted liquid to a rectifying tower for reduced pressure rectification, wherein the rectifying pressure is-0.05 MPa, collecting components with the temperature of 37-38 ℃ to obtain a product, and carrying out gas chromatographic analysis.
TABLE 5 reaction Effect at different maturation times
| Sequence number | Curing time/min | Yield/% | Purity/% |
| 1 | 10 | 84.25 | 90.20 |
| 2 | 20 | 88.67 | 94.17 |
| 3 | 30 | 91.94 | 96.37 |
| 4 | 40 | 92.47 | 97.45 |
| 5 | 50 | 91.16 | 95.93 |
| 6 | 60 | 89.28 | 94.62 |
| 7 | 70 | 88.75 | 90.38 |
The experimental results show that: when the curing time is short, part of reactants are not reacted, and a certain amount of methyl-methoxy chlorosilane exists, so that the yield and purity are affected. When the aging time is too long, the target product tends to self-polymerize to form a polymer, and the yield decreases. Therefore, the curing time is reasonably controlled to be 30-50 min, preferably 30-40 min.
Example 6
The embodiment provides a preparation method of methyldimethoxyhydrosilane, which is a laboratory small-scale amplification test process and specifically comprises the following steps: 176g of methyl tertiary butyl ether and 5.3g of 15% concentrated sulfuric acid methanol solution are mixed and poured into a constant pressure dropping funnel, 120g of methyl dichlorosilane is added into a 500mL three-neck flask, magnetic stirring is started, the temperature is raised, when the isothermal temperature is raised to above 35 ℃, methyl tertiary butyl ether mixed solution is started to be dropped, the reaction temperature is controlled to be 39-40 ℃, and after three hours of dropping, the mixture is continuously kept at the temperature for curing for 30 minutes. And transferring the reacted liquid to a rectifying tower for reduced pressure rectification, wherein the rectifying pressure is-0.05 MPa, collecting components with the temperature of 37-38 ℃ to obtain a product, and performing gas chromatographic analysis, wherein the yield is 91.05%, and the purity is 97.89%.
Example 7
The embodiment provides a preparation method of methyldimethoxyhydrosilane, which is a laboratory small-scale amplifying parallel test process and specifically comprises the following steps: 176g of methyl tertiary butyl ether and 5.3g of 15% concentrated sulfuric acid methanol solution are mixed and poured into a constant pressure dropping funnel, 120g of methyl dichlorosilane is added into a 500mL three-neck flask, magnetic stirring is started, the temperature is raised, when the isothermal temperature is raised to above 35 ℃, methyl tertiary butyl ether mixed solution is started to be dropped, the reaction temperature is controlled to be 39-40 ℃, and after three hours of dropping, the mixture is continuously kept at the temperature for curing for 30 minutes. And transferring the reacted liquid to a rectifying tower for reduced pressure rectification, wherein the rectifying pressure is-0.05 MPa, collecting components with the temperature of 37-38 ℃ to obtain a product, and carrying out gas chromatographic analysis, wherein the yield is 90.57%, and the purity is 98.02%.
Example 8
The embodiment provides a preparation method of methyldimethoxyhydrosilane, which is a pilot test process and specifically comprises the following steps: 8.8kg of methyl tertiary butyl ether and 265g of 15% concentrated sulfuric acid methanol solution are mixed, poured into a raw material tank and placed with nitrogen for 3 times, 6kg of methyl dichlorosilane is added into a 25L kettle type reactor, stirring is started and the temperature is raised after nitrogen is placed at normal temperature, when the temperature in the kettle is raised to above 35 ℃, methyl tertiary butyl ether mixed solution in the raw material tank is pumped into a reaction kettle by a peristaltic pump, the reaction temperature is controlled to be 39-40 ℃, and heat preservation and curing are continued for 30min after three hours of feeding are completed. And (3) transferring the reacted liquid to a rectifying tower for reduced pressure rectification, wherein the rectifying pressure is-0.05 MPa, collecting components with the temperature of 37-38 ℃ to obtain a product, and performing gas chromatographic analysis, wherein the yield is 89.65%, and the purity is 97.64%.
Example 9
The embodiment provides a preparation method of methyldimethoxyhydrosilane, which is a pilot test process and specifically comprises the following steps: 10.6kg of methyl tertiary butyl ether and 318g of 15% concentrated sulfuric acid methanol solution are mixed, poured into a raw material tank and placed with nitrogen for 3 times, 7.2kg of methyl dichlorosilane is added into a 25L kettle type reactor, stirring is started and heating is carried out after nitrogen is placed at normal temperature, when the temperature in the kettle is increased to above 35 ℃, methyl tertiary butyl ether mixed solution in the raw material tank is pumped into a reaction kettle by a peristaltic pump, the reaction temperature is controlled to be 39-40 ℃, and heat preservation and curing are continued for 30min after three hours of feeding are completed. And transferring the reacted liquid to a rectifying tower for reduced pressure rectification, wherein the rectifying pressure is-0.05 MPa, collecting components with the temperature of 37-38 ℃ to obtain a product, and carrying out gas chromatographic analysis, wherein the yield is 90.92%, and the purity is 98.04%.
In conclusion, the methyl dichlorosilane and methyl tertiary butyl ether react under the catalysis of the concentrated sulfuric acid methanol solution to generate the methyl dimethoxysilane, so that the generation of hydrogen chloride is avoided, the acidity of a product is controlled, the reaction condition is mild, the reaction raw materials are cheap and easy to obtain, the reaction result is stable, the product yield is high, and the method has a good industrial mass production prospect.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. A preparation method of methyldimethoxyhydrosilane is characterized in that: methyl tertiary butyl ether and methyl dichlorosilane are used as raw materials, and methyl dimethoxysilane is obtained through the reaction under the catalysis of a strong acid catalyst; the reaction equation involved is: CH (CH) 3 SiCl 2 H+2CH 3 OC(CH 3 ) 3 →CH 3 Si(OCH 3 ) 2 H+2(CH 3 ) 3 CCl; the strong acid catalyst in the step (1) is a methanol solution of 98% concentrated sulfuric acid.
2. The method for preparing methyldimethoxyhydrosilane according to claim 1, wherein: the preparation method comprises the following steps:
(1) Firstly, mixing a strong acid catalyst and methyl tertiary butyl ether, adding the methyl tertiary butyl ether into methyl dichlorosilane in a continuous feeding mode under the stirring condition, controlling the temperature of a reaction system to be not more than 40 ℃, and keeping the temperature for curing after the feeding is completed;
(2) After the reaction is finished, the mixture is subjected to vacuum rectification and purification to obtain the methyldimethoxy hydrosilane.
3. The method for preparing methyldimethoxyhydrosilane according to claim 2, characterized in that: the mass fraction of the 98% concentrated sulfuric acid in the methanol is 10% -30%.
4. A process for the preparation of methyldimethoxyhydrosilane as claimed in claim 3, wherein: in the step (1), the mass fraction of 98% concentrated sulfuric acid in methanol is 15% -20%.
5. The method for producing methyldimethoxyhydrosilane according to claim 3 or 4, wherein: the addition amount of the methanol solution of the 98% concentrated sulfuric acid is 3% -5% of the mass of the methyl tertiary butyl ether.
6. The method for producing methyldimethoxyhydrosilane according to claim 1 or 2, characterized in that: the feeding mole ratio of the methyldichlorosilane to the methyl tertiary butyl ether in the step (1) is (1.01-1.07): 2.
7. The method for preparing methyldimethoxyhydrosilane according to claim 6, wherein: the feeding mole ratio of the methyl dichlorosilane to the methyl tertiary butyl ether in the step (1) is (1.03-1.05): 2.
8. The method for preparing methyldimethoxyhydrosilane according to claim 2, characterized in that: the control conditions of the heat preservation and curing in the step (1) are as follows: the temperature is controlled to be between 35 and 40 ℃, and the heat preservation and curing time is 30 to 50 minutes.
9. The method for preparing methyldimethoxyhydrosilane according to claim 8, wherein: the control conditions of the heat preservation and curing in the step (1) are as follows: the temperature is controlled to be 39-40 ℃, and the heat preservation and curing time is 30-40 min.
10. The method for preparing methyldimethoxyhydrosilane according to claim 2, characterized in that: the pressure of the reduced pressure rectification in the step (2) is minus 0.05MPa, and the temperature of the target product extracted in the reduced pressure rectification is 37-38 ℃.
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