CN105859766A - Method for solvent-free preparation of N, N-dimethyl-3-aminopropyltrimethoxysilane - Google Patents
Method for solvent-free preparation of N, N-dimethyl-3-aminopropyltrimethoxysilane Download PDFInfo
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- CN105859766A CN105859766A CN201610332356.4A CN201610332356A CN105859766A CN 105859766 A CN105859766 A CN 105859766A CN 201610332356 A CN201610332356 A CN 201610332356A CN 105859766 A CN105859766 A CN 105859766A
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- Prior art keywords
- dimethylamine
- autoclave
- solvent
- reaction
- dimethyl
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- 238000000034 method Methods 0.000 title claims abstract description 17
- QIOYHIUHPGORLS-UHFFFAOYSA-N n,n-dimethyl-3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN(C)C QIOYHIUHPGORLS-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 15
- XHFGWHUWQXTGAT-UHFFFAOYSA-N dimethylamine hydrochloride Natural products CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 claims abstract description 14
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000007664 blowing Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 5
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012267 brine Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- ZLDHYRXZZNDOKU-UHFFFAOYSA-N n,n-diethyl-3-trimethoxysilylpropan-1-amine Chemical compound CCN(CC)CCC[Si](OC)(OC)OC ZLDHYRXZZNDOKU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 8
- 238000009835 boiling Methods 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007792 gaseous phase Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000009941 weaving Methods 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
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
The invention discloses a method for solvent-free preparation of N, N-dimethyl-3-aminopropyltrimethoxysilane. According to the invention, dimethylamine and 3-aminopropyltrimethoxysilane are heated in an autoclave in a molar ratio of (3-6):1, nitrogen is introduced to react for 6-8 hours, then an exhaust gas is introduced to the other autoclave to absorb excessive dimethylamine, the temperature is lowered to be 20 DEG C, and solid dimethylamine hydrochloride is filtered out and leached by an N, N-dimethylformamide solvent for one time. A filtrate is decompressed and concentrated to recover the N, N-dimethylformamide solvent and then rectified to obtain the product. In the reaction process of the invention, no solvent is used and the nitrogen is introduced to keep the reaction performed under a certain pressure, so that the reaction time is greatly shortened, the excessive exhaust gas of a low boiling point raw material, namely dimethylamine (at normal temperature of 7 DEG C), in a use process is effectively reused and controlled to protect the environment, and the content of the product yield is 99% or above.
Description
Technical field
The present invention relates to silane coupler and manufacture field, a kind of method particularly relating to solvent-free preparation N, N-dimethyl-3-aminopropyl trimethoxysilane.
Background technology
Organo silane coupling agent, as a kind of new material, is increasingly widely used in construction material, weaving, in coating, in fiberglass surfacing processes, improve bond properties, in filler processes, improve dispersibility and the bonding force of resin, it is additionally operable to sealant, coating and bonding agent.Demand both domestic and external just steps up.
N, N-dimethyl-3-aminopropyl trimethoxysilane has obtained the accreditation of most of client as a kind of silane coupler therein, prior art uses raw material dimethylamine and 3-r-chloropropyl trimethoxyl silane sintetics, external relevant this product synthetic method Journal of Organic
Chemistry; vol. 36; (1971);P. introduce in 3,120 3126 with (3.5mol) 3-r-chloropropyl trimethoxyl silane and (14mol) dimethylamine and 400ml petroleum solvents in autoclave 100 DEG C react 22 hours.Obtaining 570g product yield is 79%, and the response time is long, and yield is low, affects industrialized mass production.
Summary of the invention
It is an object of the invention to overcome above deficiency; provide solvent-free preparation N; the method of N-dimethyl-3-aminopropyl trimethoxysilane; course of reaction of the present invention does not use any solvent and is passed through nitrogen and makes reaction be maintained under a certain pressure carrying out; the response time is not only made to be greatly shortened; and make the tail gas of low boiling raw material dimethylamine (normal pressure 7 DEG C) excess in use obtain effective reuse governance and protection environment, improve product yield content more than 99%.
The technical scheme that the present invention provides is:
A kind of method of solvent-free preparation N, N-dimethyl-3-aminopropyl trimethoxysilane, the method comprises the following steps:
A) in the first autoclave, 3-r-chloropropyl trimethoxyl silane is put into, stirring evacuation keep negative pressure in making still, close and be passed through liquid dimethylamine after vacuum valve and stir and start afterwards slowly to heat up, finally it is warmed up to 120 DEG C and the slowest unlatching in nitrogen makes still keeps pressure 0.8Mpa to react 6-8 hour, course of reaction samples material content 3-r-chloropropyl trimethoxyl silane being detected and terminates less than 0.2% reaction；
B) after step a) reaction terminates, by tail gas lactogenesis the second autoclave, and in the second autoclave, put into raw material 3-r-chloropropyl trimethoxyl silane, absorb the first autoclave and react the dimethylamine of remaining excess；
C) by the first autoclave pressure release after reaction terminates, again temperature in the kettle is cooled to 20 DEG C of blowings and leach dimethylamine hydrochloride, and with N, dinethylformamide rinsing dimethylamine hydrochloride solid, filtrate merges concentration and recovery N, dinethylformamide rectification obtain N, N-diethyl-3-aminopropyl trimethoxysilane；
D) it is dissolved in water and is made into 50% aqueous solution by step c) reacts remaining dimethylamine hydrochloride solid and is added drop-wise in 30% sodium hydrate aqueous solution and heat temperature raising, and use collection tower to carry out fraction less than 20 DEG C at gas phase temperature to cool down and obtain dimethylamine and be re-used in course of reaction.
Preferably, in the method for described solvent-free preparation N, N-dimethyl-3-aminopropyl trimethoxysilane, in described step a), 3-r-chloropropyl trimethoxyl silane is 1:3-6 with the mol ratio of the raw material input of diethylamine.
Preferably, in described step d), cooling uses chilled brine to cool down.
The invention has the beneficial effects as follows not use any solvent in course of reaction of the present invention and be passed through nitrogen makes reaction be maintained under a certain pressure carrying out; the response time is not only made to be greatly shortened; and make the tail gas of low boiling raw material dimethylamine excess in use obtain effective reuse governance and protection environment; improve product yield content more than 99%; the second autoclave is used to reclaim excess dimethylamine in course of reaction; effectively utilize raw material, prevent tail gas pollution.Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but should not limit the scope of the invention with this.
A kind of method of solvent-free preparation N, N-dimethyl-3-aminopropyl trimethoxysilane, the method comprises the following steps:
A) in the first autoclave, 3-r-chloropropyl trimethoxyl silane is put into, stirring evacuation keep negative pressure in making still, close and be passed through liquid dimethylamine after vacuum valve and stir and start afterwards slowly to heat up, finally it is warmed up to 120 DEG C and the slowest unlatching in nitrogen makes still keeps pressure 0.8Mpa to react 6-8 hour, course of reaction samples material content 3-r-chloropropyl trimethoxyl silane being detected and terminates less than 0.2% reaction；
B) after step a) reaction terminates, by tail gas lactogenesis the second autoclave, and in the second autoclave, put into raw material 3-r-chloropropyl trimethoxyl silane, absorb the first autoclave and react the dimethylamine of remaining excess；
C) by the first autoclave pressure release after reaction terminates, again temperature in the kettle is cooled to 20 DEG C of blowings and leach dimethylamine hydrochloride, and with N, dinethylformamide rinsing dimethylamine hydrochloride solid, filtrate merges concentration and recovery N, dinethylformamide rectification obtain N, N-diethyl-3-aminopropyl trimethoxysilane；
D) it is dissolved in water and is made into 50% aqueous solution by step c) reacts remaining dimethylamine hydrochloride solid and is added drop-wise in 30% sodium hydrate aqueous solution and heat temperature raising, and use collection tower to carry out fraction less than 20 DEG C at gas phase temperature to cool down and obtain dimethylamine and be re-used in course of reaction.The mol ratio that wherein in step a), the raw material of 3-r-chloropropyl trimethoxyl silane and diethylamine puts into is 1:3-6, and in step d), cooling uses chilled brine to cool down.
Embodiment 1
In first autoclave of 3000L, put into evacuation under the 3-r-chloropropyl trimethoxyl silane stirring of 1200Kg keep negative pressure in making still, simultaneously close off vacuum valve to be passed through 1200Kg liquid dimethylamine reactor and stir and start afterwards slowly to heat up, finally it is warmed up to 120 DEG C and the slowest unlatching in nitrogen makes still keeps pressure 0.8Mpa to react 6 hours, sample and make raw material 3-r-chloropropyl trimethoxyl silane terminate less than 0.2% reaction.
In the second autoclave, put into raw material 3-r-chloropropyl trimethoxyl silane equally and open dimethylamine inlet valve, absorbing the dimethylamine of the first autoclave reaction excess.
Again temperature in the kettle is cooled to 20 DEG C of blowings after first autoclave pressure release is complete and leach dimethylamine hydrochloride, and rinse solid with the solvent DMF of 100Kg, filtrate merges concentration and recovery N, dinethylformamide rectification obtain 1100Kg product, content 99.6%, yield 87.5%
Dimethylamine hydrochloride solid is dissolved in water and is made into 50% aqueous solution, is added drop-wise in 30% sodium hydrate aqueous solution of 900Kg and heat temperature raising collects top gaseous phase temperature fraction obtain qualified dimethylamine with cooling and be back in course of reaction below 20 DEG C.
Embodiment 2
Second autoclave of 3000L puts into absorb under the 3-r-chloropropyl trimethoxyl silane stirring of 1200Kg and be passed through 500Kg liquid dimethylamine reactor from repressurization after the dimethylamine of the second autoclave excess and stir and start afterwards slowly to heat up, finally it is warmed up to 110 DEG C and the slowest unlatching in nitrogen makes still keeps pressure 1.0Mpa to react 6 hours, sample and make raw material 3-r-chloropropyl trimethoxyl silane terminate less than 0.2% reaction.
In the first autoclave, put into raw material 3-r-chloropropyl trimethoxyl silane equally equally and open dimethylamine inlet valve, absorbing the dimethylamine of the second autoclave reaction excess.
Again temperature in the kettle is cooled to 20 DEG C of blowings after second autoclave pressure release is complete and leach dimethylamine hydrochloride, and rinse solid with the solvent DMF of 100Kg, filtrate merges concentration and recovery N, dinethylformamide rectification obtain 1050Kg product, content 99.1%, yield 83.5%
Dimethylamine hydrochloride solid is dissolved in water and is made into 50% aqueous solution, is added drop-wise in 30% sodium hydrate aqueous solution of 900Kg and heat temperature raising collects top gaseous phase temperature fraction obtain qualified dimethylamine and be back in course of reaction below 20 DEG C with chilled brine cooling.
Although the embodiment of invention is disclosed as above, but it is not restricted in description and embodiment listed utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, it is easily achieved other amendment, therefore, under the general concept limited without departing substantially from claim and equivalency range, the present invention is not limited to specific details and shown here as the proportioning example with description.
Claims (3)
1. the method for a solvent-free preparation N, N-dimethyl-3-aminopropyl trimethoxysilane, it is characterised in that the method comprises the following steps:
A) in the first autoclave, 3-r-chloropropyl trimethoxyl silane is put into, stirring evacuation keep negative pressure in making still, close and be passed through liquid dimethylamine after vacuum valve and stir and start afterwards slowly to heat up, finally it is warmed up to 120 DEG C and the slowest unlatching in nitrogen makes still keeps pressure 0.8Mpa to react 6-8 hour, course of reaction samples material content 3-r-chloropropyl trimethoxyl silane being detected and terminates less than 0.2% reaction；
B) after step a) reaction terminates, by tail gas lactogenesis the second autoclave, and in the second autoclave, put into raw material 3-r-chloropropyl trimethoxyl silane, absorb the first autoclave and react the dimethylamine of remaining excess；
C) by the first autoclave pressure release after reaction terminates, again temperature in the kettle is cooled to 20 DEG C of blowings and leach dimethylamine hydrochloride, and with N, dinethylformamide rinsing dimethylamine hydrochloride solid, filtrate merges concentration and recovery N, dinethylformamide rectification obtain N, N-diethyl-3-aminopropyl trimethoxysilane；
D) it is dissolved in water and is made into 50% aqueous solution by step c) reacts remaining dimethylamine hydrochloride solid and is added drop-wise in 30% sodium hydrate aqueous solution and heat temperature raising, and use collection tower to carry out fraction less than 20 DEG C at gas phase temperature to cool down and obtain dimethylamine and be re-used in course of reaction.
The method of solvent-free preparation N, N-dimethyl-3-aminopropyl trimethoxysilane the most as claimed in claim 1, it is characterised in that in described step a), 3-r-chloropropyl trimethoxyl silane is 1:3-6 with the mol ratio of the raw material input of diethylamine.
The method of solvent-free preparation N, N-dimethyl-3-aminopropyl trimethoxysilane the most as claimed in claim 1, it is characterised in that in described step d), cooling uses chilled brine to cool down.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610332356.4A CN105859766A (en) | 2016-05-19 | 2016-05-19 | Method for solvent-free preparation of N, N-dimethyl-3-aminopropyltrimethoxysilane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610332356.4A CN105859766A (en) | 2016-05-19 | 2016-05-19 | Method for solvent-free preparation of N, N-dimethyl-3-aminopropyltrimethoxysilane |
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| Publication Number | Publication Date |
|---|---|
| CN105859766A true CN105859766A (en) | 2016-08-17 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610332356.4A Pending CN105859766A (en) | 2016-05-19 | 2016-05-19 | Method for solvent-free preparation of N, N-dimethyl-3-aminopropyltrimethoxysilane |
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| CN (1) | CN105859766A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113214311A (en) * | 2021-05-27 | 2021-08-06 | 湖北君健新材料股份有限公司 | Synthesis method of N, N-dimethyl-3-aminopropyltrimethoxysilane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3919276A (en) * | 1974-07-31 | 1975-11-11 | Dow Corning | Method of preparing amines and amides |
| CN101307068A (en) * | 2007-05-18 | 2008-11-19 | 德古萨有限责任公司 | Method for preparing aminoalkyl silanes |
| CN102558219A (en) * | 2011-12-16 | 2012-07-11 | 山东轻工业学院 | Production process of tertiary amine silane |
| CN102898460A (en) * | 2012-10-21 | 2013-01-30 | 荆州市江汉精细化工有限公司 | Technology for preparing double-amino silane and treating by-product |
-
2016
- 2016-05-19 CN CN201610332356.4A patent/CN105859766A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3919276A (en) * | 1974-07-31 | 1975-11-11 | Dow Corning | Method of preparing amines and amides |
| CN101307068A (en) * | 2007-05-18 | 2008-11-19 | 德古萨有限责任公司 | Method for preparing aminoalkyl silanes |
| CN102558219A (en) * | 2011-12-16 | 2012-07-11 | 山东轻工业学院 | Production process of tertiary amine silane |
| CN102898460A (en) * | 2012-10-21 | 2013-01-30 | 荆州市江汉精细化工有限公司 | Technology for preparing double-amino silane and treating by-product |
Non-Patent Citations (1)
| Title |
|---|
| JOHN L. SPEIER等: "Syntheses of (3-Aminoalky1)silicon Compounds", 《J. ORG. CHEM.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113214311A (en) * | 2021-05-27 | 2021-08-06 | 湖北君健新材料股份有限公司 | Synthesis method of N, N-dimethyl-3-aminopropyltrimethoxysilane |
| CN113214311B (en) * | 2021-05-27 | 2024-04-26 | 湖北君健新材料股份有限公司 | Synthesis method of N, N-dimethyl-3-aminopropyl trimethoxy silane |
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Application publication date: 20160817 |