CN105669739A - Synthesis method of aminopropyl triethoxysilane - Google Patents
Synthesis method of aminopropyl triethoxysilane Download PDFInfo
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- CN105669739A CN105669739A CN201610142413.2A CN201610142413A CN105669739A CN 105669739 A CN105669739 A CN 105669739A CN 201610142413 A CN201610142413 A CN 201610142413A CN 105669739 A CN105669739 A CN 105669739A
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- triethoxysilane
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- 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
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Abstract
The invention relates to a synthesis method of aminopropyl triethoxysilane and belongs to the technical field of fine chemical engineering.According to the method, acetone and allyl amine are put into a reactor according to a proportion, a water absorbing agent is added, after a stirring and temperature-raising reaction, reactants are distilled and filtered, filter residues are reused after being regenerated, filter liquor and triethoxysilane are subjected to an addition reaction through a Custer catalyst, purified products obtained after being distilled react with deionized water, and after low-boiling-point acetone is obtained through distillation, an aminopropyl triethoxysilane product is obtained.The yield of the aminopropyl triethoxysilane product is high, energy consumption is low, production cost is low, side products and raw materials can be recycled, and environmental pollution is avoided.
Description
Technical field
The present invention relates to the synthetic method of a kind of aminopropyl triethoxysilane, belong to technical field of fine.
Background technology
Aminopropyl triethoxysilane is a kind of purposes silane coupler product widely, it is mainly used in the industrial circles such as coating, rubber, plastics, paint, machinery, glass, electronics, casting, it is one of most widely used silane in the market, play thickening, hand over the effects such as viscous, coupling, and the application performance such as wear-resisting, ageing-resistant of product can be increased. This production development is with a long history, domestic and international Jun You big companies produces, as the KH-550 of the Chinese Academy of Sciences, the Z-6011 of Dow corning, the AMEO of Germany Di Gaosha, the Japan KBM-903 of SHIN-ETSU HANTOTAI, the U.S. step the A-1100 of figure and the GF-93 etc. of Germany watt gram, also there are a lot of patent about aminopropyl triethoxysilane synthesis and report both at home and abroad, according to available data, the synthetic method of aminopropyl triethoxysilane is broadly divided into three kinds:
The first: addition process. With triethoxysilane and allyl amine additive reaction under catalyst, obtain aminopropyl triethoxysilane product after distillation, product yield about 85%.
The second: ammonolysis process. Reacting at high temperature under high pressure with liquefied ammonia and chloropropyl triethoxysilane, filter, distillation obtains aminopropyl triethoxysilane product, product yield about 70%.
The third: hydrogenating reduction method. Under pressurization and catalyst, carry out reduction reaction with hydrogen with cyanoethyl triethoxysilane, obtain aminopropyl triethoxysilane product, product yield about 95%.
The shortcoming of addition process synthesis aminopropyl triethoxysilane is because allyl amine activity is higher, cause that the product that addition goes out is the isomers product of a certain proportion of γ position and β position, being difficult to separate and purify, product yield is very low, substantially produces without the method so now industrial. Ammonolysis process is the main approach of current industrial production aminopropyl triethoxysilane, and the shortcoming of the method is that equipment requirements is significantly high, it is necessary to a whole set of reaction under high pressure and recovery system, additionally also can produce some by-products. The shortcoming of hydrogenating reduction method has two: one to be that the synthesis of raw material cyanoethyl triethoxysilane is significantly high to technological requirement, and production cost is significantly high; Two is that equipment and technique are had certain requirement by hydrogenating reduction process.
Summary of the invention
It is an object of the invention to: providing a kind of technological operation easy, raw material is easy to get, and can effectively ensure that the synthetic method of the aminopropyl triethoxysilane of product quality and yield.
The technical scheme is that
A kind of synthetic method of aminopropyl triethoxysilane; It is characterized in that: it comprises the following steps:
1), the rate of charge of acetone and allyl amine 1.1～1.5:1 in molar ratio is put in reaction vessel; Water absorbing agent is added by the 45% of thrown allyl amine weight; After having fed intake, being warmed up to 50～55 DEG C under the mixing speed of 120～150 revs/min, insulation reaction, after 5～6 hours, is then warmed up to 60～70 DEG C again and distills out the raw material acetone that unreacted is complete;
2), acetone distillation after be cooled to less than 30 DEG C filtrations, obtain Schiff's base ketimide; Filtering residue is moisture magnesium sulfate, and magnesium sulfate can be reused after thermal regeneration; The complete raw material acetone of unreacted can be recycled;
3), the Schiff's base ketimide being filtrated to get is put into in the reactor of magnetic agitation, 70～75 DEG C it are warmed up under the mixing speed of 60～90 revs/min, add Karst catalyst, triethoxysilane is dripped again in 4 hours, triethoxysilane and Schiff's base ketimide molar ratio are 1:1.01～1.05, triethoxysilane distills after aging 1～2 hour after dropwising at 75～80 DEG C under-0.098MPa condition, obtains silane intermediate;
4), silane intermediate is put into in the reactor of magnetic agitation, 60～70 DEG C it are warmed up under the mixing speed of 60～90 revs/min, deionized water is dripped again in 2 hours, the molar ratio of silane intermediate and deionized water is 1.01:1, distill 2 hours under-0.098MPa again after aging 1～2 hour at 70～80 DEG C after dropwising, steam low-boiling point material acetone; Then reactor is lowered the temperature, obtain aminopropyl triethoxysilane finished product; The low-boiling point material acetone distilled out can be recycled.
Described water absorbing agent is anhydrous magnesium sulfate or aqueous magnesium sulfate that quality is 55%-65% circular regeneration.
The described mixed solution that Karst catalyst is chloroplatinic acid and t etram-ethyltetravinylcyclotetrasiloxane;
Described Schiff's base ketimine structure formula is: (CH3)2C=NCH2CH=CH2
Described silane intermediate structural formula is: (CH3)2C=NCH2CH2CH2Si(OC2H5)3
The composition principle of the present invention is:
CH3COCH3+NH2CH2CH=CH2---(CH3)2C=NCH2CH=CH2+H2O
(Schiff's base ketimide)
MgSO4+H2O----MgSO4·7H2O
(CH3)2C=NCH2CH=CH2+HSi(OC2H5)3—
(CH3)2C=NCH2CH2CH2Si(OC2H5)3
(silane intermediate)
(CH3)2C=NCH2CH2CH2Si(OC2H5)3+H2O-----
N2CH2CH2CH2Si(OC2H5)3+CH3COCH3
(aminopropyl triethoxysilane product)
Water absorbing agent anhydrous magnesium sulfate regenerates:
MgSO4·7H2OHeatingMgSO4·2H2O
The beneficial effects of the present invention is:
1. the present invention is first with acetone and allyl amine synthesis Schiff's base ketimide, protect the amino group of allyl amine, change activity and the structure of allyl amine, making it is the generation not having isomers in same triethoxysilane addition, the only appearance of γ position addition compound product, improve quality and the yield of addition compound product, thus ensure that the quality of aminopropyl triethoxysilane product and yield;
2. pair equipment requirements is not high, and technological operation is easy, and raw material is easy to get;
3. no coupling product produces, safety and environmental protection, and raw material acetone can be recycled, and anhydrous magnesium sulfate can regenerate after drying dewater 4 hours at 100～120 DEG C after using, and reuses.
Detailed description of the invention
Embodiment 1:
1L four-hole boiling flask adds 2.2mol(127.8 gram) acetone and 2mol(114.2 gram) allyl amine, add 51.0 grams of anhydrous magnesium sulfates, after having fed intake, open stirring, speed of agitator is 120 revs/min, after still temperature rise to 55 DEG C insulation reaction 5 hours, then temperature is raised to 70 DEG C of distillations, obtains 0.17mol(9.8 gram) the complete raw material acetone of unreacted.Flask is finally cooled to less than 30 DEG C filtrations, and filtrate is 1.95mol(189.4 gram) Schiff's base ketimide, filtering residue is magnesium sulfate crystals 92.7 grams moisture. The 92.7 grams moisture magnesium sulfate crystals of filtering residue obtains 66.8 grams containing the magnesium sulfate of the regeneration of two molecular waters after toasting 4 hours in 110 DEG C of baking ovens, keeps and reuses.
1L four-hole boiling flask adds 1.95mol(189.4 gram) above-mentioned filtrate Schiff's base ketimide and 1 microlitre Karst catalyst, open magnetic stirring apparatus, rotating speed is 60 revs/min, by still temperature rise to 75 DEG C, by 1.99mol(326.9 gram in 4 hours) triethoxysilane is added drop-wise in flask, distill under-0.098MPa after aging 2 hours at 75 DEG C after dropwising, obtain 1.95mol(508.8 gram) silane intermediate.
1L four-hole boiling flask adds 1.95mol(508.8 gram) silane intermediate that obtains of above-mentioned distillation, open magnetic stirring apparatus, rotating speed is 60 revs/min, by still temperature rise to 70 DEG C, by 1.94mol(34.7 gram in 2 hours) deionized water is added drop-wise in flask, after dropwising at 80 DEG C after aging 1 hour, 1.94mol(112.8 gram of the low-boiling point material acetone that reaction generates is distilled out again) under-0.098MPa, after cooling, flask is 1.93mol(428.6 gram) aminopropyl triethoxysilane product, its content of gas chromatographic detection is 98.8%, product yield about 96%.
Embodiment 2:
1L four-hole boiling flask adds 9.8 grams and 112.8 grams of the acetone of embodiment 1 Distillation recovery, add 2.2mol(127.8 gram altogether of 5.2 grams of new acetone) and 2mol(114.2 gram) allyl amine, add embodiment 1 and regenerate rear 68.8 grams of magnesium sulfate containing two molecular waters, after having fed intake, opening stirring, speed of agitator is 120 revs/min, after still temperature rise to 55 DEG C insulation reaction 5 hours, temperature is raised to 60 DEG C of distillations again, obtains 0.16mol(9.2 gram) the complete raw material acetone of unreacted. Flask is finally cooled to less than 30 DEG C filtrations, and filtrate is 1.95mol(189.7 gram) Schiff's base ketimide, filtering residue is magnesium sulfate crystals 110.4 grams moisture.
The 110.4 grams moisture magnesium sulfate crystals of filtering residue obtains 74.2 grams containing the magnesium sulfate of two molecular waters after toasting 4 hours in 110 DEG C of baking ovens, keeps and reuses.
1L four-hole boiling flask adds 1.95mol(189.7 gram) above-mentioned filtrate Schiff's base ketimide and 1 microlitre Karst catalyst, open magnetic stirring apparatus, rotating speed is 60 revs/min, by still temperature rise to 70 DEG C, by 1.99mol(326.9 gram in 4 hours) triethoxysilane is added drop-wise in flask, distill under-0.098MPa after aging 2 hours at 80 DEG C after dropwising, obtain 1.93mol(505.7 gram) silane intermediate.
1L four-hole boiling flask adds 1.93mol(505.7 gram) silane intermediate that obtains of above-mentioned distillation, open magnetic stirring apparatus, rotating speed is 60 revs/min, by still temperature rise to 60 DEG C, by 1.93mol(34.4 gram in 2 hours) deionized water is added drop-wise in flask, after dropwising at 70 DEG C after aging 1 hour, 1.92mol(111.2 gram of the low-boiling point material acetone that reaction generates is distilled out again) under-0.098MPa, after cooling, flask is 1.92mol(425.7 gram) aminopropyl triethoxysilane product, its content of gas chromatographic detection is 99.0%, product yield about 96%.
Embodiment 3:
10L four-hole boiling flask adds 22mol(1278 gram) acetone and 20mol(1142 gram) allyl amine, add 510 grams of anhydrous magnesium sulfates, after having fed intake, open stirring, speed of agitator is 120 revs/min, after still temperature rise to 55 DEG C insulation reaction 5 hours, then temperature is raised to 65 DEG C of distillations, obtains 1.92mol(112 gram) the complete raw material acetone of unreacted.Flask is finally cooled to less than 30 DEG C filtrations, and filtrate is 19.6mol(1908 gram) Schiff's base ketimide, filtering residue is magnesium sulfate crystals 907 grams moisture.
The 907 grams moisture magnesium sulfate crystals of filtering residue obtains 665 grams containing the magnesium sulfate of the regeneration of two molecular waters after toasting 4 hours in 110 DEG C of baking ovens, keeps and reuses.
10L four-hole boiling flask adds 19.6mol(1908 gram) above-mentioned filtrate Schiff's base ketimide and 10 microlitre Karst catalyst, open magnetic stirring apparatus, rotating speed is 60 revs/min, by still temperature rise to 73 DEG C, by 20.0mol(3286 gram in 4 hours) triethoxysilane is added drop-wise in flask, after dropwising at 78 DEG C after aging 2 hours, then distill under-0.098MPa, obtain 19.6mol(5123 gram) silane intermediate.
10L four-hole boiling flask adds 19.6mol(5123 gram) silane intermediate that obtains of above-mentioned distillation, open magnetic stirring apparatus, rotating speed is 60 revs/min, by still temperature rise to 65 DEG C, by 19.4mol(349 gram in 2 hours) deionized water is added drop-wise in flask, at 75 DEG C, under-0.098MPa, 19.3mol(1121 gram of the low-boiling point material acetone that reaction generates after aging 1 hour, is distilled out) after dropwising, after cooling, flask is 19.6mol(4348 gram) aminopropyl triethoxysilane product, its content of gas chromatographic detection is 98.9%, product yield about 98%.
Embodiment 4:
10L four-hole boiling flask adds 112 grams and 1121 grams of the acetone of embodiment 3 Distillation recovery, add 22mol(1278 gram altogether of 45 grams of new acetone) and 20mol(1142 gram) allyl amine, add embodiment 3 and regenerate rear 665 grams of magnesium sulfate containing two molecular waters, after having fed intake, opening stirring, speed of agitator is 120 revs/min, after still temperature rise to 55 DEG C insulation reaction 5 hours, temperature is raised to 68 DEG C of distillations again, obtains 1.90mol(110 gram) the complete raw material acetone of unreacted. Flask is finally cooled to less than 30 DEG C filtrations, and filtrate is 19.5mol(1894 gram) Schiff's base ketimide, filtering residue is magnesium sulfate crystals 1077 grams moisture.
The 1077 grams moisture magnesium sulfate crystals of filtering residue obtains 708 grams containing the magnesium sulfate of two molecular waters after toasting 4 hours in 110 DEG C of baking ovens, keeps and reuses.
10L four-hole boiling flask adds 19.5mol(1894 gram) above-mentioned filtrate Schiff's base ketimide and 10 microlitre Karst catalyst, open magnetic stirring apparatus, rotating speed is 60 revs/min, by still temperature rise to 72 DEG C, by 19.9mol(3270 gram in 4 hours) triethoxysilane is added drop-wise in flask, after dropwising at 75～80 DEG C after aging 2 hours, then distill under-0.098MPa, obtain 19.4mol(5073 gram) silane intermediate.
10L four-hole boiling flask adds 19.4mol(5073 gram) silane intermediate that obtains of above-mentioned distillation, open magnetic stirring apparatus, rotating speed is 60 revs/min, by still temperature rise to 68 DEG C, by 19.2mol(346 gram in 2 hours) deionized water is added drop-wise in flask, after dropwising at 75 DEG C after aging 1 hour, 19.2mol(1116 gram of the low-boiling point material acetone that reaction generates is distilled out again) under-0.098MPa, after cooling, flask is 19.3mol(4281 gram) aminopropyl triethoxysilane product, its content of gas chromatographic detection is 99.1%, product yield about 97%.
Claims (3)
1. the synthetic method of an aminopropyl triethoxysilane; It is characterized in that: it comprises the following steps:
1), the rate of charge of acetone and allyl amine 1.1～1.5:1 in molar ratio is put in reaction vessel;Water absorbing agent is added by the 45% of thrown allyl amine weight; After having fed intake, being warmed up to 50～55 DEG C under the mixing speed of 120～150 revs/min, insulation reaction, after 5～6 hours, is then warmed up to 60～70 DEG C again and distills out the raw material acetone that unreacted is complete;
2), acetone distillation after be cooled to less than 30 DEG C filtrations, obtain Schiff's base ketimide; Filtering residue is moisture magnesium sulfate, and magnesium sulfate can be reused after thermal regeneration; The complete raw material acetone of unreacted can be recycled;
3), the Schiff's base ketimide being filtrated to get is put into in the reactor of magnetic agitation, 70～75 DEG C it are warmed up under the mixing speed of 60～90 revs/min, add Karst catalyst, triethoxysilane is dripped again in 4 hours, triethoxysilane and Schiff's base ketimide molar ratio are 1:1.01～1.05, triethoxysilane distills after aging 1～2 hour after dropwising at 75～80 DEG C under-0.098MPa condition, obtains silane intermediate;
4), silane intermediate is put into in the reactor of magnetic agitation, 60～70 DEG C it are warmed up under the mixing speed of 60～90 revs/min, deionized water is dripped again in 2 hours, the molar ratio of silane intermediate and deionized water is 1.01:1, distill 2 hours under-0.098MPa again after aging 1～2 hour at 70～80 DEG C after dropwising, steam low-boiling point material acetone; Then reactor is lowered the temperature, obtain aminopropyl triethoxysilane finished product; The low-boiling point material acetone distilled out can be recycled.
2. the synthetic method of a kind of aminopropyl triethoxysilane according to claim 1; It is characterized in that: described water absorbing agent is anhydrous magnesium sulfate or aqueous magnesium sulfate that quality is 55%-65% circular regeneration.
3. the synthetic method of a kind of aminopropyl triethoxysilane according to claim 1; It is characterized in that: the described mixed solution that Karst catalyst is chloroplatinic acid and t etram-ethyltetravinylcyclotetrasiloxane.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111495429A (en) * | 2020-04-14 | 2020-08-07 | 南昌大学 | Preparation method of efficient composite catalyst and preparation method of silane coupling agent KH-560 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2185984B (en) * | 1986-01-30 | 1989-12-06 | Dow Corning | Preparation of primary aminosiloxanes |
| JPH03184983A (en) * | 1989-12-13 | 1991-08-12 | Toshiba Silicone Co Ltd | Amino group-containing silane |
-
2016
- 2016-03-14 CN CN201610142413.2A patent/CN105669739B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2185984B (en) * | 1986-01-30 | 1989-12-06 | Dow Corning | Preparation of primary aminosiloxanes |
| JPH03184983A (en) * | 1989-12-13 | 1991-08-12 | Toshiba Silicone Co Ltd | Amino group-containing silane |
Non-Patent Citations (3)
| Title |
|---|
| S. K. DUPLOCK等,: "Synthesis of Siloxanes Containing Reactive Side Chains", 《JOURNAL OF INORGANIC ORGANOMETALLIC POLYMERS》 * |
| YINGJIAN BO等,: "Alpha-amino silanes via metalated imines as an approach to the synthesis of silanediol protease inhibitors", 《TETRAHEDRON》 * |
| 幸松民等: "《有机硅合成工艺及产品应用》", 30 September 2000 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111495429A (en) * | 2020-04-14 | 2020-08-07 | 南昌大学 | Preparation method of efficient composite catalyst and preparation method of silane coupling agent KH-560 |
| CN111495429B (en) * | 2020-04-14 | 2023-11-10 | 南昌大学 | Preparation method of efficient composite catalyst and preparation method of silane coupling agent KH-560 |
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Address after: Luochang Town, Shashi District, Jingzhou City, Hubei Province Patentee after: Hubei Jianghan New Material Co.,Ltd. Address before: 434000 No.2 Road, Shashi District Economic and Technological Development Zone, Jingzhou City, Hubei Province Patentee before: JINGZHOU JIANGHAN FINE CHEMICAL Co.,Ltd. |