CN102115480A - Preparation method for 3-aminopropyl trisiloxane - Google Patents
Preparation method for 3-aminopropyl trisiloxane Download PDFInfo
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- CN102115480A CN102115480A CN2010101501146A CN201010150114A CN102115480A CN 102115480 A CN102115480 A CN 102115480A CN 2010101501146 A CN2010101501146 A CN 2010101501146A CN 201010150114 A CN201010150114 A CN 201010150114A CN 102115480 A CN102115480 A CN 102115480A
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- aminopropyl
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Abstract
The invention relates to a new one-step method for preparing 3-aminopropyl trisiloxane with high yield and high purity. To solve the problems existing in the background art, the invention provides a new method, which is simple in process and easy for industrial production, dispenses with a platinum catalyst and is high in yield of products, high in purity and free from an isomeric compound. The method comprises the following steps: aminopropyl siloxane, an end-capping reagent and a catalyst are added into a reactor according to the mol ratio of 1(1 to 20):(0 to 5) to react for 1 to 10 hours after temperature rises to 40 to 110 DEG C during the stirring, and simultaneously, a low-boiling by-product is vaporized through a rectifying column with filler to obtain a mixed product; the catalyst is inactivated to obtain a light yellow clear liquid; and then low-boiling residues are vaporized through atmospheric distillation and then distilled under reduced pressure to obtain 3-aminopropyl trisiloxane.
Description
Technical field
The present invention relates to organic chemistry filed, specifically is a kind of one-step preppn process of high yield high purity 3-aminopropyl trisiloxanes newly.
Background technology
3-aminopropyl trisiloxanes can be used as raw material and removes further synthetic number of chemical material, all is to be the raw material synthetic with it such as the staining agent of Silicon surfactant, ultraviolet absorbers, protein fibre etc.
Zhang Guodong etc. at periodical " New Chemical Materials " 2005,33 (10), it is raw material that the paper of delivering on the P52-54 " synthesizing of aminopropyl trisiloxanes " discloses with aminopropyl methyl diethoxy siloxanes, hexamethyldisiloxane and three kinds of materials of Tetramethylammonium hydroxide, reaction directly obtains the method for 3-aminopropyl seven methyl trisiloxanes, and the highest yield is 42.8%.This method technology is simple, but yield is lower.
Application number is 200710027244.9, denomination of invention is finished with hydrolytie polycondensation and catalytic equilibration two-step approach for the Chinese patent of " preparation method of 3-ammonia alkyl trisiloxanes " discloses and prepared 3-ammonia alkyl trisiloxanes, but the preparation process more complicated, and product purity is not too high.
Summary of the invention
The present invention need solve the problem that background technology exists, and an a kind of step novel preparation method of high yield high purity 3-aminopropyl trisiloxanes is provided, and this method technology is simple, be easy to suitability for industrialized production, do not need platinum catalyst, the product yield height, the purity height, the non-isomerization thing.
The preparation method of high yield high purity 3-aminopropyl trisiloxanes of the present invention, comprise the steps: aminopropyl siloxanes, end-capping reagent, catalyzer are preferably 1:5～12: 0.001～0.5 by 1:1～20: 0～5() the mole proportioning join in the reactor, under agitation be warming up to 40～110 ℃ of reactions 1～10 hour, meanwhile steam the low by product that boils, obtain mix products by having the filling extract rectification post; Make catalyst deactivation then, obtain light yellow transparent liquid; Carry out air distillation then earlier, steam low-boiling-point substance, carry out underpressure distillation again, obtain product;
The structure of described aminopropyl siloxanes is a formula I:
Described end-capping reagent is the siloxanes of structure formula II:
(II), R in the formula
2, R
3, R
4Independently be selected from a kind of in the alkyl or aryl
(each methyl commonly used, ethyl and phenyl etc. respectively are preferably methyl); X
2Be selected from hydroxyl, methoxy or ethoxy (being preferably hydroxyl);
Described catalyzer is a kind of in Tetramethylammonium hydroxide, potassium hydroxide or the sodium hydroxide.
When catalyzer is potassium hydroxide or sodium hydroxide, need to add the acidic cpd catalyst neutralisation, make it inactivation, described acidic cpd is selected from a kind of in acetate, silica-based phosphoric acid ester, carbonic acid gas, the phosphoric acid; When catalyzer was Tetramethylammonium hydroxide, thermal degradation made it inactivation.
The present invention prepares route:
The product structure formula that obtains is as follows:
Compare with background technology, it is simple that the present invention has method technology, is easy to suitability for industrialized production, do not need platinum catalyst, product purity height, non-isomerization thing, environmentally safe, no noxious solvent, characteristics such as yield height.
Description of drawings
Fig. 1 is embodiment 1 product
1H NMR collection of illustrative plates;
Fig. 2 is embodiment 1 product
13C NMR collection of illustrative plates;
Fig. 3 is embodiment 1 product
29Si NMR collection of illustrative plates.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1
---aminopropyl methyl dimethoxy oxygen radical siloxane, 180.4g (being 2.0mo1) end-capping reagent---the pure and mild 1.0g of trimethyl silicane (being 0.055mo1) catalyzer---Tetramethylammonium hydroxide adds in the 500m1 there-necked flask with 40.8g (being 0.25mo1) aminopropyl siloxanes, under agitation be warming up to 95 ℃ of reactions 3.5 hours, meanwhile steam the low-boiling-point substance by product by having the filling extract rectification post, obtain mix products, then mixture is continued reaction 0.5 hour during at 150 ℃ at autoclave, obtain yellowish transparent liquid.Have in the flask of filling extract rectification post in adding then, carry out air distillation earlier, steam boiling point less than 100 ℃ low boiling, carry out underpressure distillation again, obtain product 51.1g, outward appearance is a colourless transparent liquid, gas chromatographic purity 98.8%, yield about 73.3%.
Embodiment 2
32.7g (being 0.20mo1) aminopropyl methyl dimethoxy oxygen radical siloxane, the pure and mild 0.3g of 207.5g (being 2.3mo1) trimethyl silicane (being 0.0053mo1) potassium hydroxide are added in the 500m1 there-necked flask, under agitation be warming up to 95 ℃ of reactions 6 hours, meanwhile steam the low-boiling-point substance by product by having the filling extract rectification post, obtain mix products, adding acidic cpd then---silica-based phosphoric acid ester neutralizes, and obtains light yellow transparent liquid.Have in the flask of filling extract rectification post in adding then, carry out air distillation earlier, steam boiling point less than 100 ℃ low boiling, carry out underpressure distillation again, obtain product 42.2g, outward appearance is a colourless transparent liquid, gas chromatographic purity 98.6%, yield about 75.7%.
Embodiment 3
42.1g (being 0.22mo1) aminopropyl methyl diethoxy siloxanes, the pure and mild 0.4g of 216.5g (being 2.4mo1) trimethyl silicane (being 0.071mo1) potassium hydroxide are added in the 500m1 there-necked flask, under agitation be warming up to 95 ℃ of reactions 3 hours, meanwhile steam the low-boiling-point substance by product by having the filling extract rectification post, obtain mix products, add acetate then and neutralize, obtain yellowish transparent liquid.Have in the flask of filling extract rectification post in adding then, carry out air distillation earlier, steam boiling point less than 100 ℃ low boiling, carry out underpressure distillation again, obtain product 42.4g, outward appearance is a colourless transparent liquid, gas chromatographic purity 98.5%, yield about 69.1%.
Embodiment 4
---aminopropyl methyl diethoxy siloxanes, 180.4g (being 2.0mo1) end-capping reagent---the pure and mild 1.0g of trimethyl silicane (being 0.055mo1) catalyzer---Tetramethylammonium hydroxide adds in the 500m1 there-necked flask with 47.8g (being 0.25mo1) aminopropyl siloxanes, under agitation be warming up to 95 ℃ of reactions 4.5 hours, meanwhile steam the low-boiling-point substance by product by having the filling extract rectification post, obtain mix products, then mixture is continued reaction 0.5 hour during at 150 ℃ at autoclave, obtain yellowish transparent liquid.Have in the flask of filling extract rectification post in adding then, carry out air distillation earlier, steam boiling point less than 100 ℃ low boiling, carry out underpressure distillation again, obtain product 49.8g, outward appearance is a colourless transparent liquid, gas chromatographic purity 98.6%, yield about 71.4%.
Embodiment 5
---aminopropyl methyl diethoxy siloxanes, 225.5g (being 2.5mo1) end-capping reagent---the pure and mild 0.8g of trimethyl silicane (being 0.044mo1) catalyzer---Tetramethylammonium hydroxide adds in the 500m1 there-necked flask with 47.8g (being 0.25mo1) aminopropyl siloxanes, under agitation be warming up to 95 ℃ of reactions 3.5 hours, meanwhile steam the low-boiling-point substance by product by having the filling extract rectification post, obtain mix products, then mixture is continued reaction 0.5 hour during at 150 ℃ at autoclave, obtain yellowish transparent liquid.Have in the flask of filling extract rectification post in adding then, carry out air distillation earlier, steam boiling point less than 100 ℃ low boiling, carry out underpressure distillation again, obtain product 52.6g, outward appearance is a colourless transparent liquid, gas chromatographic purity 98.7%, yield about 75.4%.
Embodiment 6
32.7g (being 0.20mo1) aminopropyl methyl dimethoxy oxygen radical siloxane, the pure and mild 0.3g of 207.5g (being 2.3mo1) trimethyl silicane (being 0.0075mo1) sodium hydroxide are added in the 500m1 there-necked flask, under agitation be warming up to 95 ℃ of reactions 7 hours, meanwhile steam the low-boiling-point substance by product by having the filling extract rectification post, obtain mix products, add then that acidic cpd---acetate neutralizes, obtain light yellow transparent liquid.Have in the flask of filling extract rectification post in adding then, carry out air distillation earlier, steam boiling point less than 100 ℃ low boiling, carry out underpressure distillation again, obtain product 39.4g, outward appearance is a colourless transparent liquid, gas chromatographic purity 98.2%, yield about 70.6%.
Claims (3)
1. the preparation method of one kind high yield high purity 3-aminopropyl trisiloxanes, comprise the steps: aminopropyl siloxanes, end-capping reagent, catalyzer are joined in the reactor by the mole proportioning of 1:1～20: 0～5, under agitation be warming up to 40～110 ℃ of reactions 1～10 hour, meanwhile steam the low by product that boils, obtain mix products by having the filling extract rectification post; Make catalyst deactivation then, obtain light yellow transparent liquid; Carry out air distillation then earlier, steam low-boiling-point substance, carry out underpressure distillation again, obtain product;
The structure of described aminopropyl siloxanes is a formula I:
Described end-capping reagent is the siloxanes of structure formula II:
Described catalyzer is a kind of in Tetramethylammonium hydroxide, potassium hydroxide or the sodium hydroxide.
2. the preparation method of 3-aminopropyl trisiloxanes according to claim 1 is characterized in that: in the structure formula I of described aminopropyl siloxanes, and R
1=methyl; X
1=methoxy or ethoxy; R in the siloxanes of described structure formula II
2, R
3, R
4Be methyl; X
2Be hydroxyl.
3. the preparation method of 3-aminopropyl trisiloxanes according to claim 1 and 2, it is characterized in that: when catalyzer is potassium hydroxide or sodium hydroxide, need to add the acidic cpd catalyst neutralisation, make it inactivation, described acidic cpd is selected from a kind of in acetate, silica-based phosphoric acid ester, carbonic acid gas, the phosphoric acid; When catalyzer was Tetramethylammonium hydroxide, thermal degradation made it inactivation.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409779A (en) * | 2018-05-15 | 2018-08-17 | 威海新元化工有限公司 | A kind of preparation method of γ-aminopropyl trisiloxane |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0700951A1 (en) * | 1994-09-08 | 1996-03-13 | Showa Denko Kabushiki Kaisha | Polyorganosiloxane and process for producing the same |
| CN101024652A (en) * | 2007-03-23 | 2007-08-29 | 广州天赐有机硅科技有限公司 | Method for preparing amino-hydrocarbyl-trisiloxane |
| CN101474545A (en) * | 2009-01-06 | 2009-07-08 | 北京工商大学 | Preparation method of trisiloxanes surfactant containing oxyethyl group |
-
2010
- 2010-04-20 CN CN2010101501146A patent/CN102115480A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0700951A1 (en) * | 1994-09-08 | 1996-03-13 | Showa Denko Kabushiki Kaisha | Polyorganosiloxane and process for producing the same |
| CN101024652A (en) * | 2007-03-23 | 2007-08-29 | 广州天赐有机硅科技有限公司 | Method for preparing amino-hydrocarbyl-trisiloxane |
| CN101474545A (en) * | 2009-01-06 | 2009-07-08 | 北京工商大学 | Preparation method of trisiloxanes surfactant containing oxyethyl group |
Non-Patent Citations (2)
| Title |
|---|
| 张国栋等，: "3-氨丙基三硅氧烷合成的研究", 《杭州师范大学学报（自然科学版）》 * |
| 张国栋等，: "氨丙基三硅氧烷的合成", 《化工新型材料》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409779A (en) * | 2018-05-15 | 2018-08-17 | 威海新元化工有限公司 | A kind of preparation method of γ-aminopropyl trisiloxane |
| CN108409779B (en) * | 2018-05-15 | 2020-06-19 | 威海新元化工有限公司 | Preparation method of gamma-aminopropyl trisiloxane |
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Application publication date: 20110706 |