CN101492468B - Method of preparing trialkoxysilanes isocyanic ester - Google Patents
Method of preparing trialkoxysilanes isocyanic ester Download PDFInfo
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- CN101492468B CN101492468B CN2009103007158A CN200910300715A CN101492468B CN 101492468 B CN101492468 B CN 101492468B CN 2009103007158 A CN2009103007158 A CN 2009103007158A CN 200910300715 A CN200910300715 A CN 200910300715A CN 101492468 B CN101492468 B CN 101492468B
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- isocyanic ester
- organic solvent
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- amine
- triphosgene
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Abstract
The invention discloses a preparation method of trialkoxy siloyl isocyanate, comprising the following steps: (1) chlorine catching agent is dissolved in water and then is added into a reaction device to be stirred, wherein, the temperature is controlled at -5-0 DEG C; (2) triphosgene and trialkoxysilane amine are respectively dissolved in organic solvent and then respectively added into the reaction device and react by stirring for 10-20min, wherein, the temperature is controlled at -5-10 DEG C; (3) the phase separation is carried out on the reacted solution, the organic solvent is used for extracting water phase for 1-3 times, the drying is carried out after organic phases are annexed, and the organic solvent is extracted, filtered and removed; (4) after the vacuum distillation, the trialkoxy siloyl isocyanate is obtained. The chlorine catching agent used by the invention has the advantages of cheap price and low production cost. The used triphosgene has the advantages of no toxicity, safety and reliability.
Description
Technical field
The present invention relates to a kind of preparation method of isocyanate compound, particularly relate to a kind of preparation method of trialkoxysilanes isocyanic ester.
Background technology
At present, the preparation method of trialkoxysilanes isocyanic ester mainly contains following two kinds:
Japanese documentation JP5540592 discloses that a kind of high temperature addition reaction under the catalysis of Trichlororhodium obtains alkoxyl silicone propyl group isocyanic ester with alkoxyl silicone and allyl group isocyanic ester, this method subject matter is that the catalyzer Trichlororhodium costs an arm and a leg, cost is higher, and the condition harshness must be at high temperature carried out in reaction.
American documentation literature US4654428 discloses a kind of with alkoxyl silicone propyl group amine, phosgene and N, accelerine reacts in toluene solution and generates tri-alkoxy silicon propyl group isocyanic ester, has reacted the back and has obtained finished product with calcium stearate washing adjusting pH extremely neutral back distillation.The shortcoming of this method maximum is to have used the very big phosgene of toxicity to participate in reaction, and is dangerous reliable, but action row is not strong.
Summary of the invention
The objective of the invention is to overcome the problems referred to above, the preparation method of lower, the safe and reliable trialkoxysilanes isocyanic ester of a kind of cost is provided.
The technical scheme that realizes the object of the invention is: a kind of preparation method of trialkoxysilanes isocyanic ester has following steps:
1. will catch the chlorine agent and be dissolved in the water, and join in the reaction unit then and stirring, controlled temperature is-5 ℃～0 ℃;
2. triphosgene and trialkoxy silane base amine are dissolved in respectively in the organic solvent, join respectively then in the reaction unit, stirring reaction 10min～20min, controlled temperature are-5 ℃～10 ℃;
3. with the reacted solution phase-splitting, water is with organic solvent extraction 1～3 time, carries out drying after merging organic phase, suction filtration, removes organic solvent;
4. underpressure distillation promptly gets trialkoxysilanes isocyanic ester.
Wherein, trialkoxy silane base amine is represented that by general formula I R1, R2, R3 all represent the alkoxy base of 1～6 carbon atom in the formula, and n is 1～4.
Represented by general formula I I that by the trialkoxysilanes isocyanic ester that this trialkoxy silane base amine and triphosgene reaction obtain R1, R2, R3 all represent the alkoxy base of 1～6 carbon atom in the formula, n is 1～4.
The catch chlorine agent of above-mentioned steps described in 1. is sodium bicarbonate or triethylamine or phosphoric acid salt.
2. above-mentioned steps is the organic solvent that does not participate in reacting with the organic solvent of step described in 3., preferred methylene dichloride.
The trialkoxy silane base amine of above-mentioned steps described in 2. is triethoxysilylpropyl amine or trimethoxy silicon propyl group amine.
The mol ratio of above-mentioned triphosgene and trialkoxy silane base amine is (1: 3)～(1.2: 3).
The present invention has positive effect: (1) the present invention is used catches chlorine agent low price, and production cost is lower.(2) the used triphosgene of the present invention does not have toxicity, and is safe and reliable.Can discharge phosgene though triphosgene is met water usually, the present invention carries out the low temperature that reaction is controlled at below 10 ℃, and the reaction times be controlled at about 10min～20min, can avoid triphosgene and water generates phosgene like this.
Embodiment
(embodiment 1)
Present embodiment is the preparation method of triethoxysilylpropyl isocyanic ester, specifically may further comprise the steps:
1. earlier the reaction unit that has agitator and thermometer of 2L is put into cryosel and bathed, controlled temperature＜0 ℃.Follow NaHCO with 60g
3Be dissolved in the water of 600ml, join in the reaction unit then and stirring, controlled temperature is-5 ℃～0 ℃.
2. the triphosgene of 25.4g is dissolved in the CH of 400ml
2Cl
2In, add in the reaction unit then; With the triethoxysilylpropyl amine solvent of 45.12g in the CH of 400ml
2Cl
2In, joining then in the reaction unit, stirring reaction 15min, controlled temperature are-5 ℃～10 ℃.
3. reacted solution is placed and phase-splitting is water and organic phase, water is with the CH of 100ml
2Cl
2Extraction at twice merges organic phase that obtains after the extraction and the organic phase of dividing phase time to obtain, and carries out drying then, and suction filtration removes CH
2Cl
2
4. underpressure distillation receives following 110 ℃～140 ℃ cut of 10mmHg, gets the triethoxysilylpropyl isocyanic ester finished product of 35g, and its content is 96.5%, and yield is 68.5%.This finished product is a colourless liquid, need avoid the moisture absorption at cryopreservation.
(embodiment 2～embodiment 5)
The preparation method of each embodiment is substantially the same manner as Example 1, and the concrete parameter of each embodiment sees Table 1, and wherein the finished product of embodiment 4 gained is a trimethoxy silicon propyl group isocyanic ester, and all the other are the triethoxysilylpropyl isocyanic ester.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| The reaction unit volume | 2L | 5L | 20L | 2L | 500L |
| Catch the chlorine agent | The NaHCO of 60g 3 | The NaHCO of 160g 3 | The NaHCO of 700g 3 | 43.1g NaHCO 3 | The NaHCO of 14kg 3 |
| The water of chlorine agent is caught in dissolving | 600ml | 2L | 7L | 600ml | 140L |
| Triphosgene | 25.4g | 60g | 250g | 25.4g | 5kg |
| The CH of triphosgene is separated in bath 2Cl 2 | 400ml | 1000ml | 3L | 400ml | 60L |
| Trialkoxy silane base amine | 45.12g triethoxysilylpropyl amine | 112.5g triethoxysilylpropyl amine | The triethoxysilylpropyl amine of 452g | 45.92g trimethoxy silicon propyl group amine | The triethoxysilylpropyl amine of 9kg |
| The CH of trialkoxy silane base amine is separated in bath 2Cl 2 | 400ml | 1000ml | 3L | 400ml | 60L |
| Reaction times | 15min | 18min | 12min | 10min | 18min |
| The CH of extraction usefulness 2Cl 2 | 100ml | 400ml | 1L | 100ml | 20L |
| Finished weight | 35g | 90g | 305g | 20g | 6kg |
| Content | 96.5％ | 97.5％ | 95％ | 98％ | 96％ |
| Yield | 68.5％ | 71％ | 61％ | 40％ | 60％ |
In the various embodiments described above, if chloride ion content is higher in the finished product, then wash chlorine operation, promptly using with the finished-product volume ratio is 1: 1 toluene solvant dilution finished product, phase-splitting, organic phase is the NaCl solution washing 3 times of 10wt% again with the concentration of same volume.Then with the dry organic phase 15min of magnesium oxide, suction filtration removes solvent toluene, and the finished product behind the chlorine is washed in the distillation reception, and chloride ion content is up to specification in finished product.
Among each embodiment of the specific embodiment of the present invention, catching the chlorine agent can also be triethylamine or phosphoric acid salt, and phosphoric acid salt can preferably phosphoric acid sodium or potassiumphosphate.
Should be appreciated that specific embodiment described above only is used to explain the present invention, and be not used in qualification the present invention.Conspicuous variation of being extended out by spirit of the present invention or change still are among protection scope of the present invention.
Claims (4)
1. the preparation method of a trialkoxysilanes isocyanic ester is characterized in that having following steps:
1. will catch the chlorine agent and be dissolved in the water, and join in the reaction unit then and stirring, controlled temperature is-5 ℃～0 ℃; It is described that to catch the chlorine agent be sodium bicarbonate;
2. triphosgene and trialkoxy silane base amine are dissolved in respectively in the organic solvent, join respectively then in the reaction unit, stirring reaction 10min～20min, controlled temperature are-5 ℃～10 ℃;
3. with the reacted solution phase-splitting, water organic solvent extraction 1～3 time is carried out drying after the merging organic phase, and suction filtration removes organic solvent;
4. underpressure distillation promptly gets trialkoxysilanes isocyanic ester.
2. the preparation method of tri-alkoxy silicon propyl group isocyanic ester according to claim 1 is characterized in that: 2. step is methylene dichloride with the organic solvent of step described in 3..
3. the preparation method of tri-alkoxy silicon propyl group isocyanic ester according to claim 1 is characterized in that: the trialkoxy silane base amine of step described in 2. is triethoxysilylpropyl amine or trimethoxy silicon propyl group amine.
4. the preparation method of tri-alkoxy silicon propyl group isocyanic ester according to claim 3 is characterized in that: the mol ratio of triphosgene and trialkoxy silane base amine is (1: 3)～(1.2: 3).
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| CN2009103007158A CN101492468B (en) | 2009-03-06 | 2009-03-06 | Method of preparing trialkoxysilanes isocyanic ester |
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|---|---|---|---|
| CN2009103007158A CN101492468B (en) | 2009-03-06 | 2009-03-06 | Method of preparing trialkoxysilanes isocyanic ester |
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| Publication Number | Publication Date |
|---|---|
| CN101492468A CN101492468A (en) | 2009-07-29 |
| CN101492468B true CN101492468B (en) | 2011-08-10 |
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| CN104371098B (en) * | 2013-08-14 | 2016-12-28 | 北京键凯科技有限公司 | Multiple-limb hydrophilic polymer isocyanate derivates |
| CN110128465A (en) * | 2019-06-25 | 2019-08-16 | 荆州市江汉精细化工有限公司 | A method of isocyanato silanes are prepared with hydrosilylation |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887888A (en) * | 2006-07-27 | 2007-01-03 | 应城市德邦化工新材料有限公司 | Prepn of isocyanate-containing alkyl silane or alkyl siloxane |
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2009
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887888A (en) * | 2006-07-27 | 2007-01-03 | 应城市德邦化工新材料有限公司 | Prepn of isocyanate-containing alkyl silane or alkyl siloxane |
Non-Patent Citations (3)
| Title |
|---|
| 常鹏等.制备HDI及IPTS的新方法.《材料科学与工艺》.2008,第16卷(第6期),第843-846页. * |
| 常鹏等.固体光气法合成HDI及IPTS.《应用化工》.2006,第35卷(第1期),第30-32页. * |
| 柏正武等.制备γ-异氰酸酯丙基三乙氧基硅烷的新方法.《化学与生物工程》.2004,(第2期),第16-17页. * |
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