CN101701023A - Method for preparing 1H, 1H, 2H, 2H-perfluoroalkyl trialkoxysilane - Google Patents
Method for preparing 1H, 1H, 2H, 2H-perfluoroalkyl trialkoxysilane Download PDFInfo
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- CN101701023A CN101701023A CN200910228919A CN200910228919A CN101701023A CN 101701023 A CN101701023 A CN 101701023A CN 200910228919 A CN200910228919 A CN 200910228919A CN 200910228919 A CN200910228919 A CN 200910228919A CN 101701023 A CN101701023 A CN 101701023A
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- perfluoroalkyl
- trialkoxysilane
- synthetic method
- reductive agent
- aibn
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Abstract
The invention relates to a method for preparing perfluoroalkyl trialkoxysilane. The method comprises the following steps of: carrying out an addition reaction on perfluoroalkyl iodides and ethenyl trialkoxysilane; and then reducing by using a reducing agent. The perfluoroalkyl trialkoxysilane prepared by the method can be used as a surface coating. The invention has simple processing equipment, easy operation, low cost and high purity, and the purity of the product can reach more than 95 percent, thus the perfluoroalkyl trialkoxysilane can be commercially prepared and produced in a large scale so as to meet the current increasing market demand.
Description
Technical field
The present invention relates to 1H, 1H, 2H, the preparation method of 2H-perfluoroalkyl trialkoxysilane (following abbreviation silicon fluoride).
Background technology
1H, 1H, 2H, the 2H-perfluoroalkyl trialkoxysilane is as the fluorochemical surface coating, no matter have important role, be clothes in the daily life, glass, still industrial cable, or even the high-tech medicine equipment in the most advanced and sophisticated medical science has all obtained using widely.Bullitin Chemistry Society JPN, 66,1754-58 reported with perfluoro capryl ethene and trichlorosilane at Platinic chloride (H in 1993
2PtCl
6) under the catalysis, obtain the perfluoro capryl ethyl trichlorosilane, and then be solvent with F113, obtain 1H with the sodium methylate reaction, 1H, 2H, 2H-perfluor decyl trialkoxy silane, yield is 75.8%.The shortcoming of this method is that perfluoro capryl ethene needs preparation, and route is long, and raw material HSiCl
3The reactive behavior height to the seriously corroded of equipment, has restricted suitability for industrialized production greatly.
Summary of the invention
The purpose of this invention is to provide a kind of 1H, 1H, 2H, the preparation method of 2H-perfluoroalkyl trialkoxysilane.Can overcome the shortcoming of prior art.Technology of the present invention is simple, processing ease, and cost is low, the yield height, equipment requirements is low, can prepare large-scale commercially and produce, and satisfies the current ever-increasing market requirement.
1H provided by the invention, 1H, 2H, the preparation method of 2H-perfluoroalkyl trialkoxysilane is that perfluoroalkyl iodo thing and vinyl trialkyl oxysilane carry out addition reaction, reduces reaction scheme then with reductive agent:
R
1, R
2And R
3Expression H, C
1-12Saturated alkyl; N is expressed as 1-6; Reductive agent is one or more in the three replacement organotin hydrogen.
1H provided by the invention, 1H, 2H, the step that the preparation method of 2H-perfluoroalkyl trialkoxysilane comprises:
1) perfluoroalkyl iodo alkane, vinyl trialkyl oxysilane and Diisopropyl azodicarboxylate (AIBN, C
8H
12N
4) mix, under the nitrogen protection, reacting by heating 6-10 hour, underpressure distillation, light brown liquid, i.e. 1H, 1I, 2H, 2H-perfluoroalkyl trialkoxysilane;
Perfluoroalkyl iodo alkane and vinyl trialkyl oxysilane amount of substance ratio: 1: 1-1: 10; Heating temperature is 100-180 ℃; Preferred 120-160 ℃;
2) with 1H, 1I, 2H, 2H-perfluoroalkyl trialkoxysilane and AIBN mix, and heat temperature raising slowly drips reductive agent three and replaces organotin hydrogen 2-4 hour, heated and stirred 2-4 hour.
1H, 1I, 2H, 2H-perfluoroalkyl trialkoxysilane and three replaces the ratio 1 of the amount of substance of organotin hydrogen: 1-1: 5; Heating temperature is 40-60 ℃;
3) gained solution carries out standing demix, takes off a layer liquid.
4) lower floor's gained liquid carries out underpressure distillation, promptly gets colourless liquid 1H, 1H, 2H, 2H-perfluoroalkyl trialkoxysilane.
Step 2) reductive agent can be tri-butyl tin hydride, triphenyl tin hydride, three (o-tolyl) stannic hydride, three (p-methylphenyl) stannic hydrides or their mixing.
The 1H of the present invention's preparation, 1H, 2H, the 2H-perfluoroalkyl trialkoxysilane can be used as fabric finishing agent, multiple material (pottery, glass, metal, paint etc.) surface treatment agent.Present device requires low, and technology is simple, processing ease, and cost is low, the purity height, product purity can reach more than 95%.Employed reductive agent three replaces organotin hydrogen commercial prod in the operating process in addition, and is cheap, is easy to get, and operation steps is simple, can prepare large-scale commercially and produce, and satisfies the current ever-increasing market requirement.
Embodiment
The present invention will be described further by following embodiment.
The reagent that the present invention uses is the commercially available prod.
Embodiment 1:1H, 1H, 2H, the preparation of 2H-perfluor decyl Trimethoxy silane
With 164g (0.3mol) perfluoro capryl iodo alkane, 51.9g (0.35mol) vinyltrimethoxy silane mixes with 0.62g (0.0038mol) AIBN, under the nitrogen protection, is heated to 120 ℃, continues to stir 10 hours.Underpressure distillation, 190.8g light brown liquid, that is: 1H, 1I, 2H, 2H-perfluor decyl Trimethoxy silane, content 94.2%.
Get 112.4g (0.162mol) 1H, 1I, 2H, 2H-perfluor decyl Trimethoxy silane adds 0.1g (0.0006mol) AIBN, under the nitrogen protection, is warming up to 50 ℃, under agitation slowly drips 49.75g (0.171mol) tri-butyl tin hydride 3 hours.Under this temperature, continue to stir 2 hours.
Gained solution carries out standing demix, takes off a layer liquid, carries out underpressure distillation, the 82.6g colourless liquid, that is: 1H, 1H, 2H, 2H-perfluor decyl Trimethoxy silane, content 95.8%.
Bp?95℃/400Pa。
1HNMR(CDCl
3)δ：0.76-0.94(m，2H)，1.82-2.42(m，2H)，3.58(s，9H)。
19FNMR(CDCl
3)δ：-14.5(m，2F)，-11.4(m，2F)，-10.8(m，2F)，-9.9(m，2F)，-5.0(m，2F)，30.4(m，3F)。
Embodiment 2:1H, 1H, 2H, the preparation of 2H-perfluor decyl Trimethoxy silane
With 164g (0.3mol) perfluoro capryl iodo alkane, 222g (1.5mol) vinyltrimethoxy silane mixes with 0.62g (0.0038mol) AIBN, under the nitrogen protection, is heated to 140 ℃, continues to stir 8 hours.Underpressure distillation, 198.5g light brown liquid, that is: 1H, 1I, 2H, 2H-perfluor decyl Trimethoxy silane, content 94.6%.
Get 112.4g (0.162mol) 1H, 1I, 2H, 2H-perfluor decyl Trimethoxy silane adds 0.1g (0.0006mol) AIBN, under the nitrogen protection, is warming up to 50 ℃, under agitation slowly drips 96.2g (0.243mol) three (o-tolyl) stannic hydride 3 hours.Under this temperature, continue to stir 2 hours.
Gained solution carries out standing demix, takes off a layer liquid, carries out underpressure distillation, the 82.6g colourless liquid, that is: 1H, 1H, 2H, 2H-perfluor decyl Trimethoxy silane, content 95.5%.
Embodiment 3:1H, 1H, 2H, the preparation of 2H-perfluor dodecyl Trimethoxy silane
With 193.8g (0.3mol) perfluor decyl idoalkane, 51.9g (0.35mol) vinyltrimethoxy silane mixes with 0.62g (0.0038mol) AIBN, under the nitrogen protection, is heated to 140 ℃, continues to stir 10 hours.Underpressure distillation, 190.8g light brown liquid, that is: 1H, 1I, 2H, 2H-perfluor dodecyl Trimethoxy silane, content 95.0%.
Get 133g (0.159mol) 1H, 1I, 2H, 2H-perfluor dodecyl Trimethoxy silane adds 0.1g (0.0006mol) AIBN, under the nitrogen protection, is warming up to 55 ℃, under agitation slowly drips 49.75g (0.171mol) tri-butyl tin hydride 3 hours.Under this temperature, continue to stir 2 hours.
Gained solution carries out standing demix, takes off a layer liquid, carries out underpressure distillation, the 100.7g colourless liquid, that is: 1H, 1H, 2H, 2H-perfluor dodecyl Trimethoxy silane, content 95.5%.
Bp?93℃/53Pa。
1HNMR(CDCl
3)δ：0.76-0.94(m，2H)，1.82-2.42(m，2H)，3.58(s，9H)。
19FNMR(CDCl
3)δ：-14.4(m，2F)，-11.4(m，2F)，-10.7(m，2F)，-9.8(m，10F)，-5.0(m，2F)，30.4(m，3F)。
Embodiment 4:1H, 1H, 2H, the preparation of 2H-perfluoro capryl Trimethoxy silane
With 133.8g (0.3mol) perfluoro hexyl iodo alkane, 51.9g (0.35mol) vinyltrimethoxy silane mixes with 0.62g (0.0038mol) AIBN, under the nitrogen protection, is heated to 140 ℃, continues to stir 10 hours.Underpressure distillation, 190.8g light brown liquid, that is: 1H, 1I, 2H, 2H-perfluoro capryl Trimethoxy silane, content 94.6%.
Get 107.8g (0.159mol) 1H, 1I, 2H, 2H-perfluoro capryl Trimethoxy silane adds 0.1g (0.0006mol) AIBN, under the nitrogen protection, is warming up to 55 ℃, under agitation slowly drips 67.7g (0.171mol) three (p-methylphenyl) stannic hydride 3 hours.Under this temperature, continue to stir 2 hours.
Gained solution carries out standing demix, takes off a layer liquid, carries out underpressure distillation, the 82.6g colourless liquid, that is: 1H, 1H, 2H, 2H-perfluoro capryl Trimethoxy silane, content 95.8%.
Bp?70℃/280Pa。
1HNMR(CDCl
3)δ：0.75-0.93(m，2H)，1.87-2.42(m，2H)，3.58(s，9H)。
19FNMR(CDCl
3)δ：-14.5(m，2F)，-11.5(m，2F)，-10.1(m，2F)，-5.0(m，2F)，30.2(m，3F)。
Embodiment 5:1H, 1H, 2H, the preparation of 2H-perfluor decyl three isopropoxy silane
With 164g (0.3mol) perfluoro capryl iodo alkane, 81.2g (0.35mol) vinyl silane triisopropoxide mixes with 0.62g (0.0038mol) AIBN, under the nitrogen protection, is heated to 140 ℃, continues to stir 10 hours.Underpressure distillation, 219.0g light brown liquid, that is: 1H, 1I, 2H, 2H-perfluor decyl three isopropoxy silane, content 95%.
Get 124g (0.159mol) 1H, 1I, 2H, 2H-perfluor decyl three isopropoxy silane add 0.1g (0.0006mol) AIBN, under the nitrogen protection, are warming up to 55 ℃, under agitation slowly drip 49.75g (0.171mol) tri-butyl tin hydride 3 hours.Under this temperature, continue to stir 2 hours.
Gained solution carries out standing demix, takes off a layer liquid, carries out underpressure distillation, the 86.1g colourless liquid, that is: 1H, 1H, 2H, 2H-perfluor decyl three isopropoxy silane, content 95.5%.
Bp?97℃/130Pa。
1HNMR(CDCl
3)δ：0.75-0.81(m，2H)，1.19-1.21(d，18H)，2.04-2.22(m，2H)，4.19-4.27(m，3H)。
19FNMR(CDCl
3)δ：-14.5(m，2F)，-11.2(m，2F)，-10.6(m，2F)，-10.0(m，2F)，-5.1(m，2F)，30.2(m，3F)。
Embodiment 6:1H, 1H, 2H, the preparation of 2H-perfluor decyl Trimethoxy silane
With 164g (0.3mol) perfluoro capryl iodo alkane, 222g (1.5mol) vinyltrimethoxy silane mixes with 0.62g (0.0038mol) AIBN, under the nitrogen protection, is heated to 150 ℃, continues to stir 8 hours.Underpressure distillation, 188.6g light brown liquid, that is: 1H, 1I, 2H, 2H-perfluor decyl Trimethoxy silane, content 95.6%.
Get 112.4g (0.162mol) 1H, 1I, 2H; 2H-perfluor decyl Trimethoxy silane adds 0.1g (0.0006mol) AIBN, under the nitrogen protection; be warming up to 60 ℃, under agitation slow Dropwise 35 .1g (0.10mol) triphenyl tin hydride and 52.4g (0.18mol) tri-butyl tin hydride 3 hours.Under this temperature, continue to stir 2 hours.
Gained solution carries out standing demix, takes off a layer liquid, carries out underpressure distillation, the 65.7g colourless liquid, that is: 1H, 1H, 2H, the preparation of 2H-perfluor decyl Trimethoxy silane, content 95.0%.
Embodiment 7:1H, 1H, 2H, the preparation of 2H-perfluor decyl Trimethoxy silane
With 164g (0.3mol) perfluoro capryl iodo alkane, 222g (1.5mol) vinyltrimethoxy silane mixes with 0.62g (0.0038mol) AIBN, under the nitrogen protection, is heated to 140 ℃, continues to stir 8 hours.Underpressure distillation, 188.6g light brown liquid, that is: 1H, 1I, 2H, 2H-perfluor decyl Trimethoxy silane, content 95.6%.
Get 112.4g (0.162mol) 1H, 1I, 2H, 2H-perfluor decyl Trimethoxy silane adds 0.1g (0.0006mol) AIBN, under the nitrogen protection, is warming up to 50 ℃, under agitation slowly drips 98.3g (0.28mol) triphenyl tin hydride 3 hours.Under this temperature, continue to stir 4 hours.
Gained solution carries out standing demix, takes off a layer liquid, carries out underpressure distillation, the 88.0g colourless liquid, that is: 1H, 1H, 2H, the preparation of 2H-perfluor decyl Trimethoxy silane, content 95.2%.
Claims (8)
1. 1H, 1H, 2H, the preparation method of 2H-perfluoroalkyl trialkoxysilane is characterized in that the step that it comprises: carry out addition reaction at perfluoroalkyl iodo thing and vinyl trialkyl oxysilane, reduce reaction scheme then with reductive agent:
R
1, R
2And R
3Expression H, C
1-12Saturated alkyl; N is expressed as 1-6; Reductive agent is one or more in the three replacement organotin hydrogen.
2. 1H, 1H, 2H, the preparation method of 2H-perfluoroalkyl trialkoxysilane is characterized in that the step that comprises:
1) perfluoroalkyl iodo alkane, vinyl trialkyl oxysilane and Diisopropyl azodicarboxylate (AIBN, C
8H
12N
4) mix, under the nitrogen protection, be heated to 100-180 ℃, to react 6-10 hour, underpressure distillation gets light brown liquid 1H, 1I, 2H, 2H-perfluoroalkyl trialkoxysilane;
2) with 1H, 1I, 2H, 2H-perfluoroalkyl trialkoxysilane and AIBN mix, and heat temperature raising slowly drips reductive agent three and replaces organotin hydrogen 2-4 hour, is heated to 40-60 ℃, stirs 2-4 hour.
3) gained solution carries out standing demix, takes off a layer liquid.
4) lower floor's gained liquid carries out underpressure distillation, promptly gets colourless liquid 1H, 1H, 2H, 2H-perfluoroalkyl trialkoxysilane.
3. synthetic method according to claim 2 is characterized in that the perfluoroalkyl iodo alkane of step 1) and the ratio of vinyltrimethoxy silane amount of substance: 1: 1-1: 10.
4. synthetic method according to claim 2 is characterized in that the Heating temperature of step 1) is: 100-180 ℃.
5. synthetic method according to claim 2 is characterized in that the Heating temperature of step 1) is preferably: 120-160 ℃.
6. synthetic method according to claim 2 is characterized in that step 2) reductive agent can be tri-butyl tin hydride, triphenyl tin hydride, three (o-tolyl) stannic hydride, three (p-methylphenyl) stannic hydrides or their mixing.
7. synthetic method according to claim 2 is characterized in that step 2) 1H, 1I, 2H, 2H-perfluoroalkyl trialkoxysilane and three replaces the ratio 1 of the amount of substance of organotin hydrogen: 1-1: 5.
8. synthetic method according to claim 2 is characterized in that step 2) Heating temperature be: 40-60 ℃.
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| WO2013031622A1 (en) * | 2011-08-30 | 2013-03-07 | Ａｇｃセイミケミカル株式会社 | Method for producing silicon compound which contains fluorine-containing aliphatic hydrocarbon group |
| CN105198729A (en) * | 2015-09-17 | 2015-12-30 | 海门德思行药业科技有限公司 | Preparation method of perfluoroalkyl acetic acid |
| CN105612165A (en) * | 2013-10-04 | 2016-05-25 | 3M创新有限公司 | Fluoroalkylsilanes and coatings therefrom |
| JPWO2019039083A1 (en) * | 2017-08-22 | 2020-10-15 | Ａｇｃ株式会社 | Fluorine-containing compounds, compositions, coating liquids, and methods for producing fluorine-containing compounds |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293893A (en) * | 2007-04-29 | 2008-10-29 | 上海远东氟材料技术有限公司 | Fluorosiloxane midbody for hard surface dressing, prepraring method and method for preparing fluorosiloxane thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013031622A1 (en) * | 2011-08-30 | 2013-03-07 | Ａｇｃセイミケミカル株式会社 | Method for producing silicon compound which contains fluorine-containing aliphatic hydrocarbon group |
| CN105612165A (en) * | 2013-10-04 | 2016-05-25 | 3M创新有限公司 | Fluoroalkylsilanes and coatings therefrom |
| CN105612165B (en) * | 2013-10-04 | 2018-05-25 | 3M创新有限公司 | Fluoroalkyl silanes and its coating |
| CN105198729A (en) * | 2015-09-17 | 2015-12-30 | 海门德思行药业科技有限公司 | Preparation method of perfluoroalkyl acetic acid |
| CN105198729B (en) * | 2015-09-17 | 2017-07-11 | 海门德思行药业科技有限公司 | The preparation method of perfluoroalkyl acetic acid |
| JPWO2019039083A1 (en) * | 2017-08-22 | 2020-10-15 | Ａｇｃ株式会社 | Fluorine-containing compounds, compositions, coating liquids, and methods for producing fluorine-containing compounds |
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