CN102634030B - Low-toxicity synthesis method of siloxane gas-sensitive material - Google Patents
Low-toxicity synthesis method of siloxane gas-sensitive material Download PDFInfo
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- CN102634030B CN102634030B CN 201210122624 CN201210122624A CN102634030B CN 102634030 B CN102634030 B CN 102634030B CN 201210122624 CN201210122624 CN 201210122624 CN 201210122624 A CN201210122624 A CN 201210122624A CN 102634030 B CN102634030 B CN 102634030B
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Abstract
The invention discloses a low-toxicity synthesis method of a siloxane gas-sensitive material, which takes liquid 2-ethylenic alkyl hexafluoride isopropyl alcohol as a raw material at the normal temperature, and the siloxane gas-sensitive material can be prepared by the addition reaction between the raw material and hydrogen-containing siloxane under the catalysis of divinyl tetramethyl disiloxane platinum coordination, so that hexafluoroacetone which is high in toxicity and is gaseous at the normal temperature can be avoided. The preparation method is simple in method, easy to operate, mild in reaction condition, lower in requirements for experimental facilities and lower in material toxicity, and can simply, practically and efficiently introduce hexafluoro-isopropanol substituent group into silicon hydrogen bond of the hydrogen-containing siloxane.
Description
Technical field
The present invention relates to siloxanes gas sensitive technical field, be specifically related to a kind of low toxicity synthetic method of siloxanes gas sensitive.
Background technology
Organo phosphorous compounds is that a class can act on acetylcholinesterase in organism, it is lost activity, and cause its nervus centralis and the serious disorderly nerve of periphery choline nervous function to suppress compounds, have the advantages that lethality is strong, speed of action fast and be difficult to protect, therefore be widely used in sterilant and chemical weapons.The study hotspot in countries in the world environmental monitoring and chemical defence field to the detection of organophosphorus toxic substance with analyzing always.In being suitable for the multiple technologies of Site Detection, the surface acoustic wave sensor technology is of greatest concern.Quality is determined by the sensor sensing material and the height of surface acoustic wave sensor sensitivity reaches optionally.Therefore, the research and development of sensor sensing material have become the emphasis of present chemical sensor area research.
End group contains the siloxanes gas sensitive of hexafluoroisopropanol responsive functional group with its unique end group electrophilic structure, the stronger proton ability of giving, and be widely used as the sensitive material that detects organophosphorus poison gas.
United States Patent (USP) 6630560 discloses a polysiloxane-based sensitive material of class, and its structural formula is:
R wherein
1Or R
2In have at least one to be alkyl or alkenyl or alkynyl or aromatic yl group, and connect halohydrin or halogenated phenols at the end of group, wherein, most halohydrin is exactly hexafluoroisopropanol.
The typical material of above-mentioned United States Patent (USP) protection is SXFA; 2007; the Wang Chao of University Of Tianjin space has been announced the synthesis step of SXFA in Master's thesis " the synthetic and Study on adsorption properties of SAW chemical sensor mould material SXFA "; fluoro-reaction is carried out in final step; take the very large Perfluoroacetone of toxicity and the double bond containing polysiloxane of side chain as raw material, equation is as follows:
As mentioned above, when synthetic end group contains the siloxanes gas sensitive of hexafluoroisopropanol responsive functional group, be at present all at first to synthesize the siloxanes intermediate that end group contains two keys, the hexafluoroisopropanol that carries out again end group at last is functionalized.In this functionalized step, be all that Perfluoroacetone gas take severe toxicity is as raw material.Common working method be at first with liquid nitrogen with the Perfluoroacetone liquefaction of gases, then pour in autoclave and mix with intermediate polymer, close autoclave and heat up and react.The Perfluoroacetone of liquefaction inevitably can be vaporized and reveal and in entered environment, serious environment pollution and the life and health that threatens operator in the process that shifts.Therefore, the method that hexafluoroisopropanol functional group prepares the siloxanes gas sensitive of introducing in hydrogen-containing siloxane of simple, the easy handling of a kind of, synthesizer little to operator and environmental toxicity of research and development has very important significance.
Summary of the invention
Problem to be solved by this invention is: how a kind of method that hexafluoroisopropanol functional group prepares the siloxanes gas sensitive of introducing in hydrogen-containing siloxane is provided, the method can overcome existing defective in prior art, its synthesizer of siloxanes gas sensitive that contains hexafluoroisopropanol responsive functional group that obtains is simple, easy to operate, and all less to the threat of operator ' s health and environment.
Technical problem proposed by the invention is to solve like this: a kind of low toxicity synthetic method of siloxanes gas sensitive is provided, it is characterized in that:
Low toxicity synthetic method according to a kind of siloxanes gas sensitive provided by the present invention, to utilize addition reaction of silicon with hydrogen to grow on hydrogen-containing siloxane to contain the side chain of hexafluoroisopropanol molecule, it is characterized in that, system utilizes 2-allylic alkylation hexafluoroisopropanol and hydrogen-containing siloxane to be the synthetic siloxanes gas sensitive of raw material, and the molecular formula of 2-allylic alkylation hexafluoroisopropanol is:
CH
2=CH-(CH
2)
n-C (CF
3)
2-OH, n is between 0～3
Low toxicity synthetic method according to a kind of siloxanes gas sensitive provided by the present invention is characterized in that, hydrogen-containing siloxane is a kind of in small molecules or linear polymer or over-expense polymkeric substance.
Low toxicity synthetic method according to a kind of siloxanes gas sensitive provided by the present invention is characterized in that, the molecular weight of hydrogen-containing siloxane is 500～10000.
Low toxicity synthetic method according to a kind of siloxanes gas sensitive provided by the present invention is characterized in that, comprises the following steps:
(1) with the stirring at normal temperature reaction under nitrogen protection of hydrogen-containing siloxane, 2-allylic alkylation hexafluoroisopropanol, catalyzer and solvent;
(2) after reaction 24～48h, add gac to continue to stir 2～4h, remove gac and solvent, obtain containing the siloxanes gas sensitive of hexafluoroisopropanol functional group.
Low toxicity synthetic method according to a kind of siloxanes gas sensitive provided by the present invention is characterized in that, in step (1), the mass ratio of 2-allylic alkylation hexafluoroisopropanol and hydrogen-containing siloxane is 3:1～4:1.
Low toxicity synthetic method according to a kind of siloxanes gas sensitive provided by the present invention is characterized in that, the catalyzer in step (1) is the divinyl tetramethyl disiloxane platinum complex.
Low toxicity synthetic method according to a kind of siloxanes gas sensitive provided by the present invention is characterized in that, the described solvent of step (1) is toluene.
Low toxicity synthetic method according to a kind of siloxanes gas sensitive provided by the present invention is characterized in that, in step (2), removes by filter gac, and underpressure distillation steams solvent, obtains containing the siloxanes gas sensitive of hexafluoroisopropanol functional group after vacuum-drying.
The present invention compared with prior art has following advantage:
The objective of the invention is in the organic gas-sensitive material to introduce hexafluoroisopropanol functional group, method in the past is all that the employing Perfluoroacetone is that raw material carries out last functionalization, essence of the present invention is to adopt 2-allylic alkylation hexafluoroisopropanol to replace Perfluoroacetone, as 2-vinyl hexafluoroisopropanol, 2-propenyl hexafluoroisopropanol etc., such industrial chemicals has commercially available commodity, do not need oneself synthetic, in its molecular structure, comprised complete hexafluoroisopropanol functional group.2-allylic alkylation hexafluoroisopropanol is compared with the Perfluoroacetone gas of severe toxicity, and toxicity greatly reduces; The more important thing is that it is a kind of liquid, therefore than easily operation and the control of Perfluoroacetone of gaseous state, solved well the personal security problem.And, synthetic can carrying out in the flask of routine at normal temperatures, not only device is simplified greatly, and has avoided the potential threat of autoclave blast.
Description of drawings
Fig. 1 is a kind of structural formula that contains the polysiloxane gas sensitive of hexafluoroisopropanol substituting group side chain;
Fig. 2 be contain hexafluoroisopropanol substituting group side chain the polysiloxane gas sensitive under 1～49ppm concentration to the real-time frequency response curve of dimethyl methyl phosphonate;
Fig. 3 is the reaction equation of the inventive method.
Embodiment
The invention will be further described below in conjunction with accompanying drawing:
The low toxicity synthetic method of a kind of siloxanes gas sensitive of the present invention:
(1) with the stirring at normal temperature reaction under nitrogen protection of hydrogen-containing siloxane, 2-allylic alkylation hexafluoroisopropanol, catalyzer and solvent;
(2) after reaction 24～48h, add gac to continue to stir 2～4h, remove gac and solvent, obtain containing the siloxanes gas sensitive of hexafluoroisopropanol functional group.
In this embodiment, synthetic is a kind of substituent linear polymethyl hydrogen siloxane of hexafluoroisopropanol that contains, its structure as shown in Figure 1, reaction equation can be expressed as:
Its preparation method is as follows:
Under nitrogen protection; 0.5 g polymethyl hydrogen siloxane is placed in three-necked bottle; add 30ml toluene and 1.6g 2-vinyl hexafluoroisopropanol; after stirring, add 1 divinyl tetramethyl disiloxane platinum complex solution in system, continued stirring reaction 30 hours under normal temperature; reaction solution becomes yellow; stopped reaction adds gac in system, continue to stir 3 hours.Remove by filter gac, underpressure distillation steams toluene solvant, and vacuum-drying obtains the polysiloxane sensitive material that contains the responsive functional group of hexafluoroisopropanol of 2.0g tawny thickness.With this sensitive material gas blowout on surface acoustic wave sensor (SAW), test result (see figure 2) to the simulant dimethyl methyl phosphonate (DMMP) of nerve poison shows, this material highly sensitive, response is fast, reversibility and repeatability absorption are all fine.
Claims (8)
1. the low toxicity synthetic method of a siloxanes gas sensitive, to utilize addition reaction of silicon with hydrogen to grow on hydrogen-containing siloxane to contain the side chain of hexafluoroisopropanol molecule, it is characterized in that, system utilizes 2-allylic alkylation hexafluoroisopropanol and hydrogen-containing siloxane to be the synthetic siloxanes gas sensitive of raw material, and the molecular formula of 2-allylic alkylation hexafluoroisopropanol is:
CH
2=CH-(CH
2)
n-C (CF
3)
2-OH, wherein, n is between 1～3.
2. the low toxicity synthetic method of a kind of siloxanes gas sensitive according to claim 1, is characterized in that, hydrogen-containing siloxane is a kind of in small molecules or linear polymer or over-expense polymkeric substance.
3. the low toxicity synthetic method of a kind of siloxanes gas sensitive according to claim 2, is characterized in that, the molecular weight of hydrogen-containing siloxane is 500～10000.
4. the low toxicity synthetic method of a kind of siloxanes gas sensitive according to claim 1, is characterized in that, comprises the following steps:
(1) with the stirring at normal temperature reaction under nitrogen protection of hydrogen-containing siloxane, 2-allylic alkylation hexafluoroisopropanol, catalyzer and solvent;
(2) after reaction 24～48h, add gac to continue to stir 2～4h, remove gac and solvent, obtain containing the siloxanes gas sensitive of hexafluoroisopropanol functional group.
5. the low toxicity synthetic method of a kind of siloxanes gas sensitive according to claim 4, is characterized in that, in step (1), the mass ratio of 2-allylic alkylation hexafluoroisopropanol and hydrogen-containing siloxane is 3:1～4:1.
6. the low toxicity synthetic method of a kind of siloxanes gas sensitive according to claim 4, is characterized in that, the catalyzer in step (1) is the divinyl tetramethyl disiloxane platinum complex.
7. the low toxicity synthetic method of a kind of siloxanes gas sensitive according to claim 4, is characterized in that, the described solvent of step (1) is toluene.
8. the low toxicity synthetic method of a kind of siloxanes gas sensitive according to claim 4, it is characterized in that, in step (2), adopt to remove by filter gac, underpressure distillation steams solvent, obtains containing the siloxanes gas sensitive of hexafluoroisopropanol functional group after vacuum-drying.
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| CN103044687B (en) * | 2012-12-21 | 2015-03-11 | 江苏美思德化学股份有限公司 | Fluorine contained organosilicon-polyether copolymer and preparation method thereof |
| CN108562621B (en) * | 2018-05-30 | 2020-11-20 | 中国农业科学院农业信息研究所 | 2-acetyl-1-pyrroline sensitive material film, preparation method thereof, 2-acetyl-1-pyrroline sensing device and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5756631A (en) * | 1994-05-27 | 1998-05-26 | The United States Of America As Represented By The Secretary Of The Navy | Siloxanes with strong hydrogen bond donating functionalities |
| US7157052B1 (en) * | 2000-06-30 | 2007-01-02 | The United States Of America As Represented By The Secretary Of The Navy | Linear chemoselective carbosilane polymers and methods for use in analytical and purification applications |
| CN101186700A (en) * | 2007-12-25 | 2008-05-28 | 电子科技大学 | Polysiloxane organic phosphine poison sensitive material and preparation method thereof |
| CN101363810A (en) * | 2008-09-11 | 2009-02-11 | 电子科技大学 | Gas-sensitive sensor and method for making same |
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| US7078548B2 (en) * | 2002-03-06 | 2006-07-18 | The United States Of America As Represented By The Secretary Of The Navy | Hyperbranched chemoselective silicon-based polymers for chemical sensor applications |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5756631A (en) * | 1994-05-27 | 1998-05-26 | The United States Of America As Represented By The Secretary Of The Navy | Siloxanes with strong hydrogen bond donating functionalities |
| US7157052B1 (en) * | 2000-06-30 | 2007-01-02 | The United States Of America As Represented By The Secretary Of The Navy | Linear chemoselective carbosilane polymers and methods for use in analytical and purification applications |
| CN101186700A (en) * | 2007-12-25 | 2008-05-28 | 电子科技大学 | Polysiloxane organic phosphine poison sensitive material and preparation method thereof |
| CN101363810A (en) * | 2008-09-11 | 2009-02-11 | 电子科技大学 | Gas-sensitive sensor and method for making same |
Non-Patent Citations (2)
| Title |
|---|
| 有机磷毒剂压电传感器敏感材料的制备及性能研究;陈苑明等;《材料导报》;20091031;第23卷(第10期);第29-31,47页 * |
| 陈苑明等.有机磷毒剂压电传感器敏感材料的制备及性能研究.《材料导报》.2009,第23卷(第10期),第29-31,47页. |
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