CN102532439A - Preparation method for polymer/inorganic nano composite material - Google Patents
Preparation method for polymer/inorganic nano composite material Download PDFInfo
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- CN102532439A CN102532439A CN2012100396917A CN201210039691A CN102532439A CN 102532439 A CN102532439 A CN 102532439A CN 2012100396917 A CN2012100396917 A CN 2012100396917A CN 201210039691 A CN201210039691 A CN 201210039691A CN 102532439 A CN102532439 A CN 102532439A
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Abstract
The invention discloses a preparation method for a polymer/inorganic nano composite material. The inorganic component of the composite material is nano doped tin oxide sol, the surface of the inorganic component is modified by using gamma-methacryloxypropyltriethoxysilane, and unsaturated double bonds are introduced to the surfaces of inorganic particles and are used as active points of surface polymerization grafting. The modified inorganic component is dissolved in methyl methacrylate monomers through solvent replacement, initiator is added under a certain condition to induce monomers to be polymerized, and then the polymer/inorganic nano composite material is obtained after thermosetting. According to the method, inorganic sol with high stability is used, and the defect that the inorganic component is easy to agglomerate, and the defect of low dispersibility in a polymer in the conventional preparation process of the polymer/inorganic nano composite material are overcome. The composite material can be used as an energy-saving window material for automobiles, airplanes, buildings and the like.
Description
Technical field
The present invention relates to a kind of method of utilizing inorganic sol to prepare the polymer/inorganic matrix material, belonged to the Composite Preparation technical field.
Background technology
Nano composite material is the type material that development in recent years is got up, and is described as one of " the most promising material of 21 century ".Because nanoparticle has characteristics such as small-size effect, bigger serface and strong interface effect, can significantly improve the mechanical property of polymkeric substance after in adding polymeric matrix, also demonstrate distinctive performance at aspects such as light, electricity, magnetic, sound and catalysis.Therefore, in recent years, the polymer/inorganic nanometer particle composite material becomes the focus of research.
But also owing to inorganic nano-particle particle diameter little (1-100nm), surface energy is big, is in the thermodynamics unsteady state, is prone to reunite, and in polymeric matrix, is difficult for disperseing, and causes it to lose the characteristic of nanoparticle.In addition, organic and inorganic component are at the incompatible nanoparticle homodisperse in polymkeric substance that also is unfavorable on the thermodynamics.Therefore, nanoparticle realizes that in polymeric matrix it is the key that obtains the high-performance nano matrix material that nano level disperses.
The method of traditional preparation process polymer/inorganic nanometer matrix material mainly is physical methods such as application machine dispersed with stirring, ultrasonic dispersing and the dispersion of high power treatment method, by mechanical energy such as extraneous shearing force or impact forces, nanoparticle is fully disperseed in medium.This method is wayward, in case external force stops, occurring nanoparticle aggregation phenomenon once more easily, can not play the effect that lasting inhibition is reunited.Perhaps with inorganic nanometer powder through after the surface-treated with the polymer monomer blend, in-situ polymerization obtains the polymer/inorganic nanometer matrix material then.In the matrix material that this method obtains, inorganic particulate is owing to have very high surface energy before adding, and serious agglomeration causes in polymkeric substance, disperseing bad, influences performance of composites.
Summary of the invention
The technical issues that need to address of the present invention provide a kind of preparation method of polymer/inorganic nanometer matrix material.This method uses nano-doped tin oxide sol as inorganic phase, and polymethylmethacrylate is as organic phase.At first nano-doped tin oxide sol is carried out surface-treated; Introduce unsaturated double-bond as the surface aggregate grafting active site on the inorganic particulate surface; Through solvent exchange inorganic nano-particle is dissolved in the MMA MONOMER again, through obtaining the polymer/inorganic matrix material behind the in-situ polymerization.This invention advantage is that inorganic nano-particle is in dissolved colloidal state at the very start, and good dispersivity more greatly reduces the possibility of reuniting between particle through after the surface treatment.Therefore; In the solvent exchange process, can be good at being dispersed in the MMA MONOMER; This makes inorganic nano-particle good dispersivity in polymeric matrix; Composite property is excellent, and good mechanics and optical property are arranged, can be as window energy-saving materials such as automobile, aircraft, buildingss.
The present invention for realizing the technical scheme that above-mentioned purpose adopted is:
A kind of preparation method of polymer/inorganic nanometer matrix material, it may further comprise the steps:
A. in the nano-doped tin oxide sol of excellent in stability, add a certain amount of γ-methacryloxypropyl trimethoxy silane, successively obtain the nano-doped tin oxide sol of modification through ultrasonic and reflow treatment.
B. the nano-doped tin oxide sol after the modification is dissolved in the MMA MONOMER, process solvent exchange process is removed the former solvent of nano-doped tin oxide sol, and obtaining with the TEB 3K is the solution of solvent.
C. above-mentioned solution is added initiator under the nitrogen protection condition, behind the back flow reaction certain hour, solution is poured in the mould at a certain temperature, obtain the polymer/inorganic nanometer matrix material after the thermofixation.
Said nano-doped tin oxide is as doping agent with villiaumite, antimonic salt or fluorine or antimonic salt.
The solvent of said nano-doped tin oxide sol is following any: ethanol, methyl alcohol, Virahol, tetracol phenixin, ETHYLE ACETATE, acetone, butanone, THF, n-propyl alcohol, methylene dichloride, trichloromethane, ether or their mixed solvent.
The quality percentage composition that said γ-methacryloxypropyl trimethoxy silane accounts for doped tin oxide sol is 0.1%-20%.
The time of said supersound process is respectively 1min-720min, and the time of reflow treatment is 30min-720min.
The quality percentage composition that said nano-doped tin oxide accounts for MMA MONOMER is 0.1%-40%.
Said solvent exchange process comprises at least a in extraction, rotary evaporation, underpressure distillation, the air distillation.
Said initiator is Diisopropyl azodicarboxylate or Lucidol, and consumption is that the quality percentage composition that accounts for MMA MONOMER is 0.01%-1.0%.
Temperature among the said step c is 65
oC-80
oC, the time is 20min-60min.
Embodiment
After specific embodiment of the present invention being described at present.
Embodiment 1:
As inorganic component, polymethylmethacrylate is as the matrix material of organic matrix with the nanometer fluorine-doped tin oxide, and its preparation process is following:
A. add in the ethanol of excellent in stability is the nanometer fluorine-doped tin oxide colloidal sol of solvent that to account for its massfraction be γ-methacryloxypropyl trimethoxy silane of 5%, successively obtain the nanometer fluorine-doped tin oxide colloidal sol of modification through ultrasonic 30min and reflow treatment 240min.
B. the nanometer fluorine-doped tin oxide colloidal sol after the modification is dissolved in the MMA MONOMER; The quality percentage composition that the consumption of nanometer fluorine-doped tin oxide accounts for MMA MONOMER is 5%; Process rotary evaporation process is removed the former solvent of nanometer fluorine-doped tin oxide colloidal sol, and obtaining with the TEB 3K is the solution of solvent.
C. with above-mentioned solution under the nitrogen protection condition, add Diisopropyl azodicarboxylate as initiator 80
oC back flow reaction 30min, the consumption of Diisopropyl azodicarboxylate are that the quality percentage composition that accounts for MMA MONOMER is 0.06%, then solution are poured in the mould, obtain gathering methylpropanoic acid methyl esters/fluorine-doped tin oxide nano composite material after the thermofixation.
Embodiment 2:
As inorganic component, polymethylmethacrylate is as the matrix material of organic matrix with nano stibium doped tin oxide, and its preparation process is following:
A. add in the methyl alcohol of excellent in stability is the nano stibium doped tin oxide colloidal sol of solvent that to account for its massfraction be γ-methacryloxypropyl trimethoxy silane of 0.1%, successively obtain the nano stibium doped tin oxide colloidal sol of modification through ultrasonic 1min and reflow treatment 720min.
B. the nano stibium doped tin oxide colloidal sol after the modification is dissolved in the MMA MONOMER; The quality percentage composition that the consumption of nano stibium doped tin oxide accounts for MMA MONOMER is 0.1%; Process air distillation process is removed the former solvent of nano stibium doped tin oxide colloidal sol, and obtaining with the TEB 3K is the solution of solvent.
C. with above-mentioned solution under the nitrogen protection condition, add Diisopropyl azodicarboxylate as initiator 70
oC back flow reaction 40min, the consumption of Diisopropyl azodicarboxylate are that the quality percentage composition that accounts for MMA MONOMER is 0.01%, then solution are poured in the mould, obtain gathering methylpropanoic acid methyl esters/antimony-doped tin oxide nano matrix material after the thermofixation.
Embodiment 3:
As inorganic component, polymethylmethacrylate is as the matrix material of organic matrix with nanometer fluorine, antimony codoped White tin oxide, and its preparation process is following:
A. add in the acetone of excellent in stability is the nanometer fluorine, antimony codoped tin oxide sol of solvent that to account for its massfraction be γ-methacryloxypropyl trimethoxy silane of 20%, successively obtain nanometer fluorine, the antimony codoped tin oxide sol of modification through ultrasonic 720min and reflow treatment 30min.
B. the nanometer fluorine after the modification, antimony codoped tin oxide sol are dissolved in the MMA MONOMER; The quality percentage composition that the consumption of nanometer fluorine, antimony codoped White tin oxide accounts for MMA MONOMER is 40%; The process vacuum distillation process is removed the former solvent of nanometer fluorine, antimony codoped tin oxide sol, and obtaining with the TEB 3K is the solution of solvent.
C. with above-mentioned solution under the nitrogen protection condition, add Diisopropyl azodicarboxylate as initiator 65
oC back flow reaction 60min, the consumption of Lucidol are that the quality percentage composition that accounts for MMA MONOMER is 1.0%, then solution are poured in the mould, obtain gathering methylpropanoic acid methyl esters/fluorine, antimony codoped tin oxide nano matrix material after the thermofixation.
Claims (9)
1. the preparation method of a polymer/inorganic nanometer matrix material is characterized in that, its be nano-doped tin oxide sol with high stability as inorganic component, polymethylmethacrylate is as the matrix material of organic matrix, its preparation process is following:
A. in the nano-doped tin oxide sol of excellent in stability, add a certain amount of γ-methacryloxypropyl trimethoxy silane, successively obtain the nano-doped tin oxide sol of modification through ultrasonic and reflow treatment;
B. the nano-doped tin oxide sol after the modification is dissolved in the MMA MONOMER, process solvent exchange process is removed the former solvent of nano-doped tin oxide sol, and obtaining with the TEB 3K is the solution of solvent;
C. above-mentioned solution is added initiator under the nitrogen protection condition, behind the back flow reaction certain hour, solution is poured in the mould at a certain temperature, obtain the polymer/inorganic nanometer matrix material after the thermofixation.
2. the preparation method of a kind of polymer/inorganic nanometer matrix material according to claim 1 is characterized in that said nano-doped tin oxide is as doping agent with villiaumite, antimonic salt or fluorine or antimonic salt.
3. the preparation method of a kind of polymer/inorganic nanometer matrix material according to claim 1; The solvent that it is characterized in that said nano-doped tin oxide sol is a kind of among following: ethanol, methyl alcohol, Virahol, tetracol phenixin, ETHYLE ACETATE, acetone, butanone, THF, n-propyl alcohol, methylene dichloride, trichloromethane, ether, perhaps their mixed solvent.
4. the preparation method of a kind of polymer/inorganic nanometer matrix material according to claim 1 is characterized in that the quality percentage composition that γ-methacryloxypropyl trimethoxy silane accounts for doped tin oxide sol is 0.1%-20%.
5. the preparation method of a kind of polymer/inorganic nanometer matrix material according to claim 1 is characterized in that the time of supersound process is respectively 1min-720min, and the time of reflow treatment is 30min-720min.
6. the preparation method of a kind of polymer/inorganic nanometer matrix material according to claim 1 is characterized in that the quality percentage composition that nano-doped tin oxide accounts for MMA MONOMER is 0.1%-40%.
7. the preparation method of a kind of polymer/inorganic nanometer matrix material according to claim 1 is characterized in that the solvent exchange process comprises at least a in extraction, rotary evaporation, underpressure distillation, the air distillation.
8. the preparation method of a kind of polymer/inorganic nanometer matrix material according to claim 1; It is characterized in that used initiator is Diisopropyl azodicarboxylate or Lucidol, consumption is that the quality percentage composition that accounts for MMA MONOMER is 0.01%-1.0%.
9. the preparation method of a kind of polymer/inorganic nanometer matrix material according to claim 1 is characterized in that the temperature among the said step c is 65
oC-80
oC, the time is 20min-60min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106967193A (en) * | 2017-03-22 | 2017-07-21 | 北京理工大学 | A kind of doping semi-conductor nanocrystalline/lucite solar energy fluorescence collector |
| CN110183563A (en) * | 2019-06-13 | 2019-08-30 | 慧迈材料科技(广东)有限公司 | A kind of preparation method for the TPO that inorganic oxide is modified |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347432A (en) * | 1999-02-15 | 2002-05-01 | Dsm有限公司 | Resin composition and cured product |
| CN1711213A (en) * | 2002-11-13 | 2005-12-21 | 日本曹达株式会社 | Dispersoid having metal-oxygen bond, metal oxide film, and monomolecular film |
| CN101121545A (en) * | 2006-06-22 | 2008-02-13 | 日产化学工业株式会社 | Conductive tin oxide sol and process for producing same |
-
2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347432A (en) * | 1999-02-15 | 2002-05-01 | Dsm有限公司 | Resin composition and cured product |
| CN1711213A (en) * | 2002-11-13 | 2005-12-21 | 日本曹达株式会社 | Dispersoid having metal-oxygen bond, metal oxide film, and monomolecular film |
| CN101121545A (en) * | 2006-06-22 | 2008-02-13 | 日产化学工业株式会社 | Conductive tin oxide sol and process for producing same |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106967193A (en) * | 2017-03-22 | 2017-07-21 | 北京理工大学 | A kind of doping semi-conductor nanocrystalline/lucite solar energy fluorescence collector |
| CN110183563A (en) * | 2019-06-13 | 2019-08-30 | 慧迈材料科技(广东)有限公司 | A kind of preparation method for the TPO that inorganic oxide is modified |
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Effective date of registration: 20180625 Address after: 200436 3, 100 Lane 1090 lane, Hu Tai Road, Baoshan District, Shanghai. Patentee after: Shanghai Shanghui Nano Technology Co., Ltd. Address before: No. 99, Baoshan District Road, Shanghai, Shanghai Patentee before: Shanghai University |
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