CN104262655A - Method for preparing unified-size and uniformly-dispersed PI/SiO2 nanocomposite film in novel coupling way - Google Patents
Method for preparing unified-size and uniformly-dispersed PI/SiO2 nanocomposite film in novel coupling way Download PDFInfo
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Abstract
The invention discloses a method for preparing a unified-size and uniformly-dispersed PI/SiO2 nanocomposite film in a novel coupling way, relating to a method for preparing a PI/SiO2 nanocomposite film and aiming to solve the problems of non-uniform distribution and aggregation of nanoparticles in a polyimide matrix in the existing PI/SiO2 nanocomposite film preparation process. The method comprises the steps of adding a coupling agent into a system on the basis of the traditional sol-gel polymerization method, and connecting SiO2 and a PI matrix together in a novel coupling way to prepare the unified-size and uniformly-dispersed PI/SiO2 nanocomposite film serving as a novel industrial material. The method is used for preparing the PI/SiO2 nanocomposite film.
Description
Technical field
The present invention relates to one and prepare PI/SiO
2the method of nano compound film.
Background technology
Over nearly 30 years, science and technology develops rapidly, particularly the advancing by leaps and bounds of top science technology, and make the requirement of people to material property more and more higher, in many aspects, traditional single-material can not meet actual needs.This just impels people to study the preparation of matrix material and performance.
Generally speaking, compared with/polymer composites inorganic with traditional, Preparing Organic-inorganic Nano Hybrid Material has lot of advantages.Because the interface between inorganic nano-filler and polymkeric substance is not macroscopical, but microcosmic, or even molecular level, interfacial area is very large, significantly can reduce interfacial stress to concentrate, eliminate the unmatched problem of thermal expansivity between inorganics and polymeric matrix, give full play to the processability of the mechanical property of the excellence of inorganic molecule, high heat resistance energy and polymkeric substance, the physical and mechanical property of nano composite material is obviously better than the conventional composites materials of like combinations.Inorganic nano-particle all shows larger advantage improving in the resistance toheat of material, mechanical property and dimensional stability etc.Therefore, the development of polymerinorganic nano-hybrid material becomes the performance improving polymkeric substance itself, expands the solution route of its range of application.
Polyimide (PI) is a kind of material of excellent combination property, is commonly referred to as the material surmounting the epoch, and at high temperature remarkable performance can match in excellence or beauty with some metallographic phase.In addition, it also has the mechanical property of excellent chemical stability, tenacity, wear resistance, flame retardant resistance, electrical insulating property and excellence.But containing phenyl ring and phthalimide ring structure on PI molecular backbone chain, due to electronic polarization and crystallinity, PI is caused to there is stronger intermolecular interaction, cause PI molecular chain tightly packed, thus result in PI there is obvious water-absorbent and thermal expansivity, which has limited its application under high temperature and accurate state.But polyimide-inorganic nano composite material can have the advantage of polymkeric substance and inorganic materials simultaneously, make the performance of polyimide more excellent, range of application is more extensive.
Summary of the invention
The present invention will solve existing PI/SiO
2there is the problem of nano particle skewness and reunion in polyimide matrix in nano compound film preparation process, and provide a kind of novel coupling mode preparation size unified and finely dispersed PI/SiO
2the method of nano compound film.
A kind of novel coupling mode preparation size of the present invention is unified and finely dispersed PI/SiO
2the method of nano compound film is carried out according to the following steps:
One, be dissolved in N,N-dimethylacetamide by monomer diamine, mechanical stirring is dissolved completely to monomer diamine; Then in mixed solution, add dianhydride, mechanical stirring to dianhydride dissolves rear continuation completely and stirs 2h ~ 4h, obtains polyamic acid solution; The quality of described monomer diamine and the volume ratio of N,N-dimethylacetamide are 1g:(15 ~ 20) mL; The mass ratio of described monomer diamine and dianhydride is 1:(0.8 ~ 1.2); The feed postition of described dianhydride is as follows: added for 5 times by dianhydride average mark;
Two, add coupling agent in the polyamic acid solution obtained in step one, after stirring 0.5h ~ 2h, add silicon source wherein again, leave standstill 12h ~ 18h, obtain polyamic acid mixing solutions; The quality of described coupling agent and the volume ratio of polyamic acid solution are 1g:(50 ~ 150) mL;
Three, polyamic acid mixing solutions step 2 obtained adopts the even blade coating of automatic spray device on the sheet glass of cleaning, obtain the sheet glass having scraped film, then the sheet glass having scraped film is put into baking oven, by the temperature in baking oven from room temperature to 80 DEG C, and be keep 0.5h under the condition of 80 DEG C in temperature, again temperature is warming up to 100 DEG C by 80 DEG C, and be keep 0.5h under the condition of 100 DEG C in temperature, then temperature is warming up to 175 DEG C by 100 DEG C, be keep 1h under the condition of 175 DEG C in temperature, again temperature is warming up to 235 DEG C by 175 DEG C, be keep 1h under the condition of 235 DEG C in temperature, again temperature is warming up to 300 DEG C by 235 DEG C, be keep 1h under the condition of 300 DEG C in temperature, obtain PI/SiO
2nano compound film, described PI/SiO
2siO in nano compound film
2massfraction is 0.1% ~ 20%.
The invention has the beneficial effects as follows:
The present invention enables nano SiO 2 particle be evenly distributed in polyimide matrix, and particle size is less, without obvious agglomeration.Polyimide/silicon dioxide nano compound film prepared by the present invention dioxide-containing silica at 8wt% to 13wt% time, in film, the size of silica dioxide granule is greatly between 20nm ~ 30nm.Polyimide/silicon dioxide laminated film prepared by the people such as Giuseppa Ragosta is when dioxide-containing silica is 10wt%-20wt%, and in film, granular size is between 50nm ~ 80nm.The polyimide/titanium dioxide nano compound film of people's synthesis such as Hojjat Seyedjamali is when content of titanium dioxide is 2wt% ~ 10wt%, and in film, granular size is between 30nm ~ 100nm.In the present invention, silica dioxide granule can be so evenly distributed in polyimide and one of less reason of particle size is that the hydrolysate in silicon source and polymer chain link together by the coupling agent added, thus hydrolysate is surrounded by polymkeric substance prevent from reuniting; And generate urea groups and polymer chain form hydrogen bond, can particle agglomeration be prevented, be uniformly dispersed.Another one reason does not add water in whole experimentation, and silicon source just utilizes the water discharged in the water in solvent and imidization to be hydrolyzed, so the size of silica dioxide granule is less.So the present invention adopts coupling agent with a kind of novel coupling mode by PI and SiO
2pI/SiO prepared by the method linked together
2nano composite membrane has polymolecularity, high heat resistance and high strength.
Accompanying drawing explanation
Fig. 1 is the SiO that embodiment one obtains
2massfraction is the PI/SiO of 13%
2the SiO that nano compound film, embodiment two obtain
2massfraction is the PI/SiO of 13%
2the FT-IR figure of the pure PI nano thin-film that nano compound film and embodiment three obtain, wherein (a) represents the pure PI nano thin-film obtained of embodiment three, and (b) represents the SiO that embodiment one obtains
2massfraction is the PI/SiO of 13%
2nano compound film, (c) represents the SiO that embodiment two obtains
2massfraction is the PI/SiO of 13%
2nano compound film;
Fig. 2 is that embodiment one and embodiment two prepare SiO
2massfraction is the PI/SiO of 13%
2the FT-IR figure of the laminated film residue produced in nano compound film process, wherein (a) represents that embodiment one prepares SiO
2massfraction is the PI/SiO of 13%
2the laminated film residue produced in nano compound film process, (b) represents that embodiment two prepares SiO
2massfraction is the PI/SiO of 13%
2the laminated film residue produced in nano compound film process;
Fig. 3 is that the section SEM of the pure PI nano thin-film that embodiment three obtains schemes;
Fig. 4 is the SiO that embodiment two obtains
2massfraction is the PI/SiO of 8%
2the section SEM of nano compound film schemes;
The SiO that Fig. 5 embodiment two obtains
2massfraction is the PI/SiO of 13%
2the section SEM of nano compound film schemes;
Fig. 6 is the SiO that embodiment one obtains
2massfraction is the PI/SiO of 8%
2the section SEM of nano compound film schemes;
The SiO that Fig. 7 embodiment one obtains
2massfraction is the PI/SiO of 13%
2the section SEM of nano compound film schemes;
Fig. 8 is the PI/SiO that embodiment one and embodiment two obtain
2the particle size distribution figure of nano compound film, wherein
represent the SiO that embodiment one obtains
2massfraction is the PI/SiO of 8%
2nano compound film,
represent the SiO that embodiment one obtains
2massfraction is the PI/SiO of 13%
2nano compound film,
represent the SiO that embodiment two obtains
2massfraction is the PI/SiO of 8%
2nano compound film,
represent the SiO that embodiment two obtains
2massfraction is the PI/SiO of 13%
2nano compound film.
Embodiment
Embodiment one: the novel coupling mode of the one described in present embodiment preparation size is unified and finely dispersed PI/SiO
2the method of nano compound film is carried out according to the following steps:
One, be dissolved in N,N-dimethylacetamide by monomer diamine, mechanical stirring is dissolved completely to monomer diamine; Then in mixed solution, add dianhydride, mechanical stirring to dianhydride dissolves rear continuation completely and stirs 2h ~ 4h, obtains polyamic acid solution; The quality of described monomer diamine and the volume ratio of N,N-dimethylacetamide are 1g:(15 ~ 20) mL; The mass ratio of described monomer diamine and dianhydride is 1:1; The feed postition of described dianhydride is as follows: added for 5 times by dianhydride average mark;
Two, add coupling agent in the polyamic acid solution obtained in step one, after stirring 0.5h ~ 2h, add silicon source wherein again, leave standstill 12h ~ 18h, obtain polyamic acid mixing solutions; The quality of described coupling agent and the volume ratio of polyamic acid solution are 1g:(50 ~ 150) mL;
Three, polyamic acid mixing solutions step 2 obtained adopts the even blade coating of automatic spray device on the sheet glass of cleaning, obtain the sheet glass having scraped film, then the sheet glass having scraped film is put into baking oven, by the temperature in baking oven from room temperature to 80 DEG C, and be keep 0.5h under the condition of 80 DEG C in temperature, again temperature is warming up to 100 DEG C by 80 DEG C, and be keep 0.5h under the condition of 100 DEG C in temperature, then temperature is warming up to 175 DEG C by 100 DEG C, be keep 1h under the condition of 175 DEG C in temperature, again temperature is warming up to 235 DEG C by 175 DEG C, be keep 1h under the condition of 235 DEG C in temperature, again temperature is warming up to 300 DEG C by 235 DEG C, be keep 1h under the condition of 300 DEG C in temperature, obtain PI/SiO
2nano compound film, described PI/SiO
2siO in nano compound film
2massfraction is 0.1% ~ 20%.
Different SiO is obtained by the quality difference adding silicon source
2the PI/SiO of massfraction
2nano compound film.
Present embodiment enables nano SiO 2 particle be evenly distributed in polyimide matrix, and particle size is less, without obvious agglomeration.Polyimide/silicon dioxide nano compound film prepared by the present invention dioxide-containing silica at 8wt% to 13wt% time, in film, the size of silica dioxide granule is greatly between 20nm ~ 30nm.Polyimide/silicon dioxide laminated film prepared by the people such as Giuseppa Ragosta is when dioxide-containing silica is 10wt%-20wt%, and in film, granular size is between 50nm ~ 80nm.The polyimide/titanium dioxide nano compound film of people's synthesis such as Hojjat Seyedjamali is when content of titanium dioxide is 2wt% ~ 10wt%, and in film, granular size is between 30nm ~ 100nm.In the present invention, silica dioxide granule can be so evenly distributed in polyimide and one of less reason of particle size is that the hydrolysate in silicon source and polymer chain link together by the coupling agent added, thus hydrolysate is surrounded by polymkeric substance prevent from reuniting; And generate urea groups and polymer chain form hydrogen bond, can particle agglomeration be prevented, be uniformly dispersed.Another one reason does not add water in whole experimentation, and silicon source just utilizes the water discharged in the water in solvent and imidization to be hydrolyzed, so the size of silica dioxide granule is less.So the present invention adopts coupling agent with a kind of novel coupling mode by PI and SiO
2pI/SiO prepared by the method linked together
2nano composite membrane has polymolecularity, high heat resistance and high strength.
Embodiment two: present embodiment and embodiment one unlike: the quality of monomer diamine described in step one and the volume ratio of N,N-dimethylacetamide are 1g:18mL.Other is identical with embodiment one.
Embodiment three: present embodiment and embodiment one or two unlike: the mass ratio of monomer diamine described in step one and dianhydride is 1:1.Other is identical with embodiment one or two.
Embodiment four: present embodiment and embodiment one to three unlike: coupling agent described in step 2 is isocyanatopropyl triethoxyl silane.Other is identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: the source of silicon described in step 2 is tetraethoxy.Other is identical with one of embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five are unlike PI/SiO described in step 3
2siO in nano compound film
2massfraction is 5%.Other is identical with one of embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six are unlike PI/SiO described in step 3
2siO in nano compound film
2massfraction is 8%.Other is identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven are unlike PI/SiO described in step 3
2siO in nano compound film
2massfraction is 10%.Other is identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight are unlike PI/SiO described in step 3
2siO in nano compound film
2massfraction is 13%.Other is identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine are unlike PI/SiO described in step 3
2siO in nano compound film
2massfraction is 15%.Other is identical with one of embodiment one to nine.
Beneficial effect of the present invention is verified by following examples:
Embodiment one: a kind of novel coupling mode preparation size is unified and finely dispersed PI/SiO
2the method of nano compound film is carried out according to the following steps:
One, 2.77g monomer diamine is dissolved in 50mLN, in N-N,N-DIMETHYLACETAMIDE, mechanical stirring is dissolved completely to monomer diamine; Then in mixed solution, add 3.018g dianhydride, mechanical stirring to dianhydride dissolves rear continuation completely and stirs 2h, obtains polyamic acid solution;
Two, add 0.5g isocyanatopropyl triethoxyl silane in the polyamic acid solution obtained in 50mL step one, after stirring 0.5h, add tetraethoxy wherein again, leave standstill 12h, obtain polyamic acid mixing solutions;
Three, polyamic acid mixing solutions step 2 obtained adopts the even blade coating of automatic spray device on the sheet glass of cleaning, obtain the sheet glass having scraped film, then the sheet glass having scraped film is put into baking oven, by the temperature in baking oven from room temperature to 80 DEG C, and be keep 0.5h under the condition of 80 DEG C in temperature, again temperature is warming up to 100 DEG C by 80 DEG C, and be keep 0.5h under the condition of 100 DEG C in temperature, then temperature is warming up to 175 DEG C by 100 DEG C, be keep 1h under the condition of 175 DEG C in temperature, again temperature is warming up to 235 DEG C by 175 DEG C, be keep 1h under the condition of 235 DEG C in temperature, again temperature is warming up to 300 DEG C by 235 DEG C, be keep 1h under the condition of 300 DEG C in temperature, obtain PI/SiO
2nano compound film, described PI/SiO
2siO in nano compound film
2massfraction is 5% ~ 15%.
Embodiment two:: one prepares PI/SiO
2the method of nano compound film is carried out according to the following steps:
One, 2.77g monomer diamine is dissolved in 50mLN, in N-N,N-DIMETHYLACETAMIDE, mechanical stirring is dissolved completely to monomer diamine; Then in mixed solution, add 3.018g dianhydride, mechanical stirring to dianhydride dissolves rear continuation completely and stirs 2h, obtains polyamic acid solution;
Two, add tetraethoxy in the polyamic acid solution obtained in 50mL step one, leave standstill 12h, obtain polyamic acid mixing solutions;
Three, polyamic acid mixing solutions step 2 obtained adopts the even blade coating of automatic spray device on the sheet glass of cleaning, obtain the sheet glass having scraped film, then the sheet glass having scraped film is put into baking oven, by the temperature in baking oven from room temperature to 80 DEG C, and be keep 0.5h under the condition of 80 DEG C in temperature, again temperature is warming up to 100 DEG C by 80 DEG C, and be keep 0.5h under the condition of 100 DEG C in temperature, then temperature is warming up to 175 DEG C by 100 DEG C, be keep 1h under the condition of 175 DEG C in temperature, again temperature is warming up to 235 DEG C by 175 DEG C, be keep 1h under the condition of 235 DEG C in temperature, again temperature is warming up to 300 DEG C by 235 DEG C, be keep 1h under the condition of 300 DEG C in temperature, obtain PI/SiO
2nano compound film, described PI/SiO
2siO in nano compound film
2massfraction is 5% ~ 15%.
Embodiment three: a kind of method of the PI of preparation nano thin-film is carried out according to the following steps:
One, 2.77g monomer diamine is dissolved in 50mLN, in N-N,N-DIMETHYLACETAMIDE, mechanical stirring is dissolved completely to monomer diamine; Then in mixed solution, add 3.018g dianhydride, mechanical stirring to dianhydride dissolves rear continuation completely and stirs 2h, obtains polyamic acid solution;
Two, add 0.5g isocyanatopropyl triethoxyl silane in the polyamic acid solution obtained in 50mL step one, after stirring 0.5h, leave standstill 12h, obtain polyamic acid mixing solutions;
Three, polyamic acid mixing solutions step 2 obtained adopts the even blade coating of automatic spray device on the sheet glass of cleaning, obtain the sheet glass having scraped film, then the sheet glass having scraped film is put into baking oven, by the temperature in baking oven from room temperature to 80 DEG C, and be keep 0.5h under the condition of 80 DEG C in temperature, again temperature is warming up to 100 DEG C by 80 DEG C, and be keep 0.5h under the condition of 100 DEG C in temperature, then temperature is warming up to 175 DEG C by 100 DEG C, be keep 1h under the condition of 175 DEG C in temperature, again temperature is warming up to 235 DEG C by 175 DEG C, be keep 1h under the condition of 235 DEG C in temperature, again temperature is warming up to 300 DEG C by 235 DEG C, be keep 1h under the condition of 300 DEG C in temperature, obtain pure PI nano thin-film.
Fig. 1 is the SiO that embodiment one obtains
2massfraction is the PI/SiO of 13%
2the SiO that nano compound film, embodiment two obtain
2massfraction is the PI/SiO of 13%
2the FT-IR figure of the pure PI nano thin-film that nano compound film and embodiment three obtain, wherein (a) represents the pure PI nano thin-film obtained of embodiment three, and (b) represents the SiO that embodiment one obtains
2massfraction is the PI/SiO of 13%
2nano compound film, (c) represents the SiO that embodiment two obtains
2massfraction is the PI/SiO of 13%
2nano compound film; As can see from Figure 1, the SiO that obtains of embodiment one and embodiment two
2massfraction is the PI/SiO of 13%
2c-NH (1650cm in the pure PI nano thin-film obtained of nano compound film and embodiment three
-1) and Si-OH (3600cm
-1) characteristic peak almost completely dissolve in spectrogram at place, this shows that polyamic acid solution imidization is relatively completely and teos hydrolysis polycondensation is also very thorough.The characteristic peak of the pure PI nano thin-film obtained of embodiment three also can significantly be told in FIG, is 1776cm respectively
-1(the asymmetric stretching vibration peak of C=O key), 1724cm
-1(the symmetrical stretching vibration peak of C=O key), 1378cm
-1(the symmetrical stretching vibration peak of C-N key) and 725cm
-1(the flexural vibration peak of C=O key).Fig. 2 is that embodiment one and embodiment two prepare SiO
2massfraction is the PI/SiO of 13%
2the FT-IR figure of the laminated film residue produced in nano compound film process, wherein (a) represents that embodiment one prepares SiO
2massfraction is the PI/SiO of 13%
2the laminated film residue produced in nano compound film process, (b) represents that embodiment two prepares SiO
2massfraction is the PI/SiO of 13%
2the laminated film residue produced in nano compound film process; As can be seen from Figure 2, embodiment one and embodiment two prepare SiO
2massfraction is the PI/SiO of 13%
2all there is silica dioxide granule in the laminated film residue produced in nano compound film process, its characteristic peak is respectively 465cm
-1, 468cm
-1(the flexural vibration peak of Si-O-Si key), 801cm
-1, 793cm
-1(the symmetrical stretching vibration peak of Si-O-Si key) and 1108cm
-1, 1037cm
-1(the asymmetric stretching vibration peak of Si-O-Si key).Fig. 3 is that the section SEM of the pure PI nano thin-film that embodiment three obtains schemes; Fig. 4 is the SiO that embodiment two obtains
2massfraction is the PI/SiO of 8%
2the section SEM of nano compound film schemes; The SiO that Fig. 5 embodiment two obtains
2massfraction is the PI/SiO of 13%
2the section SEM of nano compound film schemes; Fig. 6 is the SiO that embodiment one obtains
2massfraction is the PI/SiO of 8%
2the section SEM of nano compound film schemes; The SiO that Fig. 7 embodiment one obtains
2massfraction is the PI/SiO of 13%
2the section SEM of nano compound film schemes; Fig. 8 is the PI/SiO that embodiment one and embodiment two obtain
2the particle size distribution figure of nano compound film, wherein
represent the SiO that embodiment one obtains
2massfraction is the PI/SiO of 8%
2nano compound film,
represent the SiO that embodiment one obtains
2massfraction is the PI/SiO of 13%
2nano compound film,
represent the SiO that embodiment two obtains
2massfraction is the PI/SiO of 8%
2nano compound film,
represent the SiO that embodiment two obtains
2massfraction is the PI/SiO of 13%
2nano compound film; Can be observed by Fig. 3 to Fig. 8, SiO
2particle is being evenly distributed in these two kinds of imine matrixes, and particle size (20nm ~ 50nm) in nanometer range, substantially there is no obvious agglomeration.But, add the SiO in the laminated film of coupling agent
2particle size and size-grade distribution less; So Fig. 4 illustrates that the two-phase consistency that novel coupling mode combines is better.
To sum up, the compound system of novel coupling mode makes the breaking tenacity of laminated film significantly improve, the PI/SiO of preparation
2nano compound film mechanical strength is excellent, has very important significance for the application in engineering materials field.
Claims (10)
1. a novel coupling mode preparation size is unified and finely dispersed PI/SiO
2the method of nano compound film, is characterized in that the unification of novel coupling mode preparation size and finely dispersed PI/SiO
2the method of nano compound film is carried out according to the following steps:
One, be dissolved in N,N-dimethylacetamide by monomer diamine, mechanical stirring is dissolved completely to monomer diamine; Then in mixed solution, add dianhydride, mechanical stirring to dianhydride dissolves rear continuation completely and stirs 2h ~ 4h, obtains polyamic acid solution; The quality of described monomer diamine and the volume ratio of N,N-dimethylacetamide are 1g:(15 ~ 20) mL; The mass ratio of described monomer diamine and dianhydride is 1:1; The feed postition of described dianhydride is as follows: added for 5 times by dianhydride average mark;
Two, add coupling agent in the polyamic acid solution obtained in step one, after stirring 0.5h ~ 2h, add silicon source wherein again, leave standstill 12h ~ 18h, obtain polyamic acid mixing solutions; The quality of described coupling agent and the volume ratio of polyamic acid solution are 1g:(50 ~ 150) mL;
Three, polyamic acid mixing solutions step 2 obtained adopts the even blade coating of automatic spray device on the sheet glass of cleaning, obtain the sheet glass having scraped film, then the sheet glass having scraped film is put into baking oven, by the temperature in baking oven from room temperature to 80 DEG C, and be keep 0.5h under the condition of 80 DEG C in temperature, again temperature is warming up to 100 DEG C by 80 DEG C, and be keep 0.5h under the condition of 100 DEG C in temperature, then temperature is warming up to 175 DEG C by 100 DEG C, be keep 1h under the condition of 175 DEG C in temperature, again temperature is warming up to 235 DEG C by 175 DEG C, be keep 1h under the condition of 235 DEG C in temperature, again temperature is warming up to 300 DEG C by 235 DEG C, be keep 1h under the condition of 300 DEG C in temperature, obtain PI/SiO
2nano compound film, described PI/SiO
2siO in nano compound film
2massfraction is 0.1% ~ 20%.
2. one according to claim 1 novel coupling mode preparation size is unified and finely dispersed PI/SiO
2the method of nano compound film, is characterized in that the quality of monomer diamine described in step one and the volume ratio of N,N-dimethylacetamide are 1g:18mL.
3. one according to claim 1 novel coupling mode preparation size is unified and finely dispersed PI/SiO
2the method of nano compound film, is characterized in that the mass ratio of monomer diamine described in step one and dianhydride is 1:1.
4. one according to claim 1 novel coupling mode preparation size is unified and finely dispersed PI/SiO
2the method of nano compound film, is characterized in that coupling agent described in step 2 is isocyanatopropyl triethoxyl silane.
5. one according to claim 1 novel coupling mode preparation size is unified and finely dispersed PI/SiO
2the method of nano compound film, is characterized in that the source of silicon described in step 2 is tetraethoxy.
6. one according to claim 1 novel coupling mode preparation size is unified and finely dispersed PI/SiO
2the method of nano compound film, is characterized in that PI/SiO described in step 3
2siO in nano compound film
2massfraction is 5%.
7. one according to claim 1 novel coupling mode preparation size is unified and finely dispersed PI/SiO
2the method of nano compound film, is characterized in that PI/SiO described in step 3
2siO in nano compound film
2massfraction is 8%.
8. one according to claim 1 novel coupling mode preparation size is unified and finely dispersed PI/SiO
2the method of nano compound film, is characterized in that PI/SiO described in step 3
2siO in nano compound film
2massfraction is 10%.
9. one according to claim 1 novel coupling mode preparation size is unified and finely dispersed PI/SiO
2the method of nano compound film, is characterized in that PI/SiO described in step 3
2siO in nano compound film
2massfraction is 13%.
10. one according to claim 1 novel coupling mode preparation size is unified and finely dispersed PI/SiO
2the method of nano compound film, is characterized in that PI/SiO described in step 3
2siO in nano compound film
2massfraction is 15%.
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| CN106751247A (en) * | 2016-12-13 | 2017-05-31 | 哈尔滨理工大学 | A kind of preparation method of the crosslinking PS@Cu/PVDF laminated films of high-k |
| CN112011074A (en) * | 2020-07-29 | 2020-12-01 | 浙江中科玖源新材料有限公司 | Organic silicon modified polyimide film and preparation method thereof |
| CN112574409A (en) * | 2020-11-16 | 2021-03-30 | 阜阳申邦新材料技术有限公司 | High-barrier polyimide film material and preparation method thereof |
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| JIAQI LIN ，YING LIU ， WENLONG YANG,ETAL.: "Structure and mechanical properties of the hybrid films of well dispersed SiO2 nanoparticle in polyimide (PI/SiO2) prepared by sol–gel process", 《J POLYM RES》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106751247A (en) * | 2016-12-13 | 2017-05-31 | 哈尔滨理工大学 | A kind of preparation method of the crosslinking PS@Cu/PVDF laminated films of high-k |
| CN106751247B (en) * | 2016-12-13 | 2019-01-08 | 哈尔滨理工大学 | A kind of preparation method of the crosslinking PS@Cu/PVDF laminated film of high dielectric constant |
| CN112011074A (en) * | 2020-07-29 | 2020-12-01 | 浙江中科玖源新材料有限公司 | Organic silicon modified polyimide film and preparation method thereof |
| CN112574409A (en) * | 2020-11-16 | 2021-03-30 | 阜阳申邦新材料技术有限公司 | High-barrier polyimide film material and preparation method thereof |
| CN112574409B (en) * | 2020-11-16 | 2023-01-17 | 贵溪穿越光电科技有限公司 | High-barrier polyimide film material and preparation method thereof |
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