CN102660024B - Electrochromatic bismaleimide resin and preparation method of film of electrochromatic bismaleimide resin - Google Patents
Electrochromatic bismaleimide resin and preparation method of film of electrochromatic bismaleimide resin Download PDFInfo
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- CN102660024B CN102660024B CN 201210163764 CN201210163764A CN102660024B CN 102660024 B CN102660024 B CN 102660024B CN 201210163764 CN201210163764 CN 201210163764 CN 201210163764 A CN201210163764 A CN 201210163764A CN 102660024 B CN102660024 B CN 102660024B
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- WDOMFMZXOLGTFA-UHFFFAOYSA-N Cc(cc1)ccc1N(c1ccccc1)c(cc1)ccc1N Chemical compound Cc(cc1)ccc1N(c1ccccc1)c(cc1)ccc1N WDOMFMZXOLGTFA-UHFFFAOYSA-N 0.000 description 1
- TZHNHNHALWWXSP-UHFFFAOYSA-N Nc(cc1)ccc1N(c1ccccc1)c(cc1)ccc1N(c1ccccc1)c(cc1)ccc1N Chemical compound Nc(cc1)ccc1N(c1ccccc1)c(cc1)ccc1N(c1ccccc1)c(cc1)ccc1N TZHNHNHALWWXSP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to electrochromatic bismaleimide resin film and a preparation method thereof, and aims to solve the problems that the existing film made of electrochromatic materials is easy to fall in test and poor in solvent corrosion resistance. The component of the electrochromatic bismaleimide resin film is the electrochromatic bismaleimide resin, and a structural formula thereof is shown as below. The preparation method includes: firstly, synthesizing N, N'- bismaleimide-4, 4'-diphenyl ether monomer; secondly, subjecting the obtained bismaleimide monomer and tertiary aromatic diamine monomer to pre-polymerizationto obtain prepolymer; and thirdly, spin-coating the prepolymer to a substrate to obtain a film, and solidifying to obtain the electrochromatic bismaleimide resin film. The preparation method is mainly sued for preparing electrochromatic bismaleimide resin films.
Description
Technical field
The present invention relates to a kind of bimaleimide resin film and preparation method thereof.
Background technology
Bismaleimides (BMI) resin has good thermotolerance, electrical insulating property, wave, flame retardant resistance, weathering resistance, mechanical property and dimensional stability.The BMI resin has been widely used in the industrial circles such as aerospace, communications and transportation, machinery and electronics as matrix resins such as advanced composite material, high-temperature insulation material and tackiness agent.
Electrochromic polymer is at the focus that has become the electrochromic material of current research aspect performance and the research of many colour developing structure applications.Has electrochromism, the existence of the bimaleimide resin of electroluminescent properties will make demonstration and sensory field burst out flourishing vitality, it is showing and sensory field all shows outstanding superiority and wide development prospect along with the stepped into information epoch that organic optoelectronic has formed the cross one another emerging research fields of subjects such as an organic chemistry, physics, information electronic science and Materials science.Particularly the organic photoelectric functional material take organic electroluminescence device (OLED), organic photovoltaic devices (OPV) and organic field effect tube (OTFT) as representative and device have manifested wide application prospect in novel flat-plate demonstration, solid state lighting, flexible demonstration, high density information transmission and the fields such as storage, new forms of energy and photochemistry utilization.Have electrochromism, the existence of the bimaleimide resin of electroluminescent properties will make demonstration and sensory field burst out flourishing vitality, and it all shows outstanding superiority and wide development prospect in demonstration and sensory field.
Existing electrochromic material film film in performance test and use procedure comes off from substrate easily, and stability is good not, and anti-solvent corrosion ability.
Summary of the invention
The present invention will solve existing electrochromic material film and exist test process to come off easily, and the problem of anti-solvent corrosion ability, and a kind of electrochromic bimaleimide resin film with formation stabilizing films and preparation method thereof is provided.
A kind of have an electrochromic bimaleimide resin, and its general structure is:
Described R is:
Or
Described Ar is:
Or
Described n is: 1＜n≤100.
A kind of have an electrochromic bimaleimide resin thin film technology method, specifically finishes according to the following steps:
One, synthetic N, N '-dimaleoyl imino-4,4 '-the phenyl ether monomer: at first low whipping speed is 20r/min～30r/min, temperature is under 20 ℃～50 ℃ the nitrogen protection MALEIC ANHYDRIDE to be added in the solvent, be stirred to MALEIC ANHYDRIDE and dissolve rear adding diaminomonomer fully, and low whipping speed is 20min～30r/min, temperature is to react 0.5h～1h under 20 ℃～50 ℃ the nitrogen protection, then add mixed catalyst, and be 65 ℃～70 ℃ in temperature and carry out condensing reflux reaction, the condensing reflux reaction times is 1.5h～3h, then place under the condition of ice bath and cool off 1h～2h, adopt at last filter method to divide isolated solid, the solid that separation is obtained is that 50 ℃～70 ℃ vacuum-dryings are to constant weight in temperature, namely obtain N, N '-dimaleoyl imino-4,4 '-phenyl ether monomer; Two, prepolymerization reaction: with the N of step 1 preparation, N '-dimaleoyl imino-4,4 '-phenyl ether monomer and binary triaromatic amine monomer add in the organic solvent, then rise to 80 ℃～90 ℃ from room temperature under nitrogen protection, and under this temperature, react 10h～30h, namely obtain prepolymer; Three, film forming is solidified: the prepolymer that obtains in the step 2 is spin-coated on the substrate, then at rotating speed be 1500 turn/min～2500 turn/min under rotational time be 8s～12s, obtaining thickness is the film of 0.5 μ m～5 μ m, then be 200 ℃～300 ℃ lower reaction 3h～6h in temperature, namely obtain having electrochromic bimaleimide resin film; The mol ratio of the MALEIC ANHYDRIDE described in the step 1 and diaminomonomer is 1:(1.5～4); The ratio of the MALEIC ANHYDRIDE amount of substance described in the step 1 and solvent volume is (0.3moL～0.7moL): 1L; The mass ratio of the MALEIC ANHYDRIDE described in the step 1 and mixed catalyst is (0.2～1): 1; The N of the preparation of step 1 described in the step 2, the mol ratio of N '-dimaleoyl imino-4,4 '-phenyl ether monomer and binary triaromatic amine monomer is 1:(1～1.2); The N of step 1 described in step 2 preparation, the amount of N '-dimaleoyl imino-4,4 '-phenyl ether monomeric substance and the ratio of organic solvent solution volume are (0.04moL～0.1moL): 1L.
Advantage of the present invention: one, the present invention preparation has an electrochromic bimaleimide resin film hardening good film-forming property, and the film that forms is not easy dissolving and comes off, mainly be because the high molecular second-order transition temperature of polyimide and fusing point are very high, and high molecular molecular structure characteristics make it be difficult to dissolving; Two, the electrochromic bimaleimide resin film that has of the present invention preparation has testing film good stability, reversible electrochromic property, better heat stability and processability; Three, there is the advantage that method is easy, simple to operate and material is cheap in preparation method provided by the invention.
Description of drawings
Fig. 1 is that test one preparation has the infrared spectrogram of electrochromic bimaleimide resin film; Fig. 2 is the cyclic voltammetric spectrogram that test one preparation has electrochromic bimaleimide resin film; Fig. 3 is the electrochromism spectrogram that test one preparation has electrochromic bimaleimide resin film; Fig. 4 is the thermogravimetric analysis spectrogram that test one preparation has electrochromic bimaleimide resin film; Fig. 5 is that test two preparations have the infrared spectrogram of electrochromic bimaleimide resin film; Fig. 6 is the cyclic voltammetric spectrogram that test two preparations have electrochromic bimaleimide resin film; Fig. 7 is the electrochromism spectrogram that test two preparations have electrochromic bimaleimide resin film; Fig. 8 is the thermogravimetric analysis spectrogram that test two preparations have electrochromic bimaleimide resin film.
Embodiment
Embodiment one: present embodiment is a kind of electrochromic bimaleimide resin thin film technology method that has, and specifically finishes according to the following steps:
One, synthetic N, N '-dimaleoyl imino-4,4 '-the phenyl ether monomer: at first low whipping speed is 20r/min～30r/min, temperature is under 20 ℃～50 ℃ the nitrogen protection MALEIC ANHYDRIDE to be added in the solvent, be stirred to MALEIC ANHYDRIDE and dissolve rear adding diaminomonomer fully, and low whipping speed is 20min～30r/min, temperature is to react 0.5h～1h under 20 ℃～50 ℃ the nitrogen protection, then add mixed catalyst, and be 65 ℃～70 ℃ in temperature and carry out condensing reflux reaction, the condensing reflux reaction times is 1.5h～3h, then place under the condition of ice bath and cool off 1h～2h, adopt at last filter method to divide isolated solid, the solid that separation is obtained is that 50 ℃～70 ℃ vacuum-dryings are to constant weight in temperature, namely obtain N, N '-dimaleoyl imino-4,4 '-phenyl ether monomer; Two, prepolymerization reaction: with the N of step 1 preparation, N '-dimaleoyl imino-4,4 '-phenyl ether monomer and binary triaromatic amine monomer add in the organic solvent, then rise to 80 ℃～90 ℃ from room temperature under nitrogen protection, and under this temperature, react 10h～30h, namely obtain prepolymer; Three, film forming is solidified: the prepolymer that obtains in the step 2 is spin-coated on the substrate, then at rotating speed be 1500 turn/min～2500 turn/min under rotational time be 8s～12s, obtaining thickness is the film of 0.5 μ m～5 μ m, then be 200 ℃～300 ℃ lower reaction 3h～6h in temperature, namely obtain having electrochromic bimaleimide resin film.
The mol ratio of the MALEIC ANHYDRIDE described in the present embodiment step 1 and diaminomonomer is 1:(1.5～4); The ratio of the MALEIC ANHYDRIDE amount of substance described in the present embodiment step 1 and solvent volume is (0.3moL～0.7moL): 1L; The mass ratio of the MALEIC ANHYDRIDE described in the present embodiment step 1 and mixed catalyst is (0.2～1): 1.
The N of the preparation of step 1 described in the present embodiment step 2, the mol ratio of N '-dimaleoyl imino-4,4 '-phenyl ether monomer and binary triaromatic amine monomer is 1:(1～1.2); The N of step 1 described in present embodiment step 2 preparation, the amount of N '-dimaleoyl imino-4,4 '-phenyl ether monomeric substance and the ratio of organic solvent solution volume are (0.04moL～0.1moL): 1L.
The second-order transition temperature of polybismaleimide family macromolecule and fusing point are very high, and its molecular structure characteristics are difficult to by the characteristics of nip swelling it, so present embodiment is utilized bismaleimides monomers B MI and formed film with the monomer binary triaromatic amine monomer that variable color can occur by Michael reaction and do not allow caducous bimaleimide resin.
Present embodiment preparation have an electrochromic bimaleimide resin film hardening good film-forming property, and the film that forms is not easy dissolving and comes off, mainly be because the high molecular second-order transition temperature of polyimide and fusing point are very high, and high molecular molecular structure characteristics make it be difficult to dissolving.
The electrochromic bimaleimide resin film that has of present embodiment preparation has testing film good stability, reversible electrochromic property, better heat stability and processability.
There is the advantage that method is easy, simple to operate and material is cheap in the preparation method that present embodiment provides.
Embodiment two: the difference of present embodiment and embodiment one is: the diaminomonomer described in the step 1 is:
Or
Other is identical with embodiment one.
Embodiment three: present embodiment and one of embodiment one or two difference are: the solvent described in the step 1 is acetone, dimethyl formamide or trichloromethane.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three difference is: the mixed catalyst described in the step 1 is to be mixed by diacetyl oxide, triethylamine and sodium-acetate; The mol ratio of wherein said diacetyl oxide and triethylamine (5～10): 1; The mol ratio of wherein said diacetyl oxide and sodium-acetate (10～15): 1.Other is identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four difference is: the binary triaromatic amine monomer described in the step 2 is:
Other is identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five difference is: the solvent in the organic solvent solution described in the step 2 is DMF, N,N-dimethylacetamide or tetrahydrofuran (THF).Other is identical with embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six difference is: the substrate described in the step 3 is the ITO conductive glass, (ZnO mixes Al to the AZO conductive glass
2O
3), FTO conductive glass (SnO
2: poly styrene sulfonate) and the layer/polyaniline conductive film glass F), transparent carbon nanotube conductive film glass, PEDOT:PSS electropane (polyethylene dioxythiophene:.Other is identical with embodiment one to six.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of have an electrochromic bimaleimide resin thin film technology method, specifically finishes according to the following steps:
One, synthetic N, N '-dimaleoyl imino-4,4 '-the phenyl ether monomer: at first low whipping speed is 25r/min, temperature is under 35 ℃ the nitrogen protection MALEIC ANHYDRIDE to be added in the solvent, be stirred to MALEIC ANHYDRIDE and dissolve rear adding diaminomonomer fully, and low whipping speed is 25r/min, temperature is to react 0.8h under 35 ℃ the nitrogen protection, then add mixed catalyst, and be 68 ℃ in temperature and carry out condensing reflux reaction, the condensing reflux reaction times is 2h, then place under the condition of ice bath and cool off 1.5h, adopt at last filter method to divide isolated solid, the solid that separation is obtained is that 60 ℃ of vacuum-dryings are to constant weight in temperature, namely obtain N, N '-dimaleoyl imino-4,4 '-phenyl ether monomer; Two, prepolymerization reaction: with the N of step 1 preparation, N '-dimaleoyl imino-4,4 '-phenyl ether monomer and binary triaromatic amine monomer add in the organic solvent, then rise to 85 ℃ from room temperature under nitrogen protection, and under this temperature, react 20h, namely obtain prepolymer; Three, film forming is solidified: the prepolymer that obtains in the step 2 is spin-coated on the substrate, then at rotating speed be 2000 turn/min under rotational time be 10s, obtaining thickness is the film of 2 μ m～4 μ m, then be 250 ℃ of lower reaction 4.5h in temperature, namely obtain having electrochromic bimaleimide resin film.
The mol ratio of the MALEIC ANHYDRIDE described in this testing sequence one and diaminomonomer is 1:2; The ratio of the MALEIC ANHYDRIDE amount of substance described in this testing sequence one and solvent volume is 0.5moL:1L; The mass ratio of the MALEIC ANHYDRIDE described in this testing sequence one and mixed catalytic is 0.6:1.
Diaminomonomer described in this testing sequence one is
Solvent described in this testing sequence one is acetone.
Mixed catalyst described in this testing sequence one is to be mixed by diacetyl oxide, triethylamine and sodium-acetate; The mol ratio 7.5:1 of wherein said diacetyl oxide and triethylamine; The mol ratio 12.5:1 of wherein said diacetyl oxide and sodium-acetate.
The N of the preparation of step 1 described in this testing sequence two, the mol ratio of N '-dimaleoyl imino-4,4 '-phenyl ether monomer and binary triaromatic amine monomer is 1:1.1; The N of the preparation of step 1 described in this testing sequence two, the amount of N '-dimaleoyl imino-4,4 '-phenyl ether monomeric substance and the ratio of organic solvent solution volume are 0.07moL:1L.
Binary triaromatic amine monomer described in this testing sequence two is
Solvent in the organic solvent solution described in this testing sequence two is DMF.
Substrate described in this testing sequence three is the ITO conductive glass.
Adopt Fourier infrared spectrograph to detect the electrochromic bimaleimide resin film that has of this test preparation, detected result as shown in Figure 1, Fig. 1 is that this test preparation has the infrared spectrogram of electrochromic bimaleimide resin film, as shown in Figure 1 3400cm
-1Represent the stretching vibration of nitrogen hydrogen; 2800cm
-1, 2900cm
-1, 3000cm
-1Represent hydrocarbon stretching vibration; 1750cm
-1Represent carbonylic stretching vibration; 1500cm
-1, 1590cm
-1Represent the skeleton stretching vibration of phenyl ring; 1237cm
-1Represent the stretching vibration of aryl oxide chain; 1180cm
-1Represent the C-N-C stretching vibration; 860～800cm
-1Representing hydrocarbon out-of-plane bending proof aromatic hydrocarbons to replacing; In conjunction with the diaminomonomer described in this testing sequence one be
With the binary triaromatic amine monomer described in this testing sequence two be
Can determine that this test prepares the structural formula with electrochromic bimaleimide resin film and is:
Adopt the electrochemistry instrument to detect the electrochromic bimaleimide resin film that has of this test preparation, the ito coated glass substrate is as working electrode, concentration is under the 0.1mol/L in the lithium perchlorate acetonitrile ionogen of drying, detected result as shown in Figure 2 under take current potential as 1.6V sensitivity as the 10mA scanning speed as 0.01 condition, Fig. 2 is the cyclic voltammetric spectrogram that this test preparation has electrochromic bimaleimide resin film, there is as shown in Figure 2 an oxidation peak at the 1.05V place, has a corresponding reduction peak at the 0.7V place; The electrochromic bimaleimide resin film that has that this test preparation is described has preferably reversibility.
Adopt the electrochromic bimaleimide resin film that has of this test of UV spectrophotometer measuring preparation, the ito coated glass substrate is as working electrode, concentration is under the 0.1mol/L in the lithium perchlorate acetonitrile ionogen of drying, take wavelength as 300～1500nm, sensitivity is that detected result is as shown in Figure 3 under the condition of 10mA, Fig. 3 is the electrochromism spectrogram that this test preparation has electrochromic bimaleimide resin film, at 500nm and 800nm place absorption peak is arranged as shown in Figure 3, this peak, three places raises along with potential rise, the product color is green by xanthochromia, green deepens gradually, and the electrochromic bimaleimide resin film that has that therefore detects this test preparation specifically has electrochromic performance.
Adopt thermogravimetric analyzer to detect the electrochromic bimaleimide resin film that has of this test preparation, under the 10 ℃/min condition of nitrogen gas, be warmed up to 750 ℃ of detected results as shown in Figure 4, Fig. 4 is the thermogravimetric analysis spectrogram that this test preparation has electrochromic bimaleimide resin film, the electrochromic bimaleimide resin film that has of this test preparation reaches 200 ℃ in temperature and locates weightless 2% as shown in Figure 4, locate weightlessness 25% at 400 ℃, so the electrochromic bimaleimide resin film that has of this test preparation has good resistance toheat.
Be the measuring stability with electrochromic bimaleimide resin film and existing electrochromic material film (adopting the film identical with this test that existing electrochromic material is made film) that the lithium perchlorate acetonitrile solution of 0.1moL/L detects this test preparation in concentration, be 40min～80min detection time, the electrochromic bimaleimide resin film that has that detects this test preparation after finishing does not come off from the ITO conductive glass, and existing electrochromic material film comes off from the ITO conductive glass when detecting 44min, by above-mentioned phenomenon as can be known this test prepare have electrochromic bimaleimide resin film difficult drop-off in test process.
In acetonitrile, detect the anti-solvent corrosion with electrochromic bimaleimide resin film and existing electrochromic material film (adopting the film identical with this test that existing electrochromic material is made film) that adopts this test preparation, with this test preparation have electrochromic bimaleimide resin film and existing electrochromic material film immerses respectively in the acetonitrile, soak time is 60min～90min, the electrochromic bimaleimide resin film that has that detects this test preparation on the ITO conductive glass after finishing does not have obvious corrosion phenomenon, and the existing electrochromic material film major part on the ITO conductive glass has been corroded, by above-mentioned phenomenon as can be known the electrochromic bimaleimide resin film that has of this test preparation have good anti-solvent corrosion.
Test two: a kind of have an electrochromic bimaleimide resin thin film technology method, specifically finishes according to the following steps:
One, synthetic N, N '-dimaleoyl imino-4,4 '-the phenyl ether monomer: at first low whipping speed is 25r/min, temperature is under 35 ℃ the nitrogen protection MALEIC ANHYDRIDE to be added in the solvent, be stirred to MALEIC ANHYDRIDE and dissolve rear adding diaminomonomer fully, and low whipping speed is 25r/min, temperature is to react 0.8h under 35 ℃ the nitrogen protection, then add mixed catalyst, and be 68 ℃ in temperature and carry out condensing reflux reaction, the condensing reflux reaction times is 2h, then place under the condition of ice bath and cool off 1.5h, adopt at last filter method to divide isolated solid, the solid that separation is obtained is that 60 ℃ of vacuum-dryings are to constant weight in temperature, namely obtain N, N '-dimaleoyl imino-4,4 '-phenyl ether monomer; Two, prepolymerization reaction: with the N of step 1 preparation, N '-dimaleoyl imino-4,4 '-phenyl ether monomer and binary triaromatic amine monomer add in the organic solvent, then rise to 85 ℃ from room temperature under nitrogen protection, and under this temperature, react 20h, namely obtain prepolymer; Three, film forming is solidified: the prepolymer that obtains in the step 2 is spin-coated on the substrate, then at rotating speed be 2000 turn/min under rotational time be 10s, obtaining thickness is the film of 2 μ m～4 μ m, then be 250 ℃ of lower reaction 4.5h in temperature, namely obtain having electrochromic bimaleimide resin film.
The mol ratio of the MALEIC ANHYDRIDE described in this testing sequence one and diaminomonomer is 1:2; The ratio of the MALEIC ANHYDRIDE amount of substance described in this testing sequence one and solvent volume is 0.5moL:1L; The mass ratio of the MALEIC ANHYDRIDE described in this testing sequence one and mixed catalytic is 0.6:1.
Diaminomonomer described in this testing sequence one is
Solvent described in this testing sequence one is acetone.
Mixed catalyst described in this testing sequence one is to be mixed by diacetyl oxide, triethylamine and sodium-acetate; The mol ratio 7.5:1 of wherein said diacetyl oxide and triethylamine; The mol ratio 12.5:1 of wherein said diacetyl oxide and sodium-acetate.
The N of the preparation of step 1 described in this testing sequence two, the mol ratio of N '-dimaleoyl imino-4,4 '-phenyl ether monomer and binary triaromatic amine monomer is 1:1.1; The N of the preparation of step 1 described in this testing sequence two, the amount of N '-dimaleoyl imino-4,4 '-phenyl ether monomeric substance and the ratio of organic solvent solution volume are 0.07moL:1L.
Binary triaromatic amine monomer described in this testing sequence two is
Solvent in the organic solvent solution described in this testing sequence two is DMF.
Substrate described in this testing sequence three is the ITO conductive glass.
Adopt Fourier infrared spectrograph to detect the electrochromic bimaleimide resin film that has of this test preparation, detected result as shown in Figure 5, Fig. 5 is that this test preparation has the infrared spectrogram of electrochromic bimaleimide resin film, as shown in Figure 5 3400cm
-1Represent the stretching vibration of nitrogen hydrogen; 2800cm
-1, 2900cm
-1, 3000cm
-1Represent hydrocarbon stretching vibration; 1750cm
-1Represent carbonylic stretching vibration; 1500cm
-1, 1590cm
-1Represent the skeleton stretching vibration of phenyl ring; 1237cm
-1Represent the stretching vibration of aryl oxide chain; 1180cm
-1Represent the C-N-C stretching vibration; 860～800cm
-1Representing hydrocarbon out-of-plane bending proof aromatic hydrocarbons to replacing in conjunction with the diaminomonomer described in this testing sequence one is
With the binary triaromatic amine monomer described in this testing sequence two be
Can determine that this test prepares the structural formula with electrochromic bimaleimide resin film and is:
Described n is: 1＜n≤100.
Adopt the electrochemistry instrument to detect the electrochromic bimaleimide resin film that has of this test preparation, the ito coated glass substrate is as working electrode, concentration is under the 0.1mol/L in the lithium perchlorate acetonitrile ionogen of drying, detected result as shown in Figure 6 under take current potential as 1.6V sensitivity as the 10mA scanning speed as 0.01 condition, Fig. 6 is the cyclic voltammetric spectrogram that this test preparation has electrochromic bimaleimide resin film, there is as shown in Figure 6 an oxidation peak at the 1.05V place, and has a corresponding reduction peak at the 0.76V place; The electrochromic bimaleimide resin film that has that this test preparation is described has preferably reversibility.
Adopt the electrochromic bimaleimide resin film that has of this test of UV spectrophotometer measuring preparation, the ito coated glass substrate is as working electrode, concentration is under the 0.1mol/L in the lithium perchlorate acetonitrile ionogen of drying, take wavelength as 300～1500nm, sensitivity is that detected result is as shown in Figure 7 under the condition of 10mA, Fig. 7 is the electrochromism spectrogram that this test preparation has electrochromic bimaleimide resin film, as shown in Figure 7 at 500nm, there is absorption peak at 700nm and 900nm place, the peak, here raises along with potential rise, the product color is green by xanthochromia, green deepens gradually, and the electrochromic bimaleimide resin film that has that therefore detects this test preparation specifically has electrochromic performance.
Adopt thermogravimetric analyzer to detect the electrochromic bimaleimide resin film that has of this test preparation, under the 10 ℃/min condition of nitrogen gas, be warming up to 750 ℃ of detected results as shown in Figure 8, Fig. 8 is the thermogravimetric analysis spectrogram that this test preparation has electrochromic bimaleimide resin film, the electrochromic bimaleimide resin film that has of this test preparation reaches 200 ℃ in temperature and locates weightless 2% as shown in Figure 8, locate weightlessness 20% at 400 ℃, so the electrochromic bimaleimide resin film that has of this test preparation has good resistance toheat.
Be the measuring stability with electrochromic bimaleimide resin film and existing electrochromic material film (adopting the film identical with this test that existing electrochromic material is made film) that the lithium perchlorate acetonitrile solution of 0.1moL/L detects this test preparation in concentration, be 40min～80min detection time, the electrochromic bimaleimide resin film that has that detects this test preparation after finishing does not come off from the ITO conductive glass, and existing electrochromic material film comes off from the ITO conductive glass when detecting 43min, by above-mentioned phenomenon as can be known this test prepare have electrochromic bimaleimide resin film difficult drop-off in test process.
In acetonitrile, detect the anti-solvent corrosion with electrochromic bimaleimide resin film and existing electrochromic material film (adopting the film identical with this test that existing electrochromic material is made film) that adopts this test preparation, with this test preparation have electrochromic bimaleimide resin film and existing electrochromic material film immerses respectively in the acetonitrile, soak time is 60min～90min, the electrochromic bimaleimide resin film that has that detects this test preparation on the ITO conductive glass after finishing does not have obvious corrosion phenomenon, and the existing electrochromic material film major part on the ITO conductive glass has been corroded, by above-mentioned phenomenon as can be known the electrochromic bimaleimide resin film that has of this test preparation have good anti-solvent corrosion.
Claims (8)
1. one kind has electrochromic bimaleimide resin film, the composition that it is characterized in that having electrochromic bimaleimide resin film is for having electrochromic bimaleimide resin, and described general structure with electrochromic bimaleimide resin is:
Described R is:
Described Ar is:
2. a kind of electrochromic bimaleimide resin thin film technology method that has as claimed in claim 1 is characterized in that having electrochromic bimaleimide resin thin film technology method and finishes according to the following steps:
One, synthetic N, N '-dimaleoyl imino-4,4 '-the phenyl ether monomer: at first low whipping speed is 20r/min～30r/min, temperature is under 20 ℃～50 ℃ the nitrogen protection MALEIC ANHYDRIDE to be added in the solvent, be stirred to MALEIC ANHYDRIDE and dissolve rear adding diaminomonomer fully, and low whipping speed is 20r/min～30r/min, temperature is to react 0.5h～1h under 20 ℃～50 ℃ the nitrogen protection, then add mixed catalyst, and be 65 ℃～70 ℃ in temperature and carry out condensing reflux reaction, the condensing reflux reaction times is 1.5h～3h, then place under the condition of ice bath and cool off 1h～2h, adopt at last filter method to divide isolated solid, the solid that separation is obtained is that 50 ℃～70 ℃ vacuum-dryings are to constant weight in temperature, namely obtain N, N '-dimaleoyl imino-4,4 '-phenyl ether monomer; Two, prepolymerization reaction: with the N of step 1 preparation, N '-dimaleoyl imino-4,4 '-phenyl ether monomer and binary triaromatic amine monomer add in the organic solvent, then rise to 80 ℃～90 ℃ from room temperature under nitrogen protection, and under this temperature, react 10h～30h, namely obtain prepolymer; Three, film forming is solidified: the prepolymer that obtains in the step 2 is spin-coated on the substrate, then be that rotational time is 8s～12s under 1500r/min～2500r/min at rotating speed, obtaining thickness is the film of 0.5 μ m～5 μ m, then be 200 ℃～300 ℃ lower reaction 3h～6h in temperature, namely obtain having electrochromic bimaleimide resin film; The mol ratio of the MALEIC ANHYDRIDE described in the step 1 and diaminomonomer is 1:(1.5～4); The ratio of the MALEIC ANHYDRIDE amount of substance described in the step 1 and solvent volume is (0.3moL～0.7moL): 1L; The mass ratio of the MALEIC ANHYDRIDE described in the step 1 and mixed catalyst is (0.2～1): 1; The N of the preparation of step 1 described in the step 2, the mol ratio of N '-dimaleoyl imino-4,4 '-phenyl ether monomer and binary triaromatic amine monomer is 1:(1～1.2); The N of step 1 described in step 2 preparation, the amount of N '-dimaleoyl imino-4,4 '-phenyl ether monomeric substance and the ratio of organic solvent solution volume are (0.04moL～0.1moL): 1L.
3. a kind of electrochromic bimaleimide resin thin film technology method that has according to claim 2 is characterized in that the diaminomonomer described in the step 1 is:
4. a kind of electrochromic bimaleimide resin thin film technology method that has according to claim 3 is characterized in that the solvent described in the step 1 is acetone, dimethyl formamide or trichloromethane.
5. a kind of electrochromic bimaleimide resin thin film technology method that has according to claim 4 is characterized in that the mixed catalyst described in the step 1 is to be mixed by diacetyl oxide, triethylamine and sodium-acetate; The mol ratio of wherein said diacetyl oxide and triethylamine (5～10): 1; The mol ratio of wherein said diacetyl oxide and sodium-acetate (10～15): 1.
6. a kind of electrochromic bimaleimide resin thin film technology method that has according to claim 5 is characterized in that the binary triaromatic amine monomer described in the step 2 is:
7. a kind of electrochromic bimaleimide resin thin film technology method that has according to claim 6, it is characterized in that the solvent in the organic solvent solution described in the step 2 is N, dinethylformamide, N,N-dimethylacetamide or tetrahydrofuran (THF).
8. according to claim 2,3,4,5,6 or 7 described a kind of electrochromic bimaleimide resin thin film technology methods that have, it is characterized in that the substrate described in the step 3 is ITO conductive glass, AZO conductive glass, FTO conductive glass, transparent carbon nanotube conductive film glass, PEDOT:PSS electropane and layer/polyaniline conductive film glass.
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| CN110894295B (en) * | 2019-10-23 | 2021-11-02 | 广东同宇新材料有限公司 | Polyether maleimide resin and synthetic method thereof |
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| CN1156733A (en) * | 1996-12-23 | 1997-08-13 | 四川联合大学 | Dimaleic type liquid crystal polyimide and its preparing process |
| CN1424340A (en) * | 2002-12-27 | 2003-06-18 | 中国科学院长春应用化学研究所 | Preparation of polyimide moulded by casting |
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| CN1156733A (en) * | 1996-12-23 | 1997-08-13 | 四川联合大学 | Dimaleic type liquid crystal polyimide and its preparing process |
| CN1424340A (en) * | 2002-12-27 | 2003-06-18 | 中国科学院长春应用化学研究所 | Preparation of polyimide moulded by casting |
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