CN105542205A - Preparation method of electrically-driven shape memory polyimide - Google Patents

Preparation method of electrically-driven shape memory polyimide Download PDF

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CN105542205A
CN105542205A CN201511018878.9A CN201511018878A CN105542205A CN 105542205 A CN105542205 A CN 105542205A CN 201511018878 A CN201511018878 A CN 201511018878A CN 105542205 A CN105542205 A CN 105542205A
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shape memory
amino
carbon fiber
rise rate
polyimide
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CN105542205B (en
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肖鑫礼
孔德艳
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Harbin Institute of Technology
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • C08K2201/00—Specific properties of additives
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    • C08K2201/004—Additives being defined by their length
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/12—Shape memory
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Abstract

The invention relates to a preparation method of polyimide, particularly a preparation method of electrically-driven shape memory polyimide. The invention aims to solve the problem of difficulty in direct heating when the shape memory polyimide prepared at present is subjected to specific application. The method comprises the following steps: 1. preparing a diamine mixed solution; 2. preparing random copolymer polyamic acid; 3. preparing a carbon-fiber-containing random copolymer polyamic acid solution; 4. carrying out thermal imidization to obtain a glass plate containing a random copolymer polyimide/carbon fiber mixed film; and 5. cleaning and drying to obtain the electrically-driven shape memory polyimide. Tg of the electrically-driven shape memory polyimide prepared by the method is 220-238 DEG C; the storage modulus is 1.63-1.92 GPa in the Tg-20 DEG C glass state, and the storage modulus is 9.23-11.68 MPa in the Tg+20 DEG C rubbery state. The method can be used for obtaining the electrically-driven shape memory polyimide.

Description

A kind of preparation method of electroluminescent driving shape memory polyimide
Technical field
The present invention relates to a kind of preparation method of polyimide.
Background technology
Shape-memory polymer (shapememorypolymers, SMP) is that a class can remember temporary shapes, can recover the intelligent macromolecule material of original shape under external stimulus.Polyimide (PI) has the advantages such as thermostability is high, mechanical property is excellent, the variation of processing approach, has been widely used in the fields such as automobile, microelectronics, photoelectricity, aerospace.Shape memory polyimide has significant application value in deployable space structures, variable flying device aileron, pyrostat and driving mechanism etc.Make type of drive relative to traditional direct heating, it is convenient and swift that electroluminescent driving shape-memory polymer has type of drive, can be adapted to the advantage of varying environment.
Summary of the invention
The shape memory polyimide that the object of the invention is to solve existing preparation carries out the problem of direct heating difficulty when application-specific, and provides a kind of preparation method of electroluminescent driving shape memory polyimide.
A kind of preparation method of electroluminescent driving shape memory polyimide completes according to the following steps:
One, by 4,4'-bis-(4-amino-benzene oxygen) biphenyl and 1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins in aprotic polar solvent, 4 are stirred to again under the nitrogen atmosphere of room gently dried, 4'-bis-(4-amino-benzene oxygen) biphenyl and 1, the mixture of two (3-amino-benzene oxygen) benzene of 3-dissolves completely, obtains diamines mixing solutions;
The amount of substance of mixture and the volume ratio of aprotic polar solvent of 4,4'-described in step one bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-are 0.05mol:(180mL ~ 200mL);
Described in step one 4,4'-bis-(4-amino-benzene oxygen) biphenyl and 1, in the mixture of two (3-amino-benzene oxygen) benzene of 3-, the mol ratio of 4,4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-is A:B; The span of A is 1≤A≤9, and the span of B is 1≤B≤9;
Two, two for 4,4-oxygen Tetra hydro Phthalic anhydride is joined in diamines mixing solutions, then polyreaction 15h ~ 20h at room temperature under nitrogen atmosphere, obtain random copolymerization polyamic acid;
The mol ratio of the mixture of the two Tetra hydro Phthalic anhydride of 4,4-oxygen described in step 2 and 4,4'-bis-(4-amino-benzene oxygen) biphenyl in diamines mixing solutions and 1,3-pair of (3-amino-benzene oxygen) benzene is 1:1;
Three, be that the chopped carbon fiber of 0.5mm ~ 3mm joins in random copolymerization polyamic acid solution by length, again under room temperature, nitrogen atmosphere and stirring velocity be stirring reaction 20h ~ 24h under the condition of 800r/min ~ 1200r/min, obtain the random copolymerization polyamic acid solution containing carbon fiber;
Length described in step 3 is the chopped carbon fiber of 0.5mm ~ 3mm is (0.005 ~ 0.12) with the mass ratio of rule copolyamide acid solution: 1;
Four, random copolymerization polyamic acid solution containing carbon fiber is evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from room temperature to 70 DEG C ~ 90 DEG C, 2h ~ 3h is incubated again at 70 DEG C ~ 90 DEG C, 150 DEG C ~ 170 DEG C are warming up to from 70 DEG C ~ 90 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 150 DEG C ~ 170 DEG C, 190 DEG C ~ 210 DEG C are warming up to from 150 DEG C ~ 170 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 190 DEG C ~ 210 DEG C, 240 DEG C ~ 260 DEG C are warming up to from 190 DEG C ~ 210 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, again at 240 DEG C ~ 260 DEG C insulation 1h ~ 2h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film,
Five, the sheet glass containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, random copolymerization polyimide/carbon fiber mixed film is come off from sheet glass, re-use distilled water random copolymerization polyimide/carbon fiber mixed film is rinsed well, dry 3h at temperature is 120 DEG C again, obtains electroluminescent driving shape memory polyimide.
Advantage of the present invention:
One, the present invention adopts 4, the mixture of 4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-, as diamine monomer, adopts 4, the two Tetra hydro Phthalic anhydride of 4-oxygen, as dianhydride monomer, prepares shape memory random copolymerization polyimide;
Two, the electroluminescent driving shape memory polyimide that prepared by the present invention has good shape-memory properties, can be applicable to high-temperature shape-memory field, as space deployable structure, high temperature driven device, high temperature detector etc.;
Three, the electroluminescent driving shape memory polyimide that prepared by the present invention has electroconductibility, can produce high temperature, its shape is recovered when extra electric field; Therefore, the electroluminescent driving shape memory polyimide that prepared by the present invention is being not suitable for having very high using value under direct-fired environment;
Four, the T of electroluminescent driving shape memory polyimide for preparing of the present invention git is 220 DEG C ~ 238 DEG C, at T gstorage modulus during-20 DEG C of vitreous states is 1.63GPa ~ 1.92GPa; At T gstorage modulus during+20 DEG C of rubbery states is 9.23MPa ~ 11.68MPa;
Five, the electroluminescent driving shape memory polyimide that prepared by the present invention has good shape memory effect, and its shape prescribed rate is 96%, and shape recovery ratio is 97%.
The present invention can obtain electroluminescent driving shape memory polyimide.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of electroluminescent driving shape memory polyimide prepared by embodiment one;
Fig. 2 is the dissipation factor figure of electroluminescent driving shape memory polyimide prepared by embodiment one;
Fig. 3 is the storage modulus figure of electroluminescent driving shape memory polyimide prepared by embodiment one;
Fig. 4 be embodiment one prepare electroluminescent driving shape memory polyimide when volts DS is 8V, the temporary shapes fixedly obtained under room temperature;
Fig. 5 be embodiment one prepare electroluminescent driving shape memory polyimide when volts DS is 8V, the situation of shape recovery process;
Fig. 6 is that electroluminescent driving shape memory polyimide prepared by embodiment one returns back to the situation of initial form when volts DS is 8V.
Embodiment
Embodiment one: present embodiment is that a kind of preparation method of electroluminescent driving shape memory polyimide completes according to the following steps:
One, by 4,4'-bis-(4-amino-benzene oxygen) biphenyl and 1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins in aprotic polar solvent, 4 are stirred to again under the nitrogen atmosphere of room gently dried, 4'-bis-(4-amino-benzene oxygen) biphenyl and 1, the mixture of two (3-amino-benzene oxygen) benzene of 3-dissolves completely, obtains diamines mixing solutions;
The amount of substance of mixture and the volume ratio of aprotic polar solvent of 4,4'-described in step one bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-are 0.05mol:(180mL ~ 200mL);
Described in step one 4,4'-bis-(4-amino-benzene oxygen) biphenyl and 1, in the mixture of two (3-amino-benzene oxygen) benzene of 3-, the mol ratio of 4,4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-is A:B; The span of A is 1≤A≤9, and the span of B is 1≤B≤9;
Two, two for 4,4-oxygen Tetra hydro Phthalic anhydride is joined in diamines mixing solutions, then polyreaction 15h ~ 20h at room temperature under nitrogen atmosphere, obtain random copolymerization polyamic acid;
The mol ratio of the mixture of the two Tetra hydro Phthalic anhydride of 4,4-oxygen described in step 2 and 4,4'-bis-(4-amino-benzene oxygen) biphenyl in diamines mixing solutions and 1,3-pair of (3-amino-benzene oxygen) benzene is 1:1;
Three, be that the chopped carbon fiber of 0.5mm ~ 3mm joins in random copolymerization polyamic acid solution by length, again under room temperature, nitrogen atmosphere and stirring velocity be stirring reaction 20h ~ 24h under the condition of 800r/min ~ 1200r/min, obtain the random copolymerization polyamic acid solution containing carbon fiber;
Length described in step 3 is the chopped carbon fiber of 0.5mm ~ 3mm is (0.005 ~ 0.12) with the mass ratio of rule copolyamide acid solution: 1;
Four, random copolymerization polyamic acid solution containing carbon fiber is evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from room temperature to 70 DEG C ~ 90 DEG C, 2h ~ 3h is incubated again at 70 DEG C ~ 90 DEG C, 150 DEG C ~ 170 DEG C are warming up to from 70 DEG C ~ 90 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 150 DEG C ~ 170 DEG C, 190 DEG C ~ 210 DEG C are warming up to from 150 DEG C ~ 170 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 190 DEG C ~ 210 DEG C, 240 DEG C ~ 260 DEG C are warming up to from 190 DEG C ~ 210 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, again at 240 DEG C ~ 260 DEG C insulation 1h ~ 2h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film,
Five, the sheet glass containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, random copolymerization polyimide/carbon fiber mixed film is come off from sheet glass, re-use distilled water random copolymerization polyimide/carbon fiber mixed film is rinsed well, dry 3h at temperature is 120 DEG C again, obtains electroluminescent driving shape memory polyimide.
The advantage of present embodiment:
One, present embodiment adopts 4, the mixture of 4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-, as diamine monomer, adopts 4, the two Tetra hydro Phthalic anhydride of 4-oxygen, as dianhydride monomer, prepares shape memory random copolymerization polyimide;
Two, the electroluminescent driving shape memory polyimide that prepared by present embodiment has good shape-memory properties, can be applicable to high-temperature shape-memory field, as space deployable structure, high temperature driven device, high temperature detector etc.;
Three, the electroluminescent driving shape memory polyimide that prepared by present embodiment has electroconductibility, can produce high temperature, its shape is recovered when extra electric field; Therefore, the electroluminescent driving shape memory polyimide that prepared by present embodiment is being not suitable for having very high using value under direct-fired environment;
Four, the T of electroluminescent driving shape memory polyimide for preparing of present embodiment git is 220 DEG C ~ 238 DEG C, at T gstorage modulus during-20 DEG C of vitreous states is 1.63GPa ~ 1.92GPa; At T gstorage modulus during+20 DEG C of rubbery states is 9.23MPa ~ 11.68MPa;
Five, the electroluminescent driving shape memory polyimide that prepared by present embodiment has good shape memory effect, and its shape prescribed rate is 96%, and shape recovery ratio is 97%.
Present embodiment can obtain electroluminescent driving shape memory polyimide.
Embodiment two: present embodiment and embodiment one difference are: the aprotic polar solvent described in step one is DMF, N,N-dimethylacetamide or N-Methyl pyrrolidone.Other steps are identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two difference is: the thickness of the electroluminescent driving shape memory polyimide described in step 5 is 50 μm ~ 120 μm.Other steps are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three difference is: 4 described in step one, the amount of substance of mixture and the volume ratio of aprotic polar solvent of 4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-are 0.05mol:180mL.Other steps are identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four difference is: 4 described in step one, the amount of substance of mixture and the volume ratio of aprotic polar solvent of 4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-are 0.05mol:190mL.Other steps are identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five difference is: 4 described in step one, the amount of substance of mixture and the volume ratio of aprotic polar solvent of 4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-are 0.05mol:200mL.Other steps are identical with embodiment one to five.
Embodiment seven: one of present embodiment and embodiment one to six difference is: in step 4, the random copolymerization polyamic acid solution containing carbon fiber is evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 90 DEG C, 2h is incubated again at 90 DEG C, 150 DEG C are warming up to from 90 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 150 DEG C, 190 DEG C are warming up to from 150 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 190 DEG C, 250 DEG C are warming up to from 190 DEG C again with the temperature rise rate of 1 DEG C/min, again at 250 DEG C of insulation 1h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film.Other steps are identical with embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven difference is: in step 4, the random copolymerization polyamic acid solution containing carbon fiber is evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 80 DEG C, 2h is incubated again at 80 DEG C, 160 DEG C are warming up to from 80 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 160 DEG C, 190 DEG C are warming up to from 160 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 190 DEG C, 250 DEG C are warming up to from 190 DEG C again with the temperature rise rate of 1 DEG C/min, again at 250 DEG C of insulation 1h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film.Other steps are identical with embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight difference is: in step 4, the random copolymerization polyamic acid solution containing carbon fiber is evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 80 DEG C, 2h is incubated again at 80 DEG C, 160 DEG C are warming up to from 80 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 160 DEG C, 190 DEG C are warming up to from 160 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 190 DEG C, 250 DEG C are warming up to from 190 DEG C again with the temperature rise rate of 1 DEG C/min, again at 250 DEG C of insulation 1h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film.Other steps are identical with embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine difference is: in step 4, the random copolymerization polyamic acid solution containing carbon fiber is evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 80 DEG C, 2h is incubated again at 80 DEG C, 160 DEG C are warming up to from 80 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 160 DEG C, 190 DEG C are warming up to from 160 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 190 DEG C, 250 DEG C are warming up to from 190 DEG C again with the temperature rise rate of 2 DEG C/min, again at 250 DEG C of insulation 1h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film.Other steps are identical with embodiment one to nine.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one: a kind of preparation method of electroluminescent driving shape memory polyimide completes according to the following steps:
One, by 0.01mol4,4'-bis-(4-amino-benzene oxygen) biphenyl and 0.04mol1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins 180mLN, in N-N,N-DIMETHYLACETAMIDE, 4 are stirred to again under the nitrogen atmosphere of room gently dried, the mixture of 4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-dissolves completely, obtains diamines mixing solutions;
Two, two for 0.05mol4,4-oxygen Tetra hydro Phthalic anhydride is joined in the diamines mixing solutions obtained in step one, then polyreaction 15h at room temperature under nitrogen atmosphere, obtain random copolymerization polyamic acid;
Three, be that the chopped carbon fiber of 0.5mm ~ 3mm joins in the random copolymerization polyamic acid solution obtained in step 2 by 1.8533g length, again under room temperature, nitrogen atmosphere and stirring velocity be stirring reaction 20h under the condition of 1000r/min, obtain the random copolymerization polyamic acid solution containing carbon fiber;
Four, random copolymerization polyamic acid solution containing carbon fiber is evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 90 DEG C, 2h is incubated again at temperature is 90 DEG C, 150 DEG C are warming up to from 90 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at temperature is 150 DEG C, 190 DEG C are warming up to from 150 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at temperature is 190 DEG C, 250 DEG C are warming up to from 190 DEG C again with the temperature rise rate of 1 DEG C/min, be 250 DEG C in temperature again and be incubated 1h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film,
Five, the sheet glass containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, random copolymerization polyimide/carbon fiber mixed film is come off from sheet glass, re-use distilled water random copolymerization polyimide/carbon fiber mixed film is rinsed well, dry 3h at temperature is 120 DEG C again, obtains electroluminescent driving shape memory polyimide.
Use infrared spectrometer to test electroluminescent driving shape memory polyimide prepared by embodiment one, as shown in Figure 1, Fig. 1 is the infrared spectrogram of electroluminescent driving shape memory polyimide prepared by embodiment one; As can be seen from Figure 1, these charateristic avsorption bands illustrate that electroluminescent driving shape memory polyimide prepared by embodiment one is the random copolymerization polyimide of height polyamides Asiaization.
Dynamic mechanical analyzer is used to test electroluminescent driving shape memory polyimide prepared by embodiment one, as shown in Figure 2;
Fig. 2 is the dissipation factor figure of electroluminescent driving shape memory polyimide prepared by embodiment one; As can be seen from Figure 2 the T of the electroluminescent driving shape memory polyimide of embodiment one preparation gbe 220 DEG C, ensure that electroluminescent driving shape memory polyimide prepared by embodiment one can be applicable to high-temperature shape-memory field.
Dynamic mechanical analyzer is used to test electroluminescent driving shape memory polyimide prepared by embodiment one, as shown in Figure 3;
Fig. 3 is the storage modulus figure of electroluminescent driving shape memory polyimide prepared by embodiment one; As can be seen from Figure 3, there are two platforms of high and low temperature section in storage modulus change curve, and electroluminescent driving shape memory polyimide prepared by embodiment one is at 200 DEG C of (T g-20 DEG C) vitreous state time storage modulus be 1.63GPa; At high temperature 240 DEG C of (T g+ 20 DEG C) rubbery state time storage modulus be 9.23MPa; Between two platforms, storage modulus sharply declines, and corresponding to the Glass Transition of material, the sharply change of this modulus is the prerequisite that polymkeric substance possesses shape memory character.
Direct current is used to test electroluminescent driving shape memory polyimide prepared by embodiment one, as shown in Figures 4 to 6.
Fig. 4 be embodiment one prepare electroluminescent driving shape memory polyimide when volts DS is 8V, the temporary shapes fixedly obtained under room temperature;
Fig. 5 be embodiment one prepare electroluminescent driving shape memory polyimide when volts DS is 8V, the situation of shape recovery process;
Fig. 6 is that electroluminescent driving shape memory polyimide prepared by embodiment one returns back to the situation of initial form when volts DS is 8V.
From Fig. 4 to Fig. 6, electroluminescent driving shape memory polyimide prepared by embodiment one has good shape memory effect, and its shape prescribed rate is 96%, and shape recovery ratio is 95%.
Embodiment two: a kind of preparation method of electroluminescent driving shape memory polyimide completes according to the following steps:
One, by 0.015mol4,4'-bis-(4-amino-benzene oxygen) biphenyl and 0.035mol1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins 190mLN, in N-N,N-DIMETHYLACETAMIDE, 4 are stirred to again under the nitrogen atmosphere of room gently dried, the mixture of 4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-dissolves completely, obtains diamines mixing solutions;
Two, two for 0.05mol4,4-oxygen Tetra hydro Phthalic anhydride is joined in the diamines mixing solutions obtained in step one, then polyreaction 16h at room temperature under nitrogen atmosphere, obtain random copolymerization polyamic acid;
Three, be that the chopped carbon fiber of 0.5mm ~ 3mm joins in the random copolymerization polyamic acid solution obtained in step 2 by 1.8762g length, again under room temperature, nitrogen atmosphere and stirring velocity be stirring reaction 20h under the condition of 900r/min, obtain the random copolymerization polyamic acid solution containing carbon fiber;
Four, random copolymerization polyamic acid solution containing carbon fiber is evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 80 DEG C, 2h is incubated again at temperature is 80 DEG C, 160 DEG C are warming up to from 80 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at temperature is 160 DEG C, 190 DEG C are warming up to from 160 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at temperature is 190 DEG C, 250 DEG C are warming up to from 190 DEG C again with the temperature rise rate of 1 DEG C/min, be 250 DEG C in temperature again and be incubated 1h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film,
Five, the sheet glass containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, random copolymerization polyimide/carbon fiber mixed film is come off from sheet glass, re-use distilled water random copolymerization polyimide/carbon fiber mixed film is rinsed well, dry 3h at temperature is 120 DEG C again, obtains electroluminescent driving shape memory polyimide.
Electroluminescent driving shape memory polyimide embodiment two prepared at high temperature is out of shape, and be reduced to room temperature and fix temporary shapes, then utilize DC plant on sample, apply the direct current of 7.8V, sample slowly returns to its original shape by temporary shapes.
The T of electroluminescent driving shape memory polyimide prepared by embodiment two gbe 222 DEG C, ensure that electroluminescent driving shape memory polyimide prepared by embodiment two can be applicable to high-temperature shape-memory field; Electroluminescent driving shape memory polyimide prepared by embodiment two is at 202 DEG C of (T g-20 DEG C) vitreous state time storage modulus be 1.70GPa; At high temperature 242 DEG C of (T g+ 20 DEG C) rubbery state time storage modulus be 9.56MPa; Electroluminescent driving shape memory polyimide prepared by embodiment two has good shape memory effect, and its shape prescribed rate is 96%, and shape recovery ratio is 96%.
Embodiment three: a kind of preparation method of electroluminescent driving shape memory polyimide completes according to the following steps:
One, by 0.02mol4,4'-bis-(4-amino-benzene oxygen) biphenyl and 0.03mol1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins 200mLN, in N-N,N-DIMETHYLACETAMIDE, 4 are stirred to again under the nitrogen atmosphere of room gently dried, the mixture of 4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-dissolves completely, obtains diamines mixing solutions;
Two, two for 0.05mol4,4-oxygen Tetra hydro Phthalic anhydride is joined in the diamines mixing solutions obtained in step one, then polyreaction 17h at room temperature under nitrogen atmosphere, obtain random copolymerization polyamic acid;
Three, be that the chopped carbon fiber of 0.5mm ~ 3mm joins in the random copolymerization polyamic acid solution obtained in step 2 by 2.532g length, again under room temperature, nitrogen atmosphere and stirring velocity be stirring reaction 20h under the condition of 900r/min, obtain the random copolymerization polyamic acid solution containing carbon fiber;
Four, random copolymerization polyamic acid solution containing carbon fiber is evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 80 DEG C, 2h is incubated again at temperature is 80 DEG C, 160 DEG C are warming up to from 80 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at temperature is 160 DEG C, 190 DEG C are warming up to from 160 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at temperature is 190 DEG C, 250 DEG C are warming up to from 190 DEG C again with the temperature rise rate of 1 DEG C/min, be 250 DEG C in temperature again and be incubated 1h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film,
Five, the sheet glass containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, random copolymerization polyimide/carbon fiber mixed film is come off from sheet glass, re-use distilled water random copolymerization polyimide/carbon fiber mixed film is rinsed well, dry 3h at temperature is 120 DEG C again, obtains electroluminescent driving shape memory polyimide.
Electroluminescent driving shape memory polyimide embodiment three prepared at high temperature is out of shape, and is reduced to room temperature and fixes temporary shapes; Then utilize DC plant on sample, apply the direct current of 7.5V, sample slowly returns to its original shape by temporary shapes.
The T of electroluminescent driving shape memory polyimide prepared by embodiment three gbe 225 DEG C, ensure that electroluminescent driving shape memory polyimide prepared by embodiment three can be applicable to high-temperature shape-memory field; Electroluminescent driving shape memory polyimide prepared by embodiment three is at 205 DEG C of (T g-20 DEG C) vitreous state time storage modulus be 1.78GPa; At high temperature 245 DEG C of (T g+ 20 DEG C) rubbery state time storage modulus be 9.76MPa; Electroluminescent driving shape memory polyimide prepared by embodiment three has good shape memory effect, and its shape prescribed rate is 95%, and shape recovery ratio is 97%.
Embodiment four: a kind of preparation method of electroluminescent driving shape memory polyimide completes according to the following steps:
One, by 0.025mol4,4'-bis-(4-amino-benzene oxygen) biphenyl and 0.025mol1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins 200mLN, in N-N,N-DIMETHYLACETAMIDE, 4 are stirred to again under the nitrogen atmosphere of room gently dried, the mixture of 4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-dissolves completely, obtains diamines mixing solutions;
Two, two for 0.05mol4,4-oxygen Tetra hydro Phthalic anhydride is joined in the diamines mixing solutions obtained in step one, then polyreaction 17h at room temperature under nitrogen atmosphere, obtain random copolymerization polyamic acid;
Three, be that the chopped carbon fiber of 0.5mm ~ 3mm joins in the random copolymerization polyamic acid solution obtained in step 2 by 2.883g length, again under room temperature, nitrogen atmosphere and stirring velocity be stirring reaction 20h under the condition of 800r/min, obtain the random copolymerization polyamic acid solution containing carbon fiber;
Four, random copolymerization polyamic acid solution containing carbon fiber is evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 80 DEG C, 2h is incubated again at temperature is 80 DEG C, 160 DEG C are warming up to from 80 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at temperature is 160 DEG C, 190 DEG C are warming up to from 160 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at temperature is 190 DEG C, 250 DEG C are warming up to from 190 DEG C again with the temperature rise rate of 2 DEG C/min, be 250 DEG C in temperature again and be incubated 1h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film,
Five, the sheet glass containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, random copolymerization polyimide/carbon fiber mixed film is come off from sheet glass, re-use distilled water random copolymerization polyimide/carbon fiber mixed film is rinsed well, dry 3h at temperature is 120 DEG C again, obtains electroluminescent driving shape memory polyimide.
Electroluminescent driving shape memory polyimide prepared by embodiment four is at high temperature out of shape, and is reduced to room temperature and fixes temporary shapes; Then utilize DC plant on sample, apply the direct current of 7.0V, sample slowly returns to its original shape by temporary shapes.
The T of electroluminescent driving shape memory polyimide prepared by embodiment four gbe 230 DEG C, ensure that electroluminescent driving shape memory polyimide prepared by embodiment four can be applicable to high-temperature shape-memory field; Electroluminescent driving shape memory polyimide prepared by embodiment four is at 210 DEG C of (T g-20 DEG C) vitreous state time storage modulus be 1.78GPa; At high temperature 250 DEG C of (T g+ 20 DEG C) rubbery state time storage modulus be 9.88MPa.Electroluminescent driving shape memory polyimide prepared by embodiment four has good shape memory effect, and its shape prescribed rate is 95%, and shape recovery ratio is 93%.
Embodiment five: a kind of preparation method of electroluminescent driving shape memory polyimide completes according to the following steps:
One, by 0.03mol4,4'-bis-(4-amino-benzene oxygen) biphenyl and 0.02mol1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins 200mLN, in N-N,N-DIMETHYLACETAMIDE, 4 are stirred to again under the nitrogen atmosphere of room gently dried, the mixture of 4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-dissolves completely, obtains diamines mixing solutions;
Two, two for 0.05mol4,4-oxygen Tetra hydro Phthalic anhydride is joined in the diamines mixing solutions obtained in step one, then polyreaction 19h at room temperature under nitrogen atmosphere, obtain random copolymerization polyamic acid;
Three, be that the chopped carbon fiber of 0.5mm ~ 3mm joins in the random copolymerization polyamic acid solution obtained in step 2 by 3.2411g length, again under room temperature, nitrogen atmosphere and stirring velocity be stirring reaction 20h under the condition of 1100r/min, obtain the random copolymerization polyamic acid solution containing carbon fiber;
Four, random copolymerization polyamic acid solution containing carbon fiber is evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 80 DEG C, 2h is incubated again at temperature is 80 DEG C, 160 DEG C are warming up to from 80 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at temperature is 160 DEG C, 190 DEG C are warming up to from 160 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at temperature is 190 DEG C, 250 DEG C are warming up to from 190 DEG C again with the temperature rise rate of 1 DEG C/min, be 250 DEG C in temperature again and be incubated 1h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film,
Five, the sheet glass containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, random copolymerization polyimide/carbon fiber mixed film is come off from sheet glass, re-use distilled water random copolymerization polyimide/carbon fiber mixed film is rinsed well, dry 3h at temperature is 120 DEG C again, obtains electroluminescent driving shape memory polyimide.
Electroluminescent driving shape memory polyimide prepared by embodiment five is at high temperature out of shape, and is reduced to room temperature and fixes temporary shapes; Then utilize DC plant on sample, apply the direct current of 6.5V, sample slowly returns to its original shape by temporary shapes.
The T of electroluminescent driving shape memory polyimide prepared by embodiment five gbe 233 DEG C, ensure that electroluminescent driving shape memory polyimide prepared by embodiment five can be applicable to high-temperature shape-memory field.Electroluminescent driving shape memory polyimide prepared by embodiment five is at 213 DEG C of (T g-20 DEG C) vitreous state time storage modulus be 1.86GPa; At high temperature 253 DEG C of (T g+ 20 DEG C) rubbery state time storage modulus be 10.2MPa.Electroluminescent driving shape memory polyimide prepared by embodiment five has good shape memory effect, and its shape prescribed rate is 95%, and shape recovery ratio is 92%.
Embodiment six: a kind of preparation method of electroluminescent driving shape memory polyimide completes according to the following steps:
One, by 0.04mol4,4'-bis-(4-amino-benzene oxygen) biphenyl and 0.01mol1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins 200mLN, in N-N,N-DIMETHYLACETAMIDE, 4 are stirred to again under the nitrogen atmosphere of room gently dried, the mixture of 4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-dissolves completely, obtains diamines mixing solutions;
Two, two for 0.05mol4,4-oxygen Tetra hydro Phthalic anhydride is joined in the diamines mixing solutions obtained in step one, then polyreaction 20h at room temperature under nitrogen atmosphere, obtain random copolymerization polyamic acid;
Three, be that the chopped carbon fiber of 0.5mm ~ 3mm joins in the random copolymerization polyamic acid solution obtained in step 2 by 3.9806g length, again under room temperature, nitrogen atmosphere and stirring velocity be stirring reaction 20h under the condition of 1200r/min, obtain the random copolymerization polyamic acid solution containing carbon fiber;
Four, random copolymerization polyamic acid solution containing carbon fiber is evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 80 DEG C, 2h is incubated again at temperature is 80 DEG C, 160 DEG C are warming up to from 80 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at temperature is 160 DEG C, 190 DEG C are warming up to from 160 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at temperature is 190 DEG C, 250 DEG C are warming up to from 190 DEG C again with the temperature rise rate of 2 DEG C/min, be 250 DEG C in temperature again and be incubated 1h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film,
Five, the sheet glass containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, random copolymerization polyimide/carbon fiber mixed film is come off from sheet glass, re-use distilled water random copolymerization polyimide/carbon fiber mixed film is rinsed well, dry 3h at temperature is 120 DEG C again, obtains electroluminescent driving shape memory polyimide.
Electroluminescent driving shape memory polyimide prepared by embodiment six is at high temperature out of shape, and is reduced to room temperature and fixes temporary shapes; Then utilize DC plant on sample, apply the direct current of 6V, sample slowly returns to its original shape by temporary shapes.
The T of electroluminescent driving shape memory polyimide prepared by embodiment six gbe 238 DEG C, ensure that electroluminescent driving shape memory polyimide prepared by embodiment six can be applicable to high-temperature shape-memory field.Electroluminescent driving shape memory polyimide prepared by embodiment six is at 218 DEG C of (T g-20 DEG C) vitreous state time storage modulus be 1.92GPa; At high temperature 258 DEG C of (T g+ 20 DEG C) rubbery state time storage modulus be 11.68MPa; Electroluminescent driving shape memory polyimide prepared by embodiment six has good shape memory effect, and its shape prescribed rate is 92%, and shape recovery ratio is 90%.

Claims (10)

1. a preparation method for electroluminescent driving shape memory polyimide, is characterized in that a kind of preparation method of electroluminescent driving shape memory polyimide completes according to the following steps:
One, by 4,4'-bis-(4-amino-benzene oxygen) biphenyl and 1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins in aprotic polar solvent, 4 are stirred to again under the nitrogen atmosphere of room gently dried, 4'-bis-(4-amino-benzene oxygen) biphenyl and 1, the mixture of two (3-amino-benzene oxygen) benzene of 3-dissolves completely, obtains diamines mixing solutions;
The amount of substance of mixture and the volume ratio of aprotic polar solvent of 4,4'-described in step one bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-are 0.05mol:(180mL ~ 200mL);
Described in step one 4,4'-bis-(4-amino-benzene oxygen) biphenyl and 1, in the mixture of two (3-amino-benzene oxygen) benzene of 3-, the mol ratio of 4,4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-is A:B; The span of A is 1≤A≤9, and the span of B is 1≤B≤9;
Two, two for 4,4-oxygen Tetra hydro Phthalic anhydride is joined in diamines mixing solutions, then polyreaction 15h ~ 20h at room temperature under nitrogen atmosphere, obtain random copolymerization polyamic acid;
The mol ratio of the mixture of the two Tetra hydro Phthalic anhydride of 4,4-oxygen described in step 2 and 4,4'-bis-(4-amino-benzene oxygen) biphenyl in diamines mixing solutions and 1,3-pair of (3-amino-benzene oxygen) benzene is 1:1;
Three, be that the chopped carbon fiber of 0.5mm ~ 3mm joins in random copolymerization polyamic acid solution by length, again under room temperature, nitrogen atmosphere and stirring velocity be stirring reaction 20h ~ 24h under the condition of 800r/min ~ 1200r/min, obtain the random copolymerization polyamic acid solution containing carbon fiber;
Length described in step 3 is the chopped carbon fiber of 0.5mm ~ 3mm is (0.005 ~ 0.12) with the mass ratio of rule copolyamide acid solution: 1;
Four, random copolymerization polyamic acid solution containing carbon fiber is evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from room temperature to 70 DEG C ~ 90 DEG C, 2h ~ 3h is incubated again at 70 DEG C ~ 90 DEG C, 150 DEG C ~ 170 DEG C are warming up to from 70 DEG C ~ 90 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 150 DEG C ~ 170 DEG C, 190 DEG C ~ 210 DEG C are warming up to from 150 DEG C ~ 170 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 190 DEG C ~ 210 DEG C, 240 DEG C ~ 260 DEG C are warming up to from 190 DEG C ~ 210 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, again at 240 DEG C ~ 260 DEG C insulation 1h ~ 2h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film,
Five, the sheet glass containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, random copolymerization polyimide/carbon fiber mixed film is come off from sheet glass, re-use distilled water random copolymerization polyimide/carbon fiber mixed film is rinsed well, dry 3h at temperature is 120 DEG C again, obtains electroluminescent driving shape memory polyimide.
2. the preparation method of a kind of electroluminescent driving shape memory polyimide according to claim 1, is characterized in that the aprotic polar solvent described in step one is DMF, N,N-dimethylacetamide or N-Methyl pyrrolidone.
3. the preparation method of a kind of electroluminescent driving shape memory polyimide according to claim 1, is characterized in that the thickness of the electroluminescent driving shape memory polyimide described in step 5 is 50 μm ~ 120 μm.
4. the preparation method of a kind of electroluminescent driving shape memory polyimide according to claim 1, it is characterized in that 4 described in step one, the amount of substance of mixture and the volume ratio of aprotic polar solvent of 4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-are 0.05mol:180mL.
5. the preparation method of a kind of electroluminescent driving shape memory polyimide according to claim 1, it is characterized in that 4 described in step one, the amount of substance of mixture and the volume ratio of aprotic polar solvent of 4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-are 0.05mol:190mL.
6. the preparation method of a kind of electroluminescent driving shape memory polyimide according to claim 1, it is characterized in that 4 described in step one, the amount of substance of mixture and the volume ratio of aprotic polar solvent of 4'-bis-(4-amino-benzene oxygen) biphenyl and two (3-amino-benzene oxygen) benzene of 1,3-are 0.05mol:200mL.
7. the preparation method of a kind of electroluminescent driving shape memory polyimide according to claim 1, it is characterized in that in step 4, the random copolymerization polyamic acid solution containing carbon fiber being evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 90 DEG C, 2h is incubated again at 90 DEG C, 150 DEG C are warming up to from 90 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 150 DEG C, 190 DEG C are warming up to from 150 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 190 DEG C, 250 DEG C are warming up to from 190 DEG C again with the temperature rise rate of 1 DEG C/min, again at 250 DEG C of insulation 1h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film.
8. the preparation method of a kind of electroluminescent driving shape memory polyimide according to claim 1, it is characterized in that in step 4, the random copolymerization polyamic acid solution containing carbon fiber being evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 80 DEG C, 2h is incubated again at 80 DEG C, 160 DEG C are warming up to from 80 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 160 DEG C, 190 DEG C are warming up to from 160 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 190 DEG C, 250 DEG C are warming up to from 190 DEG C again with the temperature rise rate of 1 DEG C/min, again at 250 DEG C of insulation 1h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film.
9. the preparation method of a kind of electroluminescent driving shape memory polyimide according to claim 1, it is characterized in that in step 4, the random copolymerization polyamic acid solution containing carbon fiber being evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 80 DEG C, 2h is incubated again at 80 DEG C, 160 DEG C are warming up to from 80 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 160 DEG C, 190 DEG C are warming up to from 160 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 190 DEG C, 250 DEG C are warming up to from 190 DEG C again with the temperature rise rate of 1 DEG C/min, again at 250 DEG C of insulation 1h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film.
10. the preparation method of a kind of electroluminescent driving shape memory polyimide according to claim 1, it is characterized in that in step 4, the random copolymerization polyamic acid solution containing carbon fiber being evenly coated on clean sheet glass, then vacuum drying oven is placed in, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 80 DEG C, 2h is incubated again at 80 DEG C, 160 DEG C are warming up to from 80 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 160 DEG C, 190 DEG C are warming up to from 160 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 190 DEG C, 250 DEG C are warming up to from 190 DEG C again with the temperature rise rate of 2 DEG C/min, again at 250 DEG C of insulation 1h, complete hot-imide, obtain the sheet glass containing random copolymerization polyimide/carbon fiber mixed film.
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CN106987112A (en) * 2017-04-11 2017-07-28 上海交通大学 Electric drive resin base shape memory composite and preparation method thereof
CN108963002A (en) * 2017-05-19 2018-12-07 哈尔滨工业大学 A kind of solar battery based on shape-memory polymer
CN107698760A (en) * 2017-10-21 2018-02-16 芮志行 A kind of preparation method of aging-resisting type shape memory polyimides
CN107987292A (en) * 2017-12-20 2018-05-04 哈尔滨工业大学 A kind of preparation method of the electroluminescent driving shape-memory polymer film of optical clear
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CN111196893A (en) * 2018-11-19 2020-05-26 中国科学院宁波材料技术与工程研究所 Functional composite wire based on carbon fiber reinforced nylon and electric heating driving element made of functional composite wire
CN111196893B (en) * 2018-11-19 2022-10-14 中国科学院宁波材料技术与工程研究所 Functional composite wire based on carbon fiber reinforced nylon and electric heating driving element made of functional composite wire
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CN111635526B (en) * 2020-07-09 2021-03-23 吉林大学 Polyether imide polymer containing carboxyl side group and preparation method and application thereof
CN114045028A (en) * 2021-12-10 2022-02-15 东华大学 Deformable thermoplastic composite material and preparation method thereof
CN114316317A (en) * 2021-12-10 2022-04-12 武汉航空仪表有限责任公司 Novel carbon fiber/polyimide composite material film and coating preparation method thereof

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