CN105542205B - A kind of preparation method of electroluminescent driving shape memory polyimides - Google Patents

A kind of preparation method of electroluminescent driving shape memory polyimides Download PDF

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CN105542205B
CN105542205B CN201511018878.9A CN201511018878A CN105542205B CN 105542205 B CN105542205 B CN 105542205B CN 201511018878 A CN201511018878 A CN 201511018878A CN 105542205 B CN105542205 B CN 105542205B
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carbon fiber
benzene
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CN105542205A (en
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肖鑫礼
孔德艳
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Harbin Institute of Technology
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    • 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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    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/12—Shape memory
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Abstract

A kind of preparation method of electroluminescent driving shape memory polyimides, it is related to a kind of preparation method of polyimides.The invention aims to solve the problems, such as that the shape memory polyimides of existing preparation carries out directly heating difficulty in application-specific.Method：First, diamines mixed solution is prepared；2nd, random copolymerization polyamic acid is prepared；3rd, the random copolymerization polyamic acid solution containing carbon fiber is prepared；4th, hot-imide, the glass plate containing random copolymerization polyimide/carbon fiber mixed film is obtained；5th, clean, dry, obtain electroluminescent driving shape memory polyimides.The T of electroluminescent driving shape memory polyimides prepared by the present inventiongFor 220 DEG C~238 DEG C, in TgStorage modulus during 20 DEG C of glassy states is 1.63GPa~1.92GPa；In TgStorage modulus during+20 DEG C of rubbery states is 9.23~11.68MPa.The present invention can obtain electroluminescent driving shape memory polyimides.

Description

A kind of preparation method of electroluminescent driving shape memory polyimides
Technical field
The present invention relates to a kind of preparation method of polyimides.
Background technology
Shape-memory polymer (shape memory polymers, SMP) is that one kind can remember temporary shapes, outside Boundary stimulates the lower intelligent macromolecule material that can recover original shape.Polyimides (PI) has heat endurance height, mechanical performance excellent It is different, process approach variation the advantages that, be widely used in the fields such as automobile, microelectronics, photoelectricity, Aero-Space.Shape is remembered Recall polyimides has important application valency in deployable space structures, variable flying device aileron, pyrostat and driver etc. Value.Making type of drive relative to traditional directly heating, electroluminescent driving shape-memory polymer has that type of drive is convenient and swift, The advantages of being adaptable to varying environment.
The content of the invention
In application-specific directly add the invention aims to solve the shape memory polyimides of existing preparation The problem of heat is difficult, and a kind of preparation method of electroluminescent driving shape memory polyimides is provided.
A kind of preparation method of electroluminescent driving shape memory polyimides is completed according to the following steps：
First, the mixture of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and double (3- amino-benzene oxygens) benzene of 1,3- is added to In aprotic polar solvent, then under the nitrogen atmosphere of room gently dried stirring to (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and The mixture of 1,3- double (3- amino-benzene oxygens) benzene is completely dissolved, and obtains diamines mixed solution；
The mixing of double (3- amino-benzene oxygens) benzene of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and 1,3- described in step 1 The amount of the material of thing and the volume ratio of aprotic polar solvent are 0.05mol:(180mL~200mL)；
The mixing of double (3- amino-benzene oxygens) benzene of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and 1,3- described in step 1 The mol ratio of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and double (3- amino-benzene oxygens) benzene of 1,3- is A in thing:B；A value model Enclose for 1≤A≤9, B span is 1≤B≤9；
2nd, the double phthalic anhydrides of 4,4- oxygen are added in diamines mixed solution, then gathered at room temperature under nitrogen atmosphere Reaction 15h~20h is closed, obtains random copolymerization polyamic acid；
The double phthalic anhydrides of 4,4- oxygen described in step 2 and (the 4- aminobenzene oxygen of 4,4'- bis- in diamines mixed solution Base) mol ratio of mixture of double (3- amino-benzene oxygens) benzene of biphenyl and 1,3- is 1:1；
3rd, the chopped carbon fiber that length is 0.5mm~3mm is added in random copolymerization polyamic acid solution, then in room Under temperature, nitrogen atmosphere and mixing speed is stirring reaction 20h~24h under conditions of 800r/min~1200r/min, is contained The random copolymerization polyamic acid solution of carbon fiber；
The quality of the chopped carbon fiber that length described in step 3 is 0.5mm~3mm and rule copolyamide acid solution Than for (0.005~0.12):1；
4th, the random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning, then put In vacuum drying chamber, then by vacuum drying chamber with 1 DEG C/min~2 DEG C/min heating rate from room temperature to 70 DEG C~90 DEG C, then 2h~3h is incubated at 70 DEG C~90 DEG C, then heated up with 1 DEG C/min~2 DEG C/min heating rate from 70 DEG C~90 DEG C To 150 DEG C~170 DEG C, then at 150 DEG C~170 DEG C be incubated 2h~3h, then with 1 DEG C/min~2 DEG C/min heating rate from 150 DEG C~170 DEG C are warming up to 190 DEG C~210 DEG C, then 2h~3h is incubated at 190 DEG C~210 DEG C, then with 1 DEG C/min~2 DEG C/ Min heating rate is warming up to 240 DEG C~260 DEG C from 190 DEG C~210 DEG C, then is incubated 1h~2h at 240 DEG C~260 DEG C, completes Hot-imide, obtain the glass plate containing random copolymerization polyimide/carbon fiber mixed film；
5th, the glass plate containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, made random common Poly- polyimide/carbon fiber mixed film comes off from glass plate, reuses distilled water by random copolymerization polyimide/carbon fiber Mixed film is rinsed well, then dries 3h at being 120 DEG C in temperature, obtains electroluminescent driving shape memory polyimides.
Advantages of the present invention：
First, the present invention uses the mixing of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and double (3- amino-benzene oxygens) benzene of 1,3- Thing, using the double phthalic anhydrides of 4,4- oxygen as dianhydride monomer, prepares shape memory random copolymerization polyamides as diamine monomer Imines；
2nd, electroluminescent driving shape memory polyimides prepared by the present invention has good shape-memory properties, can apply In high-temperature shape-memory field, such as space deployable structure, high temperature driven device, high temperature detector；
3rd, the electroluminescent driving shape memory polyimides that prepared by the present invention is conductive, can be produced in extra electric field Raw high temperature, recovers its shape；Therefore, the electroluminescent driving shape memory polyimides that prepared by the present invention is being not suitable for directly heating In the environment of there is very high application value；
4th, the T of electroluminescent driving shape memory polyimides prepared by the present inventiongFor 220 DEG C~238 DEG C, in Tg- 20 DEG C of glass Storage modulus during glass state is 1.63GPa~1.92GPa；In TgStorage modulus during+20 DEG C of rubbery states for 9.23MPa~ 11.68MPa；
5th, electroluminescent driving shape memory polyimides prepared by the present invention has good SME, its shape Prescribed rate is 96%, shape recovery ratio 97%.
The present invention can obtain electroluminescent driving shape memory polyimides.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of electroluminescent driving shape memory polyimides prepared by embodiment one；
Fig. 2 is the fissipation factor figure of electroluminescent driving shape memory polyimides prepared by embodiment one；
Fig. 3 is the storage modulus figure of electroluminescent driving shape memory polyimides prepared by embodiment one；
Fig. 4 be embodiment one prepare electroluminescent driving shape memory polyimides when DC voltage be 8V, at room temperature consolidate Surely the temporary shapes obtained；
Fig. 5 be embodiment one prepare electroluminescent driving shape memory polyimides when DC voltage be 8V, shape recovery The situation of process；
Fig. 6 is that electroluminescent driving shape memory polyimides prepared by embodiment one returns back to starting when DC voltage is 8V The situation of form.
Embodiment
Embodiment one：Present embodiment be it is a kind of it is electroluminescent driving shape memory polyimides preparation method be by What following steps were completed：
First, the mixture of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and double (3- amino-benzene oxygens) benzene of 1,3- is added to In aprotic polar solvent, then under the nitrogen atmosphere of room gently dried stirring to (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and The mixture of 1,3- double (3- amino-benzene oxygens) benzene is completely dissolved, and obtains diamines mixed solution；
The mixing of double (3- amino-benzene oxygens) benzene of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and 1,3- described in step 1 The amount of the material of thing and the volume ratio of aprotic polar solvent are 0.05mol:(180mL~200mL)；
The mixing of double (3- amino-benzene oxygens) benzene of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and 1,3- described in step 1 The mol ratio of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and double (3- amino-benzene oxygens) benzene of 1,3- is A in thing:B；A value model Enclose for 1≤A≤9, B span is 1≤B≤9；
2nd, the double phthalic anhydrides of 4,4- oxygen are added in diamines mixed solution, then gathered at room temperature under nitrogen atmosphere Reaction 15h~20h is closed, obtains random copolymerization polyamic acid；
The double phthalic anhydrides of 4,4- oxygen described in step 2 and (the 4- aminobenzene oxygen of 4,4'- bis- in diamines mixed solution Base) mol ratio of mixture of double (3- amino-benzene oxygens) benzene of biphenyl and 1,3- is 1:1；
3rd, the chopped carbon fiber that length is 0.5mm~3mm is added in random copolymerization polyamic acid solution, then in room Under temperature, nitrogen atmosphere and mixing speed is stirring reaction 20h~24h under conditions of 800r/min~1200r/min, is contained The random copolymerization polyamic acid solution of carbon fiber；
The quality of the chopped carbon fiber that length described in step 3 is 0.5mm~3mm and rule copolyamide acid solution Than for (0.005~0.12):1；
4th, the random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning, then put In vacuum drying chamber, then by vacuum drying chamber with 1 DEG C/min~2 DEG C/min heating rate from room temperature to 70 DEG C~90 DEG C, then 2h~3h is incubated at 70 DEG C~90 DEG C, then heated up with 1 DEG C/min~2 DEG C/min heating rate from 70 DEG C~90 DEG C To 150 DEG C~170 DEG C, then at 150 DEG C~170 DEG C be incubated 2h~3h, then with 1 DEG C/min~2 DEG C/min heating rate from 150 DEG C~170 DEG C are warming up to 190 DEG C~210 DEG C, then 2h~3h is incubated at 190 DEG C~210 DEG C, then with 1 DEG C/min~2 DEG C/ Min heating rate is warming up to 240 DEG C~260 DEG C from 190 DEG C~210 DEG C, then is incubated 1h~2h at 240 DEG C~260 DEG C, completes Hot-imide, obtain the glass plate containing random copolymerization polyimide/carbon fiber mixed film；
5th, the glass plate containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, made random common Poly- polyimide/carbon fiber mixed film comes off from glass plate, reuses distilled water by random copolymerization polyimide/carbon fiber Mixed film is rinsed well, then dries 3h at being 120 DEG C in temperature, obtains electroluminescent driving shape memory polyimides.
The advantages of present embodiment：
First, present embodiment is using double (3- amino-benzene oxygens) benzene of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and 1,3- Mixture, using the double phthalic anhydrides of 4,4- oxygen as dianhydride monomer, prepares shape memory random copolymerization as diamine monomer Polyimides；
2nd, electroluminescent driving shape memory polyimides prepared by present embodiment has good shape-memory properties, can Applied to high-temperature shape-memory field, such as space deployable structure, high temperature driven device, high temperature detector；
3rd, the electroluminescent driving shape memory polyimides that prepared by present embodiment is conductive, can be in extra electric field When produce high temperature, make its shape recover；Therefore, the electroluminescent driving shape memory polyimides that prepared by present embodiment is being not suitable for There is very high application value in the environment of directly heating；
4th, the T of electroluminescent driving shape memory polyimides prepared by present embodimentgFor 220 DEG C~238 DEG C, in Tg-20 Storage modulus during DEG C glassy state is 1.63GPa~1.92GPa；In TgStorage modulus during+20 DEG C of rubbery states for 9.23MPa~ 11.68MPa；
5th, electroluminescent driving shape memory polyimides prepared by present embodiment has good SME, its Shape prescribed rate is 96%, shape recovery ratio 97%.
Present embodiment can obtain electroluminescent driving shape memory polyimides.
Embodiment two：Present embodiment is with the difference of embodiment one：Non- matter described in step 1 Sub- polar solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.Other steps with it is specific Embodiment one is identical.
Embodiment three：Present embodiment is with one of embodiment one or two difference：Institute in step 5 The thickness for the electroluminescent driving shape memory polyimides stated is 50 μm~120 μm.Other steps and embodiment one or two It is identical.
Embodiment four：Present embodiment is with one of embodiment one to three difference：Institute in step 1 The amount and non-matter of the material of the mixture of double (3- amino-benzene oxygens) benzene of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and 1,3- stated The volume ratio of sub- polar solvent is 0.05mol:180mL.Other steps are identical with embodiment one to three.
Embodiment five：Present embodiment is with one of embodiment one to four difference：Institute in step 1 The amount and non-matter of the material of the mixture of double (3- amino-benzene oxygens) benzene of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and 1,3- stated The volume ratio of sub- polar solvent is 0.05mol:190mL.Other steps are identical with embodiment one to four.
Embodiment six：Present embodiment is with one of embodiment one to five difference：Institute in step 1 The amount and non-matter of the material of the mixture of double (3- amino-benzene oxygens) benzene of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and 1,3- stated The volume ratio of sub- polar solvent is 0.05mol:200mL.Other steps are identical with embodiment one to five.
Embodiment seven：Present embodiment is with one of embodiment one to six difference：Will in step 4 Random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning, is subsequently placed in vacuum drying chamber In, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 90 DEG C, then 2h is incubated at 90 DEG C, then with 1 DEG C/min heating rate is warming up to 150 DEG C from 90 DEG C, then 2h is incubated at 150 DEG C, then with 1 DEG C/min heating rate from 150 DEG C are warming up to 190 DEG C, then 2h are incubated at 190 DEG C, then are warming up to 250 DEG C from 190 DEG C with 1 DEG C/min heating rate, then 1h is incubated at 250 DEG C, hot-imide is completed, obtains the glass plate containing random copolymerization polyimide/carbon fiber mixed film. Other steps are identical with embodiment one to six.
Embodiment eight：Present embodiment is with one of embodiment one to seven difference：Will in step 4 Random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning, is subsequently placed in vacuum drying chamber In, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 80 DEG C, then 2h is incubated at 80 DEG C, then with 2 DEG C/min heating rate is warming up to 160 DEG C from 80 DEG C, then 2h is incubated at 160 DEG C, then with 1 DEG C/min heating rate from 160 DEG C are warming up to 190 DEG C, then 2h are incubated at 190 DEG C, then are warming up to 250 DEG C from 190 DEG C with 1 DEG C/min heating rate, then 1h is incubated at 250 DEG C, hot-imide is completed, obtains the glass plate containing random copolymerization polyimide/carbon fiber mixed film. Other steps are identical with embodiment one to seven.
Embodiment nine：Present embodiment is with one of embodiment one to eight difference：Will in step 4 Random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning, is subsequently placed in vacuum drying chamber In, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 80 DEG C, then 2h is incubated at 80 DEG C, then with 2 DEG C/min heating rate is warming up to 160 DEG C from 80 DEG C, then 2h is incubated at 160 DEG C, then with 2 DEG C/min heating rate from 160 DEG C are warming up to 190 DEG C, then 2h are incubated at 190 DEG C, then are warming up to 250 DEG C from 190 DEG C with 1 DEG C/min heating rate, then 1h is incubated at 250 DEG C, hot-imide is completed, obtains the glass plate containing random copolymerization polyimide/carbon fiber mixed film. Other steps are identical with embodiment one to eight.
Embodiment ten：Present embodiment is with one of embodiment one to nine difference：Will in step 4 Random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning, is subsequently placed in vacuum drying chamber In, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 80 DEG C, then 2h is incubated at 80 DEG C, then with 1 DEG C/min heating rate is warming up to 160 DEG C from 80 DEG C, then 2h is incubated at 160 DEG C, then with 1 DEG C/min heating rate from 160 DEG C are warming up to 190 DEG C, then 2h are incubated at 190 DEG C, then are warming up to 250 DEG C from 190 DEG C with 2 DEG C/min heating rate, then 1h is incubated at 250 DEG C, hot-imide is completed, obtains the glass plate containing random copolymerization polyimide/carbon fiber mixed film. Other steps are identical with embodiment one to nine.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：A kind of preparation method of electroluminescent driving shape memory polyimides is completed according to the following steps：
First, it is (4- amino-benzene oxygens) biphenyl of 0.01mol 4,4'- bis- and 0.04mol 1,3- is double (3- amino-benzene oxygens) The mixture of benzene is added in 180mL DMAs, then under the nitrogen atmosphere of room gently dried stirring to 4, The mixture of (4- amino-benzene oxygens) biphenyl of 4'- bis- and double (3- amino-benzene oxygens) benzene of 1,3- is completely dissolved, and obtains diamines mixing Solution；
2nd, 0.05mol 4, the double phthalic anhydrides of 4- oxygen are added in the diamines mixed solution obtained in step 1, Polymerisation 15h at room temperature under nitrogen atmosphere again, obtains random copolymerization polyamic acid；
The 3rd, the chopped carbon fiber that 1.8533g length is 0.5mm~3mm is added to the random copolymerization obtained in step 2 In polyamic acid solution, then under room temperature, nitrogen atmosphere and mixing speed be 1000r/min under conditions of stirring reaction 20h, obtain To the random copolymerization polyamic acid solution containing carbon fiber；
4th, the random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning, then put In vacuum drying chamber, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 90 DEG C, then temperature be 90 2h is incubated at DEG C, then 150 DEG C are warming up to from 90 DEG C with 1 DEG C/min heating rate, then 2h is incubated at being 150 DEG C in temperature, then 190 DEG C are warming up to from 150 DEG C with 1 DEG C/min heating rate, then 2h, then the liter with 1 DEG C/min are incubated at being 190 DEG C in temperature Warm speed is warming up to 250 DEG C from 190 DEG C, then is 250 DEG C in temperature and is incubated 1h, completes hot-imide, obtains containing random common The glass plate of poly- polyimide/carbon fiber mixed film；
5th, the glass plate containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, made random common Poly- polyimide/carbon fiber mixed film comes off from glass plate, reuses distilled water by random copolymerization polyimide/carbon fiber Mixed film is rinsed well, then dries 3h at being 120 DEG C in temperature, obtains electroluminescent driving shape memory polyimides.
Electroluminescent driving shape memory polyimides prepared by embodiment one is tested using infrared spectrometer, such as Fig. 1 Shown, Fig. 1 is the infrared spectrogram of electroluminescent driving shape memory polyimides prepared by embodiment one；From fig. 1, it can be seen that these are special Sign absworption peak illustrates that electroluminescent driving shape memory polyimides prepared by embodiment one gathers for the random copolymerization of height polyamides Asiaization Acid imide.
Electroluminescent driving shape memory polyimides prepared by embodiment one is tested using dynamic mechanical analyzer, such as Shown in Fig. 2；
Fig. 2 is the fissipation factor figure of electroluminescent driving shape memory polyimides prepared by embodiment one；Can from Fig. 2 Go out the T of the electroluminescent driving shape memory polyimides of the preparation of embodiment onegFor 220 DEG C, it ensure that embodiment one is prepared electroluminescent Driving shape memory polyimides can be applied to high-temperature shape-memory field.
Electroluminescent driving shape memory polyimides prepared by embodiment one is tested using dynamic mechanical analyzer, such as Shown in Fig. 3；
Fig. 3 is the storage modulus figure of electroluminescent driving shape memory polyimides prepared by embodiment one；As can be seen from Figure 3, deposit There is two platforms of high and low temperature section, electroluminescent driving shape memory polyamides prepared by embodiment one in storage modulus change curve Imines is in 200 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 1.63GPa；In 240 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when Storage modulus is 9.23MPa；Storage modulus drastically declines between two platforms, corresponding to the Glass Transition of material, The drastically change of this modulus is the necessary condition that polymer possesses shape memory property.
Electroluminescent driving shape memory polyimides prepared by embodiment one is tested using direct current, such as Fig. 4 to Fig. 6 It is shown.
Fig. 4 be embodiment one prepare electroluminescent driving shape memory polyimides when DC voltage be 8V, at room temperature consolidate Surely the temporary shapes obtained；
Fig. 5 be embodiment one prepare electroluminescent driving shape memory polyimides when DC voltage be 8V, shape recovery The situation of process；
Fig. 6 is that electroluminescent driving shape memory polyimides prepared by embodiment one returns back to starting when DC voltage is 8V The situation of form.
It was found from Fig. 4 to Fig. 6, there is electroluminescent driving shape memory polyimides prepared by embodiment one good shape to remember Recall effect, its shape prescribed rate is 96%, shape recovery ratio 95%.
Embodiment two：A kind of preparation method of electroluminescent driving shape memory polyimides is completed according to the following steps：
First, by (4- amino-benzene oxygens) biphenyl of 0.015mol 4,4'- bis- and double (the 3- aminobenzene oxygen of 0.035mol 1,3- Base) mixture of benzene is added in 190mL DMAs, then stir under the nitrogen atmosphere of room gently dried to The mixture of 4,4'- bis- (4- amino-benzene oxygens) biphenyl and double (3- amino-benzene oxygens) benzene of 1,3- is completely dissolved, and is obtained diamines and is mixed Close solution；
2nd, 0.05mol 4, the double phthalic anhydrides of 4- oxygen are added in the diamines mixed solution obtained in step 1, Polymerisation 16h at room temperature under nitrogen atmosphere again, obtains random copolymerization polyamic acid；
The 3rd, the chopped carbon fiber that 1.8762g length is 0.5mm~3mm is added to the random copolymerization obtained in step 2 In polyamic acid solution, then under room temperature, nitrogen atmosphere and mixing speed be 900r/min under conditions of stirring reaction 20h, obtain To the random copolymerization polyamic acid solution containing carbon fiber；
4th, the random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning, then put In vacuum drying chamber, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 80 DEG C, then temperature be 80 2h is incubated at DEG C, then 160 DEG C are warming up to from 80 DEG C with 2 DEG C/min heating rate, then 2h is incubated at being 160 DEG C in temperature, then 190 DEG C are warming up to from 160 DEG C with 1 DEG C/min heating rate, then 2h, then the liter with 1 DEG C/min are incubated at being 190 DEG C in temperature Warm speed is warming up to 250 DEG C from 190 DEG C, then is 250 DEG C in temperature and is incubated 1h, completes hot-imide, obtains containing random common The glass plate of poly- polyimide/carbon fiber mixed film；
5th, the glass plate containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, made random common Poly- polyimide/carbon fiber mixed film comes off from glass plate, reuses distilled water by random copolymerization polyimide/carbon fiber Mixed film is rinsed well, then dries 3h at being 120 DEG C in temperature, obtains electroluminescent driving shape memory polyimides.
Electroluminescent driving shape memory polyimides prepared by embodiment two deforms at high temperature, is reduced to room temperature and fixes temporarily When shape, then apply 7.8V direct current on sample using DC plant, sample slowly returns to it by temporary shapes Original shape.
The T of electroluminescent driving shape memory polyimides prepared by embodiment twogFor 222 DEG C, it ensure that prepared by embodiment two Electroluminescent driving shape memory polyimides can be applied to high-temperature shape-memory field；Electroluminescent driving shape prepared by embodiment two Polyimides is remembered in 202 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 1.70GPa；In 242 DEG C of (T of high temperatureg+ 20 DEG C) rubber Storage modulus during colloidal state is 9.56MPa；Electroluminescent driving shape memory polyimides prepared by embodiment two has good shape Shape memory effect, its shape prescribed rate are 96%, shape recovery ratio 96%.
Embodiment three：A kind of preparation method of electroluminescent driving shape memory polyimides is completed according to the following steps：
First, it is (4- amino-benzene oxygens) biphenyl of 0.02mol 4,4'- bis- and 0.03mol 1,3- is double (3- amino-benzene oxygens) The mixture of benzene is added in 200mL DMAs, then under the nitrogen atmosphere of room gently dried stirring to 4, The mixture of (4- amino-benzene oxygens) biphenyl of 4'- bis- and double (3- amino-benzene oxygens) benzene of 1,3- is completely dissolved, and obtains diamines mixing Solution；
2nd, 0.05mol 4, the double phthalic anhydrides of 4- oxygen are added in the diamines mixed solution obtained in step 1, Polymerisation 17h at room temperature under nitrogen atmosphere again, obtains random copolymerization polyamic acid；
The 3rd, the chopped carbon fiber that 2.532g length is 0.5mm~3mm is added to the random copolymerization obtained in step 2 gather In acid amides acid solution, then under room temperature, nitrogen atmosphere and mixing speed be 900r/min under conditions of stirring reaction 20h, obtain Random copolymerization polyamic acid solution containing carbon fiber；
4th, the random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning, then put In vacuum drying chamber, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 80 DEG C, then temperature be 80 2h is incubated at DEG C, then 160 DEG C are warming up to from 80 DEG C with 2 DEG C/min heating rate, then 2h is incubated at being 160 DEG C in temperature, then 190 DEG C are warming up to from 160 DEG C with 2 DEG C/min heating rate, then 2h, then the liter with 1 DEG C/min are incubated at being 190 DEG C in temperature Warm speed is warming up to 250 DEG C from 190 DEG C, then is 250 DEG C in temperature and is incubated 1h, completes hot-imide, obtains containing random common The glass plate of poly- polyimide/carbon fiber mixed film；
5th, the glass plate containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, made random common Poly- polyimide/carbon fiber mixed film comes off from glass plate, reuses distilled water by random copolymerization polyimide/carbon fiber Mixed film is rinsed well, then dries 3h at being 120 DEG C in temperature, obtains electroluminescent driving shape memory polyimides.
Electroluminescent driving shape memory polyimides prepared by embodiment three deforms at high temperature, is reduced to room temperature and fixes temporarily When shape；Then 7.5V direct current is applied on sample using DC plant, sample slowly returns to it by temporary shapes Original shape.
The T of electroluminescent driving shape memory polyimides prepared by embodiment threegFor 225 DEG C, it ensure that prepared by embodiment three Electroluminescent driving shape memory polyimides can be applied to high-temperature shape-memory field；Electroluminescent driving shape prepared by embodiment three Polyimides is remembered in 205 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 1.78GPa；In 245 DEG C of (T of high temperatureg+ 20 DEG C) rubber Storage modulus during colloidal state is 9.76MPa；Electroluminescent driving shape memory polyimides prepared by embodiment three has good shape Shape memory effect, its shape prescribed rate are 95%, shape recovery ratio 97%.
Example IV：A kind of preparation method of electroluminescent driving shape memory polyimides is completed according to the following steps：
First, by (4- amino-benzene oxygens) biphenyl of 0.025mol 4,4'- bis- and double (the 3- aminobenzene oxygen of 0.025mol 1,3- Base) mixture of benzene is added in 200mL DMAs, then stir under the nitrogen atmosphere of room gently dried to The mixture of 4,4'- bis- (4- amino-benzene oxygens) biphenyl and double (3- amino-benzene oxygens) benzene of 1,3- is completely dissolved, and is obtained diamines and is mixed Close solution；
2nd, 0.05mol 4, the double phthalic anhydrides of 4- oxygen are added in the diamines mixed solution obtained in step 1, Polymerisation 17h at room temperature under nitrogen atmosphere again, obtains random copolymerization polyamic acid；
The 3rd, the chopped carbon fiber that 2.883g length is 0.5mm~3mm is added to the random copolymerization obtained in step 2 gather In acid amides acid solution, then under room temperature, nitrogen atmosphere and mixing speed be 800r/min under conditions of stirring reaction 20h, obtain Random copolymerization polyamic acid solution containing carbon fiber；
4th, the random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning, then put In vacuum drying chamber, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 80 DEG C, then temperature be 80 2h is incubated at DEG C, then 160 DEG C are warming up to from 80 DEG C with 1 DEG C/min heating rate, then 2h is incubated at being 160 DEG C in temperature, then 190 DEG C are warming up to from 160 DEG C with 1 DEG C/min heating rate, then 2h, then the liter with 2 DEG C/min are incubated at being 190 DEG C in temperature Warm speed is warming up to 250 DEG C from 190 DEG C, then is 250 DEG C in temperature and is incubated 1h, completes hot-imide, obtains containing random common The glass plate of poly- polyimide/carbon fiber mixed film；
5th, the glass plate containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, made random common Poly- polyimide/carbon fiber mixed film comes off from glass plate, reuses distilled water by random copolymerization polyimide/carbon fiber Mixed film is rinsed well, then dries 3h at being 120 DEG C in temperature, obtains electroluminescent driving shape memory polyimides.
Electroluminescent driving shape memory polyimides prepared by example IV deforms at high temperature, is reduced to room temperature and fixes temporarily Shape；Then 7.0V direct current is applied on sample using DC plant, sample slowly returns to it by temporary shapes Beginning shape.
The T of electroluminescent driving shape memory polyimides prepared by example IVgFor 230 DEG C, it ensure that prepared by example IV Electroluminescent driving shape memory polyimides can be applied to high-temperature shape-memory field；Electroluminescent driving shape prepared by example IV Polyimides is remembered in 210 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 1.78GPa；In 250 DEG C of (T of high temperatureg+ 20 DEG C) rubber Storage modulus during colloidal state is 9.88MPa.Electroluminescent driving shape memory polyimides prepared by example IV has good shape Shape memory effect, its shape prescribed rate are 95%, shape recovery ratio 93%.
Embodiment five：A kind of preparation method of electroluminescent driving shape memory polyimides is completed according to the following steps：
First, it is (4- amino-benzene oxygens) biphenyl of 0.03mol 4,4'- bis- and 0.02mol 1,3- is double (3- amino-benzene oxygens) The mixture of benzene is added in 200mL DMAs, then under the nitrogen atmosphere of room gently dried stirring to 4, The mixture of (4- amino-benzene oxygens) biphenyl of 4'- bis- and double (3- amino-benzene oxygens) benzene of 1,3- is completely dissolved, and obtains diamines mixing Solution；
2nd, 0.05mol 4, the double phthalic anhydrides of 4- oxygen are added in the diamines mixed solution obtained in step 1, Polymerisation 19h at room temperature under nitrogen atmosphere again, obtains random copolymerization polyamic acid；
The 3rd, the chopped carbon fiber that 3.2411g length is 0.5mm~3mm is added to the random copolymerization obtained in step 2 In polyamic acid solution, then under room temperature, nitrogen atmosphere and mixing speed be 1100r/min under conditions of stirring reaction 20h, obtain To the random copolymerization polyamic acid solution containing carbon fiber；
4th, the random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning, then put In vacuum drying chamber, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 80 DEG C, then temperature be 80 2h is incubated at DEG C, then 160 DEG C are warming up to from 80 DEG C with 2 DEG C/min heating rate, then 2h is incubated at being 160 DEG C in temperature, then 190 DEG C are warming up to from 160 DEG C with 2 DEG C/min heating rate, then 2h, then the liter with 1 DEG C/min are incubated at being 190 DEG C in temperature Warm speed is warming up to 250 DEG C from 190 DEG C, then is 250 DEG C in temperature and is incubated 1h, completes hot-imide, obtains containing random common The glass plate of poly- polyimide/carbon fiber mixed film；
5th, the glass plate containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, made random common Poly- polyimide/carbon fiber mixed film comes off from glass plate, reuses distilled water by random copolymerization polyimide/carbon fiber Mixed film is rinsed well, then dries 3h at being 120 DEG C in temperature, obtains electroluminescent driving shape memory polyimides.
Electroluminescent driving shape memory polyimides prepared by embodiment five deforms at high temperature, is reduced to room temperature and fixes temporarily Shape；Then 6.5V direct current is applied on sample using DC plant, sample slowly returns to it by temporary shapes Beginning shape.
The T of electroluminescent driving shape memory polyimides prepared by embodiment fivegFor 233 DEG C, it ensure that prepared by embodiment five Electroluminescent driving shape memory polyimides can be applied to high-temperature shape-memory field.Electroluminescent driving shape prepared by embodiment five Polyimides is remembered in 213 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 1.86GPa；In 253 DEG C of (T of high temperatureg+ 20 DEG C) rubber Storage modulus during colloidal state is 10.2MPa.Electroluminescent driving shape memory polyimides prepared by embodiment five has good shape Shape memory effect, its shape prescribed rate are 95%, shape recovery ratio 92%.
Embodiment six：A kind of preparation method of electroluminescent driving shape memory polyimides is completed according to the following steps：
First, it is (4- amino-benzene oxygens) biphenyl of 0.04mol 4,4'- bis- and 0.01mol 1,3- is double (3- amino-benzene oxygens) The mixture of benzene is added in 200mL DMAs, then under the nitrogen atmosphere of room gently dried stirring to 4, The mixture of (4- amino-benzene oxygens) biphenyl of 4'- bis- and double (3- amino-benzene oxygens) benzene of 1,3- is completely dissolved, and obtains diamines mixing Solution；
2nd, 0.05mol 4, the double phthalic anhydrides of 4- oxygen are added in the diamines mixed solution obtained in step 1, Polymerisation 20h at room temperature under nitrogen atmosphere again, obtains random copolymerization polyamic acid；
The 3rd, the chopped carbon fiber that 3.9806g length is 0.5mm~3mm is added to the random copolymerization obtained in step 2 In polyamic acid solution, then under room temperature, nitrogen atmosphere and mixing speed be 1200r/min under conditions of stirring reaction 20h, obtain To the random copolymerization polyamic acid solution containing carbon fiber；
4th, the random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning, then put In vacuum drying chamber, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 80 DEG C, then temperature be 80 2h is incubated at DEG C, then 160 DEG C are warming up to from 80 DEG C with 2 DEG C/min heating rate, then 2h is incubated at being 160 DEG C in temperature, then 190 DEG C are warming up to from 160 DEG C with 1 DEG C/min heating rate, then 2h, then the liter with 2 DEG C/min are incubated at being 190 DEG C in temperature Warm speed is warming up to 250 DEG C from 190 DEG C, then is 250 DEG C in temperature and is incubated 1h, completes hot-imide, obtains containing random common The glass plate of poly- polyimide/carbon fiber mixed film；
5th, the glass plate containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, made random common Poly- polyimide/carbon fiber mixed film comes off from glass plate, reuses distilled water by random copolymerization polyimide/carbon fiber Mixed film is rinsed well, then dries 3h at being 120 DEG C in temperature, obtains electroluminescent driving shape memory polyimides.
Electroluminescent driving shape memory polyimides prepared by embodiment six deforms at high temperature, is reduced to room temperature and fixes temporarily Shape；Then 6V direct current is applied on sample using DC plant, sample is slowly returned to its starting by temporary shapes Shape.
The T of electroluminescent driving shape memory polyimides prepared by embodiment sixgFor 238 DEG C, it ensure that prepared by embodiment six Electroluminescent driving shape memory polyimides can be applied to high-temperature shape-memory field.Electroluminescent driving shape prepared by embodiment six Polyimides is remembered in 218 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 1.92GPa；In 258 DEG C of (T of high temperatureg+ 20 DEG C) rubber Storage modulus during colloidal state is 11.68MPa；Electroluminescent driving shape memory polyimides prepared by embodiment six has preferable shape Shape memory effect, its shape prescribed rate are 92%, shape recovery ratio 90%.

Claims (10)

1. a kind of preparation method of electroluminescent driving shape memory polyimides, it is characterised in that a kind of electroluminescent driving shape memory gathers Imido preparation method is completed according to the following steps：
First, the mixture of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and double (3- amino-benzene oxygens) benzene of 1,3- is added to non-matter In sub- polar solvent, then stirred under the nitrogen atmosphere of room gently dried to 4,4'- bis- (4- amino-benzene oxygens) biphenyl and 1,3- The mixture of double (3- amino-benzene oxygens) benzene is completely dissolved, and obtains diamines mixed solution；
The mixture of double (3- amino-benzene oxygens) benzene of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and 1,3- described in step 1 The amount of material and the volume ratio of aprotic polar solvent are 0.05mol:(180mL~200mL)；
In the mixture of double (3- amino-benzene oxygens) benzene of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and 1,3- described in step 1 The mol ratio of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and double (3- amino-benzene oxygens) benzene of 1,3- is A:B；A span is 1 ≤ A≤9, B span are 1≤B≤9；
2nd, the double phthalic anhydrides of 4,4- oxygen are added in diamines mixed solution, then polymerization is anti-at room temperature under nitrogen atmosphere 15h~20h is answered, obtains random copolymerization polyamic acid；
The double phthalic anhydrides of 4,4- oxygen described in step 2 join with 4,4'- bis- (4- amino-benzene oxygens) in diamines mixed solution The mol ratio of the mixture of benzene and double (3- amino-benzene oxygens) benzene of 1,3- is 1:1；
3rd, the chopped carbon fiber that length is 0.5mm~3mm is added in random copolymerization polyamic acid solution, then in room temperature, nitrogen Under gas atmosphere and mixing speed is stirring reaction 20h~24h under conditions of 800r/min~1200r/min, is obtained fine containing carbon The random copolymerization polyamic acid solution of dimension；
Mass ratio of the chopped carbon fiber with random copolymerization polyamic acid solution that length described in step 3 is 0.5mm~3mm For (0.005~0.12):1；
4th, the random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning, be subsequently placed in true In empty drying box, then by vacuum drying chamber with 1 DEG C/min~2 DEG C/min heating rate from room temperature to 70 DEG C~90 DEG C, 2h~3h is incubated at 70 DEG C~90 DEG C again, then is warming up to 1 DEG C/min~2 DEG C/min heating rate from 70 DEG C~90 DEG C 150 DEG C~170 DEG C, then 2h~3h is incubated at 150 DEG C~170 DEG C, then with 1 DEG C/min~2 DEG C/min heating rate from 150 DEG C~170 DEG C be warming up to 190 DEG C~210 DEG C, then 2h~3h be incubated at 190 DEG C~210 DEG C, then with 1 DEG C/min~2 DEG C/min Heating rate be warming up to 240 DEG C~260 DEG C from 190 DEG C~210 DEG C, then be incubated 1h~2h at 240 DEG C~260 DEG C, complete heat Imidizate, obtain the glass plate containing random copolymerization polyimide/carbon fiber mixed film；
5th, the glass plate containing random copolymerization polyimide/carbon fiber mixed film is placed in distilled water, gathers random copolymerization Acid imide/carbon fiber mixed film comes off from glass plate, reuses distilled water and mixes random copolymerization polyimide/carbon fiber Film is rinsed well, then dries 3h at being 120 DEG C in temperature, obtains electroluminescent driving shape memory polyimides.
A kind of 2. preparation method of electroluminescent driving shape memory polyimides according to claim 1, it is characterised in that step Aprotic polar solvent described in rapid one is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N- crassitudes Ketone.
A kind of 3. preparation method of electroluminescent driving shape memory polyimides according to claim 1, it is characterised in that step The thickness of electroluminescent driving shape memory polyimides described in rapid five is 50 μm~120 μm.
A kind of 4. preparation method of electroluminescent driving shape memory polyimides according to claim 1, it is characterised in that step The material of the mixture of double (3- amino-benzene oxygens) benzene of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and 1,3- described in rapid one Amount and the volume ratio of aprotic polar solvent are 0.05mol:180mL.
A kind of 5. preparation method of electroluminescent driving shape memory polyimides according to claim 1, it is characterised in that step The material of the mixture of double (3- amino-benzene oxygens) benzene of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and 1,3- described in rapid one Amount and the volume ratio of aprotic polar solvent are 0.05mol:190mL.
A kind of 6. preparation method of electroluminescent driving shape memory polyimides according to claim 1, it is characterised in that step The material of the mixture of double (3- amino-benzene oxygens) benzene of (4- amino-benzene oxygens) biphenyl of 4,4'- bis- and 1,3- described in rapid one Amount and the volume ratio of aprotic polar solvent are 0.05mol:200mL.
A kind of 7. preparation method of electroluminescent driving shape memory polyimides according to claim 1, it is characterised in that step The random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning in rapid four, is subsequently placed in vacuum In drying box, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 90 DEG C, then be incubated 2h at 90 DEG C, 150 DEG C are warming up to from 90 DEG C with 1 DEG C/min heating rate again, then 2h is incubated at 150 DEG C, then the heating speed with 1 DEG C/min Rate is warming up to 190 DEG C from 150 DEG C, then 2h is incubated at 190 DEG C, then is warming up to 250 from 190 DEG C with 1 DEG C/min heating rate DEG C, then 1h is incubated at 250 DEG C, hot-imide is completed, obtains the glass containing random copolymerization polyimide/carbon fiber mixed film Glass plate.
A kind of 8. preparation method of electroluminescent driving shape memory polyimides according to claim 1, it is characterised in that step The random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning in rapid four, is subsequently placed in vacuum In drying box, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 80 DEG C, then be incubated 2h at 80 DEG C, 160 DEG C are warming up to from 80 DEG C with 2 DEG C/min heating rate again, then 2h is incubated at 160 DEG C, then the heating speed with 1 DEG C/min Rate is warming up to 190 DEG C from 160 DEG C, then 2h is incubated at 190 DEG C, then is warming up to 250 from 190 DEG C with 1 DEG C/min heating rate DEG C, then 1h is incubated at 250 DEG C, hot-imide is completed, obtains the glass containing random copolymerization polyimide/carbon fiber mixed film Glass plate.
A kind of 9. preparation method of electroluminescent driving shape memory polyimides according to claim 1, it is characterised in that step The random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning in rapid four, is subsequently placed in vacuum In drying box, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 80 DEG C, then be incubated 2h at 80 DEG C, 160 DEG C are warming up to from 80 DEG C with 2 DEG C/min heating rate again, then 2h is incubated at 160 DEG C, then the heating speed with 2 DEG C/min Rate is warming up to 190 DEG C from 160 DEG C, then 2h is incubated at 190 DEG C, then is warming up to 250 from 190 DEG C with 1 DEG C/min heating rate DEG C, then 1h is incubated at 250 DEG C, hot-imide is completed, obtains the glass containing random copolymerization polyimide/carbon fiber mixed film Glass plate.
A kind of 10. preparation method of electroluminescent driving shape memory polyimides according to claim 1, it is characterised in that step The random copolymerization polyamic acid solution containing carbon fiber is coated uniformly on the glass plate of cleaning in rapid four, is subsequently placed in vacuum In drying box, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 80 DEG C, then be incubated 2h at 80 DEG C, 160 DEG C are warming up to from 80 DEG C with 1 DEG C/min heating rate again, then 2h is incubated at 160 DEG C, then the heating speed with 1 DEG C/min Rate is warming up to 190 DEG C from 160 DEG C, then 2h is incubated at 190 DEG C, then is warming up to 250 from 190 DEG C with 2 DEG C/min heating rate DEG C, then 1h is incubated at 250 DEG C, hot-imide is completed, obtains the glass containing random copolymerization polyimide/carbon fiber mixed film Glass plate.
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