CN105399951B - A kind of adjustable shape memory random copolymerization polyimides of glass transition temperature and preparation method thereof - Google Patents

A kind of adjustable shape memory random copolymerization polyimides of glass transition temperature and preparation method thereof Download PDF

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CN105399951B
CN105399951B CN201511018901.4A CN201511018901A CN105399951B CN 105399951 B CN105399951 B CN 105399951B CN 201511018901 A CN201511018901 A CN 201511018901A CN 105399951 B CN105399951 B CN 105399951B
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polyimides
incubated
glass transition
transition temperature
benzene
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CN105399951A (en
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肖鑫礼
孔德艳
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Harbin Institute of Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2280/00—Compositions for creating shape memory

Abstract

A kind of adjustable shape memory random copolymerization polyimides of glass transition temperature and preparation method thereof, it is related to one kind and prepares polyimides and preparation method thereof.The invention aims to solve existing to make the T of the shape memory polyimides of preparation by adjusting the ratio of reactantgCertain limit changes the problem of.A kind of adjustable shape memory random copolymerization polyimides of glass transition temperature is prepared by mixture and the Bisphenol A Type Diether Dianhydride of 4,4' diaminodiphenyl ethers and 1,3 pairs of (3 amino-benzene oxygen) benzene.Method：First, diamine mixture solution is prepared；2nd, two anhydride solutions are prepared；3rd, polyamic acid solution is prepared；4th, hot-imide, the glass plate containing polyimides is obtained；5th, clean, dry, obtain the adjustable shape memory random copolymerization polyimides of glass transition temperature.The present invention can obtain a kind of adjustable shape memory random copolymerization polyimides of glass transition temperature.

Description

A kind of adjustable shape memory random copolymerization polyimides of glass transition temperature and Its preparation method
Technical field
The present invention relates to one kind to prepare polyimides and preparation method thereof.
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 to combine the excellent properties of polyimides and shape-memory properties, in deployable space structures, variable flying device pair The wing, pyrostat and driver etc. have significant application value.The transfer of shapes temperature of shape memory polyimides is usual It is its glass transition temperature (Tg), usually require that TgHigher than environment temperature to prevent that recovery of shape from being triggered in advance.Different rings Border needs different TgMaterial.Therefore, shape memory polyimides TgIt is adjustable significant.
The content of the invention
The invention aims to solve existing to make the shape memory polyamides of preparation by adjusting the ratio of reactant The T of iminesgCertain limit changes the problem of, and provide a kind of glass transition temperature adjustable shape memory random copolymerization Polyimides and preparation method thereof.
A kind of adjustable shape memory random copolymerization polyimides of glass transition temperature is by 4,4'- diaminodiphenyl ethers It is prepared with the mixture and Bisphenol A Type Diether Dianhydride of double (3- amino-benzene oxygens) benzene of 1,3-；Described 4,4'- diaminourea two The mol ratio of the mixture and Bisphenol A Type Diether Dianhydride of phenylate and double (3- amino-benzene oxygens) benzene of 1,3- is 1:1；Described 4, 4,4'- diaminodiphenyl ethers and the double (3- of 1,3- in the mixture of 4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzene of 1,3- Amino-benzene oxygen) mol ratio of benzene is A:B, A span are 1≤A≤9, and B span is 1≤B≤9.
A kind of preparation method of the adjustable shape memory random copolymerization polyimides of glass transition temperature, is by following What step was completed：
First, the mixture of 4,4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzene of 1,3- is added to non-proton pole Property solvent in, then stir under dry nitrogen atmosphere to 4,4'- diaminodiphenyl ethers and 1, double (3- amino-benzene oxygens) benzene of 3- Mixture be completely dissolved, obtain diamine mixture solution；
The material of the mixture of double (3- amino-benzene oxygens) benzene of 4,4'- diaminodiphenyl ethers and 1,3- described in step 1 Amount and the volume ratio of aprotic polar solvent be 0.05mol:(60mL~100mL)；
4 in the mixture of double (3- amino-benzene oxygens) benzene of 4,4'- diaminodiphenyl ethers and 1,3- described in step 1, The mol ratio of 4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzene of 1,3- is A:B, A span are 1≤A≤9, B's Span is 1≤B≤9；
2nd, Bisphenol A Type Diether Dianhydride is dissolved into aprotic polar solvent, obtains two anhydride solutions；
The amount of the material of Bisphenol A Type Diether Dianhydride described in step 2 and the volume ratio of aprotic polar solvent are 0.05mol:(60mL~100mL)；
3rd, two anhydride solutions are added in diamine mixture solution, then in nitrogen atmosphere and mixing speed are 300r/min Stirring reaction 15h~20h, obtains polyamic acid solution under conditions of~400r/min；
4,4'- diaminodiphenyl ethers and 1,3- are double (3- amino-benzene oxygens) in diamine mixture solution described in step 3 The mol ratio of Bisphenol A Type Diether Dianhydride is 1 in the mixture of benzene and two anhydride solutions:1；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, placed into vacuum drying chamber, then by vacuum Drying box, from room temperature to 70 DEG C~90 DEG C, then is incubated with 1 DEG C/min~2 DEG C/min heating rate at 70 DEG C~90 DEG C 2h~3h, then 160 DEG C~180 DEG C are warming up to from 70 DEG C~90 DEG C with 1 DEG C/min~2 DEG C/min heating rate, then at 160 DEG C 2h~3h is incubated at~180 DEG C, then be warming up to from 160 DEG C~180 DEG C with 1 DEG C/min~2 DEG C/min heating rate 200 DEG C~ 220 DEG C, then 2h~3h is incubated at 200 DEG C~220 DEG C, then with 1 DEG C/min~2 DEG C/min heating rate from 200 DEG C~220 240 DEG C~260 DEG C DEG C are warming up to, then 1h~2h is incubated at 240 DEG C~260 DEG C, completes hot-imide, then make vacuum drying Case self-heating is cooled to room temperature, obtains the glass plate containing polyimides；
5th, the glass plate containing polyimides is placed in distilled water, polyimides is come off from glass plate, reused Distilled water rinses polyimides well, then dries 3h~4h at being 120 DEG C in temperature, obtains glass transition temperature and can adjust Shape memory random copolymerization polyimides.
Advantages of the present invention：
First, the present invention uses the mixture of 4,4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzene of 1,3- as two Amine monomers, using Bisphenol A Type Diether Dianhydride as dianhydride monomer, the adjustable shape memory of glass transition temperature of preparation without Advise copolyimide；
2nd, the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by the present invention has fine Shape-memory properties, high-temperature shape-memory field is can be applied to, such as space deployable structure, high temperature driven device, high temperature detection Device etc.；
3rd, the T of the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by the present inventiongCan be with It is adjusted by the ratio for changing reactant monomer, varying environment can be adapted to TgRequirement；
4th, the T of the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by the present inventiongFor 196 DEG C~223 DEG C, in TgStorage modulus during -20 DEG C of glassy states is 1.70GPa~1.88GPa；In TgDuring+20 DEG C of rubbery states Storage modulus is 4.6MPa~5.6MPa；
5th, the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by the present invention has fine SME, its shape fixed rate is up to 99%, and shape recovery ratio is up to 99%.
The present invention can obtain a kind of adjustable shape memory random copolymerization polyimides of glass transition temperature.
Brief description of the drawings
Fig. 1 is the red of the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment one External spectrum figure；
Fig. 2 is the damage of the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment one Consume factor graph；
Fig. 3 is depositing for the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment one Store up modulus figure；
Fig. 4 is that the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment one exists Deformed in 206 DEG C of thermal station, at room temperature fixed obtained temporary shapes；
Fig. 5 is that the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment one exists Shape in 206 DEG C of thermal station in recovery of shape；
Fig. 6 is that the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment one exists State in 206 DEG C of thermal station after recovery of shape.
Embodiment
Embodiment one：Present embodiment is a kind of adjustable shape memory random copolymerization of glass transition temperature Polyimides is by 4,4'- diaminodiphenyl ethers and the mixture and Bisphenol A Type Diether Dianhydride of double (3- amino-benzene oxygens) benzene of 1,3- It is prepared；The mixture and bisphenol A-type diether of described 4,4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzene of 1,3- The mol ratio of dianhydride is 1:1；4 in the mixture of described 4,4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzene of 1,3-, The mol ratio of 4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzene of 1,3- is A:B, A span are 1≤A≤9, B's Span is 1≤B≤9.
Embodiment two：Present embodiment is a kind of adjustable shape memory random copolymerization of glass transition temperature The preparation method of polyimides is completed according to the following steps：
First, the mixture of 4,4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzene of 1,3- is added to non-proton pole Property solvent in, then stir under dry nitrogen atmosphere to 4,4'- diaminodiphenyl ethers and 1, double (3- amino-benzene oxygens) benzene of 3- Mixture be completely dissolved, obtain diamine mixture solution；
The material of the mixture of double (3- amino-benzene oxygens) benzene of 4,4'- diaminodiphenyl ethers and 1,3- described in step 1 Amount and the volume ratio of aprotic polar solvent be 0.05mol:(60mL~100mL)；
4 in the mixture of double (3- amino-benzene oxygens) benzene of 4,4'- diaminodiphenyl ethers and 1,3- described in step 1, The mol ratio of 4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzene of 1,3- is A:B, A span are 1≤A≤9, B's Span is 1≤B≤9；
2nd, Bisphenol A Type Diether Dianhydride is dissolved into aprotic polar solvent, obtains two anhydride solutions；
The amount of the material of Bisphenol A Type Diether Dianhydride described in step 2 and the volume ratio of aprotic polar solvent are 0.05mol:(60mL~100mL)；
3rd, two anhydride solutions are added in diamine mixture solution, then in nitrogen atmosphere and mixing speed are 300r/min Stirring reaction 15h~20h, obtains polyamic acid solution under conditions of~400r/min；
4,4'- diaminodiphenyl ethers and 1,3- are double (3- amino-benzene oxygens) in diamine mixture solution described in step 3 The mol ratio of Bisphenol A Type Diether Dianhydride is 1 in the mixture of benzene and two anhydride solutions:1；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, placed into vacuum drying chamber, then by vacuum Drying box, from room temperature to 70 DEG C~90 DEG C, then is incubated with 1 DEG C/min~2 DEG C/min heating rate at 70 DEG C~90 DEG C 2h~3h, then 160 DEG C~180 DEG C are warming up to from 70 DEG C~90 DEG C with 1 DEG C/min~2 DEG C/min heating rate, then at 160 DEG C 2h~3h is incubated at~180 DEG C, then be warming up to from 160 DEG C~180 DEG C with 1 DEG C/min~2 DEG C/min heating rate 200 DEG C~ 220 DEG C, then 2h~3h is incubated at 200 DEG C~220 DEG C, then with 1 DEG C/min~2 DEG C/min heating rate from 200 DEG C~220 240 DEG C~260 DEG C DEG C are warming up to, then 1h~2h is incubated at 240 DEG C~260 DEG C, completes hot-imide, then make vacuum drying Case self-heating is cooled to room temperature, obtains the glass plate containing polyimides；
5th, the glass plate containing polyimides is placed in distilled water, polyimides is come off from glass plate, reused Distilled water rinses polyimides well, then dries 3h~4h at being 120 DEG C in temperature, obtains glass transition temperature and can adjust Shape memory random copolymerization polyimides.
The advantages of present embodiment：
First, present embodiment is made using the mixture of 4,4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzene of 1,3- For diamine monomer, remembered using Bisphenol A Type Diether Dianhydride as dianhydride monomer, the adjustable shape of glass transition temperature of preparation Recall random copolymerization polyimides；
2nd, the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by present embodiment has Good shape-memory properties, high-temperature shape-memory field is can be applied to, such as space deployable structure, high temperature driven device, high temperature Detector etc.；
3rd, the T of the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by present embodimentg It can be adjusted by changing the ratio of reactant monomer, varying environment can be adapted to TgRequirement；
4th, the T of the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by present embodimentg For 196 DEG C~223 DEG C, in TgStorage modulus during -20 DEG C of glassy states is 1.70GPa~1.88GPa；In TgDuring+20 DEG C of rubbery states Storage modulus be 4.6MPa~5.6MPa；
5th, the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by present embodiment has Good SME, its shape fixed rate is up to 99%, and shape recovery ratio is up to 99%.
Present embodiment can obtain a kind of adjustable shape memory random copolymerization polyimides of glass transition temperature.
Embodiment three：The difference of present embodiment and embodiment two is：It is non-described in step 1 Proton polar solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.
Other steps are identical with embodiment two.
Embodiment four：Present embodiment is with one of embodiment two to three difference：Institute in step 2 The aprotic polar solvent stated is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.Other steps Suddenly it is identical with embodiment two to three.
Embodiment five：Present embodiment is with one of embodiment two to four difference：Institute in step 5 The thickness for the adjustable shape memory random copolymerization polyimides of glass transition temperature stated is 60 μm~160 μm.Other steps Suddenly it is identical with embodiment two to four.
Embodiment six：Present embodiment is with one of embodiment two to five difference：Institute in step 1 The amount and aprotonic polar of the material of the mixture of double (3- amino-benzene oxygens) benzene of 4,4'- diaminodiphenyl ethers and 1,3- stated are molten The volume ratio of agent is 0.05mol:60mL.Other steps are identical with embodiment two to five.
Embodiment seven：Present embodiment is with one of embodiment two to six difference：Institute in step 2 The amount of the material for the Bisphenol A Type Diether Dianhydride stated and the volume ratio of aprotic polar solvent are 0.05mol:100mL.Other steps It is identical with embodiment two to six.
Embodiment eight：Present embodiment is with one of embodiment two to seven difference：Will in step 4 Polyamic acid solution be coated uniformly on cleaning glass plate on, place into vacuum drying chamber, then by vacuum drying chamber with 1 DEG C/ Min heating rate is from room temperature to 90 DEG C, then 2h is incubated at 90 DEG C, then is risen with 1 DEG C/min heating rate from 90 DEG C Temperature is to 170 DEG C, then 2h is incubated at 170 DEG C, then 215 DEG C are warming up to from 170 DEG C with 1 DEG C/min heating rate, then at 215 DEG C Lower insulation 2h, then 250 DEG C are warming up to from 215 DEG C with 1 DEG C/min heating rate, then 1h is incubated at 250 DEG C, it is sub- to complete hot acyl Amination, then vacuum drying chamber self-heating is cooled to room temperature, obtain the glass plate containing polyimides.Other steps and specific implementation Mode two to seven is identical.
Embodiment nine：Present embodiment is with one of embodiment two to eight difference：Will in step 4 Polyamic acid solution be coated uniformly on cleaning glass plate on, place into vacuum drying chamber, then by vacuum drying chamber with 1 DEG C/ Min heating rate is from room temperature to 80 DEG C, then 2h is incubated at 80 DEG C, then is risen with 2 DEG C/min heating rate from 80 DEG C Temperature is to 160 DEG C, then 2h is incubated at 160 DEG C, then 210 DEG C are warming up to from 160 DEG C with 1 DEG C/min heating rate, then at 210 DEG C Lower insulation 2h, then 240 DEG C are warming up to from 210 DEG C with 2 DEG C/min heating rate, then 1h is incubated at 240 DEG C, it is sub- to complete hot acyl Amination, then vacuum drying chamber self-heating is cooled to room temperature, obtain the glass plate containing polyimides.Other steps and specific implementation Mode two to eight is identical.
Embodiment ten：Present embodiment is with one of embodiment two to nine difference：Will in step 4 Polyamic acid solution be coated uniformly on cleaning glass plate on, place into vacuum drying chamber, then by vacuum drying chamber with 2 DEG C/ Min heating rate is from room temperature to 90 DEG C, then 2h is incubated at 90 DEG C, then is risen with 2 DEG C/min heating rate from 90 DEG C Temperature is to 180 DEG C, then 2h is incubated at 180 DEG C, then 220 DEG C are warming up to from 180 DEG C with 1 DEG C/min heating rate, then at 220 DEG C Lower insulation 2h, then 250 DEG C are warming up to from 220 DEG C with 1 DEG C/min heating rate, then 1h is incubated at 250 DEG C, it is sub- to complete hot acyl Amination, then vacuum drying chamber self-heating is cooled to room temperature, obtain the glass plate containing polyimides.Other steps and specific implementation Mode two to nine is identical.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：A kind of preparation method of the adjustable shape memory random copolymerization polyimides of glass transition temperature Complete according to the following steps：
First, by the mixed of 1,3- pairs of (3- amino-benzene oxygens) benzene of 0.005mol 4,4'- diaminodiphenyl ethers and 0.045mol Compound is added in 60mL DMAs, then is stirred under dry nitrogen atmosphere to 4,4'- diaminodiphenyl ethers It is completely dissolved with the mixture of double (3- amino-benzene oxygens) benzene of 1,3-, obtains diamine mixture solution；
2nd, 0.05mol Bisphenol A Type Diether Dianhydrides are dissolved into 100mL DMAs, it is molten obtains dianhydride Liquid；
3rd, two anhydride solutions are added in diamine mixture solution, then in nitrogen atmosphere and mixing speed are 400r/min Under conditions of stirring reaction 16h, obtain polyamic acid solution；
4,4'- diaminodiphenyl ethers and 1,3- are double (3- amino-benzene oxygens) in diamine mixture solution described in step 3 The mol ratio of Bisphenol A Type Diether Dianhydride is 1 in the mixture of benzene and two anhydride solutions:1；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, placed into vacuum drying chamber, then by vacuum Drying box, from room temperature to 90 DEG C, then is incubated 2h with 1 DEG C/min heating rate at 90 DEG C, then the heating with 1 DEG C/min Speed is warming up to 170 DEG C from 90 DEG C, then 2h is incubated at 170 DEG C, then is warming up to 215 from 170 DEG C with 1 DEG C/min heating rate DEG C, then 2h is incubated at 215 DEG C, then 250 DEG C are warming up to from 215 DEG C with 1 DEG C/min heating rate, then be incubated at 250 DEG C 1h, hot-imide is completed, then vacuum drying chamber self-heating is cooled to room temperature, obtain the glass plate containing polyimides；Complete Hot-imide, then vacuum drying chamber self-heating is cooled to room temperature, obtain the glass plate containing polyimides；
5th, the glass plate containing polyimides is placed in distilled water, polyimides is come off from glass plate, reused Distilled water rinses polyimides well, then dries 3h at being 120 DEG C in temperature, obtains the adjustable shape of glass transition temperature Shape remembers random copolymerization polyimides.
The adjustable shape memory random copolymerization polyimides of glass transition temperature described in the step 5 of embodiment one Thickness be 100 μm.
The adjustable shape memory random copolymerization of glass transition temperature prepared using infrared spectrometer to embodiment one Polyimides is tested, as shown in Figure 1；
Fig. 1 is the red of the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment one External spectrum figure；
From fig. 1, it can be seen that these characteristic absorption peaks illustrate the adjustable shape of glass transition temperature prepared by embodiment one Remember the polyimides that random copolymerization polyimides is height imidizate.
The adjustable shape memory of glass transition temperature prepared using dynamic mechanical analyzer to embodiment one is random Copolyimide is tested, as shown in Figure 2；
Fig. 2 is the damage of the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment one Consume factor graph；
As can be seen from Figure 2 the adjustable shape memory random copolymerization of glass transition temperature that prepared by embodiment one gathers Imido TgFor 196 DEG C, the adjustable shape memory random copolymerization of glass transition temperature prepared by embodiment one ensure that Polyimides can be applied to high-temperature shape-memory field.
The adjustable shape memory of glass transition temperature prepared using dynamic mechanical analyzer to embodiment one is random Copolyimide is tested, as shown in Figure 3；
Fig. 3 is depositing for the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment one Store up modulus figure；
As can be seen from Figure 3, the adjustable shape memory random copolymerization polyamides of glass transition temperature that prepared by embodiment one is sub- There are two platforms of high and low temperature section in amine storage modulus change curve, in 176 DEG C of (Tg- 20 DEG C) glassy state when storage Modulus is 1.88GPa；In 216 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be 5.1MPa；Deposited between two platforms Storage modulus drastically declines, and corresponding to the Glass Transition of material, the drastically change of this modulus is that polymer possesses shape Remember the necessary condition of property.
The adjustable shape memory random copolymerization of glass transition temperature prepared using high-temperature stage to embodiment one is gathered Acid imide is tested, as shown in Figures 4 to 6；
Fig. 4 is that the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment one exists Deformed in 206 DEG C of thermal station, at room temperature fixed obtained temporary shapes；
Fig. 5 is that the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment one exists Shape in 206 DEG C of thermal station in recovery of shape；
Fig. 6 is that the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment one exists State in 206 DEG C of thermal station after recovery of shape.
It was found from Fig. 4 to Fig. 6, the adjustable shape memory random copolymerization of glass transition temperature prepared by embodiment one gathers Acid imide has good SME, and its shape fixed rate is 98%, shape recovery ratio 96%.
Embodiment two：A kind of preparation method of the adjustable shape memory random copolymerization polyimides of glass transition temperature Complete according to the following steps：
First, by the mixing of 0.01mol 4,4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzene of 0.04mol 1,3- Thing is added in 70mL DMAs, then stir under dry nitrogen atmosphere to 4,4'- diaminodiphenyl ethers and The mixture of 1,3- double (3- amino-benzene oxygens) benzene is completely dissolved, and obtains diamine mixture solution；
2nd, 0.05mol Bisphenol A Type Diether Dianhydrides are dissolved into 90mL DMAs, it is molten obtains dianhydride Liquid；
3rd, two anhydride solutions are added in diamine mixture solution, then in nitrogen atmosphere and mixing speed are 400r/min Under conditions of stirring reaction 15h, obtain polyamic acid solution；
4,4'- diaminodiphenyl ethers and 1,3- are double (3- amino-benzene oxygens) in diamine mixture solution described in step 3 The mol ratio of Bisphenol A Type Diether Dianhydride is 1 in the mixture of benzene and two anhydride solutions:1；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, placed into vacuum drying chamber, then by vacuum Drying box, from room temperature to 80 DEG C, then is incubated 2h with 1 DEG C/min heating rate at 80 DEG C, then the heating with 2 DEG C/min Speed is warming up to 160 DEG C from 80 DEG C, then 2h is incubated at 160 DEG C, then is warming up to 210 from 160 DEG C with 1 DEG C/min heating rate DEG C, then 2h is incubated at 210 DEG C, then 240 DEG C are warming up to from 210 DEG C with 2 DEG C/min heating rate, then be incubated at 240 DEG C 1h, hot-imide is completed, then vacuum drying chamber self-heating is cooled to room temperature, obtain the glass plate containing polyimides；Complete Hot-imide, then vacuum drying chamber self-heating is cooled to room temperature, obtain the glass plate containing polyimides；
5th, the glass plate containing polyimides is placed in distilled water, polyimides is come off from glass plate, reused Distilled water rinses polyimides well, then dries 3h at being 130 DEG C in temperature, obtains the adjustable shape of glass transition temperature Shape remembers random copolymerization polyimides.
The adjustable shape memory random copolymerization polyimides of glass transition temperature described in the step 5 of embodiment two Thickness be 100 μm.
The T of the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment twogFor 201 DEG C, it ensure that its SME can be applied to high-temperature shape-memory field；Glass transition temperature prepared by embodiment two Adjustable shape memory random copolymerization polyimides is in 181 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 1.76Gpa, 221 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be 5.3MPa.Glass transition temperature prepared by embodiment two is adjustable The shape fixed rate of the shape memory random copolymerization polyimides of section is 99%, shape recovery ratio 99%.
Embodiment three：A kind of preparation method of the adjustable shape memory random copolymerization polyimides of glass transition temperature Complete according to the following steps：
First, by the mixing of 0.02mol 4,4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzene of 0.03mol 1,3- Thing is added in 70mL DMFs, then stir under dry nitrogen atmosphere to 4,4'- diaminodiphenyl ethers and The mixture of 1,3- double (3- amino-benzene oxygens) benzene is completely dissolved, and obtains diamine mixture solution；
2nd, 0.05mol Bisphenol A Type Diether Dianhydrides are dissolved into 100mL DMFs, it is molten obtains dianhydride Liquid；
3rd, two anhydride solutions are added in diamine mixture solution, then in nitrogen atmosphere and mixing speed are 400r/min Under conditions of stirring reaction 17h, obtain polyamic acid solution；
4,4'- diaminodiphenyl ethers and 1,3- are double (3- amino-benzene oxygens) in diamine mixture solution described in step 3 The mol ratio of Bisphenol A Type Diether Dianhydride is 1 in the mixture of benzene and two anhydride solutions:1；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, placed into vacuum drying chamber, then by vacuum Drying box, from room temperature to 90 DEG C, then is incubated 2h with 2 DEG C/min heating rate at 90 DEG C, then the heating with 2 DEG C/min Speed is warming up to 180 DEG C from 90 DEG C, then 2h is incubated at 180 DEG C, then is warming up to 220 from 180 DEG C with 1 DEG C/min heating rate DEG C, then 2h is incubated at 220 DEG C, then 250 DEG C are warming up to from 220 DEG C with 1 DEG C/min heating rate, then be incubated at 250 DEG C 1h, hot-imide is completed, then vacuum drying chamber self-heating is cooled to room temperature, obtain the glass plate containing polyimides；Complete Hot-imide, then vacuum drying chamber self-heating is cooled to room temperature, obtain the glass plate containing polyimides；
5th, the glass plate containing polyimides is placed in distilled water, polyimides is come off from glass plate, reused Distilled water rinses polyimides well, then dries 3h at being 130 DEG C in temperature, obtains the adjustable shape of glass transition temperature Shape remembers random copolymerization polyimides.
The adjustable shape memory random copolymerization polyimides of glass transition temperature described in the step 5 of embodiment three Thickness be 100 μm.
The T of the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment threegFor 207 DEG C, it ensure that its SME can be applied to high-temperature shape-memory field；Glass transition temperature prepared by embodiment three Adjustable shape memory random copolymerization polyimides is in 187 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 1.78Gpa, In 227 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be 5.6MPa.Glass transition temperature prepared by embodiment three can The shape fixed rate of the shape memory random copolymerization polyimides of regulation is 97%, shape recovery ratio 98%.
Example IV：A kind of preparation method of the adjustable shape memory random copolymerization polyimides of glass transition temperature Complete according to the following steps：
First, by the mixing of 0.03mol 4,4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzene of 0.02mol 1,3- Thing is added in 80mL DMFs, then stir under dry nitrogen atmosphere to 4,4'- diaminodiphenyl ethers and The mixture of 1,3- double (3- amino-benzene oxygens) benzene is completely dissolved, and obtains diamine mixture solution；
2nd, 0.05mol Bisphenol A Type Diether Dianhydrides are dissolved into 100mL DMFs, it is molten obtains dianhydride Liquid；
3rd, two anhydride solutions are added in diamine mixture solution, then in nitrogen atmosphere and mixing speed are 400r/min Under conditions of stirring reaction 18h, obtain polyamic acid solution；
4,4'- diaminodiphenyl ethers and 1,3- are double (3- amino-benzene oxygens) in diamine mixture solution described in step 3 The mol ratio of Bisphenol A Type Diether Dianhydride is 1 in the mixture of benzene and two anhydride solutions:1；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, placed into vacuum drying chamber, then by vacuum Drying box, from room temperature to 80 DEG C, then is incubated 2h with 1 DEG C/min heating rate at 80 DEG C, then the heating with 2 DEG C/min Speed is warming up to 170 DEG C from 80 DEG C, then 2h is incubated at 170 DEG C, then is warming up to 210 from 170 DEG C with 1 DEG C/min heating rate DEG C, then 2h is incubated at 210 DEG C, then 240 DEG C are warming up to from 210 DEG C with 1 DEG C/min heating rate, then be incubated at 240 DEG C 1h, hot-imide is completed, then vacuum drying chamber self-heating is cooled to room temperature, obtain the glass plate containing polyimides；Complete Hot-imide, then vacuum drying chamber self-heating is cooled to room temperature, obtain the glass plate containing polyimides；
5th, the glass plate containing polyimides is placed in distilled water, polyimides is come off from glass plate, reused Distilled water rinses polyimides well, then dries 3h at being 130 DEG C in temperature, obtains the adjustable shape of glass transition temperature Shape remembers random copolymerization polyimides.
The adjustable shape memory random copolymerization polyimides of glass transition temperature described in example IV step 5 Thickness be 100 μm.
The T of the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by example IVgFor 212 DEG C, it ensure that its SME can be applied to high-temperature shape-memory field；The adjustable shape note of glass transition temperature Random copolymerization polyimides is recalled in 192 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 1.75GPa；232 DEG C of (T of high temperatureg+20 DEG C) rubbery state when storage modulus be 4.6MPa.Example IV prepare the adjustable shape memory of glass transition temperature without The shape fixed rate for advising copolyimide is 99%, shape recovery ratio 99%.
Embodiment five：A kind of preparation method of the adjustable shape memory random copolymerization polyimides of glass transition temperature Complete according to the following steps：
First, by the mixing of 0.04mol 4,4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzene of 0.01mol 1,3- Thing is added in 80mL DMFs, then stir under dry nitrogen atmosphere to 4,4'- diaminodiphenyl ethers and The mixture of 1,3- double (3- amino-benzene oxygens) benzene is completely dissolved, and obtains diamine mixture solution；
2nd, 0.05mol Bisphenol A Type Diether Dianhydrides are dissolved into 100mL DMFs, it is molten obtains dianhydride Liquid；
3rd, two anhydride solutions are added in diamine mixture solution, then in nitrogen atmosphere and mixing speed are 400r/min Under conditions of stirring reaction 19h, obtain polyamic acid solution；
4,4'- diaminodiphenyl ethers and 1,3- are double (3- amino-benzene oxygens) in diamine mixture solution described in step 3 The mol ratio of Bisphenol A Type Diether Dianhydride is 1 in the mixture of benzene and two anhydride solutions:1；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, placed into vacuum drying chamber, then by vacuum Drying box, from room temperature to 80 DEG C, then is incubated 2h with 1 DEG C/min heating rate at 80 DEG C, then the heating with 2 DEG C/min Speed is warming up to 180 DEG C from 80 DEG C, then 2h is incubated at 180 DEG C, then is warming up to 220 from 180 DEG C with 2 DEG C/min heating rate DEG C, then 2h is incubated at 220 DEG C, then 250 DEG C are warming up to from 220 DEG C with 1 DEG C/min heating rate, then be incubated at 250 DEG C 1h, hot-imide is completed, then vacuum drying chamber self-heating is cooled to room temperature, obtain the glass plate containing polyimides；Complete Hot-imide, then vacuum drying chamber self-heating is cooled to room temperature, obtain the glass plate containing polyimides；
5th, the glass plate containing polyimides is placed in distilled water, polyimides is come off from substrate, reuse steaming Distilled water rinses polyimides well, then dries 3h at being 130 DEG C in temperature, obtains the adjustable shape of glass transition temperature Remember random copolymerization polyimides.
The adjustable shape memory random copolymerization polyimides of glass transition temperature described in the step 5 of embodiment five Thickness be 100 μm.
The T of the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment fivegFor 218 DEG C, it ensure that its SME can be applied to high-temperature shape-memory field；The adjustable shape note of glass transition temperature Random copolymerization polyimides is recalled in 198 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 1.72GPa；238 DEG C of (T of high temperatureg+20 DEG C) rubbery state when storage modulus be 5.6MPa.Embodiment five prepare the adjustable shape memory of glass transition temperature without The shape fixed rate for advising copolyimide is 100%, shape recovery ratio 98%.
Embodiment six：A kind of preparation method of the adjustable shape memory random copolymerization polyimides of glass transition temperature Complete according to the following steps：
First, by the mixed of 1,3- pairs of (3- amino-benzene oxygens) benzene of 0.045mol 4,4'- diaminodiphenyl ethers and 0.005mol Compound is added in 90mL 1-METHYLPYRROLIDONEs, then stir under dry nitrogen atmosphere to 4,4'- diaminodiphenyl ethers and The mixture of 1,3- double (3- amino-benzene oxygens) benzene is completely dissolved, and obtains diamine mixture solution；
2nd, 0.05mol Bisphenol A Type Diether Dianhydrides are dissolved into 100mL 1-METHYLPYRROLIDONEs, obtain two anhydride solutions；
3rd, two anhydride solutions are added in diamine mixture solution, then in nitrogen atmosphere and mixing speed are 400r/min Under conditions of stirring reaction 20h, obtain polyamic acid solution；
4,4'- diaminodiphenyl ethers and 1,3- are double (3- amino-benzene oxygens) in diamine mixture solution described in step 3 The mol ratio of Bisphenol A Type Diether Dianhydride is 1 in the mixture of benzene and two anhydride solutions:1；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, placed into vacuum drying chamber, then by vacuum Drying box, from room temperature to 90 DEG C, then is incubated 2h with 2 DEG C/min heating rate at 90 DEG C, then the heating with 2 DEG C/min Speed is warming up to 180 DEG C from 90 DEG C, then 2h is incubated at 180 DEG C, then is warming up to 220 from 180 DEG C with 2 DEG C/min heating rate DEG C, then 2h is incubated at 220 DEG C, then 260 DEG C are warming up to from 220 DEG C with 2 DEG C/min heating rate, then be incubated at 260 DEG C 1h, hot-imide is completed, then vacuum drying chamber self-heating is cooled to room temperature, obtain the glass plate containing polyimides；Complete Hot-imide, then vacuum drying chamber self-heating is cooled to room temperature, obtain the glass plate containing polyimides；
5th, the glass plate containing polyimides is placed in distilled water, polyimides is come off from glass plate, reused Distilled water rinses polyimides well, then dries 3h at being 130 DEG C in temperature, obtains the adjustable shape of glass transition temperature Shape remembers random copolymerization polyimides.
The adjustable shape memory random copolymerization polyimides of glass transition temperature described in the step 5 of embodiment six Thickness be 100 μm.
The T of the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment sixgFor 223 DEG C, it ensure that its SME can be applied to high-temperature shape-memory field；Glass transition temperature prepared by embodiment six Adjustable shape memory random copolymerization polyimides is in 203 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 1.70GPa； 243 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be 5.2MPa.
The shape of the adjustable shape memory random copolymerization polyimides of glass transition temperature prepared by embodiment six is consolidated It is 98% to determine rate, shape recovery ratio 96%.

Claims (6)

  1. A kind of 1. preparation method of the adjustable shape memory random copolymerization polyimides of glass transition temperature, it is characterised in that This method is completed according to the following steps：
    First, that the mixture of double (3- amino-benzene oxygens) benzene of 4,4'- diaminodiphenyl ethers and 1,3- is added into aprotonic polar is molten In agent, then stir under dry nitrogen atmosphere mixed to double (3- amino-benzene oxygens) benzene of 4,4'- diaminodiphenyl ethers and 1,3- Compound is completely dissolved, and obtains diamine mixture solution；
    Aprotic polar solvent described in step 1 is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N- methyl pyrroles Pyrrolidone；
    The amount of the material of the mixture of double (3- amino-benzene oxygens) benzene of 4,4'- diaminodiphenyl ethers and 1,3- described in step 1 Volume ratio with aprotic polar solvent is 0.05mol:(60mL~100mL)；
    4,4'- bis- in the mixture of double (3- amino-benzene oxygens) benzene of 4,4'- diaminodiphenyl ethers and 1,3- described in step 1 The mol ratio of amino-diphenylethers and double (3- amino-benzene oxygens) benzene of 1,3- is A:B, A span are 1≤A≤9, B value Scope is 1≤B≤9；
    2nd, Bisphenol A Type Diether Dianhydride is dissolved into aprotic polar solvent, obtains two anhydride solutions；
    The amount of the material of Bisphenol A Type Diether Dianhydride described in step 2 and the volume ratio of aprotic polar solvent are 0.05mol: (60mL~100mL)；
    Aprotic polar solvent described in step 2 is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N- methyl pyrroles Pyrrolidone；
    3rd, two anhydride solutions are added in diamine mixture solution, then nitrogen atmosphere and mixing speed be 300 r/min~ Stirring reaction 15h~20h under conditions of 400r/min, obtains polyamic acid solution；
    Double (3- amino-benzene oxygens) benzene of 4,4'- diaminodiphenyl ethers and 1,3- in diamine mixture solution described in step 3 The mol ratio of Bisphenol A Type Diether Dianhydride is 1 in mixture and two anhydride solutions:1；
    4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, placed into vacuum drying chamber, then will vacuum drying Case with 1 DEG C/min~2 DEG C/min heating rate from room temperature to 70 DEG C~90 DEG C, then at 70 DEG C~90 DEG C be incubated 2h~ 3h, then 160 DEG C~180 DEG C are warming up to from 70 DEG C~90 DEG C with 1 DEG C/min~2 DEG C/min heating rate, then 160 DEG C~ 2h~3h is incubated at 180 DEG C, then be warming up to from 160 DEG C~180 DEG C with 1 DEG C/min~2 DEG C/min heating rate 200 DEG C~ 220 DEG C, then 2h~3h is incubated at 200 DEG C~220 DEG C, then with 1 DEG C/min~2 DEG C/min heating rate from 200 DEG C~220 240 DEG C~260 DEG C DEG C are warming up to, then 1h~2h is incubated at 240 DEG C~260 DEG C, completes hot-imide, then make vacuum drying Case self-heating is cooled to room temperature, obtains the glass plate containing polyimides；
    5th, the glass plate containing polyimides is placed in distilled water, polyimides is come off from glass plate, reuse distillation Water rinses polyimides well, then dries 3h~4h at being 120 DEG C in temperature, obtains the adjustable shape of glass transition temperature Shape remembers random copolymerization polyimides；
    The thickness of the adjustable shape memory random copolymerization polyimides of glass transition temperature described in step 5 is 60 μm ~160 μm.
  2. 2. the adjustable shape memory random copolymerization polyimides of a kind of glass transition temperature according to claim 1 Preparation method, it is characterised in that double (3- amino-benzene oxygens) benzene of 4,4'- diaminodiphenyl ethers and 1,3- described in step 1 The amount of the material of mixture and the volume ratio of aprotic polar solvent are 0.05mol:60mL.
  3. 3. the adjustable shape memory random copolymerization polyimides of a kind of glass transition temperature according to claim 1 Preparation method, it is characterised in that the amount of the material of the Bisphenol A Type Diether Dianhydride described in step 2 and aprotic polar solvent Volume ratio is 0.05mol:100mL.
  4. 4. the adjustable shape memory random copolymerization polyimides of a kind of glass transition temperature according to claim 1 Preparation method, it is characterised in that polyamic acid solution is coated uniformly on the glass plate of cleaning in step 4, places into 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, 170 DEG C are warming up to from 90 DEG C with 1 DEG C/min heating rate again, then 2h is incubated at 170 DEG C, then the heating speed with 1 DEG C/min Rate is warming up to 215 DEG C from 170 DEG C, then 2h is incubated at 215 DEG C, then is warming up to 250 from 215 DEG C with 1 DEG C/min heating rate DEG C, then 1h is incubated at 250 DEG C, hot-imide is completed, then vacuum drying chamber self-heating is cooled to room temperature, obtain containing polyamides The glass plate of imines.
  5. 5. the adjustable shape memory random copolymerization polyimides of a kind of glass transition temperature according to claim 1 Preparation method, it is characterised in that polyamic acid solution is coated uniformly on the glass plate of cleaning in step 4, places into 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 210 DEG C from 160 DEG C, then 2h is incubated at 210 DEG C, then is warming up to 240 from 210 DEG C with 2 DEG C/min heating rate DEG C, then 1h is incubated at 240 DEG C, hot-imide is completed, then vacuum drying chamber self-heating is cooled to room temperature, obtain containing polyamides The glass plate of imines.
  6. 6. the adjustable shape memory random copolymerization polyimides of a kind of glass transition temperature according to claim 1 Preparation method, it is characterised in that polyamic acid solution is coated uniformly on the glass plate of cleaning in step 4, places into vacuum In drying box, then by vacuum drying chamber with 2 DEG C/min heating rate from room temperature to 90 DEG C, then be incubated 2h at 90 DEG C, 180 DEG C are warming up to from 90 DEG C with 2 DEG C/min heating rate again, then 2h is incubated at 180 DEG C, then the heating speed with 1 DEG C/min Rate is warming up to 220 DEG C from 180 DEG C, then 2h is incubated at 220 DEG C, then is warming up to 250 from 220 DEG C with 1 DEG C/min heating rate DEG C, then 1h is incubated at 250 DEG C, hot-imide is completed, then vacuum drying chamber self-heating is cooled to room temperature, obtain containing polyamides The glass plate of imines.
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