CN105418922B - A kind of shape memory random copolymerization polyimides that can be recycled and preparation method thereof - Google Patents
A kind of shape memory random copolymerization polyimides that can be recycled and preparation method thereof Download PDFInfo
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Abstract
A kind of shape memory random copolymerization polyimides that can be recycled and preparation method thereof, it is related to a kind of polyimides and preparation method thereof.The invention aims to solve the shape memory polyimides cost of existing preparation height, the problem of shape memory polyimides of preparation can not recycle.A kind of shape memory random copolymerization polyimides that can be recycled is prepared by the mixture of 1,3 pairs of (3 amino-benzene oxygen) benzene and the double phthalic anhydrides of Bisphenol A Type Diether Dianhydride and 4,4 oxygen.Method：First, diamine 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, the shape memory random copolymerization polyimides that can be recycled.The present invention can obtain a kind of shape memory random copolymerization polyimides that can be recycled.
Description
Technical field
The present invention relates to a kind of 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.Relative to memory shape metal alloy, the reversible strains of SMP are big,
The advantages that density is low, handling ease and recovery of shape temperature are easy to control, biologic medical, Intelligent prevention and cure, deployable structure,
Applied in the fields such as drive assembly.Polyimides (PI) is excellent with heat endurance height, mechanical performance, and processing approach is more
The advantages that sample, the fields such as automobile, microelectronics, photoelectricity, Aero-Space have been widely used in it.Shape memory polyimides is in sky
Between deployed configuration, variable flying device aileron, pyrostat and driver etc. also have significant application value.
Shape memory polyimides cost is higher, therefore shape memory polyimides can be recycled for practical application
With very high application value, substantial amounts of fund can be saved.It there is no the report that shape memory polyimides can be recycled at present.
The content of the invention
The invention aims to solve the shape memory polyimides cost of existing preparation height, the shape memory of preparation gathers
The problem of acid imide can not recycle, and a kind of shape memory random copolymerization polyimides that can be recycled and its system are provided
Preparation Method.
A kind of shape memory random copolymerization polyimides that can be recycled by double (3- amino-benzene oxygens) benzene of 1,3- with it is double
The mixture of the ether dianhydride of phenol A types two and the double phthalic anhydrides of 4,4- oxygen is prepared；Double (the 3- aminobenzene oxygen of described 1,3-
Base) mol ratios of mixture of benzene and Bisphenol A Type Diether Dianhydride and the double phthalic anhydrides of 4,4- oxygen is 1:1；Described bisphenol-A
Bisphenol A Type Diether Dianhydride and the double phthalic acids of 4,4- oxygen in the mixture of the ether dianhydride of type two and the double phthalic anhydrides of 4,4- oxygen
The mol ratio of acid anhydride is A:B, A span are 1≤A≤9, and B span is 1≤B≤9.
A kind of preparation method for the shape memory random copolymerization polyimides that can be recycled is completed according to the following steps：
First, double (3- amino-benzene oxygens) benzene of 1,3- are added in aprotic polar solvent, then in dry nitrogen atmosphere
Lower stirring to double (3- amino-benzene oxygens) benzene of 1,3- are completely dissolved, and obtain diamine solution；
The amount of material and the volume of aprotic polar solvent of double (3- amino-benzene oxygens) benzene of 1,3- described in step 1
Than for 0.05mol:(80mL~130mL)；
2nd, that the mixture of Bisphenol A Type Diether Dianhydride and the double phthalic anhydrides of 4,4- oxygen is dissolved in into aprotonic polar is molten
In agent, two anhydride solutions are obtained；
Bisphenol A-type in the mixture of the double phthalic anhydrides of Bisphenol A Type Diether Dianhydride and 4,4- oxygen described in step 2
The mol ratio of two ether dianhydrides and the double phthalic anhydrides of 4,4- oxygen is A:B, A span are 1≤A≤9, B span
For 1≤B≤9；
The amount of the material of the mixture of the double phthalic anhydrides of Bisphenol A Type Diether Dianhydride and 4,4- oxygen described in step 2
Volume ratio with aprotic polar solvent is 0.05mol:(80mL~130mL)；
3rd, two anhydride solutions are added in diamine solution, then in nitrogen atmosphere and mixing speed are 300r/min~400r/
Stirring reaction 15h~20h under conditions of min, obtains polyamic acid solution；
The mixture of Bisphenol A Type Diether Dianhydride and the double phthalic anhydrides of 4,4- oxygen in two anhydride solutions described in step 3
Mol ratio with double (3- amino-benzene oxygens) benzene of 1,3- in diamine solution is 1:1；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, placed into vacuum drying chamber, then by vacuum
Drying box with 1 DEG C/min~2 DEG C/min heating rate from room temperature to 70 DEG C~95 DEG C, then temperature be 70 DEG C~95 DEG C
Lower insulation 2h~3h, then it is warming up to 150 DEG C~175 DEG C from 70 DEG C~95 DEG C with 1 DEG C/min~2 DEG C/min heating rate, then
2h~3h is incubated at 150 DEG C~175 DEG C, then is warming up to 1 DEG C/min~2 DEG C/min heating rate from 150 DEG C~175 DEG C
190 DEG C~215 DEG C, then 2h~3h is incubated at 190 DEG C~215 DEG C, then with 1 DEG C/min~2 DEG C/min heating rate from 190
DEG C~215 DEG C be warming up to 230 DEG C~250 DEG C, then 2h~3h be incubated at being 230 DEG C~250 DEG C in temperature, complete hot acid imide
Change, then vacuum drying chamber is naturally 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 temperature be 120 DEG C at dry 3h~4h, the shape memory that can be recycled without
Advise copolyimide.
The good effect that the present invention has：
First, the present invention is used as diamine monomer using double (3- amino-benzene oxygens) benzene of 1,3-, using Bisphenol A Type Diether Dianhydride with
The mixture of the double phthalic anhydrides of 4,4- oxygen prepares the random copolymerization shape memory polyamides that can be recycled as dianhydride monomer
Imines；
2nd, the shape memory random copolymerization polyimides that can be recycled prepared by the present invention has good shape memory
Performance, it can be applied to high-temperature shape-memory field, such as space deployable structure, high temperature driven device, high temperature detector；
3rd, the shape memory random copolymerization polyimides that can be recycled prepared by the present invention has preferable solubility property,
It may be dissolved in aprotic polar solvent DMF, DMA, 1-METHYLPYRROLIDONE solvent,
The shape memory random copolymerization polyimides that can be recycled prepared by the used or damaged present invention is dissolved in non-matter
In sub- polar solvent, the solution that mass fraction is 10%~20% is made into, then impurity is removed with membrane filtration, then by the solution
Again pour on a glass, then heated in vacuum drying oven, to remove organic solvent, the shape that can be recycled can be retrieved
Shape remembers polyimides；
4th, the T of the shape memory random copolymerization polyimides that can be recycled prepared by the present inventiongFor 192 DEG C~208
DEG C, in TgStorage modulus during -20 DEG C of glassy states is 1.72GPa~1.92Gpa, in high temperature TgStorage mould during+20 DEG C of rubbery states
Measure as 4.9MPa~5.3MPa；
5th, the shape memory random copolymerization polyimides that can be recycled prepared by the present invention has good shape note
Recall effect, its shape prescribed rate is 97%~99%, and shape recovery ratio is 96%~99%.
The present invention can obtain a kind of shape memory random copolymerization polyimides that can be recycled.
Brief description of the drawings
Fig. 1 is that the shape memory random copolymerization that can be recycled obtained in embodiment one using hot-imide method is gathered
Imido infrared spectrogram；
Fig. 2 is that the shape memory random copolymerization that can be recycled obtained in embodiment one using hot-imide method is gathered
Imido fissipation factor figure；
Fig. 3 is that the shape memory random copolymerization that can be recycled obtained in embodiment one using hot-imide method is gathered
Imido storage modulus figure；
Fig. 4 is that the shape memory random copolymerization that can be recycled obtained in embodiment one using hot-imide method is gathered
The temporary shapes that acid imide is fixed；
Fig. 5 is that the shape memory random copolymerization that can be recycled obtained in embodiment one using hot-imide method is gathered
State in acid imide recovery of shape；
Fig. 6 is that the shape memory random copolymerization that can be recycled obtained in embodiment one using hot-imide method is gathered
State after acid imide recovery of shape；
After Fig. 7 is the shape memory random copolymerization polyimides that can be recycled dissolving prepared by damaged embodiment one,
Utilize transition condition of the Kapton after alteration of form made from solution casting method；
After Fig. 8 is the shape memory random copolymerization polyimides that can be recycled dissolving prepared by damaged embodiment one,
Utilize state of the Kapton in shape recovery process made from solution casting method；
After Fig. 9 is the shape memory random copolymerization polyimides that can be recycled dissolving prepared by damaged embodiment one,
Utilize state of the Kapton after recovery of shape made from solution casting method.
Embodiment
Embodiment one：Present embodiment be a kind of shape memory random copolymerization polyimides that can be recycled by
The mixture of double (3- amino-benzene oxygens) benzene of 1,3- and Bisphenol A Type Diether Dianhydride and the double phthalic anhydrides of 4,4- oxygen prepare and
Into；The mixing of double (3- amino-benzene oxygens) benzene of described 1,3- and Bisphenol A Type Diether Dianhydride and the double phthalic anhydrides of 4,4- oxygen
The mol ratio of thing is 1:1；Bisphenol A-type in the mixture of the described double phthalic anhydrides of Bisphenol A Type Diether Dianhydride and 4,4- oxygen
The mol ratio of two ether dianhydrides and the double phthalic anhydrides of 4,4- oxygen is A:B, A span are 1≤A≤9, B span
For 1≤B≤9.
The good effect that present embodiment has：
First, present embodiment uses double (3- amino-benzene oxygens) benzene of 1,3- as diamine monomer, using bisphenol A-type diether two
The mixture of acid anhydride and the double phthalic anhydrides of 4,4- oxygen prepares the random copolymerization shape memory that can be recycled as dianhydride monomer
Polyimides；
2nd, the shape memory random copolymerization polyimides that can be recycled prepared by present embodiment has good shape
Memory performance, it can be applied to high-temperature shape-memory field, such as space deployable structure, high temperature driven device, high temperature detector；
3rd, the shape memory random copolymerization polyimides that can be recycled prepared by present embodiment has preferable dissolubility
Can, it may be dissolved in aprotic polar solvent DMF, DMA, 1-METHYLPYRROLIDONE solvent
In, prepared by the used or damaged present invention shape memory random copolymerization polyimides that can be recycled is dissolved in non-
In proton polar solvent, the solution that mass fraction is 10%~20% is made into, then impurity is removed with membrane filtration, it is then that this is molten
Liquid pours on a glass again, then is heated in vacuum drying oven, to remove organic solvent, can retrieve what be can be recycled
Shape memory polyimides；
4th, the T of the shape memory random copolymerization polyimides that can be recycled prepared by present embodimentgFor 192 DEG C~
208 DEG C, in TgStorage modulus during -20 DEG C of glassy states is 1.72GPa~1.92Gpa, in high temperature TgDepositing during+20 DEG C of rubbery states
Storage modulus is 4.9MPa~5.3MPa；
5th, the shape memory random copolymerization polyimides that can be recycled prepared by present embodiment has good shape
Shape memory effect, its shape prescribed rate are 97%~99%, and shape recovery ratio is 96%~99%.
Present embodiment can obtain a kind of shape memory random copolymerization polyimides that can be recycled.
Embodiment two：Present embodiment is a kind of shape memory random copolymerization polyimides that can be recycled
Preparation method is completed according to the following steps：
First, double (3- amino-benzene oxygens) benzene of 1,3- are added in aprotic polar solvent, then in dry nitrogen atmosphere
Lower stirring to double (3- amino-benzene oxygens) benzene of 1,3- are completely dissolved, and obtain diamine solution；
The amount of material and the volume of aprotic polar solvent of double (3- amino-benzene oxygens) benzene of 1,3- described in step 1
Than for 0.05mol:(80mL~130mL)；
2nd, that the mixture of Bisphenol A Type Diether Dianhydride and the double phthalic anhydrides of 4,4- oxygen is dissolved in into aprotonic polar is molten
In agent, two anhydride solutions are obtained；
Bisphenol A-type in the mixture of the double phthalic anhydrides of Bisphenol A Type Diether Dianhydride and 4,4- oxygen described in step 2
The mol ratio of two ether dianhydrides and the double phthalic anhydrides of 4,4- oxygen is A:B, A span are 1≤A≤9, B span
For 1≤B≤9；
The amount of the material of the mixture of the double phthalic anhydrides of Bisphenol A Type Diether Dianhydride and 4,4- oxygen described in step 2
Volume ratio with aprotic polar solvent is 0.05mol:(80mL~130mL)；
3rd, two anhydride solutions are added in diamine solution, then in nitrogen atmosphere and mixing speed are 300r/min~400r/
Stirring reaction 15h~20h under conditions of min, obtains polyamic acid solution；
The mixture of Bisphenol A Type Diether Dianhydride and the double phthalic anhydrides of 4,4- oxygen in two anhydride solutions described in step 3
Mol ratio with double (3- amino-benzene oxygens) benzene of 1,3- in diamine solution is 1:1；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, placed into vacuum drying chamber, then by vacuum
Drying box with 1 DEG C/min~2 DEG C/min heating rate from room temperature to 70 DEG C~95 DEG C, then temperature be 70 DEG C~95 DEG C
Lower insulation 2h~3h, then it is warming up to 150 DEG C~175 DEG C from 70 DEG C~95 DEG C with 1 DEG C/min~2 DEG C/min heating rate, then
2h~3h is incubated at 150 DEG C~175 DEG C, then is warming up to 1 DEG C/min~2 DEG C/min heating rate from 150 DEG C~175 DEG C
190 DEG C~215 DEG C, then 2h~3h is incubated at 190 DEG C~215 DEG C, then with 1 DEG C/min~2 DEG C/min heating rate from 190
DEG C~215 DEG C be warming up to 230 DEG C~250 DEG C, then 2h~3h be incubated at being 230 DEG C~250 DEG C in temperature, complete hot acid imide
Change, then vacuum drying chamber is naturally 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 temperature be 120 DEG C at dry 3h~4h, the shape memory that can be recycled without
Advise copolyimide.
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 and tool
Body embodiment two is identical.
Embodiment four：Present embodiment is with one of embodiment two to three difference：Institute in step 2
The aprotic polar solvent stated is dimethylformamide, dimethyl acetamide or 1-METHYLPYRROLIDONE.Other steps with it is specific
Embodiment two to three is identical.
Embodiment five：Present embodiment is with one of embodiment two to four difference：Described in step 5
The shape memory random copolymerization polyimides that can be recycled thickness be 50 μm~150 μm.Other steps and specific implementation
Mode two to four is identical.
Embodiment six：Present embodiment is with one of embodiment two to five difference：Institute in step 1
The amount of material and the volume ratio of aprotic polar solvent of double (3- amino-benzene oxygens) benzene of 1,3- stated are 0.05mol:100mL.
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 of the mixture of the Bisphenol A Type Diether Dianhydride stated and the double phthalic anhydrides of 4,4- oxygen and aprotic polar solvent
Volume ratio is 0.05mol:100mL.Other steps are 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 incubated 2h from room temperature to 95 DEG C, then at being 95 DEG C in temperature, then with 1 DEG C/min heating rate from
95 DEG C are warming up to 175 DEG C, then 2h are incubated at 175 DEG C, then are warming up to 215 DEG C from 175 DEG C with 1 DEG C/min heating rate, then
2h is incubated at 215 DEG C, then 235 DEG C are warming up to from 215 DEG C with 1 DEG C/min heating rate, then is incubated at being 235 DEG C in temperature
2h, hot-imide is completed, then vacuum drying chamber is naturally cooled to room temperature, obtain the glass plate containing polyimides.Other
Step is identical with embodiment two to seven.
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 incubated 2h from room temperature to 90 DEG C, then at being 90 DEG C in temperature, then with 1 DEG C/min heating rate from
90 DEG C are warming up to 170 DEG C, then 2h are incubated at 170 DEG C, then are warming up to 210 DEG C from 170 DEG C with 2 DEG C/min heating rate, 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 is incubated at being 240 DEG C in temperature
2h, hot-imide is completed, then vacuum drying chamber is naturally cooled to room temperature, obtain the glass plate containing polyimides.Other
Step is identical with embodiment two to eight.
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 1 DEG C/
Min heating rate is incubated 2h from room temperature to 85 DEG C, then at being 85 DEG C in temperature, then with 1 DEG C/min heating rate from
85 DEG C are warming up to 165 DEG C, then 2h are incubated at 165 DEG C, then are warming up to 205 DEG C from 165 DEG C with 1 DEG C/min heating rate, then
2h is incubated at 205 DEG C, then 230 DEG C are warming up to from 205 DEG C with 1 DEG C/min heating rate, then is incubated at being 230 DEG C in temperature
2h, hot-imide is completed, then vacuum drying chamber is naturally cooled to room temperature, obtain the glass plate containing polyimides.Other
Step is identical with embodiment two to nine.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：A kind of preparation method for the shape memory random copolymerization polyimides that can be recycled is by following step
Suddenly complete：
First, 0.05mol 1, double (3- amino-benzene oxygens) benzene of 3- are added in 80mL DMAs, then
Stirring to double (3- amino-benzene oxygens) benzene of 1,3- are completely dissolved under dry nitrogen atmosphere, obtain diamine solution；
2nd, it is the mixture of 0.015mol Bisphenol A Type Diether Dianhydrides and the double phthalic anhydrides of 0.035mol 4,4- oxygen is molten
Solution obtains two anhydride solutions in 85mL DMAs；
3rd, two anhydride solutions are added in diamine solution, then in the condition that nitrogen atmosphere and mixing speed are 400r/min
Lower stirring reaction 16h, obtains polyamic acid solution；
The mixture of Bisphenol A Type Diether Dianhydride and the double phthalic anhydrides of 4,4- oxygen in two anhydride solutions described in step 3
Mol ratio with double (3- amino-benzene oxygens) benzene of 1,3- in diamine solution is 1:1；
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 95 DEG C, then is incubated 2h with 1 DEG C/min heating rate at 95 DEG C, then the heating with 1 DEG C/min
Speed is warming up to 175 DEG C from 95 DEG C, then 2h is incubated at 175 DEG C, then is warming up to 215 from 175 DEG C with 1 DEG C/min heating rate
DEG C, then 2h is incubated at 215 DEG C, then 235 DEG C are warming up to 1 DEG C/min 215 DEG C of heating rate, then 2h is incubated at 235 DEG C,
Hot-imide is completed, then vacuum drying chamber is naturally 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 substrate, reuse steaming
Distilled water rinses polyimides well, then dries 3h at being 120 DEG C in temperature, and the shape memory that can be recycled is randomly common
Poly- polyimides.
The thickness of the shape memory random copolymerization polyimides that can be recycled prepared by embodiment one is 150 μm；
The shape that can be recycled obtained using infrared spectrometer to direct hot-imide method prepared by embodiment one
Shape memory random copolymerization polyimides is tested, as shown in Figure 1；
Fig. 1 is that the shape memory random copolymerization that can be recycled obtained in embodiment one using hot-imide method is gathered
Imido infrared spectrogram；From fig. 1, it can be seen that these characteristic absorption peaks illustrate to obtain using hot-imide method in embodiment one
To the shape memory random copolymerization polyimides that can be recycled be height imidizate polyimides.
It is can be recycled using dynamic mechanical analyzer to what direct hot-imide method prepared by embodiment one obtained
Shape memory random copolymerization polyimides tested, as shown in Figure 2；
Fig. 2 is that the shape memory random copolymerization that can be recycled obtained in embodiment one using hot-imide method is gathered
Imido fissipation factor figure；As can be seen from Figure 2 recyclable made using what hot-imide method obtained in embodiment one
The T of shape memory random copolymerization polyimidesgFor 203 DEG C, direct hot-imide side prepared by embodiment one ensure that
The shape memory random copolymerization polyimides that what method obtained can be recycled can be applied to high-temperature shape-memory field.
It is can be recycled using dynamic mechanical analyzer to what direct hot-imide method prepared by embodiment one obtained
Shape memory random copolymerization polyimides tested, as shown in Figure 3；
Fig. 3 is that the shape memory random copolymerization that can be recycled obtained in embodiment one using hot-imide method is gathered
Imido storage modulus figure；
As can be seen from Figure 3, there are two platforms of high and low temperature section in storage modulus change curve, is utilized in embodiment one
The shape memory random copolymerization polyimides that what hot-imide method obtained can be recycled is in 183 DEG C of (Tg- 20 DEG C) glass
Storage modulus during state is 1.92GPa；In 223 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be 5.2MPa；At two
Storage modulus drastically declines between platform, and corresponding to the Glass Transition of material, the drastically change of this modulus is polymerization
Thing possesses the necessary condition of shape memory property.
The shape that can be recycled obtained using high-temperature stage to direct hot-imide method prepared by embodiment one
Memory random copolymerization polyimides is tested, as shown in Figures 4 to 6.
Fig. 4 is that the shape memory random copolymerization that can be recycled obtained in embodiment one using hot-imide method is gathered
The temporary shapes that acid imide is fixed；
Fig. 5 is that the shape memory random copolymerization that can be recycled obtained in embodiment one using hot-imide method is gathered
State in acid imide recovery of shape；
Fig. 6 is that the shape memory random copolymerization that can be recycled obtained in embodiment one using hot-imide method is gathered
State after acid imide recovery of shape.
It was found from Fig. 4 to Fig. 6, the shape memory that can be recycled that is obtained in embodiment one using hot-imide method
Random copolymerization polyimides has good SME, and its shape prescribed rate is 99%, shape recovery ratio 98%.
The shape memory random copolymerization polyimides that can be recycled prepared by the embodiment one of breakage is dissolved into N, N-
In dimethyl acetamide, it is randomly common to obtain the shape memory that can be recycled prepared by the embodiment one that mass fraction is 13.8%
Poly- polyimide solution, the shape memory random copolymerization that can be recycled prepared by the embodiment one that mass fraction is 13.8%
Polyimide 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 95 DEG C, then 2h is incubated at 95 DEG C, then is risen with 1 DEG C/min heating rate from 95 DEG C
Temperature is incubated 1h to 175 DEG C so that the volatilization of organic solvent DMA is clean.Then glass plate is placed in distilled water
In, polyimides is come off from substrate, dry, be utilized shape memory polyimides made from solution casting method.
The shape memory random copolymerization that can be recycled that embodiment one is prepared using hot-imide method is gathered
After acid imide use, it is redissolved in DMA, the Kapton tool for recycling solution casting method to obtain
There is the SME as the shape memory random copolymerization polyimides that can be recycled prepared with embodiment one.
After Fig. 7 is the shape memory random copolymerization polyimides that can be recycled dissolving prepared by damaged embodiment one,
Utilize transition condition of the Kapton after alteration of form made from solution casting method；
After Fig. 8 is the shape memory random copolymerization polyimides that can be recycled dissolving prepared by damaged embodiment one,
Utilize state of the Kapton in shape recovery process made from solution casting method；
After Fig. 9 is the shape memory random copolymerization polyimides that can be recycled dissolving prepared by damaged embodiment one,
Utilize state of the Kapton after recovery of shape made from solution casting method；
It was found from Fig. 7~Fig. 9, the shape memory random copolymerization polyamides that can be recycled prepared by damaged embodiment one is sub-
Upon dissolution, the Kapton obtained using solution casting method still has good SME to amine, therefore,
The shape memory random copolymerization polyimides that can be recycled prepared by embodiment one is a kind of shape memory that can be recycled
Polyimides.
Embodiment two：A kind of preparation method for the shape memory random copolymerization polyimides that can be recycled is by following step
Suddenly complete：
First, 0.05mol 1, double (3- amino-benzene oxygens) benzene of 3- are added in 80mL DMAs, then
Stirring to double (3- amino-benzene oxygens) benzene of 1,3- are completely dissolved under dry nitrogen atmosphere, obtain diamine solution；
2nd, the mixture of 0.04mol Bisphenol A Type Diether Dianhydrides and the double phthalic anhydrides of 0.01mol 4,4- oxygen is dissolved
In 80mL DMAs, two anhydride solutions are obtained；
3rd, two anhydride solutions are added in diamine solution, then in the condition that nitrogen atmosphere and mixing speed are 400r/min
Lower stirring reaction 15h, obtains polyamic acid solution；
The mixture of Bisphenol A Type Diether Dianhydride and the double phthalic anhydrides of 4,4- oxygen in two anhydride solutions described in step 3
Mol ratio with double (3- amino-benzene oxygens) benzene of 1,3- in diamine solution is 1:1；
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 210 from 170 DEG C with 2 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
2h, hot-imide is completed, then vacuum drying chamber is naturally 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 120 DEG C in temperature, and the shape memory that can be recycled is randomly common
Poly- polyimides.
The thickness of the shape memory random copolymerization polyimides that can be recycled prepared by embodiment two is 150 μm.
The T of the shape memory random copolymerization polyimides that can be recycled prepared by embodiment twogFor 192 DEG C, ensure that
Its SME can be applied to high-temperature shape-memory field；It is in 172 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be
1.85GPa；212 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be 4.9MPa.Prepared by embodiment two can be recycled
The sub- shape fixed rate of shape memory random copolymerization polyamides be 99%, shape recovery ratio 99%.
Embodiment three：A kind of preparation method for the shape memory random copolymerization polyimides that can be recycled is by following step
Suddenly complete：
First, 0.05mol 1, double (3- amino-benzene oxygens) benzene of 3- are added in 80mL 1-METHYLPYRROLIDONEs, then dry
Stirring to double (3- amino-benzene oxygens) benzene of 1,3- are completely dissolved under dry nitrogen atmosphere, obtain diamine solution；
2nd, it is the mixture of 0.035mol Bisphenol A Type Diether Dianhydrides and the double phthalic anhydrides of 0.015mol 4,4- oxygen is molten
Solution obtains two anhydride solutions in 90mL 1-METHYLPYRROLIDONEs；
3rd, two anhydride solutions are added in diamine solution, then in the condition that nitrogen atmosphere and mixing speed are 400r/min
Lower stirring reaction 15h, obtains polyamic acid solution；
The mixture of Bisphenol A Type Diether Dianhydride and the double phthalic anhydrides of 4,4- oxygen in two anhydride solutions described in step 3
Mol ratio with double (3- amino-benzene oxygens) benzene of 1,3- in diamine solution is 1:1；
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 85 DEG C, then is incubated 2h with 1 DEG C/min heating rate at 85 DEG C, then the heating with 1 DEG C/min
Speed is warming up to 165 DEG C from 85 DEG C, then 2h is incubated at 165 DEG C, then is warming up to 205 from 165 DEG C with 1 DEG C/min heating rate
DEG C, then 2h is incubated at 205 DEG C, then 230 DEG C are warming up to from 205 DEG C with 1 DEG C/min heating rate, then in temperature be 230 DEG C
Lower insulation 2h, hot-imide is completed, then vacuum drying chamber is naturally cooled to room temperature, obtain the glass containing polyimides
Plate；
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 120 DEG C in temperature, and the shape memory that can be recycled is randomly common
Poly- polyimides.
The thickness of the shape memory random copolymerization polyimides that can be recycled prepared by embodiment three is 50 μm~150 μ
m；
The T of the shape memory random copolymerization polyimides that can be recycled prepared by embodiment threegFor 195 DEG C, ensure that
Its SME can be applied to high-temperature shape-memory field.It is in 175 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be
1.80GPa；215 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be 5.1MPa.Prepared by embodiment three can be recycled
Shape memory random copolymerization polyimides shape fixed rate be 98%, shape recovery ratio 99%.
Example IV：A kind of preparation method for the shape memory random copolymerization polyimides that can be recycled, is by following
What step was completed：
First, 0.05mol 1, double (3- amino-benzene oxygens) benzene of 3- are added in 80mL 1-METHYLPYRROLIDONEs, then dry
Stirring to double (3- amino-benzene oxygens) benzene of 1,3- are completely dissolved under dry nitrogen atmosphere, obtain diamine solution；
2nd, the mixture of 0.03mol Bisphenol A Type Diether Dianhydrides and the double phthalic anhydrides of 0.02mol 4,4- oxygen is dissolved
In 100mL 1-METHYLPYRROLIDONEs, two anhydride solutions are obtained；
3rd, two anhydride solutions are added in diamine solution, then in the condition that nitrogen atmosphere and mixing speed are 400r/min
Lower stirring reaction 19h, obtains polyamic acid solution；
The mixture of Bisphenol A Type Diether Dianhydride and the double phthalic anhydrides of 4,4- oxygen in two anhydride solutions described in step 3
Mol ratio with double (3- amino-benzene oxygens) benzene of 1,3- in diamine solution is 1:1；
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 165 DEG C from 90 DEG C, then 2h is incubated at 165 DEG C, then 1 DEG C/min heating rate is warming up to 210 from 165 DEG C
DEG C, then 2h is incubated at 210 DEG C, then 250 DEG C are warming up to from 210 DEG C with 2 DEG C/min heating rate, then be incubated at 250 DEG C
2h, hot-imide is completed, then vacuum drying chamber is naturally 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 120 DEG C in temperature, and the shape memory that can be recycled is randomly common
Poly- polyimides.
The thickness of the shape memory random copolymerization polyimides that can be recycled prepared by example IV is 150 μm.
The T of the shape memory random copolymerization polyimides that can be recycled prepared by example IVgFor 198 DEG C, ensure that
Its SME can be applied to high-temperature shape-memory field；It is in 178 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be
1.82GPa；218 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be 5.6MPa.Prepared by example IV can be recycled
Shape memory random copolymerization polyimides shape fixed rate be 99%, shape recovery ratio 97%.
Embodiment five：A kind of preparation method for the shape memory random copolymerization polyimides that can be recycled is by following step
Suddenly complete：
First, 0.05mol 1, double (3- amino-benzene oxygens) benzene of 3- are added in 80mL 1-METHYLPYRROLIDONEs, then dry
Stirring to double (3- amino-benzene oxygens) benzene of 1,3- are completely dissolved under dry nitrogen atmosphere, obtain diamine solution；
2nd, the mixture of 0.02mol Bisphenol A Type Diether Dianhydrides and the double phthalic anhydrides of 0.03mol 4,4- oxygen is dissolved
In 100mL 1-METHYLPYRROLIDONEs, two anhydride solutions are obtained；
3rd, two anhydride solutions are added in diamine solution, then in the condition that nitrogen atmosphere and mixing speed are 400r/min
Lower stirring reaction 17h, obtains polyamic acid solution；
The mixture of Bisphenol A Type Diether Dianhydride and the double phthalic anhydrides of 4,4- oxygen in two anhydride solutions described in step 3
Mol ratio with double (3- amino-benzene oxygens) benzene of 1,3- in diamine solution is 1:1；
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 1 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 200 from 160 DEG C with 2 DEG C/min heating rate
DEG C, then 2h is incubated at 200 DEG C, then 240 DEG C are warming up to from 200 DEG C with 2 DEG C/min heating rate, then be incubated at 240 DEG C
2h, hot-imide is completed, then vacuum drying chamber is naturally 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 120 DEG C in temperature, and the shape memory that can be recycled is randomly common
Poly- polyimides.
The thickness of the shape memory random copolymerization polyimides that can be recycled prepared by embodiment five is 50 μm~150 μ
m；
The T of the shape memory random copolymerization polyimides that can be recycled prepared by embodiment fivegFor 201 DEG C, ensure that
Its SME can be applied to high-temperature shape-memory field；It is in 181 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be
1.78GPa；221 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be 5.7MPa.Prepared by embodiment five can be recycled
Shape memory random copolymerization polyimides shape fixed rate be 97%, shape recovery ratio 96%.
Embodiment six：A kind of preparation method for the shape memory random copolymerization polyimides that can be recycled is by following step
Suddenly complete：
First, 0.05mol 1, double (3- amino-benzene oxygens) benzene of 3- are added in 80mL 1-METHYLPYRROLIDONEs, then dry
Stirring to double (3- amino-benzene oxygens) benzene of 1,3- are completely dissolved under dry nitrogen atmosphere, obtain diamine solution；
2nd, the mixture of 0.01mol Bisphenol A Type Diether Dianhydrides and the double phthalic anhydrides of 0.04mol 4,4- oxygen is dissolved
In 112mL 1-METHYLPYRROLIDONEs, two anhydride solutions are obtained；
3rd, two anhydride solutions are added in diamine solution, then in the condition that nitrogen atmosphere and mixing speed are 400r/min
Lower stirring reaction 20h, obtains polyamic acid solution；
The mixture of Bisphenol A Type Diether Dianhydride and the double phthalic anhydrides of 4,4- oxygen in two anhydride solutions described in step 3
Mol ratio with double (3- amino-benzene oxygens) benzene of 1,3- in diamine solution is 1:1；
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 being 90 DEG C in temperature, then with 2 DEG C/min
Heating rate be 90 DEG C from temperature and be warming up to 160 DEG C, then 2h is incubated at being 160 DEG C in temperature, then the heating speed with 2 DEG C/min
Rate is warming up to 200 DEG C from 160 DEG C, then is incubated 2h at being 200 DEG C in temperature, then is heated up with 2 DEG C/min heating rate from 200 DEG C
To 250 DEG C, then 2h is incubated at being 250 DEG C in temperature, completes hot-imide, then vacuum drying chamber is naturally 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 120 DEG C in temperature, and the shape memory that can be recycled is randomly common
Poly- polyimides.
The thickness of the shape memory random copolymerization polyimides that can be recycled prepared by embodiment six is 150 μm.
The T of the shape memory random copolymerization polyimides that can be recycled prepared by embodiment sixgFor 208 DEG C, ensure that
Its SME can be applied to high-temperature shape-memory field；It is in 188 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be
1.72GPa；228 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be 5.3MPa.Prepared by embodiment six can be recycled
Shape memory random copolymerization polyimides shape fixed rate be 99%, shape recovery ratio 98%.
Claims (6)
- A kind of a kind of 1. shape memory random copolymerization polyimides that can be recycled, it is characterised in that shape that can be recycled The preparation method of memory random copolymerization polyimides is completed according to the following steps：First, by 1,3- double (3- amino-benzene oxygens), benzene is added in aprotic polar solvent, then is stirred under dry nitrogen atmosphere Mix to double (3- amino-benzene oxygens) benzene of 1,3- and be completely dissolved, obtain diamine 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 material and the volume ratio of aprotic polar solvent of double (3- amino-benzene oxygens) benzene of 1,3- described in step 1 be 0.05mol:(80mL~130mL)；2nd, Bisphenol A Type Diether Dianhydride and 4, the mixture of the double phthalic anhydrides of 4- oxygen are dissolved in aprotic polar solvent, Obtain two anhydride solutions；Aprotic polar solvent described in step 2 is dimethylformamide, dimethyl acetamide or 1-METHYLPYRROLIDONE；Bisphenol A-type diether in the mixture of the double phthalic anhydrides of Bisphenol A Type Diether Dianhydride and 4,4- oxygen described in step 2 The mol ratio of dianhydride and the double phthalic anhydrides of 4,4- oxygen is A:B, A span are 1≤A≤9, B span for 1≤ B≤9；The amount of the material of the mixture of Bisphenol A Type Diether Dianhydride described in step 2 and the double phthalic anhydrides of 4,4- oxygen with it is non- The volume ratio of proton polar solvent is 0.05mol:(80mL~130mL)；3rd, two anhydride solutions are added in diamine solution, then in nitrogen atmosphere and mixing speed are 300r/min~400r/min Under conditions of stirring reaction 15h~20h, obtain polyamic acid solution；The mixture and two of Bisphenol A Type Diether Dianhydride and the double phthalic anhydrides of 4,4- oxygen in two anhydride solutions described in step 3 The mol ratio of double (3- amino-benzene oxygens) benzene of 1,3- is 1 in amine aqueous solution: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~95 DEG C, then temperature be 70 DEG C~95 DEG C at protect Warm 2h~3h, then 150 DEG C~175 DEG C are warming up to from 70 DEG C~95 DEG C with 1 DEG C/min~2 DEG C/min heating rate, then 150 DEG C~175 DEG C at be incubated 2h~3h, then be warming up to 190 DEG C from 150 DEG C~175 DEG C with 1 DEG C/min~2 DEG C/min heating rate ~215 DEG C, then at 190 DEG C~215 DEG C be incubated 2h~3h, then with 1 DEG C/min~2 DEG C/min heating rate from 190 DEG C~ 215 DEG C are warming up to 230 DEG C~250 DEG C, then are incubated 2h~3h at being 230 DEG C~250 DEG C in temperature, complete hot-imide, then Vacuum drying chamber is naturally 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 distilled water Polyimides is rinsed well, then 3h~4h is dried at being 120 DEG C in temperature, the shape memory that can be recycled is randomly common Poly- polyimides；The thickness of the shape memory random copolymerization polyimides that can be recycled described in step 5 is 50 μm~150 μm.
- 2. a kind of preparation method of shape memory random copolymerization polyimides that can be recycled according to claim 1, It is characterized in that the amount of material and the body of aprotic polar solvent of double (3- amino-benzene oxygens) benzene of 1,3- described in step 1 Product ratio is 0.05mol:80mL.
- 3. a kind of preparation method of shape memory random copolymerization polyimides that can be recycled according to claim 1, It is characterized in that the material of the mixture of Bisphenol A Type Diether Dianhydride described in step 2 and the double phthalic anhydrides of 4,4- oxygen Amount and the volume ratio of aprotic polar solvent are 0.05mol:85mL.
- 4. a kind of preparation method of shape memory random copolymerization polyimides that can be recycled according to claim 1, It is characterized in that polyamic acid solution is coated uniformly on the glass plate of cleaning in step 4, place into vacuum drying chamber, Again by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 95 DEG C, then be incubated 2h at being 95 DEG C in temperature, then with 1 DEG C/min heating rate is warming up to 175 DEG C from 95 DEG C, then 2h is incubated at 175 DEG C, then with 1 DEG C/min heating rate from 175 DEG C are warming up to 215 DEG C, then 2h are incubated at 215 DEG C, then are warming up to 235 DEG C from 215 DEG C with 1 DEG C/min heating rate, then 2h is incubated at being 235 DEG C in temperature, completes hot-imide, then vacuum drying chamber is naturally cooled to room temperature, is obtained containing poly- Imido glass plate.
- 5. a kind of preparation method of shape memory random copolymerization polyimides that can be recycled according to claim 1, It is characterized in that polyamic acid solution is coated uniformly on the glass plate of cleaning in step 4, place into vacuum drying chamber, Again by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 90 DEG C, then be incubated 2h at being 90 DEG C in temperature, then with 1 DEG C/min heating rate is warming up to 170 DEG C from 90 DEG C, then 2h is incubated at 170 DEG C, then with 2 DEG C/min heating rate from 170 DEG C are warming up to 210 DEG C, then 2h are incubated at 210 DEG C, then are warming up to 240 DEG C from 210 DEG C with 2 DEG C/min heating rate, then 2h is incubated at being 240 DEG C in temperature, completes hot-imide, then vacuum drying chamber is naturally cooled to room temperature, is obtained containing poly- Imido glass plate.
- 6. a kind of preparation method of shape memory random copolymerization polyimides that can be recycled according to claim 1, It is characterized in that polyamic acid solution is coated uniformly on the glass plate of cleaning in step 4, place into vacuum drying chamber, Again by vacuum drying chamber with 1 DEG C/min heating rate from room temperature to 85 DEG C, then be incubated 2h at being 85 DEG C in temperature, then with 1 DEG C/min heating rate is warming up to 165 DEG C from 85 DEG C, then 2h is incubated at 165 DEG C, then with 1 DEG C/min heating rate from 165 DEG C are warming up to 205 DEG C, then 2h are incubated at 205 DEG C, then are warming up to 230 DEG C from 205 DEG C with 1 DEG C/min heating rate, then 2h is incubated at being 230 DEG C in temperature, completes hot-imide, then vacuum drying chamber is naturally cooled to room temperature, is obtained containing poly- Imido glass plate.
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