CN105418922A - Shape memory random-copolymerized polyimide capable of being circularly used and preparation method thereof - Google Patents
Shape memory random-copolymerized polyimide capable of being circularly used and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a shape memory random-copolymerized polyimide capable of being circularly used and a preparation method thereof, relates to polyimide and a preparation method thereof, and aims to solve the problems that in the prior art, the preparation cost of shape memory polyimide is high, and the prepared shape memory polyimide cannot be repeatedly used. The provided polyimide is prepared from a mixture of 1,3-bis(3-aminophenoxyl)benzene, 4,4'-(4,4'-isopropylidenediphenoxy)bis(phthalic anhydride), and 4,4'-oxydiphthalic anhydride. The preparation method comprises the following steps: step one, preparing a diamine solution; step two, preparing a dianhydride solution; step three, preparing a polyamide acid solution; step four, carrying out thermal imidization to obtain a glass plate containing polyimide; step five, cleaning and drying to obtain the shape memory random-copolymerized polyimide capable of being circularly used. The provided method can obtain shape memory random-copolymerized polyimide capable of being circularly used.
Description
Technical field
The present invention relates to a kind of polyimide and preparation method thereof.
Background technology
Shape-memory polymer (shapememorypolymers, SMP) is that a class can remember temporary shapes, can recover the intelligent macromolecule material of original shape under external stimulus.Relative to memory shape metal alloy, the reversible strain of SMP is large, density is low, handling ease and recovery of shape temperature are convenient to the advantages such as control, obtains application in fields such as biologic medical, Intelligent prevention and cure, deployable structure, drive assemblies.Polyimide (PI) has the advantages such as thermostability is high, mechanical property is excellent, the variation of processing approach, has been widely used in the fields such as automobile, microelectronics, photoelectricity, aerospace.Shape memory polyimide also has significant application value in deployable space structures, variable flying device aileron, pyrostat and driving mechanism etc.
Shape memory polyimide cost is higher, and the shape memory polyimide that therefore can be recycled has very high using value to practical application, can save a large amount of funds.There is no the report of the shape memory polyimide that can be recycled at present.
Summary of the invention
The shape memory polyimide cost that the object of the invention is to solve existing preparation is high, the problem that the shape memory polyimide of preparation can not recycle, and provides a kind of shape memory random copolymerization polyimide that can be recycled and preparation method thereof.
A kind of shape memory random copolymerization polyimide that can be recycled is prepared from by the mixture of two (3-amino-benzene oxygen) benzene of 1,3-and Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen; The mol ratio of the mixture of described 1,3-two (3-amino-benzene oxygen) benzene and Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen is 1:1; In the mixture of described Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen, the mol ratio of Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen is the span of A:B, A is 1≤A≤9, and the span of B is 1≤B≤9.
A kind of preparation method of the shape memory random copolymerization polyimide that can be recycled completes according to the following steps:
One, two for 1,3-(3-amino-benzene oxygen) benzene is joined in aprotic polar solvent, then be stirred to two (3-amino-benzene oxygen) benzene of 1,3-under dry nitrogen atmosphere and dissolve completely, obtain two amine aqueous solutions;
The two amount of substance of (3-amino-benzene oxygen) benzene of described in step one 1,3-and the volume ratio of aprotic polar solvent are 0.05mol:(80mL ~ 130mL);
Two, the mixture of Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen is dissolved in aprotic polar solvent, obtains two anhydride solutions;
In the mixture of the Bisphenol A Type Diether Dianhydride described in step 2 and the two Tetra hydro Phthalic anhydride of 4,4-oxygen, the mol ratio of Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen is the span of A:B, A is 1≤A≤9, and the span of B is 1≤B≤9;
The amount of substance of mixture and the volume ratio of aprotic polar solvent of the Bisphenol A Type Diether Dianhydride described in step 2 and the two Tetra hydro Phthalic anhydride of 4,4-oxygen are 0.05mol:(80mL ~ 130mL);
Three, two anhydride solutions are joined in two amine aqueous solutions, then under nitrogen atmosphere and stirring velocity are the condition of 300r/min ~ 400r/min stirring reaction 15h ~ 20h, obtain polyamic acid solution;
In two anhydride solutions described in step 3, the mixture of the two Tetra hydro Phthalic anhydride of Bisphenol A Type Diether Dianhydride and 4,4-oxygen is 1:1 with the mol ratio of 1,3-pair of (3-amino-benzene oxygen) benzene in two amine aqueous solutions;
Four, polyamic acid solution is evenly coated on clean sheet glass, put into vacuum drying oven again, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from room temperature to 70 DEG C ~ 95 DEG C, 2h ~ 3h is incubated again at temperature is 70 DEG C ~ 95 DEG C, 150 DEG C ~ 175 DEG C are warming up to from 70 DEG C ~ 95 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 150 DEG C ~ 175 DEG C, 190 DEG C ~ 215 DEG C are warming up to from 150 DEG C ~ 175 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 190 DEG C ~ 215 DEG C, 230 DEG C ~ 250 DEG C are warming up to from 190 DEG C ~ 215 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at temperature is 230 DEG C ~ 250 DEG C, complete hot-imide, vacuum drying oven is made to naturally cool to room temperature again, obtain the sheet glass containing polyimide,
Five, the sheet glass containing polyimide is placed in distilled water, polyimide is come off from substrate, re-use distilled water polyimide is rinsed well, then at temperature is 120 DEG C dry 3h ~ 4h, obtain the shape memory random copolymerization polyimide that can be recycled.
The positively effect that the present invention has:
One, the present invention adopts 1, two (3-amino-benzene oxygen) benzene of 3-is as diamine monomer, adopt the mixture of Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen as dianhydride monomer, prepare the random copolymerization shape memory polyimide that can be recycled;
The shape memory random copolymerization polyimide that what two, prepared by the present invention can be recycled has good shape-memory properties, can be applicable to high-temperature shape-memory field, as space deployable structure, high temperature driven device, high temperature detector etc.;
Three, the shape memory random copolymerization polyimide that prepared by the present invention can be recycled has good solubility property, may be dissolved in aprotic polar solvent N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, in N-Methyl pyrrolidone solvent, by with cross or prepared by the present invention of the breakage shape memory random copolymerization polyimide that can be recycled be dissolved in aprotic polar solvent, be made into the solution that massfraction is 10% ~ 20%, impurity is removed again with membrane filtration, then this solution is cast on sheet glass again, heat in vacuum drying oven again, to remove organic solvent, again the shape memory polyimide that can be recycled can be obtained,
The T of the shape memory random copolymerization polyimide that what four, prepared by the present invention can be recycled
git is 192 DEG C ~ 208 DEG C, at T
gstorage modulus during-20 DEG C of vitreous states is 1.72GPa ~ 1.92Gpa, at high temperature T
gstorage modulus during+20 DEG C of rubbery states is 4.9MPa ~ 5.3MPa;
The shape memory random copolymerization polyimide that what five, prepared by the present invention can be recycled there is good shape memory 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 polyimide that can be recycled.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of the shape memory random copolymerization polyimide that can be recycled utilizing hot-imide method to obtain in embodiment one;
Fig. 2 is the dissipation factor figure of the shape memory random copolymerization polyimide that can be recycled utilizing hot-imide method to obtain in embodiment one;
Fig. 3 is the storage modulus figure of the shape memory random copolymerization polyimide that can be recycled utilizing hot-imide method to obtain in embodiment one;
Fig. 4 is the temporary shapes that the shape memory random copolymerization polyimide that can be recycled utilizing hot-imide method to obtain in embodiment one is fixed;
Fig. 5 is the state in the shape memory random copolymerization polyimide recovery of shape that can be recycled utilizing hot-imide method to obtain in embodiment one;
Fig. 6 is the state after the shape memory random copolymerization polyimide recovery of shape that can be recycled utilizing hot-imide method to obtain in embodiment one;
Fig. 7 is after the shape memory random copolymerization polyimide that can be recycled of embodiment one preparation of breakage dissolves, the momentary state of Kapton after alteration of form utilizing solution casting method to obtain;
Fig. 8 is after the shape memory random copolymerization polyimide that can be recycled of embodiment one preparation of breakage dissolves, the state of Kapton in shape recovery process utilizing solution casting method to obtain;
Fig. 9 is after the shape memory random copolymerization polyimide that can be recycled of embodiment one preparation of breakage dissolves, the state of Kapton after recovery of shape utilizing solution casting method to obtain.
Embodiment
Embodiment one: present embodiment is that a kind of shape memory random copolymerization polyimide that can be recycled is prepared from by the mixture of two (3-amino-benzene oxygen) benzene of 1,3-and Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen; The mol ratio of the mixture of described 1,3-two (3-amino-benzene oxygen) benzene and Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen is 1:1; In the mixture of described Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen, the mol ratio of Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen is the span of A:B, A is 1≤A≤9, and the span of B is 1≤B≤9.
The positively effect that present embodiment has:
One, present embodiment adopts 1, two (3-amino-benzene oxygen) benzene of 3-is as diamine monomer, adopt the mixture of Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen as dianhydride monomer, prepare the random copolymerization shape memory polyimide that can be recycled;
The shape memory random copolymerization polyimide that what two, prepared by present embodiment can be recycled has good shape-memory properties, can be applicable to high-temperature shape-memory field, as space deployable structure, high temperature driven device, high temperature detector etc.;
Three, the shape memory random copolymerization polyimide that prepared by present embodiment can be recycled has good solubility property, may be dissolved in aprotic polar solvent N, dinethylformamide, N, N-N,N-DIMETHYLACETAMIDE, in N-Methyl pyrrolidone solvent, by with cross or prepared by the present invention of the breakage shape memory random copolymerization polyimide that can be recycled be dissolved in aprotic polar solvent, be made into the solution that massfraction is 10% ~ 20%, impurity is removed again with membrane filtration, then this solution is cast on sheet glass again, heat in vacuum drying oven again, to remove organic solvent, again the shape memory polyimide that can be recycled can be obtained,
The T of the shape memory random copolymerization polyimide that what four, prepared by present embodiment can be recycled
git is 192 DEG C ~ 208 DEG C, at T
gstorage modulus during-20 DEG C of vitreous states is 1.72GPa ~ 1.92Gpa, at high temperature T
gstorage modulus during+20 DEG C of rubbery states is 4.9MPa ~ 5.3MPa;
The shape memory random copolymerization polyimide that what five, prepared by present embodiment can be recycled there is good shape memory effect, its shape prescribed rate is 97% ~ 99%, and shape recovery ratio is 96% ~ 99%.
Present embodiment can obtain a kind of shape memory random copolymerization polyimide that can be recycled.
Embodiment two: present embodiment is that a kind of preparation method of the shape memory random copolymerization polyimide that can be recycled completes according to the following steps:
One, two for 1,3-(3-amino-benzene oxygen) benzene is joined in aprotic polar solvent, then be stirred to two (3-amino-benzene oxygen) benzene of 1,3-under dry nitrogen atmosphere and dissolve completely, obtain two amine aqueous solutions;
The two amount of substance of (3-amino-benzene oxygen) benzene of described in step one 1,3-and the volume ratio of aprotic polar solvent are 0.05mol:(80mL ~ 130mL);
Two, the mixture of Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen is dissolved in aprotic polar solvent, obtains two anhydride solutions;
In the mixture of the Bisphenol A Type Diether Dianhydride described in step 2 and the two Tetra hydro Phthalic anhydride of 4,4-oxygen, the mol ratio of Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen is the span of A:B, A is 1≤A≤9, and the span of B is 1≤B≤9;
The amount of substance of mixture and the volume ratio of aprotic polar solvent of the Bisphenol A Type Diether Dianhydride described in step 2 and the two Tetra hydro Phthalic anhydride of 4,4-oxygen are 0.05mol:(80mL ~ 130mL);
Three, two anhydride solutions are joined in two amine aqueous solutions, then under nitrogen atmosphere and stirring velocity are the condition of 300r/min ~ 400r/min stirring reaction 15h ~ 20h, obtain polyamic acid solution;
In two anhydride solutions described in step 3, the mixture of the two Tetra hydro Phthalic anhydride of Bisphenol A Type Diether Dianhydride and 4,4-oxygen is 1:1 with the mol ratio of 1,3-pair of (3-amino-benzene oxygen) benzene in two amine aqueous solutions;
Four, polyamic acid solution is evenly coated on clean sheet glass, put into vacuum drying oven again, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from room temperature to 70 DEG C ~ 95 DEG C, 2h ~ 3h is incubated again at temperature is 70 DEG C ~ 95 DEG C, 150 DEG C ~ 175 DEG C are warming up to from 70 DEG C ~ 95 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 150 DEG C ~ 175 DEG C, 190 DEG C ~ 215 DEG C are warming up to from 150 DEG C ~ 175 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 190 DEG C ~ 215 DEG C, 230 DEG C ~ 250 DEG C are warming up to from 190 DEG C ~ 215 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at temperature is 230 DEG C ~ 250 DEG C, complete hot-imide, vacuum drying oven is made to naturally cool to room temperature again, obtain the sheet glass containing polyimide,
Five, the sheet glass containing polyimide is placed in distilled water, polyimide is come off from substrate, re-use distilled water polyimide is rinsed well, then at temperature is 120 DEG C dry 3h ~ 4h, obtain the shape memory random copolymerization polyimide that can be recycled.
Embodiment three: the difference of present embodiment and embodiment two is: the aprotic polar solvent described in step one is DMF, N,N-dimethylacetamide or N-Methyl pyrrolidone.Other steps are identical with embodiment two.
Embodiment four: one of present embodiment and embodiment two to three difference is: the aprotic polar solvent described in step 2 is dimethyl formamide, N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone.Other steps are identical with embodiment two to three.
Embodiment five: one of present embodiment and embodiment two to four difference is: the thickness of the shape memory random copolymerization polyimide that can be recycled described in step 5 is 50 μm ~ 150 μm.Other steps are identical with embodiment two to four.
Embodiment six: one of present embodiment and embodiment two to five difference is: the two amount of substance of (3-amino-benzene oxygen) benzene of 1,3-described in step one and the volume ratio of aprotic polar solvent are 0.05mol:100mL.Other steps are identical with embodiment two to five.
Embodiment seven: one of present embodiment and embodiment two to six difference is: the amount of substance of mixture and the volume ratio of aprotic polar solvent of the Bisphenol A Type Diether Dianhydride described in step 2 and the two Tetra hydro Phthalic anhydride of 4,4-oxygen are 0.05mol:100mL.Other steps are identical with embodiment two to six.
Embodiment eight: one of present embodiment and embodiment two to seven difference is: in step 4, polyamic acid solution is evenly coated on clean sheet glass, put into vacuum drying oven again, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 95 DEG C, 2h is incubated again at temperature is 95 DEG C, 175 DEG C are warming up to from 95 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 175 DEG C, 215 DEG C are warming up to from 175 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 215 DEG C, 235 DEG C are warming up to from 215 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at temperature is 235 DEG C, complete hot-imide, vacuum drying oven is made to naturally cool to room temperature again, obtain the sheet glass containing polyimide.Other steps are identical with embodiment two to seven.
Embodiment nine: one of present embodiment and embodiment two to eight difference is: in step 4, polyamic acid solution is evenly coated on clean sheet glass, put into vacuum drying oven again, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 90 DEG C, 2h is incubated again at temperature is 90 DEG C, 170 DEG C are warming up to from 90 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 170 DEG C, 210 DEG C are warming up to from 170 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 210 DEG C, 240 DEG C are warming up to from 210 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at temperature is 240 DEG C, complete hot-imide, vacuum drying oven is made to naturally cool to room temperature again, obtain the sheet glass containing polyimide.Other steps are identical with embodiment two to eight.
Embodiment ten: one of present embodiment and embodiment two to nine difference is: in step 4, polyamic acid solution is evenly coated on clean sheet glass, put into vacuum drying oven again, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 85 DEG C, 2h is incubated again at temperature is 85 DEG C, 165 DEG C are warming up to from 85 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 165 DEG C, 205 DEG C are warming up to from 165 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 205 DEG C, 230 DEG C are warming up to from 205 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at temperature is 230 DEG C, complete hot-imide, vacuum drying oven is made to naturally cool to room temperature again, obtain the sheet glass containing polyimide.Other steps are identical with embodiment two to nine.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment one: a kind of preparation method of the shape memory random copolymerization polyimide that can be recycled completes according to the following steps:
One, two to 0.05mol1,3-(3-amino-benzene oxygen) benzene is joined 80mLN, in N-N,N-DIMETHYLACETAMIDE, then be stirred to two (3-amino-benzene oxygen) benzene of 1,3-under dry nitrogen atmosphere and dissolve completely, obtain two amine aqueous solutions;
Two, the mixture of 0.015mol Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 0.035mol4,4-oxygen is dissolved in 85mLN, in N-N,N-DIMETHYLACETAMIDE, obtains two anhydride solutions;
Three, two anhydride solutions are joined in two amine aqueous solutions, then under nitrogen atmosphere and stirring velocity are the condition of 400r/min stirring reaction 16h, obtain polyamic acid solution;
In two anhydride solutions described in step 3, the mixture of the two Tetra hydro Phthalic anhydride of Bisphenol A Type Diether Dianhydride and 4,4-oxygen is 1:1 with the mol ratio of 1,3-pair of (3-amino-benzene oxygen) benzene in two amine aqueous solutions;
Four, polyamic acid solution is evenly coated on clean sheet glass, put into vacuum drying oven again, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 95 DEG C, 2h is incubated again at 95 DEG C, 175 DEG C are warming up to from 95 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 175 DEG C, 215 DEG C are warming up to from 175 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 215 DEG C, 235 DEG C are warming up to again with the temperature rise rate 215 DEG C of 1 DEG C/min, 2h is incubated again at 235 DEG C, complete hot-imide, vacuum drying oven is made to naturally cool to room temperature again, obtain the sheet glass containing polyimide,
Five, the sheet glass containing polyimide is placed in distilled water, polyimide is come off from substrate, re-use distilled water and polyimide is rinsed well, then at temperature is 120 DEG C dry 3h, obtain the shape memory random copolymerization polyimide that can be recycled.
The thickness of the shape memory random copolymerization polyimide that can be recycled prepared by embodiment one is 150 μm;
Infrared spectrometer is used to test the shape memory random copolymerization polyimide that can be recycled that direct hot-imide method prepared by embodiment one obtains, as shown in Figure 1;
Fig. 1 is the infrared spectrogram of the shape memory random copolymerization polyimide that can be recycled utilizing hot-imide method to obtain in embodiment one; As can be seen from Figure 1, these charateristic avsorption bands illustrate the polyimide that the shape memory random copolymerization polyimide that can be recycled utilizing hot-imide method to obtain in embodiment one is height imidization.
Dynamic mechanical analyzer is used to test the shape memory random copolymerization polyimide that can be recycled that direct hot-imide method prepared by embodiment one obtains, as shown in Figure 2;
Fig. 2 is the dissipation factor figure of the shape memory random copolymerization polyimide that can be recycled utilizing hot-imide method to obtain in embodiment one; The T of the shape memory random copolymerization polyimide that can be recycled as can be seen from Figure 2 utilizing hot-imide method to obtain in embodiment one
gbe 203 DEG C, ensure that the shape memory random copolymerization polyimide that can be recycled that direct hot-imide method prepared by embodiment one obtains can be applicable to high-temperature shape-memory field.
Dynamic mechanical analyzer is used to test the shape memory random copolymerization polyimide that can be recycled that direct hot-imide method prepared by embodiment one obtains, as shown in Figure 3;
Fig. 3 is the storage modulus figure of the shape memory random copolymerization polyimide that can be recycled utilizing hot-imide method to obtain in embodiment one;
As can be seen from Figure 3, there are two platforms of high and low temperature section in storage modulus change curve, and the shape memory random copolymerization polyimide that can be recycled utilizing hot-imide method to obtain in embodiment one is at 183 DEG C of (T
g-20 DEG C) vitreous state time storage modulus be 1.92GPa; At high temperature 223 DEG C of (T
g+ 20 DEG C) rubbery state time storage modulus be 5.2MPa; Between two platforms, storage modulus sharply declines, and corresponding to the Glass Transition of material, the sharply change of this modulus is the prerequisite that polymkeric substance possesses shape memory character.
High-temperature stage is used to test the shape memory random copolymerization polyimide that can be recycled that direct hot-imide method prepared by embodiment one obtains, as shown in Figures 4 to 6.
Fig. 4 is the temporary shapes that the shape memory random copolymerization polyimide that can be recycled utilizing hot-imide method to obtain in embodiment one is fixed;
Fig. 5 is the state in the shape memory random copolymerization polyimide recovery of shape that can be recycled utilizing hot-imide method to obtain in embodiment one;
Fig. 6 is the state after the shape memory random copolymerization polyimide recovery of shape that can be recycled utilizing hot-imide method to obtain in embodiment one.
From Fig. 4 to Fig. 6, the shape memory random copolymerization polyimide that can be recycled utilizing hot-imide method to obtain in embodiment one has good shape memory effect, and its shape prescribed rate is 99%, and shape recovery ratio is 98%.
The shape memory random copolymerization polyimide that the can be recycled embodiment one of breakage prepared is dissolved into N, in N-N,N-DIMETHYLACETAMIDE, obtain the shape memory random copolymerization polyimide solution that can be recycled that massfraction is embodiment one preparation of 13.8%, by massfraction be 13.8% the shape memory random copolymerization polyimide solution that can be recycled prepared of embodiment one be evenly coated on clean sheet glass, put into vacuum drying oven again, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 95 DEG C, 2h is incubated again at 95 DEG C, 175 DEG C are warming up to from 95 DEG C again with the temperature rise rate of 1 DEG C/min, insulation 1h, make organic solvent N, the volatilization of N-N,N-DIMETHYLACETAMIDE is clean.Then sheet glass is placed in distilled water, polyimide is come off from substrate, dry, obtain the shape memory polyimide utilizing solution casting method obtained.
After the shape memory random copolymerization polyimide that can be recycled utilizing hot-imide method to prepare embodiment one uses, be dissolved into N again, in N-N,N-DIMETHYLACETAMIDE, the Kapton that recycling solution casting method obtains has the shape memory effect the same with the shape memory random copolymerization polyimide that can be recycled prepared by embodiment one.
Fig. 7 is after the shape memory random copolymerization polyimide that can be recycled of embodiment one preparation of breakage dissolves, the momentary state of Kapton after alteration of form utilizing solution casting method to obtain;
Fig. 8 is after the shape memory random copolymerization polyimide that can be recycled of embodiment one preparation of breakage dissolves, the state of Kapton in shape recovery process utilizing solution casting method to obtain;
Fig. 9 is after the shape memory random copolymerization polyimide that can be recycled of embodiment one preparation of breakage dissolves, the state of Kapton after recovery of shape utilizing solution casting method to obtain;
From Fig. 7 ~ Fig. 9, the shape memory random copolymerization polyimide that can be recycled prepared by damaged embodiment one upon dissolution, the Kapton utilizing solution casting method to obtain still has good shape memory effect, therefore, the shape memory random copolymerization polyimide that can be recycled that prepared by embodiment one is a kind of shape memory polyimide that can be recycled.
Embodiment two: a kind of preparation method of the shape memory random copolymerization polyimide that can be recycled completes according to the following steps:
One, two to 0.05mol1,3-(3-amino-benzene oxygen) benzene is joined 80mLN, in N-N,N-DIMETHYLACETAMIDE, then be stirred to two (3-amino-benzene oxygen) benzene of 1,3-under dry nitrogen atmosphere and dissolve completely, obtain two amine aqueous solutions;
Two, the mixture of 0.04mol Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 0.01mol4,4-oxygen is dissolved in 80mLN, in N-N,N-DIMETHYLACETAMIDE, obtains two anhydride solutions;
Three, two anhydride solutions are joined in two amine aqueous solutions, then under nitrogen atmosphere and stirring velocity are the condition of 400r/min stirring reaction 15h, obtain polyamic acid solution;
In two anhydride solutions described in step 3, the mixture of the two Tetra hydro Phthalic anhydride of Bisphenol A Type Diether Dianhydride and 4,4-oxygen is 1:1 with the mol ratio of 1,3-pair of (3-amino-benzene oxygen) benzene in two amine aqueous solutions;
Four, polyamic acid solution is evenly coated on clean sheet glass, put into vacuum drying oven again, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 90 DEG C, 2h is incubated again at 90 DEG C, 170 DEG C are warming up to from 90 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 170 DEG C, 210 DEG C are warming up to from 170 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 210 DEG C, 240 DEG C are warming up to from 210 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 240 DEG C, complete hot-imide, vacuum drying oven is made to naturally cool to room temperature again, obtain the sheet glass containing polyimide,
Five, the sheet glass containing polyimide is placed in distilled water, polyimide is come off from substrate, re-use distilled water and polyimide is rinsed well, then at temperature is 120 DEG C dry 3h, obtain the shape memory random copolymerization polyimide that can be recycled.
The thickness of the shape memory random copolymerization polyimide that can be recycled prepared by embodiment two is 150 μm.
The T of the shape memory random copolymerization polyimide that can be recycled prepared by embodiment two
gbe 192 DEG C, ensure that its shape memory effect can be applicable to high-temperature shape-memory field; It is at 172 DEG C of (T
g-20 DEG C) vitreous state time storage modulus be 1.85GPa; High temperature 212 DEG C of (T
g+ 20 DEG C) rubbery state time storage modulus be 4.9MPa.The shape fixed rate of the shape memory random copolymerization polyamides Asia that can be recycled prepared by embodiment two is 99%, and shape recovery ratio is 99%.
Embodiment three: a kind of preparation method of the shape memory random copolymerization polyimide that can be recycled completes according to the following steps:
One, two to 0.05mol1,3-(3-amino-benzene oxygen) benzene is joined in 80mLN-methyl-2-pyrrolidone, then be stirred to two (3-amino-benzene oxygen) benzene of 1,3-under dry nitrogen atmosphere and dissolve completely, obtain two amine aqueous solutions;
Two, the mixture of 0.035mol Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 0.015mol4,4-oxygen is dissolved in 90mLN-methyl-2-pyrrolidone, obtains two anhydride solutions;
Three, two anhydride solutions are joined in two amine aqueous solutions, then under nitrogen atmosphere and stirring velocity are the condition of 400r/min stirring reaction 15h, obtain polyamic acid solution;
In two anhydride solutions described in step 3, the mixture of the two Tetra hydro Phthalic anhydride of Bisphenol A Type Diether Dianhydride and 4,4-oxygen is 1:1 with the mol ratio of 1,3-pair of (3-amino-benzene oxygen) benzene in two amine aqueous solutions;
Four, polyamic acid solution is evenly coated on clean sheet glass, put into vacuum drying oven again, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 85 DEG C, 2h is incubated again at 85 DEG C, 165 DEG C are warming up to from 85 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 165 DEG C, 205 DEG C are warming up to from 165 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 205 DEG C, 230 DEG C are warming up to from 205 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at temperature is 230 DEG C, complete hot-imide, vacuum drying oven is made to naturally cool to room temperature again, obtain the sheet glass containing polyimide,
Five, the sheet glass containing polyimide is placed in distilled water, polyimide is come off from substrate, re-use distilled water and polyimide is rinsed well, then at temperature is 120 DEG C dry 3h, obtain the shape memory random copolymerization polyimide that can be recycled.
The thickness of the shape memory random copolymerization polyimide that can be recycled prepared by embodiment three is 50 μm ~ 150 μm;
The T of the shape memory random copolymerization polyimide that can be recycled prepared by embodiment three
gbe 195 DEG C, ensure that its shape memory effect can be applicable to high-temperature shape-memory field.It is at 175 DEG C of (T
g-20 DEG C) vitreous state time storage modulus be 1.80GPa; High temperature 215 DEG C of (T
g+ 20 DEG C) rubbery state time storage modulus be 5.1MPa.The shape fixed rate of the shape memory random copolymerization polyimide that can be recycled prepared by embodiment three is 98%, and shape recovery ratio is 99%.
Embodiment four: a kind of preparation method of the shape memory random copolymerization polyimide that can be recycled, completes according to the following steps:
One, two to 0.05mol1,3-(3-amino-benzene oxygen) benzene is joined in 80mLN-methyl-2-pyrrolidone, then be stirred to two (3-amino-benzene oxygen) benzene of 1,3-under dry nitrogen atmosphere and dissolve completely, obtain two amine aqueous solutions;
Two, the mixture of 0.03mol Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 0.02mol4,4-oxygen is dissolved in 100mLN-methyl-2-pyrrolidone, obtains two anhydride solutions;
Three, two anhydride solutions are joined in two amine aqueous solutions, then under nitrogen atmosphere and stirring velocity are the condition of 400r/min stirring reaction 19h, obtain polyamic acid solution;
In two anhydride solutions described in step 3, the mixture of the two Tetra hydro Phthalic anhydride of Bisphenol A Type Diether Dianhydride and 4,4-oxygen is 1:1 with the mol ratio of 1,3-pair of (3-amino-benzene oxygen) benzene in two amine aqueous solutions;
Four, polyamic acid solution is evenly coated on clean sheet glass, put into vacuum drying oven again, again by vacuum drying oven with the temperature rise rate of 2 DEG C/min from room temperature to 90 DEG C, 2h is incubated again at 90 DEG C, 165 DEG C are warming up to from 90 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 165 DEG C, the temperature rise rate of 1 DEG C/min is warming up to 210 DEG C from 165 DEG C again, 2h is incubated again at 210 DEG C, 250 DEG C are warming up to from 210 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 250 DEG C, complete hot-imide, vacuum drying oven is made to naturally cool to room temperature again, obtain the sheet glass containing polyimide,
Five, the sheet glass containing polyimide is placed in distilled water, polyimide is come off from substrate, re-use distilled water and polyimide is rinsed well, then at temperature is 120 DEG C dry 3h, obtain the shape memory random copolymerization polyimide that can be recycled.
The thickness of the shape memory random copolymerization polyimide that can be recycled prepared by embodiment four is 150 μm.
The T of the shape memory random copolymerization polyimide that can be recycled prepared by embodiment four
gbe 198 DEG C, ensure that its shape memory effect can be applicable to high-temperature shape-memory field; It is at 178 DEG C of (T
g-20 DEG C) vitreous state time storage modulus be 1.82GPa; High temperature 218 DEG C of (T
g+ 20 DEG C) rubbery state time storage modulus be 5.6MPa.The shape fixed rate of the shape memory random copolymerization polyimide that can be recycled prepared by embodiment four is 99%, and shape recovery ratio is 97%.
Embodiment five: a kind of preparation method of the shape memory random copolymerization polyimide that can be recycled completes according to the following steps:
One, two to 0.05mol1,3-(3-amino-benzene oxygen) benzene is joined in 80mLN-methyl-2-pyrrolidone, then be stirred to two (3-amino-benzene oxygen) benzene of 1,3-under dry nitrogen atmosphere and dissolve completely, obtain two amine aqueous solutions;
Two, the mixture of 0.02mol Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 0.03mol4,4-oxygen is dissolved in 100mLN-methyl-2-pyrrolidone, obtains two anhydride solutions;
Three, two anhydride solutions are joined in two amine aqueous solutions, then under nitrogen atmosphere and stirring velocity are the condition of 400r/min stirring reaction 17h, obtain polyamic acid solution;
In two anhydride solutions described in step 3, the mixture of the two Tetra hydro Phthalic anhydride of Bisphenol A Type Diether Dianhydride and 4,4-oxygen is 1:1 with the mol ratio of 1,3-pair of (3-amino-benzene oxygen) benzene in two amine aqueous solutions;
Four, polyamic acid solution is evenly coated on clean sheet glass, put into vacuum drying oven again, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 80 DEG C, 2h is incubated again at 80 DEG C, 160 DEG C are warming up to from 80 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 160 DEG C, 200 DEG C are warming up to from 160 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 200 DEG C, 240 DEG C are warming up to from 200 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 240 DEG C, complete hot-imide, vacuum drying oven is made to naturally cool to room temperature again, obtain the sheet glass containing polyimide,
Five, the sheet glass containing polyimide is placed in distilled water, polyimide is come off from substrate, re-use distilled water and polyimide is rinsed well, then at temperature is 120 DEG C dry 3h, obtain the shape memory random copolymerization polyimide that can be recycled.
The thickness of the shape memory random copolymerization polyimide that can be recycled prepared by embodiment five is 50 μm ~ 150 μm;
The T of the shape memory random copolymerization polyimide that can be recycled prepared by embodiment five
gbe 201 DEG C, ensure that its shape memory effect can be applicable to high-temperature shape-memory field; It is at 181 DEG C of (T
g-20 DEG C) vitreous state time storage modulus be 1.78GPa; High temperature 221 DEG C of (T
g+ 20 DEG C) rubbery state time storage modulus be 5.7MPa.The shape fixed rate of the shape memory random copolymerization polyimide that can be recycled prepared by embodiment five is 97%, and shape recovery ratio is 96%.
Embodiment six: a kind of preparation method of the shape memory random copolymerization polyimide that can be recycled completes according to the following steps:
One, two to 0.05mol1,3-(3-amino-benzene oxygen) benzene is joined in 80mLN-methyl-2-pyrrolidone, then be stirred to two (3-amino-benzene oxygen) benzene of 1,3-under dry nitrogen atmosphere and dissolve completely, obtain two amine aqueous solutions;
Two, the mixture of 0.01mol Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 0.04mol4,4-oxygen is dissolved in 112mLN-methyl-2-pyrrolidone, obtains two anhydride solutions;
Three, two anhydride solutions are joined in two amine aqueous solutions, then under nitrogen atmosphere and stirring velocity are the condition of 400r/min stirring reaction 20h, obtain polyamic acid solution;
In two anhydride solutions described in step 3, the mixture of the two Tetra hydro Phthalic anhydride of Bisphenol A Type Diether Dianhydride and 4,4-oxygen is 1:1 with the mol ratio of 1,3-pair of (3-amino-benzene oxygen) benzene in two amine aqueous solutions;
Four, polyamic acid solution is evenly coated on clean sheet glass, put into vacuum drying oven again, again by vacuum drying oven with the temperature rise rate of 2 DEG C/min from room temperature to 90 DEG C, 2h is incubated again at temperature is 90 DEG C, be 90 DEG C with the temperature rise rate of 2 DEG C/min from temperature again and be warming up to 160 DEG C, 2h is incubated again at temperature is 160 DEG C, 200 DEG C are warming up to from 160 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at temperature is 200 DEG C, 250 DEG C are warming up to from 200 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at temperature is 250 DEG C, complete hot-imide, vacuum drying oven is made to naturally cool to room temperature again, obtain the sheet glass containing polyimide,
Five, the sheet glass containing polyimide is placed in distilled water, polyimide is come off from substrate, re-use distilled water and polyimide is rinsed well, then at temperature is 120 DEG C dry 3h, obtain the shape memory random copolymerization polyimide that can be recycled.
The thickness of the shape memory random copolymerization polyimide that can be recycled prepared by embodiment six is 150 μm.
The T of the shape memory random copolymerization polyimide that can be recycled prepared by embodiment six
gbe 208 DEG C, ensure that its shape memory effect can be applicable to high-temperature shape-memory field; It is at 188 DEG C of (T
g-20 DEG C) vitreous state time storage modulus be 1.72GPa; High temperature 228 DEG C of (T
g+ 20 DEG C) rubbery state time storage modulus be 5.3MPa.The shape fixed rate of the shape memory random copolymerization polyimide that can be recycled prepared by embodiment six is 99%, and shape recovery ratio is 98%.
Claims (10)
1. the shape memory random copolymerization polyimide that can be recycled, it is characterized in that a kind of shape memory random copolymerization polyimide that can be recycled is by 1, the mixture of two (3-amino-benzene oxygen) benzene of 3-and Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen is prepared from; The mol ratio of the mixture of described 1,3-two (3-amino-benzene oxygen) benzene and Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen is 1:1; In the mixture of described Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen, the mol ratio of Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen is the span of A:B, A is 1≤A≤9, and the span of B is 1≤B≤9.
2. a kind of shape memory random copolymerization polyimide that can be recycled as claimed in claim 1, is characterized in that a kind of preparation method of the shape memory random copolymerization polyimide that can be recycled completes according to the following steps:
One, two for 1,3-(3-amino-benzene oxygen) benzene is joined in aprotic polar solvent, then be stirred to two (3-amino-benzene oxygen) benzene of 1,3-under dry nitrogen atmosphere and dissolve completely, obtain two amine aqueous solutions;
The two amount of substance of (3-amino-benzene oxygen) benzene of described in step one 1,3-and the volume ratio of aprotic polar solvent are 0.05mol:(80mL ~ 130mL);
Two, the mixture of Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen is dissolved in aprotic polar solvent, obtains two anhydride solutions;
In the mixture of the Bisphenol A Type Diether Dianhydride described in step 2 and the two Tetra hydro Phthalic anhydride of 4,4-oxygen, the mol ratio of Bisphenol A Type Diether Dianhydride and the two Tetra hydro Phthalic anhydride of 4,4-oxygen is the span of A:B, A is 1≤A≤9, and the span of B is 1≤B≤9;
The amount of substance of mixture and the volume ratio of aprotic polar solvent of the Bisphenol A Type Diether Dianhydride described in step 2 and the two Tetra hydro Phthalic anhydride of 4,4-oxygen are 0.05mol:(80mL ~ 130mL);
Three, two anhydride solutions are joined in two amine aqueous solutions, then under nitrogen atmosphere and stirring velocity are the condition of 300r/min ~ 400r/min stirring reaction 15h ~ 20h, obtain polyamic acid solution;
In two anhydride solutions described in step 3, the mixture of the two Tetra hydro Phthalic anhydride of Bisphenol A Type Diether Dianhydride and 4,4-oxygen is 1:1 with the mol ratio of 1,3-pair of (3-amino-benzene oxygen) benzene in two amine aqueous solutions;
Four, polyamic acid solution is evenly coated on clean sheet glass, put into vacuum drying oven again, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from room temperature to 70 DEG C ~ 95 DEG C, 2h ~ 3h is incubated again at temperature is 70 DEG C ~ 95 DEG C, 150 DEG C ~ 175 DEG C are warming up to from 70 DEG C ~ 95 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 150 DEG C ~ 175 DEG C, 190 DEG C ~ 215 DEG C are warming up to from 150 DEG C ~ 175 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 190 DEG C ~ 215 DEG C, 230 DEG C ~ 250 DEG C are warming up to from 190 DEG C ~ 215 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at temperature is 230 DEG C ~ 250 DEG C, complete hot-imide, vacuum drying oven is made to naturally cool to room temperature again, obtain the sheet glass containing polyimide,
Five, the sheet glass containing polyimide is placed in distilled water, polyimide is come off from substrate, re-use distilled water polyimide is rinsed well, then at temperature is 120 DEG C dry 3h ~ 4h, obtain the shape memory random copolymerization polyimide that can be recycled.
3. the preparation method of a kind of shape memory random copolymerization polyimide that can be recycled according to claim 2, it is characterized in that the aprotic polar solvent described in step one is N, dinethylformamide, N,N-dimethylacetamide or N-Methyl pyrrolidone.
4. the preparation method of a kind of shape memory random copolymerization polyimide that can be recycled according to claim 2, is characterized in that the aprotic polar solvent described in step 2 is dimethyl formamide, N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone.
5. the preparation method of a kind of shape memory random copolymerization polyimide that can be recycled according to claim 2, is characterized in that the thickness of the shape memory random copolymerization polyimide that can be recycled described in step 5 is 50 μm ~ 150 μm.
6. the preparation method of a kind of shape memory random copolymerization polyimide that can be recycled according to claim 2, it is characterized in that the two amount of substance of (3-amino-benzene oxygen) benzene of 1,3-described in step one and the volume ratio of aprotic polar solvent are 0.05mol:80mL.
7. the preparation method of a kind of shape memory random copolymerization polyimide that can be recycled according to claim 2, the amount of substance of mixture and the volume ratio of aprotic polar solvent that it is characterized in that the two Tetra hydro Phthalic anhydride of the Bisphenol A Type Diether Dianhydride described in step 2 and 4,4-oxygen are 0.05mol:85mL.
8. the preparation method of a kind of shape memory random copolymerization polyimide that can be recycled according to claim 2, it is characterized in that in step 4, polyamic acid solution being evenly coated on clean sheet glass, put into vacuum drying oven again, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 95 DEG C, 2h is incubated again at temperature is 95 DEG C, 175 DEG C are warming up to from 95 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 175 DEG C, 215 DEG C are warming up to from 175 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 215 DEG C, 235 DEG C are warming up to from 215 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at temperature is 235 DEG C, complete hot-imide, vacuum drying oven is made to naturally cool to room temperature again, obtain the sheet glass containing polyimide.
9. the preparation method of a kind of shape memory random copolymerization polyimide that can be recycled according to claim 2, it is characterized in that in step 4, polyamic acid solution being evenly coated on clean sheet glass, put into vacuum drying oven again, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 90 DEG C, 2h is incubated again at temperature is 90 DEG C, 170 DEG C are warming up to from 90 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 170 DEG C, 210 DEG C are warming up to from 170 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 210 DEG C, 240 DEG C are warming up to from 210 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at temperature is 240 DEG C, complete hot-imide, vacuum drying oven is made to naturally cool to room temperature again, obtain the sheet glass containing polyimide.
10. the preparation method of a kind of shape memory random copolymerization polyimide that can be recycled according to claim 2, it is characterized in that in step 4, polyamic acid solution being evenly coated on clean sheet glass, put into vacuum drying oven again, again by vacuum drying oven with the temperature rise rate of 1 DEG C/min from room temperature to 85 DEG C, 2h is incubated again at temperature is 85 DEG C, 165 DEG C are warming up to from 85 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 165 DEG C, 205 DEG C are warming up to from 165 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 205 DEG C, 230 DEG C are warming up to from 205 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at temperature is 230 DEG C, complete hot-imide, vacuum drying oven is made to naturally cool to room temperature again, obtain the sheet glass containing polyimide.
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| CN110894294A (en) * | 2019-12-09 | 2020-03-20 | 中国科学院长春应用化学研究所 | High-temperature-resistant fluorine-containing polyimide heat-shrinkable tube and preparation method thereof |
| CN111635526A (en) * | 2020-07-09 | 2020-09-08 | 吉林大学 | Polyether imide polymer containing carboxyl side group and preparation method and application thereof |
| CN114773601A (en) * | 2022-05-24 | 2022-07-22 | 哈尔滨工业大学 | high-Tg and high-modulus shape memory flame-retardant polyimide and preparation method and application thereof |
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| US20100063241A1 (en) * | 2008-09-09 | 2010-03-11 | Spirit Aerosystems, Inc. | High performance polyaspartimide resin |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110894294A (en) * | 2019-12-09 | 2020-03-20 | 中国科学院长春应用化学研究所 | High-temperature-resistant fluorine-containing polyimide heat-shrinkable tube and preparation method thereof |
| CN111635526A (en) * | 2020-07-09 | 2020-09-08 | 吉林大学 | Polyether imide polymer containing carboxyl side group and preparation method and application thereof |
| CN111635526B (en) * | 2020-07-09 | 2021-03-23 | 吉林大学 | Polyether imide polymer containing carboxyl side group and preparation method and application thereof |
| CN114773601A (en) * | 2022-05-24 | 2022-07-22 | 哈尔滨工业大学 | high-Tg and high-modulus shape memory flame-retardant polyimide and preparation method and application thereof |
| CN114773601B (en) * | 2022-05-24 | 2023-08-22 | 哈尔滨工业大学 | High Tg and high modulus shape memory flame-retardant polyimide, and preparation method and application thereof |
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