CN105399951A - Shape-memory random-copolymerization polyimide with adjustable glass-transition temperature and preparation method thereof - Google Patents
Shape-memory random-copolymerization polyimide with adjustable glass-transition temperature and preparation method thereof Download PDFInfo
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Abstract
The invention relates to polyimide and a preparation method thereof, and provides shape-memory random-copolymerization polyimide with an adjustable glass-transition temperature and a preparation method thereof. The objective of the invention is to overcome the problem that the Tg of shape-memory polyimide prepared by using conventional methods cannot change in a certain range by adjusting the proportions of reactants. The shape-memory random-copolymerization polyimide with an adjustable glass-transition temperature is prepared from a mixture of 4,4'-diamino diphenyl ether and 1,3-bis(3-aminophenoxyl)benzene and bisphenol A type diether dianhydride. The preparation method comprises the following steps: 1, preparing a solution of a diamine mixture; 2, preparing a dianhydride solution; 3, preparing a polyamide acid solution; 4, carrying out thermal imidization so as to obtain a glass plate containing polyimide; and 5, carrying out cleaning and drying so as to obtain the shape-memory random-copolymerization polyimide with an adjustable glass-transition temperature. The shape-memory random-copolymerization polyimide with an adjustable glass-transition temperature is obtained in the invention.
Description
Technical field
The present invention relates to one and prepare 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.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.The excellent properties of polyimide and shape-memory properties combine by shape memory polyimide, in deployable space structures, variable flying device aileron, pyrostat and driving mechanism etc., have significant application value.Transfer of shapes temperature normally its second-order transition temperature (T of shape memory polyimide
g), usually require T
gcaused in advance to prevent recovery of shape higher than envrionment temperature.The different T of different need for environments
gmaterial.Therefore, shape memory polyimide T
gadjustable significant.
Summary of the invention
The object of the invention is to solve existing not by regulating the ratio of reactant, making the T of the shape memory polyimide of preparation
gin the problem of certain limit change, and provide a kind of second-order transition temperature adjustable shape memory random copolymerization polyimide and preparation method thereof.
A kind of second-order transition temperature adjustable shape memory random copolymerization polyimide is prepared from by the mixture of 4,4'-diaminodiphenyl oxide and two (3-amino-benzene oxygen) benzene of 1,3-and Bisphenol A Type Diether Dianhydride; The two mixture of (3-amino-benzene oxygen) benzene of 4,4'-described diaminodiphenyl oxides and 1,3-and the mol ratio of Bisphenol A Type Diether Dianhydride are 1:1; In the mixture of two (3-amino-benzene oxygen) benzene of 4,4'-described diaminodiphenyl oxides and 1,3-4,4'-diaminodiphenyl oxide and 1, the mol ratio of two (3-amino-benzene oxygen) benzene of 3-is the span of A:B, A is 1≤A≤9, and the span of B is 1≤B≤9.
A preparation method for second-order transition temperature adjustable shape memory random copolymerization polyimide, completes according to the following steps:
One, by 4,4'-diaminodiphenyl oxide and 1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins in aprotic polar solvent, be stirred to 4 under dry nitrogen atmosphere again, 4'-diaminodiphenyl oxide and 1, the mixture of two (3-amino-benzene oxygen) benzene of 3-dissolves completely, obtains diamine mixture solution;
The amount of substance of mixture and the volume ratio of aprotic polar solvent of 4,4'-diaminodiphenyl oxides described in step one and two (3-amino-benzene oxygen) benzene of 1,3-are 0.05mol:(60mL ~ 100mL);
Described in step one 4,4'-diaminodiphenyl oxide and 1, in the mixture of two (3-amino-benzene oxygen) benzene of 3-4,4'-diaminodiphenyl oxide and 1, the mol ratio of two (3-amino-benzene oxygen) benzene of 3-is A:B, the span of A is 1≤A≤9, and the span of B is 1≤B≤9;
Two, Bisphenol A Type Diether Dianhydride is dissolved in aprotic polar solvent, obtains two anhydride solutions;
The amount of substance of the Bisphenol A Type Diether Dianhydride described in step 2 and the volume ratio of aprotic polar solvent are 0.05mol:(60mL ~ 100mL);
Three, two anhydride solutions are joined in diamine mixture solution, then under nitrogen atmosphere and stirring velocity are the condition of 300r/min ~ 400r/min stirring reaction 15h ~ 20h, obtain polyamic acid solution;
In diamine mixture solution described in step 3, in the mixture of two (3-amino-benzene oxygen) benzene of 4,4'-diaminodiphenyl oxides and 1,3-and two anhydride solutions, the mol ratio of Bisphenol A Type Diether Dianhydride is 1:1;
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 ~ 90 DEG C, 2h ~ 3h is incubated again at 70 DEG C ~ 90 DEG C, 160 DEG C ~ 180 DEG C are warming up to from 70 DEG C ~ 90 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 160 DEG C ~ 180 DEG C, 200 DEG C ~ 220 DEG C are warming up to from 160 DEG C ~ 180 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 200 DEG C ~ 220 DEG C, 240 DEG C ~ 260 DEG C are warming up to from 200 DEG C ~ 220 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 1h ~ 2h is incubated again at 240 DEG C ~ 260 DEG C, complete hot-imide, vacuum drying oven self-heating is made to be cooled 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 sheet glass, re-use distilled water polyimide is rinsed well, then at temperature is 120 DEG C dry 3h ~ 4h, obtain second-order transition temperature adjustable shape memory random copolymerization polyimide.
Advantage of the present invention:
One, the present invention adopts 4,4'-diaminodiphenyl oxide and 1, the mixture of two (3-amino-benzene oxygen) benzene of 3-, as diamine monomer, adopts Bisphenol A Type Diether Dianhydride as dianhydride monomer, second-order transition temperature adjustable shape memory random copolymerization polyimide of preparation;
Two, second-order transition temperature adjustable shape memory random copolymerization polyimide that prepared by the present invention has good shape-memory properties, can be applicable to high-temperature shape-memory field, as space deployable structure, high temperature driven device, high temperature detector etc.;
Three, the T of second-order transition temperature adjustable shape memory random copolymerization polyimide for preparing of the present invention
gcan be regulated by the ratio changing reactant monomer, varying environment can be adapted to T
grequirement;
Four, the T of second-order transition temperature adjustable shape memory random copolymerization polyimide for preparing of the present invention
git is 196 DEG C ~ 223 DEG C, at T
gstorage modulus during-20 DEG C of vitreous states is 1.70GPa ~ 1.88GPa; At T
gstorage modulus during+20 DEG C of rubbery states is 4.6MPa ~ 5.6MPa;
Five, second-order transition temperature adjustable shape memory random copolymerization polyimide that prepared by the present invention has good shape memory effect, and its shape fixed rate can reach 99%, and shape recovery ratio can reach 99%.
The present invention can obtain a kind of second-order transition temperature adjustable shape memory random copolymerization polyimide.
Accompanying drawing explanation
Fig. 1 is the infrared spectrogram of second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment one;
Fig. 2 is the dissipation factor figure of second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment one;
Fig. 3 is the storage modulus figure of second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment one;
Fig. 4 is that second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment one is out of shape in 206 DEG C of thermal station, the temporary shapes fixedly obtained under room temperature;
Fig. 5 is the shape of second-order transition temperature adjustable shape memory random copolymerization polyimide in 206 DEG C of thermal station in recovery of shape prepared by embodiment one;
Fig. 6 is the state of second-order transition temperature adjustable shape memory random copolymerization polyimide in 206 DEG C of thermal station after recovery of shape prepared by embodiment one.
Embodiment
Embodiment one: present embodiment is that a kind of second-order transition temperature adjustable shape memory random copolymerization polyimide is by 4, mixture and the Bisphenol A Type Diether Dianhydride of 4'-diaminodiphenyl oxide and two (3-amino-benzene oxygen) benzene of 1,3-are prepared from; The two mixture of (3-amino-benzene oxygen) benzene of 4,4'-described diaminodiphenyl oxides and 1,3-and the mol ratio of Bisphenol A Type Diether Dianhydride are 1:1; In the mixture of two (3-amino-benzene oxygen) benzene of 4,4'-described diaminodiphenyl oxides and 1,3-4,4'-diaminodiphenyl oxide and 1, the mol ratio of two (3-amino-benzene oxygen) benzene of 3-is the span of A:B, A is 1≤A≤9, and the span of B is 1≤B≤9.
Embodiment two: present embodiment is that the preparation method of a kind of second-order transition temperature adjustable shape memory random copolymerization polyimide completes according to the following steps:
One, by 4,4'-diaminodiphenyl oxide and 1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins in aprotic polar solvent, be stirred to 4 under dry nitrogen atmosphere again, 4'-diaminodiphenyl oxide and 1, the mixture of two (3-amino-benzene oxygen) benzene of 3-dissolves completely, obtains diamine mixture solution;
The amount of substance of mixture and the volume ratio of aprotic polar solvent of 4,4'-diaminodiphenyl oxides described in step one and two (3-amino-benzene oxygen) benzene of 1,3-are 0.05mol:(60mL ~ 100mL);
Described in step one 4,4'-diaminodiphenyl oxide and 1, in the mixture of two (3-amino-benzene oxygen) benzene of 3-4,4'-diaminodiphenyl oxide and 1, the mol ratio of two (3-amino-benzene oxygen) benzene of 3-is A:B, the span of A is 1≤A≤9, and the span of B is 1≤B≤9;
Two, Bisphenol A Type Diether Dianhydride is dissolved in aprotic polar solvent, obtains two anhydride solutions;
The amount of substance of the Bisphenol A Type Diether Dianhydride described in step 2 and the volume ratio of aprotic polar solvent are 0.05mol:(60mL ~ 100mL);
Three, two anhydride solutions are joined in diamine mixture solution, then under nitrogen atmosphere and stirring velocity are the condition of 300r/min ~ 400r/min stirring reaction 15h ~ 20h, obtain polyamic acid solution;
In diamine mixture solution described in step 3, in the mixture of two (3-amino-benzene oxygen) benzene of 4,4'-diaminodiphenyl oxides and 1,3-and two anhydride solutions, the mol ratio of Bisphenol A Type Diether Dianhydride is 1:1;
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 ~ 90 DEG C, 2h ~ 3h is incubated again at 70 DEG C ~ 90 DEG C, 160 DEG C ~ 180 DEG C are warming up to from 70 DEG C ~ 90 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 160 DEG C ~ 180 DEG C, 200 DEG C ~ 220 DEG C are warming up to from 160 DEG C ~ 180 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 200 DEG C ~ 220 DEG C, 240 DEG C ~ 260 DEG C are warming up to from 200 DEG C ~ 220 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 1h ~ 2h is incubated again at 240 DEG C ~ 260 DEG C, complete hot-imide, vacuum drying oven self-heating is made to be cooled 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 sheet glass, re-use distilled water polyimide is rinsed well, then at temperature is 120 DEG C dry 3h ~ 4h, obtain second-order transition temperature adjustable shape memory random copolymerization polyimide.
The advantage of present embodiment:
One, present embodiment adopts 4,4'-diaminodiphenyl oxide and 1, the mixture of two (3-amino-benzene oxygen) benzene of 3-, as diamine monomer, adopts Bisphenol A Type Diether Dianhydride as dianhydride monomer, second-order transition temperature adjustable shape memory random copolymerization polyimide of preparation;
Two, second-order transition temperature adjustable shape memory random copolymerization polyimide that prepared by present embodiment has good shape-memory properties, can be applicable to high-temperature shape-memory field, as space deployable structure, high temperature driven device, high temperature detector etc.;
Three, the T of second-order transition temperature adjustable shape memory random copolymerization polyimide for preparing of present embodiment
gcan be regulated by the ratio changing reactant monomer, varying environment can be adapted to T
grequirement;
Four, the T of second-order transition temperature adjustable shape memory random copolymerization polyimide for preparing of present embodiment
git is 196 DEG C ~ 223 DEG C, at T
gstorage modulus during-20 DEG C of vitreous states is 1.70GPa ~ 1.88GPa; At T
gstorage modulus during+20 DEG C of rubbery states is 4.6MPa ~ 5.6MPa;
Five, second-order transition temperature adjustable shape memory random copolymerization polyimide that prepared by present embodiment has good shape memory effect, and its shape fixed rate can reach 99%, and shape recovery ratio can reach 99%.
Present embodiment can obtain a kind of second-order transition temperature adjustable shape memory random copolymerization polyimide.
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 DMF, 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 adjustable shape memory random copolymerization of the second-order transition temperature described in step 5 polyimide is 60 μm ~ 160 μm.Other steps are identical with embodiment two to four.
Embodiment six: one of present embodiment and embodiment two to five difference is: 4 described in step one, the amount of substance of mixture and the volume ratio of aprotic polar solvent of 4'-diaminodiphenyl oxide and two (3-amino-benzene oxygen) benzene of 1,3-are 0.05mol:60mL.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 the Bisphenol A Type Diether Dianhydride described in step 2 and the volume ratio of aprotic polar solvent 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 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, 215 DEG C are warming up to from 170 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 215 DEG C, 250 DEG C are warming up to from 215 DEG C again with the temperature rise rate of 1 DEG C/min, 1h is incubated again at 250 DEG C, complete hot-imide, vacuum drying oven self-heating is made to be cooled 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 80 DEG C, 2h is incubated again at 80 DEG C, 160 DEG C are warming up to from 80 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 160 DEG C, 210 DEG C are warming up to from 160 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 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, 1h is incubated again at 240 DEG C, complete hot-imide, vacuum drying oven self-heating is made to be cooled 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 2 DEG C/min from room temperature to 90 DEG C, 2h is incubated again at 90 DEG C, 180 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 180 DEG C, 220 DEG C are warming up to from 180 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 220 DEG C, 250 DEG C are warming up to from 220 DEG C again with the temperature rise rate of 1 DEG C/min, 1h is incubated again at 250 DEG C, complete hot-imide, vacuum drying oven self-heating is made to be cooled 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: the preparation method of a kind of second-order transition temperature adjustable shape memory random copolymerization polyimide completes according to the following steps:
One, by 0.005mol4,4'-diaminodiphenyl oxide and 0.045mol1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins 60mLN, in N-N,N-DIMETHYLACETAMIDE, be stirred to 4 under dry nitrogen atmosphere again, the mixture of 4'-diaminodiphenyl oxide and two (3-amino-benzene oxygen) benzene of 1,3-dissolves completely, obtains diamine mixture solution;
Two, 0.05mol Bisphenol A Type Diether Dianhydride is dissolved into 100mLN, in N-N,N-DIMETHYLACETAMIDE, obtains two anhydride solutions;
Three, two anhydride solutions are joined in diamine mixture solution, then under nitrogen atmosphere and stirring velocity are the condition of 400r/min stirring reaction 16h, obtain polyamic acid solution;
In diamine mixture solution described in step 3, in the mixture of two (3-amino-benzene oxygen) benzene of 4,4'-diaminodiphenyl oxides and 1,3-and two anhydride solutions, the mol ratio of Bisphenol A Type Diether Dianhydride is 1:1;
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, 215 DEG C are warming up to from 170 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 215 DEG C, 250 DEG C are warming up to from 215 DEG C again with the temperature rise rate of 1 DEG C/min, 1h is incubated again at 250 DEG C, complete hot-imide, vacuum drying oven self-heating is made to be cooled to room temperature again, obtain the sheet glass containing polyimide, complete hot-imide, then make vacuum drying oven self-heating be cooled to room temperature, obtain the sheet glass containing polyimide,
Five, the sheet glass containing polyimide is placed in distilled water, polyimide is come off from sheet glass, re-use distilled water polyimide is rinsed well, then at temperature is 120 DEG C dry 3h, obtain second-order transition temperature adjustable shape memory random copolymerization polyimide.
The thickness of the second-order transition temperature adjustable shape memory random copolymerization polyimide described in embodiment one step 5 is 100 μm.
Infrared spectrometer is used to test second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment one, as shown in Figure 1;
Fig. 1 is the infrared spectrogram of second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment one;
As can be seen from Figure 1, these charateristic avsorption bands illustrate that second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment one is the polyimide of height imidization.
Dynamic mechanical analyzer is used to test second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment one, as shown in Figure 2;
Fig. 2 is the dissipation factor figure of second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment one;
As can be seen from Figure 2 the T of second-order transition temperature adjustable shape memory random copolymerization polyimide of embodiment one preparation
gbe 196 DEG C, ensure that second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment one can be applicable to high-temperature shape-memory field.
Dynamic mechanical analyzer is used to test second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment one, as shown in Figure 3;
Fig. 3 is the storage modulus figure of second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment one;
As can be seen from Figure 3, there are two platforms of high and low temperature section in second-order transition temperature adjustable shape memory random copolymerization polyimide storage modulus change curve prepared by embodiment one, at 176 DEG C of (T
g-20 DEG C) vitreous state time storage modulus be 1.88GPa; At high temperature 216 DEG C of (T
g+ 20 DEG C) rubbery state time storage modulus be 5.1MPa; 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 second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment one, as shown in Figures 4 to 6;
Fig. 4 is that second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment one is out of shape in 206 DEG C of thermal station, the temporary shapes fixedly obtained under room temperature;
Fig. 5 is the shape of second-order transition temperature adjustable shape memory random copolymerization polyimide in 206 DEG C of thermal station in recovery of shape prepared by embodiment one;
Fig. 6 is the state of second-order transition temperature adjustable shape memory random copolymerization polyimide in 206 DEG C of thermal station after recovery of shape prepared by embodiment one.
From Fig. 4 to Fig. 6, second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment one has good shape memory effect, and its shape fixed rate is 98%, and shape recovery ratio is 96%.
Embodiment two: the preparation method of a kind of second-order transition temperature adjustable shape memory random copolymerization polyimide completes according to the following steps:
One, by 0.01mol4,4'-diaminodiphenyl oxide and 0.04mol1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins 70mLN, in N-N,N-DIMETHYLACETAMIDE, be stirred to 4 under dry nitrogen atmosphere again, the mixture of 4'-diaminodiphenyl oxide and two (3-amino-benzene oxygen) benzene of 1,3-dissolves completely, obtains diamine mixture solution;
Two, 0.05mol Bisphenol A Type Diether Dianhydride is dissolved into 90mLN, in N-N,N-DIMETHYLACETAMIDE, obtains two anhydride solutions;
Three, two anhydride solutions are joined in diamine mixture solution, then under nitrogen atmosphere and stirring velocity are the condition of 400r/min stirring reaction 15h, obtain polyamic acid solution;
In diamine mixture solution described in step 3, in the mixture of two (3-amino-benzene oxygen) benzene of 4,4'-diaminodiphenyl oxides and 1,3-and two anhydride solutions, the mol ratio of Bisphenol A Type Diether Dianhydride is 1:1;
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 2 DEG C/min, 2h is incubated again at 160 DEG C, 210 DEG C are warming up to from 160 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 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, 1h is incubated again at 240 DEG C, complete hot-imide, vacuum drying oven self-heating is made to be cooled to room temperature again, obtain the sheet glass containing polyimide, complete hot-imide, then make vacuum drying oven self-heating be cooled to room temperature, obtain the sheet glass containing polyimide,
Five, the sheet glass containing polyimide is placed in distilled water, polyimide is come off from sheet glass, re-use distilled water polyimide is rinsed well, then at temperature is 130 DEG C dry 3h, obtain second-order transition temperature adjustable shape memory random copolymerization polyimide.
The thickness of the second-order transition temperature adjustable shape memory random copolymerization polyimide described in embodiment two step 5 is 100 μm.
The T of second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment two
gbe 201 DEG C, ensure that its shape memory effect can be applicable to high-temperature shape-memory field; Second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment two is at 181 DEG C of (T
g-20 DEG C) vitreous state time storage modulus be 1.76Gpa, high temperature 221 DEG C of (T
g+ 20 DEG C) rubbery state time storage modulus be 5.3MPa.The shape fixed rate of second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment two is 99%, and shape recovery ratio is 99%.
Embodiment three: the preparation method of a kind of second-order transition temperature adjustable shape memory random copolymerization polyimide completes according to the following steps:
One, by 0.02mol4,4'-diaminodiphenyl oxide and 0.03mol1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins 70mLN, in dinethylformamide, be stirred to 4 under dry nitrogen atmosphere again, the mixture of 4'-diaminodiphenyl oxide and two (3-amino-benzene oxygen) benzene of 1,3-dissolves completely, obtains diamine mixture solution;
Two, 0.05mol Bisphenol A Type Diether Dianhydride is dissolved into 100mLN, in dinethylformamide, obtains two anhydride solutions;
Three, two anhydride solutions are joined in diamine mixture solution, then under nitrogen atmosphere and stirring velocity are the condition of 400r/min stirring reaction 17h, obtain polyamic acid solution;
In diamine mixture solution described in step 3, in the mixture of two (3-amino-benzene oxygen) benzene of 4,4'-diaminodiphenyl oxides and 1,3-and two anhydride solutions, the mol ratio of Bisphenol A Type Diether Dianhydride is 1:1;
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, 180 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 180 DEG C, 220 DEG C are warming up to from 180 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 220 DEG C, 250 DEG C are warming up to from 220 DEG C again with the temperature rise rate of 1 DEG C/min, 1h is incubated again at 250 DEG C, complete hot-imide, vacuum drying oven self-heating is made to be cooled to room temperature again, obtain the sheet glass containing polyimide, complete hot-imide, then make vacuum drying oven self-heating be cooled to room temperature, obtain the sheet glass containing polyimide,
Five, the sheet glass containing polyimide is placed in distilled water, polyimide is come off from sheet glass, re-use distilled water polyimide is rinsed well, then at temperature is 130 DEG C dry 3h, obtain second-order transition temperature adjustable shape memory random copolymerization polyimide.
The thickness of the second-order transition temperature adjustable shape memory random copolymerization polyimide described in embodiment three step 5 is 100 μm.
The T of second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment three
gbe 207 DEG C, ensure that its shape memory effect can be applicable to high-temperature shape-memory field; Second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment three is at 187 DEG C of (T
g-20 DEG C) vitreous state time storage modulus be 1.78Gpa, at high temperature 227 DEG C of (T
g+ 20 DEG C) rubbery state time storage modulus be 5.6MPa.The shape fixed rate of second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment three is 97%, and shape recovery ratio is 98%.
Embodiment four: the preparation method of a kind of second-order transition temperature adjustable shape memory random copolymerization polyimide completes according to the following steps:
One, by 0.03mol4,4'-diaminodiphenyl oxide and 0.02mol1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins 80mLN, in dinethylformamide, be stirred to 4 under dry nitrogen atmosphere again, the mixture of 4'-diaminodiphenyl oxide and two (3-amino-benzene oxygen) benzene of 1,3-dissolves completely, obtains diamine mixture solution;
Two, 0.05mol Bisphenol A Type Diether Dianhydride is dissolved into 100mLN, in dinethylformamide, obtains two anhydride solutions;
Three, two anhydride solutions are joined in diamine mixture solution, then under nitrogen atmosphere and stirring velocity are the condition of 400r/min stirring reaction 18h, obtain polyamic acid solution;
In diamine mixture solution described in step 3, in the mixture of two (3-amino-benzene oxygen) benzene of 4,4'-diaminodiphenyl oxides and 1,3-and two anhydride solutions, the mol ratio of Bisphenol A Type Diether Dianhydride is 1:1;
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, 170 DEG C are warming up to from 80 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 170 DEG C, 210 DEG C are warming up to from 170 DEG C again with the temperature rise rate of 1 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 1 DEG C/min, 1h is incubated again at 240 DEG C, complete hot-imide, vacuum drying oven self-heating is made to be cooled to room temperature again, obtain the sheet glass containing polyimide, complete hot-imide, then make vacuum drying oven self-heating be cooled to room temperature, obtain the sheet glass containing polyimide,
Five, the sheet glass containing polyimide is placed in distilled water, polyimide is come off from sheet glass, re-use distilled water polyimide is rinsed well, then at temperature is 130 DEG C dry 3h, obtain second-order transition temperature adjustable shape memory random copolymerization polyimide.
The thickness of the second-order transition temperature adjustable shape memory random copolymerization polyimide described in embodiment four step 5 is 100 μm.
The T of second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment four
gbe 212 DEG C, ensure that its shape memory effect can be applicable to high-temperature shape-memory field; Second-order transition temperature adjustable shape memory random copolymerization polyimide is at 192 DEG C of (T
g-20 DEG C) vitreous state time storage modulus be 1.75GPa; High temperature 232 DEG C of (T
g+ 20 DEG C) rubbery state time storage modulus be 4.6MPa.The shape fixed rate of second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment four is 99%, and shape recovery ratio is 99%.
Embodiment five: the preparation method of a kind of second-order transition temperature adjustable shape memory random copolymerization polyimide completes according to the following steps:
One, by 0.04mol4,4'-diaminodiphenyl oxide and 0.01mol1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins 80mLN, in dinethylformamide, be stirred to 4 under dry nitrogen atmosphere again, the mixture of 4'-diaminodiphenyl oxide and two (3-amino-benzene oxygen) benzene of 1,3-dissolves completely, obtains diamine mixture solution;
Two, 0.05mol Bisphenol A Type Diether Dianhydride is dissolved into 100mLN, in dinethylformamide, obtains two anhydride solutions;
Three, two anhydride solutions are joined in diamine mixture solution, then under nitrogen atmosphere and stirring velocity are the condition of 400r/min stirring reaction 19h, obtain polyamic acid solution;
In diamine mixture solution described in step 3, in the mixture of two (3-amino-benzene oxygen) benzene of 4,4'-diaminodiphenyl oxides and 1,3-and two anhydride solutions, the mol ratio of Bisphenol A Type Diether Dianhydride is 1:1;
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, 180 DEG C are warming up to from 80 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 180 DEG C, 220 DEG C are warming up to from 180 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 220 DEG C, 250 DEG C are warming up to from 220 DEG C again with the temperature rise rate of 1 DEG C/min, 1h is incubated again at 250 DEG C, complete hot-imide, vacuum drying oven self-heating is made to be cooled to room temperature again, obtain the sheet glass containing polyimide, complete hot-imide, then make vacuum drying oven self-heating be cooled to room temperature, 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 130 DEG C dry 3h, obtain second-order transition temperature adjustable shape memory random copolymerization polyimide.
The thickness of the second-order transition temperature adjustable shape memory random copolymerization polyimide described in embodiment five step 5 is 100 μm.
The T of second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment five
gbe 218 DEG C, ensure that its shape memory effect can be applicable to high-temperature shape-memory field; Second-order transition temperature adjustable shape memory random copolymerization polyimide is at 198 DEG C of (T
g-20 DEG C) vitreous state time storage modulus be 1.72GPa; High temperature 238 DEG C of (T
g+ 20 DEG C) rubbery state time storage modulus be 5.6MPa.The shape fixed rate of second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment five is 100%, and shape recovery ratio is 98%.
Embodiment six: the preparation method of a kind of second-order transition temperature adjustable shape memory random copolymerization polyimide completes according to the following steps:
One, by 0.045mol4,4'-diaminodiphenyl oxide and 0.005mol1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins in 90mLN-methyl-2-pyrrolidone, be stirred to 4 under dry nitrogen atmosphere again, 4'-diaminodiphenyl oxide and 1, the mixture of two (3-amino-benzene oxygen) benzene of 3-dissolves completely, obtains diamine mixture solution;
Two, 0.05mol Bisphenol A Type Diether Dianhydride is dissolved in 100mLN-methyl-2-pyrrolidone, obtains two anhydride solutions;
Three, two anhydride solutions are joined in diamine mixture solution, then under nitrogen atmosphere and stirring velocity are the condition of 400r/min stirring reaction 20h, obtain polyamic acid solution;
In diamine mixture solution described in step 3, in the mixture of two (3-amino-benzene oxygen) benzene of 4,4'-diaminodiphenyl oxides and 1,3-and two anhydride solutions, the mol ratio of Bisphenol A Type Diether Dianhydride is 1:1;
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, 180 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 180 DEG C, 220 DEG C are warming up to from 180 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 220 DEG C, 260 DEG C are warming up to from 220 DEG C again with the temperature rise rate of 2 DEG C/min, 1h is incubated again at 260 DEG C, complete hot-imide, vacuum drying oven self-heating is made to be cooled to room temperature again, obtain the sheet glass containing polyimide, complete hot-imide, then make vacuum drying oven self-heating be cooled to room temperature, obtain the sheet glass containing polyimide,
Five, the sheet glass containing polyimide is placed in distilled water, polyimide is come off from sheet glass, re-use distilled water polyimide is rinsed well, then at temperature is 130 DEG C dry 3h, obtain second-order transition temperature adjustable shape memory random copolymerization polyimide.
The thickness of the second-order transition temperature adjustable shape memory random copolymerization polyimide described in embodiment six step 5 is 100 μm.
The T of second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment six
gbe 223 DEG C, ensure that its shape memory effect can be applicable to high-temperature shape-memory field; Second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment six is at 203 DEG C of (T
g-20 DEG C) vitreous state time storage modulus be 1.70GPa; High temperature 243 DEG C of (T
g+ 20 DEG C) rubbery state time storage modulus be 5.2MPa.
The shape fixed rate of second-order transition temperature adjustable shape memory random copolymerization polyimide prepared by embodiment six is 98%, and shape recovery ratio is 96%.
Claims (10)
1. second-order transition temperature adjustable shape memory random copolymerization polyimide, it is characterized in that a kind of second-order transition temperature adjustable shape memory random copolymerization polyimide is by 4, mixture and the Bisphenol A Type Diether Dianhydride of 4'-diaminodiphenyl oxide and two (3-amino-benzene oxygen) benzene of 1,3-are prepared from; The two mixture of (3-amino-benzene oxygen) benzene of 4,4'-described diaminodiphenyl oxides and 1,3-and the mol ratio of Bisphenol A Type Diether Dianhydride are 1:1; In the mixture of two (3-amino-benzene oxygen) benzene of 4,4'-described diaminodiphenyl oxides and 1,3-4,4'-diaminodiphenyl oxide and 1, the mol ratio of two (3-amino-benzene oxygen) benzene of 3-is the span of A:B, A is 1≤A≤9, and the span of B is 1≤B≤9.
2. a kind of second-order transition temperature as claimed in claim 1 adjustable shape memory random copolymerization polyimide, is characterized in that the preparation method of a kind of second-order transition temperature adjustable shape memory random copolymerization polyimide completes according to the following steps:
One, by 4,4'-diaminodiphenyl oxide and 1, the mixture of two (3-amino-benzene oxygen) benzene of 3-joins in aprotic polar solvent, be stirred to 4 under dry nitrogen atmosphere again, 4'-diaminodiphenyl oxide and 1, the mixture of two (3-amino-benzene oxygen) benzene of 3-dissolves completely, obtains diamine mixture solution;
The amount of substance of mixture and the volume ratio of aprotic polar solvent of 4,4'-diaminodiphenyl oxides described in step one and two (3-amino-benzene oxygen) benzene of 1,3-are 0.05mol:(60mL ~ 100mL);
Described in step one 4,4'-diaminodiphenyl oxide and 1, in the mixture of two (3-amino-benzene oxygen) benzene of 3-4,4'-diaminodiphenyl oxide and 1, the mol ratio of two (3-amino-benzene oxygen) benzene of 3-is A:B, the span of A is 1≤A≤9, and the span of B is 1≤B≤9;
Two, Bisphenol A Type Diether Dianhydride is dissolved in aprotic polar solvent, obtains two anhydride solutions;
The amount of substance of the Bisphenol A Type Diether Dianhydride described in step 2 and the volume ratio of aprotic polar solvent are 0.05mol:(60mL ~ 100mL);
Three, two anhydride solutions are joined in diamine mixture solution, then under nitrogen atmosphere and stirring velocity are the condition of 300r/min ~ 400r/min stirring reaction 15h ~ 20h, obtain polyamic acid solution;
In diamine mixture solution described in step 3, in the mixture of two (3-amino-benzene oxygen) benzene of 4,4'-diaminodiphenyl oxides and 1,3-and two anhydride solutions, the mol ratio of Bisphenol A Type Diether Dianhydride is 1:1;
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 ~ 90 DEG C, 2h ~ 3h is incubated again at 70 DEG C ~ 90 DEG C, 160 DEG C ~ 180 DEG C are warming up to from 70 DEG C ~ 90 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 160 DEG C ~ 180 DEG C, 200 DEG C ~ 220 DEG C are warming up to from 160 DEG C ~ 180 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 2h ~ 3h is incubated again at 200 DEG C ~ 220 DEG C, 240 DEG C ~ 260 DEG C are warming up to from 200 DEG C ~ 220 DEG C again with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, 1h ~ 2h is incubated again at 240 DEG C ~ 260 DEG C, complete hot-imide, vacuum drying oven self-heating is made to be cooled 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 sheet glass, re-use distilled water polyimide is rinsed well, then at temperature is 120 DEG C dry 3h ~ 4h, obtain second-order transition temperature adjustable shape memory random copolymerization polyimide.
3. the preparation method of a kind of second-order transition temperature according to claim 2 adjustable shape memory random copolymerization polyimide, 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 second-order transition temperature according to claim 2 adjustable shape memory random copolymerization polyimide, it is characterized in that the aprotic polar solvent described in step 2 is N, dinethylformamide, N,N-dimethylacetamide or N-Methyl pyrrolidone.
5. the preparation method of a kind of second-order transition temperature according to claim 2 adjustable shape memory random copolymerization polyimide, is characterized in that the thickness of the second-order transition temperature adjustable shape memory random copolymerization polyimide described in step 5 is 60 μm ~ 160 μm.
6. the preparation method of a kind of second-order transition temperature according to claim 2 adjustable shape memory random copolymerization polyimide, it is characterized in that 4 described in step one, the amount of substance of mixture and the volume ratio of aprotic polar solvent of 4'-diaminodiphenyl oxide and two (3-amino-benzene oxygen) benzene of 1,3-are 0.05mol:60mL.
7. the preparation method of a kind of second-order transition temperature according to claim 2 adjustable shape memory random copolymerization polyimide, is characterized in that the amount of substance of the Bisphenol A Type Diether Dianhydride described in step 2 and the volume ratio of aprotic polar solvent are 0.05mol:100mL.
8. the preparation method of a kind of second-order transition temperature according to claim 2 adjustable shape memory random copolymerization polyimide, 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 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, 215 DEG C are warming up to from 170 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 215 DEG C, 250 DEG C are warming up to from 215 DEG C again with the temperature rise rate of 1 DEG C/min, 1h is incubated again at 250 DEG C, complete hot-imide, vacuum drying oven self-heating is made to be cooled to room temperature again, obtain the sheet glass containing polyimide.
9. the preparation method of a kind of second-order transition temperature according to claim 2 adjustable shape memory random copolymerization polyimide, 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 80 DEG C, 2h is incubated again at 80 DEG C, 160 DEG C are warming up to from 80 DEG C again with the temperature rise rate of 2 DEG C/min, 2h is incubated again at 160 DEG C, 210 DEG C are warming up to from 160 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 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, 1h is incubated again at 240 DEG C, complete hot-imide, vacuum drying oven self-heating is made to be cooled to room temperature again, obtain the sheet glass containing polyimide.
10. the preparation method of a kind of second-order transition temperature according to claim 2 adjustable shape memory random copolymerization polyimide, 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 2 DEG C/min from room temperature to 90 DEG C, 2h is incubated again at 90 DEG C, 180 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 180 DEG C, 220 DEG C are warming up to from 180 DEG C again with the temperature rise rate of 1 DEG C/min, 2h is incubated again at 220 DEG C, 250 DEG C are warming up to from 220 DEG C again with the temperature rise rate of 1 DEG C/min, 1h is incubated again at 250 DEG C, complete hot-imide, vacuum drying oven self-heating is made to be cooled to room temperature again, obtain the sheet glass containing polyimide.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740054A (en) * | 2013-12-17 | 2014-04-23 | 中航复合材料有限责任公司 | Preparation method of thermosetting shape memory resin with two glass transition temperatures |
| CN103980491A (en) * | 2014-05-23 | 2014-08-13 | 哈尔滨工业大学 | Quick-response thermoset shape memory polyimide and preparation method thereof |
| CN103980490A (en) * | 2014-05-22 | 2014-08-13 | 冷劲松 | Shape memory polyimide prepared by virtue of chemical imidization and preparation method thereof |
| CN104017213A (en) * | 2014-06-19 | 2014-09-03 | 冷劲松 | Shape memory polyether imide with high glass-transition temperature and preparation method thereof |
| CN104788675A (en) * | 2015-04-22 | 2015-07-22 | 哈尔滨工业大学 | Optical transparent light-colored high temperature-resisting shape memory polymer and preparation method thereof |
-
2015
- 2015-12-29 CN CN201511018901.4A patent/CN105399951B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740054A (en) * | 2013-12-17 | 2014-04-23 | 中航复合材料有限责任公司 | Preparation method of thermosetting shape memory resin with two glass transition temperatures |
| CN103980490A (en) * | 2014-05-22 | 2014-08-13 | 冷劲松 | Shape memory polyimide prepared by virtue of chemical imidization and preparation method thereof |
| CN103980491A (en) * | 2014-05-23 | 2014-08-13 | 哈尔滨工业大学 | Quick-response thermoset shape memory polyimide and preparation method thereof |
| CN104017213A (en) * | 2014-06-19 | 2014-09-03 | 冷劲松 | Shape memory polyether imide with high glass-transition temperature and preparation method thereof |
| CN104788675A (en) * | 2015-04-22 | 2015-07-22 | 哈尔滨工业大学 | Optical transparent light-colored high temperature-resisting shape memory polymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| XINLI XIAO等: "《Optically transparent high temperature shape memory polymers》", 《SOFT MATTER》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109825079A (en) * | 2019-01-16 | 2019-05-31 | 复旦大学 | A kind of light-coloured transparent high temperature resistant shape memory polyimide film material and preparation method thereof |
| CN109825079B (en) * | 2019-01-16 | 2021-08-17 | 复旦大学 | Light-colored transparent high-temperature-resistant shape memory polyimide film material and preparation method thereof |
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