CN104788675B - Optical transparent light-colored high temperature-resisting shape memory polymer and preparation method thereof - Google Patents
Optical transparent light-colored high temperature-resisting shape memory polymer and preparation method thereof Download PDFInfo
- Publication number
- CN104788675B CN104788675B CN201510194023.5A CN201510194023A CN104788675B CN 104788675 B CN104788675 B CN 104788675B CN 201510194023 A CN201510194023 A CN 201510194023A CN 104788675 B CN104788675 B CN 104788675B
- Authority
- CN
- China
- Prior art keywords
- high temperature
- transparent light
- memory polymer
- temperature
- shape
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an optical transparent light-colored polymer and a preparation method thereof, in particular to an optical transparent light-colored high temperature-resisting shape memory polymer and a preparation method thereof, and aims to solve the problems, in the prior art, that an optical transparent shape memory polymer is relatively low in phase inversion temperature and existing transparent polyimide is difficult to generate a shape memory effect due to relatively small thickness, so that the use requirement of a photoelectronic device cannot be met in a high temperature environment. The optical transparent light-colored high temperature-resisting shape memory polymer is prepared from 1,3-Bis(3-aminophenoxy)benzene and 4,4'- Bisphenol A dianhydride as reactive monomers, and has the structural formula shown in the specification. The preparation method comprises the following steps: firstly, dissolving 1,3-Bis(3-aminophenoxy)benzene; secondly, preparing a sol-gel polyamide acid; thirdly, removing residual bubbles; fourthly, performing thermal imidization; fifthly, stripping to obtain the optical transparent light-colored high temperature-resisting shape memory polymer. Through the invention, the optical transparent light-colored high temperature-resisting shape memory polymer can be obtained.
Description
Technical field
The present invention relates to a kind of optically transparent low color polymers and preparation method thereof.
Background technology
Shape-memory polymer (shape memory polymers, SMP) is that a class can remember temporary shapes, outside
Boundary stimulates such as heat, light, electricity, the lower intelligent macromolecule material that can recover original shape of magnetic field effect.Relative to shape memory gold
Category alloy, the reversible strains of SMP are big, low density, handling ease and recovery of shape temperature are easy to the advantages of controlling, in biological doctor
Applied in the fields such as treatment, Intelligent prevention and cure, deployable structure, drive assembly.Wherein, optical clear and phase transition temperature is
63 DEG C of poly (ethylene-co-vinyl acetate) SMP material shows huge application in field of optoelectronic devices
Potentiality, because being capable of achieving the real-time optimization of its optical property based on the grating of the transparent SMP, the first-class optics of optical frames.
However, under many circumstances, photoelectric device runs at high temperature, therefore needs the exploitation note of the transparent shape with high phase transition temperature badly
Recall polymer to realize its optical property optimization at high temperature.
Polyimides (PI) have the advantages of heat stability height, mechanical performance are excellent, and processing approach is diversified, extensive
It is applied to the fields such as automobile, microelectronics, photoelectricity, Aero-Space.Wherein, optically transparent polyimides are such as aobvious to photoelectric device
Show and use non-transparent flexible substrate, waveguide material optical switch, lightwave circuit optics half-wave plate etc. with special important meaning however,
Traditional polyimides are not suitable for photoelectric device because of its stronger yellow or brown.People are carried using various methods
The optical property of high polyimides, such as introduce flexible bridge linkage group or larger side base in main chain, introduces fluoro-containing group, introduces
Alicyclic ring hydrocarbon structure etc..But most transparent light color or colorless polyimide film thicknesses at several microns to ten microns,
It is difficult to fix a temporary shapes, the report with regard to optical clear light color shape memory polyimides is there is no at present.
Used as high-temperature shape-memory polymer, this shape memory polyimides are in deployable space structures, variable flying device
The aspects such as aileron, pyrostat and driver also have significant application value.This material combines high-temperature shape-memory effect
And optical transparence, it is expected to further expand polyimides in optical field and shape memory field range of application.
The content of the invention
The invention aims to it is relatively low and existing to solve existing optical clear shape-memory polymer phase transition temperature
Bright polyimide thickness is relatively low to be difficult to produce shape memory effect, it is impossible to meet opto-electronic device use requirement in hot environment
Problem, and a kind of optically transparent light-coloured high temperature resistant shape-memory polymer and preparation method thereof is provided.
A kind of optically transparent light-coloured high temperature resistant shape-memory polymer is by double (3- amino-benzene oxygens) benzene of 1,3- and bisphenol-A
The ether dianhydride of type two is prepared from as reaction monomers；Double (3- amino-benzene oxygens) benzene of described 1,3- and Bisphenol A Type Diether Dianhydride
Material amount ratio be (0.9～1.1):1.
A kind of preparation method of optically transparent light-coloured high temperature resistant shape-memory polymer, is specifically realized by the following steps
's：
First, double (3- amino-benzene oxygens) benzene of 1,3- are dissolved：Double (3- amino-benzene oxygens) benzene of 1,3- are added to into N, N'- diformazans
In yl acetamide, stir under the nitrogen atmosphere of room gently dried to double (3- amino-benzene oxygens) benzene of 1,3- and be completely dissolved, obtain
Diamine solution；
The amount and the body of N, N'- dimethyl acetylamide of the material of double (3- amino-benzene oxygens) benzene of 1,3- described in step one
Product is than being (0.2mmol～0.50mmol):1mL；
2nd, collosol and gel shape polyamic acid is prepared：Bisphenol A Type Diether Dianhydride is divided 5 times～7 times and is added to diamine solution
In, stirring reaction 16h～20h under conditions of temperature is 20 DEG C～35 DEG C and mixing speed is 600r/min～900r/min,
Obtain collosol and gel shape polyamic acid；
The thing of double (3- amino-benzene oxygens) benzene of the 1,3- in Bisphenol A Type Diether Dianhydride and diamine solution described in step 2
The amount ratio of matter is 1:(0.9～1.1)；
3rd, residual bubble is removed：By collosol and gel shape polyamic acid at drying in 30 DEG C～45 DEG C of vacuum drying oven
Reason 2h～3h, obtains the collosol and gel shape polyamic acid of not bubbles；
4th, hot-imide：The collosol and gel shape polyamic acid of not bubbles is poured on substrate, with 1 DEG C/min～2
DEG C/heating rate of min started to warm up to 70 DEG C～90 DEG C from room temperature, and be to be incubated 1h～2h at 70 DEG C～90 DEG C in temperature；
Again 100 DEG C～120 DEG C are warming up to from 70 DEG C～90 DEG C with the heating rate of 1 DEG C/min～2 DEG C/min, and in temperature
To be incubated 1h～2h at 100 DEG C～120 DEG C；
Again 150 DEG C～170 DEG C are warming up to from 100 DEG C～120 DEG C with the heating rate of 1 DEG C/min～2 DEG C/min, and in temperature
Spend to be incubated 1h～2h at 150 DEG C～170 DEG C；
Again 180 DEG C～200 DEG C are warming up to from 150 DEG C～170 DEG C with the heating rate of 1 DEG C/min～2 DEG C/min, and in temperature
Spend to be incubated 1h～2h at 180 DEG C～200 DEG C；
Again 220 DEG C～240 DEG C are warming up to from 180 DEG C～200 DEG C with the heating rate of 1 DEG C/min～2 DEG C/min, and in temperature
Spend to be incubated 1h～2h at 220 DEG C～240 DEG C；
Finally room temperature is cooled to as 220 DEG C～240 DEG C from temperature with the rate of temperature fall of 1 DEG C/min～2 DEG C/min, is contained
There is the substrate of polyimides；
5th, demoulding：Substrate containing polyimides is placed in distilled water, makes polyimides come off from substrate, then made
Polyimides are rinsed well with distilled water, then 2h～3h is dried in the case where temperature is for 80 DEG C～120 DEG C, obtain optically transparent shallow
Color high temperature resistant shape memory polymer, the structural formula of described optically transparent light-coloured high temperature resistant shape-memory polymer is：
Wherein, described n
Scope be integer for 25～65, n.
Chemical equation in step 2 of the present invention is：
Chemical equation in step 4 of the present invention is：
Advantages of the present invention：
First, optically transparent light-coloured high temperature resistant shape-memory polymer phase transition temperature T prepared by the present inventiongFor 168 DEG C
～177 DEG C, compared with 63 DEG C of the phase transition temperature of the optical clear light color shape-memory polymer of current reported in literature, its phase turns
Temperature Tg105 DEG C～114 DEG C are improve, the opto-electronic device under high temperature is can be applicable to；
2nd, when the thickness of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by the present invention can reach 300 μm
Still have can be intact fixation and memory temporary shapes；And the thickness of Common transparent light color or colorless polyimide thin film is several microns
Or more than ten microns, but it is difficult to fix temporary shapes and realize shape memory effect；
Dividing when the 3rd, optically transparent light-coloured high temperature resistant shape-memory polymer mass loss prepared by the present invention is 5%
Solution temperature is 480 DEG C～502 DEG C, and the residual at 650 DEG C illustrates that the optically transparent light color of present invention preparation is resistance to more than 50%
High-temperature shape-memory polymer has excellent heat stability；
4th, optically transparent light-coloured high temperature resistant shape-memory polymer prepared by the present invention is in Tg-20℃(Tg20 DEG C below)
When storage moduluses be 1.61Gpa～1.92GPa, high temperature, Tg+20℃(Tg20 DEG C of the above) rubbery state when storage moduluses be
3.9MPa～5.2MPa；Optically transparent light-coloured high temperature resistant shape-memory polymer prepared by the present invention can ensure it at high temperature
Integrally-built stability can still be kept.
The present invention can obtain a kind of optically transparent light-coloured high temperature resistant shape-memory polymer.
Description of the drawings
Fig. 1 is the digital photograph of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1；
Fig. 2 is the X-ray diffractogram of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1；
Fig. 3 is the infrared spectrogram of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1；
Fig. 4 is the ultraviolet-visible spectrum of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1
Figure；
Fig. 5 is the fissipation factor figure of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1；
Fig. 6 is the storage moduluses figure of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1；
Fig. 7 is the thermogravimetric analysis figure of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1；
Fig. 8 is that optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 deforms at 210 DEG C, room
The temporary shapes that the lower fixation of temperature is obtained；
Fig. 9 is the optically transparent light-coloured high temperature resistant shape-memory polymer of the preparation of embodiment 1 after 2s in 210 DEG C of thermal station
Shape recovery situation；
Optically transparent light-coloured high temperature resistant shape-memory polymer prepared by Figure 10 embodiments 1 is after 4s in 210 DEG C of thermal station
Shape recovery situation；
Figure 11 be embodiment 1 prepare optically transparent light-coloured high temperature resistant shape-memory polymer in 250 DEG C of thermal station 9s
Shape recovery situation afterwards；
Figure 12 be embodiment 1 prepare optically transparent light-coloured high temperature resistant shape-memory polymer in 250 DEG C of thermal station 16s
Shape recovery situation afterwards；
Figure 13 be embodiment 1 prepare optically transparent light-coloured high temperature resistant shape-memory polymer in 250 DEG C of thermal station 22s
Shape recovery situation afterwards；
Figure 14 be embodiment 1 prepare optically transparent light-coloured high temperature resistant shape-memory polymer in 250 DEG C of thermal station 29s
Shape recovery situation afterwards；
Figure 15 is that the stress of optical clear light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 varies with temperature song
Line, 1 is temperature curve in Figure 15, and 2 is stress curve；
Figure 16 is that the strain of optical clear light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 varies with temperature song
Line, 1 is temperature curve in Figure 16, and 2 is strain curve.
Specific embodiment
Specific embodiment one：Present embodiment be a kind of optically transparent light-coloured high temperature resistant shape-memory polymer by 1,
Double (3- amino-benzene oxygens) benzene of 3- and Bisphenol A Type Diether Dianhydride are prepared from as reaction monomers；Double (the 3- amino of described 1,3-
Phenoxy group) the amount ratio of material of benzene and Bisphenol A Type Diether Dianhydride is (0.9～1.1):1.
The advantage of present embodiment：
First, optically transparent light-coloured high temperature resistant shape-memory polymer phase transition temperature T prepared by present embodimentgFor
168 DEG C～177 DEG C, compared with 63 DEG C of the phase transition temperature of the optical clear light color shape-memory polymer of current reported in literature,
Its phase transition temperature Tg105 DEG C～114 DEG C are improve, the opto-electronic device under high temperature is can be applicable to；
2nd, the thickness of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by present embodiment can reach 300 μ
Still have during m can be intact fixation and memory temporary shapes；And the thickness of Common transparent light color or colorless polyimide thin film is several
Micron or more than ten microns, be but difficult to fix temporary shapes and realize shape memory effect；
3rd, when optically transparent light-coloured high temperature resistant shape-memory polymer mass loss prepared by present embodiment is 5%
Decomposition temperature be 480 DEG C～502 DEG C, the residual at 650 DEG C more than 50%, illustrate present embodiment preparation optical clear
Light-coloured high temperature resistant shape-memory polymer there is excellent heat stability；
4th, optically transparent light-coloured high temperature resistant shape-memory polymer prepared by present embodiment is in Tg-20℃(TgBelow
20 DEG C) when storage moduluses be 1.61Gpa～1.92GPa, high temperature, Tg+20℃(Tg20 DEG C of the above) rubbery state when storage moduluses
For 3.9MPa～5.2MPa；Present embodiment prepare optically transparent light-coloured high temperature resistant shape-memory polymer can ensure its
Integrally-built stability can be still kept under high temperature.
Present embodiment can obtain a kind of optically transparent light-coloured high temperature resistant shape-memory polymer.
Specific embodiment two：Present embodiment is with the difference of specific embodiment one：It is characterized in that a kind of light
The structural formula for learning transparent light-coloured high temperature resistant shape-memory polymer is：
Wherein, the scope of described n is integer for 20～85, n.Other are identical with specific embodiment one.
Specific embodiment three：Present embodiment is with the difference of specific embodiment one or two：A kind of described light
The number-average molecular weight for learning transparent light-coloured high temperature resistant shape-memory polymer is 20.1kg/mol～52.2kg/mol.Other and tool
Body embodiment one or two is identical.
Specific embodiment four：Present embodiment is with the difference of specific embodiment one to three：The scope of described n
For 25～65.Other are identical with specific embodiment one to three.
Specific embodiment five：Present embodiment is a kind of system of optically transparent light-coloured high temperature resistant shape-memory polymer
Preparation Method, is specifically realized by the following steps：
First, double (3- amino-benzene oxygens) benzene of 1,3- are dissolved：Double (3- amino-benzene oxygens) benzene of 1,3- are added to into N, N'- diformazans
In yl acetamide, stir under the nitrogen atmosphere of room gently dried to double (3- amino-benzene oxygens) benzene of 1,3- and be completely dissolved, obtain
Diamine solution；
The amount and the body of N, N'- dimethyl acetylamide of the material of double (3- amino-benzene oxygens) benzene of 1,3- described in step one
Product is than being (0.2mmol～0.50mmol):1mL；
2nd, collosol and gel shape polyamic acid is prepared：Bisphenol A Type Diether Dianhydride is divided 5 times～7 times and is added to diamine solution
In, stirring reaction 16h～20h under conditions of temperature is 20 DEG C～35 DEG C and mixing speed is 600r/min～900r/min,
Obtain collosol and gel shape polyamic acid；
The thing of double (3- amino-benzene oxygens) benzene of the 1,3- in Bisphenol A Type Diether Dianhydride and diamine solution described in step 2
The amount ratio of matter is 1:(0.9～1.1)；
3rd, residual bubble is removed：By collosol and gel shape polyamic acid at drying in 30 DEG C～45 DEG C of vacuum drying oven
Reason 2h～3h, obtains the collosol and gel shape polyamic acid of not bubbles；
4th, hot-imide：The collosol and gel shape polyamic acid of not bubbles is poured on substrate, with 1 DEG C/min～2
DEG C/heating rate of min started to warm up to 70 DEG C～90 DEG C from room temperature, and be to be incubated 1h～2h at 70 DEG C～90 DEG C in temperature；
Again 100 DEG C～120 DEG C are warming up to from 70 DEG C～90 DEG C with the heating rate of 1 DEG C/min～2 DEG C/min, and in temperature
To be incubated 1h～2h at 100 DEG C～120 DEG C；
Again 150 DEG C～170 DEG C are warming up to from 100 DEG C～120 DEG C with the heating rate of 1 DEG C/min～2 DEG C/min, and in temperature
Spend to be incubated 1h～2h at 150 DEG C～170 DEG C；
Again 180 DEG C～200 DEG C are warming up to from 150 DEG C～170 DEG C with the heating rate of 1 DEG C/min～2 DEG C/min, and in temperature
Spend to be incubated 1h～2h at 180 DEG C～200 DEG C；
Again 220 DEG C～240 DEG C are warming up to from 180 DEG C～200 DEG C with the heating rate of 1 DEG C/min～2 DEG C/min, and in temperature
Spend to be incubated 1h～2h at 220 DEG C～240 DEG C；
Finally room temperature is cooled to as 220 DEG C～240 DEG C from temperature with the rate of temperature fall of 1 DEG C/min～2 DEG C/min, is contained
There is the substrate of polyimides；
5th, demoulding：Substrate containing polyimides is placed in distilled water, makes polyimides come off from substrate, then made
Polyimides are rinsed well with distilled water, then 2h～3h is dried in the case where temperature is for 80 DEG C～120 DEG C, obtain optically transparent shallow
Color high temperature resistant shape memory polymer, the structural formula of described optically transparent light-coloured high temperature resistant shape-memory polymer is：
Wherein, described n
Scope be integer for 25～65, n.
Chemical equation in present embodiment step 2 is：
Chemical equation in present embodiment step 4 is：
The advantage of present embodiment：
First, optically transparent light-coloured high temperature resistant shape-memory polymer phase transition temperature T prepared by present embodimentgFor
168 DEG C～177 DEG C, compared with 63 DEG C of the phase transition temperature of the optical clear light color shape-memory polymer of current reported in literature,
Its phase transition temperature Tg105 DEG C～114 DEG C are improve, the opto-electronic device under high temperature is can be applicable to；
2nd, the thickness of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by present embodiment can reach 300 μ
Still have during m can be intact fixation and memory temporary shapes；And the thickness of Common transparent light color or colorless polyimide thin film is several
Micron or more than ten microns, be but difficult to fix temporary shapes and realize shape memory effect；
3rd, when optically transparent light-coloured high temperature resistant shape-memory polymer mass loss prepared by present embodiment is 5%
Decomposition temperature be 480 DEG C～502 DEG C, the residual at 650 DEG C more than 50%, illustrate present embodiment preparation optical clear
Light-coloured high temperature resistant shape-memory polymer there is excellent heat stability；
4th, optically transparent light-coloured high temperature resistant shape-memory polymer prepared by present embodiment is in Tg-20℃(TgBelow
20 DEG C) when storage moduluses be 1.61Gpa～1.92GPa, high temperature, Tg+20℃(Tg20 DEG C of the above) rubbery state when storage moduluses
For 3.9MPa～5.2MPa；Present embodiment prepare optically transparent light-coloured high temperature resistant shape-memory polymer can ensure its
Integrally-built stability can be still kept under high temperature.
Present embodiment can obtain a kind of optically transparent light-coloured high temperature resistant shape-memory polymer.
Specific embodiment six：Present embodiment is with the difference of specific embodiment five：Described in step one 1,
The amount of material and the volume ratio of N, N'- dimethyl acetylamide of double (3- amino-benzene oxygens) benzene of 3- for (0.2mmol～
0.3mmol):1mL.Other are identical with specific embodiment five.
Specific embodiment seven：Present embodiment is with the difference of specific embodiment five or six：Described in step
The purity of double (3- amino-benzene oxygens) benzene of 1,3- be more than 97%.Other are identical with specific embodiment five or six.
Specific embodiment eight：Present embodiment is with the difference of specific embodiment five to seven：Described in step 2
Bisphenol A Type Diether Dianhydride purity be more than 97%.Other are identical with specific embodiment five to seven.
Specific embodiment nine：Present embodiment is with the difference of specific embodiment five to eight：Will be molten in step 3
The gluey polyamic acid dried 2.5h～3h in 35 DEG C～45 DEG C of vacuum drying oven of gelling, obtains the colloidal sol of not bubbles
Gel polyamic acid.Other are identical with specific embodiment five to eight.
Specific embodiment ten：Present embodiment is with the difference of specific embodiment five to nine：Will not in step 4
The collosol and gel shape polyamic acid of bubbles is poured on substrate, with the heating rate of 1.5 DEG C/min～2 DEG C/min from the beginning of room temperature
80 DEG C～90 DEG C are warming up to, and 1.5h～2h is incubated in the case where temperature is for 80 DEG C～90 DEG C；
Again 110 DEG C～120 DEG C are warming up to from 80 DEG C～90 DEG C with the heating rate of 1.5 DEG C/min～2 DEG C/min, and in temperature
Spend to be incubated 1.5h～2h at 110 DEG C～120 DEG C；
It is warming up to 160 DEG C～170 DEG C from 110 DEG C～120 DEG C with the heating rate of 1.5 DEG C/min～2 DEG C/min again, and
Temperature is insulation 1.5h～2h at 160 DEG C～170 DEG C；
It is warming up to 190 DEG C～200 DEG C from 160 DEG C～170 DEG C with the heating rate of 1.5 DEG C/min～2 DEG C/min again, and
Temperature is insulation 1.5h～2h at 190 DEG C～200 DEG C；
It is warming up to 230 DEG C～240 DEG C from 190 DEG C～200 DEG C with the heating rate of 1.5 DEG C/min～2 DEG C/min again, and
Temperature is insulation 1.5h～2h at 230 DEG C～240 DEG C；
Finally room temperature is cooled to as 230 DEG C～240 DEG C from temperature with the rate of temperature fall of 1.5 DEG C/min～2 DEG C/min, is obtained
Substrate containing polyimides.Other are identical with specific embodiment five to nine.
Specific embodiment 11：Present embodiment is with the difference of specific embodiment five to ten：Will in step 4
The collosol and gel shape polyamic acid of bubbles is not poured on substrate, is started to warm up to 80 from room temperature with the heating rate of 1 DEG C/min
DEG C, and it is incubated 2h in the case where temperature is for 80 DEG C；
Again 110 DEG C are warming up to from 80 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 110 DEG C；
Again 160 DEG C are warming up to from 110 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 160 DEG C；
Again 190 DEG C are warming up to from 160 DEG C with the heating rate of 2 DEG C/min, and 2h is incubated in the case where temperature is for 190 DEG C；
Again 230 DEG C are warming up to from 190 DEG C with the heating rate of 2 DEG C/min, and 1h is incubated in the case where temperature is for 230 DEG C；
Finally room temperature is cooled to as 230 DEG C from temperature with the rate of temperature fall of 2 DEG C/min, obtains the base containing polyimides
Plate.Other are identical with specific embodiment five to ten.
Specific embodiment 12：Present embodiment is with the difference of specific embodiment five to 11：In step 4
The collosol and gel shape polyamic acid of not bubbles is poured on substrate, with the heating rate of 1 DEG C/min from room temperature start to warm up to
70 DEG C, and it is incubated 2h in the case where temperature is for 70 DEG C；
Again 100 DEG C are warming up to from 70 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 100 DEG C；
Again 150 DEG C are warming up to from 100 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 150 DEG C；
Again 190 DEG C are warming up to from 150 DEG C with the heating rate of 2 DEG C/min, and 1h is incubated in the case where temperature is for 190 DEG C；
Again 220 DEG C are warming up to from 190 DEG C with the heating rate of 2 DEG C/min, and 1h is incubated in the case where temperature is for 220 DEG C；
Finally room temperature is cooled to as 220 DEG C from temperature with the rate of temperature fall of 1 DEG C/min, obtains the base containing polyimides
Plate.Other are identical with specific embodiment five to 11.
Specific embodiment 13：Present embodiment is with the difference of specific embodiment five to 12：In step 4
The collosol and gel shape polyamic acid of not bubbles is poured on substrate, with the heating rate of 1 DEG C/min from room temperature start to warm up to
80 DEG C, and it is incubated 2h in the case where temperature is for 80 DEG C；
Again 120 DEG C are warming up to from 80 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 120 DEG C；
Again 160 DEG C are warming up to from 120 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 160 DEG C；
Again 200 DEG C are warming up to from 160 DEG C with the heating rate of 2 DEG C/min, and 1h is incubated in the case where temperature is for 200 DEG C；
Again 240 DEG C are warming up to from 200 DEG C with the heating rate of 2 DEG C/min, and 1h is incubated in the case where temperature is for 240 DEG C；
Finally room temperature is cooled to as 240 DEG C from temperature with the rate of temperature fall of 1 DEG C/min, obtains the base containing polyimides
Plate.Other are identical with specific embodiment five to 12.
Specific embodiment 14：Present embodiment is with the difference of specific embodiment five to 13：In step 4
The collosol and gel shape polyamic acid of not bubbles is poured on substrate, with the heating rate of 1 DEG C/min from room temperature start to warm up to
80 DEG C, and it is incubated 1.5h in the case where temperature is for 80 DEG C；
Again 110 DEG C are warming up to from 80 DEG C with the heating rate of 1 DEG C/min, and 1.5h is incubated in the case where temperature is for 110 DEG C；
Again 160 DEG C are warming up to from 110 DEG C with the heating rate of 2 DEG C/min, and 2h is incubated in the case where temperature is for 160 DEG C；
Again 200 DEG C are warming up to from 160 DEG C with the heating rate of 2 DEG C/min, and 2h is incubated in the case where temperature is for 200 DEG C；
Again 230 DEG C are warming up to from 200 DEG C with the heating rate of 2 DEG C/min, and 2h is incubated in the case where temperature is for 230 DEG C；
Finally room temperature is cooled to as 230 DEG C from temperature with the rate of temperature fall of 2 DEG C/min, obtains the base containing polyimides
Plate.Other are identical with specific embodiment five to 13.
Specific embodiment 15：Present embodiment is with the difference of specific embodiment five to 14：In step 4
The collosol and gel shape polyamic acid of not bubbles is poured on substrate, with the heating rate of 2 DEG C/min from room temperature start to warm up to
70 DEG C, and it is incubated 2h in the case where temperature is for 70 DEG C；
Again 110 DEG C are warming up to from 70 DEG C with the heating rate of 2 DEG C/min, and 2h is incubated in the case where temperature is for 110 DEG C；
Again 160 DEG C are warming up to from 110 DEG C with the heating rate of 2 DEG C/min, and 2h is incubated in the case where temperature is for 160 DEG C；
Again 190 DEG C are warming up to from 160 DEG C with the heating rate of 2 DEG C/min, and 1h is incubated in the case where temperature is for 190 DEG C；
Again 220 DEG C are warming up to from 200 DEG C with the heating rate of 2 DEG C/min, and 1h is incubated in the case where temperature is for 220 DEG C；
Finally room temperature is cooled to as 220 DEG C from temperature with the rate of temperature fall of 2 DEG C/min, obtains the base containing polyimides
Plate.Other are identical with specific embodiment five to 14.
Specific embodiment 16：Present embodiment is with the difference of specific embodiment five to 15：In step
The amount of material and the volume ratio of N, N'- dimethyl acetylamide of double (3- amino-benzene oxygens) benzene of described 1,3- be
0.2275mmol:1mL.Other are identical with specific embodiment five to 15.
Specific embodiment 17：Present embodiment is with the difference of specific embodiment five to 16：In step
The amount of material and the volume ratio of N, N'- dimethyl acetylamide of double (3- amino-benzene oxygens) benzene of described 1,3- is 0.235mmol:
1mL.Other are identical with specific embodiment five to 16.
Specific embodiment 18：Present embodiment is with the difference of specific embodiment five to 17：In step
The amount of material and the volume ratio of N, N'- dimethyl acetylamide of double (3- amino-benzene oxygens) benzene of described 1,3- be
0.2425mmol:1mL.Other are identical with specific embodiment five to 17.
Specific embodiment 19：Present embodiment is with the difference of specific embodiment five to 18：In step
The amount of material and the volume ratio of N, N'- dimethyl acetylamide of double (3- amino-benzene oxygens) benzene of described 1,3- is 0.4mmol:
1mL.Other are identical with specific embodiment five to 18.
Specific embodiment 20：Present embodiment is with the difference of specific embodiment five to 19：In step
The amount of material and the volume ratio of N, N'- dimethyl acetylamide of double (3- amino-benzene oxygens) benzene of described 1,3- is 0.50mmol:
1mL.Other are identical with specific embodiment five to 19.
Specific embodiment 21：Present embodiment is with the difference of specific embodiment five to 20：Step 2
Described in Bisphenol A Type Diether Dianhydride and diamine solution in the amount ratio of material of double (3- amino-benzene oxygens) benzene of 1,3- be 1:
(0.9～0.95).Other are identical with specific embodiment five to 20.
Specific embodiment 22：Present embodiment is with the difference of specific embodiment five to 21：Step
The amount ratio of the material of double (3- amino-benzene oxygens) benzene of the 1,3- in Bisphenol A Type Diether Dianhydride and diamine solution described in two is 1:
(0.95～1).Other are identical with specific embodiment five to 21.
Beneficial effects of the present invention are verified using tests below：
Embodiment 1：A kind of preparation method of optically transparent light-coloured high temperature resistant shape-memory polymer is specifically by following
What step was completed：
First, double (3- amino-benzene oxygens) benzene of 1,3- are dissolved：Double (3- amino-benzene oxygens) benzene of 4.55mmol 1,3- are added to
In 20mL N, N'- dimethyl acetylamide, (3- amino-benzene oxygens) benzene double to 1,3- are stirred under the nitrogen atmosphere of room gently dried
It is completely dissolved, obtains diamine solution；
2nd, collosol and gel shape polyamic acid is prepared：5mmol Bisphenol A Type Diether Dianhydrides are divided 6 times and is added to diamine solution
In, stirring reaction 20h under conditions of temperature is 20 DEG C and mixing speed is 760r/min obtains collosol and gel shape polyamide
Acid；
3rd, residual bubble is removed：By collosol and gel shape polyamic acid in 40 DEG C of vacuum drying oven dried 2h, obtain
To the collosol and gel shape polyamic acid of not bubbles；
4th, hot-imide：The collosol and gel shape polyamic acid of not bubbles is poured on substrate, with the liter of 1 DEG C/min
Warm speed is started to warm up to 80 DEG C from room temperature, and is incubated 2h in the case where temperature is for 80 DEG C；
Again 110 DEG C are warming up to from 80 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 110 DEG C；
Again 160 DEG C are warming up to from 110 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 160 DEG C；
Again 190 DEG C are warming up to from 160 DEG C with the heating rate of 2 DEG C/min, and 2h is incubated in the case where temperature is for 190 DEG C；
Again 230 DEG C are warming up to from 190 DEG C with the heating rate of 2 DEG C/min, and 1h is incubated in the case where temperature is for 230 DEG C；
Finally room temperature is cooled to as 230 DEG C from temperature with the rate of temperature fall of 2 DEG C/min, obtains the base containing polyimides
Plate；
5th, demoulding：Substrate containing polyimides is placed in distilled water, makes polyimides come off from substrate, then made
Polyimides are rinsed well with distilled water, then 2h is dried in the case where temperature is for 120 DEG C, obtain optically transparent light-coloured high temperature resistant shape
Shape memory polymer.
The optically transparent light-coloured high temperature resistant shape-memory polymer of the preparation of embodiment 1 is measured using chromatograph of gel permeation
Number-average molecular weight be 20.1kg/mol；
The optically transparent light-coloured high temperature resistant shape-memory polymer of the preparation of embodiment 1 is measured using chromatograph of gel permeation
Structural formula be：
Fig. 1 is the digital photograph of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1；From Fig. 1
It can be seen that, optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 has good optical transparence；
The optically transparent light-coloured high temperature resistant shape-memory polymer structure for using X-ray diffractometer being prepared by embodiment 1
Studied, as shown in Fig. 2 Fig. 2 is the X of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 penetrating
Ray diffraction diagram；Can be to from Fig. 2, there is wider amorphous diffraction envelope near 18 °, illustrate the optically transparent shallow of the preparation of embodiment 1
Color high temperature resistant shape memory polymer is amorphous state；
The optically transparent light-coloured high temperature resistant shape-memory polymer prepared to embodiment 1 using infrared spectrometer is tested,
As shown in figure 3, Fig. 3 is the infrared spectrogram of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1；From
As can be seen that 1778cm in Fig. 3-1The absworption peak at place is the asymmetric stretch absworption peak (v of acid imide carbonylAs C=O), and
1722cm-1The absworption peak at place is the feature symmetrical stretching vibration peak (v of acid imide carbonylS C=O), 1372cm-1For the flexible of C-N keys
Vibration absorption peak (vC-N), optically transparent light-coloured high temperature resistant shape memory prepared by these characteristic absorption peak explanation embodiments 1 gathers
Compound is the polyimides of height imidizate.
The optical property of sample is tested using ultraviolet-visible spectrophotometer, as a result as shown in Figure 4；Fig. 4 is real
Apply the UV-visible spectrum of the optically transparent light-coloured high temperature resistant shape-memory polymer of the preparation of example 1；From fig. 4, it can be seen that
When the thickness of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 is 150 μm, its cutoff wavelength is
388nm, the transmitance at 450nm, 500nm and 600nm is respectively 82%, 85% and 88%；
Optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 is entered using dynamic mechanical analyzer
Row test, as shown in figure 5, Fig. 5 be embodiment 1 prepare optically transparent light-coloured high temperature resistant shape-memory polymer loss because
Subgraph；As can be seen from Figure 5, the T of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1gFor 168 DEG C, protect
The optically transparent light-coloured high temperature resistant shape-memory polymer shape memory effect for having demonstrate,proved the preparation of embodiment 1 can be applicable to high temperature light
Electrical domain.
Optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 is entered using dynamic mechanical analyzer
Row test, as shown in fig. 6, Fig. 6 is the storage mould of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1
Spirogram；As can be seen from Figure 6, storage moduluses change curve occurs in that two platforms of high and low temperature section, 148 DEG C of (Tg- 20 DEG C) glass
Storage moduluses during state are 1.67GPa；188 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage moduluses be 3.9MPa；It is flat at two
Storage moduluses drastically decline between platform, and corresponding to the Glass Transition of material, the drastically change of this modulus is polymer
Possesses the essential condition of shape memory property.
Optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 is surveyed using thermogravimetric analyzer
Examination, as shown in fig. 7, Fig. 7 is the thermogravimetric analysiss of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1
Figure；When the optically transparent light-coloured high temperature resistant shape-memory polymer mass loss that as can be seen from Figure 7, prepared by embodiment 1 is 5%
Decomposition temperature is 480 DEG C, and the residual at 650 DEG C is 51%, illustrates optically transparent light-coloured high temperature resistant shape prepared by embodiment 1
Shape memory polymer has excellent heat resistance.
Optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 is surveyed using high-temperature stage
Examination, as shown in Fig. 8 to Figure 14；Fig. 8 is the optically transparent light-coloured high temperature resistant shape-memory polymer of the preparation of embodiment 1 210
DEG C when deform, the temporary shapes that obtain of fixation under room temperature；
Fig. 9 is the optically transparent light-coloured high temperature resistant shape-memory polymer of the preparation of embodiment 1 after 2s in 210 DEG C of thermal station
Shape recovery situation；
Optically transparent light-coloured high temperature resistant shape-memory polymer prepared by Figure 10 embodiments 1 is after 4s in 210 DEG C of thermal station
Shape recovery situation；
Figure 11 be embodiment 1 prepare optically transparent light-coloured high temperature resistant shape-memory polymer in 250 DEG C of thermal station 9s
Shape recovery situation afterwards；
Figure 12 be embodiment 1 prepare optically transparent light-coloured high temperature resistant shape-memory polymer in 250 DEG C of thermal station 16s
Shape recovery situation afterwards；
Figure 13 be embodiment 1 prepare optically transparent light-coloured high temperature resistant shape-memory polymer in 250 DEG C of thermal station 22s
Shape recovery situation afterwards；
Figure 14 be embodiment 1 prepare optically transparent light-coloured high temperature resistant shape-memory polymer in 250 DEG C of thermal station 29s
Shape recovery situation afterwards；
Knowable to Fig. 8 to Figure 14, embodiment 1 prepare optically transparent light-coloured high temperature resistant shape-memory polymer have compared with
Good shape memory effect.
The optically transparent light-coloured high temperature resistant shape memory prepared to embodiment 1 using Stress Control circulation shape memory is gathered
Compound carries out shape fixed rate and shape recovery ratio test, as shown in Figure 15 and Figure 16.
Figure 15 is that the stress of optical clear light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 varies with temperature song
Line, 1 is temperature curve in Figure 15, and 2 is stress curve；
Figure 16 is that the strain of optical clear light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 varies with temperature song
Line, 1 is temperature curve in Figure 16, and 2 is strain curve.As can be seen from Figure 16, the optically transparent light-coloured high temperature resistant that prepared by embodiment 1
Shape-memory polymer shape fixed rate is 99.3%, and its shape recovery ratio is 97.2%.
Embodiment 2：A kind of preparation method of optically transparent light-coloured high temperature resistant shape-memory polymer is specifically by following
What step was completed：
First, double (3- amino-benzene oxygens) benzene of 1,3- are dissolved：Double (3- amino-benzene oxygens) benzene of 4.7mmol 1,3- are added to
In 20mL N, N'- dimethyl acetylamide, (3- amino-benzene oxygens) benzene double to 1,3- are stirred under the nitrogen atmosphere of room gently dried
It is completely dissolved, obtains diamine solution；
2nd, collosol and gel shape polyamic acid is prepared：5mmol Bisphenol A Type Diether Dianhydrides are divided 5 times and is added to diamine solution
In, stirring reaction 18h under conditions of temperature is 20 DEG C and mixing speed is 800r/min obtains collosol and gel shape polyamide
Acid；
3rd, residual bubble is removed：By collosol and gel shape polyamic acid in 40 DEG C of vacuum drying oven dried 2h, obtain
To the collosol and gel shape polyamic acid of not bubbles；
4th, hot-imide：The collosol and gel shape polyamic acid of not bubbles is poured on substrate, with the liter of 1 DEG C/min
Warm speed is started to warm up to 80 DEG C from room temperature, and is incubated 2h in the case where temperature is for 80 DEG C；
Again 110 DEG C are warming up to from 80 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 110 DEG C；
Again 160 DEG C are warming up to from 110 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 160 DEG C；
Again 190 DEG C are warming up to from 160 DEG C with the heating rate of 2 DEG C/min, and 2h is incubated in the case where temperature is for 190 DEG C；
Again 230 DEG C are warming up to from 190 DEG C with the heating rate of 2 DEG C/min, and 1h is incubated in the case where temperature is for 230 DEG C；
Finally room temperature is cooled to as 230 DEG C from temperature with the rate of temperature fall of 2 DEG C/min, obtains the base containing polyimides
Plate；
5th, demoulding：Substrate containing polyimides is placed in distilled water, makes polyimides come off from substrate, then made
Polyimides are rinsed well with distilled water, then 2.5h is dried in the case where temperature is for 100 DEG C, obtain optically transparent light-coloured high temperature resistant
Shape-memory polymer.
The optically transparent light-coloured high temperature resistant shape-memory polymer of the preparation of embodiment 2 is measured using chromatograph of gel permeation
Number-average molecular weight be 26.8kg/mol；
The optically transparent light-coloured high temperature resistant shape-memory polymer of the preparation of embodiment 2 is measured using chromatograph of gel permeation
Structural formula be：
Its cut-off wave when optically transparent light-coloured high temperature resistant shape-memory polymer thickness prepared by embodiment 2 is 150 μm
A length of 391nm, the transmitance at 450nm, 500nm and 600nm is respectively 66%, 73% and 85%；
The T of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 2gFor 172 DEG C, it is ensured that its shape
Shape memory effect can be applicable to the photoelectric device of high-temperature field；Optically transparent light-coloured high temperature resistant shape note prepared by embodiment 2
Recall 152 DEG C of (T of polymerg- 20 DEG C) glassy state when storage moduluses be 1.61G Pa；192 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when
Storage moduluses be about 4.2MPa；
Decomposition temperature when transparent shape memory polyimides mass loss prepared by embodiment 2 is 5% is 485 DEG C, is said
Transparent shape memory polyimides prepared by bright embodiment 2 have excellent heat resistance.Transparent shape note prepared by embodiment 2
The shape fixed rate for recalling polyimides is 99.2%, and shape recovery ratio is 97.6%.
Embodiment 3：A kind of preparation method of optically transparent light-coloured high temperature resistant shape-memory polymer is specifically by following
What step was completed：
First, double (3- amino-benzene oxygens) benzene of 1,3- are dissolved：Double (3- amino-benzene oxygens) benzene of 4.85mmol 1,3- are added to
In 20mL N, N'- dimethyl acetylamide, (3- amino-benzene oxygens) benzene double to 1,3- are stirred under the nitrogen atmosphere of room gently dried
It is completely dissolved, obtains diamine solution；
2nd, collosol and gel shape polyamic acid is prepared：5mmol Bisphenol A Type Diether Dianhydrides are divided 5 times～7 times and is added to diamidogen
In solution, stirring reaction 18h under conditions of temperature is 20 DEG C and mixing speed is 600r/min obtains collosol and gel shape polyamides
Amino acid；
3rd, residual bubble is removed：By collosol and gel shape polyamic acid in 40 DEG C of vacuum drying oven dried 2h, obtain
To the collosol and gel shape polyamic acid of not bubbles；
4th, hot-imide：The collosol and gel shape polyamic acid of not bubbles is poured on substrate, with the liter of 1 DEG C/min
Warm speed is started to warm up to 80 DEG C from room temperature, and is incubated 2h in the case where temperature is for 80 DEG C；
Again 110 DEG C are warming up to from 80 DEG C with the heating rate of 1 DEG C/min, and 1h is incubated in the case where temperature is for 110 DEG C；
Again 160 DEG C are warming up to from 110 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 160 DEG C；
Again 190 DEG C are warming up to from 160 DEG C with the heating rate of 2 DEG C/min, and 2h is incubated in the case where temperature is for 190 DEG C；
Again 230 DEG C are warming up to from 190 DEG C with the heating rate of 2 DEG C/min, and 2h is incubated in the case where temperature is for 230 DEG C；
Finally room temperature is cooled to as 230 DEG C from temperature with the rate of temperature fall of 2 DEG C/min, obtains the base containing polyimides
Plate；
5th, demoulding：Substrate containing polyimides is placed in distilled water, makes polyimides come off from substrate, then made
Polyimides are rinsed well with distilled water, then 3h is dried in the case where temperature is for 80 DEG C, obtain optically transparent light-coloured high temperature resistant shape
Shape memory polymer.
The optically transparent light-coloured high temperature resistant shape-memory polymer of the preparation of embodiment 3 is measured using chromatograph of gel permeation
Number-average molecular weight be 37.9kg/mol；
The optically transparent light-coloured high temperature resistant shape-memory polymer of the preparation of embodiment 3 is measured using chromatograph of gel permeation
Structural formula be：
Its cut-off wave when optically transparent light-coloured high temperature resistant shape-memory polymer thickness prepared by embodiment 3 is 150 μm
A length of 394nm, the transmitance at 450nm, 500nm and 600nm is respectively 52%, 66% and 81%；
The T of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 3gFor 174 DEG C, it is ensured that its shape
Shape memory effect can be applicable to the photoelectric device of high-temperature field；Optically transparent light-coloured high temperature resistant shape note prepared by embodiment 3
Polymer is recalled in 154 DEG C of (Tg- 20 DEG C) glassy state when storage moduluses be 1.83G Pa；194 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state
When storage moduluses be about 4.7MPa；Optically transparent light-coloured high temperature resistant shape-memory polymer quality prepared by embodiment 3 is damaged
Lose for 5% when decomposition temperature be 487 DEG C, illustrate embodiment 3 preparation optically transparent light-coloured high temperature resistant shape memory polymers
Thing has excellent heat resistance；The shape of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 3 is consolidated
It is 99.5% to determine rate, and shape recovery ratio is 98.2%.
Embodiment 4：A kind of preparation method of optically transparent light-coloured high temperature resistant shape-memory polymer is specifically by following
What step was completed：
First, double (3- amino-benzene oxygens) benzene of 1,3- are dissolved：Double (3- amino-benzene oxygens) benzene of 4.925mmol 1,3- are added
To 20mL N, in N'- dimethyl acetylamide, stir double (3- amino-benzene oxygens) to 1,3- under the nitrogen atmosphere of room gently dried
Benzene is completely dissolved, and obtains diamine solution；
2nd, collosol and gel shape polyamic acid is prepared：5mmol Bisphenol A Type Diether Dianhydrides are divided 5 times～7 times and is added to diamidogen
In solution, stirring reaction 20h under conditions of temperature is 20 DEG C and mixing speed is 700r/min obtains collosol and gel shape polyamides
Amino acid；
3rd, residual bubble is removed：By collosol and gel shape polyamic acid in 45 DEG C of vacuum drying oven dried 2h, obtain
To the collosol and gel shape polyamic acid of not bubbles；
4th, hot-imide：The collosol and gel shape polyamic acid of not bubbles is poured on substrate, with the liter of 1 DEG C/min
Warm speed is started to warm up to 80 DEG C from room temperature, and is incubated 2h in the case where temperature is for 80 DEG C；
Again 110 DEG C are warming up to from 80 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 110 DEG C；
Again 160 DEG C are warming up to from 110 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 160 DEG C；
Again 190 DEG C are warming up to from 160 DEG C with the heating rate of 2 DEG C/min, and 2h is incubated in the case where temperature is for 190 DEG C；
Again 230 DEG C are warming up to from 190 DEG C with the heating rate of 2 DEG C/min, and 1h is incubated in the case where temperature is for 230 DEG C；
Finally room temperature is cooled to as 230 DEG C from temperature with the rate of temperature fall of 2 DEG C/min, obtains the base containing polyimides
Plate；
5th, demoulding：Substrate containing polyimides is placed in distilled water, makes polyimides come off from substrate, then made
Polyimides are rinsed well with distilled water, then 3h is dried in the case where temperature is for 80 DEG C, obtain optically transparent light-coloured high temperature resistant shape
Shape memory polymer.
The optically transparent light-coloured high temperature resistant shape-memory polymer of the preparation of embodiment 4 is measured using chromatograph of gel permeation
Number-average molecular weight be 42.6kg/mol；
The optically transparent light-coloured high temperature resistant shape-memory polymer of the preparation of embodiment 4 is measured using chromatograph of gel permeation
Structural formula be：
Its cut-off wave when optically transparent light-coloured high temperature resistant shape-memory polymer thickness prepared by embodiment 4 is 150 μm
A length of 396nm, the transmitance at 450nm, 500nm and 600nm is respectively 42%, 63% and 80%；
The T of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 4gFor 176 DEG C, it is ensured that its shape
Shape memory effect can be applicable to the photoelectric device of high-temperature field；
Optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 4 is in 156 DEG C of (Tg- 20 DEG C) glassy state
When storage moduluses be 1.92G Pa；196 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage moduluses be about 5.2MPa；
Decomposition when optically transparent light-coloured high temperature resistant shape-memory polymer mass loss prepared by embodiment 4 is 5%
Temperature is 495 DEG C, illustrate the preparation of embodiment 4 optically transparent light-coloured high temperature resistant shape-memory polymer have it is excellent heat-resisting
Performance.The shape fixed rate for learning transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 4 is 99.4%, and shape is extensive
Multiple rate is 99.1%.
Embodiment 5：A kind of preparation method of optically transparent light-coloured high temperature resistant shape-memory polymer is specifically by following
What step was completed：
First, double (3- amino-benzene oxygens) benzene of 1,3- are dissolved：Double (3- amino-benzene oxygens) benzene of 5mmol 1,3- are added to
In 20mL N, N'- dimethyl acetylamide, (3- amino-benzene oxygens) benzene double to 1,3- are stirred under the nitrogen atmosphere of room gently dried
It is completely dissolved, obtains diamine solution；
2nd, collosol and gel shape polyamic acid is prepared：5mmol Bisphenol A Type Diether Dianhydrides are divided 6 times and is added to diamine solution
In, stirring reaction 20h under conditions of temperature is 30 DEG C and mixing speed is 900r/min obtains collosol and gel shape polyamide
Acid；
3rd, residual bubble is removed：By collosol and gel shape polyamic acid in 45 DEG C of vacuum drying oven dried 2h, obtain
To the collosol and gel shape polyamic acid of not bubbles；
4th, hot-imide：The collosol and gel shape polyamic acid of not bubbles is poured on substrate, with the liter of 1 DEG C/min
Warm speed is started to warm up to 80 DEG C from room temperature, and is incubated 2h in the case where temperature is for 80 DEG C；
Again 110 DEG C are warming up to from 80 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 110 DEG C；
Again 160 DEG C are warming up to from 110 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 160 DEG C；
Again 190 DEG C are warming up to from 160 DEG C with the heating rate of 2 DEG C/min, and 2h is incubated in the case where temperature is for 190 DEG C；
Again 230 DEG C are warming up to from 190 DEG C with the heating rate of 2 DEG C/min, and 1h is incubated in the case where temperature is for 230 DEG C；
Finally room temperature is cooled to as 220 DEG C from temperature with the rate of temperature fall of 2 DEG C/min, obtains the base containing polyimides
Plate；
5th, demoulding：Substrate containing polyimides is placed in distilled water, makes polyimides come off from substrate, then made
Polyimides are rinsed well with distilled water, then 3h is dried in the case where temperature is for 90 DEG C, obtain optically transparent light-coloured high temperature resistant shape
Shape memory polymer.
The optically transparent light-coloured high temperature resistant shape-memory polymer of the preparation of embodiment 5 is measured using chromatograph of gel permeation
Number-average molecular weight be 52.2kg/mol；
The optically transparent light-coloured high temperature resistant shape-memory polymer of the preparation of embodiment 5 is measured using chromatograph of gel permeation
Structural formula be：
Its cut-off when the thickness of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 5 is 150 μm
Wavelength is 402nm, and the transmitance at 450nm, 500nm and 600nm is respectively 24%, 47% and 75%；
The T of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 5gFor 177 DEG C, it is ensured that its shape
Shape memory effect can be applicable to the photoelectric device of high-temperature field；
Optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 5 is in 157 DEG C of (Tg- 20 DEG C) glassy state
When storage moduluses be 1.92G Pa；197 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage moduluses be about 5.1MPa；
Decomposition when optically transparent light-coloured high temperature resistant shape-memory polymer mass loss prepared by embodiment 5 is 5%
Temperature is 502 DEG C, illustrate the preparation of embodiment 5 optically transparent light-coloured high temperature resistant shape-memory polymer have it is excellent heat-resisting
Performance；
The shape fixed rate of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 5 is 99.6%,
Shape recovery ratio is 98.6%.
Claims (1)
1. a kind of preparation method of optically transparent light-coloured high temperature resistant shape-memory polymer, it is characterised in that the method is specifically
Complete according to the following steps：
First, double (3- amino-benzene oxygens) benzene of 1,3- are dissolved：Double (3- amino-benzene oxygens) benzene of 4.55mmol 1,3- are added to into 20mL
In N, N'- dimethyl acetylamide, stir complete to double (3- amino-benzene oxygens) benzene of 1,3- under the nitrogen atmosphere of room gently dried
Dissolving, obtains diamine solution；
2nd, collosol and gel shape polyamic acid is prepared：5mmol Bisphenol A Type Diether Dianhydrides are divided 6 times and is added in diamine solution,
It is stirring reaction 20h under conditions of 760r/min with mixing speed that temperature is 20 DEG C, obtains collosol and gel shape polyamic acid；
3rd, residual bubble is removed：By collosol and gel shape polyamic acid in 40 DEG C of vacuum drying oven dried 2h, obtain not
The collosol and gel shape polyamic acid of bubbles；
4th, hot-imide：The collosol and gel shape polyamic acid of not bubbles is poured on substrate, with the intensification speed of 1 DEG C/min
Rate is started to warm up to 80 DEG C from room temperature, and is incubated 2h in the case where temperature is for 80 DEG C；
Again 110 DEG C are warming up to from 80 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 110 DEG C；
Again 160 DEG C are warming up to from 110 DEG C with the heating rate of 1 DEG C/min, and 2h is incubated in the case where temperature is for 160 DEG C；
Again 190 DEG C are warming up to from 160 DEG C with the heating rate of 2 DEG C/min, and 2h is incubated in the case where temperature is for 190 DEG C；
Again 230 DEG C are warming up to from 190 DEG C with the heating rate of 2 DEG C/min, and 1h is incubated in the case where temperature is for 230 DEG C；
Finally room temperature is cooled to as 230 DEG C from temperature with the rate of temperature fall of 2 DEG C/min, obtains the substrate containing polyimides；
5th, demoulding：Substrate containing polyimides is placed in distilled water, makes polyimides come off from substrate, reuse steaming
Distilled water rinses well polyimides, then is dried 2h in the case where temperature is for 120 DEG C, obtains optically transparent light-coloured high temperature resistant shape note
Recall polymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510194023.5A CN104788675B (en) | 2015-04-22 | 2015-04-22 | Optical transparent light-colored high temperature-resisting shape memory polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510194023.5A CN104788675B (en) | 2015-04-22 | 2015-04-22 | Optical transparent light-colored high temperature-resisting shape memory polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104788675A CN104788675A (en) | 2015-07-22 |
| CN104788675B true CN104788675B (en) | 2017-04-26 |
Family
ID=53553891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510194023.5A Active CN104788675B (en) | 2015-04-22 | 2015-04-22 | Optical transparent light-colored high temperature-resisting shape memory polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104788675B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105226185A (en) * | 2015-08-25 | 2016-01-06 | 哈尔滨工业大学 | A kind of preparation method with the non-oxidation indium tin polymer solar battery of shape memory effect |
| CN105576153B (en) * | 2015-12-28 | 2017-11-17 | 哈尔滨工业大学 | A kind of preparation method of the non-oxidation indium tin flexibility Organic Light Emitting Diode with SME |
| CN105399951B (en) * | 2015-12-29 | 2018-03-30 | 哈尔滨工业大学 | A kind of adjustable shape memory random copolymerization polyimides of glass transition temperature and preparation method thereof |
| CN107987292B (en) * | 2017-12-20 | 2021-06-08 | 哈尔滨工业大学 | Preparation method of optical transparent electrodrive type shape memory polymer film |
| CN108587164B (en) * | 2018-05-09 | 2020-07-07 | 哈尔滨工业大学 | Color-adjustable shape memory polyimide and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5218077A (en) * | 1991-08-26 | 1993-06-08 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Diphenylmethane-containing dianhydride and polyimides prepared therefrom |
| US5550199A (en) * | 1994-12-02 | 1996-08-27 | Exxon Research And Engineering Company | Diepoxide crosslinked/esterified polyimide-aliphatic polyester copolymers |
| US5986036A (en) * | 1997-06-27 | 1999-11-16 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Substrate material for holographic emulsions utilizing fluorinated polyimide film |
| 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 |
| CN104004188A (en) * | 2014-06-19 | 2014-08-27 | 冷劲松 | High-temperature-resistant thermoset shape memory polyimide and preparing 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 |
-
2015
- 2015-04-22 CN CN201510194023.5A patent/CN104788675B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5218077A (en) * | 1991-08-26 | 1993-06-08 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Diphenylmethane-containing dianhydride and polyimides prepared therefrom |
| US5550199A (en) * | 1994-12-02 | 1996-08-27 | Exxon Research And Engineering Company | Diepoxide crosslinked/esterified polyimide-aliphatic polyester copolymers |
| US5986036A (en) * | 1997-06-27 | 1999-11-16 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Substrate material for holographic emulsions utilizing fluorinated polyimide film |
| 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 |
| CN104004188A (en) * | 2014-06-19 | 2014-08-27 | 冷劲松 | High-temperature-resistant thermoset shape memory polyimide and preparing 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 |
Non-Patent Citations (1)
| Title |
|---|
| 四甲基联苯二胺及有机可溶聚酰亚胺的合成与性能;武迪蒙 等;《高分子材料科学与工程》;20121115;第28卷(第11期);第13-16页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104788675A (en) | 2015-07-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104788675B (en) | Optical transparent light-colored high temperature-resisting shape memory polymer and preparation method thereof | |
| KR101922791B1 (en) | A quick responsive, shape memory thermoset polyimide and preparation method thereof | |
| CN106164132B (en) | Polyimide compositions | |
| CN108699242A (en) | polyimide precursor solution and its manufacturing method | |
| CN104004188A (en) | High-temperature-resistant thermoset shape memory polyimide and preparing method thereof | |
| CN106928481A (en) | The optimization preparation method of Kapton | |
| CN103980490B (en) | A kind of chemistry acid imide method prepares shape memory polyimides and method thereof | |
| CN104804188B (en) | A kind of preparation method of Kapton | |
| CN108456309B (en) | High-performance thermosetting shape memory polyimide capable of being laminated and welded | |
| CN114874440B (en) | Polyimide/reduced graphene oxide composite material and preparation method and application thereof | |
| CN109762166A (en) | A kind of preparation method of polyimide precursor and Kapton | |
| CN107459649A (en) | A kind of polyimide polymer, a kind of transparent polyimide film and preparation method thereof | |
| CN103282416A (en) | Method for preparing polyimide film | |
| CN104017213A (en) | Shape memory polyether imide with high glass-transition temperature and preparation method thereof | |
| CN112961349B (en) | High-performance transparent polyimide, polyimide film and preparation method thereof | |
| CN110218330A (en) | A kind of selfreparing modified silicon rubber and preparation method thereof | |
| CN105254888A (en) | Polyimide ionomer and preparation method thereof | |
| CN110684175B (en) | High-light-transmittance super-tough room-temperature intrinsic self-repairing elastomer material and preparation method thereof | |
| CN112574411A (en) | Polyimide precursor, polyimide film, preparation method of polyimide film and display device | |
| CN114163637A (en) | Azobenzene polyimide film material with reversible photoinduced deformability and preparation method thereof | |
| CN105418922B (en) | A kind of shape memory random copolymerization polyimides that can be recycled and preparation method thereof | |
| KR20160105378A (en) | Preparation method of polyimide film, and the polyimide film thereby | |
| CN102660024B (en) | Electrochromatic bismaleimide resin and preparation method of film of electrochromatic bismaleimide resin | |
| CN111690135B (en) | Diamine monomer containing adamantane structure, polyimide film, preparation method and application thereof | |
| CN104987506B (en) | Soluble polyimide containing the tert-butyl group and benzofuran structure and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |