CN104788675A - 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 PDF

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CN104788675A
CN104788675A CN201510194023.5A CN201510194023A CN104788675A CN 104788675 A CN104788675 A CN 104788675A CN 201510194023 A CN201510194023 A CN 201510194023A CN 104788675 A CN104788675 A CN 104788675A
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high temperature
memory polymer
transparent light
temperature
optically transparent
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CN104788675B (en
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肖鑫礼
孔德艳
邱雪英
张文博
张申
胡杨
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Harbin Institute of Technology
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Harbin Institute of Technology
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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

A kind of optically transparent light-coloured high temperature resistant shape-memory polymer and preparation method thereof
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, can recover the intelligent macromolecule material of original shape under external stimulus is as effects such as hot, optical, electrical, magnetic fields.Relative to memory shape metal alloy, the reversible strain of SMP is large, density is low, handling ease and recovery of shape temperature are convenient to the advantages such as control, obtains application in fields such as biologic medical, Intelligent prevention and cure, deployable structure, drive assemblies.Wherein, optical clear and poly (ethylene-co-vinyl acetate) the SMP material that phase transition temperature is 63 DEG C demonstrates huge application potential in field of optoelectronic devices, because the real-time optimization that can realize its optical property based on the grating of this transparent SMP, the first-class optics of optical frames.But under many circumstances, photoelectric device at high temperature runs, therefore need exploitation badly and there is the transparent shape memory polymer of high transformation temperature to realize its optical property optimization at high temperature.
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.Wherein, optically transparent polyimide to photoelectric device, as display non-transparent flexible substrate, waveguide material optical switch, lightwave circuit optics half-wave plate etc. there is special important meaning but, traditional polyimide is because its stronger yellow or brown and be not suitable for photoelectric device.People have adopted multiple method to improve the optical property of polyimide, such as, in main chain, introduce flexible bridge linkage group or larger side base, introduce fluoro-containing group, introduce alicyclic hydrocarbon structure etc.But most transparent light color or colorless polyimide film thickness at several microns to ten microns, be difficult to fix a temporary shapes, there is no the report about optical clear light color shape memory polyimide at present.
As high-temperature shape-memory polymkeric substance, this shape memory polyimide also has significant application value in deployable space structures, variable flying device aileron, pyrostat and driving mechanism etc.This material combines high-temperature shape-memory effect and optical transparence, is expected to expand polyimide further in optical field and shape memory field range of application.
Summary of the invention
The object of the invention is to solve existing optical clear shape-memory polymer phase transition temperature lower and existing clear polyimides thickness lower being difficult to produces shape memory effect, the problem of opto-electronic device service requirements in hot environment can not be met, 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 prepared from as reaction monomers by two (3-amino-benzene oxygen) benzene of 1,3-and Bisphenol A Type Diether Dianhydride; Described 1,3-two (3-amino-benzene oxygen) benzene is (0.9 ~ 1.1) with the amount of substance ratio of Bisphenol A Type Diether Dianhydride: 1.
A preparation method for optically transparent light-coloured high temperature resistant shape-memory polymer, specifically completes according to the following steps:
One, 1 is dissolved, two (3-amino-benzene oxygen) benzene of 3-: by 1, two (3-amino-benzene oxygen) benzene of 3-joins N, in N'-N,N-DIMETHYLACETAMIDE, 1 is stirred under the nitrogen atmosphere of room gently dried, two (3-amino-benzene oxygen) benzene of 3-dissolves completely, obtains two amine aqueous solutions;
The two amount of substance of (3-amino-benzene oxygen) benzene of described in step one 1,3-and the volume ratio of N, N'-N,N-DIMETHYLACETAMIDE are (0.2mmol ~ 0.50mmol): 1mL;
Two, collosol and gel shape polyamic acid is prepared: divided by Bisphenol A Type Diether Dianhydride and join in two amine aqueous solutions 5 times ~ 7 times, stirring reaction 16h ~ 20h under temperature is 20 DEG C ~ 35 DEG C and stirring velocity is the condition of 600r/min ~ 900r/min, obtains collosol and gel shape polyamic acid;
The amount of substance of in the Bisphenol A Type Diether Dianhydride described in step 2 and two amine aqueous solutions 1,3-two (3-amino-benzene oxygen) benzene is than being 1:(0.9 ~ 1.1);
Three, residual bubble is removed: by collosol and gel shape polyamic acid drying treatment 2h ~ 3h in the vacuum drying oven of 30 DEG C ~ 45 DEG C, obtain the collosol and gel shape polyamic acid of not bubbles;
Four, hot-imide: pour on substrate by the collosol and gel shape polyamic acid of not bubbles, is warming up to 70 DEG C ~ 90 DEG C with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, and is incubated 1h ~ 2h at temperature is 70 DEG C ~ 90 DEG C from room temperature;
Be warming up to 100 DEG C ~ 120 DEG C with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from 70 DEG C ~ 90 DEG C again, and be incubated 1h ~ 2h at temperature is 100 DEG C ~ 120 DEG C;
Be warming up to 150 DEG C ~ 170 DEG C with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from 100 DEG C ~ 120 DEG C again, and be incubated 1h ~ 2h at temperature is 150 DEG C ~ 170 DEG C;
Be warming up to 180 DEG C ~ 200 DEG C with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from 150 DEG C ~ 170 DEG C again, and be incubated 1h ~ 2h at temperature is 180 DEG C ~ 200 DEG C;
Be warming up to 220 DEG C ~ 240 DEG C with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from 180 DEG C ~ 200 DEG C again, and be incubated 1h ~ 2h at temperature is 220 DEG C ~ 240 DEG C;
Finally be 220 DEG C ~ 240 DEG C from temperature be cooled to room temperature with the 1 DEG C/min ~ 2 DEG C/rate of temperature fall of min, obtain the substrate containing polyimide;
Five, demoulding: the substrate containing polyimide is placed in distilled water, polyimide is come off from substrate, re-use distilled water polyimide is rinsed well, dry 2h ~ 3h at temperature is 80 DEG C ~ 120 DEG C again, obtain optically transparent light-coloured high temperature resistant shape-memory polymer, the structural formula of described optically transparent light-coloured high temperature resistant shape-memory polymer is:
wherein, the scope of described n is 25 ~ 65, n is integer.
Chemical equation in step 2 of the present invention is:
Chemical equation in step 4 of the present invention is:
Advantage of the present invention:
One, the optically transparent light-coloured high temperature resistant shape-memory polymer phase transition temperature T for preparing of the present invention gbe 168 DEG C ~ 177 DEG C, compared with the phase transition temperature 63 DEG C of the optical clear light color shape-memory polymer of current reported in literature, its phase transition temperature T gimprove 105 DEG C ~ 114 DEG C, can be applicable to the opto-electronic device under high temperature;
Two, the thickness of optically transparent light-coloured high temperature resistant shape-memory polymer that prepared by the present invention still has fixing and memory temporary shapes that can be intact when can reach 300 μm; And the thickness of Common transparent light color or colorless polyimide film is several microns or tens microns, is but difficult to fixing temporary shapes and realizes shape memory effect;
Three, decomposition temperature when the optically transparent light-coloured high temperature resistant shape-memory polymer mass loss that prepared by the present invention is 5% is 480 DEG C ~ 502 DEG C, residual more than 50% at 650 DEG C, illustrates that optically transparent light-coloured high temperature resistant shape-memory polymer prepared by the present invention has excellent thermostability;
Four, the optically transparent light-coloured high temperature resistant shape-memory polymer prepared of the present invention is at T g-20 DEG C of (T g20 DEG C below) time storage modulus be 1.61Gpa ~ 1.92GPa, high temperature, T g+ 20 DEG C of (T gabove 20 DEG C) rubbery state time storage modulus be 3.9MPa ~ 5.2MPa; Optically transparent light-coloured high temperature resistant shape-memory polymer prepared by the present invention can ensure that it at high temperature still can keep integrally-built stability.
The present invention can obtain a kind of optically transparent light-coloured high temperature resistant shape-memory polymer.
Accompanying drawing explanation
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 light spectrogram of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1;
Fig. 5 is the dissipation factor figure of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1;
Fig. 6 is the storage modulus 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 is out of shape 210 DEG C time, the temporary shapes fixedly obtained under room temperature;
Fig. 9 is optically transparent light-coloured high temperature resistant shape-memory polymer shape recovery situation after 2s in 210 DEG C of thermal station prepared by embodiment 1;
Optically transparent light-coloured high temperature resistant shape-memory polymer shape recovery situation after 4s in 210 DEG C of thermal station prepared by Figure 10 embodiment 1;
Figure 11 is optically transparent light-coloured high temperature resistant shape-memory polymer shape recovery situation after 9s in 250 DEG C of thermal station prepared by embodiment 1;
Figure 12 is optically transparent light-coloured high temperature resistant shape-memory polymer shape recovery situation after 16s in 250 DEG C of thermal station prepared by embodiment 1;
Figure 13 is optically transparent light-coloured high temperature resistant shape-memory polymer shape recovery situation after 22s in 250 DEG C of thermal station prepared by embodiment 1;
Figure 14 is optically transparent light-coloured high temperature resistant shape-memory polymer shape recovery situation after 29s in 250 DEG C of thermal station prepared by embodiment 1;
Figure 15 is that the stress of optical clear light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 varies with temperature curve, and in Figure 15,1 is temperature curve, 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 curve, and in Figure 16,1 is temperature curve, and 2 is strain curve.
Embodiment
Embodiment one: present embodiment is that a kind of optically transparent light-coloured high temperature resistant shape-memory polymer is prepared from as reaction monomers by two (3-amino-benzene oxygen) benzene of 1,3-and Bisphenol A Type Diether Dianhydride; Described 1,3-two (3-amino-benzene oxygen) benzene is (0.9 ~ 1.1) with the amount of substance ratio of Bisphenol A Type Diether Dianhydride: 1.
The advantage of present embodiment:
One, the optically transparent light-coloured high temperature resistant shape-memory polymer phase transition temperature T for preparing of present embodiment gbe 168 DEG C ~ 177 DEG C, compared with the phase transition temperature 63 DEG C of the optical clear light color shape-memory polymer of current reported in literature, its phase transition temperature T gimprove 105 DEG C ~ 114 DEG C, can be applicable to the opto-electronic device under high temperature;
Two, the thickness of optically transparent light-coloured high temperature resistant shape-memory polymer that prepared by present embodiment still has fixing and memory temporary shapes that can be intact when can reach 300 μm; And the thickness of Common transparent light color or colorless polyimide film is several microns or tens microns, is but difficult to fixing temporary shapes and realizes shape memory effect;
Three, decomposition temperature when the optically transparent light-coloured high temperature resistant shape-memory polymer mass loss that prepared by present embodiment is 5% is 480 DEG C ~ 502 DEG C, residual more than 50% at 650 DEG C, illustrates that optically transparent light-coloured high temperature resistant shape-memory polymer prepared by present embodiment has excellent thermostability;
Four, the optically transparent light-coloured high temperature resistant shape-memory polymer prepared of present embodiment is at T g-20 DEG C of (T g20 DEG C below) time storage modulus be 1.61Gpa ~ 1.92GPa, high temperature, T g+ 20 DEG C of (T gabove 20 DEG C) rubbery state time storage modulus be 3.9MPa ~ 5.2MPa; Optically transparent light-coloured high temperature resistant shape-memory polymer prepared by present embodiment can ensure that it at high temperature still can keep integrally-built stability.
Present embodiment can obtain a kind of optically transparent light-coloured high temperature resistant shape-memory polymer.
Embodiment two: the difference of present embodiment and embodiment one is: it is characterized in that a kind of structural formula of optically transparent light-coloured high temperature resistant shape-memory polymer is:
Wherein, the scope of described n is 20 ~ 85, n is integer.Other are identical with embodiment one.
Embodiment three: the difference of present embodiment and embodiment one or two is: the number-average molecular weight of described a kind of optically transparent light-coloured high temperature resistant shape-memory polymer is 20.1kg/mol ~ 52.2kg/mol.Other are identical with embodiment one or two.
Embodiment four: the difference of present embodiment and embodiment one to three is: the scope of described n is 25 ~ 65.Other are identical with embodiment one to three.
Embodiment five: present embodiment is a kind of preparation method of optically transparent light-coloured high temperature resistant shape-memory polymer, specifically completes according to the following steps:
One, 1 is dissolved, two (3-amino-benzene oxygen) benzene of 3-: by 1, two (3-amino-benzene oxygen) benzene of 3-joins N, in N'-N,N-DIMETHYLACETAMIDE, 1 is stirred under the nitrogen atmosphere of room gently dried, two (3-amino-benzene oxygen) benzene of 3-dissolves completely, obtains two amine aqueous solutions;
The two amount of substance of (3-amino-benzene oxygen) benzene of described in step one 1,3-and the volume ratio of N, N'-N,N-DIMETHYLACETAMIDE are (0.2mmol ~ 0.50mmol): 1mL;
Two, collosol and gel shape polyamic acid is prepared: divided by Bisphenol A Type Diether Dianhydride and join in two amine aqueous solutions 5 times ~ 7 times, stirring reaction 16h ~ 20h under temperature is 20 DEG C ~ 35 DEG C and stirring velocity is the condition of 600r/min ~ 900r/min, obtains collosol and gel shape polyamic acid;
The amount of substance of in the Bisphenol A Type Diether Dianhydride described in step 2 and two amine aqueous solutions 1,3-two (3-amino-benzene oxygen) benzene is than being 1:(0.9 ~ 1.1);
Three, residual bubble is removed: by collosol and gel shape polyamic acid drying treatment 2h ~ 3h in the vacuum drying oven of 30 DEG C ~ 45 DEG C, obtain the collosol and gel shape polyamic acid of not bubbles;
Four, hot-imide: pour on substrate by the collosol and gel shape polyamic acid of not bubbles, is warming up to 70 DEG C ~ 90 DEG C with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, and is incubated 1h ~ 2h at temperature is 70 DEG C ~ 90 DEG C from room temperature;
Be warming up to 100 DEG C ~ 120 DEG C with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from 70 DEG C ~ 90 DEG C again, and be incubated 1h ~ 2h at temperature is 100 DEG C ~ 120 DEG C;
Be warming up to 150 DEG C ~ 170 DEG C with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from 100 DEG C ~ 120 DEG C again, and be incubated 1h ~ 2h at temperature is 150 DEG C ~ 170 DEG C;
Be warming up to 180 DEG C ~ 200 DEG C with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from 150 DEG C ~ 170 DEG C again, and be incubated 1h ~ 2h at temperature is 180 DEG C ~ 200 DEG C;
Be warming up to 220 DEG C ~ 240 DEG C with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from 180 DEG C ~ 200 DEG C again, and be incubated 1h ~ 2h at temperature is 220 DEG C ~ 240 DEG C;
Finally be 220 DEG C ~ 240 DEG C from temperature be cooled to room temperature with the 1 DEG C/min ~ 2 DEG C/rate of temperature fall of min, obtain the substrate containing polyimide;
Five, demoulding: the substrate containing polyimide is placed in distilled water, polyimide is come off from substrate, re-use distilled water polyimide is rinsed well, dry 2h ~ 3h at temperature is 80 DEG C ~ 120 DEG C again, obtain optically transparent light-coloured high temperature resistant shape-memory polymer, the structural formula of described optically transparent light-coloured high temperature resistant shape-memory polymer is:
wherein, the scope of described n is 25 ~ 65, n is integer.
Chemical equation in present embodiment step 2 is:
Chemical equation in present embodiment step 4 is:
The advantage of present embodiment:
One, the optically transparent light-coloured high temperature resistant shape-memory polymer phase transition temperature T for preparing of present embodiment gbe 168 DEG C ~ 177 DEG C, compared with the phase transition temperature 63 DEG C of the optical clear light color shape-memory polymer of current reported in literature, its phase transition temperature T gimprove 105 DEG C ~ 114 DEG C, can be applicable to the opto-electronic device under high temperature;
Two, the thickness of optically transparent light-coloured high temperature resistant shape-memory polymer that prepared by present embodiment still has fixing and memory temporary shapes that can be intact when can reach 300 μm; And the thickness of Common transparent light color or colorless polyimide film is several microns or tens microns, is but difficult to fixing temporary shapes and realizes shape memory effect;
Three, decomposition temperature when the optically transparent light-coloured high temperature resistant shape-memory polymer mass loss that prepared by present embodiment is 5% is 480 DEG C ~ 502 DEG C, residual more than 50% at 650 DEG C, illustrates that optically transparent light-coloured high temperature resistant shape-memory polymer prepared by present embodiment has excellent thermostability;
Four, the optically transparent light-coloured high temperature resistant shape-memory polymer prepared of present embodiment is at T g-20 DEG C of (T g20 DEG C below) time storage modulus be 1.61Gpa ~ 1.92GPa, high temperature, T g+ 20 DEG C of (T gabove 20 DEG C) rubbery state time storage modulus be 3.9MPa ~ 5.2MPa; Optically transparent light-coloured high temperature resistant shape-memory polymer prepared by present embodiment can ensure that it at high temperature still can keep integrally-built stability.
Present embodiment can obtain a kind of optically transparent light-coloured high temperature resistant shape-memory polymer.
Embodiment six: the difference of present embodiment and embodiment five is: 1 described in step one, the two amount of substance of (3-amino-benzene oxygen) benzene of 3-and the volume ratio of N, N'-N,N-DIMETHYLACETAMIDE are (0.2mmol ~ 0.3mmol): 1mL.Other are identical with embodiment five.
Embodiment seven: the difference of present embodiment and embodiment five or six is: the purity of two (3-amino-benzene oxygen) benzene of 1,3-described in step one is greater than 97%.Other are identical with embodiment five or six.
Embodiment eight: the difference of present embodiment and embodiment five to seven is: the purity of the Bisphenol A Type Diether Dianhydride described in step 2 is greater than 97%.Other are identical with embodiment five to seven.
Embodiment nine: the difference of present embodiment and embodiment five to eight is: by collosol and gel shape polyamic acid drying treatment 2.5h ~ 3h in the vacuum drying oven of 35 DEG C ~ 45 DEG C in step 3, obtain the collosol and gel shape polyamic acid of not bubbles.Other are identical with embodiment five to eight.
Embodiment ten: the difference of present embodiment and embodiment five to nine is: in step 4, the collosol and gel shape polyamic acid of not bubbles is poured on substrate, from room temperature, be warming up to 80 DEG C ~ 90 DEG C with the temperature rise rate of 1.5 DEG C/min ~ 2 DEG C/min, and be incubated 1.5h ~ 2h at temperature is 80 DEG C ~ 90 DEG C;
Be warming up to 110 DEG C ~ 120 DEG C with the temperature rise rate of 1.5 DEG C/min ~ 2 DEG C/min from 80 DEG C ~ 90 DEG C again, and be incubated 1.5h ~ 2h at temperature is 110 DEG C ~ 120 DEG C;
Be warming up to 160 DEG C ~ 170 DEG C with the temperature rise rate of 1.5 DEG C/min ~ 2 DEG C/min from 110 DEG C ~ 120 DEG C again, and be incubated 1.5h ~ 2h at temperature is 160 DEG C ~ 170 DEG C;
Be warming up to 190 DEG C ~ 200 DEG C with the temperature rise rate of 1.5 DEG C/min ~ 2 DEG C/min from 160 DEG C ~ 170 DEG C again, and be incubated 1.5h ~ 2h at temperature is 190 DEG C ~ 200 DEG C;
Be warming up to 230 DEG C ~ 240 DEG C with the temperature rise rate of 1.5 DEG C/min ~ 2 DEG C/min from 190 DEG C ~ 200 DEG C again, and be incubated 1.5h ~ 2h at temperature is 230 DEG C ~ 240 DEG C;
Finally be 230 DEG C ~ 240 DEG C from temperature be cooled to room temperature with the 1.5 DEG C/min ~ 2 DEG C/rate of temperature fall of min, obtain the substrate containing polyimide.Other are identical with embodiment five to nine.
Embodiment 11: the difference of present embodiment and embodiment five to ten is: in step 4, the collosol and gel shape polyamic acid of not bubbles is poured on substrate, from room temperature, be warming up to 80 DEG C with the temperature rise rate of 1 DEG C/min, and be incubated 2h at temperature is 80 DEG C;
Be warming up to 110 DEG C with the temperature rise rate of 1 DEG C/min from 80 DEG C again, and be incubated 2h at temperature is 110 DEG C;
Be warming up to 160 DEG C with the temperature rise rate of 1 DEG C/min from 110 DEG C again, and be incubated 2h at temperature is 160 DEG C;
Be warming up to 190 DEG C with the temperature rise rate of 2 DEG C/min from 160 DEG C again, and be incubated 2h at temperature is 190 DEG C;
Be warming up to 230 DEG C with the temperature rise rate of 2 DEG C/min from 190 DEG C again, and be incubated 1h at temperature is 230 DEG C;
Finally being 230 DEG C with the rate of temperature fall of 2 DEG C/min from temperature is cooled to room temperature, obtains the substrate containing polyimide.Other are identical with embodiment five to ten.
Embodiment 12: the difference of present embodiment and embodiment five to ten one is: in step 4, the collosol and gel shape polyamic acid of not bubbles is poured on substrate, from room temperature, be warming up to 70 DEG C with the temperature rise rate of 1 DEG C/min, and be incubated 2h at temperature is 70 DEG C;
Be warming up to 100 DEG C with the temperature rise rate of 1 DEG C/min from 70 DEG C again, and be incubated 2h at temperature is 100 DEG C;
Be warming up to 150 DEG C with the temperature rise rate of 1 DEG C/min from 100 DEG C again, and be incubated 2h at temperature is 150 DEG C;
Be warming up to 190 DEG C with the temperature rise rate of 2 DEG C/min from 150 DEG C again, and be incubated 1h at temperature is 190 DEG C;
Be warming up to 220 DEG C with the temperature rise rate of 2 DEG C/min from 190 DEG C again, and be incubated 1h at temperature is 220 DEG C;
Finally being 220 DEG C with the rate of temperature fall of 1 DEG C/min from temperature is cooled to room temperature, obtains the substrate containing polyimide.Other are identical with embodiment five to ten one.
Embodiment 13: the difference of present embodiment and embodiment five to ten two is: in step 4, the collosol and gel shape polyamic acid of not bubbles is poured on substrate, from room temperature, be warming up to 80 DEG C with the temperature rise rate of 1 DEG C/min, and be incubated 2h at temperature is 80 DEG C;
Be warming up to 120 DEG C with the temperature rise rate of 1 DEG C/min from 80 DEG C again, and be incubated 2h at temperature is 120 DEG C;
Be warming up to 160 DEG C with the temperature rise rate of 1 DEG C/min from 120 DEG C again, and be incubated 2h at temperature is 160 DEG C;
Be warming up to 200 DEG C with the temperature rise rate of 2 DEG C/min from 160 DEG C again, and be incubated 1h at temperature is 200 DEG C;
Be warming up to 240 DEG C with the temperature rise rate of 2 DEG C/min from 200 DEG C again, and be incubated 1h at temperature is 240 DEG C;
Finally being 240 DEG C with the rate of temperature fall of 1 DEG C/min from temperature is cooled to room temperature, obtains the substrate containing polyimide.Other are identical with embodiment five to ten two.
Embodiment 14: the difference of present embodiment and embodiment five to ten three is: in step 4, the collosol and gel shape polyamic acid of not bubbles is poured on substrate, from room temperature, be warming up to 80 DEG C with the temperature rise rate of 1 DEG C/min, and be incubated 1.5h at temperature is 80 DEG C;
Be warming up to 110 DEG C with the temperature rise rate of 1 DEG C/min from 80 DEG C again, and be incubated 1.5h at temperature is 110 DEG C;
Be warming up to 160 DEG C with the temperature rise rate of 2 DEG C/min from 110 DEG C again, and be incubated 2h at temperature is 160 DEG C;
Be warming up to 200 DEG C with the temperature rise rate of 2 DEG C/min from 160 DEG C again, and be incubated 2h at temperature is 200 DEG C;
Be warming up to 230 DEG C with the temperature rise rate of 2 DEG C/min from 200 DEG C again, and be incubated 2h at temperature is 230 DEG C;
Finally being 230 DEG C with the rate of temperature fall of 2 DEG C/min from temperature is cooled to room temperature, obtains the substrate containing polyimide.Other are identical with embodiment five to ten three.
Embodiment 15: the difference of present embodiment and embodiment five to ten four is: in step 4, the collosol and gel shape polyamic acid of not bubbles is poured on substrate, from room temperature, be warming up to 70 DEG C with the temperature rise rate of 2 DEG C/min, and be incubated 2h at temperature is 70 DEG C;
Be warming up to 110 DEG C with the temperature rise rate of 2 DEG C/min from 70 DEG C again, and be incubated 2h at temperature is 110 DEG C;
Be warming up to 160 DEG C with the temperature rise rate of 2 DEG C/min from 110 DEG C again, and be incubated 2h at temperature is 160 DEG C;
Be warming up to 190 DEG C with the temperature rise rate of 2 DEG C/min from 160 DEG C again, and be incubated 1h at temperature is 190 DEG C;
Be warming up to 220 DEG C with the temperature rise rate of 2 DEG C/min from 200 DEG C again, and be incubated 1h at temperature is 220 DEG C;
Finally being 220 DEG C with the rate of temperature fall of 2 DEG C/min from temperature is cooled to room temperature, obtains the substrate containing polyimide.Other are identical with embodiment five to ten four.
Embodiment 16: the difference of present embodiment and embodiment five to ten five is: 1 described in step one, the two amount of substance of (3-amino-benzene oxygen) benzene of 3-and the volume ratio of N, N'-N,N-DIMETHYLACETAMIDE are 0.2275mmol:1mL.Other are identical with embodiment five to ten five.
Embodiment 17: the difference of present embodiment and embodiment five to ten six is: 1 described in step one, the two amount of substance of (3-amino-benzene oxygen) benzene of 3-and the volume ratio of N, N'-N,N-DIMETHYLACETAMIDE are 0.235mmol:1mL.Other are identical with embodiment five to ten six.
Embodiment 18: the difference of present embodiment and embodiment five to ten seven is: 1 described in step one, the two amount of substance of (3-amino-benzene oxygen) benzene of 3-and the volume ratio of N, N'-N,N-DIMETHYLACETAMIDE are 0.2425mmol:1mL.Other are identical with embodiment five to ten seven.
Embodiment 19: the difference of present embodiment and embodiment five to ten eight is: the two amount of substance of (3-amino-benzene oxygen) benzene of 1,3-described in step one and the volume ratio of N, N'-N,N-DIMETHYLACETAMIDE are 0.4mmol:1mL.Other are identical with embodiment five to ten eight.
Embodiment 20: the difference of present embodiment and embodiment five to ten nine is: 1 described in step one, the two amount of substance of (3-amino-benzene oxygen) benzene of 3-and the volume ratio of N, N'-N,N-DIMETHYLACETAMIDE are 0.50mmol:1mL.Other are identical with embodiment five to ten nine.
Embodiment 21: the difference of present embodiment and embodiment five to two ten is: the amount of substance of in the Bisphenol A Type Diether Dianhydride described in step 2 and two amine aqueous solutions 1,3-two (3-amino-benzene oxygen) benzene is than being 1:(0.9 ~ 0.95).Other are identical with embodiment five to two ten.
Embodiment 22: the difference of present embodiment and embodiment five to two 11 is: the amount of substance of 1,3-two (3-amino-benzene oxygen) benzene in the Bisphenol A Type Diether Dianhydride described in step 2 and two amine aqueous solutions is than being 1:(0.95 ~ 1).Other are five to two ten one identical with embodiment.
Adopt following verification experimental verification beneficial effect of the present invention:
Embodiment 1: a kind of preparation method of optically transparent light-coloured high temperature resistant shape-memory polymer specifically completes according to the following steps:
One, 1 is dissolved, two (3-amino-benzene oxygen) benzene of 3-: by 4.55mmol 1, two (3-amino-benzene oxygen) benzene of 3-joins 20mL N, in N'-N,N-DIMETHYLACETAMIDE, 1 is stirred under the nitrogen atmosphere of room gently dried, two (3-amino-benzene oxygen) benzene of 3-dissolves completely, obtains two amine aqueous solutions;
Two, prepare collosol and gel shape polyamic acid: divided by 5mmol Bisphenol A Type Diether Dianhydride and join for 6 times in two amine aqueous solutions, stirring reaction 20h under temperature is 20 DEG C and stirring velocity is the condition of 760r/min, obtains collosol and gel shape polyamic acid;
Three, residual bubble is removed: by collosol and gel shape polyamic acid drying treatment 2h in the vacuum drying oven of 40 DEG C, obtain the collosol and gel shape polyamic acid of not bubbles;
Four, hot-imide: the collosol and gel shape polyamic acid of not bubbles is poured on substrate, is warming up to 80 DEG C with the temperature rise rate of 1 DEG C/min from room temperature, and is incubated 2h at temperature is 80 DEG C;
Be warming up to 110 DEG C with the temperature rise rate of 1 DEG C/min from 80 DEG C again, and be incubated 2h at temperature is 110 DEG C;
Be warming up to 160 DEG C with the temperature rise rate of 1 DEG C/min from 110 DEG C again, and be incubated 2h at temperature is 160 DEG C;
Be warming up to 190 DEG C with the temperature rise rate of 2 DEG C/min from 160 DEG C again, and be incubated 2h at temperature is 190 DEG C;
Be warming up to 230 DEG C with the temperature rise rate of 2 DEG C/min from 190 DEG C again, and be incubated 1h at temperature is 230 DEG C;
Finally being 230 DEG C with the rate of temperature fall of 2 DEG C/min from temperature is cooled to room temperature, obtains the substrate containing polyimide;
Five, demoulding: the substrate containing polyimide is placed in distilled water, polyimide is come off from substrate, re-use distilled water polyimide is rinsed well, then at temperature is 120 DEG C dry 2h, obtain optically transparent light-coloured high temperature resistant shape-memory polymer.
The number-average molecular weight using gel permeation chromatograph to record optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 is 20.1kg/mol;
The structural formula using gel permeation chromatograph to record optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 is:
Fig. 1 is the digital photograph of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1; As seen from Figure 1, the optically transparent light-coloured high temperature resistant shape-memory polymer that prepared by embodiment 1 has good optical transparence;
Use X-ray diffractometer to study optically transparent light-coloured high temperature resistant shape-memory polymer structure prepared by embodiment 1, as shown in Figure 2, Fig. 2 is the X-ray diffractogram of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1; Can be to from Fig. 2, near 18 °, there is wider amorphous diffraction envelope, illustrate that optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 is non-crystalline state;
Use the optically transparent light-coloured high temperature resistant shape-memory polymer test that infrared spectrometer is prepared embodiment 1, 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; As can be seen from Figure 3,1778cm -1the absorption peak at place is the asymmetric stretch absorption peak (v of imide carbonyl as C=O), and 1722cm -1the absorption peak at place is the feature symmetrical stretching vibration peak (v of imide carbonyl s C=O), 1372cm -1for the stretching vibration absorption peak (v of C-N key c-N), these charateristic avsorption bands illustrate that the optically transparent light-coloured high temperature resistant shape-memory polymer of embodiment 1 preparation is the polyimide of height imidization.
Use the optical property of ultraviolet-visible spectrophotometer to sample to test, result as shown in Figure 4; Fig. 4 is the ultraviolet-visible light spectrogram of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1; As can be seen from Figure 4, 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, is respectively 82%, 85% and 88% in the transmitance at 450nm, 500nm and 600nm place;
Use dynamic mechanical analyzer to test optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1, as shown in Figure 5, Fig. 5 is the dissipation factor figure of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1; As can be seen from Figure 5, the T of the optically transparent light-coloured high temperature resistant shape-memory polymer of embodiment 1 preparation gbe 168 DEG C, ensure that optically transparent light-coloured high temperature resistant shape-memory polymer shape memory effect prepared by embodiment 1 can be applicable to high temperature photoelectric field.
Use dynamic mechanical analyzer to test optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1, as shown in Figure 6, Fig. 6 is the storage modulus figure of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1; As can be seen from Figure 6, there are two platforms of high and low temperature section in storage modulus change curve, 148 DEG C of (T g-20 DEG C) vitreous state time storage modulus be 1.67GPa; High temperature 188 DEG C of (T g+ 20 DEG C) rubbery state time storage modulus be 3.9MPa; 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.
Use thermogravimetric analyzer to test optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1, as shown in Figure 7, Fig. 7 is the thermogravimetric analysis figure of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1; As can be seen from Figure 7, decomposition temperature when optically transparent light-coloured high temperature resistant shape-memory polymer mass loss prepared by embodiment 1 is 5% is 480 DEG C, remaining at 650 DEG C is 51%, illustrates that optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 has excellent resistance toheat.
High-temperature stage is used to test, as shown in Fig. 8 to Figure 14 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 is out of shape 210 DEG C time, the temporary shapes fixedly obtained under room temperature;
Fig. 9 is optically transparent light-coloured high temperature resistant shape-memory polymer shape recovery situation after 2s in 210 DEG C of thermal station prepared by embodiment 1;
Optically transparent light-coloured high temperature resistant shape-memory polymer shape recovery situation after 4s in 210 DEG C of thermal station prepared by Figure 10 embodiment 1;
Figure 11 is optically transparent light-coloured high temperature resistant shape-memory polymer shape recovery situation after 9s in 250 DEG C of thermal station prepared by embodiment 1;
Figure 12 is optically transparent light-coloured high temperature resistant shape-memory polymer shape recovery situation after 16s in 250 DEG C of thermal station prepared by embodiment 1;
Figure 13 is optically transparent light-coloured high temperature resistant shape-memory polymer shape recovery situation after 22s in 250 DEG C of thermal station prepared by embodiment 1;
Figure 14 is optically transparent light-coloured high temperature resistant shape-memory polymer shape recovery situation after 29s in 250 DEG C of thermal station prepared by embodiment 1;
From Fig. 8 to Figure 14, optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1 has good shape memory effect.
Service stress controlled circulation shape memory carries out shape fixed rate and shape recovery ratio test to optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 1, 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 curve, and in Figure 15,1 is temperature curve, 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 curve, and in Figure 16,1 is temperature curve, and 2 is strain curve.As can be seen from Figure 16, optically transparent light-coloured high temperature resistant shape-memory polymer shape fixed rate prepared by embodiment 1 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 specifically completes according to the following steps:
One, 1 is dissolved, two (3-amino-benzene oxygen) benzene of 3-: by 4.7mmol 1, two (3-amino-benzene oxygen) benzene of 3-joins 20mL N, in N'-N,N-DIMETHYLACETAMIDE, 1 is stirred under the nitrogen atmosphere of room gently dried, two (3-amino-benzene oxygen) benzene of 3-dissolves completely, obtains two amine aqueous solutions;
Two, prepare collosol and gel shape polyamic acid: divided by 5mmol Bisphenol A Type Diether Dianhydride and join for 5 times in two amine aqueous solutions, stirring reaction 18h under temperature is 20 DEG C and stirring velocity is the condition of 800r/min, obtains collosol and gel shape polyamic acid;
Three, residual bubble is removed: by collosol and gel shape polyamic acid drying treatment 2h in the vacuum drying oven of 40 DEG C, obtain the collosol and gel shape polyamic acid of not bubbles;
Four, hot-imide: the collosol and gel shape polyamic acid of not bubbles is poured on substrate, is warming up to 80 DEG C with the temperature rise rate of 1 DEG C/min from room temperature, and is incubated 2h at temperature is 80 DEG C;
Be warming up to 110 DEG C with the temperature rise rate of 1 DEG C/min from 80 DEG C again, and be incubated 2h at temperature is 110 DEG C;
Be warming up to 160 DEG C with the temperature rise rate of 1 DEG C/min from 110 DEG C again, and be incubated 2h at temperature is 160 DEG C;
Be warming up to 190 DEG C with the temperature rise rate of 2 DEG C/min from 160 DEG C again, and be incubated 2h at temperature is 190 DEG C;
Be warming up to 230 DEG C with the temperature rise rate of 2 DEG C/min from 190 DEG C again, and be incubated 1h at temperature is 230 DEG C;
Finally being 230 DEG C with the rate of temperature fall of 2 DEG C/min from temperature is cooled to room temperature, obtains the substrate containing polyimide;
Five, demoulding: the substrate 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 100 DEG C dry 2.5h, obtain optically transparent light-coloured high temperature resistant shape-memory polymer.
The number-average molecular weight using gel permeation chromatograph to record optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 2 is 26.8kg/mol;
The structural formula using gel permeation chromatograph to record optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 2 is:
When optically transparent light-coloured high temperature resistant shape-memory polymer thickness prepared by embodiment 2 is 150 μm, its cutoff wavelength is 391nm, is respectively 66%, 73% and 85% in the transmitance at 450nm, 500nm and 600nm place;
The T of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 2 gbe 172 DEG C, ensure that its shape memory effect can be applicable to the photoelectric device of high-temperature field; Optically transparent light-coloured high temperature resistant shape-memory polymer 152 DEG C of (T prepared by embodiment 2 g-20 DEG C) vitreous state time storage modulus be 1.61G Pa; High temperature 192 DEG C of (T g+ 20 DEG C) rubbery state time storage modulus be about 4.2MPa;
Decomposition temperature when transparent shape memory polyimide mass loss prepared by embodiment 2 is 5% is 485 DEG C, illustrates that transparent shape memory polyimide prepared by embodiment 2 has excellent resistance toheat.The shape fixed rate of transparent shape memory polyimide prepared by embodiment 2 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 specifically completes according to the following steps:
One, 1 is dissolved, two (3-amino-benzene oxygen) benzene of 3-: by 4.85mmol 1, two (3-amino-benzene oxygen) benzene of 3-joins 20mL N, in N'-N,N-DIMETHYLACETAMIDE, 1 is stirred under the nitrogen atmosphere of room gently dried, two (3-amino-benzene oxygen) benzene of 3-dissolves completely, obtains two amine aqueous solutions;
Two, prepare collosol and gel shape polyamic acid: divided by 5mmol Bisphenol A Type Diether Dianhydride and join in two amine aqueous solutions 5 times ~ 7 times, stirring reaction 18h under temperature is 20 DEG C and stirring velocity is the condition of 600r/min, obtains collosol and gel shape polyamic acid;
Three, residual bubble is removed: by collosol and gel shape polyamic acid drying treatment 2h in the vacuum drying oven of 40 DEG C, obtain the collosol and gel shape polyamic acid of not bubbles;
Four, hot-imide: the collosol and gel shape polyamic acid of not bubbles is poured on substrate, is warming up to 80 DEG C with the temperature rise rate of 1 DEG C/min from room temperature, and is incubated 2h at temperature is 80 DEG C;
Be warming up to 110 DEG C with the temperature rise rate of 1 DEG C/min from 80 DEG C again, and be incubated 1h at temperature is 110 DEG C;
Be warming up to 160 DEG C with the temperature rise rate of 1 DEG C/min from 110 DEG C again, and be incubated 2h at temperature is 160 DEG C;
Be warming up to 190 DEG C with the temperature rise rate of 2 DEG C/min from 160 DEG C again, and be incubated 2h at temperature is 190 DEG C;
Be warming up to 230 DEG C with the temperature rise rate of 2 DEG C/min from 190 DEG C again, and be incubated 2h at temperature is 230 DEG C;
Finally being 230 DEG C with the rate of temperature fall of 2 DEG C/min from temperature is cooled to room temperature, obtains the substrate containing polyimide;
Five, demoulding: the substrate 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 80 DEG C dry 3h, obtain optically transparent light-coloured high temperature resistant shape-memory polymer.
The number-average molecular weight using gel permeation chromatograph to record optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 3 is 37.9kg/mol;
The structural formula using gel permeation chromatograph to record optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 3 is:
When optically transparent light-coloured high temperature resistant shape-memory polymer thickness prepared by embodiment 3 is 150 μm, its cutoff wavelength is 394nm, is respectively 52%, 66% and 81% in the transmitance at 450nm, 500nm and 600nm place;
The T of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 3 gbe 174 DEG C, ensure that its 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 3 is at 154 DEG C of (T g-20 DEG C) vitreous state time storage modulus be 1.83G Pa; High temperature 194 DEG C of (T g+ 20 DEG C) rubbery state time storage modulus be about 4.7MPa; Decomposition temperature when optically transparent light-coloured high temperature resistant shape-memory polymer mass loss prepared by embodiment 3 is 5% is 487 DEG C, illustrates that optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 3 has excellent resistance toheat; The shape fixed rate of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 3 is 99.5%, 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 specifically completes according to the following steps:
One, 1 is dissolved, two (3-amino-benzene oxygen) benzene of 3-: by 4.925mmol 1, two (3-amino-benzene oxygen) benzene of 3-joins 20mL N, in N'-N,N-DIMETHYLACETAMIDE, 1 is stirred under the nitrogen atmosphere of room gently dried, two (3-amino-benzene oxygen) benzene of 3-dissolves completely, obtains two amine aqueous solutions;
Two, prepare collosol and gel shape polyamic acid: divided by 5mmol Bisphenol A Type Diether Dianhydride and join in two amine aqueous solutions 5 times ~ 7 times, stirring reaction 20h under temperature is 20 DEG C and stirring velocity is the condition of 700r/min, obtains collosol and gel shape polyamic acid;
Three, residual bubble is removed: by collosol and gel shape polyamic acid drying treatment 2h in the vacuum drying oven of 45 DEG C, obtain the collosol and gel shape polyamic acid of not bubbles;
Four, hot-imide: the collosol and gel shape polyamic acid of not bubbles is poured on substrate, is warming up to 80 DEG C with the temperature rise rate of 1 DEG C/min from room temperature, and is incubated 2h at temperature is 80 DEG C;
Be warming up to 110 DEG C with the temperature rise rate of 1 DEG C/min from 80 DEG C again, and be incubated 2h at temperature is 110 DEG C;
Be warming up to 160 DEG C with the temperature rise rate of 1 DEG C/min from 110 DEG C again, and be incubated 2h at temperature is 160 DEG C;
Be warming up to 190 DEG C with the temperature rise rate of 2 DEG C/min from 160 DEG C again, and be incubated 2h at temperature is 190 DEG C;
Be warming up to 230 DEG C with the temperature rise rate of 2 DEG C/min from 190 DEG C again, and be incubated 1h at temperature is 230 DEG C;
Finally being 230 DEG C with the rate of temperature fall of 2 DEG C/min from temperature is cooled to room temperature, obtains the substrate containing polyimide;
Five, demoulding: the substrate 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 80 DEG C dry 3h, obtain optically transparent light-coloured high temperature resistant shape-memory polymer.
The number-average molecular weight using gel permeation chromatograph to record optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 4 is 42.6kg/mol;
The structural formula using gel permeation chromatograph to record optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 4 is:
When optically transparent light-coloured high temperature resistant shape-memory polymer thickness prepared by embodiment 4 is 150 μm, its cutoff wavelength is 396nm, is respectively 42%, 63% and 80% in the transmitance at 450nm, 500nm and 600nm place;
The T of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 4 gbe 176 DEG C, ensure that its 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 at 156 DEG C of (T g-20 DEG C) vitreous state time storage modulus be 1.92G Pa; High temperature 196 DEG C of (T g+ 20 DEG C) rubbery state time storage modulus be about 5.2MPa;
Decomposition temperature when optically transparent light-coloured high temperature resistant shape-memory polymer mass loss prepared by embodiment 4 is 5% is 495 DEG C, illustrates that optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 4 has excellent resistance toheat.The shape fixed rate of transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 4 is 99.4%, and shape recovery ratio is 99.1%.
Embodiment 5: a kind of preparation method of optically transparent light-coloured high temperature resistant shape-memory polymer specifically completes according to the following steps:
One, 1 is dissolved, two (3-amino-benzene oxygen) benzene of 3-: by 5mmol 1, two (3-amino-benzene oxygen) benzene of 3-joins 20mL N, in N'-N,N-DIMETHYLACETAMIDE, 1 is stirred under the nitrogen atmosphere of room gently dried, two (3-amino-benzene oxygen) benzene of 3-dissolves completely, obtains two amine aqueous solutions;
Two, prepare collosol and gel shape polyamic acid: divided by 5mmol Bisphenol A Type Diether Dianhydride and join for 6 times in two amine aqueous solutions, stirring reaction 20h under temperature is 30 DEG C and stirring velocity is the condition of 900r/min, obtains collosol and gel shape polyamic acid;
Three, residual bubble is removed: by collosol and gel shape polyamic acid drying treatment 2h in the vacuum drying oven of 45 DEG C, obtain the collosol and gel shape polyamic acid of not bubbles;
Four, hot-imide: the collosol and gel shape polyamic acid of not bubbles is poured on substrate, is warming up to 80 DEG C with the temperature rise rate of 1 DEG C/min from room temperature, and is incubated 2h at temperature is 80 DEG C;
Be warming up to 110 DEG C with the temperature rise rate of 1 DEG C/min from 80 DEG C again, and be incubated 2h at temperature is 110 DEG C;
Be warming up to 160 DEG C with the temperature rise rate of 1 DEG C/min from 110 DEG C again, and be incubated 2h at temperature is 160 DEG C;
Be warming up to 190 DEG C with the temperature rise rate of 2 DEG C/min from 160 DEG C again, and be incubated 2h at temperature is 190 DEG C;
Be warming up to 230 DEG C with the temperature rise rate of 2 DEG C/min from 190 DEG C again, and be incubated 1h at temperature is 230 DEG C;
Finally being 220 DEG C with the rate of temperature fall of 2 DEG C/min from temperature is cooled to room temperature, obtains the substrate containing polyimide;
Five, demoulding: the substrate 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 90 DEG C dry 3h, obtain optically transparent light-coloured high temperature resistant shape-memory polymer.
The number-average molecular weight using gel permeation chromatograph to record optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 5 is 52.2kg/mol;
The structural formula using gel permeation chromatograph to record optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 5 is:
When the thickness of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 5 is 150 μm, its cutoff wavelength is 402nm, is respectively 24%, 47% and 75% in the transmitance at 450nm, 500nm and 600nm place;
The T of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 5 gbe 177 DEG C, ensure that its 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 at 157 DEG C of (T g-20 DEG C) vitreous state time storage modulus be 1.92G Pa; High temperature 197 DEG C of (T g+ 20 DEG C) rubbery state time storage modulus be about 5.1MPa;
Decomposition temperature when optically transparent light-coloured high temperature resistant shape-memory polymer mass loss prepared by embodiment 5 is 5% is 502 DEG C, illustrates that optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 5 has excellent resistance toheat;
The shape fixed rate of optically transparent light-coloured high temperature resistant shape-memory polymer prepared by embodiment 5 is 99.6%, and shape recovery ratio is 98.6%.

Claims (10)

1. an optically transparent light-coloured high temperature resistant shape-memory polymer, it is characterized in that a kind of optically transparent light-coloured high temperature resistant shape-memory polymer is prepared from as reaction monomers by two (3-amino-benzene oxygen) benzene of 1,3-and Bisphenol A Type Diether Dianhydride; Described 1,3-two (3-amino-benzene oxygen) benzene is (0.9 ~ 1.1) with the amount of substance ratio of Bisphenol A Type Diether Dianhydride: 1.
2. the optically transparent light-coloured high temperature resistant shape-memory polymer of one according to claim 1, is characterized in that a kind of structural formula of optically transparent light-coloured high temperature resistant shape-memory polymer is:
Wherein, the scope of described n is 20 ~ 85, n is integer.
3. the optically transparent light-coloured high temperature resistant shape-memory polymer of one according to claim 2, is characterized in that the number-average molecular weight of described a kind of optically transparent light-coloured high temperature resistant shape-memory polymer is 20.1kg/mol ~ 52.2kg/mol.
4. the optically transparent light-coloured high temperature resistant shape-memory polymer of one according to claim 2, is characterized in that the scope of described n is 25 ~ 65.
5. a preparation method for optically transparent light-coloured high temperature resistant shape-memory polymer, is characterized in that what a kind of preparation method of optically transparent light-coloured high temperature resistant shape-memory polymer specifically completed according to the following steps:
One, 1 is dissolved, two (3-amino-benzene oxygen) benzene of 3-: by 1, two (3-amino-benzene oxygen) benzene of 3-joins N, in N'-N,N-DIMETHYLACETAMIDE, 1 is stirred under the nitrogen atmosphere of room gently dried, two (3-amino-benzene oxygen) benzene of 3-dissolves completely, obtains two amine aqueous solutions;
The two amount of substance of (3-amino-benzene oxygen) benzene of described in step one 1,3-and the volume ratio of N, N'-N,N-DIMETHYLACETAMIDE are (0.2mmol ~ 0.50mmol): 1mL;
Two, collosol and gel shape polyamic acid is prepared: divided by Bisphenol A Type Diether Dianhydride and join in two amine aqueous solutions 5 times ~ 7 times, stirring reaction 16h ~ 20h under temperature is 20 DEG C ~ 35 DEG C and stirring velocity is the condition of 600r/min ~ 900r/min, obtains collosol and gel shape polyamic acid;
The amount of substance of in the Bisphenol A Type Diether Dianhydride described in step 2 and two amine aqueous solutions 1,3-two (3-amino-benzene oxygen) benzene is than being 1:(0.9 ~ 1.1);
Three, residual bubble is removed: by collosol and gel shape polyamic acid drying treatment 2h ~ 3h in the vacuum drying oven of 30 DEG C ~ 45 DEG C, obtain the collosol and gel shape polyamic acid of not bubbles;
Four, hot-imide: pour on substrate by the collosol and gel shape polyamic acid of not bubbles, is warming up to 70 DEG C ~ 90 DEG C with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min, and is incubated 1h ~ 2h at temperature is 70 DEG C ~ 90 DEG C from room temperature;
Be warming up to 100 DEG C ~ 120 DEG C with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from 70 DEG C ~ 90 DEG C again, and be incubated 1h ~ 2h at temperature is 100 DEG C ~ 120 DEG C;
Be warming up to 150 DEG C ~ 170 DEG C with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from 100 DEG C ~ 120 DEG C again, and be incubated 1h ~ 2h at temperature is 150 DEG C ~ 170 DEG C;
Be warming up to 180 DEG C ~ 200 DEG C with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from 150 DEG C ~ 170 DEG C again, and be incubated 1h ~ 2h at temperature is 180 DEG C ~ 200 DEG C;
Be warming up to 220 DEG C ~ 240 DEG C with the temperature rise rate of 1 DEG C/min ~ 2 DEG C/min from 180 DEG C ~ 200 DEG C again, and be incubated 1h ~ 2h at temperature is 220 DEG C ~ 240 DEG C;
Finally be 220 DEG C ~ 240 DEG C from temperature be cooled to room temperature with the 1 DEG C/min ~ 2 DEG C/rate of temperature fall of min, obtain the substrate containing polyimide;
Five, demoulding: the substrate containing polyimide is placed in distilled water, polyimide is come off from substrate, re-use distilled water polyimide is rinsed well, dry 2h ~ 3h at temperature is 80 DEG C ~ 120 DEG C again, obtain optically transparent light-coloured high temperature resistant shape-memory polymer, the structural formula of described optically transparent light-coloured high temperature resistant shape-memory polymer is:
wherein, the scope of described n is 25 ~ 65, n is integer.
6. the preparation method of a kind of optically transparent light-coloured high temperature resistant shape-memory polymer according to claim 5, it is characterized in that 1 described in step one, the two amount of substance of (3-amino-benzene oxygen) benzene of 3-and the volume ratio of N, N'-N,N-DIMETHYLACETAMIDE are (0.2mmol ~ 0.3mmol): 1mL.
7. the preparation method of a kind of optically transparent light-coloured high temperature resistant shape-memory polymer according to claim 5, is characterized in that the purity of two (3-amino-benzene oxygen) benzene of 1,3-described in step one is greater than 97%.
8. the preparation method of a kind of optically transparent light-coloured high temperature resistant shape-memory polymer according to claim 5, is characterized in that the purity of the Bisphenol A Type Diether Dianhydride described in step 2 is greater than 97%.
9. the preparation method of a kind of optically transparent light-coloured high temperature resistant shape-memory polymer according to claim 5, to it is characterized in that in step 3, by collosol and gel shape polyamic acid drying treatment 2.5h ~ 3h in the vacuum drying oven of 35 DEG C ~ 45 DEG C, obtaining the collosol and gel shape polyamic acid of not bubbles.
10. the preparation method of a kind of optically transparent light-coloured high temperature resistant shape-memory polymer according to claim 5, it is characterized in that in step 4, the collosol and gel shape polyamic acid of not bubbles being poured on substrate, from room temperature, be warming up to 80 DEG C ~ 90 DEG C with the temperature rise rate of 1.5 DEG C/min ~ 2 DEG C/min, and be incubated 1.5h ~ 2h at temperature is 80 DEG C ~ 90 DEG C;
Be warming up to 110 DEG C ~ 120 DEG C with the temperature rise rate of 1.5 DEG C/min ~ 2 DEG C/min from 80 DEG C ~ 90 DEG C again, and be incubated 1.5h ~ 2h at temperature is 110 DEG C ~ 120 DEG C;
Be warming up to 160 DEG C ~ 170 DEG C with the temperature rise rate of 1.5 DEG C/min ~ 2 DEG C/min from 110 DEG C ~ 120 DEG C again, and be incubated 1.5h ~ 2h at temperature is 160 DEG C ~ 170 DEG C;
Be warming up to 190 DEG C ~ 200 DEG C with the temperature rise rate of 1.5 DEG C/min ~ 2 DEG C/min from 160 DEG C ~ 170 DEG C again, and be incubated 1.5h ~ 2h at temperature is 190 DEG C ~ 200 DEG C;
Be warming up to 230 DEG C ~ 240 DEG C with the temperature rise rate of 1.5 DEG C/min ~ 2 DEG C/min from 190 DEG C ~ 200 DEG C again, and be incubated 1.5h ~ 2h at temperature is 230 DEG C ~ 240 DEG C;
Finally be 230 DEG C ~ 240 DEG C from temperature be cooled to room temperature with the 1.5 DEG C/min ~ 2 DEG C/rate of temperature fall of min, obtain the substrate containing polyimide.
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Cited By (5)

* Cited by examiner, † Cited by third party
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
CN105399951A (en) * 2015-12-29 2016-03-16 哈尔滨工业大学 Shape-memory random-copolymerization polyimide with adjustable glass-transition temperature and preparation method thereof
CN105576153A (en) * 2015-12-28 2016-05-11 哈尔滨工业大学 Preparation method for indium tin oxide (ITO)-free flexible organic light emitting diode with shape memory effect
CN107987292A (en) * 2017-12-20 2018-05-04 哈尔滨工业大学 A kind of preparation method of the electroluminescent driving shape-memory polymer film of optical clear
CN108587164A (en) * 2018-05-09 2018-09-28 哈尔滨工业大学 A kind of shape memory polyimides of color tunable section and preparation method thereof

Citations (7)

* Cited by examiner, † Cited by third party
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
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
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

Patent Citations (7)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Title
武迪蒙 等: "四甲基联苯二胺及有机可溶聚酰亚胺的合成与性能", 《高分子材料科学与工程》 *

Cited By (7)

* Cited by examiner, † Cited by third party
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
CN105576153A (en) * 2015-12-28 2016-05-11 哈尔滨工业大学 Preparation method for indium tin oxide (ITO)-free flexible organic light emitting diode with shape memory effect
CN105399951A (en) * 2015-12-29 2016-03-16 哈尔滨工业大学 Shape-memory random-copolymerization polyimide with adjustable glass-transition temperature and preparation method thereof
CN107987292A (en) * 2017-12-20 2018-05-04 哈尔滨工业大学 A kind of preparation method of the electroluminescent driving shape-memory polymer film of optical clear
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
CN108587164A (en) * 2018-05-09 2018-09-28 哈尔滨工业大学 A kind of shape memory polyimides of color tunable section and preparation method thereof
CN108587164B (en) * 2018-05-09 2020-07-07 哈尔滨工业大学 Color-adjustable shape memory polyimide and preparation method thereof

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