CN105542460B - A kind of high temperature polyimide heat-shrink tube and preparation method thereof - Google Patents
A kind of high temperature polyimide heat-shrink tube and preparation method thereof Download PDFInfo
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- CN105542460B CN105542460B CN201610115902.9A CN201610115902A CN105542460B CN 105542460 B CN105542460 B CN 105542460B CN 201610115902 A CN201610115902 A CN 201610115902A CN 105542460 B CN105542460 B CN 105542460B
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 104
- 229920001721 polyimide Polymers 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 239000011521 glass Substances 0.000 claims abstract description 90
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 89
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 claims abstract description 51
- 150000004985 diamines Chemical class 0.000 claims abstract description 24
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 68
- 238000010792 warming Methods 0.000 claims description 55
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 45
- -1 4,4'- diaminodiphenyl ethers Chemical class 0.000 claims description 44
- 238000001291 vacuum drying Methods 0.000 claims description 33
- 239000012153 distilled water Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 239000002798 polar solvent Substances 0.000 claims description 23
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 18
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 6
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 6
- 229940113088 dimethylacetamide Drugs 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- VUSYFNXNYLAECV-UHFFFAOYSA-N 2,3-bis(chloromethyl)oxirane Chemical compound ClCC1OC1CCl VUSYFNXNYLAECV-UHFFFAOYSA-N 0.000 claims 1
- 239000004020 conductor Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 73
- 239000004952 Polyamide Substances 0.000 description 11
- 229920002647 polyamide Polymers 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000009413 insulation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- 0 Cc1cccc(*C2=CCCC=C2)c1 Chemical compound Cc1cccc(*C2=CCCC=C2)c1 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/12—Shape memory
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/16—Applications used for films
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The present invention provides a kind of high temperature polyimide heat-shrink tube and preparation method thereof, and the high temperature polyimide heat-shrink tube uses shape memory random copolymerization polyimide material, and its molecular formula is as follows：Preparation method step is as follows：First, diamine mixture solution is prepared；2nd, two anhydride solutions are prepared；3rd, polyamic acid solution is prepared；4th, hot-imide, Kapton is obtained on a glass；5th, demoulding and clean, obtain random copolymerization Kapton；6th, polyimides heat-shrink tube is prepared；7th, clean, dry.High temperature heat-shrink tube is made using the mode of solvent volatilization in the present invention；The high temperature heat-shrink tube of preparation has adjustable complete heat shrink temperature between 230 300 DEG C, the sheath of its area conductor cable between 230 DEG C~300 DEG C and the high temperature protection field of wire harness is had broad application prospects.
Description
Technical field
The present invention relates to a kind of high temperature polyimide heat-shrink tube and preparation method thereof.
Background technology
Internal diameter can extend heat-shrinkable T bush at high temperature, during use heating can make its contraction, so as to close or even
The effect such as connect wires, part etc., play anti-corrosion, protection against the tide and continue, extensively sent out in industries such as electric power, oil, building, military projects
Using.Nineteen sixty Charlesby is found that heat-shrink tube, and prepares polyethylene heat-shrink tube.Common heat-shrink tube has PVC pyrocondensations
Set, be heated to more than 98 DEG C it is i.e. collapsible, it is easy to use.
But under the conditions of a lot, especially big machinery, heavy-duty motor etc. needs the heat-shrink tube of high temperature, and high temperature heat-shrink tube
Research it is less.High temperature heat-shrink tube such as polyvinylidene fluoride complete shrinkage temperature is 150 DEG C, silicon rubber
Complete shrinkage temperature is 175 DEG C, and polytetrafluoroethylene (Teflon) complete shrinkage temperature is then higher than 300 DEG C.
However, the report of heat shrink temperature heat-shrink tube between 230-300 DEG C is there is no at present.Heat-shrink tube can be used between 230 DEG C~300 DEG C
In protection of sheath and wire harness of areas of higher temperature leader cable etc..
The content of the invention
Based on above weak point, it is an object of the invention to provide a kind of high temperature polyimide heat-shrink tube and its preparation side
Method, solve existing high temperature heat-shrink tube and there is no complete shrinkage temperature between 230-300 DEG C, it is impossible to meet in temperature 230 DEG C~300
Between DEG C the problems such as the protection of the sheath of leader cable and wire harness.
The technology used in the present invention is as follows：
A kind of high temperature polyimide heat-shrink tube, using shape memory random copolymerization polyimide material, described shape note
It is as follows to recall random copolymerization polyimide molecule formula：
M=5-28, n=6-25.
The present invention also has following technical characteristic：
1st, a kind of preparation method of high temperature polyimide heat-shrink tube, step are as follows：
Step 1: it is molten that 4,4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzene of 1,3- are added into aprotonic polar
In agent, then stir in a nitrogen atmosphere to being completely dissolved, obtain diamines blend solution；The amount of the material of described diamines and non-matter
The volume ratio of sub- polar solvent is 0.05mol：100mL~150mL；Described 4,4'- diaminodiphenyl ethers and double (the 3- ammonia of 1,3-
Phenoxyl) benzene mol ratio be 1：9-9：1；
Step 2: 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids are dissolved into aprotic polar solvent, it is molten to obtain dianhydride
Liquid；The amount of described dianhydride material and the volume ratio of aprotic polar solvent are 0.05mol：80mL~150mL；
It is added to Step 3: two anhydride solutions are divided 3-10 times in diamine solution, then in room temperature, nitrogen atmosphere and mixing speed
For polymerisation 5h~30h under conditions of 300r/min~800r/min, polyamic acid solution is obtained；In two described anhydride solutions
4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids and 4,4'- diaminodiphenyl ethers in diamine solution and 1,3- are double (3- amino-benzene oxygens)
The mixture mol ratio of benzene is 1:1；
Step 4: polyamic acid solution is coated uniformly on the glass plate of cleaning, it is subsequently placed in vacuum drying chamber, then
By vacuum drying chamber with 1 DEG C/min~2 DEG C/min heating rate from room temperature to 70 DEG C~90 DEG C, then at 70 DEG C~90 DEG C
Lower insulation 2h~3h, then it is warming up to 150 DEG C~170 DEG C from 70 DEG C~90 DEG C with 1 DEG C/min~2 DEG C/min heating rate, then
2h~3h is incubated at 150 DEG C~170 DEG C, then is warming up to 1 DEG C/min~2 DEG C/min heating rate from 150 DEG C~170 DEG C
190 DEG C~210 DEG C, then 2h~3h is incubated at 190 DEG C~210 DEG C, then with 1 DEG C/min~2 DEG C/min heating rate from 190
DEG C~210 DEG C be warming up to 230 DEG C~260 DEG C, then 1h~2h be incubated at 230 DEG C~260 DEG C, then with 1 DEG C/min~2 DEG C/min
Heating rate be warming up to 280 DEG C~300 DEG C from 230 DEG C~260 DEG C, then 1h~2h is incubated at 280 DEG C~300 DEG C, completed
Hot-imide, then vacuum drying chamber is cooled down, obtain the glass plate containing Kapton；
Step 5: the glass plate containing Kapton is put into distilled water, make Kapton from glass
Come off on plate, reuse distilled water and rinse Kapton well, obtain shape memory random copolymerization Kapton；
Step 6: shape memory random copolymerization Kapton is dissolved into aprotic polar solvent, shape is obtained
Remember random copolymerization polyimide solution；Shape memory random copolymerization polyimide solution is poured into glass tube, then by glass
It is to be dried in 150 DEG C~200 DEG C that glass pipe, which is put into temperature, obtains the glass containing shape memory random copolymerization polyimide tube
Pipe；The mass fraction of shape memory random copolymerization polyimides is in described shape memory random copolymerization polyimide solution
5%~15%；
Step 7: the glass tube containing shape memory random copolymerization polyimide tube is put into distilled water, then make shape
Shape memory random copolymerization polyimide tube is come off from glass tube, then shape memory random copolymerization polyimide tube is dried, and is obtained
To high temperature polyimide heat-shrink tube.
2nd, the aprotic polar solvent described in step 1 as described above be N,N-dimethylformamide, N, N- dimethyl
Acetamide or 1-METHYLPYRROLIDONE.
3rd, the aprotic polar solvent described in step 2 as described above be N,N-dimethylformamide, N, N- dimethyl
Acetamide or 1-METHYLPYRROLIDONE.
4th, the aprotic polar solvent described in step 6 as described above be N,N-dimethylformamide, N, N- dimethyl
Acetamide or 1-METHYLPYRROLIDONE.
5th, polyamic acid solution is coated uniformly on the glass plate of cleaning in step 4 as described above, be subsequently placed in true
In empty drying box, then by vacuum drying chamber with 1 DEG C/min~2 DEG C/min heating rate from room temperature to 80 DEG C~90 DEG C,
2h~3h is incubated at 80 DEG C~90 DEG C again, then is warming up to 1 DEG C/min~2 DEG C/min heating rate from 80 DEG C~90 DEG C
150 DEG C~170 DEG C, then 2h~3h is incubated at 150 DEG C~170 DEG C, then with 1 DEG C/min~2 DEG C/min heating rate from 150
DEG C~170 DEG C be warming up to 190 DEG C~210 DEG C, then 2h~3h be incubated at 190 DEG C~210 DEG C, then with 1 DEG C/min~2 DEG C/min
Heating rate be warming up to 230 DEG C~260 DEG C from 190 DEG C~210 DEG C, then 1h~2h is incubated at 230 DEG C~260 DEG C, then with 1
DEG C/min~2 DEG C/min heating rate is warming up to 280 DEG C~290 DEG C from 230 DEG C~260 DEG C, then at 280 DEG C~290 DEG C
1h~2h is incubated, completes hot-imide, then cool down vacuum drying chamber.
Advantages of the present invention：High-temperature thermoplastic pipe is made using the mode of solvent volatilization in the present invention；The high temperature heat-shrink tube of preparation
With adjustable complete heat shrink temperature between 230-300 DEG C, it is set to have broad application prospects in high-temperature field；This hair
The high temperature heat-shrink tube of bright preparation can be good at fixing its diameter after extending and recover its initial diameter.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the high temperature polyimide heat-shrink tube prepared；
Fig. 2 is the fissipation factor figure of the high temperature polyimide heat-shrink tube prepared；
Fig. 3 is the storage modulus figure of the high temperature polyimide heat-shrink tube prepared；
Fig. 4 is the shape graph after the high temperature polyimide heat-shrink tube extension prepared；
Fig. 5 is the shape graph after the high temperature polyimide heat-shrink tube prepared shrinks.
Embodiment
Embodiment 1：
A kind of high temperature polyimide heat-shrink tube, using shape memory random copolymerization polyimide material, described shape note
It is as follows to recall random copolymerization polyimide molecule formula：
M=5-28, n=6-25.
Embodiment 2：
A kind of preparation method of high temperature polyimide heat-shrink tube is completed according to the following steps：
First, 4,4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzol mixtures of 1,3- are added to aprotonic polar
In solvent, then stir to it be completely dissolved in a nitrogen atmosphere, obtain diamine solution；
The material of double (3- amino-benzene oxygens) benzol mixtures of 4,4'- diaminodiphenyl ethers and 1,3- described in step 1
Amount and the volume ratio of aprotic polar solvent are 0.05mol：100mL~150mL；
4,4'- in double (3- amino-benzene oxygens) benzol mixtures of 4,4'- diaminodiphenyl ethers and 1,3- described in step 1
The mol ratio of diaminodiphenyl ether and double (3- amino-benzene oxygens) benzene of 1,3- is 1：9-9：1；
2nd, 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids are dissolved into aprotic polar solvent, obtain two anhydride solutions；
The amount of material and the body of aprotic polar solvent of 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids described in step 2
Product ratio is 0.05mol：100mL~150mL；
3rd, two anhydride solutions are divided 3 times~10 times and be added in diamine mixture solution, then in room temperature, nitrogen atmosphere and stirred
Speed is mixed as polymerisation 5h~30h under conditions of 300r/min~800r/min, obtains polyamic acid solution；
4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids and in diamine mixture solution 4 in two anhydride solutions described in step 3,
The mol ratio of 4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzol mixtures of 1,3- is 1:1；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, be subsequently placed in vacuum drying chamber, then will be true
Empty drying box, from room temperature to 70 DEG C~90 DEG C, then is protected with 1 DEG C/min~2 DEG C/min heating rate at 70 DEG C~90 DEG C
Warm 2h~3h, then 150 DEG C~170 DEG C are warming up to from 70 DEG C~90 DEG C with 1 DEG C/min~2 DEG C/min heating rate, then 150
DEG C~170 DEG C at be incubated 2h~3h, then be warming up to 190 DEG C from 150 DEG C~170 DEG C with 1 DEG C/min~2 DEG C/min heating rate
~210 DEG C, then at 190 DEG C~210 DEG C be incubated 2h~3h, then with 1 DEG C/min~2 DEG C/min heating rate from 190 DEG C~
210 DEG C are warming up to 230 DEG C~260 DEG C, then 1h~2h are incubated at 230 DEG C~260 DEG C, then the liter with 1 DEG C/min~2 DEG C/min
Warm speed is warming up to 280 DEG C~300 DEG C from 230 DEG C~260 DEG C, then 1h~2h is incubated at 280 DEG C~300 DEG C, completes hot acyl
Imidization, then vacuum drying chamber is naturally cooled to room temperature, obtain the glass plate containing Kapton；
5th, the glass plate containing Kapton is put into distilled water, makes Kapton from glass plate
Come off, reuse distilled water and rinse Kapton well, obtain random copolymerization Kapton；
6th, random copolymerization Kapton is dissolved into aprotic polar solvent, obtains random copolymerization polyimides
Solution；Random copolymerization polyimide solution is poured into glass tube, then glass tube is put into temperature as 150 DEG C~200 DEG C
Middle drying, obtain containing random copolymerization polyimide tube；
In random copolymerization polyimide solution described in step 6 the mass fraction of random copolymerization polyimides be 5%~
15%；
7th, the glass tube containing random copolymerization polyimide tube is put into distilled water, it is come off from glass tube,
Dried at being 120 DEG C in temperature, obtain high temperature polyimide heat-shrink tube.
Embodiment 3：
Present embodiment is with the difference of embodiment 2：Aprotic polar solvent N, N- dimethyl methyl described in step 1
Acid amides, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.Other steps are same as Example 2.
Embodiment 4：
Present embodiment is with one of embodiment 2 to 3 difference：Aprotic polar solvent N, N- bis- described in step 2
NMF, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.Other steps are identical with embodiment 2 to 3.
Embodiment 5：
Present embodiment is with one of embodiment 2 to 4 difference：Aprotic polar solvent N, N- bis- described in step 6
NMF, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.Other steps are identical with embodiment 2 to 4.
Embodiment 6：
Present embodiment is with one of embodiment 2 to 5 difference：4,4'- diaminodiphenyl ethers described in step 1 and
The double amounts of (3- amino-benzene oxygens) benzol mixture material of 1,3- and the volume ratio of aprotic polar solvent are 0.05mol:110mL.
Other steps are identical with embodiment 2 to 5.
Embodiment 7：
Present embodiment is with one of embodiment 2 to 6 difference：4,4'- diaminodiphenyl ethers described in step 1 and
The double amounts of (3- amino-benzene oxygens) benzol mixture material of 1,3- and the volume ratio of aprotic polar solvent are 0.05mol:120mL.
Other steps are identical with embodiment 2 to 6.
Embodiment 8：
Present embodiment is with one of embodiment 2 to 7 difference：Polyamic acid solution is coated uniformly in step 4 clean
On net glass plate, be subsequently placed in vacuum drying chamber, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature
To 90 DEG C, then 2h is incubated at 90 DEG C, then 170 DEG C are warming up to from 90 DEG C with 1 DEG C/min heating rate, then protected at 170 DEG C
Warm 2h, then 210 DEG C are warming up to from 170 DEG C with 1 DEG C/min heating rate, then 2h is incubated at 210 DEG C, then with 1 DEG C/min's
Heating rate is warming up to 250 DEG C from 210 DEG C, then 290 DEG C are warming up to from 250 DEG C with 1 DEG C/min heating rate, then at 290 DEG C
Lower insulation 1h, hot-imide is completed, then cool down vacuum drying chamber, obtain the glass plate containing Kapton.Other
Step is identical with embodiment 2 to 7.
Embodiment 9：
Present embodiment is with one of embodiment 2 to 8 difference：Polyamic acid solution is coated uniformly in step 4 clean
On net glass plate, be subsequently placed in vacuum drying chamber, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature
To 80 DEG C, then 2h is incubated at 80 DEG C, then 170 DEG C are warming up to from 80 DEG C with 1 DEG C/min heating rate, then protected at 170 DEG C
Warm 2h, then 210 DEG C are warming up to from 170 DEG C with 1 DEG C/min heating rate, then 2h is incubated at 210 DEG C, then with 1 DEG C/min's
Heating rate is warming up to 260 DEG C from 210 DEG C, then 1h is incubated at 260 DEG C, then is heated up with 1 DEG C/min heating rate from 260 DEG C
To 300 DEG C, then 1h is incubated at 300 DEG C, completes hot-imide, then cool down vacuum drying chamber, obtained containing polyimides
The glass plate of film.Other steps are identical with embodiment 2 to 8.
Embodiment 10：
Present embodiment is with one of embodiment 2 to 9 difference：Polyamic acid solution is coated uniformly in step 4 clean
On net glass plate, be subsequently placed in vacuum drying chamber, then by vacuum drying chamber with 1 DEG C/min heating rate from room temperature
To 80 DEG C, then 2h is incubated at 80 DEG C, then 170 DEG C are warming up to from 80 DEG C with 1 DEG C/min heating rate, then protected at 170 DEG C
Warm 2h, then 210 DEG C are warming up to from 70 DEG C with 2 DEG C/min heating rate, then 2h is incubated at 210 DEG C, then the liter with 2 DEG C/min
Warm speed is warming up to 260 DEG C from 210 DEG C, then 1h is incubated at 260 DEG C, then is warming up to 2 DEG C/min heating rate from 260 DEG C
300 DEG C, then 1h is incubated at 300 DEG C, hot-imide is completed, then vacuum drying chamber is cooled down, obtain thin containing polyimides
The glass plate of film.Other steps are identical with embodiment 2 to 9.
Embodiment 11：
A kind of preparation method of high temperature polyimide heat-shrink tube is completed according to the following steps：
First, by 1,3- pairs of (3- amino-benzene oxygens) benzene of 0.0075mol 4,4'- diaminodiphenyl ethers and 0.0425mol
Mixture is added in 110mL DMAs, then is stirred in a nitrogen atmosphere to being completely dissolved, and it is molten to obtain diamines
Liquid；
2nd, 0.05mol 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids are dissolved into 90mL DMAs,
Obtain two anhydride solutions；
3rd, two anhydride solutions are divided 5 times and be added in diamine mixture solution, then in room temperature, nitrogen atmosphere and mixing speed
For polymerisation 15h under conditions of 400r/min, polyamic acid solution is obtained；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, be subsequently placed in vacuum drying chamber, then will be true
Empty drying box, from room temperature to 90 DEG C, then is incubated 2h with 1 DEG C/min heating rate at being 90 DEG C in temperature, then with 1 DEG C/
Min heating rate is warming up to 170 DEG C from 90 DEG C, then is incubated 2h, then the heating rate with 1 DEG C/min at being 170 DEG C in temperature
210 DEG C are warming up to from 170 DEG C, then 2h is incubated at being 210 DEG C in temperature, then is warming up to 1 DEG C/min heating rate from 210 DEG C
250 DEG C, then 1h is incubated at being 250 DEG C in temperature, then 290 DEG C are warming up to from 250 DEG C with 1 DEG C/min heating rate, then in temperature
Spend to be incubated 1h at 290 DEG C, complete hot-imide, then cool down vacuum drying chamber, obtain the glass containing Kapton
Glass plate；
5th, the glass plate containing Kapton is put into distilled water, makes Kapton from glass plate
Come off, reuse distilled water and rinse Kapton well, obtain random copolymerization Kapton；
6th, random copolymerization Kapton is dissolved into DMA, obtains random copolymerization polyamides Asia
Amine aqueous solution；Random copolymerization polyimide solution is poured into glass tube, then it is to be done in 150 DEG C that glass tube is put into temperature
It is dry, obtain the glass tube containing random copolymerization polyimide tube；Nothing in random copolymerization polyimide solution described in step 6
The mass fraction for advising copolyimide is 10%；
7th, the glass tube containing random copolymerization polyimide tube is put into distilled water, then makes random copolymerization polyamides sub-
Amine pipe comes off from glass tube, dries, obtains high temperature polyimide heat-shrink tube.
The random copolymerization polyimides of preparation is tested using infrared spectrometer, as shown in Figure 1.From fig. 1, it can be seen that system
Standby random copolymerization polyimides is the polyimides of height imidizate.
The high temperature polyimide heat-shrink tube of preparation is tested using dynamic mechanical analyzer, Fig. 2 is the high temperature prepared
The fissipation factor figure of polyimides heat-shrink tube, it can be seen that the vitrifying of the high temperature heat-shrink tube random copolymerization polyimides of preparation
Transition temperature (Tg) it is 232 DEG C, it ensure that it can be applied to high-temperature field.
The high temperature polyimide heat-shrink tube of preparation is tested using dynamic mechanical analyzer, Fig. 3 is the high temperature prepared
The storage modulus figure of heat-shrink tube random copolymerization polyimides.As can be seen from Figure 3, there is high and low temperature in storage modulus change curve
Two platforms of section are spent, in 212 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be 1.682GPa；In 252 DEG C of (T of high temperatureg+20
DEG C) rubbery state when storage modulus be 6.6MPa.
Fig. 4 is extension diameter of the high temperature polyimide heat-shrink tube prepared at 232 DEG C；
Fig. 5 is that the high temperature polyimide heat-shrink tube prepared replys its initial diameter at 232 DEG C.
As can be seen that the heat-shrink tube has good pyrocondensation effect from Fig. 4 and Fig. 5.
Embodiment 12
A kind of preparation method of high temperature polyimide heat-shrink tube is completed according to the following steps；
First, by the mixed of 1,3- pairs of (3- amino-benzene oxygens) benzene of 0.015mol 4,4'- diaminodiphenyl ethers and 0.035mol
Compound is added in 120mL DMAs, then is stirred in a nitrogen atmosphere to being completely dissolved, and obtains diamine solution；
2nd, 0.05mol 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids are dissolved into 90mL DMAs,
Obtain two anhydride solutions；
3rd, two anhydride solutions are divided 5 times and be added in diamine mixture solution, then in room temperature, nitrogen atmosphere and mixing speed
For polymerisation 16h under conditions of 400r/min, polyamic acid solution is obtained；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, be subsequently placed in vacuum drying chamber, then will be true
Empty drying box, from room temperature to 80 DEG C, then is incubated 2h with 1 DEG C/min heating rate at being 80 DEG C in temperature, then with 1 DEG C/
Min heating rate is warming up to 170 DEG C from 80 DEG C, then is incubated 2h, then the heating rate with 1 DEG C/min at being 170 DEG C in temperature
210 DEG C are warming up to from 170 DEG C, then 2h is incubated at being 210 DEG C in temperature, then is warming up to 1 DEG C/min heating rate from 210 DEG C
260 DEG C, then 1h is incubated at being 260 DEG C in temperature, then 290 DEG C are warming up to from 260 DEG C with 1 DEG C/min heating rate, then in temperature
Spend to be incubated 1h at 290 DEG C, complete hot-imide, then cool down vacuum drying chamber, obtain the glass containing Kapton
Glass plate；
5th, the glass plate containing Kapton is put into distilled water, makes Kapton from glass plate
Come off, reuse distilled water and rinse Kapton well, obtain random copolymerization Kapton；
6th, random copolymerization Kapton is dissolved into DMA, obtains random copolymerization polyamides Asia
Amine aqueous solution；Random copolymerization polyimide solution is poured into glass tube, then it is to be done in 150 DEG C that glass tube is put into temperature
It is dry, obtain the glass tube containing random copolymerization polyimide tube；Nothing in random copolymerization polyimide solution described in step 6
The mass fraction for advising copolyimide is 12%；
7th, the glass tube containing random copolymerization polyimide tube is put into distilled water, then makes random copolymerization polyamides sub-
Amine pipe comes off from glass tube, dries, obtains high temperature heat-shrink tube.
The T of the high temperature polyimide heat-shrink tube of preparationgFor 242 DEG C, high temperature heat-shrink tube field can be applied to.In 222 DEG C of (Tg-
20 DEG C) glassy state when storage modulus be 1.972GPa；In 262 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be
8.8MPa.With good pyrocondensation effect.
Embodiment 13：
A kind of preparation method of high temperature polyimide heat-shrink tube is completed according to the following steps：
First, by the mixed of 1,3- pairs of (3- amino-benzene oxygens) benzene of 0.025mol 4,4'- diaminodiphenyl ethers and 0.025mol
Compound is added in 120mL DMFs, then is stirred in a nitrogen atmosphere to being completely dissolved, and obtains diamine solution；
2nd, 0.05mol 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids are dissolved into 90mL DMFs,
Obtain two anhydride solutions；
3rd, two anhydride solutions are added in diamine solution points for 5 times, then in room temperature, nitrogen atmosphere and mixing speed are 400r/
Polymerisation 17h under conditions of min, obtains polyamic acid solution；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, be subsequently placed in vacuum drying chamber, then will be true
Empty drying box, from room temperature to 80 DEG C, then is incubated 2h with 1 DEG C/min heating rate at being 80 DEG C in temperature, then with 1 DEG C/
Min heating rate is warming up to 170 DEG C from 80 DEG C, then is incubated 2h, then the heating rate with 2 DEG C/min at being 170 DEG C in temperature
210 DEG C are warming up to from 170 DEG C, then 2h is incubated at being 210 DEG C in temperature, then is warming up to 2 DEG C/min heating rate from 210 DEG C
260 DEG C, then 1h is incubated at being 260 DEG C in temperature, then 280 DEG C are warming up to from 260 DEG C with 2 DEG C/min heating rate, then in temperature
Spend to be incubated 1h at 280 DEG C, complete hot-imide, then cool down vacuum drying chamber, obtain the glass containing Kapton
Glass plate；
5th, the glass plate containing Kapton is put into distilled water, makes Kapton from glass plate
Come off, reuse distilled water and rinse Kapton well, obtain random copolymerization Kapton；
6th, random copolymerization Kapton is dissolved into DMF, obtains random copolymerization polyamides Asia
Amine aqueous solution；Random copolymerization polyimide solution is poured into glass tube, then it is to be done in 150 DEG C that glass tube is put into temperature
It is dry, obtain the glass tube containing random copolymerization polyimide tube；Nothing in random copolymerization polyimide solution described in step 6
The mass fraction for advising copolyimide is 13%；
7th, the glass tube containing random copolymerization polyimide tube is put into distilled water, then makes random copolymerization polyamides sub-
Amine pipe comes off from glass tube, dries, obtains high temperature heat-shrink tube.
The T of the high temperature polyimide heat-shrink tube of preparationgFor 257 DEG C, high temperature heat-shrink tube field can be applied to.In 237 DEG C of (Tg-
20 DEG C) glassy state when storage modulus be 1.656GPa；In 277 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be
8.7MPa.With good pyrocondensation effect.
Embodiment 14：
A kind of preparation method of high temperature polyimide heat-shrink tube is completed according to the following steps：
First, by the mixed of 1,3- pairs of (3- amino-benzene oxygens) benzene of 0.035mol 4,4'- diaminodiphenyl ethers and 0.015mol
Compound is added in 120mL DMFs, then is stirred in a nitrogen atmosphere to being completely dissolved, and obtains diamine solution；
2nd, 0.05mol4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids are dissolved into 90mL DMFs, obtained
To two anhydride solutions；
3rd, two anhydride solutions are divided 5 times and be added in diamine mixture solution, then in room temperature, nitrogen atmosphere and mixing speed
For polymerisation 18h under conditions of 400r/min, polyamic acid solution is obtained；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, be subsequently placed in vacuum drying chamber, then will be true
Empty drying box, from room temperature to 80 DEG C, then is incubated 2h with 1 DEG C/min heating rate at being 80 DEG C in temperature, then with 2 DEG C/
Min heating rate is warming up to 170 DEG C from 80 DEG C, then is incubated 2h, then the heating rate with 2 DEG C/min at being 170 DEG C in temperature
210 DEG C are warming up to from 170 DEG C, then 2h is incubated at being 210 DEG C in temperature, then is warming up to 2 DEG C/min heating rate from 210 DEG C
260 DEG C, then 1h is incubated at being 260 DEG C in temperature, then 300 DEG C are warming up to from 260 DEG C with 2 DEG C/min heating rate, then in temperature
Spend to be incubated 1h at 300 DEG C, complete hot-imide, then cool down vacuum drying chamber, obtain the glass containing Kapton
Glass plate；
5th, the glass plate containing Kapton is put into distilled water, makes Kapton from glass plate
Come off, reuse distilled water and rinse Kapton well, obtain random copolymerization Kapton；
6th, random copolymerization Kapton is dissolved into DMF, obtains random copolymerization polyamides Asia
Amine aqueous solution；Random copolymerization polyimide solution is poured into glass tube, then it is to be done in 150 DEG C that glass tube is put into temperature
It is dry, obtain the glass tube containing random copolymerization polyimide tube；Nothing in random copolymerization polyimide solution described in step 6
The mass fraction for advising copolyimide is 13%；
7th, the glass tube containing random copolymerization polyimide tube is put into distilled water, then makes random copolymerization polyamides sub-
Amine pipe comes off from glass tube, dries, obtains high temperature heat-shrink tube.
The T of the high temperature polyimide heat-shrink tube of preparationgFor 276 DEG C, high temperature heat-shrink tube field can be applied to.In 256 DEG C of (Tg-
20 DEG C) glassy state when storage modulus be 1.602GPa；In 296 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be
8.9MPa.With good pyrocondensation effect.
Embodiment 15：
A kind of preparation method of high temperature polyimide heat-shrink tube is completed according to the following steps：
First, by the mixed of 1,3- pairs of (3- amino-benzene oxygens) benzene of 0.044mol 4,4'- diaminodiphenyl ethers and 0.006mol
Compound is added in 120mL DMFs, then is stirred in a nitrogen atmosphere to being completely dissolved, and obtains diamine solution；
2nd, 0.05mol4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids are dissolved into 90mL DMFs, obtained
To two anhydride solutions；
3rd, dianhydride mixture solution is divided 5 times and be added in diamine solution, then in room temperature, nitrogen atmosphere and mixing speed
For polymerisation 19h under conditions of 400r/min, polyamic acid solution is obtained；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, be subsequently placed in vacuum drying chamber, then will be true
Empty drying box, from room temperature to 80 DEG C, then is incubated 2h with 1 DEG C/min heating rate at being 80 DEG C in temperature, then with 2 DEG C/
Min heating rate is warming up to 170 DEG C from 80 DEG C, then is incubated 2h, then the heating rate with 2 DEG C/min at being 170 DEG C in temperature
210 DEG C are warming up to from 170 DEG C, then 2h is incubated at being 210 DEG C in temperature, then is warming up to 1 DEG C/min heating rate from 210 DEG C
260 DEG C, then 1h is incubated at being 260 DEG C in temperature, then 290 DEG C are warming up to from 260 DEG C with 1 DEG C/min heating rate, then in temperature
Spend to be incubated 1h at 290 DEG C, complete hot-imide, then cool down vacuum drying chamber, obtain the glass containing Kapton
Glass plate；
5th, the glass plate containing Kapton is put into distilled water, makes Kapton from glass plate
Come off, reuse distilled water and rinse Kapton well, obtain random copolymerization Kapton；
6th, random copolymerization Kapton is dissolved into DMF, obtains random copolymerization polyamides Asia
Amine aqueous solution；Random copolymerization polyimide solution is poured into glass tube, then it is to be done in 150 DEG C that glass tube is put into temperature
It is dry, obtain the glass tube containing random copolymerization polyimide tube；Nothing in random copolymerization polyimide solution described in step 6
The mass fraction for advising copolyimide is 14%；
7th, the glass tube containing random copolymerization polyimide tube is put into distilled water, then makes random copolymerization polyamides sub-
Amine pipe comes off from glass tube, dries, obtains high temperature heat-shrink tube.
The T of the high temperature polyimide heat-shrink tube of preparationgFor 295 DEG C, it ensure that and can be applied to high temperature heat-shrink tube field.
275℃(Tg- 20 DEG C) glassy state when storage modulus be 1.409GPa；In 315 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage
Modulus is 9.5MPa, has good pyrocondensation effect.
Embodiment 16：
A kind of preparation method of high temperature polyimide heat-shrink tube is completed according to the following steps：
First, by the mixed of 1,3- pairs of (3- amino-benzene oxygens) benzene of 0.045mol 4,4'- diaminodiphenyl ethers and 0.005mol
Compound is added in 100mL 1-METHYLPYRROLIDONEs, then is stirred in a nitrogen atmosphere to being completely dissolved, and obtains diamine solution；
2nd, 0.05mol4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids are dissolved into 90mL 1-METHYLPYRROLIDONEs, obtained
Dianhydride mixture solution；
3rd, dianhydride mixture solution is divided 5 times and be added in diamine solution, then in room temperature, nitrogen atmosphere and mixing speed
For polymerisation 20h under conditions of 400r/min, polyamic acid solution is obtained；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, be subsequently placed in vacuum drying chamber, then will be true
Empty drying box, from room temperature to 80 DEG C, then is incubated 2h with 1 DEG C/min heating rate at being 80 DEG C in temperature, then with 2 DEG C/
Min heating rate is warming up to 170 DEG C from 80 DEG C, then is incubated 2h, then the heating rate with 1 DEG C/min at being 170 DEG C in temperature
210 DEG C are warming up to from 170 DEG C, then 2h is incubated at being 210 DEG C in temperature, then is warming up to 2 DEG C/min heating rate from 210 DEG C
260 DEG C, then 1h is incubated at being 260 DEG C in temperature, then 300 DEG C are warming up to from 260 DEG C with 2 DEG C/min heating rate, then in temperature
Spend to be incubated 1h at 300 DEG C, complete hot-imide, then cool down vacuum drying chamber, obtain the glass containing Kapton
Glass plate；
5th, the glass plate containing Kapton is put into distilled water, makes Kapton from glass plate
Come off, reuse distilled water and rinse Kapton well, obtain random copolymerization Kapton；
6th, random copolymerization Kapton is dissolved into 1-METHYLPYRROLIDONE, obtains random copolymerization polyimides
Solution；Random copolymerization polyimide solution is poured into glass tube, then it is to be dried in 150 DEG C that glass tube is put into temperature,
Obtain the glass tube containing random copolymerization polyimide tube；Random copolymerization in random copolymerization polyimide solution described in rapid six
The mass fraction of polyimides is 15%；
7th, the glass tube containing random copolymerization polyimide tube is put into distilled water, then makes random copolymerization polyamides sub-
Amine pipe comes off from glass tube, dries, obtains high temperature heat-shrink tube.
The high temperature polyimide heat-shrink tube T of preparationgFor 300 DEG C, high temperature heat-shrink tube field is can be applied to, in 280 DEG C of (Tg-20
DEG C) glassy state when storage modulus be 1.568GPa；In 320 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be
8.2MPa, there is good pyrocondensation effect.
Claims (6)
1. a kind of preparation method of high temperature polyimide heat-shrink tube, it is characterised in that step is as follows：
Step 1: 4,4'- diaminodiphenyl ethers and double (3- amino-benzene oxygens) benzene of 1,3- are added in aprotic polar solvent,
Stir in a nitrogen atmosphere to being completely dissolved again, obtain diamines blend solution；The amount of the material of described diamines and non-proton pole
The volume ratio of property solvent is 0.05mol：100mL~150mL；Described 4,4'- diaminodiphenyl ethers and double (the 3- aminobenzenes of 1,3-
Epoxide) benzene mol ratio be 1：9-9：1；
Step 2: 4,4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids are dissolved into aprotic polar solvent, two anhydride solutions are obtained；Institute
The amount for the dianhydride material stated and the volume ratio of aprotic polar solvent are 0.05mol：80mL~150mL；
It is added to Step 3: two anhydride solutions are divided 3-10 times in diamine solution, then is in room temperature, nitrogen atmosphere and mixing speed
Polymerisation 5h~30h under conditions of 300r/min~800r/min, obtains polyamic acid solution；4 in two described anhydride solutions,
4'- (hexafluoro isopropyl alkene) two anhydride phthalic acids and 4,4'- diaminodiphenyl ethers in diamine solution and double (3- amino-benzene oxygens) benzene of 1,3-
Mixture mol ratio be 1:1；
Step 4: polyamic acid solution is coated uniformly on the glass plate of cleaning, it is subsequently placed in vacuum drying chamber, then will be true
Empty drying box, from room temperature to 70 DEG C~90 DEG C, then is protected with 1 DEG C/min~2 DEG C/min heating rate at 70 DEG C~90 DEG C
Warm 2h~3h, then 150 DEG C~170 DEG C are warming up to from 70 DEG C~90 DEG C with 1 DEG C/min~2 DEG C/min heating rate, then 150
DEG C~170 DEG C at be incubated 2h~3h, then be warming up to 190 DEG C from 150 DEG C~170 DEG C with 1 DEG C/min~2 DEG C/min heating rate
~210 DEG C, then at 190 DEG C~210 DEG C be incubated 2h~3h, then with 1 DEG C/min~2 DEG C/min heating rate from 190 DEG C~
210 DEG C are warming up to 230 DEG C~260 DEG C, then 1h~2h are incubated at 230 DEG C~260 DEG C, then the liter with 1 DEG C/min~2 DEG C/min
Warm speed is warming up to 280 DEG C~300 DEG C from 230 DEG C~260 DEG C, then 1h~2h is incubated at 280 DEG C~300 DEG C, completes hot acyl
Imidization, then vacuum drying chamber is cooled down, obtain the glass plate containing Kapton；
Step 5: the glass plate containing Kapton is put into distilled water, make Kapton from glass plate
Come off, reuse distilled water and rinse Kapton well, obtain shape memory random copolymerization Kapton；
Step 6: shape memory random copolymerization Kapton is dissolved into aprotic polar solvent, shape memory is obtained
Random copolymerization polyimide solution；Shape memory random copolymerization polyimide solution is poured into glass tube, then by glass tube
It is to be dried in 150 DEG C~200 DEG C to be put into temperature, obtains the glass tube containing shape memory random copolymerization polyimide tube；Institute
In the shape memory random copolymerization polyimide solution stated the mass fraction of shape memory random copolymerization polyimides be 5%~
15%；
Step 7: the glass tube containing shape memory random copolymerization polyimide tube is put into distilled water, then remember shape
Recall random copolymerization polyimide tube to come off from glass tube, then shape memory random copolymerization polyimide tube is dried, obtain height
Warm polyimides heat-shrink tube.
2. the preparation method of a kind of high temperature polyimide heat-shrink tube according to claim 1, it is characterised in that in step 1
Described aprotic polar solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.
3. the preparation method of a kind of high temperature polyimide heat-shrink tube according to claim 1, it is characterised in that in step 2
Described aprotic polar solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.
4. the preparation method of a kind of high temperature polyimide heat-shrink tube according to claim 1, it is characterised in that in step 6
Described aprotic polar solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.
5. the preparation method of a kind of high temperature polyimide heat-shrink tube according to claim 1, it is characterised in that in step 4
Polyamic acid solution is coated uniformly on the glass plate of cleaning, be subsequently placed in vacuum drying chamber, then by vacuum drying chamber with 1
DEG C/min~2 DEG C/min heating rate is from room temperature to 80 DEG C~90 DEG C, then 2h~3h is incubated at 80 DEG C~90 DEG C, then
150 DEG C~170 DEG C are warming up to from 80 DEG C~90 DEG C with 1 DEG C/min~2 DEG C/min heating rate, then at 150 DEG C~170 DEG C
2h~3h is incubated, then 190 DEG C~210 DEG C are warming up to from 150 DEG C~170 DEG C with 1 DEG C/min~2 DEG C/min heating rate, then
2h~3h is incubated at 190 DEG C~210 DEG C, then is warming up to 1 DEG C/min~2 DEG C/min heating rate from 190 DEG C~210 DEG C
230 DEG C~260 DEG C, then 1h~2h is incubated at 230 DEG C~260 DEG C, then with 1 DEG C/min~2 DEG C/min heating rate from 230
DEG C~260 DEG C be warming up to 280 DEG C~290 DEG C, then 1h~2h be incubated at 280 DEG C~290 DEG C, complete hot-imide, then make
Vacuum drying chamber cools down.
6. a kind of high temperature polyimide heat-shrink tube prepared according to any one of claim 1-5 preparation method, it is characterised in that adopt
It is as follows with shape memory random copolymerization polyimide material, shape memory random copolymerization polyimide molecule formula：
M=5-28, n=6-25.
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