CN105778092B - A kind of PEI high temperature heat-shrink tube and preparation method thereof - Google Patents
A kind of PEI high temperature heat-shrink tube and preparation method thereof Download PDFInfo
- Publication number
- CN105778092B CN105778092B CN201610133420.6A CN201610133420A CN105778092B CN 105778092 B CN105778092 B CN 105778092B CN 201610133420 A CN201610133420 A CN 201610133420A CN 105778092 B CN105778092 B CN 105778092B
- Authority
- CN
- China
- Prior art keywords
- pei
- high temperature
- temperature heat
- shrink tube
- incubated
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Formation Of Insulating Films (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
A kind of PEI high temperature heat-shrink tube and preparation method thereof, it is related to a kind of high temperature heat-shrink tube and preparation method thereof.It is less the invention aims to solve sample of the complete shrinkage temperature of existing high temperature heat-shrink tube between 190 DEG C~210 DEG C, it is impossible to the problem of applying the protection of the sheath of area conductor cable and wire harness between temperature is 190~210 DEG C.PEI high temperature heat-shrink tube is prepared by 1,3 pairs of (3 amino-benzene oxygen) benzene and the mixture of 3,3', 4,4' benzophenone tetracarboxylic dianhydride (BTDA) and 4,4 oxo phthalic anhydrides.Method：First, diamine solution is prepared；2nd, two anhydride solutions are prepared；3rd, polyamic acid solution is prepared；4th, the glass plate containing PEI film is prepared；5th, dry PEI film is prepared；6th, the glass tube containing PEI pipe is prepared；7th, PEI high temperature heat-shrink tube is prepared.The present invention can obtain a kind of PEI high temperature heat-shrink tube.
Description
Technical field
The present invention relates to a kind of high temperature heat-shrink tube and preparation method thereof.
Background technology
Heat-shrinkable T bush also known as thermal contraction protection sleeve pipe, can be that electric wire, cable or wire terminal etc. provide insulation protection.Pyrocondensation
Pipe with performances such as high-temperature shrinkage, soft fire-retardant, insulation corrosion protections, protect by the insulation for being widely used for various wire harness, solder joint, inductance
Shield and metal tube, the antirust of rod, corrosion protection etc..The application that heat-shrink tube is extensively sent out in industries such as electric power, oil, building, military projects.Often
The heat-shrink tube seen has PVC thermal shrinkable sleeves, 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 (polyvinylidene fluoride) complete shrinkage temperature is
150 DEG C, the complete shrinkage temperature of silicon rubber is 175 DEG C, polytetrafluoroethylene (polytetrafluoroethylene (PTFE)) complete receipts
Contracting temperature is then higher than 300 DEG C.However, the report of heat shrink temperature heat-shrink tube between 190 DEG C~210 DEG C is less at present.
Complete shrinkage temperature can be used for the shield of areas of higher temperature leader cable for the heat-shrink tube between 190 DEG C~210 DEG C
The protection of set and wire harness.
The content of the invention
The invention aims to solve the complete shrinkage temperature of existing high temperature heat-shrink tube between 190 DEG C~210 DEG C
Sample is less, it is impossible to apply be 190 DEG C~210 DEG C in temperature between the protection of sheath and wire harness of area conductor cable ask
Topic, and a kind of PEI high temperature heat-shrink tube and preparation method thereof is provided.
A kind of PEI high temperature heat-shrink tube is by double (3- amino-benzene oxygens) benzene of 1,3- and 3,3', 4,4'- benzophenone four
The mixture of formic acid dianhydride and 4,4- oxo phthalic anhydrides is prepared；Double (3- amino-benzene oxygens) benzene of described 1,3- with
The mol ratio of the mixture of 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA) and 4,4- oxo phthalic anhydrides is 1:1；Described
3,3' in the mixture of 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA) and 4,4- oxo phthalic anhydrides, 4,4'- benzophenone four
The mol ratio of formic acid dianhydride and 4,4- oxo phthalic anhydrides is A:B；A span is 0≤A≤1；B span
For 0≤B≤1.
A kind of preparation method of PEI high temperature heat-shrink tube is completed according to the following steps：
First, by 1,3- double (3- amino-benzene oxygens), benzene is added in aprotic polar solvent, then is stirred in a nitrogen atmosphere
It is completely dissolved to double (3- amino-benzene oxygens) benzene of 1,3-, obtains diamine solution；
The amount of material and the volume of aprotic polar solvent of double (3- amino-benzene oxygens) benzene of 1,3- described in step 1
Than for 0.05mol:(100mL~150mL)；
2nd, by 3,3', the mixture of 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo phthalic anhydrides is dissolved into non-
In proton polar solvent, two anhydride solutions are obtained；
The mixing of 3,3' described in step 2,4,4'- benzophenone tetracarboxylic dianhydride (BTDA) and 4,4- oxo phthalic anhydrides
The amount of the material of thing and the volume ratio of aprotic polar solvent are 0.05mol:(80mL~150mL)；
3,3' in the mixture of described 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA) and 4,4- oxo phthalic anhydrides,
The mol ratio of 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo phthalic anhydrides is A:B；A span be 0≤A≤
1；B span is 0≤B≤1；
3rd, two anhydride solutions are divided 3 times~10 times and be added 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；
3,3' in two anhydride solutions described in step 3,4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo O-phthalics
The mol ratio of double (3- amino-benzene oxygens) benzene of 1,3- is 1 in the mixture and diamine solution of acid anhydrides: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 cool down, and obtain containing polyetherimide
The glass plate of amine film；
5th, the glass plate containing PEI film is put into distilled water, makes PEI film from glass plate
On come off, reuse distilled water and rinse PEI film well, then temperature be 100 DEG C~150 DEG C at dry 1h~
3h, obtain dry PEI film；
6th, dry PEI Film Fractionation is obtained into polyetherimide solution into aprotic polar solvent；Will
Polyetherimide solution is poured into glass tube, then glass tube is put into temperature for dry in 150 DEG C~200 DEG C 100h~
600h, obtain the glass tube containing PEI pipe；
The mass fraction of PEI is 10%~15% in polyetherimide solution described in step 6；
7th, the glass tube containing PEI pipe is put into distilled water, makes PEI pipe from glass tube
Come off, then PEI pipe is dried, obtain PEI high temperature heat-shrink tube.
Advantages of the present invention：
First, the present invention uses 3,3', and 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo phthalic anhydrides are as dianhydride
Monomer, using double (3- amino-benzene oxygens) benzene of 1,3- as diamine monomer, it is prepared for PEI high temperature heat-shrink tube；
2nd, PEI film prepared by the present invention may be dissolved in aprotic solvents, using solvent volatilization
PEI high temperature heat-shrink tube is made in mode；
3rd, PEI high temperature heat-shrink tube prepared by the present invention has adjustable complete between 190 DEG C~210 DEG C
Heat shrink temperature, it is set to have broad application prospects in high-temperature field；
4th, PEI high temperature heat-shrink tube prepared by the present invention can be good at fixing its diameter after extending and recovery
Its initial diameter；
5th, the T of PEI high temperature heat-shrink tube prepared by the present inventiongFor 192 DEG C~211 DEG C, the present invention is prepared poly-
Etherimide high temperature heat-shrink tube is in TgStorage modulus during -20 DEG C of glassy states is 1.638GPa~2.106GPa；In high temperature Tg+20
Storage modulus during DEG C rubbery state is 5.8MPa~7.9MPa.PEI high temperature heat-shrink tube prepared by the present invention has fine
Pyrocondensation effect.
The present invention can obtain a kind of PEI high temperature heat-shrink tube.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of PEI high temperature heat-shrink tube prepared by embodiment one；
Fig. 2 is the fissipation factor figure of PEI high temperature heat-shrink tube prepared by embodiment one；
Fig. 3 is the storage modulus figure of PEI high temperature heat-shrink tube prepared by embodiment one；
Fig. 4 is shape fixed after PEI high temperature heat-shrink tube prepared by embodiment one extends；
Fig. 5 is the shape recovered after PEI high temperature heat-shrink tube prepared by embodiment one shrinks.
Embodiment
Embodiment one：Present embodiment is a kind of PEI high temperature heat-shrink tube by double (the 3- aminobenzenes of 1,3-
Epoxide) benzene and the mixture of 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA) and 4,4- oxo phthalic anhydrides be prepared；Institute
Double (3- amino-benzene oxygens) benzene of 1,3- and 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA) and 4,4- oxo phthalic anhydrides stated
Mixture mol ratio be 1:1；Described 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA) and 4,4- oxo phthalic anhydrides
Mixture in 3,3', the mol ratio of 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo phthalic anhydrides is A:B；A's takes
Value scope is 0≤A≤1；B span is 0≤B≤1.
The advantages of present embodiment：
First, present embodiment uses 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo phthalic anhydride conducts
Dianhydride monomer, using double (3- amino-benzene oxygens) benzene of 1,3- as diamine monomer, it is prepared for PEI high temperature heat-shrink tube；
2nd, PEI high temperature heat-shrink tube prepared by present embodiment has adjustable between 190 DEG C~210 DEG C
Complete heat shrink temperature, makes it have broad application prospects in high-temperature field；
3rd, PEI high temperature heat-shrink tube prepared by present embodiment can be good at fixing its diameter after extending simultaneously
Recover its initial diameter；
4th, the T of PEI high temperature heat-shrink tube prepared by present embodimentgFor 192 DEG C~211 DEG C, present embodiment
The PEI high temperature heat-shrink tube of preparation is in TgStorage modulus during -20 DEG C of glassy states is 1.638GPa~2.106GPa；
High temperature TgStorage modulus during+20 DEG C of rubbery states is 5.8MPa~7.9MPa.PEI high temperature prepared by present embodiment
Heat-shrink tube has good pyrocondensation effect.
Present embodiment can obtain a kind of PEI high temperature heat-shrink tube.
Embodiment two：Present embodiment is that a kind of preparation method of PEI high temperature heat-shrink tube is by following
What step was completed：
First, by 1,3- double (3- amino-benzene oxygens), benzene is added in aprotic polar solvent, then is stirred in a nitrogen atmosphere
It is completely dissolved to double (3- amino-benzene oxygens) benzene of 1,3-, obtains diamine solution；
The amount of material and the volume of aprotic polar solvent of double (3- amino-benzene oxygens) benzene of 1,3- described in step 1
Than for 0.05mol:(100mL~150mL)；
2nd, by 3,3', the mixture of 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo phthalic anhydrides is dissolved into non-
In proton polar solvent, two anhydride solutions are obtained；
The mixing of 3,3' described in step 2,4,4'- benzophenone tetracarboxylic dianhydride (BTDA) and 4,4- oxo phthalic anhydrides
The amount of the material of thing and the volume ratio of aprotic polar solvent are 0.05mol:(80mL~150mL)；
3,3' in the mixture of described 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA) and 4,4- oxo phthalic anhydrides,
The mol ratio of 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo phthalic anhydrides is A:B；A span be 0≤A≤
1；B span is 0≤B≤1；
3rd, two anhydride solutions are divided 3 times~10 times and be added 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；
3,3' in two anhydride solutions described in step 3,4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo O-phthalics
The mol ratio of double (3- amino-benzene oxygens) benzene of 1,3- is 1 in the mixture and diamine solution of acid anhydrides: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 cool down, and obtain containing polyetherimide
The glass plate of amine film；
5th, the glass plate containing PEI film is put into distilled water, makes PEI film from glass plate
On come off, reuse distilled water and rinse PEI film well, then temperature be 100 DEG C~150 DEG C at dry 1h~
3h, obtain dry PEI film；
6th, dry PEI Film Fractionation is obtained into polyetherimide solution into aprotic polar solvent；Will
Polyetherimide solution is poured into glass tube, then glass tube is put into temperature for dry in 150 DEG C~200 DEG C 100h~
600h, obtain the glass tube containing PEI pipe；
The mass fraction of PEI is 10%~15% in polyetherimide solution described in step 6；
7th, the glass tube containing PEI pipe is put into distilled water, makes PEI pipe from glass tube
Come off, then PEI pipe is dried, obtain PEI high temperature heat-shrink tube.
The advantages of present embodiment：
First, present embodiment uses 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo phthalic anhydride conducts
Dianhydride monomer, using double (3- amino-benzene oxygens) benzene of 1,3- as diamine monomer, it is prepared for PEI high temperature heat-shrink tube；
2nd, PEI film prepared by present embodiment may be dissolved in aprotic solvents, be waved using solvent
PEI high temperature heat-shrink tube is made in the mode of hair；
3rd, PEI high temperature heat-shrink tube prepared by present embodiment has adjustable between 190 DEG C~210 DEG C
Complete heat shrink temperature, makes it have broad application prospects in high-temperature field；
4th, PEI high temperature heat-shrink tube prepared by present embodiment can be good at fixing its diameter after extending simultaneously
Recover its initial diameter；
5th, the T of PEI high temperature heat-shrink tube prepared by present embodimentgFor 192 DEG C~211 DEG C, present embodiment
The PEI high temperature heat-shrink tube of preparation is in TgStorage modulus during -20 DEG C of glassy states is 1.638GPa~2.106GPa；
High temperature TgStorage modulus during+20 DEG C of rubbery states is 5.8MPa~7.9MPa.PEI high temperature prepared by present embodiment
Heat-shrink tube has good pyrocondensation effect.
Present embodiment can obtain a kind of PEI high temperature heat-shrink tube.
Embodiment three：The difference of present embodiment and embodiment two is：It is non-described in step 1
Proton polar solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.Other and specific reality
It is identical to apply mode two.
Embodiment four：The difference of present embodiment and one of embodiment two to three is：In step 2
Described aprotic polar solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.Other
It is identical with embodiment two to three.
Embodiment five：The difference of present embodiment and one of embodiment two to four is：In step 6
Described aprotic polar solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.Other
It is identical with embodiment two to four.
Embodiment six：The difference of present embodiment and one of embodiment two to five is：In step 1
The amount of material and the volume ratio of aprotic polar solvent of double (3- amino-benzene oxygens) benzene of described 1,3- are 0.05mol:
110mL.Other are identical with embodiment two to five.
Embodiment seven：The difference of present embodiment and one of embodiment two to six is：In step 1
The amount of material and the volume ratio of aprotic polar solvent of double (3- amino-benzene oxygens) benzene of described 1,3- are 0.05mol:
120mL.Other are identical with embodiment two to six.
Embodiment eight：The difference of present embodiment and one of embodiment two to seven is：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 heating rate is from room temperature to 80 DEG C, then 2h is incubated at 80 DEG C, then with 1 DEG C/min heating rate from 80 DEG C
170 DEG C are warming up to, then 2h is incubated at 170 DEG C, then 210 DEG C are warming up to from 170 DEG C with 1 DEG C/min heating rate, then 210
2h is incubated at DEG C, then 260 DEG C are warming up to from 210 DEG C with 1 DEG C/min heating rate, then 1h is incubated at 260 DEG C, then is cooled down,
Obtain the glass plate containing PEI film.Other are identical with embodiment two to seven.
Embodiment nine：The difference of present embodiment and one of embodiment two to eight is：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 heating rate is from room temperature to 90 DEG C, then 2h is incubated at 90 DEG C, then with 1 DEG C/min heating rate from 90 DEG C
170 DEG C are warming up to, then 2h is incubated at 170 DEG C, then 210 DEG C are warming up to from 170 DEG C with 1 DEG C/min heating rate, then 210
2h is incubated at DEG C, then 250 DEG C are warming up to from 210 DEG C with 1 DEG C/min heating rate, then 1h~2h is incubated at 250 DEG C, then it is cold
But, the glass plate containing PEI film is obtained.Other are identical with embodiment two to eight.
Embodiment ten：The difference of present embodiment and one of embodiment two to ten is：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 heating rate is from room temperature to 80 DEG C, then 2h is incubated at 80 DEG C, then with 2 DEG C/min heating rate from 80 DEG C
170 DEG C are warming up to, then 2h is incubated at 170 DEG C, then 210 DEG C are warming up to from 170 DEG C with 2 DEG C/min heating rate, then 210
2h is incubated at DEG C, then 260 DEG C are warming up to from 210 DEG C with 2 DEG C/min heating rate, then 1h is incubated at 260 DEG C, then is cooled down,
Obtain the glass plate containing PEI film.Other are identical with embodiment two to ten.
Beneficial effects of the present invention are verified using following examples：
Embodiment one：A kind of preparation method of PEI high temperature heat-shrink tube, is completed according to the following steps：
First, 0.05mol 1, double (3- amino-benzene oxygens) benzene of 3- are added in 110mL DMAs, then
Stir to double (3- amino-benzene oxygens) benzene of 1,3- and be completely dissolved in a nitrogen atmosphere, obtain diamine solution；
2nd, 0.05mol 4,4- oxo phthalic anhydrides are dissolved into 90mL DMAs, obtained
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 15h under conditions of min, obtains polyamic acid solution；
3,3' in two anhydride solutions described in step 3,4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo O-phthalics
The mol ratio of double (3- amino-benzene oxygens) benzene of 1,3- is 1 in the mixture and diamine solution of acid anhydrides: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 90 DEG C, then is incubated 2h with 1 DEG C/min heating rate at 90 DEG C, then the liter with 1 DEG C/min
Warm speed is warming up to 170 DEG C from 90 DEG C, then 2h is incubated at 170 DEG C, then is warming up to 1 DEG C/min heating rate from 170 DEG C
210 DEG C, then 2h is incubated at 210 DEG C, then 250 DEG C are warming up to from 210 DEG C with 1 DEG C/min heating rate, then protected at 250 DEG C
Warm 1h, then cool down, obtain the glass plate containing PEI film；
5th, the glass plate containing PEI film is put into distilled water, makes PEI film from glass plate
On come off, reuse distilled water and rinse PEI film well, then temperature be 100 DEG C at dry 3h, obtain drying
PEI film；
6th, dry PEI Film Fractionation is obtained into polyetherimide solution into DMA；
Polyetherimide solution is poured into glass tube, then it is that 200h is dried in 150 DEG C that glass tube is put into temperature, is contained
The glass tube of PEI pipe；
The mass fraction of PEI is 10% in polyetherimide solution described in step 6；
7th, the glass tube containing PEI pipe is put into distilled water, makes PEI pipe from glass tube
Come off, then PEI pipe is dried, obtain PEI high temperature heat-shrink tube.
PEI high temperature heat-shrink tube prepared by embodiment one is tested using infrared spectrometer, as shown in Figure 1.
Fig. 1 is the infrared spectrogram of PEI high temperature heat-shrink tube prepared by embodiment one；From fig. 1, it can be seen that prepared by embodiment one
PEI is the polyimides of height imidizate.
PEI high temperature heat-shrink tube prepared by embodiment one is tested using dynamic mechanical analyzer, such as Fig. 2
Shown, Fig. 2 is the fissipation factor figure of PEI high temperature heat-shrink tube prepared by embodiment one；Embodiment as can be seen from Figure 2
Glass transition temperature (the T of the one PEI high temperature heat-shrink tube preparedg) it is 192 DEG C, it ensure that it can be applied to high temperature
Field.
PEI high temperature heat-shrink tube prepared by embodiment one is tested using dynamic mechanical analyzer, such as Fig. 3
It is shown；Fig. 3 is the storage modulus figure of PEI high temperature heat-shrink tube prepared by embodiment one；As can be seen from Figure 3, storage modulus becomes
Change curve and two platforms of high and low temperature section occur, in 172 DEG C of (Tg- 20 DEG C) glassy state when storage modulus be
2.086GPa；In 212 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be 5.8MPa.
Fig. 4 is shape fixed after PEI high temperature heat-shrink tube prepared by embodiment one extends；
Fig. 5 is the shape recovered after PEI high temperature heat-shrink tube prepared by embodiment one shrinks.
As can be seen that PEI high temperature heat-shrink tube prepared by embodiment one has good pyrocondensation from Fig. 4 and Fig. 5
Effect.
Embodiment two：A kind of preparation method of PEI high temperature heat-shrink tube is completed according to the following steps：
First, 0.05mol 1, double (3- amino-benzene oxygens) benzene of 3- are added in 120mL DMAs, then
Stir to double (3- amino-benzene oxygens) benzene of 1,3- and be completely dissolved in a nitrogen atmosphere, obtain diamine solution；
2nd, by 0.01mol 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 0.04mol 4,4- oxo phthalic anhydrides
It is dissolved into 90mL DMAs, obtains 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 16h under conditions of min, obtains polyamic acid solution；
3,3' in two anhydride solutions described in step 3,4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo O-phthalics
The amount ratio of the material of double (3- amino-benzene oxygens) benzene of 1,3- is 1 in the amount and diamine solution of total material of acid anhydrides: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 80 DEG C, then is incubated 2h with 1 DEG C/min heating rate at 80 DEG C, then the liter with 1 DEG C/min
Warm speed is warming up to 170 DEG C from 80 DEG C, then 2h is incubated at 170 DEG C, then is warming up to 1 DEG C/min heating rate from 170 DEG C
210 DEG C, then 2h is incubated at 210 DEG C, then 260 DEG C are warming up to from 210 DEG C with 1 DEG C/min heating rate, then protected at 260 DEG C
Warm 1h, then cool down, obtain the glass plate containing PEI film；
5th, the glass plate containing PEI film is put into distilled water, makes PEI film from glass plate
On come off, reuse distilled water and rinse PEI film well, then temperature be 110 DEG C at dry 2h, obtain drying
PEI film；
6th, dry PEI Film Fractionation is obtained into polyetherimide solution into DMA；
Polyetherimide solution is poured into glass tube, then it is 150 DEG C of dry 300h that glass tube is put into temperature, is obtained containing poly-
The glass tube of etherimide pipe；
The mass fraction of PEI is 12% in polyetherimide solution described in step 6；
7th, the glass tube containing PEI pipe is put into distilled water, makes PEI pipe from glass tube
Come off, then PEI pipe is dried, obtain PEI high temperature heat-shrink tube.
The T of PEI high temperature heat-shrink tube prepared by embodiment twogFor 196 DEG C, ensure polyethers prepared by embodiment two
Acid imide high temperature heat-shrink tube can be applied to high temperature heat-shrink tube field.PEI high temperature heat-shrink tube prepared by embodiment two exists
176℃(Tg- 20 DEG C) glassy state when storage modulus be 1.826GPa；In 216 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage
Modulus is 7.6MPa.PEI high temperature heat-shrink tube prepared by embodiment two has good pyrocondensation effect.
Embodiment three：A kind of preparation method of PEI high temperature heat-shrink tube, is completed according to the following steps：
First, 0.05mol 1, double (3- amino-benzene oxygens) benzene of 3- are added in 120mL DMFs, then
Stir to double (3- amino-benzene oxygens) benzene of 1,3- and be completely dissolved in a nitrogen atmosphere, obtain diamine solution；
2nd, by 0.02mol 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 0.03mol 4,4- oxo phthalic anhydrides
It is dissolved into 90mL DMAs, obtains 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；
3,3' in two anhydride solutions described in step 3,4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo O-phthalics
The amount ratio of the material of double (3- amino-benzene oxygens) benzene of 1,3- is 1 in the amount and diamine solution of total material of acid anhydrides: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 80 DEG C, then is incubated 2h with 1 DEG C/min heating rate at 80 DEG C, then the liter with 1 DEG C/min
Warm speed is warming up to 170 DEG C from 80 DEG C, then 2h is incubated at 170 DEG C, then is warming up to 2 DEG C/min heating rate from 170 DEG C
210 DEG C, then 2h is incubated at 210 DEG C, then 260 DEG C are warming up to from 210 DEG C with 2 DEG C/min heating rate, then protected at 260 DEG C
Warm 1h, then cool down, obtain the glass plate containing PEI film；
5th, the glass plate containing PEI film is put into distilled water, makes PEI film from glass plate
On come off, reuse distilled water and rinse PEI film well, then temperature be 120 DEG C at dry 2h, obtain drying
PEI film；
6th, dry PEI Film Fractionation is obtained into polyetherimide solution into DMF；
Polyetherimide solution is poured into glass tube, then it is that 500h is dried in 150 DEG C that glass tube is put into temperature, is contained
The glass tube of PEI pipe；
The mass fraction of PEI is 13% in polyetherimide solution described in step 6；
7th, the glass tube containing PEI pipe is put into distilled water, makes PEI pipe from glass tube
Come off, then PEI pipe is dried, obtain PEI high temperature heat-shrink tube.
The T of PEI high temperature heat-shrink tube prepared by embodiment threegFor 200 DEG C, ensure polyethers prepared by embodiment three
Acid imide high temperature heat-shrink tube can be applied to high temperature heat-shrink tube field.PEI high temperature heat-shrink tube prepared by embodiment three exists
180℃(Tg- 20 DEG C) glassy state when storage modulus be 1.768GPa；In 220 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage
Modulus is 7.9MPa.PEI high temperature heat-shrink tube prepared by embodiment three has good pyrocondensation effect.
Example IV：A kind of preparation method of PEI high temperature heat-shrink tube, is completed according to the following steps：
First, 0.05mol 1, double (3- amino-benzene oxygens) benzene of 3- are added in 120mL DMFs, then
Stir to double (3- amino-benzene oxygens) benzene of 1,3- and be completely dissolved in a nitrogen atmosphere, obtain diamine solution；
2nd, by 0.03mol 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 0.02mol 4,4- oxo phthalic anhydrides
It is dissolved into 90mL DMAs, obtains 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 18h under conditions of min, obtains polyamic acid solution；
3,3' in two anhydride solutions described in step 3,4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo O-phthalics
The amount ratio of the material of double (3- amino-benzene oxygens) benzene of 1,3- is 1 in the amount and diamine solution of total material of acid anhydrides: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 80 DEG C, then is incubated 2h with 1 DEG C/min heating rate at 80 DEG C, then the liter with 2 DEG C/min
Warm speed is warming up to 170 DEG C from 80 DEG C, then 2h is incubated at 170 DEG C, then is warming up to 2 DEG C/min heating rate from 170 DEG C
210 DEG C, then 2h is incubated at 210 DEG C, then 260 DEG C are warming up to from 210 DEG C with 2 DEG C/min heating rate, then protected at 260 DEG C
Warm 1h, then cool down, obtain the glass plate containing PEI film；
5th, the glass plate containing PEI film is put into distilled water, makes PEI film from glass plate
On come off, reuse distilled water and rinse PEI film well, then temperature be 100 DEG C at dry 3h, obtain drying
PEI film；
6th, dry PEI Film Fractionation is obtained into polyetherimide solution into DMF；
Polyetherimide solution is poured into glass tube, then it is that 600h is dried in 150 DEG C that glass tube is put into temperature, is contained
The glass tube of PEI pipe；
The mass fraction of PEI is 13% in polyetherimide solution described in step 6；
7th, the glass tube containing PEI pipe is put into distilled water, makes PEI pipe from glass tube
Come off, then PEI pipe is dried, obtain PEI high temperature heat-shrink tube.
The T of PEI high temperature heat-shrink tube prepared by example IVgFor 204 DEG C, it ensure that example IV is prepared poly-
Etherimide high temperature heat-shrink tube can be applied to high-temperature field.The standby PEI high temperature heat-shrink tube of example IV is at 184 DEG C
(Tg- 20 DEG C) glassy state when storage modulus be 1.763GPa；In 224 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be
7.6MPa.PEI high temperature heat-shrink tube prepared by example IV has good pyrocondensation effect.
Embodiment five：A kind of preparation method of PEI high temperature heat-shrink tube, is completed according to the following steps：
First, 0.05mol 1, double (3- amino-benzene oxygens) benzene of 3- are added in 120mL DMFs, then
Stir to double (3- amino-benzene oxygens) benzene of 1,3- and be completely dissolved in a nitrogen atmosphere, obtain diamine solution；
2nd, by 0.04mol 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 0.01mol 4,4- oxo phthalic anhydrides
It is dissolved into 90mL DMAs, obtains 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 19h under conditions of min, obtains polyamic acid solution；
3,3' in two anhydride solutions described in step 3,4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo O-phthalics
The amount ratio of the material of double (3- amino-benzene oxygens) benzene of 1,3- is 1 in the amount and diamine solution of total material of acid anhydrides: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 80 DEG C, then is incubated 2h with 1 DEG C/min heating rate at 80 DEG C, then the liter with 2 DEG C/min
Warm speed is warming up to 170 DEG C from 80 DEG C, then 2h is incubated at 170 DEG C, then is warming up to 2 DEG C/min heating rate from 170 DEG C
210 DEG C, then 2h is incubated at 210 DEG C, then 260 DEG C are warming up to from 210 DEG C with 1 DEG C/min heating rate, then protected at 260 DEG C
Warm 1h, then cool down, obtain the glass plate containing PEI film；
5th, the glass plate containing PEI film is put into distilled water, makes PEI film from glass plate
On come off, reuse distilled water and rinse PEI film well, then temperature be 120 DEG C at dry 2h, obtain drying
PEI film；
6th, dry PEI Film Fractionation is obtained into polyetherimide solution into DMF；
Polyetherimide solution is poured into glass tube, then it is that 360h is dried in 150 DEG C that glass tube is put into temperature, is contained
The glass tube of PEI pipe；
The mass fraction of PEI is 15% in polyetherimide solution described in step 6；
7th, the glass tube containing PEI pipe is put into distilled water, makes PEI pipe from glass tube
Come off, then PEI pipe is dried, obtain PEI high temperature heat-shrink tube.
The T of PEI high temperature heat-shrink tube prepared by embodiment fivegFor 208 DEG C, it ensure that embodiment five is prepared poly-
Etherimide high temperature heat-shrink tube can be applied to high temperature heat-shrink tube field.PEI high temperature heat-shrink tube prepared by embodiment five exists
188℃(Tg- 20 DEG C) glassy state when storage modulus be 1.638GPa；In 228 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage
Modulus is 7.5MPa.PEI high temperature heat-shrink tube prepared by embodiment five has good pyrocondensation effect.
Embodiment six：A kind of preparation method of PEI high temperature heat-shrink tube, is completed according to the following steps：
First, 0.05mol 1, double (3- amino-benzene oxygens) benzene of 3- are added in 100mL 1-METHYLPYRROLIDONEs, then
Stirring to double (3- amino-benzene oxygens) benzene of 1,3- are completely dissolved under nitrogen atmosphere, obtain diamine solution；
2nd, the benzophenone tetracarboxylic dianhydride (BTDA)s of 0.05mol 3,3', 4,4'- are dissolved into 90mL 1-METHYLPYRROLIDONEs, obtained
To 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 20h under conditions of min, obtains polyamic acid solution；
3,3' in two anhydride solutions described in step 3,4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo O-phthalics
The amount ratio of the material of double (3- amino-benzene oxygens) benzene of 1,3- is 1 in the amount and diamine solution of total material of acid anhydrides: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 80 DEG C, then is incubated 2h with 1 DEG C/min heating rate at 80 DEG C, then the liter with 2 DEG C/min
Warm speed is warming up to 170 DEG C from 80 DEG C, then 2h is incubated at 170 DEG C, then is warming up to 1 DEG C/min heating rate from 170 DEG C
210 DEG C, then 2h is incubated at 210 DEG C, then 260 DEG C are warming up to from 210 DEG C with 2 DEG C/min heating rate, then protected at 260 DEG C
Warm 1h, then cool down, obtain the glass plate containing PEI film；
5th, the glass plate containing PEI film is put into distilled water, makes PEI film from glass plate
On come off, reuse distilled water and rinse PEI film well, then temperature be 100 DEG C at dry 2h, obtain drying
PEI film；
6th, dry PEI Film Fractionation is obtained into polyetherimide solution into 1-METHYLPYRROLIDONE；Will
Polyetherimide solution is poured into glass tube, then it is that 450h is dried in 150 DEG C that glass tube is put into temperature, is obtained containing poly-
The glass tube of etherimide pipe；
The mass fraction of PEI is 15% in polyetherimide solution described in step 6；
7th, the glass tube containing PEI pipe is put into distilled water, makes PEI pipe from glass tube
Come off, then PEI pipe is dried, obtain PEI high temperature heat-shrink tube.
PEI high temperature heat-shrink tube T prepared by embodiment sixgFor 211 DEG C, polyethers prepared by embodiment six ensure that
Acid imide high temperature heat-shrink tube can be applied to high-temperature field.PEI high temperature heat-shrink tube prepared by embodiment six is at 191 DEG C
(Tg- 20 DEG C) glassy state when storage modulus be 2.106GPa；In 231 DEG C of (T of high temperatureg+ 20 DEG C) rubbery state when storage modulus be
6.8MPa.PEI high temperature heat-shrink tube prepared by embodiment six has good pyrocondensation effect.
Claims (9)
1. a kind of preparation method of PEI high temperature heat-shrink tube, it is characterised in that a kind of PEI high temperature heat-shrink tube
Preparation method is completed according to the following steps：
First, double (3- amino-benzene oxygens) benzene of 1,3- are added in aprotic polar solvent, then stirred in a nitrogen atmosphere to 1,
Double (3- amino-benzene oxygens) benzene of 3- are completely dissolved, and obtain diamine solution；
The amount of material and the volume ratio of aprotic polar solvent of double (3- amino-benzene oxygens) benzene of 1,3- described in step 1 be
0.05mol:(100mL~150mL)；
2nd, by 3,3', the mixture of 4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo phthalic anhydrides is dissolved into non-proton
In polar solvent, two anhydride solutions are obtained；
The mixture of 3,3' described in step 2,4,4'- benzophenone tetracarboxylic dianhydride (BTDA) and 4,4- oxo phthalic anhydrides
The amount of material and the volume ratio of aprotic polar solvent are 0.05mol:(80mL~150mL)；
3,3' in the mixture of described 3,3', 4,4'- benzophenone tetracarboxylic dianhydride (BTDA) and 4,4- oxo phthalic anhydrides, 4,
The mol ratio of 4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo phthalic anhydrides is A:B；A span is 0≤A≤1；B
Span be 0≤B≤1；
3rd, two anhydride solutions are divided 3 times~10 times and be added in diamine solution, then be in room temperature, nitrogen atmosphere and mixing speed
Polymerisation 5h~30h under conditions of 300r/min~800r/min, obtains polyamic acid solution；
3,3' in two anhydride solutions described in step 3,4,4'- benzophenone tetracarboxylic dianhydride (BTDA)s and 4,4- oxo phthalic anhydrides
Mixture and diamine solution in the mol ratio of double (3- amino-benzene oxygens) benzene of 1,3- be 1:1；
4th, polyamic acid solution is coated uniformly on the glass plate of cleaning, be subsequently placed in vacuum drying chamber, then vacuum is done
Dry case, from room temperature to 70 DEG C~90 DEG C, then is incubated 2h with 1 DEG C/min~2 DEG C/min heating rate at 70 DEG C~90 DEG C
~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~
2h~3h is incubated at 170 DEG C, then be warming up to from 150 DEG C~170 DEG C with 1 DEG C/min~2 DEG C/min heating rate 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
230 DEG C~260 DEG C DEG C are warming up to, then 1h~2h is incubated at 230 DEG C~260 DEG C, then is cooled down, is obtained thin containing PEI
The glass plate of film；
5th, the glass plate containing PEI film is put into distilled water, PEI film is taken off from glass plate
Fall, reuse distilled water and rinse PEI film well, then 1h~3h is dried at being 100 DEG C~150 DEG C in temperature, obtain
To dry PEI film；
6th, dry PEI Film Fractionation is obtained into polyetherimide solution into aprotic polar solvent；By polyethers
Imide solution is poured into glass tube, then it is that 100h~600h is dried in 150 DEG C~200 DEG C that glass tube is put into temperature,
Obtain the glass tube containing PEI pipe；
The mass fraction of PEI is 10%~15% in polyetherimide solution described in step 6；
7th, the glass tube containing PEI pipe is put into distilled water, PEI pipe is come off from glass tube,
PEI pipe is dried again, obtains PEI high temperature heat-shrink tube.
A kind of 2. preparation method of PEI high temperature heat-shrink tube according to claim 1, it is characterised in that step 1
Described in aprotic polar solvent be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.
A kind of 3. preparation method of PEI high temperature heat-shrink tube according to claim 1, it is characterised in that step 2
Described in aprotic polar solvent be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.
A kind of 4. preparation method of PEI high temperature heat-shrink tube according to claim 1, it is characterised in that step 6
Described in aprotic polar solvent be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or 1-METHYLPYRROLIDONE.
A kind of 5. preparation method of PEI high temperature heat-shrink tube according to claim 1, it is characterised in that step 1
Described in double (3- amino-benzene oxygens) benzene of 1,3- the amount of material and the volume ratio of aprotic polar solvent be 0.05mol:
110mL。
A kind of 6. preparation method of PEI high temperature heat-shrink tube according to claim 1, it is characterised in that step 1
Described in double (3- amino-benzene oxygens) benzene of 1,3- the amount of material and the volume ratio of aprotic polar solvent be 0.05mol:
120mL。
A kind of 7. preparation method of PEI high temperature heat-shrink tube according to claim 1, it is characterised in that step 4
It is middle to be coated uniformly on polyamic acid solution on the glass plate of cleaning, it is 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 with 1 DEG C/min heating rate from
80 DEG C are warming up to 170 DEG C, then 2h are incubated at 170 DEG C, then are warming up to 210 DEG C from 170 DEG C with 1 DEG C/min heating rate, then
2h is incubated at 210 DEG C, then 260 DEG C are warming up to from 210 DEG C with 1 DEG C/min heating rate, then 1h is incubated at 260 DEG C, then
Cooling, obtains the glass plate containing PEI film.
A kind of 8. preparation method of PEI high temperature heat-shrink tube according to claim 1, it is characterised in that step 4
It is middle to be coated uniformly on polyamic acid solution on the glass plate of cleaning, it is 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 with 1 DEG C/min heating rate from
90 DEG C are warming up to 170 DEG C, then 2h are incubated at 170 DEG C, then are warming up to 210 DEG C from 170 DEG C with 1 DEG C/min heating rate, then
Be incubated 2h at 210 DEG C, then 250 DEG C be warming up to from 210 DEG C with 1 DEG C/min heating rate, then be incubated at 250 DEG C 1h~
2h, then cool down, obtain the glass plate containing PEI film.
A kind of 9. preparation method of PEI high temperature heat-shrink tube according to claim 1, it is characterised in that step 4
It is middle to be coated uniformly on polyamic acid solution on the glass plate of cleaning, it is 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 with 2 DEG C/min heating rate from
80 DEG C are warming up to 170 DEG C, then 2h are incubated at 170 DEG C, then are warming up to 210 DEG C from 170 DEG C with 2 DEG C/min heating rate, then
2h is incubated at 210 DEG C, then 260 DEG C are warming up to from 210 DEG C with 2 DEG C/min heating rate, then 1h is incubated at 260 DEG C, then
Cooling, obtains the glass plate containing PEI film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610133420.6A CN105778092B (en) | 2016-03-09 | 2016-03-09 | A kind of PEI high temperature heat-shrink tube and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610133420.6A CN105778092B (en) | 2016-03-09 | 2016-03-09 | A kind of PEI high temperature heat-shrink tube and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105778092A CN105778092A (en) | 2016-07-20 |
| CN105778092B true CN105778092B (en) | 2018-03-16 |
Family
ID=56386618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610133420.6A Active CN105778092B (en) | 2016-03-09 | 2016-03-09 | A kind of PEI high temperature heat-shrink tube and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105778092B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107099033B (en) * | 2017-06-15 | 2020-05-12 | 哈尔滨工业大学 | Thin-wall polyimide special pipe and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980492A (en) * | 2014-05-23 | 2014-08-13 | 哈尔滨工业大学 | High-temperature-resistant thermoplastic shape memory polyimide and preparation method thereof |
| CN103980491A (en) * | 2014-05-23 | 2014-08-13 | 哈尔滨工业大学 | Quick-response thermoset shape memory polyimide and preparation method thereof |
| CN104017213A (en) * | 2014-06-19 | 2014-09-03 | 冷劲松 | Shape memory polyether imide with high glass-transition temperature and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6476177B2 (en) * | 2000-12-21 | 2002-11-05 | E. I. Du Pont De Nemours And Company | Melt-processible, thermoplastic random copolyimides having recoverable crystallinity and associated processes |
-
2016
- 2016-03-09 CN CN201610133420.6A patent/CN105778092B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980492A (en) * | 2014-05-23 | 2014-08-13 | 哈尔滨工业大学 | High-temperature-resistant thermoplastic shape memory polyimide and preparation method thereof |
| CN103980491A (en) * | 2014-05-23 | 2014-08-13 | 哈尔滨工业大学 | Quick-response thermoset shape memory polyimide and preparation method thereof |
| CN104017213A (en) * | 2014-06-19 | 2014-09-03 | 冷劲松 | Shape memory polyether imide with high glass-transition temperature and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Opticallly transparent high temperature shape memory polymers;xinli Xiao et al;《Soft.Matter》;20151209;2807-2978 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105778092A (en) | 2016-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103554533B (en) | A kind of Corona-resistant polyimide/silica nano composite film and preparation method thereof | |
| CN109401313B (en) | Polyimide film and preparation method thereof | |
| CN109181522B (en) | Aramid fiber coating liquid, lithium ion battery diaphragm and preparation method thereof | |
| CN105576176B (en) | A kind of preparation method of high security lithium ion battery diaphragm | |
| CN105778092B (en) | A kind of PEI high temperature heat-shrink tube and preparation method thereof | |
| CN106750290A (en) | A kind of method that in-situ polymerization prepares polyimides Graphene composite aerogel | |
| CN105254882B (en) | A kind of polyimides of the structure containing bipyridyl and preparation method thereof | |
| CN105542460B (en) | A kind of high temperature polyimide heat-shrink tube and preparation method thereof | |
| CN105111433A (en) | Low dielectric constant polyamide aerogel thermal insulation material and preparation method thereof | |
| CN109206906A (en) | A kind of low dielectric coefficient polyimide film of excellent water resistance | |
| CN105504280B (en) | A kind of high temperature heat-shrink tube random copolymerization polyimides and preparation method thereof | |
| CN109293978B (en) | High-porosity polyimide aerogel and normal-pressure drying preparation method thereof | |
| US8261492B2 (en) | Vibration resistant civil structure block for buildings | |
| CN106084271A (en) | New method prepared by three layers of laminated film of nanoparticle/polyimides | |
| CN112143000B (en) | Preparation method of all-organic PI/PVDF film composite material | |
| CN115537026B (en) | Polyimide aerogel and preparation method thereof | |
| CN108822544B (en) | Preparation method of polyimide/metal organic framework composite film | |
| CN106751788A (en) | A kind of thermal diffusivity good electric armour clamp fire-retardant nylon composite and preparation method thereof | |
| CN106380844A (en) | Preparation method of boron nitride and aluminum nitride co-doped high-heat-conduction and high-insulation polyimide composite thin film | |
| CN105820572A (en) | Preparation method of polyimide/graphene nanoribbon composite film | |
| TW201720857A (en) | Thermal conductive resin and thermal interface material comprising the same | |
| CN108610629A (en) | A kind of modified enhancing Inverter fed motor electric wire and preparation method thereof | |
| CN105837122B (en) | High-insulation polymer concrete for power transmission pipeline and preparation method thereof | |
| Steinfeld et al. | Stress induced electrochemical degradation of the inner semicon layer of XLPE-insulated cables and model samples | |
| CN107033592A (en) | A kind of polyimide resin enhancing composite and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210107 Address after: Building 9, accelerator, 14955 Zhongyuan Avenue, Songbei District, Harbin City, Heilongjiang Province Patentee after: INDUSTRIAL TECHNOLOGY Research Institute OF HEILONGJIANG PROVINCE Address before: 150001 No. 92 West straight street, Nangang District, Heilongjiang, Harbin Patentee before: HARBIN INSTITUTE OF TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230223 Address after: 150027 Room 412, Unit 1, No. 14955, Zhongyuan Avenue, Building 9, Innovation and Entrepreneurship Plaza, Science and Technology Innovation City, Harbin Hi tech Industrial Development Zone, Heilongjiang Province Patentee after: Heilongjiang Industrial Technology Research Institute Asset Management Co.,Ltd. Address before: Building 9, accelerator, 14955 Zhongyuan Avenue, Songbei District, Harbin City, Heilongjiang Province Patentee before: INDUSTRIAL TECHNOLOGY Research Institute OF HEILONGJIANG PROVINCE |