CN106478949A - Polyetherimide heat shrinkage film matrix material and preparation method thereof - Google Patents
Polyetherimide heat shrinkage film matrix material and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of Polyetherimide heat shrinkage film matrix material, including in protective gas atmosphere, in molar ratio 3:2～2:Bisphenol A Type Diether Dianhydride and double (4- amino-benzene oxygen) biphenyl of 4,4'- are dissolved in solvent and obtain mixed liquor by 1, and mixed liquor stirring reaction 20～22 hours at room temperature obtain the solution of the polyamic acid performed polymer containing acid anhydride end-blocking；In protective gas atmosphere, add three (4- aminophenyl) amine to the solution of the polyamic acid performed polymer blocking containing acid anhydride, stirring 6～7h obtains collosol and gel at room temperature；It is coated on after collosol and gel bubble removing on substrate, is cooled to room temperature from room temperature again to 290～300 DEG C, form Polyetherimide thin film in substrate surface, obtain sample；And the Polyetherimide thin film in sample is peeled off from substrate, the step obtaining Polyetherimide heat shrinkage film matrix material, the high temperature resistant and decay resistance obtaining Polyetherimide heat shrinkage film matrix material is preferable.
Description
Technical field
The present invention relates to a kind of Polyetherimide heat shrinkage film matrix material and preparation method thereof.
Background technology
Cylindrical lithium ion battery has the advantages that energy density is big, good cycle, is widely used in each
The field such as mobile device and electric automobile of kind.The heat shrinkage film matrix material one of traditional cylindrical lithium ion battery
As be the thermoplastic polymer such as polrvinyl chloride (PVC), polyethylene (PE).Such matrix material has light weight, glass
Glass transition temperature (Tg) is low, low cost, easy processing the advantages of, but there is also the defect itself being difficult to overcome,
For example, poor, easily aging, corrosion-resistant of heat-resisting quantity etc..Therefore traditional cylindrical lithium ion battery
Heat shrinkage film in use, due to the change of environmental condition, As time goes on can occur in various degree
Aging, corrosion and degrade, particularly under hot environment and hot abuse state, heat shrinkage film can be in the short time
Interior soften, deform and even decompose, thus losing protection and insulating properties.Now, pyrocondensation membrane technology
Development has become the important bottleneck limiting safety performance of cylindrical lithium ion battery raising to a certain extent.
With the raising to lithium ion battery safety consciousness for the people, the pyrocondensation of traditional cylindrical lithium ion battery
Film matrix material has been difficult to meet the requirement of security performance under severe rugged environment, develops new high temperature resistant and corrosion resistant
Corrosion energy preferably heat shrinkage film matrix material is urgently to be resolved hurrily.
Content of the invention
Based on this it is necessary to provide a kind of preparation method of Polyetherimide heat shrinkage film matrix material, to prepare
High temperature resistant and decay resistance preferable Polyetherimide heat shrinkage film matrix material.
Further provide for a kind of high temperature resistant and decay resistance preferable Polyetherimide heat shrinkage film matrix material.
A kind of preparation method of Polyetherimide heat shrinkage film matrix material, comprises the steps：
In protective gas atmosphere, in molar ratio 3:2～2:1 by double to Bisphenol A Type Diether Dianhydride and 4,4'- (4- ammonia
Phenoxyl) biphenyl is dissolved in solvent and obtains mixed liquor, by described mixed liquor stirring reaction 20～22 at room temperature
Hour, obtain the solution of the polyamic acid performed polymer containing acid anhydride end-blocking；
In protective gas atmosphere, add three (4- to the solution of the described polyamic acid performed polymer containing acid anhydride end-blocking
Aminophenyl) amine, stirs 6～7h at room temperature and obtains collosol and gel；
It is coated on after described collosol and gel bubble removing on substrate, be cooled to 290～300 DEG C from room temperature again
Room temperature, thus forming Polyetherimide thin film in described substrate surface, obtains sample；And
Described Polyetherimide thin film in described sample is peeled off from described substrate, obtains described polyethers acyl
Imines heat shrinkage film matrix material.
Wherein in an embodiment, in the described atmosphere in protective gas, in molar ratio 3:2～2:1 by bisphenol-A
Double (4- amino-benzene oxygen) biphenyl of type two ether dianhydride and 4,4'- is dissolved in and obtains the step of mixed liquor in solvent and be specially：
In protective gas atmosphere, double for 4,4'- (4- amino-benzene oxygen) biphenyl are added in solvent, stirs at room temperature
Mix 30～40 minutes and obtain solution；
In protective gas atmosphere, Bisphenol A Type Diether Dianhydride is added in described solution, is uniformly mixing to obtain
Described mixed liquor.
Wherein in an embodiment, described Bisphenol A Type Diether Dianhydride is added the step in described solution be
Bisphenol A Type Diether Dianhydride is added in described solution by point n times, and in first N-1 time, each addition is remaining
/ 2nd of amount, stir 10～20min after adding every time, described N is 5～6.
Wherein in an embodiment, double (4- amino-benzene oxygen) biphenyl of described 4,4'- and described three (4- aminobenzenes
Base) amine the anhydride group functional group of the integral molar quantity of amido functional group and described Bisphenol A Type Diether Dianhydride mole
Amount is equal.
Wherein in an embodiment, the method by described collosol and gel bubble removing is：By described collosol and gel
It is placed in application of vacuum 2～3h in 50～60 DEG C of vacuum drying oven.
Wherein in an embodiment, described from room temperature to 290～300 DEG C of steps being cooled to room temperature again
In, the method being heated up using the stage from room temperature to 290～300 DEG C, method that described stage heats up be with
50 DEG C is gradient, is incubated 30 minutes in each gradient.
Wherein in an embodiment, described by the described Polyetherimide thin film in described sample from described base
The method peeled off on plate is to put into described sample to be dipped to described Polyetherimide thin film in distilled water from described
Come off on substrate.
Wherein in an embodiment, by the described Polyetherimide thin film in described sample from described substrate
After stripping, the step that also includes drying, the step of described drying is that to fix described Polyetherimide with fixture thin
Film is placed in drying baker and is dried.
Wherein in an embodiment, described solvent is N,N-dimethylacetamide or phenol.
A kind of Polyetherimide heat shrinkage film of the preparation method preparation of above-mentioned Polyetherimide heat shrinkage film matrix material
Matrix material.
The preparation method of above-mentioned Polyetherimide heat shrinkage film matrix material adopts double (4- amino-benzene oxygen) biphenyl of 4,4'-
As monomer and three (4- aminophenyl) amine as cross-linking agent so that the film property of synthesized Polyetherimide
Good, advantageously form Polyetherimide thin film, finally give Polyetherimide heat shrinkage film matrix material.Polyethers
Imido heat decomposition temperature is typically larger than 500 DEG C so that the resistance to height of this Polyetherimide heat shrinkage film matrix material
Warm better performances.And, due to containing highly polar group in Polyetherimide, solvent resistance is good, substantially
Upper do not dissolve in any solvent, only in minority intensive polar solvent, there is dissolving so that preparation-obtained polyethers
The decay resistance of acid imide heat shrinkage film matrix material is preferable.
Brief description
Fig. 1 is the flow chart of the preparation method of Polyetherimide heat shrinkage film matrix material of an embodiment；
Fig. 2 is the infrared spectrum curve of the preparation-obtained Polyetherimide heat shrinkage film matrix material of embodiment 1；
Fig. 3 is the XRD curve of the preparation-obtained Polyetherimide heat shrinkage film matrix material of embodiment 1；
Fig. 4 is the DSC curve of the preparation-obtained Polyetherimide heat shrinkage film matrix material of embodiment 1；
Fig. 5 is the thermogravimetric curve of the preparation-obtained Polyetherimide heat shrinkage film matrix material of embodiment 1；
Fig. 6 is that the shape memory of the preparation-obtained Polyetherimide heat shrinkage film matrix material of embodiment 1 is replied
Procedure chart.
Specific embodiment
Understandable for enabling the above objects, features and advantages of the present invention to become apparent from, right below in conjunction with the accompanying drawings
The specific embodiment of the present invention is described in detail.Elaborate in the following description a lot of details with
It is easy to fully understand the present invention.But the present invention can be come in fact with being much different from alternate manner described here
Apply, those skilled in the art can doing similar improvement without prejudice in the case of intension of the present invention, therefore this
Bright it is not embodied as being limited by following public.
Refer to Fig. 1, the preparation method of the Polyetherimide heat shrinkage film matrix material of an embodiment, including such as
Lower step：
Step S110：In protective gas atmosphere, in molar ratio 3:2～2:1 by Bisphenol A Type Diether Dianhydride and
4,4'- double (4- amino-benzene oxygen) biphenyl are dissolved in solvent and obtain mixed liquor, by mixed liquor stirring reaction at room temperature
20～22 hours, obtain the solution of the polyamic acid performed polymer containing acid anhydride end-blocking.
Protective gas can be noble gases or nitrogen.Solvent is preferably DMAC N,N' dimethyl acetamide or phenol.
The mol ratio of Bisphenol A Type Diether Dianhydride and double (4- amino-benzene oxygen) biphenyl of 4,4'- is preferably 10:7.
Bisphenol A Type Diether Dianhydride and double (4- amino-benzene oxygen) biphenyl of 4,4'- are dissolved in solvent and obtain mixed liquor
Step is specially：
In protective gas atmosphere, double for 4,4'- (4- amino-benzene oxygen) biphenyl are added in solvent, stirs at room temperature
Mix 30～40 minutes and obtain solution；
In protective gas atmosphere, Bisphenol A Type Diether Dianhydride is added in solution, is uniformly mixing to obtain mixing
Liquid.
Preferably, in solution, the concentration of 4,4'- double (4- amino-benzene oxygen) biphenyl is 0.4～0.7mol/L.
Bisphenol A Type Diether Dianhydride is added the step in solution to add Bisphenol A Type Diether Dianhydride for point n times
In solution, in first N-1 time, each addition is 1/2nd of surpluses, stirs after adding every time
10～20min, to react fully, N is 5～6.
Above-mentioned surpluses refer to the residual mass of Bisphenol A Type Diether Dianhydride.Using above-mentioned charging process, energy
Enough react fully, improve yield.
Step S120：In protective gas atmosphere, the solution to the polyamic acid performed polymer blocking containing acid anhydride adds
Enter three (4- aminophenyl) amine, stirring 6～7h obtains collosol and gel at room temperature.
Protective gas can be noble gases or nitrogen.Three (4- aminophenyl) amine is flexible cross-linking agent.From
Double (4- amino-benzene oxygen) biphenyl monomer of above-mentioned 4, the 4'- containing ehter bond and this flexible cross-linking agent are so that polyetherimide
Amine has large deformation and good film property, thus having good shape-memory properties, meets heat shrinkage film
Performance requirement.
Preferably, the amido functional group of double (4- amino-benzene oxygen) biphenyl of 4,4'- and three (4- aminophenyl) amine
Integral molar quantity is equal with the mole of the anhydride group functional group of Bisphenol A Type Diether Dianhydride.
Step S130：It is coated on after collosol and gel bubble removing on substrate, from room temperature to 290～300 DEG C
Being cooled to room temperature again, thus forming Polyetherimide thin film in described substrate surface, obtaining sample.
Method by collosol and gel bubble removing is：Collosol and gel is placed at vacuum in 50～60 DEG C of vacuum drying oven
Reason 2～3h.
Collosol and gel after bubble removing is poured on the substrate of surfacing, then with film-laying machine by collosol and gel
It is laid into certain thickness, be then cooled to room temperature from room temperature again to 290～300 DEG C, so that polyamic acid
Performed polymer dehydration forms Polyetherimide.
Preferably, using the interim method heating up from room temperature to 290～300 DEG C, the method that the stage heats up
It is with 50 DEG C as gradient, be incubated 30 minutes in each gradient.
The thickness of Polyetherimide thin film is 30～100 μm.
Step S140：Polyetherimide thin film in sample is peeled off from substrate, obtains Polyetherimide heat
Contracting film matrix material.
The method that Polyetherimide thin film is peeled off from substrate is to put into sample to be dipped to polyethers in distilled water
Imide membrane comes off from substrate.The method of this stripping will not cause to Polyetherimide thin film to damage,
Be conducive to subsequently preparing high-quality Polyetherimide heat shrinkage film matrix material.
Preferably, after the Polyetherimide thin film in sample being peeled off from described substrate, also include drying
Step, the step of drying is to fix Polyetherimide thin film with fixture to be placed in drying in drying baker.The temperature being dried
Spend for 150～200 DEG C.
Preferably, Polyetherimide thin film is fixed between two pieces of glass plates, is conducive to avoiding to polyethers acyl
Imines thin film causes to damage.
The thickness of preparation-obtained Polyetherimide heat shrinkage film matrix material is 30～100 μm.
The preparation method of above-mentioned Polyetherimide heat shrinkage film matrix material adopts double (4- amino-benzene oxygen) biphenyl of 4,4'-
As monomer and three (4- aminophenyl) amine as cross-linking agent so that the film property of synthesized Polyetherimide
Good, advantageously form Polyetherimide thin film, finally give Polyetherimide heat shrinkage film matrix material.
Polyetherimide is a subclass of polyimides, has half forge piece of step type structure, with traditional polymer
Compare and there is higher resistance to elevated temperatures, be the temperature classification highest polymer being currently known, thermal decomposition temperature
Degree is typically larger than 500 DEG C so that the resistance to elevated temperatures of preparation-obtained Polyetherimide heat shrinkage film matrix material
Preferably.Highly polar group is contained, solvent resistance is good, is substantially insoluble in any solvent in Polyetherimide,
Only dissolve in minority intensive polar solvent, therefore, preparation-obtained Polyetherimide heat shrinkage film matrix
The decay resistance of material is preferable.
The Polyetherimide of said method synthesis has flexibility, and filming performance is preferable, to a certain extent simultaneously
Reduce glass transition temperature (Tg), be conducive to improving processing and serviceability.Additionally, Polyetherimide pyrocondensation
Film matrix material also have good creep resistance, good mechanical property, insulating properties, radiation-resistant property and
Anti-flammability etc..Therefore, said method preparation Polyetherimide heat shrinkage film matrix material can be as battery outside
Casing tube film is applied in column lithium ion battery, is conducive to improving the security performance of column lithium ion battery.
It is expanded on further below by way of specific embodiment.
Embodiment 1
1st, 15mL DMAC N,N' dimethyl acetamide is added to the three-necked bottle with agitating device and nitrogen protection
In, weigh double (4- amino-benzene oxygen) biphenyl monomer of 2.576g (0.007mol) 4,4'- and add in this three-necked bottle, dry
Stir 30 minutes under dry nitrogen protection and room temperature condition, to being completely dissolved, obtain solution；
2nd, weigh Bisphenol A Type Diether Dianhydride 5.2g (0.01mol), points 5 times (front 4 each additions are
/ 2nd of surpluses) it is added in above-mentioned solution and obtain mixed liquor, all stir after adding every time 10 minutes
It is made fully to react；By mixed liquor stirring reaction 20h at room temperature, obtain the polyamic acid containing acid anhydride end-blocking
The solution of performed polymer；
3rd, to solution disposable addition three (4- aminophenyl) amine of the polyamic acid performed polymer blocking containing acid anhydride
0.58g (0.002mol), makes amino official in three (4- aminophenyl) amine and double (4- amino-benzene oxygen) biphenyl of 4,4'-
Integral molar quantity can be rolled into a ball identical with the mole of anhydride group functional group in Bisphenol A Type Diether Dianhydride monomer, stir under room temperature
Mix 6h and obtain sticky collosol and gel；
4th, by sticky collosol and gel in 50 DEG C of vacuum drying oven application of vacuum 2h, make residual bubble removal
After clean, collosol and gel is poured on the steel plate of surfacing, then with film-laying machine, collosol and gel liquid is spread
Become the layer structure of 50 μ m-thick, take the method that the stage heats up, with 50 DEG C as gradient, protect in each gradient
Temperature 30 minutes, starts to warm up to 290 DEG C from room temperature, then naturally cools to room temperature, thus the table in steel plate
Form Polyetherimide thin film on face, obtain sample；
5th, sample is put into and be dipped to Polyetherimide thin film in distilled water and come off from substrate, then use distilled water
The Polyetherimide obtaining thin film is rinsed well, then Polyetherimide thin film is placed between two pieces of glass plates
Fixing, it is dried to remove moisture in 150 DEG C of baking oven, obtain final product the Polyetherimide heat that thickness is about 50 μm
Contracting film matrix material.
The infrared spectrum curve of the preparation-obtained Polyetherimide heat shrinkage film matrix material of embodiment 1 is shown in Fig. 2,
As seen from Figure 2, in 1375cm-1The absworption peak at place is the stretching vibration peak of C-N key, 1150-1350cm-1
Locate the stretching vibration peak for C-O key, and in 3200-3400cm-1And 1600-1700cm-1Place no amide and carbonyl
The stretching vibration peak of base, illustrates the sample for complete imidizate.1770cm-1The absworption peak at place is polyethers acyl
The asymmetric stretch absworption peak of carbonimidoyl, 1720cm-1The absworption peak at place is the feature of Polyetherimide carbonyl
Stretching vibration peak, 1300-1100cm-1It is the bending vibration absworption peak of imide ring.Infrared spectrum from Fig. 2
In curve it can be seen that typical absorption peak, illustrates the Polyetherimide that gained is complete imidizate.
The XRD curve of the preparation-obtained Polyetherimide heat shrinkage film matrix material of embodiment 1 is shown in Fig. 3, by
Fig. 3 understands, has a short and gentle diffraction maximum in a very wide angular range, and the polyethers synthesizing is described
Acid imide is a kind of amorphous structure.Amorphous structure polymer is loose irregular due to molecular structure, molecule
Intermolecular forces are weak, and molecule segment and whole strand have bigger motor capacity and less frictional force, more
Easily in the presence of external force, produce bigger deformation, thus having more preferable shape-memory properties.This
Outward, molecular structure is irregular and loose, and material also can be caused to have higher mobility under liquid condition,
Polyetherimide is made to have good filming performance, experiment proves that Polyetherimide has good film property.
The DSC curve of the preparation-obtained Polyetherimide heat shrinkage film matrix material of embodiment 1 is shown in Fig. 4, by
Fig. 4 understands, the glass transition temperature (Tg) of Polyetherimide heat shrinkage film matrix material is 220 DEG C.
The thermogravimetric curve of the preparation-obtained Polyetherimide heat shrinkage film matrix material of embodiment 1 is shown in Fig. 5, by scheming
5 understand, the heat decomposition temperature of this material is 552.5 DEG C, and at 800 DEG C, its residual quantity is 53.8%, high temperature resistant
Better performances.
The preparation-obtained Polyetherimide heat shrinkage film matrix material of embodiment 1 shape memory Recovery Process
See Fig. 6, it will be appreciated from fig. 6 that the shape memory regeneration rate of this Polyetherimide heat shrinkage film matrix material is very fast,
Can quickly recover in 26s, its shape fixed rate is 98%, shape recovery ratio is 97%.Repeat 20
After secondary, its shape-memory properties does not substantially change.
Embodiment 2
1st, 15mL DMAC N,N' dimethyl acetamide is added to the three-necked bottle with agitating device and nitrogen protection
In, weigh double (4- amino-benzene oxygen) biphenyl monomer of 2.944g (0.008mol) 4,4'- and add in this three-necked bottle, dry
Stir 40 minutes under dry nitrogen protection and room temperature condition, to being completely dissolved, obtain solution；
2nd, weigh Bisphenol A Type Diether Dianhydride 5.2g (0.01mol), point 6 times (front 5 each additions are surplus
/ 2nd of surplus) it is added in above-mentioned first solution and obtain mixed liquor, all stir 20 points after adding every time
Clock makes it fully react；By mixed liquor stirring reaction 22h at room temperature, obtain the polyamide containing acid anhydride end-blocking
The solution of sour performed polymer；
3rd, to solution disposable addition three (4- aminophenyl) amine of the polyamic acid performed polymer blocking containing acid anhydride
0.387g (0.00133mol), makes amino in three (4- aminophenyl) amine and double (4- amino-benzene oxygen) biphenyl of 4,4'-
Functional group's integral molar quantity is identical with the mole of anhydride group functional group in Bisphenol A Type Diether Dianhydride monomer, under room temperature
Stirring 7h obtains sticky collosol and gel；
4th, by sticky collosol and gel in 60 DEG C of vacuum drying oven application of vacuum 3h, make residual bubble removal
After clean, collosol and gel is poured on the steel plate of surfacing, then with film-laying machine, collosol and gel liquid is spread
Become the layer structure of 30 μ m-thick, take the method that the stage heats up, with 50 DEG C as gradient, protect in each gradient
Temperature 30 minutes, starts to warm up to 300 DEG C from room temperature, then naturally cools to room temperature, thus the table in steel plate
Form Polyetherimide thin film on face, obtain sample；
5th, sample is put into and be dipped to Polyetherimide thin film in distilled water and come off from substrate, then use distilled water
The Polyetherimide obtaining thin film is rinsed well, then Polyetherimide thin film is placed between two pieces of glass plates
Fixing, it is dried to remove moisture in 200 DEG C of baking oven, obtain final product thickness and be about 30 μm of Polyetherimide pyrocondensations
Film matrix material.
Embodiment 3
1st, 18mL DMAC N,N' dimethyl acetamide is added to the three-necked bottle with agitating device and nitrogen protection
In, weigh double (4- amino-benzene oxygen) biphenyl monomer of 3.312g (0.009mol) 4,4'- and add in this three-necked bottle, dry
Stir 35 minutes under dry nitrogen protection and room temperature condition, to being completely dissolved, obtain solution；
2nd, weigh Bisphenol A Type Diether Dianhydride 5.2g (0.01mol), points 5 times (front 4 each additions are
/ 2nd of surpluses) it is added in above-mentioned solution and obtain mixed liquor, all stir after adding every time 15 minutes
It is made fully to react；By mixed liquor stirring reaction 21h at room temperature, obtain the polyamic acid containing acid anhydride end-blocking
The solution of performed polymer；
3rd, to solution disposable addition three (4- aminophenyl) amine of the polyamic acid performed polymer blocking containing acid anhydride
0.193g (0.000667mol), makes ammonia in three (4- aminophenyl) amine and double (4- amino-benzene oxygen) biphenyl of 4,4'-
Base functional group integral molar quantity is identical with the mole of anhydride group functional group in Bisphenol A Type Diether Dianhydride monomer, room temperature
Lower stirring 7h obtains sticky collosol and gel；
4th, by sticky collosol and gel in 50 DEG C of vacuum drying oven application of vacuum 2h, make residual bubble removal
After clean, collosol and gel poured on smooth steel plate, then with film-laying machine, collosol and gel liquid is paved into
The layer structure of 30 μ m-thick, takes the method that the stage heats up, with 50 DEG C as gradient, in the insulation of each gradient
30 minutes, start to warm up to 300 DEG C from room temperature, then naturally cool to room temperature, thus the surface in steel plate
Upper formation Polyetherimide thin film, obtains sample；
5th, sample is put into and be dipped to Polyetherimide thin film in distilled water and come off from substrate, then use distilled water
The Polyetherimide obtaining thin film is rinsed well, then Polyetherimide thin film is placed between two pieces of glass plates
Fixing, it is dried to remove moisture in 180 DEG C of baking ovens, obtain final product the Polyetherimide pyrocondensation that thickness is about 30 μm
Film matrix material.
Embodiment described above only have expressed the several embodiments of the present invention, and its description is more concrete and detailed,
But therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for this area
Those of ordinary skill for, without departing from the inventive concept of the premise, can also make some deformation and
Improve, these broadly fall into protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be with appended
Claim is defined.
Claims (10)
1. a kind of preparation method of Polyetherimide heat shrinkage film matrix material is it is characterised in that include following walking
Suddenly：
In protective gas atmosphere, in molar ratio 3:2～2:1 by double to Bisphenol A Type Diether Dianhydride and 4,4'- (4- ammonia
Phenoxyl) biphenyl is dissolved in solvent and obtains mixed liquor, by described mixed liquor stirring reaction 20～22 at room temperature
Hour, obtain the solution of the polyamic acid performed polymer containing acid anhydride end-blocking；
In protective gas atmosphere, add three (4- to the solution of the described polyamic acid performed polymer containing acid anhydride end-blocking
Aminophenyl) amine, stirs 6～7h at room temperature and obtains collosol and gel；
It is coated on after described collosol and gel bubble removing on substrate, be cooled to 290～300 DEG C from room temperature again
Room temperature, thus forming Polyetherimide thin film in described substrate surface, obtains sample；
Described Polyetherimide thin film in described sample is peeled off from described substrate, obtains described polyethers acyl
Imines heat shrinkage film matrix material.
2. the preparation method of Polyetherimide heat shrinkage film matrix material according to claim 1, its feature
It is, in the described atmosphere in protective gas, in molar ratio 3:2～2:1 by Bisphenol A Type Diether Dianhydride and 4,4'-
Double (4- amino-benzene oxygen) biphenyl is dissolved in and obtains the step of mixed liquor in solvent and be specially：
In protective gas atmosphere, double for 4,4'- (4- amino-benzene oxygen) biphenyl are added in solvent, stirs at room temperature
Mix 30～40 minutes and obtain solution；
In protective gas atmosphere, Bisphenol A Type Diether Dianhydride is added in described solution, is uniformly mixing to obtain
Described mixed liquor.
3. the preparation method of Polyetherimide heat shrinkage film matrix material according to claim 2, its feature
It is, described Bisphenol A Type Diether Dianhydride is added step in described solution is point n times by bisphenol A-type two
Ether dianhydride adds in described solution, and in first N-1 time, each addition is 1/2nd of surpluses, adds every time
Stirring 10～20min after complete, described N are 5～6.
4. the preparation method of Polyetherimide heat shrinkage film matrix material according to claim 1, its feature
It is, the amido functional group of double (4- amino-benzene oxygen) biphenyl of described 4,4'- and described three (4- aminophenyl) amine
Integral molar quantity equal with the mole of the anhydride group functional group of described Bisphenol A Type Diether Dianhydride.
5. the preparation method of Polyetherimide heat shrinkage film matrix material according to claim 1, its feature
It is, the method by described collosol and gel bubble removing is：The vacuum that described collosol and gel is placed in 50～60 DEG C is dried
Application of vacuum 2～3h in case.
6. the preparation method of Polyetherimide heat shrinkage film matrix material according to claim 1, its feature
It is, the described side from room temperature to 290～300 DEG C of steps being cooled to room temperature again, heated up using the stage
From room temperature to 290～300 DEG C, the method that the described stage heats up is with 50 DEG C as gradient to method, in each ladder
Degree insulation 30 minutes.
7. the preparation method of Polyetherimide heat shrinkage film matrix material according to claim 1, its feature
Be, described method that described Polyetherimide thin film in described sample is peeled off from described substrate be by
Described sample is put into and is dipped to described Polyetherimide thin film in distilled water and comes off from described substrate.
8. the preparation method of Polyetherimide heat shrinkage film matrix material according to claim 1, its feature
It is, after the described Polyetherimide thin film in described sample is peeled off from described substrate, also include drying
Step, the step of described drying is to fix described Polyetherimide thin film with fixture and be placed in drying baker to be dried.
9. the preparation method of Polyetherimide heat shrinkage film matrix material according to claim 1, its feature
It is, described solvent is N,N-dimethylacetamide or phenol.
10. the preparation of the Polyetherimide heat shrinkage film matrix material described in a kind of any one by claim 1～9
The Polyetherimide heat shrinkage film matrix material of method preparation.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980491A (en) * | 2014-05-23 | 2014-08-13 | 哈尔滨工业大学 | Quick-response thermoset shape memory polyimide and preparation method thereof |
| CN104004188A (en) * | 2014-06-19 | 2014-08-27 | 冷劲松 | High-temperature-resistant thermoset shape memory polyimide and preparing method thereof |
| CN104017213A (en) * | 2014-06-19 | 2014-09-03 | 冷劲松 | Shape memory polyether imide with high glass-transition temperature and preparation method thereof |
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