CN104804188B - A kind of preparation method of Kapton - Google Patents

A kind of preparation method of Kapton Download PDF

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CN104804188B
CN104804188B CN201510200891.XA CN201510200891A CN104804188B CN 104804188 B CN104804188 B CN 104804188B CN 201510200891 A CN201510200891 A CN 201510200891A CN 104804188 B CN104804188 B CN 104804188B
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compound
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dianhydride
polyimide resin
kapton
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CN104804188A (en
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李璐
王超
王金青
解乐福
杜辉
邵军强
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Weihai Xinyuan Keshengxin Material Co. Ltd.
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Weihai Xinyuan Keshengxin Material Co Ltd
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Abstract

The invention discloses a kind of preparation method of Kapton, diamine compound is dissolved in by its elder generation in autoclaveN,NDimethylformamide orN,NIn dimethylacetamide solvent；Inert gas is then passed through, adds dianhydride compound；Question response thing all after dissolving, adds organic alkali catalyst, dehydrating agent, and reactor is closed；Heating 120~150 DEG C of temperature of rise, carries out reflux dewatering, removes toluene after terminating, continue to heat up, and carries out imidization 1~10 hour under the conditions of being 0.1~1 MPa in 160~190 DEG C of reaction temperature, pressure, obtains polyimide resin；Obtained polyimide resin is dissolved in organic solvent, transparent polyimide film is further prepared.Processing and fabricating of the present invention is easy, and technological process is simple, and strong operability, process conditions are gentleer, and reaction temperature is relatively low, and production security is high, has environment friendly and practicality.

Description

A kind of preparation method of Kapton
Technical field
The present invention relates to a kind of preparation method of high-molecular organic material, specifically a kind of system of polyimide resin Preparation Method.
Background technology
Polyimides is the high-molecular organic material containing imide ring in molecule structure.Polyimides is generally by virtue Fragrant race's dianhydride compound is made with diamine compound by polycondensation method.Rigid imidizate and polar molecular structure assign The excellent heat-resistant stability of polyimide material, insulation characterisitic, mechanical characteristic and resistance to environmental stability.But meanwhile polyamides Dianhydride primitive easily forms therebetween electric charge as electron donor, diamines primitive as electron acceptor in imines molecular structure Transfer Complexes（CTC）.CTC formation causes Kapton to produce significant absorb to visible ray so that traditional is complete Aromatic polyimide film shows the outward appearance of dark-brown or buff.Which greatly limits Kapton Application in optoelectronic areas.
In recent years, as photoelectron is assembled towards densification, highly integrated, multiple stratification, the continuous hair for being thinned direction Exhibition, require to improve constantly for the temperature resistant grade of optical thin film used.For example, in flexible active matrix Organic Light Emitting Diode （AMOLED）In assembling, low temperature polycrystalline silicon is prepared on flexible substrates（LTPS）Temperature exceeded 350 oC, this requires to be made Flexible plastic substrates will also have excellent heat-resistant stability while with the better optical transparency.Traditional is poly- Compound optical thin film, such as polyethylene terephthalate（PET）（Glass transition temperatureT g：~78oC）, poly- naphthalenedicarboxylic acid second Diol ester（PEN）（T g：~122oC）Deng can not meet above-mentioned application demand.Therefore, in recent years for water white transparency high temperature resistant The demand of polymeric optical film is increasingly urgent.Kapton has excellent heat-resistant stability, how to be set by structure Meter has obtained extensive research in recent years to improve its optical transparence.For example, patent CN101195682（Patentee：China Changchun applied chemistry study institute of the academy of sciences）Disclose a kind of preparation method of Flexible transparent polyimide thin film.This method uses Aromatic dianhydride compound is made with fluorinated diamine compound by " two-step method " polymerization technique, i.e., is made poly- at ambient pressure first Acid imide presoma-polyamic acid（PAA）Solution, then 80 ~ 350oKapton is made in imidization under C high temperature. Patent CN101674923（Patentee：Mitsubishi Gas Chemical Co., Ltd）Disclose a kind of transparent polyimide film Preparation method and preparation facilities.This method uses alicyclic dianhydride compound 1,2,4,5- hexamethylenes tetracarboxylic dianhydride and two amine compounds Thing is made by " one-step method " polymerization technique, i.e., using 1,2,4,5- hexamethylene tetracarboxylic dianhydride and diamine compound in the non-matter of polarity Sub- property mixed solvent（Such asN,N- dimethyl acetamide and gamma-butyrolacton, weight ratio：1:4）In in 180oThe step system of C high temperature polymerizations one Soluble polyimide solution is obtained, transparent polyimide film is directly finally prepared using the solution.Obtained thickness is The light transmittance of 200 μm of films is 89.8%, yellowness index 1.74, mist degree 1.10%.The technique usesN,N- dimethylacetamide Amine（Boiling point：166oC, normal pressure 0.1MPa）And gamma-butyrolacton（Boiling point：204oC, normal pressure 0.1MPa）Primarily to make reaction temperature Degree reaches 180oC polymerization temperature, so as to promote the imidization degree of polyimide resin to tend to be complete.The said firm is other one In piece patent（CN101160202）In report using 1,2,4,5- hexamethylenes tetracarboxylic dianhydride and diamine compound at another Polar aprotic solventN- methyl pyrrolidone（NMP）（Boiling point：202oC, normal pressure 0.1MPa）In in 180oC high temperature one-step method Polyimide resin solution is made, the thickness for using the solution to prepare for the light transmittance of 100 μm of films is 90%.
Tradition can be significantly reduced it can be seen from above-mentioned document using high electronegativity fluoro-containing group or alicyclic structure to gather The color of imide membrane.In addition, the selection of thin film preparation process and dicyandiamide solution is often to final Kapton Color produces certain influence.Two step high temperature imidization methods are due to that will use up to 300oMore than C hot imidization technique, because The Kapton color that this is often prepared is relatively deep.And prepare water white transparency polyamides using a step pyrosol condensation methods During imide resin, in order that polyimide resin imidization is close to completely（Reaction temperature >=180oC, normal pressure）Then often Need to select high boiling solvent, such asN- methyl pyrrolidone（Boiling point：202oC）, gamma-butyrolacton（Boiling point：204oC）Deng.These are molten Agent is prone to xanthochromia at high temperature, and then influences the ginseng such as light transmittance, yellowness index and mist degree of final Kapton Number.And the relatively low polar solvent of boiling point is used, such asN,N- dimethylformamide（DMF, boiling point：155 oC）、N,N- dimethyl Acetamide（DMAc, boiling point：166oC）Imidization can not often carried out complete.
The content of the invention
The technical problems to be solved by the invention are to overcome above-mentioned the deficiencies in the prior art, there is provided a kind of processing and fabricating holds Easily, technological process is simple, and strong operability, process conditions are gentleer, and reaction temperature is relatively low, and production security is high, has environment friend The preparation method of the Kapton of good property and practicality.
The present invention solves the technical scheme that above-mentioned technical problem uses：A kind of preparation method of Kapton, its It is characterised by：Comprise the following steps：
（1）In autoclave, diamine compound is dissolved inN,N- dimethylformamide（DMF）OrN,N- dimethyl Acetamide（DMAc）In solvent；
（2）Inert gas is passed through into autoclave, adds dianhydride compound；
（3）Question response thing all after dissolving, adds organic alkali catalyst, dehydrating agent, and reactor is closed；
（4）Heating 120 ~ 150 DEG C of temperature of rise, reflux dewatering is carried out, the time is 3 ~ 10 hours, after dehydration terminates, is removed Toluene, continue to heat up, in 160 ~ 190 DEG C of reaction temperature, reaction pressure carries out imidization under the conditions of being 0.1 ~ 1 MPa, when Between be 1 ~ 10 hour, obtain polyimide resin；
（5）By step（4）The polyimide resin of preparation, which is dissolved in organic solvent, is configured to solution, in nitrogen ceiling Under part, transparent polyimide film is prepared in heating.
Further, the dianhydride compound is 1,2,4,5- hexamethylene tetracarboxylic dianhydrides or 3,3 ', 4,4 '-dicyclohexyl tetracid Dianhydride.
Further, the mol ratio of the diamine compound and dianhydride compound is（0.95~1.05）：1, preferably（0.98~ 1.02）：1.The gross mass percent concentration of the dianhydride compound and dianhydride compound in reaction system is 5-40%.
Further, the solvent boiling point is less than 170oC, the preferred DMAc of solvent.
Further, the organic alkali catalyst is selected from least one of isoquinolin, triethylamine, pyridine, piperidines, preferably different Quinoline.
Further, the water-break agent is selected from least one of toluene, dimethylbenzene, chlorobenzene, preferably dimethylbenzene.
Further, dehydration temperaturre is 130 ~ 140 DEG C in the reflux dewatering reaction；Time is 5 ~ 8 hours.
Further, reaction temperature is 175 ~ 185 DEG C in the imidization, and reaction pressure is 0.2 ~ 0.5 MPa, the time For 3 ~ 8 hours.
The present invention uses alicyclic dianhydride compound, including 1,2,4,5- hexamethylene tetracarboxylic dianhydrides or 3,3 ', 4,4 '-it is bicyclic oneself Base tetracarboxylic dianhydride is with diamine compound in low boiling-point and polarity solvent（Boiling point≤170oC）, relatively low under appropriate pressure At a temperature of carry out polymerisation, imidization complete polyimide resin is made, and then transparent polyimide is prepared Film.Against existing technologies, processing and fabricating of the present invention is easy, and technological process is simple, and strong operability, process conditions are gentleer, instead Answer temperature relatively low, production security is high, has environment friendly and practicality.Polyimide resin prepared by the present invention can be by It is relatively low in the temperature for preparing polyimide resin, therefore avoid the deterioration of Kapton color under high temperature.It is colourless Transparent polyimide film has the characteristics such as optical transparence is good, yellowness index and mist degree are low.Transparent polyimide film High temperature resistant substrate can be applied to the assembling of flexible AMOLED, TFT-LCD display device, can also be applied to the base of flexible solar cell Plate, it can also be applied in the fields such as the making of flexible and transparent printed wiring board.
Brief description of the drawings
The present invention will be further described with reference to the accompanying drawings and examples.
Fig. 1 is the general structure figure of the polyimide resin of the present invention；
Fig. 2 is the structural formula figure of the dianhydride compound 1,2,4,5- cyclohexanetetracarboxylic acid dianhydrides of the present invention；
Fig. 3 is the structural formula figure of dianhydride compound 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride of the present invention；
Fig. 4 is the structural formula figure of the polyimide resin in 1-4 of the embodiment of the present invention；
Fig. 5 is the structural formula figure of the polyimide resin in the embodiment of the present invention 5.
Embodiment
With reference to specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.
A kind of preparation method of Kapton, it comprises the following steps：
（1）It is anti-in a high pressure equipped with mechanical agitation, thermometer, inert gas gateway, Dean-Stark water knockout drums Answer in kettle, diamine compound is dissolved inN,N- dimethylformamide（DMF）OrN,N- dimethyl acetamide（DMAc）In solvent；
（2）Inert gas is passed through into autoclave, adds dianhydride compound；
（3）Question response thing all after dissolving, adds organic alkali catalyst, dehydrating agent, and reactor is closed；
（4）Heating 120 ~ 150 DEG C of temperature of rise, reflux dewatering is carried out, the time is 3 ~ 10 hours, after dehydration terminates, is removed Toluene, continue to heat up, in 160 ~ 190 DEG C of reaction temperature, reaction pressure carries out imidization under the conditions of being 0.1 ~ 1 MPa, when Between be 1 ~ 10 hour, obtain polyimide resin；
（5）By step（4）The polyimide resin of preparation, which is dissolved in organic solvent, is configured to solution, in nitrogen ceiling Under part, transparent polyimide film is prepared in heating.
The general structure of the polyimide resin, as shown in Figure 1.
The diamine compound is 4,4'- diaminodiphenyl ethers（ODA）.The dianhydride compound is 1,2,4,5- hexamethylenes Tetracarboxylic dianhydride or 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride.
1,2,4,5- hexamethylene tetracarboxylic dianhydrides（HPMDA）Synthesis：The methyl esters of 1,2,4,5- cyclohexanetetracarboxylic acids four uses It is prepared by method disclosed in CN102381977.It is furnished with mechanical agitation, thermometer, 1000 mL there-necked flasks of reflux condensing tube at one 162 g of middle addition（0.513 mol）The methyl esters of 1,2,4,5- cyclohexanetetracarboxylic acid four, 333g（3.284 mol）36% concentrated hydrochloric acid, 470 ML deionized waters, 0.9g catalyst.Backflow is warming up under stirring.By-product methanol is steamed while backflow, maintains back flow reaction 6.0 H is slightly cold to be filtered to remove insoluble matter.Filtrate concentrates, and steams 500ml water, and cooling is filtrated to get white solid.80oC is dried in vacuo 24h, obtain the cyclohexanetetracarboxylic acid of 128.1 g white solids 1,2,4,5-, yield 96.1%.
One equipped with mechanical agitation, thermometer, reflux condensing tube 1000 mL there-necked flasks in add 234 g（0.9 mol）1,2,4,5- cyclohexanetetracarboxylic acid, add 320 mL acetic anhydrides, 300 mL glacial acetic acid.Backflow is warming up under stirring.Keep Flow back 3h.Room temperature is naturally cooling to, the white crystal of precipitation is collected by filtration, the white crystal of collection washs 3 repeatedly with toluene Secondary, petroleum ether washs 3 times repeatedly.80oC is dried in vacuo 24h, obtains the cyclohexanetetracarboxylic acid two of 191 g white crystals 1,2,4,5- Acid anhydride, yield 94.7%.
The structure of the cyclohexanetetracarboxylic acid dianhydride of compound 1,2,4,5-, as shown in Figure 2.
It is as follows that it detects data：
Fusing point：298.9 ℃（DSC peak temperatures）.
Nucleus magnetic hydrogen spectrum（400MHz, DMSO-d 6）：3.31~3.36 (m, 2H), 2.15-2.18 (m, 2H), 1.95- 1.98 (m, 4H)。
Mass spectrum：224 (M+, 100%)。
Elementary analysis（%）：C10H8O6（M w: 224.17）.Theoretical value：C, 53.58；H, 3.60；Measured value：C, 53.52；H, 3.63。
It is really target compound 1,2,4,5- hexamethylene tetracarboxylic dianhydrides through the compound synthesized by Structural Identification（HPMDA）.
3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride（HBPDA）Synthesis：3,3 ', 4,4 '-dicyclohexyl tetracarboxylic acid tetramethyl Ester uses method disclosed in CN102381977 to prepare.It is furnished with mechanical agitation, thermometer, 1000 mL of reflux condensing tube at one 100 g are added in there-necked flask（0.251 mol）3,3 ', 4, the methyl esters of 4 '-dicyclohexyl tetracarboxylic acid four, 208 g（2.05 mol）36% Concentrated hydrochloric acid, 304 mL deionized waters, 0.7g catalyst.Backflow is warming up under stirring.By-product methanol is steamed while backflow, is maintained The h of back flow reaction 6.0, cooling are filtrated to get white solid.It is filtrated to get white solid.80oC is dried in vacuo 24h, obtains 82.4 G white solids 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic acid, yield 95.9%.
One equipped with mechanical agitation, thermometer, reflux condensing tube 1000 mL there-necked flasks in add 100 g（0.292 mol）3,3 ', 4,4 '-dicyclohexyl tetracarboxylic acid, add 104 mL acetic anhydrides, 96 mL glacial acetic acid.Backflow is warming up under stirring.Protect Hold backflow 3h.Room temperature is naturally cooling to, the white crystal of precipitation is collected by filtration, the white crystal of collection is washed repeatedly with toluene 3 times, petroleum ether washs 3 times repeatedly.80oC is dried in vacuo 24h, obtains 82.67 g white crystals 3, and 3 ', 4,4 '-dicyclohexyl Tetracarboxylic dianhydride, yield 92.4%.
The compound 3,3 ', 4, the structure of 4 '-dicyclohexyl tetracarboxylic dianhydride, as shown in Figure 3.
It is as follows that it detects data：
Fusing point：226.9 ℃（DSC peak temperatures）.
Nucleus magnetic hydrogen spectrum（400MHz, CDCl3）：3.69 (m, 4H), 3.21 (m, 2H), 3.06-3.08 (m, 2H), 2.35-2.39 (m, 2H), 2.18-2.20 (m, 2H), 1.69-1.71 (m, 2H), 1.05-1.20 (m, 4H)。
Mass spectrum：306 (M+, 100%)。
Elementary analysis（%）：C16H18O6（M w: 306.31）.Theoretical value：C, 62.74；H, 5.92；Measured value：C, 62.68； H, 6.02.
It is really target compound 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride through the compound synthesized by Structural Identification （HBPDA）.
Further, the mol ratio of the diamine compound and dianhydride compound is（0.95~1.05）：1, preferably（0.98~ 1.02）：1.The gross mass percent concentration of the dianhydride compound and dianhydride compound in reaction system is 5-40%, preferably 25-35%。
Further, the solvent boiling point is less than 170oC, the preferred DMAc of solvent.
Further, the organic alkali catalyst is selected from least one of isoquinolin, triethylamine, pyridine, piperidines, preferably different Quinoline.
Further, the water-break agent is selected from least one of toluene, dimethylbenzene, chlorobenzene, preferably dimethylbenzene.
Further, dehydration temperaturre is 130 ~ 140 DEG C in the reflux dewatering reaction；Time is 5 ~ 8 hours.
Further, reaction temperature is 175 ~ 185 DEG C in the imidization, and reaction pressure is 0.2 ~ 0.5 MPa, the time For 3 ~ 8 hours.
In addition, the transparent polyimide film that as shown in Figure 1 prepared by polyimide resin can be used for photoelectric device Prepare.The photoelectric device includes flexible display device [including flexible active matrix Organic Light Emitting Diode（AMOLED）, it is flexible Thin film transistor (TFT) drives liquid crystal display（TFT-LCD）], flexible solar cell, flexible and transparent printed wiring board（FPCB）.
Method described in following embodiments is conventional method unless otherwise instructed.The material can unless otherwise instructed Obtained from open commercial sources.The method that following embodiments carry out structure and performance detection to products therefrom compound or polymer Unless otherwise instructed, it is common detection methods.
Embodiment 1：A kind of preparation method of Kapton, it comprises the following steps：
It is furnished with nitrogen inlet at one and thermometer, water knockout drum, condenser pipe and churned mechanically 1000 mL autoclaves is housed 20.024 g of middle addition（100 mmol）ODA and 60 g DMAc.It is stirred at room temperature after being completely dissolved it, under nitrogen protection, adds Enter 22.417 g（100 mmol）HPMDA and 18.8 g DMAc, 35% is adjusted to DMAc by solid content（Mass percent）, treat All after dissolving, 0.5 g isoquinolin and 250 g dimethylbenzene are added, backflow is heated to, divides water 4h.Then put by water knockout drum Go out dimethylbenzene.Reaction system is closed, it is continuously heating to 165oC, now system pressure is 0.12 MPa, continues to react 6 h, stops Only react, removal pressure, be cooled to room temperature, gained thick pale yellow solution is poured slowly into a large amount of ethanol, obtains white silk Shape resin, 100oC is dried under reduced pressure 24 h, obtains the g of white resin 37.3, yield 96%.
The structure of the compound polyimide resin, as shown in Figure 4.
From infrared spectrum testing result, the compound structure is correct, is polyimide resin shown in Fig. 4.
GPC measure is carried out to polyimides shown in gained Fig. 4 using gel permeation chromatography, NMP is solvent, and polystyrene is Standard, measureM n=24100 g/mol, n=62.
Dissolubility：At room temperature, polyimide resin as shown in Figure 4 can be dissolved in 15% weight percent solids contentN- Methyl pyrrolidone（NMP）、N,N- dimethyl acetamide（DMAc）, gamma-butyrolacton, in cyclopentanone.It is not dissolved in chloroform, tetrahydrochysene In furans.
Kapton is prepared using the polyimide resin as shown in Figure 4 of above-mentioned preparation：Weigh 30 g such as Fig. 4 institutes Show polyimide resin, add the g of DMAc solvents 70.After solid is completely dissolved, it is 30 % to obtain solid content（Mass percent） Polyimide solution.Measure viscosity is 60 Pas, and after the filter filtering that aperture is 0.5 μm, polymer solution is applied It is overlying on stainless steel plate, by 80 DEG C, 2h；150 DEG C, 1h；200 DEG C, 1h；230 DEG C, 1h program heating, nitrogen protection.Cooling To room temperature, it is 50 um to measure solidification film thickness.
Test result is as follows：
5% weightless temperature（DEG C, blanket of nitrogen）：501.
Glass transition temperature（℃）：346.
Optical transparence at 400 nm wavelength：95%.
Optical transparence at 350 nm wavelength：93%.
Yellowness index：1.21.
Mist degree：0.49%.
Embodiment 2：A kind of preparation method of Kapton, it comprises the following steps：
It is furnished with nitrogen inlet at one and thermometer, water knockout drum, condenser pipe and churned mechanically 1000 mL autoclaves is housed 20.024 g of middle addition（100 mmol）ODA and 68.8 g DMAc.It is stirred at room temperature after being completely dissolved it, under nitrogen protection, Add 22.417 g（100 mmol）HPMDA and 10 g DMAc, 35% is adjusted to DMAc by solid content（Mass percent）, treat All after dissolving, 0.5 g isoquinolin and 250 g dimethylbenzene are added, backflow is heated to, divides water 4h.Then put by water knockout drum Go out dimethylbenzene.Reaction system is closed, it is continuously heating to 180oC, now system pressure is 0.15 MPa, continues to react 6 h, stops Only react, removal pressure, be cooled to room temperature, gained thick pale yellow solution is poured slowly into a large amount of ethanol, obtains white silk Shape resin, 100oC is dried under reduced pressure 24 h, obtains the g of white resin 36.9, yield 95%.
The structure of the compound polyimide resin, as shown in Figure 4.
GPC measure is carried out to gained polyimide resin using gel permeation chromatography, NMP is solvent, and polystyrene is mark Standard, measureM n=26500 g/mol, n=68.
Dissolubility：Obtained polyimide resin can be dissolved in 15% percentage by weight at room temperatureN- methyl pyrrole Pyrrolidone（NMP）、N,N- dimethyl acetamide（DMAc）, gamma-butyrolacton, in cyclopentanone.It is not dissolved in chloroform, tetrahydrofuran In.
Kapton is prepared using prepared polyimides：
30 g polyimide resins are weighed, add the g of DMAc solvents 70.After solid is completely dissolved, solid content is obtained as 30 %（Mass percent）Polyimide solution.Measure viscosity is 75 Pas.Polyimide solution is coated on stainless steel plate On, by 80 DEG C, 2h；150 DEG C, 1h；200 DEG C, 1h；230 DEG C, 1h program heating, nitrogen protection.After being cooled to room temperature, measure Solidification film thickness is 50 um.
Test result is as follows：
5% weightless temperature（DEG C, blanket of nitrogen）：500.
Glass transition temperature（℃）：342.
Optical transparence at 400 nm wavelength：95%.
Optical transparence at 350 nm wavelength：92%.
Yellowness index：1.25.
Mist degree：0.68%.
Embodiment 3：A kind of preparation method of Kapton, it comprises the following steps：
It is furnished with nitrogen inlet at one and thermometer, water knockout drum, condenser pipe and churned mechanically 1000 mL autoclaves is housed 20.024 g of middle addition（100 mmol）ODA and 68.8 g DMAc.It is stirred at room temperature after being completely dissolved it, under nitrogen protection, Add 22.417 g（100 mmol）HPMDA and 10 g DMAc, 35% is adjusted to DMAc by solid content（Mass percent）, treat All after dissolving, 0.5 g isoquinolin and 250 g dimethylbenzene are added, backflow is heated to, divides water 4h.Then put by water knockout drum Go out dimethylbenzene.Reaction system is closed, it is continuously heating to 185oC, now system pressure is 0.25 MPa, continues to react 6 h, stops Only react, removal pressure, be cooled to room temperature, gained thick pale yellow solution is poured slowly into a large amount of ethanol, obtains white silk Shape resin, 100oC is dried under reduced pressure 24 h, obtains the g of white resin 36.5, yield 94%.
The structure of the compound polyimide resin, as shown in Figure 4.
GPC measure is carried out to gained polyimide resin using gel permeation chromatography, NMP is solvent, and polystyrene is mark Standard, measureM n=29600 g/mol, n=76.
Dissolubility：Obtained polyimide resin can be dissolved in 15% percentage by weight at room temperatureN- methyl pyrrole Pyrrolidone（NMP）、N,N- dimethyl acetamide（DMAc）, gamma-butyrolacton, in cyclopentanone.It is not dissolved in chloroform, tetrahydrofuran In.
Kapton is prepared using prepared polyimides：
30 g polyimide resins are weighed, add the g of DMAc solvents 70.After solid is completely dissolved, solid content is obtained as 30 %（Mass percent）Polyimide solution.Measure viscosity is 90 Pas.Polyimide solution is coated on stainless steel plate On, by 80 DEG C, 2h；150 DEG C, 1h；200 DEG C, 1h；230 DEG C, 1h program heating, nitrogen protection.After being cooled to room temperature, measure Solidification film thickness is 50 um.
Test result is as follows：
5% weightless temperature（DEG C, blanket of nitrogen）：500.
Glass transition temperature（℃）：343.
Optical transparence at 400 nm wavelength：92%.
Optical transparence at 350 nm wavelength：90%.
Yellowness index：1.43.
Mist degree：0.66%.
Embodiment 4：A kind of preparation method of Kapton, it comprises the following steps：
It is furnished with nitrogen inlet at one and thermometer, water knockout drum, condenser pipe and churned mechanically 1000 mL autoclaves is housed 20.024 g of middle addition（100 mmol）ODA and 68.8 g DMAc.It is stirred at room temperature after being completely dissolved it, under nitrogen protection, Add 22.417 g（100 mmol）HPMDA and 10 g DMAc, 35% is adjusted to DMAc by solid content（Mass percent）, treat All after dissolving, 0.5 g isoquinolin and 250 g dimethylbenzene are added, backflow is heated to, divides water 4h.Then put by water knockout drum Go out dimethylbenzene.Reaction system is closed, it is continuously heating to 190oC, now system pressure is 0.40 MPa, continues to react 6 h, stops Only react, removal pressure, be cooled to room temperature, gained thick pale yellow solution is poured slowly into a large amount of ethanol, obtains white silk Shape resin, 100oC is dried under reduced pressure 24 h, obtains the g of white resin 36.9, yield 95%.
The structure of the compound polyimide resin, as shown in Figure 4.
GPC measure is carried out to gained polyimide resin using gel permeation chromatography, NMP is solvent, and polystyrene is mark Standard, measureM n=30400 g/mol, n=78.
Dissolubility：Obtained polyimide resin can be dissolved in 15% percentage by weight at room temperatureN- methyl pyrrole Pyrrolidone（NMP）、N,N- dimethyl acetamide（DMAc）, gamma-butyrolacton, in cyclopentanone.It is not dissolved in chloroform, tetrahydrofuran In.
Kapton is prepared using prepared polyimides：
30 g polyimide resins are weighed, add the g of DMAc solvents 70.After solid is completely dissolved, solid content is obtained as 30 %（Mass percent）Polyimide solution.Measure viscosity is 90 Pas.Polyimide solution is coated on stainless steel plate On, by 80 DEG C, 2h；150 DEG C, 1h；200 DEG C, 1h；230 DEG C, 1h program heating, nitrogen protection.After being cooled to room temperature, measure Solidification film thickness is 50 um.
Test result is as follows：
5% weightless temperature（DEG C, blanket of nitrogen）：502.
Glass transition temperature（℃）：343.
Optical transparence at 400 nm wavelength：91%.
Optical transparence at 350 nm wavelength：90%.
Yellowness index：1.52.
Mist degree：0.59%.
Embodiment 5：A kind of preparation method of Kapton, it comprises the following steps：
It is furnished with nitrogen inlet at one and thermometer, water knockout drum, condenser pipe and churned mechanically 1000 mL autoclaves is housed 20.024 g of middle addition（100 mmol）ODA and 80 g DMAc.It is stirred at room temperature after being completely dissolved it, adds 30.631 g （100 mmol）HBPDA and 14 g DMAc, 35% is adjusted to DMAc by solid content（Mass percent）, after all dissolving, 0.5 g isoquinolin and 30 g toluene are added, is heated to backflow, divides water 4h, toluene is then released by water knockout drum and continues to heat up, Reaction system is closed, it is continuously heating to 185oC, now system pressure is 0.40 MPa, is warming up to 180oC continues to react 6 h, Stop reaction, cooling.Room temperature is down to, gained clear yellow viscous solution resin solution is poured into a large amount of ethanol, it is thread to obtain white PI resins, 100oC is dried under reduced pressure 24 h and obtains the g of white resin 44.7, yield 95%.
The structure of the compound polyimide resin, as shown in Figure 5.
From infrared spectrum testing result, the compound structure is correct, is polyimide resin as shown in Figure 5.
GPC measure is carried out to gained polyimide resin as shown in Figure 5 using gel permeation chromatography, NMP is solvent, polyphenyl Ethene is standard, is measuredM n=32500 g/mol, n=69.
Dissolubility：At room temperature, polyimide resin as shown in Figure 5 can be dissolved in 15% weight percent solids contentN- Methyl pyrrolidone（NMP）、N,N- dimethyl acetamide（DMAc）, gamma-butyrolacton, in cyclopentanone.It is not dissolved in chloroform, tetrahydrochysene In furans.
Kapton is prepared using the polyimide resin as shown in Figure 5 of above-mentioned preparation：
30 g polyimide resins as shown in Figure 5 are weighed, add the g of DMAc solvents 70.After solid is completely dissolved, obtain Solid content is 30%（Mass percent）Polyimide solution.Measure viscosity is 65 Pas, with the filtering that aperture is 0.5 μm After device filtering, by polymer solution coated on stainless steel plate, by 80 DEG C, 2h；150 DEG C, 1h；200 DEG C, 1h；230 DEG C, 1h's Program heats.After being cooled to room temperature, it is 50 um to measure solidification film thickness.
Test result is as follows：
5% weightless temperature（DEG C, blanket of nitrogen）：482.
Glass transition temperature（℃）：246.
Optical transparence at 400 nm wavelength：88%.
Optical transparence at 350 nm wavelength：85%.
Yellowness index：1.85.
Mist degree：0.78%.
Comparative example 1：By HPMDA and 4,4'- diaminodiphenyl ethers（ODA）Prepare polyimide resin（Normal pressure）.At one Equipped with nitrogen inlet and equipped with adding 20.024 g in thermometer, water knockout drum, condenser pipe and churned mechanically 1000 mL reaction bulbs （100 mmol）ODA and 68.8 gN- methyl pyrrolidone（NMP）.It is stirred at room temperature after being completely dissolved it, nitrogen protection Under, add 22.417 g（100 mmol）HPMDA and 10 g NMP, 35% is adjusted to NMP by solid content（Mass percent）, After all dissolving, 0.5 g isoquinolin and 250 g dimethylbenzene are added, backflow is heated to, divides water 4h.Then by water knockout drum Release dimethylbenzene.It is continuously heating to 180oC, 6 h are reacted, stop reaction, be cooled to room temperature, gained pale yellow solution is slowly fallen Enter in a large amount of ethanol, obtain white filament resin, 100oC is dried under reduced pressure 24 h, obtains the g of white resin 36.9, yield 95%.
The structure of the compound polyimide resin, as shown in Figure 4.
GPC measure is carried out to gained polyimide resin as shown in Figure 4 using gel permeation chromatography, NMP is solvent, polyphenyl Ethene is standard, is measuredM n=17900 g/mol, n=46.
Dissolubility：At room temperature, prepared polyimide resin can be dissolved in 15% weight percent solids contentN- methyl Pyrrolidones（NMP）、N,N- dimethyl acetamide（DMAc）, gamma-butyrolacton, in cyclopentanone.It is not dissolved in chloroform, tetrahydrofuran In.
Kapton is prepared using the polyimides of above-mentioned preparation：The polyimide resin prepared by 30g is weighed, Add DMAc solvents 70g.After solid is completely dissolved, it is 30 % to obtain solid content（Mass percent）Polyimide solution. Measure viscosity is 6 Pas, and after the sand core funnel filtering that aperture is 0.5 um, polymer solution is coated on into stainless steel plate On, by 80 DEG C, 2h；150 DEG C, 1h；200 DEG C, 1h；230 DEG C, 1h program heating.After being cooled to room temperature, film has chap, into Film segment thickness is 50 um.
Test result is as follows：
5% weightless temperature（DEG C, blanket of nitrogen）：496.
Glass transition temperature（℃）：338.
Optical transparence at 400 nm wavelength：88%.
Optical transparence at 350 nm wavelength：75%.
Yellowness index：3.71.
Mist degree：2.41%.
The present invention uses the relatively low solvent of boiling point it can be seen from the effect of embodiment 1-5 and comparative example 1, Transparent polyimide resin is prepared under high pressure, it is thin then to prepare transparent polyimide into solution using the resin formulations Film, the film have a higher molecular weight relative to the film prepared using atmospheric processes, more excellent mechanical strength and more excellent Optical characteristics.

Claims (7)

  1. A kind of 1. preparation method of Kapton, it is characterised in that：Comprise the following steps：
    （1）In autoclave, diamine compound is dissolved in DMA（DMAc）In solvent；
    （2）Inert gas is passed through into autoclave, adds dianhydride compound；
    （3）Question response thing all after dissolving, adds organic alkali catalyst, dehydrating agent, and reactor is closed；
    （4）Heating 120 ~ 150 DEG C of temperature of rise, reflux dewatering being carried out, the time is 4 hours, after dehydration terminates, removes dehydrating agent, Continue to heat up, in 165 ~ 180 DEG C of reaction temperature, reaction pressure carries out imidization, time under the conditions of being 0.12 ~ 0.15MPa For 6 hours, polyimide resin is obtained；
    （5）By step（4）The polyimide resin of preparation, which is dissolved in organic solvent, is configured to solution, in nitrogen protective condition Under, transparent polyimide film is prepared in heating.
  2. 2. the preparation method of polyimide resin according to claim 1, it is characterised in that：The dianhydride compound is 1,2, 4,5- hexamethylenes tetracarboxylic dianhydride or 3,3 ', 4,4 '-dicyclohexyl tetracarboxylic dianhydride.
  3. 3. the preparation method of Kapton according to claim 1, it is characterised in that：The diamine compound and dianhydride The mol ratio of compound is（0.95~1.05）：1, the gross mass of the dianhydride compound and dianhydride compound in reaction system Percent concentration is 5-40%.
  4. 4. the preparation method of Kapton according to claim 1, it is characterised in that：The diamine compound and dianhydride The mol ratio of compound is（0.98~1.02）：1, the gross mass of the dianhydride compound and dianhydride compound in reaction system Percent concentration is 25-35%.
  5. 5. the preparation method of Kapton according to claim 1, it is characterised in that：The organic alkali catalyst is selected from At least one of isoquinolin, triethylamine, pyridine, piperidines.
  6. 6. the preparation method of Kapton according to claim 1, it is characterised in that：The dehydrating agent be selected from toluene, At least one of dimethylbenzene, chlorobenzene.
  7. 7. the preparation method of Kapton according to claim 1, it is characterised in that：Taken off in the reflux dewatering reaction Coolant-temperature gage is 130 ~ 140 DEG C.
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