CN102199290B - Thermoplastic polyimide adhesive film as well as preparation method and application thereof - Google Patents
Thermoplastic polyimide adhesive film as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a thermoplastic polyimide adhesive film as well as a preparation method and application thereof. A structural formula of a polymer for manufacturing the adhesive film is as shown in a formula I in the specification. The preparation method comprises the following steps of: (1) uniformly mixing aromatic diamine, aromatic tetracid dianhydride and a blocking agent in an organic solvent to obtain a homogeneous solution, then adding methylbenzene and isoquinoline to be mixed uniformly, heating to 170-190 DEG C and reacting for 10-24 hours to evaporate the methylbenzene, stopping heating after heating a reaction system to above 200 DEG C, precipitating after cooling to 80-120 DEG C; and (2) dissolving the obtained polymer in an organic solvent to obtain a glue solution of polyimide, coating the glue solution of polyimide on a baseplate, and drying to obtain the polyimide adhesive film. The adhesive film has excellent room-temperature and high-temperature splicing performance when being used for splicing metal materials, resin composite materials and the like.
Description
Technical field
The present invention relates to a kind of thermoplastic polyimide glued membrane and preparation method thereof and application.
Background technology
Tackiness agent can be divided into solution shape, cream pasty state, glued membrane shape etc. by its physical aspect.Wherein glued membrane shape sizing agent has even thickness, and resin added is accurate, and construction technology is easy, can be used for the advantages such as big area is bonding, and especially bonding for honeycomb sandwich construction, have the unrivaled advantage of other several bonding forms.In existing high temperature resistant glued membrane, widely used is the modified epoxy glued membrane, however this class glued membrane because its heat-resistant stability is limited, bonding strength significantly descends when using more than 200 ℃ usually, is difficult to be applied as the structural adhesive bonding material.The polyimide glued membrane owing to having good heat-resistant stability and high temperature bonding performance, can as the bonding use of structure under 200-320 ℃, be the highest class adhesive film material of present temperature resistant grade.
The polyimide glued membrane can be divided into thermoset and the large class of thermoplasticity two, and wherein the Thermocurable polyimide glued membrane has excellent resistance toheat, can be as the bonding use of structure under 280-320 ℃.Yet because it has the chemical structure of rigidity, so toughness is relatively poor, and film-forming properties is not good, usually can't obtain the self-supporting glued membrane, and the form of the carrier glued membrane that supports mainly with woven fiber glass is used.And poor and cured product is more crisp due to its thermally melting, therefore glued joint mold temperature high (340-370 ℃), after glueing joint stripping strength lower (＜1kN/m), limited its further application.For satisfying the aerospace flight vehicle manufacturing to the demand of the high temperature resistant glued membrane that is applicable to big area and glueds joint, from nineteen seventies, the NASA Langley of US National Aeronautics and Space Administration has carried out a large amount of research work to the thermoplastic polyimide glued membrane in the research centre.Took the lead in developing polyimide glued membrane LARC-TPI (A.K.St.Clair in 1980, T.L.St.Clair, A Multipurpose Thermoplastic Polyimide, SAMPE Q, 1981,13 (1), 20), LARC-TPI is by 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) and 3,3 '-diamino benzophenone (3,3 '-DABP) a kind of thermoplastic polyimide that reaction makes in diglyme, it has good toughness, and film forming properties is good, can be used for big area bonding and do not produce bubble.The second-order transition temperature of this glued membrane is about 260 ℃, has good heat-resisting oxidative stability, glued membrane is after 325 ℃ of lower hot melts glued joint titanium alloy, and the single lap shear strength under room temperature and 232 ℃ is respectively 36.5MPa and 13.1MPa, and 232 ℃ is 20.7MPa after aging 3000 hours.Subsequently, the human BTDA and 3 such as Progar, (3,3 '-DDS) has synthesized a kind of polyimide glued membrane PISO that contains the sulfuryl structure to 3 '-diaminodiphenylsulfone(DDS)
2(D.J.Progar, Processing study of a high temperature adhesive, International Journal of Adhesion and Adhesives, 1984,4 (2), 79-86), it has the thermoplasticity of polysulfones and the thermotolerance of polyimide concurrently, second-order transition temperature is 273 ℃, and after through 343 ℃/1.38MPa/5 minute hot melt adhesion titanium alloy, the shearing resistance under room temperature and 232 ℃ is respectively 25.2MPa and 19.8MPa.in addition, they also use 3, 3 ', 4, 4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA) and 3, 4 '-diaminodiphenyl oxide (3, 4 '-ODA) has synthesized a kind of polyimide glued membrane LARC-IA (D.J.Progar that contains the bis ether bond structure, T.L.St.Clair, LARC-IA:A flexible backbone polyimide, NASATM-1990-102586), reduced the synthetic cost of LARC-TPI, approximately 243 ℃ of its second-order transition temperatures, after through 371 ℃/2.07MPa/1 hour hot melt adhesion, room temperature and 232 ℃ of shearing resistances of glueing joint titanium alloy are respectively 31.8MPa and 9.1MPa.Yet generally speaking, these thermoplastic polyimide glued membranes are promoting bonding use temperature, and the aspects such as reduction hot melt adhesion temperature all remain further to be improved.
Saeed etc. are take Tetra hydro Phthalic anhydride (PA) as end-capping reagent, 3, 4 '-diaminodiphenyl oxide (3, 4 '-ODA) is diamines, 3, 3 ', 4, 4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA) or 3, 3 ', 4, 4 '-BPDA (s-BPDA) but prepare two kinds of self-supporting polyimide glued membrane (M.B.Saeed for dianhydride, M.S.Zhan, Adhesive strength of partially imidized thermoplastic polyimide films in bonded joints, International Journal of Adhesion and Adhesives, 2007, 27 (1), 9-19), the design molecular weight is 24000g/mol.The author adopts the polyamic acid resin solution coating, after heat treatment obtains the self-supporting glued membrane of part imidization, this glued membrane to stainless steel carry out bonding after, the shearing resistance under its room temperature is greater than 25MPa, is 5-12MPa under 250 ℃.Yet because the hot melting temperature of glued membrane is higher, for reach with by the abundant infiltration of gluing of surfaces, its bonding temp is up to 350-375 ℃.Although and the glued membrane of part imidization can promote by the wetting property of maxxaedium, in bonding process, due to the water molecules of emitting that is accompanied by imidization reaction, so splicing face easily produces pore and causes defective.
Summary of the invention
The purpose of this invention is to provide a kind of thermoplastic polyimide glued membrane and preparation method thereof and application.
Polyimide polymer provided by the invention, its general structure is suc as formula shown in I:
(formula I)
In above-mentioned formula I general structure, R is selected from any one in following radicals:
Ar is selected from any one in following radicals:
X: y=1: 0.5-2, n are 2-60.
Preferably, x: y=1: 1, n is 20-25, and n specifically can be 2-23,2-24,2-25,23-60,24-60,25-60,23-25,23-24 or 24-25.
The method of polyimide polymer shown in the described formula I of preparation provided by the invention, after comprising the steps: aromatic diamine, aromatic series tetracarboxylic dianhydride and end-capping reagent are obtained homogeneous phase solution after mixing in organic solvent, add again toluene and isoquinoline 99.9 mixing, be warming up to 170-190 ℃ of reaction after 10-24 hour, steam toluene, stopped heating when the question response system temperature is raised to more than 200 ℃, the question response system adds precipitation agent to precipitate when being cooled to 80-120 ℃, obtains polyimide polymer shown in described formula I.
In the method, described aromatic diamine is 1, the mixture of any one composition in two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB) of 4-and following compound: 3,3 '-sulfonyldianiline (3,3 '-DADPS), 4,4 '-sulfonyldianiline (4,4 '-DADPS), 3,3 '-diaminobenzene ketone (3,3 '-DABP), 4,4 '-diaminobenzene ketone (4,4 '-DABP), mphenylenediamine (m-PDA) and Ursol D (p-PDA);
Described aromatic series tetracarboxylic dianhydride is selected from 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA), 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) and 2,3,3 ', 4 '-BPDA (at least a in α-BPDA);
Described end-capping reagent is Tetra hydro Phthalic anhydride shown in formula II (PA);
Described organic solvent is selected from N-Methyl pyrrolidone (NMP), N, at least a in dinethylformamide (DMF), N,N-dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO), tetrahydrofuran (THF) (THF) and meta-cresol;
Described precipitation agent is selected from least a in ethanol, first alcohol and water, preferred alcohol.
Described 1, the mol ratio of any one in two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene of 4-and following compound is 1: 0.5-2: 3,3 '-sulfonyldianiline, 4,4 '-sulfonyldianiline, 3,3 '-diaminobenzene ketone, 4,4 '-diaminobenzene ketone, mphenylenediamine and Ursol D, preferred 1: 1 of described mol ratio;
described aromatic diamine, described aromatic series tetracarboxylic dianhydride, end-capping reagent, described organic solvent, the quality amount ratio of described toluene and described isoquinoline 99.9 is 20-770: 25-800: 0.5-15: 450-14000: 25-600: 5-100, specifically can be 26-769: 29-792: 0.6-14.4: 500-14000: 25-575: 8-95, 66-736: 60-736: 1.2-13.8: 1100-13000: 50-550: 15-90, 140-726: 96-693: 1.8-13.2: 1500-12000: 75-525: 20-80, 175-546: 150-665: 3-12.6: 2800-11000: 125-475: 25-55, 192-520: 180-638: 5.4-11.4: 3200-7000: 150-325: 40-100, 288-770: 315-377: 7.8-15: 5000-14000: 325-600: 40-100, preferred 140-726: 96-693: 1.8-13.2: 1500-12000: 75-525: 20-80, more preferably 192-520: 180-638: 5.4-11.4: 3200-7000: 150-325: 25-55.Described being warming up in 10-24 hour step of 170-190 ℃ of reaction, temperature of reaction specifically can be 170-180 ℃ or 180-190 ℃, and the reaction times specifically can be 10-20 hour, 10-12 hour, 12-24 hour, 12-20 hour or 20-24 hour.
In addition, the polyimide glued membrane with polyimide polymer shown in above-mentioned formula I is made also belongs to protection scope of the present invention.The thickness of this polyimide glued membrane is 50-250 μ m, specifically can be 100-250 μ m, 100-200 μ m, 100-150 μ m, 50-200 μ m, 50-150 μ m, 50-100 μ m, 150-250 μ m or 150-200 μ m, preferred 200-250 μ m.
The method of the above-mentioned polyimide glued membrane of preparation provided by the invention, comprise the steps: polyimide polymer shown in formula I is dissolved in organic solvent, obtain the glue of polyimide, the glue of described polyimide is coated on substrate, obtain described polyimide glued membrane after oven dry.
In the method, described organic solvent is selected from least a in N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) and meta-cresol; The quality amount ratio of polyimide polymer and described organic solvent shown in described formula I is 30-70: 100, and preferred 30-50: 100; In described baking step, temperature is 80-250 ℃, and preferred 80-200 ℃, the time is 0.5-6 hour, preferred 2-5 hour; This baking step can be selected different heating modes according to the difference of organic solvent kind used, when organic solvent used is tetrahydrofuran (THF), can directly 80 ℃ of oven dry 0.5 hour, can obtain the polyimide glued membrane; When organic solvent used is selected from N-Methyl pyrrolidone, N, dinethylformamide, N, during at least a in N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO) and meta-cresol, can dry according to following ladder-elevating temperature step: first be warming up to 120 ℃ of insulations 1 hour after 2 hours 80 ℃ of insulations, be warming up to again 150-180 ℃ of insulation after 1 hour, then 200-250 ℃ of insulation 1 hour.Described substrate is sheet glass.After described baking step, also can after baking step, substrate be immersed according to existing method glued membrane is peeled off from substrate automatically, clean glued membrane and dry with ethanol, obtain polyimide glued membrane provided by the invention, this glued membrane is faint yellow, and is transparent.
In addition, the application of the polyimide glued membrane that the invention described above provides in the preparation structural film adhesive also belongs to protection scope of the present invention.
The preparation method of polyimide glued membrane provided by the invention, simple process, easy handling, good film-forming property stores convenient transportation.Glued membrane has good thermally melting, carries out bondingly under 280-320 ℃ for metallic substance such as stainless steel, aluminium alloy, titanium alloy etc. and fire resistant resin based composites such as composite polyimide material etc., all shows excellent room temperature and high temperature bonding performance.This glued membrane is 20-27MPa under room temperature to the bonding shearing resistance of stainless steel, 220 ℃ of lower 17-23MPa, 250 ℃ of lower 15-19MPa, 280 ℃ of lower 4-9MPa; Be 1-3kN/m under room temperature to the bonding T-shaped stripping strength of aluminium alloy.Thermoplastic polyimide glued membrane provided by the invention can be used as metal and composite product and honeycomb sandwich construction spare that the high-temperature-resistant structure tackiness agent is applied to Aeronautics and Astronautics, precision optical machinery, field of petrochemical industry.
Description of drawings
Fig. 1 is the infrared spectrum of embodiment 1 preparation gained polyimide.
Fig. 2 is the infrared spectrum of embodiment 2 preparation gained polyimide.
Fig. 3 is the infrared spectrum of embodiment 3 preparation gained polyimide.
Fig. 4 is the infrared spectrum of embodiment 7 preparation gained polyimide.
Embodiment
The present invention is further elaborated below in conjunction with specific embodiment, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.In following each embodiment, described part is mass fraction.Described reactant all can get from open commercial sources if no special instructions.
In following embodiment, second-order transition temperature, 5% weightless temperature, shearing resistance, the T-shaped stripping strength of preparation gained polyimide glued membrane are measured and are got according to following ordinary method respectively:
Second-order transition temperature is measured (DSC) by TAQ100 differential scanning calorimetric analysis instrument, and Range of measuring temp is 50～400 ℃, and temperature rise rate is 10 ℃/min, and nitrogen flow is 20cm
3/ min.
5% weightless temperature is measured (TGA) by the TAQ50 thermogravimetric analyzer, and Range of measuring temp is 50～750 ℃, and temperature rise rate is that 20 ℃/min, nitrogen flow are 20cm
3/ min.
Single lap shear strength is measured by INSTRON 5567 type microcomputer control universal testing machines, the single lap shear strength of room temperature is measured with reference to standard GB/T 7124-86, shear at high temperature intensity is measured with reference to national military standard GJB 444-88, when measuring under high temperature, sample is being begun after constant temperature 5min under probe temperature, it is 5mm/min that the translational speed of crossbeam is.Bonding test piece is that (AISI 321, and Fe/Cr18/Ni9/Ti), specimen size 100 * 25 * 2mm glueds joint area 25 * 12.5mm, 320 ℃/1h of Sticking condition for stainless steel.
T-shaped stripping strength is at room temperature measured by INSTRON 5567 type microcomputer control universal testing machines, and reference standard is GB/T 7122-1996, and the translational speed of crossbeam is 100mm/min.Bonding test piece is aluminium foil and aluminium alloy (LY12-CZ), and specimen size 200 * 25 * 2mm glueds joint area 180 * 25mm, 320 ℃/1h of Sticking condition.
Embodiment 1, preparation polyimide glued membrane
In three mouthfuls of round-bottomed flasks being furnished with mechanical stirring, nitrogen inlet and thermometer; with 42 part 1; two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB) of 4-and 24 part 4; 4 '-sulfonyldianiline (4; 4 '-DADPS) joins in 550 parts of meta-cresols, stirs 0.5 hour.With 60 part 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA) and 1.2 parts of end-capping reagent Tetra hydro Phthalic anhydrides (PA) join in 550 parts of meta-cresols, stir 0.5 hour.Mentioned solution mixed and stir, obtaining homogeneous phase solution.
50 parts of toluene and 8 parts of isoquinoline 99.9 are joined in above-mentioned homogeneous phase solution, be warmed up to 180 ℃ of reactions after 12 hours, steam toluene, stopped heating when the question response system is warmed up to 220 ℃.
Pour in ethanol after reaction solution is cooled to 80 ℃, collect the solid of separating out, with filtering, pulverize, dry after second alcohol and water repetitive scrubbing, obtain polyimide pressed powder shown in formula I, productive rate is 98%.
50 parts of this toners are dissolved in 100 parts of N, in N-N,N-DIMETHYLACETAMIDE (DMAc), obtain the glue of polyimide, this glue is coated on ganoid sheet glass, through 80 ℃/2 hours, 120 ℃/1 hour, 150 ℃/1 hour, 180 ℃/1 hour, after the baking of 200 ℃/1 hour ladder-elevating temperature heat, sheet glass is immersed glued membrane is peeled off from sheet glass automatically, clean glued membrane and dry with ethanol, obtain faint yellow clear polyimides glued membrane shown in formula I.Film thickness is 150 μ m.
(formula I)
In described formula I general structure, R is 4, and 4 '-alkylsulfonyl phenylbenzene, Ar are 3,3 ', 4, and 4 '-two methyl-phenoxide bases, x: y=1: 1, n are 24.
Fig. 1 prepares the infrared spectrum of gained polyimide for this embodiment.As shown in Figure 1,1782cm
-1And 1726cm
-1Asymmetric and the symmetrical stretching vibration absorption peak for the carbonyl of imide group, 1369cm
-1C-N stretching vibration absorption peak for imide group illustrates to have formed imide ring.1242cm
-1The left and right is the trifluoromethyl absorption peak, 1319cm
-1And 1138cm
-1Be sulfuryl S=O stretching vibration absorption peak.As from the foregoing, it is correct that this embodiment prepares the products therefrom structure, is polymkeric substance shown in formula I.
This polyimide glued membrane is affixed on by the sticky object surface, and under the pressure of 0.5-1.5MPa, between 280-320 ℃, curing obtained firmly convered structure in 0.5-2 hour.
The second-order transition temperature of above-mentioned polyimide glued membrane is greater than 250 ℃, and 5% weightless temperature surpasses 550 ℃, and the adhesiveproperties of this glued membrane is as shown in table 1, illustrates that polyimide glued membrane provided by the invention has excellent resistance toheat and adhesiveproperties.
The adhesiveproperties of table 1, polyimide glued membrane
| Title | Performance |
| The normal temperature shearing resistance (stainless steel, MPa) | 20-27 |
| 220 ℃ of shearing resistances (stainless steel, MPa) | 17-23 |
| 250 ℃ of shearing resistances (stainless steel, MPa) | 15-19 |
| 280 ℃ of shearing resistances (stainless steel, MPa) | 4-9 |
| T-shaped stripping strength (aluminium alloy, kN/m) | 1-3 |
Embodiment 2, preparation polyimide glued membrane
In three mouthfuls of round-bottomed flasks being furnished with mechanical stirring, nitrogen inlet and thermometer; with 135 part 1; two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB) of 4-and 40 part 3; 3 '-sulfonyldianiline (3; 3 '-DADPS) joins 1400 parts of N; in dinethylformamide (DMF), stirred 0.5 hour.With 150 part 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA) and 3 parts of end-capping reagent Tetra hydro Phthalic anhydrides (PA) join in 1400 parts of N-Methyl pyrrolidone (NMP), stir 0.5 hour.Mentioned solution mixed and stir, obtaining homogeneous phase solution.
125 parts of toluene and 20 parts of isoquinoline 99.9 are joined in above-mentioned homogeneous phase solution, be warmed up to 170 ℃ of reactions after 10 hours, steam toluene, stopped heating when the question response system is warmed up to 210 ℃.
Pour in methyl alcohol after reaction solution is cooled to 80 ℃, collect the solid of separating out, with filtering, pulverize, dry after first alcohol and water repetitive scrubbing, obtain the pressed powder of polyimide shown in formula I, productive rate is 95%.
60 parts of this toners are dissolved in 100 parts of tetrahydrofuran (THF)s (THF), obtain the glue of polyimide, this glue is coated on ganoid sheet glass, after heat baking in 80 ℃/0.5 hour, sheet glass is immersed makes glued membrane automatically peel off from sheet glass in hot water, clean glued membrane and dry with ethanol, obtaining faint yellow clear polyimides glued membrane shown in formula I.Film thickness is 200 μ m.
(formula I)
In described formula I general structure, R is 3, and 3 '-alkylsulfonyl phenylbenzene, Ar are 3,3 ', 4, and 4 '-two methyl-phenoxide bases, x: y=2: 1, n are 24.
Fig. 2 prepares the infrared spectrum of gained polyimide for this embodiment.As shown in Figure 2,1780cm
-1And 1726cm
-1Asymmetric and the symmetrical stretching vibration absorption peak for the carbonyl of imide group, 1371cm
-1C-N stretching vibration absorption peak for imide group illustrates to have formed imide ring.1242cm
-1The left and right is the trifluoromethyl absorption peak, 1319cm
-1And 1140cm
-1Be sulfuryl S=O stretching vibration absorption peak.As from the foregoing, it is correct that this embodiment prepares the products therefrom structure, is polymkeric substance shown in formula I.
Embodiment 3, preparation polyimide glued membrane
In three mouthfuls of round-bottomed flasks being furnished with mechanical stirring, nitrogen inlet and thermometer, with 54 part 1, two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB) of 4-and 27 part 3,3 '-diaminobenzene ketone (3,3 '-DABP) joins in 650 parts of N-Methyl pyrrolidone (NMP), stirs 0.5 hour.With 75 part 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA) and 0.6 part of end-capping reagent Tetra hydro Phthalic anhydride (PA) join in 650 parts of N-Methyl pyrrolidone (NMP), stir 0.5 hour.Mentioned solution mixed and stir, obtaining homogeneous phase solution.
60 parts of toluene and 10 parts of isoquinoline 99.9 are joined in above-mentioned homogeneous phase solution, be warmed up to 190 ℃ of reactions after 10 hours, steam toluene, stopped heating when the question response system is warmed up to 210 ℃.
Reaction solution is cooled to 80 ℃ falls back, collect the solid of separating out, with filter after second alcohol and water repetitive scrubbing, pulverize, oven dry, obtain the pressed powder of polyimide shown in formula I, productive rate is 96%.
50 parts of this toners are dissolved in 100 parts of dimethyl sulfoxide (DMSO) (DMSO), obtain the glue of polyimide, this glue is coated on ganoid sheet glass, through 80 ℃/2 hours, 120 ℃/1 hour, 180 ℃/1 hour, after the baking of 250 ℃/1 hour ladder-elevating temperature heat, sheet glass is immersed glued membrane is peeled off from sheet glass automatically, clean glued membrane and dry with ethanol, obtain faint yellow clear polyimides glued membrane shown in formula I.Film thickness is 150 μ m.
(formula I)
In described formula I general structure, R is 3, and 3 '-benzophenone base, Ar are 3,3 ', 4, and 4 '-two methyl-phenoxide bases, x: y=1: 1, n are 60.
Fig. 3 prepares the infrared spectrum of gained polyimide for this embodiment.As shown in Figure 3,1780cm
-1And 1724cm
-1Asymmetric and the symmetrical stretching vibration absorption peak for the carbonyl of imide group, 1373cm
-1C-N stretching vibration absorption peak for imide group illustrates to have formed imide ring.1242cm
-1The left and right is the trifluoromethyl absorption peak, 1319cm
-1And 1138cm
-1Be sulfuryl S=O stretching vibration absorption peak.As from the foregoing, it is correct that this embodiment prepares the products therefrom structure, is polymkeric substance shown in formula I.
Embodiment 4, preparation polyimide glued membrane
In three mouthfuls of round-bottomed flasks being furnished with mechanical stirring, nitrogen inlet and thermometer, with 260 part 1, two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB) of 4-and 260 part 4,4 '-diaminobenzene ketone (4,4 '-DABP) joins 5000 parts of N, in N-N,N-DIMETHYLACETAMIDE (DMAc), stirred 0.5 hour.With 665 part 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) and 11.4 parts of end-capping reagent Tetra hydro Phthalic anhydrides (PA) join in 6000 parts of meta-cresols, stir 0.5 hour.Mentioned solution mixed and stir, obtaining homogeneous phase solution.
475 parts of toluene and 80 parts of isoquinoline 99.9 are joined in above-mentioned homogeneous phase solution, be warmed up to 170 ℃ of reactions after 24 hours, steam toluene, stopped heating when the question response system is warmed up to 200 ℃.
Pour in ethanol after reaction solution is cooled to 80 ℃, collect the solid of separating out, with filtering, pulverize, dry after second alcohol and water repetitive scrubbing, obtain the pressed powder of polyimide shown in formula I, productive rate is 93%.
30 parts of this toners are dissolved in 50 parts of N, in dinethylformamide (DMF) and 50 parts of tetrahydrofuran (THF)s (THF), obtain the glue of polyimide, this glue is coated on ganoid sheet glass, through 80 ℃/2 hours, 120 ℃/1 hour, 150 ℃/1 hour, after the baking of 180 ℃/1 hour ladder-elevating temperature heat, sheet glass is immersed glued membrane is peeled off from sheet glass automatically, clean glued membrane and dry with ethanol, obtaining faint yellow clear polyimides glued membrane shown in formula I.Film thickness is 50 μ m.
In described formula I general structure, R is 4, and 4 '-benzophenone base, Ar are 3,3 ', 4, and 4 '-diphenyl sulfone, x: y=1: 2, n are 24.
Embodiment 5, preparation polyimide glued membrane
In three mouthfuls of round-bottomed flasks being furnished with mechanical stirring, nitrogen inlet and thermometer, with 62 part 1, two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB) of 4-and 31 part 3,3 '-diaminobenzene ketone (3,3 '-DABP) joins in 330 parts of N-Methyl pyrrolidone (NMP), stirs 0.5 hour.With 52 part 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) and 10.8 parts of end-capping reagent Tetra hydro Phthalic anhydrides (PA) join in 500 parts of N-Methyl pyrrolidone (NMP), stir 0.5 hour.Mentioned solution mixed and stir, obtaining homogeneous phase solution.
40 parts of toluene and 7 parts of isoquinoline 99.9 are joined in above-mentioned homogeneous phase solution, be warmed up to 180 ℃ of reactions after 20 hours, steam toluene, stopped heating when the question response system is warmed up to 210 ℃.
Reaction solution is cooled to 80 ℃ falls back, collect the solid of separating out, with filter after second alcohol and water repetitive scrubbing, pulverize, oven dry, obtain the pressed powder of polyimide shown in formula I, productive rate is 94%.
50 parts of this toners are dissolved in 40 parts of dimethyl sulfoxide (DMSO) (DMSO) and 60 parts of N, in N-N,N-DIMETHYLACETAMIDE (DMAc), obtain the glue of polyimide, this glue is coated on ganoid sheet glass, through 80 ℃/2 hours, 120 ℃/1 hour, 150 ℃/1 hour, 180 ℃/1 hour, after the baking of 200 ℃/1 hour ladder-elevating temperature heat, sheet glass is immersed glued membrane is peeled off from sheet glass automatically, clean glued membrane and dry with ethanol, obtain faint yellow clear polyimides glued membrane shown in formula I.Film thickness is 150 μ m.
(formula I)
In described formula I general structure, R is 3, and 3 '-benzophenone base, Ar are 3,3 ', 4, and 4 '-diphenyl sulfone, x: y=1: 1, n are 2.
Embodiment 6, preparation polyimide glued membrane
In three mouthfuls of round-bottomed flasks being furnished with mechanical stirring, nitrogen inlet and thermometer, with 21 part 1, two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB) of 4-and 5 parts of Ursol D (p-PDA) join 200 parts of N, in N-N,N-DIMETHYLACETAMIDE (DMAc), stirred 0.5 hour.With 29 part 2,3, (α-BPDA) He 0.6 a part end-capping reagent Tetra hydro Phthalic anhydride (PA) joins in 300 parts of N-Methyl pyrrolidone (NMP) 3 ', 4 '-BPDA, stirs 0.5 hour.Mentioned solution mixed and stir, obtaining homogeneous phase solution.
25 parts of toluene and 5 parts of isoquinoline 99.9 are joined in above-mentioned homogeneous phase solution, be warmed up to 180 ℃ of reactions after 12 hours, steam toluene, stopped heating when the question response system is warmed up to 220 ℃.
Pour in ethanol after reaction solution is cooled to 80 ℃, collect the solid of separating out, with filtering, pulverize, dry after second alcohol and water repetitive scrubbing, obtain the pressed powder of polyimide shown in formula I, productive rate is 92%.
70 parts of this toners are dissolved in 50 parts of N-Methyl pyrrolidone (NMP) and 50 parts of meta-cresols, obtain the glue of polyimide, this glue is coated on ganoid sheet glass, through 80 ℃/2 hours, 120 ℃/1 hour, 180 ℃/1 hour, after the baking of 250 ℃/1 hour ladder-elevating temperature heat, sheet glass is immersed glued membrane is peeled off from sheet glass automatically, clean glued membrane and dry with ethanol, obtain faint yellow clear polyimides glued membrane shown in formula I.Film thickness is 250 μ m.
(formula I)
In described formula I general structure, R is the contraposition phenyl, and Ar is 2,3,3 ', 4 '-xenyl, and x: y=1: 1, n is 24.
Embodiment 7, preparation polyimide glued membrane
In three mouthfuls of round-bottomed flasks being furnished with mechanical stirring, nitrogen inlet and thermometer; with 180 part 1; two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB) of 4-and 210 part 4; 4 '-sulfonyldianiline (4; 4 '-DADPS) joins in 3000 parts of meta-cresols, stirs 0.5 hour.With 195 part 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA), 182 part 2,3, (α-BPDA) He 7.8 a part end-capping reagent Tetra hydro Phthalic anhydride (PA) joins in 4000 parts of meta-cresols 3 ', 4 '-BPDA, stirs 0.5 hour.Mentioned solution mixed and stir, obtaining homogeneous phase solution.
325 parts of toluene and 55 parts of isoquinoline 99.9 are joined in above-mentioned homogeneous phase solution, be warmed up to 190 ℃ of reactions after 24 hours, steam toluene, stopped heating when the question response system is warmed up to 220 ℃.
Pour in ethanol after reaction solution is cooled to 80 ℃, collect the solid of separating out, with filtering, pulverize, dry after second alcohol and water repetitive scrubbing, obtain the pressed powder of polyimide shown in formula I, productive rate is 93%.
50 parts of this toners are dissolved in 100 parts of N-Methyl pyrrolidone (NMP), obtain the glue of polyimide, this glue is coated on ganoid sheet glass, through 80 ℃/2 hours, 120 ℃/1 hour, 180 ℃/1 hour, after the baking of 250 ℃/1 hour ladder-elevating temperature heat, sheet glass is immersed glued membrane is peeled off from sheet glass automatically, clean glued membrane and dry with ethanol, obtain faint yellow clear polyimides glued membrane shown in formula I.Film thickness is 150 μ m.
In described formula I general structure, R is 4, and 4 '-alkylsulfonyl phenylbenzene, Ar are 3,3 ', 4,4 '-two methyl-phenoxide bases and 2,3, and the mixture of 3 ', 4 '-xenyl, x: y=1: 2, n are 23.
Fig. 4 prepares the infrared spectrum of gained polyimide for this embodiment.As seen from the figure, 1780cm
-1And 1726cm
-1Asymmetric and the symmetrical stretching vibration absorption peak for the carbonyl of imide group, 1371cm
-1C-N stretching vibration absorption peak for imide group illustrates to have formed imide ring.1242cm
-1The left and right is the trifluoromethyl absorption peak, 1319cm
-1And 1137cm
-1Be sulfuryl S=O stretching vibration absorption peak.As from the foregoing, it is correct that this embodiment prepares the products therefrom structure, is polymkeric substance shown in formula I.
Embodiment 8, preparation polyimide glued membrane
In three mouthfuls of round-bottomed flasks being furnished with mechanical stirring, nitrogen inlet and thermometer, with 504 part 1, two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB) of 4-and 265 part 4,4 '-diaminobenzene ketone (4,4 '-DABP) joins 7000 parts of N, in dinethylformamide (DMF), stirred 0.5 hour.With 360 part 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA), 432 part 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) and 14.4 parts of end-capping reagent Tetra hydro Phthalic anhydrides (PA) join in 7000 parts of meta-cresols, stir 0.5 hour.Mentioned solution mixed and stir, obtaining homogeneous phase solution.
600 parts of toluene and 100 parts of isoquinoline 99.9 are joined in above-mentioned homogeneous phase solution, be warmed up to 180 ℃ of reactions after 20 hours, steam toluene, stopped heating when the question response system is warmed up to 210 ℃.
Pour in ethanol after reaction solution is cooled to 80 ℃, collect the solid of separating out, with filtering, pulverize, dry after second alcohol and water repetitive scrubbing, obtain the pressed powder of polyimide shown in formula I, productive rate is 94%.
50 parts of this toners are dissolved in 100 parts of N, in dinethylformamide (DMF), obtain the glue of polyimide, this glue is coated on ganoid sheet glass, 80 ℃/2 hours, 120 ℃/1 hour, 150 ℃/1 hour, 180 ℃/1 hour, after the baking of 200 ℃/1 hour ladder-elevating temperature heat, sheet glass is immersed glued membrane is peeled off from sheet glass automatically, clean glued membrane and dry with ethanol, obtain faint yellow clear polyimides glued membrane shown in formula I.Film thickness is 150 μ m.
(formula I)
In described formula I general structure, R is 4, and 4 '-benzophenone base, Ar are 3,3 ', 4,4 '-two methyl-phenoxide bases and 3,3 ', 4, and the mixture of 4 '-diphenyl sulfone, x: y=1: 1, n is 25.
Embodiment 9, preparation polyimide glued membrane
In three mouthfuls of round-bottomed flasks being furnished with mechanical stirring, nitrogen inlet and thermometer, with 85 part 1, two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB) of 4-and 55 parts of Ursol D (p-PDA) join in 700 parts of meta-cresols, stir 0.5 hour.With 54 part 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA), 42 part 2,3, (α-BPDA) He 1.8 a part end-capping reagent Tetra hydro Phthalic anhydride (PA) joins in 800 parts of meta-cresols 3 ', 4 '-BPDA, stirs 0.5 hour.Mentioned solution mixed and stir, obtaining homogeneous phase solution.
75 parts of toluene and 15 parts of isoquinoline 99.9 are joined in above-mentioned homogeneous phase solution, be warmed up to 180 ℃ of reactions after 10 hours, steam toluene, stopped heating when the question response system is warmed up to 210 ℃.
Pour in ethanol after reaction solution is cooled to 80 ℃, collect the solid of separating out, with filtering, pulverize, dry after second alcohol and water repetitive scrubbing, obtain the pressed powder of polyimide shown in formula I, productive rate is 93%.
40 parts of this toners are dissolved in 100 parts of meta-cresols, obtain the glue of polyimide, this glue is coated on ganoid sheet glass, through 80 ℃/2 hours, 120 ℃/1 hour, 180 ℃/1 hour, after the baking of 250 ℃/1 hour ladder-elevating temperature heat, sheet glass is immersed glued membrane is peeled off from sheet glass automatically, clean glued membrane and dry with ethanol, obtain faint yellow clear polyimides glued membrane shown in formula I.Film thickness is 100 μ m.
In described formula I general structure, R is the contraposition phenyl, and Ar is 3,3 ', 4,4 '-diphenyl sulfone and 2,3, and the mixture of 3 ', 4 '-xenyl, x: y=2: 1, n are 23.
Embodiment 10, preparation polyimide glued membrane
In three mouthfuls of round-bottomed flasks being furnished with mechanical stirring, nitrogen inlet and thermometer; with 462 part 1; two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB) of 4-and 264 part 3; 3 '-sulfonyldianiline (3; 3 '-DADPS) joins in 6000 parts of N-Methyl pyrrolidone (NMP), stirs 0.5 hour.With 330 part 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA), 308 part 2,3,3 ', (α-BPDA) He 13.2 a part end-capping reagent Tetra hydro Phthalic anhydride (PA) joins in 6000 parts of meta-cresols 4 '-BPDA, stirs 0.5 hour.Mentioned solution mixed and stir, obtaining homogeneous phase solution.
550 parts of toluene and 95 parts of isoquinoline 99.9 are joined in above-mentioned homogeneous phase solution, be warmed up to 190 ℃ of reactions after 10 hours, steam toluene, stopped heating when the question response system is warmed up to 220 ℃.
Reaction solution is cooled to 80 ℃ falls back, collect the solid of separating out, with filter after second alcohol and water repetitive scrubbing, pulverize, oven dry, obtain the pressed powder of polyimide shown in formula I, productive rate is 92%.
50 parts of this toners are dissolved in 70 parts of N-Methyl pyrrolidone (NMP) and 30 parts of tetrahydrofuran (THF)s (THF), obtain the glue of polyimide, this glue is coated on ganoid sheet glass, through 80 ℃/2 hours, 120 ℃/1 hour, 150 ℃/1 hour, after the baking of 180 ℃/1 hour ladder-elevating temperature heat, sheet glass is immersed glued membrane is peeled off from sheet glass automatically, clean glued membrane and dry with ethanol, obtain faint yellow clear polyimides glued membrane shown in formula I.Film thickness is 150 μ m.
(formula I)
In described formula I general structure, R is 3, and 3 '-alkylsulfonyl phenylbenzene, Ar are 3,3 ', 4,4 '-two methyl-phenoxide bases and 2,3, and the mixture of 3 ', 4 '-xenyl, x: y=1: 1, n are 25.
Embodiment 11, preparation polyimide glued membrane
In three mouthfuls of round-bottomed flasks being furnished with mechanical stirring, nitrogen inlet and thermometer, with 441 part 1, two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB) of 4-and 105 parts of mphenylenediamines (m-PDA) join in 5000 parts of N-Methyl pyrrolidone (NMP), stir 0.5 hour.With 315 part 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides (ODPA), 378 part 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA) and 12.6 parts of end-capping reagent Tetra hydro Phthalic anhydrides (PA) join in 6000 parts of N-Methyl pyrrolidone (NMP), stir 0.5 hour.Mentioned solution mixed and stir, obtaining homogeneous phase solution.
525 parts of toluene and 90 parts of isoquinoline 99.9 are joined in above-mentioned homogeneous phase solution, be warmed up to 180 ℃ of reactions after 12 hours, steam toluene, stopped heating when the question response system is warmed up to 210 ℃.
Pour in ethanol after reaction solution is cooled to 80 ℃, collect the solid of separating out, with filtering, pulverize, dry after second alcohol and water repetitive scrubbing, obtain the pressed powder of polyimide shown in formula I, productive rate is 91%.
50 parts of this toners are dissolved in 50 parts of dimethyl sulfoxide (DMSO) (DMSO) and 50 parts of meta-cresols, obtain the glue of polyimide, this glue is coated on ganoid sheet glass, through 80 ℃/2 hours, 120 ℃/1 hour, 180 ℃/1 hour, after the baking of 250 ℃/1 hour ladder-elevating temperature heat, sheet glass is immersed glued membrane is peeled off from sheet glass automatically, clean glued membrane and dry with ethanol, obtain faint yellow clear polyimides glued membrane shown in formula I.Film thickness is 150 μ m.
In described formula I general structure, R be between the position phenyl, Ar is 3,3 ', 4,4 '-two methyl-phenoxide bases and 3,3 ', 4, the mixture of 4 '-diphenyl sulfone, x: y=1: 1, n are 24.
Embodiment 12, preparation polyimide glued membrane
In three mouthfuls of round-bottomed flasks being furnished with mechanical stirring, nitrogen inlet and thermometer, with 483 part 1, two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene (6FAPB) of 4-and 253 part 3,3 '-diaminobenzene ketone (3,3 '-DABP) joins in 6000 parts of meta-cresols, stirs 0.5 hour.With 414 part 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride (DSDA), 322 part 2,3,3 ', (α-BPDA) He 13.8 a part end-capping reagent Tetra hydro Phthalic anhydride (PA) joins in 7000 parts of N-Methyl pyrrolidone (NMP) 4 '-BPDA, stirs 0.5 hour.Mentioned solution mixed and stir, obtaining homogeneous phase solution.
575 parts of toluene and 100 parts of isoquinoline 99.9 are joined in above-mentioned homogeneous phase solution, be warmed up to 180 ℃ of reactions after 12 hours, steam toluene, stopped heating when the question response system is warmed up to 220 ℃.
Pour in ethanol after reaction solution is cooled to 80 ℃, collect the solid of separating out, with filtering, pulverize, dry after second alcohol and water repetitive scrubbing, obtain the pressed powder of polyimide shown in formula I, productive rate is 93%.
50 parts of this toners are dissolved in 50 parts of N, dinethylformamide (DMF) and 50 parts of N, in N-N,N-DIMETHYLACETAMIDE (DMAc), obtain the glue of polyimide, this glue is coated on ganoid sheet glass, through 80 ℃/2 hours, 120 ℃/1 hour, 150 ℃/1 hour, 180 ℃/1 hour, after the baking of 200 ℃/1 hour ladder-elevating temperature heat, sheet glass is immersed glued membrane is peeled off from sheet glass automatically, clean glued membrane and dry with ethanol, obtaining faint yellow clear polyimides glued membrane shown in formula I.Film thickness is 150 μ m.
(formula I)
In described formula I general structure, R is 3, and 3 '-benzophenone base, Ar are 3,3 ', 4,4 '-diphenyl sulfone and 2,3, and the mixture of 3 ', 4 '-xenyl, x: y=1: 1, n are 24.
Claims (10)
1. polyimide polymer shown in formula I,
In described formula I general structure, R is selected from any one in following radicals:
Ar is selected from least a in following radicals:
X: y=1: 0.5-2, n are 23-60.
2. polymkeric substance according to claim 1 is characterized in that: in described formula I general structure, and x: y=1: 1.
3. method for preparing polyimide polymer shown in the arbitrary described formula I of claim 1 or 2, after comprising the steps: aromatic diamine, aromatic series tetracarboxylic dianhydride and end-capping reagent are obtained homogeneous phase solution after mixing in organic solvent, add again toluene and isoquinoline 99.9 mixing, be warming up to 170-190 ℃ of reaction after 10-24 hour, steam toluene, stopped heating when the question response system temperature is raised to more than 200 ℃, the question response system adds precipitation agent to precipitate when being cooled to 80-120 ℃, obtains polyimide polymer shown in described formula I.
4. method according to claim 3, it is characterized in that: described aromatic diamine is 1, the mixture of any one composition in two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene of 4-and following compound: 3,3 '-sulfonyldianiline, 4,4 '-sulfonyldianiline, 3,3 '-diaminobenzene ketone, 4,4 '-diaminobenzene ketone, mphenylenediamine and Ursol D;
Described aromatic series tetracarboxylic dianhydride is selected from 3,3 ', 4,4 '-two methyl-phenoxide tetracarboxylic dianhydrides, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride and 2,3, at least a in 3 ', 4 '-BPDA;
Described end-capping reagent is Tetra hydro Phthalic anhydride;
Described organic solvent is selected from least a in N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) and meta-cresol;
Described precipitation agent is selected from least a in ethanol, first alcohol and water.
5. according to claim 3 or 4 described methods, it is characterized in that: described 1, the mol ratio of any one in two (4 '-amino-2 '-4-trifluoromethylphenopendant) benzene of 4-and following compound is 1: 0.5-2:3,3 '-sulfonyldianiline, 4,4 '-sulfonyldianiline, 3,3 '-diaminobenzene ketone, 4,4 '-diaminobenzene ketone, mphenylenediamine and Ursol D;
The quality amount ratio of described aromatic diamine, described aromatic series tetracarboxylic dianhydride, end-capping reagent, described organic solvent, described toluene and described isoquinoline 99.9 is 20-770: 25-800: 0.5-15: 450-14000: 25-600: 5-100.
6. the polyimide glued membrane made from polyimide polymer shown in the arbitrary described formula I of claim 1 or 2.
7. polyimide glued membrane according to claim 6, it is characterized in that: the thickness of described polyimide glued membrane is 50-250 μ m.
8. method for preparing the described polyimide glued membrane of claim 6 or 7, comprise the steps: polyimide polymer shown in the arbitrary described formula I of claim 1 or 2 is dissolved in organic solvent, obtain the glue of polyimide, the glue of described polyimide is coated on substrate, obtains described polyimide glued membrane after oven dry.
9. method according to claim 8, it is characterized in that: described organic solvent is selected from N-Methyl pyrrolidone, N, at least a in N-METHYLFORMAMIDE, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) and meta-cresol; Shown in the arbitrary described formula I of described claim 1 or 2, the quality amount ratio of polyimide polymer and described organic solvent is 30-70: 100; In described baking step, temperature is 80-250 ℃, and the time is 0.5-6 hour; Described substrate is sheet glass.
10. the application of the described polyimide glued membrane of claim 6 or 7 in the preparation structural film adhesive.
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| CN102675637B (en) * | 2012-05-24 | 2014-04-02 | 黑龙江大学 | Electrochromatic polyimide and preparation method thereof |
| EP3049459B1 (en) | 2013-09-26 | 2019-02-27 | PolyOne Corporation | Aromatic polyimides suitable for 3d printing processes |
| CN105566630B (en) * | 2014-10-14 | 2018-03-02 | 株洲时代电气绝缘有限责任公司 | A kind of Kapton and preparation method thereof |
| CN107108888B (en) * | 2015-01-05 | 2021-06-08 | 沙特基础工业全球技术有限公司 | Reactive fragile polyimide and preparation method thereof |
| CN105001793A (en) * | 2015-07-27 | 2015-10-28 | 东莞市毅联电子科技有限公司 | Polyimide adhesive film with storage performance and preparing method thereof |
| CN106564198A (en) * | 2015-10-10 | 2017-04-19 | 陕西飞机工业（集团）有限公司 | Method for bonding foam layer and aluminum alloy skin |
| WO2018105676A1 (en) * | 2016-12-08 | 2018-06-14 | 日産化学工業株式会社 | Release layer production method |
| CN106515130B (en) * | 2016-12-27 | 2019-04-30 | 广东生益科技股份有限公司 | The polyimides of low water absorption a kind of and its preparation without offset plate material and the preparation method without offset plate material |
| CN107417917A (en) * | 2017-09-22 | 2017-12-01 | 长春理工大学 | A kind of solvable fusible type polyimides and preparation method thereof |
| CN107856383B (en) * | 2017-12-07 | 2020-04-14 | 株洲时代华昇新材料技术有限公司 | Corona-resistant polyimide composite film and preparation method thereof |
| CN109438702A (en) * | 2018-09-29 | 2019-03-08 | 苏州市新广益电子有限公司 | It is a kind of for the TPI film of FPC industry and its preparation and processing method |
| CN110591358A (en) * | 2019-09-23 | 2019-12-20 | 中国航空工业集团公司基础技术研究院 | Preparation method of light high-temperature-resistant polyimide glass bead core material |
| CN111154449B (en) * | 2020-01-10 | 2022-12-23 | 湖北君邦新材料科技有限公司 | Preparation method of photosensitive adhesive for building bonding |
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