CN116003794A - High-frequency high-heat-resistance heat-sealable poly (aryl ester-imide) resin and preparation method and application thereof - Google Patents
High-frequency high-heat-resistance heat-sealable poly (aryl ester-imide) resin and preparation method and application thereof Download PDFInfo
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- 229920005989 resin Polymers 0.000 title claims abstract description 67
- 239000011347 resin Substances 0.000 title claims abstract description 67
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 38
- LOCTYHIHNCOYJZ-UHFFFAOYSA-N (4-aminophenyl) 4-aminobenzoate Chemical compound C1=CC(N)=CC=C1OC(=O)C1=CC=C(N)C=C1 LOCTYHIHNCOYJZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 18
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 17
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims abstract description 15
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 60
- 239000007787 solid Substances 0.000 claims description 46
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 34
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 24
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 16
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 8
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- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
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- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 4
- JCRRFJIVUPSNTA-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 JCRRFJIVUPSNTA-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- ZBMISJGHVWNWTE-UHFFFAOYSA-N 3-(4-aminophenoxy)aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(N)=C1 ZBMISJGHVWNWTE-UHFFFAOYSA-N 0.000 claims description 2
- DKKYOQYISDAQER-UHFFFAOYSA-N 3-[3-(3-aminophenoxy)phenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=C(OC=3C=C(N)C=CC=3)C=CC=2)=C1 DKKYOQYISDAQER-UHFFFAOYSA-N 0.000 claims description 2
- LDFYRFKAYFZVNH-UHFFFAOYSA-N 4-[4-[4-(4-aminophenoxy)phenoxy]phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC(C=C1)=CC=C1OC(C=C1)=CC=C1OC1=CC=C(N)C=C1 LDFYRFKAYFZVNH-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 238000007789 sealing Methods 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 12
- 238000010521 absorption reaction Methods 0.000 abstract description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 4
- 230000001070 adhesive effect Effects 0.000 abstract description 4
- 239000011889 copper foil Substances 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 2
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- 239000002994 raw material Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 36
- 238000002329 infrared spectrum Methods 0.000 description 22
- 229920001721 polyimide Polymers 0.000 description 18
- OPVHOFITDJSMOD-UHFFFAOYSA-N 4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C=1C=C2C(=O)OC(=O)C2=CC=1OC1=CC=CC2=C1C(=O)OC2=O OPVHOFITDJSMOD-UHFFFAOYSA-N 0.000 description 17
- 239000004642 Polyimide Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 239000011521 glass Substances 0.000 description 16
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- 235000019441 ethanol Nutrition 0.000 description 9
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- 229910021641 deionized water Inorganic materials 0.000 description 8
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- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 7
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- 101150059231 CPI1 gene Proteins 0.000 description 4
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- XROLBZOMVNMIFN-UHFFFAOYSA-N 1-(1-benzofuran-4-yl)propan-2-amine Chemical compound CC(N)CC1=CC=CC2=C1C=CO2 XROLBZOMVNMIFN-UHFFFAOYSA-N 0.000 description 2
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- WUPRYUDHUFLKFL-UHFFFAOYSA-N 4-[3-(4-aminophenoxy)phenoxy]aniline Chemical compound C1=CC(N)=CC=C1OC1=CC=CC(OC=2C=CC(N)=CC=2)=C1 WUPRYUDHUFLKFL-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
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- 125000001624 naphthyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- -1 phenyl ester Chemical class 0.000 description 1
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Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a high-frequency high-heat-resistance heat-sealable poly (aryl ester-imide) resin and a preparation method and application thereof, belonging to the field of materials. The poly (aryl ester-imide) resin provided by the invention is prepared from 4-aminophenyl 4-aminobenzoate, ether-containing aromatic diamine and 2, 3',4' -diphenyl ether tetracarboxylic dianhydride serving as raw materials through chemical imidization; the wideband dielectric property, the heat resistance and the heat sealing strength of the poly (aryl ester-imide) resin material can be regulated and controlled by controlling the proportion of 4-aminophenyl 4-aminobenzoate and ether-containing aromatic diamine; the poly (aryl ester-imide) resin material has the characteristics of high heat resistance, high heat sealing strength, low dielectric loss and low water absorption, can be used as an adhesive for preparing a three-layer flexible copper-clad plate between a copper foil and a film, and is applied to the high technical fields of aerospace, electronics, electricity, automobiles and the like.
Description
Technical Field
The invention relates to the field of materials, in particular to a high-frequency high-heat-resistance heat-sealable poly (aryl ester-imide) resin, and a preparation method and application thereof.
Background
The Liquid Crystal Polymer (LCP) film has excellent broadband high-frequency performance, low moisture absorption rate, chemical resistance and dimensional stability, can meet the manufacturing requirements of high-speed digital and high-frequency circuits, and is often applied to mobile interconnection equipment, vehicle-mounted radars and interconnection systems. The LCP material is composed of phenyl ester and naphthyl ester groups in a certain proportion, and has high symmetry of molecular structure; the para-aryl ester chain segment presents a fold-line rigid rod-shaped structure, and can play a role similar to a crank shaft in a molecular chain, so that a molecular main chain structure has better linear arrangement, and the molecular polarity is lower, and the dielectric constant and the dielectric loss factor are lower. However, the LCP film has lower surface free energy and poorer wettability with metal, and quality defects such as copper sheet bubbles, stripes and the like easily occur in the process of preparing the double-sided copper-clad plate by a high-temperature lamination process. For this reason, surface chemical treatment, plasma treatment, surface coating, and the like have been adopted to improve compatibility of the LCP surface with the adhered surface. However, these methods often cause damage to the bulk properties of the LCP material, or affect the reliability of the overall application of the material due to the low heat resistance of the coated adhesive. Thus, polyimide (PI) research with low dielectric loss, intrinsic heat sealing properties is attracting increasing attention.
The introduction of the aryl ester group into the PI molecular chain can reduce the dielectric loss and the water absorption of the material. The aryl ester group can shorten the chain distance of the molecular chains, increase the ordered stacking of the molecular chains and the dipole-dipole action among the molecular chains, inhibit the local deflection of the dipoles, be beneficial to reducing the dielectric loss factor and improving the high-frequency transmission performance (Kou C, et al ACS Applied Polymer Materials,2022,3 (1): 362-371). However, the aryl ester groups are more rigid and excessive incorporation results in a more brittle material.
The introduction of flexible and isomerised structures in PI molecular chains is two main approaches. The flexible structure can reduce the acting force in the PI molecule and between molecules and improve the movement capability of a molecular chain, thereby being beneficial to improving the PI hot-melt sealing performance. U.S. Pat. No. 5, 5298331A,1994 discloses a process for producing a polyester resin composition comprising an ether-containing dianhydride, 3',4' -diphenyl ether tetracarboxylic dianhydride (ODPA), 1, 4-bis (4-aminophenoxy) benzene (1, 4-APB), 1, 3-bis (4-aminophenoxy) benzene (1, 3, 4-APB) and the likeThe ether type aromatic diamine is introduced into a non-heat-sealing PI system to prepare heat-sealing PI with good heat-sealing strength. Commercial DuPont company
The KJ product is based on the above structure. The asymmetric, isomerised aromatic dianhydride distorted steric structure gives the polymer a higher free volume and thus more efficient thermoplastic of PI (Hasegawa, et al macromolecules 1999,32 (2): 387-396) to produce PI with good heat sealing properties. Japanese patent (JP 2004285103A) discloses a PI system containing an asymmetric ether-containing dianhydride 2, 3',4' -diphenylether tetracarboxylic dianhydride (a-ODPA) and 3 or more benzene rings in number and having good adhesive strength with low profile copper foil and the like. However, the introduction of excessive flexible structures generally causes great damage to the heat resistance of PI. For example, duPont Corp Ltd
KJ and glass transition temperature (T) g ) Only 220 ℃.
Disclosure of Invention
The invention aims to provide high-frequency high-heat-resistance heat-sealable poly (aryl ester-imide) resin, and a preparation method and application thereof.
The invention firstly provides poly (aryl ester-imide) resin, and the structural general formula of the poly (aryl ester-imide) resin is shown as formula I:
in the formula I, ar is selected from any one of the following groups:
m is an integer of 0 to 200 and is not 0, n is an integer of 0 to 200;
and when n is not 0, m: n=0:100 to 100:0; specifically, m: n=10:90, 20:80, 30:70, 40:60, 50:50 or 60:40.
In the formula I, m is preferably m is equal to n=40:60-60:40; specifically, m: n=40:60, 50:50, or 60:40;
m can be specifically, 16, 27, 37, 50, 51, 152 or 150-180;
n may be, in particular, 146, 111, 86, 76, 51 or 102;
when n is 0, m may specifically be 100.
The poly (aryl ester-imide) resin has an absolute number average molecular weight of 25000 to 150000g/mol.
Second, the present invention further provides a method for preparing the above poly (aryl ester-imide) resin, comprising the steps of:
mixing 4-aminophenyl 4-aminobenzoate, ether-containing aromatic diamine and 2, 3',4' -diphenyl ether tetracarboxylic dianhydride in a solvent for polymerization reaction, adding acetic anhydride and pyridine for chemical imidization reaction after the reaction is finished, and obtaining the poly (aryl ester-imide) resin with n being not 0 after the reaction is finished;
or mixing 4-aminophenyl 4-aminobenzoate and 2, 3',4' -diphenyl ether tetracarboxylic dianhydride in a solvent for polymerization reaction, adding acetic anhydride and pyridine for chemical imidization reaction after the reaction is finished, and obtaining the poly (aryl ester-imide) resin with n being 0 after the reaction is finished.
In the above preparation method, the ether-containing aromatic diamine is at least one selected from the group consisting of 4,4' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, and 4,4' -bis (4-aminophenoxy) diphenyl ether.
In the method for producing the poly (aryl ester-imide) resin in which n is not 0, the 4-aminophenyl 4-aminobenzoate accounts for 0 to 100% but is not 0 and 100%, preferably 40 to 60% of the total mole number of the 4-aminophenyl 4-aminobenzoate and the ether-containing aromatic diamine; more specifically 40%, 50% or 60%;
the ratio of the total feeding mole number of the 4-aminophenyl 4-aminobenzoate and the ether-containing aromatic diamine to the feeding mole number of the 2, 3',4' -diphenyl ether tetracarboxylic dianhydride is 0.97-1.00: 1.00, preferably 0.99 to 1.00:1.00; more specifically, can be 1.00:1.00;
the ratio of the total feeding mole number of the 4-aminophenyl 4-aminobenzoate and the ether-containing aromatic diamine to the feeding mole number of the acetic anhydride is 1.00:3.00 to 10.00, preferably 1.00:5.00;
the feeding mole ratio of the acetic anhydride to the pyridine is 1.00:1.00;
in the method for preparing the poly (aryl ester-imide) with n being 0, the ratio of the feeding mole number of the 4-aminophenyl 4-aminobenzoate to the feeding mole number of the 2, 3',4' -diphenyl ether tetracarboxylic dianhydride is 0.97-1.00: 1.00, preferably 0.99 to 1.00:1.00;
the feeding mole ratio of the 4-aminophenyl 4-aminobenzoate to the acetic anhydride is 1.00:3.00 to 10.00, preferably 1.00:5.00;
the feeding mole ratio of the acetic anhydride to the pyridine is 1.00:1.00.
in the preparation method, the solvent is at least one selected from N-methylpyrrolidone, m-cresol, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and gamma-butyrolactone;
the solvent is used in an amount such that the mass percentage of solids in the reaction system is 10% -30%, preferably 15% -20%; more specifically 18%;
the solid in the reaction system refers to 4-aminophenyl 4-aminobenzoate and/or ether-containing aromatic diamine and 2, 3',4' -diphenyl ether tetracarboxylic dianhydride.
In the above preparation method, in the polymerization step, the time is 12 to 30 hours, preferably 20 to 25 hours, more preferably 24 hours; the temperature is 0-35 ℃, preferably 20-25 ℃;
in the chemical imidization step, the time is 15 to 30 hours, preferably 20 to 25 hours, more preferably 24 hours; the temperatures are in each case from 0 to 35℃and preferably from 20 to 25 ℃.
In the preparation method, the step of mixing the reaction product with absolute ethyl alcohol for precipitation to obtain a filamentous solid is carried out after the chemical imidization reaction;
the above preparation method further comprises washing the filamentous solid with ethanol and drying.
The invention also provides a film prepared from the poly (aryl ester-imide) resin.
Specifically, the poly (aryl ester-imide) resin is prepared into a corresponding film according to a conventional film forming method.
The application of the poly (aryl ester-imide) resin or film in preparing the heat-sealing coating or heat-sealing film of the microwave circuit substrate also belongs to the protection scope of the invention.
Finally, the present invention also provides a microwave circuit substrate comprising the above poly (aryl ester-imide) resin or the film. The microwave circuit substrate can be used for constructing a microwave millimeter wave module and/or a flexible conformal antenna.
The poly (aryl ester-imide) resin provided by the invention is prepared from 4-aminophenyl 4-aminobenzoate, ether-containing aromatic diamine and 2, 3',4' -diphenyl ether tetracarboxylic dianhydride serving as raw materials through chemical imidization. The wideband dielectric property, the heat resistance and the heat sealing strength of the poly (aryl ester-imide) resin material can be regulated and controlled by controlling the proportion of 4-aminophenyl 4-aminobenzoate and ether-containing aromatic diamine; the poly (aryl ester-imide) resin material has the characteristics of high heat resistance, high heat sealing strength, low dielectric loss and low water absorption, can be used as an adhesive for preparing a three-layer flexible copper-clad plate between a copper foil and a film, and is applied to the high technical fields of aerospace, electronics, electricity, automobiles and the like.
Drawings
FIG. 1 is an infrared spectrum of a poly (arylene ester-imide) film prepared in examples 1-7.
FIG. 2 is a DSC chart of the poly (aryl ester-imide) film prepared in examples 1-7.
FIG. 3 is a thermal weight loss (TGA) curve of the poly (aryl ester-imide) films prepared in examples 1-7.
FIG. 4 is a DMA curve of the poly (aryl ester-imide) films prepared in examples 1-7.
FIG. 5 is a bar graph of glass transition temperature and heat seal strength of poly (aryl ester-imide) films prepared in examples 1-7.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof.
The experimental methods in the following examples are conventional methods unless otherwise specified.
The quantitative tests in the following examples were all set up in triplicate and the results averaged.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
The room temperature was 20 to 25℃in the examples described below.
The performance test methods for the polymer films of the following examples are as follows:
1. the molecular weight of the resulting polymer was determined by Laser Light Scattering (LLS) GPC and was the absolute number average molecular weight.
2. Calorimetric Differential Scanning (DSC): the prepared poly (arylene ester-imide) film was tested on a thermal differential scanner (TA company, Q100 series, usa) at a rate of temperature increase: 10 ℃/min.
3. Dynamic thermo-mechanical analysis (DMA): the prepared poly (aryl ester-imide) film was tested with a dynamic thermo-mechanical analyzer (TA company, Q100 series, usa) at a rate of temperature increase: 5 ℃/min, frequency 1Hz.
4. Thermogravimetric analysis (TGA): the prepared poly (aryl ester-imide) film was tested with a thermogravimetric analyzer (TA company, Q50 series, usa) at a rate of temperature increase: 20 ℃/min, the test atmosphere is nitrogen.
5. Water absorption test: the prepared poly (arylene ester-imide) film was placed in water for 24 hours and the mass change before and after immersion was weighed using a precision balance.
6. Dielectric property test: the prepared poly (aryl ester-imide) film was placed in a vector network analyzer according to IPC-TM-650 2.5.5.5c:1998 the samples were tested for dielectric constant (Dk) and dielectric dissipation factor (Df) at 10GHz frequency at room temperature.
7. The heat sealing performance evaluation method comprises the following steps: the heat-sealing was performed on an L0001 laboratory heat-sealing machine from IDM instruments, australia, with a heat-sealing pressure of 0.3MPa and a heat-sealing temperature set at 20-50deg.C above the starting point of the DMA curve rubber platform. The heat-seal performance test was performed according to the national light industry standard QB/T2358-98.
Example 1, the molar ratio of the feed is 10: preparation of poly (aryl ester-imide) (CPI-1) resins from APAB (4-aminophenyl 4-aminobenzoate) and 4,4'-ODA (4, 4' -diaminodiphenyl ether) with a-ODPA (2, 3',4' -diphenylether tetracarboxylic dianhydride)
1.0271g (4.5 mmol) of APAB and 8.1097g (40.5 mmol) of 4,4' -ODA were added to a 250mL three-necked flask equipped with a nitrogen inlet at room temperature, and 50g of N-methylpyrrolidone (NMP) were added. After it was completely dissolved, 13.9595g (45 mmol) of a-ODPA was added, and 53g of NMP was added to adjust the solid content (weight fraction) to 18%. After polymerization was carried out at room temperature with stirring for 24 hours, 22.97g (225 mmol) of acetic anhydride and 17.80g (225 mmol) of pyridine were added, and the reaction was continued at room temperature with stirring for chemical imidization for 24 hours to obtain a yellow viscous solution. The solution was poured into 1000mL of absolute ethanol to precipitate, and a yellow filamentous solid was obtained. The solid was washed three times with ethanol and dried under vacuum at 140℃to finally give CPI-1 resin.
4G of dry filamentous CPI-1 resin was dissolved in 18G of NMP, and after complete dissolution of the solid, the mixture was filtered through a G1 sand funnel to give a poly (aryl ester-imide) resin solution having a solids content of 18%. The solution was coated on a clean glass plate and placed in an oven and heated at a heating rate of 2 c/min, with a program of 80 c/2 hours, 120 c/1 hour, 160 c/1 hour, 180 c/1 hour, 240 c/2 hours, 280 c/30 min. After natural cooling, the glass plate was placed in deionized water and peeled off to give a self-supporting yellow CPI-1 film.
The structural formula of the poly (aryl ester-imide) resin is shown as follows, wherein m: n=10:90;
infrared spectrum (cm) -1 )：1779，1725，1606，1502，1381，1243，746；
The infrared spectrum is shown in figure 1;
molecular weight (g/mol): 75530, corresponding to m being 16, n being 146;
the DSC curve is shown in figure 2;
the TGA curve is shown in fig. 3;
the DMA curves are shown in fig. 4;
dielectric constant (Dk), dielectric dissipation factor (Df), thermal decomposition temperature, glass transition temperature (T) g ) And heat seal strengths are shown in table 1;
from the infrared spectrum data, the structure of the compound was correct, as indicated above.
Example 2, the molar ratio of the feed is 20: preparation of Poly (aryl ester-imide) (CPI-2) resin from APAB and 4,4' -ODA of 80 and a-ODPA
2.0543g (9.0 mmol) of APAB and 7.2086g (36.0 mmol) of 4,4' -ODA were added to a 250mL three-necked flask equipped with a nitrogen inlet at room temperature, and 50g of N-methylpyrrolidone (NMP) were added. After it was completely dissolved, 13.9595g (45 mmol) of a-ODPA was added, and 51g of NMP was added to adjust the solid content (weight fraction) to 18%. After polymerization was carried out at room temperature with stirring for 24 hours, 22.97g (225 mmol) of acetic anhydride and 17.80g (225 mmol) of pyridine were added, and the reaction was continued at room temperature with stirring for chemical imidization for 24 hours to obtain a yellow viscous solution. The solution was poured into 1000mL of absolute ethanol to precipitate, and a yellow filamentous solid was obtained. The solid was washed three times with ethanol and dried under vacuum at 140℃to finally give CPI-2 resin.
4G of dry filamentous CPI-2 resin was dissolved in 18G of NMP, and after complete dissolution of the solid, the mixture was filtered through a G1 sand funnel to give a poly (aryl ester-imide) resin solution having a solids content of 18%. The solution was coated on a clean glass plate and placed in an oven and heated at a heating rate of 2 c/min, with a program of 80 c/2 hours, 120 c/1 hour, 160 c/1 hour, 180 c/1 hour, 240 c/2 hours, 280 c/30 min. After natural cooling, the glass plate was placed in deionized water and peeled off to give a self-supporting yellow CPI-2 film.
The structural formula of the poly (aryl ester-imide) resin is shown as follows, wherein m: n=20:80;
infrared spectrum (cm) -1 )：1778，1724，1606，1505，1379，1243，746；
The infrared spectrum is shown in figure 1;
molecular weight (g/mol): 63440, corresponding to m being 27 and n being 111;
the DSC curve is shown in figure 2;
the TGA curve is shown in fig. 3;
the DMA curves are shown in fig. 4;
dielectric constant (Dk), dielectric dissipation factor (Df), thermal decomposition temperature, glass transition temperature (T) g ) And heat seal strengths are shown in table 1;
from the infrared spectrum data, the structure of the compound was correct, as indicated above.
Example 3, feed mole ratio of 30:70 APAB and 4,4' -ODA with a-ODPA preparation of Poly (aryl ester-imide) (CPI-3) resin of formula I
3.0814g (13.5 mmol) of APAB and 6.3076g (31.5 mmol) of 4,4' -ODA were added to a 250mL three-necked flask equipped with a nitrogen inlet at room temperature, and 50g of N-methylpyrrolidone (NMP) were added. After it was completely dissolved, 13.9595g (45 mmol) of a-ODPA was added, and 56g of NMP was added to adjust the solid content (weight fraction) to 18%. After polymerization was carried out at room temperature with stirring for 24 hours, 22.97g (225 mmol) of acetic anhydride and 17.80g (225 mmol) of pyridine were added, and the reaction was continued at room temperature with stirring for chemical imidization for 24 hours to obtain a yellow viscous solution. The solution was poured into 1000mL of absolute ethanol to precipitate, and a yellow filamentous solid was obtained. The solid was washed three times with ethanol and dried under vacuum at 140℃to finally give CPI-3 resin.
4G of dry filamentous CPI-3 resin was dissolved in 18G of NMP, and after complete dissolution of the solid, the mixture was filtered through a G1 sand funnel to give a poly (aryl ester-imide) resin solution having a solids content of 18%. The solution was coated on a clean glass plate and placed in an oven and heated at a heating rate of 2 c/min, with a program of 80 c/2 hours, 120 c/1 hour, 160 c/1 hour, 180 c/1 hour, 240 c/2 hours, 280 c/30 min. After natural cooling, the glass plate was placed in deionized water and peeled off to give a self-supporting yellow CPI-3 film.
The structural formula of the poly (aryl ester-imide) resin is shown as follows, wherein m: n=30:70;
infrared spectrum (cm) -1 )：1778，1724，1606，1506，1378，1243，746；
The infrared spectrum is shown in figure 1;
molecular weight (g/mol): 55060, corresponding to m being 37, n being 86;
the DSC curve is shown in figure 2;
the TGA curve is shown in fig. 3;
the DMA curves are shown in fig. 4;
dielectric constant (Dk), dielectric dissipation factor (Df), thermal decomposition temperature, glass transition temperature (T) g ) And heat seal strengths are shown in table 1;
from the infrared spectrum data, the structure of the compound was correct, as indicated above.
Example 4, feed mole ratio 40:60 APAB and 4,4' -ODA with a-ODPA preparation of Poly (aryl ester-imide) (CPI-4) resin of formula I
4.3824g (19.2 mmol) of APAB and 5.7669g (28.8 mmol) of 4,4' -ODA were added to a 250mL three-necked flask equipped with a nitrogen inlet at room temperature, and 50g of N-methylpyrrolidone (NMP) were added. After it was completely dissolved, 14.8901g (48 mmol) of a-ODPA was added, and 64g of NMP was added to adjust the solid content (weight fraction) to 18%. After polymerization was carried out at room temperature with stirring for 24 hours, 24.50g (240 mmol) of acetic anhydride and 18.98 (240 mmol) of pyridine were added, and the reaction was continued at room temperature with stirring for chemical imidization for 24 hours to obtain a yellow viscous solution. The solution was poured into 1000mL of absolute ethanol to precipitate, and a yellow filamentous solid was obtained. The solid was washed three times with ethanol and dried under vacuum at 140℃to finally give CPI-4 resin.
4G of dry filamentous CPI-4 resin was dissolved in 18G of NMP, and after complete dissolution of the solid, the mixture was filtered through a G1 sand funnel to give a poly (aryl ester-imide) resin solution having a solids content of 18%. The solution was coated on a clean glass plate and placed in an oven and heated at a heating rate of 2 c/min, with a program of 80 c/2 hours, 120 c/1 hour, 160 c/1 hour, 180 c/1 hour, 240 c/2 hours, 280 c/30 min. After natural cooling, the glass plate was placed in deionized water and peeled off to give a self-supporting yellow CPI-4 film.
The structural formula of the poly (aryl ester-imide) resin is shown as follows, wherein m: n=40:60;
infrared spectrum (cm) -1 )：1778，1724，1607，1507，1375，1243，746；
The infrared spectrum is shown in figure 1;
molecular weight (g/mol): 55510, corresponding to m being 50 and n being 76;
the DSC curve is shown in figure 2;
the TGA curve is shown in fig. 3;
the DMA curves are shown in fig. 4;
dielectric constant (Dk), dielectric dissipation factor (Df), thermal decomposition temperature, glass transition temperature (T) g ) And heat seal strengths are shown in table 1;
from the infrared spectrum data, the structure of the compound was correct, as indicated above.
Example 5, feed mole ratio 50:50 APAB and 4,4' -ODA with a-ODPA preparation of Poly (aryl ester-imide) (CPI-5) resin of formula I
5.4780g (24.0 mmol) of APAB and 4.8058g (24.0 mmol) of 4,4' -ODA were added to a 250mL three-necked flask equipped with a nitrogen inlet at room temperature, and 50g of N-methylpyrrolidone (NMP) were added. After it was completely dissolved, 14.8901g (48 mmol) of a-ODPA was added, and 65g of NMP was added to adjust the solid content (weight fraction) to 18%. After polymerization was carried out at room temperature with stirring for 24 hours, 24.50g (240 mmol) of acetic anhydride and 18.98 (240 mmol) of pyridine were added, and the reaction was continued at room temperature with stirring for chemical imidization for 24 hours to obtain a yellow viscous solution. The solution was poured into 1000mL of absolute ethanol to precipitate, and a yellow filamentous solid was obtained. The solid was washed three times with ethanol and dried under vacuum at 140℃to finally give CPI-5 resin.
4G of dry filamentous CPI-5 resin was dissolved in 18G of NMP, and after complete dissolution of the solid, the mixture was filtered through a G1 sand funnel to give a poly (aryl ester-imide) resin solution having a solids content of 18%. The solution was coated on a clean glass plate and placed in an oven and heated at a heating rate of 2 c/min, with a program of 80 c/2 hours, 120 c/1 hour, 160 c/1 hour, 180 c/1 hour, 240 c/2 hours, 280 c/30 min. After natural cooling, the glass plate was placed in deionized water and peeled off to give a self-supporting yellow CPI-5 film.
The structural formula of the poly (aryl ester-imide) resin is shown as follows, wherein m: n=50:50;
infrared spectrum (cm) -1 )：1778，1725，1607，1508，1372，1243，746；
The infrared spectrum is shown in figure 1;
molecular weight (g/mol): 43760, corresponding to m being 51 and n being 51;
the DSC curve is shown in figure 2;
the TGA curve is shown in fig. 3;
the DMA curves are shown in fig. 4;
dielectric constant (Dk), dielectric dissipation factor (Df), thermal decomposition temperature, glass transition temperature (T) g ) And heat seal strengths are shown in table 1;
from the infrared spectrum data, the structure of the compound was correct, as indicated above.
Example 6, the molar ratio of the feed is 60:40 APAB and 4,4' -ODA with a-ODPA preparation of Poly (aryl ester-imide) (CPI-6) resin of formula I
6.5736g (28.8 mmol) of APAB and 3.8446g (19.2 mmol) of 4,4' -ODA were added to a 250mL three-necked flask equipped with a nitrogen inlet at room temperature, and 50g of N-methylpyrrolidone (NMP) were added. After it was completely dissolved, 14.8901g (48 mmol) of a-ODPA was added, and 63g of NMP was added to adjust the solid content (weight fraction) to 18%. After polymerization was carried out at room temperature with stirring for 24 hours, 24.50g (240 mmol) of acetic anhydride and 18.98 (240 mmol) of pyridine were added, and the reaction was continued at room temperature with stirring for chemical imidization for 24 hours to obtain a yellow viscous solution. The solution was poured into 1000mL of absolute ethanol to precipitate, and a yellow filamentous solid was obtained. The solid was washed three times with ethanol and dried under vacuum at 140℃to finally give CPI-6 resin.
4G of dry filamentous CPI-6 resin was dissolved in 18G of NMP, and after complete dissolution of the solid, the mixture was filtered through a G1 sand funnel to give a poly (aryl ester-imide) resin solution having a solids content of 18%. The solution was coated on a clean glass plate and placed in an oven and heated at a heating rate of 2 c/min, with a program of 80 c/2 hours, 120 c/1 hour, 160 c/1 hour, 180 c/1 hour, 240 c/2 hours, 280 c/30 min. After natural cooling, the glass plate was placed in deionized water and peeled off to give a self-supporting yellow CPI-6 film.
The structural formula of the poly (aryl ester-imide) resin is shown as follows, wherein m: n=60:40;
infrared spectrum (cm) -1 )：1778，1725，1607，1508，1369，12444，746；
The infrared spectrum is shown in figure 1;
molecular weight (g/mol): 106300, corresponding to m being 152 and n being 102;
the DSC curve is shown in figure 2;
the TGA curve is shown in fig. 3;
the DMA curves are shown in fig. 4;
dielectric constant (Dk), dielectric dissipation factor (Df), thermal decomposition temperature, glass transition temperature (T) g ) And heat seal strengths are shown in table 1;
from the infrared spectrum data, the structure of the compound was correct, as indicated above.
Example 7, molar ratio of feed was 100: APAB and 4,4-' ODA with a-ODPA preparation of Poly (aryl ester-imide) (CPI-7) resin of formula II
10.2713g (45.0 mmol) of APAB and 50g of N-methylpyrrolidone (NMP) are added at room temperature to a 250mL three-necked flask equipped with a nitrogen inlet. After it was completely dissolved, 14.0990g (45.45 mmol) of a-ODPA was added, and 61g of NMP was added to adjust the solid content (weight fraction) to 18%. After polymerization was carried out at room temperature with stirring for 24 hours, 25.52g (250 mmol) of acetic anhydride and 19.78 (250 mmol) of pyridine were added, and the reaction was continued at room temperature with stirring for chemical imidization for 24 hours to obtain a yellow viscous solution. The solution was poured into 1000mL of absolute ethanol to precipitate, and a yellow filamentous solid was obtained. The solid was washed three times with ethanol and dried under vacuum at 140℃to finally give CPI-7 resin.
4G of dry filamentous CPI-7 resin is taken and dissolved in 18G of NMP, and after the solid is completely dissolved, the mixture is filtered by a G1 sand core funnel to obtain polyimide solution with the solid content of 18 percent. The solution was coated on a clean glass plate and placed in an oven and heated at a heating rate of 2 c/min, with a program of 80 c/2 hours, 120 c/1 hour, 160 c/1 hour, 180 c/1 hour, 240 c/2 hours, 280 c/30 min. After natural cooling, the glass plate was placed in deionized water and peeled off to give a self-supporting yellow CPI-7 film.
The structural formula of the poly (aryl ester-imide) resin is shown below, wherein m=165;
infrared spectrum (cm) -1 )：1778，1728，1608，1517，1370，1270，744；
The infrared spectrum is shown in figure 1;
molecular weight (g/mol): 115000;
the DSC curve is shown in figure 2;
the TGA curve is shown in fig. 3;
the DMA curves are shown in fig. 4;
dielectric constant (Dk), dielectric dissipation factor (Df), thermal decomposition temperature, glass transition temperature (T) g ) And heat seal strengths are shown in table 1;
as shown by infrared spectrum data, the compound has correct structure and is shown as a formula II.
Comparative example 1 preparation of polyimide from a-ODPA and 4,4' -ODA
Into a 250mL three-necked flask equipped with a nitrogen inlet, 10.012g (50 mmol) of 4,4' -ODA and 50g of N-methylpyrrolidone (NMP) were added at room temperature. After it was completely dissolved, 15.5105g (50 mmol) of a-ODPA was added, and 68g of NMP was added to adjust the solid content (weight fraction) to 18%. After stirring at room temperature for 24 hours, 25.52g (250 mmol) of acetic anhydride and 19.78 (250 mmol) of pyridine were added, and stirring was continued at room temperature for 24 hours to give a yellow viscous solution. The solution was poured into 1000mL of absolute ethanol to precipitate, and a yellow filamentous solid was obtained. The solid was washed three times with ethanol and dried under vacuum at 140℃to finally give CPI-10 resin.
4G of dry filamentous CPI-10 resin is taken and dissolved in 18G of NMP, and after the solid is completely dissolved, the mixture is filtered by a G1 sand core funnel to obtain polyimide solution with the solid content of 18 percent. The solution was coated on a clean glass plate and placed in an oven and heated at a heating rate of 2 c/min, with a program of 80 c/2 hours, 120 c/1 hour, 160 c/1 hour, 180 c/1 hour, 240 c/2 hours, 280 c/30 min. After natural cooling, the glass plate is placed in deionized water, and the self-supporting yellow film is obtained after stripping.
The polyimide has the structural formula shown below, wherein n=180:
molecular weight (g/mol): 138200;
the film has dielectric constant (Dk), dielectric dissipation factor (Df), thermal decomposition temperature, glass transition temperature (T) g ) And heat seal strength are shown in table 1.
The performance data for the poly (aryl ester-imide) films of examples 1-7 are summarized in Table 1 for ease of visualization, with the glass transition temperatures and heat seal strengths plotted in bar chart form in FIG. 5.
As can be seen from comparison with comparative example 1 (the diamine component does not contain APAB), the incorporation of APAB component into diamine in the present invention effectively improves the glass transition temperature and dielectric properties of the polyimide film. Meanwhile, when the molar content of APAB in diamine is between 40% and 60%, the glass transition temperature of PI reaches above 300 ℃, dielectric loss is reduced to 0.0026, water absorption is reduced to 0.4%, and meanwhile, the poly (aryl ester-imide) film has good heat sealing strength.
TABLE 1 comprehensive Properties of Poly (aryl ester-imide) film
Claims (10)
1. A poly (aryl ester-imide) resin has a structural general formula shown in formula I:
in the formula I, ar is selected from any one of the following groups:
m is an integer of 0 to 200 and is not 0, n is an integer of 0 to 200;
and when n is not 0, m: n=0:100 to 100:0.
2. The poly (aryl ester-imide) resin of claim 1 wherein: in the formula I, m is n=40:60-60:40.
3. The method for producing a poly (aryl ester-imide) resin according to claim 1 or 2, comprising the steps of:
mixing 4-aminophenyl 4-aminobenzoate, ether-containing aromatic diamine and 2, 3',4' -diphenyl ether tetracarboxylic dianhydride in a solvent for polymerization reaction, adding acetic anhydride and pyridine for chemical imidization reaction after the reaction is finished, and obtaining the poly (aryl ester-imide) resin with n being not 0 after the reaction is finished;
or mixing 4-aminophenyl 4-aminobenzoate and 2, 3',4' -diphenyl ether tetracarboxylic dianhydride in a solvent for polymerization reaction, adding acetic anhydride and pyridine for chemical imidization reaction after the reaction is finished, and obtaining the poly (aryl ester-imide) resin with n being 0 after the reaction is finished.
4. A method of preparation according to claim 3, characterized in that: the ether-containing aromatic diamine is at least one selected from the group consisting of 4,4' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, and 4,4' -bis (4-aminophenoxy) diphenyl ether.
5. The method according to claim 3 or 4, wherein: in the method for producing the poly (aryl ester-imide) resin in which n is not 0, the 4-aminophenyl 4-aminobenzoate accounts for 0 to 100% but is not 0 and 100%, preferably 40 to 60% of the total mole number of the 4-aminophenyl 4-aminobenzoate and the ether-containing aromatic diamine;
the ratio of the total feeding mole number of the 4-aminophenyl 4-aminobenzoate and the ether-containing aromatic diamine to the feeding mole number of the 2, 3',4' -diphenyl ether tetracarboxylic dianhydride is 0.97-1.00: 1.00, preferably 0.99 to 1.00:1.00;
the ratio of the total feeding mole number of the 4-aminophenyl 4-aminobenzoate and the ether-containing aromatic diamine to the feeding mole number of the acetic anhydride is 1.00:3.00 to 10.00, preferably 1.00:5.00;
the feeding mole ratio of the acetic anhydride to the pyridine is 1.00:1.00;
in the method for preparing the poly (aryl ester-imide) with n being 0, the ratio of the feeding mole number of the 4-aminophenyl 4-aminobenzoate to the feeding mole number of the 2, 3',4' -diphenyl ether tetracarboxylic dianhydride is 0.97-1.00: 1.00, preferably 0.99 to 1.00:1.00;
the feeding mole ratio of the 4-aminophenyl 4-aminobenzoate to the acetic anhydride is 1.00:3.00 to 10.00, preferably 1.00:5.00;
the feeding mole ratio of the acetic anhydride to the pyridine is 1.00:1.00.
6. the method of any one of claims 3-5, wherein: the solvent is at least one selected from N-methylpyrrolidone, m-cresol, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and gamma-butyrolactone;
the solvent is used in an amount such that the mass percentage of solids in the reaction system is 10% -30%, preferably 15% -20%;
the solid in the reaction system refers to 4-aminophenyl 4-aminobenzoate and/or ether-containing aromatic diamine and 2, 3',4' -diphenyl ether tetracarboxylic dianhydride.
7. The production method according to any one of claims 3 to 6, characterized in that: in the polymerization step, the time is 12 to 30 hours, preferably 20 to 25 hours, more preferably 24 hours; the temperature is 0-35 ℃, preferably 20-25 ℃;
in the chemical imidization step, the time is 15 to 30 hours, preferably 20 to 25 hours, more preferably 24 hours; the temperatures are in each case from 0 to 35℃and preferably from 20 to 25 ℃.
8. A film prepared from the poly (aryl ester-imide) resin of claim 1 or 2.
9. Use of the poly (aryl ester-imide) resin of claim 1 or 2 or the film of claim 8 in the preparation of a heat sealable coating or film for microwave circuit substrates;
a microwave circuit substrate comprising the poly (aryl ester-imide) resin of claim 1 or 2 or the film of claim 8.
10. The use or microwave circuit substrate according to claim 9, wherein: the microwave circuit substrate is used for constructing a microwave millimeter wave module and/or a flexible conformal antenna.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5298331A (en) * | 1990-08-27 | 1994-03-29 | E. I. Du Pont De Nemours And Company | Flexible multi-layer polyimide film laminates and preparation thereof |
| CN105131284A (en) * | 2015-07-16 | 2015-12-09 | 中国科学院化学研究所 | High-heat-resistant thermal-sealable polyimide thin film, preparation method and application thereof |
| CN105175725A (en) * | 2015-11-03 | 2015-12-23 | 中国科学院化学研究所 | Preparation method of polyimide film, and polyimide film and application thereof |
| CN107250277A (en) * | 2015-02-10 | 2017-10-13 | 日产化学工业株式会社 | Peel ply formation composition |
| CN109563341A (en) * | 2016-08-03 | 2019-04-02 | 日产化学株式会社 | Peeling layer formation composition for transparent resin substrate |
| CN110218315A (en) * | 2018-03-01 | 2019-09-10 | 中天电子材料有限公司 | The preparation method and substrate of Kapton |
| CN113563585A (en) * | 2021-07-29 | 2021-10-29 | 上海八亿时空先进材料有限公司 | Polyimide and application thereof in metal laminated plate |
-
2022
- 2022-12-29 CN CN202211702396.5A patent/CN116003794A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5298331A (en) * | 1990-08-27 | 1994-03-29 | E. I. Du Pont De Nemours And Company | Flexible multi-layer polyimide film laminates and preparation thereof |
| CN107250277A (en) * | 2015-02-10 | 2017-10-13 | 日产化学工业株式会社 | Peel ply formation composition |
| CN105131284A (en) * | 2015-07-16 | 2015-12-09 | 中国科学院化学研究所 | High-heat-resistant thermal-sealable polyimide thin film, preparation method and application thereof |
| CN105175725A (en) * | 2015-11-03 | 2015-12-23 | 中国科学院化学研究所 | Preparation method of polyimide film, and polyimide film and application thereof |
| CN109563341A (en) * | 2016-08-03 | 2019-04-02 | 日产化学株式会社 | Peeling layer formation composition for transparent resin substrate |
| CN110218315A (en) * | 2018-03-01 | 2019-09-10 | 中天电子材料有限公司 | The preparation method and substrate of Kapton |
| CN112920602A (en) * | 2018-03-01 | 2021-06-08 | 中天电子材料有限公司 | High-modulus low-thermal-expansion-coefficient polyimide film and preparation method thereof |
| CN113563585A (en) * | 2021-07-29 | 2021-10-29 | 上海八亿时空先进材料有限公司 | Polyimide and application thereof in metal laminated plate |
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