CN113845674B - Polyimide film with low expansion coefficient and preparation method thereof - Google Patents
Polyimide film with low expansion coefficient and preparation method thereof Download PDFInfo
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- CN113845674B CN113845674B CN202111066583.4A CN202111066583A CN113845674B CN 113845674 B CN113845674 B CN 113845674B CN 202111066583 A CN202111066583 A CN 202111066583A CN 113845674 B CN113845674 B CN 113845674B
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 128
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000945 filler Substances 0.000 claims abstract description 78
- 239000004642 Polyimide Substances 0.000 claims abstract description 72
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 40
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims description 51
- 239000002904 solvent Substances 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 24
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 22
- 150000008064 anhydrides Chemical class 0.000 claims description 20
- 150000004985 diamines Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000002798 polar solvent Substances 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 238000010345 tape casting Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 4
- 238000004100 electronic packaging Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 150000003949 imides Chemical class 0.000 abstract 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical group FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- 239000011159 matrix material Substances 0.000 description 11
- 238000001000 micrograph Methods 0.000 description 10
- 239000004952 Polyamide Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 229920002647 polyamide Polymers 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 230000009477 glass transition Effects 0.000 description 6
- 239000002121 nanofiber Substances 0.000 description 6
- 230000000930 thermomechanical effect Effects 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 4
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 3
- 229940008309 acetone / ethanol Drugs 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- SXGMVGOVILIERA-UHFFFAOYSA-N (2R,3S)-2,3-diaminobutanoic acid Natural products CC(N)C(N)C(O)=O SXGMVGOVILIERA-UHFFFAOYSA-N 0.000 description 2
- -1 1,4,5, 8-naphthalene tetracarboxylic anhydride Chemical class 0.000 description 2
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- WFRXSXUDWCVSPI-UHFFFAOYSA-N 3h-benzimidazol-5-amine Chemical compound NC1=CC=C2NC=NC2=C1 WFRXSXUDWCVSPI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- BBRLKRNNIMVXOD-UHFFFAOYSA-N bis[4-(3-aminophenoxy)phenyl]methanone Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)C(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 BBRLKRNNIMVXOD-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 229920006259 thermoplastic polyimide Polymers 0.000 description 1
- 229920006352 transparent thermoplastic Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the technical field of electronic packaging, and particularly relates to a polyimide film with a low expansion coefficient and a preparation method thereof. The technical scheme of the invention is that (1) polyimide micro-nano filler with higher molecular chain rigidity and better interface compatibility is prepared by a hydrothermal method; (2) Then adding the dispersed polyimide micro-nano filler into a second part of polyamic acid precursor solution; (3) Finally, the polyimide film modified by the imide micro-nano filler is obtained through the steps of high-temperature cyclization and the like. The invention can reduce the thermal expansion coefficient of the film on the premise of ensuring the excellent heat resistance and mechanical property of the polyimide film.
Description
Technical Field
The invention belongs to the technical field of electronic packaging, and particularly relates to a polyimide film with a low expansion coefficient and a preparation method thereof.
Background
Polyimide material has excellent heat stability, mechanical performance and insulating performance, and is suitable for electronic package, large scale integrated circuit manufacture and substrate material selection. However, the precision electronic device may face continuous temperature change during the use process, which requires that the packaging substrate material and the heat conducting layer material (copper foil, etc.) have a thermal linear expansion Coefficient (CTE) matched, so as to avoid interlayer peeling, cracking, warping, curling, etc. from directly affecting the use performance of the device. The CTE of the conventional polyimide film is: 40-65 ppm/K, the CTE of the copper foil is: 16-17 ppm/K. Therefore, it is one of the important points of research to reduce the coefficient of thermal linear expansion of polyimide films while maintaining the high modulus, high heat resistance, and excellent mechanical properties of the materials.
The incorporation of specific rigid inorganic particles into polyimide films is a viable way to reduce the thermal linear expansion coefficient of polyimide films, but this way tends to be accompanied by a decrease in the mechanical and dielectric properties of polyimide films due to the problem of compatibility between the inorganic filler and polyimide. The addition of organic nanofillers to polyimide films is beneficial to solving the problem of compatibility between the fillers and the matrix. In addition, literature (Zhao Yichun, liu Feiyan, sun Zhiteng, et al, report on the preparation of transparent low expansion coefficient polyimide [ J ]. Composite materials by homogeneous nanofiber reinforcement, 2021:1-8.) reports that the method of compounding a relatively stiff nano PI fiber with a colorless transparent thermoplastic fluorine-containing polyimide, due to the introduction of PI nanofibers having a relatively small CTE, the continuous fiber network skeleton can effectively inhibit the dimensional deformation of the material when the composite material is expanded by heating, so that the CTE of the prepared composite material is reduced from 47ppm/K to 27ppm/K, and the modulus and tensile strength of the film are also improved, but as can be seen from SEM pictures thereof, the distribution of nanofibers in the thickness direction of the film prepared by the method is not uniform. Similarly, chinese patent document CN109593216a discloses a method for preparing polyimide films with low expansion coefficient of polyimide nanofibers homogeneous reinforcement, which pours thermoplastic polyimide onto polyimide nanofiber network films to reduce the expansion coefficient, but the thickness of nanofiber network limits the thickness of the finally prepared polyimide film and uniformity of the film.
In order to reduce the coefficient of thermal linear expansion of polyimide films, there is also a method of improving the rigidity of molecular chains from the standpoint of molecular structure design. However, due to the difference in polymerization activity of the high-rigidity monomer, it is difficult to polymerize to form a polymer solution with high molecular weight and high viscosity, or the production process is severe in condition and high in cost, and is not suitable for large-scale industrial production, and it is also difficult to produce polyimide film with excellent comprehensive properties.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a polyimide film with a low expansion coefficient and a preparation method thereof. The object of the present invention is to obtain a polyimide film having a low coefficient of thermal linear expansion, excellent in mechanical properties, and not limited in uniformity and thickness, which is suitable for industrial production.
The technical scheme provided by the invention is that polyimide micro-nano filler prepared by a hydrothermal method is introduced into a polyamic acid precursor solution, and then a composite polyimide film which is homogeneously modified by the polyimide micro-nano filler is obtained by a thermal cyclization process.
Specifically, the polyimide film provided by the invention is prepared by the following method:
(1) Adding a first part of diamine monomer and a first part of anhydride monomer into a first aprotic polar solvent, and reacting for 6-20 hours at a low temperature (-5-60 ℃) to obtain a first part of polyamic acid solution;
(2) Transferring the first part of polyamic acid solution into a hydrothermal kettle, then reacting for a period of time (0.5-36 hours) at a high temperature (180-250 ℃), naturally cooling, and filtering, washing and drying the reaction solution to obtain the micro-nano polyimide filler;
(3) Adding a second part of diamine monomer and a second part of anhydride monomer into a second aprotic polar solvent, and reacting for 8-20 hours at a low temperature (-5-120 ℃) to obtain a second part of polyamic acid solution;
(4) Dispersing polyimide filler in a second aprotic polar solvent, adding the second aprotic polar solvent into a second part of polyamic acid solution after ultrasonic treatment (1-30 min), and stirring for 10-300 min to obtain polyimide filler modified polyamic acid solution;
(5) And (3) under the protection of nitrogen, carrying out tape casting film forming, drying and high-temperature cyclization on the polyimide filler modified polyamic acid solution in the step (4) to obtain the polyimide film.
The first part of diamine monomer and the first part of anhydride monomer are raw materials for preparing polyimide filler, and both the first part of diamine monomer and the first part of anhydride monomer contain a ring-containing framework, wherein the ring-containing framework has a rigid aromatic ring structure. Further, the ring-containing framework has a ring structure therein; or have multiple ring structures, and the ring structures are connected through parallel ring connection, interlink connection or through one non-ring-forming atom. In the first part of diamine monomer, amino is directly connected with a ring structure in a ring-containing framework; in the first partial anhydride monomer, the anhydride is directly attached to the ring structure in the ring-containing backbone.
Wherein, the size of the prepared polyimide filler particles is in the range of 0.5-5 mu m, and the preferable microscopic morphology of the polyimide filler particles is flower-ball-shaped particles, round single-chip and multi-chip laminated particles.
Further, the first portion of diamine monomer is preferably one or more of the following structures:
the first partial anhydride monomer is preferably one or more of the following structures:
the main film forming portion of the polyimide film (i.e., the polyimide film bulk) is prepared by reacting a second portion of diamine monomer, preferably one or more of the following structures, with a second portion of anhydride monomer:
the second partial anhydride monomer is preferably one or more of the following structures:
in the step (1), the first aprotic polar solvent is one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone; the solid content of polymerization is 0.5-10wt%.
In the step (2), the volume of the first part of the polyamic acid solution is 1/4 to 2/3 of the volume of the hydrothermal kettle; the washing solvent is one or more of deionized water, ethanol, methanol, acetone, tetrahydrofuran, diethyl ether and ethyl acetate; washing for 3-10 times; the drying conditions are as follows: drying in a blast oven at 50-150 deg.c for 3-10 hr.
In the step (3), the second aprotic polar solvent is one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, m-cresol, butyrolactone and tetrahydrofuran; the solid content of polymerization is 10wt% to 50wt%.
In the step (4), the polyimide filler is added in an amount of 0.1 to 50 percent of the mass of the polymer; the polyimide filler has a solids content of 5wt% to 50wt% in the second aprotic polar solvent.
In the step (5), the drying and high-temperature cyclization adopts a stage heating mode under the nitrogen atmosphere, and the cyclization temperature is 250-400 ℃.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) The polyimide particles prepared from the diamine monomer and the anhydride monomer are used as the filler to be dispersed into the polyimide film, and the filler and the matrix are polyimide, so that the polyimide film has good interfacial compatibility and is not easy to cause negative influence, and the polyimide film with excellent mechanical properties is prepared.
(2) The first part of diamine monomer and the first part of anhydride monomer used in the invention are provided with the ring-containing framework, and the adopted ring-containing framework has smaller rotation freedom, so that the filler with high rigidity is prepared, the thermal linear expansion coefficient of the polyimide film is effectively reduced, and the modulus of the material is improved.
(3) The first part of diamine monomer and the first part of anhydride monomer used in the invention are provided with the ring-containing framework, the interior of the ring-containing framework is provided with smaller rotation freedom degree, and the first part of diamine monomer and the first part of anhydride monomer are matched with an optimized hydrothermal synthesis process to prepare filler particles with specific morphology, so that better compatibility can be formed between the filler particles and a polyimide film body; specifically, the flower-ball filler has a large surface area, a large surface roughness and a non-closed surface structure; the plurality of laminated filler particles have a certain interlayer gap and a rougher side surface; the filler with single-chip morphology has extremely large surface area; the above characteristics are all beneficial to the full contact fusion of the filler and the polyamic acid solution.
(4) The invention prepares the homogeneous filler with high rigidity and high compatibility by a hydrothermal method and disperses the homogeneous filler into a polyimide film body, thereby avoiding the problems of low molecular weight, difficult polymerization, poor film flexibility, low mechanical property and the like caused by the difference of monomer activities when different monomers are directly mixed and polymerized, and avoiding the difficulties of large-scale industrialization caused by comprehensively adopting the harsh process conditions accompanied by the high-rigidity monomers.
(5) The polyimide film of the invention does not contain a fiber network skeleton, and avoids the limitation on the thickness of the film and the influence on the uniformity of the film, so that the polyimide film material with small thickness and high uniformity can be obtained.
Drawings
FIG. 1 is a scanning electron microscope image of a polyimide micro-nano filler prepared in example 1 of the present invention; FIG. 2 is a scanning electron microscope image of the polyimide micro-nano filler prepared in example 2 of the present invention; FIG. 3 is a scanning electron microscope image of the polyimide micro-nano filler prepared in example 3 of the present invention; FIG. 4 is a scanning electron microscope image of the polyimide micro-nano filler prepared in example 4 of the present invention; fig. 5 is a scanning electron microscope image of the polyimide micro-nano filler prepared in example 5 of the present invention.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to illustrate the problem and to explain the invention, without limiting it.
Example 1
(1) 0.01mol (2.0 g) of 4,4' -diaminodiphenyl ether (ODA) monomer is added into 80ml of N-methylpyrrolidone solvent at room temperature, after stirring until the monomer is completely dissolved, 0.01mol (2.2 g) of 1,2,4, 5-pyromellitic dianhydride (PMDA) is added, and stirring is continued for 6 hours, to obtain a first part of polyamic acid solution with a certain viscosity;
(2) Adding 20ml of a first part of polyamic acid solution into a 50ml hydrothermal kettle, then placing the kettle in a vacuum box at 180 ℃ for standing for 12 hours, naturally cooling to room temperature, then decompressing and filtering a reaction matrix, repeatedly washing the reaction matrix for 5 times by using a mixed solvent of acetone/ethanol/NMP=4:4:2 (volume ratio, the same applies below), and drying the obtained precipitate in a vacuum drying box at 80 ℃ for 24 hours to obtain a first part of polyimide micro-nano filler;
(3) 9.6g (0.03 mol) of 4,4 '-diamino-2, 2' -bistrifluoromethyl biphenyl (TFMB) was added to 40ml of medium anhydrous N, N-dimethylacetamide solvent under ice water bath conditions, stirred for 30min, 13.2g (0.03 mol) of 4, 4-hexafluoroisopropyl phthalic anhydride (6 FDA) was further added, and 30ml of anhydrous N, N-dimethylacetamide solvent was added and stirring was continued for 8 hours to obtain a second part of polyamic acid solution;
(4) At normal temperature, adding 1.14g of a first part of polyimide micro-nano filler into 20ml of anhydrous N, N-dimethylacetamide solvent, performing ultrasonic treatment for 10min, adding into a second part of polyamic acid solution, and stirring for 30min to obtain polyimide micro-nano filler modified polyamic acid solution;
(5) And (3) under the protection of nitrogen, carrying out tape casting on the polyimide micro-nano filler modified polyamide acid solution in the step (4) and the polyamide acid solution without polyimide micro-nano filler modified polyamide acid solution, removing the solvent under the conditions of 60 ℃,4 hours, 80 ℃,2 hours and 100 ℃ and 1 hour, and carrying out high-temperature cyclization treatment under the conditions of 200 ℃,1 hour and 300 ℃ and 1 hour to obtain the polyimide film modified by the homogeneous polyimide micro-nano filler and the polyimide film of the pure TFMB/6 FDA.
A scanning electron microscope image of the polyimide micro-nano filler prepared in the embodiment 1 of the invention is shown in figure 1, and the polyimide micro-nano filler is flower-ball-shaped particles. The polyimide film prepared according to the technical scheme has a glass transition temperature of 315 ℃ (DMA method test: dynamic thermo-mechanical analyzer) which is higher than that of a pure TFMB/6FDA film (309 ℃); and the linear thermal expansion Coefficient (CTE) (TMA test: thermo-mechanical analysis, test range: 50-250 ℃) is reduced from 48ppm/K of pure TFMB/6FDA to about 35ppm/K, and meanwhile, the mechanical property of the film is also slightly improved.
Example 2
(1) 0.01mol (2.0 g) of 4,4' -diaminodiphenyl ether (ODA) monomer is added into 80ml of N-methylpyrrolidone solvent at room temperature, after stirring until the monomer is completely dissolved, 0.01mol (2.2 g) of 1,2,4, 5-pyromellitic dianhydride (PMDA) is added, and stirring is continued for 6 hours, to obtain a first part of polyamic acid solution with a certain viscosity;
(2) Adding 20ml of a first part of polyamic acid solution into a 50ml hydrothermal kettle, then placing the kettle in a vacuum box at 180 ℃ for standing for 2 hours, naturally cooling to room temperature, filtering a reaction matrix under reduced pressure, repeatedly washing the reaction matrix for 5 times by using a mixed solvent of acetone/ethanol/NMP=4:4:2, and drying the obtained precipitate in a vacuum drying box at 80 ℃ for 24 hours to obtain a first part of polyimide micro-nano filler;
(3) 9.6g (0.03 mol) of 4,4 '-diamino-2, 2' -bistrifluoromethyl biphenyl (TFMB) was added to 40ml of medium anhydrous N, N-dimethylacetamide solvent under ice water bath conditions, stirred for 30min, 13.2g (0.03 mol) of 4, 4-hexafluoroisopropyl phthalic anhydride (6 FDA) was further added, and 30ml of anhydrous N, N-dimethylacetamide solvent was added and stirring was continued for 8 hours to obtain a second part of polyamic acid solution;
(4) At normal temperature, adding 2.28g of a first part of polyimide micro-nano filler into 20ml of anhydrous N, N-dimethylacetamide solvent, performing ultrasonic treatment for 10min, adding into a second part of polyamic acid solution, and stirring for 30min to obtain polyimide micro-nano filler modified polyamic acid solution;
(5) And (3) under the protection of nitrogen, carrying out tape casting on the polyimide micro-nano filler modified polyamide acid solution in the step (4) to form a film, removing the solvent at 60 ℃,4 hours, 80 ℃,2 hours and 100 ℃ for 1 hour, and carrying out high-temperature cyclization treatment at 200 ℃,1 hour and 300 ℃ for 1 hour to obtain the homogenous polyimide micro-nano filler modified polyimide film.
The scanning electron microscope image of the polyimide micro-nano filler prepared in the embodiment 2 of the invention is shown in figure 2, and the polyimide micro-nano filler is flower-ball-shaped particles. The polyimide film prepared according to the technical scheme has a glass transition temperature of 314 ℃ (DMA method test: dynamic thermo-mechanical analyzer) which is higher than that of a pure TFMB/6FDA film (309 ℃); the linear thermal expansion Coefficient (CTE) of the polyimide film (TMA method test: thermo-mechanical analysis, test range: 50-250 ℃) is reduced from 48ppm/K of pure TFMB/6FDA to about 31 ppm/K; meanwhile, the tensile modulus and tensile strength of the film respectively reach 3.7GPa and 109MPa (pure TFMB/6FDA:2.4GPa and 79 MPa).
Example 3
(1) 0.01mol (1.1 g) of p-Phenylenediamine (PDA) monomer is added into 80ml of N-methyl pyrrolidone solvent at room temperature, after the monomer is completely dissolved by stirring, 0.01mol (2.2 g) of 1,2,4, 5-pyromellitic dianhydride (PMDA) is added, and stirring is continued for 6 hours, so that a first part of polyamide acid solution with certain viscosity is obtained;
(2) Adding 20ml of a first part of polyamic acid solution into a 50ml hydrothermal kettle, then placing the kettle in a vacuum box at 180 ℃ for 12 hours, naturally cooling to room temperature, filtering a reaction matrix under reduced pressure, repeatedly washing for 5 times by using a mixed solvent of acetone/ethanol/NMP=5:2:3, and drying the obtained precipitate in a vacuum drying box at 80 ℃ for 24 hours to obtain a first part of polyimide micro-nano filler;
(3) 9.6g (0.03 mol) of 4,4 '-diamino-2, 2' -bistrifluoromethyl biphenyl (TFMB) was added to 40ml of medium anhydrous N, N-dimethylacetamide solvent under ice water bath conditions, stirred for 30min, 13.2g (0.03 mol) of 4, 4-hexafluoroisopropyl phthalic anhydride (6 FDA) was further added, and 30ml of anhydrous N, N-dimethylacetamide solvent was added and stirring was continued for 8 hours to obtain a second part of polyamic acid solution;
(4) At normal temperature, adding 1.14g of a first part of polyimide micro-nano filler into 20ml of anhydrous N, N-dimethylacetamide solvent, performing ultrasonic treatment for 10min, adding into a second part of polyamic acid solution, and stirring for 30min to obtain polyimide micro-nano filler modified polyamic acid solution;
(5) And (3) under the protection of nitrogen, carrying out tape casting on the polyimide micro-nano filler modified polyamide acid solution in the step (4) to form a film, removing the solvent at 60 ℃,4 hours, 80 ℃,2 hours and 100 ℃ for 1 hour, and carrying out high-temperature cyclization treatment at 200 ℃,1 hour and 300 ℃ for 1 hour to obtain the homogenous polyimide micro-nano filler modified polyimide film.
The scanning electron microscope image of the polyimide micro-nano filler prepared in the embodiment 3 of the invention is shown in figure 3, and the polyimide micro-nano filler is a uniform round single piece. The CTE (TMA method test: thermo-mechanical analysis, test range: 50-250 ℃) of the composite polyimide film prepared according to the technical scheme is reduced to 32ppm/K (CTE of pure TFMB/6FDA: 48 ppm/K), the elastic modulus of the film is improved from 2.4GPa to 3.6GPa, and meanwhile, the glass transition temperature of the film is hardly changed obviously.
Example 4
(1) 0.01mol (2.0 g) of 4,4' -diaminodiphenyl ether (ODA) monomer is added into 80ml of N-methylpyrrolidone solvent at room temperature, after stirring until the monomer is completely dissolved, 0.01mol (2.7 g) of 1,4,5, 8-naphthalene tetracarboxylic anhydride (NTDA) is added, and stirring is continued for 6 hours, so as to obtain a first part of polyamide acid solution with certain viscosity;
(2) Adding 20ml of a first part of polyamic acid solution into a 50ml hydrothermal kettle, then placing the kettle in a vacuum box at 180 ℃ for standing for 12 hours, naturally cooling to room temperature, filtering a reaction matrix under reduced pressure, respectively and repeatedly washing the reaction matrix with ethanol and acetone solvent for 2 times, and drying the obtained precipitate in a vacuum drying box at 80 ℃ for 24 hours to obtain a first part of polyimide micro-nano filler;
(3) Under the ice water bath condition, adding 11.9g (0.03 mol) of 4, 4-bis (3-aminophenoxy) benzophenone into 40ml of medium anhydrous N, N-dimethylacetamide solvent, stirring for 30min, adding 13.2g (0.03 mol) of 4, 4-hexafluoroisopropyl phthalic anhydride, adding 30ml of anhydrous N, N-dimethylacetamide solvent, and continuously stirring for 8 hours to obtain a second part of polyamic acid solution with higher solution viscosity;
(4) At normal temperature, adding 1.14g of a first part of polyimide micro-nano filler into 20ml of anhydrous N, N-dimethylacetamide solvent, performing ultrasonic treatment for 10min, adding into a second part of polyamic acid solution, and stirring for 30min to obtain polyimide micro-nano filler modified polyamic acid solution;
(5) And (3) under the protection of nitrogen, carrying out tape casting on the polyimide micro-nano filler modified polyamide acid solution in the step (4) to form a film, removing the solvent at 60 ℃,4 hours, 80 ℃,2 hours and 100 ℃ for 1 hour, and carrying out high-temperature cyclization treatment at 200 ℃,1 hour and 300 ℃ for 1 hour to obtain the homogenous polyimide micro-nano filler modified polyimide film.
The scanning electron microscope image of the polyimide micro-nano filler prepared in the embodiment 4 of the invention is shown in the figure 4, and the polyimide micro-nano filler is a micro-nano sheet aggregate of flower-like spherical particles. The glass transition temperature of the polyimide film prepared according to the technical scheme is 310 ℃ (DMA method test: dynamic thermo-mechanical analyzer) and the glass transition temperature of the pure TFMB/6FDA film (309 ℃) are similar; the thermal linear expansion coefficient (TMA method test: thermal mechanical analysis, test range: 50-250 ℃) of the polyimide film is reduced by about 20ppm/K, and the film still has excellent flexibility and mechanical properties.
Example 5
(1) 0.01mol (2.2 g) of 2- (diaminophenyl) benzimidazol-5 amine (BIA) monomer is added to 80ml of N-methylpyrrolidone solvent at room temperature, after stirring until the monomer is completely dissolved, 0.01mol (3.2 g) of 3,3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) is added, and stirring is continued for 8 hours to obtain a first part of polyamic acid solution having a certain viscosity;
(2) Adding 20ml of a first part of polyamic acid solution into a 50ml hydrothermal kettle, then placing the kettle in a vacuum box at 180 ℃ for standing for 12 hours, naturally cooling to room temperature, filtering a reaction matrix under reduced pressure, repeatedly washing the reaction matrix with an ethanol solvent for 5 times, and drying the obtained precipitate in a vacuum drying box at 80 ℃ for 24 hours to obtain a first part of polyimide micro-nano filler;
(3) Adding 6.8g (0.03 mol) of 4, 4-Diaminobenzidine (DABA) to 40ml of medium anhydrous N, N-dimethylacetamide solvent under ice water bath conditions, stirring for 30min, adding 15.6g (0.03 mol) of 2,2' -bis [4- (3, 4-dicarboxyphenoxy) phenyl ] propane tetracarboxylic dianhydride (BPADA), and adding 50ml of the medium anhydrous N, N-dimethylacetamide solvent, and stirring for 8 hours to obtain a second part of polyamic acid solution with certain viscosity;
(4) At normal temperature, adding 0.45g of a first part of polyimide micro-nano filler into 20ml of anhydrous N, N-dimethylacetamide solvent, performing ultrasonic treatment for 10min, adding into a second part of polyamic acid solution, and stirring for 30min to obtain polyimide micro-nano filler modified polyamic acid solution;
(5) And (3) under the protection of nitrogen, carrying out tape casting on the polyimide micro-nano filler modified polyamide acid solution in the step (4) to form a film, removing the solvent at 60 ℃,4 hours, 80 ℃,2 hours and 100 ℃ for 1 hour, and carrying out high-temperature cyclization treatment at 200 ℃,1 hour and 300 ℃ for 1 hour to obtain the homogenous polyimide micro-nano filler modified polyimide film.
The scanning electron microscope image of the polyimide micro-nano filler prepared in the embodiment 5 of the invention is shown in the figure 5, and the polyimide micro-nano filler is uniform multi-sheet laminated particles. The glass transition temperature of the polyimide film prepared according to the technical scheme is not obviously changed; however, the thermal linear expansion coefficient (TMA method test: thermal mechanical analysis, test range: 50-250 ℃) of the prepared film is 40ppm/K, which is obviously reduced compared with pure DABA/BPADA (52 ppm/K); and the film still has excellent flexibility and mechanical properties.
The above embodiments are illustrative for the purpose of illustrating the technical concept and features of the present invention so that those skilled in the art can understand the content of the present invention and implement it accordingly, and thus do not limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (7)
1. A polyimide film having a low coefficient of expansion, characterized in that: comprises a polyimide film body and polyimide filler dispersed in the polyimide film body; the polyimide filler is prepared by reacting a first part of diamine monomer and a first part of anhydride monomer, wherein the first part of diamine monomer and the first part of anhydride monomer both contain a ring-containing framework, and the ring-containing framework is provided with an aromatic ring structure;
the polyimide filler particles have a size within the range of 0.5-5 mu m and are dispersed as micro-nano fillers in the polyimide film body;
the first portion of diamine monomer is one or more of the following structures:
the first part of anhydride monomer is one or more of the following structures:
the polyimide film body is prepared by reacting a second part of diamine monomer and a second part of anhydride monomer, wherein the second part of diamine monomer is one or more of the following structures:
the second part of anhydride monomer is one or more of the following structures:
2. the polyimide film having a low expansion coefficient according to claim 1, wherein: the microscopic morphology of the polyimide filler particles is of flower ball type particles, round single-chip or multi-chip laminated particles.
3. The method for producing a polyimide film having a low expansion coefficient according to claim 1 or 2, characterized in that: the method comprises the following steps:
(1) Adding a first part of diamine monomer and a first part of anhydride monomer into a first aprotic polar solvent, and reacting for 6-20 hours at the temperature of-5-60 ℃ to obtain a first part of polyamic acid solution;
(2) Transferring the first part of polyamic acid solution into a hydrothermal kettle, then reacting for 0.5-36 hours at 180-250 ℃, naturally cooling, and filtering, washing and drying the reaction solution to obtain the micro-nano polyimide filler;
(3) Adding a second part of diamine monomer and a second part of anhydride monomer into a second aprotic polar solvent, and reacting for 8-20 hours at the temperature of-5-120 ℃ to obtain a second part of polyamic acid solution;
(4) Dispersing polyimide filler in a second aprotic polar solvent, adding the second aprotic polar solvent into a second part of polyamic acid solution after ultrasonic treatment for 1-30 min, and stirring for 10-300 min to obtain polyimide filler modified polyamic acid solution;
(5) And (3) under the protection of nitrogen, carrying out tape casting film forming, drying and high-temperature cyclization on the polyimide filler modified polyamic acid solution in the step (4) to obtain the polyimide film.
4. The method for producing a polyimide film having a low expansion coefficient according to claim 3, characterized in that: in the step (1), the first aprotic polar solvent is one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide and N-methylpyrrolidone; the solid content of polymerization is 0.5-10wt%;
in the step (3), the second aprotic polar solvent is one of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, m-cresol, butyrolactone and tetrahydrofuran; the solid content of polymerization is 10wt% to 50wt%.
5. The method for producing a polyimide film having a low expansion coefficient according to claim 3, characterized in that: in the step (2), the volume of the first part of polyamic acid solution is 1/4-2/3 of the volume of the hydrothermal kettle; the washing solvent is one or more of deionized water, ethanol, methanol, acetone, tetrahydrofuran, diethyl ether and ethyl acetate; washing for 3-10 times; the drying conditions are as follows: drying in a blast oven at 50-150 deg.c for 3-10 hr.
6. The method for producing a polyimide film having a low expansion coefficient according to claim 3, characterized in that: in the step (4), the addition amount of polyimide filler is 0.1-50% of the mass of the polymer; the polyimide filler has a solids content of 5wt% to 50wt% in the second aprotic polar solvent.
7. The method for producing a polyimide film having a low expansion coefficient according to claim 3, characterized in that: in the step (5), the drying and high-temperature cyclization adopts a stage heating mode under the nitrogen atmosphere, and the cyclization temperature is 250-400 ℃.
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| JPH07316290A (en) * | 1994-05-24 | 1995-12-05 | New Japan Chem Co Ltd | Polyimide film with rough surface and production thereof |
| KR20170054835A (en) * | 2015-11-10 | 2017-05-18 | 주식회사 엘지화학 | Composition for preparinig polyimide-based film and transparent polyimide-based film prepared by using same |
| CN112574445A (en) * | 2020-12-09 | 2021-03-30 | 太原工业学院 | Preparation method of self-reinforced polyimide film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH07316290A (en) * | 1994-05-24 | 1995-12-05 | New Japan Chem Co Ltd | Polyimide film with rough surface and production thereof |
| KR20170054835A (en) * | 2015-11-10 | 2017-05-18 | 주식회사 엘지화학 | Composition for preparinig polyimide-based film and transparent polyimide-based film prepared by using same |
| CN112574445A (en) * | 2020-12-09 | 2021-03-30 | 太原工业学院 | Preparation method of self-reinforced polyimide film |
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