CN115260492B - Preparation method of polyimide film with low thermal expansion coefficient - Google Patents
Preparation method of polyimide film with low thermal expansion coefficient Download PDFInfo
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- CN115260492B CN115260492B CN202210667584.2A CN202210667584A CN115260492B CN 115260492 B CN115260492 B CN 115260492B CN 202210667584 A CN202210667584 A CN 202210667584A CN 115260492 B CN115260492 B CN 115260492B
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- dianhydride
- polyimide film
- thermal expansion
- expansion coefficient
- diamine
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 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 45
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 40
- 150000004985 diamines Chemical class 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000011521 glass Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000012024 dehydrating agents Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000002798 polar solvent Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 30
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical group CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 108010025899 gelatin film Proteins 0.000 claims description 14
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 13
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 12
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 claims description 4
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 claims description 3
- CNDRGCONXQJWNY-UHFFFAOYSA-N FC(CC(F)(F)F)(F)F.NC1=CC=C(OC2=CC=CC=C2)C=C1 Chemical compound FC(CC(F)(F)F)(F)F.NC1=CC=C(OC2=CC=CC=C2)C=C1 CNDRGCONXQJWNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 3
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 3
- 150000003931 anilides Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 230000008569 process Effects 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 49
- 239000007787 solid Substances 0.000 description 36
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 24
- 239000002904 solvent Substances 0.000 description 22
- 239000000203 mixture Substances 0.000 description 20
- 239000002184 metal Substances 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 238000007605 air drying Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000004090 dissolution Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 125000005462 imide group Chemical group 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000004642 Polyimide Substances 0.000 description 4
- SXGMVGOVILIERA-UHFFFAOYSA-N (2R,3S)-2,3-diaminobutanoic acid Natural products CC(N)C(N)C(O)=O SXGMVGOVILIERA-UHFFFAOYSA-N 0.000 description 3
- BIXGISJFDUHZEB-UHFFFAOYSA-N 2-[9,9-bis(4-methylphenyl)fluoren-2-yl]-9,9-bis(4-methylphenyl)fluorene Chemical compound C1=CC(C)=CC=C1C1(C=2C=CC(C)=CC=2)C2=CC(C=3C=C4C(C5=CC=CC=C5C4=CC=3)(C=3C=CC(C)=CC=3)C=3C=CC(C)=CC=3)=CC=C2C2=CC=CC=C21 BIXGISJFDUHZEB-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 238000009776 industrial production Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000005022 packaging material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 238000004377 microelectronic Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
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- 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
-
- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
-
- 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
- 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
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- 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
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Abstract
The invention discloses a preparation method of a polyimide film with a low thermal expansion coefficient, which relates to the technical field of polyimide films and comprises the following steps: dissolving diamine I containing a rigid structure and dianhydride I containing a rigid structure in an aprotic polar solvent, and stirring for reaction to prepare an amino-terminated amic acid oligomer; adding a dehydrating agent and a catalyst to carry out imidization reaction; then adding diamine II and dianhydride II, and stirring for reaction to obtain a polyamic acid solution containing imidization groups; coating the solution on a glass plate, drying, stripping and imidizing to obtain the glass plate. According to the invention, imidization is carried out on the amic acid oligomer, and then diamine and dianhydride are added for reaction, so that the polyamic acid molecular chain contains a large amount of imidization groups, the orientation degree of the molecular chain is greatly improved, and meanwhile, the in-plane orientation degree of the film is further improved through a synergistic orientation effect in the imidization process, so that the polyimide film with a low thermal expansion coefficient is obtained.
Description
Technical Field
The invention relates to the technical field of polyimide films, in particular to a preparation method of a polyimide film with a low thermal expansion coefficient.
Background
Polyimide has excellent high and low temperature resistance, excellent insulating property and good mechanical property, and is widely applied to various fields of aerospace, automobile electronics, mechanical and chemical industry and the like. Polyimide films are the most mature and most widely used of all polyimide materials, and the largest application scene is the microelectronics field at present.
With the development of the microelectronics industry, the integration level and precision of the electronic circuit board are higher and higher, the requirement on the stability of the packaging material is also more severe, and the thermal expansion coefficient is one of the most critical performance indexes affecting the stability of the packaging material. The thermal expansion coefficient of the common polyimide film is above 30 ppm/DEG C, the thermal expansion coefficient of Cu compounded or contacted with the polyimide film in the circuit board is about 17 ppm/DEG C, the thermal expansion coefficient of Si is only 4-5 ppm/DEG C, and serious mismatch of the thermal expansion coefficients can lead to layering and cracking of the packaging material in the heat treatment of the packaging process or the use process of the circuit, thereby not only affecting the normal operation of the electronic element, but also reducing the service life of the electronic element. Therefore, it is important to develop polyimide films with low coefficients of thermal expansion that match the conductive layers of the packaged circuitry.
Most of the existing researches on reducing the thermal expansion coefficient of the polyimide film focus on molecular structure optimization, the aim is achieved by introducing rigid groups into a polyimide main chain, for example, chinese patent application Nos. CN201610954820.3 and CN202011548582.9 successfully prepare polyimide film samples with low thermal expansion coefficient by introducing rigid groups such as imidazole/oxazole or pyridazine, but the synthesis process of related monomers is complex, the cost is high, and the method is not suitable for industrial production. The Chinese patent CN202111066583.4 reduces the thermal expansion coefficient of the film to a certain extent by filling polyimide micro-nano filler in the polyimide film, but the thermal expansion coefficient of the filled film is still generally above 30 ppm/DEG C. At present, few studies are reported on the reduction of the thermal expansion coefficient of polyimide films by adjusting the synthesis process of polyamic acid.
Disclosure of Invention
Based on the technical problems in the background technology, the invention provides a preparation method of a polyimide film with low thermal expansion coefficient, and the thermal expansion coefficient of the prepared polyimide film can be less than or equal to 17 ppm/DEG C by optimizing a polyamic acid synthesis process.
The invention provides a preparation method of a polyimide film with a low thermal expansion coefficient, which comprises the following steps:
S1, dissolving diamine I containing a rigid structure and dianhydride I containing a rigid structure in an aprotic polar solvent, and stirring for reaction to prepare an amino-terminated amic acid oligomer;
S2, adding a dehydrating agent and a catalyst into the reaction system of the S1 to carry out imidization reaction;
s3, adding diamine II and dianhydride II into the reaction system of the S2, and stirring for reaction to obtain a polyamic acid solution containing imidization groups;
s4, coating the polyamic acid solution in the S3 on a glass plate, drying, stripping to obtain a gel film, and carrying out imidization treatment to obtain the polyimide film.
Preferably, the diamine I containing a rigid structure is one of 4,4' -phenylenediamine and 4,4' -diamino-2, 2' -dimethylbiphenyl;
The dianhydride I containing a rigid structure is one of pyromellitic dianhydride and 3,3', 4' -biphenyl tetracarboxylic dianhydride;
Diamine II is one or more than one of 4,4' -diamino-2, 2' -dimethylbiphenyl, 4' -diaminodiphenyl ether, 4' -diaminobenzil anilide, 4' -diaminodiphenyl methane, 4' -diaminobenzophenone, diaminodiphenyl sulfone, 2' -bis (trifluoromethyl) diaminobiphenyl and 2, 2-bis [4- (4-aminophenoxy) benzene ] hexafluoropropane;
The dianhydride II is one or more than one of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 3', 4' -diphenyl ether tetracarboxylic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, bisphenol A type diether dianhydride and 4,4' - (hexafluoroisopropenyl) diphthalic anhydride.
Preferably, the aprotic polar solvent is one or a combination of more than one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
Preferably, the molar ratio of diamine i to dianhydride i is 2.5:1, a step of; the molar quantity of diamine II added is as follows: n (diamine II) is more than or equal to 0 and less than or equal to 0.4n (diamine I); the molar amount of dianhydride added is as follows: 1.5n (dianhydride I) is less than or equal to n (dianhydride II) is less than or equal to 2.5n (dianhydride I); and n (diamine i) +n (diamine ii) =n (dianhydride i) +n (dianhydride ii).
Preferably, in S1, the reaction is carried out at 0-30 ℃ for 0.5-6 h under nitrogen atmosphere.
Preferably, in S2, the dehydrating agent is acetic anhydride, and the catalyst is one of pyridine and isoquinoline; wherein, the mole ratio of the dehydrating agent to the dianhydride I is 2:1, a step of; the molar ratio of catalyst to dianhydride I was 0.5:1.
In the present invention, the selection of the dehydrating agent and the catalyst is not limited to the above-described optimization scheme, and may be a dehydrating agent and a catalyst conventional in the art.
Preferably, in S2, the imidization is carried out under a nitrogen atmosphere at 160-200 ℃ for 2-12 hours.
Preferably, in S3, the reaction is carried out at 0-30 ℃ for 0.5-6 h under nitrogen atmosphere.
Preferably, in S3, the viscosity of the polyamic acid solution is controlled to be 200 to 3000 poise.
Preferably, in S4, the drying temperature is 60-180 ℃ and the drying time is 30-120 min; imidization temperature is 330-420 ℃, and imidization time is 10-30 min.
Compared with the prior art, the invention has the following technical effects:
1. The traditional polyamic acid synthesis process comprises the following steps: diamine monomer is dissolved in aprotic solvent, dianhydride monomer is added into the solvent for polymerization reaction, and polyamic acid solution is obtained. Through researches, the polyamic acid casting film can be influenced by adjacent molecular chain structures in the imidization process, and the existence of the high-orientation structure can guide the polyamic acid casting film to be cooperatively oriented in the imidization process, so that the polyimide film with high in-plane orientation is obtained, and the thermal expansion coefficient of the film is reduced. In the traditional polyamide acid synthesis process, amide and carboxylic acid groups in a polymer molecular chain are unfavorable for forming a high-orientation structure, and polyimide films with high in-plane orientation are difficult to imidize. The polyimide film with low thermal expansion coefficient is prepared by optimizing the synthesis process of polyamide acid, specifically, diamine and dianhydride with rigid structure are polymerized to obtain an amic acid oligomer, the diamine and dianhydride with rigid structure are selected to induce imidization trend, a dehydrating agent and a catalyst are added to carry out imidization treatment to obtain components with imidization groups, and diamine and dianhydride are added to carry out polymerization reaction.
2. Compared with the polyimide film prepared by the traditional process, the polyimide film prepared by the method has higher molecular regularity, and even under the condition of the same chemical structure composition, the polyimide film prepared by the method has obviously better performances of tensile strength, modulus, glass transition temperature Tg and the like than the polyimide film prepared by the traditional process.
3. The polyimide film prepared by the method has the lowest thermal expansion coefficient reaching 2 ppm/DEG C, good mechanical property, simple method and strong feasibility, and has certain reference value for industrial production.
Detailed Description
In the examples below, the raw material names and corresponding abbreviations used are as follows:
Diamine: 4,4 '-Phenylenediamine (PDA), 4' -diamino-2, 2 '-dimethylbiphenyl (M-Tol), 4' -diaminodiphenyl ether (ODA), 4 '-Diaminoanilide (DABA), 4' -diaminodiphenylmethane (DDM), a catalyst system 4,4 '-Diaminobenzophenone (DABP), diaminodiphenyl sulfone (DDS), 2' -bis (trifluoromethyl) diaminobiphenyl (TFMB), 2-bis [4- (4-aminophenoxy) benzene ] hexafluoropropane (BDAF);
Dianhydride: pyromellitic dianhydride (PMDA), 3', 4' -biphenyl tetracarboxylic dianhydride (BPDA), 3',4,4' -diphenyl ether tetracarboxylic dianhydride (ODPA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), bisphenol a type diether dianhydride (BPADA), 4' - (hexafluoroisopropenyl) diphthalic anhydride (6 FDA);
Aprotic polar solvents: n, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP).
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
A preparation method of polyimide film with low thermal expansion coefficient comprises the following steps:
(1) 0.25mol of PDA solid is added into a 500ml three-neck flask A, DMAc solvent is added, and the mixture is stirred and dissolved to obtain 15wt% of PDA solution; adding 0.10mol of PMDA solid into a 500ml three-neck flask B, adding DMAc solvent, and stirring to dissolve to obtain 15wt% PMDA solution; all PMDA solution in the three-neck flask B is poured into the three-neck flask A, and stirred and reacted for 6 hours under the condition of nitrogen atmosphere and 0 ℃ to obtain the mixed solution of the amino-terminated amic acid oligomer and the PDA.
(2) Into a three-necked flask A, 0.2mol of acetic anhydride and 0.05mol of pyridine solvent were added, and the mixture was stirred under a nitrogen atmosphere at 160℃for reaction for 12 hours to obtain a mixed solution containing an imide group.
(3) 0.15Mol of BPDA solid is added into a three-neck flask A, and stirred and reacted for 6 hours under the condition of nitrogen atmosphere and 0 ℃ to obtain the polyamic acid solution containing imidization groups, wherein the viscosity is 3000 poise.
(4) Vacuum defoaming treatment is carried out on the polyamic acid solution, then the polyamic acid solution is coated on a glass plate, and the glass plate is placed in a blast drying box and respectively dried for 90min, 15min and 15min at the temperature of 60 ℃ and the temperature of 120 ℃ and the temperature of 150 ℃. The gel film obtained was peeled off and fixed on a metal frame, and was imidized in an imidization furnace at 330℃for 30 minutes to obtain a polyimide film having a thickness of 13. Mu.m.
Example 2
A preparation method of polyimide film with low thermal expansion coefficient comprises the following steps:
(1) 0.25mol of M-Tol solid is added into a 500ml three-neck flask A, DMF solvent is added, and stirring and dissolving are carried out, thus obtaining 15wt% of M-Tol solution; adding 0.10mol of BPDA solid into a 500ml three-neck flask B, adding DMF solvent, stirring and dissolving to obtain 15wt% of BPDA solution; all the BPDA solution in the three-neck flask B is poured into the three-neck flask A, and stirred and reacted for 5 hours under the condition of nitrogen atmosphere and 5 ℃ to obtain the mixed solution of the amino-terminated amic acid oligomer and the M-Tol.
(2) Into a three-necked flask A, 0.2mol of acetic anhydride and 0.05mol of pyridine solvent were added, and the mixture was stirred under a nitrogen atmosphere at 170℃for 10 hours to obtain a mixed solution containing an imide group.
(3) 0.1Mol of DABA and 0.25mol of BPDA solid were added to a three-necked flask A, and the mixture was stirred under a nitrogen atmosphere at 5℃for 5 hours to give a polyamic acid solution containing an imidization group, the viscosity of which was 2750 poise.
(4) The polyamic acid solution was subjected to vacuum defoaming treatment, and then coated on a glass plate, and dried in a forced air drying oven at 60℃and 130℃for 60min and 30min, respectively. The gel film obtained was peeled off and fixed on a metal frame, and was imidized in an imidization furnace at 350℃for 25 minutes to obtain a polyimide film having a thickness of 13. Mu.m.
Example 3
A preparation method of polyimide film with low thermal expansion coefficient comprises the following steps:
(1) 0.25mol of PDA solid is added into a 500ml three-neck flask A, NMP solvent is added, and stirring and dissolving are carried out, thus obtaining 15wt% PDA solution; adding 0.10mol of BPDA solid into a 500ml three-neck flask B, adding NMP solvent, stirring and dissolving to obtain 15wt% of BPDA solution; all the BPDA solution in the three-neck flask B is poured into the three-neck flask A, and stirred and reacted for 4 hours under the condition of nitrogen atmosphere and 10 ℃ to obtain the mixed solution of the amino-terminated amic acid oligomer and the PDA.
(2) Into a three-necked flask A, 0.20mol of acetic anhydride and 0.05mol of pyridine solvent were added, and the mixture was stirred under a nitrogen atmosphere at 175℃for reaction for 8 hours to obtain a mixed solution containing an imide group.
(3) 0.05Mol of ODA and 0.20mol of BPADA solid are added into a three-necked flask A, and stirred and reacted for 4 hours under the condition of nitrogen atmosphere and 10 ℃ to obtain a polyamic acid solution containing an imidization group, wherein the viscosity is 2300 poise.
(4) The polyamic acid solution was vacuum defoamed, coated on a glass plate, and dried in a forced air drying oven at 80℃and 160℃for 60min and 20min, respectively. The gel film obtained was peeled off and fixed on a metal frame, and was put into an imidization furnace to imidize for 25min at 360℃to obtain a polyimide film having a thickness of 13. Mu.m.
Example 4
A preparation method of polyimide film with low thermal expansion coefficient comprises the following steps:
(1) Adding 0.25mol of PDA solid into a 500ml three-neck flask A, adding a mixed solvent of DMAc and DMF (the mass ratio of the DMAc to the DMF is 1:1), and stirring for dissolution to obtain 15wt% of PDA solution; adding 0.10mol of BPDA solid into a 500ml three-neck flask B, adding a mixed solvent of DMAc and DMF (the mass ratio of the DMAc to the DMF is 1:1), and stirring and dissolving to obtain a 15wt% BPDA solution; all the BPDA solution in the three-neck flask B is poured into the three-neck flask A, and stirred and reacted for 3 hours under the condition of nitrogen atmosphere and 15 ℃ to obtain the mixed solution of the amino-terminated amic acid oligomer and the PDA.
(2) Into a three-necked flask A, 0.20mol of acetic anhydride and 0.05mol of pyridine solvent were added, and the mixture was stirred under a nitrogen atmosphere at 180℃for reaction for 6 hours to obtain a mixed solution containing an imide group.
(3) 0.05Mol of DDM and 0.20mol of BTDA solid are added into a three-necked flask A, and stirred and reacted for 3 hours under the condition of nitrogen atmosphere and 15 ℃ to obtain a polyamic acid solution containing an imidization group, wherein the viscosity is 1200 poise.
(4) The polyamic acid solution was subjected to vacuum defoaming treatment, and then coated on a glass plate, and dried in a forced air drying oven at 100℃and 150℃for 40min and 20min, respectively. The gel film obtained was peeled off and fixed on a metal frame, and was put into an imidization furnace to imidize for 20min at 380℃to obtain a polyimide film having a thickness of 13. Mu.m.
Example 5
A preparation method of polyimide film with low thermal expansion coefficient comprises the following steps:
(1) 0.25mol of PDA solid is added into a 500ml three-neck flask A, NMP solvent is added, and stirring and dissolving are carried out, thus obtaining 15wt% PDA solution; adding 0.10mol of BPDA solid into a 500ml three-neck flask B, adding NMP solvent, stirring and dissolving to obtain 15wt% of BPDA solution; all the BPDA solution in the three-neck flask B is poured into the three-neck flask A, and stirred and reacted for 2 hours under the condition of nitrogen atmosphere and 20 ℃ to obtain the mixed solution of the amino-terminated amic acid oligomer and the PDA.
(2) Into a three-necked flask A, 0.20mol of acetic anhydride and 0.05mol of pyridine solvent were added, and the mixture was stirred under a nitrogen atmosphere at 190℃for 4 hours to obtain a mixed solution containing an imide group.
(3) 0.05Mol of DABP and 0.20mol of 6FDA solid are added into a three-necked flask A, and stirred and reacted for 2 hours under the condition of nitrogen atmosphere and 20 ℃ to obtain a polyamic acid solution containing an imidization group, wherein the viscosity is 450 poise.
(4) The polyamic acid solution was subjected to vacuum defoaming treatment, and then coated on a glass plate, and dried in a forced air drying oven at 120℃and 160℃for 20min and 20min, respectively. The gel film obtained was peeled off and fixed on a metal frame, and was imidized in an imidization furnace at 400℃for 15 minutes to obtain a polyimide film having a thickness of 13. Mu.m.
Example 6
A preparation method of polyimide film with low thermal expansion coefficient comprises the following steps:
(1) 0.25mol of PDA solid is added into a 500ml three-neck flask A, NMP solvent is added, and stirring and dissolving are carried out, thus obtaining 15wt% PDA solution; adding 0.10mol of BPDA solid into a 500ml three-neck flask B, adding NMP solvent, stirring and dissolving to obtain 15wt% of BPDA solution; all the BPDA solution in the three-neck flask B is poured into the three-neck flask A, and stirred and reacted for 0.5h under the condition of nitrogen atmosphere and 30 ℃ to obtain the mixed solution of the amino-terminated amic acid oligomer and the PDA.
(2) Into a three-necked flask A, 0.20mol of acetic anhydride and 0.05mol of pyridine solvent were added, and the mixture was stirred under a nitrogen atmosphere at 200℃for 2 hours to obtain a mixed solution containing an imide group.
(3) 0.05Mol of TFMB, 0.05mol of BDAF, 0.10mol of ODPA and 0.15mol of BPADA solid are added into a three-necked flask A, and the mixture is stirred and reacted for 0.5h under the condition of 30 ℃ in a nitrogen atmosphere, so as to obtain a polyamic acid solution containing an imidization group, wherein the viscosity of the polyamic acid solution is 200 poise.
(4) The polyamic acid solution was vacuum defoamed, and then coated on a glass plate, and dried in a forced air drying oven at 180℃for 30 minutes, respectively. The gel film obtained was peeled off and fixed on a metal frame, and was imidized in an imidization furnace at 420℃for 10 minutes to obtain a polyimide film having a thickness of 13. Mu.m.
Comparative example 1
A preparation method of polyimide film comprises the following steps:
(1) 0.25mol of PDA solid is added into a 500ml three-neck flask, DMAc solvent is added, and stirring and dissolution are carried out; 0.1mol PMDA and 0.15mol BPDA solid are added into the mixture, and the mixture is stirred and reacted for 6 hours under the condition of nitrogen atmosphere and 0 ℃ to obtain a polyamic acid solution with the solid content of 20 weight percent and the viscosity of 2600 poise.
(2) Vacuum defoaming treatment is carried out on the polyamic acid solution, then the polyamic acid solution is coated on a glass plate, and the glass plate is placed in a blast drying box and respectively dried for 90min, 15min and 15min at the temperature of 60 ℃ and the temperature of 120 ℃ and the temperature of 150 ℃. The gel film obtained was peeled off and fixed on a metal frame, and was imidized in an imidization furnace at 330℃for 30 minutes to obtain a polyimide film having a thickness of 13. Mu.m.
Comparative example 2
A preparation method of polyimide film comprises the following steps:
(1) 0.25mol of M-Tol and 0.10mol of DABA solid are added into a 500ml three-neck flask, and DMF solvent is added for stirring and dissolution; 0.35mol of BPDA solid is continuously added into the mixture, and the mixture is stirred and reacted for 5 hours under the condition of nitrogen atmosphere and 5 ℃ to obtain a polyamic acid solution with the solid content of 20 weight percent and the viscosity of 2700 poise.
(2) The polyamic acid solution was subjected to vacuum defoaming treatment, and then coated on a glass plate, and dried in a forced air drying oven at 60℃and 130℃for 60min and 30min, respectively. The gel film obtained was peeled off and fixed on a metal frame, and was imidized in an imidization furnace at 350℃for 25 minutes to obtain a polyimide film having a thickness of 13. Mu.m.
Comparative example 3
A preparation method of polyimide film comprises the following steps:
(1) 0.25mol PDA and 0.05mol ODA solid are added into a 500ml three-neck flask, NMP solvent is added, and stirring and dissolution are carried out; to this was added 0.10mol of BPDA and 0.20mol of BPADA solid, and the mixture was stirred under a nitrogen atmosphere at 10℃for 4 hours to give a polyamic acid solution having a solid content of 20% by weight and a viscosity of 2400 poise.
(2) The polyamic acid solution was vacuum defoamed, coated on a glass plate, and dried in a forced air drying oven at 80℃and 160℃for 60min and 20min, respectively. The gel film obtained was peeled off and fixed on a metal frame, and was put into an imidization furnace to imidize for 25min at 360℃to obtain a polyimide film having a thickness of 13. Mu.m.
Comparative example 4
A preparation method of polyimide film comprises the following steps:
(1) Adding 0.25mol of PDA and 0.05mol of DDM solid into a 500ml three-neck flask, adding a mixed solvent of DMAc and DMF (the mass ratio of the two is 1:1), and stirring for dissolution; 0.10mol of BPDA and 0.20mol of BTDA solid are continuously added into the mixture, and the mixture is stirred and reacted for 3 hours under the condition of nitrogen atmosphere and 15 ℃ to obtain a polyamic acid solution with the solid content of 20 weight percent and the viscosity of 1500 poise.
(2) The polyamic acid solution was subjected to vacuum defoaming treatment, and then coated on a glass plate, and dried in a forced air drying oven at 100℃and 150℃for 40min and 20min, respectively. The gel film obtained was peeled off and fixed on a metal frame, and was put into an imidization furnace to imidize for 20min at 380℃to obtain a polyimide film having a thickness of 13. Mu.m.
Comparative example 5
A preparation method of polyimide film comprises the following steps:
(1) 0.25mol of PDA and 0.05mol of DABP solid are added into a 500ml three-neck flask, and NMP solvent is added for stirring and dissolution; to this was added 0.10mol of BPDA and 0.20mol of 6FDA solid, and the mixture was stirred under a nitrogen atmosphere at 20℃for 2 hours to give a polyamic acid solution having a solid content of 20% by weight and a viscosity of 400 poise.
(2) The polyamic acid solution was subjected to vacuum defoaming treatment, and then coated on a glass plate, and dried in a forced air drying oven at 120℃and 160℃for 20min and 20min, respectively. The gel film obtained was peeled off and fixed on a metal frame, and was imidized in an imidization furnace at 400℃for 15 minutes to obtain a polyimide film having a thickness of 13. Mu.m.
Comparative example 6
A preparation method of polyimide film comprises the following steps:
(1) Into a 500ml three-neck flask, 0.25mol of PDA, 0.05mol of DABP and 0.05mol of BDAF solid are added, NMP solvent is added, and stirring and dissolution are carried out; to this was added 0.10mol of BPDA, 0.10mol of ODPA and 0.15mol of BPADA solid, and the mixture was stirred under a nitrogen atmosphere at 30℃for 0.5 hour to obtain a polyamic acid solution having a solid content of 20% by weight and a viscosity of 150 poise.
(2) The polyamic acid solution was vacuum defoamed, and then coated on a glass plate, and dried in a forced air drying oven at 180℃for 30 minutes, respectively. The gel film obtained was peeled off and fixed on a metal frame, and was imidized in an imidization furnace at 420℃for 10 minutes to obtain a polyimide film having a thickness of 13. Mu.m.
The polyimide films prepared in examples 1 to 6 and comparative examples 1 to 6 were compared with performance test, and the results are shown in Table 1.
TABLE 1 Performance test data for polyimide films
As can be seen from Table 1, the polyimide film prepared by the method has a thermal expansion coefficient which is obviously lower than that of the polyimide film prepared by the traditional process under the condition that the chemical structure compositions are completely the same, and the tensile strength, modulus, glass transition temperature and other properties of the polyimide film are improved to different degrees. The preparation method has simple operation process and strong feasibility, has obvious improvement effect on the comprehensive performance of the film including the thermal expansion coefficient, and has potential application value in the field of industrial production.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (9)
1. The preparation method of the polyimide film with low thermal expansion coefficient is characterized by comprising the following steps:
S1, dissolving diamine I containing a rigid structure and dianhydride I containing a rigid structure in an aprotic polar solvent, and stirring for reaction to prepare an amino-terminated amic acid oligomer;
S2, adding a dehydrating agent and a catalyst into the reaction system of the S1 to carry out imidization reaction;
s3, adding diamine II and dianhydride II into the reaction system of the S2, and stirring for reaction to obtain a polyamic acid solution containing imidization groups;
s4, coating the polyamide acid solution in the step S3 on a glass plate, drying, stripping to obtain a gel film, and performing imidization treatment to obtain the glass plate;
diamine I containing a rigid structure is one of 4,4' -phenylenediamine and 4,4' -diamino-2, 2' -dimethylbiphenyl;
The dianhydride I containing a rigid structure is one of pyromellitic dianhydride and 3,3', 4' -biphenyl tetracarboxylic dianhydride;
the molar ratio of diamine I to dianhydride I is 2.5:1, a step of; the molar quantity of diamine II added is as follows: n (diamine II) is more than 0 and less than or equal to 0.4n (diamine I); the molar amount of dianhydride added is as follows: 1.5n (dianhydride I) is less than or equal to n (dianhydride II) is less than or equal to 2.5n (dianhydride I); and n (diamine i) +n (diamine ii) =n (dianhydride i) +n (dianhydride ii).
2. The method for producing a polyimide film having a low thermal expansion coefficient according to claim 1, wherein, diamine II is one or more than one of 4,4' -diamino-2, 2' -dimethylbiphenyl, 4' -diaminodiphenyl ether, 4' -diaminobenzil anilide, 4' -diaminodiphenyl methane, 4' -diaminobenzophenone, diaminodiphenyl sulfone, 2' -bis (trifluoromethyl) diaminobiphenyl and 2, 2-bis [4- (4-aminophenoxy) benzene ] hexafluoropropane;
The dianhydride II is one or more than one of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 3', 4' -diphenyl ether tetracarboxylic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, bisphenol A type diether dianhydride and 4,4' - (hexafluoroisopropenyl) diphthalic anhydride.
3. The method for producing a polyimide film having a low thermal expansion coefficient according to claim 1, wherein the aprotic polar solvent is one or a combination of more than one of N, N-dimethylformamide, N-dimethylacetamide and N-methylpyrrolidone.
4. The method for producing a polyimide film having a low thermal expansion coefficient according to claim 1, wherein the reaction is carried out in S1 at 0 to 30℃for 0.5 to 6 hours under a nitrogen atmosphere.
5. The method for preparing a polyimide film with low thermal expansion coefficient according to claim 1, wherein in S2, the dehydrating agent is acetic anhydride, and the catalyst is one of pyridine and isoquinoline; wherein, the mole ratio of the dehydrating agent to the dianhydride I is 2:1, a step of; the molar ratio of catalyst to dianhydride I was 0.5:1.
6. The method for producing a polyimide film having a low thermal expansion coefficient according to claim 1, wherein the imidization reaction in S2 is carried out at 160 to 200 ℃ for 2 to 12 hours under a nitrogen atmosphere.
7. The method for producing a polyimide film having a low thermal expansion coefficient according to claim 1, wherein the reaction is carried out in S3 at 0 to 30℃for 0.5 to 6 hours under a nitrogen atmosphere.
8. The method for producing a polyimide film having a low thermal expansion coefficient according to claim 1, wherein in S3, the viscosity of the polyamic acid solution is controlled to be 200 to 3000 poise.
9. The method for preparing a polyimide film with low thermal expansion coefficient according to claim 1, wherein in S4, the drying temperature is 60-180 ℃ and the time is 30-120 min; the imidization temperature is 330-420 ℃, and the imidization time is 10-30min.
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| CN110885465A (en) * | 2019-11-22 | 2020-03-17 | 桂林电器科学研究院有限公司 | Preparation method of low-thermal expansion coefficient thermoplastic polyimide film for two-layer flexible copper clad laminate |
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