CN117417528A - Low-dielectric PI resin derived from ortho-hydroxy polyimide, and preparation method and application thereof - Google Patents
Low-dielectric PI resin derived from ortho-hydroxy polyimide, and preparation method and application thereof Download PDFInfo
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- CN117417528A CN117417528A CN202311149822.1A CN202311149822A CN117417528A CN 117417528 A CN117417528 A CN 117417528A CN 202311149822 A CN202311149822 A CN 202311149822A CN 117417528 A CN117417528 A CN 117417528A
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 183
- 239000004642 Polyimide Substances 0.000 title claims abstract description 159
- 229920005989 resin Polymers 0.000 title claims abstract description 58
- 239000011347 resin Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 238000006462 rearrangement reaction Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 229920005575 poly(amic acid) Polymers 0.000 claims description 40
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 31
- 150000004985 diamines Chemical class 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 16
- 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 description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 238000006068 polycondensation reaction Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- HDGLPTVARHLGMV-UHFFFAOYSA-N 2-amino-4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenol Chemical compound NC1=CC(C(C(F)(F)F)C(F)(F)F)=CC=C1O HDGLPTVARHLGMV-UHFFFAOYSA-N 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 238000004100 electronic packaging Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 239000005022 packaging material Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 5
- 239000000463 material Substances 0.000 abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 238000010521 absorption reaction Methods 0.000 abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 10
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract description 10
- 239000000126 substance Substances 0.000 abstract description 9
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 8
- 125000001165 hydrophobic group Chemical group 0.000 abstract description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 5
- 239000001569 carbon dioxide Substances 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 4
- 239000003989 dielectric material Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 18
- 239000011521 glass Substances 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 14
- 101100296544 Caenorhabditis elegans pbo-5 gene Proteins 0.000 description 11
- 238000004321 preservation Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 150000003949 imides Chemical group 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 206010001497 Agitation Diseases 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000008707 rearrangement Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000036618 natural shedding Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
- 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
- C08G73/22—Polybenzoxazoles
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
- H01L23/293—Organic, e.g. plastic
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
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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
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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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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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- Power Engineering (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to the technical field of low dielectric material preparation, in particular to low dielectric PI resin derived from o-hydroxy polyimide, a preparation method and application thereof, wherein a benzoxazole-polyimide structure, namely the low dielectric PI resin, is obtained by utilizing an o-hydroxy polyimide structure obtained after thermal imidization reaction or chemical imidization reaction to perform thermal rearrangement reaction at high temperature. The thermal rearrangement reaction can increase the average spacing between molecular chains by releasing carbon dioxide gas, and more free volume is introduced to help reduce the dielectric constant of polyimide; on the other hand, a low polarizability at high frequencies and a trifluoromethyl group having a large volume can lower the dielectric constant of the material; and fluorine atoms are hydrophobic groups, and an aggregation phenomenon exists on the surface of the material after the fluorine atoms are introduced, so that water molecules can be effectively prevented from entering the material, and the water absorption of the material is reduced.
Description
Technical Field
The invention relates to the technical field of low dielectric material preparation, in particular to low dielectric PI resin derived from ortho-hydroxy polyimide, and a preparation method and application thereof.
Background
Polyimide (PI) is a high-performance engineering polymer material, named by the imide structure in the main chain. Although PI contains polar groups such as c=o, the carbonyl groups in the conjugated imide ring are symmetrical, and thus the mobility of free electrons is greatly limited, which imparts excellent electrical insulating properties to PI. Meanwhile, PI also has excellent thermal stability, mechanical properties, radiation resistance, low water absorption and chemical stability, so PI thin films are ideal choices for use as ILD materials. In recent years, however, with the rapid development of industry, there is a demand for PI films having lower dielectric constant and dielectric loss, better solubility, etc. at high frequencies.
Currently, lowering the dielectric constant of a polymer by lowering the molar polarizability or increasing the molar volume of a molecule is the most effective method, and thus by introducing fluorine-containing groups, aliphatic or alicyclic structures, large side groups into the polymer backbone is an effective method for lowering the dielectric constant of polyimide. In order to prepare PI resins with low dielectric constant and dielectric loss, researchers tend to further reduce the dielectric constant and dielectric loss of PI by increasing the free volume of the polymer molecular chains and by introducing air (dielectric constant of 1). The increase in free volume does improve the dielectric properties of PI well, but the increase in intermolecular voids further leads to an increase in thermal expansion coefficient, which makes it difficult to efficiently complex with a carrier such as copper.
In addition, too many rigid structures are introduced into PI to further cause the mechanical property of the material to be poor, and the reduction effect on the water absorption rate is not obvious; along with the development of economy, the environment-friendly idea is more in depth, the demand for environment-friendly materials is continuously increased, so that the demand for reusable polyimide is continuously increased, but most of PI has the problems of poor solubility and the like, and needs to be further improved.
The introduction of holes into polyimide by using organic and inorganic nano particles is one of the common ways of reducing the dielectric constant, the dielectric constant of air is 1, and the introduction of holes can effectively introduce air into polyimide, so that the dielectric constant is reduced, but the way can bring great negative influence on the mechanical properties of polyimide, and polyimide with high performance is difficult to prepare.
Accordingly, the prior art is still in need of improvement and development.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a low dielectric PI resin derived from ortho-hydroxy polyimide, and a preparation method and application thereof, and aims to solve the problems of poor mechanical properties, poor dissolution properties and the like of the existing PI resin.
The technical scheme of the invention is as follows:
a method for preparing low dielectric PI resins derived from ortho-hydroxy polyimides, comprising the steps of:
carrying out polycondensation reaction on dianhydride, diamine monomer and 2,2' -bis (3-amino-4-hydroxyphenyl) -hexafluoropropane in a solvent to obtain polyamic acid solution;
forming the polyamic acid solution to obtain a polyamic acid film;
performing thermal imidization reaction on the polyamic acid film to obtain a polyimide film containing hydroxyl;
and carrying out thermal rearrangement reaction on the polyimide film containing the hydroxyl group to obtain the low dielectric PI resin.
A method for preparing low dielectric PI resins derived from ortho-hydroxy polyimides, comprising the steps of:
carrying out polycondensation reaction on dianhydride, diamine monomer and 2,2' -bis (3-amino-4-hydroxyphenyl) -hexafluoropropane in a solvent to obtain polyamic acid solution;
adding a catalyst and pyridine into the polyamic acid solution, and heating and stirring to obtain a polyimide solution containing hydroxyl groups;
molding the polyimide solution containing hydroxyl groups to obtain a polyimide film containing hydroxyl groups;
and carrying out thermal rearrangement reaction on the polyimide film containing the hydroxyl group to obtain the low dielectric PI resin.
The preparation method of the low dielectric PI resin from the ortho-hydroxyl polyimide comprises the following steps:
one of them.
The preparation method of the low dielectric PI resin from the ortho-hydroxyl polyimide comprises the following steps of:
one of the following; wherein R is 1 、R 2 Independently selected from-CF 3 、-CH 3 (C n H 2n+1 )、/>One of the following; r is selected from-H, -CH 3 、One of them.
The preparation method of the low dielectric PI resin from the ortho-hydroxy polyimide comprises the step of preparing the low dielectric PI resin from the ortho-hydroxy polyimide, wherein the solvent is selected from one of N, N-dimethylformamide, N-methylpyrrolidone, dimethylacetamide and gamma-butyrolactone.
The preparation method of the low dielectric PI resin from the ortho-hydroxyl polyimide comprises the steps of carrying out polycondensation reaction at the temperature of-5-30 ℃ for 6-24 hours; the temperature rising rate of the thermal rearrangement reaction is 1.0-10 ℃/min, the temperature of the thermal rearrangement reaction is 400-450 ℃, and the time of the thermal rearrangement reaction is 60-120min.
The preparation method of the low dielectric PI resin from the ortho-hydroxyl polyimide comprises the steps of heating the polyimide at a speed of 1.0-20 ℃/min, and heating the polyimide at a temperature of 30-400 ℃; wherein the thermal imidization reaction is carried out at 100-300 ℃ for 60-120min.
The preparation method of the low dielectric PI resin from the ortho-hydroxyl polyimide comprises the steps of heating and stirring at 60-190 ℃ for 12-24 hours.
A low dielectric PI resin derived from an ortho-hydroxy polyimide is prepared by using the preparation method of the low dielectric PI resin derived from the ortho-hydroxy polyimide.
Use of low dielectric PI resins derived from ortho-hydroxy polyimides in electronic packaging materials or circuit substrates.
The beneficial effects are that: the invention provides a low dielectric PI resin derived from ortho-hydroxy polyimide, a preparation method and application thereof, wherein the ortho-hydroxy polyimide structure obtained after thermal imidization reaction or chemical imidization reaction is utilized to generate thermal rearrangement reaction at high temperature to obtain a benzoxazole-polyimide structure, namely the low dielectric PI resin. The thermal rearrangement reaction can increase the average spacing between molecular chains by releasing carbon dioxide gas, and more free volume is introduced to help reduce the dielectric constant of polyimide; on the other hand, the trifluoromethyl group in the reaction raw material has low polarizability and hydrophobic group, and also has larger volume. Low polarizability at high frequency and trifluoromethyl with larger volume can lower the dielectric constant of the material; and fluorine atoms are hydrophobic groups, and an aggregation phenomenon exists on the surface of the material after the fluorine atoms are introduced, so that water molecules can be effectively prevented from entering the material, and the water absorption of the material is reduced. According to the invention, the polyimide containing the benzoxazole structure is introduced, so that the average distance between molecular chains of PI can be increased, and simultaneously, the dielectric constant and the hydrophobic property of the material are further reduced by superposing trifluoromethyl, so that polyimide with excellent performance is prepared.
Drawings
FIG. 1 is a nuclear magnetic resonance diagram of PBO-5 of example 1;
FIG. 2 is a nuclear magnetic resonance image of PBO-10 of example 2;
FIG. 3 is a nuclear magnetic resonance diagram of PBO-5-immobilization in example 4;
FIG. 4 is an infrared plot of the correspondence of PBO-5, PBO-10, PBO-20, PBO-30, and PBO-40;
FIG. 5 is a DSC of the corresponding PBO-5, PBO-10, PBO-20, PBO-30, PBO-40;
FIG. 6 is a TGA plot of PBO-5, PBO-10, PBO-20, PBO-30, and PBO-40, respectively;
FIG. 7 is a graph showing water contact angles corresponding to PBO-5, PBO-10, PBO-20, PBO-30, and PBO-40.
Detailed Description
The invention provides a low dielectric PI resin derived from ortho-hydroxy polyimide, a preparation method and application thereof, and the invention is further described in detail below in order to make the purposes, technical schemes and effects of the invention clearer and more definite. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
It will be understood by those skilled in the art that all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs unless defined otherwise. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
With the development of technology, the number of transistors on an Integrated Circuit (IC) chip is increasing, and information technology is rapidly developing. The increasing integration of devices and the decreasing size of components lead to increased resistance and capacitance, which in turn leads to increased power consumption, signal hysteresis and cross-talk. Some devices (including wearable devices, unmanned devices, smart homes, etc.) require lower signal delay times, and effectively lowering the dielectric constant (k) of the material is considered to be the most effective and straightforward method to solve these problems, so lowering the dielectric constant and dielectric loss of the material is becoming a popular research effort for a large number of researchers.
At present, the air is introduced to increase the intermolecular gaps, further increase the thermal expansion coefficient, and effectively complex with carriers such as copper. In addition, too many rigid structures are introduced into PI to further cause the mechanical property of the material to be poor, and the reduction effect on the water absorption rate is not obvious; along with the development of economy, the environment-friendly idea is more in depth, the demand for environment-friendly materials is continuously increased, so that the demand for reusable polyimide is continuously increased, but most of PI has the problems of poor solubility and the like, and needs to be further improved.
The introduction of holes into polyimide by using organic and inorganic nano particles is one of the common ways of reducing the dielectric constant, the dielectric constant of air is 1, and the introduction of holes can effectively introduce air into polyimide, so that the dielectric constant is reduced, but the way can bring great negative influence on the mechanical properties of polyimide, and polyimide with high performance is difficult to prepare.
Based on this, the present invention provides a method for preparing a low dielectric PI resin derived from an ortho-hydroxy polyimide, comprising the steps of:
step S10: carrying out polycondensation reaction on dianhydride, diamine monomer and 2,2' -bis (3-amino-4-hydroxyphenyl) -hexafluoropropane in a solvent to obtain polyamic acid solution;
step S20: forming the polyamic acid solution to obtain a polyamic acid film;
step S30: performing thermal imidization reaction on the polyamic acid film to obtain a polyimide film containing hydroxyl;
step S40: and carrying out thermal rearrangement reaction on the polyimide film containing the hydroxyl group to obtain the low dielectric PI resin.
Meanwhile, the invention also provides a preparation method of the low dielectric PI resin from the ortho-hydroxyl polyimide, which comprises the following steps:
step SS10: carrying out polycondensation reaction on dianhydride, diamine monomer and 2,2' -bis (3-amino-4-hydroxyphenyl) -hexafluoropropane in a solvent to obtain polyamic acid solution;
step SS20: adding a catalyst and pyridine into the polyamic acid solution, and heating and stirring to obtain a polyimide solution containing hydroxyl groups;
step SS30: molding the polyimide solution containing hydroxyl groups to obtain a polyimide film containing hydroxyl groups;
step SS40: and carrying out thermal rearrangement reaction on the polyimide film containing the hydroxyl group to obtain the low dielectric PI resin.
In this embodiment, two methods for preparing low dielectric PI resins derived from ortho-hydroxy polyimide are provided, in which a hydroxy-containing polyimide is prepared by thermal imidization or chemical imidization, and then a thermal rearrangement reaction is performed at a high temperature to obtain a benzoxazole-polyimide structure, i.e., a low dielectric PI resin.
Specifically, the thermal rearrangement reaction can be utilized to increase the average spacing between molecular chains by releasing carbon dioxide gas, introducing more free volume, helping to lower the dielectric constant of polyimide. On the other hand, trifluoromethyl has low polarizability and hydrophobic group and also has larger volume; the trifluoromethyl with low polarizability and large volume under high frequency can reduce the dielectric constant of the material, meanwhile, fluorine atoms are hydrophobic groups, and after the fluorine atoms are introduced, an aggregation phenomenon exists on the surface of the material, so that water molecules can be effectively prevented from entering the material, and the water absorption of the material is reduced. By combining the advantages, the average distance between molecular chains of PI can be increased by introducing polyimide containing a benzoxazole structure, and simultaneously, the dielectric constant and the hydrophobic property of the material are further reduced by superposing trifluoromethyl, so that polyimide with excellent properties is prepared.
In some embodiments, the polyimide is synthesized using a two-step process (thermal imidization + thermal rearrangement) based on the total molar amount of diamine monomer, dianhydride, wherein the amount of 2,2' -bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (APAF) species in the diamine monomer is named; if APAF is 5% of the diamine monomer, the low dielectric PI resin produced is designated as PBO-5, and so on.
The polyimide is synthesized by a chemical imine method, wherein the mass fraction of the polymer in the polymer solution is adjusted to be 10-30% based on the total mass of diamine monomers and dianhydride, and the diamine monomers are as follows: dianhydride: catalyst: the ratio of pyridine addition was 1mol:1mol: (1-3) ml: (0.5-2) ml.
In some embodiments, the catalyst is selected from, but not limited to, at least one of acetic anhydride, quinoline, isoquinoline.
In some embodiments, the dianhydride includes, but is not limited to:
one of them.
In some embodiments, the diamine monomer is a compound containing two or more amine groups, including but not limited to:
one of the following; wherein R is 1 、R 2 Independently selected from-CF 3 、-CH 3 (C n H 2n+1 )、/>One of the following; r is selected from-H, -CH 3 、One of them.
In some embodiments, the solvent is selected from, but not limited to, one of N, N-dimethylformamide, N-methylpyrrolidone, dimethylacetamide, gamma-butyrolactone, which is utilized to provide an environment for the reaction to form the polyamic acid.
In some embodiments, the temperature of the polycondensation reaction is from-5 to 30 ℃ and the time of the polycondensation reaction is from 6 to 24 hours, at which the dianhydride, diamine monomer, and APAF can be polycondensed in the presence of a solvent to form a polyamic acid; the temperature rising rate of the thermal rearrangement reaction is 1.0-10 ℃/min, the temperature of the thermal rearrangement reaction is 400-450 ℃, the time of the thermal rearrangement reaction is 60-120min, the average spacing between molecular chains can be increased by releasing carbon dioxide gas in the hydroxyl-containing polyimide film by utilizing the thermal rearrangement reaction, more free volume is introduced, and the dielectric constant of polyimide is reduced.
In a preferred embodiment, the polycondensation reaction is conducted under an inert atmosphere including, but not limited to, one of nitrogen, helium, neon, argon.
Specifically, when the low dielectric PI resin (polyimide film) is prepared by adopting a two-step method, firstly, carrying out suction filtration on a polyamic acid (PAA) solution obtained by polycondensation reaction, then, coating the polyamic acid solution on a glass plate to obtain a polyamic acid film, then, carrying out heating drying, then, carrying out vacuum drying, taking down or attaching the polyamic acid film on the glass plate after the polyamic acid film is formed, carrying out thermal imidization reaction, and finally, putting the glass plate into a tubular furnace to carry out thermal rearrangement reaction. The low dielectric PI resin (polyimide film) is prepared by chemical imine method, namely, imidized polymer solution (polyimide solution containing hydroxyl) is coated on a glass plate, then the glass plate is put into a vacuum oven (100-170 ℃) for drying for 24 hours to remove the solvent, finally, the glass plate is put into a tube furnace for thermal rearrangement reaction, and the glass plate is cooled to room temperature and then put into water for natural shedding.
In some embodiments, after the thermal rearrangement reaction, the polyimide film attached to the substrate is removed by immersing in deionized water and/or hot water, but is not limited thereto.
In some embodiments, the thermal imidization reaction has a heating rate of 1.0 to 20 ℃/min and a temperature of 30 to 400 ℃; wherein the thermal imidization reaction is carried out at 100-300 ℃ for 60-120min. Under the reaction condition, the polyamic acid film can be reacted to obtain the polyimide film containing hydroxyl.
In some embodiments, the temperature of the heat-agitation treatment is 60-190 ℃, and the time of the heat-agitation treatment is 12-24 hours.
In some embodiments, in the step SS20, a catalyst and pyridine are added to the polyamic acid solution, and the solution is subjected to a heating and stirring treatment, and specifically includes the steps of: adding a catalyst and pyridine into the polyamic acid solution, and heating and stirring to obtain a polymer solution; carrying out suction filtration on the polymer solution to obtain polyimide powder containing hydroxyl groups; and mixing the hydroxyl-containing polyimide powder with a solvent to obtain a hydroxyl-containing polyimide solution.
In addition, the invention also provides a low dielectric PI resin derived from the ortho-hydroxyl polyimide, which is prepared by the preparation method of the low dielectric PI resin derived from the ortho-hydroxyl polyimide.
In addition, the invention also provides application of the low dielectric PI resin derived from the ortho-hydroxyl polyimide in an electronic packaging material or a circuit substrate.
The following examples are further given to illustrate the invention in detail. It is also to be understood that the following examples are given solely for the purpose of illustration and are not to be construed as limitations upon the scope of the invention, since numerous insubstantial modifications and variations will now occur to those skilled in the art in light of the foregoing disclosure.
Example 1
In the embodiment, polyimide PBO-5 is synthesized by a two-step method, and the preparation steps comprise the following steps:
weighing diamine monomer PBAP6F 2.5923g and APAF 0.1055g, adding a three-neck flask filled with nitrogen, adding a proper amount of anhydrous DMAC, stirring and the like, adding dianhydride BPADA 3g after the diamine monomer is completely dissolved, adding the DMAC to adjust the solid content of the polymer to 20%, stirring and reacting for 8 hours at normal temperature, and filtering out insoluble impurities to obtain polyamic acid solution.
The polyamic acid solution was evacuated for 3 hours to remove air bubbles, then the polyamic acid solution was scraped off a film on a glass plate with a 750 μm doctor blade, then placed in an oven to remove the solvent, and finally the glass plate loaded with the polyamic acid film was placed in a muffle furnace to perform thermal imidization according to a temperature-rising program of 30 to 80 ℃ (3 ℃/min, heat-retaining 60 min), 80 to 150 ℃ (3 ℃/min, heat-retaining 60 min), 150 to 200 ℃ (3 ℃/min, heat-retaining 50 min), 200 to 250 ℃ (3 ℃/min, heat-retaining 50 min). After the thermal imidization is finished, the glass plate is cooled to room temperature, and then is soaked in cold water, and the PI film naturally drops off (polyimide film containing hydroxyl groups).
The peeled polyimide film containing hydroxyl is placed between two graphite plates, and is placed into a tube furnace under the argon atmosphere for thermal rearrangement reaction to obtain low dielectric PI resin (PBO-5), and the nuclear magnetic resonance chart of the low dielectric PI resin is shown in figure 1. Wherein, the temperature rise program is: 30 ℃ -300 ℃ (3 ℃/min, 60min of heat preservation), 300 ℃ -350 ℃ (3 ℃/min, 60min of heat preservation), 350 ℃ -400 ℃ (3 ℃/min, 60min of heat preservation).
It should be noted that the ratio of the amount of APAF material in the diamine monomer is named. Such as: APAF represents 5% of the amount of diamine monomer material, i.e., n (PBAP 6F): n (APAF) =95:5, designated PBO-5, and so on.
Example 2
In the embodiment, polyimide PBO-10 is synthesized by a two-step method, and the preparation steps comprise the following steps:
diamine monomer PBAP6F 1.6372g and APAF 0.1291g are weighed into a three-necked flask filled with nitrogen, a proper amount of anhydrous DMAC is added, and dianhydride BPADA 2g is added after diamine monomer is completely dissolved by stirring. DMAC is added to adjust the solid content of the polymer to 20 percent, and insoluble impurities are filtered out after stirring reaction is carried out for 8 hours at normal temperature, thus obtaining polyamic acid solution.
The polyamic acid solution was evacuated for 3 hours to remove air bubbles, then the polyamic acid solution was scraped off a film on a glass plate with a 750 μm doctor blade, then placed in an oven to remove the solvent, and finally the glass plate loaded with the polyamic acid film was placed in a muffle furnace to perform thermal imidization according to a temperature-rising program of 30 to 80 ℃ (3 ℃/min, heat-retaining 60 min), 80 to 150 ℃ (3 ℃/min, heat-retaining 60 min), 150 to 200 ℃ (3 ℃/min, heat-retaining 50 min), 200 to 250 ℃ (3 ℃/min, heat-retaining 50 min). After the thermal imidization is finished, the glass plate is cooled to room temperature, and then is soaked in cold water, and the PI film naturally drops off (polyimide film containing hydroxyl groups).
The peeled polyimide film containing hydroxyl groups is placed between two graphite plates, and is placed into a tube furnace under the argon atmosphere for thermal rearrangement reaction to obtain low dielectric PI resin (PBO-10), and the nuclear magnetic resonance chart of the low dielectric PI resin is shown in figure 2. Wherein, the temperature rise program is: 30 ℃ -300 ℃ (3 ℃/min, 60min of heat preservation), 300 ℃ -350 ℃ (3 ℃/min, 60min of heat preservation), 350 ℃ -400 ℃ (3 ℃/min, 60min of heat preservation).
The following is a reaction chemical formula for preparing a polyimide film in a two-step process represented by example 1 and example 2:
example 3
This example utilizes a two-step process to synthesize polyimides, PBO-20, PBO-30, and PBO-40, which differ from example 1 in that: the molar ratio of diamine monomer PBAP6F to APAF is different, and the specific steps are as follows:
n(PBAP6F):n(APAF)＝80:20＝PBO-20；
n(PBAP6F):n(APAF)＝70:30＝PBO-30；
n(PBAP6F):n(APAF)＝60:40＝PBO-40。
example 4
Synthesizing polyimide PBO-5-by a chemical imine method, wherein the preparation method comprises the following steps:
diamine monomer PBAP6F 2.5923g and APAF 0.1055g are weighed into a three-neck flask filled with nitrogen, a proper amount of anhydrous DMAC is added, and diamine monomer is completely dissolved after stirring. Then adding 3g of dianhydride BPADA, adding DMAC again to adjust the solid content of the polymer to 15%, and stirring and reacting for 8 hours at normal temperature to obtain the uniform polyamic acid solution.
Acetic anhydride/pyridine (2 ml/1 ml) was added to the polyamic acid solution, and the mixture was heated and stirred at 60℃for 24 hours. The resulting polymer solution was poured into 300ml of ethanol, and suction filtration was performed to obtain yellow polyimide powder. The obtained powder was dried in a vacuum oven at 200℃for 24 hours to obtain a polyimide powder containing no solvent. 2g of dried polyimide powder is weighed, 8g of anhydrous DMAC is added, the mixture is stirred for 5 hours at normal temperature to obtain a uniform polymer solution, and insoluble impurities are filtered out.
And vacuumizing the filtered solution for 3 hours to remove bubbles, scraping a film from the polymer solution on a glass plate by using a 750 mu m scraper, then placing the glass plate into a vacuum oven (200 ℃) to dry for 24 hours to remove the solvent, soaking the glass plate in cold water after the drying is finished, and waiting for the PI film to naturally fall off to obtain the hydroxyl-containing polyimide film.
The peeled polyimide film containing hydroxyl groups is placed between two graphite plates, and is placed into a tube furnace under the argon atmosphere for thermal rearrangement reaction to obtain low dielectric PI resin (PBO-5-melting), and the nuclear magnetic resonance chart of the low dielectric PI resin is shown in figure 3. Wherein, the temperature rise program is: 30 ℃ -300 ℃ (3 ℃/min, 60min of heat preservation), 300 ℃ -350 ℃ (3 ℃/min, 60min of heat preservation), 350 ℃ -400 ℃ (3 ℃/min, 60min of heat preservation).
The PBO-5, PBO-10, PBO-20, PBO-30, and PBO-40 prepared in examples 1-3 were subjected to performance test,
the PI was subjected to Fourier transform infrared spectrum characterization, the test results are shown in FIG. 4, and as can be seen from FIG. 4, the amide is between 3300 cm and 3500cm -1 (N-H) and 1660cm -1 The characteristic absorption peak (C=O) disappeared at 1775cm -1 、1715cm -1 、716cm -1 There appears a symmetrical or asymmetrical stretching vibration peak of c=o, a bending vibration stretching peak of C-N, indicating that an imide ring is formed. Furthermore, at 1727cm -1 、1599cm -1 、1205cm -1 、1132cm -1 Symmetrical or asymmetrical stretching vibration peaks of c= O, C = N, C-O, C-F occur, respectively. Furthermore, at 1526cm -1 、1386cm -1 The skeleton vibration absorption peak of the benzene ring and the characteristic absorption peak of the methyl also appear, which indicates that the PAA molecule is successfully prepared according to the expected design.
The obtained PI was subjected to DSC test, and the test results are shown in fig. 5. The obtained PI has a glass transition temperature above 289 ℃ which indicates that the PI has better thermal stability. As the amount of APAF incorporated increases, the glass transition temperature of PI also gradually increases, indicating that its thermal stability increases.
The PI was subjected to a thermal decomposition test, and the results are shown in fig. 6. The 5% decomposition temperature of the obtained PI is above 450 ℃, which shows that the PI has better thermal stability.
The contact angle of the obtained PI was measured, and the water contact angle chart is shown in fig. 7, and the contact angle of the film gradually decreases with increasing the amount of the APAF incorporated, indicating that the hydrophobicity thereof decreases. This is attributable to the fact that the more APAF increases, the more gas is generated during thermal rearrangement, the average spacing between molecular chains increases, the contact area with water molecules increases, and the hydrophobicity becomes poor. Overall, the PI obtained has a better hydrophobicity.
As can be seen from the figures, the data of the dielectric constants, dielectric losses, glass transition temperatures, contact angles and water absorption of PBO-5, PBO-10, PBO-20, PBO-30 and PBO-40 are shown in the following tables:
in summary, the low dielectric PI resin derived from the ortho-hydroxy polyimide, the preparation method and the application thereof provided by the invention, the ortho-hydroxy polyimide structure obtained after the thermal imidization reaction or the chemical imidization reaction is utilized to generate the benzoxazole-polyimide structure, namely the low dielectric PI resin, through the thermal rearrangement reaction at high temperature. The thermal rearrangement reaction can increase the average spacing between molecular chains by releasing carbon dioxide gas, and more free volume is introduced to help reduce the dielectric constant of polyimide; on the other hand, the trifluoromethyl group in the reaction raw material has low polarizability and hydrophobic group, and also has larger volume. Low polarizability at high frequency and trifluoromethyl with larger volume can lower the dielectric constant of the material; and fluorine atoms are hydrophobic groups, and an aggregation phenomenon exists on the surface of the material after the fluorine atoms are introduced, so that water molecules can be effectively prevented from entering the material, and the water absorption of the material is reduced. According to the invention, the polyimide containing the benzoxazole structure is introduced, so that the average distance between molecular chains of PI can be increased, and simultaneously, the dielectric constant and the hydrophobic property of the material are further reduced by superposing trifluoromethyl, so that polyimide with excellent performance is prepared.
It is to be understood that the invention is not limited in its application to the examples described above, but is capable of modification and variation in light of the above teachings by those skilled in the art, and that all such modifications and variations are intended to be included within the scope of the appended claims.
Claims (10)
1. A method for preparing a low dielectric PI resin derived from an ortho-hydroxy polyimide, comprising the steps of:
carrying out polycondensation reaction on dianhydride, diamine monomer and 2,2' -bis (3-amino-4-hydroxyphenyl) -hexafluoropropane in a solvent to obtain polyamic acid solution;
forming the polyamic acid solution to obtain a polyamic acid film;
performing thermal imidization reaction on the polyamic acid film to obtain a polyimide film containing hydroxyl;
and carrying out thermal rearrangement reaction on the polyimide film containing the hydroxyl group to obtain the low dielectric PI resin.
2. A method for preparing a low dielectric PI resin derived from an ortho-hydroxy polyimide, comprising the steps of:
carrying out polycondensation reaction on dianhydride, diamine monomer and 2,2' -bis (3-amino-4-hydroxyphenyl) -hexafluoropropane in a solvent to obtain polyamic acid solution;
adding a catalyst and pyridine into the polyamic acid solution, and heating and stirring to obtain a polyimide solution containing hydroxyl groups;
molding the polyimide solution containing hydroxyl groups to obtain a polyimide film containing hydroxyl groups;
and carrying out thermal rearrangement reaction on the polyimide film containing the hydroxyl group to obtain the low dielectric PI resin.
3. The method for producing a low dielectric PI resin derived from an ortho-hydroxy polyimide according to claim 1 or 2, wherein the dianhydride comprises:
one of them.
4. The method for producing a low dielectric PI resin derived from an ortho-hydroxy polyimide according to claim 1 or 2, wherein the diamine monomer comprises:
one of the following; wherein R is 1 、R 2 Independently selected from-CF 3 、-CH 3 (C n H 2n+1 )、/>One of the following; r is selected from-H, -CH 3 、One of them.
5. The method for producing a low dielectric PI resin derived from an ortho-hydroxy polyimide according to claim 1 or 2, wherein the solvent is one selected from the group consisting of N, N-dimethylformamide, N-methylpyrrolidone, dimethylacetamide, and γ -butyrolactone.
6. The method for producing a low dielectric PI resin derived from an ortho-hydroxy polyimide according to claim 1 or 2, wherein the temperature of the polycondensation reaction is-5 to 30 ℃, and the time of the polycondensation reaction is 6 to 24 hours; the temperature rising rate of the thermal rearrangement reaction is 1.0-10 ℃/min, the temperature of the thermal rearrangement reaction is 400-450 ℃, and the time of the thermal rearrangement reaction is 60-120min.
7. The method for preparing low dielectric PI resin derived from ortho-hydroxy polyimide according to claim 1, wherein the temperature rise rate of the thermal imidization reaction is 1.0 to 20 ℃/min, and the temperature of the thermal imidization reaction is 30 to 400 ℃; wherein the thermal imidization reaction is carried out at 100-300 ℃ for 60-120min.
8. The method for producing a low dielectric PI resin derived from an ortho-hydroxy polyimide according to claim 2, wherein the temperature of the heat-stirring treatment is 60 to 190 ℃, and the time of the heat-stirring treatment is 12 to 24 hours.
9. A low dielectric PI resin derived from an ortho-hydroxy polyimide, characterized by being produced by the process for producing a low dielectric PI resin derived from an ortho-hydroxy polyimide as claimed in any one of claims 1 to 8.
10. Use of the low dielectric PI resin derived from an ortho-hydroxy polyimide as claimed in claim 9 in electronic packaging materials or circuit substrates.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150004239A (en) * | 2013-07-01 | 2015-01-12 | 한양대학교 산학협력단 | Crosslinked thermally rearranged poly(benzoxazole-co-imide), gas separation membranes comprising the same and preparation method thereof |
| CN111498827A (en) * | 2020-04-12 | 2020-08-07 | 辽宁科技大学 | 3D thermally-induced rearrangement polymer-based porous nitrogen-doped carbon material and preparation method thereof |
| CN113996193A (en) * | 2021-11-15 | 2022-02-01 | 南京工业大学 | Copolyimide membrane, preparation method and application thereof in helium purification |
| CN115970522A (en) * | 2022-08-18 | 2023-04-18 | 齐齐哈尔大学 | Preparation method of silanization thermal rearrangement polybenzoxazole gas separation membrane material |
| CN116041761A (en) * | 2023-01-04 | 2023-05-02 | 深圳大学 | Polyimide film capable of multiplexing high frequency, low dielectric and low loss, and preparation method and application thereof |
-
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20150004239A (en) * | 2013-07-01 | 2015-01-12 | 한양대학교 산학협력단 | Crosslinked thermally rearranged poly(benzoxazole-co-imide), gas separation membranes comprising the same and preparation method thereof |
| CN111498827A (en) * | 2020-04-12 | 2020-08-07 | 辽宁科技大学 | 3D thermally-induced rearrangement polymer-based porous nitrogen-doped carbon material and preparation method thereof |
| CN113996193A (en) * | 2021-11-15 | 2022-02-01 | 南京工业大学 | Copolyimide membrane, preparation method and application thereof in helium purification |
| CN115970522A (en) * | 2022-08-18 | 2023-04-18 | 齐齐哈尔大学 | Preparation method of silanization thermal rearrangement polybenzoxazole gas separation membrane material |
| CN116041761A (en) * | 2023-01-04 | 2023-05-02 | 深圳大学 | Polyimide film capable of multiplexing high frequency, low dielectric and low loss, and preparation method and application thereof |
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