CN113277950A - Asymmetric aromatic diamine monomer containing terphenyl large-substitution side group and polyimide - Google Patents
Asymmetric aromatic diamine monomer containing terphenyl large-substitution side group and polyimide Download PDFInfo
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- CN113277950A CN113277950A CN202110497984.9A CN202110497984A CN113277950A CN 113277950 A CN113277950 A CN 113277950A CN 202110497984 A CN202110497984 A CN 202110497984A CN 113277950 A CN113277950 A CN 113277950A
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- polyimide
- terphenyl
- diphenyl
- side group
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 86
- 239000004642 Polyimide Substances 0.000 title claims abstract description 83
- 239000000178 monomer Substances 0.000 title claims abstract description 59
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 150000004984 aromatic diamines Chemical class 0.000 title claims abstract description 22
- 238000006467 substitution reaction Methods 0.000 title claims abstract description 18
- 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 34
- 150000004985 diamines Chemical class 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000004377 microelectronic Methods 0.000 claims abstract description 10
- MRBZYVMZUBUDAX-UHFFFAOYSA-N (3,5-diphenylphenyl)boronic acid Chemical compound C=1C(B(O)O)=CC(C=2C=CC=CC=2)=CC=1C1=CC=CC=C1 MRBZYVMZUBUDAX-UHFFFAOYSA-N 0.000 claims abstract description 8
- PBOPJYORIDJAFE-UHFFFAOYSA-N 2,4-dinitrobromobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C([N+]([O-])=O)=C1 PBOPJYORIDJAFE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- -1 dinitro compound Chemical class 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 21
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- AWJUIBRHMBBTKR-UHFFFAOYSA-N iso-quinoline Natural products C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 7
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-methyl-PhOH Natural products CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- JVERADGGGBYHNP-UHFFFAOYSA-N 5-phenylbenzene-1,2,3,4-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C=2C=CC=CC=2)=C1C(O)=O JVERADGGGBYHNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 2
- 125000003717 m-cresyl group Chemical group [H]C1=C([H])C(O*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
- 238000004062 sedimentation Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 6
- 125000001424 substituent group Chemical group 0.000 claims 6
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 239000012528 membrane Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 13
- 229920006254 polymer film Polymers 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 235000010290 biphenyl Nutrition 0.000 description 9
- 239000004305 biphenyl Substances 0.000 description 9
- 125000006267 biphenyl group Chemical group 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229920003002 synthetic resin Polymers 0.000 description 3
- 239000000057 synthetic resin Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Substances [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 230000008863 intramolecular interaction Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000004806 packaging method and process 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
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
- C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/51—Phenylenediamines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/325—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups reduction by other means than indicated in C07C209/34 or C07C209/36
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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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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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
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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
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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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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- 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
Abstract
The invention belongs to the field of high polymer materials, and particularly relates to an asymmetric aromatic diamine monomer containing a terphenyl large-substitution side group and polyimide. 2, 4-dinitrobromobenzene and 3, 5-diphenyl phenylboronic acid react under the alkaline condition according to the molar ratio to obtain an intermediate compound, and then the intermediate dinitro compound is reduced through reduction reaction to obtain the asymmetric aromatic diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene containing a terphenyl large substitution structure. Adding diamine monomers and commercial aromatic dianhydride monomers with equal mass into an organic solvent, stirring and reacting under the action of a catalyst, and then settling, washing and drying to obtain the fibrous polyimide with the asymmetric structure containing the terphenyl large-substitution side group. The solubility of the polyimide in a specific solvent can reach more than 30 wt%, and the polyimide has excellent film forming property, and the prepared polymer film has potential application value in the field of microelectronics.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an asymmetric aromatic diamine monomer containing a terphenyl large-substituted side group and polyimide.
Background
Polyimide (PI) is a high-performance polymer material with wide application, and has unique structural characteristics and excellent comprehensive performance. The functionalized PI film can be used in high and new technical fields of gas separation films, flexible photoelectric device substrates, motor insulation, microelectronic manufacturing and packaging and the like. With the rapid development of the microelectronic industry, the wire density of the integrated circuit is continuously increased, which leads to the problems of slow signal transmission speed and increased power loss, and in order to solve the problems, the insulating layer material of the integrated circuit must have a low dielectric constant k (1.6-2.8), but the dielectric constant k of pure polyimide is about 3.6, which cannot meet the requirement of the modern microelectronic industry for low dielectric materials. Therefore, reducing the dielectric constant of PI is now a research focus of researchers, and this is one of the keys of future integrated circuits towards further miniaturization. In addition, the thermal performance plays an important role in many microelectronic manufacturing processes, and PI has a rigid and conjugated skeleton and strong intermolecular and intramolecular interactions, so that PI has superior high-temperature resistance, but has the problems of difficult dissolution and difficult dissolution.
Junction of researchers on low dielectric PI high polymer materialThe structure and composition design develops research aiming at modification of the body structure: (1) introducing fluorine-containing group (-F), methylene (-CH)2-), alicyclic groups (e.g., cyclohexyl, etc.), etc., are effective in reducing the dielectric constant of the PI; (2) introduction of functional groups having high molar volumes, such as phenyl, naphthyl, fluorenyl, and the like, can also be effective in reducing the dielectric constant of PI. PI containing alicyclic substituents and fluorine-containing groups generally combine low molar polarizability with high molar volume characteristics, but its thermal stability and mechanical properties are lost to some extent.
Disclosure of Invention
The invention aims to improve the dissolution and film-forming properties of polyimide polymer and further improve the dielectric property of a polymer film, and designs and prepares an asymmetric aromatic diamine monomer containing terphenyl large-substituent side groups and polyimide based on molecular design; by introducing nonpolar terphenyl with large free volume and an asymmetric structure into a polymer molecular main chain, the polymer has high solubility and excellent film forming property in a specific solvent, and can further effectively improve the dielectric property of a polyimide film material, and the polyimide polymer has important potential application value in the field of microelectronics.
The invention adopts 2, 4-dinitrobromobenzene and 3, 5-diphenyl phenylboronic acid as starting materials, successfully prepares an asymmetric aromatic diamine monomer containing a terphenyl large-substitution side group structure through two steps of reactions of Suzuki coupling and redox, successfully introduces the terphenyl large-side group and the asymmetric structure onto a polyimide main chain by using the prepared aromatic diamine monomer containing the diphenyl substitution asymmetric structure and a dianhydride monomer through one-step solution polycondensation, increases the space free volume by interfering the close accumulation of polymer molecular chains, keeps the inherent rigid structure, and effectively avoids the loss of thermal and mechanical properties caused by the introduction of fat or fluorine-containing groups to PI. And the nonpolar terphenyl bulky side group structure increases the free volume, reduces the density of polarizable groups and reduces hygroscopicity. Therefore, the polyimide has higher solubility, lower dielectric constant and hygroscopicity, so that the polyimide has potential application value in the field of microelectronic industry.
The invention provides an asymmetric aromatic diamine monomer containing terphenyl large-substitution side group, wherein the structural formula of 3,5- (diphenyl) phenyl-2, 4-diaminobenzene is as follows:
the preparation method of the asymmetric aromatic diamine monomer containing the terphenyl large-substitution side group comprises the following steps:
(1) under the protection of nitrogen, 2, 4-dinitrobromobenzene and 3, 5-diphenyl phenylboronic acid in a certain molar ratio are added into a three-neck flask with a mechanical stirrer, an appropriate amount of organic solvent, sodium carbonate aqueous solution and catalyst are further added respectively, the mixture is stirred at room temperature for half an hour, then the temperature is raised to 60-120 ℃ for reaction for 6-12 hours, the reaction is finished, and a white intermediate dinitro compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene can be obtained after settlement, filtration, drying and recrystallization.
(2) Adding an intermediate dinitro compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene into a three-neck flask with mechanical stirring, further adding a proper amount of organic solvent, a reducing agent and a catalyst respectively, reacting for 4-12 h under reflux, ending the reaction, pouring the solution into a beaker, standing, performing suction filtration after a product is separated out, washing with ethanol, and performing vacuum drying to obtain a monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene.
The invention also provides a highly soluble polyimide containing terphenyl large-substituted side group with asymmetric structure, which has the structural formula:
wherein ,
can be that
Wherein the repeating unit n is 40 to 100.
The preparation method of the highly soluble polyimide polymer containing the terphenyl large-substitution side group asymmetric structure comprises the following specific steps:
under the protection of nitrogen, adding an asymmetric aromatic diamine monomer containing a terphenyl large-substitution side group and an aromatic dianhydride monomer with equal mass into an organic solvent, adding a catalyst, stirring at 80-100 ℃ for half an hour until the monomers are completely dissolved, continuing heating to 180-200 ℃ for reaction for 6-10 hours to obtain a viscous polymer solution, finishing the reaction, pouring the polymer solution into ethanol for settling, and further filtering, washing and drying to obtain the fibrous highly soluble polyimide containing the terphenyl large-substitution side group asymmetric structure.
The asymmetric aromatic diamine monomer containing terphenyl large-substitution side group is 3,5- (diphenyl) phenyl-2, 4-diaminobenzene, and the dianhydride monomer is one of diphenyl ether tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride.
The organic solvent is m-cresol or N-methyl pyrrolidone, and the dosage of the organic solvent is 7-15 times of the total mass of diamine and dianhydride monomers; the catalyst is isoquinoline, and the dosage of the catalyst is 1 to 3 percent of the mass of the diamine.
The specific synthetic route of the asymmetric aromatic diamine monomer containing the terphenyl large-substitution side group and the polyimide polymer is as follows:
(1) synthesis of asymmetric aromatic diamine monomer containing terphenyl large-substituted side group:
(2) synthesizing a polyimide polymer containing terphenyl large-substituent side group asymmetric structure:
the asymmetric polyimide polymer film containing the terphenyl large-substitution side group has important potential application value in the field of microelectronics.
The invention has the beneficial effects that:
(1) the asymmetric aromatic diamine monomer containing the terphenyl large-substitution side group prepared by the invention has the advantages that the used starting raw materials are easy to obtain, the adopted synthetic route is relatively simple and convenient, the product is easy to purify and separate, the yield is high, and the product is stable at normal temperature;
(2) the polyimide film material prepared by the invention can directly obtain a polyimide polymer by adopting one-step solution polycondensation, does not need to be converted into polyimide by polyamide acid, and has simple synthesis preparation process and easy industrialization;
(3) the polyimide film material prepared by the invention has good dissolving and film-forming properties, heat resistance and dielectric properties due to the introduction of bulky terphenyl large-substituted side groups and asymmetric structures in the polymer molecular structure, and the prepared film has potential application value in the field of microelectronics.
Drawings
FIG. 1 shows the reaction product of an intermediate dinitro compound and a diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene in an example of the present invention1H NMR spectrum.
FIG. 2 shows a polyimide PI prepared from diamine monomers 3,5- (diphenyl) phenyl-2, 4-diaminobenzene and diphenyl ether tetracarboxylic dianhydride in example 11H NMR spectrum.
FIG. 3 is an infrared spectrum of an intermediate dinitro compound, a diamine monomer and a polyimide PI a in example 1.
FIG. 4 is a DSC chart of 3 polyimides PI a-c prepared from diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene and diphenyl ether tetracarboxylic dianhydride, diphenyl tetracarboxylic dianhydride, and benzophenone tetracarboxylic dianhydride, respectively, in examples.
FIG. 5 shows the preparation of polyimide PI b prepared from diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene and biphenyltetracarboxylic dianhydride in N2And thermogravimetric plot under air.
FIG. 6 is a UV-VIS spectrum of 3 polyimide PI a-c films prepared from diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene and diphenyl ether tetracarboxylic dianhydride, diphenyl tetracarboxylic dianhydride, and benzophenone tetracarboxylic dianhydride, respectively, according to the examples.
FIG. 7 is a graph showing the relationship between the dielectric constant and the frequency of an electric field for 3 types of polyimides PI a to c and a standard Kapton film prepared from a diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene and diphenyl ether tetracarboxylic dianhydride, diphenyl tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride, respectively, in examples.
Detailed Description
Preferred embodiments of the present invention will be described in more detail with reference to specific examples.
The following are the raw materials and drugs used in the examples:
2, 4-dinitrobromobenzene: wuhan grown into science and technology development Limited company with purity of 98%.
3, 5-diphenylphenylboronic acid: suzhou Sukai Lu chemical technology, Inc., purity 98%.
Tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4): shanxi Kaida chemical Co., Ltd., palladium content: not less than 9.20 percent.
Pd/C catalyst: shanxi Kaida chemical Co., Ltd., palladium content: 5.0 percent.
3,5- (diphenyl) phenyl-2, 4-diaminobenzene: the product is prepared by a laboratory, and the purity is 99%.
Diphenyl ether tetracarboxylic dianhydride: shanghai institute for synthetic resins, purity 99%.
Biphenyl tetracarboxylic dianhydride: shanghai institute for synthetic resins, purity 99%.
Benzophenone tetracarboxylic dianhydride: shanghai institute for synthetic resins, purity 99%.
Toluene: chemical reagent of national drug group limited company, purity 99%.
Ethylene glycol dimethyl ether: alfa corporation, 99% pure.
Hydrazine hydrate: the purity of the chemical reagent of the national medicine group is more than or equal to 50 percent.
M-cresol: aladdin reagent, Inc., 99% pure.
Isoquinoline: alfa corporation, 99% pure.
N-methylpyrrolidone, N-dimethylacetamide: jiangsu Shengqiang functional chemical company, 99 percent.
Example 1
(1) Preparation of asymmetric aromatic diamine monomer containing terphenyl large-substituted side group
(a) Under the protection of nitrogen, 19.76g (8mmol) of 2, 4-dinitrobromobenzene, 24.12g (88mmol) of 3, 5-diphenyl phenylboronic acid and 1.85g (0.16mmol) of tetrakis (triphenylphosphine) palladium are added into a 500mL three-neck flask, 150mL of mixed solvent of 2:1 toluene and ethylene glycol dimethyl ether and 120mL of 1mol/L sodium carbonate solution are respectively added, the mixture is stirred at room temperature for half an hour and then heated to 100 ℃ for reaction for 8 hours, and after the reaction is finished, the intermediate compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene is obtained through suction filtration, drying and further recrystallization, wherein the yield is 91% (the yield is obtained by the ratio of the mass of the actually obtained intermediate compound to the mass of the theoretically obtained intermediate compound).
(b) Adding 18.82g (0.05mol) of intermediate compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene into a three-neck flask provided with a stirrer and a spherical condenser, respectively adding 180mL of ethanol, 12.01g (0.23mol) of hydrazine hydrate reducing agent and 0.95g of 5% solid content Pd/C catalyst, reacting for 8 hours at 90 ℃ under reflux, pouring the solution into a beaker after the reaction is finished, standing, performing suction filtration and washing with ethanol after the product is separated out, and performing vacuum drying to obtain yellow crystal 3,5- (diphenyl) phenyl-2, 4-diaminobenzene with the yield of 85% (the yield is obtained by the ratio of the mass of the actually obtained diamine monomer to the mass of the theoretically obtained diamine monomer)1H NMR(DMSO-d6400MHz) as shown in figure 1; FT-IR (KBr) is shown in FIG. 3.
(2) Preparation of asymmetric polyimide containing terphenyl large-substituted side group
In a 100mL dry three-neck flask provided with a nitrogen protection and a condenser tube, 1.3457g (4mmol) of diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene and 1.2408g (4mmol) of diphenyl ether tetracarboxylic dianhydride are respectively added, 14mL of m-cresol (the solid content of the system is 5-20%) and 0.08mmol of isoquinoline are sequentially added, the mixture is stirred at 80 ℃ for half an hour until the monomer is completely dissolved, the temperature is continuously raised to 180 ℃ for reaction for 10 hours to obtain a viscous polymer solution, and the reaction is finishedAnd (3) reacting, pouring the polymer solution into ethanol for settling, further filtering, washing and drying to obtain the fibrous polyimide polymer (PI a) containing the terphenyl large-substitution side group asymmetric structure. The yield is 99 percent;1H NMR(DMSO-d6400MHz) as shown in figure 2; FT-IR (KBr) is shown in FIG. 3.
Example 2
(1) Preparation of aromatic diamine monomer containing terphenyl large-substituted side group asymmetric structure
(a) Under the protection of nitrogen, 19.76g (8mmol) of 2, 4-dinitrobromobenzene, 24.12g (88mmol) of 3, 5-diphenylphenylboronic acid and 2.10g (0.18mmol) of tetrakis (triphenylphosphine) palladium are added into a 1000mL three-neck flask, 320mL of mixed solvent of 4:1 toluene and ethylene glycol dimethyl ether and 240mL of 2mol/L sodium carbonate solution are respectively added, the mixture is stirred at room temperature for half an hour and then heated to 110 ℃ for reaction for 7 hours, and after the reaction is finished, the intermediate compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene is obtained through suction filtration, drying and further recrystallization, wherein the yield is 88% (the yield is obtained by the ratio of the mass of the actually obtained intermediate compound to the mass of the theoretically obtained intermediate compound).
(b) 18.82g (0.05mol) of intermediate compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene is added into a three-neck flask provided with a stirrer and a spherical condenser, 250mL of ethanol, 15.01g (0.3mol) of hydrazine hydrate reducing agent and 1.80g of 10% solid content Pd/C catalyst are respectively added, the mixture is reacted for 10 hours under reflux at 95 ℃, after the reaction is finished, the solution is poured into a beaker, the solution is kept stand, after the product is separated out, the solution is filtered and washed by ethanol, and after vacuum drying, yellow crystal-shaped 3,5- (diphenyl) phenyl-2, 4-diaminobenzene is obtained with the yield of 81 percent (the yield is obtained by the ratio of the mass of the actually obtained diamine monomer to the mass of the theoretically obtained diamine monomer).
(2) Preparation of highly soluble polyimide containing terphenyl large-substituted side group asymmetric structure
1.3457g (4mmol) of diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene and 1.1769g (4mmol) of biphenyltetracarboxylic dianhydride are respectively added into a 100mL dry three-neck flask provided with a nitrogen protection and a condensing tube, 13mL of N-methylpyrrolidone (with the solid content of the system being 5-20%) and 0.12mmol of isoquinoline are sequentially added, the mixture is stirred at 100 ℃ for half an hour until the monomer is completely dissolved, then the mixture is continuously heated to 200 ℃ for reaction for 6 hours, the reaction is ended, the polymer solution is poured into ethanol for sedimentation, and then the fibrous polyimide polymer (PI b) containing the terphenyl large-substituted side group asymmetric structure is obtained after further filtration, washing and drying. The yield was 98%.
Example 3
(1) Preparation of aromatic diamine monomer containing terphenyl large-substituted side group asymmetric structure
(a) Under the protection of nitrogen, 14.82g (6mmol) of 2, 4-dinitrobromobenzene, 18.09g (66mmol) of 3, 5-diphenyl phenylboronic acid and 1.39g (0.13mmol) of tetrakis (triphenylphosphine) palladium are added into a 500mL three-neck flask, 250mL of a mixed solvent of 3:1 toluene and ethylene glycol dimethyl ether and 150mL of a 2mol/L sodium carbonate solution are respectively added, the mixture is stirred at room temperature for half an hour, then the temperature is raised to 100 ℃ for reaction for 10 hours, and after the reaction is finished, the intermediate compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene is obtained through suction filtration, drying and further recrystallization, wherein the yield is 89% (the yield is obtained by the ratio of the mass of the actually obtained intermediate compound to the mass of the theoretically obtained intermediate compound).
(b) 10.16g (0.03mol) of an intermediate compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene is added into a three-neck flask provided with a stirrer and a spherical condenser, 120mL of ethanol, 9.72g (0.2mol) of hydrazine hydrate reducing agent and 0.51g of 10% solid content Pd/C catalyst are respectively added, the mixture is reacted for 9 hours under reflux at 90 ℃, after the reaction is finished, the solution is poured into a beaker, the solution is kept stand, after a product is separated out, the solution is filtered and washed by ethanol, and after vacuum drying, yellow crystal-shaped 3,5- (diphenyl) phenyl-2, 4-diaminobenzene is obtained, wherein the yield is 84% (the yield is obtained by the ratio of the mass of the actually obtained diamine monomer to the mass of the theoretically obtained diamine monomer).
(2) Preparation of highly soluble polyimide containing terphenyl large-substituted side group asymmetric structure
In a 100mL dry three-neck flask provided with a nitrogen protection and a condensation tube, 1.3457g (4mmol) of diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene and 1.2890g (4mmol) of benzophenonetetracarboxylic dianhydride are respectively added, then 16mL of m-cresol (the solid content of the system is 5-20%) and 0.06mmol of isoquinoline are sequentially added, the mixture is stirred at 90 ℃ for half an hour until the monomer is completely dissolved, the mixture is continuously heated to 200 ℃ for reaction for 8 hours, the reaction is ended, the polymer solution is poured into ethanol for settling, and then the mixture is further filtered, washed and dried, so that the fibrous polyimide polymer (PI c) containing the terphenyl large-substituted side group asymmetric structure is obtained. The yield was 99%.
TABLE 1 intrinsic viscosity and molecular weight of the polyimides
aUsing polystyrene as a standard,DMF was used as an eluent.
Table 1 shows the intrinsic viscosity of 3 polyimides PI a-c prepared from diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene and diphenyl ether tetracarboxylic dianhydride, diphenyl tetracarboxylic dianhydride, and benzophenone tetracarboxylic dianhydride, respectively, in DMAc and the M obtained by dissolving polyimides PI a-c in DMFw、MnValues and polydispersity index (PDI).
TABLE 2 solubility Properties of polyimides
Note: + + +,0.1g sample dissolved in 1mL solvent (10 wt%); + + soluble at 5 wt%; +, soluble at 1 wt%; s, shelling; -, insoluble.
Table 2 shows the solubility of 3 polyimides PI a-c prepared from diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene with diphenyl ether tetracarboxylic dianhydride, diphenyl tetracarboxylic dianhydride, and benzophenone tetracarboxylic dianhydride, respectively.
TABLE 3 thermal Properties of the polyimides
a.10％weight loss temperature in TGA；
b.Residual weight retention at 800℃in nitrogen.
Table 3 shows the thermal properties of 3 polyimides PI a-c prepared from diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene and diphenyl ether tetracarboxylic dianhydride, diphenyl tetracarboxylic dianhydride, and benzophenone tetracarboxylic dianhydride, respectively.
TABLE 4 mechanical and optical Properties of the polyimides
a.Transmittance(％)at 450nm(T450)；
Table 4 shows the mechanical and optical properties of 3 polyimides PI a-c prepared from diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene with diphenyl ether tetracarboxylic dianhydride, diphenyl tetracarboxylic dianhydride, and benzophenone tetracarboxylic dianhydride, respectively.
TABLE 5 dielectric properties, contact angle and Water absorption of polyimide
Table 5 shows the dielectric properties and water absorption of 3 polyimides PI a-c prepared from diamine monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene and diphenyl ether tetracarboxylic dianhydride, diphenyl tetracarboxylic dianhydride, and benzophenone tetracarboxylic dianhydride, respectively.
Claims (9)
1. A kind of asymmetric aromatic diamine monomer containing terphenyl large-substituted side group is characterized in that: the aromatic diamine monomer is 3,5- (diphenyl) phenyl-2, 4-diaminobenzene, and the structural formula is as follows:
2. the method of claim 1, wherein the asymmetric aromatic diamine monomer containing the terphenyl bulky substituent group comprises: the preparation method comprises the following steps:
(1) under the protection of nitrogen, adding 2, 4-dinitrobromobenzene and 3, 5-diphenyl phenylboronic acid into a three-neck flask with mechanical stirring, further respectively adding an organic solvent, a sodium carbonate aqueous solution and a catalyst, stirring at room temperature for half an hour, heating to 60-120 ℃, reacting for 6-12 h, finishing the reaction, and settling, filtering, drying and recrystallizing to obtain a white intermediate dinitro compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene;
(2) adding an intermediate dinitro compound 3,5- (diphenyl) phenyl-2, 4-dinitrobenzene into a three-neck flask with mechanical stirring, further respectively adding an organic solvent, a reducing agent and a catalyst, reacting for 4-12 h under reflux, ending the reaction, pouring the solution into a beaker, standing, performing suction filtration after a product is separated out, washing with ethanol, and performing vacuum drying to obtain a monomer 3,5- (diphenyl) phenyl-2, 4-diaminobenzene.
3. Polyimide containing terphenyl large-substituted side group asymmetric structure is characterized in that: the structural formula of the polyimide is as follows:
wherein ,
is composed of
Wherein the repeating unit n is 40 to 100.
4. A method for preparing the polyimide containing the asymmetric structure of the terphenyl large-substituent side group as claimed in claim 3, characterized in that: the preparation method comprises the following steps: under the protection of nitrogen, adding an equal amount of aromatic diamine monomer containing terphenyl large-substitution side group and aromatic dianhydride monomer into an organic solvent, adding a catalyst, stirring at 80-100 ℃ for half an hour until the monomers are completely dissolved, continuing heating to 180-200 ℃ for reaction for 6-10 hours to obtain a viscous polymer solution, finishing the reaction, pouring the polymer solution into ethanol for sedimentation, and further filtering, washing and drying to obtain the fibrous polyimide polymer.
5. The method for preparing polyimide containing terphenyl large substituent side group asymmetric structure as claimed in claim 4, characterized in that: the dianhydride monomer is one of diphenyl ether tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride.
6. The method for preparing polyimide containing terphenyl large substituent side group asymmetric structure as claimed in claim 4, characterized in that: the organic solvent is m-cresol or N-methyl pyrrolidone, and the dosage of the organic solvent is 7-15 times of the total mass of diamine and dianhydride monomers.
7. The method for preparing polyimide containing terphenyl large substituent side group asymmetric structure as claimed in claim 4, characterized in that: the catalyst is isoquinoline, and the dosage of the catalyst is 1 to 3 percent of the mass of the diamine.
8. The use of a polyimide having asymmetric structural groups containing terphenyl bulky substituent groups as claimed in claim 3, wherein: the polyimide is used as a film material in the field of microelectronics.
9. The use of a polyimide having asymmetric structural groups containing terphenyl bulky substituent groups as claimed in claim 8, wherein: the application method comprises the following steps: adding a polyimide polymer into an organic solvent to prepare a solution with the concentration of 5-10 wt%, filtering, coating, and further vacuum-drying at 60-100 ℃ for 12-24 h to obtain the polyimide membrane material with the asymmetric terphenyl large-substituent side group.
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