CN114805803A - Organic silicon modified polyimide resin and preparation method and application thereof - Google Patents
Organic silicon modified polyimide resin and preparation method and application thereof Download PDFInfo
- Publication number
- CN114805803A CN114805803A CN202210402858.5A CN202210402858A CN114805803A CN 114805803 A CN114805803 A CN 114805803A CN 202210402858 A CN202210402858 A CN 202210402858A CN 114805803 A CN114805803 A CN 114805803A
- Authority
- CN
- China
- Prior art keywords
- polyimide resin
- modified polyimide
- equal
- silicone
- less
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 67
- 239000009719 polyimide resin Substances 0.000 title claims abstract description 65
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 37
- 239000010703 silicon Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- -1 oxy, carbonyl Chemical group 0.000 claims abstract description 45
- 239000000853 adhesive Substances 0.000 claims abstract description 21
- 230000001070 adhesive effect Effects 0.000 claims abstract description 21
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 21
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 11
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 6
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims abstract description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 3
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 36
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 24
- BXEKEYIMSPFKRP-UHFFFAOYSA-N Br[SiH]1O[SiH2]O[SiH2]O[SiH2]O1 Chemical compound Br[SiH]1O[SiH2]O[SiH2]O[SiH2]O1 BXEKEYIMSPFKRP-UHFFFAOYSA-N 0.000 claims description 18
- 125000004799 bromophenyl group Chemical group 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 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 6
- 239000003054 catalyst Substances 0.000 claims description 6
- DDJSWKLBKSLAAZ-UHFFFAOYSA-N cyclotetrasiloxane Chemical class O1[SiH2]O[SiH2]O[SiH2]O[SiH2]1 DDJSWKLBKSLAAZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 229910052736 halogen Chemical class 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000005046 Chlorosilane Substances 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000005658 halogenation reaction Methods 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 239000011889 copper foil Substances 0.000 abstract description 6
- 238000005336 cracking Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229920006332 epoxy adhesive Polymers 0.000 abstract 1
- 239000004814 polyurethane Substances 0.000 abstract 1
- 229920002635 polyurethane Polymers 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 37
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- 235000019441 ethanol Nutrition 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 12
- 230000001376 precipitating effect Effects 0.000 description 10
- 239000011734 sodium Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- MCLXOMWIZZCOCA-UHFFFAOYSA-N 3-[methoxy(dimethyl)silyl]propan-1-amine Chemical compound CO[Si](C)(C)CCCN MCLXOMWIZZCOCA-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- CBVJWBYNOWIOFJ-UHFFFAOYSA-N chloro(trimethoxy)silane Chemical compound CO[Si](Cl)(OC)OC CBVJWBYNOWIOFJ-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 2
- VSIKJPJINIDELZ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octakis-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VSIKJPJINIDELZ-UHFFFAOYSA-N 0.000 description 1
- OXKAXHPVFLEQHV-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropan-1-amine Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCN OXKAXHPVFLEQHV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 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
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
- C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J179/00—Adhesives based on 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 C09J161/00 - C09J177/00
- C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2170/00—Compositions for adhesives
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Silicon Polymers (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses an organic silicon modified polyimide resin and a preparation method and application thereof, wherein the structural formula of the organic silicon modified polyimide resin is shown as the formula (I):
wherein R is 1 Selected from the group consisting of oxy, carbonyl, -C (CH) 3 ) 2 -or-C (CF) 3 ) 2 ‑；R 2 Is selected from
Or
R 3 Selected from methyl, ethyl, phenyl, vinyl, methoxy, ethoxy or isopropoxy; r 4 Selected from methyl,
Or
R 51 、R 52 、R 53 、R 54 Are respectively selected from H, Br or
Wherein R is 51 、R 52 、R 53 、R 54 Not being H and/or B simultaneously r ；R 6 Selected from methyl or ethyl; m is not less than 1 and not more than 20; the value of n is more than or equal to 1 and less than or equal to 20. The organic silicon modified polyimide resin prepared by the invention is applied to preparing the adhesive, the bonding force of the obtained adhesive to metal and copper foil is moderate, and the problem of open circuit of the copper-clad wire caused by the problems of overlarge shrinkage rate, easy cracking due to cold and hot impact, low bonding strength and the like of the traditional polyurethane, organic silicon and modified epoxy adhesives is solved.
Description
Technical Field
The invention belongs to the field of polymer materials, and particularly relates to an organic silicon modified polyimide resin, and a preparation method and application thereof.
Background
Polyimide resin is a material having outstanding properties such as excellent electrical insulation, wear resistance, high temperature resistance, and radiation resistance, and has excellent adhesion properties to metals, but polyimide resin has a rigid skeleton, has a high elastic modulus, and an adhesive layer made of polyimide has high hardness, high brittleness, and is prone to cracking. The organic silicon resin has excellent electrical insulation, high and low temperature resistance, moisture resistance and weather resistance, flexible molecular structure and excellent processing performance. The organic silicon is used for modifying the polyimide resin, so that the problems of high hardness, high brittleness and the like of polyimide can be solved, and the prepared bonding layer is not easy to crack.
However, the adhesive prepared from the organic silicon modified polyimide resin generally has the problems of low bonding strength, small bonding force, overhigh bonding strength, overlarge bonding force and the like, and when the adhesive is used for bonding a base material such as glass and the like and a copper foil, the base material such as glass and the like and the copper foil are easy to slip due to the low bonding strength and the small bonding force of the adhesive; when the adhesive strength of the adhesive is too high and the adhesive force is too high, stress is generated in the adhesive layer, and cracking is likely to occur, resulting in a decrease in adhesive performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the organic silicon modified polyimide resin, the organic silicon modified polyimide resin is applied to preparation and bonding to obtain the bonding agent with moderate expansion coefficient and good dimensional stability before and after curing, the expansion coefficient and bonding force of the obtained bonding agent to metal and copper foil are moderate, and the problems that glass and other base materials and copper foil are easy to crack and slip or a bonding layer is easy to crack due to stress and the like can be avoided.
The invention aims to provide an organic silicon modified polyimide resin, which has a structural formula shown as a formula (I):
wherein R is 1 Selected from oxy, carbonyl, -C (CH) 3 ) 2 -or-C (CF) 3 ) 2 -；
R 2 Is selected from
R 3 Selected from methyl, ethyl, phenyl, vinyl, methoxy, ethoxy or isopropoxy;
R 4 selected from methyl,
R 51 、R 52 、R 53 、R 54 Are respectively selected from H, Br or
Wherein R is 51 、R 52 、R 53 、R 54 Not H and/or Br at the same time;
R 6 selected from methyl or ethyl;
m is not less than 1 and not more than 20;
the value of n is more than or equal to 1 and less than or equal to 20.
Preferably, the structure of the silicone-modified polyimide resin is as follows:
wherein m is greater than or equal to 1 and less than or equal to 20, and n is greater than or equal to 1 and less than or equal to 20.
Preferably, the structure of the silicone-modified polyimide resin is as follows:
wherein m is more than or equal to 2 and less than or equal to 5, and n is more than or equal to 5 and less than or equal to 10.
The molecular weight and the substituent group structure of the organic silicon modified polyimide resin are changed, so that the organic silicon modified polyimide resin with good dimensional stability and high thermal stability is provided.
Preferably, the structure of the silicone-modified polyimide resin is as follows:
wherein m is more than or equal to 8 and less than or equal to 12, and n is more than or equal to 12 and less than or equal to 18.
The molecular weight and the substituent group structure of the organic silicon modified polyimide resin are changed, so that the organic silicon modified polyimide resin with low water absorption rate is provided.
The invention also aims to provide a preparation method of the organic silicon modified polyimide resin, which comprises the following steps:
s1, performing halogenation reaction on substituted cyclotetrasiloxane and halogen according to a molar ratio of 1: 1-8 to obtain bromo-cyclotetrasiloxane;
the substituted cyclotetrasiloxane has the structure:
wherein R is 4 Selected from methyl or phenyl;
s2, adding an alkali catalyst into the bromocyclotetrasiloxane, reacting at 60-110 ℃, and adding a silane coupling agent substituted by a terminal amino group to prepare amino-terminated bromophenyl polysiloxane, wherein the molar ratio of the bromocyclotetrasiloxane to the silane coupling agent substituted by the terminal amino group to the alkali catalyst is 1: 2-40: 0.02-0.04;
s3, mixing and reacting the amino-terminated bromophenyl polysiloxane, alkali metal and alkoxy chlorosilane in a weight ratio of 1: 0.1-0.2: 0.5-0.8 to obtain alkoxylated amino-terminated phenyl polysiloxane;
s4, mixing and reacting the alkoxylated amino-terminated phenyl polysiloxane and acid dianhydride in a weight ratio of 1: 1-1.5, and adding acetic anhydride for dehydration to obtain organic silicon modified polyimide resin;
the acid dianhydride has the structure:
Preferably, in step S1, the molar ratio of the substituted cyclotetrasiloxane to the halogen is 1: 4-6.
Preferably, in step S2, the base catalyst is selected from strong organic bases.
Preferably, in step S3, the amino-terminated bromophenyl polysiloxane, alkali metal, and alkoxychlorosilane are in a weight ratio of 1:0.2: 0.6.
Preferably, in the step S3, the reaction temperature is 45-65 ℃.
The invention also aims to provide application of the organic silicon modified polyimide resin in preparation of adhesives.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present invention, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1: and (3) preparing the organic silicon modified polyimide resin.
Step (ii) ofS1, under the protection of nitrogen, dissolving 1,3,5, 7-tetramethyl tetraphenyl cyclotetrasiloxane (1mol), iron powder (0.1mol) and anhydrous ferric trichloride (0.03mol) in 50mL of dichloromethane, stirring, and dropwise adding Br dissolved in 5mL of dichloromethane at room temperature 2 (1mol), stirring and reacting for 5h, and reacting the reaction liquid with Na 2 SO 3 The solution is fully mixed and stood for reaction, CH 2 Cl 2 Extracting, concentrating and precipitating with ethanol to obtain bromocyclotetrasiloxane;
s2, adding tetramethylammonium hydroxide (0.02mol) and tetrahydrofuran (50mL) into the bromocyclotetrasiloxane (1mol), reacting at 60 ℃ for 30min, adding 3-aminopropyl dimethyl methoxysilane (2mol), and continuing to react for 4h to obtain amino-terminated bromophenyl polysiloxane;
step S3, under the protection of nitrogen, mixing the amino-terminated bromophenyl polysiloxane (10g), sodium (1g), trimethoxychlorosilane (5g) and tetrahydrofuran (100mL), and reacting at 45 ℃ for 24 hours to obtain alkoxylated amino-terminated phenyl polysiloxane;
and S4, mixing the alkoxylated amino-terminated phenyl polysiloxane (20g), 3',4,4' -benzophenone tetracarboxylic dianhydride (20g) and 100mL of NMP, stirring at room temperature for reacting for 8h, adding acetic anhydride (5mL) and pyridine (5mL) for reacting for 4h, adding ethanol for precipitating, filtering, washing and drying to obtain the organic silicon modified polyimide resin.
The chemical structural formula of the prepared organic silicon modified polyimide resin is as follows:
wherein m is greater than or equal to 1 and less than or equal to 20, and n is greater than or equal to 1 and less than or equal to 20.
Example 2: and (3) preparing the organic silicon modified polyimide resin.
Step S1, under the protection of nitrogen, dissolving octaphenylcyclotetrasiloxane (1mol), iron powder (0.4mol) and anhydrous ferric trichloride (0.08mol) in 50mL of dichloromethane, stirring, and dropwise adding Br dissolved in 5mL of dichloromethane at room temperature 2 (8mol), stirring and reacting for 5h, and reacting the reaction liquid with Na 2 SO 3 The solution is fully mixed and stood for reaction, CH 2 Cl 2 Extracting, concentrating and precipitating with ethanol to obtain bromocyclotetrasiloxane;
s2, adding tetramethylammonium hydroxide (0.04mol) and toluene (50mL) into the bromocyclotetrasiloxane (1mol), reacting at 80 ℃ for 30min, adding 3-aminopropyl dimethyl methoxysilane (40mol), heating to 90 ℃ and reacting for 4h to obtain amino-terminated bromophenyl polysiloxane;
step S3, under the protection of nitrogen, mixing the amino-terminated bromophenyl polysiloxane (10g), potassium (2g), triethoxysilane (8g) and tetrahydrofuran (100mL), and reacting at 65 ℃ for 24 hours to obtain alkoxylated amino-terminated phenyl polysiloxane;
and S4, mixing the alkoxylated amino-terminated phenyl polysiloxane (20g), 2,3,3',4' -diphenyl ether tetracarboxylic dianhydride (30g) and 100mL of NMP, stirring at room temperature for reacting for 8h, adding acetic anhydride (6mL) and pyridine (6mL) for reacting for 4h, adding ethanol for precipitating, filtering, washing and drying to obtain the organic silicon modified polyimide resin.
Wherein R is
m is greater than or equal to 1 and less than or equal to 20, and n is greater than or equal to 1 and less than or equal to 20.
Example 3: and (3) preparing the organic silicon modified polyimide resin.
Step S1, under the protection of nitrogen, dissolving 1,3,5, 7-tetramethyl tetraphenyl cyclotetrasiloxane (1mol), iron powder (0.2mol) and anhydrous ferric trichloride (0.05mol) in 50mL of dichloromethane, stirring, and dropwise adding Br dissolved in 5mL of dichloromethane at room temperature 2 (2mol), stirring and reacting for 5h, and reacting the reaction liquid with Na 2 SO 3 The solution is fully mixed and stood for reaction, CH 2 Cl 2 Extracting, concentrating, precipitating with ethanol to obtain bromocyclotetrasiloxane;
s2, adding tetramethylammonium hydroxide (0.03mol) and toluene (50mL) into the bromocyclotetrasiloxane (1mol), reacting at 100 ℃ for 30min, adding N- (2-aminoethyl) -3-aminopropyltrimethoxysilane (20mol), heating to 110 ℃ and reacting for 4h to obtain amino-terminated bromophenyl polysiloxane;
step S3, under the protection of nitrogen, mixing the amino-terminated bromophenyl polysiloxane (10g), potassium (2g), triethoxysilane (6g) and tetrahydrofuran (100mL), and reacting at 55 ℃ for 24 hours to obtain alkoxylated amino-terminated phenyl polysiloxane;
and S4, mixing the alkoxylated amino-terminated phenyl polysiloxane (20g), 4' - (isopropylene) diphthalic anhydride (25g) and 100mL of NMP, stirring at room temperature for reaction for 8h, adding acetic anhydride (6mL) and pyridine (6mL) for reaction for 4h, adding ethanol for precipitation, filtering, washing and drying to obtain the organic silicon modified polyimide resin.
Wherein m is greater than or equal to 1 and less than or equal to 20, and n is greater than or equal to 1 and less than or equal to 20.
Example 4: and (3) preparing the organic silicon modified polyimide resin.
Step S1, under the protection of nitrogen, dissolving 1,3,5, 7-tetramethyl tetraphenyl cyclotetrasiloxane (1mol), iron powder (0.2mol) and anhydrous ferric trichloride (0.05mol) in 50mL of dichloromethane, stirring, and dropwise adding Br dissolved in 5mL of dichloromethane at room temperature 2 (4mol), stirring and reacting for 5h, and reacting the reaction liquid with Na 2 SO 3 The solution is fully mixed and stood, CH 2 Cl 2 Extracting, concentrating and precipitating with ethanol to obtain bromocyclotetrasiloxane;
s2, adding tetramethylammonium hydroxide (0.03mol) and toluene (50mL) into the bromocyclotetrasiloxane (1mol), reacting at 80 ℃ for 30min, adding 3-aminopropyl dimethyl methoxysilane (40mol), heating to 100 ℃ and reacting for 4h to obtain amino-terminated bromophenyl polysiloxane;
step S3, under the protection of nitrogen, mixing the amino-terminated bromophenyl polysiloxane (10g), potassium (2g), trimethoxychlorosilane (6g) and tetrahydrofuran (100mL), and reacting at 55 ℃ for 24 hours to obtain alkoxylated amino-terminated phenyl polysiloxane;
and S4, mixing the alkoxylated amino-terminated phenyl polysiloxane (20g), 3',4,4' -benzophenone tetracarboxylic dianhydride (25g) and 100mL of NMP, stirring at room temperature for reacting for 8h, adding acetic anhydride (6mL) and pyridine (6mL) for reacting for 4h, adding ethanol for precipitating, filtering, washing and drying to obtain the organic silicon modified polyimide resin.
Wherein m is greater than or equal to 1 and less than or equal to 20, and n is greater than or equal to 1 and less than or equal to 20.
Example 5: and (3) preparing the organic silicon modified polyimide resin.
Step S1, under the protection of nitrogen, dissolving 1,3,5, 7-tetramethyl tetraphenyl cyclotetrasiloxane (1mol), iron powder (0.2mol) and anhydrous ferric trichloride (0.05mol) in 50mL of dichloromethane, stirring, and dropwise adding Br dissolved in 5mL of dichloromethane at room temperature 2 (4mol), stirring and reacting for 5h, and reacting the reaction liquid with Na 2 SO 3 The solution is fully mixed and stood for reaction, CH 2 Cl 2 Extracting, concentrating and precipitating with ethanol to obtain bromocyclotetrasiloxane;
s2, adding tetramethylammonium hydroxide (0.03mol) and toluene (50mL) into the bromocyclotetrasiloxane (1mol), reacting at 70 ℃ for 15min, adding 3-aminopropyltriisopropoxysilane (40mol), and continuing to react for 2h to obtain amino-terminated bromophenyl polysiloxane;
step S3, under the protection of nitrogen, mixing the amino-terminated bromophenyl polysiloxane (10g), potassium (2g), trimethoxychlorosilane (3g) and tetrahydrofuran (100mL), and reacting at 65 ℃ for 24 hours to obtain alkoxylated amino-terminated phenyl polysiloxane;
and S4, mixing the alkoxylated amino-terminated phenyl polysiloxane (20g), 4' - (hexafluoroisopropylidene) diphthalic anhydride (25g) and 100mL of NMP, stirring at room temperature for reacting for 6h, adding acetic anhydride (6mL) and pyridine (6mL) for reacting for 6h, adding ethanol for precipitating, filtering, washing and drying to obtain the organic silicon modified polyimide resin.
Wherein m is more than or equal to 2 and less than or equal to 5, and n is more than or equal to 5 and less than or equal to 10.
Example 6: and (3) preparing the organic silicon modified polyimide resin.
Step S1, under the protection of nitrogen, dissolving 1,3,5, 7-tetramethyl tetraphenyl cyclotetrasiloxane (1mol), iron powder (0.2mol) and anhydrous ferric trichloride (0.05mol) in 50mL of dichloromethane, stirring, and dropwise adding Br dissolved in 5mL of dichloromethane at room temperature 2 (4mol), stirring and reacting for 5h, and reacting the reaction liquid with Na 2 SO 3 The solution is fully mixed and stood for reaction, CH 2 Cl 2 Extracting, concentrating and precipitating with ethanol to obtain bromocyclotetrasiloxane;
s2, adding tetramethylammonium hydroxide (0.03mol) and toluene (50mL) into the bromocyclotetrasiloxane (1mol), reacting at 80 ℃ for 15min, adding 3-aminopropyl dimethyl methoxysilane (40mol), and continuing to react for 2h to obtain amino-terminated bromophenyl polysiloxane;
step S3, under the protection of nitrogen, mixing the amino-terminated bromophenyl polysiloxane (10g), potassium (2g), trimethoxychlorosilane (6g) and tetrahydrofuran (100mL), and reacting at 65 ℃ for 24 hours to obtain alkoxylated amino-terminated phenyl polysiloxane;
and S4, mixing the alkoxylated amino-terminated phenyl polysiloxane (20g), 3',4,4' -diphenyl ether tetracarboxylic dianhydride (25g) and 100mL of NMP, stirring at room temperature for reaction for 7h, adding acetic anhydride (6mL) and pyridine (6mL) for reaction for 5h, adding ethanol for precipitation, filtering, washing and drying to obtain the organic silicon modified polyimide resin.
Wherein m is more than or equal to 8 and less than or equal to 12, and n is more than or equal to 12 and less than or equal to 18.
Example 7: and (4) preparing the adhesive.
Mixing 0-10 parts by weight of barium titanate, 0-2 parts by weight of titanium dioxide, 5-10 parts by weight of phenyltrimethoxysilane, 1-3 parts by weight of silane coupling agent KH-5501, 0.5-1 part by weight of glass microspheres, 2-6 parts by weight of toluene, 0-6 parts by weight of absolute ethyl alcohol and 2-6 parts by weight of butanone, and then ball-milling for 6 hours in a ball mill; and adding 0-10 parts by weight of hydrogenated terpene resin and 30-40 parts by weight of the organic silicon modified polyimide resin prepared in the example 1, and continuing ball milling for 8 hours to obtain the adhesive.
Example 8: and (4) preparing the adhesive.
The silicone-modified polyimide resin prepared in example 1 of example 7 was replaced with the silicone-modified polyimide resin prepared in example 2, and the remaining steps were unchanged.
Example 9: and (4) preparing the adhesive.
The silicone-modified polyimide resin prepared in example 1 of example 7 was replaced with the silicone-modified polyimide resin prepared in example 3, and the remaining steps were unchanged.
Example 10: and (4) preparing the adhesive.
The silicone-modified polyimide resin prepared in example 1 of example 7 was replaced with the silicone-modified polyimide resin prepared in example 4, and the remaining steps were unchanged.
Example 11: and (4) preparing the adhesive.
The silicone-modified polyimide resin prepared in example 1 of example 7 was replaced with the silicone-modified polyimide resin prepared in example 5, and the remaining steps were unchanged.
Example 12: and (4) preparing the adhesive.
The silicone-modified polyimide resin prepared in example 1 of example 7 was replaced with the silicone-modified polyimide resin prepared in example 6, and the remaining steps were unchanged.
And (3) performance testing:
testing the adhesive force: the adhesives prepared in examples 7-11 were coated on copper foils, respectively, and then placed in a preheated oven and baked at 220 ℃ for 30min to remove residual solvent, to obtain test pieces of examples 7-11, and the adhesion tests were performed on the test pieces of examples 7-11 by 180-degree reverse peeling.
And (3) testing thermal stability: the silicone modified polyimide resins obtained in examples 1-6 were each tested using differential thermal scanning and the temperature at which the silicone modified polyimide resins obtained in examples 1-6 lost 10% thermal weight was recorded.
Water absorption test: 2g of each of the silicone-modified polyimide resins prepared in examples 1 to 6 was left in distilled water at room temperature for 24 hours, taken out and then dried at 110 ℃ for 2 hours, taken out and weighed according to the standard of IPC-TM-650 in the United states, and the water absorption was calculated from the weight difference.
TABLE 1 results of the performance tests of the resins obtained in examples 1 to 6 and the adhesives obtained in examples 7 to 11.
Finally, it should be noted that the above-mentioned embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the same, and although the present invention is described in detail with reference to the above-mentioned embodiments, it should be understood by those skilled in the art that the modifications and equivalents of the specific embodiments of the present invention can be made by those skilled in the art after reading the present specification, but these modifications and variations do not depart from the scope of the claims of the present application.
Claims (10)
1. An organic silicon modified polyimide resin is characterized in that the structural formula of the organic silicon modified polyimide resin is shown as the formula (I):
wherein R is 1 Selected from the group consisting of oxy, carbonyl, -C (CH) 3 ) 2 -or-C (CF) 3 ) 2 -；
R 2 Is selected from
R 3 Selected from methyl, ethyl, phenyl, vinyl, methoxy, ethoxy or isopropoxy;
R 4 selected from methyl,
R 51 、R 52 、R 53 、R 54 Are respectively selected from H, Br or
Wherein R is 51 、R 52 、R 53 、R 54 Not H and/or Br at the same time;
R 6 selected from methyl or ethyl;
m is not less than 1 and not more than 20;
the value of n is more than or equal to 1 and less than or equal to 20.
2. The silicone-modified polyimide resin of claim 1, wherein the silicone-modified polyimide resin has the following structure:
wherein m is greater than or equal to 1 and less than or equal to 20, and n is greater than or equal to 1 and less than or equal to 20.
3. The silicone-modified polyimide resin of claim 1, wherein the silicone-modified polyimide resin has the following structure:
wherein m is more than or equal to 2 and less than or equal to 5, and n is more than or equal to 5 and less than or equal to 10.
4. The silicone-modified polyimide resin of claim 1, wherein the silicone-modified polyimide resin has the following structure:
wherein m is more than or equal to 8 and less than or equal to 12, and n is more than or equal to 12 and less than or equal to 18.
5. A method for producing the silicone-modified polyimide resin according to any one of claims 1 to 4, comprising the steps of:
s1, performing halogenation reaction on substituted cyclotetrasiloxane and halogen according to a molar ratio of 1: 1-8 to obtain bromo-cyclotetrasiloxane;
the substituted cyclotetrasiloxane has the structure:
wherein R is 4 Selected from methyl or phenyl;
s2, adding an alkali catalyst into the bromocyclotetrasiloxane, reacting at 60-110 ℃, and adding a silane coupling agent substituted by a terminal amino group to prepare amino-terminated bromophenyl polysiloxane, wherein the molar ratio of the bromocyclotetrasiloxane to the silane coupling agent substituted by the terminal amino group to the alkali catalyst is 1: 2-40: 0.02-0.04;
s3, mixing and reacting the amino-terminated bromophenyl polysiloxane, alkali metal and alkoxy chlorosilane in a weight ratio of 1: 0.1-0.2: 0.5-0.8 to obtain alkoxylated amino-terminated phenyl polysiloxane;
s4, mixing and reacting the alkoxylated amino-terminated phenyl polysiloxane and acid dianhydride in a weight ratio of 1: 1-1.5, and adding acetic anhydride for dehydration to obtain organic silicon modified polyimide resin;
the acid dianhydride has the structure as follows:
6. The method of preparing the silicone-modified polyimide resin according to claim 3, wherein in step S1, the molar ratio of the substituted cyclotetrasiloxane to the halogen is 1:4 to 6.
7. The method for producing the silicone-modified polyimide resin according to claim 3, wherein in step S2, the alkali catalyst is selected from strong organic bases.
8. The method of preparing the silicone-modified polyimide resin according to claim 3, wherein in step S3, the amino-terminated bromophenyl polysiloxane, alkali metal, and alkoxychlorosilane are in a weight ratio of 1:0.2: 0.6.
9. The method for preparing the silicone-modified polyimide resin according to claim 3, wherein in step S3, the reaction temperature is 45 to 65 ℃.
10. Use of the silicone-modified polyimide resin according to any one of claims 1 to 2 in the preparation of an adhesive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210402858.5A CN114805803B (en) | 2022-04-18 | 2022-04-18 | Organosilicon modified polyimide resin and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210402858.5A CN114805803B (en) | 2022-04-18 | 2022-04-18 | Organosilicon modified polyimide resin and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114805803A true CN114805803A (en) | 2022-07-29 |
| CN114805803B CN114805803B (en) | 2024-01-12 |
Family
ID=82537071
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210402858.5A Active CN114805803B (en) | 2022-04-18 | 2022-04-18 | Organosilicon modified polyimide resin and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114805803B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003252991A (en) * | 2002-02-28 | 2003-09-10 | Dow Corning Toray Silicone Co Ltd | Acrylic or methacrylic functional silicone-modified polyimide resin, its manufacturing method and photosensitive resin composition |
| CN104387546A (en) * | 2014-12-17 | 2015-03-04 | 武汉大学 | Phenyl organic silicon modified polyurethane resin, preparation method and application thereof |
| CN108864932A (en) * | 2017-05-11 | 2018-11-23 | 信越化学工业株式会社 | Silicone-modified polyimides resin combination |
| JP2018188626A (en) * | 2017-05-11 | 2018-11-29 | 信越化学工業株式会社 | Silicone-modified polyimide resin composition |
| CN113831534A (en) * | 2021-11-05 | 2021-12-24 | 江西有泽新材料科技有限公司 | Preparation and application of organic silicon modified hyperbranched polyimide resin |
-
2022
- 2022-04-18 CN CN202210402858.5A patent/CN114805803B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003252991A (en) * | 2002-02-28 | 2003-09-10 | Dow Corning Toray Silicone Co Ltd | Acrylic or methacrylic functional silicone-modified polyimide resin, its manufacturing method and photosensitive resin composition |
| CN104387546A (en) * | 2014-12-17 | 2015-03-04 | 武汉大学 | Phenyl organic silicon modified polyurethane resin, preparation method and application thereof |
| CN108864932A (en) * | 2017-05-11 | 2018-11-23 | 信越化学工业株式会社 | Silicone-modified polyimides resin combination |
| JP2018188626A (en) * | 2017-05-11 | 2018-11-29 | 信越化学工業株式会社 | Silicone-modified polyimide resin composition |
| CN113831534A (en) * | 2021-11-05 | 2021-12-24 | 江西有泽新材料科技有限公司 | Preparation and application of organic silicon modified hyperbranched polyimide resin |
Non-Patent Citations (1)
| Title |
|---|
| 徐伟箭, 王旭东, 黄翠华, 梁志武, 刘永利: "羧酸衍生物取代甲基苯基聚硅烷制备杂取代聚硅烷", 高分子学报, no. 05, pages 571 - 575 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114805803B (en) | 2024-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1184403B1 (en) | Polyimide silicone resin, process for its production, and polyimide silicone resin composition | |
| JP3669429B2 (en) | Electrode composition and electrode material | |
| JP5903789B2 (en) | Copolymer polyimide precursor and copolymer polyimide | |
| CN103409103B (en) | Environment-friendly high-temperature-resistant organic silicon pressure-sensitive adhesive and preparation method thereof | |
| JP4367622B2 (en) | Method for producing polyimide / inorganic composite material | |
| JP2009062435A (en) | Heat-curable polyimide silicone resin composition and cured film therefrom | |
| CN105315454A (en) | Method for preparing silicon containing di-hydroxyl polyphenyl ether through organosilicone modification and application of product | |
| JPH08193189A (en) | Adhesive for electronic component | |
| JP2609140B2 (en) | Low modulus polyimide and its manufacturing method | |
| US4996293A (en) | Composition comprising polyimide resin from diphenyl sulfone -3,3',4,4'-tetracarboxylic acid dianhydride | |
| JP3012903B2 (en) | New soluble polyimide resin | |
| CN114805803A (en) | Organic silicon modified polyimide resin and preparation method and application thereof | |
| CN116675820B (en) | Organosilicon modified boron phenolic resin and preparation method thereof | |
| JP3026201B2 (en) | Novel soluble polyimide resin having alkoxy substituent and method for producing the same | |
| JP2619515B2 (en) | Silicon polyimide precursor composition | |
| CN111777541A (en) | high-Tg low-dielectric active ester curing agent, preparation method and application | |
| CN1256365C (en) | Polyimide material, and its preparing method and use | |
| CN111040168A (en) | Epoxy modified organic silicon resin and preparation method thereof | |
| CN115449211A (en) | Flexible corrosion-resistant PPO resin-based copper-clad plate and preparation method thereof | |
| CN114736163A (en) | Nitrogen-containing heterocyclic diamine compound, preparation method thereof, polyimide precursor, polyimide film and application thereof | |
| CN115710338A (en) | Benzoxazine resin for flexible non-adhesive copper-clad plate, benzoxazine monomer, preparation method and application thereof | |
| CN106589832A (en) | Cage-like silsesquioxane modified epoxy adhesive solution for high-Tg low-dielectric copper-clad plate and preparation method of adhesive solution | |
| JPH07242820A (en) | Resin composition improved in physical property at high temperature | |
| CN101445602A (en) | Dissoluble polyetherimide containing silicon and preparation method thereof | |
| JPH07242821A (en) | Resin composition improved in physical property at high temperature |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |