CN114891479B - Heat-resistant pressure-resistant sizing material, and preparation method and application thereof - Google Patents
Heat-resistant pressure-resistant sizing material, and preparation method and application thereof Download PDFInfo
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- CN114891479B CN114891479B CN202210570020.7A CN202210570020A CN114891479B CN 114891479 B CN114891479 B CN 114891479B CN 202210570020 A CN202210570020 A CN 202210570020A CN 114891479 B CN114891479 B CN 114891479B
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- polyimide
- sizing material
- polyimide solution
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- 239000000463 material Substances 0.000 title claims abstract description 28
- 238000004513 sizing Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000004642 Polyimide Substances 0.000 claims abstract description 55
- 229920001721 polyimide Polymers 0.000 claims abstract description 55
- 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 19
- 239000000945 filler Substances 0.000 claims abstract description 14
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 12
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 150000004984 aromatic diamines Chemical class 0.000 claims description 8
- CJAOGUFAAWZWNI-UHFFFAOYSA-N 1-n,1-n,4-n,4-n-tetramethylbenzene-1,4-diamine Chemical group CN(C)C1=CC=C(N(C)C)C=C1 CJAOGUFAAWZWNI-UHFFFAOYSA-N 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000003475 lamination Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- STTDQWBKXQKNIK-UHFFFAOYSA-N trimethyl-[2-[2,3,4,5,6-pentakis(2-trimethylsilylethynyl)phenyl]ethynyl]silane Chemical group C[Si](C)(C)C#CC1=C(C#C[Si](C)(C)C)C(C#C[Si](C)(C)C)=C(C#C[Si](C)(C)C)C(C#C[Si](C)(C)C)=C1C#C[Si](C)(C)C STTDQWBKXQKNIK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012456 homogeneous solution Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 13
- 230000001070 adhesive effect Effects 0.000 abstract description 13
- 239000006229 carbon black Substances 0.000 abstract description 4
- 239000002981 blocking agent Substances 0.000 abstract description 3
- 150000004985 diamines Chemical class 0.000 abstract description 3
- 239000000178 monomer Substances 0.000 abstract description 3
- 241000872198 Serjania polyphylla Species 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 229920001971 elastomer Polymers 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 3
- AXMANIZPMQZKTG-UHFFFAOYSA-N 4-(2-phenylethynyl)-2-benzofuran-1,3-dione Chemical compound O=C1OC(=O)C2=C1C=CC=C2C#CC1=CC=CC=C1 AXMANIZPMQZKTG-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 description 1
- QQGMRDZQQKVAIA-UHFFFAOYSA-N 1,2,3-triethynylbenzene Chemical compound C#CC1=CC=CC(C#C)=C1C#C QQGMRDZQQKVAIA-UHFFFAOYSA-N 0.000 description 1
- SAVOJCMTUWNCLL-UHFFFAOYSA-N 1-ethyl-4-[2-(4-propylphenyl)ethynyl]benzene Chemical compound C1=CC(CCC)=CC=C1C#CC1=CC=C(CC)C=C1 SAVOJCMTUWNCLL-UHFFFAOYSA-N 0.000 description 1
- MODAETKWQRGIHI-UHFFFAOYSA-N 1-ethynyl-9,10-diphenylanthracene Chemical compound C12=CC=CC=C2C(C=2C=CC=CC=2)=C2C(C#C)=CC=CC2=C1C1=CC=CC=C1 MODAETKWQRGIHI-UHFFFAOYSA-N 0.000 description 1
- KJAAWBYLNVBKPI-UHFFFAOYSA-N 2-n-methoxybenzene-1,2-diamine Chemical compound CONC1=CC=CC=C1N KJAAWBYLNVBKPI-UHFFFAOYSA-N 0.000 description 1
- JBHXVPWMLQFNPL-UHFFFAOYSA-N 3-methoxy-6-methylbenzene-1,2-diamine Chemical compound COC1=CC=C(C)C(N)=C1N JBHXVPWMLQFNPL-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- VCJUSEFXUWAMHH-UHFFFAOYSA-N 4-ethynyl-2-benzofuran-1,3-dione Chemical compound C1=CC=C(C#C)C2=C1C(=O)OC2=O VCJUSEFXUWAMHH-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AOWKSNWVBZGMTJ-UHFFFAOYSA-N calcium titanate Chemical compound [Ca+2].[O-][Ti]([O-])=O AOWKSNWVBZGMTJ-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical compound C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- NGKSKVYWPINGLI-UHFFFAOYSA-N prop-2-ynylbenzene Chemical compound C#CCC1=CC=CC=C1 NGKSKVYWPINGLI-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- 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
- C08G73/12—Unsaturated polyimide precursors
- C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a heat-resistant pressure-resistant sizing material, which comprises the following preparation raw materials in parts by weight: 50-80 parts of polyimide solution I, 10-40 parts of polyimide solution II, 3-5 parts of filler and 0.1-3 parts of cross-linking agent. According to the invention, 3', 4' -biphenyl tetracarboxylic dianhydride reacts with diamine monomer and ethynyl diphthalic anhydride is used as a blocking agent, so that the high temperature resistance of the polyimide adhesive can be obviously improved; and polyimide solutions with different viscosities are adopted for crosslinking reaction, so that the density of polyimide crosslinked network is increased, the high temperature resistance of polyimide sizing material is further improved, and the polyimide sizing material can be recycled for multiple times in a high temperature environment at 400 ℃; meanwhile, by introducing the gas phase white carbon black with the particle size of 10-100nm, the mechanical property of the polyimide sizing material can be improved on the basis of maintaining the dispersion uniformity of the polyimide sizing material, and the polyimide sizing material has good peel strength and excellent tear strength and breaking elongation.
Description
Technical Field
The invention relates to a heat-resistant pressure-resistant sizing material, a preparation method and application thereof, and relates to C09J, in particular to the field of adhesives.
Background
The PCB board is a printed circuit board, which is an important component in the field of electronic machinery, and with the development of technology, the development trend of electronics, precision, and integration, the single-layer printed circuit board has become unable to meet the requirements of electronic devices, and the use requirements of electronic devices with increasingly complex functions are increasingly met by using double-layer or even multi-layer circuit boards. The multi-layer PCB needs high-frequency and high-speed multiple pressing processes in the preparation process, pressing buffer pads are arranged on the upper surface and the lower surface of the PCB to prevent the PCB from being damaged in the pressing process, and the surface structure of the PCB is prevented from being damaged under high pressure. The common pressing cushion pad can only be used at 250 ℃ and 35kg/cm 2 The lamination operation is performed in the environment of (1), but when the filler material of the PCB is polytetrafluoroethylene, 400 ℃ and 100kg/cm are required 2 The rubber material can be fully filled and solidified under the condition of lamination, so that development of the rubber material with higher heat resistance temperature and stronger pressure resistance is important to be applied to lamination cushions.
Chinese patent No. 201610344797.6 discloses a polyimide insulating tape reinforced by nano calcium titanate, which is prepared by introducing methyl vinyl silicone rubber, carboxyl nitrile rubber and chloroprene rubber to perform synergistic effect, so that the adhesive has excellent bonding strength and high temperature resistance, but the highest heat-resistant temperature is 250 ℃, and the effect of resisting the high temperature of 400 ℃ cannot be achieved. The Chinese patent No. 200810104459.0 discloses a high-temperature resistant thermosetting polyimide adhesive and a preparation method thereof, wherein fluorine-containing aromatic diamine is introduced to ensure that the polyamide adhesive still has better bonding strength in the environment of 300 ℃, but gradually loses weight in the environment of higher temperature, thereby affecting the application of the adhesive in a pressing cushion pad.
Disclosure of Invention
In order to improve the service life of the rubber in a high-temperature and high-pressure environment at 400 ℃, the first aspect of the invention provides a heat-resistant and pressure-resistant rubber, which is prepared from the following raw materials in parts by weight: 50-80 parts of polyimide solution I, 10-40 parts of polyimide solution II, 3-5 parts of filler and 0.1-3 parts of cross-linking agent.
As a preferred embodiment, the absolute viscosity of the polyimide solution II is more than or equal to 20000 Pa.s at 25 ℃; the absolute viscosity of the polyimide solution I at 25 ℃ is 5000-10000 Pa.s.
As a preferred embodiment, the crosslinking agent is selected from one or a combination of several of tri-ethynyl benzene, hexa (trimethylsilylethynyl) benzene, 9, 10-diphenylethynyl anthracene, 3-phenyl-1-propyne, 1-ethyl-4- [ (4-propylphenyl) ethynyl ] benzene.
As a preferred embodiment, the crosslinking agent is hexakis (trimethylsilylethynyl) benzene.
As a preferred embodiment, the filler is a nano-scale filler, and is selected from one or a combination of a plurality of gas-phase white carbon black, precipitation white carbon black, calcium carbonate, silicon nitride, titanium oxide and aluminum oxide.
As a preferred embodiment, the filler is fumed silica and has a particle size of 10-100nm.
As a preferred embodiment, the particle size of the fumed silica is 30-50nm.
As a preferred embodiment, the polyimide solution I is self-made, and the preparation raw materials of the polyimide solution I comprise the following components in parts by weight: 40-50 parts of aromatic diamine, 30-40 parts of aromatic dianhydride, 70-100 parts of organic solvent and 10-15 parts of end capping agent.
As a preferred embodiment, the aromatic diamine is selected from one or a combination of several of tetramethyl-p-phenylenediamine, 3-methoxy-6-methyl-1, 2-phenylenediamine, methoxy-phenylenediamine, diamino diphenyl sulfone, diamino benzophenone and diamino diphenyl ether.
As a preferred embodiment, the aromatic diamine is tetramethyl-p-phenylenediamine.
As a preferred embodiment, the aromatic dianhydride is selected from one or a combination of several of 3,3', 4' -biphenyl tetracarboxylic dianhydride, 4 '-biphenyl ether dianhydride, 4' - (4, 4 '-isopropyl diphenoxy) diphthalic anhydride and 4,4' -hexafluoroisopropyl phthalic anhydride.
As a preferred embodiment, the aromatic dianhydride is 3,3', 4' -biphenyl tetracarboxylic dianhydride.
As a preferred embodiment, the end-capping agent is an alkynyl-containing phthalic anhydride, preferably, the alkynyl-containing phthalic anhydride is one or a combination of several selected from phenylethynyl phthalic anhydride, ethynyl phthalic anhydride and ethynyl diphthalic anhydride.
As a preferred embodiment, the capping agent is ethynyl diphthalic anhydride.
The applicant finds that in the experimental process, 3', 4' -biphenyl tetracarboxylic dianhydride reacts with diamine monomer and ethynyl diphthalic anhydride is used as a blocking agent, so that the high temperature resistance of the polyimide adhesive can be obviously improved, and the polyimide adhesive can be recycled for multiple times under the high temperature and high pressure environment. The possible reasons for the guess are: the introduction of 3,3', 4' -biphenyl tetracarboxylic dianhydride can improve the internal molecular structure of polyimide, so that the molecular structure of polyimide is more regular, and the polyimide has good high temperature resistance. And the introduction of biphenyl groups increases the hardness among molecular structures, thereby further improving the high temperature resistance effect of polyimide. The applicant further found that the use of ethynyl diphthalic anhydride as the end-capping agent can increase the pressure-resistant effect of polyimide in a high-temperature environment, and the gaps between the glass fibers are relatively large when the polyimide adhesive is compounded with the glass fibers, so that the polyimide adhesive and the glass fiber base cloth have good wetting and compounding effects, and meanwhile, the introduction of the end-capping agent alkynyl and the diphenyl further improves the high-temperature resistance, so that the polyimide adhesive still can keep good bonding effects in an environment of 400 ℃.
As a preferred embodiment, the organic solvent is selected from one or a combination of several of N, N-dimethylformamide, methylpyrrolidone, dimethyl sulfoxide and N, N-dimethylacetamide.
As a preferred embodiment, the preparation method of the polyimide solution I comprises the following steps: dissolving tetramethyl p-phenylenediamine in N, N-dimethylformamide, stirring for 0.5-2h, adding 3,3', 4' -biphenyl tetracarboxylic dianhydride and ethynyl diphthalic anhydride, stirring for reacting for 0.5-1h, heating to 70-90 ℃, stirring for reacting for 4-8h to obtain a homogeneous solution, and discharging to obtain the finished product.
The second aspect of the invention provides a preparation method of a heat-resistant and pressure-resistant sizing material, which comprises the following steps:
(1) Uniformly mixing the polyimide solution I and the polyimide solution II, adding the filler and the cross-linking agent, and uniformly mixing and stirring;
(2) Coating at 150-200deg.C, and standing for 0.5-1 hr.
The third aspect of the invention provides application of a heat-resistant and pressure-resistant sizing material, which is applied to the field of high-temperature lamination cushions.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the heat-resistant pressure-resistant sizing material, 3', 4' -biphenyl tetracarboxylic dianhydride reacts with diamine monomer and ethynyl diphthalic anhydride is used as a blocking agent, so that the high temperature resistance of the polyimide adhesive can be obviously improved, and the polyimide adhesive can be recycled for multiple times under high temperature and high pressure environments.
(2) According to the heat-resistant pressure-resistant sizing material, polyimide solutions with different viscosities are adopted for crosslinking reaction, so that the density of polyimide crosslinked network is increased, the high temperature resistance of the polyimide sizing material is further improved, and the polyimide sizing material can be recycled for multiple times in a high-temperature environment at 400 ℃.
(3) According to the heat-resistant pressure-resistant sizing material, the gas-phase white carbon black with the particle size of 10-100nm is introduced, so that the mechanical property of the polyimide sizing material can be improved on the basis of maintaining the dispersion uniformity of the polyimide sizing material, the heat-resistant pressure-resistant sizing material has good peel strength with a glass fiber substrate, and the cured sizing material has excellent tear strength and breaking tensile rate.
Detailed Description
The present invention will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of further illustration and are not to be construed as limitations on the scope of the invention, as will be apparent to those skilled in the art in light of the foregoing disclosure.
In addition, the raw materials used are commercially available unless otherwise indicated.
Example 1
The heat-resistant and pressure-resistant sizing material comprises the following preparation raw materials in parts by weight: 80 parts of polyimide solution I, 20 parts of polyimide solution II, 3 parts of filler and 0.5 part of cross-linking agent.
The polyimide solution II has an absolute viscosity of 20000 Pa.s at 25 ℃ and is purchased from Chemiebang polymer materials Co., ltd.
The cross-linking agent is hexakis (trimethylsilylethynyl) benzene. The filler is fumed silica, and the particle size is 50nm.
The polyimide solution I is self-made, and the preparation raw materials comprise the following components in parts by weight: 45 parts of aromatic diamine, 35 parts of aromatic dianhydride, 80 parts of organic solvent and 10 parts of end capping agent.
The aromatic diamine is tetramethyl p-phenylenediamine; the aromatic dianhydride is 3,3', 4' -biphenyl tetracarboxylic dianhydride; the end capping agent is ethynyl diphthalic anhydride; the organic solvent is N, N-dimethylformamide.
The preparation method of the polyimide solution I comprises the following steps: dissolving tetramethyl p-phenylenediamine in N, N-dimethylformamide, stirring for 1h, adding 3,3', 4' -biphenyl tetracarboxylic dianhydride and ethynyl diphthalic anhydride, stirring for reacting for 40min, heating to 90 ℃, stirring for reacting for 5h to obtain a homogeneous solution, and discharging to obtain the catalyst.
A preparation method of a heat-resistant and pressure-resistant sizing material comprises the following steps:
(1) Uniformly mixing the polyimide solution I and the polyimide solution II, adding the filler and the cross-linking agent, and uniformly mixing and stirring;
(2) Coating at 195 deg.C, and standing for 30 min.
Example 2
A heat and pressure resistant rubber material was prepared in the same manner as in example 1, except that the filler had a particle diameter of 0.5mm.
Example 3
The specific procedure of the heat-resistant and pressure-resistant rubber material is the same as in example 1, except that the end-capping agent is phenylethynyl phthalic anhydride.
Performance testing
1. The cured peel strength of the compound prepared in accordance with the GB/T2792-2014 standard test example was then tested again after 10 hours of standing at 400℃with the bonded substrate being a glass fiber substrate available from Guangdong as a technology Co., ltd.
2. The cured compound prepared according to the GB/T30776-2014 standard test example had tensile breaking strength and elongation at break (the bonding substrate was glass fiber base cloth, available from Guangdong Co., ltd.).
3. The compounds prepared in the examples were tested for tear strength after curing according to GB/T5573-1985 standard.
The test results are shown in Table 1.
TABLE 1
Claims (3)
1. The heat-resistant pressure-resistant sizing material is characterized by comprising the following preparation raw materials in parts by weight: 80 parts of polyimide solution I, 20 parts of polyimide solution II, 3 parts of filler and 0.5 part of cross-linking agent;
the polyimide solution I is self-made, and the preparation raw materials of the polyimide solution I comprise the following components in parts by weight: 45 parts of aromatic diamine, 35 parts of aromatic dianhydride, 80 parts of organic solvent and 10 parts of end capping agent;
the end capping agent is alkynyl-containing phthalic anhydride, and the alkynyl-containing phthalic anhydride is ethynyl diphthalic anhydride; the aromatic diamine is tetramethyl p-phenylenediamine; the aromatic dianhydride is 3,3', 4' -biphenyl tetracarboxylic dianhydride; the organic solvent is N, N-dimethylformamide;
the preparation method of the polyimide solution I comprises the following steps: dissolving tetramethyl p-phenylenediamine in N, N-dimethylformamide, stirring for 1h, adding 3,3', 4' -biphenyl tetracarboxylic dianhydride and ethynyl diphthalic anhydride, stirring for reacting for 40min, heating to 90 ℃, stirring for reacting for 5h to obtain a homogeneous solution, and discharging to obtain the catalyst;
the absolute viscosity of the polyimide solution II is more than or equal to 20000 Pa.s at 25 ℃;
the absolute viscosity of the polyimide solution I in the environment of 25 ℃ is 5000-10000 Pa.s;
the cross-linking agent is hexa (trimethylsilylethynyl) benzene, the filler is fumed silica, and the particle size is 50nm.
2. A process for the preparation of a heat and pressure resistant compound according to claim 1, comprising the steps of:
(1) Uniformly mixing the polyimide solution I and the polyimide solution II, adding the filler and the cross-linking agent, and uniformly mixing and stirring;
(2) Coating at 150-200deg.C, and standing for 0.5-1 hr.
3. The use of a heat and pressure resistant compound according to claim 1, in the field of high temperature lamination cushioning pads.
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| CN103965824A (en) * | 2014-05-16 | 2014-08-06 | 黑龙江省科学院石油化学研究院 | Acetenyl polyimide modified cyanate ester adhesive and preparation method thereof |
| CN107629755A (en) * | 2017-10-16 | 2018-01-26 | 黑龙江省科学院石油化学研究院 | A kind of fire resistant polyimide glued membrane and preparation method thereof |
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| CN101560371B (en) * | 2008-04-18 | 2012-08-08 | 中国科学院化学研究所 | High temperature resistant thermosetting polyimide adhesive and preparation method thereof |
| EP2694572A1 (en) * | 2011-04-01 | 2014-02-12 | Nexam Chemical AB | Improved oligo- and polyimides |
| CN109021234B (en) * | 2018-07-12 | 2020-12-29 | 浙江福斯特新材料研究院有限公司 | Thermosetting polyimide with high glass transition temperature and high heat resistance and preparation method thereof |
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| CN107629755A (en) * | 2017-10-16 | 2018-01-26 | 黑龙江省科学院石油化学研究院 | A kind of fire resistant polyimide glued membrane and preparation method thereof |
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