CN111171353A - Latent catalyst and preparation method of cyanate resin prepreg - Google Patents
Latent catalyst and preparation method of cyanate resin prepreg Download PDFInfo
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- CN111171353A CN111171353A CN202010057075.9A CN202010057075A CN111171353A CN 111171353 A CN111171353 A CN 111171353A CN 202010057075 A CN202010057075 A CN 202010057075A CN 111171353 A CN111171353 A CN 111171353A
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- Prior art keywords
- cyanate ester
- cyanate
- latent catalyst
- ester resin
- prepreg
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- 229920005989 resin Polymers 0.000 title claims abstract description 76
- 239000011347 resin Substances 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000004643 cyanate ester Substances 0.000 claims abstract description 54
- 239000003094 microcapsule Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 11
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000011162 core material Substances 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 239000004744 fabric Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000010453 quartz Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 4
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 3
- 150000002989 phenols Chemical class 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 2
- PVFQHGDIOXNKIC-UHFFFAOYSA-N 4-[2-[3-[2-(4-hydroxyphenyl)propan-2-yl]phenyl]propan-2-yl]phenol Chemical compound C=1C=CC(C(C)(C)C=2C=CC(O)=CC=2)=CC=1C(C)(C)C1=CC=C(O)C=C1 PVFQHGDIOXNKIC-UHFFFAOYSA-N 0.000 claims description 2
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229920000858 Cyclodextrin Polymers 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000001116 FEMA 4028 Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920002396 Polyurea Polymers 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims description 2
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims description 2
- 229960004853 betadex Drugs 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000000805 composite resin Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- AHZMUXQJTGRNHT-UHFFFAOYSA-N [4-[2-(4-cyanatophenyl)propan-2-yl]phenyl] cyanate Chemical compound C=1C=C(OC#N)C=CC=1C(C)(C)C1=CC=C(OC#N)C=C1 AHZMUXQJTGRNHT-UHFFFAOYSA-N 0.000 claims 1
- JYDYWDJQFNNNCK-UHFFFAOYSA-N cyanic acid;phenol Chemical compound OC#N.OC1=CC=CC=C1 JYDYWDJQFNNNCK-UHFFFAOYSA-N 0.000 claims 1
- 239000012783 reinforcing fiber Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 7
- 239000011159 matrix material Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 238000003860 storage Methods 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 7
- 239000000499 gel Substances 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
Classifications
-
- 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
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
-
- 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
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
-
- 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
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention relates to a cyanate ester resin latent catalyst and a preparation method thereof, belonging to the technical field of preparation of catalytic cyanate ester resin and composite materials thereof; the invention adopts the cyanate ester latent catalyst prepared by the microcapsule technology, when the prepreg needs to be cured, the microcapsule is broken after the prepreg is given proper pressure or temperature, and the curing agent enters the matrix, thereby achieving the purpose of catalyzing the curing of the cyanate ester resin. In addition, the latent catalyst/cyanate resin prepreg provided by the invention has better paving manufacturability, and is beneficial to forming of cyanate resin matrix composite materials. The application range of the cyanate resin-based related material is widened, and the cyanate resin-based related material has wide application prospect. The latent catalyst and the cyanate ester resin prepreg can be used for preparing skins for integrated parts of wave-transparent structures, meet the requirements of parts such as antenna radomes and the like on high wave-transparent rate, can be used as copper-clad plate base materials, and can be widely applied to the fields of electronics, aviation and aerospace.
Description
Technical Field
The invention relates to a cyanate ester resin latent catalyst, a preparation method thereof and a preparation method of a corresponding cyanate ester prepreg. Belongs to the technical field of preparation of catalytic cyanate resin and composite material thereof.
Background
Cyanate (CE) resin is a high-performance resin with excellent dielectric property, mechanical property and humidity resistance, has very wide application in the fields of electronic packaging, aerospace, insulating materials and the like, and becomes a resin matrix with great social and economic benefits in the 21 st century. However, since the curing time of CE is long, under the condition of no adding catalyst, curing is generally carried out for a long time (more than 7 h) at a higher temperature (more than 200 ℃) to obtain a larger curing crosslinking degree. However, the high-temperature long-time curing often causes more residual stress in the obtained cured product, so that the service performance stability of the material is poor, the preparation period of the product is prolonged, and the development and large-scale application of the CE resin and related materials are seriously hindered. Therefore, the research on the curing catalysis of the CE resin shows important theoretical significance and great application value. However, although the curing temperature and time are reduced (177 ℃ by 2h) by adding the catalyst (such as phenols, transition metals and the like), the storage life of the cyanate ester resin system and the prepreg product thereof is greatly shortened, low-temperature transportation and low-temperature storage (-20 ℃) are required to be adopted for prolonging the storage life, so that the manufacturing cost of the composite material is greatly increased, and in addition, the laying manufacturability of the prepreg is also reduced, and the laying and molding of the composite material product are not facilitated.
Disclosure of Invention
The invention aims to
The storage period of the cyanate resin system and the prepreg product thereof is short at present, low-temperature transportation and low-temperature storage have to be adopted in order to prolong the storage period, so that the manufacturing cost of the composite material is greatly increased, the construction window period of the cyanate resin is short, and the prepreg paving manufacturability is poor. Compared with the prior art, the invention prolongs the storage life of the cyanate resin system and the prepreg, and prolongs the construction window period of the cyanate resin, and has better paving manufacturability.
The invention adopts the following technical scheme:
the latent catalyst is characterized by being of a microcapsule structure and comprising a wall material and a core material, wherein the core material is a cyanate ester catalyst, and the mass ratio of the core material to the wall material is 2-5: 10.
the wall material comprises any one or a mixture of more of polyurethane, urea-formaldehyde resin, polyamide, polyurea, polyethylene glycol, PMMA, polystyrene and β -cyclodextrin.
The catalyst comprises any one or a mixture of more of organic compounds containing active hydrogen such as phenols, amines, imidazoles and transition metals.
The particle size of the microcapsule is 1-500 microns.
The preparation method of the cyanate resin prepreg comprises the following specific steps:
(1) placing the cyanate monomer into a container, stirring at the temperature of 80-150 ℃ until the cyanate monomer is completely melted, continuing stirring at the temperature of 100-180 ℃ for 0.5-5 h, cooling to below 50 ℃ at the cooling rate of 2-10 ℃/min, adding a solvent and dissolving the cyanate;
(2) adding the latent catalyst into the cyanate ester resin solution in proportion, and fully stirring until the latent catalyst and the cyanate ester resin solution are uniformly mixed to prepare a latent catalyst/cyanate ester resin solution;
(3) calculating the using amount of the latent catalyst/cyanate ester resin solution according to the required gel content of the prepreg, and uniformly coating the latent catalyst/cyanate ester resin solution on the surface of the reinforced fiber to prepare the latent catalyst/cyanate ester resin prepreg;
(4) curing the latent catalyst/cyanate resin prepreg by adopting a heating and pressurizing mode, wherein the structure of the latent catalyst microcapsule is damaged in the curing process, the catalyst is released from the latent catalyst microcapsule, and then the curing of the cyanate resin is catalyzed to prepare the cyanate resin composite material, wherein the curing temperature is 100-180 ℃, and the pressure is 0.1-1 MPa.
The cyanate resin is one or a mixture of more of bisphenol A cyanate, phenolic cyanate, dicyclopentadiene bisphenol cyanate, bisphenol F cyanate and bisphenol M cyanate.
The solvent used by the latent catalyst/cyanate ester resin solution comprises one or a mixture of more of acetone, 1, 2-dichloroethane, cyclohexane, N 'N-dimethylformamide and N' N-dimethylacetamide.
The mass ratio of the latent catalyst to the cyanate ester resin is (1-20): 100.
the reinforced fiber is any one or more of glass fiber, carbon fiber, quartz fiber, polyimide fiber, aramid fiber or fabrics thereof.
The content of the rubber in the prepreg is 30-50%.
The invention has the beneficial effects
The cyanate ester latent catalyst prepared by the microcapsule technology has the blocking effect of the capsule wall, so that the latent catalyst cannot contact matrix resin, and physical and chemical reactions cannot occur, thereby greatly prolonging the latent period. When the prepreg needs to be cured, after the prepreg is given appropriate pressure or temperature, the microcapsules are broken, and the curing agent enters the matrix, so that the purpose of catalyzing the curing of the cyanate ester resin is achieved. In addition, the latent catalyst/cyanate resin prepreg provided by the invention has better paving manufacturability, and is beneficial to forming of cyanate resin matrix composite materials. The application range of the cyanate resin-based related material is widened, and the cyanate resin-based related material has wide application prospect. The latent catalyst and the cyanate ester resin prepreg can be used for preparing skins for integrated parts of wave-transparent structures, meet the requirements of parts such as antenna radomes and the like on high wave-transparent rate, can be used as copper-clad plate base materials, and can be widely applied to the fields of electronics, aviation and aerospace.
Detailed Description
Example 1
(1) Dissolving 8g of urea and 20g of formaldehyde solution (mass percentage is 37%) in distilled water, adjusting the pH value to 8.5 by using triethanolamine, and stirring at the constant temperature of 70 ℃ for 1h at the rotating speed of 400r/min to obtain a transparent urea-formaldehyde resin prepolymer solution for later use. And mixing a certain amount of emulsifier with 20g of dibutyltin dilaurate, emulsifying in a water bath at 50 ℃ for 15min at a certain rotating speed, and dropwise adding 80mL of distilled water to obtain the core material emulsion. And simultaneously, dripping a prepolymer solution into the core material nonyl phenol emulsion, acidifying the solution by using a 10% citric acid solution for a period of time to adjust the pH value to 2-5, heating the solution to 70 ℃ after the microcapsule is formed, continuously stirring the solution at a constant temperature for 2 hours, carrying out suction filtration on the obtained product, washing the product twice by using petroleum ether and distilled water to obtain a filter cake, putting the filter cake into a constant-temperature air-blast drying oven, drying the product at 100 ℃ to constant weight, and obtaining solid powder which is a latent catalyst microcapsule, wherein the SEM appearance of the solid powder is characterized by: the particle size range is 10-100 μm.
(2) Putting the bisphenol A cyanate monomer into a container, stirring at the temperature of 80 ℃ until the cyanate monomer is completely melted, and continuing stirring at the temperature of 130 ℃ for 4 hours. Cooling to below 50 ℃ at the cooling rate of 5 ℃/min, adding acetone and dissolving cyanate ester to prepare the cyanate ester resin solution.
(3) Adding the microcapsules in the step (1) into a cyanate ester resin solution according to the mass ratio of 20:100, and fully stirring until the microcapsules are uniformly mixed to prepare the latent catalyst/cyanate ester resin solution. Latent catalyst/cyanate ester resin DSC characterization: the curing temperature is 130-140 ℃.
(4) According to the design that the gel content is 30%, the latent catalyst/cyanate resin solution is uniformly coated on the surface of the quartz fiber fabric, and the latent catalyst/cyanate resin prepreg is prepared. And (3) storage period characterization: the prepreg is stored for 7 days at 50 ℃, the gel time growth rate of the prepreg is less than 12 percent, and the fluidity growth rate is less than 12 percent.
Example 2
(1) Dissolving 4g of urea and 9.46g of formaldehyde solution (mass fraction is 37%) in distilled water, adjusting the pH value to 8.5 by using triethanolamine, and stirring at the constant temperature of 70 ℃ for 1h at the rotating speed of 400r/m in to obtain a transparent urea-formaldehyde resin prepolymer solution for later use. Mixing a certain amount of emulsifier and 15g of organic tin, emulsifying for 15min in a water bath at 50 ℃ at a certain rotating speed, and dropwise adding 40mL of distilled water to obtain the core material emulsion. And simultaneously, dripping a prepolymer solution into the core material nonyl phenol emulsion, acidifying the prepolymer solution by using a 10% citric acid solution for a period of time to adjust the pH value to 2-5, heating the solution to 70 ℃ after the microcapsule is formed, and continuously stirring the solution at constant temperature for 2 hours. And (3) carrying out suction filtration on the obtained product, washing with petroleum ether and distilled water twice to obtain a filter cake, putting the filter cake into a constant-temperature air-blast drying oven, and drying at 100 ℃ to constant weight to obtain solid powder which is a latent catalyst microcapsule, wherein the SEM appearance of the solid powder is characterized by: the particle size range is 10-100 μm.
(2) Putting the bisphenol A cyanate monomer into a container, stirring at the temperature of 80 ℃ until the cyanate monomer is completely melted, and continuously stirring at the temperature of 120 ℃ for 5 hours. Cooling to below 50 ℃ at the cooling rate of 8 ℃/min, adding 1, 2-dichloroethane, and dissolving cyanate ester to prepare the cyanate ester resin solution.
(3) Adding the latent catalyst microcapsule in the step (1) into a cyanate ester resin solution according to the mass ratio of 10:100, and fully stirring until the mixture is uniformly mixed to prepare the latent catalyst/cyanate ester resin solution. Latent catalyst/cyanate ester resin DSC characterization: the curing temperature is 150-160 ℃.
(4) According to the design that the gel content is 50%, the latent catalyst/cyanate resin solution is uniformly coated on the surface of the quartz fiber fabric, and the latent catalyst/cyanate resin prepreg is prepared. And (3) storage period characterization: the prepreg is stored for 7 days at 50 ℃, the gel time growth rate of the prepreg is less than 10 percent, and the fluidity growth rate is less than 10 percent.
Example 3
(1) Stirring methyl methacrylate, copper acetylacetonate, divinylbenzene and 2, 2' -azobisisobutyronitrile for 10min by a constant-temperature magnetic heating stirrer under the water bath heating condition of 40 ℃ to form a uniform oil phase; adding the oil phase into a continuous phase consisting of sodium salt of styrene-maleic anhydride copolymer, gelatin and water which is heated and stirred in advance under a constant-temperature magnetic heating stirrer, and violently stirring for 15min under the heating of the constant-temperature magnetic heating stirrer to form emulsion; dispersing the emulsion for 3min at a dispersion speed of 10000rpm by using a digital display high-speed dispersion homogenizer to form a stable oil-in-water emulsion; transferring the emulsion into a 250ml three-neck flask, reacting the reaction system for 6 hours under the conditions of water bath heating at 75 ℃ and mechanical stirring at 550rpm, then heating to 85 ℃, and reacting for 1 hour under the mechanical stirring at 550rpm to complete the polymerization reaction; the prepared product is washed for 3 times by hot deionized water and then dried for 48 hours in an electric heating constant temperature air drying oven at the temperature of 45 ℃. Namely preparing latent catalyst microcapsules. The SEM appearance is characterized in that: the particle size range is 15-50 μm.
(2) Putting the bisphenol A cyanate monomer into a container, stirring at the temperature of 80 ℃ until the cyanate monomer is completely melted, and continuing stirring at the temperature of 130 ℃ for 4 hours. Cooling to below 50 ℃ at the cooling rate of 5 ℃/min, adding acetone and dissolving cyanate ester to prepare the cyanate ester resin solution.
(3) Adding the latent catalyst microcapsule in the step (1) into a cyanate ester resin solution according to the mass ratio of 15:100, and fully stirring until the mixture is uniformly mixed. Preparing the latent catalyst/cyanate resin solution. Latent catalyst/cyanate ester resin DSC characterization: the curing temperature is 135-145 ℃.
(4) According to the design that the gel content is 40%, the latent catalyst/cyanate resin solution is uniformly coated on the surface of the quartz fiber fabric, and the latent catalyst/cyanate resin prepreg is prepared. And (3) storage period characterization: the prepreg is stored for 7 days at 50 ℃, the gel time growth rate of the prepreg is less than 10 percent, and the fluidity growth rate is less than 10 percent.
Claims (10)
1. The latent catalyst is characterized by being of a microcapsule structure and comprising a wall material and a core material, wherein the core material is a cyanate ester catalyst, and the mass ratio of the core material to the wall material is 2-5: 10.
2. a latent catalyst according to claim 1, wherein the wall material comprises any one or more of polyurethane, urea-formaldehyde resin, polyamide, polyurea, polyethylene glycol, PMMA, polystyrene, and β -cyclodextrin.
3. A latent catalyst according to claim 1, wherein said catalyst comprises any one or more of organic compounds containing active hydrogen such as phenols, amines, imidazoles, and transition metals.
4. A latent catalyst according to claim 1, wherein said microcapsules have a particle size of 1 to 500 microns.
5. The method for preparing the cyanate ester resin prepreg according to any one of claims 1 to 4, wherein the method comprises the following steps:
(1) placing the cyanate monomer into a container, stirring at the temperature of 80-150 ℃ until the cyanate monomer is completely melted, continuing stirring at the temperature of 100-180 ℃ for 0.5-5 h, cooling to below 50 ℃ at the cooling rate of 2-10 ℃/min, adding a solvent and dissolving the cyanate;
(2) adding the latent catalyst into the cyanate ester resin solution in proportion, and fully stirring until the latent catalyst and the cyanate ester resin solution are uniformly mixed to prepare a latent catalyst/cyanate ester resin solution;
(3) calculating the using amount of the latent catalyst/cyanate ester resin solution according to the required gel content of the prepreg, and uniformly coating the latent catalyst/cyanate ester resin solution on the surface of the reinforced fiber to prepare the latent catalyst/cyanate ester resin prepreg;
(4) curing the latent catalyst/cyanate resin prepreg by adopting a heating and pressurizing mode, wherein the structure of the latent catalyst microcapsule is damaged in the curing process, the catalyst is released from the latent catalyst microcapsule, and then the curing of the cyanate resin is catalyzed to prepare the cyanate resin composite material, wherein the curing temperature is 100-180 ℃, and the pressure is 0.1-1 MPa.
6. The method for preparing the cyanate ester resin prepreg according to claim 5, wherein the cyanate ester resin is one or a mixture of bisphenol A cyanate ester, phenol cyanate ester, dicyclopentadiene bisphenol cyanate ester, bisphenol F cyanate ester, and bisphenol M cyanate ester.
7. The method for preparing cyanate ester resin prepreg according to claim 5, wherein the solvent used in the latent catalyst/cyanate ester resin solution comprises one or more of acetone, 1, 2-dichloroethane, cyclohexane, N 'N-dimethylformamide, and N' N-dimethylacetamide.
8. The method for preparing the cyanate ester resin prepreg according to claim 5, wherein the mass ratio of the latent catalyst to the cyanate ester resin is (1-20): 100.
9. the method for preparing the cyanate ester resin prepreg according to claim 5, wherein the reinforcing fiber is any one or more of glass fiber, carbon fiber, quartz fiber, polyimide fiber, aramid fiber or fabric thereof.
10. The method for preparing the cyanate ester resin prepreg according to claim 5, wherein the prepreg contains 30% to 50% of the gel.
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| CN115386190A (en) * | 2022-09-14 | 2022-11-25 | 成都飞机工业（集团）有限责任公司 | Polydicyclopentadiene resin composite material and preparation method and application thereof |
| CN115433459A (en) * | 2022-09-14 | 2022-12-06 | 成都飞机工业（集团）有限责任公司 | Cyanate ester resin prepolymer and preparation method and application thereof |
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