CN114380963A - Dual-curing high-carbon-residue phenolic resin and preparation method thereof - Google Patents
Dual-curing high-carbon-residue phenolic resin and preparation method thereof Download PDFInfo
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- CN114380963A CN114380963A CN202111581239.9A CN202111581239A CN114380963A CN 114380963 A CN114380963 A CN 114380963A CN 202111581239 A CN202111581239 A CN 202111581239A CN 114380963 A CN114380963 A CN 114380963A
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- phenolic resin
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000005011 phenolic resin Substances 0.000 title claims abstract description 41
- 229920001568 phenolic resin Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 63
- 229920005989 resin Polymers 0.000 claims abstract description 59
- 239000011347 resin Substances 0.000 claims abstract description 59
- 239000002131 composite material Substances 0.000 claims abstract description 44
- 230000008569 process Effects 0.000 claims abstract description 37
- 239000004831 Hot glue Substances 0.000 claims abstract description 22
- 238000000465 moulding Methods 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 11
- 238000001721 transfer moulding Methods 0.000 claims abstract description 10
- 238000001723 curing Methods 0.000 claims description 40
- 239000000835 fiber Substances 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000004744 fabric Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 150000002989 phenols Chemical class 0.000 claims description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 14
- -1 aldehyde compounds Chemical class 0.000 claims description 14
- 229910052796 boron Inorganic materials 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000007598 dipping method Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 239000003292 glue Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000002210 silicon-based material Substances 0.000 claims description 10
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002313 adhesive film Substances 0.000 claims description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 8
- 239000012943 hotmelt Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 6
- 229920002866 paraformaldehyde Polymers 0.000 claims description 6
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 230000009977 dual effect Effects 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 150000003377 silicon compounds Chemical class 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 230000005250 beta ray Effects 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 4
- 239000004246 zinc acetate Substances 0.000 claims description 4
- YDMRDHQUQIVWBE-UHFFFAOYSA-N (2-hydroxyphenyl)boronic acid Chemical compound OB(O)C1=CC=CC=C1O YDMRDHQUQIVWBE-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000013461 design Methods 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 238000012360 testing method Methods 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000008098 formaldehyde solution Substances 0.000 claims description 2
- 239000012945 sealing adhesive Substances 0.000 claims description 2
- 238000012546 transfer Methods 0.000 claims description 2
- 238000002679 ablation Methods 0.000 abstract description 19
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000001276 controlling effect Effects 0.000 abstract description 7
- 229910018557 Si O Inorganic materials 0.000 abstract description 3
- CFOAUMXQOCBWNJ-UHFFFAOYSA-N [B].[Si] Chemical compound [B].[Si] CFOAUMXQOCBWNJ-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 12
- 238000005520 cutting process Methods 0.000 description 5
- 229960004011 methenamine Drugs 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PZRPBPMLSSNFOM-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]boronic acid Chemical compound OCC1=CC=C(B(O)O)C=C1 PZRPBPMLSSNFOM-UHFFFAOYSA-N 0.000 description 1
- 238000013006 addition curing Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000005375 organosiloxane group Chemical class 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
- C08G8/30—Chemically modified polycondensates by unsaturated compounds, e.g. terpenes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
- B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
- B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
-
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/14—Modified phenol-aldehyde condensates
Abstract
The invention relates to a dual-curing high-carbon-residue phenolic resin and a preparation method thereof, wherein a double-bond silicon-boron-containing modified phenolic resin (DBSIBPR) is synthesized by body copolymerization, a B-O (561kJ/mol) structure and a Si-O (443.7kJ/mol) structure with high bond energy are introduced into a resin structure, so that the ablation resistance of the phenolic resin is improved, and meanwhile, the requirements of a hot melt adhesive film prepreg preparation process and a VARTM (vacuum transfer molding) molding process are met by regulating and controlling the viscosity of the modified resin, so that the high-performance and low-cost manufacture of an ablation phenolic resin-based composite material is realized. The problems that the existing ablation type phenolic resin matrix composite material cannot meet the increasing performance requirements, and is high in manufacturing cost and unstable in quality are solved.
Description
Technical Field
The invention belongs to phenolic resin and a preparation method thereof, in particular to an ablation type thermal protection composite material prepared by a hot melt adhesive film method and a vacuum assisted resin transfer molding forming method (VARTM). Relates to a dual-curing high-carbon-residue phenolic resin and a preparation method thereof, which are suitable for a hot melt adhesive film method and a vacuum-assisted resin transfer molding forming process.
Background
At present, phenolic resin-based composite materials are still the main materials of thermal protection of missile warhead cone parts and thermal insulation layers of expansion sections of solid rocket engine nozzles. The traditional ablation type phenolic resin matrix composite material adopts a prepreg winding-autoclave molding technology, the prepreg is prepared by a solution method, and in the process of preparing the prepreg, a solvent in a glue groove can continuously volatilize, the concentration of the solution is gradually increased, the resin content in the prepreg is increased, the fluctuation of the gel content of the prepreg reaches 13%, the fluctuation of the gel content has great influence on the density and ablation performance of the final material, and the ablation of the product in the working process of an engine is unstable. In order to ensure the reliability of the product use, the method can only be used for solving the problem by thickening the ablation layer of the product, which increases the negative quality of the product. In addition, the production process uses a large amount of organic solvents, so that environmental pollution and certain harm to the health of operators are caused, and potential safety hazards such as fire and the like are brought. The prepreg prepared by the hot melt adhesive film method has accurate glue content, low volatile matter and good batch stability, and can obtain a composite material product with low porosity, low ablation rate and stable quality through winding-hot press molding, thereby having important theoretical significance and practical application value for improving the thrust-weight ratio of the solid rocket engine.
The VARTM molding process is a low-cost advanced composite liquid molding process, and adopts a closed/semi-closed mold, so that the prepared composite product has good product surface quality and high-precision product size and can be used for preparing products with complex structures; the production process has less volatile matter, is favorable for the health of operators and environmental protection, and can meet the requirements of novel weaponry on high-performance, low-cost and high-quality manufacturing technology of ablation-resistant composite materials. Therefore, the phenolic resin is modified through reasonable structural design, so that the modified resin meets the requirements of the VARTM forming process, and the preparation of the ablative thermal protection composite material by the VARTM forming process can be realized.
The high-temperature pyrolysis of the existing phenolic resin is mainly because the C-O bond energy is 384kJ/mol and the C-C bond energy is 334.72kJ/mol, and aims to solve the problems that the existing ablation type phenolic resin matrix composite material cannot meet the increasing performance requirements, and is high in manufacturing cost and unstable in quality.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides a dual-curing high-carbon-residue phenolic resin and a preparation method thereof, the double-bond silicon-boron-containing modified phenolic resin (DBSIBPR) is synthesized by body copolymerization, a B-O (561kJ/mol) structure and a Si-O (443.7kJ/mol) structure with high bond energy are introduced into the resin structure, the ablation resistance of the phenolic resin is improved, and simultaneously the requirements of a hot melt adhesive film prepreg preparation process and a VARTM (vacuum-assisted resin transfer molding) molding process are met respectively by regulating and controlling the viscosity of the modified resin, so that the high-performance and low-cost manufacture of the ablation phenolic resin-based composite material is realized.
Technical scheme
A dual-curing high-carbon-residue phenolic resin is characterized by comprising phenolic compounds, aldehyde compounds, boron-containing compounds, silicon-containing compounds and curing agents; the molar ratio of the phenolic compound to the aldehyde compound to the boron-containing compound to the silicon-containing compound is 1: 1.0-1.5: 0.1-0.3; the dosage of the curing agent is 4 to 12 percent of that of the phenolic compound; the silicon-containing compound is a double-bond-containing silicon compound; the curing agent is hexamethylenetetramine.
The phenolic compound comprises one or more of phenol, o-methyl phenol or resorcinol.
The aldehyde compound comprises one or more of aqueous formaldehyde solution, paraformaldehyde or benzaldehyde and the like.
The boron-containing compound comprises one or more of boric acid, phenylboronic acid or hydroxyphenylboronic acid.
The double-bond silicon compounds comprise vinyl triethoxysilane, vinyl trimethoxysilane and KH-570 double-bond one or more organic siloxane combinations.
A preparation method of the dual-curing high-carbon-residue phenolic resin hot melt adhesive film method and the vacuum assisted resin transfer molding forming process is characterized by comprising the following steps:
step 1: proportionally adding the boron-containing compound into a phenolic compound at the temperature of 50-60 ℃, and then reacting for 2-5h at the temperature of 80-160 ℃;
step 2: cooling to 60-90 ℃, adding a catalyst and an aldehyde compound into a reaction system, and reacting for 4-8h at the current temperature; the dosage of the catalyst is 2 to 6 percent of the dosage of the phenolic compound;
and step 3: keeping the current temperature, adding the silicon-containing compound into the reaction system, and continuing to react for 2-4 h;
and 4, step 4: adding a solvent, cooling to room temperature, and separating out a water phase;
and 5: and (3) heating to 80-100 ℃, removing the solvent under the condition that the vacuum degree is more than or equal to-0.09 MPa, and determining the reaction end point when testing the viscosity of the resin. Obtaining the liquid or semi-solid phenolic resin containing silicon and boron.
The catalyst is selected from zinc acetate, oxalic acid or p-toluenesulfonic acid.
A method for preparing the dual-curing high carbon residue phenolic resin composite material by adopting a VARTM (vacuum assisted transfer molding) process is characterized by comprising the following steps of: 1. coating a layer of release agent on the surface of the mould, and paving n layers of fiber fabrics on a bottom plate of the mould to be used as a preformed body; sequentially laying demolding cloth and a flow guide net on the outer surface of the preformed body, then laying a vacuum bag on a mold, sealing the vacuum bag and the periphery of the mold by using a sealing adhesive tape, and respectively connecting a flow guide pipe at a glue injection port and an air outlet; clamping a nozzle guide pipe by a clamp, connecting a vacuum pump at a dead head, vacuumizing the vacuum bag, and checking the air tightness to ensure that the vacuum degree reaches-0.09 to-0.095 MPa to the maximum; 2. the mold assembly was placed in an oven and preheated at 90 ℃ for 10 minutes. And (3) taking down the clamp of the nozzle guide pipe, vacuumizing and filling the mold, applying an external pressure of 0-6 MPa (preferably 3MPa) when the preform is completely filled with the resin, continuously vacuumizing for 15-20 min at the same time, completely infiltrating the preform with the resin, and closing the resin inlet. Curing according to the curing process of 90 ℃/1h +130 ℃/1h +150 ℃/1h +180 ℃/1h +200 ℃/2 h; 3. and naturally cooling the cured mold to room temperature along with an oven, releasing pressure and opening the mold, and taking out the laminated board to prepare the dual-curing high-carbon-residue phenolic resin composite material.
A method for preparing the dual-curing high-carbon-residue phenolic resin composite material by a hot melt adhesive membrane method is characterized by comprising the following steps of: 1. the hot-melt adhesive film can be prepared by a hot-melt pre-dipping machine, the temperature of a dipping roller of the hot-melt pre-dipping machine is controlled to be 55-75 ℃, the transfer rate of conveying release paper is 3-6m/min, the distance between the dipping rollers is adjusted, and the thickness is detected by a beta-ray apparatus, so that the unit mass of the resin film meets the design requirement of the content of prepreg resin; 2. leading out fiber bundles on an unreeling device, flattening the fiber bundles by a flattening roller, then sandwiching the fiber bundles with a prepared adhesive film, melting a resin matrix by a heating roller, controlling the temperature to be 60-80 ℃, soaking the resin matrix in fibers, cooling, adding a PE film, and rolling to prepare a prepreg; 3. laying/winding the prepreg, placing the prepreg in a mold coated with a release agent, and molding in a flat vulcanizing machine/autoclave, wherein the curing process comprises the following steps: 130 ℃/1h +150 ℃/1h +180 ℃/1h +200 ℃/2hr, and the molding pressure is 2-6 MPa; 4. and (3) naturally cooling the formed composite material product along with a furnace, and then taking out the product from the die to obtain the dual-curing high-carbon-residue phenolic resin composite material.
When the resin is applied to a VARTM forming process to prepare a composite material, the viscosity of the resin is 200-400 mPa & s/90 ℃; the viscosity of the composite material resin prepared by applying the method to a hot melt adhesive membrane method is 5000-10000 mPa & s/60 ℃.
Advantageous effects
According to the dual-curing high-carbon-residue phenolic resin and the preparation method thereof, a double-bond silicon-boron-containing modified phenolic resin (DBSIBPR) is synthesized through body copolymerization, a B-O (561kJ/mol) structure and a Si-O (443.7kJ/mol) structure with high bond energy are introduced into a resin structure, the ablation resistance of the phenolic resin is improved, and meanwhile, the requirements of a hot melt adhesive film prepreg preparation process and a VARTM (vacuum transfer molding) forming process are met respectively through regulating and controlling the viscosity of the modified resin, so that the high-performance and low-cost manufacturing of an ablation phenolic resin-based composite material is realized. The problems that the existing ablation type phenolic resin matrix composite material cannot meet the increasing performance requirements, and is high in manufacturing cost and unstable in quality are solved.
Advantageous effects of the invention
The DBSIBPR prepared by the method introduces structures of-B-O-and-O-Si-with high bond energy and the like into the modified resin, and can improve the ablation resistance and the thermal stability of the phenolic resin; meanwhile, double bond functional groups in the modified resin structure realize addition curing under the heating condition, and the release of small molecular water in the curing process is reduced; hexamethylene tetramine is added as an external curing agent to perform addition reaction with active points on the phenolic resin, so that the crosslinking degree is increased, the heat resistance of the cured resin is improved, small molecular water is not released (the curing principle is shown in figure 4), the porosity of the composite material is reduced, and the performance of the composite material is improved. The modified phenolic resin is used as a matrix, and a VARTM (vacuum transfer molding) forming process is combined to prepare the ablation-resistant composite material, so that the efficiency is high, and the cost is low; the modified phenolic resin is used as a matrix, a hot melt adhesive film method is adopted to prepare prepreg, the prepreg is used for preparing a composite material, no solvent is used, the harm to the environment and operators is reduced, the potential safety hazard is eliminated, the product quality can be effectively improved, the requirements of new-age weaponry on high efficiency, low cost and high quality of an ablation-resistant composite material can be met, and the prepreg is expected to play an important role in advanced fields such as aerospace, weaponry and the like.
Drawings
FIG. 1: synthetic principle and characteristic structure of DBSIBPR (R in figure)1Can be-OH, phenyl, hydroxymethyl benzene, etc.; r2、R3And R4Can be methoxy, ethoxy, methyl, phenyl, etc.)
FIG. 2: diagram of VARTM apparatus
FIG. 3: prepreg prepared by hot melt adhesive membrane method
1. Preparing an adhesive film by a hot-melting pre-dipping machine; 2. compounding the adhesive film and the fiber fabric; 3. prepreg
FIG. 4: DBSIBPR dual cure principle
FIG. 5: infrared spectrogram of DBSIBPR
FIG. 6: viscosity-time curve for DBSIBPR at 90 deg.C
FIG. 7: viscosity-time curve for DBSIBPR at 60 deg.C
FIG. 8: TGA spectrum of DBSiBPR cured product
Detailed Description
The invention will now be further described with reference to the following examples and drawings:
5.1 starting Material
Phenolic compounds: phenol, o-methyl phenol or resorcinol, and the like.
Aldehyde compound: one or more of formaldehyde aqueous solution, paraformaldehyde or benzaldehyde.
Catalyst: zinc acetate, oxalic acid or p-toluenesulfonic acid and the like
Boron-containing compounds: boric acid, phenylboronic acid, hydroxyphenylboronic acid, and the like.
Silicon-containing compounds: vinyltriethoxysilane, vinyltrimethoxysilane, KH-570, and the like, contain a bis-substituted organosiloxane combination or combinations.
Curing agent: hexamethylenetetramine
Solvent: methyl isobutyl ketone, isobutanol, and the like.
The molar ratio of the phenolic compound to the aldehyde compound to the boron-containing compound to the double-bond-containing silicon compound is 1: 1.0-1.5: 0.1-0.3, the dosage of the catalyst is 2% -6% of that of the phenolic compound, and the solvent is: (phenol + formaldehyde) (mass ratio) is more than or equal to 1.0: 1.0; the dosage of the curing agent is 4 to 12 percent of the phenolic compound.
5.2 preparation of silicon-boron-modified phenolic resin containing double bonds
(1) Adding phenolic compounds into a three-neck flask, and controlling the temperature to be 50-60 ℃;
(2) adding the boron-containing compound into a reaction system according to a proportion, controlling the temperature at 80-160 ℃, and reacting for 2-5 h;
(3) cooling to 60-90 ℃, adding a catalyst and an aldehyde compound into a reaction system, and reacting for 4-8h at the current temperature;
(4) keeping the current temperature, adding the silicon-containing compound into the reaction system, and continuing to react for 2-4 h;
(5) adding a solvent, cooling to room temperature, and separating out a water phase;
(6) and (3) heating to 80-100 ℃, removing the solvent under the condition that the vacuum degree is more than or equal to-0.09 MPa, and determining the reaction end point by testing the viscosity of the resin. Obtaining the liquid or semi-solid phenolic resin containing silicon and boron (the synthesis principle and the characteristic structure are shown in figure 1).
The viscosity of the composite material resin prepared by the VARTM forming process is 200-400 mPas (90 ℃), and the viscosity of the composite material resin prepared by the hot melt adhesive membrane method is 5000-10000 mPas (60 ℃)
5.3 preparation of composite Material by VARTM/Molding Process
Step 1: cleaning the surface of the mold with alcohol, drying, and coating a layer of mold release agent on the surface of the mold; cutting fibers according to the size of the prefabricated part;
step 2: n layers of fiber fabric are laid on the bottom plate of the mold to be used as a preformed body. And sequentially laying demolding cloth and a flow guide net on the outer surface of the preforming body, then laying a vacuum bag on the mold, sealing the vacuum bag and the periphery of the mold by using a sealing rubber strip, and respectively connecting a flow guide pipe at the glue injection port and the gas outlet. The nozzle guide pipe is clamped by a clamp, a vacuum pump is connected to a dead head, the vacuum bag is vacuumized, the air tightness is checked, the vacuum degree reaches-0.09 MPa to-0.095 MPa at most, and the device is shown in figure 2.
And step 3: the mold assembly was placed in an oven and preheated at 90 ℃ for 10 minutes. And (3) taking down the clamp of the nozzle guide pipe, vacuumizing and filling the mold, applying an external pressure of 0-6 MPa (preferably 3MPa) when the preform is completely filled with the resin, continuously vacuumizing for 15-20 min at the same time, completely infiltrating the preform with the resin, and closing the resin inlet. Curing according to the curing process of 90 ℃/1h +130 ℃/1h +150 ℃/1h +180 ℃/1h +200 ℃/2 h.
And 4, step 4: and (4) naturally cooling the mould solidified in the step (3) to room temperature along with an oven, releasing pressure and opening the mould, taking out the laminated board, and cutting the sample according to the corresponding performance test standard for performance test.
5.4 preparation of composite material by hot melt adhesive membrane method
Step 1: preparation of Hot melt adhesive films
The hot melt adhesive film can be prepared by a hot melt pre-dipping machine, the temperature of a dipping roller of the hot melt pre-dipping machine is controlled to be 55-75 ℃ (the preferred temperature is 65 ℃), the migration rate of the conveying release paper is 3-6m/min (the preferred traction rate is 4m/min), the distance between the dipping rollers is adjusted, and the thickness is detected by a beta-ray apparatus, so that the unit mass of the resin film meets the requirement of the content of the prepreg resin.
Step 2: preparation of prepregs
The method comprises the steps of leading out a fiber bundle on an unwinding device under the action of certain tension, flattening the fiber bundle by a flattening roller, then sandwiching the fiber bundle together with a prepared adhesive film, melting a resin matrix by a heating roller, controlling the temperature to be 60-80 ℃ (preferably 70 ℃), soaking the fiber bundle in the fiber, and then cooling, adding a PE film and rolling the fiber bundle to prepare the prepreg. The equipment used and the prepreg processed in step one and step two are shown in figure 3.
And step 3: preparation of composite materials
And (3) cutting, laying/winding the prepreg prepared in the step (2) according to the use requirement, placing the prepreg in a mold coated with a release agent, and forming in a flat vulcanizing machine/autoclave. The curing process comprises the following steps: 130 ℃/1h +150 ℃/1h +180 ℃/1h +200 ℃/2hr, and the molding pressure is 2-6 MPa (preferably 3 MPa).
And 4, step 4: demoulding
And (4) naturally cooling the composite material product formed in the step (3) along with a furnace, then taking out the composite material product from the mold, and cutting the sample according to the performance test requirement.
Example (best mode of implementation)
(1) Example 1
The process comprises the following steps:
1) preparing a 500ml three-neck bottle provided with a condenser tube, a stirring device and a thermometer, putting the bottle into an oil bath pot, heating to 50 ℃, opening a stirrer, adding phenol for melting, then adding boric acid, stirring uniformly at the current temperature, heating to 150 ℃ and reacting for 3 hours;
2) cooling the reaction system in the step 1) to 60-70 ℃, adding oxalic acid and paraformaldehyde, and continuing to react for 8 hours at the temperature.
3) Adding vinyl trimethoxy silane into the reaction system in the step 2), and continuously reacting for 2 hours;
4) adding methyl isobutyl ketone into the reaction system in the step 3), uniformly stirring, standing for layering, and separating out a water layer;
5) decompressing the solvent layer in the step 4) for 30min under a vacuum environment of-0.09 to-0.095 MPa, discharging to obtain DBSiBPR liquid resin suitable for VARTM forming process;
6) adding hexamethylenetetramine into the DBSIBPR obtained in the step 5), uniformly mixing, placing the mixture in a glue tank connected with a flow guide pipe, laying fiber cloth on a mould according to the thickness of a sample, placing demoulding cloth and a flow guide net on the fiber cloth, sealing the vacuum bag and the mould by using a sealant, placing the mould in a drying oven at 90 ℃ for preheating, and opening a vacuum pump to vacuumize to-0.88 to-0.90 MPa. When the resin completely impregnates the fiber cloth, an external pressure of 3MPa is applied, and the resin inlet is closed. Curing according to the curing process of 90 ℃/1h +130 ℃/1h +150 ℃/1h +180 ℃/1h +200 ℃/2h, naturally cooling, releasing pressure and demoulding, and obtaining the DBSIBPR/high silica glass fiber composite laminated board.
(2) Example 2
The process comprises the following steps:
1) preparing a 500ml three-neck bottle provided with a condenser tube, a stirring device and a thermometer, putting the bottle into an oil bath pot, heating to 50 ℃, opening a stirrer, adding phenol for melting, then adding boric acid, stirring uniformly at the current temperature, heating to 130 ℃ and reacting for 3 hours;
2) cooling the reaction system in the step 1) to 60-70 ℃, adding p-toluenesulfonic acid, paraformaldehyde and benzaldehyde, heating to 85 ℃, and reacting for 7h at the temperature.
3) Adding vinyltriethoxysilane into the reaction system in the step 2), and continuing to react for 1.5 h;
4) cooling to 60 ℃, adding methyl isobutyl ketone into the reaction system in the step 3), uniformly stirring, standing for layering, and separating out a water layer;
5) decompressing the solvent layer in the step 4) for 45min under the vacuum environment of-0.09 to-0.095 MPa, discharging to obtain DBSiBPR liquid resin suitable for VARTM forming process;
6) the composite was prepared as in example 1.
(3) Example 3
The process comprises the following steps:
1) preparing a 500ml three-neck bottle provided with a condenser tube, a stirring device and a thermometer, putting the bottle into an oil bath pot, heating to 50 ℃, opening a stirrer, adding phenol for melting, then adding boric acid, stirring uniformly at the current temperature, heating to 130 ℃ and reacting for 3 hours;
2) cooling the reaction system in the step 1) to 70 ℃, adding o-methyl phenol, zinc acetate and paraformaldehyde, and continuing to react for 8 hours at the temperature.
3) Adding vinyltriethoxysilane into the reaction system in the step 2), and continuing to react for 2.5 h;
4) cooling to 60 ℃, adding isobutanol into the reaction system in the step 3), uniformly stirring, standing for layering, and separating out a water layer;
5) decompressing the solvent layer in the step 4) for 60min under a vacuum environment of-0.09 to-0.095 MPa, discharging to obtain DBSIBPR resin suitable for the hot melt adhesive film forming process;
6) adding hexamethylenetetramine into the DBSIBPR obtained in the step 5), uniformly mixing, heating a glue spreader of a hot-melt pre-dipping machine to 60-65 ℃, pouring resin into a glue tank, adjusting the distance between the glue spreader and the speed of release paper to control the thickness of the resin glue film, detecting the thickness of the glue film by a beta-ray detection instrument, then covering a polyethylene film on the surface of the glue film and rolling to obtain a packaged resin glue film;
7) compounding a resin film and a fiber cloth to obtain a prepreg: drawing out fiber cloth from a fiber cloth roll, flattening the fiber cloth under certain tension, then compounding an upper adhesive film layer and a lower adhesive film layer with the fiber cloth through an adhesive film roller, melting resin at 65-70 ℃ through a hot pressing roller, and lens-fitting the fiber cloth under the action of pressure and heat to prepare a prepreg, then cooling the prepreg, covering the prepreg on release paper, covering a polyethylene film on the surface of the prepreg, and rolling to form a prepreg product;
8) curing and molding the prepreg to obtain the DBSIBPR resin-based composite material: cutting the prepreg into a certain size, laminating according to the thickness of a sample, placing on a hot press, curing according to the process of 130 ℃/1h +150 ℃/1h +180 ℃/1h +200 ℃/2h, keeping the temperature at 130 ℃ for half an hour, pressurizing to 2MPa, keeping the pressure till the end, naturally cooling, then unloading and taking out to obtain the DBSIBPR/high silica glass fiber composite laminated board.
Example 4
The process comprises the following steps:
1) preparing a 500ml three-neck flask provided with a condenser pipe, a stirring device and a thermometer, putting the flask into an oil bath pot, heating to 50 ℃, opening a stirrer, adding phenol for melting, then adding hydroxymethylphenylboronic acid, uniformly stirring at the current temperature, heating to 160 ℃, and reacting for 4 hours;
2) cooling the reaction system in the step 1) to 70 ℃, adding p-toluenesulfonic acid and liquid formaldehyde, heating to 85 ℃, and reacting for 8h at the temperature.
3) Adding vinyltriethoxysilane and KH 570 into the reaction system obtained in the step 2), and continuously reacting for 1.5 h;
4) cooling to 60 ℃, adding methyl isobutyl ketone into the reaction system in the step 3), uniformly stirring, standing for layering, and separating out a water layer;
5) decompressing the solvent layer in the step 4) for 60min under a vacuum environment of-0.09 to-0.095 MPa, discharging to obtain DBSIBPR resin suitable for the hot melt adhesive film forming process;
6) resin films, prepregs and composites were prepared as in example 3.
DBSIBPR/high silica glass cloth composite material performance
Characteristic peaks corresponding to the infrared spectrogram: -OH structure (3500 cm)-1～3200cm-1) (ii) a Benzene ring structure (1610 cm)-1～1596cm-1) (ii) a -B-OH Structure (655 cm)-1) (ii) a -B-O-C-structure (1360 cm)-1And 1376cm-1) (ii) a -Si-O-Si-structure (1049 cm)-1)；-Si-CH＝CH2Structure (1462 cm)-1And 972cm-1) (ii) a -B-O-Si-structure (867 cm)-1)。
The corresponding characteristic values are as follows:
Claims (10)
1. a dual-curing high-carbon-residue phenolic resin is characterized by comprising phenolic compounds, aldehyde compounds, boron-containing compounds, silicon-containing compounds and curing agents; the molar ratio of the phenolic compound to the aldehyde compound to the boron-containing compound to the silicon-containing compound is 1: 1.0-1.5: 0.1-0.3; the dosage of the curing agent is 4 to 12 percent of that of the phenolic compound; the silicon-containing compound is a double-bond-containing silicon compound; the curing agent is hexamethylenetetramine.
2. The dual cure high carbon residue phenolic resin of claim 1, wherein: the phenolic compound comprises one or more of phenol, o-methyl phenol or resorcinol.
3. The dual cure high carbon residue phenolic resin of claim 1, wherein: the aldehyde compound comprises one or more of aqueous formaldehyde solution, paraformaldehyde or benzaldehyde and the like.
4. The dual cure high carbon residue phenolic resin of claim 1, wherein: the boron-containing compound comprises one or more of boric acid, phenylboronic acid or hydroxyphenylboronic acid.
5. The dual cure high carbon residue phenolic resin of claim 1, wherein: the double-bond silicon compounds comprise vinyl triethoxysilane, vinyl trimethoxysilane and KH-570 double-bond one or more organic siloxane combinations.
6. A preparation method of the dual-curing high-carbon-residue phenolic resin hot melt adhesive film method and the vacuum assisted resin transfer molding forming process as claimed in any one of claims 1 to 5 is characterized by comprising the following steps:
step 1: proportionally adding the boron-containing compound into a phenolic compound at the temperature of 50-60 ℃, and then reacting for 2-5h at the temperature of 80-160 ℃;
step 2: cooling to 60-90 ℃, adding a catalyst and an aldehyde compound into a reaction system, and reacting for 4-8h at the current temperature; the dosage of the catalyst is 2 to 6 percent of the dosage of the phenolic compound;
and step 3: keeping the current temperature, adding the silicon-containing compound into the reaction system, and continuing to react for 2-4 h;
and 4, step 4: adding a solvent, cooling to room temperature, and separating out a water phase;
and 5: and (3) heating to 80-100 ℃, removing the solvent under the condition that the vacuum degree is more than or equal to-0.09 MPa, and determining the reaction end point when testing the viscosity of the resin. Obtaining the liquid or semi-solid phenolic resin containing silicon and boron.
7. The method of claim 6, wherein: the catalyst is selected from zinc acetate, oxalic acid or p-toluenesulfonic acid.
8. A method for preparing the dual-curing high carbon residue phenolic resin composite material as claimed in any one of claims 1 to 5 by adopting a VARTM (vacuum transfer molding) process/forming process, which is characterized by comprising the following steps: 1. coating a layer of release agent on the surface of the mould, and paving n layers of fiber fabrics on a bottom plate of the mould to be used as a preformed body; sequentially laying demolding cloth and a flow guide net on the outer surface of the preformed body, then laying a vacuum bag on a mold, sealing the vacuum bag and the periphery of the mold by using a sealing adhesive tape, and respectively connecting a flow guide pipe at a glue injection port and an air outlet; clamping a nozzle guide pipe by a clamp, connecting a vacuum pump at a dead head, vacuumizing the vacuum bag, and checking the air tightness to ensure that the vacuum degree reaches-0.09 to-0.095 MPa to the maximum; 2. the mold assembly was placed in an oven and preheated at 90 ℃ for 10 minutes. And (3) taking down the clamp of the nozzle guide pipe, vacuumizing and filling the mold, applying an external pressure of 0-6 MPa (preferably 3MPa) when the preform is completely filled with the resin, continuously vacuumizing for 15-20 min at the same time, completely infiltrating the preform with the resin, and closing the resin inlet. Curing according to the curing process of 90 ℃/1h +130 ℃/1h +150 ℃/1h +180 ℃/1h +200 ℃/2 h; 3. and naturally cooling the cured mold to room temperature along with an oven, releasing pressure and opening the mold, and taking out the laminated board to prepare the dual-curing high-carbon-residue phenolic resin composite material.
9. A method for preparing the dual-curing high-carbon-residue phenolic resin composite material as claimed in any one of claims 1 to 5 by a hot melt adhesive membrane method is characterized in that: 1. the hot-melt adhesive film can be prepared by a hot-melt pre-dipping machine, the temperature of a dipping roller of the hot-melt pre-dipping machine is controlled to be 55-75 ℃, the transfer rate of conveying release paper is 3-6m/min, the distance between the dipping rollers is adjusted, and the thickness is detected by a beta-ray apparatus, so that the unit mass of the resin film meets the design requirement of the content of prepreg resin; 2. leading out fiber bundles on an unreeling device, flattening the fiber bundles by a flattening roller, then sandwiching the fiber bundles with a prepared adhesive film, melting a resin matrix by a heating roller, controlling the temperature to be 60-80 ℃, soaking the resin matrix in fibers, cooling, adding a PE film, and rolling to prepare a prepreg; 3. laying/winding the prepreg, placing the prepreg in a mold coated with a release agent, and molding in a flat vulcanizing machine/autoclave, wherein the curing process comprises the following steps: 130 ℃/1h +150 ℃/1h +180 ℃/1h +200 ℃/2hr, and the molding pressure is 2-6 MPa; 4. and (3) naturally cooling the formed composite material product along with a furnace, and then taking out the product from the die to obtain the dual-curing high-carbon-residue phenolic resin composite material.
10. The method according to claim 8 or 9, characterized in that: when the resin is applied to a VARTM forming process to prepare a composite material, the viscosity of the resin is 200-400 mPa & s/90 ℃; the viscosity of the composite material resin prepared by applying the method to a hot melt adhesive membrane method is 5000-10000 mPa & s/60 ℃.
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