CN116144139A - Resin for ship composite material and preparation method thereof - Google Patents
Resin for ship composite material and preparation method thereof Download PDFInfo
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- CN116144139A CN116144139A CN202310003590.2A CN202310003590A CN116144139A CN 116144139 A CN116144139 A CN 116144139A CN 202310003590 A CN202310003590 A CN 202310003590A CN 116144139 A CN116144139 A CN 116144139A
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- epoxy resin
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- bismaleimide
- aromatic
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- 229920005989 resin Polymers 0.000 title claims abstract description 120
- 239000011347 resin Substances 0.000 title claims abstract description 120
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003822 epoxy resin Substances 0.000 claims abstract description 115
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 115
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims abstract description 81
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 77
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000945 filler Substances 0.000 claims abstract description 20
- 238000010521 absorption reaction Methods 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 71
- 150000004984 aromatic diamines Chemical class 0.000 claims description 58
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 50
- 125000003118 aryl group Chemical group 0.000 claims description 50
- -1 glycidyl ester Chemical class 0.000 claims description 46
- 239000003960 organic solvent Substances 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 21
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000006297 dehydration reaction Methods 0.000 claims description 10
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 150000004982 aromatic amines Chemical class 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 238000012661 block copolymerization Methods 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000012024 dehydrating agents Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- JWRLKLYWXKMAFL-UHFFFAOYSA-N 4-[4-(4-aminophenoxy)-3-phenylphenoxy]aniline Chemical group C1=CC(N)=CC=C1OC(C=C1C=2C=CC=CC=2)=CC=C1OC1=CC=C(N)C=C1 JWRLKLYWXKMAFL-UHFFFAOYSA-N 0.000 claims description 4
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical group C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000001914 filtration Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000013535 sea water Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000835 fiber Substances 0.000 description 17
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 16
- 239000011159 matrix material Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 238000005191 phase separation Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 238000002791 soaking Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000004427 diamine group Chemical group 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000002466 imines Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920005575 poly(amic acid) Polymers 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 1
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical group C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 description 1
- FAFCDPCRODNSLM-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)pentoxymethyl]oxirane Chemical group C1OC1COC(CCCC)OCC1CO1 FAFCDPCRODNSLM-UHFFFAOYSA-N 0.000 description 1
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 description 1
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical group OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- 229920002748 Basalt fiber Polymers 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical group C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- XCDAQRPDPPVVEF-UHFFFAOYSA-N N-[diethoxy(prop-2-enoxy)silyl]aniline Chemical compound N(C1=CC=CC=C1)[Si](OCC=C)(OCC)OCC XCDAQRPDPPVVEF-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 1
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000002460 imidazoles Chemical group 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical group C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 230000000007 visual effect 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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)
- Epoxy Resins (AREA)
Abstract
The invention relates to a resin for a ship composite material and a preparation method thereof, in particular to an epoxy resin and a preparation method thereof. Solves the problems that the existing epoxy resin has higher water absorption rate and poor toughness and does not meet the requirements of marine application environment. The resin for the ship composite material is prepared from epoxy resin, a curing agent, segmented bismaleimide resin and a filler; the preparation method comprises the following steps: 1. preparing a segmented bismaleimide resin; 2. and (3) preparing the modified epoxy resin. The invention relates to a resin for a ship composite material and a preparation method thereof.
Description
Technical Field
The invention relates to an epoxy resin and a preparation method thereof.
Background
The traditional ship materials mainly comprise metal, however, seawater is highly corrosive, and marine microorganisms, attached organisms and metabolites thereof have direct or indirect corrosion effects on the metal materials. With the advent of glass fiber reinforced thermosets, composite technology that uses fiber reinforced resin matrix composites as the primary engineering application object began to be continually focused and developed. The fiber reinforced resin matrix composite material has the advantages of high specific strength, corrosion resistance, marine organism corrosion resistance and the like, and the excellent structural function designability of the fiber reinforced resin matrix composite material opens up a brand-new way for the development of ship structures.
In the fiber reinforced composite material, the matrix resin not only plays a role in consolidating the reinforced material into a whole, but also can uniformly distribute load and transfer the load to the reinforced material such as fiber, so that the performance of the matrix resin directly influences the overall performance of the composite material. Although the resin matrix in the aerospace field has formed a relatively complete system, unlike the performance-first requirements of composite materials for aerospace, the cost performance of the raw materials is first considered in the marine field. Therefore, in the field of ships, resins having a wide range of applications mainly include unsaturated polyesters, vinyl resins, epoxy resins, and the like.
Marine environments are complex and harsh environments, and their high humidity, high salt, high pressure, multiple wave applications present significant challenges to marine materials. The ship composite material needs to bear high-pressure and multi-fluctuation alternating load, so that the improvement of the modulus, strength and toughness of the resin matrix is a key to meet the application requirement. On the other hand, in the long-term seawater soaking process, the water absorption of the resin matrix can damage the interface of the composite material, reduce the interlayer performance, not only cause the increase of the structural weight, but also cause the wet aging phenomenon, so that the fiber-resin interface is damaged, and the irreversible performance is reduced and fails. The key of the application of the composite material in the marine field is mainly that the resin matrix can bear complex mechanical load and complex environment of seawater medium coupling. Therefore, how to further improve toughness and reduce water absorption of materials while maintaining excellent strength and modulus becomes a difficult problem to be solved by scientific researchers and engineers.
At present, research on resin in the ocean field is concentrated on aspects of anti-corrosion and anti-fouling coatings and the like, reports on high-toughness low-water-absorption matrix resin are few, and particularly, research on toughening of epoxy resin based on siloxane block copolymerization long-chain-segment bismaleimide and modification of water absorption reduction are not reported.
Disclosure of Invention
The invention aims to solve the problems that the existing epoxy resin has higher water absorption and poor toughness and does not meet the requirements of marine application environments, and further provides the resin for the ship composite material and a preparation method thereof.
The resin for the ship composite material is prepared from epoxy resin, a curing agent, segmented bismaleimide resin and a filler; the mass ratio of the epoxy resin to the curing agent is 1 (0.05-0.30); the mass ratio of the epoxy resin to the segmented bismaleimide resin is 1 (0.05-0.30); the mass ratio of the epoxy resin to the filler is 1 (0.005-0.15);
the block copolymerized bismaleimide resin has a molecular structural formula:
said R is 1 Is that
said R is 2 Is that
Wherein m is n= (0.2-0.4) 1.
The preparation method of the resin for the ship composite material comprises the following steps:
1. preparation of a block-copolymerized bismaleimide resin:
(1) weighing aromatic diamine, aromatic dianhydride, siloxane diamine, maleic anhydride and organic solvent, dividing the aromatic diamine into a first part of aromatic diamine and a second part of aromatic diamine, dividing the aromatic dianhydride into a first part of aromatic dianhydride and a second part of aromatic dianhydride according to the weight ratio, and dividing the organic solvent into a first part of organic solvent and a second part of organic solvent;
the mol ratio of the aromatic diamine to the aromatic dianhydride is 1 (1.05-1.36); the molar ratio of the aromatic diamine to the siloxane diamine is 1 (0.29-0.58); the molar ratio of the aromatic diamine to the maleic anhydride is 1 (0.23-0.58); the mass ratio of the total mole of the aromatic diamine, the aromatic dianhydride, the siloxane diamine and the maleic anhydride to the organic solvent is 1mol (600-12000 g);
the aromatic dianhydride is 4,4' -oxydiphthalic anhydride; the aromatic diamine is 1, 4-bis- (4' -aminophenoxy) -2- (phenyl) benzene; the siloxane diamine is aminopropyl end-capped polydimethylsiloxane;
(2) stirring and mixing the first part of aromatic diamine and the first part of organic solvent at room temperature under nitrogen atmosphere until the aromatic diamine is completely dissolved, adding the first part of aromatic dianhydride for three times in average, and continuously stirring to obtain a reaction liquid I;
(3) stirring and mixing the second part of aromatic dianhydride and the second part of organic solvent at room temperature under nitrogen atmosphere until the aromatic dianhydride is completely dissolved, adding siloxane diamine for three times in average, and continuously stirring to obtain a reaction solution II;
(4) adding a second part of aromatic diamine into the reaction solution II at room temperature under nitrogen atmosphere, stirring and dissolving, adding the reaction solution I, mixing and stirring, adding maleic anhydride, continuously stirring to obtain a reaction solution III, carrying out dehydration reaction on the reaction solution III to obtain a bismaleimide acid solution, and carrying out solid precipitation, washing and drying on the bismaleimide acid solution to obtain the segmented bismaleimide resin;
2. preparation of modified epoxy resin:
(1) weighing epoxy resin, curing agent, segmented bismaleimide resin and filler;
the mass ratio of the epoxy resin to the curing agent is 1 (0.05-0.30); the mass ratio of the epoxy resin to the segmented bismaleimide resin is 1 (0.05-0.30); the mass ratio of the epoxy resin to the filler is 1 (0.005-0.15);
(2) adding filler into epoxy resin at room temperature, stirring and mixing uniformly, sequentially adding bismaleimide resin with block copolymerization and a curing agent, stirring to be homogeneous, and continuing stirring to obtain the marine modified epoxy resin with low water absorption;
and the interval time between the addition of the segmented bismaleimide resin and the curing agent is 10-20 min.
The beneficial effects of the invention are as follows:
the modified resin provided by the invention adopts segmented bismaleimide formed by combining a diamine structure of siloxane and an aromatic diamine structure containing ether bonds. Compared with the traditional method adopting the short-chain branched aromatic amine curing agent, the method can improve the toughness and the shock resistance of the epoxy resin by modifying the internal toughening mode of the main chain structure. Typically, conventional aromatic amine-based curing agents require additional toughening resins to improve the toughness of the epoxy resin. However, the external toughening mode can lead to phase separation with the epoxy resin after curing, and further generate the phenomena of uneven dispersion, uneven toughening particle size and the like, so that the overall heat resistance and mechanical property of the material are reduced. On the one hand, the modified resin of the invention contains the maleic anhydride with carbon-carbon double bond, which can be subjected to co-curing reaction with the epoxy resin, and simultaneously combines the benzene ring, the ether bond and the siloxane group, so that the modified bismaleimide can realize good compatibility with the epoxy resin, and unexpectedly realize the effect that the product does not have phase separation in the curing process and after the curing. The block polymer of the aromatic amine containing ether bond and the diamine containing siloxane can realize good toughening effect on the premise of realizing compatibility in epoxy resin. The modification of epoxy resins with long chain segment bismaleimides has not been reported to improve the toughening and impact resistance effects. Meanwhile, the modifier with fixed block proportion can realize better combination of compatibility and intrinsic strength, thereby improving the most excellent toughening and impact resistance.
In addition, siloxane is reported as a technology of low water absorbability and hydrolysis stability, but the siloxane is introduced into bismaleimide resin as a block unit, and the siloxane chain segment has good flexibility and strong chain segment movement capability and is easy to attach and migrate on the surface and between layers of a polymer, so that the good water absorbability of the bismaleimide modified epoxy resin containing a siloxane structure is not reported. Based on the problems of low surface energy and low polarity of the siloxane chain segment, difficult dispersion in epoxy resin and the like, the invention blocks the siloxane into a high-polarity ether bond structure, thereby obtaining good similar compatibility effect with epoxy polar resin and realizing good dispersion and compatibility of the toughening modified resin in micro and macro scale in an epoxy resin system. Aiming at the patent, bismaleimide resin containing siloxane fixed block proportion is used as a modifier in epoxy resin under the marine environment, the water absorbability of an epoxy resin system is unexpectedly and obviously reduced, meanwhile, the compatibility of siloxane and epoxy resin is improved by introducing polar ether bonds, and the wet state stability of the material in water, saline water and complex marine environment is finally obtained. This is not reported in the prior art.
Drawings
FIG. 1 is an infrared spectrum of a block-copolymerized bismaleimide resin prepared in the first step of example.
Detailed Description
The first embodiment is as follows: the resin for the ship composite material is prepared from epoxy resin, a curing agent, segmented bismaleimide resin and a filler; the mass ratio of the epoxy resin to the curing agent is 1 (0.05-0.30); the mass ratio of the epoxy resin to the segmented bismaleimide resin is 1 (0.05-0.30); the mass ratio of the epoxy resin to the filler is 1 (0.005-0.15);
the block copolymerized bismaleimide resin has a molecular structural formula:
said R is 1 Is that
said R is 2 Is that
Wherein m is n= (0.2-0.4) 1.
The resin application of the composite material for the ship mainly comprises parts such as a deck of the ship, a mast, a seawater pipe, a watertight door, a light wall plate, outfitting and the like.
The resin for the ship composite material and the reinforcing material can be compounded to prepare the reinforced resin-based composite material, and the reinforcing material is mainly aimed at carbon fibers, glass fibers, basalt fibers, quartz fibers and aramid fibers.
The beneficial effects of this concrete implementation are:
the modified resin provided by the specific embodiment adopts segmented bismaleimide formed by combining a diamine structure of siloxane and an aromatic diamine structure containing ether bonds. Compared with the traditional method adopting the short-chain branched aromatic amine curing agent, the method can improve the toughness and the shock resistance of the epoxy resin by modifying the internal toughening mode of the main chain structure. Typically, conventional aromatic amine-based curing agents require additional toughening resins to improve the toughness of the epoxy resin. However, the external toughening mode can lead to phase separation with the epoxy resin after curing, and further generate the phenomena of uneven dispersion, uneven toughening particle size and the like, so that the overall heat resistance and mechanical property of the material are reduced. On the one hand, the maleic anhydride containing carbon-carbon double bonds of the modified resin of the specific embodiment can be subjected to co-curing reaction with the epoxy resin, and meanwhile, the benzene ring, the ether bond and the siloxane group are combined, so that the modified bismaleimide can realize good compatibility with the epoxy resin, and the effect that phase separation does not occur in the curing process and after the product is cured is unexpectedly realized. The block polymer of the aromatic amine containing ether bond and the diamine containing siloxane can realize good toughening effect on the premise of realizing compatibility in epoxy resin. The modification of epoxy resins with long chain segment bismaleimides has not been reported to improve the toughening and impact resistance effects. Meanwhile, the modifier with fixed block proportion can realize better combination of compatibility and intrinsic strength, thereby improving the most excellent toughening and impact resistance.
In addition, siloxane is reported as a technology of low water absorbability and hydrolysis stability, but the siloxane is introduced into bismaleimide resin as a block unit, and the siloxane chain segment has good flexibility and strong chain segment movement capability and is easy to attach and migrate on the surface and between layers of a polymer, so that the good water absorbability of the bismaleimide modified epoxy resin containing a siloxane structure is not reported. Based on the problems of low surface energy and low polarity of a siloxane chain segment, difficult dispersion in epoxy resin and the like, the specific embodiment blocks the siloxane into a high-polarity ether bond structure, so that a good similar compatibility effect with epoxy polar resin is obtained, and the toughened modified resin is well dispersed and compatible in micro and macro scale in an epoxy resin system. Aiming at the patent, bismaleimide resin containing siloxane fixed block proportion is used as a modifier in epoxy resin under the marine environment, the water absorbability of an epoxy resin system is unexpectedly and obviously reduced, meanwhile, the compatibility of siloxane and epoxy resin is improved by introducing polar ether bonds, and the wet state stability of the material in water, saline water and complex marine environment is finally obtained. This is not reported in the prior art.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the epoxy resin is non-halogen epoxy resin, and is specifically one or a combination of more of bisphenol A epoxy resin, bisphenol F epoxy resin, naphthalene epoxy resin, biphenyl epoxy resin, tetrafunctional epoxy resin, trifunctional epoxy resin, alicyclic epoxy resin, glycidyl ester epoxy resin and silicon epoxy resin; the viscosity of the epoxy resin is 50-40000 mPa.s; the curing agent is one or the combination of a plurality of aromatic amine curing agents, alicyclic amine curing agents, aliphatic amine curing agents and heterocyclic amine curing agents; the filler is one or the combination of a plurality of curing accelerator, silane coupling agent, diluent, flexibilizer and solvent. The other is the same as in the first embodiment.
The curing accelerator is imidazoles and derivatives or tertiary amines thereof.
The silane coupling agent is not particularly limited, and may be one or a combination of several of chloropropyl trimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ - (methacryloxy) propyltrimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, γ -glycidoxypropyl trimethoxysilane, γ -mercaptopropyl trimethoxysilane, γ -aminopropyl triethoxysilane, N- β (3, 4-epoxycyclohexyl) γ -aminopropyl trimethoxysilane, γ -ureidopropyl triethoxysilane and anilino methylene triethoxysilane.
The diluent is not particularly limited, and may be one or a combination of several of n-butyl glycidyl ether, allyl glycidyl ether, 2-ethyl-hexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, tolyl glycidyl ether, glycidyl methacrylate, vinylcyclohexene monoepoxide, diglycidyl ether, (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether, butylene glycol diglycidyl ether, vinylcyclohexene dioxide, quaternary pentanediol diglycidyl ether, diglycidyl aniline, trimethylolpropane triglycidyl ether, and glycerol triglycidyl ether.
And a third specific embodiment: this embodiment differs from one or both of the embodiments in that: the molecular weight of the block copolymerized bismaleimide resin is smaller than 7000. The other is the same as the first or second embodiment.
The specific embodiment IV is as follows: the preparation method of the resin for the ship composite material comprises the following steps:
1. preparation of a block-copolymerized bismaleimide resin:
(1) weighing aromatic diamine, aromatic dianhydride, siloxane diamine, maleic anhydride and organic solvent, dividing the aromatic diamine into a first part of aromatic diamine and a second part of aromatic diamine, dividing the aromatic dianhydride into a first part of aromatic dianhydride and a second part of aromatic dianhydride according to the weight ratio, and dividing the organic solvent into a first part of organic solvent and a second part of organic solvent;
the mol ratio of the aromatic diamine to the aromatic dianhydride is 1 (1.05-1.36); the molar ratio of the aromatic diamine to the siloxane diamine is 1 (0.29-0.58); the molar ratio of the aromatic diamine to the maleic anhydride is 1 (0.23-0.58); the mass ratio of the total mole of the aromatic diamine, the aromatic dianhydride, the siloxane diamine and the maleic anhydride to the organic solvent is 1mol (600-12000 g);
the aromatic dianhydride is 4,4' -oxydiphthalic anhydride; the aromatic diamine is 1, 4-bis- (4' -aminophenoxy) -2- (phenyl) benzene; the siloxane diamine is aminopropyl end-capped polydimethylsiloxane;
(2) stirring and mixing the first part of aromatic diamine and the first part of organic solvent at room temperature under nitrogen atmosphere until the aromatic diamine is completely dissolved, adding the first part of aromatic dianhydride for three times in average, and continuously stirring to obtain a reaction liquid I;
(3) stirring and mixing the second part of aromatic dianhydride and the second part of organic solvent at room temperature under nitrogen atmosphere until the aromatic dianhydride is completely dissolved, adding siloxane diamine for three times in average, and continuously stirring to obtain a reaction solution II;
(4) adding a second part of aromatic diamine into the reaction solution II at room temperature under nitrogen atmosphere, stirring and dissolving, adding the reaction solution I, mixing and stirring, adding maleic anhydride, continuously stirring to obtain a reaction solution III, carrying out dehydration reaction on the reaction solution III to obtain a bismaleimide acid solution, and carrying out solid precipitation, washing and drying on the bismaleimide acid solution to obtain the segmented bismaleimide resin;
2. preparation of modified epoxy resin:
(1) weighing epoxy resin, curing agent, segmented bismaleimide resin and filler;
the mass ratio of the epoxy resin to the curing agent is 1 (0.05-0.30); the mass ratio of the epoxy resin to the segmented bismaleimide resin is 1 (0.05-0.30); the mass ratio of the epoxy resin to the filler is 1 (0.005-0.15);
(2) adding filler into epoxy resin at room temperature, stirring and mixing uniformly, sequentially adding bismaleimide resin with block copolymerization and a curing agent, stirring to be homogeneous, and continuing stirring to obtain the marine modified epoxy resin with low water absorption;
and the interval time between the addition of the segmented bismaleimide resin and the curing agent is 10-20 min.
Step one (2), controlling the molar ratio to produce an anhydride-terminated polyamic acid of a target number of repeating units;
controlling the molar ratio in step one (3) to produce an amino-terminated polyamic acid of a target repeating unit number.
Fifth embodiment: the fourth difference between this embodiment and the third embodiment is that: the organic solvent N, N-dimethylformamide in the step (1). The other is the same as in the fourth embodiment.
Specific embodiment six: this embodiment differs from the fourth or fifth embodiment in that: in the first step (1), the aromatic diamine is divided into a first part of aromatic diamine and a second part of aromatic diamine according to the mole ratio of 1 (0.13-0.4); in the first step (1), the aromatic dianhydride is divided into a first part of aromatic dianhydride and a second part of aromatic dianhydride according to the mole ratio of 1 (0.14-0.36); in the first step (1), the organic solvent is divided into a first part of organic solvent and a second part of organic solvent according to the mass ratio of (0.20-0.70). The others are the same as those of the fourth or fifth embodiment.
Seventh embodiment: the present embodiment differs from one of the fourth to sixth embodiments in that: the dehydration reaction in the step one (4) is specifically that acetic anhydride is used as a dehydrating agent, triethylamine and nickel acetate are used as catalysts, the dehydrating agent and the catalysts are added into a reaction solution III, and the dehydration reaction is carried out for 2 to 10 hours at the temperature of 60 to 65 ℃ to obtain the bismaleic acid solution. The others are the same as those of the fourth to sixth embodiments.
Eighth embodiment: the present embodiment differs from one of the fourth to seventh embodiments in that: in the first step (4), the bismaleimide acid solution is subjected to solid precipitation, washing and drying, specifically, the bismaleimide acid solution is cooled to below 5 ℃ by ice water, water is dripped until the solid is precipitated, water is used as a washing liquid, the solid is washed for 5 times until the washing liquid is neutral, and the solid is filtered and dried. The others are the same as in the fourth to seventh embodiments.
Detailed description nine: the present embodiment differs from one of the fourth to eighth embodiments in that: in the first step (2), under the conditions of room temperature, nitrogen atmosphere and stirring speed of 100-500 r/min, stirring and mixing the first part of aromatic diamine and the first part of organic solvent until the aromatic diamine is completely dissolved, then adding the first part of aromatic dianhydride for three times in average, and continuing stirring for 4-6 hours to obtain a reaction solution I; step one, stirring and mixing a second part of aromatic dianhydride and a second part of organic solvent at room temperature under nitrogen atmosphere at a stirring speed of 100-500 r/min until the aromatic dianhydride is completely dissolved, adding siloxane diamine three times in average, and continuing stirring for 4-6 h to obtain a reaction solution II; and (3) in the first step (4), adding a second part of aromatic diamine into the reaction solution II under the condition of stirring speed of 100-500 r/min, stirring for dissolving, adding the reaction solution I, mixing and stirring for 6-8 h, adding maleic anhydride, and continuing stirring for 2-4 h to obtain a reaction solution III. The others are the same as in embodiments four to eight.
Detailed description ten: this embodiment differs from one of the fourth to ninth embodiments in that: and step two, in the step 2, under the conditions of room temperature and stirring speed of 100 r/min-500 r/min, adding filler into the epoxy resin, stirring for 20 min-40 min, then sequentially adding the segmented bismaleimide resin and the curing agent, stirring to be homogeneous, and then continuing stirring for 1 h-2 h. The others are the same as in the fourth to ninth embodiments.
The following examples are used to verify the benefits of the present invention:
embodiment one:
the resin for the ship composite material is prepared from epoxy resin, a curing agent, segmented bismaleimide resin and a silane coupling agent; the mass ratio of the epoxy resin to the curing agent is 1:0.1; the mass ratio of the epoxy resin to the segmented bismaleimide resin is 1:0.15; the mass ratio of the epoxy resin to the silane coupling agent is 1:0.01;
the block copolymerized bismaleimide resin has a molecular structural formula:
said R is 1 Is that
said R is 2 Is that
Wherein m: n=0.25:1, specifically m is 1 and n is 4.
The epoxy resin is bisphenol A type epoxy resin, the epoxy value is 0.51, the viscosity is 200mPa.s, and the structural formula is
The curing agent is 4,4' -diaminodiphenyl sulfone, and the structural formula is
The silane coupling agent is gamma- (methacryloyloxy) propyl trimethoxy silane.
The molecular weight of the segmented bismaleimide resin is 4900g/mol.
The preparation method of the resin for the ship composite material comprises the following steps:
1. preparation of a block-copolymerized bismaleimide resin:
(1) weighing 0.05mol of aromatic diamine, 0.06mol of aromatic dianhydride, 0.02mol of siloxane diamine, 0.02mol of maleic anhydride and 320g of organic solvent, dividing the aromatic diamine into a first part of aromatic diamine and a second part of aromatic diamine according to a molar ratio of 4:1, dividing the aromatic dianhydride into a first part of aromatic dianhydride and a second part of aromatic dianhydride according to a molar ratio of 5:1, and dividing the organic solvent into a first part of organic solvent and a second part of organic solvent according to a mass ratio of 3:1;
the aromatic dianhydride is 4,4' -oxydiphthalic anhydride; the aromatic diamine is 1, 4-bis- (4' -aminophenoxy) -2- (phenyl) benzene; the siloxane diamine is aminopropyl end-capped polydimethylsiloxane;
(2) stirring and mixing 0.04mol of first aromatic diamine and 240g of first organic solvent for 30min at room temperature under nitrogen atmosphere with stirring speed of 300r/min until the aromatic diamine is completely dissolved, adding 0.05mol of first aromatic dianhydride three times, and continuously stirring for 5h to obtain a reaction solution I;
(3) stirring and mixing 0.01mol of the second aromatic dianhydride and 80g of the second organic solvent for 30min at room temperature under a nitrogen atmosphere and a stirring speed of 300r/min until the aromatic dianhydride is completely dissolved, adding 0.02mol of siloxane diamine for three times in average, and continuously stirring for 5h to obtain a reaction solution II;
(4) adding 0.01mol of second aromatic diamine into the reaction solution II under the conditions of room temperature, nitrogen atmosphere and stirring speed of 300r/min, stirring and dissolving, adding the reaction solution I, mixing and stirring for 6 hours, adding 0.02mol of maleic anhydride, continuously stirring for 3 hours to obtain a reaction solution III, carrying out dehydration reaction on the reaction solution III to obtain a bismaleimide acid solution, and carrying out solid precipitation, washing and drying on the bismaleimide acid solution to obtain segmented bismaleimide resin;
2. preparation of modified epoxy resin:
(1) weighing epoxy resin, curing agent, segmented bismaleimide resin and silane coupling agent;
the mass ratio of the epoxy resin to the curing agent is 1:0.1; the mass ratio of the epoxy resin to the segmented bismaleimide resin is 1:0.15; the mass ratio of the epoxy resin to the silane coupling agent is 1:0.01;
(2) adding a silane coupling agent into epoxy resin at room temperature and stirring speed of 300r/min, stirring for 30min, sequentially adding a bismaleimide resin and a curing agent for block copolymerization, stirring to be homogeneous, and continuing stirring for 2h to obtain resin for the ship composite material;
and the interval time between the addition of the segmented bismaleimide resin and the curing agent is 15min.
The organic solvent N, N-dimethylformamide in the step (1).
The dehydration reaction in the step one (4) is specifically that acetic anhydride is used as a dehydrating agent, triethylamine and nickel acetate are used as catalysts, the dehydrating agent and the catalysts are added into a reaction solution III, and the dehydration reaction is carried out for 6 hours at the temperature of 60 ℃ to obtain the bismaleic acid solution.
In the first step (4), the bismaleimide acid solution is subjected to solid precipitation, washing and drying, specifically, the bismaleimide acid solution is cooled to below 5 ℃ by ice water, water is dripped until the solid is precipitated, water is used as a washing liquid, the solid is washed for 5 times until the washing liquid is neutral, and the solid is filtered and dried.
The resin for the ship composite material is subjected to gradient heating solidification, and specifically comprises the following steps: curing for 4h at 60 ℃, then curing for 2h at 100 ℃, then curing for 2h at 150 ℃, and finally curing for 2h at 200 ℃ to finish the curing.
Embodiment two: the first difference between this embodiment and the first embodiment is that: in the molecular structural formula of the block-copolymerized bismaleimide resin, m is 1, n=0.2:1, and n is 5. The other is the same as in the first embodiment.
Embodiment III: the first difference between this embodiment and the first embodiment is that: the mass ratio of the epoxy resin to the curing agent is 1:0.15; the mass ratio of the epoxy resin to the segmented bismaleimide resin is 1:0.1; the mass ratio of the epoxy resin to the silane coupling agent is 1:0.01. The other is the same as in the first embodiment.
Embodiment four: the first difference between this embodiment and the first embodiment is that: compounding the resin for the ship composite material prepared in the first embodiment with fibers to prepare a fiber reinforced resin matrix composite material, wherein the fibers are T700 unidirectional carbon fibers, unidirectional layering is carried out, and the volume percentage of the fibers in the fiber reinforced resin matrix composite material is 60%; the fiber reinforced resin matrix composite is subjected to gradient heating solidification, and specifically comprises the following steps: curing for 4h at 60 ℃, then for 2h at 100 ℃, then for 2h at 150 ℃, and finally for 2h at 200 ℃. The other is the same as in the first embodiment.
Comparative example one: the first difference between this comparative example and the example is: adding the segmented bismaleimide resin, wherein the mass ratio of the epoxy resin to the curing agent is 1:0.25; the mass ratio of the epoxy resin to the silane coupling agent is 1:0.01. The other is the same as in the first embodiment.
Comparative example two: the first difference between this comparative example and the example is: in the molecular structural formula of the block-copolymerized bismaleimide resin, m is expressed as n=1:1, and specifically, m is expressed as 3, and n is expressed as 3. The other is the same as in the first embodiment.
Comparative example three: the first difference between this comparative example and the example is: the mass ratio of the epoxy resin to the curing agent is 1:0.1; the mass ratio of the epoxy resin to the segmented bismaleimide resin is 1:0.4; the mass ratio of the epoxy resin to the silane coupling agent is 1:0.01. The other is the same as in the first embodiment.
Comparative example four: the first difference between this comparative example and the comparative example is: the modified epoxy resin prepared in the first comparative example is compounded with fibers to prepare a fiber reinforced resin matrix composite, wherein the fibers are T700 unidirectional carbon fibers, unidirectional layering is carried out, and the volume percentage of the fibers in the fiber reinforced resin matrix composite is 60%. The other is the same as comparative example one.
Resin compatibility tests were performed on the resins for ship composite materials prepared in examples one to three and the modified epoxy resins prepared in comparative examples one to three. The compatibility of the cured material was observed on a macro-microscopic scale such as visual observation, microscopic observation, and scanning electron microscopic observation. Wherein, the visual inspection material is a uniform system which is marked by a square, and the interior of the visual inspection material is marked by a square; for the microscope and the scanning electron microscope, the observation result is that the homogeneous phase system is considered to have no phase separation, which is represented by the fridge, the observation result is that the phase separation system is considered to have phase separation, which is represented by the o, and the test results are summarized in table 1.
The resins for ship composite materials prepared in examples one to three and the modified epoxy resins prepared in comparative examples one to two were subjected to toughness and performance after alternating load, artificial seawater was prepared according to the standard ASTM D1141-98, and the test items are as follows.
Impact properties: test bars were prepared according to the requirements of standard GB/T2567-2021 and the impact properties of the cured material were tested.
Mass change rate after seawater immersion: and repeatedly soaking the sample in artificial seawater for 30 times at room temperature for 12 hours each time, and testing the mass change rate (%) of the soaked sample.
Strength retention rate after seawater immersion: tensile test bars are prepared according to the requirements of GB1040.2-2006, artificial seawater is repeatedly soaked for 30 times at room temperature, each time for 12 hours, and the tensile strength retention (%) after soaking is tested.
Mass change rate after alternating environmental test: and (3) performing alternating temperature impact by adopting a rapid high-low temperature impact tester, wherein the temperature range is-20-40 ℃, the temperature cycle time is less than 10s each time, the cycle temperature is changed to impact 500 times, then immersing the test sample in artificial seawater at room temperature for 500 hours, and testing the mass change rate (%).
Intensity retention after alternating environmental test: preparing a tensile test spline according to the requirements of GB1040.2-2006, performing alternating temperature impact by adopting a rapid high-low temperature impact tester, wherein the temperature range is-20-40 ℃, the temperature cycle time is less than 10s each time, the temperature is changed for 500 times in a circulating way, then immersing in artificial seawater for 500 hours at room temperature, and testing the tensile strength retention (%).
The fiber reinforced resin matrix composites prepared in example four and comparative example four were tested for alternating loads, and the test items were as follows.
Mass change rate after seawater immersion: and repeatedly soaking the composite material sample in artificial seawater for 30 times at room temperature for 12 hours each time, and testing the mass change rate (%) of the composite material sample after soaking.
Strength retention rate after seawater immersion: tensile test bars were prepared according to the requirements of GB1040.5-2008, and were repeatedly soaked with artificial seawater at room temperature for 30 times, each soaking for 12 hours, and the tensile strength retention (%) after soaking was tested.
Mass change rate after alternating environmental test: and (3) performing alternating temperature impact by adopting a rapid high-low temperature impact tester, wherein the temperature range is-20-40 ℃, the temperature cycle time is less than 10s each time, the cycle temperature is changed to impact 500 times, artificial seawater is soaked for 500 hours at room temperature, and the mass change rate (%) of the composite material sample is tested.
Intensity retention after alternating environmental test: and (3) performing alternating temperature impact by adopting a rapid high-low temperature impact tester, wherein the temperature range is-20-40 ℃, the temperature cycle time is less than 10s each time, the cycle temperature is changed to impact 500 times, then immersing the artificial seawater at room temperature for 500 hours, and testing the tensile strength retention (%).
Compared with the unmodified resin (comparative example one), the modified resin ensures the water resistance and toughness of the material by introducing the siloxane chain segment with low water absorption and flexibility. It can be seen from comparative experiments that for the cured resin compositions, examples one to three were free from phase separation and had good compatibility in the given ratio range, but comparative examples two and three resulted in phase separation of the material system when the content of modified bismaleimide was too high or the segment of the silicon diamine was too long.
Meanwhile, the epoxy resin without introducing modified bismaleimide has poor performances in terms of water absorption, seawater resistance and alternating load resistance, and has great limitation in marine environment application. The resin composition of the bismaleimide resin with the block copolymerization introduced in a fixed proportion has certain improvement in the aspects of toughness, sea water resistance, alternating environment resistance and the like. From the results of the water absorption and the strength retention of the materials after the first to third examples and the first and second comparative examples, the impact property, the water resistance, the alternating-resistant complex load and the like of the materials are improved well, and the water resistance and the alternating-resistant environment capability of the carbon fiber reinforced epoxy resin composite material are improved greatly.
The first to third examples adopt modified bismaleimide to modify epoxy resin, the compatibility of the siloxane in a resin system is improved by controlling the length and the introduction proportion of a siloxane chain segment and combining with high-polarity ether bond in the bismaleimide structure, the phase separation phenomenon is improved, the toughness of the resin is improved by an internal toughening mode, and the shock resistance and the seawater and alternating load resistance of the resin are improved.
FIG. 1 is an infrared spectrum of a block-copolymerized bismaleimide resin prepared in the first step of the example; as can be seen from the graph, the characteristic imine ring absorption peak appears at 1776cm -1 (C=O asymmetric stretching vibration), 1713cm -1 (symmetrical c=o stretching), revealing the successful formation of imine rings.
Claims (10)
1. The resin for the ship composite material is characterized by being prepared from epoxy resin, a curing agent, segmented bismaleimide resin and a filler; the mass ratio of the epoxy resin to the curing agent is 1 (0.05-0.30); the mass ratio of the epoxy resin to the segmented bismaleimide resin is 1 (0.05-0.30); the mass ratio of the epoxy resin to the filler is 1 (0.005-0.15);
the block copolymerized bismaleimide resin has a molecular structural formula:
said R is 1 Is that
said R is 2 Is that
Wherein m is n= (0.2-0.4) 1.
2. The resin for the ship composite material according to claim 1, wherein the epoxy resin is a non-halogen epoxy resin, in particular one or a combination of a plurality of bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, tetrafunctional epoxy resin, trifunctional epoxy resin, alicyclic epoxy resin, glycidyl ester epoxy resin and silicon epoxy resin; the viscosity of the epoxy resin is 50-40000 mPa.s; the curing agent is one or the combination of a plurality of aromatic amine curing agents, alicyclic amine curing agents, aliphatic amine curing agents and heterocyclic amine curing agents; the filler is one or the combination of a plurality of curing accelerator, silane coupling agent, diluent, flexibilizer and solvent.
3. A resin for marine composite according to claim 2, wherein said block copolymerized bismaleimide resin has a molecular weight of less than 7000.
4. A method for preparing a resin for marine composite material according to claim 1, characterized in that it is carried out according to the following steps:
1. preparation of a block-copolymerized bismaleimide resin:
(1) weighing aromatic diamine, aromatic dianhydride, siloxane diamine, maleic anhydride and organic solvent, dividing the aromatic diamine into a first part of aromatic diamine and a second part of aromatic diamine, dividing the aromatic dianhydride into a first part of aromatic dianhydride and a second part of aromatic dianhydride according to the weight ratio, and dividing the organic solvent into a first part of organic solvent and a second part of organic solvent;
the mol ratio of the aromatic diamine to the aromatic dianhydride is 1 (1.05-1.36); the molar ratio of the aromatic diamine to the siloxane diamine is 1 (0.29-0.58); the molar ratio of the aromatic diamine to the maleic anhydride is 1 (0.23-0.58); the mass ratio of the total mole of the aromatic diamine, the aromatic dianhydride, the siloxane diamine and the maleic anhydride to the organic solvent is 1mol (600-12000 g);
the aromatic dianhydride is 4,4' -oxydiphthalic anhydride; the aromatic diamine is 1, 4-bis- (4' -aminophenoxy) -2- (phenyl) benzene; the siloxane diamine is aminopropyl end-capped polydimethylsiloxane;
(2) stirring and mixing the first part of aromatic diamine and the first part of organic solvent at room temperature under nitrogen atmosphere until the aromatic diamine is completely dissolved, adding the first part of aromatic dianhydride for three times in average, and continuously stirring to obtain a reaction liquid I;
(3) stirring and mixing the second part of aromatic dianhydride and the second part of organic solvent at room temperature under nitrogen atmosphere until the aromatic dianhydride is completely dissolved, adding siloxane diamine for three times in average, and continuously stirring to obtain a reaction solution II;
(4) adding a second part of aromatic diamine into the reaction solution II at room temperature under nitrogen atmosphere, stirring and dissolving, adding the reaction solution I, mixing and stirring, adding maleic anhydride, continuously stirring to obtain a reaction solution III, carrying out dehydration reaction on the reaction solution III to obtain a bismaleimide acid solution, and carrying out solid precipitation, washing and drying on the bismaleimide acid solution to obtain the segmented bismaleimide resin;
2. preparation of modified epoxy resin:
(1) weighing epoxy resin, curing agent, segmented bismaleimide resin and filler;
the mass ratio of the epoxy resin to the curing agent is 1 (0.05-0.30); the mass ratio of the epoxy resin to the segmented bismaleimide resin is 1 (0.05-0.30); the mass ratio of the epoxy resin to the filler is 1 (0.005-0.15);
(2) adding filler into epoxy resin at room temperature, stirring and mixing uniformly, sequentially adding bismaleimide resin with block copolymerization and a curing agent, stirring to be homogeneous, and continuing stirring to obtain the marine modified epoxy resin with low water absorption;
and the interval time between the addition of the segmented bismaleimide resin and the curing agent is 10-20 min.
5. The method for producing a resin for marine composite material according to claim 4, wherein said organic solvent N, N-dimethylformamide in the step one (1).
6. The method for producing a resin for a marine composite material according to claim 4, wherein in the step one (1), aromatic diamine is separated into a first aromatic diamine and a second aromatic diamine in a molar ratio of 1 (0.13 to 0.4); in the first step (1), the aromatic dianhydride is divided into a first part of aromatic dianhydride and a second part of aromatic dianhydride according to the mole ratio of 1 (0.14-0.36); in the first step (1), the organic solvent is divided into a first part of organic solvent and a second part of organic solvent according to the mass ratio of (0.20-0.70).
7. The method of preparing resin for ship composite material according to claim 4, wherein the dehydration reaction in step one (4) is specifically performed by using acetic anhydride as a dehydrating agent and triethylamine and nickel acetate as catalysts, adding the dehydrating agent and the catalysts into the reaction solution III, and performing dehydration reaction at 60-65 ℃ for 2-10 hours to obtain the bismaleimide acid solution.
8. The method for preparing resin for ship composite material according to claim 4, wherein in step one (4), solid precipitation, washing and drying are carried out on the bismaleimide acid solution, specifically, the bismaleimide acid solution is cooled to below 5 ℃ by ice water, water is added dropwise until the solid precipitation, water is used as washing liquid, the solid is washed for 5 times until the washing liquid is neutral, and filtration and drying are carried out.
9. The method for preparing resin for ship composite material according to claim 4, wherein in step one (2), under the conditions of room temperature, nitrogen atmosphere and stirring speed of 100-500 r/min, stirring and mixing the first part of aromatic diamine and the first part of organic solvent until the aromatic diamine is completely dissolved, adding the first part of aromatic dianhydride for three times in average, and continuing stirring for 4-6 hours to obtain reaction liquid I; step one, stirring and mixing a second part of aromatic dianhydride and a second part of organic solvent at room temperature under nitrogen atmosphere at a stirring speed of 100-500 r/min until the aromatic dianhydride is completely dissolved, adding siloxane diamine three times in average, and continuing stirring for 4-6 h to obtain a reaction solution II; and (3) in the first step (4), adding a second part of aromatic diamine into the reaction solution II under the condition of stirring speed of 100-500 r/min, stirring for dissolving, adding the reaction solution I, mixing and stirring for 6-8 h, adding maleic anhydride, and continuing stirring for 2-4 h to obtain a reaction solution III.
10. The method for preparing a resin for a marine composite material according to claim 4, wherein in the second step (2), a filler is added to the epoxy resin at room temperature and at a stirring speed of 100r/min to 500r/min, stirring is performed for 20min to 40min, then the block-copolymerized bismaleimide resin and the curing agent are sequentially added and stirred until the mixture is homogeneous, and then stirring is continued for 1h to 2h.
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| CN111019576A (en) * | 2019-11-22 | 2020-04-17 | 南京工程学院 | Aromatic bismaleimide modified liquid polysulfide rubber toughened epoxy adhesive and preparation method thereof |
| CN113999490A (en) * | 2021-11-09 | 2022-02-01 | 中国科学院山西煤炭化学研究所 | Tough epoxy resin system and preparation method and application thereof |
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| JP2008189794A (en) * | 2007-02-05 | 2008-08-21 | Toray Ind Inc | Epoxy resin composition, prepreg and fiber-reinforced composite material |
| RU2587169C1 (en) * | 2014-12-15 | 2016-06-20 | Российская Федерация, от имени которой выступает Министерство промышленности и торговли Российской Федерации (Минпромторг России) | Epoxy-bis-maleimide resin composition and preparation method thereof |
| CN106751503A (en) * | 2016-12-08 | 2017-05-31 | 北京化工大学常州先进材料研究院 | The high-modules carbon fibre prepreg preparation method of intermediate temperature setting epoxy-resin systems |
| CN111019576A (en) * | 2019-11-22 | 2020-04-17 | 南京工程学院 | Aromatic bismaleimide modified liquid polysulfide rubber toughened epoxy adhesive and preparation method thereof |
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