CN108192082B - Method for preparing reversible crosslinking toughening epoxy resin by using body click chemical reaction - Google Patents
Method for preparing reversible crosslinking toughening epoxy resin by using body click chemical reaction Download PDFInfo
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- CN108192082B CN108192082B CN201810092901.6A CN201810092901A CN108192082B CN 108192082 B CN108192082 B CN 108192082B CN 201810092901 A CN201810092901 A CN 201810092901A CN 108192082 B CN108192082 B CN 108192082B
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- epoxy resin
- toughened
- reaction
- diglycidyl ether
- monomer
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 178
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 178
- 238000004132 cross linking Methods 0.000 title claims abstract description 58
- 230000002441 reversible effect Effects 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 title claims description 42
- 239000000178 monomer Substances 0.000 claims abstract description 33
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 29
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 25
- ZFFTZDQKIXPDAF-UHFFFAOYSA-N 2-Furanmethanethiol Chemical compound SCC1=CC=CO1 ZFFTZDQKIXPDAF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000004593 Epoxy Substances 0.000 claims abstract description 11
- 238000012650 click reaction Methods 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 claims abstract description 9
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 7
- 238000005698 Diels-Alder reaction Methods 0.000 claims abstract description 6
- -1 functional group compound Chemical class 0.000 claims description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 12
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 11
- 229920001451 polypropylene glycol Polymers 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical group CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 7
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 6
- NIAAGQAEVGMHPM-UHFFFAOYSA-N 4-methylbenzene-1,2-dithiol Chemical compound CC1=CC=C(S)C(S)=C1 NIAAGQAEVGMHPM-UHFFFAOYSA-N 0.000 claims description 6
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 6
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 claims description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 6
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 claims description 4
- SRZXCOWFGPICGA-UHFFFAOYSA-N 1,6-Hexanedithiol Chemical compound SCCCCCCS SRZXCOWFGPICGA-UHFFFAOYSA-N 0.000 claims description 4
- 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 description 4
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical group CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 claims description 4
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 claims description 4
- HDPLHDGYGLENEI-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COC(C)COCC1CO1 HDPLHDGYGLENEI-UHFFFAOYSA-N 0.000 claims description 4
- VSZSIEBALNXIFG-UHFFFAOYSA-N 2-hydroxyethyl 2,2-bis(sulfanyl)acetate Chemical compound OCCOC(=O)C(S)S VSZSIEBALNXIFG-UHFFFAOYSA-N 0.000 claims description 4
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical compound NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 claims description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 4
- AHIPJALLQVEEQF-UHFFFAOYSA-N 4-(oxiran-2-ylmethoxy)-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1COC(C=C1)=CC=C1N(CC1OC1)CC1CO1 AHIPJALLQVEEQF-UHFFFAOYSA-N 0.000 claims description 4
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical group C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 239000004305 biphenyl Substances 0.000 claims description 4
- JRPRCOLKIYRSNH-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,2-dicarboxylate Chemical compound C=1C=CC=C(C(=O)OCC2OC2)C=1C(=O)OCC1CO1 JRPRCOLKIYRSNH-UHFFFAOYSA-N 0.000 claims description 4
- ZXOATMQSUNJNNG-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,3-dicarboxylate Chemical compound C=1C=CC(C(=O)OCC2OC2)=CC=1C(=O)OCC1CO1 ZXOATMQSUNJNNG-UHFFFAOYSA-N 0.000 claims description 4
- NEPKLUNSRVEBIX-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) benzene-1,4-dicarboxylate Chemical compound C=1C=C(C(=O)OCC2OC2)C=CC=1C(=O)OCC1CO1 NEPKLUNSRVEBIX-UHFFFAOYSA-N 0.000 claims description 4
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- IGZBSJAMZHNHKE-UHFFFAOYSA-N 2-[[4-[bis[4-(oxiran-2-ylmethoxy)phenyl]methyl]phenoxy]methyl]oxirane Chemical compound C1OC1COC(C=C1)=CC=C1C(C=1C=CC(OCC2OC2)=CC=1)C(C=C1)=CC=C1OCC1CO1 IGZBSJAMZHNHKE-UHFFFAOYSA-N 0.000 claims description 3
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical group C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 3
- VHCOFKDAUBOOTH-UHFFFAOYSA-N ethane pyrrole-2,5-dione Chemical compound CC.C1(C=CC(N1)=O)=O VHCOFKDAUBOOTH-UHFFFAOYSA-N 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- LFTMJBWNOFFSRW-UHFFFAOYSA-N 1,2-Butanedithiol Chemical compound CCC(S)CS LFTMJBWNOFFSRW-UHFFFAOYSA-N 0.000 claims description 2
- OYDGRFZMWQLWGV-UHFFFAOYSA-N 1-(2-cyclopenta-1,3-dien-1-ylethyl)cyclopenta-1,3-diene Chemical compound C=1C=CCC=1CCC1=CC=CC1 OYDGRFZMWQLWGV-UHFFFAOYSA-N 0.000 claims description 2
- HASUCEDGKYJBDC-UHFFFAOYSA-N 1-[3-[[bis(oxiran-2-ylmethyl)amino]methyl]cyclohexyl]-n,n-bis(oxiran-2-ylmethyl)methanamine Chemical compound C1OC1CN(CC1CC(CN(CC2OC2)CC2OC2)CCC1)CC1CO1 HASUCEDGKYJBDC-UHFFFAOYSA-N 0.000 claims description 2
- 229940018563 3-aminophenol Drugs 0.000 claims description 2
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 claims description 2
- VHJLVAABSRFDPM-ZXZARUISSA-N dithioerythritol Chemical compound SC[C@H](O)[C@H](O)CS VHJLVAABSRFDPM-ZXZARUISSA-N 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 claims description 2
- ACTRVOBWPAIOHC-XIXRPRMCSA-N succimer Chemical compound OC(=O)[C@@H](S)[C@@H](S)C(O)=O ACTRVOBWPAIOHC-XIXRPRMCSA-N 0.000 claims description 2
- 229960005346 succimer Drugs 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 abstract description 9
- 239000004416 thermosoftening plastic Substances 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 6
- 238000010382 chemical cross-linking Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 48
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 239000000203 mixture Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 238000010907 mechanical stirring Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 239000004970 Chain extender 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
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004843 novolac epoxy resin Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- WFCQTAXSWSWIHS-UHFFFAOYSA-N 4-[bis(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 WFCQTAXSWSWIHS-UHFFFAOYSA-N 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical class C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/506—Amines heterocyclic containing only nitrogen as a heteroatom having one nitrogen atom in the ring
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3236—Heterocylic compounds
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/3254—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen
- C08G59/3263—Epoxy compounds containing three or more epoxy groups containing atoms other than carbon, hydrogen, oxygen or nitrogen containing sulfur
-
- 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
- C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
Landscapes
- 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 preparation method of thermoplastic toughened epoxy resin with a thermal reversible chemical crosslinking characteristic, which comprises the following steps: 1) mixing bifunctional epoxy resin and polyfunctional epoxy resin, and carrying out click reaction with furfuryl mercaptan to obtain an intermediate with a furan functional group as a terminal group; the bifunctional epoxy resin is an epoxy monomer containing two epoxy groups, and the polyfunctional epoxy resin is an epoxy monomer containing three or more epoxy groups; 2) and the intermediate and a cross-linking agent containing maleimide groups are subjected to Diels-Alder reaction to form the reversibly crosslinked toughened epoxy resin. The invention overcomes the defects of difficult dissolution and difficult dissolution of the traditional cured epoxy resin; the thermoplastic reversible crosslinking toughening epoxy resin realizes the recycling of the crosslinking epoxy resin by utilizing Diels-Alder covalent bonds, can still maintain the performance of the traditional epoxy resin, has simple and convenient method and has industrial application prospect.
Description
Technical Field
The invention relates to a thermoplastic toughened epoxy resin with a thermal reversible chemical crosslinking characteristic and a preparation method thereof, namely, under the action of a tertiary amine catalyst, bifunctional epoxy resin and polyfunctional epoxy resin are mixed according to a certain proportion and then are subjected to click reaction with furfuryl mercaptan to obtain an intermediate with a furan functional group as a terminal group, and the intermediate and a crosslinking agent containing maleimide groups are subjected to Diels-Alder reaction to form the reversibly crosslinked toughened epoxy resin which can be subjected to decrosslinking at high temperature, so that the toughened epoxy resin can be recycled and processed again.
Background
Epoxy resin is an important thermosetting polymer, and is widely applied to the fields of adhesives, structural materials, printed circuit boards, electronic packaging and the like due to strong chemical stability, low shrinkage and high dielectric property. The traditional covalent crosslinking epoxy resin has higher crosslinking density and higher brittleness, so the application of the traditional covalent crosslinking epoxy resin is limited. And the cured and molded epoxy resin is difficult to reprocess by some methods such as heat treatment due to the irreversibility of the crosslinking reaction, so that the repeated recycling of the epoxy resin is limited, and the resource is greatly wasted.
The toughening modification based on epoxy resin has been studied more, and chinese patent CN106674902A discloses a toughened epoxy resin and a preparation method thereof, which adopts toughening means of adding plasticizer, low molecular weight toughening agent, thermoplastic resin and rubber elastomer to improve the toughness of the epoxy resin and maintain better mechanical properties, but the product cured by epoxy resin curing agent cannot be processed and utilized again, and the use efficiency is greatly reduced. Some research has been devoted to the preparation of reversibly crosslinked epoxy resins at this stage. Chinese patent CN103483605A discloses a reversible covalent crosslinking epoxy resin and a preparation method thereof, wherein the method comprises the steps of adopting diene monoamine to react with epoxy resin monomer to synthesize linear epoxy resin with a crosslinking site on a side chain, dissolving the linear epoxy resin into a solvent, fully mixing the solvent with a dienophile crosslinking agent, removing the solvent in a vacuum oven, and then carrying out crosslinking reaction at 20-90 ℃ to prepare the reversible covalent crosslinking epoxy resin. However, this method is more traditional, the reaction rate of amine and epoxy group is slower, the crosslinking reaction can be performed only after the solvent is removed, the operation is more complicated, and the method is difficult to be applied to practical application in large scale. Chinese patent CN101348560A discloses an epoxy resin containing furan group and a preparation method thereof, wherein the epoxy resin can realize reversible crosslinking by curing with polyfunctional maleimide. However, the method for preparing the furan group-containing epoxy resin needs to undergo multiple steps of dehydration cyclization, organic extraction, reduced pressure distillation and the like, and is complicated. Chinese patent CN103249712A discloses a process for preparing a novel compound of recyclable epoxy resin, which uses polyamine, polythiol or curing agent with acid tendency to cure epoxy resin. The resin can be decomposed in acid under the condition of gradually increasing temperature so as to realize the recycling of the epoxy resin. However, this recovery method needs to be carried out under specific acidity conditions, and the operation conditions are limited.
There are also a number of reports in the literature on the preparation and performance of reversibly crosslinked polymers. Reversibly crosslinked butadiene-modified rubbers were prepared by Bai sting et al, see Macromolecules, Vol.48, 3539-3546 (2015). In a toluene solvent, furan groups are introduced on a side chain through the click reaction of furfurylthiol and double bonds in butadiene rubber, and DA reaction is adopted to obtain the cured rubber. The modified butadiene rubber has certain mechanical property and repeated processing property.
Turkenburg et al, reference Polymer, Vol.79, 187-194(2015), prepared a thermally reversible epoxy resin with self-healing properties. The preparation method comprises the following steps: the furfuryl amine and the epoxy resin are cured for a period of time at 125 ℃ to generate a prepolymer with a side chain having a furan crosslinking site. And (3) reacting and extruding the prepolymer and maleimide through a double-screw extruder body, and curing to obtain the self-repairable epoxy resin. The technical defects are as follows: the reaction rate of amine and epoxy is slow, the reaction conditions are harsh, and the reaction conversion rate cannot reach 100%, which is 94% in the literature. And the mechanical properties, especially toughness, of self-healing epoxy resins are not addressed in this context.
Kuang Xiao et al, see Polymer, Vol.84, 1-9(2016) prepared epoxy resins having shape memory properties. Different glass transition temperatures are obtained by controlling the proportion of the components of the substance, and a novel material with a shape memory function is designed by matching with a thermal reversible bond of DA. However, the above reports basically adopt amine to cure the epoxy resin, the reaction time is long, and the curing efficiency is generally low; the mechanical property of the obtained modified epoxy resin is generally poor, and the industrial application value needs to be improved.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing reversible crosslinking toughening epoxy resin by utilizing a body click chemical reaction, thereby overcoming the defects that the traditional cured epoxy resin is difficult to dissolve and infusible; the thermoplastic reversible crosslinking toughening epoxy resin realizes the recycling of the crosslinking epoxy resin by utilizing Diels-Alder covalent bonds, can still maintain the performance of the traditional epoxy resin, has simple and convenient method and has industrial application prospect.
In order to solve the technical problems, the invention provides a method for preparing reversible crosslinking toughening epoxy resin by using a body click chemical reaction, which comprises the following steps:
1) mixing bifunctional epoxy resin and polyfunctional epoxy resin, and carrying out click reaction with furfuryl mercaptan to obtain an intermediate with a furan functional group as a terminal group;
the bifunctional epoxy resin is an epoxy monomer containing two epoxy groups, and the polyfunctional epoxy resin is an epoxy monomer containing three or more epoxy groups;
2) and the intermediate and a cross-linking agent containing maleimide groups are subjected to Diels-Alder reaction to form the reversibly crosslinked toughened epoxy resin.
The improvement of the method for preparing the reversible crosslinking toughening epoxy resin by utilizing the body click chemical reaction comprises the following steps:
step 1), intermediate with furan functional group as end group:
under the protection of inert gas (argon or nitrogen and the like), under the condition of no solvent, uniformly mixing 50-140 parts of bifunctional epoxy resin and 20-100 parts of polyfunctional epoxy resin at 20-100 ℃, adding 15-80 parts of furfuryl mercaptan, fully stirring, adding 0.5-5 parts of tertiary amine catalyst, and reacting at constant temperature for 0.1-3 hours to obtain an intermediate with a furan functional group as a terminal group;
or under the protection of inert gas (argon or nitrogen and the like), under the condition of no solvent, uniformly mixing 50-140 parts of epoxy resin generated after chain extension and 20-100 parts of polyfunctional epoxy resin at 20-100 ℃, adding 15-80 parts of furfuryl mercaptan, fully stirring, and reacting at constant temperature for 0.1-3 hours to obtain an intermediate with a furan functional group as a terminal group;
step 2), preparing the reversible crosslinking toughening epoxy resin by using the intermediate with the end group of furan functional group:
under the protection of inert gas (argon or nitrogen), under the condition of no solvent, adding 60-100 parts of cross-linking agent containing maleimide group into the intermediate with the end group of furan functional group obtained in the step 1) at 100-160 ℃, fully stirring, firstly reacting for 0.1-0.5 h at 100-160 ℃, and then carrying out cross-linking reaction for 0.1-48 h at 20-90 ℃ (preferably 60-90 ℃), thus obtaining the reversible cross-linking toughened epoxy resin.
The method for preparing the reversible crosslinking toughening epoxy resin by utilizing the body click chemical reaction is further improved as follows:
the epoxy resin generated after chain extension is the epoxy resin generated after at least one of aromatic epoxy resin monomers and non-aromatic epoxy resin monomers is subjected to click reaction chain extension through a dimercapto functional group compound under the action of a tertiary amine catalyst;
the preparation method comprises the following steps:
under the protection of inert gas (argon or nitrogen), under the condition of no solvent, uniformly mixing 30-90 parts of at least one of aromatic epoxy resin monomer and non-aromatic epoxy resin monomer with 19-45 parts of bifunctional mercapto compound (namely, bifunctional mercapto compound) at 20-80 ℃, fully stirring, and then adding 0.5-5 parts of tertiary amine catalyst to react at 20-80 ℃ for 0.1-5 h to obtain chain-extended epoxy resin with an epoxy functional group as an end group;
the bifunctional mercapto compound is a mercapto compound monomer containing two mercapto groups.
The method for preparing the reversible crosslinking toughening epoxy resin by utilizing the body click chemical reaction is further improved as follows:
the difunctional mercapto compound is ethylene glycol dimercaptoacetate, 1, 6-hexanedithiol, meso-2, 3-dimercaptosuccinic acid, dithioerythritol, 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 2-butanedithiol, 4' -thiobisthiophenol, dimercaptopropanol and toluene-3, 4-dithiol.
The method for preparing the reversible crosslinking toughening epoxy resin by utilizing the body click chemical reaction is further improved as follows:
the bifunctional epoxy resin is at least one of aromatic epoxy resin monomer and non-aromatic epoxy resin monomer; the aromatic epoxy resin monomer is bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester;
the non-aromatic epoxy resin monomer is ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and polypropylene oxide diglycidyl ether;
the polyfunctional epoxy resin is glycidyl amine epoxy resin monomer and glycidyl ether epoxy resin monomer;
the glycidyl amine epoxy resin monomer is 4,4' -diaminodiphenylmethane epoxy resin, triglycidyl p-aminophenol, triglycidyl m-aminophenol, epoxidized m-xylylenediamine, and 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane;
the glycidyl ether epoxy resin monomer is phenolic epoxy resin, tris (4-hydroxyphenyl) methane triglycidyl ether, 1,1, 1-tris (4-hydroxyphenyl) ethyl triglycidyl ether, 2' - [1, 2-dimethylene tetra (4, 1-phenylene methoxyl) ] tetracyclo-ethylene oxide and dicyclopentadiene-phenol glycidyl ether resin.
The method for preparing the reversible crosslinking toughening epoxy resin by utilizing the body click chemical reaction is further improved as follows:
the tertiary amine catalyst is 2,4, 6-tri (dimethylaminomethyl) phenol, N-dimethylbenzylamine, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, triethylamine and N, N-dimethylaniline.
The method for preparing the reversible crosslinking toughening epoxy resin by utilizing the body click chemical reaction is further improved as follows:
the cross-linking agent containing maleimide group is N-N ' - (4, 4-methylene diphenyl) bismaleimide, N-N- (4-methyl-1, 3-phenylene) bismaleimide, N-N ' -m-phenylene bismaleimide, 1, 2-bis (maleimide) ethane or 4-4 ' -bismaleimide diphenylmethane.
The reversibly crosslinked toughened epoxy resin can be subjected to decrosslinking at high temperature, so that the toughened epoxy resin can be recycled and processed for the second time.
The thermoplastic reversible crosslinking toughened epoxy resin provided by the invention has excellent mechanical properties of thermosetting chemical crosslinking materials, and has obviously enhanced toughness compared with the traditional epoxy resin; meanwhile, the method also has the advantage of repeated processing (can be repeatedly processed and utilized) of the thermoplastic material, thereby realizing the recycling of resources.
The thermoplastic reversible crosslinking toughened epoxy resin provided by the invention can adjust the material performance in a larger range by changing the number of crosslinking sites, the crosslinking density and the components of the epoxy resin, meets the requirements of various products, and has an industrial application prospect. Particularly, the quantity of crosslinking sites can be regulated and controlled by the quantity of the added furfuryl mercaptan substances, and the method has the technical advantages of simplicity, convenience and controllability; by varying the amount of species of crosslinker added, the crosslink density can be controlled.
The preparation process of the thermoplastic reversible crosslinking toughened epoxy resin provided by the invention does not need a solvent, so that the mass transfer efficiency is greatly improved; the reaction steps are efficient and quick; the furan crosslinking sites are introduced by adopting click reaction, the reaction condition is mild and convenient, and the reaction process is accurate and efficient.
According to the invention, a substance containing maleimide groups is added into a high-temperature body for melting, the substance is uniformly mixed under the action of a mechanical stirrer, and the substance is directly taken out and solidified under a certain condition without removing a solvent.
The thermoplastic reversible crosslinking toughened epoxy resin provided by the invention is low in production cost, simple and convenient in preparation method and easy for industrial production.
In conclusion, the thermoplastic toughened epoxy resin with the thermal reversible chemical crosslinking characteristic is synthesized, furan functional groups are quickly and efficiently introduced to the tail end of the epoxy resin in one step by utilizing the click reaction of sulfydryl-epoxy in the body, the crosslinking and curing are carried out by adopting the dienophile crosslinking agent, and the decrosslinking can be carried out at high temperature, so that the repeated recycling and secondary processing of the toughened epoxy resin are realized; the cured epoxy resin has higher Young modulus and elongation at break, and the toughness is obviously enhanced. The mass click reaction does not need to add any solvent, so that the time required by mass transfer is greatly reduced, the click reaction is quick and efficient, the method steps are simple and convenient, and the method has an industrial application prospect.
Detailed Description
The present invention is specifically described below by way of examples, but the scope of the present invention is not limited to these examples.
Embodiment 1, a method for preparing a reversible crosslinking toughened epoxy resin, the bifunctional epoxy resin being propylene glycol diglycidyl ether, the polyfunctional epoxy resin being novolac epoxy resin, the tertiary amine catalyst being 2,4, 6-tris (dimethylaminomethyl) phenol, the steps being as follows:
1) under the protection of nitrogen, 50g of propylene glycol diglycidyl ether and 27.5g of novolac epoxy resin are added into a 150ml three-neck round-bottom flask in a constant-temperature oil bath kettle at the temperature of 20 ℃, and are uniformly mixed by mechanical stirring; then, 24.3g of furfuryl mercaptan and 1.1g of 2,4, 6-tris (dimethylaminomethyl) phenol are sequentially added to react for 3 hours at constant temperature to obtain an intermediate with a furan functional group as a terminal group, and the grafting rate reaches 99.5 percent.
2) And under the protection of nitrogen, uniformly stirring the intermediate obtained by the reaction and 62g N-N' - (4, 4-methylene diphenyl) bismaleimide in a constant-temperature oil bath kettle at 160 ℃, fully reacting for 0.1 hour, pouring into a polytetrafluoroethylene mould placed in an oven, and carrying out crosslinking reaction for 24 hours at 70 ℃ to obtain the yellow transparent reversible toughening epoxy resin.
Embodiment 2, a method for preparing a reversible crosslinking toughened epoxy resin, the bifunctional epoxy resin being selected from bisphenol a diglycidyl ether, the polyfunctional epoxy resin being selected from triglycidyl p-aminophenol, the tertiary amine catalyst being selected from N, N-dimethylbenzylamine, the steps being as follows:
1) adding 72g of bisphenol A diglycidyl ether and 54g of triglycidyl p-aminophenol into a 250ml three-neck round-bottom flask in a constant-temperature oil bath kettle at 100 ℃ under the protection of nitrogen, and uniformly mixing by mechanical stirring; then 45g of furfuryl mercaptan and 3.5g N, N-dimethylbenzylamine are sequentially added to react for 0.1 hour at constant temperature to obtain an intermediate with a furan functional group as a terminal group, and the grafting rate reaches 99.8 percent.
2) And under the protection of nitrogen, uniformly stirring the intermediate obtained by the reaction and 78g of 1, 2-bis (maleimide) ethane in a constant-temperature oil bath kettle at 100 ℃, fully reacting for 0.5 hour, pouring into a polytetrafluoroethylene mould placed in an oven, and carrying out crosslinking reaction for 0.1 hour at 90 ℃ to obtain the yellow transparent reversible toughening epoxy resin.
Embodiment 3 discloses a method for preparing a reversible crosslinking toughened epoxy resin, in which a mixture of bisphenol F diglycidyl ether and butanediol diglycidyl ether is selected as a bifunctional epoxy resin, 1, 6-hexanedithiol is selected as a chain extender, tris (4-hydroxyphenyl) methane triglycidyl ether is selected as a polyfunctional epoxy resin, and N, N-dimethylaniline is selected as a tertiary amine catalyst, the method comprising the steps of:
1) under the protection of nitrogen, in a constant-temperature oil bath kettle at 20 ℃, 20g of bisphenol F diglycidyl ether and 28g of butanediol diglycidyl ether are added into a 100ml three-neck round-bottom flask and are uniformly mixed by mechanical stirring; then 22g of 1, 6-hexanedithiol and 1.5g N, N-dimethylaniline are added in sequence to react for 5 hours at constant temperature, and the difunctional epoxy resin with the chain extended by sulfydryl is obtained.
2) Under the protection of nitrogen, in a constant-temperature oil bath kettle at 55 ℃, the obtained difunctional epoxy resin with the chain extended by the sulfydryl is mixed with 52g of tri (4-hydroxyphenyl) methane triglycidyl ether and 48g of furfuryl mercaptan, and the mixture is reacted for 1.5 hours at constant temperature to obtain an intermediate with the end group of furan functional group, wherein the grafting rate reaches 99.9%.
3) And under the protection of nitrogen, uniformly stirring the intermediate obtained by the reaction and 72g N-N- (4-methyl-1, 3-phenylene) bismaleimide in a constant-temperature oil bath kettle at 120 ℃, fully reacting for 0.4 hour, pouring into a polytetrafluoroethylene mould placed in an oven, and carrying out crosslinking reaction for 24 hours at 80 ℃ to obtain the yellow transparent reversible toughening epoxy resin.
Embodiment 4, a method for preparing a reversible crosslinking toughened epoxy resin, wherein a mixture of bisphenol S diglycidyl ether and diglycidyl phthalate is selected as a bifunctional epoxy resin, 4' -thiobisthiophenol is selected as a chain extender, 2 ', 2 ", 2" ' - [1, 2-bismethylenetetrakis (4, 1-phenylenemethoxy) ] tetracyclooxirane is selected as a polyfunctional epoxy resin, and triethylamine is selected as a tertiary amine catalyst, the method comprises the following steps:
1) under the protection of nitrogen, in a constant-temperature oil bath kettle at 80 ℃, 27g of bisphenol S diglycidyl ether and 48g of diglycidyl phthalate are added into a 150ml three-neck round-bottom flask, and are stirred and mixed uniformly by a machine; then 36g of 4,4' -thiobisthiophenol and 4g of triethylamine are added in sequence to react for 0.1 hour at constant temperature, and the difunctional epoxy resin with the mercapto chain extension is obtained.
2) Under the protection of nitrogen, in a constant-temperature oil bath kettle at 40 ℃, the obtained difunctional epoxy resin with the chain extended by the sulfydryl is mixed with 56g of 2, 2' - [1, 2-dimethylene tetra (4, 1-phenylene methoxyl) ] tetracyclo-ethylene oxide and 76g of furfuryl mercaptan, and the mixture is reacted for 2.5 hours at constant temperature to obtain an intermediate with a furan functional group as a terminal group, wherein the grafting rate reaches 99.6 percent.
3) And under the protection of nitrogen, uniformly stirring the intermediate obtained by the reaction and 69g N-N' -m-phenylene bismaleimide in a constant-temperature oil bath kettle at 140 ℃, fully reacting for 0.2 hour, pouring into a polytetrafluoroethylene mould placed in an oven, and carrying out crosslinking reaction for 36 hours at 60 ℃ to obtain the yellow transparent reversible toughening epoxy resin.
Embodiment 5 discloses a method for preparing a reversible crosslinking toughened epoxy resin, wherein a mixture of diglycidyl isophthalate and diglycidyl terephthalate is selected as a bifunctional epoxy resin, 1, 2-ethanedithiol is selected as a chain extender, 4' -diaminodiphenylmethane epoxy resin is selected as a polyfunctional epoxy resin, and N, N-dimethylcyclohexylamine is selected as a tertiary amine catalyst, and the method comprises the following steps:
1) under the protection of nitrogen, 22g of diglycidyl isophthalate and 22g of diglycidyl terephthalate are added into a 100ml three-neck round-bottom flask in a constant-temperature oil bath kettle at 40 ℃, and are stirred and mixed uniformly by a machine; then 20g of 1, 2-ethanedithiol and 1.4g of N, N-dimethylcyclohexylamine are sequentially added, and the constant temperature reaction is carried out for 2 hours, so as to obtain the mercapto chain-extended bifunctional epoxy resin.
2) Under the protection of nitrogen, in a constant-temperature oil bath kettle at 40 ℃, the obtained difunctional epoxy resin with the chain extended by the sulfydryl group is mixed with 58g of 4,4' -diaminodiphenylmethane epoxy resin and 36g of furfuryl mercaptan, and the mixture is reacted for 2.5 hours at constant temperature to obtain an intermediate with the end group of furan functional group, wherein the grafting rate reaches 99.6 percent.
3) And under the protection of nitrogen, uniformly stirring the intermediate obtained by the reaction and 90g of 4-4' -bismaleimide diphenylmethane in a constant-temperature oil bath kettle at 120 ℃, fully reacting for 0.4 hour, pouring into a polytetrafluoroethylene mould placed in an oven, and carrying out crosslinking reaction for 24 hours at 80 ℃ to obtain the yellow transparent reversible toughening epoxy resin.
Embodiment 6 discloses a method for preparing a reversibly crosslinked and toughened epoxy resin, wherein a mixture of ethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether is selected as a bifunctional epoxy resin, toluene-3, 4-dithiol is selected as a chain extender, epoxidized m-xylylenediamine is selected as a polyfunctional epoxy resin, and bis (2-dimethylaminoethyl) ether is selected as a tertiary amine catalyst, the method comprising the following steps:
1) 39g of ethylene glycol diglycidyl ether and 8g of polypropylene glycol diglycidyl ether were put into a 100ml three-neck round-bottom flask in a constant temperature oil bath at 80 ℃ under nitrogen protection, and mixed uniformly with mechanical stirring. Then 23g of toluene-3, 4-dithiol and 1.8g of bis (2-dimethylaminoethyl) ether are added in sequence and reacted for 0.1 hour at constant temperature to obtain the mercapto chain-extended difunctional epoxy resin.
2) Under the protection of nitrogen, in a constant-temperature oil bath kettle at 40 ℃, mixing the obtained difunctional epoxy resin with the chain extended by the sulfydryl, 24g of epoxidized m-xylylenediamine and 21g of furfuryl mercaptan, and reacting at constant temperature for 2.5 hours to obtain an intermediate with a furan functional group as a terminal group, wherein the grafting rate reaches 99.6%.
3) And under the protection of nitrogen, uniformly stirring the intermediate obtained by the reaction and 62g of 4-4' -bismaleimide diphenylmethane in a constant-temperature oil bath kettle at 140 ℃, fully reacting for 0.2 hour, pouring into a polytetrafluoroethylene mould placed in an oven, and carrying out crosslinking reaction for 42 hours at 40 ℃ to obtain the yellow transparent reversible toughened epoxy resin.
Embodiment 7 discloses a method for preparing a reversible crosslinking toughened epoxy resin, wherein a mixture of polyethylene glycol diglycidyl ether, bisphenol F diglycidyl ether and polypropylene oxide diglycidyl ether is selected as a bifunctional epoxy resin, ethylene glycol dimercaptoacetate is selected as a chain extender, 1,1, 1-tris (4-hydroxyphenyl) ethyl triglycidyl ether is selected as a polyfunctional epoxy resin, and triethylamine is selected as a tertiary amine catalyst, and the method comprises the following steps:
1) under the protection of nitrogen, in a constant-temperature oil bath kettle at 55 ℃, adding 25g of polyethylene glycol diglycidyl ether, 10g of bisphenol F diglycidyl ether and 2g of polypropylene oxide diglycidyl ether into a 100ml three-neck round-bottom flask, and uniformly mixing by mechanical stirring; then, 22g of ethylene glycol dimercaptoacetate and 2.1g of triethylamine are sequentially added, and the constant temperature reaction is carried out for 0.7 hour, so as to obtain the difunctional group epoxy resin with the mercapto chain extended.
2) Under the protection of nitrogen, in a constant-temperature oil bath kettle at 75 ℃, the obtained difunctional epoxy resin with the chain extended by the sulfydryl group is mixed with 37g of 1,1, 1-tri (4-hydroxyphenyl) ethyl triglycidyl ether and 21g of furfuryl mercaptan, and the mixture is placed in a nitrogen protection atmosphere to react for 0.6 hour to obtain an intermediate with a furan functional group as a terminal group, wherein the grafting rate reaches 99.9 percent.
3) And under the protection of nitrogen, uniformly stirring the intermediate obtained by the reaction and 88g N-N' - (4, 4-methylene diphenyl) bismaleimide in a constant-temperature oil bath kettle at 140 ℃, fully reacting for 0.2 hour, pouring into a polytetrafluoroethylene mould placed in an oven, and carrying out crosslinking reaction for 30 hours at 70 ℃ to obtain the yellow transparent reversible toughening epoxy resin.
Comparative example 1-1, "39 g of ethylene glycol diglycidyl ether and 8g of polypropylene glycol diglycidyl ether of example 6 were added to a 100ml three-necked round-bottomed flask, and mixed well by mechanical stirring. 23g of toluene-3, 4-dithiol and 1.8g of bis (2-dimethylaminoethyl) ether "changed to" 71.8g of ethylene glycol diglycidyl ether "were then added in this order, the remainder being identical to example 6.
Comparative examples 1-2 "39 g of ethylene glycol diglycidyl ether and 8g of polypropylene glycol diglycidyl ether of example 6 were charged into a 100ml three-necked round-bottomed flask, and mixed well by mechanical stirring. 23g of toluene-3, 4-dithiol and 1.8g of bis (2-dimethylaminoethyl) ether "changed to" 71.8g of polypropylene glycol diglycidyl ether "were then added in this order, and the rest was identical to example 6.
Comparative examples 1 to 3, step 1) in example 6 was removed, and the "mercapto-extended bifunctional epoxy resin obtained and 24g of epoxidized m-xylylenediamine" in step 2) in example 6 was changed to "95.8 g of epoxidized m-xylylenediamine", and the rest was identical to example 6.
The tensile test of the standard tensile sample strip of the reversible crosslinking toughened epoxy resin obtained in the above case is carried out, and the test result is shown in table 1.
TABLE 1 summary of tensile Properties of reversibly crosslinked toughened epoxy resins
The data show that the reversible crosslinking toughened epoxy resin prepared by the invention has better elongation at break and tensile strength, and is obviously improved compared with the traditional epoxy toughness.
The reversible crosslinking toughened epoxy resin obtained in example 6 is subjected to tensile fracture, then is heated and melted at 95 ℃, is poured into a polytetrafluoroethylene mold placed in an oven, and is subjected to crosslinking reaction at 70 ℃ for 48 hours. And (4) carrying out a tensile test on the obtained standard tensile sample strip, and testing the mechanical property of the sample strip which is utilized for many times. The test cycle was 5 times, and the test results are shown in Table 2.
TABLE 2 summary of tensile Properties of reversibly crosslinked toughened epoxy resins
| Number of repetitions | Tensile strength/MPa | Tensile modulus/MPa | Elongation at break/% |
| 1 | 70.6±3.5 | 2584±177 | 134.8±7.5 |
| 2 | 68.7±4.1 | 2368±142 | 128.4±9.3 |
| 3 | 66.4±2.3 | 2494±136 | 126.2±5.4 |
| 4 | 69.9±3.1 | 2511±192 | 131.1±8.2 |
| 5 | 68.5±2.6 | 2460±148 | 129.2±7.7 |
Finally, it is also noted that the above-mentioned lists merely illustrate a few specific embodiments of the invention. It is obvious that the invention is not limited to the above embodiments, but that many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (7)
1. The method for preparing the reversible crosslinking toughened epoxy resin by utilizing the body click chemical reaction is characterized by comprising the following steps of:
1) mixing bifunctional epoxy resin and polyfunctional epoxy resin, and carrying out click reaction with furfuryl mercaptan to obtain an intermediate with a furan functional group as a terminal group;
the bifunctional epoxy resin is an epoxy monomer containing two epoxy groups, and the polyfunctional epoxy resin is an epoxy monomer containing three or more epoxy groups;
2) and the intermediate and a cross-linking agent containing maleimide groups are subjected to Diels-Alder reaction to form the reversibly crosslinked toughened epoxy resin.
2. The method for preparing reversibly crosslinked toughened epoxy resin using bulk click chemistry according to claim 1, wherein:
step 1), intermediate with furan functional group as end group:
under the protection of inert gas, under the condition of no solvent, uniformly mixing 50-140 parts of bifunctional epoxy resin and 20-100 parts of polyfunctional epoxy resin at 20-100 ℃, adding 15-80 parts of furfuryl mercaptan, fully stirring, adding 0.5-5 parts of tertiary amine catalyst, and reacting at constant temperature for 0.1-3 hours to obtain an intermediate with a furan functional group as a terminal group;
or under the protection of inert gas, under the condition of no solvent, uniformly mixing 50-140 parts of chain extended epoxy resin and 20-100 parts of polyfunctional epoxy resin at 20-100 ℃, adding 15-80 parts of furfuryl mercaptan, fully stirring, and reacting at constant temperature for 0.1-3 hours to obtain an intermediate with a furan functional group as an end group;
step 2), preparing the reversible crosslinking toughening epoxy resin by using the intermediate with the end group of furan functional group:
under the protection of inert gas and under the condition of no solvent, 60-100 parts of cross-linking agent containing maleimide group is added into the intermediate with the end group of furan functional group obtained in the step 1) at 100-160 ℃ and fully stirred, the reaction is carried out for 0.1-0.5 h at 100-160 ℃, and then the cross-linking reaction is carried out for 0.1-48 h at 20-90 ℃ to obtain the reversible cross-linking toughened epoxy resin.
3. The method for preparing reversibly crosslinked toughened epoxy resin using bulk click chemistry according to claim 2, wherein:
the epoxy resin generated after chain extension is the epoxy resin generated after at least one of aromatic epoxy resin monomers and non-aromatic epoxy resin monomers is subjected to click reaction chain extension through a dimercapto functional group compound under the action of a tertiary amine catalyst;
the preparation method comprises the following steps:
under the protection of inert gas, under the condition of no solvent, uniformly mixing 30-90 parts of at least one of aromatic epoxy resin monomer and non-aromatic epoxy resin monomer with 19-45 parts of bifunctional mercapto compound at 20-80 ℃, fully stirring, then adding 0.5-5 parts of tertiary amine catalyst to react at 20-80 ℃ for 0.1-5 h, and obtaining chain-extended epoxy resin with the end group being epoxy functional group;
the bifunctional mercapto compound is a mercapto compound monomer containing two mercapto groups.
4. The method for preparing reversibly crosslinked toughened epoxy resin using bulk click chemistry according to claim 3, wherein:
the difunctional mercapto compound is ethylene glycol dimercaptoacetate, 1, 6-hexanedithiol, meso-2, 3-dimercaptosuccinic acid, dithioerythritol, 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 2-butanedithiol, 4' -thiobisthiophenol, dimercaptopropanol and toluene-3, 4-dithiol.
5. The method for preparing the reversibly crosslinked and toughened epoxy resin by using the bulk click chemical reaction according to any one of claims 2 to 4, wherein:
the bifunctional epoxy resin is at least one of aromatic epoxy resin monomer and non-aromatic epoxy resin monomer; the aromatic epoxy resin monomer is bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, phthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, terephthalic acid diglycidyl ester;
the non-aromatic epoxy resin monomer is ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether and polypropylene oxide diglycidyl ether;
the polyfunctional epoxy resin is glycidyl amine epoxy resin monomer and glycidyl ether epoxy resin monomer;
the glycidyl amine epoxy resin monomer is 4,4' -diaminodiphenylmethane epoxy resin, triglycidyl p-aminophenol, triglycidyl m-aminophenol, epoxidized m-xylylenediamine, and 1, 3-bis (N, N-diglycidylaminomethyl) cyclohexane;
the glycidyl ether epoxy resin monomer is phenolic epoxy resin, tris (4-hydroxyphenyl) methane triglycidyl ether, 1,1, 1-tris (4-hydroxyphenyl) ethyl triglycidyl ether, 2' - [1, 2-dimethylene tetra (4, 1-phenylene methoxyl) ] tetracyclo-ethylene oxide and dicyclopentadiene-phenol glycidyl ether resin.
6. The method for preparing reversibly crosslinked toughened epoxy resin using bulk click chemistry according to claim 5, wherein:
the tertiary amine catalyst is 2,4, 6-tri (dimethylaminomethyl) phenol, N-dimethylbenzylamine, N-dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, triethylamine and N, N-dimethylaniline.
7. The method for preparing reversibly crosslinked toughened epoxy resin using bulk click chemistry according to claim 6, wherein: the cross-linking agent containing maleimide group is N-N ' - (4, 4-methylene diphenyl) bismaleimide, N-N- (4-methyl-1, 3-phenylene) bismaleimide, N-N ' -m-phenylene bismaleimide, 1, 2-bis (maleimide) ethane or 4-4 ' -bismaleimide diphenylmethane.
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