CN114605603A - Composite modified polyurethane epoxy toughening agent and epoxy resin composition composed of same - Google Patents
Composite modified polyurethane epoxy toughening agent and epoxy resin composition composed of same Download PDFInfo
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- CN114605603A CN114605603A CN202210322804.8A CN202210322804A CN114605603A CN 114605603 A CN114605603 A CN 114605603A CN 202210322804 A CN202210322804 A CN 202210322804A CN 114605603 A CN114605603 A CN 114605603A
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- Prior art keywords
- epoxy
- epoxy resin
- modified polyurethane
- composite modified
- parts
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 55
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 55
- 239000004593 Epoxy Substances 0.000 title claims abstract description 52
- 239000004814 polyurethane Substances 0.000 title claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 40
- 239000012745 toughening agent Substances 0.000 title claims abstract description 39
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 229920001971 elastomer Polymers 0.000 claims abstract description 31
- 239000005060 rubber Substances 0.000 claims abstract description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 22
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 239000010703 silicon Substances 0.000 claims abstract description 16
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 150000002009 diols Chemical class 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 claims description 6
- 239000005062 Polybutadiene Substances 0.000 claims description 6
- 125000005442 diisocyanate group Chemical group 0.000 claims description 6
- 229920002857 polybutadiene Polymers 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920003006 Polybutadiene acrylonitrile Polymers 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- -1 small molecule diol Chemical class 0.000 claims description 5
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical group NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical group OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- CQHKDHVZYZUZMJ-UHFFFAOYSA-N [2,2-bis(hydroxymethyl)-3-prop-2-enoyloxypropyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CO)COC(=O)C=C CQHKDHVZYZUZMJ-UHFFFAOYSA-N 0.000 claims description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 150000003384 small molecules Chemical class 0.000 claims description 3
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 claims description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 239000011159 matrix material Substances 0.000 abstract description 6
- 125000003700 epoxy group Chemical group 0.000 abstract description 4
- 238000005191 phase separation Methods 0.000 abstract description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 13
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 7
- 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 6
- 239000000463 material Substances 0.000 description 6
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 4
- 239000004721 Polyphenylene oxide Substances 0.000 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 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 4
- 239000004843 novolac epoxy resin Substances 0.000 description 4
- 229920000570 polyether Polymers 0.000 description 4
- JVVXZOOGOGPDRZ-SLFFLAALSA-N [(1R,4aS,10aR)-1,4a-dimethyl-7-propan-2-yl-2,3,4,9,10,10a-hexahydrophenanthren-1-yl]methanamine Chemical compound NC[C@]1(C)CCC[C@]2(C)C3=CC=C(C(C)C)C=C3CC[C@H]21 JVVXZOOGOGPDRZ-SLFFLAALSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical group 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
- C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
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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)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention belongs to the technical field of macromolecules, and particularly relates to a composite modified polyurethane epoxy toughening agent and an epoxy resin composition composed of the same. The invention organically combines the alcoholic hydroxyl organic silicon and the liquid rubber into the polyurethane chain segment to obtain the composite modified polyurethane epoxy flexibilizer. The toughening agent contains organic silicon and liquid rubber chain segments which are not compatible thermodynamically, and also contains epoxy groups which have good compatibility with epoxy resin; the organosilicon and the liquid rubber chain segment provide flexibility and form micro-phase separation with a matrix, thereby playing a role in effective toughening; the epoxy group and the acrylate group provide compatibility with epoxy resin, and can generate chemical bonding with an epoxy resin matrix in the curing process of the epoxy resin, so that the high strength of the epoxy resin is ensured, and the unification of the high strength and the high toughness of the epoxy resin is realized. The high-strength high-toughness epoxy resin composition with the elongation at break of 30-100% can be prepared by blending, and the formula is wide in application range and strong in designability.
Description
Technical Field
The invention belongs to the technical field of macromolecules, and particularly relates to a composite modified polyurethane epoxy toughening agent and an epoxy resin composition composed of the same.
Background
The epoxy resin has good heat resistance, high strength, strong adhesion to base materials and wide application range. However, epoxy resins have the major disadvantage of being brittle and not impact resistant.
The organosilicon and the liquid rubber are traditional materials for toughening the epoxy resin, but the compatibility of the organosilicon and the liquid rubber with the epoxy resin is poor, macroscopic phase separation is easy to generate, and although a certain toughening effect is achieved, the strength of the epoxy resin material is greatly influenced. Systems that phase separate severely can negatively impact the appearance and clarity of the material, in addition to affecting strength. Polyurethane resins are also one of the materials commonly used to toughen epoxy resins. However, the isocyanate group-terminated polyurethane resin has the defects of high toxicity, short storage period, poor storage stability and the like; and the isocyanate and the amine curing agent react very fast, so that internal stress is easily generated in the curing process, and the negative influence is generated on the strength of the epoxy resin material.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an organosilicon and liquid rubber composite modified polyurethane epoxy toughening agent and a high-strength and high-toughness epoxy resin composition composed of the same. According to the invention, organosilicon and liquid rubber which are commonly used for epoxy resin toughening are organically combined into a polyurethane chain segment through chemical modification, so that the composite modified polyurethane epoxy toughening agent is obtained. The toughening agent contains organic silicon and liquid rubber chain segments which are not compatible with each other in thermodynamics, and the organic silicon and the liquid rubber chain segments can form micro-phase separation with a matrix while providing flexibility to play a role in effective toughening; the toughening agent also contains an epoxy group and an acrylate group which have good compatibility with the epoxy resin, and can generate chemical bonding with an epoxy resin matrix in the curing process of the epoxy resin, so that the high strength of the epoxy resin is ensured, and the unification of the high strength and the high toughness of the epoxy resin is realized. The organosilicon and liquid rubber composite modified polyurethane epoxy toughening agent can be prepared into a high-strength and high-toughness epoxy resin composition with the elongation at break of 30-100% by virtue of different adjustable effects, and has a wide formula application range and strong designability.
The invention relates to a composite modified polyurethane epoxy toughening agent, which is obtained by the following method, and comprises the following specific steps:
(1) mixing macrodiol, micromolecular dihydric alcohol, alcoholic hydroxyl organic silicon, liquid rubber, epoxy resin and diisocyanate, and reacting at 70-95 ℃ for 2-3 hours to obtain a prepolymer;
(2) cooling to 60-85 ℃, adding a capping agent into the prepolymer, and reacting for 2-4 h to obtain a composite modified polyurethane epoxy toughening agent;
by mass ratio, macroglycol: small molecule dihydric alcohol: alcoholic hydroxyl silicone: liquid rubber: epoxy resin: diisocyanate: the end-capping reagent is 30-60:0-5:5-20:5-20:5-20:40-60: 25-50.
The macrodiol is selected from polypropylene glycol or polytetrahydrofuran diol or polyester diol or polycaprolactone diol or polycarbonate diol or a mixture thereof; the molecular weight of the macrodiol is 500-3000.
The small molecule dihydric alcohol is selected from pentaerythritol diacrylate or ethylene glycol or butanediol or neopentyl glycol or a mixture thereof.
The alcoholic hydroxyl organic silicon is at least one of alcoholic hydroxyl organic silicon with the molecular weight of 1000-4000; the liquid rubber is at least one of liquid polybutadiene (the hydroxyl content is 0.5-1.4 mmol/g) and liquid polybutadiene acrylonitrile (the hydroxyl content is 0.5-0.7 mmol/g, and the acrylonitrile content is 5-20%).
The epoxy resin is an epoxy compound having an epoxy equivalent of 140-: such as at least one of bisphenol A type epoxy resins (e.g., E-20, E-44, Dow DER331, south Asia NPEL-128S), bisphenol F type epoxy resins (e.g., Dow DER354, south Asia NPEF-170), novolac epoxy resins (e.g., Dow DER438, F-51), epoxy diluents (e.g., Epodil 746, Epodil 750);
the diisocyanate is selected from isophorone diisocyanate or hexamethylene diisocyanate or 4,4 '-dicyclohexylmethane diisocyanate or toluene diisocyanate or diphenylmethane-4, 4' -diisocyanate or a mixture thereof.
The end capping agent is selected from hydroxyethyl acrylate, hydroxypropyl acrylate, caprolactone acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate or their mixture.
The epoxy resin composition comprises the following components in parts by weight:
100 parts of epoxy resin;
30-100 parts of a composite modified polyurethane epoxy toughening agent;
25-50 parts of curing agent.
The epoxy resin is an epoxy compound having an epoxy equivalent of 140-: such as at least one of bisphenol A type epoxy resins (e.g., E-20, E-44, Dow DER331, south Asia NPEL-128S), bisphenol F type epoxy resins (e.g., Dow DER354, south Asia NPEF-170), novolac epoxy resins (e.g., Dow DER438, F-51), and epoxy diluents (e.g., Epodil 746, Epodil 750).
The curing agent is selected from diethylenetriamine or isophorone diamine or polyether amine D230 or aminoethyl piperazine or a mixture thereof.
Compared with the prior art, the invention has the following beneficial effects:
the molecular structure of the organosilicon and liquid rubber composite modified polyurethane epoxy toughening agent contains organosilicon and liquid rubber chain segments, can provide flexibility and form micro-phase separation with a matrix, and plays a role in effectively toughening
Epoxy groups and acrylate groups in the molecular structure of the organosilicon and liquid rubber composite modified polyurethane epoxy toughening agent can generate chemical bonding with an epoxy resin matrix through an amine curing agent in the curing process of the epoxy resin, so that the high strength of the epoxy resin is ensured, and the unification of the high strength and the high toughness of the epoxy resin is realized.
The organosilicon and liquid rubber composite modified polyurethane epoxy toughening agent can be prepared into a high-strength and high-toughness epoxy resin composition with the elongation at break of 30-100% by virtue of different adjustable effects, and has a wide formula application range and strong designability.
Detailed Description
Example 1
A composite modified polyurethane epoxy toughening agent is obtained by the following method, and comprises the following specific steps:
a. mixing 45 parts of polypropylene glycol (molecular weight 1000), 10 parts of polycaprolactone diol (molecular weight 2000), 1 part of ethylene glycol, 4 parts of neopentyl glycol, 5 parts of liquid polybutadiene acrylonitrile (hydroxyl content is 0.6mmol/g, acrylonitrile content is 10%), 10 parts of liquid polybutadiene (hydroxyl content is 1.0mmol/g), 7.5 parts of NEPL-128S, 3 parts of E-44 and 55 parts of hexamethylene diisocyanate, and reacting at 85 ℃ for 2 hours to obtain a prepolymer;
b. cooling to 75 ℃, adding 35 parts of hydroxypropyl acrylate into the prepolymer, and reacting for 2 hours to obtain the organic silicon and liquid rubber composite modified polyurethane epoxy toughening agent;
the epoxy resin composition is characterized by comprising the following components in parts by weight:
bisphenol A epoxy resin E-2065 parts;
phenol epoxy DER 43830 weight parts;
epoxy diluent Epodil 7505 parts
40 parts of the organosilicon and liquid rubber composite modified polyurethane epoxy toughening agent;
25 parts of aminoethyl piperazine and 2305 parts of polyether amine D;
the curing conditions were 25 ℃ for 7 days and the test results are summarized in table 1.
Example 2
A composite modified polyurethane epoxy toughening agent is obtained by the following method, and the concrete steps are as follows:
a. mixing 30 parts of polycarbonate diol (molecular weight 1000), 30 parts of polypropylene glycol (molecular weight 3000), 5 parts of alcoholic hydroxyl organic silicon (molecular weight 1000), 20 parts of liquid polybutadiene (hydroxyl content is 0.8mmol/g), 5 parts of E-44, 60 parts of 4,4' -dicyclohexyl methane diisocyanate, and reacting at 95 ℃ for 3 hours to obtain a prepolymer;
b. cooling to 85 ℃, and adding 35 parts of pentaerythritol triacrylate into the prepolymer for 4 hours; obtaining the organosilicon and liquid rubber composite modified polyurethane epoxy toughening agent;
the epoxy resin composition is characterized by comprising the following components in parts by weight:
DER 33185 parts of bisphenol A epoxy resin;
15 parts of bisphenol A epoxy resin NPEL-128S;
30 parts of the organosilicon and liquid rubber composite modified polyurethane epoxy toughening agent;
23045 parts of polyether amine D and 5 parts of diethylenetriamine;
the curing conditions were 25 ℃ for 7 days and the test results are summarized in Table 2.
Example 3
A composite modified polyurethane epoxy toughening agent is obtained by the following method, and comprises the following specific steps:
a. mixing 25 parts of polyester diol (molecular weight 3000), 25 parts of polytetrahydrofuran diol (molecular weight 1000), 4 parts of butanediol, 8 parts of alcoholic hydroxyl organic silicon (molecular weight 1700), 10 parts of liquid polybutadiene (hydroxyl content is 1.4mmol/g), 5 parts of F-51, 5 parts of E-20 and 50 parts of toluene diisocyanate, and reacting at 70 ℃ for 3 hours to obtain a prepolymer;
b. cooling to 60 ℃, adding 50 parts of dipentaerythritol tetraacrylate into the prepolymer, and reacting for 4 hours to obtain the organic silicon and liquid rubber composite modified polyurethane epoxy toughening agent;
the epoxy resin composition is characterized by comprising the following components in parts by weight:
novolac epoxy resin DER 43860 parts;
DER 35440 parts of bisphenol F epoxy resin;
74610 parts of epoxy diluent Epodil
100 parts of the organosilicon and liquid rubber composite modified polyurethane epoxy toughening agent;
23050 parts of polyether amine D;
the curing conditions were 25 ℃ for 7 days and the test results are summarized in Table 3.
Example 4
A composite modified polyurethane epoxy toughening agent is obtained by the following method, and comprises the following specific steps:
a. mixing 40 parts of polycaprolactone diol (molecular weight 2000), 10 parts of polypropylene glycol (molecular weight 500), 5 parts of pentaerythritol diacrylate, 10 parts of alcoholic hydroxyl organic silicon (molecular weight 4000), 5 parts of liquid polybutadiene acrylonitrile (hydroxyl content is 0.7mmol/g, acrylonitrile content is 20%), 7.5 parts of liquid polybutadiene (hydroxyl content is 0.5mmol/g), 7.5 parts of DER331, 8 parts of F-51, 45 parts of diphenylmethane-4, 4' -diisocyanate and 20 parts of toluene diisocyanate, and reacting at 85 ℃ for 2 hours to obtain a prepolymer;
b. cooling to 75 ℃, adding 45 parts of acrylic caprolactone into the prepolymer, and reacting for 3 hours to obtain the organic silicon and liquid rubber composite modified polyurethane epoxy toughening agent;
the epoxy resin composition is characterized by comprising the following components in parts by weight:
bisphenol F epoxy resin NPEF-17030 parts;
DER 35410 parts of bisphenol F epoxy resin;
novolac epoxy resin F-5150 parts;
epodil 75010 parts of epoxy diluent
50 parts of the organosilicon and liquid rubber composite modified polyurethane epoxy toughening agent;
28 parts of isophorone diamine and 8 parts of aminoethyl piperazine;
the curing conditions were 25 ℃ for 7 days and the test results are summarized in Table 4.
Example 5
A composite modified polyurethane epoxy toughening agent is obtained by the following method, and the concrete steps are as follows:
a. mixing 20 parts of polytetrahydrofuran diol (molecular weight is 1000), 10 parts of polycaprolactone diol (molecular weight is 1000), 2 parts of neopentyl glycol, 20 parts of alcoholic hydroxyl organic silicon (molecular weight is 2000), 5 parts of liquid polybutadiene acrylonitrile (hydroxyl content is 0.5mmol/g, acrylonitrile content is 5%), 10 parts of E-20, 5 parts of bisphenol F epoxy resin NPEF-170, 5 parts of NPEL-128S and 40 parts of isophorone diisocyanate, and reacting at 90 ℃ for 2 hours to obtain a prepolymer;
b. cooling to 75 ℃, adding 25 parts of hydroxyethyl acrylate into the prepolymer, and reacting for 2 hours to obtain an organic silicon and liquid rubber composite modified polyurethane epoxy flexibilizer;
the epoxy resin composition is characterized by comprising the following components in parts by weight:
bisphenol F epoxy resin NPEF-170100 parts;
35 parts of the organosilicon and liquid rubber composite modified polyurethane epoxy toughening agent;
15 parts of diethylenetriamine and 10 parts of isophorone diamine;
the curing conditions were 25 ℃ for 7 days and the test results are summarized in Table 5.
TABLE 1 cured epoxy resin Strength and elongation at Break
Claims (10)
1. The composite modified polyurethane epoxy toughening agent is characterized by being prepared from organosilicon and liquid rubber by the following steps:
(1) mixing macrodiol, micromolecular dihydric alcohol, alcoholic hydroxyl organic silicon, liquid rubber, epoxy resin and diisocyanate, and reacting at 70-95 ℃ for 2-3 hours to obtain a prepolymer;
(2) cooling to 60-85 ℃, adding a capping agent into the prepolymer, and reacting for 2-4 h to obtain a composite modified polyurethane epoxy toughening agent;
by mass ratio, macroglycol: small molecule dihydric alcohol: alcoholic hydroxyl silicone: liquid rubber: epoxy resin: diisocyanate: the end-capping reagent is 30-60:0-5:5-20:5-20:5-20:40-60: 25-50.
2. The composite modified polyurethane epoxy toughener of claim 1, wherein the macrodiol is selected from polypropylene glycol or polytetrahydrofuran diol or polyester diol or polycaprolactone diol or polycarbonate diol or a mixture thereof; the molecular weight of the macrodiol is 500-3000.
3. The composite modified polyurethane epoxy toughener as defined in claim 1, wherein the small molecule diol is selected from pentaerythritol diacrylate or ethylene glycol or butylene glycol or neopentyl glycol or a mixture thereof.
4. The composite modified polyurethane epoxy toughening agent according to claim 1, wherein the alcoholic hydroxyl silicone is at least one of alcoholic hydroxyl silicones with molecular weight of 1000-4000; the liquid rubber is liquid polybutadiene or liquid polybutadiene acrylonitrile or a mixture thereof.
5. The composite modified polyurethane epoxy toughening agent as claimed in claim 1, wherein the epoxy resin is an epoxy compound having an epoxy equivalent of 140-2000.
6. The composite modified polyurethane epoxy toughening agent of claim 1, wherein the diisocyanate is selected from isophorone diisocyanate or hexamethylene diisocyanate or 4,4 '-dicyclohexylmethane diisocyanate or toluene diisocyanate or diphenylmethane-4, 4' -diisocyanate or a mixture thereof.
7. The composite modified polyurethane epoxy toughening agent of claim 1, wherein the capping agent is selected from hydroxyethyl acrylate, hydroxypropyl acrylate, caprolactone acrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, or a mixture thereof.
8. The epoxy resin composition is characterized by comprising the following components in parts by weight:
100 parts of epoxy resin;
30-100 parts of a composite modified polyurethane epoxy toughening agent;
25-50 parts of curing agent.
9. The epoxy resin composition as claimed in claim 8, wherein the epoxy resin is an epoxy compound having an epoxy equivalent of 140-2000.
10. The epoxy resin composition of claim 8, wherein the curing agent is selected from diethylenetriamine or isophoronediamine or polyetheramine D230 or aminoethylpiperazine or mixtures thereof.
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