CN112646452B - Water-based hyperbranched epoxy resin and preparation method thereof - Google Patents
Water-based hyperbranched epoxy resin and preparation method thereof Download PDFInfo
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- CN112646452B CN112646452B CN202011505180.0A CN202011505180A CN112646452B CN 112646452 B CN112646452 B CN 112646452B CN 202011505180 A CN202011505180 A CN 202011505180A CN 112646452 B CN112646452 B CN 112646452B
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- epoxy resin
- hyperbranched epoxy
- acid
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 40
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 33
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 239000002086 nanomaterial Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 235000011037 adipic acid Nutrition 0.000 claims description 5
- 239000001361 adipic acid Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical group Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 4
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- LDMOEFOXLIZJOW-UHFFFAOYSA-N 1-dodecanesulfonic acid Chemical compound CCCCCCCCCCCCS(O)(=O)=O LDMOEFOXLIZJOW-UHFFFAOYSA-N 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- SYEWHONLFGZGLK-UHFFFAOYSA-N 2-[1,3-bis(oxiran-2-ylmethoxy)propan-2-yloxymethyl]oxirane Chemical compound C1OC1COCC(OCC1OC1)COCC1CO1 SYEWHONLFGZGLK-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- YGUFXEJWPRRAEK-UHFFFAOYSA-N dodecyl(triethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OCC)(OCC)OCC YGUFXEJWPRRAEK-UHFFFAOYSA-N 0.000 claims description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 2
- KEMQGTRYUADPNZ-UHFFFAOYSA-N heptadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)=O KEMQGTRYUADPNZ-UHFFFAOYSA-N 0.000 claims description 2
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- BNCXNUWGWUZTCN-UHFFFAOYSA-N trichloro(dodecyl)silane Chemical compound CCCCCCCCCCCC[Si](Cl)(Cl)Cl BNCXNUWGWUZTCN-UHFFFAOYSA-N 0.000 claims description 2
- LFXJGGDONSCPOF-UHFFFAOYSA-N trichloro(hexyl)silane Chemical compound CCCCCC[Si](Cl)(Cl)Cl LFXJGGDONSCPOF-UHFFFAOYSA-N 0.000 claims description 2
- RCHUVCPBWWSUMC-UHFFFAOYSA-N trichloro(octyl)silane Chemical compound CCCCCCCC[Si](Cl)(Cl)Cl RCHUVCPBWWSUMC-UHFFFAOYSA-N 0.000 claims description 2
- SZHOJFHSIKHZHA-UHFFFAOYSA-N tridecanoic acid Chemical compound CCCCCCCCCCCCC(O)=O SZHOJFHSIKHZHA-UHFFFAOYSA-N 0.000 claims description 2
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 claims description 2
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000404 tripotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019798 tripotassium phosphate Nutrition 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 239000003595 mist Substances 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229910001631 strontium chloride Inorganic materials 0.000 description 2
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 2
- 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 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- OEYOHULQRFXULB-UHFFFAOYSA-N arsenic trichloride Chemical compound Cl[As](Cl)Cl OEYOHULQRFXULB-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 229910001627 beryllium chloride Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a water-based hyperbranched epoxy resin and a preparation method thereof, wherein the water-based hyperbranched epoxy resin comprises the following components in parts by weight: 40-60 parts of hyperbranched epoxy resin; 5-10 parts of nano material dispersion liquid and 40-60 parts of deionized water. The waterborne hyperbranched epoxy resin has excellent adhesive force, water resistance and salt mist resistance.
Description
Technical Field
The invention belongs to the field of water-based paint, and particularly relates to water-based hyperbranched epoxy resin and a preparation method thereof.
Background
The hyperbranched resin structure is a densely-distributed terminal functional group with high reaction activity, and the crosslinking density is extremely high after curing, so the hyperbranched resin structure is widely applied to the fields of adhesives, coatings, repair materials, composite materials and the like. The hyperbranched resin is used for preparing the anticorrosive paint, and a large amount of organic solvent is often needed to be added to reduce the viscosity so as to obtain the workability, so that the ultrahigh VOC emission is caused and the environment is harmful. At present, no report about aqueous hyperbranched resin exists in the industry.
Disclosure of Invention
The invention aims to solve the problems and provides a waterborne hyperbranched epoxy resin and a preparation method thereof, which have excellent adhesive force, water resistance and salt fog resistance.
The purpose of the invention is realized as follows:
the invention relates to a waterborne hyperbranched epoxy resin which comprises the following components in parts by weight:
40-60 parts of hyperbranched epoxy resin;
5-10 parts of a nano material dispersion liquid;
40-60 parts of deionized water;
the hyperbranched epoxy resin comprises the following components in parts by weight: 15-35 parts of dibasic acid, 65-85 parts of trifunctional triglycidyl ether and 0.03-0.08 part of catalyst are reacted for 3-6 hours at 140-160 ℃ to synthesize the compound, wherein the catalyst is selected from one of N, N-dimethylbenzylamine, triphenylphosphine and tetrabutylammonium bromide;
the nano dispersion liquid comprises the following components in parts by weight:
the main element precursor is selected from at least one of sodium chloride, calcium chloride, magnesium chloride, titanium tetrachloride, aluminum trichloride, ferrous chloride, copper chloride, beryllium chloride, strontium chloride, barium chloride, boron chloride, germanium chloride, tin chloride, lead chloride, arsenic chloride, strontium chloride, nickel chloride, vanadium chloride and gallium chloride;
the doping element precursor is selected from at least one of sodium dihydrogen phosphate, tripotassium phosphate, potassium nitrate, sodium sulfate and potassium sulfate;
the lipophilic donor is at least one selected from n-hexyltrichlorosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrichlorosilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecylcarboxylic acid, hexadecylcarboxylic acid and dodecylsulfonic acid.
The pH value of the nano dispersion liquid in the waterborne hyperbranched epoxy resin is 2-5, and/or the solid content is 15% -25%, and/or the viscosity value is controlled to be 10-25s when the nano dispersion liquid is coated in a cup of-4 at the temperature of 25 ℃.
The particle size of the nano material in the nano dispersion liquid in the aqueous hyperbranched epoxy resin is 15nm-200 nm.
The dibasic acid in the aqueous hyperbranched epoxy resin is one or any combination of oxalic acid, adipic acid, sebacic acid, terephthalic acid, phthalic acid and isophthalic acid.
The tri-functionality triglycidyl ether in the waterborne hyperbranched epoxy resin is one or any combination of trimethylolpropane triglycidyl ether and glycerol triglycidyl ether.
The preparation method of the nano dispersion liquid in the waterborne hyperbranched epoxy resin comprises the following steps:
(1) hydrolysis:
sequentially putting 20-30 parts of deionized water, 1-5 parts of alkali neutralizing agent and 4-7 parts of lower alcohol into a reaction kettle, and starting stirring; adding the rest deionized water and the rest lower alcohol into a head tank, stirring at the speed of 300-800r/min, sequentially adding the main element precursor, the doping element precursor and the lipophilic donor at a low speed, and stirring to form a uniform solution; dropwise adding the solution in the elevated tank into the reaction kettle at a constant speed for 2-5h, continuously reacting for 1-5h after dropwise adding, heating to 80-120 ℃, reacting for 2-8h, and cooling to room temperature;
(2) centrifugal separation:
introducing the liquid in the reactor into a centrifuge for centrifugal separation at the speed of 3000-5000r/min for 30-60 min;
(3) and (3) suction filtration:
and (3) carrying out suction filtration on the liquid after centrifugal separation under the vacuum pressure of-0.4 Mpa to-0.9 Mpa, and filtering out solid matters to obtain clear liquid, namely the nano dispersion liquid for emulsion polymerization.
The alkali neutralizing agent in the aqueous hyperbranched epoxy resin is at least one selected from potassium hydroxide, lithium hydroxide, ammonia water, monoethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine and triethylamine.
The lower alcohol in the aqueous hyperbranched epoxy resin is at least one selected from methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol and pentanol
The preparation method of the waterborne hyperbranched epoxy resin comprises the following steps:
(1) putting the hyperbranched epoxy resin into a dispersion kettle, heating to 60-100 ℃, and starting high-speed dispersion;
(2) dripping nano material dispersion liquid, and dispersing at high speed for 1-2 h;
(3) adding deionized water, stirring, and filtering.
The invention adopts a nano material modification method to prepare the waterborne hyperbranched epoxy resin, the components do not contain an emulsifier, and a high content of hydrophilic groups are not introduced, the components are uniformly distributed on the interface of water-polymer colloidal particles by utilizing the special water-oil balance function of the nano material, in addition, the used nano dispersion liquid can be self-cured, the paint film is cured after being dried to form water-insoluble sediments which are uniformly distributed in the paint film, and the water resistance, the chemical medium resistance and the salt fog resistance of the paint film can be improved.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
the hyperbranched epoxy resin comprises the following components in parts by weight:
22 parts of adipic acid (industrial grade);
77.5 parts of trimethylolpropane triglycidyl ether (industrial grade);
0.5 part of N, N-dimethylbenzylamine (industrial grade);
in a four-necked flask were charged 77.5 parts of trimethylolpropane triglycidyl ether, 22 parts of adipic acid, and 0.5 part of N, N-dimethylbenzylamine. And (4) starting condensed water, heating to 150 ℃, reacting for 4 hours, then cooling to room temperature, and filtering for later use.
The nano dispersion liquid comprises the following components in parts by weight:
adding 26 parts of deionized water and 2 parts of ethanol into a head tank, then slowly adding 28 parts of titanium tetrachloride, 1.2 parts of sodium dihydrogen phosphate and 4.8 parts of dodecyl trimethoxy silane in turn, and uniformly stirring for later use. 30 parts of deionized water, 5 parts of ethanol and 3 parts of ammonia water are added into a reaction kettle and stirred at the speed of 500 r/min. And (5) dropwise adding the solution in the head tank, finishing dropwise adding for 3 hours, and reacting for 2 hours after dropwise adding. Then the temperature is increased to 90 ℃, the reaction is carried out for 3 hours, and then the temperature is reduced to the room temperature.
Centrifuging the reaction solution for 45min at 4000r/min by using a centrifuge, then performing suction filtration under the vacuum pressure of-0.4 Mpa to-0.9 Mpa, and filtering out solids to obtain clear liquid, namely the nano dispersion liquid of the embodiment 1. The dispersion had a solids content of 20%, a pH of 3.2, an average particle size of 35nm and a viscosity of 12s at 25 ℃ over-4 cups.
The waterborne hyperbranched epoxy resin comprises the following components in parts by weight:
48 parts of hyperbranched epoxy resin;
8 parts of a nano material dispersion liquid;
44 parts of deionized water;
the preparation process comprises the following steps: putting 48 parts of hyperbranched epoxy resin into a dispersion kettle, heating to 80 ℃, and starting high-speed dispersion; 8 parts of nano material dispersion liquid is dripped, and high-speed dispersion is carried out for 1 hour; and finally, adding 44 parts of deionized water, uniformly stirring and filtering.
Example 2:
the hyperbranched epoxy resin comprises the following components in parts by weight:
28 parts of sebacic acid (industrial grade);
71.6 parts of trimethylolpropane triglycidyl ether (industrial grade);
0.4 part of N, N-dimethylbenzylamine (industrial grade);
71.6 parts of trimethylolpropane triglycidyl ether, 28 parts of adipic acid and 0.4 part of N, N-dimethylbenzylamine are added into a four-neck flask, condensed water is started, the temperature is raised to 150 ℃, the reaction is carried out for 4 hours, then the temperature is reduced to room temperature, and the mixture is filtered for later use.
The nano dispersion liquid comprises the following components in parts by weight:
adding 25 parts of deionized water and 3 parts of isopropanol into a head tank, then slowly adding 22 parts of titanium tetrachloride, 10 parts of aluminum chloride, 2.5 parts of sodium dihydrogen phosphate and 7 parts of dodecyl trimethoxy silane in sequence, and uniformly stirring for later use. 20 parts of deionized water, 6 parts of isopropanol and 4.5 parts of N, N-dimethylethanolamine are added into a reaction kettle, and stirring is started. And dropwise adding the solution in the head tank, finishing dropwise adding for 2.5 hours, and reacting for 3 hours after dropwise adding. Then the temperature is increased to 80 ℃, the reaction is carried out for 4 hours, and then the temperature is reduced to the room temperature. The reaction solution was centrifuged by a centrifuge, and then filtered to remove the solid, to obtain a clear solution, i.e., the nanodispersion of example 2, having a solid content of 23%, a pH of 3, an average particle diameter of 60nm, and a viscosity of 13s in 4 cups at 25 ℃.
The aqueous hyperbranched epoxy resin comprises the following components in parts by weight:
50 parts of hyperbranched epoxy resin;
5 parts of a nano material dispersion liquid;
45 parts of deionized water;
the preparation process comprises the following steps: putting 50 parts of hyperbranched epoxy resin into a dispersion kettle, heating to 80 ℃, and starting high-speed dispersion; 5 parts of nano material dispersion liquid is dripped, and high-speed dispersion is carried out for 1 hour; and finally, adding 45 parts of deionized water, uniformly stirring and filtering.
The properties of the aqueous hyperbranched epoxy emulsions of examples 1 and 2, together with the curing agent isophorone diamine, compared to a commercially available epoxy emulsion Epikote 6520 are shown in Table 1:
TABLE 1 results of Performance testing of examples 1-2 and Epikote 6520
| Item | Example 1 | Example 2 | Epikote 6520 |
| Hardness of | 3H | 3H | 2H |
| Water resistance (50 ℃ C.) | ≥500h | ≥500 | ≤500h |
| Resistance to salt fog | ≥500h | ≥720 | ≤480h |
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, therefore all equivalent technical solutions should also fall into the scope of the present invention, and should be defined by the claims.
Claims (6)
1. The waterborne hyperbranched epoxy resin is characterized by comprising the following components in parts by weight:
40-60 parts of hyperbranched epoxy resin;
5-10 parts of a nano material dispersion liquid;
40-60 parts of deionized water;
the hyperbranched epoxy resin comprises the following components in parts by weight: 15-35 parts of dibasic acid, 65-85 parts of trifunctional triglycidyl ether and 0.03-0.08 part of catalyst are reacted for 3-6 hours at 140-160 ℃ to synthesize the compound, wherein the catalyst is selected from one of N, N-dimethylbenzylamine, triphenylphosphine and tetrabutylammonium bromide;
the nano dispersion liquid comprises the following components in parts by weight:
25-35 parts of a main element precursor;
1-4 parts of a doping element precursor;
3-8 parts of a lipophilic donor;
1-5 parts of an alkali neutralizing agent;
5-10 parts of lower alcohol;
50-85 parts of deionized water;
the main element precursor is selected from titanium tetrachloride, or titanium tetrachloride and aluminum trichloride;
the doping element precursor is selected from at least one of sodium dihydrogen phosphate, tripotassium phosphate, potassium nitrate, sodium sulfate and potassium sulfate;
the oleophylic donor is selected from at least one of n-hexyltrichlorosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrichlorosilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecylcarboxylic acid, hexadecylcarboxylic acid and dodecylsulfonic acid;
the preparation method of the nano dispersion liquid comprises the following steps:
(1) hydrolysis:
sequentially putting 20-30 parts of the deionized water, 1-5 parts of the alkali neutralizing agent and 4-7 parts of the lower alcohol into a reaction kettle, and starting stirring; adding the rest deionized water and the rest lower alcohol into a head tank, stirring at the speed of 300-800r/min, sequentially and slowly adding the main element precursor, the doped element precursor and the lipophilic donor, and stirring to form a uniform solution; dropwise adding the solution in the elevated tank into the reaction kettle at a constant speed for 2-5h, continuously reacting for 1-5h after dropwise adding is completed, heating to 80-120 ℃, reacting for 2-8h, and cooling to room temperature;
(2) centrifugal separation:
introducing the liquid in the reactor into a centrifuge for centrifugal separation at the speed of 3000-5000r/min for 30-60 min;
(3) and (3) suction filtration:
carrying out suction filtration on the liquid after centrifugal separation under the vacuum pressure of-0.4 Mpa to-0.9 Mpa, and filtering out solid matters to obtain clear liquid, namely the nano dispersion liquid for emulsion polymerization;
the pH value of the nano dispersion liquid is 2-5, and/or the solid content is 15% -25%, and/or the viscosity value is controlled to be 10-25s when the nano dispersion liquid is coated in a 4-cup mode at 25 ℃;
the particle size of the nano material in the nano dispersion liquid is 15nm-200 nm;
the preparation method of the aqueous hyperbranched epoxy resin comprises the following steps:
(1) putting the hyperbranched epoxy resin into a dispersion kettle, heating to 60-100 ℃, and starting high-speed dispersion;
(2) dropwise adding the nano material dispersion liquid, and dispersing at high speed for 1-2 h;
(3) adding deionized water, stirring, and filtering.
2. The aqueous hyperbranched epoxy resin of claim 1, wherein the dibasic acid is one or any combination of oxalic acid, adipic acid, sebacic acid, terephthalic acid, phthalic acid, isophthalic acid.
3. The aqueous hyperbranched epoxy resin of claim 1, wherein the trifunctional triglycidyl ether is one or any combination of trimethylolpropane triglycidyl ether and glycerol triglycidyl ether.
4. The aqueous hyperbranched epoxy resin of claim 1, wherein the alkali neutralizing agent is at least one selected from the group consisting of potassium hydroxide, lithium hydroxide, ammonia, monoethanolamine, diethanolamine, triethanolamine, N-dimethylethanolamine, and triethylamine.
5. The aqueous hyperbranched epoxy resin of claim 1, wherein the lower alcohol is selected from at least one of methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, pentanol
6. The method for preparing the aqueous hyperbranched epoxy resin according to claim 1, comprising the steps of:
(1) putting the hyperbranched epoxy resin into a dispersion kettle, heating to 60-100 ℃, and starting high-speed dispersion;
(2) dropwise adding the nano material dispersion liquid, and dispersing at high speed for 1-2 h;
(3) adding deionized water, stirring, and filtering.
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Denomination of invention: A water-based hyperbranched epoxy resin and its preparation method Granted publication date: 20220909 Pledgee: Shanghai Rural Commercial Bank Co.,Ltd. Jinshan sub branch Pledgor: SHANGHAI MORFANT NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2024310000172 |