CN110078893A - Preparation method of ultraviolet-cured hyperbranched abienol polyurethane acrylate resin - Google Patents
Preparation method of ultraviolet-cured hyperbranched abienol polyurethane acrylate resin Download PDFInfo
- Publication number
- CN110078893A CN110078893A CN201910443378.1A CN201910443378A CN110078893A CN 110078893 A CN110078893 A CN 110078893A CN 201910443378 A CN201910443378 A CN 201910443378A CN 110078893 A CN110078893 A CN 110078893A
- Authority
- CN
- China
- Prior art keywords
- abienol
- polyurethane
- added
- reaction
- gross mass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- ZAZVCYBIABTSJR-UHFFFAOYSA-N (+)-Abienol Natural products CC1(C)CCCC2(C)C(CC=C(C=C)C)C(C)(O)CCC21 ZAZVCYBIABTSJR-UHFFFAOYSA-N 0.000 title claims abstract description 117
- ZAZVCYBIABTSJR-KOQQBVACSA-N Abienol Chemical compound CC1(C)CCC[C@]2(C)C(CC=C(C=C)C)[C@](C)(O)CC[C@H]21 ZAZVCYBIABTSJR-KOQQBVACSA-N 0.000 title claims abstract description 117
- KKTBXRFTXPLJNN-UHFFFAOYSA-N ent-labd-8beta-ol-14-ene Natural products CC(CCC1C(C)(O)CCC2C(C)(C)CCCC12C)C=C KKTBXRFTXPLJNN-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 239000004814 polyurethane Substances 0.000 title claims abstract description 75
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 29
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 29
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 29
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 11
- -1 alcohol amine Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 116
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 47
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 45
- 235000019441 ethanol Nutrition 0.000 claims description 45
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 41
- 229920000728 polyester Polymers 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 37
- 238000010438 heat treatment Methods 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 33
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 32
- 229940043237 diethanolamine Drugs 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 239000002253 acid Substances 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000012024 dehydrating agents Substances 0.000 claims description 24
- 238000009413 insulation Methods 0.000 claims description 24
- 238000010992 reflux Methods 0.000 claims description 24
- 238000011049 filling Methods 0.000 claims description 19
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 16
- 150000001298 alcohols Chemical class 0.000 claims description 16
- 150000001263 acyl chlorides Chemical class 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000003786 synthesis reaction Methods 0.000 claims description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical class OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 claims description 8
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 7
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical group CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 2
- 239000005457 ice water Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 3
- 150000001412 amines Chemical class 0.000 claims 2
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 claims 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims 1
- 235000011613 Pinus brutia Nutrition 0.000 claims 1
- 241000018646 Pinus brutia Species 0.000 claims 1
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 claims 1
- 229920005989 resin Polymers 0.000 abstract description 12
- 239000011347 resin Substances 0.000 abstract description 12
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000001070 adhesive effect Effects 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 33
- 239000012975 dibutyltin dilaurate Substances 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 21
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 20
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 20
- 238000005070 sampling Methods 0.000 description 20
- 239000005058 Isophorone diisocyanate Substances 0.000 description 19
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- 229920000180 alkyd Polymers 0.000 description 15
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 10
- 235000017557 sodium bicarbonate Nutrition 0.000 description 10
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 8
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000005639 Lauric acid Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WBYWAXJHAXSJNI-VOTSOKGWSA-M .beta-Phenylacrylic acid Natural products [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- DTTDXHDYTWQDCS-UHFFFAOYSA-N 1-phenylcyclohexan-1-ol Chemical compound C=1C=CC=CC=1C1(O)CCCCC1 DTTDXHDYTWQDCS-UHFFFAOYSA-N 0.000 description 1
- LJRSZGKUUZPHEB-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxypropoxy)propoxy]propyl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COC(C)COC(=O)C=C LJRSZGKUUZPHEB-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- WBYWAXJHAXSJNI-SREVYHEPSA-N Cinnamic acid Chemical compound OC(=O)\C=C/C1=CC=CC=C1 WBYWAXJHAXSJNI-SREVYHEPSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000555268 Dendroides Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 235000019082 Osmanthus Nutrition 0.000 description 1
- 241000333181 Osmanthus Species 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 229930016911 cinnamic acid Natural products 0.000 description 1
- 235000013985 cinnamic acid Nutrition 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- WBYWAXJHAXSJNI-UHFFFAOYSA-N methyl p-hydroxycinnamate Natural products OC(=O)C=CC1=CC=CC=C1 WBYWAXJHAXSJNI-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000004672 propanoic acids Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009967 tasteless effect Effects 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
- 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
-
- 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
- C08G18/4286—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones prepared from a combination of hydroxycarboxylic acids and/or lactones with polycarboxylic acids or ester forming derivatives thereof and polyhydroxy 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
- 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
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
-
- 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
- C08G18/83—Chemically modified polymers
- C08G18/831—Chemically modified polymers by oxygen-containing compounds inclusive of carbonic acid halogenides, carboxylic acid halogenides and epoxy halides
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
A preparation method of ultraviolet light curing hyperbranched rosin alcohol polyurethane acrylate resin comprises the steps of synthesizing a nuclear-added hyperbranched rosin alcohol polyurethane containing 12 terminal hydroxyl groups by using saturated rosin trihydric alcohol synthesized by using renewable rosin as a raw material, and using alcohol amine and diisocyanate as raw materials, and introducing double bonds by adding raw materials such as acryloyl chloride and the like to prepare the hyperbranched rosin alcohol polyurethane acrylate resin. The hardness and strength of the resin are improved because the resin obtained has a rigid condensed ring structure. Meanwhile, the hyperbranched abienol urethane acrylate can improve the impact resistance and weather resistance of a coating film and has higher boiling resistance and adhesive force to a base material.
Description
Technical field:
The invention belongs to light-cured resin fields, and in particular to a kind of hyperbranched abienol polyurethane propylene of ultraviolet light solidification
The preparation method of acid ester resin.
Background technique:
It is the developing direction for complying fully with " 5E principle " that ultraviolet light, which solidifies, i.e., economy, efficiency, ecology, the energy, be applicable in
Property.Main component, that is, prepolymer as used in system generally has viscosity higher, for convenient for constructing, improving curing membrane performance,
It needs that reactive diluent is added to adjust viscosity before use, changes rheological characteristic.Although the volatility of these reactive diluents is very low,
It is still to have certain damage to environmental and human health impacts, and during curing of coating, be difficult 100% and be converted into painting
Film, the permeability of residual activity diluent, it is possible to influence the sanitary safety index and Long-Term Properties of product.Therefore,
The content that reactive diluent is reduced in ultraviolet-curing paint formula has become a main trend.
Solving this problem most efficient method is prepolymer big using molecular weight, that viscosity is low, functional group content is high, and
Highly branched polymer meets these requirements, is divided into two major classes: dendritic macromole and dissaving polymer.Although over-expense
The structure of fluidized polymer does not have that dendritic macromole is regular, and relative molecular mass distribution is generally also wider, but its preparation side
Method is fairly simple, both can be obtained without purifying or only need to simply purify.Meanwhile dissaving polymer have divide greatly with dendroid
Structure as subclass and performance, such as good hydrodynamic performance, easily film forming, low-viscosity, more terminal functionalities and strand without
The advantages that entanglement.UV solidification super branched polyurethane acrylic resin combines UV curing technology, dissaving polymer and poly- ammonia
The advantages of ester resin etc., has curing rate fast, water resistance, thermal stability, is easy to the excellent performances such as other materials are miscible.
Rosin trihydroxylic alcohol is a kind of biomass resource of natural reproducible of downstream derivative object of rosin, non-toxic and tasteless, and valence
Lattice are cheap, containing the hexa-atomic condensed ring of rigidity in its structure, are applied in resin, the hardness of energy reinforced resin, are main former with it
Expect synthesis of super branched urethane acrylate, both met current coating industry development trend, it is abundant can also to efficiently use China
Rosin resource, widen it using field, the deep processing research of China's rosin resource be of great significance to.
Summary of the invention:
Goal of the invention: for the deficiency of currently available technology, provide a kind of ultraviolet light solidification hyperbranched abienol polyurethane
The preparation method of acrylate, using reproducible saturation rosin trihydroxylic alcohol as core, hydramine and diisocyanate are raw material,
Containing the 12 terminal hydroxy groups plus hyperbranched abienol polyurethane of caryogram is synthesized, then introduces poly- ammonia by the way that the raw materials such as acryloyl chloride are added
Hyperbranched abienol polyurethane acrylate resin is made in ester group and double bond.Hyperbranched abienol polyurethane made from this method
The rate of drying, impact resistance and weatherability of film can be improved in acrylate.
The technical solution of the present invention is as follows: a kind of ultraviolet light solidifies the preparation of hyperbranched abienol polyurethane acrylate resin
Method, the specific steps of which are as follows:
(1) under dehydrating agent existence condition, saturation rosin ternary is added into the reaction kettle with stirring and temperature control device
Alcohol and carboxylic acid or derivatives thereof, molar ratio of alcohol to acid are 1:(3.5-4)；Catalyst is added, heating systems are to 160-200 DEG C；
After 4-5h of isothermal reaction, stop heating and stirring, vacuum distillation obtains product abienol cardinal extremity hydroxyl polyester；
(2) it is passed through dry N2 in the reaction kettle for filling blender, temperature control, reflux condensing tube, diisocyanate is then added
The abienol cardinal extremity hydroxyl polyester prepared in step (1) and catalyst is added, wherein diisocyanate and rosin in ester under stiring
Alcohol radical hydroxyl telechelic polyester molar ratio is 1:(8-10), reaction temperature is controlled between 60-70 DEG C, after reacting 2.5-3h, is continued
Isocyanate groups terminated polyurethane prepolymers are made to 75-85 DEG C of temperature, 1-1.5h of insulation reaction in heating；
(3) alcohols catalyst is continuously added after being cooled to 40-45 DEG C in the isocyanate groups terminated polyurethane prepolymers of above-mentioned synthesis
And hydramine, wherein isocyanate groups terminated polyurethane prepolymers and hydramine molar ratio are 1:(7-9), under N2 protection, insulation reaction 4-5h system
Obtain abienol polyurethane；
(4) it is poly- that abienol made from step (3) is sequentially added in the reaction kettle for filling blender, temperature control, reflux condensing tube
Urethane, solvent, acid binding agent, polymerization inhibitor, ice bath is cooling, is sufficiently stirred, and a certain amount of acyl chlorides is slowly added dropwise；Wherein abienol is poly-
Urethane and the molar ratio of acyl chlorides are 1:(16-24)；After being added dropwise to complete, stir evenly；Then, 20-25 DEG C are risen to, the reaction was continued
5—6h；It after reaction stops, filtering, evaporates, wash, extraction takes supernatant liquor to obtain amber transparent liquid.
One of dehydrating agent benzene, toluene or hexamethylene described in preferred steps (1), dosage are that rosin alcohol and carboxylic acid is total
20%-the 30% of weight；The carboxylic acid and its derivative are 2,2 dihydromethyl propionic acids or 2,2 dimethylolpropionic acids；It is described to urge
Agent is p-methyl benzenesulfonic acid or sodium bisulfate monobydrate, and dosage is 0.08-the 2% of rosin alcohol and carboxylic acid gross mass.
Diisocyanate described in preferred steps (2) is isophorone diisocyanate (IPDI), diphenyl methane two
Isocyanates (MDI), toluene di-isocyanate(TDI) (TDI).
Catalyst described in preferred steps (2) is dibutyl tin dilaurate (DBTDL), and dosage is diisocyanate and rosin
0.1-the 0.2% of alcohol radical hydroxyl telechelic polyester gross mass.
Hydramine described in preferred steps (3) is diethanol amine；The alcohols catalyst is two kinds of one kind of methanol or ethyl alcohol,
Wherein alcohols catalyst is 1-3 times of isocyanate groups terminated polyurethane prepolymers and hydramine gross mass.
Acyl chlorides is that acryloyl chloride or methacrylic chloride are at least one in preferred steps (4)；Controlling time for adding is
0.75—1h。
Acid binding agent described in preferred steps (4) is one kind of diethylamine, triethylamine or pyridine；The acid binding agent is that acyl chlorides is total
The 50~150% of quality.
Solvent described in preferred steps (4) is one of acetone, methylene chloride, toluene or ethyl acetate；The solvent
For abienol polyurethane and 4~10 times of acyl chlorides gross mass.
Polymerization inhibitor described in preferred steps (4) is the one or more of hydroquinone, phenthazine or p-hydroxyanisole
Combination, polymerization inhibitor dosage are the 0.01~0.4% of abienol polyurethane and acyl chlorides gross mass；The ice water bath temperature is 0~5
℃。
The utility model has the advantages that
Saturation rosin trihydroxylic alcohol of the present invention by introducing recyclable materials reduces cost, reduces to petroleum as raw material
The dependence of product also has biology can be with degradability.Simultaneously because resin obtained has rigid condensed cyclic structure, so resin
Hardness, intensity are good.Meanwhile the impact resistance of film, weatherability can be improved in hyperbranched abienol urethane acrylate, to base
Material also has higher boiling fastness and adhesive force.
Specific embodiment:
Example 1:
(1) under dehydrating agent existence condition, 95.6 rosin ternarys are added into the reaction kettle with stirring and temperature control device
Pure and mild 2,2 dihydromethyl propionic acid of 53.6g, 29.84g cyclohexane are as dehydrating agent (the 20% of alkyd gross mass), alkyd mole
Than for 1:4, p-methyl benzenesulfonic acid 2.984g is added in heating after alcohol is completely dissolved, and heating systems are to 160 DEG C.After isothermal reaction 5h,
Stop heating and stirring, cooled to room temperature.Being evaporated under reduced pressure and calculating its acid value is 26mg KOH/g；
(2) dry N is passed through in the reaction kettle for filling blender, temperature control, reflux condensing tube2, it is different that 55.57g is then added
Fluorine that ketone diisocyanate, is added the abienol cardinal extremity hydroxyl polyester 32.6g and catalyst two prepared in step (1) under stiring
Two fourth tin (DBTDL) of lauric acid, wherein isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester molar ratio are 10:1, two
Two fourth tin (DBTDL) of lauric acid is 0.176g (isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester gross mass
0.2%), control reaction temperature after reacting 3h, continues to heat between 60 DEG C, to 80 DEG C of temperature in bottle, insulation reaction 1.5h,
Sampling and measuring-NCO content, at this time-NCO content are 15.5%, isocyanate groups terminated polyurethane prepolymers are made；
(3) alcohols catalyst methanol is continuously added after being cooled to 40 DEG C in the isocyanate groups terminated polyurethane prepolymers of above-mentioned synthesis
171.32g (twice of isocyanate groups terminated polyurethane prepolymers and diethanol amine gross mass), diethanol amine 19.7g, terminal isocyanate group
Prepolymer and diethanol amine molar ratio are 1:7.5, in N2Under protection, insulation reaction 4h, sampling and measuring-NCO content, at this time-
NCO content is 0.12%, terminates reaction, and abienol polyurethane is made；
(4) dress blender, temperature control, reflux condensing tube reaction kettle in sequentially add above-mentioned abienol polyurethane 81.7g,
Methylene chloride 597.5g (5 times of abienol polyurethane and acryloyl chloride gross mass), (the 1 of acryloyl chloride quality triethylamine 37.8g
Again), hydroquinone 0.478g (the 0.4% of abienol polyurethane and acryloyl chloride gross mass), ice bath is cooling, is sufficiently stirred, and
It is slowly added dropwise 37.8g acryloyl chloride 1h, the molar ratio of abienol polyurethane and acryloyl chloride is 1:16.7.After being added dropwise to complete, after
Continuous stirring 0.5h.Then, 20 DEG C are risen to, the reaction was continued 6h.After reaction stops, filtering removes triethylamine hydrochloride, then steams two
Chloromethanes.Then, with concentration be 10% sodium bicarbonate aqueous solution washed, wash repeatedly three times, again be added distilled water into
Row washing, is washed three times repeatedly.Finally, supernatant liquor is taken to obtain hyperbranched abienol urethane acrylate.
Example 2:
(1) under dehydrating agent existence condition, 95.6 rosin ternarys are added into the reaction kettle with stirring and temperature control device
Pure and mild 2,2 dihydromethyl propionic acid of 53.6g, 37.3g cyclohexane are as dehydrating agent (the 25% of alkyd gross mass), alkyd mole
Than for 1:4, p-methyl benzenesulfonic acid 2.387g is added in heating after alcohol is completely dissolved, and heating systems are to 180 DEG C.Isothermal reaction 4.7h
Afterwards, stop heating and stirring, cooled to room temperature.Being evaporated under reduced pressure and calculating its acid value is 16mg KOH/g；
(2) dry N is passed through in the reaction kettle for filling blender, temperature control, reflux condensing tube2, it is different that 50.58g is then added
Fluorine that ketone diisocyanate, is added the abienol cardinal extremity hydroxyl polyester 32.6g and catalyst two prepared in step (1) under stiring
Two fourth tin (DBTDL) of lauric acid, wherein isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester molar ratio are 9.1:1,
Dibutyl tin dilaurate (DBTDL) is 0.166g (isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester gross mass
0.2%), control reaction temperature after reacting 3h, continues to heat between 70 DEG C, to 80 DEG C of temperature in bottle, insulation reaction 1.5h,
Sampling and measuring-NCO content, at this time-NCO content are 15.5%, isocyanate groups terminated polyurethane prepolymers are made；
(3) alcohols catalyst methanol is continuously added after being cooled to 40 DEG C in the isocyanate groups terminated polyurethane prepolymers of above-mentioned synthesis
86.99g (1 times of isocyanate groups terminated polyurethane prepolymers and diethanol amine gross mass), diethanol amine 21.03g, terminal isocyanate group are pre-
Polymers and diethanol amine molar ratio are 1:8, in N2Under protection, insulation reaction 4h, sampling and measuring-NCO content, at this time-NCO contains
Amount is 0.1%, terminates reaction, and abienol polyurethane is made；
(4) dress blender, temperature control, reflux condensing tube reaction kettle in sequentially add above-mentioned abienol polyurethane 81.7g,
Methylene chloride 507.9g (4 times of abienol polyurethane and acryloyl chloride gross mass), triethylamine 45.25g be (acryloyl chloride quality
1 times), hydroquinone 0.508g the 0.4% of acryloyl chloride gross mass (abienol polyurethane and), ice bath is cooling, be sufficiently stirred, and
It is slowly added dropwise 45.25g acryloyl chloride 1h, the molar ratio of abienol polyurethane and acryloyl chloride is 1:20.After being added dropwise to complete, continue
Stir 0.5h.Then, 20 DEG C are risen to, the reaction was continued 6h.After reaction stops, filtering removes triethylamine hydrochloride, then steams dichloro
Methane.Then, it is that 10% sodium bicarbonate aqueous solution is washed with concentration, washs repeatedly three times, distilled water is added again and carries out
Washing, is washed three times repeatedly.Finally, supernatant liquor is taken to obtain hyperbranched abienol urethane acrylate.
Example 3:
(1) under dehydrating agent existence condition, 95.6 rosin ternarys are added into the reaction kettle with stirring and temperature control device
Pure and mild 2,2 dihydromethyl propionic acid of 53.6g, 44.76g cyclohexane are as dehydrating agent (the 30% of alkyd gross mass), alkyd mole
Than for 1:4, p-methyl benzenesulfonic acid 2.686g is added in heating after alcohol is completely dissolved, and heating systems are to 200 DEG C.After isothermal reaction 4h,
Stop heating and stirring, cooled to room temperature.Being evaporated under reduced pressure and calculating its acid value is 15mg KOH/g；
(2) dry N is passed through in the reaction kettle for filling blender, temperature control, reflux condensing tube2, it is different that 48.35g is then added
Fluorine that ketone diisocyanate, is added the abienol cardinal extremity hydroxyl polyester 32.6g and catalyst two prepared in step (1) under stiring
Two fourth tin (DBTDL) of lauric acid, wherein isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester molar ratio are 8.7:1,
Dibutyl tin dilaurate (DBTDL) is 0.121g (isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester gross mass
0.15%), control reaction temperature after reacting 3h, continues to heat between 60 DEG C, to 80 DEG C of temperature in bottle, insulation reaction 1.5h,
Sampling and measuring-NCO content, at this time-NCO content are 13.9%, isocyanate groups terminated polyurethane prepolymers are made；
(3) alcohols catalyst methanol is continuously added after being cooled to 40 DEG C in the isocyanate groups terminated polyurethane prepolymers of above-mentioned synthesis
265.7g (3 times of isocyanate groups terminated polyurethane prepolymers and diethanol amine gross mass), diethanol amine 22.6g, terminal isocyanate group are pre-
Polymers and diethanol amine molar ratio are 1:8.6, in N2Under protection, insulation reaction 5h, sampling and measuring-NCO content, at this time-NCO
Content is 0.07%, terminates reaction, and abienol polyurethane is made；
(4) dress blender, temperature control, reflux condensing tube reaction kettle in sequentially add above-mentioned abienol polyurethane 81.7g,
Methylene chloride 1195.3g (10 times of abienol polyurethane and acryloyl chloride gross mass), triethylamine 37.8g (acryloyl chloride quality
1 times), hydroquinone 0.239g the 0.2% of acryloyl chloride gross mass (abienol polyurethane and), ice bath is cooling, be sufficiently stirred,
And 37.8g acryloyl chloride 1h is slowly added dropwise, the molar ratio of abienol polyurethane and acryloyl chloride is 1:16.7.After being added dropwise to complete,
Continue to stir 0.5h.Then, 25 DEG C are risen to, the reaction was continued 6h.After reaction stops, filtering removes triethylamine hydrochloride, then steams
Methylene chloride.Then, it is that 10% sodium bicarbonate aqueous solution is washed with concentration, washs repeatedly three times, distilled water is added again
It is washed, is washed repeatedly three times.Finally, supernatant liquor is taken to obtain hyperbranched abienol urethane acrylate.
Example 4:
(1) under dehydrating agent existence condition, 95.6 rosin ternarys are added into the reaction kettle with stirring and temperature control device
Pure and mild 2,2 dimethylolpropionic acid of 51.8g, 29.48g toluene are as dehydrating agent (the 20% of alkyd gross mass), molar ratio of alcohol to acid
For 1:3.5, p-methyl benzenesulfonic acid 2.387g is added in heating after alcohol is completely dissolved, and heating systems are to 180 DEG C.Isothermal reaction 4.5h
Afterwards, stop heating and stirring, cooled to room temperature.Being evaporated under reduced pressure and calculating its acid value is 19mg KOH/g；
(2) dry N is passed through in the reaction kettle for filling blender, temperature control, reflux condensing tube2, the different fluorine of 37.9g is then added
That ketone diisocyanate, is added the abienol cardinal extremity hydroxyl polyester 35.018g and catalyst two prepared in step (1) under stiring
Two fourth tin (DBTDL) of lauric acid, wherein isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester molar ratio are 8.7:1,
Dibutyl tin dilaurate (DBTDL) is 0.0729g (isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester gross mass
0.1%), control reaction temperature after reacting 3h, continues to heat between 65 DEG C, to 80 DEG C of temperature in bottle, insulation reaction 1.5h,
Sampling and measuring-NCO content, at this time-NCO content are 15.5%, isocyanate groups terminated polyurethane prepolymers are made；
(3) alcohols catalyst ethyl alcohol is continuously added after being cooled to 45 DEG C in the isocyanate groups terminated polyurethane prepolymers of above-mentioned synthesis
176.122g (2 times of isocyanate groups terminated polyurethane prepolymers and diethanol amine gross mass), diethanol amine 19.7g, terminal isocyanate group
Prepolymer and diethanol amine molar ratio are 1:7.5, in N2Under protection, insulation reaction 4h, sampling and measuring-NCO content, at this time-
NCO content is 0.1%, terminates reaction, and abienol polyurethane is made；
(4) above-mentioned abienol polyurethane is sequentially added in the reaction kettle for filling blender, temperature control, reflux condensing tube
84.1321g, toluene 692.16g (5 times of abienol polyurethane and acryloyl chloride gross mass), triethylamine 81.45g (acryloyl chloride
1.5 times of quality), p-hydroxyanisole 0.0138g the 0.01% of acryloyl chloride gross mass (abienol polyurethane and), ice bath is cold
But, it is sufficiently stirred, and 54.3g acryloyl chloride 1h is slowly added dropwise, the molar ratio of abienol polyurethane and acryloyl chloride is 1:24.Drop
After the completion of adding, continue to stir 0.5h.Then, 25 DEG C are risen to, the reaction was continued 6h.After reaction stops, filtering removes triethylamine hydrochloric acid
Salt, then steam toluene.Then, it is that 10% sodium bicarbonate aqueous solution is washed with concentration, washs repeatedly three times, be added steam again
Distilled water is washed, and is washed repeatedly three times.Finally, supernatant liquor is taken to obtain hyperbranched abienol urethane acrylate.
Example 5:
(1) under dehydrating agent existence condition, 95.6 rosin ternarys are added into the reaction kettle with stirring and temperature control device
Pure and mild 2,2 dimethylolpropionic acid of 54.8g, 37.6g toluene are as dehydrating agent (the 25% of alkyd gross mass), molar ratio of alcohol to acid
For 1:3.7, p-methyl benzenesulfonic acid 2.256g is added in heating after alcohol is completely dissolved, and heating systems are to 180 DEG C.Isothermal reaction 4.5h
Afterwards, stop heating and stirring, cooled to room temperature.Being evaporated under reduced pressure and calculating its acid value is 13mg KOH/g；
(2) dry N is passed through in the reaction kettle for filling blender, temperature control, reflux condensing tube2, 43.5g toluene is then added
The abienol cardinal extremity hydroxyl polyester 35.018g prepared in step (1) and catalyst dibutyltin osmanthus is added in diisocyanate under stiring
Sour two fourth tin (DBTDL), wherein toluene di-isocyanate(TDI) and abienol cardinal extremity hydroxyl polyester molar ratio are 10:1, tin dilaurate two
Fourth tin (DBTDL) is 0.157g (the 0.2% of isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester gross mass), control
Reaction temperature after reacting 3h, continues to heat between 70 DEG C, to 80 DEG C of temperature in bottle, insulation reaction 1.5h, sampling and measuring-
NCO content, at this time-NCO content are 14.2%, isocyanate groups terminated polyurethane prepolymers are made；
(3) alcohols catalyst methanol is continuously added after being cooled to 45 DEG C in the isocyanate groups terminated polyurethane prepolymers of above-mentioned synthesis
161.68g (twice of isocyanate groups terminated polyurethane prepolymers and diethanol amine gross mass), diethanol amine 19.7g, terminal isocyanate group
Prepolymer and diethanol amine molar ratio are 1:7.5, in N2Under protection, insulation reaction 4h, sampling and measuring-NCO content, at this time-
NCO content is 0.08%, terminates reaction, and abienol polyurethane is made；
(4) above-mentioned abienol polyurethane is sequentially added in the reaction kettle for filling blender, temperature control, reflux condensing tube
76.91g, ethyl acetate 610.805g (5 times of abienol polyurethane and acryloyl chloride gross mass), diethylamine 22.65g (propylene
0.5 times of acyl chlorides quality), p-hydroxyanisole 0.4886g the 0.4% of acryloyl chloride gross mass (abienol polyurethane and), ice
Bath cooling, is sufficiently stirred, and 45.25g acryloyl chloride 1h is slowly added dropwise, and the molar ratio of abienol polyurethane and acryloyl chloride is 1:
20.After being added dropwise to complete, continue to stir 0.5h.Then, 23 DEG C are risen to, the reaction was continued 5h.After reaction stops, filtering removes diethyl
Amine hydrochlorate, then steam ethyl acetate.Then, it is that 10% sodium bicarbonate aqueous solution is washed with concentration, washs repeatedly three times,
Distilled water is added again to be washed, washs repeatedly three times.Finally, supernatant liquor is taken to obtain hyperbranched abienol polyurethane
Acrylate.
Example 6:
(1) under dehydrating agent existence condition, 95.6g rosin ternary is added into the reaction kettle with stirring and temperature control device
Pure and mild 2,2 dimethylolpropionic acid of 59.3g, 30.98g toluene are as dehydrating agent (the 20% of alkyd gross mass), molar ratio of alcohol to acid
For 1:4, heating, sodium bisulfate monobydrate 0.124g, heating systems are to 160 DEG C.After isothermal reaction 5h, stop heating and stirring,
Cooled to room temperature.Being evaporated under reduced pressure and calculating its acid value is 25mg KOH/g；
(2) dry N is passed through in the reaction kettle for filling blender, temperature control, reflux condensing tube2, it is different that 55.57g is then added
Fluorine that ketone diisocyanate, is added the abienol cardinal extremity hydroxyl polyester 35.01g and catalyst prepared in step (1) under stiring
Dibutyl tin dilaurate (DBTDL), wherein isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester molar ratio are 10:1,
Dibutyl tin dilaurate (DBTDL) is 0.181g isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester gross mass
0.2%), control reaction temperature after reacting 3h, continues to heat between 60 DEG C, to 80 DEG C of temperature in bottle, insulation reaction 1.5h,
Sampling and measuring-NCO content, at this time-NCO content are 15.2%, and isocyanate groups terminated polyurethane prepolymers are made；
(3) alcohols catalyst methanol is continuously added after being cooled to 45 DEG C in the isocyanate groups terminated polyurethane prepolymers of above-mentioned synthesis
182.44g (twice of isocyanate groups terminated polyurethane prepolymers and diethanol amine gross mass), diethanol amine 22.86g, terminal isocyanate group
Prepolymer and diethanol amine molar ratio are 1:8.7, in N2Under protection, insulation reaction 5h, sampling and measuring-NCO content, at this time-
NCO content is 0.02%, terminates reaction, and abienol polyurethane is made；
(4) above-mentioned abienol polyurethane is sequentially added in the reaction kettle for filling blender, temperature control, reflux condensing tube
84.13g, ethyl acetate 638.9g (5 times of abienol polyurethane and methacrylic chloride gross mass), pyridine 43.7g (methyl-prop
1 times of alkene acyl chlorides gross mass), hydroquinone 0.5g the 0.4% of methacrylic chloride gross mass (abienol polyurethane and), ice bath
It is cooling, it is sufficiently stirred, and 43.64g methacrylic chloride 1h, mole of abienol polyurethane and methacrylic chloride is slowly added dropwise
Than for 1:16.7.After being added dropwise to complete, continue to stir 0.5h.Then, 25 DEG C are risen to, the reaction was continued 6h.After reaction stops, filtering,
Pyridine hydrochloride is removed, then steams ethyl acetate.It is that 10% sodium bicarbonate aqueous solution is washed with concentration, washs three repeatedly
It is secondary, distilled water is added again and is washed, washs repeatedly three times.Finally, it is poly- to take supernatant liquor to obtain hyperbranched abienol
Urethane acrylate.
Example 7:
(1) under dehydrating agent existence condition, 95.6g rosin ternary is added into the reaction kettle with stirring and temperature control device
Pure and mild 2,2 dimethylolpropionic acid of 59.3g, 30.98g dimethylbenzene are as dehydrating agent (the 20% of alkyd gross mass), alkyd mole
Than for 1:4, heating, sodium bisulfate monobydrate 0.124g, heating systems are to 180 DEG C.After isothermal reaction 4h, stops heating and stir
It mixes, cooled to room temperature.Being evaporated under reduced pressure and calculating its acid value is 22mg KOH/g；
(2) dry N is passed through in the reaction kettle for filling blender, temperature control, reflux condensing tube2, it is different that 50.6g is then added
Fluorine that ketone diisocyanate, is added the abienol cardinal extremity hydroxyl polyester 35.01g and catalyst prepared in step (1) under stiring
Dibutyl tin dilaurate (DBTDL), wherein isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester molar ratio are 10:1,
Dibutyl tin dilaurate (DBTDL) is 0.0856g isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester gross mass
0.1%), control reaction temperature after reacting 3h, continues to heat between 60 DEG C, to 80 DEG C of temperature in bottle, insulation reaction 1.5h,
Sampling and measuring-NCO content, at this time-NCO content are 14.4%, and isocyanate groups terminated polyurethane prepolymers are made；
(3) alcohols catalyst methanol is continuously added after being cooled to 40 DEG C in the isocyanate groups terminated polyurethane prepolymers of above-mentioned synthesis
175.722g (twice of isocyanate groups terminated polyurethane prepolymers and diethanol amine gross mass), diethanol amine 19.5g, terminal isocyanate group
Prepolymer and diethanol amine molar ratio are 1:7.4, in N2Under protection, insulation reaction 4h, sampling and measuring-NCO content, at this time-
NCO content is 0.05%, terminates reaction, and abienol polyurethane is made；
(4) above-mentioned abienol polyurethane is sequentially added in the reaction kettle for filling blender, temperature control, reflux condensing tube
84.13g, acetone 653.15g (5 times of abienol polyurethane and methacrylic chloride gross mass), pyridine 46.5g (metering system
1 times of acyl chlorides gross mass), phenthazine 0.523g the 0.4% of methacrylic chloride gross mass (abienol polyurethane and), ice bath is cold
But, it is sufficiently stirred, and 46.5g methacrylic chloride 1h, the molar ratio of abienol polyurethane and methacrylic chloride is slowly added dropwise
For 1:17.8.After being added dropwise to complete, continue to stir 0.5h.Then, 20 DEG C are risen to, the reaction was continued 6h.After reaction stops, filtering is removed
Pyridine hydrochloride is removed, then steams acetone.It is that 10% sodium bicarbonate aqueous solution is washed with concentration, washs repeatedly three times, again
Distilled water is added to be washed, washs repeatedly three times.Finally, supernatant liquor is taken to obtain hyperbranched abienol polyurethane propylene
Acid esters.
Example 8:
(1) under dehydrating agent existence condition, 95.6g rosin ternary is added into the reaction kettle with stirring and temperature control device
As dehydrating agent (the 25% of alkyd gross mass), alkyd rubs for pure and mild 2,2 dimethylolpropionic acid of 59.3g, 38.725g dimethylbenzene
You are than being 1:4, and heating, sodium bisulfate monobydrate 0.124g, heating systems are to 160 DEG C.After isothermal reaction 5h, stops heating and stir
It mixes, cooled to room temperature.Being evaporated under reduced pressure and calculating its acid value is 25mg KOH/g；
(2) dry N is passed through in the reaction kettle for filling blender, temperature control, reflux condensing tube2, it is different that 55.57g is then added
Fluorine that ketone diisocyanate, is added the abienol cardinal extremity hydroxyl polyester 35.017g and catalyst prepared in step (1) under stiring
Dibutyl tin dilaurate (DBTDL), wherein isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester molar ratio are 10:1,
Dibutyl tin dilaurate (DBTDL) is 0.1359g isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester gross mass
0.15%), control reaction temperature after reacting 3h, continues to heat between 70 DEG C, to 80 DEG C of temperature in bottle, insulation reaction 1.5h,
Sampling and measuring-NCO content, at this time-NCO content are 14.2%, and isocyanate groups terminated polyurethane prepolymers are made；
(3) alcohols catalyst ethyl alcohol is continuously added after being cooled to 45 DEG C in the isocyanate groups terminated polyurethane prepolymers of above-mentioned synthesis
268.95g (3 times of isocyanate groups terminated polyurethane prepolymers and diethanol amine gross mass), diethanol amine 21.29g, terminal isocyanate group
Prepolymer and diethanol amine molar ratio are 1:8.7, in N2Under protection, insulation reaction 4h, sampling and measuring-NCO content, at this time-
NCO content is 0.07%, terminates reaction, and abienol polyurethane is made；
(4) above-mentioned abienol polyurethane is sequentially added in the reaction kettle for filling blender, temperature control, reflux condensing tube
84.13g, ethyl acetate 894.39g (7 times of abienol polyurethane and methacrylic chloride gross mass), pyridine 65.4g (methyl
1 times of acryloyl chloride gross mass), hydroquinone 0.5g the 0.4% of methacrylic chloride gross mass (abienol polyurethane and), ice
Bath cooling, is sufficiently stirred, and 43.64g methacrylic chloride 1h is slowly added dropwise, and abienol polyurethane and methacrylic chloride rub
You are than being 1:16.7.After being added dropwise to complete, continue to stir 0.5h.Then, 25 DEG C are risen to, the reaction was continued 6h.After reaction stops, mistake
Filter removes pyridine hydrochloride, then steams ethyl acetate.It is that 10% sodium bicarbonate aqueous solution is washed with concentration, washs repeatedly
Three times, distilled water is added again to be washed, washs repeatedly three times.Finally, supernatant liquor is taken to obtain hyperbranched abienol
Urethane acrylate.
Example 9:
(1) under dehydrating agent existence condition, 95.6g rosin ternary is added into the reaction kettle with stirring and temperature control device
Pure and mild 2,2 dimethylolpropionic acid of 59.3g, 46.47g toluene are as dehydrating agent (the 30% of alkyd gross mass), molar ratio of alcohol to acid
For 1:4, heating, sodium bisulfate monobydrate 0.18g, heating systems are to 200 DEG C.After isothermal reaction 4h, stop heating and stirring, from
So it is cooled to room temperature.Being evaporated under reduced pressure and calculating its acid value is 17mg KOH/g；
(2) dry N is passed through in the reaction kettle for filling blender, temperature control, reflux condensing tube2, 43.54g first is then added
The abienol cardinal extremity hydroxyl polyester 35g and catalyst dibutyltin cinnamic acid prepared in step (1) is added in phenylene diisocyanate under stiring
Two fourth tin (DBTDL), wherein isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester molar ratio are 10:1, tin dilaurate
Two fourth tin (DBTDL) are the 0.1% of 0.0786g isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester gross mass), control
Reaction temperature processed after reacting 3h, continues to heat between 70 DEG C, to 85 DEG C of temperature in bottle, insulation reaction 1h, sampling and measuring-
NCO content, at this time-NCO content are 13.9%, and isocyanate groups terminated polyurethane prepolymers are made；
(3) alcohols catalyst ethyl alcohol is continuously added after being cooled to 45 DEG C in the isocyanate groups terminated polyurethane prepolymers of above-mentioned synthesis
98.21g (1 times of isocyanate groups terminated polyurethane prepolymers and diethanol amine gross mass), diethanol amine 21.3g, terminal isocyanate group are pre-
Polymers and diethanol amine molar ratio are 1:8.1, in N2Under protection, insulation reaction 4h, sampling and measuring-NCO content, at this time-NCO
Content is 0.02%, terminates reaction, and abienol polyurethane is made；
(4) dress blender, temperature control, reflux condensing tube reaction kettle in sequentially add above-mentioned abienol polyurethane 76.9g,
Acetone 723.31g 6 times of methacrylic chloride gross mass (abienol polyurethane with), (methacrylic chloride is total by triethylamine 43.7g
1 times of quality), hydroquinone 0.4822g the 0.4% of methacrylic chloride gross mass (abienol polyurethane and), ice bath is cooling,
It is sufficiently stirred, and 43.64g methacrylic chloride 1h is slowly added dropwise, the molar ratio of abienol polyurethane and methacrylic chloride is
1:16.7.After being added dropwise to complete, continue to stir 0.5h.Then, 20 DEG C are risen to, the reaction was continued 6h.It after reaction stops, filtering, removes
Triethylamine hydrochloride, then steam acetone.It is that 10% sodium bicarbonate aqueous solution is washed with concentration, washs repeatedly three times, again
Distilled water is added to be washed, washs repeatedly three times.Finally, supernatant liquor is taken to obtain hyperbranched abienol polyurethane propylene
Acid esters.
Example 10:
(1) under dehydrating agent existence condition, 95.6g rosin ternary is added into the reaction kettle with stirring and temperature control device
Pure and mild 2,2 dimethylolpropionic acid of 50.3g, 43.77g toluene are as dehydrating agent (the 30% of alkyd gross mass), molar ratio of alcohol to acid
For 1:3.75, heating, sodium bisulfate monobydrate 0.13g, heating systems are to 180 DEG C.After isothermal reaction 4.5h, stops heating and stir
It mixes, cooled to room temperature.Being evaporated under reduced pressure and calculating its acid value is 19mg KOH/g；
(2) dry N is passed through in the reaction kettle for filling blender, temperature control, reflux condensing tube2, it is different that 50.7g is then added
Fluorine that ketone diisocyanate, is added the abienol cardinal extremity hydroxyl polyester 35.017g and catalyst prepared in step (1) under stiring
Dibutyl tin dilaurate (DBTDL), wherein isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester molar ratio are 8.7:
1, dibutyl tin dilaurate (DBTDL) is 0.171g isophorone diisocyanate and abienol cardinal extremity hydroxyl polyester gross mass
0.2%), control reaction temperature after reacting 2.5h, continues to heat, to 75 DEG C of temperature, insulation reaction in bottle between 70 DEG C
1.5h, sampling and measuring-NCO content, at this time-NCO content are 13.7%, and isocyanate groups terminated polyurethane prepolymers are made；
(3) alcohols catalyst methanol is continuously added after being cooled to 45 DEG C in the isocyanate groups terminated polyurethane prepolymers of above-mentioned synthesis
182.442g twice of diethanol amine gross mass (isocyanate groups terminated polyurethane prepolymers and), diethanol amine 22.86g, it is isocyanate terminated
Based prepolymers and diethanol amine molar ratio are 1:8.7, in N2Under protection, insulation reaction 4h, sampling and measuring-NCO content, this
When-NCO content be 0.02%, terminate reaction, be made abienol polyurethane；
(4) above-mentioned abienol polyurethane is sequentially added in the reaction kettle for filling blender, temperature control, reflux condensing tube
84.13g, methylene chloride 700.16g (5 times of abienol polyurethane and methacrylic chloride gross mass), pyridine 55.9g (methyl
1 times of acryloyl chloride gross mass), p-hydroxyanisole 0.28g (abienol polyurethane and methacrylic chloride gross mass
0.2%), ice bath is cooling, is sufficiently stirred, and 55.9g methacrylic chloride 0.75h, abienol polyurethane and methyl is slowly added dropwise
The molar ratio of acryloyl chloride is 1:21.4.After being added dropwise to complete, continue to stir 0.5h.Then, 25 DEG C are risen to, the reaction was continued 6h.Instead
After should stopping, filtering removes pyridine hydrochloride, then steams methylene chloride.It is that 10% sodium bicarbonate aqueous solution is washed with concentration
It washs, washs repeatedly three times, distilled water is added again and is washed, washs repeatedly three times.Finally, supernatant liquor is taken to be surpassed
Branching abienol urethane acrylate.
The preparation of ultraviolet light cured coating film
Example 11
Resin prepared by the examples 1~10 of 60 mass parts, 4 mass parts photoinitiators (1-hydroxy-cyclohexyl benzene first copper and
2,4,6-trimethyl benzoyl diphenyl base phosphine oxides are compounded with mass ratio 1:1 and are obtained), the dilution of 35 mass parts activity it is single
Body (trimethylolpropane trimethacrylate and tri (propylene glycol) diacrylate are compounded with mass ratio 7:3 and obtained) and stream
Flat agent (modest 810), 0.7 mass parts of moral and defoaming agent (BYK -011) 0.3 mass parts be uniformly mixed and example 1~10 coating.
Comparative example 1
Resin prepared by example 1~10 is changed to the resin of commercially available same type, in addition to this, with identical as example 11
Mode operated, be made comparative example 1 coating.
Curing time carries out according to GB/T 1728-1979, and pencil hardness is carried out according to GB/T 6739-2006, attachment
Power is carried out according to GB/T 9286-1998, and flexibility is carried out according to standard GB/T1731-1993, and impact resistance is according to standard
GB/T 1732-93, the quasi- GB/T 9274-1988 of resistance to acid and alkali sighting target are measured.
1 film performance test result table of table
As can be seen from Table 1, compared with the coating film of comparative example 1, over-expense obtained by 1~example of present example 10
The film for changing photocureable coating obtained by abienol urethane acrylate, in hardness and flexible balance, shock resistance, right
On the adhesive force of substrate, there is superior performance.
As described above, shall not be construed as although having indicated and having described the present invention referring to specific preferred embodiment
Limitation to invention itself.It without prejudice to the spirit and scope of the invention as defined in the appended claims, can be to it
Various changes can be made in the form and details.
Claims (9)
1. a kind of ultraviolet light solidifies the preparation method of hyperbranched abienol polyurethane acrylate resin, the specific steps of which are as follows:
(1) under dehydrating agent existence condition, to stirring and temperature control device reaction kettle in be added saturation rosin trihydroxylic alcohol and
Carboxylic acid or derivatives thereof, molar ratio of alcohol to acid are 1:(3.5-4)；Catalyst is added, heating systems are to 160-200 DEG C；Constant temperature
After reacting 4-5h, stop heating and stirring, vacuum distillation obtains product abienol cardinal extremity hydroxyl polyester；
(2) it is passed through dry N2 in the reaction kettle for filling blender, temperature control, reflux condensing tube, diisocyanate is then added,
It is added with stirring the abienol cardinal extremity hydroxyl polyester prepared in step (1) and catalyst, wherein diisocyanate and rosin alcohol radical
Hydroxyl telechelic polyester molar ratio is 1:(8-10), reaction temperature is controlled between 60-70 DEG C, after reacting 2.5-3h, continues to add
Isocyanate groups terminated polyurethane prepolymers are made to 75-85 DEG C of temperature, 1-1.5h of insulation reaction in heat；
(3) alcohols catalyst and alcohol are continuously added after being cooled to 40-45 DEG C in the isocyanate groups terminated polyurethane prepolymers of above-mentioned synthesis
Amine, wherein isocyanate groups terminated polyurethane prepolymers and hydramine molar ratio are 1:(7-9), under N2 protection, pine is made in 4-5h of insulation reaction
Aromatic polyurethane；
(4) dress blender, temperature control, reflux condensing tube reaction kettle in sequentially add abienol polyurethane made from step (3),
Solvent, acid binding agent, polymerization inhibitor, ice bath is cooling, is sufficiently stirred, and acyl chlorides is added dropwise；Wherein mole of abienol polyurethane and acyl chlorides
Than for 1:(16-24)；After being added dropwise to complete, stir evenly；Then, 20-25 DEG C are risen to, the reaction was continued 5-6h；Reaction stops
Afterwards, it filters, evaporates, wash, extraction takes supernatant liquor to obtain amber transparent liquid.
2. preparation method according to claim 1, which is characterized in that dehydrating agent benzene, toluene or ring described in step (1)
One of hexane, dosage are 20%-the 30% of rosin alcohol and carboxylic acid total weight；The carboxylic acid and its derivative are 2,2 dihydroxies
Methylpropanoic acid or 2,2 dimethylolpropionic acids；The catalyst is p-methyl benzenesulfonic acid or sodium bisulfate monobydrate, and dosage is abienol
With 0.08-the 2% of carboxylic acid gross mass.
3. preparation method according to claim 1, which is characterized in that diisocyanate described in step (2) is different Buddhist
That ketone diisocyanate, methyl diphenylene diisocyanate, toluene di-isocyanate(TDI).
4. preparation method according to claim 1, which is characterized in that catalyst described in step (2) is tin dilaurate two
Fourth tin, dosage are 0.1-the 0.2% of diisocyanate and abienol cardinal extremity hydroxyl polyester gross mass.
5. preparation method according to claim 1, which is characterized in that hydramine described in step (3) is diethanol amine；It is described
Alcohols catalyst is two kinds of one kind of methanol or ethyl alcohol, and wherein alcohols catalyst is isocyanate groups terminated polyurethane prepolymers and the total matter of hydramine
1-3 times of amount.
6. preparation method according to claim 1, which is characterized in that acyl chlorides is acryloyl chloride or methyl-prop in step (4)
Alkene acyl chlorides is at least one；Control time for adding is 0.75-1h.
7. preparation method according to claim 1, which is characterized in that acid binding agent described in step (4) is diethylamine, three second
One kind of amine or pyridine；The acid binding agent is the 50~150% of acyl chlorides gross mass.
8. preparation method according to claim 1, which is characterized in that solvent described in step (4) is acetone, dichloromethane
One of alkane, toluene or ethyl acetate；The solvent is 4~10 times of abienol polyurethane and acyl chlorides gross mass.
9. preparation method according to claim 1, which is characterized in that polymerization inhibitor described in step (4) is hydroquinone, pheno
One or more combinations of thiazine or p-hydroxyanisole, polymerization inhibitor dosage are abienol polyurethane and acyl chlorides gross mass
0.01~0.4%；The ice water bath temperature is 0~5 DEG C.
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| CN115093536A (en) * | 2022-06-02 | 2022-09-23 | 西安工业大学 | Polyurethane resin, preparation method thereof and application thereof in preparation of photocureable coating |
| CN117925004A (en) * | 2023-12-20 | 2024-04-26 | 东莞德芳油墨科技有限公司 | High-performance environment-friendly water-based ink and preparation process thereof |
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