CN102786637A - Composite modified aqueous polyurethane resin and its preparation method - Google Patents
Composite modified aqueous polyurethane resin and its preparation method Download PDFInfo
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- CN102786637A CN102786637A CN2011101271242A CN201110127124A CN102786637A CN 102786637 A CN102786637 A CN 102786637A CN 2011101271242 A CN2011101271242 A CN 2011101271242A CN 201110127124 A CN201110127124 A CN 201110127124A CN 102786637 A CN102786637 A CN 102786637A
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- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000004970 Chain extender Substances 0.000 claims abstract description 26
- 239000003822 epoxy resin Substances 0.000 claims abstract description 19
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 16
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 12
- 150000003077 polyols Chemical class 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- ZEMPKEQAKRGZGQ-AAKVHIHISA-N 2,3-bis[[(z)-12-hydroxyoctadec-9-enoyl]oxy]propyl (z)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCCC(O)C\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CC(O)CCCCCC)COC(=O)CCCCCCC\C=C/CC(O)CCCCCC ZEMPKEQAKRGZGQ-AAKVHIHISA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 9
- 150000003384 small molecules Chemical group 0.000 claims description 8
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000009775 high-speed stirring Methods 0.000 claims description 6
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 238000009736 wetting Methods 0.000 claims description 6
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical class NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 4
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical group COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical group CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 3
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 claims description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- RINWGRJHXCCLOV-UHFFFAOYSA-N BPO Chemical compound BPO RINWGRJHXCCLOV-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 2
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- JKJJSJJGBZXUQV-UHFFFAOYSA-N methyl 2-methylidenebutanoate Chemical compound CCC(=C)C(=O)OC JKJJSJJGBZXUQV-UHFFFAOYSA-N 0.000 claims description 2
- -1 methyl-2-Hydroxy ethyl Chemical group 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920003009 polyurethane dispersion Polymers 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 claims description 2
- 238000010526 radical polymerization reaction Methods 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N tolylenediamine group Chemical group CC1=C(C=C(C=C1)N)N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 229920002635 polyurethane Polymers 0.000 abstract description 2
- 239000004814 polyurethane Substances 0.000 abstract description 2
- 239000004359 castor oil Substances 0.000 abstract 2
- 235000019438 castor oil Nutrition 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 2
- 125000005442 diisocyanate group Chemical group 0.000 abstract 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 abstract 2
- 238000001914 filtration Methods 0.000 abstract 1
- 239000003973 paint Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000009413 insulation Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
A composite modified aqueous polyurethane resin comprises 6-19wt% of diisocyanate, 6-15wt% of a macro-molecular polyol, 2-15wt% of castor oil, 1-5wt% of a micro-molecular chain extender, 1-8wt% of an epoxy resin, 2-10wt% of a hydrophilic chain extender, 1-4wt% of a neutralizer, 0.01-0.1wt% of a catalyst, 5-15wt% of a vinyl monomer, 2-15wt% of a solvent, 0.5-2wt% of a post chain extender, 0.01-0.5wt% of an initiator and 50-60wt% of deionized water. A preparation method of the composite modified aqueous polyurethane resin comprises the following steps: 1, adding the macro-molecular polyol, the castor oil and the diisocyanate to a reaction vessel, stirring, heating to 80-90DEG C, and maintaining the temperature for 2h; 2, adding the micro-molecular chain extender, the epoxy resin, the catalyst, the hydrophilic chain extender and the solvent, and maintaining the temperature at 80-84DEG C for 30min; 3, detecting NCO, cooling to below 40DEG C, and adding the vinyl monomer; 4, adding the neutralizer, stirring at a high speed for 30ming, adding the deionized water and the post chain extender, stirring at a middle speed for 10min, and heating to 80DEG C; and 5, adding the initiator, maintaining the temperature for 2h, cooling to 30DEG C, and filtering to obtain the composite modified aqueous polyurethane. The composite modified aqueous polyurethane resin synthesized in the invention has the advantages of very good water dispersity and very good storage stability.
Description
Technical field
The invention belongs to the technical field of coating, specifically, is a kind of composite modified waterborne polyurethane resin and preparation method thereof, is used in particular for preparing aqueous woodware paint.
Background technology
Aqueous woodware paint is a dispersion medium with water, has nonpoisonous and tasteless, environmental protection, characteristics such as harmless and gains great popularity, and is widely used in the decoration protection of wooden doors and windows, furniture, floor and bamboo utensil, becomes the new focus of environmental protection coating material development.
With abroad compare, the range of application of China's aqueous woodware paint is also very limited, aqueous woodware paint is gone back dependence on import to a great extent with resin.The paint film that mainly is domestic aqueous woodware paint is compared a certain distance in addition in performances such as hardness, water tolerance, solvent resistance, gloss with solvent based coating.
Aqueous pu dispersions is the common resins of aqueous woodware paint, and single modified waterborne polyurethane resin is relatively poor at aspects such as water tolerance, solvent resistance, weathering resistancies, mainly is because the cross-linking density of paint film is high not enough.
Summary of the invention
The objective of the invention is to, a kind of composite modified waterborne polyurethane resin and preparation method thereof is provided,, be used to prepare aqueous woodware paint to overcome the above-mentioned shortcoming and defect of existing in prior technology.
Another object of the present invention provides a kind of preparation method of composite modified waterborne polyurethane resin.
The technical problem that will solve required for the present invention, can realize through following technical scheme:
First aspect of the present invention, a kind of composite modified waterborne polyurethane resin is characterized in that, said resin comprises following components in weight percentage:
Set of dispense compares %
Vulcabond 6-19;
Macromolecular polyol 6-15;
Viscotrol C 2-15;
Small molecule chain extender 1-5;
Epoxy resin 1-8;
Wetting ability chainextender 2-10;
Neutralizing agent 1-4;
Catalyzer 0.01-0.1;
Vinyl monomer 5-15;
Solvent 2-15;
Back chainextender 0.5-2;
Initiator 0.01-0.5;
Deionized water 50-60.
Wherein, Said vulcabond be tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4 '-any one and arbitrary combination thereof of diphenylmethanediisocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, tetramethylxylylene diisocyanate.
Wherein, said macromolecular polyol is any one and an arbitrary combination thereof of polyether glycol, polycaprolactone polyol, polycarbonate polyol, THF homopolymer polyvalent alcohol.Preferred molecular weight is the polyvalent alcohol between the 1000-2000.
Wherein, said small molecule chain extender is a molecular weight in any one and arbitrary combination thereof of the divalent alcohol below 400, trivalent alcohol, tetravalent alcohol.
Further, small molecule chain extender is terepthaloyl moietie, Ucar 35,1,4-butyleneglycol, glycol ether, 1, any one of 6-pinakon, NSC 6366, TriMethylolPropane(TMP), tetramethylolmethane and arbitrary combination thereof.Preferred 1,4-butyleneglycol, glycol ether, 1,6-pinakon.
Wherein, said epoxy resin is that epoxy resin E20, the molecular-weight average of molecular-weight average 1000 are that 450 epoxy resin E44, molecular-weight average are any one and the arbitrary combination thereof among 370 the epoxy resin E51.
Wherein, said wetting ability chainextender comprises dimethylol propionic acid, dimethylolpropionic acid.
Wherein, said neutralizing agent is Trimethylamine 99, triethylamine, Tributylamine, triethylene diamine, N, N-dimethylethanolamine, N, any one in the N-diethylethanolamine and arbitrary combination thereof.Be preferably triethylamine.
Wherein, said catalyzer is any one and the arbitrary combination thereof in dibutyl tin laurate, stannous octoate, the N-methylmorpholine.Be preferably dibutyl tin laurate.
Wherein, said vinyl monomer is a lower alkyl acrylate, and the methylacrylic acid lower alkyl esters replaces or unsubstituted acrylic amide, vinyl cyanide, cinnamic any one and arbitrary combination thereof.
Further, said vinyl monomer is methyl acrylate, methyl-methyl acrylate, ethyl propenoate, methyl-ethyl propenoate, Bing Xisuandingzhi, methyl-Bing Xisuandingzhi, ethyl acrylate, methyl-ethyl acrylate, vinylformic acid stearyl, methyl-vinylformic acid stearyl, IBOA, methyl-IBOA, 2-Hydroxy ethyl acrylate, methyl-2-Hydroxy ethyl acrylate, acrylic amide, methyl-acrylic amide, N hydroxymethyl acrylamide, vinyl cyanide, cinnamic any one and arbitrary combination thereof.
Wherein, said solvent comprises any one of N-Methyl pyrrolidone, N-ethyl pyrrolidone.
Wherein, Said back chainextender is the polyamine that polyurethane dispersions is carried out chain extension, comprises any one and arbitrary combination thereof of quadrol, tn, tetramethylenediamine, isophorone diamine, phenylenediamine, tolylene diamine, hydrazine, diethylenetriamine, triethylene tetramine, TEPA.Be preferably dibutyl tin laurate.
Wherein, said initiator is for causing the water-soluble or oil-soluble initiator that vinyl monomer carries out radical polymerization.
Further, initiator is any one of Potassium Persulphate, ammonium persulphate, Sodium Persulfate, Diisopropyl azodicarboxylate, BPO.
Second aspect of the present invention, a kind of preparation method of composite modified waterborne polyurethane resin is characterized in that, according to weight percent meter, may further comprise the steps:
(1) in reaction kettle, adds macromolecular polyol, Viscotrol C, vulcabond successively, start simultaneously and stir and heating, be warming up to 80-90 ℃, be incubated 2 hours;
(2) add small molecule chain extender, epoxy resin, catalyzer, wetting ability chainextender, solvent,, be incubated 30 minutes at 80-84 ℃;
(3) survey NCO; After nco value reaches theoretical value, be cooled to below 40 ℃, add vinyl monomer;
(4) add neutralizing agent, high-speed stirring 30 minutes adds deionized water and back chainextender under high-speed stirring, and middling speed stirred after 10 minutes, was warmed up to 80 ℃;
(5) add initiator, be incubated after 2 hours, cool to 30 ℃, filter discharging.
Wherein, in the step (4), the rotating speed of said high-speed stirring is 2000-3000rpm.
Wherein, in the step (4), the rotating speed that said middling speed stirs is 500-2000_rpm.
Its compared with prior art, the present invention has following advantage:
Adopt the above-mentioned prescription and the composite modified waterborne polyurethane resin of prepared, have good water dispersible, stability in storage.The water-borne wood coating that is mixed with, hardness is high, gloss is high, water-tolerant, solvent resistance are good.
1, adopt Viscotrol C, epoxy resin, propenoate etc. composite modified, coating is high at the film process middle crosslink density, and hardness of paint film is high, gloss is high, water-tolerant, solvent resistance are good.
2, do not use low boiling point solvents such as acetone, cost is low, less energy consumption.
3, prepared composite modified aqueous polyurethane resin of the present invention is used for aqueous woodware paint, and its main performance index satisfies the requirement of GB/T 23999-2009 indoor decorating use woodwork coating.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.Should be understood that following examples only are used to the present invention is described but not are used to limit scope of the present invention.
The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition, or the condition that manufacturer provides is carried out.
Embodiment 1
A kind of preparation method of composite modified waterborne polyurethane resin may further comprise the steps:
(1) in a 1000mL four-hole boiling flask that whipping appts, TM and logical nitrogen protection be housed, adds 102.5g polyether Glycols, 23g Viscotrol C, 90.5g isophorone diisocyanate successively, start simultaneously and stir and heating, 80-90 ℃ of insulation 2 hours;
(2) add 11.6g 1,4-butyleneglycol, 10g epoxy resin E20 (Suzhou logical resin ltd of Soviet Union product), 0.1g dibutyl tin laurate, 15.6g dimethylol propionic acid, 80g N-Methyl pyrrolidone at 80-84 ℃, are incubated 30 minutes;
(3) begin to survey NCO, after nco value reaches 1.97%, be cooled to and add vinyl monomer (50g TEB 3K, 10g Bing Xisuandingzhi, 8g N hydroxymethyl acrylamide) below 40 ℃;
(4) add the 10.1g triethylamine, 2100rpm stirred 30 minutes, under 2500rpm stirs, added 450g deionized water and 4.0g quadrol.600rpm stirred after 10 minutes, was warmed up to 80 ℃;
(5) add the 0.5g Sodium Persulfate, be incubated after 2 hours, cool to 30 ℃, filter discharging.
Embodiment 2
A kind of preparation method of composite modified waterborne polyurethane resin may further comprise the steps:
(1) in a 1000mL four-hole boiling flask that whipping appts, TM and logical nitrogen protection be housed, adds 90g polyester diol, 35g Viscotrol C, 63g tolylene diisocyanate successively, start simultaneously and stir and heating, 80-90 ℃ of insulation 2 hours;
(2) add 10.4g glycol ether, 10g epoxy resin E44 (Suzhou logical resin ltd of Soviet Union product), 0.1g stannous octoate, 13.6g dimethylol propionic acid, 80g N-Methyl pyrrolidone,, be incubated 30 minutes at 80-84 ℃;
(3) begin to survey NCO, after nco value reaches 1.88%, be cooled to below 40 ℃, add vinyl monomer (52g TEB 3K, 8g Bing Xisuandingzhi, 2g methylacrylic acid-2-hydroxy methacrylate, 8g N hydroxymethyl acrylamide);
(4) add the 10.3g triethylene diamine,
2100rpm stirred 30 minutes, under 2500rpm stirs, added 450g deionized water and 4.5g isophorone diamine.600rpm stirred after 10 minutes, was warmed up to 80 ℃;
(5) add the 0.5g Diisopropyl azodicarboxylate, be incubated after 2 hours, cool to 30 ℃, filter discharging.
Embodiment 3
A kind of preparation method of composite modified waterborne polyurethane resin may further comprise the steps:
(1) in a 1000mL four-hole boiling flask that whipping appts, TM and logical nitrogen protection be housed, adds 112.5g polyether Glycols, 33g Viscotrol C, 90.5g 4 successively; 4 '-diphenylmethanediisocyanate; Start simultaneously and stir and heating, 80-90 ℃ of insulation 2 hours;
(2) add 12.6g 1,6-pinakon, 10g epoxy resin E51 (Suzhou logical resin ltd of Soviet Union product), 0.1g N-methylmorpholine, 14.8g dimethylolpropionic acid, 80g N-ethyl pyrrolidone at 80-84 ℃, are incubated 30 minutes;
(3) begin to survey NCO, after nco value reaches 1.16%, be cooled to below 40 ℃, add vinyl monomer (51g TEB 3K, 9g Bing Xisuandingzhi, 2g isobornyl methacrylate, 8g N hydroxymethyl acrylamide), be cooled to below 40 ℃;
(4) add 11.2g N, the N-dimethylethanolamine, 2100rpm stirred 30 minutes, under 2500rpm stirs, added 515g deionized water and 4.5g diethylenetriamine.600rpm stirred after 10 minutes, was warmed up to 80 ℃;
(5) add the 0.5g BPO, be incubated after 2 hours, cool to 30 ℃, filter discharging.
Adopt the above-mentioned prescription and the composite modified waterborne polyurethane resin of prepared, it is detected.As shown in table 1.
The main performance index of table 1 prepared composite modified waterborne polyurethane of the present invention resin sees the following form:
The composite modified waterborne polyurethane resin of the present invention's preparation has good water dispersible, stability in storage.The water-borne wood coating that is mixed with, hardness is high, gloss is high, water-tolerant, solvent resistance are good.It compared with prior art has following advantage:
1, adopt Viscotrol C, epoxy resin, propenoate etc. composite modified, coating is high at the film process middle crosslink density, and hardness of paint film is high, gloss is high, water-tolerant, solvent resistance are good.
2, do not use low boiling point solvents such as acetone, cost is low, less energy consumption.
3, prepared composite modified aqueous polyurethane resin of the present invention is used for aqueous woodware paint, and its main performance index satisfies the requirement of GB/T 23999-2009 indoor decorating use woodwork coating.
More than show and described ultimate principle of the present invention, principal character and advantage of the present invention.The technician of the industry should understand; The present invention is not restricted to the described embodiments; That describes in the foregoing description and the specification sheets just explains principle of the present invention; The present invention also has various changes and modifications under the prerequisite that does not break away from spirit and scope of the invention, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain to be defined by appending claims and equivalent thereof.
Claims (18)
1. a composite modified waterborne polyurethane resin is characterized in that, said resin comprises following components in weight percentage:
Set of dispense compares %
Vulcabond 6-19;
Macromolecular polyol 6-15;
Viscotrol C 2-15;
Small molecule chain extender 1-5;
Epoxy resin 1-8;
Wetting ability chainextender 2-10;
Neutralizing agent 1-4;
Catalyzer 0.01-0.1;
Vinyl monomer 5-15;
Solvent 2-15;
Back chainextender 0.5-2;
Initiator 0.01-0.5;
Deionized water 50-60.
2. resin according to claim 1; It is characterized in that; Said vulcabond be tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 4,4 '-any one and arbitrary combination thereof of diphenylmethanediisocyanate, xylylene diisocyanate, cyclohexyl diisocyanate, tetramethylxylylene diisocyanate.
3. resin according to claim 1 is characterized in that, said macromolecular polyol is any one and an arbitrary combination thereof of polyether glycol, polycaprolactone polyol, polycarbonate polyol, THF homopolymer polyvalent alcohol.
4. resin according to claim 1 is characterized in that, said small molecule chain extender is a molecular weight in any one and arbitrary combination thereof of the divalent alcohol below 400, trivalent alcohol, tetravalent alcohol.
5. resin according to claim 4; It is characterized in that; Said small molecule chain extender is terepthaloyl moietie, Ucar 35,1,4-butyleneglycol, glycol ether, 1, any one of 6-pinakon, NSC 6366, TriMethylolPropane(TMP), tetramethylolmethane and arbitrary combination thereof.
6. resin according to claim 1; It is characterized in that said epoxy resin is that epoxy resin E20, the molecular-weight average of molecular-weight average 1000 is that 450 epoxy resin E44, molecular-weight average are any one and the arbitrary combination thereof among 370 the epoxy resin E51.
7. resin according to claim 1 is characterized in that, said wetting ability chainextender comprises dimethylol propionic acid, dimethylolpropionic acid.
8. resin according to claim 1 is characterized in that, said neutralizing agent is Trimethylamine 99, triethylamine, Tributylamine, triethylene diamine, N, N-dimethylethanolamine, N, any one in the N-diethylethanolamine and arbitrary combination thereof.
9. resin according to claim 1 is characterized in that, said catalyzer is any one and the arbitrary combination thereof in dibutyl tin laurate, stannous octoate, the N-methylmorpholine.
10. resin according to claim 1 is characterized in that, said vinyl monomer is a lower alkyl acrylate, methylacrylic acid lower alkyl esters, replacement or unsubstituted acrylic amide, vinyl cyanide, cinnamic a kind of and arbitrary combination.
11. vinyl monomer according to claim 10; It is characterized in that said vinyl monomer is methyl acrylate, methyl-methyl acrylate, ethyl propenoate, methyl-ethyl propenoate, Bing Xisuandingzhi, methyl-Bing Xisuandingzhi, ethyl acrylate, methyl-ethyl acrylate, vinylformic acid stearyl, methyl-vinylformic acid stearyl, IBOA, methyl-IBOA, 2-Hydroxy ethyl acrylate, methyl-2-Hydroxy ethyl acrylate, acrylic amide, methyl-acrylic amide, N hydroxymethyl acrylamide, vinyl cyanide, cinnamic any one and arbitrary combination thereof.
12. resin according to claim 1 is characterized in that, said solvent comprises any one of N-Methyl pyrrolidone, N-ethyl pyrrolidone.
13. resin according to claim 1; It is characterized in that; Said back chainextender is the polyamine that polyurethane dispersions is carried out chain extension, comprises any one and arbitrary combination thereof of quadrol, tn, tetramethylenediamine, isophorone diamine, phenylenediamine, tolylene diamine, hydrazine, diethylenetriamine, triethylene tetramine, TEPA.
14. resin according to claim 1 is characterized in that, said initiator is for causing the water-soluble or oil-soluble initiator that vinyl monomer carries out radical polymerization.
15. resin according to claim 14 is characterized in that, said initiator is any one of Potassium Persulphate, ammonium persulphate, Sodium Persulfate, Diisopropyl azodicarboxylate, BPO.
16. the preparation method of a composite modified waterborne polyurethane resin as claimed in claim 1 is characterized in that, according to weight percent meter, may further comprise the steps:
(1) in reaction kettle, adds macromolecular polyol, Viscotrol C, vulcabond successively, start simultaneously and stir and heating, be warming up to 80-90 ℃, be incubated 2 hours;
(2) add small molecule chain extender, epoxy resin, catalyzer, wetting ability chainextender, solvent,, be incubated 30 minutes at 80-84 ℃;
(3) survey NCO; After nco value reaches theoretical value, be cooled to below 40 ℃, add vinyl monomer;
(4) add neutralizing agent, high-speed stirring 30 minutes adds deionized water and back chainextender under high-speed stirring, and middling speed stirred after 10 minutes, was warmed up to 80 ℃;
(5) add initiator, be incubated after 2 hours, cool to 30 ℃, filter discharging.
17. preparation method according to claim 16 is characterized in that, in the step (4), the rotating speed of said high-speed stirring is 2000-3000rpm.
18. preparation method according to claim 16 is characterized in that, in the step (4), the rotating speed that said middling speed stirs is 500-2000rpm.
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Address after: 8555 No. 201700 Shanghai city Qingpu District Songze Avenue Applicant after: Shanghai Zhanchen Paint Co., Ltd. Applicant after: CHINA ZHANCHEN PAINTS GROUP LTD. Applicant after: Beijing Zhan Chen novel material company limited Address before: 8555 No. 201700 Shanghai city Qingpu District Songze Avenue Applicant before: Shanghai Zhanchen Paint Co., Ltd. Applicant before: Zhanchen Coatings Group Co., Ltd. Applicant before: Beijing Zhanchen Chemical Industry Co., Ltd. |
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Application publication date: 20121121 |