CN115746243A - Waterborne polyurethane resin and preparation method thereof - Google Patents
Waterborne polyurethane resin and preparation method thereof Download PDFInfo
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- CN115746243A CN115746243A CN202211415585.4A CN202211415585A CN115746243A CN 115746243 A CN115746243 A CN 115746243A CN 202211415585 A CN202211415585 A CN 202211415585A CN 115746243 A CN115746243 A CN 115746243A
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- aqueous polyurethane
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- 229920005749 polyurethane resin Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 16
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 16
- 229920000570 polyether Polymers 0.000 claims abstract description 16
- 229920005862 polyol Polymers 0.000 claims abstract description 16
- 150000003077 polyols Chemical class 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- 150000003839 salts Chemical class 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 61
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 6
- 238000004945 emulsification Methods 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 229960004063 propylene glycol Drugs 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 5
- -1 polyhexamethylene Polymers 0.000 claims description 5
- YRTNMMLRBJMGJJ-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;hexanedioic acid Chemical compound OCC(C)(C)CO.OC(=O)CCCCC(O)=O YRTNMMLRBJMGJJ-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- DHTGRDDBCWWKQJ-UHFFFAOYSA-N 2-(2,2-dihydroxyethoxy)ethane-1,1-diol Chemical compound OC(O)COCC(O)O DHTGRDDBCWWKQJ-UHFFFAOYSA-N 0.000 claims description 3
- CTNICFBTUIFPOE-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)ethane-1,1-diol Chemical compound OC(O)COC1=CC=C(O)C=C1 CTNICFBTUIFPOE-UHFFFAOYSA-N 0.000 claims description 3
- VYZKQGGPNIFCLD-UHFFFAOYSA-N 3,3-dimethylhexane-2,2-diol Chemical compound CCCC(C)(C)C(C)(O)O VYZKQGGPNIFCLD-UHFFFAOYSA-N 0.000 claims description 3
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 3
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 3
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 claims description 3
- CVNPKVXQUCOSOI-UHFFFAOYSA-N 3-ethylheptane-2,3-diol Chemical compound CCCCC(O)(CC)C(C)O CVNPKVXQUCOSOI-UHFFFAOYSA-N 0.000 claims description 3
- CHPNMYQJQQGAJS-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCOC(=O)C(C)=C CHPNMYQJQQGAJS-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000004970 Chain extender Substances 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 claims description 3
- JOUWRCGZMOSOCD-UHFFFAOYSA-N cyclopentyl-dimethoxy-propan-2-ylsilane Chemical compound CO[Si](OC)(C(C)C)C1CCCC1 JOUWRCGZMOSOCD-UHFFFAOYSA-N 0.000 claims description 3
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 3
- MEBJLVMIIRFIJS-UHFFFAOYSA-N hexanedioic acid;propane-1,2-diol Chemical compound CC(O)CO.OC(=O)CCCCC(O)=O MEBJLVMIIRFIJS-UHFFFAOYSA-N 0.000 claims description 3
- 238000009775 high-speed stirring Methods 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
- 230000007246 mechanism Effects 0.000 claims description 3
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 claims description 3
- YLBPOJLDZXHVRR-UHFFFAOYSA-N n'-[3-[diethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CCO[Si](C)(OCC)CCCNCCN YLBPOJLDZXHVRR-UHFFFAOYSA-N 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- 238000003756 stirring Methods 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
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 claims description 3
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 claims description 3
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 3
- WUMSTCDLAYQDNO-UHFFFAOYSA-N triethoxy(hexyl)silane Chemical compound CCCCCC[Si](OCC)(OCC)OCC WUMSTCDLAYQDNO-UHFFFAOYSA-N 0.000 claims description 3
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000000811 xylitol Substances 0.000 claims description 3
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 claims description 3
- 229960002675 xylitol Drugs 0.000 claims description 3
- 235000010447 xylitol Nutrition 0.000 claims description 3
- PTIXVVCRANICNC-UHFFFAOYSA-N butane-1,1-diol;hexanedioic acid Chemical compound CCCC(O)O.OC(=O)CCCCC(O)=O PTIXVVCRANICNC-UHFFFAOYSA-N 0.000 claims description 2
- 238000010411 cooking Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 235000013772 propylene glycol Nutrition 0.000 claims 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 1
- 229940035437 1,3-propanediol Drugs 0.000 claims 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims 1
- 238000005406 washing Methods 0.000 abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 229920000715 Mucilage Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a waterborne polyurethane resin and a preparation method thereof, which is mainly prepared from the following raw materials, by weight, 10-50 parts of polyether polyol, 150-200 parts of polyester polyol, 60-80 parts of isocyanate, 10-20 parts of dimethylolpropionic acid, 1-5 parts of a cross-linking agent, 0.5 part of a catalyst, 10-20 parts of a salt forming agent, 3-6 parts of a monohydric alcohol, 1-5 parts of organic silicon and 300-350 parts of deionized water. The waterborne polyurethane resin and the preparation method thereof have the advantages of simple preparation process and low requirement, and the waterborne polyurethane resin obtained by preparation has good washing resistance and heat resistance after being printed, and has good glossiness after being subjected to high temperature.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a waterborne polyurethane resin and a preparation method thereof.
Background
Polyurethane is one of the most important polymeric materials, and has unique advantages, such as low density, low thermal conductivity, good moisture permeability, excellent mechanical properties, good chemical stability, and the like. The polyurethane product family extends through thermoplastic materials and thermosetting materials and is widely applied in daily life, such as foams, elastomers, adhesives, coatings and the like. In the prior art, a plurality of preparation methods of polyurethane emulsion exist, and most of polyurethane mucilage resin has the problems of poor water washing resistance and low glossiness after baking after printing, thereby affecting the mucilage printing quality.
Disclosure of Invention
The invention aims to provide the waterborne polyurethane resin and the preparation method thereof, the preparation process is simple, the requirement is low, the prepared waterborne polyurethane resin has good washing resistance and good heat resistance after being printed, and the glossiness is good after high temperature.
The invention relates to a water-based polyurethane resin, which is mainly prepared from the following raw materials, by weight, 10-50 parts of polyether polyol, 150-200 parts of polyester polyol, 60-80 parts of isocyanate, 10-20 parts of dimethylolpropionic acid, 1-5 parts of a cross-linking agent, 0.5 part of a catalyst, 10-20 parts of a salt forming agent, 3-6 parts of a monohydric alcohol, 1-5 parts of organic silicon and 300-350 parts of deionized water.
Preferably, the polyether polyol is one or at least two of polypropylene oxide glycol, polypropylene oxide triol, polyethylene oxide glycol, polyethylene oxide triol, polytetramethylene ether glycol and propylene glycol.
Preferably, the polyester polyol is at least one or at least two of polyethylene glycol adipate glycol, polyethylene glycol neopentyl glycol adipate glycol, polybutylene adipate glycol, polyethylene glycol butanediol adipate glycol, polyethylene glycol propylene glycol adipate glycol, and polyethylene glycol neopentyl glycol adipate glycol.
Preferably, the isocyanate is one or at least two of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate.
Preferably, the crosslinking agent is at least one or at least two of ethylene glycol, 1,4 butanediol, diethylene glycol, triethylene glycol, 1,2 propylene glycol, neopentyl glycol, methyl propylene glycol, 1,6 hexanediol, 1,3 propylene glycol, dipropylene glycol, butyl ethyl propylene glycol, trimethyl pentanediol, trihydroxypropane, glycerol, xylitol, triethanolamine, hydroquinone dihydroxyethyl ether, and bisphenol a dihydroxyethyl ether.
Preferably, the monohydric alcohol is at least one or at least two of methanol, ethanol, isopropanol, n-butanol, isooctanol and n-decanol.
Preferably, the organosilicon is one or at least two of 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-divinyltriaminopropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, vinylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropyltriisopropoxysilane, 2- (3, 4-epoxycyclohexylalkyl) ethyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, isopropylcyclopentyldimethoxysilane, N-hexyltriethoxysilane, and isobutyltriethoxysilane.
Preferably, the salt forming agent is one or at least two of trimethylamine, triethylamine, tripropylamine, sodium hydroxide and ammonia water.
A preparation method of aqueous polyurethane resin, which is used for preparing the aqueous polyurethane resin, comprises the following steps;
s1, weighing polyether polyol and polyester polyol according to a proportion, and dehydrating the polyether polyol and the polyester polyol at the temperature of 110-120 ℃ for 0.5-1h;
s2, adding polyether polyol, polyester polyol and isocyanate into a reaction kettle, and reacting for 2 hours at the temperature of 88-95 ℃;
s3, adding a proper amount of acetone, dimethylolpropionic acid, a small molecular chain extender and a cross-linking agent into the reaction kettle, and reacting for 1 hour at 80-85 ℃;
s4, adding a proper amount of acetone into the reaction kettle, controlling the temperature of the reaction kettle to be 60-65 ℃, adding a catalyst and unit alcohol, and continuing to react for 3.5 hours;
s5, adding organic silicon into the reaction kettle for reaction for 5-10min to obtain a prepolymer;
s6, transferring the prepolymer into an emulsification barrel, and adding a salt forming agent into the emulsification barrel for neutralization; starting an emulsification stirring mechanism, adding deionized water under the condition of high-speed stirring, and dispersing and emulsifying for 10min to obtain an emulsion;
and S7, removing acetone from the emulsion to obtain the waterborne polyurethane resin.
Preferably, the method for removing acetone is a reduced pressure cooking method.
The technical scheme of the invention relates to a waterborne polyurethane resin and a preparation method thereof, and the waterborne polyurethane resin has the beneficial effects that: through organic silicon modification, the obtained waterborne polyurethane resin has good fastness to washing, and can keep good glossiness after high-temperature treatment. The preparation process is simple and quick, acetone is used as an organic solvent, the organic solvent is removed, the use of toxic organic solvents is reduced, and environmental pollution caused by volatilization of organic solvents with high toxicity is avoided.
Detailed Description
In order to facilitate the understanding of the technical solutions of the present invention for those skilled in the art, the technical solutions of the present invention will now be further described with reference to specific embodiments.
The invention relates to a water-based polyurethane resin, which is mainly prepared from the following raw materials, by weight, 10-50 parts of polyether polyol, 150-200 parts of polyester polyol, 60-80 parts of isocyanate, 10-20 parts of dimethylolpropionic acid, 1-5 parts of a cross-linking agent, 0.5 part of a catalyst, 10-20 parts of a salt forming agent, 3-6 parts of a monohydric alcohol, 1-5 parts of organic silicon and 300-350 parts of deionized water.
The polyether polyol is one or at least two of polypropylene oxide glycol, polypropylene oxide triol, polyethylene oxide glycol, polyethylene oxide triol, polytetramethylene ether glycol and propylene alcohol.
The polyester polyol is at least one or two of polyethylene glycol adipate glycol, polybutylene glycol adipate glycol, polyethylene glycol propylene glycol adipate glycol and polyethylene glycol adipate glycol neopentyl glycol adipate glycol.
The isocyanate is one or at least two of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate and xylylene diisocyanate.
The cross-linking agent is at least one or two of ethylene glycol, 1,4 butanediol, diethylene glycol, triethylene glycol, 1,2 propylene glycol, neopentyl glycol, methyl propylene glycol, 1,6 hexanediol, 1,3 propylene glycol, dipropylene glycol, butyl ethyl propylene glycol, trimethyl pentanediol, trihydroxypropane, glycerol, xylitol, triethanolamine, hydroquinone dihydroxyethyl ether and bisphenol A dihydroxyethyl ether.
The unit alcohol is at least one or two of methanol, ethanol, isopropanol, n-butanol, isooctanol and n-decanol.
The organic silicon is one or at least two of 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-diethylenetriaminopropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, vinylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropyltriisopropoxysilane, 2- (3, 4-epoxycyclohexylalkyl) ethyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, isopropylcyclopentyldimethoxysilane, N-hexyltriethoxysilane and isobutyltriethoxysilane.
The salt forming agent is one or at least two of trimethylamine, triethylamine, tripropylamine, sodium hydroxide and ammonia water.
In order to further verify the performance of the waterborne polyurethane resin prepared in the technical scheme, several specific examples are provided below, and the following table 1 shows.
Table 1:
the aqueous polyurethane resins were prepared by mixing the components of examples 1 to 7 and the following steps.
The method comprises the following specific steps:
firstly, weighing polyether polyol and polyester polyol according to a proportion, and dehydrating the polyether polyol and the polyester polyol at the temperature of 110-120 ℃ for 0.5-1h.
Secondly, adding polyether polyol, polyester polyol and isocyanate into a reaction kettle, and reacting for 2 hours at the temperature of 88-95 ℃.
Thirdly, adding a proper amount of acetone, dimethylolpropionic acid, a micromolecule chain extender 1,2 propylene glycol and a cross-linking agent into the reaction kettle, and reacting for 1 hour at 80-85 ℃. The amount of acetone added in this step is equivalent to the amount of salt forming agent added in the embodiment.
Fourthly, adding a proper amount of acetone into the reaction kettle, controlling the temperature of the reaction kettle to be 60-65 ℃, adding a catalyst of bismuth isooctanoate and monoalcohol, and continuing to react for 3.5 hours. The addition amount of acetone in the step is equal to that of dimethylolpropionic acid in the embodiment.
Fifthly, adding organic silicon into the reaction kettle for reaction for 5-10min to obtain a prepolymer.
Sixthly, transferring the prepolymer into an emulsifying barrel, and adding a salt forming agent into the emulsifying barrel for neutralization; and starting an emulsifying and stirring mechanism, adding deionized water under the condition of high-speed stirring, and dispersing and emulsifying for 10min to obtain the emulsion.
And seventhly, removing acetone from the emulsion to obtain the waterborne polyurethane resin.
The aqueous polyurethane resins prepared according to the first to seventh steps were prepared according to the raw material composition ratios of the above examples 1 to 7, and then the aqueous polyurethane resins prepared according to the above examples 1 to 7 were compared with a common polyurethane resin (comparative example 1) purchased in the market (innoxin materials corporation) in terms of dry and wet friction and gloss before and after heating, and the comparison results are shown in table 2 below.
Table 2:
the dry and wet rubbing standard is an execution standard of GB/T3920-2008 'color fastness to rubbing of textile test'.
As can be seen from the upper right table 2, the waterborne polyurethane resin prepared according to the technical scheme of the invention has good dry-wet friction degree, can have high-brightness glossiness after being subjected to mucilage printing, and can keep the high-brightness glossiness after being baked and baked at high temperature.
Technical solution of the present invention is described above with reference to the embodiments, and it is obvious that the specific implementation of the present invention is not limited by the above-mentioned manner, and it is within the scope of the present invention to adopt various insubstantial modifications of the method concept and technical solution of the present invention, or to directly apply the concept and technical solution of the present invention to other occasions without any modification.
Claims (10)
1. The waterborne polyurethane resin is characterized by mainly comprising the following raw materials, by weight, 10-50 parts of polyether polyol, 150-200 parts of polyester polyol, 60-80 parts of isocyanate, 10-20 parts of dimethylolpropionic acid, 1-5 parts of a crosslinking agent, 0.5 part of a catalyst, 10-20 parts of a salt forming agent, 3-6 parts of a monohydric alcohol, 1-5 parts of organic silicon and 300-350 parts of deionized water.
2. The aqueous polyurethane resin according to claim 1, wherein the polyether polyol is one or at least two of polypropylene oxide glycol, polypropylene oxide triol, polyethylene oxide glycol, polyethylene oxide triol, polytetramethylene ether glycol, and propylene glycol.
3. The aqueous polyurethane resin according to claim 1, wherein the polyester polyol is at least one or at least two of polyethylene glycol adipate glycol, polyhexamethylene glycol adipate glycol, polyethylene glycol adipate ester glycol, polybutylene adipate glycol, polyethylene glycol butanediol adipate glycol, polyethylene glycol propylene glycol adipate glycol, and polyethylene glycol neopentyl glycol adipate glycol.
4. The aqueous polyurethane resin according to claim 1, wherein the isocyanate is one or at least two of toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and xylylene diisocyanate.
5. The aqueous polyurethane resin according to claim 1, wherein the crosslinking agent is at least one or at least two of ethylene glycol, 1, 4-butanediol, diethylene glycol, triethylene glycol, 1, 2-propanediol, neopentyl glycol, methyl propylene glycol, 1, 6-hexanediol, 1, 3-propanediol, dipropylene glycol, butyl ethyl propylene glycol, trimethyl pentanediol, trimethylolpropane, glycerol, xylitol, triethanolamine, hydroquinone bis hydroxyethyl ether, and bisphenol a bis hydroxyethyl ether.
6. The aqueous polyurethane resin according to claim 1, wherein the unit alcohol is at least one or two of methanol, ethanol, isopropanol, n-butanol, isooctanol, and n-decanol.
7. The aqueous polyurethane resin according to claim 1, wherein the silicone is one or at least two of 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, 3-divinyltriaminopropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, vinylmethyldimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropyltriisopropoxysilane, 2- (3, 4-epoxycyclohexylalkyl) ethyltriethoxysilane, 3-glycidoxypropyltriethoxysilane, isopropylcyclopentyldimethoxysilane, N-hexyltriethoxysilane, and isobutyltriethoxysilane.
8. The waterborne polyurethane resin of claim 1, wherein the salt forming agent is one or at least two of trimethylamine, triethylamine, tripropylamine, sodium hydroxide and ammonia water.
9. A method for producing an aqueous polyurethane resin according to any one of claims 1 to 8, comprising the steps of;
s1, weighing polyether polyol and polyester polyol according to a proportion, and dehydrating the polyether polyol and the polyester polyol at 110-120 ℃ for 0.5-1h;
s2, adding polyether polyol, polyester polyol and isocyanate into a reaction kettle, and reacting for 2 hours at the temperature of 88-95 ℃;
s3, adding a proper amount of acetone, dimethylolpropionic acid, a small molecular chain extender and a cross-linking agent into the reaction kettle, and reacting for 1h at 80-85 ℃;
s4, adding a proper amount of acetone into the reaction kettle, controlling the temperature of the reaction kettle to be 60-65 ℃, adding a catalyst and unit alcohol, and continuing to react for 3.5 hours;
s5, adding organic silicon into the reaction kettle for reaction for 5-10min to obtain a prepolymer;
s6, transferring the prepolymer into an emulsification barrel, and adding a salt forming agent into the emulsification barrel for neutralization; starting an emulsification stirring mechanism, adding deionized water under the condition of high-speed stirring, and dispersing and emulsifying for 10min to obtain an emulsion;
and S7, removing acetone from the emulsion to obtain the waterborne polyurethane resin.
10. The method for producing an aqueous polyurethane resin according to claim 9, wherein the method for removing acetone is a reduced-pressure cooking method.
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