CN103588951A - Preparation of high-strength hydrophobic photo-curing waterborne polyurethane nano-composite emulsion - Google Patents
Preparation of high-strength hydrophobic photo-curing waterborne polyurethane nano-composite emulsion Download PDFInfo
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 48
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 48
- 239000000839 emulsion Substances 0.000 title claims abstract description 37
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 34
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000000016 photochemical curing Methods 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 238000004945 emulsification Methods 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 3
- -1 diisocyanate compound Chemical class 0.000 claims description 35
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 12
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 11
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 11
- 150000002009 diols Chemical class 0.000 claims description 11
- 229920005862 polyol Polymers 0.000 claims description 11
- 150000003077 polyols Chemical class 0.000 claims description 11
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 8
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000004566 IR spectroscopy Methods 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 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 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 229940008099 dimethicone Drugs 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 3
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 claims description 2
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 2
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
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- 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
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 150000001875 compounds Chemical class 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
- NYMPGSQKHIOWIO-UHFFFAOYSA-N hydroxy(diphenyl)silicon Chemical class C=1C=CC=CC=1[Si](O)C1=CC=CC=C1 NYMPGSQKHIOWIO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
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- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 2
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- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000921 polyethylene adipate Polymers 0.000 claims description 2
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- 238000006116 polymerization reaction Methods 0.000 claims description 2
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- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- UZMKOEWHQQPOBJ-UHFFFAOYSA-M sodium;2,3-dihydroxypropane-1-sulfonate Chemical compound [Na+].OCC(O)CS([O-])(=O)=O UZMKOEWHQQPOBJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 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 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 229920000139 polyethylene terephthalate Polymers 0.000 claims 1
- 239000005020 polyethylene terephthalate Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 150000003377 silicon compounds Chemical class 0.000 abstract 1
- 229920006264 polyurethane film Polymers 0.000 description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
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- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- VKEQBMCRQDSRET-UHFFFAOYSA-N Methylone Chemical compound CNC(C)C(=O)C1=CC=C2OCOC2=C1 VKEQBMCRQDSRET-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- 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
- C08G18/61—Polysiloxanes
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- 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
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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Abstract
本发明具体涉及一种高强度疏水性光固化水性聚氨酯纳米复合乳液的制备方法。本发明以二元醇和有机硅化合物为软段，并在乳化过程中原位引入纳米二氧化硅，制得光固化水性聚氨酯纳米复合乳液。该方法制得的光固化水性聚氨酯纳米复合膜具有较高的杨氏模量、拉伸强度及断裂伸长率，膜表面疏水性增强，吸水率降低且膜具有较高透明性。用该方法制备的光固化聚氨酯纳米复合乳液可广泛应用于涂料、胶粘剂、油墨、弹性体等领域。The invention specifically relates to a preparation method of a high-strength hydrophobic photocurable waterborne polyurethane nanocomposite emulsion. In the invention, dihydric alcohol and organic silicon compound are used as soft segments, and nano-silica is introduced in situ during the emulsification process to prepare photocurable water-based polyurethane nano-composite emulsion. The light-cured water-based polyurethane nanocomposite film prepared by the method has higher Young's modulus, tensile strength and elongation at break, the hydrophobicity of the film surface is enhanced, the water absorption rate is reduced, and the film has high transparency. The photocurable polyurethane nanocomposite emulsion prepared by the method can be widely used in the fields of coatings, adhesives, inks, elastomers and the like.
Description
技术领域technical field
本发明涉及一种高强度疏水性光固化水性聚氨酯纳米复合乳液的制备方法，特别涉及水性聚氨酯纳米复合乳液改性制备方法，属于紫外光固化水性涂料技术领域。The invention relates to a method for preparing a high-strength hydrophobic photocurable waterborne polyurethane nanocomposite emulsion, in particular to a method for preparing a modified waterborne polyurethane nanocomposite emulsion, and belongs to the technical field of ultraviolet light curable waterborne coatings.
背景技术Background technique
近年来，光固化水性聚氨酯乳液以其环保、节能、综合性能好、使用方便，清洁生产理念而日益被人们所关注，同时其固化膜具有良好的弹性及韧性而在涂层、胶黏剂、油墨等领域得到了较多的应用。然而，其力学性能(强度及模量)、耐水性及表面性能等方面还不能与传统光交联型聚氨酯相媲美，而且光固化水性聚氨酯膜表面在使用过程中易受到磨损而损伤，因而限制了光固化水性聚氨酯乳液的广泛应用。因此，在实际应用中急需提高光固化水性聚氨酯乳液的力学性能、耐水性及表面性能。针对此问题，《反应性与功能聚合物》(Reactive ＆ Functional Polymers，2011，71(6)，655-665)介绍在光固化水性聚氨酯体系中引入有机硅化合物对其进行改性，《胶体与界面科学》(J Colloid Interf Sci.2011，362，274-284)介绍在光固化水性聚氨酯体系中引入有机氟化合物对其进行改性，以上改性显著提高了光固化水性聚氨酯膜的表面疏水性，有效降低了膜的吸水率，但是膜的力学性能降低。将无机纳米材料如二氧化硅、粘土等引入光固化水性聚氨酯体系可以有效提高聚氨酯膜的模量、拉伸强度、硬度、耐磨性及表面耐划伤性等，但是膜的耐水性及表面疏水性提高不明显。本发明尝试在光固化水性聚氨酯体系引入有机硅化合物，同时在光固化水性聚氨酯乳液制备过程中原位引入纳米二氧化硅，制备光固化水性聚氨酯纳米复合乳液。采用上述方法制备的纳米复合乳液稳定性好，而且光固化膜具有较高的杨氏模量、拉伸强度及断裂伸长率，膜表面疏水性增强，吸水率降低且膜具有高透明性。用该方法制备的光固化聚氨酯纳米复合乳液可广泛应用于涂料、胶粘剂、油墨、弹性体等领域。In recent years, light-cured water-based polyurethane emulsion has attracted increasing attention due to its environmental protection, energy saving, good comprehensive performance, convenient use, and clean production concept. At the same time, its cured film has good elasticity and toughness and is used in coatings, adhesives, Ink and other fields have been widely used. However, its mechanical properties (strength and modulus), water resistance and surface properties are still not comparable to traditional photo-crosslinked polyurethane, and the surface of photo-cured water-based polyurethane film is easily damaged by abrasion during use, thus limiting Wide application of photocurable waterborne polyurethane emulsion. Therefore, there is an urgent need to improve the mechanical properties, water resistance and surface properties of photocurable waterborne polyurethane emulsions in practical applications. In response to this problem, "Reactive & Functional Polymers" (Reactive & Functional Polymers, 2011, 71 (6), 655-665) introduces the introduction of organosilicon compounds into photocurable waterborne polyurethane systems to modify it, "Colloids and Functional Polymers" Interface Science" (J Colloid Interf Sci.2011, 362, 274-284) introduces the introduction of organic fluorine compounds into the photocurable waterborne polyurethane system to modify it. The above modification significantly improves the surface hydrophobicity of the photocurable waterborne polyurethane film. , effectively reducing the water absorption of the membrane, but the mechanical properties of the membrane are reduced. Introducing inorganic nanomaterials such as silica, clay, etc. into the photocurable waterborne polyurethane system can effectively improve the modulus, tensile strength, hardness, abrasion resistance and surface scratch resistance of the polyurethane film, but the water resistance of the film and the surface Hydrophobic improvement is not obvious. The present invention attempts to introduce organosilicon compounds into the light-curable water-based polyurethane system, and at the same time introduce nano-silica in situ during the preparation of the light-curable water-based polyurethane emulsion to prepare the light-curable water-based polyurethane nano-composite emulsion. The nanocomposite emulsion prepared by the method has good stability, and the light-cured film has higher Young's modulus, tensile strength and elongation at break, the hydrophobicity of the film surface is enhanced, the water absorption rate is reduced, and the film has high transparency. The photocurable polyurethane nanocomposite emulsion prepared by the method can be widely used in the fields of coatings, adhesives, inks, elastomers and the like.
发明内容Contents of the invention
本发明目的是提供一种高强度疏水性光固化水性聚氨酯纳米复合乳液。在光固化水性聚氨酯体系中引入有机硅化合物，在光固化水性聚氨酯乳液制备过程中原位引入纳米二氧化硅，制备光固化水性聚氨酯纳米复合乳液，该方法制备的聚氨酯膜具有较高杨氏模量、拉伸强度及断裂伸长率，膜表面疏水性增强，吸水率降低且膜具有高透明性。The purpose of the present invention is to provide a high-strength hydrophobic photocurable water-based polyurethane nanocomposite emulsion. Introducing organosilicon compounds into the photocurable waterborne polyurethane system, and introducing nano-silica in situ during the preparation of photocurable waterborne polyurethane emulsion to prepare photocurable waterborne polyurethane nanocomposite emulsion. The polyurethane film prepared by this method has a higher Young's modulus , Tensile strength and elongation at break, the hydrophobicity of the film surface is enhanced, the water absorption rate is reduced and the film has high transparency.
本发明的技术方案：Technical scheme of the present invention:
1、一种高强度疏水性光固化水性聚氨酯纳米复合乳液的制备方法，其特征在于组成包括：50wt％-60wt％的低聚物多元醇，20wt％-30wt％的二异氰酸酯化合物，5wt％-30wt％的有机硅化合物，2wt％-4wt％的亲水单体，5wt％-15wt％的含羟基的不饱和双键丙烯酸酯化合物，1.5wt％-4wt％的胺类化合物，0wt％-20wt％的二氧化硅；制备方法步骤为：1. A method for preparing a high-strength hydrophobic photocurable water-based polyurethane nanocomposite emulsion, characterized in that the composition includes: 50wt%-60wt% oligomer polyol, 20wt%-30wt% diisocyanate compound, 5wt%- 30wt% organosilicon compound, 2wt%-4wt% hydrophilic monomer, 5wt%-15wt% hydroxyl-containing unsaturated double bond acrylate compound, 1.5wt%-4wt% amine compound, 0wt%-20wt% % silicon dioxide; The preparation method steps are:
按配比在二异氰酸酯化合物中，滴加低聚物多元醇和催化剂，滴加完毕后在45±5℃反应1-2h，向其中加入有机硅化合物，反应0.5-1h，然后逐渐升温至60℃，加入多羟基羧酸化合物粉末，在60℃进行反应4-5h，将阻聚剂均匀分散在甲基丙烯酸羟乙酯(HEMA)中，然后将其滴加到预聚体中，升温至75±5℃反应2-3h，直至红外光谱检测NCO基团特征峰完全消失。滴加胺类化合物，在30-40℃反应1-2h，滴加纳米二氧化硅水溶胶，在30-40℃反应1h，最后加入去离子水，强烈搅拌乳化，得到光固化水性聚氨酯纳米复合乳液，最后制备光固化水性聚氨酯纳米复合膜。In the diisocyanate compound according to the proportion, add oligomer polyol and catalyst dropwise, and react at 45±5°C for 1-2h after the dropwise addition, add organosilicon compound to it, react for 0.5-1h, and then gradually raise the temperature to 60°C, Add polyhydroxycarboxylic acid compound powder, react at 60°C for 4-5h, uniformly disperse the polymerization inhibitor in hydroxyethyl methacrylate (HEMA), then add it dropwise to the prepolymer, and raise the temperature to 75± React at 5°C for 2-3h until the characteristic peak of the NCO group detected by infrared spectroscopy completely disappears. Add amine compounds dropwise, react at 30-40°C for 1-2h, add nano-silica hydrosol dropwise, react at 30-40°C for 1h, finally add deionized water, emulsify vigorously, and obtain photocurable water-based polyurethane nanocomposite emulsion, and finally prepare a light-cured waterborne polyurethane nanocomposite film.
2、根据权利要求1所述一种高强度疏水性光固化水性聚氨酯纳米复合乳液的制备方法，其特征在于：所述的低聚物多元醇选用聚乙二醇、聚丙二醇、聚四氢呋喃二醇、聚己内酯多元醇、聚碳酸酯二醇、聚氧乙烯-聚氧丙烯-聚氧乙烯、聚己二酸乙二醇酯二醇、聚己二酸丁二醇酯二醇、聚对苯二甲酸乙二醇酯二醇、聚对苯二甲酸丁二醇酯二醇之一种，其分子量范围为400-6000。2. A method for preparing a high-strength hydrophobic light-curable water-based polyurethane nanocomposite emulsion according to
3、根据权利要求1所述一种高强度疏水性光固化水性聚氨酯纳米复合乳液的制备方法，其特征在于：所述的二异氰酸酯化合物选用2，4-甲苯二异氰酸酯、2，6-甲苯二异氰酸酯、异佛尔酮二异氰酸酯、二苯基甲烷4，4’-二异氰酸酯、己二撑二异氰酸酯、甲基环己基二异氰酸酯、2，2，4-三甲基己二异氰酸酯中之一种。3. A method for preparing a high-strength hydrophobic photocurable water-based polyurethane nanocomposite emulsion according to
4、根据权利要求1所述一种高强度疏水性光固化水性聚氨酯纳米复合乳液的制备方法，其特征在于：有机硅化合物选用α，ω-二羟基聚二甲基硅氧烷、二羟基聚二苯基硅氧烷、二羟基聚三氟丙基甲基硅氧烷、氨丙基聚二甲基硅氧烷、氨乙基氨丙基聚二甲基硅氧烷、氨乙基氨异丁基聚二甲基硅氧烷、N-乙基氨异丁基聚二甲基硅氧烷、中之一种，其分子量范围为400-35000。4. A method for preparing a high-strength hydrophobic light-curable water-based polyurethane nanocomposite emulsion according to
5、根据权利要求1所述一种高强度疏水性光固化水性聚氨酯纳米复合乳液的制备方法，其特征在于：所述的亲水单体选用二羟甲基丙酸，二羟甲基丁酸，1，2-二羟基-3-丙磺酸钠中之一种。5. A method for preparing a high-strength hydrophobic light-curable water-based polyurethane nanocomposite emulsion according to
6、根据权利要求1所述一种高强度疏水性光固化水性聚氨酯纳米复合乳液的制备方法，其特征在于：所述的含羟基的不饱和双键丙烯酸酯化合物选用丙烯酸羟乙酯、甲基丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟丙酯、丙烯酸羟丁酯、季戊四醇三丙烯酸酯中之一种。6. A method for preparing a high-strength hydrophobic light-curable water-based polyurethane nanocomposite emulsion according to
7、根据权利要求1所述一种高强度疏水性光固化水性聚氨酯纳米复合乳液的制备方法，其特征在于：所述的中和剂选用三乙胺、三乙醇胺、N-甲基二乙醇胺、甲基丙烯酸N，N-二甲胺基乙酯丙烯酸甲酯、N，N-二甲胺基对苯甲酸异辛酯、氨水、氢氧化钠中之一种。7. A method for preparing a high-strength hydrophobic light-curable water-based polyurethane nanocomposite emulsion according to
8、根据权利要求1所述一种高强度疏水性光固化水性聚氨酯纳米复合乳液的制备方法，其特征在于：所述的二氧化硅选用粒径范围为10-1000nm，PH范围为3-11，其固含量为10-50％。8. A method for preparing a high-strength hydrophobic light-curable water-based polyurethane nanocomposite emulsion according to
本发明的有益效果：本发明制备的高强度疏水性光固化水性聚氨酯纳米复合乳液的制备方法与现有的光固化水性聚氨酯相比具有以下优点：Beneficial effects of the present invention: the preparation method of the high-strength hydrophobic light-curable water-based polyurethane nano-composite emulsion prepared by the present invention has the following advantages compared with the existing light-curable water-based polyurethane:
通过在合成聚氨酯过程中引入有机硅化合物，同时在光固化水性聚氨酯乳液制备过程中引入纳米二氧化硅，制备光固化水性聚氨酯纳米复合乳液，得到的聚氨酯复合膜的力学性能及表面性能都有了较大的提高。By introducing organosilicon compounds in the process of synthesizing polyurethane, and introducing nano-silica in the preparation process of photocurable waterborne polyurethane emulsion, the photocurable waterborne polyurethane nanocomposite emulsion is prepared, and the mechanical properties and surface properties of the obtained polyurethane composite film are improved. Big improvement.
附图说明Description of drawings
图1光固化水性聚氨酯-有机硅-二氧化硅膜的水接触角Figure 1 Water contact angle of photocured waterborne polyurethane-organosilicon-silica film
图2光固化水性聚氨酯-有机硅-二氧化硅膜的拉伸性能Figure 2 Tensile properties of light-cured waterborne polyurethane-organic silicon-silica film
图3光固化水性聚氨酯-有机硅-二氧化硅膜的断面扫描图Figure 3 Cross-section scan of photocured waterborne polyurethane-organic silicon-silica film
具体实施方式Detailed ways
为了更好的解释本发明，下面结合具体实施例对本发明进行进一步详细解释。In order to better explain the present invention, the present invention will be further explained in detail below in conjunction with specific examples.
实施例1Example 1
制备光固化水性聚氨酯膜：在装有搅拌器、温度计和回流冷凝管的250mL四颈烧瓶中加入17.4g异佛尔酮二异氰酸酯(IPDI)，室温下一边搅拌一边用滴液漏斗滴加57.1g聚碳酸酯多元醇(PCD2000)和0.05g催化剂二月桂酸二丁基锡(DBTDL)，滴加速度控制在1.5h内，滴加完毕后在45±5℃反应1-2h；然后升温至60℃，加入3.75g二羟甲基丙酸(DMPA)，反应3-4h，通过甲苯-二正丁胺反滴定法测定反应程度，直到测定NCO基团含量达到理论值；将0.01g阻聚剂对羟基苯甲醚均匀分散在5.68g甲基丙烯酸羟乙酯(HEMA)中，然后将其滴加到预聚体中，升温至75±5℃反应，直至用红外光谱检测不到NCO在2265cm-1处的吸收峰，得到有机硅改性的光固化水性聚氨酯树脂，然后向树脂中加入2.83g的三乙胺，反应0.5-1h；向体系中滴加198.3g的去离子水进行乳化；最后制得光固化水性聚氨酯膜。Preparation of light-cured water-based polyurethane film: Add 17.4g of isophorone diisocyanate (IPDI) in a 250mL four-necked flask equipped with a stirrer, thermometer and reflux condenser, and add 57.1g of it dropwise with a dropping funnel while stirring at room temperature Polycarbonate polyol (PCD2000) and 0.05g catalyst dibutyltin dilaurate (DBTDL), the dropping rate is controlled within 1.5h, after the dropwise addition is completed, react at 45±5°C for 1-2h; then raise the temperature to 60°C, add 3.75g dimethylol propionic acid (DMPA), react 3-4h, measure reaction degree by toluene-di-n-butylamine back titration, reach theoretical value until measuring NCO group content; Dimethyl ether is uniformly dispersed in 5.68g of hydroxyethyl methacrylate (HEMA), and then it is added dropwise to the prepolymer, and the temperature is raised to 75±5°C to react until NCO cannot be detected by infrared spectroscopy at 2265cm -1 The absorption peak of organic silicon modified light-cured water-based polyurethane resin was obtained, and then 2.83g of triethylamine was added to the resin for 0.5-1h reaction; 198.3g of deionized water was added dropwise to the system for emulsification; finally Light-curing water-based polyurethane film.
实施例2Example 2
制备有机硅改性光固化水性聚氨酯膜：在装有搅拌器、温度计和回流冷凝管的250mL四颈烧瓶中加入17.4g异佛尔酮二异氰酸酯(IPDI)，室温下一边搅拌一边用滴液漏斗滴加51.3g聚碳酸酯多元醇(PCD2000)和0.05g催化剂二月桂酸二丁基锡(DBTDL)，滴加速度控制在1.5h内，滴加完毕后在45±5℃反应1-2h；向其中加入6.85g有机硅化合物，反应0.5-1h；然后升温至60℃，加入3.75g二羟甲基丙酸(DMPA)，反应3-4h，通过甲苯-二正丁胺反滴定法测定反应程度，直到测定NCO基团含量达到理论值；将0.01g阻聚剂对羟基苯甲醚均匀分散在5.68g甲基丙烯酸羟乙酯(HEMA)中，然后将其滴加到预聚体中，升温至75±5℃反应，直至用红外光谱检测不到NCO在2265cm-1处的吸收峰，得到有机硅改性的光固化水性聚氨酯树脂，然后向树脂中加入2.83g的三乙胺，反应0.5-1h；向体系中滴加198.3g的去离子水进行乳化；最后制得光固化水性聚氨酯膜。Preparation of silicone-modified light-cured water-based polyurethane film: Add 17.4 g of isophorone diisocyanate (IPDI) to a 250 mL four-neck flask equipped with a stirrer, a thermometer and a reflux condenser, and use a dropping funnel while stirring at room temperature Add 51.3g of polycarbonate polyol (PCD2000) and 0.05g of catalyst dibutyltin dilaurate (DBTDL) dropwise, the dropping speed is controlled within 1.5h, and react at 45±5°C for 1-2h after the dropping; 6.85g organosilicon compound, react for 0.5-1h; then raise the temperature to 60°C, add 3.75g dimethylolpropionic acid (DMPA), react for 3-4h, measure the reaction degree by toluene-di-n-butylamine back titration method, until Measure that the NCO group content reaches the theoretical value; 0.01g inhibitor p-hydroxyanisole is uniformly dispersed in 5.68g hydroxyethyl methacrylate (HEMA), then it is added dropwise in the prepolymer, and the temperature is raised to 75 React at ±5°C until the absorption peak of NCO at 2265cm -1 cannot be detected by infrared spectroscopy to obtain a silicone-modified light-curable water-based polyurethane resin, then add 2.83g of triethylamine to the resin and react for 0.5-1h ; Add 198.3g of deionized water dropwise to the system for emulsification; finally make a light-cured water-based polyurethane film.
实施例3Example 3
制备二氧化硅改性光固化水性聚氨酯-有机硅膜：在装有搅拌器、温度计和回流冷凝管的250mL四颈烧瓶中加入17.4g异佛尔酮二异氰酸酯(IPDI)，室温下一边搅拌一边用滴液漏斗滴加51.3g聚碳酸酯多元醇(PCD2000)和0.05g催化剂二月桂酸二丁基锡(DBTDL)，滴加速度控制在1.5h内，滴加完毕后在45±5℃反应1-2h；向其中加入6.85g有机硅化合物，反应0.5-1h；然后升温至60℃，加入3.75g二羟甲基丙酸(DMPA)，反应3-4h，通过甲苯-二正丁胺反滴定法测定反应程度，直到测定NCO基团含量达到理论值；将0.01g阻聚剂对羟基苯甲醚均匀分散在5.68g甲基丙烯酸羟乙酯(HEMA)中，然后将其滴加到预聚体中，升温至75±5℃反应，直至用红外光谱检测不到NCO在2265cm-1处的吸收峰，得到有机硅改性的光固化水性聚氨酯树脂，然后向树脂中加入2.83g的三乙胺，反应0.5-1h；加入14.91g的二氧化硅，反应0.5-1h；向体系中滴加198.3g的去离子水进行乳化；最后制得二氧化硅改性的光固化水性聚氨酯膜。Preparation of silica-modified photocurable waterborne polyurethane-organosilicon film: Add 17.4g of isophorone diisocyanate (IPDI) to a 250mL four-necked flask equipped with a stirrer, thermometer and reflux condenser, and stir while stirring at room temperature Add 51.3g of polycarbonate polyol (PCD2000) and 0.05g of catalyst dibutyltin dilaurate (DBTDL) dropwise with a dropping funnel, the dropping rate is controlled within 1.5h, and react at 45±5°C for 1-2h after dropping ; Add 6.85g organosilicon compound to it, react for 0.5-1h; then raise the temperature to 60°C, add 3.75g dimethylol propionic acid (DMPA), react for 3-4h, and measure by toluene-di-n-butylamine back titration method The degree of reaction until the NCO group content reaches the theoretical value; 0.01g of inhibitor p-hydroxyanisole is uniformly dispersed in 5.68g of hydroxyethyl methacrylate (HEMA), and then added dropwise to the prepolymer , be heated to 75 ± 5 ℃ and react until the absorption peak of NCO at 2265cm -1 cannot be detected by infrared spectroscopy to obtain a silicone-modified light-curable water-based polyurethane resin, and then add 2.83g of triethylamine to the resin, React for 0.5-1h; add 14.91g of silicon dioxide and react for 0.5-1h; drop 198.3g of deionized water into the system for emulsification; finally prepare a silicon dioxide-modified photocurable water-based polyurethane film.
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| CN102336884A (en) * | 2011-06-23 | 2012-02-01 | 江南大学 | Preparation method for macromonomer modified nanometer silica aqueous silica sol and light-cured aqueous polyurethane nanometer composite emulsion of same |
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| CN102336884A (en) * | 2011-06-23 | 2012-02-01 | 江南大学 | Preparation method for macromonomer modified nanometer silica aqueous silica sol and light-cured aqueous polyurethane nanometer composite emulsion of same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104045802B (en) * | 2014-06-17 | 2017-01-18 | 四川国和新材料有限公司 | No-peculiar-smell alcohol-soluble modified acrylate resin and preparation method thereof |
| CN104045802A (en) * | 2014-06-17 | 2014-09-17 | 四川国和新材料有限公司 | No-peculiar-smell alcohol-soluble modified acrylate resin and preparation method thereof |
| CN105837840B (en) * | 2016-05-11 | 2018-07-10 | 江南大学 | A kind of polymer/ZnO/SiO2The preparation method of composite nano-microsphere |
| CN105837840A (en) * | 2016-05-11 | 2016-08-10 | 江南大学 | A kind of preparation method of polymer/ZnO/SiO2 nanocomposite microsphere |
| CN107902946A (en) * | 2017-06-01 | 2018-04-13 | 广东中涂联涂料科技有限公司 | A kind of sponge-type pervious concrete enhancing material and preparation method thereof |
| CN107902946B (en) * | 2017-06-01 | 2020-09-15 | 广东砂鸵涂料科技有限公司 | Sponge type pervious concrete reinforcing material and preparation method thereof |
| CN107602796A (en) * | 2017-09-26 | 2018-01-19 | 苏州米颜生物科技有限公司 | A kind of preparation method of compounded rubber for solid tyre |
| CN108102519A (en) * | 2017-12-23 | 2018-06-01 | 陈建峰 | A kind of preparation method of high rigidity hydrophobic type ultraviolet-curing paint |
| CN108101405A (en) * | 2017-12-29 | 2018-06-01 | 深圳市嘉达高科产业发展有限公司 | A kind of pervious concrete reinforcing agent and preparation method thereof |
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| CN108864929A (en) * | 2018-07-27 | 2018-11-23 | 武汉理工大学 | A kind of water-soluble low surface energy resin/nano zine oxide compound anti-fouling paint and preparation method thereof |
| CN108864929B (en) * | 2018-07-27 | 2019-11-08 | 武汉理工大学 | A kind of waterborne low surface energy resin/nanometer zinc oxide composite antifouling coating and preparation method thereof |
| CN111019502A (en) * | 2019-12-06 | 2020-04-17 | 浙江工业大学之江学院 | A kind of preparation method, product and application of polyurethane coating |
| CN111019502B (en) * | 2019-12-06 | 2021-05-25 | 浙江工业大学之江学院 | A kind of preparation method, product and application of polyurethane coating |
| CN112940595A (en) * | 2019-12-11 | 2021-06-11 | 武汉惠帮地平工程有限公司 | Insulating high-resistance terrace and construction method |
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