CN116375967A - Sulfo aqueous polyurethane dispersoid and preparation method thereof - Google Patents
Sulfo aqueous polyurethane dispersoid and preparation method thereof Download PDFInfo
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- CN116375967A CN116375967A CN202310040088.9A CN202310040088A CN116375967A CN 116375967 A CN116375967 A CN 116375967A CN 202310040088 A CN202310040088 A CN 202310040088A CN 116375967 A CN116375967 A CN 116375967A
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- aqueous polyurethane
- sulfonic acid
- polyurethane dispersion
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 18
- 239000004814 polyurethane Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 title description 2
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 26
- 229920003009 polyurethane dispersion Polymers 0.000 claims abstract description 26
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 22
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 19
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 11
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 10
- 239000000839 emulsion Substances 0.000 claims description 10
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004970 Chain extender Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 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 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010907 mechanical stirring Methods 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 235000011037 adipic acid Nutrition 0.000 claims description 4
- 239000001361 adipic acid Substances 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 3
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical group CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 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 2
- 239000002253 acid Substances 0.000 abstract description 5
- 238000006277 sulfonation reaction Methods 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 4
- 229920001225 polyester resin Polymers 0.000 description 4
- 239000004645 polyester resin Substances 0.000 description 4
- 230000001681 protective effect Effects 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- -1 coatings Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6614—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6618—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3234—Polyamines cycloaliphatic
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
- C08G18/3246—Polyamines heterocyclic, the heteroatom being oxygen or nitrogen in the form of an amino group
-
- 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
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
-
- 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
- C08G18/48—Polyethers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a sulfonic aqueous polyurethane dispersion and a preparation method thereof. The invention prepares polyester polyol by dehydrating and condensing itaconic acid and dibasic acid and dihydric alcohol, obtains water-soluble polyester polyol containing sulfonic acid groups after sulfonation, and then prepares sulfonic acid group water-based polyurethane dispersoid by taking sulfonate group water-soluble polyester polyol and diisocyanate as main raw materials. The method for synthesizing the waterborne polyurethane by taking the bio-based itaconic acid as the main raw material is environment-friendly, pollution-free in the production process, low in price and high in cost performance, and has important significance for protecting the ecological environment and sustainable development.
Description
Technical Field
The invention belongs to the technical field of preparation of waterborne polyurethane, and particularly relates to a sulfonic acid group waterborne polyurethane dispersoid and a preparation method thereof.
Background
Polyurethane dispersion (PUDs) is an environment-friendly material using water as a dispersion medium, and has the characteristics of low VOC content, low toxicity, incombustibility and the like. By combining new monomer research, research and development of a synthetic method and development of a crosslinking modification technology, the structural composition of polyurethane molecules can be effectively designed, so that the mechanical property and the thermal property of the polyurethane molecules are improved, and the polyurethane molecules are widely applied to the fields of adhesives, coatings, leather making, textile assistants, medicine and health, building materials, printing and the like.
Most polyurethane dispersions are currently anionic aqueous polyurethanes, with hydrophilic groups being carboxyl or sulfonic groups. The aqueous polyurethane containing carboxyl has low solid content and high viscosity, and needs to be added with a neutralizing agent to adjust the pH value, and compared with carboxylate, sulfonate belongs to strong acid and strong alkali salt and has stronger hydrophilicity, so that the dosage is less when the polyurethane dispersion is synthesized; the dispersion has a more stable 'double electric layer' structure, and has better acid, alkali, electrolyte, mechanical stability, compatibility with auxiliary agents and dispersion adhesive film performance. However, sulfonate-type polyester polyols have a large amount of ester bonds and are relatively high in sulfonate hydrophilicity, so that the polyester polyols are easy to hydrolyze in the storage process, low-molecular-weight polyester polyols are produced, the molecular weight of the prepared polyurethane resin is influenced, and adverse effects on the properties such as impact resistance, compactness and the like of related products are further produced.
The itaconic acid is an unsaturated dibasic acid synthesized by taking agricultural byproducts such as starch, sucrose, wood dust and the like as raw materials, has no pollution to the environment in the production process, is low in price and high in cost performance, and is a bio-based raw material. Since itaconic acid contains two active-COOH and one-c=c-in the molecule, itaconic acid can undergo addition reaction and polymerization reaction to form stable high molecular polyester. Its methylene group can provide strong hydrophilic-SO after sulfonation 3 Na groups change the polyester molecules from conventional oil solubility to water solubility. The aqueous polyurethane dispersion prepared based on the water-soluble polyurethane has excellent performance, good dissolution property in water and environmental protection. And the cost is low, the cost performance is high, and the method has wide application prospect and development space.
Disclosure of Invention
The invention aims to effectively solve the problems and provide a sulfonic acid group aqueous polyurethane dispersion and a preparation method thereof.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a method for preparing a sulfonic acid group aqueous polyurethane dispersion, comprising the following steps:
1) Preparation of sulfonic acid group-containing polyester polyol:
1-1) adding 10-20 parts of itaconic acid, 0-10 parts of adipic acid, 10-23 parts of dihydric alcohol and a catalyst accounting for 0.03-0.05% of the total mass of the raw materials into the mixture at 70-72 ℃ in parts by mol, heating the mixture to 150 ℃ for reaction for 30-35 min, gradually heating the mixture to 180-200 ℃ in 40-60 min, and continuing the reaction for 2-3 h;
1-2) cooling to 70-72 ℃, and dripping NaHSO with the concentration of 0.1M/L 3 Aqueous solution of NaHSO 3 The molar ratio of the mixture to the itaconic acid is 1:1.5-2, the dripping is completed within 1h, the temperature is raised to 85-105 ℃, and the rapid stirring reaction is carried out for 4-8 h;
1-3) cooling to 70-72 ℃, distilling under reduced pressure for 30-60 min under 10mmHg, discharging, drying and preserving to obtain the polyester polyol containing sulfonic groups.
The dihydric alcohol is one or a combination of more of 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol and triethylene glycol. Further, the dihydric alcohol is a mixture of 1, 6-hexanediol and neopentyl glycol with a molar ratio of 1:1-1:0.3.
The catalyst is monobutyl tin oxide, dibutyl tin dilaurate, tetraisopropyl titanate or tetrabutyl titanate.
2) Preparation of sulfonic acid group aqueous polyurethane dispersion:
2-1) adding 10-50 parts of polyester polyol containing sulfonic groups and 0-50 parts of polyether glycol into a polyester resin with N according to parts by weight 2 The method comprises the steps of (1) in a flask with protective atmosphere, temperature control, mechanical stirring and reflux condensation, heating to 105-110 ℃, performing reduced pressure distillation for 1h under 10mmHg to remove water, and then cooling to 78-80 ℃;
2-2) adding 20-40 parts of diisocyanate and 0.05-0.15 part of catalyst according to parts by weight, continuously stirring to control the reaction temperature to 80-85 ℃, reacting for 2-4 hours, and adding acetone to control the viscosity of the system in the reaction process;
2-3) cooling to 50-52 ℃, adding 8-15 parts of chain extender and 80-120 parts of deionized water according to parts by weight, rapidly stirring for 2 hours to obtain emulsion, and distilling under reduced pressure at normal temperature to remove acetone to obtain the sulfonic acid aqueous polyurethane dispersoid.
The dihydric alcohol is one or a combination of more of 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol and triethylene glycol. Further, the dihydric alcohol is a mixture of 1, 6-hexanediol and neopentyl glycol with a molar ratio of 1:1-1:0.3.
The catalyst is monobutyl tin oxide, dibutyl tin dilaurate, tetraisopropyl titanate or tetrabutyl titanate.
The diisocyanate is one or a combination of a plurality of TDI, MDI, IPDI, HDI.
The chain extender is one or a combination of more of ethylene glycol, 1, 4-butanediol, neopentyl glycol, diethylene glycol, ethylenediamine, hexamethylenediamine, piperazine and isophorone diamine.
Further, the chain extender is piperazine or isophorone diamine.
Further, the solid content of the sulfonic acid group aqueous polyurethane dispersion is 40-60%.
The invention adopts itaconic acid, dibasic acid and dihydric alcohol to prepare polyester polyol through dehydration condensation, and the water-soluble polyester polyol containing sulfonic group is obtained after sulfonation, and the water-soluble polyurethane dispersoid is synthesized with isocyanate, and the structure of a soft segment and a hard segment is further adjusted by increasing the steric hindrance of the dihydric alcohol component and a chain extender in the synthesis process, so that the crystallization performance of the water-soluble polyester polyol is reduced, and the solid content of emulsion is improved.
The invention has the following beneficial effects:
1. the bio-based raw materials itaconic acid and dihydric alcohol are adopted to synthesize polyester polyol, and the sulfonic polyester polyol serving as a soft segment is obtained after sulfonation, so that the prepared aqueous polyurethane dispersion can be endowed with good hydrophilicity, good comprehensive performance and better stability. The method is green and environment-friendly, low in price and high in cost performance.
2. The steric hindrance of the soft and hard segments of polyurethane molecular chains is adjusted by respectively using nonlinear dihydric alcohol (such as neopentyl glycol) and a chain extender (such as piperazine or isophorone diamine), so that the acting force of intermolecular hydrogen bonds is reduced, the crystallization performance is further reduced, and the high-solid-content aqueous polyurethane emulsion is prepared.
Detailed Description
The following examples will enable those skilled in the art to better understand the present invention and are not intended to limit the present invention in any way.
Example 1
1) Preparation of polyester polyol containing sulfonic acid group
Adding 20 parts of itaconic acid, 23 parts of hexanediol and dibutyltin oxide accounting for 0.05% of the total mass of the raw materials in parts by mol at 70 ℃, heating to 150 ℃ for reaction 30min, gradually heating to 200 ℃ in 60min, and continuing to react for 3h; cooling to 70 ℃, and dripping NaHSO with the concentration of 0.1M/L 3 Aqueous solution of NaHSO 3 The molar ratio of the itaconic acid to the itaconic acid is 1:1.5, the dropwise addition is completed within 1h, the temperature is raised to 95 ℃, and the reaction is carried out for 5h by rapid stirring; cooling to 70 ℃, distilling under reduced pressure for 60min under 10mmHg, discharging, drying and preserving to obtain the polyester polyol A containing sulfonic groups.
2) Preparation of sulfonic acid-based aqueous polyurethane dispersions
Adding 30 parts of polyester polyol A containing sulfonic groups and 20 parts of polyether glycol into a polyester resin with N in parts by mass 2 The method comprises the steps of (1) in a flask with protective atmosphere, temperature control, mechanical stirring and reflux condensation, heating to 110 ℃, performing reduced pressure distillation for 1h under 10mmHg to remove water, and then cooling to 80 ℃; adding 40 parts of MDI and 0.1 part of dibutyltin oxide according to parts by weight, continuously stirring to control the reaction temperature to 85 ℃, reacting for 4 hours, and adding acetone to control the viscosity of the system in the reaction process; cooling to 50 ℃, adding 10 parts of piperazine and 100 parts of deionized water according to parts by weight, rapidly stirring for 2 hours to form emulsion, and distilling under reduced pressure at normal temperature to remove acetone to obtain sulfonic acid group water-based polymerA urethane dispersion.
Example 2
1) Preparation of polyester polyol containing sulfonic acid group
Adding 10 parts of itaconic acid, 10 parts of adipic acid, 17 parts of hexanediol and 6 parts of neopentyl glycol in parts by mol at 70 ℃, heating to 150 ℃ for reaction for 30min, gradually heating to 190 ℃ in 60min, and continuing the reaction for 3h; cooling to 70 ℃, and dripping NaHSO with the concentration of 0.1M/L 3 Aqueous solution of NaHSO 3 The molar ratio of the itaconic acid to the itaconic acid is 1:2, the dripping is completed within 1h, the temperature is raised to 95 ℃, and the reaction is rapidly stirred for 6h; cooling to 70 ℃, distilling under reduced pressure for 60min under 10mmHg, discharging, drying and preserving to obtain the polyester polyol B containing sulfonic groups.
2) Preparation of sulfonic acid-based aqueous polyurethane dispersions
Adding 20 parts of polyester polyol B containing sulfonic groups and 30 parts of polyether glycol into a polyester resin with N in parts by mass 2 The method comprises the steps of (1) in a flask with protective atmosphere, temperature control, mechanical stirring and reflux condensation, heating to 110 ℃, performing reduced pressure distillation for 1h under 10mmHg to remove water, and then cooling to 80 ℃; adding 40 parts of MDI and 0.1 part of dibutyltin oxide according to parts by weight, continuously stirring to control the reaction temperature to 85 ℃, reacting for 4 hours, and adding acetone to control the viscosity of the system in the reaction process; cooling to 50 ℃, adding 15 parts of isophorone diamine and 120 parts of deionized water according to parts by weight, rapidly stirring for 2 hours to obtain emulsion, and distilling under reduced pressure at normal temperature to remove acetone to obtain the sulfonic acid group aqueous polyurethane dispersoid.
Example 3
1) Preparation of polyester polyol containing sulfonic acid group
Adding 15 parts of itaconic acid, 5 parts of adipic acid, 17 parts of hexanediol and 6 parts of neopentyl glycol in parts by mol at 70 ℃, heating to 150 ℃ for reaction for 30min, gradually heating to 190 ℃ in 60min, and continuing the reaction for 3h; cooling to 70 ℃, and dripping NaHSO with the concentration of 0.1M/L 3 Aqueous solution of NaHSO 3 The molar ratio of the itaconic acid to the itaconic acid is 1:2, the dripping is completed within 1h, the temperature is raised to 95 ℃, and the reaction is rapidly stirred for 6h; cooling to 70deg.C under 10mmHgAnd (3) distilling under reduced pressure for 60min, discharging, drying and preserving to obtain the polyester polyol C containing sulfonic groups.
2) Preparation of sulfonic acid-based aqueous polyurethane dispersions
Adding 20 parts of polyester polyol C containing sulfonic groups and 30 parts of polyether glycol into a polyester resin with N in parts by mass 2 The method comprises the steps of (1) in a flask with protective atmosphere, temperature control, mechanical stirring and reflux condensation, heating to 110 ℃, performing reduced pressure distillation for 1h under 10mmHg to remove water, and then cooling to 80 ℃; adding 40 parts of MDI and 0.1 part of dibutyltin oxide according to parts by weight, continuously stirring to control the reaction temperature to 85 ℃, reacting for 4 hours, and adding acetone to control the viscosity of the system in the reaction process; cooling to 50 ℃, adding 10 parts of piperazine and 120 parts of deionized water according to parts by weight, rapidly stirring for 2 hours to obtain emulsion, and distilling under reduced pressure at normal temperature to remove acetone to obtain the sulfonic aqueous polyurethane dispersion.
TABLE 1 polyurethane Dispersion Components and Performance comparison
The aqueous sulfonic polyurethane dispersions prepared in examples 1-3 were observed to be non-gelled within 15 days, the emulsion appearance was milky blue, and the average particle size of the emulsion slightly increased and the viscosity decreased with the adjustment of the diacid and diol species. The viscosity is reduced, so that the difficulty in selecting the emulsion polymerization equipment is reduced, the shearing strength is improved, the difficulty in processing in the coating process is reduced, and the stability of emulsion products is further improved.
The above examples of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. It is to be understood by persons skilled in the art that the foregoing detailed description is illustrative and not restrictive, and that this invention is not limited to the details shown and described.
Claims (9)
1. A method for preparing a sulfonic acid group aqueous polyurethane dispersion, which is characterized by comprising the following steps:
1) According to parts by mass10 to 50 parts of polyester polyol containing sulfonic groups and 0 to 50 parts of polyether glycol are added into the mixture with N 2 Heating the mixture to 105-110 ℃ in a flask with protection atmosphere, temperature control, mechanical stirring and reflux condensation, performing reduced pressure distillation under 10mmHg to remove water, and then cooling to 78-80 ℃;
2) Adding 20-40 parts of diisocyanate and 0.05-0.15 part of catalyst according to parts by weight, continuously stirring to control the reaction temperature to 80-85 ℃, reacting for 2-4 hours, and adding acetone to control the viscosity of the system in the reaction process;
3) Cooling to 50-52 ℃, adding 8-15 parts of chain extender and 80-120 parts of water according to parts by weight, stirring to form emulsion, and distilling under reduced pressure at normal temperature to remove acetone to obtain the sulfonic acid group aqueous polyurethane dispersoid.
2. The method for preparing the aqueous polyurethane dispersion containing the sulfonic acid group according to claim 1, wherein the polyester polyol containing the sulfonic acid group is prepared by the following method:
1) Adding 10-20 parts of itaconic acid, 0-10 parts of adipic acid, 10-23 parts of dihydric alcohol and a catalyst accounting for 0.03-0.05% of the total mass of the raw materials in parts by mol at 70-72 ℃, heating to 145-150 ℃ for reaction for 30-35 min, gradually heating to 180-200 ℃ in 40-60 min, and continuing to react for 2-3 h;
2) Cooling to 70-72 ℃, and dripping NaHSO with the concentration of 0.1M/L 3 Aqueous solution of NaHSO 3 The mixture is added dropwise within 1:1.5-2 in a molar ratio of 1h, the temperature is raised to 85-105 ℃, and the mixture is stirred and reacted for 4-8 h;
3) Cooling to 70-72 ℃, distilling under reduced pressure for 30-60 min under 10mmHg, discharging, drying and preserving to obtain the polyester polyol containing sulfonic groups.
3. The method for preparing a sulfonic aqueous polyurethane dispersion according to claim 2, wherein the dihydric alcohol is one or a combination of several of 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol and triethylene glycol.
4. A method for preparing a sulfonic acid group aqueous polyurethane dispersion according to claim 3, wherein said glycol is a mixture of 1, 6-hexanediol and neopentyl glycol in a molar ratio of 1:1 to 1:0.3.
5. The method for preparing the aqueous polyurethane dispersion with sulfonic acid groups according to claim 1 or 2, wherein the catalyst is monobutyl tin oxide, dibutyl tin dilaurate, tetraisopropyl titanate or tetrabutyl titanate.
6. The method for preparing the sulfonic aqueous polyurethane dispersion according to claim 1, wherein the chain extender is one or a combination of several of ethylene glycol, 1, 4-butanediol, neopentyl glycol, diethylene glycol, ethylenediamine, hexamethylenediamine, piperazine and isophorone diamine.
7. The method for preparing a sulfonic acid group aqueous polyurethane dispersion according to claim 1, wherein the diisocyanate is one or a combination of a plurality of TDI, MDI, IPDI, HDI.
8. A sulfonic acid group aqueous polyurethane dispersion, characterized in that it is obtained by the production method according to claim 1 or 2.
9. The sulfonic acid group aqueous polyurethane dispersion according to claim 8, wherein the solid content is 40 to 60%.
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