CN102093534B - Preparation method of polyurethane aqueous dispersion and waterborne polyurethane paint containing polyurethane aqueous dispersion - Google Patents
Preparation method of polyurethane aqueous dispersion and waterborne polyurethane paint containing polyurethane aqueous dispersion Download PDFInfo
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- CN102093534B CN102093534B CN 201010605593 CN201010605593A CN102093534B CN 102093534 B CN102093534 B CN 102093534B CN 201010605593 CN201010605593 CN 201010605593 CN 201010605593 A CN201010605593 A CN 201010605593A CN 102093534 B CN102093534 B CN 102093534B
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- polyurethane
- diisocyanate
- carboxylate
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- diol
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 138
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 137
- 239000006185 dispersion Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title abstract description 39
- 239000003973 paint Substances 0.000 title abstract description 3
- 239000004970 Chain extender Substances 0.000 claims abstract description 68
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000007787 solid Substances 0.000 claims abstract description 37
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 150000001412 amines Chemical group 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 65
- -1 C2-C6 alkyl diol Chemical class 0.000 claims description 62
- 239000000178 monomer Substances 0.000 claims description 61
- 229920000642 polymer Polymers 0.000 claims description 59
- 239000011527 polyurethane coating Substances 0.000 claims description 59
- 125000003158 alcohol group Chemical group 0.000 claims description 58
- 125000005442 diisocyanate group Chemical group 0.000 claims description 58
- 239000003431 cross linking reagent Substances 0.000 claims description 57
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 52
- 229920003009 polyurethane dispersion Polymers 0.000 claims description 49
- 150000002009 diols Chemical class 0.000 claims description 46
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 33
- 229920000570 polyether Polymers 0.000 claims description 33
- 229920005862 polyol Polymers 0.000 claims description 33
- 125000006528 (C2-C6) alkyl group Chemical group 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 150000003077 polyols Chemical class 0.000 claims description 28
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 26
- 239000003822 epoxy resin Substances 0.000 claims description 26
- 229920000647 polyepoxide Polymers 0.000 claims description 26
- 239000000376 reactant Substances 0.000 claims description 26
- 229920000728 polyester Polymers 0.000 claims description 21
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 20
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 19
- 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 19
- 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 18
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 14
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 13
- 239000013638 trimer Substances 0.000 claims description 13
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 12
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 12
- 230000003472 neutralizing effect Effects 0.000 claims description 12
- 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 11
- 230000001105 regulatory effect Effects 0.000 claims description 11
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 10
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 10
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 9
- JVYDLYGCSIHCMR-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)butanoic acid Chemical compound CCC(CO)(CO)C(O)=O JVYDLYGCSIHCMR-UHFFFAOYSA-N 0.000 claims description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 8
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 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 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 claims description 5
- 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
- 239000005062 Polybutadiene Substances 0.000 claims description 5
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920002857 polybutadiene Polymers 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- 229920000515 polycarbonate Polymers 0.000 claims description 5
- 239000004417 polycarbonate Substances 0.000 claims description 5
- 229960001124 trientine Drugs 0.000 claims description 5
- UHAMPPWFPNXLIU-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)pentanoic acid Chemical compound CCCC(CO)(CO)C(O)=O UHAMPPWFPNXLIU-UHFFFAOYSA-N 0.000 claims description 4
- 239000004359 castor oil Substances 0.000 claims description 4
- 235000019438 castor oil Nutrition 0.000 claims description 4
- 238000004945 emulsification Methods 0.000 claims description 4
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- ULMZOZMSDIOZAF-UHFFFAOYSA-N 3-hydroxy-2-(hydroxymethyl)propanoic acid Chemical compound OCC(CO)C(O)=O ULMZOZMSDIOZAF-UHFFFAOYSA-N 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 14
- 238000010276 construction Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000004816 latex Substances 0.000 abstract description 3
- 229920000126 latex Polymers 0.000 abstract description 3
- 239000002932 luster Substances 0.000 abstract description 2
- 238000005034 decoration Methods 0.000 abstract 1
- 229920000620 organic polymer Polymers 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 21
- 238000009472 formulation Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 239000002518 antifoaming agent Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 12
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 11
- 229910001424 calcium ion Inorganic materials 0.000 description 11
- 238000003860 storage Methods 0.000 description 11
- 150000001734 carboxylic acid salts Chemical class 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
- 230000001804 emulsifying effect Effects 0.000 description 10
- 239000000080 wetting agent Substances 0.000 description 10
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- 229940035437 1,3-propanediol Drugs 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- RNFAKTRFMQEEQE-UHFFFAOYSA-N Tripropylene glycol butyl ether Chemical compound CCCCOC(CC)OC(C)COC(O)CC RNFAKTRFMQEEQE-UHFFFAOYSA-N 0.000 description 1
- RQFBBPNVEJATBH-UHFFFAOYSA-N [Cr].[Cd] Chemical compound [Cr].[Cd] RQFBBPNVEJATBH-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- PJMICNUGBHGMKQ-UHFFFAOYSA-N ethane-1,1,2-triamine Chemical group NCC(N)N PJMICNUGBHGMKQ-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000675 fabric finishing Substances 0.000 description 1
- 238000009962 finishing (textile) Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
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- 239000012855 volatile organic compound Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method of polyurethane aqueous dispersion, belonging to the field of the organic polymer compound. The method comprises the following steps: (1) mixing polyurethane with carboxylate and polyurethane without carboxylate in a weight ratio of 1:0.1-3, adding deionized water which is 1-10 times of polyurethane with carboxylate to emulsify; (2) adding amine chain extender which is 0.1-1w% of polyurethane with carboxylate to react and ensure that the content of NCO is less than 0.5%; (3) distilling to remove solvent, adjusting the pH value to 6-8 to obtain the polyurethane aqueous dispersion, wherein the solid content of the polyurethane aqueous dispersion is 40-70% and the latex particle size is 60-500nm. The aqueous dispersion prepared by the method has high solid content; and by adopting the waterborne polyurethane paint prepared from the aqueous dispersion, the construction quality of the polyurethane aqueous dispersion can be increased, the construction cost can be reduced and the luster and decoration performance of the film can be increased.
Description
Technical Field
The invention belongs to the field of organic high molecular compounds, relates to a high molecular compound obtained by using isocyanate or isothiocyanate, and particularly relates to a polyurethane aqueous dispersion.
Background
Urethane bonds, urea bonds, biuret, ester bonds and the like contained in the polyurethane structure endow the polyurethane coating film with excellent wear resistance, flexibility, low temperature resistance and chemical medium resistance, and can be widely used as coatings, printing inks, adhesives, elastomers and sealing materials. The water-based polyurethane coating takes water as a main dispersion medium, has the advantages of non-inflammability, environmental friendliness, easiness in cleaning and the like, and is successfully applied to the fields of leather finishing agents, fabric finishing agents, shoe adhesives and the like. With the increasing awareness of the environment and health of people, the aqueous polyurethane dispersions are increasingly regarded as important. The existing polyurethane aqueous dispersion (PUD) has low solid content and poor self-thickening property, and limits the popularization and application of the PUD in coatings, adhesives and printing ink. The high-solid-content polyurethane aqueous dispersion has high film-forming speed by drying, high film fullness and high gloss, and can improve the construction efficiency when being used as paint, adhesive and printing ink. However, due to the particularity of the PUD synthesis process, when the solid content of PUD is increased, particularly when the dispersed phase content is higher than the continuous phase, the viscosity of the system is increased sharply and finally the PUD becomes PU hydrogel. The preparation of high solids aqueous polyurethane dispersions is therefore a hot spot and difficulty of current research. U.S. Pat. Nos. USP 5977215, USP5652291 and USP 6001924 increase the solid content of PUD by preparing a polyurethane acrylic hybrid emulsion by copolymerizing polyurethane with an acrylate monomer, but reduce the abrasion resistance and cold resistance of the polyurethane material and have a complicated process. In the aspect of improving the solid content of PUD, the existing literature only stays in the change of raw materials and a formula, for example, two isocyanates of isophorone diisocyanate and hexamethylene diisocyanate are mixed in Riqing, and polyester type anionic waterborne polyurethane with the solid content of more than 50% is successfully prepared under the condition of high dimethylolpropionic acid content; and the solid content is improved by changing hydrophilic monomers, the improvement of the emulsion solidification amount is limited, and the PUD adhesive film generally contains higher hydrophilic groups, so that the water resistance and the performance of resisting other chemical media of the PUD adhesive film are reduced.
Disclosure of Invention
The invention aims to provide a preparation method of a polyurethane aqueous dispersion, and the polyurethane aqueous dispersion prepared by the method has the advantage of high solid content.
In order to solve the technical problems, the invention adopts the technical scheme that:
a process for preparing an aqueous polyurethane dispersion, the process comprising the steps of:
(1) mixing polyurethane containing carboxylate and polyurethane without carboxylate according to the weight ratio of 1: 0.1-3, and adding deionized water with the weight 1-10 times that of the polyurethane containing carboxylate for emulsification;
(2) adding amine chain extender accounting for 0.1-1.0% of the weight of the carboxylate-containing polyurethane to react until the NCO content is lower than 0.5%;
(3) distilling to remove the solvent until the solid content is 40-70%, and adjusting the pH value to 6-8 to obtain the polyurethane aqueous dispersion;
wherein,
the carboxylate-containing polyurethane is prepared from 30-70 parts by weight of a polymer alcohol chain extender, 1-10 parts by weight of a polyfunctional cross-linking agent, 30-60 parts by weight of a diisocyanate monomer, 0-10 parts by weight of C2-C6 alkyl diol and 4-10 parts by weight of dimethylol alkyl carboxylic acid according to the following method:
adding a polymer alcohol chain extender, a polyfunctional crosslinking agent and a diisocyanate monomer into a reaction kettle, heating to 60-100 ℃, and preserving heat for 1.0-2.0 hours; adding C2-C6 alkyl dihydric alcohol, and reacting at 70-80 ℃ until the content of NCO groups is 5-15%; adding dimethylol alkyl carboxylic acid, and reacting at 50-70 ℃ until the content of NCO groups is lower than 4%; adjusting the viscosity of the reactant to 300-3000 cps with acetone, cooling to below 50 ℃, adding a neutralizer with the weight of 0.8-1.2 times of that of the hydrophilic monomer for neutralization to obtain the carboxylate-containing polyurethane.
The neutralizing agent is one or a mixture of more than two of N, N-dimethylethanolamine, ammonia water and triethylamine.
The carboxylate-free polyurethane is prepared from 30-70 parts by weight of a polymer alcohol chain extender, 0-10 parts by weight of a polyfunctional cross-linking agent, 30-60 parts by weight of a diisocyanate monomer and 1-12 parts by weight of C2-C6 alkyl diol by the following method:
adding a polymer alcohol chain extender, a polyfunctional crosslinking agent and a diisocyanate monomer into a reaction kettle, heating to 60-100 ℃, and preserving heat for 1.0-2.0 hours; adding C2-C6 alkyl dihydric alcohol, and reacting at 70-80 ℃ until the content of NCO groups is lower than 4%; adjusting the viscosity of the reactant to 300-3000 cps with acetone, and cooling to room temperature to obtain the carboxylate-free polyurethane.
The polymer alcohol chain extender has the number average molecular mass of 300-10000, the hydroxyl value of 30-200mgKOH/g, and is one or a mixture of more than two of CMA-1044 polyester Diol of Shandong Dagaku, CMA-1042 polyester Diol of Shandong Daku, T-1136 polyester Diol of Hessian, N210 polyether polyol, N220 polyether polyol, Diol1000 polyether polyol, Diol2000 polyether polyol, polycarbonate Diol, polytetrahydrofuran Diol, polyurethane Diol, polyacrylate Diol, polybutadiene Diol and polycaprolactone Diol.
The diisocyanate monomer is one or a mixture of more than two of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl m-xylylene diisocyanate and xylylene diisocyanate.
The polyfunctional crosslinking agent is one or a mixture of two or more of trimethylolpropane, trimethylolethane, castor oil, E-20 epoxy resin, E-12 epoxy resin, E-44 epoxy resin, E-51 epoxy resin, an adduct of toluene diisocyanate and trimethylolpropane, toluene diisocyanate trimer, biuret and trimer of hexamethylene diisocyanate, and trimer of isophorone diisocyanate.
The C2-C6 alkyl diol is one or a mixture of more than two of ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol and neopentyl glycol.
The dimethylol alkyl carboxylic acid is one or more of dimethylol acetic acid, dimethylol propionic acid, dimethylol butyric acid and dimethylol valeric acid.
The amine chain extender is one or a mixture of more than two of hydrazine, ethylenediamine, hexamethylenediamine, isophoronediamine, diethylenetriamine and triethylene tetramine.
The polyurethane aqueous dispersion of the present invention may further include a defoaming agent during the emulsification in step 1 of the preparation method. The defoaming agent is commonly used in the field, such as TEGO-810, TEGO-805, TEGO-825 and TEGO-845, or a mixture of more than two thereof.
The method of distillation in step 3 of the preparation method of the aqueous polyurethane dispersion of the present invention is a method commonly used in the art, and may be a method of conventional distillation, or a method of distillation under reduced pressure, preferably a method of distillation under reduced pressure. Wherein, the reduced pressure distillation is preferably carried out at the temperature of 50-120 ℃ and the vacuum degree of 0.02-0.1 Mpa.
The invention relates to a preparation method of a polyurethane aqueous dispersion, which adopts a better technical scheme that: a process for preparing an aqueous polyurethane dispersion, the process comprising the steps of:
(1) mixing polyurethane containing carboxylate and polyurethane without carboxylate according to the weight ratio of 1: 0.1-3, and adding deionized water with the weight 1-10 times that of the polyurethane containing carboxylate for emulsification;
(2) adding an amine chain extender accounting for 0.1-1% of the weight of the carboxylate-containing polyurethane to react until the NCO content is lower than 0.5%;
(3) distilling to remove the solvent until the solid content is 40-70%, and adjusting the pH value to 6-8 to obtain the polyurethane aqueous dispersion;
wherein,
the carboxylate-containing polyurethane is prepared from 40-60 parts by weight of a polymer alcohol chain extender, 2-5 parts by weight of a polyfunctional cross-linking agent, 35-50 parts by weight of a diisocyanate monomer, 0-8 parts by weight of C2-C6 alkyl diol and 5-8 parts by weight of dimethylol alkyl carboxylic acid according to the following method:
adding a polymer alcohol chain extender, a polyfunctional crosslinking agent and a diisocyanate monomer into a reaction kettle, heating to 70-90 ℃, and preserving heat for 1.0-2.0 hours; adding C2-C6 alkyl dihydric alcohol, and reacting at 70-80 ℃ until the content of NCO groups is 5-15%; adding dimethylol alkyl carboxylic acid, and reacting at 50-70 ℃ until the content of NCO groups is lower than 4%; and adjusting the viscosity of the reactant to 300-3000 CPS by using acetone, cooling to room temperature, and adjusting the pH value to 6-8 to obtain the carboxylate-containing polyurethane.
The carboxylate-free polyurethane is prepared from 40-60 parts by weight of a polymer alcohol chain extender, 2-5 parts by weight of a polyfunctional cross-linking agent, 35-50 parts by weight of a diisocyanate monomer and 1-12 parts by weight of C2-C6 alkyl diol by the following method:
adding a polymer alcohol chain extender, a polyfunctional crosslinking agent and a diisocyanate monomer into a reaction kettle, heating to 60-100 ℃, and preserving heat for 1.0-2.0 hours; adding C2-C6 alkyl dihydric alcohol, and reacting at 70-80 ℃ until the content of NCO groups is 5-15%; and adjusting the viscosity of the reactant to 300-3000 CPS by using acetone, and cooling to room temperature to obtain the carboxylate-free polyurethane.
The polymer alcohol chain extender has the number average molecular weight of 300-10000, the hydroxyl value of 30-200mgKOH/g, and is one or the mixture of more than one of CMA-1044 polyester Diol of Shandong Dai company, CMA-1042 polyester Diol of Shandong Dai company, T-1136 polyester Diol of Huiss company, N210 polyether polyol, N220 polyether polyol, Diol1000 polyether polyol and Diol2000 polyether polyol.
The diisocyanate monomer is one or a mixture of more than two of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl m-xylylene diisocyanate and xylylene diisocyanate.
The polyfunctional crosslinking agent is one or a mixture of two or more of trimethylolpropane, trimethylolethane, E-20 epoxy resin, E-12 epoxy resin, E-44 epoxy resin, E-51 epoxy resin, biuret of toluene diisocyanate, trimer of hexamethylene diisocyanate, and trimer of isophorone diisocyanate.
The C2-C6 alkyl diol is one or a mixture of more than two of ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol and 1, 4-cyclohexanediol.
The dimethylol alkyl carboxylic acid is one or a mixture of dimethylol propionic acid and dimethylol butyric acid.
The amine chain extender is one or a mixture of more than two of hydrazine, ethylenediamine, hexamethylenediamine, isophoronediamine, diethylenetriamine and triethylene tetramine.
The invention provides a water-based polyurethane coating, which contains 60-90 w% of the polyurethane aqueous dispersion prepared by the method.
The waterborne polyurethane coating of the invention can also contain an auxiliary agent, a pigment or a filler. The kind and amount of auxiliaries, pigments, fillers can be determined by the person skilled in the art on the basis of the knowledge in the art.
The polyurethane aqueous dispersion prepared by the method has high solid content, can improve the film forming performance of the aqueous polyurethane coating, improve the fullness of a coating film and improve the gloss and the decorative performance of the coating film; the dispersion has excellent electrolyte (calcium ion) resistance stability, high tolerance to various film forming aids (various high-boiling-point organic solvents), no low-molecular emulsifier, low concentration of hydrophilic carboxylate, high crosslinking density and hardness of a coating film, good chemical medium resistance, good thermal stability, high drying speed, easy polishing and other performances, and is non-toxic and non-flammable. Can be used for water-based wood coatings, water-based leather finishing agents, water-based adhesives, water-based ink and water-based metal coatings.
Compared with the prior art, the preparation method of the polyurethane aqueous dispersion has the following advantages:
(1) the aqueous polyurethane dispersions prepared by the process of the invention have solids contents of up to 70% and good storage stability.
(2) The polyurethane aqueous dispersion prepared by the method has high solid content, can improve the construction quality of the polyurethane aqueous dispersion, reduce the construction cost and improve the luster and the decorative performance of a coating film.
(3) The polyurethane aqueous dispersion prepared by the method does not contain a low-molecular emulsifier, the concentration of carboxylate is low, and a coating film has excellent water resistance, scrubbing resistance and stain resistance.
(4) The polyurethane aqueous dispersion prepared by the method is non-toxic and non-flammable. Halogenated hydrocarbon, benzene, toluene, xylene, formaldehyde and polymers thereof and heavy metal compounds of lead, cadmium chromium and mercury are not artificially added. The total volatile organic compound content (TVOC) in the product is less than 50 g/L. The waterborne polyurethane coating HJ/T201-2005 standard completely meets the technical requirements of environmental sign product authentication, and belongs to a green environment-friendly product.
The polyurethane aqueous dispersion of the invention is detected by the following method: the particle size and distribution of the dispersion was determined using a nanometer particle size analyzer (ZS Nano S); the latex particle morphology of the dispersion was determined by scanning electron microscopy (TEM).
The performance of the coating film containing the waterborne polyurethane coating can be characterized by the following method: testing the mechanical property of the coating film by using an Instron electronic tensile testing machine; the cross-linking density of the latex film is measured by MEK (methyl ethyl ketone) heating reflux extraction; the hardness of the swing rod of the coating is measured according to GB/T1730-93; the adhesive force is measured according to GB/T9286-88 cross grid cutting method; chemical solvent resistance (MEK) was tested by double scrubbing the surface of the coating film with a non-woven paper saturated with MEK and recording the number of times the coating film has just been rubbed.
Detailed Description
The following are specific examples of the present invention, but are not limited to the examples.
Example 1
(1) Preparation of polyurethanes containing Carboxylic acid salts
(a) Composition of raw materials
Polymer alcohol chain extender: 70g of polyether polyol N220;
a polyfunctional group crosslinking agent: 1.0g hexamethylene diisocyanate trimer N3300;
diisocyanate monomer: 35g of isophorone diisocyanate;
dimethylol alkyl carboxylic acid: 4.0g dimethylolpropionic acid;
neutralizing agent: 4.0g triethylamine.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 80 ℃, and preserving heat for 1.5 hours; adding dimethylol alkyl carboxylic acid, and reacting at 60 ℃ until the content of NCO groups is 3%; regulating the viscosity of the reactant to 300CPS by using acetone, cooling to 45 ℃, and adding a neutralizer for neutralization to obtain the carboxylate-containing polyurethane.
(2) Preparation of carboxylate-free polyurethanes
(a) Composition of raw materials
Polymer alcohol chain extender: 68g of polyether polyol N220; 2g of polybutadiene diol;
a polyfunctional group crosslinking agent: 1g of isophorone diisocyanate trimer;
diisocyanate monomer: 30g of hexamethylene diisocyanate;
C2-C6 alkyl diol: 1g of 1, 6-hexanediol.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 100 ℃, and preserving heat for 1.0 hour; adding C2-C6 alkyl dihydric alcohol, and reacting at 80 ℃ until the content of NCO groups is 3%; adjusting the viscosity of the reactant to 1000CPS by using acetone, and cooling to room temperature to obtain the carboxylate-free polyurethane.
(3) Preparation of an aqueous polyurethane Dispersion
(a) Mixing 50g of the polyurethane containing carboxylate obtained in the step 1 and 120g of the polyurethane containing no carboxylate obtained in the step 2, adding 200g of deionized water, and emulsifying at a high speed;
(b) adding 0.5g of ethylenediamine amine chain extender, and reacting at 50 ℃ for 2 hours, wherein the content of NCO groups is 0.4%;
(c) then, the solvent was distilled off under reduced pressure at a temperature of 80 ℃ and a vacuum degree of 0.06MPa, and the solid content was adjusted to 45%.
(d) The pH was adjusted to 7 to give an aqueous polyurethane dispersion.
(4) Properties of the aqueous polyurethane Dispersion
Solid content: 45 percent; viscosity: 300 cps; dispersion average particle diameter (Dp) ═ 87 nm; the storage stability is 1 year at normal temperature; the stability of calcium ion resistance is excellent; excellent tolerance to film forming aids;
(5) aqueous polyurethane coating
(a) Formulation of
80g of the aqueous polyurethane dispersion prepared above
Wetting agent TEGO2450.2g
Antifoam TEGO8050.1g
SN612 0.2
Film-forming aid dipropylene glycol butyl ether 3g
pH regulator AMP-951.0 g
15.5g of water
A total of 100g
(b) Formulation method and use
According to the formula, the polyurethane aqueous dispersion, a wetting agent, a defoaming agent, a viscosity regulator, a film-forming aid, a pH value regulator and water are mixed and dispersed for 15 minutes to obtain the waterborne polyurethane coating. The obtained waterborne polyurethane coating is cured and dried for 7 days at normal temperature.
(c) The properties of the prepared waterborne polyurethane coating are shown in the table:
TABLE 1 comprehensive Properties of aqueous polyurethane coatings
Example 2
(1) Preparation of polyurethanes containing Carboxylic acid salts
(a) Composition of raw materials
Polymer alcohol chain extender: 40g of polycaprolactone diol; 20g of polycarbonate diol;
a polyfunctional group crosslinking agent: 2.0g trimethylolpropane;
diisocyanate monomer: 30g of isophorone diisocyanate;
C2-C6 alkyl diol: 2g of 1, 4-butanediol;
dimethylol alkyl carboxylic acid: 5g dimethylolpropionic acid;
neutralizing agent: 1.0g triethylamine; 3.0g of ammonia water.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 80 ℃, and preserving heat for 1.5 hours; adding C2-C6 alkyl dihydric alcohol, reacting at 70 ℃ until the content of NCO groups is 13.5 percent, adding dimethylol alkyl carboxylic acid, and reacting at 60 ℃ until the content of NCO groups is below 3 percent; regulating the viscosity of the reactant to 400CPS by using acetone, cooling to 45 ℃, and adding a neutralizer to obtain the carboxylate-containing polyurethane.
(2) Preparation of carboxylate-free polyurethane:
(a) composition of raw materials
Polymer alcohol chain extender: 58g of polyacrylate glycol; 2g of polybutadiene diol
A polyfunctional group crosslinking agent: 3g of trimethylolethane;
diisocyanate monomer: 30g of hexamethylene diisocyanate;
C2-C6 alkyl diol: 7g of neopentyl glycol.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 100 ℃, and preserving heat for 1.0 hour; adding C2-C6 alkyl dihydric alcohol, and reacting at 80 ℃ until the content of NCO groups is below 3%; adjusting the viscosity of the reactant to be 100CPS by using acetone, and cooling to room temperature to obtain the polyurethane without carboxylate.
(3) Preparation of an aqueous polyurethane Dispersion
(a) Mixing 50g of the polyurethane containing carboxylate obtained in the step 1 and 80g of the polyurethane containing no carboxylate obtained in the step 2, adding 150g of deionized water, and emulsifying at a high speed;
(b) adding 0.5g of isophorone diamine, and reacting for 2 hours at 50 ℃ until the content of NCO groups is lower than 0.5%;
(c) then, the solvent was distilled off under reduced pressure at a temperature of 80 ℃ and a vacuum degree of 0.06MPa, and the solid content was adjusted to 55%.
(d) The pH was adjusted to 7 to give an aqueous polyurethane dispersion.
(4) Properties of the aqueous polyurethane Dispersion
Solid content: 55 percent; viscosity: 800 cPs; dispersion average particle diameter (Dp) ═ 114 nm; the storage stability is 1 year at normal temperature; the stability of calcium ion resistance is excellent; excellent tolerance to film forming aids;
(5) aqueous polyurethane coating
(a) Formulation of
60g of the aqueous polyurethane dispersion prepared above
35.5g of water
A total of 100g
(b) Formulation method and use
According to the formula, the polyurethane aqueous dispersion and water are mixed and dispersed for 20 minutes to obtain the aqueous polyurethane coating. The obtained waterborne polyurethane coating is cured and dried for 7 days at normal temperature.
(c) The properties of the prepared waterborne polyurethane coating are shown in the table:
TABLE 2 comprehensive properties of waterborne polyurethane coatings
Example 3
(1) Preparation of polyurethanes containing Carboxylic acid salts
(a) Composition of raw materials
Polymer alcohol chain extender: 40g of polyester diol T1136; 10g of polycaprolactone diol;
a polyfunctional group crosslinking agent: 2.0g trimethylolpropane;
diisocyanate monomer: 35g of isophorone diisocyanate;
C2-C6 alkyl diol: 6g of 1, 4-butanediol;
dimethylol alkyl carboxylic acid: 7g dimethylolpropionic acid;
neutralizing agent: 3g of triethylamine, 4g N, N-dimethylethanolamine.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 80 ℃, and preserving heat for 1.5 hours; adding C2-C6 alkyl dihydric alcohol, reacting at 70 ℃ until the content of NCO groups is 13.5 percent, adding dimethylol alkyl carboxylic acid, and reacting at 60 ℃ until the content of NCO groups is 2.1 percent; regulating the viscosity of the reactant to 500CPS by using acetone, cooling to 45 ℃, and adding a neutralizer to obtain the carboxylate-containing polyurethane.
(2) Preparation of carboxylate-free polyurethanes
(a) Composition of raw materials
Polymer alcohol chain extender: 48g of polyester diol CMA-1042; 2g of polybutadiene diol;
a polyfunctional group crosslinking agent: 3g of trimethylolpropane;
diisocyanate monomer: 35g of hexamethylene diisocyanate;
C2-C6 alkyl diol: 1g of neopentyl glycol.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 100 ℃, and preserving heat for 1.0 hour; adding C2-C6 alkyl dihydric alcohol, and reacting at 80 ℃ until the content of NCO groups is 1.51%; adjusting the viscosity of the reactant to 1000CPS by using acetone, and cooling to room temperature to obtain the carboxylate-free polyurethane.
(3) Preparation of an aqueous polyurethane dispersion:
(a) mixing 50g of the polyurethane containing carboxylate obtained in the step 1 and 60g of the polyurethane containing no carboxylate obtained in the step 2, adding 150g of deionized water, and emulsifying at a high speed;
(b) adding 0.05g of hydrazine, and reacting at 50 ℃ until the content of NCO groups is lower than 0.5%;
(c) then, the solvent is removed by reduced pressure distillation under the conditions that the temperature is 80 ℃ and the vacuum degree is 0.06Mpa, and the solid content is adjusted to be 40 percent.
(d) The pH was adjusted to 7 to give an aqueous polyurethane dispersion.
(4) Properties of the aqueous polyurethane Dispersion
Solid content: 40 percent; viscosity: 100 cps; dispersion average particle diameter (Dp) 60 nm; the storage stability is 1 year at normal temperature; the stability of calcium ion resistance is excellent; excellent tolerance to film forming aids;
(5) aqueous polyurethane coating
(a) Formulation of
95g of the aqueous polyurethane dispersion prepared above
Antifoam TEGO8050.1g
SN-612 0.2
Film-forming assistant tripropylene glycol butyl ether 3g
2.0g of water
A total of 100g
(b) Formulation method and use
According to the formula, the polyurethane aqueous dispersion, the defoaming agent, the viscosity regulator, the film-forming assistant and the water are mixed and dispersed for 15 minutes to obtain the waterborne polyurethane coating. The obtained waterborne polyurethane coating is cured and dried for 7 days at normal temperature. (c) The properties of the prepared waterborne polyurethane coating are shown in the table:
TABLE 3 comprehensive Properties of aqueous polyurethane coatings
Example 4
(1) Preparation of polyurethanes containing Carboxylic acid salts
(a) Composition of raw materials
Polymer alcohol chain extender: 20g of polyester diol CMA-1042; 20g of polyether polyol Diol-2000;
a polyfunctional group crosslinking agent: 2g of castor oil; 8g of TDI trimer;
diisocyanate: 40g of diphenylmethane diisocyanate;
C2-C6 alkyl diol: 1g of diethylene glycol;
dimethylol alkyl carboxylic acid: 8g dimethylolpropionic acid;
neutralizing agent: 6.0g N, N-dimethylethanolamine; 3g of aqueous ammonia.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional group cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 70 ℃, and preserving heat for 1.8 hours; adding C2-C6 alkyl dihydric alcohol, and reacting at 75 ℃ until the content of NCO groups reaches 9.5%; adding dimethylol alkyl carboxylic acid, and reacting at 65 ℃ until the content of NCO groups is 3.2%; regulating the viscosity of the reactant to 2000CPS by using acetone, cooling to 30 ℃, and adding a neutralizer to obtain the carboxylate-containing polyurethane.
(2) Preparation of carboxylate-free polyurethanes
(a) Composition of raw materials
Polymer alcohol chain extender: 40g of polyacrylate glycol;
a polyfunctional group crosslinking agent: 6g E-44 epoxy resin;
diisocyanate monomer: 45g of toluene diisocyanate;
C2-C6 alkyl diol: 9g of neopentyl glycol.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional group cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 90 ℃, and preserving heat for 1.3 hours; adding C2-C6 alkyl dihydric alcohol, and reacting at 80 ℃ until the content of NCO groups reaches 3.8%; adjusting the viscosity of the reactant to 1000CPS by using acetone, and cooling to room temperature to obtain the polyurethane without carboxylate.
(3) Preparation of an aqueous polyurethane Dispersion
(a) Mixing 50g of the polyurethane containing carboxylate obtained in the step 1 and 5g of the polyurethane containing no carboxylate obtained in the step 2, adding 100g of deionized water, and emulsifying at a high speed;
(b) adding 0.1g of isophorone diamine, 0.1g of ethylene diamine and 0.1g of diethylenetriamine, and reacting at normal temperature until the content of NCO groups is lower than 0.5%;
(c) then, the solvent was distilled off under reduced pressure at a temperature of 80 ℃ and a vacuum degree of 0.06MPa, and the solid content was adjusted to 50%.
(d) Adjusting the pH value to 7 to obtain the polyurethane aqueous dispersion with high solid content.
(4) Properties of the aqueous polyurethane Dispersion
Solid content: 50 percent; viscosity: 600 cps; dispersion average particle diameter (Dp) 140 nm; the storage stability is 1 year at normal temperature; the stability of calcium ion resistance is excellent; excellent tolerance to film forming aids;
(5) aqueous polyurethane coating
(a) Formulation of
65g of the aqueous polyurethane dispersion prepared above
Wetting agent BYK3460.3g
film-Forming auxiliary agent dipropylene glycol methyl Ether 3g
31.7g of water
A total of 100g
(b) Formulation method and use
According to the formula, the polyurethane aqueous dispersion, the wetting agent, the film-forming assistant and water are mixed and dispersed for 15 minutes to obtain the waterborne polyurethane coating. The obtained waterborne polyurethane coating is cured and dried for 7 days at normal temperature. (c) The properties of the prepared waterborne polyurethane coating are shown in the table:
TABLE 4 comprehensive Properties of waterborne polyurethane coatings
Example 5
(1) Preparation of polyurethanes containing Carboxylic acid salts
(a) Composition of raw materials
Polymer alcohol chain extender: 10g of polycarbonate diol; 25g of the polyether polyol Diol 1000;
a polyfunctional group crosslinking agent: 10g E-44 epoxy resin;
diisocyanate monomer: 50g of diphenylmethane diisocyanate;
C2-C6 alkyl diol: 8g of 1, 4-cyclohexyldiol;
dimethylol alkyl carboxylic acid: 6g of dimethylolbutanoic acid;
neutralizing agent: 6.0g triethylamine.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional group cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 85 ℃, and keeping the temperature for 1.5 hours; adding C2-C6 alkyl dihydric alcohol, and reacting at 80 ℃ until the content of NCO groups is 10.5%; adding dimethylol alkyl carboxylic acid, and reacting at 50 ℃ until the content of NCO groups is 2.1%; regulating the viscosity of the reactant to 3000CPS by using acetone, cooling to 40 ℃, and adding a neutralizer to obtain the carboxylate-containing polyurethane.
(2) Preparation of carboxylate-free polyurethanes
(a) Composition of raw materials
Polymer alcohol chain extender: 10g of polytetrahydrofuran diol; 28g polyether polyol N210;
polyfunctional crosslinking agents: 6g E-44 epoxy resin;
diisocyanate monomer: 50g of isophorone diisocyanate;
C2-C6 alkyl diol: 12g of 1, 6-hexanediol.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional group cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 95 ℃, and preserving heat for 1.0 hour; adding C2-C6 alkyl dihydric alcohol, and reacting at 70 ℃ until the content of NCO groups reaches 3.0%; adjusting the viscosity of the reactant to 3000CPS by using acetone, and cooling to room temperature to obtain the carboxylate-free polyurethane.
(3) Preparation of an aqueous polyurethane Dispersion
(a) Mixing 50g of the polyurethane containing carboxylate obtained in the step 1 and 40g of the polyurethane containing no carboxylate obtained in the step 2, adding 100g of deionized water, and emulsifying at a high speed;
(b) adding 0.1g of hexamethylene diamine, 0.1g of triethylene tetramine and 0.05g of hydrazine, and reacting at normal temperature until the content of NCO groups is lower than 0.5%;
(c) then, the solvent was distilled off under reduced pressure at a temperature of 80 ℃ and a vacuum degree of 0.09MPa, and the solid content was adjusted to 55%.
(d) The pH was adjusted to 7 to give an aqueous polyurethane dispersion.
(4) Properties of the aqueous polyurethane Dispersion
Solid content: 55 percent; viscosity: 1000 cps; dispersion average particle diameter (Dp) ═ 110 nm; the storage stability is 1 year at normal temperature; the stability of calcium ion resistance is excellent; excellent tolerance to film forming aids;
(5) aqueous polyurethane coating
(a) Formulation of
90g of the aqueous polyurethane dispersion prepared above
10g of water
A total of 100g
(b) Formulation method and use
According to the formula, the polyurethane aqueous dispersion and water are mixed and dispersed for 30 minutes to obtain the aqueous polyurethane coating. The obtained waterborne polyurethane coating is cured and dried for 7 days at normal temperature.
(c) The properties of the prepared waterborne polyurethane coating are shown in the table:
TABLE 5 comprehensive Properties of aqueous polyurethane coatings
Example 6
(1) Preparation of polyurethanes containing Carboxylic acid salts
(a) Composition of raw materials
Polymer alcohol chain extender: 20g of polycaprolactone diol (molecular weight 1000); 10g of polytetrahydrofuran diol;
a polyfunctional group crosslinking agent: 10g E-51 epoxy resin;
diisocyanate monomer: 50g of hexamethylene diisocyanate;
C2-C6 alkyl diol: 2g of 1, 3-propanediol;
dimethylol alkyl carboxylic acid: 8g dimethylolpropionic acid;
neutralizing agent: 7.5g of triethylamine, 7.5 g.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 65 ℃, and preserving heat for 2.0 hours; adding C2-C6 alkyl dihydric alcohol, and reacting at 75 ℃ until the content of NC0 groups reaches 8.5%; adding dimethylol alkyl carboxylic acid, and reacting at 55 ℃ until the content of NCO groups is 1.0%; regulating the viscosity of the reactant to 500cPs by using acetone, cooling to 45 ℃, and adding a neutralizer to obtain the carboxylate-containing polyurethane.
(2) Preparation of carboxylate-free polyurethanes
(a) Composition of raw materials
Polymer alcohol chain extender: 30g of a polyurethane diol;
diisocyanate monomer: 60g of isophorone diisocyanate;
C2-C6 alkyl diol: 8g of diethylene glycol; 2g of ethylene glycol.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 70 ℃, and preserving heat for 2.0 hours; adding C2-C6 alkyl dihydric alcohol, and reacting at 70 ℃ until the content of NCO groups is 3.4%; adjusting the viscosity of the reactant to 300cPs by using acetone, and cooling to 5 room temperature to obtain the polyurethane without carboxylate.
(3) preparation of an aqueous polyurethane Dispersion
(a) Mixing 50g of the polyurethane containing carboxylate obtained in the step 1 and 80g of the polyurethane containing no carboxylate obtained in the step 2, adding 100g of deionized water, and emulsifying at a high speed;
(b) adding 0.5g of diethylenetriamine chain extender, and reacting at normal temperature until the content of NCO groups is lower than 0.5%;
(c) then, the solvent was distilled off under reduced pressure at a temperature of 80 ℃ and a vacuum degree of 0.06MPa, and the solid content was adjusted to 50%.
(d) The pH was adjusted to 6 to give an aqueous polyurethane dispersion.
(4) Properties of the aqueous polyurethane Dispersion
Solid content: 50 percent; viscosity: 600 cps; dispersion average particle diameter (Dp) ═ 110 nm; the storage stability is 1 year at normal temperature; the stability of calcium ion resistance is excellent; excellent tolerance to film forming aids;
(5) aqueous polyurethane coating
(a) Formulation of
80g of the aqueous polyurethane dispersion prepared above
Wetting agent TEGO2450.25g
Antifoaming agent TEG08250.15g
19.6g of water
A total of 100g
(b) Formulation method and use
According to the formula, the polyurethane aqueous dispersion, the wetting agent, the defoaming agent and the water are mixed and dispersed for 15 minutes to obtain the waterborne polyurethane coating. The obtained waterborne polyurethane coating is cured and dried for 7 days at normal temperature. (c) The properties of the prepared waterborne polyurethane coating are shown in the table:
TABLE 6 comprehensive Properties of waterborne polyurethane coatings
Example 7
(1) Preparation of polyurethanes containing Carboxylic acid salts
(a) Composition of raw materials
Polymer alcohol chain extender: 50g of polyester diol CA-1044;
a polyfunctional group crosslinking agent: 2g E-12 epoxy resin; 2g E-20 epoxy resin;
diisocyanate monomer: 30g of toluene diisocyanate; 10g of diphenylmethane diisocyanate;
dimethylol alkyl carboxylic acid: 3g dimethylolpentanoic acid; 3g dimethylolpropionic acid;
neutralizing agent: 5.0g triethylamine.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 95 ℃, and preserving heat for 2.0 hours; adding dimethylol alkyl carboxylic acid, and reacting at 50 ℃ until the content of NCO groups is 3.1%; regulating the viscosity of the reactant to 1000cPs by using acetone, cooling to 35 ℃, and adding a neutralizer to obtain the carboxylate-containing polyurethane.
(2) Preparation of carboxylate-free polyurethanes
(a) Composition of raw materials
Polymer alcohol chain extender: 38g N220 polyether polyol; 10g of n210 polyether polyol;
a polyfunctional group crosslinking agent: 5g of tolylene diisocyanate trimer;
diisocyanate monomer: 40g of diphenylmethane diisocyanate;
C2-C6 alkyl diol: 3g of neopentyl glycol; 4g of propylene glycol.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 65 ℃, and preserving heat for 2.0 hours; adding C2-C6 alkyl dihydric alcohol, and reacting at 75 ℃ until the content of NCO groups is 2.7%; adjusting the viscosity of the reactant to 600cPs by using acetone, and cooling to room temperature to obtain the polyurethane without carboxylate.
(3) Preparation of an aqueous polyurethane Dispersion
(a) Mixing 50g of the carboxylate-containing hydroxy polyacrylate obtained in the step 1 and 40g of the carboxylate-free hydroxy polyacrylate obtained in the step 2, adding 100g of deionized water, and emulsifying at a high speed;
(b) adding 0.8g of triethylene tetramine chain extender, and reacting at normal temperature until the content of NCO groups is lower than 0.5%;
(c) then, the solvent was distilled off under reduced pressure at a temperature of 100 ℃ and a vacuum degree of 0.06MPa, and the solid content was adjusted to 70%.
(d) The pH was adjusted to 7.5 to give an aqueous polyurethane dispersion.
(4) Properties of the aqueous polyurethane Dispersion
Solid content: 70 percent; viscosity: 1860 cps; dispersion average particle diameter (Dp) 100 nm; the storage stability is 1 year at normal temperature; the stability of calcium ion resistance is excellent; excellent tolerance to film forming aids;
(5) aqueous polyurethane coating
(a) Formulation of
70g of the aqueous polyurethane dispersion prepared above
Viscosity modifier RM20200.2g
film-Forming auxiliary agent dipropylene glycol methyl Ether 3g
pH regulator AMP-951.0 g
25.3g of water
A total of 100g
(b) Formulation method and use
According to the formula, the polyurethane aqueous dispersion, the viscosity regulator, the film forming aid, the pH value regulator and water are mixed and dispersed for 15 minutes to obtain the waterborne polyurethane coating. The obtained waterborne polyurethane coating is cured and dried for 7 days at normal temperature.
(c) The properties of the prepared waterborne polyurethane coating are shown in the table:
TABLE 7 comprehensive Properties of waterborne polyurethane coatings
Example 8
(1) Preparation of polyurethanes containing Carboxylic acid salts
(a) Composition of raw materials
Polymer alcohol chain extender: 20g of polyester diol CMA-1044; 10g of the polyether polyol Diol 1000; ,
a polyfunctional group crosslinking agent: 0.5g of trimethylolethane; 3.0g E-12 epoxy resin; 1.5g of toluene diisocyanate/trimethylolpropane adduct;
diisocyanate monomer: 40g of isophorone diisocyanate; 10g of diphenylmethane diisocyanate;
C2-C6 alkyl diol: 3g of ethylene glycol; 3g of neopentyl glycol;
dimethylol alkyl carboxylic acid: 5g dimethylolpropionic acid; 5g of dimethylolbutanoic acid;
neutralizing agent: 8g of triethylamine; 4g of aqueous ammonia.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 80 ℃, and preserving heat for 2 hours; adding C2-C6 alkyl dihydric alcohol, reacting at 80 ℃ until the content of NCO groups is 14%, adding dimethylol alkyl carboxylic acid, and reacting at 65 ℃ until the content of NCO groups is 4%; regulating the viscosity of the reactant to 2000CPS by using acetone, cooling to 40 ℃, and adding a neutralizer to obtain the carboxylate-containing polyurethane.
(2) Preparation of carboxylate-free polyurethanes
(a) Composition of raw materials
Polymer alcohol chain extender: 30g N220 polyether polyol; 8g N210 polyether polyol;
a polyfunctional group crosslinking agent: 3g hexamethylene diisocyanate biuret; 4g of tolylene diisocyanate trimer;
diisocyanate monomer: 45g of toluene diisocyanate;
C2-C6 alkyl diol: 5g of 1, 4-cyclohexanol; 5g of 1, 6-hexanediol.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 80 ℃, and preserving heat for 2 hours; adding C2-C6 alkyl dihydric alcohol, and reacting at 80 ℃ until the content of NC0 groups is 2.7%; adjusting the viscosity of the reactant to 3000cPs by using acetone, and cooling to room temperature to obtain the carboxylate-free polyurethane.
(3) Preparation of an aqueous polyurethane Dispersion
(a) Mixing 50g of the polyurethane containing carboxylate obtained in the step 1 and 100g of the polyurethane containing no carboxylate obtained in the step 2, adding 300g of deionized water, and emulsifying at a high speed;
(b) adding 0.2g of ethylenediamine and 0.2g of hexamethylenediamine, and reacting at 40 ℃ until the content of NCO groups is 0.5%;
(b) then, the solvent was distilled off under reduced pressure at a temperature of 60 ℃ and a vacuum degree of 0.07MPa, and the solid content was adjusted to 65%.
(c) The pH was adjusted to 8 to give an aqueous polyurethane dispersion.
(4) Properties of the aqueous polyurethane Dispersion
Solid content: 65 percent; viscosity: 1000 cps; dispersion average particle diameter (Dp) 500 nm; the storage stability is 1 year at normal temperature; the stability of calcium ion resistance is excellent; excellent tolerance to film forming aids;
(5) aqueous polyurethane coating
(a) Formulation of
60g of the aqueous polyurethane dispersion prepared above
Wetting agent TEGO2450.2g
Antifoam TEGO8050.1g
SN612 0.2
Film-forming aid dipropylene glycol butyl ether 3g
pH regulator AMP-951.0 g
35.5g of water
A total of 100g
(b) Formulation method and use
According to the formula, the polyurethane aqueous dispersion, a wetting agent, a defoaming agent, a viscosity regulator, a film-forming aid, a pH value regulator and water are mixed and dispersed for 15 minutes to obtain the waterborne polyurethane coating. The obtained waterborne polyurethane coating is cured and dried for 7 days at normal temperature.
(c) The properties of the prepared waterborne polyurethane coating are shown in the table:
TABLE 8 comprehensive Properties of waterborne polyurethane coatings
Example 9
(1) Preparation of polyurethanes containing Carboxylic acid salts
(a) Composition of raw materials
Polymer alcohol chain extender: 15g of polyester diol T-1136; 15g of polyester diol CMA-1042; 8g of the polyether polyol Diol 1000; 2g of the polyether polyol Diol 2000;
a polyfunctional group crosslinking agent: 0.5g of trimethylolethane; 3.0g E-20 epoxy resin; 0.5g of toluene diisocyanate/trimethylolpropane adduct; 0.5g of a trimer of isophorone diisocyanate;
diisocyanate monomer: 40g of isophorone diisocyanate; 8g of xylylene diisocyanate; 10g of tetramethylm-xylylene diisocyanate;
C2-C6 alkyl diol: 3g of propylene glycol; 3g of 1, 4-butanediol; 2g of neopentyl glycol;
dimethylol alkyl carboxylic acid: 5g dimethylolpropionic acid; 5g of dimethylolbutanoic acid; 3g dimethylolpentanoic acid;
neutralizing agent: 8g of triethylamine; 2g of ammonia water; 4g of N, N-dimethylethanolamine.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 60 ℃, and preserving heat for 2 hours; adding C2-C6 alkyl dihydric alcohol, reacting at 80 ℃ until the content of NCO groups is 5%, adding dimethylol alkyl carboxylic acid, and reacting at 50 ℃ until the content of NCO groups is 3.4%; regulating the viscosity of the reactant to 2000cPs by using acetone, cooling to 35 ℃, and adding a neutralizer to obtain the carboxylate-containing polyurethane.
(2) Preparation of carboxylate-free polyurethanes
(a) Composition of raw materials
Polymer alcohol chain extender: 20g of polyether polyol N220; 8g of polyether polyol N210; 5g of polycarbonate diol; 12g of a polyurethane diol;
a polyfunctional group crosslinking agent: 3g hexamethylene diisocyanate biuret (N75); 2g E-51 epoxy resin; 3g of castor oil;
diisocyanate monomer: 30g of toluene diisocyanate; 5g of diphenylmethane diisocyanate; 3g of hexamethylene diisocyanate;
C2-C6 alkyl diol: 5g of diethylene glycol; 2g of propylene glycol; 2g of 1, 6-hexanediol.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 100 ℃, and preserving heat for 1 hour; adding C2-C6 alkyl dihydric alcohol, and reacting at 75 ℃ until the content of NCO groups is 3.8%; adjusting the viscosity of the reactant to 1500cPs by using acetone, and cooling to room temperature to obtain the carboxylate-free polyurethane.
(3) Preparation of an aqueous polyurethane Dispersion
(a) Mixing 50g of the polyurethane containing carboxylate obtained in the step 1 and 150g of the polyurethane containing no carboxylate obtained in the step 2, adding 450g of deionized water, and emulsifying at a high speed;
(b) adding 0.2g of diethylenetriamine and 0.1g of triethylene tetramine, and reacting at room temperature until the content of NCO groups is 0.5%;
(b) then, the solvent was distilled off under reduced pressure at a temperature of 60 ℃ and a vacuum degree of 0.07MPa, and the solid content was adjusted to 70%.
(c) The pH was adjusted to 7.5 to give an aqueous polyurethane dispersion.
(4) Properties of the aqueous polyurethane Dispersion
Solid content: 70 percent; viscosity: 1000 cps; dispersion average particle diameter (Dp) 500 nm; the storage stability is 1 year at normal temperature; the stability of calcium ion resistance is excellent; excellent tolerance to film forming aids;
(5) aqueous polyurethane coating
(a) Formulation of
60g of the aqueous polyurethane dispersion prepared above
Wetting agent TEGO2450.2g
Antifoam TEGO8050.1g
SN612 0.2
Film-forming aid dipropylene glycol butyl ether 3g
pH regulator AMP-951.0 g
35.5g of water
A total of 100g
(b) Formulation method and use
According to the formula, the polyurethane aqueous dispersion, the defoaming agent, the film-forming assistant, the viscosity regulator, the pH value regulator and the water are mixed and dispersed for 15 minutes to obtain the waterborne polyurethane coating. The obtained waterborne polyurethane coating is cured and dried for 7 days at normal temperature.
(c) The properties of the prepared waterborne polyurethane coating are shown in the table:
TABLE 9 comprehensive Properties of waterborne polyurethane coatings
Example 10
(1) Preparation of polyurethanes containing Carboxylic acid salts
(a) Composition of raw materials
Polymer alcohol chain extender: 5g of a polyurethane diol; 15g of polyester diol CMA-1042; 15g of the polyether polyol Diol 2000;
a polyfunctional group crosslinking agent: 0.5g of trimethylolethane; 1.5g of a trimer of hexamethylene diisocyanate; 1.0g E-20 epoxy resin;
diisocyanate monomer: 40g of isophorone diisocyanate; 15g of xylylene diisocyanate;
C2-C6 alkyl diol: 3g of propylene glycol; 4g of 1, 6-hexanediol; 3g of 1, 4-cyclohexanediol;
dimethylol alkyl carboxylic acid: 5g dimethylolacetic acid; 10g of dimethylolbutanoic acid (I) in the total amount of 10g,
neutralizing agent: 8g of triethylamine; 2g of ammonia water; 4g N, N-dimethylethanolamine.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 60 ℃, and preserving heat for 2 hours; adding C2-C6 alkyl dihydric alcohol, reacting at 80 ℃ until the content of NCO groups is 5%, adding dimethylol alkyl carboxylic acid, and reacting at 50 ℃ until the content of NCO groups is 3.4%; regulating the viscosity of the reactant to 600CPS by using acetone, cooling to 35 ℃, and adding a neutralizer to obtain the carboxylate-containing polyurethane.
(2) Preparation of carboxylate-free polyurethanes
(a) Composition of raw materials
Polymer alcohol chain extender: 25g polyether polyol N220; 15g of polyether polyol N210;
a polyfunctional group crosslinking agent: 5g hexamethylene diisocyanate biuret; 3g of trimethylolpropane;
diisocyanate monomer: 30g of toluene diisocyanate; 5g of diphenylmethane diisocyanate; 3g of hexamethylene diisocyanate;
C2-C6 alkyl diol: 5g of diethylene glycol; 2g of propylene glycol; 2g of 1, 6-hexanediol.
(b) Process step
Adding a polymer alcohol chain extender, a polyfunctional cross-linking agent and a diisocyanate monomer into a reaction kettle provided with a stirring paddle, a thermometer and a condenser, heating to 100 ℃, and preserving heat for 1 hour; adding C2-C6 alkyl dihydric alcohol, and reacting at 75 ℃ until the content of NCO groups is 3.8%; adjusting the viscosity of the reactant to 800CPS by using acetone, and cooling to room temperature to obtain the polyurethane without carboxylate.
(3) Preparation of an aqueous polyurethane Dispersion
(a) Mixing 50g of the polyurethane containing carboxylate obtained in the step 1 and 120g of the polyurethane containing no carboxylate obtained in the step 2, adding 450g of deionized water, and emulsifying at a high speed;
(b) adding 0.2g of ethylenediamine and 0.05g of hexamethylenediamine, and reacting at room temperature until the content of NCO groups is 0.5%;
(b) then, the solvent was distilled off under reduced pressure at a temperature of 60 ℃ and a vacuum degree of 0.07MPa, and the solid content was adjusted to 70%.
(c) The pH was adjusted to 7.5 to give an aqueous polyurethane dispersion.
(4) Properties of the aqueous polyurethane Dispersion
Solid content: 70 percent; viscosity: 1000 cps; dispersion average particle diameter (Dp) 500 nm; the storage stability is 1 year at normal temperature; the stability of calcium ion resistance is excellent; excellent tolerance to film forming aids;
(5) aqueous polyurethane coating
(a) Formulation of
60g of the aqueous polyurethane dispersion prepared above
Carbon Black 1.5g
Wetting agent TEGO2450.2g
Antifoam TEGO8050.1g
SN612 0.2
Film-forming aid dipropylene glycol butyl ether 3g
pH regulator AMP-951.0 g
34g of water
A total of 100g
(b) Formulation method and use
According to the formula, the polyurethane aqueous dispersion, the carbon black, the defoaming agent, the film forming additive, the viscosity regulator, the pH value regulator and the water are mixed and dispersed for 15 minutes to obtain the waterborne polyurethane coating. The obtained waterborne polyurethane coating is cured and dried for 7 days at normal temperature.
(c) The properties of the prepared waterborne polyurethane coating are shown in the table:
TABLE 10 combination of properties of waterborne polyurethane coatings
Claims (4)
1. A process for preparing an aqueous polyurethane dispersion, the process comprising the steps of:
(1) mixing polyurethane containing carboxylate and polyurethane without carboxylate according to the mass ratio of 1: 0.1-3, and adding deionized water with the weight being 1-10 times that of the polyurethane containing carboxylate for emulsification;
(2) adding 0.1-1 wt% of amine chain extender of carboxylate-containing polyurethane to react until the NCO content is lower than 0.5%;
(3) distilling to remove the solvent until the solid content is 40-70%, and adjusting the pH value to 6-8 to obtain the polyurethane aqueous dispersion;
wherein,
the carboxylate-containing polyurethane is prepared from 30-70 parts of a polymer alcohol chain extender, 1-10 parts of a polyfunctional crosslinking agent, 30-60 parts of a diisocyanate monomer, 0-10 parts of a C2-C6 alkyl diol and 4-10 parts of a dimethylol alkyl carboxylic acid by the following method:
adding a polymer alcohol chain extender, a polyfunctional crosslinking agent and a diisocyanate monomer into a reaction kettle, heating to 60-100 ℃, and preserving heat for 1.0-2.0 hours; adding C2-C6 alkyl dihydric alcohol, and reacting at 70-80 ℃ until the content of NCO groups is 5-15%; adding dimethylol alkyl carboxylic acid, and reacting at 50-70 ℃ until the content of NCO groups is lower than 4%; adjusting the viscosity of the reactant to 300-3000 cps by using acetone, cooling to below 50 ℃, adding 80-120% of neutralizer of the weight of the hydrophilic monomer for neutralization to obtain carboxylate-containing polyurethane;
the carboxylate-free polyurethane is prepared from 30-70 parts of a polymer alcohol chain extender, 0-10 parts of a polyfunctional cross-linking agent, 30-60 parts of a diisocyanate monomer and 1-12 parts of C2-C6 alkyl dihydric alcohol by the following method:
adding a polymer alcohol chain extender, a polyfunctional crosslinking agent and a diisocyanate monomer into a reaction kettle, heating to 60-100 ℃, and preserving heat for 1.0-2.0 hours; adding C2-C6 alkyl dihydric alcohol, and reacting at 70-80 ℃ until the content of NCO groups is lower than 4%; regulating the viscosity of the reactant to 3003000cps with acetone, and cooling to room temperature to obtain polyurethane containing no carboxylate;
the neutralizing agent is one or a mixture of more than two of N, N-dimethylethanolamine, ammonia water and triethylamine;
the polymer alcohol chain extender has the number average molecular mass of 300-10000, the hydroxyl value of 30-200mgKOH/g, and is one or a mixture of more than two of CMA-1044 polyester Diol of Shandong Dagaku, CMA-1042 polyester Diol of Shandong Daku, T-1136 polyester Diol of Hessian, N210 polyether polyol, N220 polyether polyol, Diol1000 polyether polyol, Diol2000 polyether polyol, polycarbonate Diol, polytetrahydrofuran Diol, polyurethane Diol, polyacrylate Diol, polybutadiene Diol and polycaprolactone Diol;
the diisocyanate monomer is one or a mixture of more than two of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl m-xylylene diisocyanate and xylylene diisocyanate.
The polyfunctional crosslinking agent is one or a mixture of more than two of trimethylolpropane, trimethylolethane, castor oil, E-20 epoxy resin, E-12 epoxy resin, E-44 epoxy resin, E-51 epoxy resin, an addition product of toluene diisocyanate and trimethylolpropane, toluene diisocyanate tripolymer, biuret of hexamethylene diisocyanate, biuret tripolymer of hexamethylene diisocyanate and tripolymer of isophorone diisocyanate;
the C2-C6 alkyl dihydric alcohol is one or a mixture of more than two of ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-cyclohexanediol and neopentyl glycol;
the dimethylol alkyl carboxylic acid is one or a mixture of more than two of dimethylol acetic acid, dimethylol propionic acid, dimethylol butyric acid and dimethylol valeric acid;
the amine chain extender is one or a mixture of more than two of hydrazine, ethylenediamine, hexamethylenediamine, isophoronediamine, diethylenetriamine and triethylene tetramine.
2. The process for preparing an aqueous polyurethane dispersion according to claim 1, wherein:
the carboxylate-containing polyurethane is prepared from 40-60 parts by weight of a polymer alcohol chain extender, 2-5 parts by weight of a polyfunctional cross-linking agent, 35-50 parts by weight of a diisocyanate monomer, 0-8 parts by weight of C2-C6 alkyl diol and 5-8 parts by weight of dimethylol alkyl carboxylic acid;
the carboxylate-free polyurethane is prepared from 40-60 parts by weight of a polymer alcohol chain extender, 2-5 parts by weight of a polyfunctional cross-linking agent, 35-50 parts by weight of a diisocyanate monomer and 1-12 parts by weight of C2-C6 alkyl dihydric alcohol;
wherein,
the polymer alcohol chain extender has the number average molecular mass of 300-10000, the hydroxyl value of 30-200mgKOH/g, and is one or the mixture of more than one of CMA-1044 polyester Diol of Shandong Dagaku, CMA-1042 polyester Diol of Shandong Daku, T-1136 polyester Diol of Hessian, N210 polyether polyol, N220 polyether polyol, Diol1000 polyether polyol and Diol2000 polyether polyol;
the diisocyanate monomer is one or a mixture of more than two of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, tetramethyl m-xylylene diisocyanate and xylylene diisocyanate;
the polyfunctional crosslinking agent is one or a mixture of more than two of trimethylolpropane, trimethylolethane, E-20 epoxy resin, E-12 epoxy resin, E-44 epoxy resin, E-51 epoxy resin and trimer of isophorone diisocyanate;
the C2-C6 alkyl dihydric alcohol is one or a mixture of more than two of propylene glycol, 1, 4-butanediol, 1, 6-hexanediol and 1, 4-cyclohexanediol;
the dimethylol alkyl carboxylic acid is one or a mixture of dimethylol propionic acid and dimethylol butyric acid.
3. The method for producing an aqueous polyurethane dispersion according to claim 1 or 2, wherein the solvent removal by distillation is carried out at a temperature of 50 to 120 ℃ and a vacuum degree of 0.02 to 0.1 Mpa.
4. An aqueous polyurethane coating comprising 60 to 90% by weight of the aqueous polyurethane dispersion prepared by the process of claim 1 or 2.
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| CN102408825A (en) * | 2011-09-14 | 2012-04-11 | 吴江市汇丰材料科技有限公司 | Single-component thermosetting polyurethane elastomer composition and preparation method thereof |
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| WO2018235921A1 (en) * | 2017-06-22 | 2018-12-27 | トーヨーポリマー株式会社 | Polyurethane aqueous dispersion, polyurethane aqueous dispersion production method, water-based coating composition, and coating film |
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