CN102432797B - Hydroxyl-terminated alkyd resin-modified waterborne polyurethane and preparation method thereof - Google Patents
Hydroxyl-terminated alkyd resin-modified waterborne polyurethane and preparation method thereof Download PDFInfo
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- CN102432797B CN102432797B CN201110237665.0A CN201110237665A CN102432797B CN 102432797 B CN102432797 B CN 102432797B CN 201110237665 A CN201110237665 A CN 201110237665A CN 102432797 B CN102432797 B CN 102432797B
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- alkyd resin
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- synolac
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 38
- 239000004814 polyurethane Substances 0.000 title claims abstract description 38
- 229920000180 alkyd Polymers 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 239000006185 dispersion Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920000768 polyamine Polymers 0.000 claims abstract description 10
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 9
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 33
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 32
- 239000002253 acid Substances 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 238000009413 insulation Methods 0.000 claims description 23
- 239000004970 Chain extender Substances 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 150000002632 lipids Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 8
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical group OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 8
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 8
- 239000005642 Oleic acid Substances 0.000 claims description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000009736 wetting Methods 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 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 6
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 claims description 4
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical group CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 235000004443 Ricinus communis Nutrition 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001530 fumaric acid Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000004807 desolvation Methods 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 2
- 229960004232 linoleic acid Drugs 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 4
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 3
- 229930195729 fatty acid Natural products 0.000 abstract description 3
- 239000000194 fatty acid Substances 0.000 abstract description 3
- 150000004665 fatty acids Chemical class 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 150000001735 carboxylic acids Chemical class 0.000 abstract 2
- 150000005846 sugar alcohols Polymers 0.000 abstract 2
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 230000032050 esterification Effects 0.000 abstract 1
- 238000005886 esterification reaction Methods 0.000 abstract 1
- 239000005457 ice water Substances 0.000 abstract 1
- 230000003472 neutralizing effect Effects 0.000 abstract 1
- 150000007519 polyprotic acids Polymers 0.000 abstract 1
- 229920005749 polyurethane resin Polymers 0.000 description 8
- 239000003973 paint Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000006115 industrial coating Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920003009 polyurethane dispersion Polymers 0.000 description 3
- -1 100% ethanolic soln Substances 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000005513 chalcones Nutrition 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 230000002708 enhancing effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229960002725 isoflurane Drugs 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
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- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
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Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to hydroxyl-terminated alkyd resin-modified waterborne polyurethane and a preparation method thereof. The hydroxyl-terminated alkyd resin-modified waterborne polyurethane has a structural formula shown in the description and is prepared by replacing general polyalcohol by hydroxyl-terminated alkyd resin. According to the preparation method, an esterification, condensation and stepwise polymerization process is adopted. The preparation method comprises the following steps of: firstly, preparing the hydroxyl-terminated alkyd resin from fatty acid, polybasic acid and polyalcohol by adopting a fatty acid method; secondly, reacting the hydroxyl-terminated alkyd resin, polyhydroxyl carboxylic acid and polyisocyanates to prepare an isocyanate-terminated prepolymer containing a hydrophilic group; thirdly, adding a salt forming agent in the prepolymer for neutralizing carboxylic acid to form salts; fourthly, dispersing the product in ice water and adding polyamine to extend a chain at the same time; and fifthly, after reaction, removing a solvent by distilling to obtain an alkyd resin-modified high-performance polyurethane aqueous dispersion. The hydroxyl-terminated alkyd resin-modified waterborne polyurethane has the advantages of high oil resistance, high chemical product resistance, high water resistance as well as excellent hardness, fullness, lustrousness, storage stability, mechanical properties and integrated performances.
Description
Technical field
The present invention relates to aqueous polyurethane and preparation method thereof field, particularly a kind of hydroxyl-terminated alkyd resin-modified waterborne polyurethane and preparation method thereof.
Background technology
Aqueous polyurethane has and the advantage such as does not fire, nontoxic, free from environmental pollution, energy-conservation, have simultaneously high strength, wear-resistant, use the excellent properties such as safety, therefore obtain a wide range of applications, become an important development direction of domestic and international field of new.Up to the present, the industrialized aqueous polyurethane kind of China is few, output is little, is difficult to meet present diversified demand, and the film-forming properties of product, snappiness, weathering resistance and water tolerance poor-performing are mainly processed and fabric treating as the leather of general property.The defect of performance has seriously limited the promotion and application of aqueous polyurethane in paint field, aqueous polyurethane adopts step-reaction polymerization, on molecular chain, contain a plurality of active groups, thereby available multiple material carries out the performance that modification improves aqueous polyurethane, the product such as acrylic acid modified, epoxy modified aqueous urethane had obtained development fast in the last few years.
Along with skyrocketing of oil price, the application of the Synolac that the vegetables oil of take is main raw material has obtained attention day by day.Synolac is that China develops the earliest, the synthetic resins of output maximum, and the component of Synolac and performance can be adjusted in wide range, adopt different polyvalent alcohols and polyprotonic acid just can obtain the different resin of performance; And the variation of the ratio of functionality can be controlled the degree of branching between alcohol and acid, carbonatoms in resin raw material between carboxyl or between hydroxyl can be adjusted the flexibility of resin etc., these features make Synolac can be applied to more field, are the desirable materials for modified aqueous polyurethane of a class.Synolac has following characteristics aspect modification: 1. in Synolac, contain poly-hydroxy, can react with making isocyanic ester, improve resin's crosslinkage.2. the Synolac of modification can make it contain terminal hydroxy group, can replace polyvalent alcohol and polyisocyanates reaction.3. in dry alkyd resin, mostly contain unsaturated link(age), can there is crosslinking reaction in modified aqueous polyurethane under the effect of oxygen or catalyzer.
Adopt alkyd modified one side can improve polyurethane film physicals and feel, can also reduce costs in addition, so Synolac day by day highlights its superiority aspect modified aqueous polyurethane.
Summary of the invention
Object of the present invention aims to provide a kind of advantage that has urethane resin, two kinds of resins of Synolac concurrently, can be applicable to hydroxyl-terminated alkyd resin-modified waterborne polyurethane of the purposes such as industrial coating, floor paint, wood lacquer, leather surface processing and preparation method thereof.
The modified aqueous polyurethane the present invention relates to replaces common polyvalent alcohol by terminal hydroxy group Synolac and is prepared from.The structural formula of this polymkeric substance is:
In structural formula, R is isocyanic ester segment, R
1for terminal hydroxy group alkyd polyester segment, n is integer, n>=1.
The preparation method that the present invention is is as follows: it is characterized in that, comprise the following steps,
1. polyvalent alcohol, lipid acid, polyprotonic acid are mixed, with dimethylbenzene, do reflux solvent, 150 ℃ ~ 220 ℃ are reacted to acid number 5 ~ 15mgKOH.g
-1after, steam dimethylbenzene, make terminal hydroxy group Synolac;
2. to above-mentioned terminal hydroxy group Synolac, add polyisocyanates, under 85 ℃ ~ 95 ℃ conditions, insulation reaction is 1 ~ 2 hour; Add again wetting ability chainextender, under 70 ℃ ~ 90 ℃ conditions, react 1 ~ 2 hour; Then add oxy-compound and solvent, 60 ℃ ~ 65 ℃ isothermal reactions to record NCO content be add-on 4 ~ 8% time, be finally cooled to 5 ℃ ~ 10 ℃ dischargings, make terminal hydroxy group Synolac modified polyurethane prepolymer;
3. terminal hydroxy group Synolac modified polyurethane prepolymer is carried out to dispersed with stirring, 10 ℃ add salt forming agent, acetone below, in and carboxyl salify, then add water to carry out dispersion and emulsion, add afterwards polyamine chainextender to carry out chain extension, make terminal hydroxy group Synolac modified polyurethane aqueous dispersions;
4. by terminal hydroxy group Synolac modified polyurethane aqueous dispersions precipitation, underpressure distillation desolvation makes hydroxyl-terminated alkyd resin-modified waterborne polyurethane.
Described polyvalent alcohol is a kind of or its any mixture containing in binary, ternary, quaternary or the hexa-atomic fatty alcohol of 2 ~ 6 carbon atoms; Described lipid acid is a kind of or its mixture containing in the unsaturated unary fatty acid of 10 ~ 20 carbon atoms; Described polyprotonic acid be binary, ternary containing 2 ~ 6 fat of carbon atom families or aromatic acid a kind of or its mixture wherein.
Described polyvalent alcohol is a kind of or its any mixture in ethylene glycol, butyleneglycol, TriMethylolPropane(TMP), neopentyl glycol, tetramethylolmethane more preferably; Described lipid acid is a kind of or its any mixture in oleic acid, linolic acid, dehydrated castor oleic acid more preferably; Described polyprotonic acid is a kind of or its any mixture in hexanodioic acid, fumaric acid, Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, m-phthalic acid more preferably.
Described polyisocyanates is tolylene diisocyanate, isophorone diisocyanate or diphenylmethanediisocyanate, and described step 2. solvent is acetone, methylethylketone or dimethyl formamide.
Described wetting ability chainextender is dimethylol propionic acid or dimethylolpropionic acid; Described is ethylene glycol, BDO or glycol ether to oxy-compound.
Described cold water is the deionized water of 0 ℃, account for step 2. ~ 3. total charging capacity 40 ~ 65%; Described salt forming agent is triethylamine.
Described polyamine chainextender is isophorone diamine, diethylenetriamine or tetraethylene pentamine.
Described step 1. in polyvalent alcohol, lipid acid, polyprotonic acid weight ratio=5 ~ 25:40 ~ 60:20 ~ 45 that feed intake; Step 2. ~ 3. in, each material weight ratio that feeds intake is terminal hydroxy group Synolac: polyisocyanates: wetting ability chainextender: to oxy-compound: solvent: triethylamine: polyamine chainextender=10 ~ 26:6 ~ 30:4 ~ 8:1 ~ 10:8 ~ 20:1 ~ 6:2 ~ 5.
The preparation method of described hydroxyl-terminated alkyd resin-modified waterborne polyurethane more preferably, described terminal hydroxy group Synolac, polyisocyanates, wetting ability chainextender, to oxy-compound, solvent, triethylamine, polyamine chainextender charging capacity account for respectively step 2. ~ 3. total charging capacity 10 ~ 26%, 6 ~ 30%, 4 ~ 8%, 1 ~ 10%, 8 ~ 20%, 1 ~ 6%, 2 ~ 5%; Described step 1. preferred version is: polyvalent alcohol, lipid acid, polyprotonic acid are mixed according to 5 ~ 25%, 40 ~ 60%, 20 ~ 45% of total charging capacity, with dimethylbenzene, do reflux solvent, 150 ℃ ~ 160 ℃ insulation reaction 1.5 ~ 2.5 hours, 175 ~ 185 ℃ of insulation reaction 2 ~ 3 hours, be warming up to 200 ~ 220 ℃, insulation reaction is to acid number 5 ~ 15mgKOH.g
-1, stop heating, steam dimethylbenzene, make terminal hydroxy group Synolac; Described step 3. preferred version is: terminal hydroxy group Synolac modified polyurethane prepolymer is added to dispersion cylinder, rotating speed is controlled at 500 ~ 1000 revs/min and carries out dispersed with stirring, 10 ℃ add triethylamine, acetone below, in and carboxyl salify, after 5 ~ 6 minutes, rotating speed is carried to 1000 ~ 2000 revs/min, then add the deionized water of 0 ℃ to carry out dispersion and emulsion, after 9 ~ 11 minutes, add polyamine chainextender to carry out chain extension, high speed dispersion 9 ~ 11 minutes, rotating speed is reduced to 450 ~ 500 revs/min, disperse 0.5 ~ 1.5 hour, make terminal hydroxy group Synolac modified polyurethane aqueous dispersions; Described step 4. preferred version is: terminal hydroxy group Synolac modified polyurethane aqueous dispersions is added to precipitation still precipitation, and 55 ~ 65 ℃ of temperature, under vacuum tightness-0.08Mpa ~-0.09Mpa, desolvation makes hydroxyl-terminated alkyd resin-modified waterborne polyurethane.
The present invention compared with prior art tool has the following advantages:
1, the product that the present invention produces has high-weatherability, chemical-resistant, water tolerance, also has excellent hardness, bonding strength, glossiness, stability in storage and over-all properties simultaneously.One large advantage of Synolac is that it does not rely on petroleum products substantially, and its raw material sources are extensive, and formula flexibly, is easy to give its various characteristics by various modifications, almost can be applied among all types coating.And in Synolac, contain poly-hydroxy and insatiable hunger key, and can replace linking agent to make urethane produce cross-linked network, both reduced cost, improve again the every technical feature of this product.
2, product of the present invention produce and use procedure in three-waste free discharge, be nontoxic, do not fire, free from environmental pollution, save energy, from root, solve environmental pollution, the able-bodied environmental protection of protection people, resource-conserving product.
3, product cost of the present invention is lower, has high-performance, and excellent combination property can be widely used in the fields such as aqueous industrial coating, floor paint, wood lacquer, hard floor paint, PVC plastic lousing lac varnish, high-performance hide finishes.Along with the enhancing of sound and people's environmental consciousness of Environmental Protection in China rules, with the high-performance multipurpose aqueous polyurethane of water replace solvents, will obtain great development, and the alternative import of product, 60% outlet, market outlook are wide.
Embodiment
Embodiment 1: in the stainless steel cauldron of 100L that agitator, thermometer, condenser, oily-water seperating equipment are housed, once add 25Kg lauric acid, 10Kg ethylene glycol and 20Kg hexanodioic acid, heat temperature raising, with dimethylbenzene 110kg, do reflux solvent simultaneously, 150～160 ℃ of insulation reaction 2 hours, 180 ℃ of insulation reaction 2～3 hours, are warming up to 210 ℃, and insulation reaction is to acid number to 6mgKOH.g
-1, stop heating, steam dimethylbenzene, make the discharging of terminal hydroxy group Synolac standby.
Get above-mentioned 38Kg terminal hydroxy group Synolac and be placed in the 250L stainless steel cauldron that agitator, thermometer, condenser are housed, heat temperature raising, 90 ℃ drip 25Kg tolylene diisocyanate (TDI), drip off rear insulation reaction 1 hour, be cooled to 85 ℃ and add dimethylol propionic acid 3.5kg, react 2 hours, be cooled to again 65 ℃ and add 4Kg 1,4-butyleneglycol and 50kg acetone insulation reaction 4～5 hours, to survey NCO content be add-on 5%, makes modified polyurethane resin performed polymer (structural formula I).Be cooled to 5 ℃, modified polyurethane resin performed polymer is added to dispersion cylinder, 500 revs/min of rotating speeds carry out dispersed with stirring, add 4Kg triethylamine and proper amount of acetone reaction 3～4min, then rotating speed is increased to 1500 revs/min, under strong stirring, adds successively frozen water, 3Kg diethylenetriamine, high speed dispersion 15 minutes, then rotating speed is adjusted to 500 revs/min and stirs 30 minutes, make hydroxyl-terminated alkyd resin-modified waterborne polyurethane dispersion liquid.Modified polyurethane aqueous dispersions is added to precipitation still, 55 ℃ ~ 65 ℃, under vacuum tightness-0.085Mpa condition, slough solvent and both obtained hydroxyl-terminated alkyd resin-modified waterborne polyurethane (structural formula II).Concrete structure formula is as follows:
Structural formula I:
Structural formula II:
In structural formula I, II, in structural formula, R is tolylene diisocyanate (TDI) segment, R
1for terminal hydroxy group alkyd polyester (take lauric acid, ethylene glycol, hexanodioic acid be raw material) segment, n is integer, n>=1.
Embodiment 2: in the stainless steel cauldron of 100L that agitator, thermometer, condenser, oily-water seperating equipment are housed, once add 30Kg dehydrated castor oleic acid, 15Kg TriMethylolPropane(TMP) and 24Kg Tetra hydro Phthalic anhydride heat temperature raising, with dimethylbenzene 100kg, do reflux solvent simultaneously, 150～160 ℃ of insulation reaction 2 hours, 180 ℃ of insulation reaction 2～3 hours, be warming up to 210 ℃, insulation reaction is to acid number to 8 mgKOH.g
-1, stop heating, steam dimethylbenzene, make the discharging of terminal hydroxy group Synolac standby.
Get above-mentioned 45Kg terminal hydroxy group Synolac and be placed in the 250L stainless steel cauldron that agitator, thermometer, condenser are housed, heat temperature raising, 90 ℃ drip 32KgMDI, drip off rear insulation reaction 1 hour, be cooled to 85 ℃ and add dimethylol propionic acid 6.5Kg, react 2 hours, be cooled to again 65 ℃ and add 8Kg ethylene glycol and 55kg acetone insulation reaction 4～5 hours, to survey NCO content be add-on 6%, is cooled to 5 ℃, makes modified polyurethane resin performed polymer.Modified polyurethane resin performed polymer is added to dispersion cylinder, 500 revs/min of rotating speeds carry out dispersed with stirring, add 9Kg triethylamine and proper amount of acetone reaction 3～4min, then rotating speed is increased to 1500 revs/min, under strong stirring, add successively frozen water, 2.5Kg diethylenetriamine, high speed dispersion 15 minutes, then rotating speed is adjusted to 500 revs/min and stirs 30min, make hydroxyl-terminated alkyd resin-modified waterborne polyurethane dispersion liquid, modified polyurethane aqueous dispersions is added to precipitation still, 55 ℃ ~ 65 ℃, under the Mpa condition of vacuum tightness-0.085, slough solvent and both obtained hydroxyl-terminated alkyd resin-modified waterborne polyurethane.
Product hardness (pencil hardness) H, gloss (gloss 60o) 110, water tolerance (filming 25 ℃, 100 hours) is non-foaming, nothing comes off, do not whiten, sticking power (cross-hatching)≤1, chemical-resistant (5% acid solution, 8% alkaline solution, 100% ethanolic soln, films and soaks 24 hours) unchanged.Be suitable as aqueous woodware paint, hard floor paint and floor paint.
In the present embodiment, the structure formation of modified polyurethane resin, modified polyurethane aqueous dispersions is substantially with embodiment 1, and difference is that the R in structural formula I, II is ditan two isocyanide ester ester segments (MDI), R
1for polyester segment (take lipid acid as dehydrated castor oleic acid, polyvalent alcohol is TriMethylolPropane(TMP), and polyprotonic acid is that Tetra hydro Phthalic anhydride is starting material), to oxy-compound, be ethylene glycol.
Embodiment 3: in the 100L stainless steel cauldron of agitator, thermometer, condenser, oily-water seperating equipment is housed, once add 35Kg oleic acid, 17Kg TriMethylolPropane(TMP) and 26Kg fumaric acid, heat temperature raising, with dimethylbenzene 105Kg, do reflux solvent simultaneously, 150～160 ℃ of insulation reaction 2 hours, 180 ℃ of insulation reaction 2～3 hours, are warming up to 210 ℃, and insulation reaction is hour .g to acid number to 9mgKOH
-1, stop heating, steam dimethylbenzene, make the discharging of terminal hydroxy group Synolac standby.
Get above-mentioned 56Kg terminal hydroxy group Synolac and be placed in the 250L stainless steel cauldron that agitator, thermometer, condenser are housed, heat temperature raising, 90 ℃ drip 45KgIPDI, drip off rear insulation reaction 1 hour, be cooled to 85 ℃ and add dimethylolpropionic acid 7.5Kg, react 2 hours, then be cooled to 65 ℃ and add 10Kg glycol ether and 60kg acetone insulation reaction 4～5 hours, to survey NCO content be add-on 4%, is cooled to 30 ℃ and makes modified polyurethane resin performed polymer.Modified polyurethane resin performed polymer is added to dispersion cylinder, 500 revs/min of rotating speeds carry out dispersed with stirring, add 7.8Kg triethylamine and proper amount of acetone reaction 18～20min, then rotating speed is increased to 1500 revs/min, under strong stirring, add successively cold water, 2.0Kg isophorone diamine, high speed dispersion 15 minutes, then rotating speed is adjusted to 500 revs/min and stirs 30min, make hydroxyl-terminated alkyd resin-modified waterborne polyurethane dispersion liquid, modified polyurethane aqueous dispersions is added to precipitation still, 55 ℃ ~ 65 ℃, under vacuum tightness-0.085Mpa condition, slough solvent and both obtained hydroxyl-terminated alkyd resin-modified waterborne polyurethane.
Shock-resistance 50kg.cm after this product film forming, thermotolerance (120 ℃ of steel plates, 1 hour) is unchanged, and xanthochromia is good, and weathering resistance (30 ℃ ~ 80 ℃, cold cycling 120 times) is without coming off, without peeling.Can be used for the industrial coatings such as automobile bottom coat, middle painting.
In the present embodiment, the structure formation of modified polyurethane resin, modified polyurethane aqueous dispersions is substantially with embodiment 1, and difference is that the R in structural formula I, II is isoflurane chalcone diisocyanate (IPDI) segment, R
1for polyester (take lipid acid as oleic acid, polyvalent alcohol is TriMethylolPropane(TMP), and polyprotonic acid is that fumaric acid is starting material), polyol is glycol ether, and wetting ability chainextender is dimethylolpropionic acid, and polyamine chainextender is isophorone diamine.
Above illustrated embodiment, can both realize the present invention, the bound value of each raw material of the present invention with and interval value all can realize the present invention, at this, do not enumerate other embodiment; The bound value of processing parameter of the present invention with and interval value all can realize the present invention, at this, do not enumerate other embodiment.
Claims (1)
1. a preparation method for hydroxyl-terminated alkyd resin-modified waterborne polyurethane, is characterized by, and comprises the following steps:
1., polyvalent alcohol, lipid acid, polyprotonic acid are mixed according to 5 ~ 25%, 40 ~ 60%, 20 ~ 45% of total charging capacity, with dimethylbenzene, do reflux solvent, 150 ℃ ~ 160 ℃ insulation reaction 1.5 ~ 2.5 hours, 175 ~ 185 ℃ of insulation reaction 2 ~ 3 hours, be warming up to 200 ~ 220 ℃, insulation reaction is to acid number 5 ~ 15mgKOH.g
-1, stop heating, steam dimethylbenzene, make terminal hydroxy group Synolac;
2. to above-mentioned terminal hydroxy group Synolac, add polyisocyanates, under 85 ℃ ~ 95 ℃ conditions, insulation reaction is 1 ~ 2 hour; Add again wetting ability chainextender, under 70 ℃ ~ 90 ℃ conditions, react 1 ~ 2 hour; Then add oxy-compound and solvent, 60 ℃ ~ 65 ℃ isothermal reactions to record NCO content be add-on 4 ~ 8% time, be finally cooled to 5 ℃ ~ 10 ℃ dischargings, make terminal hydroxy group Synolac modified polyurethane prepolymer;
3. terminal hydroxy group Synolac modified polyurethane prepolymer is added to dispersion cylinder, rotating speed is controlled at 500 ~ 1000 revs/min and carries out dispersed with stirring, 10 ℃ add salt forming agent, acetone below, in and carboxyl salify, after 5 ~ 6 minutes, rotating speed is carried to 1000 ~ 2000 revs/min, then add frozen water to carry out dispersion and emulsion, after 9 ~ 11 minutes, add polyamine chainextender to carry out chain extension, high speed dispersion 9 ~ 11 minutes, rotating speed is reduced to 450 ~ 500 revs/min, disperse 0.5 ~ 1.5 hour, make terminal hydroxy group Synolac modified polyurethane aqueous dispersions;
4. terminal hydroxy group Synolac modified polyurethane aqueous dispersions is added to precipitation still precipitation, 55 ~ 65 ℃ of temperature, under vacuum tightness-0.08Mpa ~-0.09Mpa, desolvation makes hydroxyl-terminated alkyd resin-modified waterborne polyurethane;
Described polyvalent alcohol is a kind of or its any mixture in ethylene glycol, butyleneglycol, TriMethylolPropane(TMP), neopentyl glycol, tetramethylolmethane; Described lipid acid is a kind of or its any mixture in oleic acid, linolic acid, dehydrated castor oleic acid; Described polyprotonic acid is a kind of or its any mixture in hexanodioic acid, fumaric acid, Tetra hydro Phthalic anhydride, MALEIC ANHYDRIDE, m-phthalic acid; Described polyisocyanates is tolylene diisocyanate, isophorone diisocyanate or diphenylmethanediisocyanate, and described step 2. solvent is acetone, methylethylketone or dimethyl formamide; Described wetting ability chainextender is dimethylol propionic acid or dimethylolpropionic acid; Described is ethylene glycol, BDO or glycol ether to oxy-compound; Described water is the deionized water of 0 ℃; Described salt forming agent is triethylamine; Described polyamine chainextender is isophorone diamine, diethylenetriamine or tetraethylene pentamine; Described terminal hydroxy group Synolac, polyisocyanates, wetting ability chainextender, to oxy-compound, solvent, salt forming agent, polyamine chainextender charging capacity account for respectively step 2. ~ 3. total charging capacity 10 ~ 26%, 6 ~ 30%, 4 ~ 8%, 1 ~ 10%, 8 ~ 20%, 1 ~ 6%, 2 ~ 5%.
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