CN103436155B - A kind of preparation method of light-resistant waterborne polyurethane coating - Google Patents
A kind of preparation method of light-resistant waterborne polyurethane coating Download PDFInfo
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- CN103436155B CN103436155B CN201310407835.4A CN201310407835A CN103436155B CN 103436155 B CN103436155 B CN 103436155B CN 201310407835 A CN201310407835 A CN 201310407835A CN 103436155 B CN103436155 B CN 103436155B
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- waterborne polyurethane
- resistant waterborne
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- 239000011527 polyurethane coating Substances 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 11
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004970 Chain extender Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 7
- 238000004945 emulsification Methods 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 15
- -1 isocyanic acid tri-methyl hexamethylene esters Chemical class 0.000 claims description 4
- KJTLQQUUPVSXIM-ZCFIWIBFSA-N (R)-mevalonic acid Chemical group OCC[C@](O)(C)CC(O)=O KJTLQQUUPVSXIM-ZCFIWIBFSA-N 0.000 claims description 3
- KJTLQQUUPVSXIM-UHFFFAOYSA-N DL-mevalonic acid Natural products OCCC(O)(C)CC(O)=O KJTLQQUUPVSXIM-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 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
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 3
- 239000004814 polyurethane Substances 0.000 abstract description 11
- 229920002635 polyurethane Polymers 0.000 abstract description 11
- 230000007613 environmental effect Effects 0.000 abstract 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 230000000176 photostabilization Effects 0.000 description 7
- 238000009835 boiling Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229920006264 polyurethane film Polymers 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical class OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric Acid Chemical compound [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- 239000007998 bicine buffer Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention discloses a kind of preparation method of light-resistant waterborne polyurethane coating, under dibutyltin dilaurate catalyst existent condition, is mixed by bisphenol S with vulcabond, and stirring reaction 1.5 ~ 3.5h at 60 ~ 85 DEG C, obtains base polyurethane prepolymer for use as A; In A, add the hydrophilic chain extender that carboxyl-content is A weight 1.2 ~ 4.6%, the stirring reaction time is 40 ~ 80min, then adds the solvent of A weight 15 ~ 35%, and stirring reaction 1.0 ~ 4.0h under 80 ~ 95 DEG C of conditions, by COOH/NH
2mol ratio be 0.6:1 ~ 1.6:1, add triethylamine and neutralize, stirring reaction 30 ~ 70min, add water and carry out emulsification, form a kind of light-resistant waterborne polyurethane coating.Prepared light-resistant waterborne polyurethane environmental protection, cheap, the demand of market to sunproof polyurethane performance can be met.
Description
Technical field
The present invention relates to a kind of preparation method of aqueous polyurethane, particularly a kind of preparation method of light-resistant waterborne polyurethane coating.
Background technology
Aqueous polyurethane take water as dispersion medium, nonpoisonous and tasteless, free from environmental pollution, is widely used in woodwork coating, automobile repairing paint, protective system, building coating, floor paint, electronic paint, speciality coating, polyurethane water-proof paint etc.But because use field often contacts sunlight, containing UV-light harmful to light object in a large number in solar ray, its wavelength 290 ~ 460nm, these UV-light, by redoxomorphism chemically, make material surface generation colour-change, affect appearance.
Current sunproof polyurethane has two kinds of preparation methods, one, substitutes polyester diol or polyether Glycols and isocyanic ester carry out pre-polymerization with polycarbonate diol, and the urethane of which synthesis has good photostabilization, but synthesized polyurethane film is too hard; Another kind of mode is by as composite in nano titanium oxide, nano zine oxide, carbon nanotube etc. to urethane and nano material, the photostabilization of raising urethane, but due to nano material emulsion intercalation method poor, the standby urethane stability in storage of this legal system is poor.
Summary of the invention
Present invention employs following technical scheme.
(1), under dibutyltin dilaurate catalyst existent condition, be 1.2:1 ~ 3.5:1, mixed by bisphenol S with vulcabond by the mol ratio of NCO/OH, stirring reaction 1.5 ~ 3.5h at 60 ~ 85 DEG C, obtains base polyurethane prepolymer for use as A; Described catalyst levels is 0.3 ~ 0.6% of bisphenol S and vulcabond gross weight;
(2), in A, add the hydrophilic chain extender that carboxyl-content is A weight 1.2 ~ 4.6%, the stirring reaction time is 40 ~ 80min, adds the solvent of A weight 15 ~ 35%, and stirring reaction 1.0 ~ 4.0h under 80 ~ 95 DEG C of conditions, by COOH/NH
2mol ratio be 0.6:1 ~ 1.6:1, add triethylamine and neutralize, stirring reaction 30 ~ 70min, add water and carry out emulsification, form a kind of light-resistant waterborne polyurethane coating B;
Vulcabond be in hexamethylene diisocyanate, isophorone diisocyanate, two isocyanic acid tri-methyl hexamethylene esters, lysinediisocyanate any one; Hydrophilic chain extender is any one in mevalonic acid, 2,3 dihydroxybutanedioic acid, N, N-bicine N-, 2,2-dimethylolpropionic acids, 3-hydroxyl-2-(methylol)-2 Methylpropionic acid; Solvent is any one in dimethyl sulfoxide (DMSO), methylethylketone, pyridine.
The present invention has following characteristics:
(1), prepared light-resistant waterborne polyurethane and material compatibility good;
(2) vulcabond, selected has good photostabilization;
(3), adopt bisphenol S to replace traditional polyester diol or polyether Glycols, prepared urethane photostabilization is good, and institute's film forming is neither too hard, nor too soft, solvent resistance and wear resistance significantly improve;
(4), dimethyl sulfoxide (DMSO), methylethylketone, pyridine replace traditional urethane and synthesize the DMF solvent used, and reduces the toxicity of urethane.
embodimentthe present invention is further illustrated below in conjunction with example.
example one
(1), be equipped with stirring arm, thermometer, prolong 500ml four-hole boiling flask in, bisphenol S 25g is mixed with hexamethylene diisocyanate 20.2g, under dibutyltin dilaurate catalyst 0.14g existent condition, stirring reaction 1.5h at 60 DEG C, obtains 45.1g base polyurethane prepolymer for use as A;
(2), in base polyurethane prepolymer for use as, hydrophilic chain extender mevalonic acid 1.64g is added, the stirring reaction time is 40min, dimethyl sulfoxide (DMSO) 6.8g is added in A, stirring reaction 1.0h under 80 DEG C of conditions, add triethylamine 2.0g to neutralize, stirring reaction 30min, the 150g that adds water carries out emulsification, forms a kind of light-resistant waterborne polyurethane coating B;
example two
(1), be equipped with stirring arm, thermometer, prolong 500ml four-hole boiling flask in, bisphenol S 25g is mixed with isophorone diisocyanate 77.7g, under dibutyltin dilaurate catalyst 0.62g existent condition, stirring reaction 3.5h at 85 DEG C, obtains 102.5g base polyurethane prepolymer for use as A;
(2), in base polyurethane prepolymer for use as, hydrophilic chain extender 2 is added, 3-dyhydrobutanedioic acid 7.9g, the stirring reaction time is 80min, methylethylketone 35.9g is added in A, stirring reaction 4.0h under 95 DEG C of conditions, adds triethylamine 6.6g and neutralizes, stirring reaction 70min, the 160g that adds water carries out emulsification, forms a kind of light-resistant waterborne polyurethane coating B;
example three
(1), be equipped with stirring arm, thermometer, prolong 500ml four-hole boiling flask in, bisphenol S 25g is mixed with two isocyanic acid tri-methyl hexamethylene ester 50.4g, under dibutyltin dilaurate catalyst 0.34g existent condition, stirring reaction 2.5h at 75 DEG C, obtains 75.1g base polyurethane prepolymer for use as A;
(2), in base polyurethane prepolymer for use as, hydrophilic chain extender N is added, N-bicine N-7.9g, the stirring reaction time is 60min, pyridine 18.8g is added in A, stirring reaction 2.5h under 90 DEG C of conditions, adds triethylamine 4.5g and neutralizes, stirring reaction 50min, the 170g that adds water carries out emulsification, forms a kind of light-resistant waterborne polyurethane coating B;
example four
(1), be equipped with stirring arm, thermometer, prolong 500ml four-hole boiling flask in, bisphenol S 25g is mixed with lysinediisocyanate 54.2g, under dibutyltin dilaurate catalyst 0.35g existent condition, stirring reaction 2.5h at 75 DEG C, obtains 78.1g base polyurethane prepolymer for use as A;
(2), in base polyurethane prepolymer for use as, hydrophilic chain extender 3-hydroxyl-2-(methylol)-2 Methylpropionic acid 5g is added, the stirring reaction time is 60min, pyridine 15.6g is added in A, stirring reaction 2.5h under 90 DEG C of conditions, add triethylamine 4.9g to neutralize, stirring reaction 50min, the 170g that adds water carries out emulsification, forms a kind of light-resistant waterborne polyurethane coating B;
In order to the light fastness of quantitative description urethane, adopt spectrophotometer to detect, to obtain inverse difference △ E, describe the photostabilization of urethane.△ E represents colour-change degree, and △ E is larger, and color change is more obvious.In general, △ E value is the slight change of 0 ~ 1.5 genus; △ E value is that 1.5 ~ 3.0 genus can feel change; △ E value be 3.0 ~ 6.0 belong to considerable changes (see Wang Fang, party's climax, Wang Liqin, the photodegradation [J] of several organic historical relic's protection polymer coating. Northwest University's journal, 2005,35 (5): 56 ~ 58).The mechanical property of polyurethane film adopts elongation at break to weigh, and elongation at break is larger, and its mechanical property is better.The testing method of elongation at break is shown in (Jiang Weiqi. leather finish physical and chemical inspection [M]. China Light Industry Press, 1999,82 ~ 96).Example one is designated as D, F, G, H respectively to the sunproof polyurethane of example four gained, selects the sunproof polyurethane PODESENG513MS on market to contrast with it.
Under the table one different UV-irradiation time, the value of chromatism △ E of urethane changes
| Time/min | PODESENG 513MS | D | F | G | H |
| 90 | 0.7 | 0.3 | 0.4 | 0.2 | 0.1 |
| 150 | 0.9 | 0.4 | 0.6 | 0.2 | 0.1 |
| 270 | 1.0 | 0.5 | 0.7 | 0.3 | 0.3 |
| 330 | 1.1 | 0.5 | 0.7 | 0.4 | 0.4 |
| 390 | 1.3 | 0.7 | 0.8 | 0.5 | 0.6 |
| 450 | 1.5 | 0.8 | 0.8 | 0.6 | 0.7 |
| 510 | 1.8 | 0.9 | 0.9 | 0.7 | 0.9 |
| 540 | 2.1 | 1.0 | 1.1 | 0.7 | 0.9 |
| 600 | 2.3 | 1.1 | 1.1 | 1.0 | 1.0 |
Can find from table one, example one all in slight variation range, show good photostabilization, and the sunproof polyurethane on market is at more than 510min, has belonged to and can feel change to four kinds of urethane photostabilization prepared by example four.
Table two light-resistant waterborne polyurethane film elongation at break
| Classification | PODESENG 513MS | D | F | G | H |
| Elongation at break/% | 188.26 | 227.67 | 222.52 | 221.80 | 223.54 |
In table two, the sunproof polyurethane film elongation at break of example one to four gained is larger than the elongation at break of the sunproof polyurethane in market.
Claims (2)
1. a preparation method for light-resistant waterborne polyurethane coating, is characterized in that:
(1), under dibutyltin dilaurate catalyst existent condition, be 1.2:1 ~ 3.5:1, mixed by bisphenol S with vulcabond by the mol ratio of NCO/OH, stirring reaction 1.5 ~ 3.5h at 60 ~ 85 DEG C, obtains base polyurethane prepolymer for use as A; Described catalyst levels is 0.3 ~ 0.6% of bisphenol S and vulcabond gross weight;
(2), in A, add the hydrophilic chain extender that carboxyl-content is A weight 1.2 ~ 4.6%, the stirring reaction time is 40 ~ 80min, adds the solvent of A weight 15 ~ 35%, and stirring reaction 1.0 ~ 4.0h under 80 ~ 95 DEG C of conditions, by COOH/NH
2mol ratio be 0.6:1 ~ 1.6:1, add triethylamine and neutralize, stirring reaction 30 ~ 70min, add water and carry out emulsification, form a kind of light-resistant waterborne polyurethane coating B, described hydrophilic chain extender is mevalonic acid, and solvent is dimethyl sulfoxide (DMSO).
2. the preparation method of a kind of light-resistant waterborne polyurethane coating as claimed in claim 1, is characterized in that: vulcabond be in hexamethylene diisocyanate, isophorone diisocyanate, two isocyanic acid tri-methyl hexamethylene esters, lysinediisocyanate any one.
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104004449B (en) * | 2014-06-15 | 2016-04-20 | 段宝荣 | A kind of fast light preparation method with aqueous flame retardant polyurethane coating |
| CN104087149B (en) * | 2014-07-21 | 2016-04-27 | 段宝荣 | A kind of preparation method of light-resistant waterborne polyurethane coating |
| CN104098995B (en) * | 2014-07-21 | 2016-05-04 | 广州市盛邦康体场地材料有限公司 | A kind of preparation method of fire-retardant and water proofing property aqueous polyurethane coating |
| CN104073145B (en) * | 2014-07-21 | 2016-08-24 | 常州市天安特种涂料有限公司 | A kind of preparation method of light-resistant waterborne polyurethane coating |
| CN104356330B (en) * | 2014-09-28 | 2017-02-08 | 陕西科技大学 | Carboxylic acid waterborne polyurethane chain extender and preparation method thereof |
| KR102536515B1 (en) * | 2015-03-06 | 2023-05-24 | 에이치. 비. 풀러, 컴퍼니 | water-based primer composition |
| CN109354681A (en) * | 2018-11-19 | 2019-02-19 | 中国科学院青岛生物能源与过程研究所 | A kind of preparation method of non-isocyanate polyurethane |
| CN111662633B (en) * | 2020-06-24 | 2021-11-30 | 广东达尔新型材料有限公司 | Anti-static wear-resistant polyurethane floor coating and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333791A (en) * | 1998-12-11 | 2002-01-30 | 陶氏化学公司 | Polyoxazolidone adhesive resin compoistion prepared from polyepoxides and polyisocyanates |
| CN1405253A (en) * | 2001-08-07 | 2003-03-26 | 拜尔公司 | Water dispersion of hydrophilic polyurethane resin |
| CN103073696A (en) * | 2013-01-30 | 2013-05-01 | 段宝荣 | Preparation method of light-resistant waterborne polyurethane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497698A (en) * | 2009-01-22 | 2009-08-05 | 南京大学 | Preparation of chitosan-polyurethane ion complex elastomer material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333791A (en) * | 1998-12-11 | 2002-01-30 | 陶氏化学公司 | Polyoxazolidone adhesive resin compoistion prepared from polyepoxides and polyisocyanates |
| CN1405253A (en) * | 2001-08-07 | 2003-03-26 | 拜尔公司 | Water dispersion of hydrophilic polyurethane resin |
| CN103073696A (en) * | 2013-01-30 | 2013-05-01 | 段宝荣 | Preparation method of light-resistant waterborne polyurethane |
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