CN103555183B - Color inhibition, weather-proof fluorine richness polyurethane finishing varnish and preparation method thereof - Google Patents
Color inhibition, weather-proof fluorine richness polyurethane finishing varnish and preparation method thereof Download PDFInfo
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- CN103555183B CN103555183B CN201310502859.8A CN201310502859A CN103555183B CN 103555183 B CN103555183 B CN 103555183B CN 201310502859 A CN201310502859 A CN 201310502859A CN 103555183 B CN103555183 B CN 103555183B
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Abstract
The invention discloses a kind of color inhibition, weather-proof fluorine richness polyurethane finishing varnish and preparation method thereof, be to react formation performed polymer by alkyl, cycloalkyl diisocyanate (HDI and IPDI) or XDI (XDI) with polytetramethylene ether diol (PTMEG).By the most modified for obtained performed polymer perfluoroalkyl ethanol, finally carry out chain extension with polyalcohol thus obtained color inhibition, weather-proof fluorine richness polyurethane finishing varnish.The preparation technology of this fluorine richness polyurethane finishing varnish is simple, has the strongest industrialization ability and application prospect.
Description
Technical field
The present invention relates to a kind of color inhibition, the preparation method of weather-proof fluorine richness polyurethane, refer more particularly to this modified poly-
Urethane prepares the method for finishing varnish.
Background technology
Finishing varnish is a procedure critically important in coating process, by the overlay treatment to coating, it is possible to right
Subbing plays a very good protection.Therefore, the finishing varnish that a performance is good can improve wear-resisting, resistance toization of coating
, the weather-proof and characteristic of washability, extend the service life of coating.Polyurethanes finishing varnish is due to high-tensile, resistance to
Chemically and weatherability, be prone to processing and good engineering properties so that in occupation of the biggest on the market of its finishing varnish
Share, especially aromatic urethane finishing varnish more becomes the important component part of polyurethanes finishing varnish
(X.F.Yang, C.Vang, D.E.Tallman, et al.Polym.Degrad.Stab.2001,74,341 351;
B.Ahmadi,M.Kassiriha,K.Khodabakhshi,et al.Prog.Org.Coat.2007,60,99–104;).Fragrance
Although adoption urethane finishing varnish is cheap, contributes to production cost control, but have many coating users in recent years and grind
The person of studying carefully finds, aromatic urethane finishing varnish in use color can gradually become dull and seriously turn to be yellow.There is research
Pointing out, ultraviolet radiation, water and oxygen are the main factors causing polyurethane finishing varnish to decompose, turn to be yellow, ultraviolet
Directly radiation can cause the decomposition of the carbamate groups being joined directly together in the middle of aromatic urethane material with phenyl ring, generates benzene
Amine, the further oxidized colour developing group that can form quinoid structure of aniline, ultimately cause change and the painting of finishing varnish color
Generation (M.M.Jalili, S.Moradian, the Prog.Org.Coat.2009,66,359 366 of layer surface crack;
D.R.Bauer, R.A.Dickie, J.L.Koenig, Ind.Eng.Chem.Prod.Res.Dev.1986,25,289 296.).
The problem being in use susceptible to xanthochromia for aromatic urethane finishing varnish, the present invention with alkyl,
Cycloalkyl diisocyanate (HDI and IPDI) or XDI (XDI) and polytetramethylene ether diol
(PTMEG) it is raw material, the most modified by perfluoroalkyl ethanol, finally carry out chain extension with polyalcohol thus obtain resistance to Huang
Change, weather-proof fluorine richness polyurethane finishing varnish.Alkyl, cycloalkyl diisocyanate (HDI and IPDI) will not under ultraviolet radiates
Form colour developing group, and XDI (XDI) is owing to introducing Asia between phenyl ring and isocyanate groups
Methyl, the most also will not issue the look that changes by ultraviolet radiation condition again.The present invention also introduces perfluor alkane on polyurethane molecular chain
Base ethanol, introduced perfluoroalkyl ethanol significantly reduces the surface of polyurethane finishing varnish can so that it is possesses greasy dirt water-fast, resistance to
Ability (S.J.Bonafede, R.F.Brady, Surf.Coat.Int.1998,4,181-185;S.Yang,L.Wang,C.-
F.Wang, et al.Langmuir2010,26,18454-18458.).Additionally, introduced fluorine atom can also give poly-ammonia
Weatherability that ester finishing varnish is good and the ability of anti-light decomposition.Fluorine richness polyurethane finishing varnish tool prepared by the present invention
There are good resistance to water, resistance to greasy dirt, color inhibition and weatherability, therefore, it is possible to the finishing varnish as multiple coating uses.
Summary of the invention
The present invention is prepared for a kind of color inhibition, weather-proof fluorine richness polyurethane finishing varnish, and this finishing varnish has fabulous
Resistance to water, resistance to greasy dirt, color inhibition and weatherability, can use as the finishing varnish of multiple coating.
The technical scheme is that with alkyl, cycloalkyl diisocyanate (HDI and IPDI) or phenylenedimethylidyne two
Isocyanates (XDI) and polytetramethylene ether diol (PTMEG) are raw material, and reaction under certain condition forms performed polymer, then
With perfluoroalkyl ethanol, performed polymer is carried out further modification, finally carry out chain extension with polyalcohol thus obtained color inhibition, resistance to
Wait fluorine richness polyurethane finishing varnish.
The color inhibition that the present invention relates to, the preparation method of weather-proof fluorine richness polyurethane finishing varnish, it specifically comprises the following steps that
(A) preparation of fluorine richness polyether polyols with reduced unsaturation
In 250ml four-hole bottle, by diisocyanate monomer (HDI, IPDI or XDI) and polytetramethylene ether diol
(PTMEG, molecular weight 600-5000) is mixed to join in the middle of organic solvent A, and wherein organic solvent A is DMF
(DMF) or carbon number is the ketone of 3-10, ether, alcohol, alkane and aromatic hydrocarbon, the mol ratio of diisocyanate monomer and PTMEG
For 1.2:1～1.8:1, reactant is 3:7～1:1 with the mass ratio of organic solvent A, by the mixture that obtains at 70-100 DEG C of bar
React 2h under part, obtain base polyurethane prepolymer for use as.
By perfluoroalkyl ethanol (CF3(CF2)nCH2CH2OH, n=6-12) dissolve by organic solvent B and be slowly dropped to above-mentioned
In the middle of base polyurethane prepolymer for use as, wherein organic solvent B be DMF (DMF) or ketone that carbon number is 3-10,
Ether, alcohol, alkane and aromatic hydrocarbon, perfluoroalkyl ethanol concentration in the middle of organic solvent B is 5wt.%～15wt.%, perfluoroalkyl
Amount of alcohol added accounts for performed polymer quality 6wt.%～10wt.%.Added after the mixture obtained is reacted 1h at 70-100 DEG C
Amount polyalcohol as chain extender, wherein polyalcohol be carbon number be dihydroxylic alcohols or the polyalcohol of 2-6, add chain extender follow-up
Continue reaction 1h at 70-100 DEG C, be eventually adding a large amount of ethanol precipitation fluorine richness polyether polyols with reduced unsaturation, and wash with a large amount of ethanol
Remove unreacted monomer, obtain fluorine richness polyether polyols with reduced unsaturation.
(B) color inhibition, the preparation of weather-proof fluorine richness polyurethane finishing varnish
Fluorine richness polyether polyols with reduced unsaturation organic solvent C heating for dissolving, wherein organic solvent C is DMF
(DMF) or carbon number is the ketone of 3-10, ether, alcohol, alkane and aromatic hydrocarbon, fluorine richness polyether polyols with reduced unsaturation is at organic solvent C
Central concentration is 10wt.%～20wt.%, is uniformly coated to base material by the fluorine richness polyurethane polymer solution obtained,
To color inhibition, weather-proof fluorine richness polyurethane finishing varnish.
Preferably XDI (XDI) prepares base polyurethane prepolymer for use as diisocyanate monomer.
The preferably molecular weight of polytetramethylene ether diol is 2000, and preferably glycerine is as chain extender.
Preferably DMF (DMF) as organic solvent A and organic solvent B, preferably isopropyl ether as organic
Solvent C.
Color inhibition, the contact angle of weather-proof fluorine richness polyurethane finishing varnish that the present invention prepares measure according to a conventional method.
The present invention is with alkyl, cycloalkyl diisocyanate (HDI and IPDI) or XDI (XDI)
Being raw material with polytetramethylene ether diol (PTMEG), reaction under certain condition forms performed polymer, then uses perfluoroalkyl ethanol
Performed polymer is carried out further modification, finally carries out chain extension with polyalcohol thus obtained color inhibition, weather-proof fluorine richness polyurethane
Finishing varnish.This polyurethane finishing varnish preparation method raw material is easy to get, and preparation process is easy, therefore have stronger application with
Industrial prospect.
Detailed description of the invention
Embodiment 1:
In 250ml four-hole bottle, by XDI (XDI) and polytetramethylene ether diol (PTMEG,
Molecular weight 2000) it is mixed to join in the middle of DMF, diisocyanate monomer is 1.3:1, reactant and DMF with the mol ratio of PTMEG
Mass ratio be 3:7, the mixture obtained is reacted 2h under the conditions of 90 DEG C, obtains base polyurethane prepolymer for use as.
By perfluor heptyl ethanol (CF3(CF2)6CH2CH2OH) dissolve with DMF and be slowly dropped to above-mentioned base polyurethane prepolymer for use as
In the middle of, wherein perfluor heptyl ethanol concentration in the middle of DMF is 10wt.%, and perfluoroalkyl ethanol addition accounts for performed polymer quality
8wt.%.The glycerine of excess is added as chain extender, after adding chain extender after the mixture obtained is reacted 1h at 90 DEG C
Continue to react 1h at 90 DEG C, be eventually adding a large amount of ethanol precipitation fluorine richness polyether polyols with reduced unsaturation, and go with the washing of a large amount of ethanol
Except unreacted monomer, obtain fluorine richness polyether polyols with reduced unsaturation.
Fluorine richness polyether polyols with reduced unsaturation isopropyl ether heating for dissolving, dense in the middle of isopropyl ether of fluorine richness polyether polyols with reduced unsaturation
The fluorine richness polyurethane polymer solution obtained for 15wt.%, is uniformly coated to base material by degree, obtains color inhibition, weather-proof fluorine changes
Property polyurethane finishing varnish.This finishing varnish is 113.8 ° to the contact angle of water, and the contact angle to dodecane hydrocarbon is 106.5 °.
Embodiment 2:
In 250ml four-hole bottle, hexamethylene diisocyanate (HDI) and polytetramethylene ether diol (PTMEG, molecule
Amount 2000) it is mixed to join in the middle of DMF, diisocyanate monomer is 1.5:1 with the mol ratio of PTMEG, reactant and the matter of DMF
Amount ratio is 3:7, the mixture obtained reacts under the conditions of 100 DEG C 2h, obtains base polyurethane prepolymer for use as.
By perfluor heptyl ethanol (CF3(CF2)6CH2CH2OH) dissolve with DMF and be slowly dropped to above-mentioned base polyurethane prepolymer for use as
In the middle of, wherein perfluor heptyl ethanol concentration in the middle of DMF is 10wt.%, and perfluoroalkyl ethanol addition accounts for performed polymer quality
8wt.%.Add the glycerine of excess after the mixture obtained is reacted 1h at 100 DEG C as chain extender, add chain extender it
1h is reacted in rear continuation at 100 DEG C, is eventually adding a large amount of ethanol precipitation fluorine richness polyether polyols with reduced unsaturation, and washs with a large amount of ethanol
Remove unreacted monomer, obtain fluorine richness polyether polyols with reduced unsaturation.
Fluorine richness polyether polyols with reduced unsaturation isopropyl ether heating for dissolving, dense in the middle of isopropyl ether of fluorine richness polyether polyols with reduced unsaturation
The fluorine richness polyurethane polymer solution obtained for 15wt.%, is uniformly coated to base material by degree, obtains color inhibition, weather-proof fluorine changes
Property polyurethane finishing varnish.This finishing varnish is 108.4 ° to the contact angle of water, and the contact angle to dodecane hydrocarbon is 101.7 °.
Claims (3)
1. a color inhibition, the preparation method of weather-proof fluorine richness polyurethane finishing varnish, it is characterised in that: its concrete steps are such as
Under:
(A) preparation of fluorine richness polyether polyols with reduced unsaturation:
In 250ml four-hole bottle, diisocyanate monomer and polytetramethylene ether diol are mixed to join organic solvent A
In the middle of, wherein diisocyanate monomer is 1.2:1 ~ 1.8:1 with the mol ratio of PTMEG, reactant and the quality of organic solvent A
Ratio is 3:7 ~ 1:1, the mixture obtained reacts under the conditions of 70-100 DEG C 2 h, obtains base polyurethane prepolymer for use as；Wherein said
Diisocyanate monomer is hexamethylene diisocyanate, IPDI or phenylenedimethylidyne two isocyanic acid
Ester；Its molecular weight of described polytetramethylene ether diol is 600-5000；
Perfluoroalkyl ethanol organic solvent B is dissolved and is slowly dropped in the middle of above-mentioned base polyurethane prepolymer for use as, wherein perfluor
Alkyl alcohol concentration in the middle of organic solvent B is 5wt.% ~ 15wt.%, and perfluoroalkyl ethanol addition accounts for performed polymer quality
6wt.%~10wt.%；Add after the mixture obtained is reacted 1 h at 70-100 DEG C excess polyalcohol as chain extender,
Continue to react 1 h at 70-100 DEG C after adding chain extender, be eventually adding the precipitation fluorine richness polyurethane polymerization of a large amount of ethanol
Thing, and remove unreacted monomer with the washing of a large amount of ethanol, obtain fluorine richness polyether polyols with reduced unsaturation；Wherein, the perfluor used
The fluorine carbon number of alkyl alcohol is 7-13；Wherein glycerine selected by chain extender；
(B) color inhibition, the preparation of weather-proof fluorine richness polyurethane finishing varnish:
Fluorine richness polyether polyols with reduced unsaturation organic solvent C heating for dissolving, wherein fluorine richness polyether polyols with reduced unsaturation is at organic solvent C
Central concentration is 10wt.% ~ 20wt.%, is uniformly coated to base material by the fluorine richness polyurethane polymer solution obtained, obtains
Color inhibition, weather-proof fluorine richness polyurethane finishing varnish；
Organic solvent A used in above-mentioned steps, B and C are N,N-dimethylformamide or carbon number is 3-10's
Ketone, ether, alcohol, alkane, aromatic hydrocarbon.
2., according to the color inhibition described in claim 1, the preparation method of weather-proof fluorine richness polyurethane finishing varnish, its feature exists
In: the molecular weight of described polytetramethylene ether diol is 2000.
3., according to the color inhibition described in claim 1, the preparation method of weather-proof fluorine richness polyurethane finishing varnish, its feature exists
In: select DMF as organic solvent A and organic solvent B, select isopropyl ether as organic solvent C.
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| CN103555183B true CN103555183B (en) | 2016-08-17 |
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| CN106279621B (en) * | 2016-08-31 | 2018-08-28 | 上海分尚网络科技有限公司 | A kind of high performance polyurethane water-keeping material and preparation method thereof |
| CN106752771A (en) * | 2016-12-26 | 2017-05-31 | 怀宁县三禾保洁服务有限公司 | A kind of lintel is turned over polyester fluorocarbon varnish and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900183A (en) * | 2006-07-20 | 2007-01-24 | 上海申真企业发展有限公司 | Self cleaning fluorocarbon resin paint and its preparing method |
| CN101838383A (en) * | 2010-04-06 | 2010-09-22 | 杭州之江有机硅化工有限公司 | Aqueous fluoro modified urethane resin and preparation of aqueous fluoro modified urethane resin paint |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900183A (en) * | 2006-07-20 | 2007-01-24 | 上海申真企业发展有限公司 | Self cleaning fluorocarbon resin paint and its preparing method |
| CN101838383A (en) * | 2010-04-06 | 2010-09-22 | 杭州之江有机硅化工有限公司 | Aqueous fluoro modified urethane resin and preparation of aqueous fluoro modified urethane resin paint |
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