CN105176367A - Preparation method of environment-friendly self-cleaning coating - Google Patents
Preparation method of environment-friendly self-cleaning coating Download PDFInfo
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- CN105176367A CN105176367A CN201510670203.6A CN201510670203A CN105176367A CN 105176367 A CN105176367 A CN 105176367A CN 201510670203 A CN201510670203 A CN 201510670203A CN 105176367 A CN105176367 A CN 105176367A
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Abstract
The invention relates to a preparation method of an environment-friendly self-cleaning coating, and mainly aims to solve the problems that nano-titanium dioxide cannot be dispersed stably and uniformly in polymer substrates and that photocatalytic performance is unavailable in the prior art. The preparation method of the environment-friendly self-cleaning coating comprises the following steps: (1) preparing NCO/OH in a ratio being (3.5-1.1):1, adding isocyanate, polyester or polyether polyol, 10-25 weight percent methylbenzene and dimethyl formamide to serve as solvents, and performing a reaction at a temperature being 75-100 DEG C for 2-8 hours under the protection of N2 in the presence of 0.1 weight percent dibutyltin laurate serving as a catalyst to obtain a polyurethane pre-polymer; (2) monitoring the change of the NCO in a reaction process, adding dihydric alcohol containing a COOTi functional group to serve as an a chain extender when a NCO value is constant in order that an equivalence ratio of the NCO to the OH is 1.1:1 in a system, drying, and performing reaction at a temperature being 75-100 DEG C for 8-24 hours under the protection of N2 to obtain the environment-friendly nano-titanium dioxide-polyurethane self-cleaning coating. Through the technical scheme, the problems are well solved. The preparation method can be applied to preparation of self-cleaning coatings.
Description
Technical field
The present invention relates to a kind of preparation method of environment-friendly type self-cleaning coating.
Background technology
After 20 world's automatically cleaning nineties concepts are suggested, it just becomes focus in scientific research and commodity development and difficult point.Self-cleaning material has and prevents dust adhesion, surface contaminant to be easy to come off under the External Force Actings such as rainwater and the performance such as photodegradation surface organic pollutant, has the advantages such as energy-saving and environmental protection.Various self-cleaning material occurs in succession, wherein, and the focus that nano titanium oxide becomes in self-cleaning material research because of effects such as photo-catalysis capability is strong, photic super amphiphilic, good light stability, antiultraviolet and fungus and mildew resistances.Although the application of self-cleaning glass coating is paid close attention in the research of most of photocatalytic self-cleaning coating, automatically cleaning high-molecular coating has very important industrial application and Scientific Research Potential.But by the end of at present, about how by chemical process, stable is distributed in polymkeric substance by nano titanium oxide, the research preparing self-cleaning coating is also few.
In addition, because the surface-area/particle diameter ratio of nano particle is very big, very easily reunite in organic polymer, poor compatibility causes dispersed bad, greatly can reduce the performance of nanometer-polymer composites.Do a lot of correlative study how improving the dispersing property of nano material in organic polymer.CN201210128728.3 relates to a kind of method of modifying of nano titanium oxide, mainly introduces functional group on nano-titania particle surface, thus improves the dispersiveness of nano titanium oxide, weathering resistance and self-cleaning property.Wherein a kind of method is broken the nano particle of dispersion reunion, as by supersound process, but this kind of method effect is extremely limited, the interaction between inorganic nanoparticles with organic polymer is with very limited compared with the interaction between inorganic nanoparticles.Another kind method is chemical bonding Graft Method, modification is carried out to nano grain surface, strengthens the interaction between nano particle and polymer chain, reduce the reunion between nano particle, promote the dispersion of nano particle in polymeric matrix, there is good photocatalysis performance simultaneously.
The present invention solves this problem targetedly.
Summary of the invention
Technical problem to be solved by this invention be in prior art nano titanium oxide cannot in polymeric matrix stable dispersion, dispersed, the problem without photocatalysis performance, a kind of preparation method of new environment-friendly type self-cleaning coating is provided.The method is used in the preparation of self-cleaning coating, have nano titanium oxide can in polymeric matrix stable dispersion, dispersed, the advantage with photocatalysis performance.
For solving the problem, the technical solution used in the present invention is as follows: a kind of preparation method of environment-friendly type self-cleaning coating, comprise the steps: that the ratio of (1) NCO/OH is 3.5 ~ 1.1:1, add isocyanic ester, polyester or polyether glycol, 10 ~ 25wt% toluene and dimethyl formamide as solvent, 0.1wt% dibutyl tin laurate as catalyzer, N
2under protection, at 75 ~ 100 DEG C, react 2-8h, obtained polyurethane prepolymer; (2) monitor the change of NCO in reaction process, when nco value is constant, add dibasic alcohol containing COOTi functional group as chainextender, make NCO and OH equivalence ratio in system be 1.1:1, dry N
2under protection, at 75 ~ 100 DEG C, react 8-24h, obtain described environment-friendly type nano titanium dioxide-polyurethane self-cleaning coating.
In technique scheme, preferably, described nano titanium oxide is made up of anatase octahedrite and rutile, and the part by weight of anatase octahedrite and rutile is from 10:90 to 90:10.
In technique scheme, preferably, described isocyanic ester is one or more in isoflurane chalcone diisocyanate, hexamethylene diisocyanate, hydrogenation of benzene dicyclohexylmethane diisocyanate, trimethylhexane diisocyanate, IPDI tripolymer or HDI tripolymer.
In technique scheme, preferably, described polyester polyol is one or more in polycarbonate diol, poly-several interior esterdiol or hexanodioic acid system polyester polyol.
In technique scheme, preferably, one or more in polyether glycol or PTMG dibasic alcohol, polypropylene glycol, polyoxypropylene polyol or polyoxyethylene glycol.
In technique scheme, preferably, the dibasic alcohol comprising COOH types of functional groups described in is 2,2-dimethylol propionic acid.
In technique scheme, preferably, the median size of described nano titanium oxide is between 1 ~ 500nm.
The present invention efficiently solve nano titanium oxide cannot stablize in polymeric matrix, dispersed, and there is the problem of photocatalysis performance, a kind of preparation method having photodegradation surface organic pollutant, prevent the environment-friendly type automatically cleaning polyurethane coating of dust adhesion and fungus and mildew resistance function can be provided, adopt chemical bonding Graft Method, nano titanium oxide is uniformly dispersed in polyurethane substrates, and stably dispersing, there is good photodegradation surface organic pollutant simultaneously, prevent dust adhesion and fungus and mildew resistance function, achieve good technique effect.
Below by embodiment, the invention will be further elaborated, but be not limited only to the present embodiment.
Embodiment
[embodiment 1]
Polytetrahydrofuran (molecular-weight average is 1000) is heated to 110 DEG C vacuumizing under state, vacuumizes 2h, remove moisture;
By 5.247g hydrogenation of benzene dicyclohexylmethane diisocyanate and the 10g polytetrahydrofuran mol ratio according to 2:1, under drying nitrogen protection, 1.5247g toluene and 1.5247g dimethyl formamide are as solvent, 0.0152g dibutyl tin laurate is as catalyzer, at 85 DEG C, successive reaction 2 hours, obtains polyurethane prepolymer;
2,2-dimethylol propionic acids 1.34g being contained COOTi functional group as chainextender, with the mol ratio of polyurethane prepolymer according to 1:1,85 DEG C of successive reactions 10 hours;
Stopped reaction, obtains described environment-friendly type nano sodium dioxide-polyurethane self-cleaning coating.
[embodiment 2]
Polycarbonate diol (molecular-weight average is 2000) is heated to 110 DEG C vacuumizing under state, vacuumizes 2h, remove moisture;
By 5.557g isophorone diisocyanate (IPDI) and the mol ratio of 20g polycarbonate glycol according to 2.5:1, under drying nitrogen protection, 5.1114g toluene and 5.1114g dimethyl formamide are as solvent, 0.0256g dibutyl tin laurate is as catalyzer, at 90 DEG C, successive reaction 4 hours, obtains polyurethane prepolymer;
2,2-dimethylol propionic acids 1.4754g being contained COOTi functional group as chainextender, with the mol ratio of polyurethane prepolymer according to 1.1:1,90 DEG C of successive reactions 12 hours;
Stopped reaction, obtains described environment-friendly type nano sodium dioxide-polyurethane self-cleaning coating.
Claims (7)
1. the preparation method of an environment-friendly type self-cleaning coating, comprise the steps: that the ratio of (1) NCO/OH is 3.5 ~ 1.1:1, add isocyanic ester, polyester or polyether glycol, 10 ~ 25wt% toluene and dimethyl formamide as solvent, 0.1wt% dibutyl tin laurate as catalyzer, N
2under protection, at 75 ~ 100 DEG C, react 2-8h, obtained polyurethane prepolymer; (2) monitor the change of NCO in reaction process, when nco value is constant, add dibasic alcohol containing COOTi functional group as chainextender, make NCO and OH equivalence ratio in system be 1.1:1, dry N
2under protection, at 75 ~ 100 DEG C, react 8-24h, obtain described environment-friendly type nano titanium dioxide-polyurethane self-cleaning coating.
2. the preparation method of environment-friendly type self-cleaning coating according to claim 1, it is characterized in that described nano titanium oxide is made up of anatase octahedrite and rutile, the part by weight of anatase octahedrite and rutile is from 10:90 to 90:10.
3. the preparation method of environment-friendly type self-cleaning coating according to claim 1, is characterized in that described isocyanic ester is one or more in isoflurane chalcone diisocyanate, hexamethylene diisocyanate, hydrogenation of benzene dicyclohexylmethane diisocyanate, trimethylhexane diisocyanate, IPDI tripolymer or HDI tripolymer.
4. the preparation method of environment-friendly type self-cleaning coating according to claim 1, is characterized in that described polyester polyol is one or more in polycarbonate diol, poly-several interior esterdiol or hexanodioic acid system polyester polyol.
5. the preparation method of environment-friendly type self-cleaning coating according to claim 1, it is characterized in that in described polyether glycol or PTMG dibasic alcohol, polypropylene glycol, polyoxypropylene polyol or polyoxyethylene glycol one or more.
6. the preparation method of environment-friendly type self-cleaning coating according to claim 1, the dibasic alcohol comprising COOH types of functional groups described in it is characterized in that is 2,2-dimethylol propionic acid.
7. the preparation method of environment-friendly type self-cleaning coating according to claim 1, is characterized in that the median size of described nano titanium oxide is between 1 ~ 500nm.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188466A (en) * | 2016-07-12 | 2016-12-07 | 南京工业职业技术学院 | A kind of vehicle glass nano modified polyurethane membrane material and preparation method thereof |
| CN108359364A (en) * | 2018-02-06 | 2018-08-03 | 广州科莱瑞迪医疗器材股份有限公司 | A kind of aqueous composite coating material for delaying poly-caprolactone degradation rate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101550224A (en) * | 2009-05-07 | 2009-10-07 | 四川大学 | Cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent |
| US20120010314A1 (en) * | 2009-01-08 | 2012-01-12 | The University Of Western Ontario | Self-cleaning coatings |
| CN102558828A (en) * | 2011-12-29 | 2012-07-11 | 华南理工大学 | Method for preparing polyurethane hybridization material for hydroxyl-containing filler |
| EP2644662A1 (en) * | 2010-11-25 | 2013-10-02 | Fundacion Tecnalia Research & Innovation | Hybrid photocatalytic coatings, method for applying said coatings to different substrates and uses of the substrates thus coated |
| CN104403548A (en) * | 2014-12-29 | 2015-03-11 | 中科院广州化学有限公司 | Water-based polyurethane paint containing polyether glycol/nano TiO2 hybrid material |
| CN104693404A (en) * | 2015-03-27 | 2015-06-10 | 四川大学 | Functional waterborne polyurethane leather finishing agent and preparation method thereof |
-
2015
- 2015-10-13 CN CN201510670203.6A patent/CN105176367A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120010314A1 (en) * | 2009-01-08 | 2012-01-12 | The University Of Western Ontario | Self-cleaning coatings |
| CN101550224A (en) * | 2009-05-07 | 2009-10-07 | 四川大学 | Cation polyurethane/inorganic nanometer material organic-inorganic hybrid coating agent |
| EP2644662A1 (en) * | 2010-11-25 | 2013-10-02 | Fundacion Tecnalia Research & Innovation | Hybrid photocatalytic coatings, method for applying said coatings to different substrates and uses of the substrates thus coated |
| CN102558828A (en) * | 2011-12-29 | 2012-07-11 | 华南理工大学 | Method for preparing polyurethane hybridization material for hydroxyl-containing filler |
| CN104403548A (en) * | 2014-12-29 | 2015-03-11 | 中科院广州化学有限公司 | Water-based polyurethane paint containing polyether glycol/nano TiO2 hybrid material |
| CN104693404A (en) * | 2015-03-27 | 2015-06-10 | 四川大学 | Functional waterborne polyurethane leather finishing agent and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| P A CHARPENTIER,ET AL: "Nano-TiO2/polyurethane composites for antibacterial and self-cleaning coatings", 《NANOTECHNOLOGY》 * |
| 刘晓英等: "涂料用纳米TiO2改性的研究进展", 《中国建材科技》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188466A (en) * | 2016-07-12 | 2016-12-07 | 南京工业职业技术学院 | A kind of vehicle glass nano modified polyurethane membrane material and preparation method thereof |
| CN108359364A (en) * | 2018-02-06 | 2018-08-03 | 广州科莱瑞迪医疗器材股份有限公司 | A kind of aqueous composite coating material for delaying poly-caprolactone degradation rate |
| CN108359364B (en) * | 2018-02-06 | 2020-09-18 | 广州科莱瑞迪医疗器材股份有限公司 | Water-based composite coating material for delaying degradation rate of polycaprolactone |
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Address after: Yanan City, Shandong province Qingdao City three road 266071 No. 218 Applicant after: Sinopec Corp. Applicant after: Qingdao Safety Engineering Research Institute of Sinopec Co., Ltd. Address before: 100728 Chaoyangmen street, Beijing, No. 22, No. Applicant before: Sinopec Corp. Applicant before: Qingdao Safety Engineering Research Institute of Sinopec Co., Ltd. |
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Application publication date: 20151223 |