CN1900183B - Self cleaning fluorocarbon resin paint and its preparing method - Google Patents
Self cleaning fluorocarbon resin paint and its preparing method Download PDFInfo
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- CN1900183B CN1900183B CN2006100291638A CN200610029163A CN1900183B CN 1900183 B CN1900183 B CN 1900183B CN 2006100291638 A CN2006100291638 A CN 2006100291638A CN 200610029163 A CN200610029163 A CN 200610029163A CN 1900183 B CN1900183 B CN 1900183B
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- vulcabond
- fluorocarbon resin
- resin
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- diisocyanate
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Abstract
The present invention relates to a kind of self-cleaning fluorocarbon resin paint and its preparation process. The preparation process includes the following steps: reaction between diisocyanate and tribasic alcohol to certain degree, adding polyglycol monoether to react to obtain branching modified diisocyanate, and reaction between the modified diisocyanate and fluorocarbon resin to introduce hydrophilic molecular radical and obtain self-cleaning fluorocarbon resin. The self-cleaning fluorocarbon resin is further compounded into paint through a conventional process. After being painted, the hydrophilic molecular radical immigrates to the surface of the coating to form hydrophilic surface with self-cleaning function while the fluorocarbon resin forms compact film in the bottom to avoid water and pollutant permeation. The present invention can eliminate current mark and oily component pollution.
Description
Technical field
The invention belongs to coating self-cleaning coating technical field, be specifically related to a kind of self cleaning fluorocarbon resin paint and preparation method thereof.
Background technology
Fluorocarbon coating is to be the general designation of the coating series of main film forming matter with fluorine resin, it is a kind of new coating material that passes through modification on the fluoro-resin basis, process, its principal feature is to contain a large amount of F-C keys in the resin, its bond energy is 116kal/mol, can be rated as first in all chemical bonds.Be heated, under the effect of light (comprising ultraviolet ray), the F-C key is difficult to fracture, therefore demonstrates the corrosion of superpower weathering resistance and resistant to chemical media, so its stability is best in all cold coatings.As a kind of high-tech functional coating and a kind of brand-new surface decoration protective material, many performances such as it is weather-proof, resistance to chemical attack all are better than at present popular urethane, organosilicon, acrylic resin paint on the market.Fluorine coating is used widely in fields such as building, chemical industry, electric, electronics, machinery, aerospace, household supplies, especially in the environment of heavily contaminated, deep-etching, has more shown the barrier propterty that it is superior.
Though the fluorocarbon resin coating surface energy is low, contamination resistance improves a lot than other cold coating.But the present various complexity of urban pollution resource, actual discovery low surface energy is filmed and is still existed certain " rainwater current mark " to pollute.Its reason is considered to film coated surface and is difficult for by water-wet, exists electrostatic adhesion to pollute on the one hand, is that rainwater is difficult for clean the pollution on the other hand.
Summary of the invention
The object of the present invention is to provide a kind of self cleaning fluorocarbon resin paint and preparation method thereof.To solve the pollution that the oiliness composition is filmed to solvent-borne type in rainwater current mark phenomenon that hydrophobic fluorocarbon coating is difficult to eliminate and the urban pollution resource.
The self cleaning fluorocarbon resin paint that the present invention proposes is that the polyoxyethylene glycol monoether that adds metering again reacts the vulcabond performed polymer that makes branched modification by vulcabond and trivalent alcohol reaction, is reacted by this performed polymer and fluorocarbon resin and obtains.
Wherein said vulcabond is selected from tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), naphthalene-1,5-vulcabond (NDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2, the sour methyl esters of 6-vulcabond (LDI), 4,4 '-methylene radical-dicyclohexyl vulcabond (H
12MDI), xylylene diisocyanate (XDI), 1,12-dodecyl vulcabond (C
12DDI) etc. a kind of in common aromatic series and the aliphatic diisocyanate.
Described trivalent alcohol is selected from TriMethylolPropane(TMP), trimethylolethane, glycerol, a kind of in the common trivalent alcohol such as triol, polyether-tribasic alcohol, polyester trivalent alcohol.
Described polyoxyethylene glycol monoether can be the compound that following general formula is represented:
R-(OCH
2CH)
nOH
R is-CH in the formula
3Or-CH
2CH
2CH
2CH
3, 10≤n≤30;
Described fluorocarbon resin is that the hydroxyl value of resin is 25～100mgKOH/g, and acid number is 2～12mgKOH/g, and fluorine content is 25～45%, and described fluoro-resin is by at least a composition the in three fluoro-resin and the tetrafluoro resin.
Wherein the mol ratio of vulcabond, trivalent alcohol and polyoxyethylene glycol monoether is:
Vulcabond 3
Trivalent alcohol 1
Polyoxyethylene glycol monoether 1
Wherein the weight ratio of vulcabond performed polymer and fluorocarbon resin is:
Vulcabond performed polymer 0.1～0.3
Fluorocarbon resin 1
The concrete preparation process of the self cleaning fluorocarbon resin paint of proposition of the present invention is: add vulcabond and trivalent alcohol by described mol ratio in the reactor, 70～85 ℃ of stirring reactions 3～4 hours; Add the polyoxyethylene glycol monoether by described mol ratio then,, make the vulcabond performed polymer 70～85 ℃ of stirring reactions 2～3 hours; Add fluorocarbon resin then by weight ratio,, reduce to room temperature 70～85 ℃ of stirring reactions 2～4 hours, discharging, self cleaning fluorocarbon resin.
According to ordinary method self cleaning fluorocarbon resin is mixed with coating during use.
Coating can be single component, also can be two-pack.During two-pack, can adopt the polyurethanes solidifying agent.For example: biuret, vulcabond pre-polymerization resin etc.
Embodiment
Below by embodiment embodiment of the present invention are described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
666gIPDI and 134g TriMethylolPropane(TMP) are dropped in the reactor, 85 ℃ of stirring reactions 3 hours.The C that adds 514g then
4H
9-(OCH
2CH
2)
10OH was 85 ℃ of stirring reactions 2 hours.The fluorocarbon resin that adds 5256g then 85 ℃ of stirring reactions 2 hours, is reduced to room temperature, discharging, self cleaning fluorocarbon resin.According to ordinary method self cleaning fluorocarbon resin and biuret solidifying agent are mixed with two-component coating then, what the construction back obtained films to 35 ° of water contact angles 1 grade of sticking power, 5000 hours no changes of ageing resistance, 1000 hours no changes of salt fog resistance.
Embodiment 2
504gHDI and 93g glycerol are dropped in the reactor,, add the CH of 692g then 75 ℃ of stirring reactions 3.5 hours
3-(OCH
2CH
2)
15OH was 70 ℃ of stirring reactions 3 hours.The fluorocarbon resin that adds 6445g then 85 ℃ of stirring reactions 3 hours, is reduced to room temperature, discharging, self cleaning fluorocarbon resin.According to ordinary method self cleaning fluorocarbon resin and isophorone diisocyanate (IPDI) pre-polymerization resin solidifying agent are mixed with two-component coating then, what the construction back obtained films to 30 ° of water contact angles, 1 grade of sticking power, 5000 hours no changes of ageing resistance, 1000 hours no changes of salt fog resistance.
Embodiment 3
522gTDI and 134g TriMethylolPropane(TMP) are dropped in the reactor 75 ℃ of stirring reactions 4 hours, add the C4H9-(OCH of 954g then
2CH
2)
20OH 75 ℃ of stirring reactions 2.5 hours, adds the fluorocarbon resin of 8050g then, 80 ℃ of stirring reactions 3.5 hours, reduces to room temperature, discharging, self cleaning fluorocarbon resin.According to ordinary method self cleaning fluorocarbon resin is mixed with onepot coating then, what the construction back obtained films to 25 ° of water contact angles 1 grade of sticking power, 5000 hours no changes of ageing resistance, 1000 hours no changes of salt fog resistance.
Embodiment 4
666gIPDI and 3000gN330 polyether-tribasic alcohol are dropped in the reactor 80 ℃ of stirring reactions 3.5 hours, add the CH of 1352g then
3-(OCH
2CH
2)
30OH is 75 ℃ of stirring reactions 2.5 hours, and the fluorocarbon resin that adds 16727g is then reduced to room temperature 70 ℃ of stirring reactions 4 hours, discharging, self cleaning fluorocarbon resin.According to ordinary method self cleaning fluorocarbon resin is mixed with onepot coating then, what the construction back obtained films to 20 ° of water contact angles 1 grade of sticking power, 5000 hours no changes of ageing resistance, 1000 hours no changes of salt fog resistance.
Claims (2)
1. self cleaning fluorocarbon resin paint, it is characterized in that it being by vulcabond and trivalent alcohol reaction, the polyoxyethylene glycol monoether that adds metering again reacts the vulcabond performed polymer that makes branched modification, modification vulcabond performed polymer and fluorocarbon resin is reacted again and obtains; Wherein:
Described vulcabond is selected from tolylene diisocyanate, diphenylmethanediisocyanate, naphthalene-1,5-vulcabond, hexamethylene diisocyanate, isophorone diisocyanate, 2, the sour methyl esters of 6-vulcabond, 4,4 '-methylene radical-dicyclohexyl vulcabond, xylylene diisocyanate, 1, a kind of in 12-dodecyl vulcabond aromatic series and the aliphatic diisocyanate;
Described trivalent alcohol is selected from TriMethylolPropane(TMP), trimethylolethane, glycerol, a kind of in triol, polyether-tribasic alcohol, the polyester trivalent alcohol;
Described polyoxyethylene glycol monoether is the compound that following general formula is represented:
R-(OCH
2CH)
nOH
R is-CH in the formula
3Or-CH
2CH
2CH
2CH
3, 10≤n≤30;
Described fluorocarbon resin is that the hydroxyl value of resin is 25～100mgKOH/g, and acid number is 2～12mgKOH/g, and fluorine content is 25～45%, and described fluoro-resin is by at least a composition the in three fluoro-resin and the tetrafluoro resin;
The mol ratio of vulcabond, trivalent alcohol and polyoxyethylene glycol monoether is:
Vulcabond 3
Trivalent alcohol 1
Polyoxyethylene glycol monoether 1
The weight ratio of vulcabond performed polymer and fluorocarbon resin is:
Vulcabond performed polymer 0.1～0.3
Fluorocarbon resin 1.
2. the preparation method of self cleaning fluorocarbon resin paint according to claim 1, it is characterized in that concrete steps are: add vulcabond and trivalent alcohol in the reactor in molar ratio, 70～85 ℃ of stirring reactions 3～4 hours, add the polyoxyethylene glycol monoether then in molar ratio, 70～85 ℃ of stirring reactions 2～3 hours, make the vulcabond performed polymer; Add fluorocarbon resin, 70～85 ℃ of stirring reactions 2～4 hours are reduced to room temperature, discharging, self cleaning fluorocarbon resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100291638A CN1900183B (en) | 2006-07-20 | 2006-07-20 | Self cleaning fluorocarbon resin paint and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2006100291638A CN1900183B (en) | 2006-07-20 | 2006-07-20 | Self cleaning fluorocarbon resin paint and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1900183A CN1900183A (en) | 2007-01-24 |
| CN1900183B true CN1900183B (en) | 2010-10-06 |
Family
ID=37656180
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100291638A Expired - Fee Related CN1900183B (en) | 2006-07-20 | 2006-07-20 | Self cleaning fluorocarbon resin paint and its preparing method |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103555183B (en) * | 2013-10-23 | 2016-08-17 | 三棵树涂料股份有限公司 | Color inhibition, weather-proof fluorine richness polyurethane finishing varnish and preparation method thereof |
| CN105440292B (en) * | 2014-09-15 | 2018-08-24 | 海洋化工研究院有限公司 | The design and preparation of branching type hydrophilic additive |
| CN105505183B (en) * | 2015-12-26 | 2017-08-25 | 杭州福斯特应用材料股份有限公司 | A kind of preparation method of high performance fluorine carbon coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1502642A (en) * | 2002-11-25 | 2004-06-09 | 中国科学院化学研究所 | Super-biphobic block polyether type polyurethane copolymer and preparation process and use thereof |
| CN1535993A (en) * | 2003-04-11 | 2004-10-13 | 中国科学院化学研究所 | Block hydrophobic/oleophobic polyether type polyurethane copolymer, its preparation method and application |
-
2006
- 2006-07-20 CN CN2006100291638A patent/CN1900183B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1502642A (en) * | 2002-11-25 | 2004-06-09 | 中国科学院化学研究所 | Super-biphobic block polyether type polyurethane copolymer and preparation process and use thereof |
| CN1535993A (en) * | 2003-04-11 | 2004-10-13 | 中国科学院化学研究所 | Block hydrophobic/oleophobic polyether type polyurethane copolymer, its preparation method and application |
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|---|---|
| CN1900183A (en) | 2007-01-24 |
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| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
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| C14 | Grant of patent or utility model | ||
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| TR01 | Transfer of patent right |
Effective date of registration: 20170703 Address after: 201703, Shanghai Qingpu District, Shanghai Qing Ping highway 3966 Patentee after: Crocodilian Paint (Shanghai) Co.,Ltd. Address before: Huaxin Town, Qingpu District 201708 of Shanghai City, No. 1889 Zhilu Patentee before: Shanghai Shenzhen Enterprise Development Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101006 Termination date: 20210720 |