CN1432613A - Fluorinated and siliceous copolymer resin and paint - Google Patents
Fluorinated and siliceous copolymer resin and paint Download PDFInfo
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- CN1432613A CN1432613A CN 02100052 CN02100052A CN1432613A CN 1432613 A CN1432613 A CN 1432613A CN 02100052 CN02100052 CN 02100052 CN 02100052 A CN02100052 A CN 02100052A CN 1432613 A CN1432613 A CN 1432613A
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- fluorine
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Abstract
The present invention relates to fluorine and silicon containing copolymer resin and paint. The composition includes fluorinated compound in 1-30 wt%, silane 2-8 wt% and alkenyl containing compound 62-97 wt%. The fluorinated compound is acrylic fluoro resin obtained through the reaction of fluorinated alcohol and acryloyl chloride or acrylic anhydride; the silane is one containing alkenyl group or containing carbon functional group with oxygen atom; and the alkenyl containing compound methacrylic acid, methacrylate, vinyl carboxylate and alkenyl containing benzene compound. The present invention has the advantages of fluorinated acrylic acid copolymer and silicon containing acrylate copolymer paint and the paint is excellent single component paint.
Description
Technical field:
The present invention relates to a kind of coating, particularly a kind of fluorine-containing, siliceous copolymer resin and coating.
Background technology:
Developing rapidly of acrylic polymer paint is because it has excellent comprehensive performances, as its weather resistance, the transparency, stability, gloss retention, tint retention, be that also it can obtain different hardness through the adjusting of prescription, the character of suppleness and other requirement, but its shortcoming is outdoor weather resisteant, water-fast scrubbing property and mechanical property are poor slightly, the improvement way has two classes: a class is a certain amount of organosilicon of importing functional group in acrylic resin is synthetic, make the oligomeric system coating of vinylformic acid organosilicon, make resin side chain or the terminal Si-O key that has higher ionic dissociation energy, improved resin to light, the stability and the anti-ultraviolet property of heat, with the coating that the vinylformic acid Organosiliconcopolymere is made, its outdoor weather resisteant, hydrophobic nature improves a lot than pure acrylic resin coating, for example the coating made from the acid-organosilicon crylic acid multipolymer has temper(ing) experiment 3000h, and coating loss of gloss rate only is 14.4%, through tanning by the sun a test, the loss of gloss rate is 33.5% report.
The multiple organosilicon-modified acrylic copolymer coating that the market of Coating Industry in Our Country circle exploitation has emerged it is said to be used to make exterior coating that its weather resisteant can reach 10～15 years, is considered to be only second at present the coating of the weather resistance of organic fluorine coating.
Another kind of is to import a certain amount of acrylic acid fluorine-containing alkyl ester in acrylic resin is synthetic, can obtain containing the multipolymer that fluoroalkyl is a side chain, make film forming matter with it, can obtain good outdoor weather resisteant, the coating of high gloss, high waterproof, high-mechanical property, this organic fluorine modified acrylic acid terpolymer coating does not also emerge on market.Commercial organic fluorine coating all is to be main body and the monomer with relevant functional group with vinylidene, trifluorochloroethylene or tetrafluoroethylene, for example: copolymerizations such as alkyl vinyl ether, vinyl fatty ester and esters of acrylic acid, owing to contain the segment that can be dissolved in solvent in the fluoropolymer molecule, make whole fluoropolymer dissolve in solvent, just can be mixed with solvent type coating, be referred to as fluoro-containing coating, also have commodity to claim fluorocarbon coating.This class coating all needs elevated pressures with the synthetic of multipolymer, and operational difficulty, and this class coating all is two components packings uses and also feels inconvenience.
Day disclosure is speciallyyed permit flat 4-15276 and is announced acrylic fluorine ester is incorporated into to contain and make fluorine-containing polyacrylic acid hydroxy ester in the alkyl acrylate copolymer, form dual-component coating with containing isocyanate crosslinking, Japan speciallys permit flat 4-184750 and announces with CH with 1-36317
2=CHCOOCH
2(CF
2CF
2)
2H and CH
2=CHCOOCH
8C
8F
17Introduce in the acrylate copolymer and make pencil hardness H, the dual-component coating that scuff resistance, stain resistance, weather resisteant, alkali resistance, water tolerance, glossiness, decorative appearance are all good.
Summary of the invention:
The objective of the invention is advantage for better performance fluorine-containing multipolymer and acrylate containing silicone copolymer coating, a kind of fluorine-containing, siliceous copolymer coating is provided, this coating has both the advantage of fluorine, siliceous copolymer, it is good to have high anti-pollution, weather resisteant, water tolerance, alkali resistance, mechanicalness, the coating of the single-component ambient cure that glossiness is good.
The present invention by the following technical solutions
A kind of fluorine-containing, siliceous copolymer resin and coating, its composition comprises fluorochemicals, silane and contain alkenyl compound;
Fluorochemicals is (methyl) acrylic fluorine ester that fluorine-containing alcohols and (methyl) acrylate chloride or (methyl) acrylic anhydride react gained, and its addition is 1-30%;
Silane is the carbon functional group silane that contains thiazolinyl or contain Sauerstoffatom, and its addition is 2～8%;
Containing alkenyl compound is (methyl) vinylformic acid and ester, vinyl carboxylates and the benzene compound that contains thiazolinyl, and its addition is 62～97%.
(methyl) acrylic fluorine ester compound wherein can be the compound that following general formula is represented:
R in the formula
1=H or CH
3, m=1-10 n=2m or 2m+1 E=H or F
The carbon functional group silane that contains thiazolinyl or contain Sauerstoffatom wherein can be the compound that following general formula is represented:
YsiRaX
3A=1-0 in the-a formula, Ra are alkyl, and Y is the carbon functional group that contains thiazolinyl or contain Sauerstoffatom, and X is functional groups such as methoxyl group, oxyethyl group, acetoxyl group.
Polymerization procedure is: add mixed solvent in the reactor, A, B, C mix the back and drip with initiator, control reaction temperature and reaction times, reacted, and the cooling blowing gets copolymer resin; According to a conventional method copolymer resin is made into coating.
The present invention has relevant monomer to carry out the multi-component copolymer reaction with following three kinds.
YSi (Ra) X ... represent with B
And R
3COOCH=CH
2Represent with C
Three class monomers can be single or mix and use, and the weight percent that three class monomers are participated in reaction is:
A：1～30％
B：2～8％
C:62～97%A: the Fluorine containing olefine ester compound can be (methyl) vinylformic acid trifluoro methyl esters, (methyl) vinylformic acid trifluoro ethyl ester, (methyl) vinylformic acid five fluorine ethyl esters, (methyl) vinylformic acid seven fluorine propyl ester, (methyl) vinylformic acid nine fluorine butyl esters, (methyl) vinylformic acid hexafluoro butyl ester, (methyl) vinylformic acid 11 fluorine pentyl esters, (methyl) vinylformic acid 15 fluorine monooctyl esters, (methyl) vinylformic acid 19 fluorine esters in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid 19 fluorine esters in the last of the ten Heavenly stems, propionic acid trifluoro-ethylene ester, acetate trifluoro propene ester, acetate hexafluoro butene esters, they can be used alone, but also also mix together.B: contain thiazolinyl or contain Sauerstoffatom carbon functional group silane and can be general formula YSiRaX
3-aThe silane of (symbolic significance is the same).They are vinyltrimethoxy silane, vinyltriethoxysilane, Vinyl toluene dimethoxy silane, the vinyl methyldiethoxysilane, methacryloxypropyl diethoxymethyl silane, the methacryloxypropyl triethoxyl silane, methyl allyl acyloxypropyl trimethoxysilane, glycidyl ether oxygen propyl trimethoxy silicane, vinyltriacetoxy silane, vinyl front three acyloxy silane and contain the alcoholysis product of thiazolinyl chlorosilane and oligopolymer etc., they can use separately, or mix and use.C: be vinylformic acid and methacrylic acid and esters monomer thereof, they can be methyl acrylate, ethyl propenoate, butyl acrylate, isobutyl acrylate, Octyl acrylate, vinylformic acid 2-ethylhexyl ester, Hydroxyethyl acrylate, Propylene glycol monoacrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, Octyl methacrylate, esters monomers such as methacrylic acid 2-ethylhexyl ester contain the alkenyl benzene thing and are: vinylbenzene, vinyl toluene, phenylallene, methylbenzene propylene and generating vinyl carboxylate ester compound are: vinyl-acetic ester, propionate, vinyl butyrate, the valeric acid vinyl acetate, n-nonanoic acid vinyl acetate and sad vinyl acetate etc., their general mixing use.
Copolyreaction of the present invention is carried out in the organic solvent in the presence of initiator, and used solvent is an alkanones, the mixture of aromatic hydrocarbons and acetates, and its weight percent is:
Alkanones: aromatic hydrocarbons: ester acid lipid=20～30%: 60～40%: 20～30%.
The alkanones solvent can be acetone, butanone, pentyl ester, pimelinketone etc.
Aromatic hydrocarbon solvent can be divided into benzene,toluene,xylene etc.The acetates solvent can be ritalin, vinyl acetic monomer, and N-BUTYL ACETATE, isoamyl acetate, the consumption of mixed solvent are the 0.8-1 of total monomer weight.
The present invention is fluorine-containing, the building-up reactions of siliceous copolymer is carried out in the presence of free-radical initiator, spendable organo-peroxide, for example: benzoyl peroxide, dichlorobenzoyl peroxide, ditertiary butyl peroxide, dicumyl peroxide and azo-compound, azo-bis-isobutyl cyanide for example, initiators such as azo isopropylformic acid dimethyl ester.Preferential benzoyl peroxide and the azo-bis-isobutyl cyanide of using among them, its consumption is 0.5～3% of a total monomer weight.
For fluorine-containing, the siliceous copolymer monomer of 100 weight parts, the preferable amount of organic solvent is the 0.8-100 weight part, and the preferable amount of initiator is the 0.5-3% weight part.
The present invention is fluorine-containing, the building-up reactions of siliceous copolymer is to add mixed solvent and monomer and initiator in reactor, and under nitrogen protection, 70～120 ℃ of normal pressure, temperature of reaction are carried out under the continuously stirring, and the reaction times is 1-20h.
The rerum natura of gained multipolymer is: solid content 50-60%, and proportion 1.040-1.080, viscosity (being coated with-4 glasss) 80-180S is the water white transparency thick liquid.
, siliceous copolymer resin fluorine-containing with the present invention made coating, its aging resistance improves greatly, artificial accelerated aging 5000h, the loss of gloss rate is 5-10%, water-fast scrubbing＞20000 of paint film time, sticking power is good, the frame method is 1 grade, and shock-resistant is 50cm, and chemical resistance is good, the paint film test piece is at 10%HCL, 10%H
2SO
4, soak 2 months no changes in the 10%NaOH solution, be higher than present commercially available silyl acrylate copolymer coating level, over-all properties also is better than the performance of fluorocarbon resin lacquer, it is used for the exterior wall dress is coated with, and the estimated service life can reach more than 20 years.
Embodiment:
With embodiment the present invention is described below, but does not limit embodiment of the invention 1-5.(1) example is executed used equipment of 1-5 and polymerization technique
Have stirrer at one, reflux exchanger, dropping funnel in the reactor of thermometer and outer wall heating jacket, adds the mixed solvent shown in the table 1, stirring is warming up to 80-90 ℃, add-on by listed each component of table 1 splashes in the reactor, drips time 2-3h, adds the back and continues to stir insulation 4-8h, reaction finishes, cooling discharge.(2) embodiment 1-5 each component add-on each component adds scale 1
Table 1 embodiment 1-5 each component add-on
See Table 2 by embodiment gained copolymer resin characteristic.Table 2 is implemented 1-5 gained multipolymer characteristic
(4) embodiment 1-5 copolymer resin is made into coating (1) and with solvent the copolymer resin of embodiment 1-5 coating is diluted to 50%, as the coating copolymer resin.(2) make pigment and filler with titanium dioxide, by the coating multipolymer: titanium dioxide=70: 30 is made into whitewash.(3) grind by sand mill, with scraper plate granularity instrumentation coating granularity, fineness is below 20 μ m.(4) make model, lining bar by national standard, detect its performance.(5) performance of fluorine-containing, the siliceous copolymer resin coating of embodiment 1-5
| Component | Monomer | Embodiment | ||||
| ????1 | ????2 | ????3 | ????4 | ????5 | ||
| ????A | Vinylformic acid tetrafluoro propyl ester | ????24 | ????12 | |||
| Vinylformic acid octafluoro pentyl ester | ????24 | ????12 | ????12 | |||
| Vinylformic acid hexafluoro butyl ester | ????24 | ????12 | ||||
| ????B | Vinyltrimethoxy silane | ????24 | ||||
| Vinyltriethoxysilane | ????24 | ????12 | ????12 | |||
| γ-glycidyl ether oxygen propyl trimethoxy silicane | ????24 | ????12 | ||||
| ????C | Vinylformic acid | ????14.4 | ????14.4 | ????14.4 | ||
| Methacrylic acid | ????14.4 | ????14.4 | ||||
| Methyl methacrylate | ????192 | ????192 | ????192 | ????192 | ????192 | |
| Butyl acrylate | ????192 | ????192 | ????192 | ????192 | ????192 | |
| Octyl acrylate | ????19.2 | |||||
| 2-EHA | ????33.6 | ????33.6 | ????19.2 | |||
| Hydroxyethyl acrylate | ????14.4 | ????14.4 | ||||
| Initiator | Benzoyl peroxide | ????2.4 | ????2.4 | ????2.4 | ||
| Azo-bis-isobutyl cyanide | ????2.4 | ????2.4 | ||||
| Solvent | Toluene, dimethylbenzene | ????192 | ????190 | ????192 | ????190 | ????192 |
| N-BUTYL ACETATE | ????64 | ????60 | ????64 | ????70 | ????64 | |
| Butanone, mibk | ????64 | ????70 | ????64 | ????60 | ????64 | |
| Characteristic | Embodiment | ||||
| 1 | ????2 | ????3 | ????4 | ????5 | |
| Solid content (%) | 59 | ????58 | ????60 | ????60 | ????59 |
| Hydroxyl value mg KOH/g | ????54 | ????50 | |||
| Acid number mg KOH/g | 5.0 | ????4.0 | ????3.4 | ????5.0 | ????6.0 |
| 25 ℃ of viscosity (being coated with-4 glasss), | 110 | ????180 | ????150 | ????140 | ????150 |
Embodiment 1-5 is fluorine-containing, the siliceous copolymer resin coating property sees Table fluorine-containing, the silicon acrylic copolymer coating property of 3 table 3 embodiment 1-5
| Performance | Embodiment | ||||
| ????1 | ????2 | ????3 | ????4 | ????5 | |
| Sticking power (cross-hatching) | ????1 | ????1 | ????1 | ????1 | ????1 |
| Gloss (60 ℃) (%) | ????90 | ????85 | ????90 | ????87 | ????90 |
| Pencil hardness | ????H | ????2H | ????2H | ????H | ????2H |
| Shock-resistant (cm) | ????50 | ????50 | ????50 | ????50 | ????5?0 |
| Abrasion resistance (inferior) | ??20000 | ??20000 | ??20000 | ??20000 | ??20000 |
| Acid resistance 10%HCL two months | ????○ | ????○ | ????○ | ????○ | ????○ |
| Acid resistance 10%H 2Two of SO | ????○ | ????○ | ????△ | ????○ | ????○ |
| Two of alkali resistance 10%NaOH | ????○ | ????○ | ????○ | ????○ | ????○ |
| Water tolerance two months | ????○ | ????○ | ????○ | ????○ | ????○ |
| Anti-artificial promotion is aging, 5000h loss of gloss rate % | ????10 | ????8 | ????8 | ????9 | ????10 |
Annotate: zero is no change, and △ is for changing slightly.
Claims (7)
1, a kind of fluorine-containing, siliceous copolymer resin and coating is characterized in that:
Its composition comprises fluorochemicals, silane and contain alkenyl compound;
Fluorochemicals is (methyl) acrylic fluorine ester that fluorine-containing alcohols and (methyl) acrylate chloride or (methyl) acrylic anhydride react gained, and its addition is 1-30%;
Silane is the carbon functional group silane that contains thiazolinyl or contain Sauerstoffatom, and its addition is 2～8%;
Containing alkenyl compound is (methyl) vinylformic acid and ester, vinyl carboxylates and the benzene compound that contains thiazolinyl, and its addition is 62～97%.
2, fluorine-containing, siliceous copolymer resin according to claim 1 and coating, it is characterized in that: described (methyl) acrylic fluorine ester compound can be the compound that following general formula is represented:
R in the formula
1=H or CH
3, m=1-10 n=2m or 2m+1 E=H or F
3, fluorine-containing, siliceous copolymer resin according to claim 1 and coating is characterized in that: the described carbon functional group silane that contains thiazolinyl or contain Sauerstoffatom can be the compound that following general formula is represented.
YsiRaX
3A=1-0 in the-a formula, Ra are alkyl, and Y is the carbon functional group that contains thiazolinyl or contain Sauerstoffatom, and X is functional groups such as methoxyl group, oxyethyl group, acetoxyl group.
4, the preparation method of fluorine-containing, siliceous copolymer resin as claimed in claim 1 and coating, it is characterized in that: the multi-component copolymer body that contains alkenyl compound and be main body is fluorine-containing, siliceous copolymer resin and coating, adopt free-radical initiator solution copolymerization method, raw materials usedly be:
YSi (Ra) X
3-aRepresent with B
And R
3COOCH=CH
2Represent with C
R wherein
1=H or CH
3, R
3Be C
1-8Alkyl, e=1-8
Three classes, the weight percent that monomer is participated in reaction is:
A：1～30％
B：2～8％
C：62～97％
5, the preparation method of fluorine-containing, siliceous copolymer resin as claimed in claim 1 and coating, it is characterized in that: the solvent that uses is alkanones, the mixture of aromatic hydrocarbons and acetates, its weight percent is:
Alkanones: aromatic hydrocarbons: acetates=20～30%: 60～40%: 20～30%.
6, the preparation method of fluorine-containing, siliceous copolymer resin as claimed in claim 1 and coating, it is characterized in that: initiator is azo-compound or acyl peroxide compound, and consumption is 0.5～3% of a reaction monomers gross weight.
7, the preparation method of fluorine-containing, siliceous copolymer resin as claimed in claim 1 and coating, it is characterized in that: polymerization procedure is: add mixed solvent in the reactor, A, B, C mix the back and drip with initiator, control reaction temperature and reaction times, reacted, the cooling blowing gets copolymer resin; According to a conventional method copolymer resin is made into coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02100052 CN1432613A (en) | 2002-01-14 | 2002-01-14 | Fluorinated and siliceous copolymer resin and paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02100052 CN1432613A (en) | 2002-01-14 | 2002-01-14 | Fluorinated and siliceous copolymer resin and paint |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1432613A true CN1432613A (en) | 2003-07-30 |
Family
ID=27626964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02100052 Pending CN1432613A (en) | 2002-01-14 | 2002-01-14 | Fluorinated and siliceous copolymer resin and paint |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1432613A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712838A (en) * | 2009-12-18 | 2010-05-26 | 威海新元化工有限公司 | Water-soluble low surface energy paint and preparation method thereof |
| CN102134296A (en) * | 2010-12-31 | 2011-07-27 | 江苏康泰氟化工有限公司 | Fluosilicic modification water-soluble acrylic resin dispersion and application thereof |
| CN102532397A (en) * | 2010-12-10 | 2012-07-04 | 深圳市嘉达高科产业发展有限公司 | Resin for low surface energy organic fluorine silicone antifouling coating, and preparation process thereof |
| CN103602121A (en) * | 2013-11-19 | 2014-02-26 | 青岛广联达精密机械有限公司 | Improved aging-resistant waterproof coating material |
| CN107384092A (en) * | 2017-06-19 | 2017-11-24 | 河北晨阳工贸集团有限公司 | Sun-proof automatically cleaning exterior wall sealing wax of energy-conservation of overlength service life and preparation method thereof |
| CN109306221A (en) * | 2018-08-31 | 2019-02-05 | 浙江帝恒实业有限公司 | A kind of new-energy automobile insulating heat-conductive coating and preparation method thereof |
-
2002
- 2002-01-14 CN CN 02100052 patent/CN1432613A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101712838A (en) * | 2009-12-18 | 2010-05-26 | 威海新元化工有限公司 | Water-soluble low surface energy paint and preparation method thereof |
| CN102532397A (en) * | 2010-12-10 | 2012-07-04 | 深圳市嘉达高科产业发展有限公司 | Resin for low surface energy organic fluorine silicone antifouling coating, and preparation process thereof |
| CN102134296A (en) * | 2010-12-31 | 2011-07-27 | 江苏康泰氟化工有限公司 | Fluosilicic modification water-soluble acrylic resin dispersion and application thereof |
| CN102134296B (en) * | 2010-12-31 | 2015-11-25 | 江苏蓝色星球环保科技股份有限公司 | Fluosilicic modification water-soluble acrylic resin dispersion and uses thereof |
| CN103602121A (en) * | 2013-11-19 | 2014-02-26 | 青岛广联达精密机械有限公司 | Improved aging-resistant waterproof coating material |
| CN103602121B (en) * | 2013-11-19 | 2016-05-25 | 青岛祥嘉知识产权服务有限公司 | A kind of improved anti-aging water-repellent paint |
| CN107384092A (en) * | 2017-06-19 | 2017-11-24 | 河北晨阳工贸集团有限公司 | Sun-proof automatically cleaning exterior wall sealing wax of energy-conservation of overlength service life and preparation method thereof |
| CN109306221A (en) * | 2018-08-31 | 2019-02-05 | 浙江帝恒实业有限公司 | A kind of new-energy automobile insulating heat-conductive coating and preparation method thereof |
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