CN1281643C - Silicofluoride containing acrylic copolyresin emulsion and paint - Google Patents
Silicofluoride containing acrylic copolyresin emulsion and paint Download PDFInfo
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- CN1281643C CN1281643C CN 02124034 CN02124034A CN1281643C CN 1281643 C CN1281643 C CN 1281643C CN 02124034 CN02124034 CN 02124034 CN 02124034 A CN02124034 A CN 02124034A CN 1281643 C CN1281643 C CN 1281643C
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- China
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- fluorine
- formula
- vinylformic acid
- thiazolinyl
- methacrylic acid
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Abstract
The present invention relates to copolymer resin emulsion containing fluorine and silicon and paint, which comprises organic fluorine compounds, organosilicon compounds and other alkene compounds, wherein organic fluoride is (methyl radical) acrylic acid ester containing fluorine, the organosilicon compounds are compounds containing alkene groups and siloxane groups which can be hydrolyzed, and other alkene compounds are (methyl radical)acrylic acid and ester compounds thereof which can be copolymerized with the (methyl radical)acrylic acid ester containing fluorine except for the organosilicon compounds of the right claim 3. The copolymer water paint containing the fluorine is copolymer water paint containing fluorine and silicon, which has excellent cohesive force to various base materials, and formed coating films have excellent acid and alkali medicine resistance and durability.
Description
Technical field
The present invention relates to a kind of copolymer resins emulsion and preparation method thereof, particularly a kind of fluorine-containing, silicon acrylic copolymeric resin emulsion and preparation method thereof.
Background technology
As base material treatment emulsions such as fiber, paper, sand, pottery, plastics, metals, the multipolymer that contains fluorine element is well-known.This be because fluorinated copolymer many premium propertiess are arranged, for example weathering resistance, chemical resistant properties, water tolerance, refuse water, oil repellent and low frictional properties.
Fluorinated copolymer is low because of its surface energy, cohesiveness to various coated materials is relatively poor, treat it is not that emulsion paint is more remarkable, therefore it is very difficult to obtain filming of high-adhesion, usually in polymkeric substance, add monomers such as hydroxyl, carboxyl to improve cohesiveness to common substrate, for example useful vinylformic acid 2-hydroxyl ethyl ester, vinylformic acid and maleic anhydride are participated in the motion of copolymerization type, the Japan flat 6-33043 of special permission describes with acrylic fluorine ester, vinylformic acid fat acid esters and hydroxyl, amido acrylate copolymer emulsion composition, is applicable to fiber and textile application.At present external commercially available water-based fluororesin coating is feature with trifluorochloroethylene, TFE copolymer structure all, and its hydrophilic monomer vinyl ethers compound is difficult to solve at home.
Summary of the invention
The object of the invention provides a kind ofly has excellent cohesive force to various coated materials, film excellent acid-and base-resisting medicine, the fluorine silicon copolymer water-soluble emulsion of weather resistance---fluorine silicon acrylic copolymeric resin emulsion and preparation method thereof of formation.Technical scheme of the present invention is as follows:
A kind of fluorine silicon copolymer emulsion, it is made up of organic fluoride monomer, silicoorganic compound, other vinyl compounds, and organic fluoride monomer wherein is (methyl) vinylformic acid fluorinated ester class, and addition is 25～40 quality %; Silicoorganic compound wherein are the organic silane compound that contains thiazolinyl and energy hydrolyzable group siloxanes, and addition is 0.1～5 quality %; Other vinyl compounds wherein can with the copolymerization of (methyl) vinylformic acid fluorinated ester, but (methyl) vinylformic acid and ester compound thereof except that silicoorganic compound, addition is 57.5～73 quality %.100 parts of above-mentioned mix monomers in the presence of emulsifying agent and free-radical initiator, are carried out emulsion copolymerization in water medium.
(methyl) vinylformic acid fluorinated ester can be a general formula:
Containing thiazolinyl and contain the hydrolyzable radical siloxane can be general formula:
R
3=-CH
3Or-C
2H
5, the integer of a=0～2, Y is for containing thiazolinyl or containing thiazolinyl acyl-oxygen group.
Other alkenyl compounds can be general formula:
The compound that III represents.R in the formula
1=H or-CH
3, the integer of n=0～12.
A kind of manufacture method of fluorine-containing, Si acrylate copolymer emulsion, it is the multi-component copolymer that will contain (methyl) acrylic fluorine ester, contain thiazolinyl and hydrolyzable siloxanes silicide and (methyl) propylene ester compound, it is characterized by in the presence of emulsifying agent, adopt the emulsion copolymerization method of free-radical initiator, raw materials used general formula is:
I, R in the formula
1=H or CH
3, R
fBe C
1-12Hydrogen atom in the alkyl is partly replaced by fluorine atom or whole metathetical Polyfluoroalkyl.
II, R in the formula
2=H or C
1-10Alkyl, R
3=-CH
3Or-C
2H
5, the integer of a=0～2, Y is for containing thiazolinyl or containing thiazolinyl acyl-oxygen group.
The monomeric mass percent of three classes is:
I∶II∶III＝(25～40)％∶(0.1～5)％∶(57.5～73)％。
Emulsion copolymerization be in the water medium in the presence of emulsifying agent and initiator routinely emulsion polymerization carry out.Method is with coating fluorine-containing, that silicon copolymer resins emulsion is mixed with the single-component ambient cure routinely.
In sum, fluorine silicon copolymer emulsion of the present invention by (1) fluorinated acrylate or fluorine-containing methacrylate 25～40 mass parts, (2) vinyl silanes or contain silane 0.1～5.0 mass parts of (methyl) acryloxy and (3) can with (1) composition copolymerization, but alkenyl monomer 57.5～73 mass parts except that (2) composition are formed.The present invention be with these monomer 100 mass parts in the presence of emulsifying agent, carry out emulsion copolymerization reaction and be feature.
Fluorinated copolymer water-based emulsion of the present invention is about various base materials being had excellent cohesive force, the excellent acid-and base-resisting medicine of filming of formation, the fluorine silicon copolymer water-soluble emulsion of weather resistance.
The present inventor discovers all of fluorine-containing copolymer emulsion, with fluorine-containing (methyl) acrylate, contain alkoxyl group and contain alkenyloxy silane or the copolymerization of (methyl) acryloyl-oxy base silane is the fluorinated copolymer emulsion of feature, base materials such as demonstration and fiber, paper, sand, enamel, plastics, metal, sand-cement slurry have firm cohesive force, and there is hydrophobic, oil repellency, ageing resistance, inadhesion and acidproof, the alkali resistance of fluorine cpd uniqueness on the cured coating film surface.Below concrete each monomeric kind of narration, proportioning and realize the present invention.
First composition of fluorine silicon copolymer emulsion of the present invention is fluorine-containing (methyl) acrylate, and its general formula is: CH
2=CR
1COOR
fThe compound of I.
R in the formula
1=H or-CH
3, R
fBe C
1-12Hydrogen atom in the alkyl is partly replaced by fluorine atom or whole metathetical Polyfluoroalkyl.R specifically
fCan be-CF
3,-C
2F
5,-nC
3F
7,-CF (CF
3)
2,-nC
4F
9,-CF
2CF (CF
3)
2,-nC
5F
11,-nC
6F
13,-nC
8F
17,-CH
2CF
3,-OH (OF
3)
2,-CH
2CH (CF
3)
2,-CH
2(CF
2)
2F ,-CH
2(CF
2)
3F ,-CH
2(CF
2)
4F ,-CH
2(CF
2)
6F ,-CH
2(CF
2)
8F ,-CH
2CH
2CF
3,-CH
2CH
2(CF
2)
2F ,-CH
2CH
2(CF
2)
3F ,-CH
2CH
2(CF
2)
4F ,-CH
2CH
2(CF
2)
6F ,-CH
2CH
2(CF
2)
8F ,-CH
2CH
2(CF
2)
10F etc.The fluorine-containing alkyl ester of above-mentioned first composition (methyl) vinylformic acid can use separately or the mixture more than two kinds.Its amount is 20～90% of total monomer quality.If the ratio of the fluorine-containing alkyl ester of (methyl) vinylformic acid is lower than 20% in the monomer mixture, then the gained copolymer emulsion surface property of filming is poor; If be higher than 90%, though can obtain high surface property, cohesiveness is low, and better amount ranges is 20～90%, preferably 30～80%.
Second composition that constitutes the copolymer, aqueous coating of fluorine silicon of the present invention is thiazolinyl silane or the silane that contains (methyl) acyloxy, and its general formula is: CH
2=CR
1-(COOCH
2CH
2CH
2)
m-SiR
2 3-C(OR
3).R in the formula
1For H or-CH
3, R
2Be the alkyl of carbonatoms 1～8, R
3For-CH
3,-C
2H
5, m=0,1, C=1,2,3.Specifically can enumerate: CH
2=CHSi (OCH
3)
3, CH
3=CHSi (OC
2H
5)
3, CH
2=CHSiCH
3(OCH
3)
2, CH
2=CHSiCH
3(OC
2H
5)
2, CH
2=CHCO
2CH
2CH
2CH
2Si (OCH
3)
3, CH
2=CHCO
2-CH
2CH
2CH
2Si (OC
2H
5)
3, CH
2=C (CH
3) CO
2CH
2CH
2CH
2-Si (OCH
3)
3, CH
2=C (CH
3) CO
2CH
2CH
2CH
2Si (OC
2H
5)
3, CH
2=CHCO
2CH
2CH
2CH
2SiCH
3(OCH
3)
2Deng.Their content in the fluorine silicon copolymer emulsion is 0.1～5%.If it is insufficient to contain quantity not sufficient 0.1% gained multipolymer bonding persistence, if content is more than 5.0%, then the cross-linking density height becomes fragile multipolymer, and easy gelation when copolymerization, is preferably 0.1～5.0 quality %, preferably 0.5～4.5%.
Constitute ternary other thiazolinyl class monomers of fluorine silicon copolymer emulsion of the present invention, they rise in multipolymer and regulate coating hardness, intensity, with the cohesiveness of base material, effects such as gloss, the transparency.Its general formula is: CH
2CR
1COOR
2(R
1And R
2Meaning the same).They can be: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) cyclohexyl acrylate, (methyl) Octyl acrylate, (methyl) octadecyl acrylate etc.Their general mixing use, and consumption is for participating in monomeric 70～20 quality % of total copolymerization.
The present invention is fluorine-containing, the siliceous copolymer emulsion is with above-mentioned 1)～3) monomer mixture of composition is in the presence of emulsifying agent, the free radical initiation reaction carries out that emulsion polymerization makes, and employed free-radical initiator is Sodium Persulfate, Potassium Persulphate, ammonium persulphate, azo-bis-isobutyl cyanide hydrochloride etc.The emulsifying agent that uses can be: anionic emulsifier, as sodium lauryl sulphate, Sodium dodecylbenzene sulfonate; Nonionic emulsifier, as the nonylphenol Soxylat A 25-7, alkylbenzene Soxylat A 25-7, aliphatic acid polyethenoxy ether; Reactive emulsifier is as vinyl sulfonic acid sodium, acrylamido methyl propane sulfonic acid (AMPS) etc.Also can add sulfydryl class chain-transfer agent in the emulsion copolymerization and regulate molecular weight.Commonly used as beta-mercaptoethanol, just-dodecyl mercaptans, uncle-dodecyl mercaptans etc.
Description of drawings
Fig. 1 is the process flow sheet of preparation exterior wall latex coating.
Embodiment
Below with embodiment the present invention is described, but do not limit the embodiment of the invention:
(1) used instrument and the manufacturing process of embodiment 1～6:
According to the listed component of table 1, the deionized water with 70%, compound emulsifying agent, initiator and all acrylate mixture at room temperature add in the container that high shear mixer is housed, under the 1000r/min rotating speed, and pre-emulsification 0.5h.The gained emulsion places the dropping funnel letting nitrogen in and deoxidizing stand-by.
At another agitator, condenser, temperature being housed takes into account and adds 30% solvent and deionized water emulsifying agent and initiator in addition in the four-hole boiling flask of dropping funnel, letting nitrogen in and deoxidizing, be heated to 80 ℃ with sheathed heater, be incubated after 15 minutes, use the 2h time, 80 ℃ of controlled temperature, drip monomer pre-emulsion down in stirring, after treating that pre-emulsion drips off, drip again with less water emulsive organic silane compound, after finishing, insulation 0.5h, be warming up to 85 ℃ then, be incubated 0.5h again, reaction is finished, naturally cool to room temperature, filter, discharging gets fluorine-containing, siliceous copolymer emulsion.
(2) embodiment 1～6 each component add-on sees Table 1:
Table 1 embodiment 1～6 each component add-on (mass parts)
| Component | Monomer | Embodiment | |||||
| 1 | 2 | 3 | 4 | 5 | 6 | ||
| 1) | Vinylformic acid hexafluoro butyl ester | 30.0 | 25.0 | 35.0 | 20.0 | 20.0 | |
| Vinylformic acid tetrafluoro propyl ester | 10.0 | 15.0 | |||||
| Vinylformic acid octafluoro pentyl ester | 10 | 25.0 | |||||
| 2) | Vinyltrimethoxy silane | 1.5 | 1.0 | ||||
| Vinyltriethoxysilane | 2.0 | ||||||
| Methyl allyl acyloxypropyl trimethoxysilane | 3.0 | 4.0 | 2.5 | ||||
| The methacryloxypropyl triethoxyl silane | 1.5 | ||||||
| 3) | Vinylformic acid | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 | 3.0 |
| Methyl methacrylate | 40.0 | 40.0 | 35.0 | 35.0 | 40.0 | 40.0 | |
| Butyl acrylate | 23.5 | 15.0 | 12.0 | 10.0 | 10.5 | ||
| Octyl acrylate | 15.0 | ||||||
| 2-EHA | 10.0 | ||||||
| Lauryl acrylate | 13.0 | ||||||
| Octadecyl acrylate | 11.0 | 10.5 | |||||
| Hydroxyethyl acrylate | 2 | 2 | 2 | 2 | 4 | 4 | |
| Emulsifying agent | The dodecylbenzene sodium sulfonate | 1.5 | 1.0 | 1.0 | 1.0 | 1.5 | 1.5 |
| Alkylphenol polyoxyethylene | 1.5 | 2.0 | 1.0 | 1.5 | 1.5 | ||
| AMPS | 2.0 | 2.0 | 3.5 | ||||
| Initiator | The azo-bis-isobutyl cyanide hydrochloride | 0.5 | |||||
| Potassium Persulphate | 0.5 | 0.5 | 0.5 | ||||
| Ammonium persulphate | 0.5 | 0.5 | |||||
| Solvent | Distilled water | 50.0 | 50.0 | 50.0 | 50.0 | 50.0 | 50.0 |
| Acetone | 50.0 | 50.0 | 50.0 | 50.0 | |||
| Methyl alcohol | 50.0 | 50.0 |
(3) see Table 2 by embodiment 1～6 gained copolymer emulsion characteristic:
Table 2 embodiment 1～6 gained copolymer emulsion characteristic
| Characteristic | Embodiment | |||||
| 1 | 2 | 3 | 4 | 5 | 6 | |
| Solid content (WT) % | 49 | 49 | 50 | 50 | 50 | 49 |
| 25 ℃ of viscosity (being coated with 4 glasss), second | 110 | 120 | 110 | 110 | 120 | 135 |
| PH | 6 | 6 | 6 | 6 | 6 | 6 |
(4) application of fluoro-silicone emulsion, embodiment 1～6 copolymer emulsion is made into coating.
Gained embodiment 1～6 copolymer emulsion is made into the exterior wall latex coating by table 3, its technical process such as Fig. 1.
Table 3 fluorine silicon copolymer emulsion formulation for coating material
| Raw material | Massfraction % |
| The fluorine-silicon copolymer emulsion | 35 |
| Titanium dioxide | 20～25 |
| Talcum powder | 10～20 |
| Zinc oxide | 2～5 |
| Dispersion agent | 1.5～3 |
| Thickening material | 0.1～0.3 |
| Defoamer | In right amount |
| Pigment | In right amount |
Make model, lining bar by national standard, detect film performance, press every index of GB/T9755-1995 standard test such as table 4.
Table 4 fluorine silicon latex coating performance
| Interventions Requested | Fluorine silicon latex coating |
| State | No lump, even |
| Application property | It is accessible to brush two roads |
| Appearance of film | Normally |
| Time of drying | ≤2h |
| Contrast ratio | ≥0.90 |
| Water tolerance | No change |
| Alkali resistance | No change |
| Washability | ＞10000 times |
| Artificial ageing resistance, h efflorescence/level | 5000 0 |
| The coating temperature-change resistance | No abnormal |
| The coating freeze-thaw resistance | Meet the requirements |
Claims (5)
1, a kind of fluorine silicon acrylic copolymeric resin emulsion, it is characterized in that it is by methacrylic acid fluorinated ester class or vinylformic acid fluorinated ester class, the organic silane compound that contains thiazolinyl and energy hydrolysising group siloxanes, methacrylic acid, vinylformic acid and ester compound thereof are formed, and wherein the mass percent of each component is: methacrylic acid fluorinated ester class or vinylformic acid fluorinated ester class 25～40%, contain thiazolinyl and organic silane compound 0.1～5%, methacrylic acid, vinylformic acid and ester compound 57.5～73% thereof that can the hydrolysising group siloxanes.
2, fluorine silicon acrylic copolymeric resin emulsion according to claim 1 is characterized in that the general formula of described methacrylic acid fluorinated ester class or vinylformic acid fluorinated ester class is:
3, fluorine silicon acrylic copolymeric resin emulsion according to claim 1 is characterized in that the described general formula that contains the organic silane compound of thiazolinyl and energy hydrolysising group siloxanes is:
In the formula: R
2=H or C
1～10Alkyl, R
3=-CH
3Or-C
2H
5, the integer of a=0～2, Y is for containing thiazolinyl or containing thiazolinyl acyl-oxygen group.
4, fluorine silicon acrylic copolymeric resin emulsion according to claim 1 is characterized in that the general formula of described methacrylic acid, vinylformic acid and ester compound thereof is:
R in the formula
1=H or CH
3, the integer of n=0～12.
5, the manufacture method of fluorine silicon acrylic copolymeric resin emulsion, it is characterized in that it carries out according to following steps: with methacrylic acid fluorinated ester class or vinylformic acid fluorinated ester class, contain thiazolinyl and the organic silane compound that contains energy hydrolysising group siloxanes, methacrylic acid, vinylformic acid and ester compound three class monomers thereof are in the presence of emulsifying agent, adopt free-radical initiator to carry out according to the conventional emulsions copolymerization method, raw materials used general formula is:
I, R in the formula
1=H or CH
3, R
fBe C
1-12Hydrogen atom in the alkyl is partly replaced by fluorine atom or whole metathetical Polyfluoroalkyl;
II, R in the formula
2=H or C
1-10Alkyl, R
3=-CH
3Or-C
2H
5, the integer of a=0～2, Y is for containing thiazolinyl or containing thiazolinyl acyl-oxygen group;
III, R in the formula
1=H or-CH
3, the integer of n=0～12;
The monomeric mass percent of three classes is:
I∶II∶III＝(25～40)％∶(0.1～5)％∶(57.5～73)％。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02124034 CN1281643C (en) | 2002-06-17 | 2002-06-17 | Silicofluoride containing acrylic copolyresin emulsion and paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02124034 CN1281643C (en) | 2002-06-17 | 2002-06-17 | Silicofluoride containing acrylic copolyresin emulsion and paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1465602A CN1465602A (en) | 2004-01-07 |
| CN1281643C true CN1281643C (en) | 2006-10-25 |
Family
ID=34142597
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02124034 Expired - Fee Related CN1281643C (en) | 2002-06-17 | 2002-06-17 | Silicofluoride containing acrylic copolyresin emulsion and paint |
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| Country | Link |
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| CN101712838B (en) * | 2009-12-18 | 2013-06-12 | 威海新元化工有限公司 | Water-soluble low surface energy paint and preparation method thereof |
| CN101831842B (en) * | 2010-05-31 | 2012-01-25 | 漯河市天马化工有限公司 | Novel fluorine-containing and silicon-containing gluing reinforcing agent and preparation method thereof |
| CN102690400B (en) * | 2011-09-28 | 2014-08-13 | 扬州大学 | Latex and synthesis method thereof, and water-based metal anticorrosive paint and synthesis method thereof |
| CN104926966A (en) * | 2014-03-19 | 2015-09-23 | 中国科学院上海有机化学研究所 | Fluorine-containing polymer for low-energy surface coating and preparation method thereof |
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| CN105602386A (en) * | 2015-12-31 | 2016-05-25 | 祁守岗 | High weather-resistant fluorocarbon paint and preparation method thereof |
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| CN107417847A (en) * | 2017-04-21 | 2017-12-01 | 苏州博纳化学科技有限公司 | Defoamer of fluorine richness polyacrylate and preparation method thereof |
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