CN1465602A - Silicofluoride containing acrylic copolyresin emulsion and paint - Google Patents
Silicofluoride containing acrylic copolyresin emulsion and paint Download PDFInfo
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- CN1465602A CN1465602A CNA021240345A CN02124034A CN1465602A CN 1465602 A CN1465602 A CN 1465602A CN A021240345 A CNA021240345 A CN A021240345A CN 02124034 A CN02124034 A CN 02124034A CN 1465602 A CN1465602 A CN 1465602A
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Abstract
The present invention relates to a fluorine and silicon contained copolymer resin emulsion and paint, it contains organo-fluorine compound, organo-silicon compound and other vinyl compound, in which the organo-fluorine compound is (methyl) acrylic fluorine-contained ester, and the organo-silicon compound is the compound containing alkylene and containing water-soluble siloxane group, and the other vinyl compound is that can be copolymerized with (methyl) acrylic fluorine-contained ester. Said invented fluorine-contained copolymer water paint has excellent cohesive force, and its formed paint film has excellent acid-resistant and alkali-resistant properties.
Description
Technical field:
The present invention relates to a kind of copolymer resins emulsion and coating, particularly a kind of fluorine-containing, silicon acrylic copolymeric resin emulsion and coating.
Background technology:
As base material treatment coating such as fiber, paper, sand, pottery, plastics, metals, the multipolymer that contains fluorine element is well-known.This is because the fluorine atom compound has unique low superficiality, so be commonly used for hydrophobic, the oleophobic agent of fiber, releasing agent and buildings outer wall protective cover, and special aspects such as Industrial materials such as optical material.
Yet exactly because its low superficiality, to the bad adhesion of various base materials, particularly emulsion paint is more remarkable, and it is very difficult therefore will to obtain filming of weather resistance.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, be applicable to fiber and textile application, but uncomfortable cooperation building coating.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:
At above-mentioned defective, the object of the invention provides a kind ofly has excellent cohesive force to various base materials, the excellent acid-and base-resisting medicine of filming of formation, the copolymer, aqueous coating of the fluorine silicon of weather resistance---fluorine silicon acrylic copolymeric resin emulsion and coating.
Technical scheme of the present invention is as follows:
A kind of fluorine-containing, silicon copolymer resins emulsion and coating, other contains organofluorine compound, silicoorganic compound and other vinyl compounds.Organic fluoride wherein is (methyl) vinylformic acid fluorinated ester class, and its addition is 20～90 quality %.Silicoorganic compound wherein are the compound that contains thiazolinyl and contain the hydrolyzable siloxanes, and its 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, its addition is 80～10 quality %.100 parts of above-mentioned mix monomers in the presence of emulsifying agent, are carried out emulsion copolymerization in water medium.(methyl) vinylformic acid fluorinated ester can be a general formula:
The compound of expression,
(R in the formula
1=H, CH
3, R
fBe C
1-12Hydrogen atom in the alkyl is partly replaced by fluorine atom or whole metathetical Polyfluoroalkyl)
Containing thiazolinyl and contain the hydrolyzable radical siloxane can be general formula:
Compound.(R in the formula
2=H or C
1～10Alkyl, R
3=-CH
3Or-C
2H
5, a=0～2 integers, Y is for containing thiazolinyl or containing thiazolinyl acyl-oxygen group)
Other alkenyl compounds can be general formula:
The compound of expression, (R in the formula
1=H or-CH
3, the n=1-12 integer)
The manufacture method of a kind of fluorine-containing, Si acrylate copolymer resins emulsion and coating, 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 usedly be:
(formula I, II, III symbolic significance the same)
The monomeric mass percent of three classes is:
I∶II∶III＝(20-90)％∶(0.1-5)％∶(80-10)％
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 and coating by (1) fluorinated acrylate or fluorine-containing methacrylate 20-90 mass parts, (2) vinyl silanes or contain silane 0.1～5.0 mass parts of (methyl) acryloxy and (3) can with the first composition copolymerization, but alkenyl monomer 70～20 mass parts except that second 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-borne coatings 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 copolymer, aqueous coating of the fluorine silicon of weather resistance.
The present invention about the copolymer, aqueous coating of fluorine silicon be by
1) following general formula (I)
CH
2＝CR
1COOR
f????(I)
(R in the formula
1For H or-CH
3, R
fCount hydrogen atom in the alkyl of 1-20 for C by the part or all of metathetical Polyfluoroalkyl of fluorine atom) fluorine-containing (methyl) acrylate of expression, consumption is the 20-90 quality % of total monomer amount;
2) remember general formula (II) down
CH
2=CR
1-(COOCH
2CH
2CH
2) m-SiR
2 3-c (OR
3)
c(II) (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) and vinyl silanes of representing or the silane that contains (methyl) acryloxy, its amount is 0.1-5.0 quality %; With 3) can and the first composition copolymerization but second composition beyond thiazolinyl be monomer, its amount is 10-80 quality %, monomer mixture 100 weight parts carry out copolymerization in the presence of emulsifying agent.
The present inventor discovers all of the copolymer, aqueous coating of fluorine-containing, with fluorine-containing (methyl) acrylate, (methyl) acryloyl-oxy base silane copolymerization of containing alkoxyl group and containing alkenyloxy thiazolinyl silane is the fluorinated copolymer water-borne coatings of feature, base materials such as demonstration and fiber, paper, sand, enamel, plastics, metal, sand-cement slurry have firm cohesiveness, 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 the copolymer, aqueous coating of fluorine silicon 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
1For H or-CH
3, R
fBe C
1-12Hydrogen atom in the alkyl is by the part or all of metathetical Polyfluoroalkyl of fluorine atom.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,-CH (CF
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 be the mixture of one or two or more 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)……II
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 more than 5.0%, then owing to the cross-linking density height, becomes fragile multipolymer, and easy gelation when copolymerization.So be preferably 0.1～5.0 quality %, preferably 0.5～4.5%.
Constitute the ternary alkyls monomer of fluorine silicon copolymer emulsion coating 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
2=CR
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) vinylformic acid ring Sheng ester, Octyl methacrylate, (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 water milk type coating 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, employed free-radical initiator is benzoyl peroxide, lauroyl peroxide, tert-butyl peroxide, Sodium Persulfate, Potassium Persulphate, ammonium persulphate, azo-bis-isobutyl cyanide 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.
Embodiment:
Below with embodiment the present invention is described, but do not limit the embodiment of the invention: instrument and manufacturing process that (one) embodiment 1～6 is used
According to the listed component of table 1, solvent with 70% and deionized water, 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, silicon copolymer resins emulsion.(2) embodiment 1～6 each component add-on sees Table 1
Table 1 embodiment 1～6 each component add-on (quality branch)
(3) see Table 2 by embodiment 1～6 gained copolymer resin fat liquor characteristic
| 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 | 10.0 | 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 |
Table 2 embodiment 1～6 gained copolymer emulsion characteristic
(4) embodiment 1～6 copolymer emulsion is made into coating
| Characteristic | Embodiment | |||||
| ??1 | ??2 | ??3 | ??4 | ??5 | ??6 | |
| Solid content (wt) % | ??49 | ??49 | ??50 | ??50 | ??50 | ??49 |
| 25 ℃ of seconds of viscosity (being coated with 4 glasss) | ??110 | ??120 | ??110 | ??110 | ??120 | ??135 |
| PH | ??6 | ??6 | ??6 | ??6 | ??6 | ??6 |
Gained embodiment 1～6 fluorine-silicon copolymer thing emulsion is made into the exterior wall latex coating by table 3, its technical process such as Fig. 1.Table 3 fluorine silicon copolymer resins emulsion coatings prescription
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
| 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 |
| 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 (9)
1, a kind of fluorine-containing, silicon copolymer resins emulsion and coating, it is characterized by: it contains organofluorine compound, silicoorganic compound and other vinyl compounds.
2, fluorine-containing, silicon copolymer resins emulsion as claimed in claim 1 and coating is characterized by: organic fluoride wherein is (methyl) vinylformic acid fluorinated ester class, and its addition is 20～90 quality %.
3, fluorine-containing, silicon copolymer resins emulsion as claimed in claim 1 and coating is characterized by: silicoorganic compound wherein are the compound that contains thiazolinyl and contain the hydrolyzable siloxanes, and its addition is 0.1～5 quality %.
4, fluorine-containing, silicon copolymer resins emulsion as claimed in claim 1 and coating, it is characterized by: other vinyl compounds wherein can with the copolymerization of (methyl) vinylformic acid fluorinated ester, but (methyl) vinylformic acid and ester compound thereof except that right requires 3 silicoorganic compound, its addition are 80～10 quality %.
5, fluorine-containing, silicon copolymer resins emulsion as claimed in claim 1 and coating is characterized by: be with 100 parts of claims 2,3,4 described mix monomers in the presence of emulsifying agent, carrying out emulsion copolymerization in water medium is feature.
6, claim 2 described (methyl) vinylformic acid fluorinated ester can be a general formula:
The compound of expression,
(R in the formula
1=H, CH
3, R
fBe C
1-12Hydrogen atom in the alkyl is partly replaced by fluorine atom or whole metathetical Polyfluoroalkyl)
7, described to contain thiazolinyl and contain the hydrolyzable radical siloxane can be general formula to claim 3:
Compound.(R in the formula
2=H or C
1～10Alkyl, R
3=-CH
3Or-C
2H
5, a=0～2 integers, Y is for containing thiazolinyl or containing thiazolinyl acyl-oxygen group)
8, the alkenyl compound of other described in the claim 4 can be general formula:
The compound of expression,
(R in the formula
1=H or-CH
3, the n=1-12 integer)
9, the manufacture method of (1) a kind of fluorine-containing, Si acrylate copolymer resins emulsion and coating, 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 usedly be:
(formula I, II, III symbolic significance the same)
The monomeric mass percent of three classes is:
I∶II∶III＝(20-90)％∶(0.1-5)％∶(80-10)％
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.
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 true CN1465602A (en) | 2004-01-07 |
| CN1281643C CN1281643C (en) | 2006-10-25 |
Family
ID=34142597
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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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 |
| CN116515357A (en) * | 2023-02-06 | 2023-08-01 | 广州大学 | Preparation method of amphiphobic flame-retardant coating for wood surface |
| CN116769211A (en) * | 2023-06-30 | 2023-09-19 | 苏州鸿科新材料科技有限公司 | Low-volume shrinkage and aging-resistant photo-curing release film and preparation process thereof |
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