CN1772777A - Fluorosilicone modified acrylic emulsion for weather resistant antifouling paint - Google Patents
Fluorosilicone modified acrylic emulsion for weather resistant antifouling paint Download PDFInfo
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- CN1772777A CN1772777A CN 200510101356 CN200510101356A CN1772777A CN 1772777 A CN1772777 A CN 1772777A CN 200510101356 CN200510101356 CN 200510101356 CN 200510101356 A CN200510101356 A CN 200510101356A CN 1772777 A CN1772777 A CN 1772777A
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Abstract
The present invention is fluorosilicone modified acrylic emulsion for weather resistant anti-fouling paint, relates to paint resin and aims at providing one kind of environment friendly paint with excellent weather resistance anti-fouling performance. The fluorosilicone modified acrylic emulsion contains methylacrylate, vinyl siloxane and organic fluoric monomer as well as composite emulsifier, pH buffering agent and initiator and is prepared into emulsion. The present invention has very low surface energy, high adhesion, high transparence, etc. and can raise the weather resistance and anti-fouling performance of resin. It has high chemical stability, mechanical stability and good machining performance.
Description
Technical field:
The present invention: a kind of super fluorinated silicone modified acrylic ester emulsion weather-proof, that anti-pollution paint is used relates to a kind of coating, is mainly used in building external paint, also can be applicable to the covering with paint of materials such as concrete, plasterboard.
Background technology:
The kind of exterior coating is a lot, can be divided into two big classes: water-based and solvent reducible coatings.Water-borne coatings such as water-borne acrylic type, water-base epoxy class, waterborne polyester class and water-based silicon Class C, its weathering resistance, resistance to soiling are relatively poor; Solvent reducible coatings weathering resistance, anti-pollution characteristic are higher, but its solvent load is many, toxicity big, the coating ventilation property is poor, easily peeling peels off.
The order that increases by weathering resistance, resistance to soiling is respectively styrene-acrylic resin, pure third resin, organosilicon acrylic resin, fluorocarbon resin.
Owing to have the phenyl ring of conjugated link(age), the poorest to anti-ultraviolet ability, the time of water-based styrene-acrylic resin artificial ageing resistance is about 100～200 hours in the styrene-acrylic resin.
The time of the pure third resin artificial ageing resistance of water-based is about 500 hours.
The anti-pollution characteristic of these two kinds of resins is relatively poor, is about 10%～20%;
The organosilicon radical that contains low surface energy in the organosilicon acrylic resin, and the bond energy of C-Si key is greater than the C-C key, its ageing-resistant and anti-pollution characteristic all is improved, but the organosilicon too high levels can cause the decline of stability of emulsion in the organosilicon crylic acid latex, can certain influence be arranged effect to its modification, the time of water-based organosilicon crylic acid latex artificial ageing resistance is about 1000～1500 hours, and anti-pollution characteristic is about 8%～15%;
Contain the bigger C-F key of bond energy in the fluorocarbon resin; and organic fluorine material is that surface energy is minimum in all material; the time of artificial ageing resistance is about 3000～5000 hours; anti-pollution characteristic is about 2%～8%; because fluorocarbon resin synthesis technique complexity costs an arm and a leg, the resin that is applied at present only is solvent-borne type; be unfavorable for environment protection, thereby limited its application.
Though the development work of water-based fluorocarbon resin has been carried out for many years, owing to technical reason, the resin of industrialization not yet, and water-based fluorocarbon at present is more expensive more than solvent-based fluorocarbon resin.
Each performance of above-mentioned resin relatively (data source-derive from the specification sheets of various product) as following table;
| Styrene-acrylic resin | Pure third resin | Organosilicon acrylic resin | Solvent-based fluorocarbon resin | Product of the present invention | |
| The artificial accelerated aging value/ | 150～ 200 | 500～ 800 | 1000～ 1500 | 3000～5000 | 1500～3000 |
| Contamination resistance/% | ≤20 | ≤15 | ≤10 | ≤3 | ≤8 |
Weather-proof, the anti-soil and the environmental-protecting performance that improve coating are present research directions.
Domestic patent publication discloses a application documents: water propyl fluorosilicate nano sol weatherability antifouling paint (application number: 01139089; Publication number: 1354211; The applying date: 20011207; The applicant; Shanghai University).
The super antifouling paint of this invention water-based fluorine silicon third Nano sol relates to a kind of coating material, is mainly used in the application of building inner, external wall, also can be applied on the coagulation, the application of materials such as plasterboard, wood fibre board and metal.The water propyl fluorosilicate nano sol weatherability antifouling paint is formed main film forming substance with the acrylic emulsions that water-base fluorocarbon emulsion, acrylic emulsions and self-cross linking type are organic-silicon-modified, and is mixed nano material.Super patience with solvent based coating excellence and strong contamination resistance have the good ventilation property and the environmental requirement of the unapproachable water-borne coatings of solvent based coating simultaneously.
This technology only is a kind of mixture, and the improvement of its weathering resistance, anti-pollution characteristic is little.
Above-mentioned coating weather-proof, antifouling property is not high; Or complex process, cost an arm and a leg, be unfavorable for environment protection; Can not satisfy the requirement of use.
Summary of the invention:
The present invention relates to a kind of fluorinated silicone modified acrylic resin paint, purpose is to have good weatherability properties, contamination resistance and environmental-protecting performance with the water-based exterior wall paint of this resin preparation.
The present invention is achieved through the following technical solutions: earlier with behind vinyl silanes and (methyl) acrylate emulsifying with continuous dripping method copolymerization, drip the organic fluorine monomer copolymerization at last.
A kind of super weather-proof, fluorinated silicone modified ACRYLIC EMULSION that anti-pollution paint is used contains (methyl) acrylate, vinyl silanes and organic fluorine monomer; Acrylate is: methyl methacrylate, butyl acrylate, acrylic or methacrylic acid; Vinyl silanes is: vinyltriethoxysilane or vinyltrimethoxy silane; The organic fluorine monomer is: trifluoroethyl methacrylate; Compound emulsifying agent, pH buffer reagent make (methyl) vinylformic acid, vinyl silanes emulsification; The polymerization of initiator trigger monomer generates resin emulsion.
Each component of the present invention charging capacity by weight percentage is:
Deionized water 36.00～55.00
Methyl methacrylate+butyl acrylate+acrylic or methacrylic acid 27.00～45.00
Vinyltriethoxysilane or vinyltrimethoxy silane 0.90～3.60
Trifluoroethyl methacrylate 4.50～10.00
Compound emulsifying agent 2.70～7.30
Initiator 0.09～0.36
PH buffer reagent 0.10～0.20
Neutralizing agent 2.00～4.50
In technique scheme
Acrylate is meant: methyl methacrylate CH
2=C (CH
3) COOCH
3, butyl acrylate CH
2=CHCOOC
4H
9, vinylformic acid CH
2=CHCOOH or methacrylic acid CH
2=C (CH
3) COOH (these two kinds of acid can replace mutually).
Vinyl silanes is: vinyltrimethoxy silane CH
2=CHSi (OCH
3)
3Or vinyltriethoxysilane CH
2=CHSi (OCH
2CH
3)
3In a kind of (can replace mutually).
The organic fluorine monomer is meant trifluoroethyl methacrylate CH
2=C (CH
3) COOCH
2CF
3
Compound emulsifying agent is meant 1. Sodium dodecylbenzene sulfonate or sodium lauryl sulphate (can replace mutually), 2. alkylphenol polyoxyethylene (OP-10) R-C
6H
5-O-(CH
2CH
2O)
10H, 3. among the FC-4 1., 2. the combination or 1., 2., 3. the combination.
Initiator is persulphate (Na
2S
2O
8Or K
2S
2O
8In any) with sulphite (Na
2SO
3Or K
2SO
3In any) combination.
The pH buffer reagent is SODIUM PHOSPHATE, MONOBASIC (NaH
2PO
4) or sodium bicarbonate (NaH
2CO
3) in any.
Neutralizing agent is sodium hydroxide (NaOH), potassium hydroxide (KOH) or ammoniacal liquor (NH
3.H
2O) any in.
The used trifluoroethyl methacrylate of the present invention has superpower C-F key and ultralow surface energy, can obviously improve weathering resistance, the resistance to soiling of resin.Organosilane monomer also has low surface energy, and segment is soft, can improve the resistance to soiling of resin and improve the characteristic that resin low temperature becomes fragile.Acrylate has the sticking power good with base material, and the transparency, gloss retention is good.Modified resin emulsion of the present invention has good chemical stability and mechanical stability, and processing characteristics is good.
Preparation technology of the present invention is as follows:
(1) the pre-emulsion process of monomer, this step can make monomer be dispersed in the water.
In reactor, add deionized water, compound emulsifying agent, pH buffer reagent under the room temperature successively, stirring velocity is transferred to 50～80 rev/mins, continue to add butyl acrylate, methyl methacrylate, (methyl) vinylformic acid, organosilane monomer, keep stirring velocity, emulsification 0.4～1 hour.
(2) polymerization process, this process is by adding initiator, and the trigger monomer polymerization generates resin emulsion.
Initiator is dissolved in the deionized water, and it is stand-by to be made into concentration and to be 0.5%～2% the aqueous solution;
Emit 50%～80% pre-emulsion, keep stirring velocity, improve temperature to 65～90 ℃ of reactor, add 30%～50% of whole initiator solutions, treat that pre-emulsion becomes light blue (illustrating that monomer is initiated) by white in the still, begin to drip the pre-emulsion of emitting, rate of addition is controlled in 1～3 hour and finishes, continue to drip the organic fluorine monomer, add in 0.5 hour that (purpose that drips fluorine monomer at last is to make fluorine element concentrate on the surface of resin as far as possible, form nucleocapsid structure, bring into play the effect of fluorine element the biglyyest); When dripping monomer pre-emulsion and fluorine monomer, drip remaining initiator solution (drip simultaneously with two conduits, purpose is constantly to replenish initiator, makes and reacts carry out more thorough).
(3) insulation reaction improves monomeric transformation efficiency.
Keep stirring velocity and temperature-resistant, continue reaction 0.5～2 hour, temperature is cooled to below 40 ℃, add neutralizing agent and regulate pH to 7～8.5, with 100 order nylon net cloth bag filtrations, packing.
The using method of product of the present invention
In agitator, add deionized water, add dispersion agent, defoamer, mould inhibitor successively, stir, under the high-speed stirring condition, add titanium dioxide, water-ground limestone, kaolin etc. and disperse.Above-mentioned scattered slurry poured into be ground in the sand mill below fineness 50 μ, filter the back and add resin emulsion of the present invention, film coalescence aid, thickening material etc., both can obtain high performance outer wall paint after the filtration.
The present invention adopts novel organic fluorine monomer and vinyltriethoxysilane and acrylic ester emulsion copolymerization; Realized the Water-borne modification of the fluoro-resin of building coating, be easy to construction, environmental protection can weather-proof 3000 hours, resistance to soiling≤8%, and product cost is low.
Specific embodiments:
Embodiment 1, super weather-proof, the soiling resistant exterior wall coating resin emulsion of a kind of white, and the each component weight percent is as follows:
Deionized water 51.30
Butyl acrylate 18.40
Methyl methacrylate 18.40
Vinylformic acid 1.10
Vinyltriethoxysilane 1.10
Trifluoroethyl methacrylate 3.0
Sodium dodecylbenzene sulfonate 1.88
OP-10 0.94
Perfluor nonyl ethers benzene sulfonic acid sodium salt 0.48
Sodium bicarbonate 0.20
Sodium Persulfate 0.20
S-WAT 0.20
Ammoniacal liquor 2.80
With ammonium persulphate and S-WAT 1%～5% the solution for later use of being made into soluble in water;
Remainder water, emulsifying agent, buffer reagent, acrylic monomer, organosilane monomer are added in the reactor, and regulating stirring velocity is 70 rev/mins, emulsification 0.5 hour;
Emitting 70% pre-emulsion prepares to drip, with still temperature rise to 76 ℃, add 1/6 initiator, cool the temperature to 72 ℃ behind the 15min, begin to drip the pre-emulsion of emitting, in 2 hours, drip off, continue to drip trifluoroethyl methacrylate then, 0.5 hour drip off, drip initiator solution simultaneously with another conduit in the dropping process;
Dropwise, temperature is controlled between 70～72 ℃, continue reaction 2 hours, temperature is cooled to below 40 ℃, add neutralizing agent and regulate pH to 7.5, with 100 order nylon net cloth bag filtrations, packing.
After this routine resin emulsion is made into exterior coating varnish, press the testing method of " anti-artificial accelerated aging ", " contamination resistance " among the GB/T9755-2001 " exterior wall coating material of synthetic resin emulsion ", measured value is respectively: 3000h ,≤4%.
Embodiment 2, a kind of white band blue light normal temperature solidifying fluorine fluorine-silicon modified acrylic ester resin emulsion, and the each component weight percent is as follows:
Deionized water 50.30
Butyl acrylate 16.50
Methyl methacrylate 20.60
Vinylformic acid 1.20
Vinyltriethoxysilane 0.80
Trifluoroethyl methacrylate 2.10
Sodium dodecylbenzene sulfonate 3.60
OP-10 1.80
SODIUM PHOSPHATE, MONOBASIC 0.20
Sodium Persulfate 0.20
Sodium hydroxide 2.80
With ammonium persulphate 2% the solution for later use of being made into soluble in water;
Remainder water, emulsifying agent, buffer reagent, acrylic monomer, organosilane monomer are added in the reactor, and regulating stirring velocity is 65 rev/mins, emulsification 0.5 hour;
Emitting 70% pre-emulsion prepares to drip, with still temperature rise to 86 ℃, add a half-value dose initiator, cool the temperature to 74 ℃ behind the 10min, begin to drip the pre-emulsion of emitting, in 2 hours, drip off, continue to drip trifluoroethyl methacrylate then, 0.5 hour drip off, drip initiator solution simultaneously with another conduit in the dropping process;
Dropwise, temperature is controlled at 72 ℃, 60 rev/mins of stirring velocitys continue reaction 1 hour, and temperature is cooled to below 40 ℃, and add neutralizing agent and regulate pH to 7.5, with 120 order nylon net cloth bag filtrations, packing.
After this routine resin emulsion is made into exterior coating varnish, press the testing method of " anti-artificial accelerated aging ", " contamination resistance " among the GB/T9755-2001 " exterior wall coating material of synthetic resin emulsion ", measured value is respectively: 2000h ,≤4.3%.
Embodiment 3, the fluorinated silicone modified acrylate paint for external wall resin emulsion of a kind of white band blue light, and the each component weight percent is as follows:
Deionized water 46.60
Butyl acrylate 16.90
Methyl methacrylate 16.00
Vinylformic acid 2.80
Vinyltriethoxysilane 2.80
Trifluoroethyl methacrylate 7.50
Sodium lauryl sulphate 1.90
OP-10 1.90
Perfluor nonyl ethers benzene sulfonic acid sodium salt 0.50
Saleratus 0.10
Potassium Persulphate 0.20
Potassium sulfite 0.20
Sodium hydroxide 2.80
With ammonium persulphate and S-WAT 3% the solution for later use of being made into soluble in water;
Remainder water, emulsifying agent, buffer reagent, acrylic monomer, organosilane monomer are added in the reactor, and regulating stirring velocity is 60 rev/mins, emulsification 0.5 hour;
Emitting 80% pre-emulsion prepares to drip, with still temperature rise to 72 ℃, add 1/4 initiator, cool the temperature to 68 ℃ after 15 minutes, begin to drip the pre-emulsion of emitting, in 1 hour, drip off, continue to drip trifluoroethyl methacrylate then, 0.5 hour drip off, drip initiator solution simultaneously with another conduit in the dropping process;
Dropwise, temperature is controlled between 68～72 ℃, continue reaction 1 hour, temperature is cooled to below 40 ℃, add neutralizing agent and regulate pH to 8, with 160 order nylon net cloth bag filtrations, packing.
After this routine resin emulsion is made into exterior coating varnish, press the testing method of " anti-artificial accelerated aging ", " contamination resistance " among the GB/T9755-2001 " exterior wall coating material of synthetic resin emulsion ", measured value is respectively: 1500h ,≤8%.
Claims (6)
1, a kind of super weather-proof, fluorinated silicone modified acrylic ester emulsion that anti-pollution paint is used contains (methyl) acrylate, vinylsiloxane and organic fluorine monomer; Acrylate is: methyl methacrylate, butyl acrylate, acrylic or methacrylic acid; Vinylsiloxane is: vinyltriethoxysilane or vinyltrimethoxy silane; The organic fluorine monomer is: trifluoroethyl methacrylate; Make (methyl) vinylformic acid, vinyl silanes emulsification with compound emulsifying agent, pH buffer reagent; With the polymerization of initiator trigger monomer, generate resin emulsion.
2, a kind of super weather-proof, fluorinated silicone modified acrylic ester emulsion that anti-pollution paint is used according to claim 1, each component per-cent by weight is:
Deionized water 36.00～55.00
Methyl methacrylate+butyl acrylate+acrylic or methacrylic acid 27.00～45.00
Vinyltriethoxysilane or vinyltrimethoxy silane 0.90～3.60
Trifluoroethyl methacrylate 4.50～10.00
Compound emulsifying agent 2.70～7.30
Initiator 0.09～0.36
PH buffer reagent 0.10～0.20
Neutralizing agent 2.00～4.50,
3, a kind of super weather-proof, fluorinated silicone modified acrylic ester emulsion that anti-pollution paint is used according to claim 1 and 2, it is characterized in that compound emulsifying agent is 1. Sodium dodecylbenzene sulfonate or sodium lauryl sulphate (can replace mutually), 2. alkylphenol polyoxyethylene (OP-10) R-C
6H
5-O-(CH
2CH
2O)
10H, 3. among the FC-4 1., 2. the combination or 1., 2., 3. the combination.
4, a kind of super weather-proof, fluorinated silicone modified acrylic ester emulsion that anti-pollution paint is used according to claim 1 and 2 is characterized in that initiator is persulphate (Na
2S
2O
8Or K
2S
2O
8) in any and sulphite (Na
2SO
3Or K
2SO
3) in any combination.
5, a kind of super weather-proof, fluorinated silicone modified acrylic ester emulsion that anti-pollution paint is used according to claim 1 and 2 is characterized in that the pH buffer reagent is SODIUM PHOSPHATE, MONOBASIC (NaH
2PO
4) or sodium bicarbonate (NaH
2CO
3) in any.
6, a kind of super weather-proof, fluorinated silicone modified acrylic ester emulsion that anti-pollution paint is used according to claim 1 and 2 is characterized in that neutralizing agent is sodium hydroxide (NaOH), potassium hydroxide (KOH) or ammoniacal liquor (NH
3H
2O) any in.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101013565A CN100343293C (en) | 2005-11-16 | 2005-11-16 | Fluorosilicone modified acrylic emulsion for weather resistant antifouling paint |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101013565A CN100343293C (en) | 2005-11-16 | 2005-11-16 | Fluorosilicone modified acrylic emulsion for weather resistant antifouling paint |
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| Publication Number | Publication Date |
|---|---|
| CN1772777A true CN1772777A (en) | 2006-05-17 |
| CN100343293C CN100343293C (en) | 2007-10-17 |
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|---|---|---|---|
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