CN102675518B - Preparation method for organic-inorganic hybrid fluorine-silicon modified nano waterborne resin - Google Patents
Preparation method for organic-inorganic hybrid fluorine-silicon modified nano waterborne resin Download PDFInfo
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Abstract
The invention discloses a preparation method for an organic-inorganic hybrid fluorine-silicon modified nano waterborne resin. The waterborne resin is prepared by a seeded emulsion polymerization method, takes an acrylic acid-styrene copolymer or nano silicon dioxide as a core, and takes methyl methacrylate-styrene-fluorine and silicon-containing organic matter as a shell. The prepared organic-inorganic hybrid fluorine-silicon modified nano waterborne resin has the effects of nano materials, the comprehensive performance of organic fluorine and silicon, high weather resistance, water resistance, stain resistance, scrub resistance, self-cleaning performance, good environmental benefits and economic benefits and the like, can be widely applied to the preparation of building coatings, waterborne anticorrosive coatings and the like, and is in line with the concept of environmental protection.
Description
Technical field
The present invention relates to the preparation method of the fluoro-silicon modified Nano of a kind of organic inorganic hybridization water-base resin, modified Nano water-base resin prepared by the present invention can be applied to prepare building coating, anticorrosion water-soluble coating etc., can make coating there are some special performances, as: weathering resistance, water tolerance, scrub resistance, contamination resistance, self-cleaning property etc.
Background technology
Along with the pay attention to day by day of the whole world to environment protection, as the friendly type product of a kind of environmental protection, aqueous acrylic emulsion, because having good gloss retention, excellent film-forming properties and the feature such as environment friendly and pollution-free, has been widely used in the multiple fields such as leather finish, fabric treating, coating and tackiness agent; But meanwhile, because also having limited it, itself some shortcomings further apply, as contained polarity ester group in acrylate resin molecular chain, although can make acrylate resin there is good adhesive power, but filming, it after water suction, easily turns white, water tolerance is poor, and ester group can occur to decompose and affects the overall performance of product even under certain condition; Acrylate resin molecule mostly is linear structure in addition, lacks cross-linking set, thus mechanical property and thermotolerance poor.
In recent years, along with constantly improving and development of polymerization technique, and the attention of people to environmentfriendly products, the research and development of modified acrylic acid emulsion get more and more people's extensive concerning, organic fluorine, organosilicon-modified acrylic emulsion are development in recent years two kinds of macromolecular materials faster, and these two kinds of modified acrylic acid emulsions are representing the direction of ACRYLIC EMULSION development.The present invention selects organic fluorine-fluorine-silicon modified acrylic emulsion, fluorine atom electronegativity is high, atomic radius is little, chemical bond energy large (486kJ/mol), so aspect excellent performances such as the weathering resistance of fluoropolymer, chemical-resistant, stain resistant, also can form hydrophobic lotus leaf effect, as outdoor coating, have a high potential; Si-O bond energy in silicone resin is larger (451kJ/mol) also, its film there is excellent heat-resisting, cold-resistant, humidity, the performance such as weather-proof, resistance to chemical attack.With organic fluorine-silicon bi-material, acrylic resin is carried out to modification, can be in conjunction with the high-performance of the two, performance synergistic effect, make organic fluorine-fluorine-silicon modified acrylic resin there is the performances such as better water tolerance, resistant of high or low temperature, guarantor's look gloss retention, sticking power and film-forming properties, thereby further expand its range of application.
After " nano composite material " proposed by Roy and Kormarneni first in 1984, mineral filler is applied to polymer-modifiedly enter the brand-new nanosecond science and technology epoch.Nanoscale scope refers to the scope of 1-100nm, nano material generally has quantum size effect, small-size effect, surface effects, macro quanta tunnel effect, the sunken territory of dielectric effect etc., can produce some properties, as: thermal property, magnetic performance, optical property, kinetic property, surfactivity and sensitivity characteristic, photocatalysis performance etc.For nano material being applied to macroscopical field, the technology that the present invention combines with inorganic materials and organic materials-" inorganic-organic hybrid " technology has been prepared the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin.The advantage of this water-base resin is integrated organosilicon, organic fluorine, nano inorganic silicon-dioxide, the over-all properties of resin has had larger lifting, so this invention has a good application prospect.
Summary of the invention
The object of the invention is to select the nano silicon of organosilane monomer vinyltriethoxysilane, organic fluorine monomer dodecafluoroheptyl methacrylate and oleic acid modification to be prepared into organic inorganic hybridization core-shell type nano water-base resin by use.Characteristic part of the present invention is: utilize that fluorine atom electronegativity is high, atomic radius is little, chemical bond energy large (486kJ/mol), making to film has the excellent properties such as weathering resistance, chemical-resistant, stain resistant, also can form lotus leaf effect; Utilize Si-O bond energy in silicone resin also larger (451kJ/mol), make to film there is excellent heat-resisting, cold-resistant, humidity, the performance such as weather-proof, resistance to chemical attack; The nanometer size effect that has utilized nano material be film there is heat-resisting, ageing-resistant, scrubbing resistance, the performance such as water-fast.Above several different principle of integrated utilization and the fluoro-silicon modified Nano of the organic inorganic hybridization water-base resin of preparing gained improves a lot than conventional ACRYLIC EMULSION performance, have a extensive future.
Technical scheme of the present invention: the preparation method of the fluoro-silicon modified Nano of a kind of organic inorganic hybridization water-base resin, is characterized in that step is:
(1) nano silicon pass through oleic acid modification, quality or the volume of each component are as follows:
Nano silicon 4g-6g
Oleic acid 1.5ml-2ml
Deionized water 90ml-100ml
The nano silicon 4g-6g that gets certain particle diameter puts into the beaker of 250ml, then adds the ultrasonic dispersion of the deionized water 2h-3h of 90ml-100ml; In ultrasonic scattered mixture, add 1.5ml-2ml oleic acid, room temperature condition lower magnetic force high-speed stirring 1.5h-2h; The ammoniacal liquor 4ml-5ml that gets concentration and be 25wt.% adds in mixing solutions, then magnetic agitation 12h left and right; To adding concentration in mixed solution, be that to be neutralized to pH be 7 for the hydrochloric acid of 30wt.% more afterwards.Take out mixing solutions and put into the centrifugal 30min of supercentrifuge, the water that is 1: 1 by volume ratio the centrifugal product obtaining and alcohol mixeding liquid clean 3 times, remove oleic acid unnecessary in nano silicon, finally by the centrifugal solid powder/particle obtaining dry 24h in the baking oven of 50 ℃, take out, make modified manometer silicon dioxide, wait until and prepare the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin.
(2) prepare the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin, the quality of each component is as follows:
Above-mentioned organosilane monomer is vinyltriethoxysilane;
Above-mentioned organic fluorine monomer is dodecafluoroheptyl methacrylate;
Above-mentioned modified manometer silicon dioxide is the nano silicon of process oleic acid modification in (1), and the particle diameter of the nano silicon before modification is 30 ± 5nm;
Above-mentioned anionic emulsifier is Sodium dodecylbenzene sulfonate;
Above-mentioned nonionic initiator is OP-10;
Above-mentioned initiator is a kind of in ammonium persulphate, Sodium Persulfate, Potassium Persulphate;
Above-mentioned buffer reagent is a kind of in sodium bicarbonate, saleratus.
The preparation method of the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin:
By 60g deionized water, above-mentioned initiator quality 1/3, above-mentioned all emulsifying agents, above-mentioned organosilane monomer quality 1/3, above-mentioned organic fluorine monomer mass 1/3,1/3 the joining agitator, constant pressure funnel, N be housed of 1/3 and above-mentioned St quality of above-mentioned AA quality
2in the 250mL four-hole bottle of control device and constant temperature water bath, again above-mentioned modified manometer silicon dioxide is put into the ultrasonic dispersion of the beaker that contains 20ml deionized water 2h, the mixed solution of gained joins in four-hole bottle in the lump, logical N under the condition that is 210r/min in normal temperature, stirring velocity
2then 30min moves into temperature control is in the water-bath of 75 ℃; Stir after 10min, by constant voltage separating funnel, drip continuously remaining monomer, stirring velocity is 210r/min, drips off, then constant temperature 30min in 2h; In remaining water, dissolve above-mentioned buffer reagent and residue initiator, then join in four-hole boiling flask, temperature maintains 75 ℃, drips wherein the mix monomer of remaining St and residue organosilicon, organic fluorine, all monomers dropwise in 2h, then at 75 ℃, react 3h; Cooling reactant regulates pH value to 7-8 afterwards, and discharging, filtration obtain the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin.
Embodiment
Embodiment 1:
A preparation method for the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin, adopts following steps:
(1) nano silicon pass through oleic acid modification, quality or the volume of each component are as follows:
The nano silicon 4g-6g that gets certain particle diameter puts into the beaker of 250ml, then adds the ultrasonic dispersion of the deionized water 2h-3h of 90ml-100ml; In ultrasonic scattered mixture, add 1.5ml-2ml oleic acid, room temperature condition lower magnetic force high-speed stirring 1.5h-2h; The ammoniacal liquor 4ml-5ml that gets concentration and be 25wt.% adds in mixing solutions, then magnetic agitation 12h left and right; To adding concentration in mixed solution, be that to be neutralized to pH be 7 for the hydrochloric acid of 30wt.% more afterwards.Take out mixing solutions and put into the centrifugal 30min of supercentrifuge, the water that is 1: 1 by volume ratio the centrifugal product obtaining and alcohol mixeding liquid clean 3 times, remove oleic acid unnecessary in nano silicon, finally by the centrifugal solid powder/particle obtaining dry 24h in the baking oven of 50 ℃, take out, make modified manometer silicon dioxide, wait until and prepare the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin.
(2) prepare the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin, the quality of each component is as follows:
By the deionized water of 60g, above-mentioned initiator quality 1/3, above-mentioned all emulsifying agents, above-mentioned organosilane monomer quality 1/3, above-mentioned organic fluorine monomer mass 1/3,1/3 the joining agitator, constant pressure funnel, N be housed of 1/3 and above-mentioned St quality of above-mentioned AA quality
2in the 250ml four-hole bottle of control device and constant temperature water bath, again above-mentioned modified manometer silicon dioxide is put into the ultrasonic dispersion of the beaker that contains 20ml deionized water 2h, the mixed solution of gained joins in four-hole bottle in the lump, logical N under the condition that is 210r/min in normal temperature, stirring velocity
230min, then moves into temperature control and is in the water-bath of 75 ℃; Stir after 10min, by constant voltage separating funnel, drip continuously remaining monomer, stirring velocity is 210r/min, drips off, then constant temperature 30min in 2h; In remaining water, dissolve above-mentioned buffer reagent and residue initiator, then join in four-hole boiling flask, temperature maintains 75 ℃, drips wherein the mix monomer of remaining St and residue organosilicon, organic fluorine, all monomers dropwise in 2h, then at 75 ℃, react 3h; Cooling reactant afterwards, adjusting pH is 7-8, discharging, filters and obtain the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin.
Embodiment 2:
A preparation method for the fluoro-silicon modified aqueous resin of organic inorganic hybridization, adopts following steps:
(1) nano silicon pass through oleic acid modification, preparation method is as described in above-described embodiment 1.
(2) prepare the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin, the quality of each component is as follows:
Preparation method is as described in above-described embodiment 1.
Embodiment 3:
A preparation method for the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin, adopts following steps:
(1) nano silicon pass through oleic acid modification, preparation method is as described in above-described embodiment 1.
(2) prepare the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin, the quality of each component is as follows:
Preparation method is as described in above-described embodiment 1.
Claims (1)
1. a preparation method for the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin, its characterization step is:
(1) nano silicon pass through oleic acid modification, quality or the volume of each component are as follows:
The nano silicon 4g-6g that gets certain particle diameter adds in the beaker of 250ml, then adds the ultrasonic dispersion of the deionized water 2h-3h of 90ml-100ml; The oleic acid that adds 1.5ml-2ml in ultrasonic scattered mixture, high speed magnetic stirring 1.5h-2h under room temperature condition; The ammoniacal liquor 4ml-5ml that gets concentration and be 25wt.% adds in mixing solutions, then magnetic agitation 12h left and right; To adding concentration in mixed solution, be that to be neutralized to pH be 7 for the hydrochloric acid of 30wt.% more afterwards, take out mixing solutions and put into the centrifugal 30min of supercentrifuge, the water that is 1: 1 by volume ratio the centrifugal product obtaining and alcohol mixeding liquid clean 3 times, remove oleic acid unnecessary in nano silicon, finally by the centrifugal solid powder/particle obtaining dry 24h in the baking oven of 50 ℃, take out, make modified manometer silicon dioxide, wait until and prepare the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin;
(2) prepare the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin, the quality of each component is as follows:
Above-mentioned organosilane monomer is vinyltriethoxysilane;
Above-mentioned organic fluorine monomer is dodecafluoroheptyl methacrylate;
Above-mentioned modified manometer silicon dioxide is the nano silicon of process oleic acid modification in (1), and the particle diameter of the nano silicon before modification is 30 ± 5nm;
Above-mentioned anionic emulsifier is Sodium dodecylbenzene sulfonate;
Above-mentioned nonionic initiator is OP-10;
Above-mentioned initiator is a kind of in ammonium persulphate, Sodium Persulfate, Potassium Persulphate;
Above-mentioned buffer reagent is a kind of in sodium bicarbonate, saleratus;
The preparation method of the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin:
By the deionized water of 60g, above-mentioned initiator quality 1/3, above-mentioned all emulsifying agents, above-mentioned organosilane monomer quality 1/3, above-mentioned organic fluorine monomer mass 1/3,1/3 the joining agitator, constant pressure funnel, N be housed of 1/3 and above-mentioned St quality of above-mentioned AA quality
2in the 250ml four-hole bottle of control device and constant temperature water bath, again above-mentioned modified manometer silicon dioxide is put into the ultrasonic dispersion of the beaker that contains 20ml deionized water 2h, the mixed solution of gained joins in four-hole boiling flask in the lump, logical N under the condition that is 210r/min in normal temperature, stirring velocity
230min, then moves into temperature control and is in the water-bath of 75 ℃; Stir after 10min, by constant voltage separating funnel, drip continuously remaining monomer, stirring velocity is 210r/min, drips off, then constant temperature 30min in 2h; In remaining water, dissolve above-mentioned buffer reagent and residue initiator, then join in four-hole boiling flask, temperature maintains 75 ℃, drips wherein the mix monomer of remaining St and residue organosilicon, organic fluorine, all monomers dropwise in 2h, then at 75 ℃, react 3h; Cooling reactant afterwards, adjusting pH is 7-8, discharging, filters and obtain the fluoro-silicon modified Nano of organic inorganic hybridization water-base resin.
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| CN104231147B (en) * | 2014-09-26 | 2017-03-29 | 江苏日出化工有限公司 | A kind of preparation method of acrylate fluorinated acrylate and Ludox hydridization latex |
| CN107266939A (en) * | 2016-04-08 | 2017-10-20 | 中国石油天然气股份有限公司 | The method of modifying of Nano carbon white |
| CN105859937A (en) * | 2016-04-25 | 2016-08-17 | 山东玉皇化工有限公司 | Fluorine-silicon modified styrene-acrylic emulsion with hydrophobic property and preparing method thereof |
| CN106318091B (en) * | 2016-08-19 | 2019-08-02 | 北京金汇利应用化工制品有限公司 | A kind of aqueous dual-component organic-inorganic hybridization coating resin and preparation method thereof |
| CN107163702B (en) * | 2017-06-02 | 2019-08-27 | 江苏晨光涂料有限公司 | A kind of erasable, antireflection coating and preparation method thereof |
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| US7241830B2 (en) * | 2004-05-07 | 2007-07-10 | Ppg Industries Ohio, Inc. | Organic solvent-free film-forming compositions, multi-layer composite coatings, and related methods |
| CN101921358A (en) * | 2010-09-02 | 2010-12-22 | 北京奥力助兴石化有限公司 | F-Si acrylate copolymer and use method thereof as paint sealant |
| CN102041681A (en) * | 2009-10-14 | 2011-05-04 | 江南大学 | Method for preparing short-chain branch water and oil repellent finishing agent containing modified nano-oxide and fluorine |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7241830B2 (en) * | 2004-05-07 | 2007-07-10 | Ppg Industries Ohio, Inc. | Organic solvent-free film-forming compositions, multi-layer composite coatings, and related methods |
| CN102041681A (en) * | 2009-10-14 | 2011-05-04 | 江南大学 | Method for preparing short-chain branch water and oil repellent finishing agent containing modified nano-oxide and fluorine |
| CN101921358A (en) * | 2010-09-02 | 2010-12-22 | 北京奥力助兴石化有限公司 | F-Si acrylate copolymer and use method thereof as paint sealant |
Non-Patent Citations (1)
| Title |
|---|
| 段涛等.核壳纳米复合材料的研究进展.《材料导报：综述篇》.2009,第23卷(第2期),第19-23页. * |
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