CN102336884B - Preparation method for macromonomer modified nanometer silica aqueous silica sol and light-cured aqueous polyurethane nanometer composite emulsion of same - Google Patents
Preparation method for macromonomer modified nanometer silica aqueous silica sol and light-cured aqueous polyurethane nanometer composite emulsion of same Download PDFInfo
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Abstract
The invention relates to a preparation method for macromonomer modified nanometer silica aqueous silica sol and light-cured aqueous polyurethane nanometer composite emulsion. According to the invention, since there are a great amount of silanol groups on the surface of unmodified nanometer silica, water-soluble polyethylene glycol acrylate macromonomers are employed and enabled to adhere to the surface of aqueous nanometer silica through hydrogen bonding, and the macromonomer modified nanometer silica aqueous silica sol is formed; the macromonomer modified nanometer silica aqueous silica sol is introduced in situ during the preparation process for light-cured aqueous polyurethane emulsion so as to prepare the light-cured aqueous polyurethane nanometer composite emulsion. The nanometer composite emulsion prepared by the method has good dispersion stability; simultaneously, nanometer silica has very good dispersibility in a polyurethane membrane; introduction of inorganic nanometer silica enables mechanical properties of a light-cured coating to be obviously improved. Obtained dispersion in the invention can be extensively applied in the field of surface coatings for high damage resistant and wear resistant woodenwares, metals, plastics, etc.
Description
Technical field
The present invention relates to a kind of novel organic-inorganic nano-composite emulsion, mainly relate to a kind of ultraviolet light solidfication water polyurethane nano-composite emulsion preparation method of environmental protection.Belong to new material technology field.
Background technology
In recent years, ultraviolet light solidfication water polyurethane emulsion (WPU) has the advantages such as good combination property, efficient, energy-saving and environmental protection, safety and sanitation, in fields such as coating, tackiness agent, is well applied.But the aspects such as the mechanical property of photo-crosslinking latex film (intensity, modulus) can't compare favourably with traditional cross-linked type polyurethane, thereby have limited this widespread use of filming.The photocuring aqueous polyurethane coating in use easily is worn and damages in addition, thereby has limited its further application, therefore be badly in need of in actual applications improving the mechanical property of coatingsurface as surface hardness, wear resistance and scratch resistance etc.Photocuring organic-inorganic nano composite emulsion combines water-based technology, nanotechnology and photocuring technology, combine organic and inorganic and nano material characteristic, be preparation high-performance, the very promising method of functional emulsion, be subject to domestic and international researchist's extensive concern.The research report of at present relevant inorganic nano material (as nano silicon, organic clay, polysilsesquioxane, carbon nanotube) composite modified water polyurethane emulsion or light-cured polyurethane system is more.Nano silicon has the advantages such as high rigidity, low refractive index, is widely used in strengthening polymeric system." colloidal polymer science " (Colloid Polym Sci 2006, 284, 1067) introduce by aqueous silica sol and photocuring aqueous urethane acrylate dispersoid carry out physical blending with the mechanical property of raising coatingsurface as hardness etc., but owing to just nano silicon dioxide sol and aqueous polyurethane acrylate system being carried out to simple physical blending, lack enough interactions between inorganic nano silicon-dioxide and organic urethane acrylate, easily making nano silicon produce reunites, it is not very remarkable that thereby the surface mechanical properties that makes coating improves.The present invention is on above working foundation, and the present invention selects water-soluble polyethylene glycol esters of acrylic acid macromonomer, by hydrogen bond action, is adsorbed on the water-based nano silicon dioxide surface, forms the macromonomer improved silica water-sol.Then introduce the nano silicon water-sol of above macromonomer modification at photocuring aqueous polyurethane emulsion preparation process situ, prepare photocuring aqueous polyurethane nano composite emulsion.The nano-composite emulsion that adopts above method to prepare has dispersion stabilization preferably, and nano silicon has extraordinary dispersiveness in polyurethane film simultaneously.
Summary of the invention
The object of the invention is to provide a kind of photocuring aqueous polyurethane film mechanical strength and modulus and coatingsurface mechanical property thereof preparation method as the ultraviolet light solidfication water polyurethane nano-composite emulsion of hardness, wear resistance that improves.Select the water-soluble polyethylene glycol esters of acrylic acid macromonomer improved silica water-sol, then prepare the aqueous polyurethane nano composite emulsion at the aqueous polyurethane emulsion building-up process situ macromonomer improved silica water-sol, make nano silicon there is good dispersiveness in the coating of resulting dispersion and preparation, thereby the mechanical property that significantly improves photocuring aqueous polyurethane film and coatingsurface is as hardness, wear resistance.
Technical scheme of the present invention:
1, the preparation method of a kind of macromonomer modified manometer silicon dioxide water silicon sol and photocuring aqueous polyurethane nano composite emulsion thereof, it is characterized in that forming and comprise: the oligomer polyol of 45-60wt%, the diisocyanate cpd of 15-30wt%, multi-hydroxy carboxy acid's compound of 3-6wt%, the unsaturated double-bond acrylic compound of the hydroxyl of 4-8wt%, the aminated compounds of 3-6wt%, the macromonomer modified manometer silicon dioxide water silicon of 5-20wt% is molten; Preparation method's step is:
(1). synthesizing of the macromonomer modified manometer silicon dioxide water-sol: add the modification macromonomer aqueous solution or modification macromonomer by proportioning in the nano silicon water-sol, 25 ℃ of stirring reactions 24 hours, obtain the macromonomer modified manometer silicon dioxide water-sol.
(2). synthesizing of photocuring aqueous polyurethane nano composite emulsion: press proportioning in diisocyanate cpd, drip oligomer polyol and catalyzer, react 1-2h at 50 ℃ after dropwising, then be warming up to gradually 60 ℃, add multi-hydroxy carboxy acid's compound powder, at 60 ℃, reacted 2-3h, drip unsaturated double-bond acrylic compound and the phenolic inhibitor of hydroxyl, at 70 ℃ of reaction 2-3h, until infrared spectra detects the completely dissolve of NCO group characteristic peak.Drip aminated compounds, at 40～50 ℃ of reaction 1-2 hour, drip the macromonomer modified manometer silicon dioxide water-sol, 50 ℃ of reactions 1 hour, finally add deionized water, violent stirring emulsification, obtain photocuring aqueous polyurethane nano composite emulsion.
2. the preparation method of ultraviolet cured silica sol modified aqueous urethane acrylate dispersoid according to claim 1, it is characterized in that described macromonomer is methoxy poly (ethylene glycol), polyethyleneglycol diacrylate. methoxy polyethylene glycol acrylate, methoxypolyethylene glycol methacrylic ester, molecular weight ranges is 400-2000.
3. the preparation method of ultraviolet cured silica sol modified aqueous urethane acrylate dispersoid according to claim 1, is characterized in that described silica hydrosol particle size range is 10-1000nm, and the pH scope is 8-11, and its solid content is 10-50%.
4. the preparation method of ultraviolet cured silica sol modified aqueous urethane acrylate dispersoid according to claim 1, it is characterized in that described diisocyanate cpd is selected from 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate or isophorone diisocyanate, ditan 4,4 '-vulcabond, oneself two the support vulcabond, Methylcyclohexyl diisocyanate, 2,2,4-trimethylammonium hexamethylene diisocyanate.
5. the preparation method of ultraviolet cured silica sol modified aqueous urethane acrylate dispersoid according to claim 1, it is characterized in that described oligomer polyol selects polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol, polycaprolactone polyol, polycarbonate diol, polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO), polyethylene glycol adipate, poly adipate succinic acid ester, ethylene glycol terephthalate, mutual-phenenyl two acid bromide two alcohol ester or copolyesters, its molecular weight ranges is 400-6000.
6. the preparation method of ultraviolet cured silica sol modified aqueous urethane acrylate dispersoid according to claim 1, is characterized in that described multi-hydroxy carboxy acid's compound selects dimethylol propionic acid or dimethylolpropionic acid.
7. the preparation method of ultraviolet cured silica sol modified aqueous urethane acrylate dispersoid according to claim 1, the unsaturated double-bond acrylic compound that it is characterized in that described hydroxyl is selected Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate or Rocryl 410, pentaerythritol triacrylate etc.
8. the preparation method of ultraviolet cured silica sol modified aqueous urethane acrylate dispersoid according to claim 1, is characterized in that described aminated compounds selects ammoniacal liquor, triethylamine, dimethylethanolamine, trolamine etc.
Beneficial effect of the present invention: the preparation method of a kind of macromonomer modified manometer silicon dioxide of the present invention water silicon sol and photocuring aqueous polyurethane nano composite emulsion thereof compared with prior art has following advantage:
(1). select the monomer modified aqueous silica sol of water-soluble macromolecule, method of modifying technique is simple, and reaction is easy to control, reproducible.
(2), adopt acetone method to synthesize the UV-curable waterborne polyaminoester emulsion, and introducing the macromonomer modified manometer silicon dioxide water-sol at Water-borne UV-Curable Polyurethane Acrylate building-up process situ compares with the unmodified nano silicon water-sol and by above both physical blendings, the macromonomer modified manometer silicon dioxide water-sol and in-situ compositing can make nano silicon well be dispersed in polyurethane matrix, and can significantly improve the mechanical property of coating.
The accompanying drawing explanation
The SEM figure of Fig. 1 embodiment 1 pure polyurethane coating.
The Polyurethane Nanocomposite Coatings SEM figure of the unmodified silicon sol of Fig. 2.
The Polyurethane Nanocomposite Coatings SEM figure of Fig. 3 macromonomer modified silicasol.
Embodiment
Below in conjunction with embodiment, the present invention is further explained in detail the present invention in order to explain better.
Reference examples prepared for not carrying out silica sol modified photocuring aqueous polyurethane emulsion and latex film by 1 example of embodiment.
Add 24.5g isophorone diisocyanate (IPDI) and four dibutyl tin laurates (DBTDL) catalyzer in the 250mL four-hole bottle, in dropping funnel, add 31.5g polyoxyethylene glycol (PEG400) to be dripped, temperature is controlled at 40-50 ℃, reaction 1-1.5 hour, survey the content of NCO by the Di-n-Butyl Amine method, when approaching theoretical value, NCO content adds 2.85g dimethylolpropionic acid (DMPA), temperature of reaction 60-70 ℃, reaction 2-3 hour, approach theoretical value at NCO content, drip 2.6g Hydroxyethyl acrylate (HEA) (containing the 0.1g stopper) and temperature is risen to 70 ℃, reaction 3-4 hour, infrared detection is carried out in sampling, observe NCO group characteristic peak 2270cm
-1, until its completely dissolve obtains polyurethane prepolymer.Get the quantitative prepolymer four-hole boiling flask of packing into, calculate the triethylamine add-on by 1: 1 mol ratio, drip triethylamine, carry out neutralization reaction approximately 0.5 hour under 50 ℃, drip a certain amount of silica hydrosol (10wt%), and react 0.5 hour, finally drip the emulsification of deionized water violent stirring and remove acetone with Rotary Evaporators and obtain the nano-composite emulsion that solid content is 20%.Take a certain amount of composite emulsion, the light trigger (Irgacure2959) that adds 3-5%, ultrasonic dissolution disperses, and in the tetrafluoroethylene template, pours into a mould film forming, in 60 ℃ of baking ovens, drying is 6 hours, and last institute's film forming photocuring under ultraviolet lamp obtains the photo-crosslinking polyurethane film in 2 minutes.
2 examples of embodiment are not for carrying out silica sol modified photocuring aqueous polyurethane composite emulsion and the reference examples of composite emulsion film preparation
Add 24.5g isophorone diisocyanate (IPDI) and four dibutyl tin laurates (DBTDL) catalyzer in the 250mL four-hole bottle, in dropping funnel, add 31.5g polyoxyethylene glycol (PEG400) to be dripped, temperature is controlled at 40-50 ℃, reaction 1-1.5 hour, survey the content of NCO by the Di-n-Butyl Amine method, when approaching theoretical value, NCO content adds 2.85g dimethylolpropionic acid (DMPA), temperature of reaction 60-70 ℃, reaction 2-3 hour, approach theoretical value at NCO content, drip 2.6g Hydroxyethyl acrylate (HEA) (containing the 0.1g stopper) and temperature is risen to 70 ℃, reaction 3-4 hour, infrared detection is carried out in sampling, observe NCO group characteristic peak 2270cm
-1, until its completely dissolve obtains polyurethane prepolymer.Get the quantitative prepolymer four-hole boiling flask of packing into, calculate the triethylamine add-on by 1: 1 mol ratio, drip triethylamine, carry out neutralization reaction approximately 0.5 hour under 50 ℃, drip a certain amount of unmodified silica hydrosol, and react 0.5 hour, finally drip the emulsification of deionized water violent stirring and remove acetone with Rotary Evaporators and obtain the nano-composite emulsion that solid content is 20%.Take a certain amount of composite emulsion, the light trigger (Irgacure2959) that adds 3-5%, ultrasonic dissolution disperses, and in the tetrafluoroethylene template, pours into a mould film forming, in 60 ℃ of baking ovens, drying is 6 hours, and last institute's film forming photocuring under ultraviolet lamp obtains the photo-crosslinking polyurethane film in 2 minutes.
Synthesizing of embodiment 3 macromonomer modified manometer silicon dioxide water silicon sol and photocuring aqueous polyurethane nano composite emulsion
(1) macromonomer modified manometer silicon dioxide water silicon sol
Get proper amount of silicon colloidal sol, add in the there-necked flask of 100mL, by 5% of the quality of silicon sol, add modification macromonomer PEGM1 or PEGM2 or PEG, stirring 24h. silica sol particle surface under 25 ℃ has hydroxyl, can and macromonomer between form hydrogen bond action,
(2) photocuring aqueous polyurethane nano composite emulsion is synthetic
Add 24.5g isophorone diisocyanate (IPDI) and four dibutyl tin laurates (DBTDL) catalyzer in the 250mL four-hole bottle, in dropping funnel, add 31.5g polyoxyethylene glycol (PEG400) to be dripped, temperature is controlled at 40-50 ℃, reaction 1-1.5 hour, survey the content of NCO by the Di-n-Butyl Amine method, when approaching theoretical value, NCO content adds 2.85g dimethylolpropionic acid (DMPA), temperature of reaction 60-70 ℃, reaction 2-3 hour, approach theoretical value at NCO content, drip 2.6g Hydroxyethyl acrylate (HEA) (containing the 0.1g stopper) and temperature is risen to 70 ℃, reaction 3-4 hour, infrared detection is carried out in sampling, observe NCO group characteristic peak 2270cm
-1, until its completely dissolve obtains polyurethane prepolymer.Get the quantitative prepolymer four-hole boiling flask of packing into, calculate the triethylamine add-on by 1: 1 mol ratio, drip triethylamine, carry out neutralization reaction approximately 0.5 hour under 50 ℃, drip a certain amount of macromonomer improved silica water-sol, and react 0.5 hour, finally drip the emulsification of deionized water violent stirring and remove acetone with Rotary Evaporators and obtain the nano-composite emulsion that solid content is 20%.Take a certain amount of composite emulsion, the light trigger (Irgacure2959) that adds 3-5%, ultrasonic dissolution disperses, and in the tetrafluoroethylene template, pours into a mould film forming, in 60 ℃ of baking ovens, drying is 6 hours, and last institute's film forming photocuring under ultraviolet lamp obtains the photo-crosslinking polyurethane film in 2 minutes.
Claims (7)
1. the preparation method of a photocuring aqueous polyurethane nano composite emulsion, it is characterized in that forming and comprise: the oligomer polyol of 45-60wt%, the diisocyanate cpd of 15-30wt%, multi-hydroxy carboxy acid's compound of 3-6wt%, the unsaturated double-bond acrylic compound of the hydroxyl of 4-8wt%, the aminated compounds of 3-6wt%, the macromonomer modified manometer silicon dioxide water-sol of 5-20wt%; Preparation method's step is:
(1) the macromonomer modified manometer silicon dioxide water-sol is synthetic: add the above-mentioned modification macromonomer aqueous solution or modification macromonomer in the nano silicon water-sol by proportioning, 25 ℃ of stirring reactions 24 hours, obtain the macromonomer modified manometer silicon dioxide water-sol; Described macromonomer is methoxy poly (ethylene glycol), polyethyleneglycol diacrylate, methoxy polyethylene glycol acrylate, methoxypolyethylene glycol methacrylic ester, and molecular weight ranges is 400-2000;
(2) photocuring aqueous polyurethane nano composite emulsion is synthetic: press proportioning in diisocyanate cpd, drip oligomer polyol and catalyzer, react 1-2h at 50 ℃ after dropwising, then be warming up to gradually 60 ℃, add multi-hydroxy carboxy acid's compound powder, reacted 2-3h at 60 ℃, drip unsaturated double-bond acrylic compound and the phenolic inhibitor of hydroxyl, at 70 ℃ of reaction 2-3h, until infrared spectra detects the completely dissolve of NCO group characteristic peak, drip aminated compounds, at 40～50 ℃ of reaction 1-2 hour, drip the macromonomer modified manometer silicon dioxide water-sol, 50 ℃ of reactions 1 hour, finally add deionized water, violent stirring emulsification, obtain photocuring aqueous polyurethane nano composite emulsion.
2. a kind of preparation method of photocuring aqueous polyurethane nano composite emulsion according to claim 1, is characterized in that described silica hydrosol particle size range is 10-1000nm, and the pH scope is 8-11, and its solid content is 10-50%.
3. a kind of preparation method of photocuring aqueous polyurethane nano composite emulsion according to claim 1, it is characterized in that described diisocyanate cpd is selected from 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate or isophorone diisocyanate, ditan 4,4 '-vulcabond, oneself two support vulcabond, Methylcyclohexyl diisocyanates, 2,2,4-trimethylammonium hexamethylene diisocyanate.
4. a kind of preparation method of photocuring aqueous polyurethane nano composite emulsion according to claim 1, it is characterized in that described oligomer polyol selects polyoxyethylene glycol, polypropylene glycol, polytetrahydrofuran diol, polycaprolactone dibasic alcohol, polycarbonate diol, polyoxyethylene-poly-oxypropylene polyoxyethylene, polyethylene glycol adipate, poly adipate succinic acid ester, its molecular weight ranges is 400-6000.
5. a kind of preparation method of photocuring aqueous polyurethane nano composite emulsion according to claim 1, is characterized in that described multi-hydroxy carboxy acid's compound selects dimethylol propionic acid or dimethylolpropionic acid.
6. a kind of preparation method of photocuring aqueous polyurethane nano composite emulsion according to claim 1, is characterized in that the unsaturated double-bond acrylic compound of described hydroxyl is selected Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate or Rocryl 410, pentaerythritol triacrylate.
7. a kind of preparation method of photocuring aqueous polyurethane nano composite emulsion according to claim 1, is characterized in that described aminated compounds selects triethylamine, dimethylethanolamine, trolamine.
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| CN106854355B (en) * | 2016-12-30 | 2018-11-27 | 深圳大学 | Waterborne, polycarbonate modified silicasol lotion and preparation method thereof |
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| CN111019502B (en) * | 2019-12-06 | 2021-05-25 | 浙江工业大学之江学院 | Preparation method of polyurethane coating, product and application thereof |
| CN112708099B (en) * | 2021-01-11 | 2022-05-03 | 北京化工大学 | Nano silica sol hybrid polyurethane acrylate with photo-curable double-bond groups and preparation method thereof |
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Application publication date: 20120201 Assignee: WUXI JIE YANG ENERGY SAVING TECHNOLOGY CO., LTD. Assignor: Jiangnan University Contract record no.: 2014320000745 Denomination of invention: Preparation method for macromonomer modified nanometer silica aqueous silica sol and light-cured aqueous polyurethane nanometer composite emulsion of same Granted publication date: 20130612 License type: Exclusive License Record date: 20141216 |
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