CN104448235A - Method for preparing water-resistant, weather-resistant, UV-curable and hyperbranched waterborne polyurethane resin - Google Patents
Method for preparing water-resistant, weather-resistant, UV-curable and hyperbranched waterborne polyurethane resin Download PDFInfo
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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- C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
- C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- C09D175/04—Polyurethanes
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Abstract
The invention relates to a method for preparing water-resistant, weather-resistant, UV-curable and hyperbranched waterborne polyurethane resin. According to the method, polyester waterborne polyurethane resin with relatively poor water resistance and weather resistance is modified by using the unique water resistance, weather resistance, solvent resistance and low-temperature resistance of macromolecular organosilicon. Polyester waterborne polyurethane is subjected to principal chain modification by organosilicon, so as to obtain polyester waterborne polyurethane, of which the principal chain contains organosilicon; after the polymer is subjected to film forming, an organosilicon chain segment in a molecular structure is prone to surface aggregation orientation, and a polyurethane chain segment in the molecular structure faces to an inner layer. Thus, a modified polyurethane coating film is endowed with excellent water resistance, solvent resistance and weather resistance while the polyester polyurethane resin can have excellent adhesive power, hardness, curing rate and the like.
Description
Technical field
The invention belongs to preparation field that is water-fast, weather-proof, uV curable polyurethane material, be specifically related to a kind of water-fast, weather-proof preparation method with the hyperbranched aqueous polyurethane emulsion of ultraviolet light polymerization performance.
Background introduction
UV-Curing Waterborne Resin inherit and development many advantages of traditional UV curing technology and water-borne coatings technology, as simple in low cost, low viscosity, good coating adaptability, equipment, nontoxicity, nonirritant, uninflammability etc.Due to the advantages of UV curable water-borne resin, developed faster in recent years, its product is applied by various fields.Most aqueous polyurethane is prepared by self-emulsification, but there is hydrophilic radical in the polyurethane structural prepared of this method, makes the water tolerance of film, solvent resistance and weathering resistance poor, thus limit its use range.Although hardness, the sticking power of polyester type aqueous polyurethane film are better than polyether type aqueous urethane, but the ester group facile hydrolysis of polyester polyol, it is poor that polyester type water-based gathers the more polyether type aqueous urethane of the cruel water tolerance of ammonia, the aqueous polyurethane mainly polyether type aqueous urethane that current domestic enterprise produces.Therefore, improvement is carried out to the water tolerance of polyester type aqueous polyurethane and there is realistic meaning.
Organosilicon be a class with repeating unit Si-O key for main chain, and organic group is connected directly between the polymkeric substance on Si atom.It is macromolecular compound that is half organic, half inorganic structure, has organic and characteristic that is mineral compound concurrently, has the performance of many excellences such as good low temperature resistant, weathering resistance, hydrophobicity, physiological inertia and electrical isolation.Use it for the modification of aqueous polyurethane, effectively can improve the water tolerance of film, weather resistant, solvent resistance and slipping.Organic silicon modified aqueous polyurethane is obtained, to improve the water tolerance of coating, solvent resistance, weathering resistance and pollution resistance by introducing Si-O key in polyester type waterborne polyurethane resin main chain.
Summary of the invention
The object of the present invention is to provide one to utilize the macromolecule organic silicon to carry out modification and prepare water-fast, weather-proof, solvent resistance polyester type aqueous polyurethane emulsion and preparation method thereof.Polyester type aqueous polyurethane of the present invention carries out backbone modification through organosilicon and obtains main chain and contain organosilicon polyester type aqueous polyurethane, and after this polymer film forming, the silicone segments in molecular structure is more prone to surface aggregation orientation, and urethane segment is towards internal layer.The excellent water tolerance of modified polyurethane film, solvent resistance and weathering resistance can be given again like this while ensureing sticking power, hardness, solidification rate etc. that polyester urethane resin is excellent.
Technical scheme of the present invention is:
A preparation method for water-fast, weather-proof UV-curable hyperbranched aqueous polyurethane resin, comprises the steps:
(1) synthesis of hyperbranched polyol alcohol: the mixing of a certain amount of tosic acid, dipentaerythritol (DPE), chainextender and dimethylbenzene is added in 250ml single port flask; under nitrogen protection; be warming up to 140 DEG C of isothermal reactions, stopped reaction after hydroxyl value reaches theoretical value.Reaction terminates rear normal hexane repeated precipitation and purifies 3 times, puts into vacuum drying oven for subsequent use, obtains hyperbranched polyol alcohol;
(2) polyester diol and end hydroxyl silicone oil are warming up to 80-100 DEG C respectively, vacuum hydro-extraction process 30min, obtain the polyester diol after dewatering and hydroxy silicon oil;
(3) synthesis of NCO half end capped polyesters type prepolymer: a certain amount of catalyzer and vulcabond are added in 250ml there-necked flask and temperature is risen to 48-50 DEG C of a certain amount of polyester diol of dropping, react and terminate when NCO reaches theoretical value for 3-4 hour, obtain just aggressiveness.Again first mer temperature is controlled at 78-80 DEG C, add chainextender reaction after NCO reaches theoretical value, within 2-3 hour, to cool to 60-65 DEG C add active termination agent, stopper, solvent orange 2 A insulation reaction 3 hours, NCO reaches theoretical value, and reaction stops, and obtains isocyanate-terminated polyester based prepolymers;
(4) synthesis of NCO half blocking silicone type prepolymer: a certain amount of catalyzer and vulcabond are added in 250ml there-necked flask and temperature is risen to 48-50 DEG C of a certain amount of end hydroxyl silicone oil of dropping, react and terminate when NCO reaches theoretical value for 3-4 hour, obtain just aggressiveness.Again first mer temperature is controlled at 78-80 DEG C, add chainextender reaction after NCO reaches theoretical value, within 2-3 hour, to cool to 60-65 DEG C add active termination agent, stopper, solvent orange 2 A insulation reaction 3 hours, NCO reaches theoretical value, and reaction stops, and obtains isocyanate-terminated organic silicon type prepolymer;
(5) preparation of hyperbranched aqueous polyurethane emulsion: a certain amount of catalyzer, hyperbranched polyol alcohol are added in 250ml there-necked flask temperature is risen to 78-80 DEG C, add the isocyanate-terminated polyester based prepolymers of different content and isocyanate-terminated organic silicon type prepolymer under nitrogen atmosphere.Reaction 3-4 hour, the termination reaction when the completely dissolve of-NCO infrared absorption peak.Temperature of reaction is down to 35-40 DEG C, adds a certain amount of neutralizing agent, high speed shear 30min, then add deionized water, emulsification pretreatment 30min, vacuum rotary steam removing solvent orange 2 A, obtains hyperbranched aqueous polyurethane emulsion.
Chainextender described in step (1), (3) and (4) is at least one in dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA);
Catalyzer described in step (3), (4) and (5) is at least one in dibutyl tin laurate, stannous octoate;
Described in step (3) and (4), vulcabond is tolylene diisocyanate (TDI), 4, at least one in 4'-diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) dicyclohexyl methyl hydride two isocyanic acid cruel (HMDI);
Active termination agent described in step (3) and (4) is at least one in Hydroxyethyl acrylate (HEA), hydroxyethyl methylacrylate (HEMA), Propylene glycol monoacrylate (HPA), Rocryl 410 (HPMA), pentaerythritol triacrylate (PETA);
Stopper described in step (3) and (4) is at least one in Resorcinol, p methoxy phenol;
Polyester diol described in step (2) and (3) is at least one in PCDL, polycaprolactone diols, adipate polyester dibasic alcohol;
End hydroxyl silicone oil described in step (2) and (4) is at least one in DOW CORNING SF-8427, OFX-3667, BY16-004;
Described in step (5), neutralizing agent is triethylamine;
Described in step (3), (4) and (5), solvent orange 2 A is acetone.
The invention has the beneficial effects as follows: by above reaction, synthesis obtains water-fast, weather-proof UV-curable hyperbranched aqueous polyurethane cold coating resin.This resin can be used for the water tolerance, weathering resistance, didirtresistance, the thermotolerance that improve coating, can be widely used in the surface that plastics, film, door and window etc. have water-fast, weather-proof, antifouling requirement.
Embodiment
Embodiment 1
The synthesis of hyperbranched polyol alcohol: by 10.16g dipentaerythritol (DPE), 32.25g dimethylol propionic acid (DMPA) and 5ml toluene 250ml there-necked flask, through vacuumizing-Tong nitrogen circulation 3 times to remove oxygen, under nitrogen protection, be warming up to 140 DEG C, react 7 hours, amount according to collecting water after esterification determines reaction end, obtains s-generation hyperbranched polyol alcohol; After experiment terminates, solution is cooled to room temperature, adds acetone solution, and afterwards with normal hexane precipitation-acetone solution-normal hexane precipitation circulation 3 times, filter, product to constant weight, obtains hyperbranched polyol alcohol 35 DEG C of vacuum-dryings;
The synthesis of NCO half end capped polyesters type prepolymer: 0.03g dibutyl tin laurate (DTBDL) and 5.62g isophorone diisocyanate (IPDI) are added in 100ml there-necked flask temperature is risen to 50 DEG C, 25g polycarbonate diol is dripped under nitrogen atmosphere, react and terminate when NCO reaches theoretical value for 4 hours, obtain just aggressiveness.Again first mer temperature is controlled at 80 DEG C, add 0.856g dimethylol propionic acid (DMPA) to react and after NCO reaches theoretical value, within 3 hours, cool to 60 DEG C add the agent of 0.829g hydroxyethyl methylacrylate (HEMA) active termination, 0.01g p methoxy phenol, 5.0g acetone insulation reaction 3 hours, NCO reaches theoretical value, reaction stops, NCO half end capped polyesters type prepolymer;
The synthesis of NCO half blocking silicone type prepolymer: 0.03g dibutyl tin laurate (DTBDL) and 5.62g isophorone diisocyanate (IPDI) are added in 100ml there-necked flask temperature is risen to 50 DEG C, 25g DOW CORNING SF-8427ABA type end hydroxyl silicone oil is dripped under nitrogen atmosphere, react and terminate when NCO reaches theoretical value for 4 hours, obtain just aggressiveness.Again first mer temperature is controlled at 80 DEG C, add 0.856g dimethylol propionic acid (DMPA) to react and after NCO reaches theoretical value, within 3 hours, cool to 60 DEG C add the agent of 0.829g hydroxyethyl methylacrylate (HEMA) active termination, 0.01g p methoxy phenol, 5.0g acetone insulation reaction 3 hours, NCO reaches theoretical value, reaction stops, NCO half blocking silicone type prepolymer;
The preparation of hyperbranched aqueous polyurethane emulsion: 0.09g dibutyl tin laurate (DTBDL), 26.70g hyperbranched polyol alcohol and 15g acetone are added temperature in 250ml there-necked flask and rises to 78 DEG C, adds above NCO half end capped polyesters type prepolymer and NCO half blocking silicone type prepolymer.React 4 hours, the termination reaction when the completely dissolve of-NCO infrared absorption peak.Temperature of reaction is down to 0 DEG C, adds 2.60g triethylamine neutralizing agent, high speed shear 30min, then add 50.0g ionized water, emulsification pretreatment 40min, vacuum rotary steam removing acetone, obtains hyperbranched aqueous polyurethane emulsion.
Embodiment 2
The synthesis of hyperbranched polyol alcohol: by 10.16g dipentaerythritol (DPE), 35.52g dimethylolpropionic acid (DMBA), 3.4g tosic acid and 5ml toluene 250ml there-necked flask, through vacuumizing-Tong nitrogen circulation 3 times to remove oxygen, under nitrogen protection, be warming up to 140 DEG C, react 7 hours, amount according to collecting water after esterification determines reaction end, obtains s-generation hyperbranched polyol alcohol; After experiment terminates, solution is cooled to room temperature, adds acetone solution, and afterwards with normal hexane precipitation-acetone solution-normal hexane precipitation circulation 3 times, filter, product to constant weight, obtains hyperbranched polyol alcohol 35 DEG C of vacuum-dryings;
The synthesis of NCO half end capped polyesters type prepolymer: 0.03g dibutyl tin laurate (DTBDL) and 5.62g isophorone diisocyanate (IPDI) are added in 100ml there-necked flask temperature is risen to 50 DEG C, 25g polycarbonate diol is dripped under nitrogen atmosphere, react and terminate when NCO reaches theoretical value for 4 hours, obtain just aggressiveness.Again first mer temperature is controlled at 80 DEG C, add 0.916g dimethylolpropionic acid (DMBA) to react and after NCO reaches theoretical value, within 3 hours, cool to 60 DEG C add the agent of 0.829g hydroxyethyl methylacrylate (HEMA) active termination, 0.01g Resorcinol, 5.0g acetone insulation reaction 3 hours, NCO reaches theoretical value, reaction stops, NCO half end capped polyesters type prepolymer;
The synthesis of NCO half blocking silicone type prepolymer: 0.03g dibutyl tin laurate (DTBDL) and 5.62g isophorone diisocyanate (IPDI) are added in 100ml there-necked flask temperature is risen to 50 DEG C, 30g DOW CORNING OFX-3667 type end hydroxyl silicone oil is dripped under nitrogen atmosphere, react and terminate when NCO reaches theoretical value for 4 hours, obtain just aggressiveness.Again first mer temperature is controlled at 80 DEG C, add 0.916g dimethylolpropionic acid (DMBA) to react and after NCO reaches theoretical value, within 3 hours, cool to 60 DEG C add the agent of 0.829g hydroxyethyl methylacrylate (HEMA) active termination, 0.01g Resorcinol, 5.0g acetone insulation reaction 3 hours, NCO reaches theoretical value, reaction stops, NCO half blocking silicone type prepolymer;
The preparation of hyperbranched aqueous polyurethane emulsion: 0.09g dibutyl tin laurate (DTBDL), 26.70g hyperbranched polyol alcohol and 15g acetone are added temperature in 250ml there-necked flask and rises to 78 DEG C, adds above NCO half end capped polyesters type prepolymer and NCO half blocking silicone type prepolymer.React 4 hours, the termination reaction when the completely dissolve of-NCO infrared absorption peak.Temperature of reaction is down to 0 DEG C, adds 2.60g triethylamine neutralizing agent, high speed shear 30min, then add 50.0g ionized water, emulsification pretreatment 40min, vacuum rotary steam removing acetone, obtains hyperbranched aqueous polyurethane emulsion.
Claims (2)
1. a preparation method for water-fast, weather-proof UV-curable hyperbranched aqueous polyurethane resin, its characterization step is:
(1) synthesis of hyperbranched polyol alcohol: the mixing of a certain amount of tosic acid, dipentaerythritol (DPE), chainextender and dimethylbenzene is added in 250ml single port flask, under nitrogen protection, be warming up to 135-140 DEG C of isothermal reaction, stopped reaction after hydroxyl value reaches theoretical value; Reaction terminates rear normal hexane repeated precipitation and purifies 3 times, puts into vacuum drying oven for subsequent use, obtains hyperbranched polyol alcohol;
(2) polyester diol and end hydroxyl silicone oil are warming up to 80-100 DEG C respectively, vacuum hydro-extraction process 30min, obtain the polyester diol after dewatering and hydroxy silicon oil;
(3) synthesis of NCO half end capped polyesters type prepolymer: a certain amount of catalyzer and vulcabond are added in 250ml there-necked flask and temperature is risen to 48-50 DEG C of a certain amount of polyester diol of dropping, react and terminate when NCO reaches theoretical value for 3-4 hour, obtain just aggressiveness; Again first mer temperature is controlled at 78-80 DEG C, add chainextender reaction after NCO reaches theoretical value, within 2-3 hour, to cool to 60-65 DEG C add active termination agent, stopper, solvent orange 2 A insulation reaction 3 hours, NCO reaches theoretical value, and reaction stops, and obtains isocyanate-terminated polyester based prepolymers;
(4) synthesis of NCO half blocking silicone type prepolymer: a certain amount of catalyzer and vulcabond are added in 250ml there-necked flask and temperature is risen to 48-50 DEG C of a certain amount of end hydroxyl silicone oil of dropping, react and terminate when NCO reaches theoretical value for 3-4 hour, obtain just aggressiveness; Again first mer temperature is controlled at 78-80 DEG C, add chainextender reaction after NCO reaches theoretical value, within 2-3 hour, to cool to 60-65 DEG C add active termination agent, stopper, solvent orange 2 A insulation reaction 3 hours, NCO reaches theoretical value, and reaction stops, and obtains isocyanate-terminated organic silicon type prepolymer;
(5) preparation of hyperbranched aqueous polyurethane emulsion: a certain amount of catalyzer, hyperbranched polyol alcohol are added in 250ml there-necked flask temperature is risen to 78-80 DEG C, add the isocyanate-terminated polyester based prepolymers of different content and isocyanate-terminated organic silicon type prepolymer under nitrogen atmosphere; Reaction 3-4 hour, the termination reaction when the completely dissolve of-NCO infrared absorption peak; Temperature of reaction is down to 35-40 DEG C, adds a certain amount of neutralizing agent, high speed shear 30min, then add deionized water, emulsification pretreatment 30min, vacuum rotary steam removing solvent orange 2 A, obtains hyperbranched aqueous polyurethane emulsion.
2. the preparation method of a kind of water-fast, weather-proof UV-curable hyperbranched aqueous polyurethane resin as claimed in claim 1, is characterized in that:
Chainextender described in step (1), (3) and (4) is at least one in dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA);
Catalyzer described in step (3), (4) and (5) is at least one in dibutyl tin laurate, stannous octoate;
Described in step (3) and (4), vulcabond is tolylene diisocyanate (TDI), 4, at least one in 4'-diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI) dicyclohexyl methyl hydride two isocyanic acid cruel (HMDI);
Active termination agent described in step (3) and (4) is at least one in Hydroxyethyl acrylate (HEA), hydroxyethyl methylacrylate (HEMA), Propylene glycol monoacrylate (HPA), Rocryl 410 (HPMA), pentaerythritol triacrylate (PETA);
Stopper described in step (3) and (4) is at least one in Resorcinol, p methoxy phenol;
Polyester diol described in step (2) and (3) is at least one in PCDL, polycaprolactone diols, adipate polyester dibasic alcohol;
End hydroxyl silicone oil described in step (2) and (4) is at least one in DOW CORNING SF-8427, OFX-3667, BY16-004;
Described in step (5), neutralizing agent is triethylamine;
Described in step (3), (4) and (5), solvent orange 2 A is acetone.
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| CN201410798979.1A CN104448235A (en) | 2014-12-19 | 2014-12-19 | Method for preparing water-resistant, weather-resistant, UV-curable and hyperbranched waterborne polyurethane resin |
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| CN201410798979.1A CN104448235A (en) | 2014-12-19 | 2014-12-19 | Method for preparing water-resistant, weather-resistant, UV-curable and hyperbranched waterborne polyurethane resin |
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| CN105482060A (en) * | 2015-12-25 | 2016-04-13 | 华南理工大学 | Hyperbranched waterborne polyurethane acrylate emulsion as well as preparation method and application thereof |
| CN105542174A (en) * | 2016-01-13 | 2016-05-04 | 广东工业大学 | Silicone-modified hyperbranched polyurethane and preparation method and application thereof |
| CN107353387A (en) * | 2017-08-03 | 2017-11-17 | 山东天庆科技发展有限公司 | A kind of aqueous anionic polyurethane emulsion and preparation method and application |
| CN107674189A (en) * | 2017-09-30 | 2018-02-09 | 合众（佛山）化工有限公司 | A kind of height divides hyperbranched Si modification unsaturated polyester resin and preparation method thereof admittedly |
| CN108752563A (en) * | 2018-05-24 | 2018-11-06 | 哈尔滨工业大学无锡新材料研究院 | Aqueous hyperbranched structurally-modified polyether polyols of one kind and preparation method thereof and selfreparing diffusing reflection coating composition |
| CN110105553A (en) * | 2019-04-04 | 2019-08-09 | 湖南师范大学 | Ester modified itaconic acid base water borne UV curing resin of hyperbranched poly and preparation method thereof |
| CN113372530A (en) * | 2021-05-19 | 2021-09-10 | 万华化学集团股份有限公司 | Polyurethane or polyurethane urea aqueous dispersion, preparation method thereof and aqueous clothing leather base |
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| CN105482060A (en) * | 2015-12-25 | 2016-04-13 | 华南理工大学 | Hyperbranched waterborne polyurethane acrylate emulsion as well as preparation method and application thereof |
| CN105542174A (en) * | 2016-01-13 | 2016-05-04 | 广东工业大学 | Silicone-modified hyperbranched polyurethane and preparation method and application thereof |
| CN107353387A (en) * | 2017-08-03 | 2017-11-17 | 山东天庆科技发展有限公司 | A kind of aqueous anionic polyurethane emulsion and preparation method and application |
| CN107674189A (en) * | 2017-09-30 | 2018-02-09 | 合众（佛山）化工有限公司 | A kind of height divides hyperbranched Si modification unsaturated polyester resin and preparation method thereof admittedly |
| CN107674189B (en) * | 2017-09-30 | 2019-08-06 | 合众（佛山）化工有限公司 | It is a kind of high to divide hyperbranched Si modification unsaturated polyester resin and preparation method thereof admittedly |
| CN108752563A (en) * | 2018-05-24 | 2018-11-06 | 哈尔滨工业大学无锡新材料研究院 | Aqueous hyperbranched structurally-modified polyether polyols of one kind and preparation method thereof and selfreparing diffusing reflection coating composition |
| CN108752563B (en) * | 2018-05-24 | 2020-12-15 | 哈尔滨工业大学无锡新材料研究院 | Waterborne hyperbranched structure modified polyurethane polymer, preparation method thereof and self-repairing diffuse reflection coating composition |
| CN110105553A (en) * | 2019-04-04 | 2019-08-09 | 湖南师范大学 | Ester modified itaconic acid base water borne UV curing resin of hyperbranched poly and preparation method thereof |
| CN113372530A (en) * | 2021-05-19 | 2021-09-10 | 万华化学集团股份有限公司 | Polyurethane or polyurethane urea aqueous dispersion, preparation method thereof and aqueous clothing leather base |
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Application publication date: 20150325 |