CN105482060A - Hyperbranched waterborne polyurethane acrylate emulsion as well as preparation method and application thereof - Google Patents
Hyperbranched waterborne polyurethane acrylate emulsion as well as preparation method and application thereof Download PDFInfo
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- CN105482060A CN105482060A CN201511005203.0A CN201511005203A CN105482060A CN 105482060 A CN105482060 A CN 105482060A CN 201511005203 A CN201511005203 A CN 201511005203A CN 105482060 A CN105482060 A CN 105482060A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
Abstract
The invention discloses hyperbranched waterborne polyurethane acrylate emulsion as well as a preparation method and an application thereof, and belongs to the field of hyperbranched polyurethane coatings. Hyperbranched polyester is used as a raw material in the process of synthesizing the hyperbranched waterborne polyurethane acrylate emulsion prepared by the method disclosed by the invention, and due to the rheological property of the raw material, the viscosity of a reaction system is relatively low, and an organic solvent is not needed to adjust the viscosity of the system in the processes of synthetic reaction and dispersion, so that the production cost can be greatly saved, the production process meets requirements of environmental protection, and the hyperbranched waterborne polyurethane acrylate emulsion is stable in performance, and has a solid content of 30-40% and a particle size of 80-200nm. Moreover, the content of double bonds of the emulsion can be adjusted by changing the content of acrylate or the types of acrylate, therefore, the film forming time and the film forming hardness are controlled, the scope of application of a product is expanded, and the emulsion can be used as a film forming substance of a wooden ware coating, an ink and an anti-rusting coating, which is applied to the fields of furniture, printing, electronic products and the like.
Description
Technical field
The invention belongs to super branched polyurethane paint field, particularly one over-expense Water-borne modification polyurethane-acrylate emulsion and preparation method thereof and application.
Background technology
Aqueous polyurethane possesses the good over-all properties of solvent borne polyurethane, as wear-resisting, corrosion-resistant, the component feature such as adjustable flexibly, again because be dispersion medium with water, compared with solvent borne polyurethane, have that price is low, use safety, the advantage such as low in the pollution of the environment, be widely used in the fields such as furniture, building, printing, weaving, automobile.But in synthetic method now, in order to solve synthesis phase solubility problem and at scatter stage adjusting viscosity, all employ a certain amount of organic solvent, which increase production cost and pollute environment.
Hyperbranched polymer has the stuctures and properties being similar to branch-shape polymer, there is a large amount of cavitys, branch point and approximate globosity, the entanglement of macromolecular chain is less likely to occur, when molecular weight increases or concentration improves, can lower viscosity be kept, thus make it have unique rheological property, well moulding property and splendid chemical resistance, weather resistance and mechanical property.Dissaving structure is introduced in aqueous polyurethane system, effectively can reduce the viscosity of product, make it can save viscosity adjustment at scatter stage, greatly reduce the consumption of organic solvent.
When the molecular weight of hyperbranched aqueous polyurethane exceedes certain limit, its viscosity still can continue to rise.In order to take into account the relation of system viscosity and molecular weight, acrylate is introduced at hyperbranched polymer end, the mode of being solidified by UV effectively improves membrane-forming molecule amount, avoids the viscosity adjustment problem before solidification, also gives the higher mechanical property of product, more energy-efficient curing mode.
The Chinese patent of publication number to be CN102504166 and publication number be CN102924689 discloses a kind of by urethane (A2 monomer) and mono amino polyvalent alcohol (bB
nmonomer) at low-temp reaction, synthesis contains the AB of an isocyanic ester and multiple hydroxyl
nmonomer, AB
nmonomer has at high temperature just synthesized hyperbranched aqueous polyurethane by the condensation of self.The product of the method synthesis, hydrophilic radical is embedded in the inside of hyperbranched aqueous polyurethane, and add the emulsion that a large amount of hydrophilic chain extenders just can obtain stability, this is unfavorable for the water tolerance after emulsion film forming.In addition, two patent product ends are not containing response type acrylate group, and the mechanical property after its product film forming must be restricted; And employ a large amount of organic solvent in CN102924689 synthesis, be unfavorable for cost and environmental protection.Publication number is the synthetic method that the Chinese patent of CN104231214 discloses a kind of ultra-branched polyurethane acrylate coating, although product terminal double link is more and adjustable, applicability is wide, but not containing hydrophilic radical in structure, cannot be distributed in water, be unfavorable for safety and environmental protection.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, primary and foremost purpose of the present invention is the preparation method providing a kind of hyperbranched aqueous polyurethane acrylic ester emulsion.
Another object of the present invention is to provide the hyperbranched aqueous polyurethane prepared by above-mentioned preparation method acrylic ester emulsion.
Another object of the present invention is the application providing above-mentioned hyperbranched aqueous polyurethane acrylic ester emulsion.
Object of the present invention is achieved through the following technical solutions:
A preparation method for hyperbranched aqueous polyurethane acrylic ester emulsion, comprises the steps:
(1) in vacuum, will the oligomer polyol of reacting be used for, and heat up, dewater, obtain the oligomer polyol after dewatering;
(2) under normal temperature and pressure, in the small molecule polyol for reacting, add 4A molecular sieve, sealing is preserved, and obtains the small molecule polyol after processing;
(3) below all by molar fraction, disposablely add 30 ~ 60 parts of vulcabond, 4 ~ 10 parts of steps (1) obtain dewater after oligomer polyol and small molecule polyol, 0.02 ~ 0.04 part of catalyzer after the process that obtains of 1 ~ 5 part of step (2), stirring reaction, synthetic product A;
(4) 10 ~ 20 parts of hydrophilic chain extenders are joined in the product A that step (3) obtains, stirring reaction, synthetic product B;
(5), in the product B obtained in step (4), 7.5 ~ 15 parts of hydroxy acrylates, 0.01 ~ 0.02 part of stopper is added, stirring reaction, synthetic product C;
(6) 0.4 ~ 1.0 part of hyper-branched polyester is added, stirring reaction in the product C obtained in step (5);
(7) in step (6), 10 ~ 20 parts of triethylamines are added, neutralized reaction product, stirring reaction;
(8) in step (7), distilled water is added slowly, high-speed stirring, obtained hyperbranched aqueous polyurethane acrylic ester emulsion;
(9) under room temperature, by molar fraction, in step (8), add 1 ~ 4 part of light trigger, stir, obtain UV solidification, hyperbranched aqueous polyurethane acrylic ester emulsion.
Intensification described in step (1) is for being warming up to 120 ~ 130 DEG C; The described time dewatered is 2 ~ 3h;
Oligomer polyol described in step (1) can be one or more in polypropylene glycol (500,1000,2000), polytetrahydrofuran (1000,2000) and polyoxyethylene glycol (1000,2000);
The time that sealing described in step (2) is preserved is sealing preservation 48 ~ 96h;
Small molecule polyol described in step (2) can be one or more in BDO, 1,3 butylene glycol, hexylene glycol, certain herbaceous plants with big flowers glycol, ethohexadiol, glycol ether and ethylene glycol;
Vulcabond described in step (3) is one or more in isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, '-diphenylmethane diisocyanate and dicyclohexyl vulcabond;
Catalyzer described in step (3) is the one in dibutyl tin laurate, stannous octoate and zinc octoate;
The condition of the stirring reaction described in step (3) is nitrogen protection, and temperature rises to 85 ~ 90 DEG C, stirring reaction 1.5 ~ 2h, and stirring velocity is 50 ~ 150r/min;
Hydrophilic chain extender described in step (4) is one or both in dimethylol propionic acid and BDO sodium disulfonate;
The condition of the stirring reaction described in step (4) is keep temperature to be 85 ~ 90 DEG C, nitrogen protection, stirring reaction 1.0 ~ 1.5h, and stirring velocity is 50 ~ 150r/min;
Hydroxy acrylate described in step (5) is one or more in Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, pentaerythritol triacrylate and Dipentaerythritol Pentaacrylate;
Stopper described in step (5) is the one in Resorcinol, 2-Tert. Butyl Hydroquinone and p methoxy phenol;
The condition of the stirring reaction described in step (5) is nitrogen protection, 70 ~ 75 DEG C of stirring reaction 1.0 ~ 1.5h, and stirring velocity is 50 ~ 150r/min;
Hyper-branched polyester described in step (6) is the one in BoltornH20, BoltornH30, HyPerH10 and HyPerH20;
The condition of the stirring reaction described in step (6) is maintenance 70 ~ 75 DEG C, nitrogen protection, stirring reaction 1.0 ~ 1.5h;
The condition of the stirring reaction described in step (7) is 30 ~ 38 DEG C of stirring reaction 20 ~ 40min, and stirring velocity is 800 ~ 1500r/min;
The condition of the high-speed stirring described in step (8) is high-speed stirring 30 ~ 40min, and stirring velocity is 2000 ~ 3000r/min;
Light trigger described in step (9) is one or more in Darocur1173, Darocur2959, EsacureKIP150, Irgacure819DW, QTX, BTC, BPQ, WB-4784, WB-4785, WB-4789 and WB-4792.
Hydrophilic chain extender described in step (4) is at 70 ~ 80 DEG C, and 1:2 is dissolved in nitrogen methyl-2-pyrrolidone by mass percentage;
The consumption of the distilled water described in step (8) is 2 ~ 3 times of added starting material total mass in step (1) ~ (7);
The structure of described product C is:
Wherein,
for the segment that vulcabond and polyether glycol, small molecule polyol and hydrophilic chain extender react; This structure take Hydroxyethyl acrylate as end, if with other hydroxy acrylates for raw material is by different;
Described hyperbranched aqueous polyurethane acrylate structural is:
Wherein, R is the hyper-branched polyester containing multiple hydroxyl, and the scope of n is 12 ~ 24;
A kind of hyperbranched aqueous polyurethane acrylic ester emulsion, is prepared by above-mentioned preparation method.
Described hyperbranched aqueous polyurethane acrylic ester emulsion solid content is 30 ~ 40%, particle diameter 80 ~ 200nm, stability in storage more than 6 months; After room temperature UV film-forming, pencil hardness is H ~ 3H, snappiness 2 ~ 3mm, water tolerance 120 ~ 150h, the solution of resistance to 3%NaCl 100 ~ 180h.
Described hyperbranched aqueous polyurethane acrylic ester emulsion can be used as the filmogen of woodwork coating, ink, rust proof paint, is applied to the fields such as furniture, printing, electronic product.
Principle of the present invention is: introduced by hyper-branched polyester in aqueous polyurethane structure, makes the viscosity of polymkeric substance in synthesis obtain control to a certain extent, does not therefore need to add solvent in the reaction and carry out regulation system viscosity, reach the object reduced costs with environmental protection; Simultaneously introduce acrylate at the end of aqueous polyurethane, make emulsion in film process by the mode of UV solidification to improve the molecular weight of film, make product have better mechanical property and curing speed faster; In addition, the double bond number of hyperbranched aqueous polyurethane acrylic ester emulsion prepared by the present invention is adjustable, therefore its cross-linking density can regulate within the specific limits, changes the physicals of the rear coating of solidification further, makes product can better meet the application requiring of different field.
The present invention, relative to prior art, has following advantage and effect:
(1) employing hyper-branched polyester in the hyperbranched aqueous polyurethane acrylic ester emulsion building-up process that prepared by the present invention is raw material, due to the rheological property of its uniqueness, make the viscosity of reaction system lower, regulation system viscosity is carried out without the need to adding organic solvent in the process of building-up reactions and dispersion, can save production cost greatly, production process meets the requirement of environmental protection.
(2) content of its double bond of hyperbranched aqueous polyurethane acrylic ester emulsion prepared of the present invention can by changing the content of acrylate or the kind of acrylate regulate, control film formation time thus, become film hardness, expand the range of application of product.
(3) the hyperbranched aqueous polyurethane acrylic ester emulsion that prepared by the present invention is a kind of photocuring aqueous product, without adding organic solvent, discharges during use without toxic gas, and the time of UV film-forming is fast, meets the requirement of energy-saving and environmental protection.
(4) the hyperbranched aqueous polyurethane acrylic ester emulsion that prepared by the present invention can introduce the polyether glycol segment of different molecular weight, is convenient to the soft durometer regulating film, expands its application scenario.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited thereto.
Embodiment 1
In vacuum, by the polypropylene glycol (1000) being used for reacting, be warming up to 120 DEG C, dewater 2h, obtains the polypropylene glycol after dewatering (1000); Under normal temperature and pressure, in the BDO for reacting, add 4A molecular sieve, 48h is preserved in sealing, obtains the BDO after processing; All by molar fraction, in reactor disposable add 30 parts of isophorone diisocyanates, 4 parts dewater after polypropylene glycol (1000) and 1 part process after 1,4-butyleneglycol, 0.02 part of dibutyl tin laurate, pass into nitrogen, temperature rises to 85 DEG C, stirring reaction 1.5h, stirring velocity is 50r/min, synthetic product A; Join in reactor by disposable for 10 parts of hydrophilic chain extender dimethylol propionic acids, keep temperature to be 85 DEG C, nitrogen protection, stirring reaction 1.5h, stirring velocity is 50r/min, synthetic product B; Temperature of reaction kettle is dropped to 70 DEG C, in reactor, add 7.5 parts of Hydroxyethyl acrylates, 0.01 part of p methoxy phenol, nitrogen protection, stirring reaction 1.5h, stirring velocity is 50r/min, synthetic product C; Disposablely in a kettle. add 0.4 part of HyPerH10 hyper-branched polyester, keep 70 DEG C, nitrogen protection, stirring reaction 1.0h; Reactor is cooled to 38 DEG C, adds 10 parts of triethylamines, neutralized reaction product in reactor, stir 20min, stirring velocity is 800r/min; Add the distilled water of raw material total mass 3 times in a kettle., high-speed stirring 30min, stirring velocity is 3000r/min, obtained hyperbranched aqueous polyurethane acrylic ester emulsion; Under room temperature, in emulsion, add 1 part of light trigger Darocur1173, stir, obtain UV solidification, hyperbranched aqueous polyurethane acrylate resin; This emulsion property is stablized, stably stored more than 6 months; After room temperature UV film-forming, pencil hardness is 3H, snappiness 2mm, water tolerance 150h, the solution of resistance to 3%NaCl 180h.
Embodiment 2
In vacuum, by the polytetrahydrofuran (2000) being used for reacting, be warming up to 130 DEG C, dewater 3h, obtains the polytetrahydrofuran after dewatering (2000); Under normal temperature and pressure, in the hexylene glycol for reacting, add 4A molecular sieve, 60h is preserved in sealing, obtains the hexylene glycol after processing; All by molar fraction, disposablely in reactor add 60 part 1, hexamethylene-diisocyanate, 10 parts dewater after polytetrahydrofuran (2000) and 5 parts process after hexylene glycol, 0.04 part of stannous octoate, pass into nitrogen, temperature rises to 90 DEG C, stirring reaction 2h, stirring velocity is 150r/min, synthetic product A; Join in reactor by disposable for 20 parts of hydrophilic chain extender dimethylol propionic acids, keep temperature to be 90 DEG C, nitrogen protection, stirring reaction 1.5h, stirring velocity is 150r/min, synthetic product B; Temperature of reaction kettle is dropped to 75 DEG C, disposablely in reactor add 15 parts of Propylene glycol monoacrylates, 0.02 part of Resorcinol, nitrogen protection, stirring reaction 1.5h, stirring velocity is 150r/min, synthetic product C; Disposablely in a kettle. add 1.0 parts of BoltornH20 hyper-branched polyesters, keep 75 DEG C, nitrogen protection, stirring reaction 1.5h; Reactor is cooled to 30 DEG C, adds 20 parts of triethylamines, neutralized reaction product in reactor, stir 20min, stirring velocity is 1500r/min; In reactor, add the distilled water of raw material total mass 2 times slowly, high-speed stirring 40min, stirring velocity is 2000r/min, obtained hyperbranched aqueous polyurethane acrylic ester emulsion; Under room temperature, in emulsion, add 4 parts of light trigger Darocur2959, stir, obtained UV solidification, hyperbranched aqueous polyurethane acrylate resin; This emulsion property is stablized, stably stored more than 6 months; After room temperature UV film-forming, pencil hardness is 2H, snappiness 3mm, water tolerance 120h, the solution of resistance to 3%NaCl 100h.
Embodiment 3
In vacuum, by the polypropylene glycol (500) being used for reacting, be warming up to 110 DEG C, dewater 2.5h, obtains the polypropylene glycol after dewatering (500); Under normal temperature and pressure, in the ethohexadiol for reacting, add 4A molecular sieve, 72h is preserved in sealing, obtains the ethohexadiol after processing; All by molar fraction, in reactor disposable add 45 parts of isophorone diisocyanates, 8 parts dewater after polypropylene glycol (500) and 2 parts process after ethohexadiol, 0.03 octoate catalyst zinc, pass into nitrogen, temperature rises to 90 DEG C, stirring reaction 2h, stirring velocity is 80r/min, synthetic product A; Join in reactor by 15 parts of hydrophilic chain extender dimethylol propionic acids, keep temperature to be 90 DEG C, nitrogen protection, stirring reaction 1.5h, stirring velocity is 80r/min, synthetic product B; Temperature of reaction kettle is dropped to 70 DEG C, in reactor, add 11 parts of pentaerythritol triacrylates, 0.02 part of stopper 2-Tert. Butyl Hydroquinone, nitrogen protection, stirring reaction 1.5h, stirring velocity is 80r/min, synthetic product C; Add 0.7 part of HyPerH10 hyper-branched polyester in a kettle., keep 70 DEG C, nitrogen protection, stirring reaction 1.5h; Reactor is cooled to 35 DEG C, adds 15 parts of triethylamines, neutralized reaction product in reactor, stir 30min, stirring velocity is 1000r/min; In reactor, add the distilled water of raw material total mass 2.5 times slowly, high-speed stirring 30min, stirring velocity is 2500r/min, obtained hyperbranched aqueous polyurethane acrylic ester emulsion; Under room temperature, in emulsion, add 4 parts of light trigger Irgacure819DW, stir, obtained UV solidification, hyperbranched aqueous polyurethane acrylate resin; This emulsion property is stablized, stably stored more than 6 months; After room temperature UV film-forming, pencil hardness is 3H, snappiness 2mm, water tolerance 130h, the solution of resistance to 3%NaCl 170h.
Embodiment 4
In vacuum, by the polypropylene glycol (2000) being used for reacting, be warming up to 120 DEG C, dewater 3h, obtains the polypropylene glycol after dewatering (2000); Under normal temperature and pressure, in the BDO for reacting, add 4A molecular sieve, 84h is preserved in sealing, obtains the BDO after processing; All by molar fraction, in reactor disposable add 35 parts of isophorone diisocyanates, 4.5 parts dewater after polypropylene glycol (2000) and 1 part process after 1,4-butyleneglycol, 0.02 part of catalyst dibutyltin dilaurylate, pass into nitrogen, temperature rises to 85 DEG C, stirring reaction 1.5h, stirring velocity is 100r/min, synthetic product A; Join in reactor by 12 parts of hydrophilic chain extender BDO sodium disulfonates, keep temperature to be 85 DEG C, nitrogen protection, stirring reaction 1.0h, stirring velocity is 100r/min, synthetic product B; Temperature of reaction kettle is dropped to 75 DEG C, in reactor, add 9 parts of Propylene glycol monoacrylates, 0.01 part of stopper 2-Tert. Butyl Hydroquinone, nitrogen protection, stirring reaction 1.0h, stirring velocity is 100r/min, synthetic product C; Add 0.6 part of BoltornH20 hyper-branched polyester in a kettle., keep 75 DEG C, nitrogen protection, stirring reaction 1.5h; Reactor is cooled to 35 DEG C, adds the distilled water of raw material total mass 2 times slowly, high-speed stirring 30min, stirring velocity is 2000r/min, obtained hyperbranched aqueous polyurethane acrylic ester emulsion; Under room temperature, in emulsion, add 3 parts of light trigger Darocur2959, stir, obtained UV solidification, hyperbranched aqueous polyurethane acrylate resin; This emulsion property is stablized, stably stored more than 6 months; After room temperature UV film-forming, pencil hardness is 3H, snappiness 3mm, water tolerance 140h, the solution of resistance to 3%NaCl 170h.
Embodiment 5
In vacuum, by the polytetrahydrofuran (2000) being used for reacting, be warming up to 130 DEG C, dewater 3h, obtains the polytetrahydrofuran after dewatering (2000); Under normal temperature and pressure, in the certain herbaceous plants with big flowers glycol for reacting, add 4A molecular sieve, 96h is preserved in sealing, obtains the certain herbaceous plants with big flowers glycol after processing; All by molar fraction, in reactor disposable add 40 parts of vulcabond, 4.5 parts dewater after polytetrahydrofuran (2000) and 2 parts process after certain herbaceous plants with big flowers glycol, 0.03 part of catalyzer p methoxy phenol, pass into nitrogen, temperature rises to 90 DEG C, stirring reaction 2h, stirring velocity is 80r/min, synthetic product A; Join in reactor by 13 parts of hydrophilic chain extender dimethylol propionic acids, keep temperature to be 90 DEG C, nitrogen protection, stirring reaction 1.5h, stirring velocity is 80r/min, synthetic product B; Temperature of reaction kettle is dropped to 75 DEG C, in reactor, add 9.8 parts of Hydroxyethyl acrylates, 0.02 part of stopper, nitrogen protection, stirring reaction 1.5h, stirring velocity is 80r/min, synthetic product C; Add 0.5 part of hyper-branched polyester in a kettle., keep 75 DEG C, nitrogen protection, stirring reaction 1.5h; Reactor is cooled to 35 DEG C, adds 13 parts of triethylamines, neutralized reaction product in reactor, stir 20min, stirring velocity is 800r/min; In reactor, add the distilled water of raw material total mass 3 times slowly, high-speed stirring 30min, stirring velocity is 2000r/min, obtained hyperbranched aqueous polyurethane acrylic ester emulsion; Under room temperature, in emulsion, add 3 parts of light trigger EsacureKIP150, stir, obtained UV solidification, hyperbranched aqueous polyurethane acrylate resin; This emulsion property is stablized, stably stored more than 6 months; After room temperature UV film-forming, pencil hardness is 2H, snappiness 3mm, water tolerance 120h, the solution of resistance to 3%NaCl 160h.
Above-described embodiment is the present invention's preferably embodiment; but embodiments of the present invention are not restricted to the described embodiments; change, the modification done under other any does not deviate from spirit of the present invention and principle, substitute, combine, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (10)
1. a preparation method for hyperbranched aqueous polyurethane acrylic ester emulsion, is characterized in that comprising the steps:
(1) in vacuum, will the oligomer polyol of reacting be used for, and heat up, dewater, obtain the oligomer polyol after dewatering;
(2) under normal temperature and pressure, in the small molecule polyol for reacting, add 4A molecular sieve, sealing is preserved, and obtains the small molecule polyol after processing;
(3) below all by molar fraction, disposablely add 30 ~ 60 parts of vulcabond, 4 ~ 10 parts of steps (1) obtain dewater after oligomer polyol and small molecule polyol, 0.02 ~ 0.04 part of catalyzer after the process that obtains of 1 ~ 5 part of step (2), stirring reaction, synthetic product A;
(4) 10 ~ 20 parts of hydrophilic chain extenders are joined in the product A that step (3) obtains, stirring reaction, synthetic product B;
(5), in the product B obtained in step (4), 7.5 ~ 15 parts of hydroxy acrylates, 0.01 ~ 0.02 part of stopper is added, stirring reaction, synthetic product C;
(6) 0.4 ~ 1.0 part of hyper-branched polyester is added, stirring reaction in the product C obtained in step (5);
(7) in step (6), 10 ~ 20 parts of triethylamines are added, neutralized reaction product, stirring reaction;
(8) in step (7), distilled water is added slowly, high-speed stirring, obtained hyperbranched aqueous polyurethane acrylic ester emulsion.
2. the preparation method of hyperbranched aqueous polyurethane acrylic ester emulsion according to claim 1, is characterized in that: also comprise the steps:
(9) under room temperature, by molar fraction, in step (8), add 1 ~ 4 part of light trigger, stir, obtain UV solidification, hyperbranched aqueous polyurethane acrylic ester emulsion.
3. the preparation method of hyperbranched aqueous polyurethane acrylic ester emulsion according to claim 1 and 2, is characterized in that:
Intensification described in step (1) is for being warming up to 120 ~ 130 DEG C; The described time dewatered is 2 ~ 3h;
Oligomer polyol described in step (1) is one or more in polypropylene glycol, polytetrahydrofuran and polyoxyethylene glycol;
Small molecule polyol described in step (2) is one or more in BDO, 1,3 butylene glycol, hexylene glycol, certain herbaceous plants with big flowers glycol, ethohexadiol, glycol ether and ethylene glycol.
4. the preparation method of hyperbranched aqueous polyurethane acrylic ester emulsion according to claim 1 and 2, is characterized in that:
Vulcabond described in step (3) is one or more in isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, '-diphenylmethane diisocyanate and dicyclohexyl vulcabond;
Catalyzer described in step (3) is the one in dibutyl tin laurate, stannous octoate and zinc octoate;
The condition of the stirring reaction described in step (3) is nitrogen protection, and temperature rises to 85 ~ 90 DEG C, stirring reaction 1.5 ~ 2h, and stirring velocity is 50 ~ 150r/min.
5. the preparation method of hyperbranched aqueous polyurethane acrylic ester emulsion according to claim 1 and 2, is characterized in that:
Hydrophilic chain extender described in step (4) is one or both in dimethylol propionic acid and BDO sodium disulfonate;
The condition of the stirring reaction described in step (4) is for keeping temperature to be 85 ~ 90 DEG C, and nitrogen protection, stirring reaction 1.0 ~ 1.5h, stirring velocity is 50 ~ 150r/min.
6. the preparation method of hyperbranched aqueous polyurethane acrylic ester emulsion according to claim 1 and 2, is characterized in that:
Hydroxy acrylate described in step (5) is one or more in Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate, Rocryl 410, pentaerythritol triacrylate and Dipentaerythritol Pentaacrylate;
Stopper described in step (5) is the one in Resorcinol, 2-Tert. Butyl Hydroquinone and p methoxy phenol;
The condition of the stirring reaction described in step (5) is nitrogen protection, 70 ~ 75 DEG C of stirring reaction 1.0 ~ 1.5h, and stirring velocity is 50 ~ 150r/min.
7. the preparation method of hyperbranched aqueous polyurethane acrylic ester emulsion according to claim 1 and 2, is characterized in that:
Hyper-branched polyester described in step (6) is the one in BoltornH20, BoltornH30, HyPerH10 and HyPerH20;
The condition of the stirring reaction described in step (6) is maintenance 70 ~ 75 DEG C, nitrogen protection, stirring reaction 1.0 ~ 1.5h;
The condition of the stirring reaction described in step (7) is 30 ~ 38 DEG C of stirring reaction 20 ~ 40min, and stirring velocity is 800 ~ 1500r/min;
The condition of the high-speed stirring described in step (8) is high-speed stirring 30 ~ 40min, and stirring velocity is 2000 ~ 3000r/min;
The consumption of the distilled water described in step (8) is 2 ~ 3 times of added starting material total mass in step (1) ~ (7).
8. the preparation method of hyperbranched aqueous polyurethane acrylic ester emulsion according to claim 2, is characterized in that:
Light trigger described in step (9) is one or more in Darocur1173, Darocur2959, EsacureKIP150, Irgacure819DW, QTX, BTC, BPQ, WB-4784, WB-4785, WB-4789 and WB-4792.
9. a hyperbranched aqueous polyurethane acrylic ester emulsion, is characterized in that being prepared by the preparation method described in any one of claim 1 ~ 8.
10. hyperbranched aqueous polyurethane acrylic ester emulsion according to claim 9 is as the application of filmogen in furniture, printing or electronics field of woodwork coating, ink or rust proof paint.
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