CN102336875B - Preparation method of aqueous polyurethane acrylate photocureable paint - Google Patents
Preparation method of aqueous polyurethane acrylate photocureable paint Download PDFInfo
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Abstract
The invention relates to a preparation method of aqueous polyurethane acrylate photocureable paint, and relates to the technical field of aqueous polyurethane acrylate emulsion preparation. The preparation method is characterized in that aqueous polyurethane acrylate photocurable prepolymer is prepared by adopting an in-situ method, and the preparation process is simple; butyl acrylate (BA) and tri(propylene glycol) diacrylate (TPGDA) are selected as diluents; and the emulsion viscosity and the ratio of soft segment to hard segment in the emulsion are adjusted by changing the ratio of BA to TPGDA, thus the generation of granules is prevented and the emulsion has uniform dispersion and good stability. At the same time, the weathering resistance, mechanical performance, gelling rate, curing time and the like of a cured film are greatly improved.
Description
Technical field
The present invention relates to the preparing technical field of aqueous polyurethane acrylate emulsion, especially a kind of preparation method of aqueous polyurethane acrylate photocureable paint.
Background technology
In recent years, environment protection is subject to people's attention day by day, and many countries have promulgated the rules of control volatile organic compounds (VOC), and operative norm is more and more stricter, and the friendly coating of development environment has become the focus of coating research field.Traditional oil soluble coating relies on the volatilization of organic solvent to come film forming, and a large amount of organic solvents enters air and causes serious environmental pollution, is detrimental to health.The coating material solidified employing reactive thinner of UV-light (UV) replaces organic solvent, wherein, reactive thinner is basically non-volatile, have the dual-use function of curing cross-linked and solvent concurrently, its molecule contains and can be caused by photosensitive free radical and can be further and functional group's (such as two keys) of prepolymer cross-linking reaction, reactive thinner is used for the rheological of adjusting coating, simultaneously dry solidification and the film performance of coating has also been produced impact.Thinner plays diluting effect on the one hand, makes coating have the viscosity of constructability; Play again on the other hand crosslinked action, so it must have good reactive behavior, it solidifies the laggard resin network that enters, and the final performance of cured product is had very large impact.Requirement to reactive thinner mainly is the response capacity of low viscosity, highly diluted and height, it is little also will to take into account simultaneously volatility, toxicity, pungency and stink, and price is low, and stability is high, good etc. to the consistency of resin, often adopt mixed diluent for adjusting various performances.Because the UV solidify material has its unique advantage, UV is coating material solidified, printing ink, solder resist and tackiness agent etc. are applied rapidly in fields such as electronics, printing, building, decoration, machinery, chemical industry and automobiles, and wherein the development as UV bamboo-wood floor coating, paper polish and solder resist is particularly rapid.Traditional natural drying or heat curing coating, its capacity usage ratio is low, pollution is large, film forming speed is slow, film quality is low and be not suitable for continuous mass production, UV is coating material solidified then effectively to have solved above problems, it is comparatively active at present research and development field, having become one of main development direction of UV curing system, is the Green Product of Twenty-First Century.
(1) Effect of average functionality on properties of UV-curable waterborne polyurethane-acrylate. Progress in Organic Coatings 68 (2010) 201-207. adopt the chainextender that contains different functionality to carry out the method for end-blocking, produce the aqueous polyurethane acrylate (WPUA) that a series of UV solidify, determine the chemical structure that contains different functionality aqueous polyurethane acrylates that makes by infrared test, studied the chainextender of different functionality to the impact of WPUA performance.The result shows that average functionality has good effect to water tolerance and the tensile strength of the WPUA film of UV curing.In addition, by to its dynamic (dynamical) research, the too high or too low conversion that all is unfavorable for the insatiable hunger degree of average functionality.But the viscosity of the WPUA emulsion that the method makes is larger, is easy to occur coacervation, and stability is not good enough, and then affects its further popularization.
(2) performance study of modified unsaturated polyester acid amides urea ultraviolet-curing paint.New Chemical Materials, 2009,37(6): 69-72. adopts the body melt phase polycondensation, with dimeracid unsaturated carbamide resin of polyester amide is carried out modification, and with infrared spectroscopy structure is characterized.Take methyl methacrylate (MMA) as reactive thinner, studied different diluent concentrations, different light trigger types and concentration are on the impact of film performance.And the performance before and after the modification compared, the result shows: it is soft not to have overcome the unsaturated polyester amide urea coating by the standby ultraviolet-curing paint of the resin after the modification, resistance to impact shock is poor, the shortcoming of poor water resistance, it is excellent to have obtained physicals, is easy to construction and eco-friendly photo-cured coating.But adopt the body melt phase polycondensation, so that produce complex steps, unstable, and when different amount of diluent are discussed the affecting of curing membrane performance, to all not making a search mechanical property and set time of cured film, be difficult to guarantee the practical application of material.
(3) Study on microstructure of UV-curable polyurethane acrylate lms. Progress in Organic Coatings 62 (2008) 245-250. have synthesized the PUA resin of a series of ultraviolet light polymerizations, characterize its structure by FT-IR.Soft section partial-length, isocyanate kind, reaction monomers type and cancellation, annealing and ultraviolet light polymerization degree all play important effect to the cured film microphase-separated.In addition, soft segment length also affects the formation of crystallization.The all samples that makes has good pencil hardness, elasticity, wear resistance and water tolerance.But the sample thermostability that makes is relatively relatively poor, and reactive thinner HDDA and TMPTA content are not made dependence test to set time and the gel fraction of emulsion, curing membrane performance and cured film yet, and then has limited its further popularization.
Summary of the invention
For above-mentioned the deficiencies in the prior art, the invention provides a kind of method for preparing the ultraviolet light solidfication water polyurethane acrylate performed polymer, carry out according to following step:
(1) in agitator, reflux condensing tube, temperature are housed take into account the container of feeding device, adds a certain amount of monomer polyvalent alcohol and isocyanic ester, add hydrophilic chain extender dimethylol propionic acid (DMPA), its consumption is the 1-10% of total monomer quality, the preferred mass ratio is 6%, take N-Methyl pyrrolidone (NMP) as solvent, its consumption is 10% of monomer polyvalent alcohol, system is warmed up to 70-80 ℃, the hydroxyl mole number ratio of the isocyano mole summation of monomeric diisocyanate and polyvalent alcohol wherein, be that the NCO/OH ratio is 1:1.5-2:1, preferred 2:1; Adding dibutyl tin dilaurate (T-12) is catalyzer again, and its consumption is the 0.1%-0.5% of polyvalent alcohol and isocyanic ester total mass, and preferred mass is best than 0.2%.
(2) behind the reaction 3-4h, system is cooled to 60-70 ℃, add hydroxyethyl methylacrylate (HEMA) and carry out end-blocking, its amount of substance equals the amount of isocyanate species in the first step.After continuing reaction 4-5h, be cooled to 30-50 ℃, additive salt agent triethylamine (TEA), wherein the triethylamine molar weight is the 80%-100 % of dimethylol propionic acid (DMPA) molar weight, and is preferred 100%, reaction 30-40min.Keep temperature-resistant, add entry and disperse, its quality is monomer polyvalent alcohol, isocyanic ester, dimethylol propionic acid (DMPA) and hydroxyethyl methylacrylate (HEMA) four total masses 3 times.About reaction 30min, can make aqueous polyurethane acrylate (PUA) performed polymer emulsion.
(3) in the performed polymer emulsion that makes, add reactive thinner butyl acrylate (BA) and tripropylene glycol double methacrylate (TPGDA), its total amount is the 90%-98% of the aqueous polyurethane acrylate performed polymer quality of the emulsion that makes in the step (2), preferred 94%, reaction 20-40min.Cool the temperature to 25-30 ℃, add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Darocure 1173), its consumption is the 3%-8% of the aqueous polyurethane acrylate performed polymer quality of the emulsion that makes in the step (2), and preferred 4% be the best.Reaction 30min can make the aqueous polyurethane acrylate photocuring system.
Wherein the polyvalent alcohol described in the step (1) can be polyester polyol, also can be polyether glycol, preferred two functionality polyether glycol NJ-210; Described isocyanic ester can be tolylene diisocyanate (TDI), '-diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI) etc., preferred isophorone diisocyanate (IPDI).
After wherein reacting 3-4h in the step (2), system is cooled to 60-70 ℃, if the system viscosity is excessive, can add a certain amount of acetone.
Technical essential of the present invention: the present invention adopts in-situ method to produce aqueous polyurethane acrylate photocuring performed polymer, preparation process is simple, selected butyl acrylate (BA) and tripropylene glycol double methacrylate (TPGDA) as thinner, regulate in the viscosity of emulsion and the emulsion again the ratio of soft section and hard section by the ratio that changes BA and TPGDA, stoped the generation of particle, thereby make emulsion dispersion even, good stability.Make simultaneously the weathering resistance of cured film, mechanical property, gel fraction and set time etc. is greatly improved.
Embodiment:The present invention is described in detail below in conjunction with example, but the present invention is not limited to following instance.
Embodiment 1
In agitator, reflux condensing tube, temperature are housed take into account the 500mL four-hole bottle of feeding device, add the polyether glycol (NJ-210) of 13.87g and the dimethylol propionic acid (DMPA) of 1.93g; Add 1.4g N-Methyl pyrrolidone (NMP) solvent, system is warming up to 60 ℃, add 8.325g isophorone diisocyanate (IPDI), drip 0.073g catalyzer dibutyl tin dilaurate (T-12), after stirring 30min, system temperature is risen to 80 ℃, if (the system viscosity is excessive, can add a certain amount of acetone), after continuing reaction 4h, be cooled to 60 ℃, methylate Hydroxyethyl acrylate (HEMA) 2.79g cools the temperature to 40 ℃ behind the reaction 5h, adds triethylamine 1.24g, reaction 0.5h, drip 82g water and disperse, add reactive thinner butyl acrylate (BA) 95.4g and tripropylene glycol double methacrylate (TPGDA) 10.6g in the backward performed polymer of 0.5h, cool the temperature to 25 ℃ behind the 40min, add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Darocure 1173) 5.63g, reaction 30min can make aqueous polyurethane acrylate photocureable paint
UV-WPUA-1
Embodiment 2
Agitator is being housed, reflux condensing tube, temperature is taken into account the polyether glycol (NJ-220) that adds 19.673g in the 500mL four-hole bottle of feeding device, 1.967g the dimethylol propionic acid (DMPA) of N-Methyl pyrrolidone (NMP) and 1.474g, system is warmed up to 60 ℃, add 8.325g isophorone diisocyanate (IPDI), drip catalyzer 0.118g dibutyl tin dilaurate (T-12), after stirring 30min, system temperature is risen to 80 ℃, if (the system viscosity is excessive, can add a certain amount of acetone), after continuing reaction 4h, be cooled to 60 ℃, methylate Hydroxyethyl acrylate (HEMA) 4.333g, the reaction 5h after with near 40 ℃ of temperature, add triethylamine 1g, reaction 0.5h drips 98g water and disperses, 0.5h add butyl acrylate (BA) 88.9g and tripropylene glycol double methacrylate (TPGDA) 38.1g in the backward performed polymer, reaction 40min.Cool the temperature to 25 ℃, add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Darocure 1173) 7.62g, reaction 30min can make aqueous polyurethane acrylate photocureable paint
UV-WPUA-2
Embodiment 3
Agitator is being housed, reflux condensing tube, temperature is taken into account the polyether glycol NJ-210 that adds 10g in the 500mL four-hole bottle of feeding device, 1.175g dimethylol propionic acid (DMPA) and 1g N-Methyl pyrrolidone (NMP) solvent, system is warmed up to 60 ℃, add 8.325g isophorone diisocyanate (IPDI), drip catalyzer 0.039g dibutyl tin dilaurate (T-12), after stirring 30min, system temperature is risen to 80 ℃, if (the system viscosity is excessive, can add a certain amount of acetone), after continuing reaction 4h, be cooled to 60 ℃, methylate Hydroxyethyl acrylate (HEMA) 4.875g, the reaction 5h after with near 40 ℃ of temperature, add triethylamine 0.884g, reaction 0.5h drips 72g water and disperses, 0.5h add reactive thinner butyl acrylate (BA) 45.7g and tripropylene glycol double methacrylate (TPGDA) 45.7g in the backward performed polymer, reaction 40min.Cool the temperature to 25 ℃, add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Darocure 1173) 3.89g, reaction 30min can make aqueous polyurethane acrylate photocureable paint
UV-WPUA-3
Embodiment 4
In agitator, reflux condensing tube, temperature are housed take into account the 500mL four-hole bottle of feeding device, add the polyether glycol (NJ-210) of 10.93g and the dimethylol propionic acid (DMPA) of 1.215g; Add 1.039g N-Methyl pyrrolidone (NMP) solvent, system is warmed up to 60 ℃, add 5.22g tolylene diisocyanate (TDI), drip catalyzer 0.061g dibutyl tin dilaurate (T-12), after stirring 30min, system temperature is risen to 80 ℃, if (the system viscosity is excessive, can add a certain amount of acetone), after continuing reaction 4h, be cooled to 60 ℃, methylate Hydroxyethyl acrylate (HEMA) 2.6g, the reaction 5h after with near 40 ℃ of temperature, add triethylamine 0.889g, reaction 0.5h drips 61g water and disperses, 0.5h add reactive thinner butyl acrylate (BA) 23.082g and tripropylene glycol double methacrylate (TPGDA) 53.858g in the backward performed polymer, reaction 40min.Cool the temperature to 25 ℃, add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Darocure 1173) 3.078g, reaction 30min can make aqueous polyurethane acrylate photocureable paint
UV-WPUA-4
Embodiment 5
Agitator is being housed, reflux condensing tube, temperature is taken into account the polyether glycol (NJ-220) that adds 22.82g in the 500mL four-hole bottle of feeding device, 2.282g the dimethylol propionic acid (DMPA) of N-Methyl pyrrolidone (NMP) and 2.659g adds in the reaction unit, system is warmed up to 60 ℃, add 12.5g '-diphenylmethane diisocyanate (MDI), drip catalyzer 0.171g dibutyl tin dilaurate (T-12), after stirring 30min, system temperature is risen to 80 ℃, if (the system viscosity is excessive, can add a certain amount of acetone), after continuing reaction 4h, be cooled to 60 ℃, methylate Hydroxyethyl acrylate (HEMA) 3.047g, the reaction 5h after with near 40 ℃ of temperature, add triethylamine 1.964g, reaction 0.5h drips 80g water and disperses, 0.5h add tripropylene glycol double methacrylate (TPGDA) 15.364g and butyl acrylate (BA) 138.276g in the backward performed polymer, reaction 40min.Cool the temperature to 25 ℃, add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Darocure 1173) 6.68g, reaction 30min can make aqueous polyurethane acrylate photocureable paint
UV-WPUA-5
Experimental technique
Measure aqueous polyurethane acrylate photocuring emulsion film forming time, cured film gel fraction and tensile strength,
The result is as shown in following table 1.
Table 1
The result shows, product of the present invention: novel aqueous urethane acrylate photo-cured coating emulsion homogeneous, stable, the adding of reactive thinner is so that cured film has preferably mechanical property.Its Application Areas is from initial wood finishing, progressively to numerous high-tech area infiltrations such as printing, packing, advertisement, building materials, household electrical appliances, electronics, communication, space flight, aviation, be described as the green industry technology of 21st century Sustainable development, have good economic benefit and social benefit.
Claims (5)
1. the preparation method of an aqueous polyurethane acrylate photocureable paint is characterized in that carrying out according to following step:
(1) in container, add a certain amount of monomer polyalcohol and isocyanates, add the hydrophilic chain extender dihydromethyl propionic acid, its consumption is the 1-10% of total monomer quality, take 1-METHYLPYRROLIDONE as solvent, its consumption is 10% of monomer polyalcohol, system is warmed up to 70-80 ℃, the hydroxyl molal quantity ratio of the isocyano of monomeric diisocyanate mole summation and polyalcohol wherein, be that the NCO/OH ratio is 1:1.5-2:1, adding dibutyl tin dilaurate is catalyst again, its consumption is the 0.1%-0.5% of polyalcohol and isocyanates gross mass
(2) behind the reaction 3-4h, system is cooled to 60-70 ℃, add hydroxyethyl methylacrylate and carry out end-blocking, its amount of substance equals the amount of isocyanate species in the step (1); After continuing reaction 4-5h, be cooled to 30-50 ℃, additive salt agent triethylamine, wherein the triethylamine molar weight is the 80%-100 % of dimethylol propionic acid molar weight, reaction 30-40min; Keep temperature-resistant, add entry and disperse, its quality is monomer polyvalent alcohol, isocyanic ester, dimethylol propionic acid and hydroxyethyl methylacrylate total mass 3 times; About reaction 30min, can make aqueous polyurethane acrylate performed polymer emulsion;
(3) add reactive thinner butyl acrylate and tripropylene glycol double methacrylate in the performed polymer emulsion that makes, its total amount is the 90%-98% of the aqueous polyurethane acrylate performed polymer quality of the emulsion that makes in the step (2), reaction 20-40min; Cool the temperature to 25-30 ℃, add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone, its consumption is the 3%-8% of the aqueous polyurethane acrylate performed polymer quality of the emulsion that makes in the step (2), and reaction 30min can make the aqueous polyurethane acrylate photocuring system.
2. the preparation method of a kind of aqueous polyurethane acrylate photocureable paint according to claim 1 is characterized in that wherein the polyvalent alcohol described in the step (1) is polyester polyol or polyether glycol; Described isocyanic ester is tolylene diisocyanate, '-diphenylmethane diisocyanate or isophorone diisocyanate (IPDI).
3. the preparation method of a kind of aqueous polyurethane acrylate photocureable paint according to claim 1 is characterized in that wherein in the step (2) behind the reaction 3-4h system being cooled to 60-70 ℃, if the system viscosity is excessive, can add a certain amount of acetone.
4. the preparation method of a kind of aqueous polyurethane acrylate photocureable paint according to claim 1, it is characterized in that wherein the consumption of step (1) hydrophilic chain extender dimethylol propionic acid is 6% of total monomer quality, the hydroxyl mole number ratio of the isocyano mole summation of monomeric diisocyanate and polyvalent alcohol wherein, namely the NCO/OH ratio is 2:1; Dibutyl tin dilaurate is catalyzer, and its consumption is 0.2% of polyvalent alcohol and isocyanic ester total mass; Wherein the triethylamine molar weight is 100% of dimethylol propionic acid molar weight in the step (2), wherein step (3) adds reactive thinner butyl acrylate (BA) and tripropylene glycol double methacrylate (TPGDA) in the performed polymer emulsion that makes, its total amount is 94% of the aqueous polyurethane acrylate performed polymer quality of the emulsion that makes in the step (2), and the consumption of light trigger 2-hydroxy-2-methyl-1-phenyl-acetone is 4% of the aqueous polyurethane acrylate performed polymer quality of the emulsion that makes in the step (2).
5. the preparation method of a kind of aqueous polyurethane acrylate photocureable paint according to claim 2 is characterized in that wherein the polyvalent alcohol described in the step (1) is two functionality polyether glycol NJ-210; Described isocyanic ester is isophorone diisocyanate.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921447A (en) * | 2010-04-16 | 2010-12-22 | 江苏大学 | Method for preparing a waterborne poly(urethane acrylate)/nano-titanium dioxide hybrid material |
| CN101974141A (en) * | 2010-09-19 | 2011-02-16 | 广州市香港科大***研究院 | Preparation method of water-based polyacrylate modified polyurethane dispersion (PUD) |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921447A (en) * | 2010-04-16 | 2010-12-22 | 江苏大学 | Method for preparing a waterborne poly(urethane acrylate)/nano-titanium dioxide hybrid material |
| CN101974141A (en) * | 2010-09-19 | 2011-02-16 | 广州市香港科大***研究院 | Preparation method of water-based polyacrylate modified polyurethane dispersion (PUD) |
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