CN102336875A - 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 photo-cured coating.
Background technology
In recent years, environment protection receives people's attention day by day, and many countries have issued 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 gets into air and causes serious environmental to pollute, and is detrimental to health.The coating material solidified employing reactive thinner of UV-light (UV) replace organic solvent; Wherein, Reactive thinner is non-volatile basically, has the dual-use function of curing cross-linked and solvent concurrently, and its molecule contains and can be caused and can be further and functional group's (like two keys) of prepolymer cross-linking reaction by photosensitive radical; Reactive thinner is used for regulating the rheological of coating, and dry solidification and the film performance to coating also produced influence simultaneously.Thinner plays diluting effect on the one hand, the viscosity that coating is had be convenient to construct; Play crosslinked action on the other hand again, so it must have good reactive behavior, it solidifies the laggard resin network of going into, and the final performance of cured product is had very big influence.Requirement to reactive thinner mainly is the response capacity of LV, highly diluted property and height; It is little also will to take into account volatility, toxicity, pungency and stink simultaneously, 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 special advantages; 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 glazing and solder resist is particularly rapid.Tradition seasoning or heat curing coating; Its capacity usage ratio is low, pollution is big, 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; Being comparatively active research and development field at present, having become one of main developing direction of ultraviolet light polymerization system, is the Green Product towards 21st 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 end capped method; Produce a series of UV solidified aqueous polyurethane acrylates (WPUA); Confirm the chemical structure that contains different functionality aqueous polyurethane acrylates that makes through infrared test, the chainextender of having studied different functionality is to the WPUA Effect on Performance.The result shows that average functionality all has good effect to the water tolerance and the tensile strength of UV solidified WPUA film.In addition, through 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 this method makes is bigger, is easy to take place coacervation, and stability is not good enough, and then influences 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.(MMA) is reactive thinner with TEB 3K, studied different diluent concentrations, and different light trigger types and concentration are to the influence of film performance.And the performance before and after the modification compared; The result shows: the ultraviolet-curing paint by the resins after the modification has overcome unsaturated polyester amide urea coating softness inadequately; 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, make and produce complex steps, instability, and when different amount of diluent are discussed the influencing of curing membrane performance,, be difficult to guarantee the practical application of material all not making a search the mechanical property and set time of cured film.
(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 through 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 crystalline formation.The all samples that makes has good pencil hardness, elasticity, wear resistance and water tolerance.But the sample thermostability that makes is relatively poor relatively, and reactive thinner HDDA and TMPTA content are not made dependence test to the 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
To the deficiency that exists in the above-mentioned 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) takes into account and add a certain amount of monomer polyvalent alcohol and isocyanic ester in the container of feeding device in that whisking appliance, reflux condensing tube, temperature are housed; Add hydrophilic chain extender dimethylol propionic acid (DMPA), its consumption is the 1-10% of total monomer quality, and the preferred mass ratio is 6%; With N-Methyl pyrrolidone (NMP) is solvent; Its consumption is 10% of a monomer polyvalent alcohol, and system is warmed up to 70-80 ℃, wherein the isocyano mole summation of monomeric diisocyanate and hydroxyl groups mole number ratio; Be that the NCO/OH ratio is 1:1.5-2:1, preferred 2:1; Adding dibutyl tin dilaurate (T-12) again is catalyzer, 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 Rocryl 400 (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 Rocryl 400 (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 Bing Xisuandingzhi (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 ℃,, can add a certain amount of acetone if the system viscosity is excessive.
Technical essential of the present invention: the present invention adopts in-situ method to produce aqueous polyurethane acrylate photocuring performed polymer; The preparation process is simple; Selected Bing Xisuandingzhi (BA) and tripropylene glycol double methacrylate (TPGDA) as thinner, in the viscosity of regulating emulsion through the ratio that changes BA and TPGDA again and the emulsion soft section with firmly section ratio, stoped the particulate generation; Thereby make emulsion dispersion even, good stability.Make the weathering resistance of cured film simultaneously, mechanical property, gel fraction and set time etc. is greatly improved.
Embodiment:Below in conjunction with instance the present invention is elaborated, but the present invention is not limited to following instance.
Embodiment 1
In that being housed, whisking appliance, reflux condensing tube, temperature take into account the polyether glycol (NJ-210) that adds 13.87g in the 500mL four-hole bottle of feeding device 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), behind the stirring 30min, system temperature is risen to 80 ℃; (if the system viscosity is excessive, can add a certain amount of acetone) is after continuing to react 4h; Be cooled to 60 ℃, methylate Hydroxyethyl acrylate (HEMA) 2.79g cools the temperature to 40 ℃ behind the reaction 5h; Add triethylamine 1.24g, reaction 0.5h drips 82g water and disperses; 0.5h the back adds reactive thinner Bing Xisuandingzhi (BA) 95.4g and tripropylene glycol double methacrylate (TPGDA) 10.6g in performed polymer; 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 the aqueous polyurethane acrylate photo-cured coating
UV-WPUA-1
Embodiment 2
Take into account the dimethylol propionic acid (DMPA) that adds polyether glycol (NJ-220), 1.967g N-Methyl pyrrolidone (NMP) and the 1.474g of 19.673g in the 500mL four-hole bottle of feeding device in that whisking appliance, reflux condensing tube, temperature are housed, system is warmed up to 60 ℃, add 8.325g isophorone diisocyanate (IPDI); Drip catalyzer 0.118g dibutyl tin dilaurate (T-12), behind the stirring 30min, system temperature is risen to 80 ℃; (if the system viscosity is excessive, can add a certain amount of acetone) is after continuing to react 4h; Be cooled to 60 ℃; Methylate Hydroxyethyl acrylate (HEMA) 4.333g with near 40 ℃ of temperature, adds triethylamine 1g behind the reaction 5h; Reaction 0.5h; Drip 98g water and disperse, in performed polymer, add Bing Xisuandingzhi (BA) 88.9g and tripropylene glycol double methacrylate (TPGDA) 38.1g behind the 0.5h, 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 the aqueous polyurethane acrylate photo-cured coating
UV-WPUA-2
Embodiment 3
Take into account the polyether glycol NJ-210 that adds 10g in the 500mL four-hole bottle of feeding device, dimethylol propionic acid (DMPA) and 1g N-Methyl pyrrolidone (NMP) solvent of 1.175g in that whisking appliance, reflux condensing tube, temperature are housed, system is warmed up to 60 ℃, add 8.325g isophorone diisocyanate (IPDI); Drip catalyzer 0.039g dibutyl tin dilaurate (T-12), behind the stirring 30min, system temperature is risen to 80 ℃; (if the system viscosity is excessive, can add a certain amount of acetone) is after continuing to react 4h; Be cooled to 60 ℃; Methylate Hydroxyethyl acrylate (HEMA) 4.875g with near 40 ℃ of temperature, adds triethylamine 0.884g behind the reaction 5h; Reaction 0.5h; Drip 72g water and disperse, in performed polymer, add reactive thinner Bing Xisuandingzhi (BA) 45.7g and tripropylene glycol double methacrylate (TPGDA) 45.7g, reaction 40min behind the 0.5h.Cool the temperature to 25 ℃, add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Darocure 1173) 3.89g, reaction 30min can make the aqueous polyurethane acrylate photo-cured coating
UV-WPUA-3
Embodiment 4
In that being housed, whisking appliance, reflux condensing tube, temperature take into account the polyether glycol (NJ-210) that adds 10.93g in the 500mL four-hole bottle of feeding device 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), behind the stirring 30min, system temperature is risen to 80 ℃; (if the system viscosity is excessive, can add a certain amount of acetone) is after continuing to react 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 the back adds reactive thinner Bing Xisuandingzhi (BA) 23.082g and tripropylene glycol double methacrylate (TPGDA) 53.858g in 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 the aqueous polyurethane acrylate photo-cured coating
UV-WPUA-4
Embodiment 5
Take into account in dimethylol propionic acid (DMPA) the adding reaction unit of the polyether glycol (NJ-220), 2.282g N-Methyl pyrrolidone (NMP) and the 2.659g that add 22.82g in the 500mL four-hole bottle of feeding device in that whisking appliance, reflux condensing tube, temperature are housed, system is warmed up to 60 ℃, add 12.5g '-diphenylmethane diisocyanate (MDI); Drip catalyzer 0.171g dibutyl tin dilaurate (T-12), behind the stirring 30min, system temperature is risen to 80 ℃; (if the system viscosity is excessive, can add a certain amount of acetone) is after continuing to react 4h; Be cooled to 60 ℃; Methylate Hydroxyethyl acrylate (HEMA) 3.047g with near 40 ℃ of temperature, adds triethylamine 1.964g behind the reaction 5h; Reaction 0.5h; Drip 80g water and disperse, in performed polymer, add tripropylene glycol double methacrylate (TPGDA) 15.364g and Bing Xisuandingzhi (BA) 138.276g, reaction 40min behind the 0.5h.Cool the temperature to 25 ℃, add light trigger 2-hydroxy-2-methyl-1-phenyl-acetone (Darocure 1173) 6.68g, reaction 30min can make the aqueous polyurethane acrylate photo-cured coating
UV-WPUA-5
Experimental technique
Measure aqueous polyurethane acrylate photocuring emulsion film forming time, cured film gel fraction and tensile strength,
Shown in result such as the 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 makes cured film have mechanical property preferably.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 industrial technology of 21st century Sustainable development, have good economic benefits and social benefit.
Claims (5)
1. the preparation method of an aqueous polyurethane acrylate photo-cured coating is characterized in that carrying out according to following step:
(1) in container, add a certain amount of monomer polyvalent alcohol and isocyanic ester, add the hydrophilic chain extender dimethylol propionic acid, its consumption is the 1-10% of total monomer quality; With the N-Methyl pyrrolidone is solvent; Its consumption is 10% of a monomer polyvalent alcohol, and system is warmed up to 70-80 ℃, wherein the isocyano mole summation of monomeric diisocyanate and hydroxyl groups mole number ratio; Be that the NCO/OH ratio is 1:1.5-2:1; Adding dibutyl tin dilaurate again is catalyzer, and its consumption is the 0.1%-0.5% of polyvalent alcohol and isocyanic ester total mass
(2) behind the reaction 3-4h, system is cooled to 60-70 ℃, add Rocryl 400 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 Rocryl 400 total mass 3 times; About reaction 30min, can make aqueous polyurethane acrylate performed polymer emulsion;
(3) in the performed polymer emulsion that makes, add reactive thinner Bing Xisuandingzhi and tripropylene glycol double methacrylate, its total amount is the 90%-98% of the aqueous polyurethane acrylate performed polymer quality of the emulsion that makes in the step (2), reacts 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 photo-cured coating 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 photo-cured coating 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 photo-cured coating according to claim 1; It is characterized in that wherein the consumption of step (1) hydrophilic chain extender dimethylol propionic acid is 6% of a total monomer quality; Wherein the isocyano mole summation of monomeric diisocyanate and hydroxyl groups mole number ratio, promptly the NCO/OH ratio is 2:1; Dibutyl tin dilaurate is a catalyzer, and its consumption is 0.2% of polyvalent alcohol and an isocyanic ester total mass; Wherein the triethylamine molar weight is 100% of a dimethylol propionic acid molar weight in the step (2); Wherein step (3) adds reactive thinner Bing Xisuandingzhi (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 photo-cured coating 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 an isophorone diisocyanate.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090111934A1 (en) * | 2007-10-02 | 2009-04-30 | Caideng Yuan | Method for preparing aqueous polyacrylate modified polyurethane dispersions |
| 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 | 广州市香港科大霍英东研究院 | Preparation method of water-based polyacrylate modified polyurethane dispersion (PUD) |
-
2011
- 2011-06-29 CN CN 201110178027 patent/CN102336875B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090111934A1 (en) * | 2007-10-02 | 2009-04-30 | Caideng Yuan | Method for preparing aqueous polyacrylate modified polyurethane dispersions |
| 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 | 广州市香港科大霍英东研究院 | Preparation method of water-based polyacrylate modified polyurethane dispersion (PUD) |
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| CN117586695A (en) * | 2023-12-01 | 2024-02-23 | 江苏众立生包装科技有限公司 | Preparation method of modified polyurethane-acrylic ester cold-stamping coating |
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