CN102702469A - Ultraviolet-curable aqueous polyurethane dispersion and preparation method thereof - Google Patents
Ultraviolet-curable aqueous polyurethane dispersion and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an ultraviolet-curable aqueous polyurethane dispersion, also provides a preparation method of the ultraviolet-curable aqueous polyurethane dispersion and aims to provide an ultraviolet-curable aqueous polyurethane dispersion with a highly-branched structure, high double bond content and storage stability. The technical solution is that the dispersion is prepared by the following steps: 1), adding castor oil into a reactor, heating and dewatering the castor oil, cooling, adding polyisocyanate, heating till reaction begins, and thus obtaining a product A; 2), cooling the product A, adding a solvent A, dripping low molecular polyol with tertiary amino groups, and reacting to obtain a product B; 3), adding a vinyl monomer with hydroxyl and an organic metal catalyst into the product B, and reacting to obtain a product C; 4), uniformly mixing 30-100 parts of acid by weight and 1000-2000 parts of water by weight, dripping the mixture into the product C, removing the solvent, and thus obtaining a product D; and 5), adding a photoinitiator and methyl pyrrolidone into the product D to obtain the ultraviolet-curable aqueous polyurethane dispersion. The preparation method of the ultraviolet-curable aqueous polyurethane dispersion belongs to the technical field of preparation of chemical dispersion.
Description
Technical field
The present invention relates to a kind of dispersion system, specifically, is a kind of photocurable aqueous pu dispersions, the invention still further relates to the preparation method of this dispersion system, belongs to chemical industry dispersion system preparing technical field.
Background technology
UV-curing technology has been widely used in the polymer cure, is characterized in that resin at room temperature can become solid-state from flowable state through UV-irradiation.Traditional ultraviolet light polymerization system generally is made up of light trigger, the oligopolymer that contains unsaturated double-bond and reactive reactive thinner.The main effect of thinner is the viscosity of reduction system, but it has the intensive smell, simultaneously sense organ and skin is had stronger stimulation.Along with to changing commanders and safe pay attention to day by day, should gradually reduce or forbid the application of this thinner.In this case, the aqueous photo-curing system is arisen at the historic moment; This system is dispersion agent with water, has both reduced the pollution to environment, has reduced the inflammableness of system simultaneously again.
CN200810039199.3 has disclosed a kind of ultraviolet light solidfication water polyurethane coating; At first be respectively the method for terminal hydroxy group through chemical bond and be incorporated in polyurethane polyol or the isocyanate-terminated base polyurethane prepolymer for use as, contain the water-borne PU dispersion coatings of multi-thiol and polynary alkene again through the self-emulsifying preparation with polyvalent alcohol and alkene; Be prepared into aqueous polyurethane coating with above-mentioned two kinds of polyurethane aqueous dispersions coating as the basis then, its solid content is 15～55%; The CN101613449A disclosure of the Invention a kind of waterborne polyurethane resin of ultraviolet light polymerization; The waterborne polyurethane resin of this kind ultraviolet light polymerization is introduced polyether glycol in the polyurethane backbone; And can introduce more two key in the such polyurethane chain of monomer end-blocking with the monohydroxy esters of acrylic acid and carry out crosslinking polymerization; Improve the crosslinked and relative molecular weight of filming, effectively improved the chemical resistance of UV curable water-borne system, can take into account hardness and snappiness two sides performance simultaneously.
But there is the defective that double bond content is low, cross-linking density is low in the above-mentioned patent, after causing solidifying, defective such as water tolerance, solvent resistance and mechanical property are not good enough, and hardness is on the low side.Because molecular weight is little, problems such as breakdown of emulsion, layering appear in poor storage stability easily in storage process simultaneously.
Summary of the invention
To above-mentioned deficiency, the present invention discloses photocurable aqueous pu dispersions of a kind of height cladodification structure, double bond content height, stable storing and preparation method thereof.
Last technical scheme of the present invention is such: a kind of aqueous pu dispersions of uV curable,, this dispersion system prepares through following step:
1) taking by weighing 300～600 weight part Viscotrol C is added in the reactor drum of belt stirrer; Be heated to 100～130 ℃ of vacuum hydro-extraction 30～120min; When being cooled to 50～60 ℃; 200～600 weight part POLYMETHYLENE POLYPHENYLISOCYANATE that add while stirring, be warming up to 60～100 ℃ of reaction 60～240min after, obtain product A;
When 2) product A being cooled to 55～65 ℃, add 100～400 parts by weight solvent,, after 1～3 hour, obtain product B 40～60 ℃ of reactions 40～50 ℃ of low molecular weight polyols that drip 60～200 weight part band tertiary amine groups while stirring;
3) add hydroxyl vinyl monomer and 0.001～0.1 weight part organo-metallic catalyst of 20～120 weight parts to product B,, obtain product C 40～80 ℃ of reactions 1～3 hour;
4) 30～100 weight parts acid and 1000～2000 weight parts waters are mixed after, drop in the product C, continuously stirring product C in the dropping process, drip finish to continue to stir 30～60min after, solvent is deviate from underpressure distillation again, obtains product D;
5) in product D, add 0.1～2% light trigger and 1～10 weight part SL 1332, stir, promptly obtain the aqueous pu dispersions of this uV curable.
The aqueous pu dispersions of above-mentioned a kind of uV curable is characterized in that, step 1) takes by weighing 300～600 weight part Viscotrol C and is added in the reactor drum of belt stirrer; After being heated to 100～130 ℃ of vacuum hydro-extraction 30～120min; Add 1～100 weight part low molecular weight polyols, when being cooled to 50～60 ℃, 200～600 weight part POLYMETHYLENE POLYPHENYLISOCYANATE that add while stirring; After being warming up to 60～100 ℃ of reaction 60～240min, obtain product A;
The aqueous pu dispersions of above-mentioned a kind of uV curable; It is characterized in that; Step 5) adds the polyfunctionality UV reactive thinner of 0.1～100 weight part to product D; The light trigger and 1～10 weight part SL 1332 of adding 0.1～2% stir after stirring, and promptly obtain the aqueous pu dispersions of this uV curable.
Back of the present invention one technical scheme is such: the preparation method of the aqueous pu dispersions of this uV curable comprises following preparation process successively:
1) takes by weighing the there-necked flask that 300～600 weight part Viscotrol C are added to belt stirrer, be heated to 100～130 ℃ of vacuum hydro-extraction 30～120min, add low molecular weight polyols 0～100 weight part while stirring; When being cooled to 50～60 ℃, POLYMETHYLENE POLYPHENYLISOCYANATE 200～600 weight parts that add while stirring are warming up to 60～100 ℃ of reaction 60～240min, obtain product A;
2) when product A is cooled to 55～65 ℃, add 100～400 parts by weight solvent, drip the low molecular weight polyols that contains 60～200 weight part tertiary amine groups while stirring at 40～50 ℃, 40～60 ℃ of reactions 1～3 hour, obtain product B;
3) add hydroxyl vinyl monomer and 0.001～0.1 weight part organo-metallic catalyst of 20～120 weight parts to product B,, obtain product C 40～80 ℃ of reactions 1～3 hour;
4) 30～100 weight parts acid and 1000～2000 weight parts waters are mixed after, drop in the product C, continuously stirring product C in the dropping process, drip finish to continue stirring 30～60min after, solvent is deviate from underpressure distillation, obtains product D;
5) in product D, add the polyfunctionality UV reactive thinner of 0～100 weight part; Stir; Add the light trigger and 1～10 weight part SL 1332 solution of 0.1～2 weight part, stir, promptly obtain the aqueous pu dispersions of this uV curable.
The preparation method of the aqueous pu dispersions of above-mentioned uV curable, step 1) and step 2) described in low molecular weight polyols be that make up arbitrarily one of them or they of terepthaloyl moietie, Ucar 35, butyleneglycol, glycol ether, Diethylene Glycol, pentanediol, NSC 6366, trishydroxymethyl propyl alcohol, USP Kosher, tetramethylolmethane.
Further, the preparation method of the aqueous pu dispersions of above-mentioned uV curable, the described POLYMETHYLENE POLYPHENYLISOCYANATE of step 1) is 1,6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, 2; 2,4-trimethylammonium-hexamethylene diisocyanate, 2; 4,4-trimethylammonium-hexamethylene diisocyanate, 4; 4 ‵-isocyanic ester cyclohexyl methylmethane, isocyanatomethyl-1,8-octane vulcabond, 1,4-hexamethylene and isocyanic ester, 1; 4-phenylene diisocyanate, 2,4 toluene diisocyanate, 2, the arbitrary combination of 6-tolylene diisocyanate one of them or they.
Further; The preparation method of the aqueous pu dispersions of above-mentioned uV curable, the hydroxyl vinyl monomer described in the step 3) is one of them of Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 400, pentaerythritol triacrylate or trimethylolpropane diacrylate or their arbitrary combination.
Further, the preparation method of the aqueous pu dispersions of above-mentioned uV curable, step 2) described solvent is acetone or butanone.
Further; The preparation method of the aqueous pu dispersions of above-mentioned uV curable, the described organo-metallic catalyst of step 3) is one of them of organic tin catalyzer, metal carboxylate catalyzer, titanate ester catalyzer, organic zirconium class catalyzer, organo-bismuth class catalyzer.
Further, the preparation method of the aqueous pu dispersions of above-mentioned uV curable, the described acid of step 4) be acetate or formic acid or hydrochloric acid or oxalic acid one of.
Further; The preparation method of the aqueous pu dispersions of above-mentioned uV curable; The described UV reactive thinner of step 5) is 1; In in 6-hexanediyl ester, dipropylene glycol two (methyl) propenoate, 1,4 butanediol diacrylate, neopentylglycol diacrylate, TriMethylolPropane(TMP) (methyl) propenoate, oxyethyl group Viscoat 295, tetramethylol methane tetraacrylate, Dipentaerythritol five propenoate, the dipentaerythritol acrylate one or their arbitrary combination.
Further; The preparation method of the aqueous pu dispersions of above-mentioned uV curable, the described light trigger of step 5) be UVNUL MS-40 or benzoin methyl ether or Alpha-hydroxy Benzoin ethyl ether or Alpha-hydroxy isopropyl benzene ketone or 4 '-(2-hydroxy ethoxy)-2-hydroxy-2-methyl Propiophenone, Alpha-hydroxy phenylcyclohexane ketone, isopropyl thioxanthone, 2-(4-methylthio phenyl formyl radical)-2-morpholinyl propane or one of them of oligomeric-hydroxyketone or their arbitrary combination.
Compared with prior art, the present invention's advantage specific as follows:
1. overcome surfaces of tacky after the preliminarily dried that prior art medium ultraviolet photocuring aqueous polyurethane causes because of molecular weight for a short time, defective that intensity is low.
2. owing to improved the content of two keys in the resin when introducing a large amount of cladodification structures, behind ultraviolet light polymerization, have very high cross-linking density, cured article has very excellent hardness, water tolerance and solvent resistance.
3. the method provided by the present invention photocurable aqueous polyurethane stability in storage of producing is very excellent, at room temperature can deposit 2 years systems and not have considerable change.
4. the photocurable aqueous polyurethane produced of method provided by the present invention can be used for the top coat of base materials such as woodenware, paper, plastics, leather, textiles.
Embodiment
The present invention confirms to build on the basis of a large amount of simultaneous tests and screening about the design of photocurable aqueous polyurethane and each component and usage quantity thereof; Specific embodiments more given below are part preferred version of the present invention; Further explain the present invention, but do not limit the invention to the scope of following embodiment.Preparing method who adopts among the embodiment and use together can be with reference to laboratory, present technique field ordinary method, concrete preparation process is exemplified below:
Embodiment 1
The 2000Ml there-necked flask is furnished with TM, stirring, heating and whipping appts.Add refined caster oil 500g in the there-necked flask, be heated with stirring to 120 ± 5 ℃.Vacuum hydro-extraction 60min is cooled to 70 ℃ and adds IPDI (isophorone diisocyanate) 370.6 grams, keeps 80 ± 5 ℃ of reactions 3 hours; Be cooled to 60 ℃, add anhydrous propanone 300g, temperature is reduced to 45 ± 5 ℃ of addings; Drip the 93g methyldiethanolamine; Dropping time 30min dripped the back and adds organic bismuth catalyst 0.5g, in 50 ± 2 ℃ of insulations 3 hours.Add the Rocryl 400 56g through processed, 60 ± 2 ℃ are reacted 2 hours to react completely (it is zero that the absorption peak that detects the NCO functionality of 2260～2280cm-1 through ir spectra disappears).Be cooled to 30 ± 2 ℃, performed polymer is transferred in the 5L emulsion tank, add the mixing solutions of 46g acetate and 1200g deionized water under the high-speed stirring; Get water dispersion, acetone is deviate from 45 ± 5 ℃ of underpressure distillation, translucent aqueous pu dispersions; Viscosity 130mpa.s, solid content are 41%; Take by weighing 0.5g Darocur 1173 (Ciba company again; 2-hydroxy-2-methyl-1-phenyl-1-acetone) and N; N-Methyl pyrrolidone 2g dissolving evenly joins in the above-mentioned aqueous pu dispersions of 100g, makes the aqueous pu dispersions of uV curable.
Embodiment 2
The 2000Ml there-necked flask is furnished with TM, stirring, heating and whipping appts.Add refined caster oil 400g in the there-necked flask, be heated with stirring to 120 ± 5 ℃, vacuum hydro-extraction 60min; Adding is cooled to 70 ℃ through the pentanediol 18g of processed, adds HMDI (dicyclohexyl methane diisocyanate; Purity >=99.5%) 324.3 grams are kept 82 ± 2 ℃ of reactions 3 hours.Be cooled to 60 ℃, add anhydrous butanone 250g, temperature is reduced to 45 ± 5 ℃, drips the 99.8g methyldiethanolamine, drips time 30min, after dripping, in 50 ± 2 ℃ of insulations 3 hours.Add Propylene glycol monoacrylate 100g through processed, organic bismuth catalyst 0.5g, 60 ± 2 ℃ are reacted 2 hours to react completely (it is zero that the absorption peak that detects the NCO functionality of 2260～2280cm-1 through ir spectra disappears).Be cooled to 30 ± 2 ℃, performed polymer is transferred in the 5L emulsion tank, add the mixing solutions of 49.2g acetate and 1600g deionized water under the high-speed stirring; Get water dispersion, acetone is deviate from 45 ± 5 ℃ of underpressure distillation, translucent aqueous pu dispersions; Viscosity 180mpa.s, solid content are 40.2%.
Take by weighing 0.5g Alpha-hydroxy phenylcyclohexane ketone and N again, N-Methyl pyrrolidone 2g dissolving evenly joins in the 100g above-mentioned steps gained aqueous pu dispersions, makes the aqueous pu dispersions of uV curable.
Embodiment 3
The 2000Ml there-necked flask is furnished with TM, stirring, heating and whipping appts.Add refined caster oil 600g in the there-necked flask, be heated with stirring to 120 ± 5 ℃, vacuum hydro-extraction 60min; Be cooled to 70 ℃, add through 1 of processed 4-butyleneglycol 20g; Add IPDI (isophorone diisocyanate) 419.3 grams, keep 82 ± 2 ℃ of reactions 3 hours.Be cooled to 60 ℃, add anhydrous propanone 250g, temperature is reduced to 45 ± 5 ℃, drips the 99.8g methyldiethanolamine, drips time 30min, after dripping, in 50 ± 2 ℃ of insulations 3 hours.Add Propylene glycol monoacrylate 100g through processed, organic bismuth catalyst 0.5g, 60 ± 2 ℃ are reacted 2 hours to react completely (it is zero that the absorption peak that detects the NCO functionality of 2260～2280cm-1 through ir spectra disappears).Be cooled to 30 ± 2 ℃, performed polymer is transferred in the 5L emulsion tank, add the mixing solutions of 49.2g acetate and 1600g deionized water under the high-speed stirring; Get water dispersion, acetone is deviate from 45 ± 5 ℃ of underpressure distillation, translucent aqueous pu dispersions; Viscosity 300mpa.s, solid content are 39.2%.
Take by weighing 0.5g Alpha-hydroxy phenylcyclohexane ketone and N again, N-Methyl pyrrolidone 3g dissolving evenly joins in the 100g above-mentioned steps gained aqueous pu dispersions, makes the aqueous pu dispersions of uV curable.
Embodiment 4
The 2000Ml there-necked flask is furnished with TM, stirring, heating and whipping appts.Add refined caster oil 275.0g in the there-necked flask, be heated with stirring to 120 ± 5 ℃, vacuum hydro-extraction 60min; Be cooled to 70 ℃, add through 1 of processed 4-butyleneglycol 50g; Add TDI (tolylene diisocyanate) 398 grams when being cooled to 50 ℃ and mix, keep 70 ± 5 ℃ of reactions 3 hours.Be cooled to 60 ℃, add anhydrous butanone 300g, temperature is reduced to 45 ± 5 ℃ of addings, drips the 128g methyldiethanolamine, drips time 30min, after dripping, in 50 ± 2 ℃ of insulations 3 hours, to NCO content 1.0%.Add TriMethylolPropane(TMP) (methyl) triacrylate ester 80g through processed; Organic bismuth catalyst 0.5g, 60 ± 2 ℃ are reacted 2 hours to react completely (it is zero that the absorption peak that detects the NCO functionality of 2260～2280cm-1 through ir spectra disappears).Be cooled to 30 ± 2 ℃, performed polymer is transferred in the 5L emulsion tank, add the mixing solutions of 64g acetate and 1400g deionized water under the high-speed stirring; Get water dispersion, butanone is deviate from 55 ± 5 ℃ of underpressure distillation, translucent aqueous pu dispersions; Viscosity 500mpa.s, solid content are 38.5%.
Take by weighing 0.6g Darocur 1173 (Ciba company again; 2-hydroxy-2-methyl-1-phenyl-1-acetone) and N; N-Methyl pyrrolidone 3g dissolving evenly joins in the 100g above-mentioned steps gained aqueous pu dispersions, makes the aqueous pu dispersions of uV curable.
Embodiment 5
The 2000Ml there-necked flask is furnished with TM, stirring, heating and whipping appts.Add refined caster oil 300g in the there-necked flask, be heated with stirring to 120 ± 5 ℃, vacuum hydro-extraction 60min adds HDI (1, the 6-hexamethylene diisocyanate) 200g and mixes when being cooled to 70 ℃, keep 90 ± 5 ℃ of reactions 3 hours.Be cooled to 60 ℃, add anhydrous butanone 200g, temperature is reduced to 45 ± 5 ℃ of addings, drips the 37.5g methyldiethanolamine, drips time 30min, after dripping, in 50 ± 2 ℃ of insulations 3 hours.Add Rocryl 400 37g through processed, organic bismuth catalyst 0.5g, 60 ± 2 ℃ are reacted 2 hours to react completely (it is zero that the absorption peak that detects the NCO functionality of 2260～2280cm-1 through ir spectra disappears).Be cooled to 30 ± 2 ℃, performed polymer is transferred in the 5L emulsion tank, add the mixing solutions of 38g acetate and 1000g deionized water under the high-speed stirring; Get water dispersion, butanone is deviate from 55 ± 5 ℃ of underpressure distillation, translucent aqueous pu dispersions; Viscosity 700mpa.s, solid content are 39.2%.
Take by weighing 0.6g Darocur 1173 (Ciba company again; 2-hydroxy-2-methyl-1-phenyl-1-acetone) and N; N-Methyl pyrrolidone 3g dissolving evenly joins in the 100g above-mentioned steps gained aqueous pu dispersions, makes the aqueous pu dispersions of uV curable.
Comparative Examples 1:
The 2000Ml there-necked flask is furnished with TM, stirring, heating and whipping appts.Add refined caster oil 500g in the there-necked flask, be heated with stirring to 120 ± 5 ℃.Vacuum hydro-extraction 60min is cooled to 70 ℃ and adds IPDI (isophorone diisocyanate) 370.6 grams, keeps 80 ± 5 ℃ of reactions 3 hours; Be cooled to 60 ℃, add anhydrous propanone 300g, temperature is reduced to 45 ± 5 ℃ of addings; Drip the 93g methyldiethanolamine; Dropping time 30min dripped the back and adds organic bismuth catalyst 0.5g, in 50 ± 2 ℃ of insulations 3 hours.Add the Rocryl 400 56g through processed, 60 ± 2 ℃ are reacted 2 hours to react completely (it is zero that the absorption peak that detects the NCO functionality of 2260～2280cm-1 through ir spectra disappears).Be cooled to 30 ± 2 ℃, performed polymer is transferred in the 5L emulsion tank, add the mixing solutions of 46g acetate and 1200g deionized water under the high-speed stirring; Get water dispersion, acetone is deviate from 45 ± 5 ℃ of underpressure distillation, translucent aqueous pu dispersions; Viscosity 130mpa.s, solid content are 41%; Take by weighing 0.5g Darocur 1173 (Ciba company again; 2-hydroxy-2-methyl-1-phenyl-1-acetone) and N; N-Methyl pyrrolidone 2g dissolving evenly joins in the above-mentioned aqueous pu dispersions of 100g, makes the aqueous pu dispersions of uV curable.
Comparative Examples 2:
The 1000Ml there-necked flask is furnished with TM, stirring, heating and whipping appts.Add two functionality polyether glycol 300g (GE210, Shanghai Gaoqiao petrochemical industry) in the there-necked flask, be heated with stirring to 120 ± 5 ℃; Vacuum hydro-extraction 60min adds IPDI186.3g when being cooled to 70 ℃ and the 0.5g organic bismuth catalyst mixes, and keeps 85 ± 5 ℃ of reactions 3 hours; Be cooled to 60 ℃; The mixing solutions that adds DMPA (dimethylol propionic acid) 40g and 80g NMP (N, N-Methyl pyrrolidone), 65 ± 2 ℃ are incubated 3 hours; Add Hydroxyethyl acrylate 55g, react 2 hours to react completely (it is zero that the absorption peak that detects the NCO functionality of 2260～2280cm-1 through ir spectra disappears) through processed.Be cooled to 50 ± 2 ℃, anhydrous propanone 150g, triethylamine 30.1g is cooled to 30 ± 2 ℃.Adding is transferred to performed polymer in the 3L emulsion tank, adds the mixing solutions of 900g deionized water under the high-speed stirring, gets water dispersion, and acetone is deviate from 45 ± 5 ℃ of underpressure distillation, gets translucent aqueous pu dispersions, and viscosity 550mpa.s, solid content are 41%.
Comparative Examples 3:
0.5g Darocur 1173 (Ciba company; 2-hydroxy-2-methyl-1-phenyl-1-acetone) and N; N-Methyl pyrrolidone 2g dissolving evenly joins in the 100g Comparative Examples 1 gained aqueous pu dispersions, makes the aqueous pu dispersions of uV curable.
The PT of aqueous polyurethane-polyurea dispersions
Get above-mentioned aqueous polyurethane-polyurea dispersions 50 grams, room temperature was placed 24 hours on the tetrafluoroethylene plate of 20cm*20cm, surface drying; And then under 60 ℃, drying is 4 hours in blast drier, puts into UV curing machine at last; Level places under the 500W medium pressure mercury lamp shone 1 minute, accomplished and solidified.Comparative Examples 1 and Comparative Examples 2 are without the UV curing schedule.
Water-fast test: cured film is cut into the 5cm*5cm size, is placed in the beaker that deionized water is housed, the surface covers with petridish, places moisture evaporation.Be placed in the baking oven, oven temperature is set at 40 ℃, the variation of the outward appearance of observation film after 24 hours.Not whitening fully is 1 grade, and the dissolved that seriously whitens is 5 ranks.
The solvent resistance test: cured film is cut into the 5cm*5cm size, is placed in the beaker that toluene and alcohol are housed respectively, the surface covers with petridish, and ambient stable is set at 25 ℃, and swelling ratio is calculated in the variation of test membrane area after 72 hours.
The test of hardness: carry out according to " GB/T 6739-2006 paint and varnish pencil method is measured hardness of paint film ".
Test result sees the following form
| Dispersion-s | Water tolerance | The toluene swell rate | The alcohol swelling ratio | Hardness |
| Embodiment 1 | 1 | 32% | 45% | 2H |
| Embodiment 2 | 1 | 30% | 41% | 2H |
| Embodiment 3 | 1 | 28% | 35% | 3H |
| Embodiment 4 | 1 | 10% | 21% | 3H |
| Embodiment 5 | 1 | 40% | 60% | H |
| Comparative Examples 1 | 2 | 210% | Dissolving | B |
| Comparative Examples 2 | Dissolving | Dissolving | Dissolving | --(annotating 1) |
| Comparative Examples 3 | 2 | 190% | Dissolving | HB |
Annotate 1: hardness is too low, and pencil hardness method can't be measured.
Show from test result; Adopt the photocurable washing leather polyurethane dispersions of the present invention's preparation; Even after drying, solidify, had excellent water tolerance, solvent resistance and physical and mechanical properties, after the UV aftertreatment without UV; Can increase substantially water tolerance, solvent resistance and hardness, performance index reach solvent-borne type or the requirement of no-solvent type UV system.
Claims (13)
1. the aqueous pu dispersions of a uV curable is characterized in that, this dispersion system prepares through following step:
1) taking by weighing 300～600 weight part Viscotrol C is added in the reactor drum of belt stirrer; Be heated to 100～130 ℃ of vacuum hydro-extraction 30～120min; When being cooled to 50～60 ℃; 200～600 weight part POLYMETHYLENE POLYPHENYLISOCYANATE that add while stirring, be warming up to 60～100 ℃ of reaction 60～240min after, obtain product A;
When 2) product A being cooled to 55～65 ℃, add 100～400 parts by weight solvent,, after 1～3 hour, obtain product B 40～60 ℃ of reactions 40～50 ℃ of low molecular weight polyols that drip 60～200 weight part band tertiary amine groups while stirring;
3) add hydroxyl vinyl monomer and 0.001～0.1 weight part organo-metallic catalyst of 20～120 weight parts to product B,, obtain product C 40～80 ℃ of reactions 1～3 hour;
4) 30～100 weight parts acid and 1000～2000 weight parts waters are mixed after, drop in the product C, continuously stirring product C in the dropping process, drip finish to continue to stir 30～60min after, solvent is deviate from underpressure distillation again, obtains product D;
5) in product D, add the light trigger and 1～10 weight part SL 1332 of 0.1～2 weight part, stir, promptly obtain the aqueous pu dispersions of this uV curable.
2. the aqueous pu dispersions of a kind of uV curable according to claim 1 is characterized in that, step 1) takes by weighing 300～600 weight part Viscotrol C and is added in the reactor drum of belt stirrer; After being heated to 100～130 ℃ of vacuum hydro-extraction 30～120min; Add 1～100 weight part low molecular weight polyols, when being cooled to 50～60 ℃, 200～600 weight part POLYMETHYLENE POLYPHENYLISOCYANATE that add while stirring; After being warming up to 60～100 ℃ of reaction 60～240min, obtain product A.
3. the aqueous pu dispersions of a kind of uV curable according to claim 1; It is characterized in that; Step 5) adds the polyfunctionality UV reactive thinner of 0.1～100 weight part to product D; The light trigger and 1～10 weight part SL 1332 of adding 0.1～2% stir after stirring, and promptly obtain the aqueous pu dispersions of this uV curable.
4. the preparation method of the aqueous pu dispersions of the arbitrary described a kind of uV curable of claim 1 to 3 is characterized in that, comprises following preparation process successively:
1) takes by weighing the there-necked flask that 300～600 weight part Viscotrol C are added to belt stirrer, be heated to 100～130 ℃ of vacuum hydro-extraction 30～120min, add low molecular weight polyols 0～100 weight part while stirring; When being cooled to 50～60 ℃, POLYMETHYLENE POLYPHENYLISOCYANATE 200～600 weight parts that add while stirring are warming up to 60～100 ℃ of reaction 60～240min, obtain product A;
2) when product A is cooled to 55～65 ℃, add 100～400 parts by weight solvent, drip the low molecular weight polyols that contains 60～200 weight part tertiary amine groups while stirring at 40～50 ℃, 40～60 ℃ of reactions 1～3 hour, obtain product B;
3) add hydroxyl vinyl monomer and 0.001～0.1 weight part organo-metallic catalyst of 20～120 weight parts to product B,, obtain product C 40～80 ℃ of reactions 1～3 hour;
4) 30～100 weight parts acid and 1000～2000 weight parts waters are mixed after, drop in the product C, continuously stirring product C in the dropping process, drip finish to continue stirring 30～60min after, solvent is deviate from underpressure distillation, obtains product D;
5) in product D, add the polyfunctionality UV reactive thinner of 0～100 weight part; Stir; The light trigger and 1～10 weight part SL 1332 solution of adding 0.1～2% stir, and promptly obtain the aqueous pu dispersions of this uV curable.
5. the preparation method of the aqueous pu dispersions of uV curable according to claim 4; It is characterized in that the described low molecular weight polyols of step 1) is that make up arbitrarily one of them or they of terepthaloyl moietie, Ucar 35, butyleneglycol, glycol ether, Diethylene Glycol, pentanediol, NSC 6366, trishydroxymethyl propyl alcohol, USP Kosher, tetramethylolmethane.
6. the preparation method of the aqueous pu dispersions of uV curable according to claim 4 is characterized in that, the described POLYMETHYLENE POLYPHENYLISOCYANATE of step 1) is 1,6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexyl methane diisocyanate, 2; 2,4-trimethylammonium-hexamethylene diisocyanate, 2; 4,4-trimethylammonium-hexamethylene diisocyanate, 4; 4 ‵-isocyanic ester cyclohexyl methylmethane, isocyanatomethyl-1,8-octane vulcabond, 1,4-hexamethylene and isocyanic ester, 1; 4-phenylene diisocyanate, 2,4 toluene diisocyanate, 2, the arbitrary combination of 6-tolylene diisocyanate one of them or they.
7. the preparation method of the aqueous pu dispersions of uV curable according to claim 4 is characterized in that, the low molecular weight polyols of the described tertiary amine groups of step 1) is a methyldiethanolamine.
8. the preparation method of the aqueous pu dispersions of uV curable according to claim 4; It is characterized in that the hydroxyl vinyl monomer described in the step 3) is one of them of Hydroxyethyl acrylate, Propylene glycol monoacrylate, Rocryl 400, pentaerythritol triacrylate or trimethylolpropane diacrylate or their arbitrary combination.
9. the preparation method of the aqueous pu dispersions of uV curable according to claim 4 is characterized in that step 2) described solvent is acetone or butanone.
10. the preparation method of the aqueous pu dispersions of uV curable according to claim 4; It is characterized in that the described organo-metallic catalyst of step 3) is one of them of organic tin catalyzer, metal carboxylate catalyzer, titanate ester catalyzer, organic zirconium class catalyzer, organo-bismuth class catalyzer.
11. the preparation method of the aqueous pu dispersions of uV curable according to claim 4 is characterized in that, the described acid of step 4) be acetate or formic acid or hydrochloric acid or oxalic acid one of.
12. the preparation method of the aqueous pu dispersions of uV curable according to claim 4; It is characterized in that; The described UV reactive thinner of step 5) is 1; In in 6-hexanediyl ester, dipropylene glycol two (methyl) propenoate, 1,4 butanediol diacrylate, neopentylglycol diacrylate, TriMethylolPropane(TMP) (methyl) propenoate, oxyethyl group Viscoat 295, tetramethylol methane tetraacrylate, Dipentaerythritol five propenoate, the dipentaerythritol acrylate one or their arbitrary combination.
13. the preparation method of the aqueous pu dispersions of uV curable according to claim 4; It is characterized in that, the described light trigger of step 5) be UVNUL MS-40 or benzoin methyl ether or Alpha-hydroxy Benzoin ethyl ether or Alpha-hydroxy isopropyl benzene ketone or 4 '-(2-hydroxy ethoxy)-2-hydroxy-2-methyl Propiophenone, Alpha-hydroxy phenylcyclohexane ketone, isopropyl thioxanthone, 2-(4-methylthio phenyl formyl radical)-2-morpholinyl propane or one of them of oligomeric-hydroxyketone or their arbitrary combination.
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| CN104031231A (en) * | 2014-06-19 | 2014-09-10 | 合肥工业大学 | Ultraviolet-curing waterborne epoxy-polyurethane-acrylate copolymer resin anticorrosive coating and preparation method thereof |
| CN105199076A (en) * | 2015-10-23 | 2015-12-30 | 青岛展辰新材料有限公司 | Preparation method of water-based ultraviolet light-cured biology-base polyurethane acrylate resin |
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| CN106866915A (en) * | 2017-03-01 | 2017-06-20 | 宝鸡文理学院 | A kind of painting canvas dope bio-based aqueous nanoemulsion and preparation method thereof |
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| CN105199076A (en) * | 2015-10-23 | 2015-12-30 | 青岛展辰新材料有限公司 | Preparation method of water-based ultraviolet light-cured biology-base polyurethane acrylate resin |
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| TWI729032B (en) * | 2015-12-08 | 2021-06-01 | 德商漢高智慧財產控股公司 | Functionalized accelerating resins derived from renewable materials |
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| CN106147587A (en) * | 2016-07-12 | 2016-11-23 | 叶有国 | A kind of antimicrobial UV coating containing castor oil-base and its preparation method and application |
| CN106189803A (en) * | 2016-07-12 | 2016-12-07 | 叶有国 | A kind of fingerprint recognition coating and its preparation method and application |
| CN106866929A (en) * | 2017-02-24 | 2017-06-20 | 中国林业科学研究院林产化学工业研究所 | A kind of polyfunctionality castor oil-base light-cured resin and its preparation method and application |
| CN106866915A (en) * | 2017-03-01 | 2017-06-20 | 宝鸡文理学院 | A kind of painting canvas dope bio-based aqueous nanoemulsion and preparation method thereof |
| CN112375197A (en) * | 2020-10-26 | 2021-02-19 | 安徽大学 | Preparation method and application of ultraviolet-cured antibacterial aqueous polyurethane emulsion |
| CN112375197B (en) * | 2020-10-26 | 2022-10-04 | 安徽大学 | Preparation method and application of ultraviolet-cured antibacterial aqueous polyurethane emulsion |
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