CN104927024A - Preparation method of fluorine modified light-cured polyurethane acrylate resin and application thereof as light-cured coating hydrophobic filling material - Google Patents
Preparation method of fluorine modified light-cured polyurethane acrylate resin and application thereof as light-cured coating hydrophobic filling material Download PDFInfo
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Abstract
The invention relates to a synthesis method of a fluorine modified UV-cured polyurethane acrylate resin and an application thereof as a light-cured coating hydrophobic filling material, and belongs to the fields of UV-curing technology and functional surface coating. The fluorine modified UV-cured polyurethane acrylate resin is prepared through three-step reactions, long-chain dihydric alcohol is taken as the soft section, isocyanate compounds containing two isocyanate radicals are taken as the hard section, and fluoro-alcohol and compounds containing hydroxy group and double bond are taken as the end-capping agent. The synthesized fluorine modified UV-cured polyurethane acrylate resin can be used as a filling material and added into a UV-cured coating formula, the water-oil contact angle of the coating can be greatly increased, while at the same time, the mechanical properties and chemical agent resistant performance of the coating are not influenced. The resin can be applied to functional coatings which have the functions of preventing water, stains, fog, and fingerprint.
Description
Technical field
The present invention relates to radiation curing and paint field, be specifically related to a kind of preparation of fluorine richness photocuring macromolecule resin material, and it is as the application of dewatering filling in photocuring hydrophobic coating.
Background technology
The raising of quality of social life has caused the update of coatings industry equally.The simple protection that traditional coating is born, the function of beautifying can not meet the demand of modern to coating, and functional coat shoulders increasing mission in the modern life.
The application that " 5E " that photocuring technology has (Efficient efficient, Enabling multipotency, Economical economy, Energy is energy-conservation, Ecology is ecological) advantage makes it in coatings industry is more and more wider.China is after 20th century, the eighties entered photo-cured coating field, and all kinds of photo-cured coating increase of production is swift and violent, and while coatings industry overall development, photo-cured coating is also constantly introduced into new function, prepares multi-functional coating.
Organic fluorine is the resin material that known at present surface energy is minimum, and perfluoro alkane surface tension can be down to about 6mN/m, but its exist in application of paints surface enrichment too serious, need hot setting, the problems such as set time is long.
Application number 200710151764.0, denomination of invention is " a kind of fluoroacrylic resin with ultra-low surface energy and preparation method thereof and the application in coating ", this patent application patent specifically discloses structural formula and the preparation method of fluoroacrylic resin, and the application in coating.Fluoro-acrylate monomer is incorporated in acrylic resin main chain by copolymerization by this invention, thus obtains having certain hydrophobic acrylic resin.The hydrophobic coating contact angle that this invention obtains can reach 120 °, but adopts chemosetting mode, and the polyisocyanates that need in use use toxicity larger, does not meet environmental requirement.Application number 201210101478.4,201210120286.8, denomination of invention is respectively " a kind of preparation method of water-soluble fluorine-containing acrylic resin and application ", " a kind of preparation method of low surface energy UV-curable water-borne fluoro-containing coating " prepares fluorine-containing hydrophobic coating by introducing fluoro-acrylate monomer, these two sections of patents also have employed water-based and photocuring technology respectively, the good coating of hydrophobicity can be obtained equally, but complicated component in these two kinds of method synthetic resins processes, reaction controllability is more difficult.Fluorine element is linked in macromolecular chain, prepares the curable urethane acrylate resin of fluorine richness and it can be used as light solidifying coating dewatering filling but to have no report.
Summary of the invention
The object of the invention there are provided a kind of curable urethane acrylate resin of fluorine richness synthetic method and with the preparation of the curable urethane acrylate resin of this fluorine richness hydrophobic coating that is dewatering filling.The defects such as, complicated component, construction trouble slow for prior art solidification, the present invention is by introducing the solid photocuring technology of light, synthesize a kind of fluorine richness polyurethane acrylate resin of uV curable, and with its for dewatering filling prepare solidification rapidly, safety non-toxic, technology maturation, easy construction hydrophobic coating, only need little addition, namely greatly can improve the water oil contact angle of coating, reduce coating surface tension.The curable urethane acrylate resin of this fluorine richness has good mechanical property equally, with matrix resin curing cross-linked process, can not cause detrimentally affect while reducing surface energy to other performances of coating.
In order to achieve the above object, the present invention selects molecular weight at the long-chain polyhydric alcohol of 400-10000 as soft section, vulcabond is selected to be hard section, fluorine alcohol and photosensitive monomer is selected to be end-capping reagent respectively, under adding the condition of catalyzer and solvothermal, synthesize the curable urethane acrylate resin of mechanical property and all good fluorine richness of thermomechanical property.
The feature of the curable urethane acrylate resin of fluorine richness of the present invention is:
Long-chain polyhydric alcohol is soft section, select polycarbonate diol, polyether Glycols (polyoxyethylene glycol, polypropylene glycol etc.), polytetrahydrofuran diol, polycaprolactone glycol, polyoxyethylene-poly-oxypropylene polyoxyethylene glycol, polyethylene glycol adipate glycol, polybutylene glyool adipate, polyethylene terephthalate glycol, polybutylene terephthalate glycol etc. wherein one or more, molecular weight ranges is 400-10000.Preferably long-chain polyhydric alcohol is PCDL, and more preferably molecular weight ranges is the PCDL of 500-3000.
Vulcabond is hard section, isophorone diisocyanate, 2 can be selected, 4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, ditan 4,4 '-vulcabond, oneself two support vulcabond, Methylcyclohexyl diisocyanates, 2, one or more in the vulcabond such as 2,4-trimethylammonium hexamethylene diisocyanate.The preferably hexamethylene diisocyanate of two active differences 10 times of isocyano group.
Chain termination introduces hydrophobic fluoro-containing group with fluorine alcohol, and the perfluor alcohol of hydrogen in the fluorine substituted alkyl chain of hydroxyl or part can be selected to replace fluorine alcohol, as 3, and 3,4,4,5,5,6,6,7,7, the fluoro-1-octanol of 8,8,8-13,2,2,3,3,4, one or more in the fluorine alcohol such as 4,5,5-octafluoro-1-amylalcohol, perfluor decyl alcohol, perfluorobutylethyl alcohol, perfluoro hexyl ethyl alcohol, C3-Fluoroalcohol.The preferably perfluor alcohol of hydrogen in fluorine substituted alkyl chain.
Chain termination photosensitive monomer is to introduce photosensitive double bond, the optional compound containing double bond and alcoholic extract hydroxyl group, as one or more in pentaerythritol triacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, dipentaerythritol five acrylate, 4-hydroxybutyl acrylate, Propylene glycol monoacrylate, Rocryl 410, TriMethylolPropane(TMP) diacrylate fat, neopentyl glycol mono acrylic ester.
Need to add catalyzer in the reaction process of hydroxyl and isocyano, triethylamine, diethylamine diamines can be selected, one or more in N monomethyl morphine beautiful jade, dibutyl tin dilaurate and stannous octoate, preferably organic tin catalyzer, more preferably dibutyl tin dilaurate.
Solvent plays dispersion dilution in system, the mixing solutions of one or more arbitrary proportions in acetic acid fourth vinegar, acetic acid second vinegar, 1-Methoxy-2-propyl acetate, ethylene glycol ether acetate, propylene-glycol ethyl ether acetic acid vinegar, dimethylbenzene, butanone, methyl iso-butyl ketone (MIBK) can be selected, the ester class that preferably toxicity is little, evaporation rate is moderate or solvent of ether ester type, as N-BUTYL ACETATE, vinyl acetic monomer, 1-Methoxy-2-propyl acetate, ethylene glycol ether acetate etc.
The synthesis step of the curable urethane acrylate resin of fluorine richness can be divided into three steps, and wherein for raising the efficiency, first two steps can synchronously be carried out:
The first step, fluorine alcohol half end-blocking vulcabond.In the three-necked flask that thermometer, mechanical stirring device be housed, add vulcabond and the catalyzer of metered amount, after adding a small amount of solvent cut, at 40-60 DEG C, drip the fluorine alcohol that solvent cut is crossed, both vulcabond and fluorine alcohol mol ratio is 1: 1.Content constantly by titration monitoring-NCO group in reaction, treats that NCO content is down to a half, stopped reaction, obtains the vulcabond of fluorine alcohol half end-blocking, and it is stand-by that sealing is placed in lucifuge drying place.Preferred temperature of reaction is 40 DEG C, and preferred catalyst content is the 0.3wt% of solid content.
Second step, photosensitive monomer half end-blocking vulcabond.Vulcabond and the catalyzer of metered amount is added in the three-necked flask that thermometer, mechanical stirring device be housed, after adding a small amount of solvent cut, at 40-60 DEG C, drip the photosensitive monomer crossed of solvent cut, both vulcabond and photosensitive monomer mol ratio is 1: 1.Content constantly by titration monitoring-NCO group in reaction, treats that NCO content is down to a half, stopped reaction, obtains the vulcabond of fluorine alcohol half end-blocking, and it is stand-by that sealing is placed in lucifuge drying place.Preferred temperature of reaction is 40 DEG C, and preferred catalyst content is the 0.3wt% of solid content.
3rd step, the di-isocyanate reaction of half end-blocking is connected to long chain diol two ends.By one end of above-mentioned two steps synthesis containing aggressiveness before-NCO group, at 50-90 DEG C, in the long chain diol that instillation solvent cut is crossed, add a small amount of catalyzer, titration monitoring-NCO content in reaction, when extremely-NCO group content is less than 1%, infrared monitoring-NCO group 2260cm is carried out in sampling
-1neighbouring charateristic avsorption band, when its completely dissolve, can obtain the light-cured type urethane acrylate of fluorine richness.Preferred temperature of reaction is 70 DEG C.
The curable urethane acrylate resin of fluorine richness prepares photocuring hydrophobic coating preparation method as dewatering filling, with certain proportion (fluorine content controls at 0.01%-7%), synthesized fluorine richness ultraviolet curing type polyurethane acrylate resin is added in photocuring hydrophobic coating formula, dispersed with stirring is even, after carrying out film, preliminary drying, ultraviolet light polymerization, obtain photocuring hydrophobic coating.This photocuring hydrophobic coating should comprise film-forming resin, reactive thinner, light trigger, also can comprise the necessary component such as color stuffing, auxiliary agent.
Accompanying drawing explanation
Fig. 1 be according to preferred version of the present invention with PCDL be soft section, hexamethylene diisocyanate is hard section, the synthetic route that ten trifluoro octanols and pentaerythritol triacrylate are end-capping reagent, dibutyl tin dilaurate is catalyzer, N-BUTYL ACETATE is the curable urethane acrylate resin of solvent synthesis fluorine richness.
Fig. 2 is that curable urethane acrylate coating adds fluorine richness ultraviolet curing type polyurethane acrylate resin as the coatingsurface water contact angle digital photograph before and after dewatering filling, A does not add the coatingsurface water contact angle of fluorine richness ultraviolet curing type polyurethane acrylate resin as dewatering filling, B adds the coatingsurface water contact angle of fluorine richness ultraviolet curing type polyurethane acrylate resin as dewatering filling, and Oil repellent is 1.54wt%.
Fig. 3 be fluorine richness ultraviolet curing type polyurethane acrylate resin as dewatering filling time, the surface contact angle of different fluorine content coating
Embodiment
In order to better explain the present invention, below in conjunction with embodiment, the present invention will be further described.It should be pointed out that specific embodiment described herein only in order to explain the present invention, be not intended to limit the present invention.
The PCDL that embodiment in the present invention long chain diol used selects Japanese Asahi Kasei Corporation to produce, vulcabond selects isophorone diisocyanate, fluorine alcohol select Harbin Xue Jiafu silicon company limited to provide 3,3,4,4,5,5,6,6,7,7,8,8,80 trifluoro octanols, photosensitive monomer selects pentaerythritol triacrylate, and dibutyl tin dilaurate selected by catalyzer, and N-BUTYL ACETATE selected by solvent.
Embodiment 1
The present embodiment to embodiment 3 is adopt the PCDL (PCDL) of different molecular weight as soft section, isophorone diisocyanate (IPDI) is hard section, with pentaerythritol triacrylate (PET3A) for photosensitive monomer end-blocking introduces photosensitive double bond, with 3,3,4,4,5,5,6,6,7,7, the ultraviolet curing type urethane acrylate elastic handfeel dumb light paint that the urethane acrylate that 8,8,8-13 fluoro-1-octanol end-blocking introduces the synthesis of hydrophobic function group is prepared as matrix resin.
The first step adds the DBTDL of IPDI and the 0.3wt% solid content of metered amount as catalyzer in the three-necked flask that thermometer, mechanical stirring device be housed, after adding the dilution of a small amount of N-BUTYL ACETATE, at 40 DEG C, drip the PET3A being mixed with appropriate stopper BHT, the two mol ratio 1: 1.Constantly by the content of titration monitoring NCO group in reaction, during theoretical value to be achieved, stopped reaction, obtains the IPDI of PET3A half end-blocking, and sealing is placed in lucifuge drying place.Second step adds the DBTDL of IPDI and the 0.3wt% solid content of metered amount as catalyzer in the three-necked flask that thermometer, mechanical stirring device be housed, after adding the dilution of a small amount of N-BUTYL ACETATE, at 40 DEG C, drip the ten trifluoro octanols that N-BUTYL ACETATE is diluted, the two mol ratio is similarly 1: 1.Content constantly by titration monitoring-NCO group in reaction, during theoretical value to be achieved, stopped reaction, obtains the IPDI of fluorine alcohol half end-blocking, and it is stand-by that sealing is placed in lucifuge drying place.3rd step by above-mentioned two kinds of one end containing aggressiveness before-NCO group, at 70 DEG C, (molecular weight is 500 to instill the diluted T5650E of N-BUTYL ACETATE respectively, in molecular structure, C5, C6 ratio is 1: 1) in, add a small amount of catalyzer DBTDL, when extremely-NCO group content is less than 1%, infrared monitoring-NCO group 2260cm is carried out in sampling
-1neighbouring charateristic avsorption band, when its completely dissolve, can obtain the light-cured type PCDL based polyurethane acrylic ester F-500-PCUA of fluorine richness.
Embodiment 2
The first step adds the DBTDL of IPDI and the 0.3wt% solid content of metered amount as catalyzer in the three-necked flask that thermometer, mechanical stirring device be housed, after adding the dilution of a small amount of N-BUTYL ACETATE, at 40 DEG C, drip the PET3A being mixed with appropriate stopper BHT, the two mol ratio 1: 1.Content constantly by titration monitoring-NCO group in reaction, during theoretical value to be achieved, stopped reaction, obtains the IPDI of PET3A half end-blocking, and sealing is placed in lucifuge drying place.Second step adds the DBTDL of IPDI and the 0.3wt% solid content of metered amount as catalyzer in the three-necked flask that thermometer, mechanical stirring device be housed, after adding the dilution of a small amount of N-BUTYL ACETATE, at 40 DEG C, drip the ten trifluoro octanols that N-BUTYL ACETATE is diluted, the two mol ratio is similarly 1: 1.Constantly by the content of titration monitoring NCO group in reaction, during theoretical value to be achieved, stopped reaction, obtains the IPDI of fluorine alcohol half end-blocking, and it is stand-by that sealing is placed in lucifuge drying place.3rd step by above-mentioned two kinds of one end containing aggressiveness before-NCO group, at 70 DEG C, (molecular weight is 1000 to instill the diluted T5651 of N-BUTYL ACETATE respectively, in molecular structure, C5, C6 ratio is 1: 1) in, add a small amount of catalyzer DBTDL, when extremely-NCO group content is less than 1%, infrared monitoring-NCO group 2260cm is carried out in sampling
-1neighbouring charateristic avsorption band, when its completely dissolve, can obtain the light-cured type PCDL based polyurethane acrylic ester F-1000-PCUA of fluorine richness.
Embodiment 3
The first step adds the DBTDL of IPDI and the 0.3wt% solid content of metered amount as catalyzer in the three-necked flask that thermometer, mechanical stirring device be housed, after adding the dilution of a small amount of N-BUTYL ACETATE, at 40 DEG C, drip the PET3A being mixed with appropriate stopper BHT, the two mol ratio 1: 1.Content constantly by titration monitoring-NCO group in reaction, during theoretical value to be achieved, stopped reaction, obtains the IPDI of PET3A half end-blocking, and sealing is placed in lucifuge drying place.Second step adds the DBTDL of IPDI and the 0.3wt% solid content of metered amount as catalyzer in the three-necked flask that thermometer, mechanical stirring device be housed, after adding the dilution of a small amount of N-BUTYL ACETATE, at 40 DEG C, drip the ten trifluoro octanols that N-BUTYL ACETATE is diluted, the two mol ratio is similarly 1: 1.Content constantly by titration monitoring-NCO group in reaction, during theoretical value to be achieved, stopped reaction, obtains the IPDI of fluorine alcohol half end-blocking, and it is stand-by that sealing is placed in lucifuge drying place.3rd step by above-mentioned two kinds of one end containing aggressiveness before-NCO group, at 70 DEG C, (molecular weight is 2000 to instill the diluted T5652 of N-BUTYL ACETATE respectively, in molecular structure, C5, C6 ratio is 1: 1) in, add a small amount of catalyzer DBTDL, when extremely-NCO group content is less than 1%, infrared monitoring NCO group 2260cm is carried out in sampling
-1neighbouring charateristic avsorption band, when its completely dissolve, can obtain the light-cured type PCDL based polyurethane acrylic ester F-2000-PCUA of fluorine richness.
Embodiment 1 to embodiment 3 all obtains the light-cured type PCDL based polyurethane acrylic ester of water white fluorine richness, and its mechanical property and thermomechanical property are in table 1 and table 2.
The light-cured type PCDL based polyurethane acrylic ester cured film mechanical property of the fluorine richness of the different soft segment molecule amount of table 1
Along with PCDL molecular weight increases, the fluorine richness light-cured type urethane acrylate molecular weight of corresponding synthesis increases, and double bond density reduces, and when forming cured film, cross-linking density is low, and cause cured film soft, elongation at break is large, but tensile strength is little.
The light-cured type PCDL based polyurethane acrylic ester cured film thermal decomposition performance of the fluorine richness of the different soft segment molecule amount of table 2
Along with PCDL molecular weight increases, the fluorine richness light-cured type urethane acrylate three phases heat decomposition temperature of corresponding synthesis all increases, but when rising to 500 DEG C, residual quantity reduces.
Embodiment 4
The present embodiment to embodiment 10 adopts the light-cured type PCDL based polyurethane acrylic ester F-2000-PCUA of the fluorine richness of synthesis in embodiment 3 as light-cured type dewatering filling, adding light-cured type PCDL (T5652 the is soft section) based polyurethane acrylic ester not carrying out fluorine richness is in the light solidifying coating of matrix resin (hydroxyethyl methylacrylate end-blocking is all used at two ends), by both adjustments mass ratio, Oil repellent in adjustment coating, obtains photocuring hydrophobic coating.
2 parts of matrix resins and 0.06 part of light trigger 184 add in container, add the dilution of proper amount of acetic acid butyl ester, and after stirring, blade coating is on PC plate, and 50 DEG C are dried 20min, are then cured under ultraviolet lamp, obtain photocuring hydrophobic coating.This coating is blank, and fluorine content is 0.
Embodiment 5
By 0.04 part of F-2000-PCUA, 1.96 parts of matrix resins, 0.06 part of light trigger 184 adds in container, add the dilution of proper amount of acetic acid butyl ester, after stirring, blade coating is on PC plate, 50 DEG C are dried 20min, are then cured under ultraviolet lamp, obtain photocuring hydrophobic coating.In coating, Oil repellent is 0.15%.
Embodiment 6
By 0.08 part of F-2000-PCUA, 1.92 parts of matrix resins, 0.06 part of light trigger 184 adds in container, add the dilution of proper amount of acetic acid butyl ester, after stirring, blade coating is on PC plate, 50 DEG C are dried 20min, are then cured under ultraviolet lamp, obtain photocuring hydrophobic coating.In coating, Oil repellent is 0.31%.
Embodiment 7
By 0.12 part of F-2000-PCUA, 1.88 parts of matrix resins, 0.06 part of light trigger 184 adds in container, add the dilution of proper amount of acetic acid butyl ester, after stirring, blade coating is on PC plate, 50 DEG C are dried 20min, are then cured under ultraviolet lamp, obtain photocuring hydrophobic coating.In coating, Oil repellent is 0.46%.
Embodiment 8
By 0.16 part of F-2000-PCUA, 1.84 parts of matrix resins, 0.06 part of light trigger 184 adds in container, add the dilution of proper amount of acetic acid butyl ester, after stirring, blade coating is on PC plate, 50 DEG C are dried 20min, are then cured under ultraviolet lamp, obtain photocuring hydrophobic coating.In coating, Oil repellent is 0.62%.
Embodiment 9
By 0.2 part of F-2000-PCUA, 1.8 parts of matrix resins, 0.06 part of light trigger 184 adds in container, add the dilution of proper amount of acetic acid butyl ester, after stirring, blade coating is on PC plate, 50 DEG C are dried 20min, are then cured under ultraviolet lamp, obtain photocuring hydrophobic coating.In coating, Oil repellent is 0.77%.
Embodiment 10
By 0.4 part of F-2000-PCUA, 1.6 parts of matrix resins, 0.06 part of light trigger 184 adds in container, add the dilution of proper amount of acetic acid butyl ester, after stirring, blade coating is on PC plate, 50 DEG C are dried 20min, are then cured under ultraviolet lamp, obtain photocuring hydrophobic coating.In coating, Oil repellent is 1.54%.
Embodiment 4 to embodiment 10 gained photocuring hydrophobic coating contact angle is shown in Fig. 3, and surface tension is in table 3.
Table 3F-PCDL-PUA is as the surface tension of the hydrophobic cured film of dewatering filling
As can be seen from the table, along with the increase of Oil repellent, the surface tension of cured film presents the trend of reduction, even if the seldom introducing (0.15%) of the fluorine of amount, the surface tension of cured film can be caused to fall sharply to 26.3mN/m from 44.0, and the capillary impact of introducing on cured film of fluorine element is very significant.
Embodiment 4 to embodiment 10 gained photocuring hydrophobic coating performance is in table 4
Table 4F-PCDL-PUA is the photocuring hydrophobic coating performance of dewatering filling
a: coating is not turned white, is bubbled after soaking, wrinkling, the phenomenon that comes off.
The sticking power of hydrophobic coating on PC plate and pencil hardness, all conventionally test.Solvent resistance respectively the hydrophobic coating be coated on PC plate is immersed in the sulphuric acid soln of 1N, the NaOH solution of 1N, in the middle of 50% aqueous ethanolic solution and oleic acid, under room temperature (25 DEG C), soak 4h, whether have after observing coating and turn white, wrinkling, the phenomenon bubble, come off occurs.As can be seen from table 3-7, add F-PCDL-PUA as dewatering filling, do not have detrimentally affect to the physico-chemical property of coating, coating still has good sticking power on PC plate, and still have excellent chemical reagent-resistant performance, hardness of paint film is also uninfluenced.
Above-described is only the preferred embodiment of the present invention, the invention is not restricted to above embodiment.Be appreciated that the oher improvements and changes that those skilled in the art directly derive without departing from the spirit and concept in the present invention or associate, all should think and be included within protection scope of the present invention.
Claims (9)
1. the preparation method of a fluorine richness ultraviolet curing type polyurethane acrylate resin, it is characterized in that: adopt three-step reaction method, it is soft section with long chain diol, being hard section containing the isocyanate ester compound of two isocyanos, the compound of fluorine alcohol and hydroxyl and double bond is end-capping reagent, add catalyzer and solvent, add the fluorine richness ultraviolet curing type polyurethane acrylate resin that a kind of end of the chain of thermal synthesis contains photosensitive double bond and hydrophobic fluorine functional group; Three-step reaction be respectively fluorine alcohol half end-blocking vulcabond, photosensitive monomer half end-blocking vulcabond, half end-blocking di-isocyanate reaction be connected to long chain diol two ends.
2. the preparation method of fluorine richness ultraviolet curing type polyurethane acrylate resin according to claim 1, it is characterized in that: described long-chain polyhydric alcohol selects polycarbonate diol, polyether Glycols (polyoxyethylene glycol, polypropylene glycol etc.), polytetrahydrofuran diol, polycaprolactone glycol, polyoxyethylene-poly-oxypropylene polyoxyethylene glycol, polyethylene glycol adipate glycol, polybutylene glyool adipate, polyethylene terephthalate glycol, polybutylene terephthalate glycol etc. wherein a kind of, and molecular weight ranges is 400-10000.
3. the preparation method of fluorine richness ultraviolet curing type polyurethane acrylate resin according to claim 1, it is characterized in that: described vulcabond selects isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, ditan 4,4 '-vulcabond, oneself two support vulcabond, Methylcyclohexyl diisocyanates, 2, one in the vulcabond such as 2,4-trimethylammonium hexamethylene diisocyanate.
4. the preparation method of fluorine richness ultraviolet curing type polyurethane acrylate resin according to claim 1, is characterized in that: described fluorine alcohol selects the perfluor alcohol of hydrogen in the fluorine substituted alkyl chain of hydroxyl or part to replace fluorine alcohol, can select 3,3,4,4,5,5,6,6,7,7, the fluoro-1-octanol of 8,8,8-13,2,2,3,3,4, one in the fluorine alcohol such as 4,5,5-octafluoro-1-amylalcohol, perfluor decyl alcohol, perfluorobutylethyl alcohol, perfluoro hexyl ethyl alcohol, C3-Fluoroalcohol.
5. the preparation method of fluorine richness ultraviolet curing type polyurethane acrylate resin according to claim 1, it is characterized in that: described photosensitive monomer is the compound containing double bond and alcoholic extract hydroxyl group, can select the one in pentaerythritol triacrylate, Hydroxyethyl acrylate, hydroxyethyl methylacrylate, dipentaerythritol five acrylate, 4-hydroxybutyl acrylate, Propylene glycol monoacrylate, Rocryl 410, TriMethylolPropane(TMP) diacrylate fat, neopentyl glycol mono acrylic ester.
6. the preparation method of fluorine richness ultraviolet curing type polyurethane acrylate resin according to claim 1, it is characterized in that: described catalyzer is triethylamine, diethylamine diamines, the one in N monomethyl morphine beautiful jade, dibutyl tin dilaurate and stannous octoate.
7. the preparation method of fluorine richness ultraviolet curing type polyurethane acrylate resin according to claim 1, is characterized in that: described solvent is the mixing solutions of one or more arbitrary proportions in acetic acid fourth vinegar, acetic acid second vinegar, 1-Methoxy-2-propyl acetate, ethylene glycol ether acetate, propylene-glycol ethyl ether acetic acid vinegar, dimethylbenzene, butanone, methyl iso-butyl ketone (MIBK).
8. the preparation method of fluorine richness ultraviolet curing type polyurethane acrylate resin according to claim 1, it is characterized in that: described resin syntheses processes is three-step approach synthesis, described fluorine richness ultraviolet curing type polyurethane acrylate resin is synthesized by three-step reaction, three-step reaction be respectively 40-60 DEG C, with under the condition of organic tin catalyst, fluorine alcohol half end-blocking vulcabond; 40-60 DEG C, with under the condition of organic tin catalyst, photosensitive monomer half end-blocking vulcabond; 50-90 DEG C, with under the condition of catalyst, the di-isocyanate reaction of half end-blocking is connected to long chain diol two ends.
9. fluorine richness ultraviolet curing type polyurethane acrylate resin according to claim 1 is as the preparation method of the hydrophobic coating of dewatering filling, it is characterized in that: with certain proportion (fluorine content controls at 0.01%-7%), synthesized fluorine richness ultraviolet curing type polyurethane acrylate resin is added in photocuring hydrophobic coating formula, dispersed with stirring is even, after carrying out film, preliminary drying, ultraviolet light polymerization, obtain photocuring hydrophobic coating.
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| CN114276486B (en) * | 2022-01-18 | 2024-01-05 | 安徽立兴新材料有限公司 | Preparation method and application of fluorine-containing acrylate resin with super-hydrophobic cross-linked structure |
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| CN116426206A (en) * | 2023-02-15 | 2023-07-14 | 湖北航天化学新材料科技有限公司 | Skin-feel coating with flame-retardant function, and preparation method and application thereof |
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