CN103642382B - Ultraviolet light curing anti-fouling paint and preparation method thereof - Google Patents
Ultraviolet light curing anti-fouling paint and preparation method thereof Download PDFInfo
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- CN103642382B CN103642382B CN201310606247.3A CN201310606247A CN103642382B CN 103642382 B CN103642382 B CN 103642382B CN 201310606247 A CN201310606247 A CN 201310606247A CN 103642382 B CN103642382 B CN 103642382B
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- GWHJZXXIDMPWGX-UHFFFAOYSA-N Cc1cc(C)c(C)cc1 Chemical compound Cc1cc(C)c(C)cc1 GWHJZXXIDMPWGX-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an ultraviolet light curing anti-fouling paint and a preparation method thereof to solve the technical problems of high cost, poor anti-fouling effect and endurance of an ultraviolet light curing anti-fouling paint in the prior art. The curing anti-fouling paint provided by the invention comprises by weight 38-116 parts of multifunctional fluorine-containing fluorosilicone containing polyurethane acrylate, 3-8 parts of multifunctional polyurethane acrylate, 12-18 parts of a multifunctional acrylate diluent, 0.4-1.5 parts of a photoinitiator, 0.15-0.55 part of a leveling agent and 0.1-0.7 part of a defoaming agent. The film of the anti-fouling paint provided by the invention has excellent compactness, fungal resistance and low surface energy, strong stain resistance and good anti-fouling endurance.
Description
Technical field
The present invention relates to a kind of ultraviolet light polymerization anti-pollution paint and preparation method thereof, belong to anti-pollution paint technical field.
Technical background
Ultraviolet light polymerization anti-pollution paint has excellent pollution resistance, energy-conservation, efficient feature, in recent years, obtains study widely in anti-soil field of coating.In prior art, the preparation method of ultraviolet light polymerization anti-pollution paint has following three kinds usually: method one, organic fluorine that is strong for stain resistance, that have ultra-low surface energy and acrylic are carried out esterification, the UV-cured resin of preparation containing organic fluorine, this resin is prepared ultraviolet light polymerization anti-pollution paint as matrix resin, but containing organic fluorine in this resin, so the cost of the anti-pollution paint obtained is higher; The organosilicon unsaturated polyester of method two, use uV curable is as matrix resin, reduce film coated surface tension force, reach the effect of anti-soil, but such silicone content contained in the silicone resin of unsaturated double-bond is not easily too high, if silicone content is higher, the organosilicon unsaturated polyester then obtained is difficult to there is good consistency with other resin, but if silicone content is lower, then antifouling effect is then undesirable; Method three, directly add in ultraviolet-curing paint and can significantly reduce capillary leveling auxiliary agent, this preparation method is simple to operate, but, the anti-soil auxiliary agent added is very easy to volatilization and easily moves to coating surface, thus, by after repeatedly wiping, anti-soil auxiliary agent can disappear, so antifouling effect is not lasting.
Chinese patent polymkeric substance and preparation method thereof reports a kind of preparation method of ultraviolet light polymerization anti-pollution paint with antifouling coating composition and antifouling coating layer material (publication number 101638482), its core technology uses flucride siloxane as matrix resin, this resin is by the Si-H key in hydrogen-containing siloxane polymkeric substance and Fluorine containing olefine compound and containing the C=C key in vinyl compound, Platinic chloride is catalyzer, prepares fluorine silicon light-cured resin by " hydrosilation reaction ".Chinese patent UV curing anti-pollution paint (publication number 101824274A) reports a kind of ultraviolet curing type anti-pollution paint, described coating comprises the straight chain type acrylate of the multiple hydroxyl of side chain band, organic silicon acrylic ester, monofunctional monomer, polyfunctional monomer, light trigger, auxiliary agent and filler composition, wherein, the straight chain type acrylate of multiple hydroxyl is obtained by esterification by hydroxyl telechelic polyester polyvalent alcohol and vinylformic acid.Above-mentioned Section 1 patent uses flucride siloxane as matrix resin, and thus, cost is higher.Above-mentioned Section 2 patent only reduces coating surface tension force using unsaturated organosilicon resin as matrix resin, and prepare anti-pollution paint, thus, antifouling effect awaits further improvement.
Summary of the invention
The object of the invention is to solve that prior art medium ultraviolet photocuring anti-pollution paint cost is high, antifouling effect is poor, the technical problem of anti-soil persistence difference, and a kind of ultraviolet light polymerization anti-pollution paint and preparation method thereof is provided.
The invention provides a kind of polyfunctionality fluorine silicon urethane acrylate, structure is such as formula shown in I:
In formula, m, n, p are integer, 10≤m≤70,10≤n≤70,12≤p≤53;
R
1-be the one in following structure:
-R
2-be the one in following structure:
The present invention also provides the preparation method of above-mentioned polyfunctionality fluorine silicon urethane acrylate, comprises the following steps:
(1) in reaction vessel, add poly-(carbonic ether-ether) dibasic alcohol, after dehydration, under inert atmosphere protection, add TriMethylolPropane(TMP) and vulcabond, reaction, obtains the first intermediate;
(2) in the first intermediate, add catalyzer and hydroxyl polydimethylsiloxane, reaction, obtains the second intermediate;
(3) in the second intermediate, add trifluoroethanol, after reaction, add stopper and polyfunctionality hydroxy-acrylate monomer, continue reaction, obtain polyfunctionality fluorine silicon urethane acrylate.
The present invention also provides the ultraviolet light polymerization anti-pollution paint containing above-mentioned polyfunctionality fluorine silicon urethane acrylate, and it comprises:
The polyfunctionality fluorine silicon urethane acrylate of 38-116 weight part;
The polyfunctionality urethane acrylate of 3-8 weight part;
The polyfunctional acrylic ester thinner of 12-18 weight part;
The light trigger of 0.4-1.5 weight part;
The flow agent of 0.15-0.55 weight part;
The defoamer of 0.1-0.7 weight part;
Described polyfunctionality urethane acrylate structure is such as formula shown in II:
In formula, q is integer, 15≤q≤78;
R
1-be the one in following structure:
-R
2-be the one in following structure:
Preferably, the weight part of described polyfunctionality fluorine silicon urethane acrylate is 45-102, the weight part of polyfunctionality urethane acrylate is 4-7.5, the weight part of polyfunctional acrylic ester thinner is 13-17, the weight part of light trigger is 0.7-1.3, the weight part of flow agent is 0.25-0.45, and the weight part of defoamer is 0.2-0.5; Preferred, the weight part of described polyfunctionality fluorine silicon urethane acrylate is 54-86, and the weight part of polyfunctionality urethane acrylate is 4.5-6, and the weight part of polyfunctional acrylic ester thinner is 14-16.
Preferably, described polyfunctionality urethane acrylate adopts following methods preparation:
(1) in reaction vessel, add polytetrahydrofuran dibasic alcohol, after dehydration, under inert atmosphere protection, add catalyzer and vulcabond, reaction, obtains the first intermediate;
(2) in the first intermediate, add stopper and polyfunctionality hydroxy-acrylate monomer, after reaction, obtain polyfunctionality urethane acrylate.
Preferably, described polyfunctional acrylic ester thinner is one or more in tetramethylol methane tetraacrylate, dipentaerythritol acrylate, Viscoat 295.
Preferably, described light trigger is Irfacure 184, Darocure 1173, Irfacure 2959 or Irfacure819, described flow agent is BYK-300, BYK-301, BYK-306, BYK-331 or BYK-310, and described defoamer is BYK-065, BYK-066, BYK-070, BYK-088, BYK-141BYK-020 or BYK-080.
The present invention also provides the preparation method of above-mentioned ultraviolet light polymerization anti-pollution paint, comprises the following steps:
(1) polyfunctionality fluorine silicon urethane acrylate, polyfunctionality urethane acrylate, flow agent and defoamer are uniformly mixed, obtain mixture;
(2) mixture, light trigger and polyfunctional acrylic ester thinner are uniformly mixed, obtain ultraviolet light polymerization anti-pollution paint.
Preferably, the stirring velocity be uniformly mixed of described step (1) is 800-1300rpm, and churning time is 1-3h; The stirring velocity be uniformly mixed of described step (2) is 1100-1500rpm, and churning time is 10-45min.
Beneficial effect of the present invention:
(1) polyfunctionality fluorine silicon urethane acrylate of the present invention as soft section, introduces siloxane groups and fluorin radical using poly-(carbonic ether-ether) dibasic alcohol in resin backbone structure, has excellent low surface energy; Further, poly-(carbonic ether-ether) dibasic alcohol is by carbonic acid gas and propylene oxide preparation, and thus, decrease the dependence to petroleum products, meanwhile, this polymkeric substance has the hydrolytic resistance of the very good mechanical properties of polyester construction and the excellence of polyether structure;
(2) compared to existing technology, anti-pollution paint of the present invention employs has polyfunctionality fluorine silicon urethane acrylate and polyfunctionality urethane acrylate as matrix resin, polyfunctionality fluorine silicon urethane acrylate is due to containing fluorine and silicon components, thus after ensure that film curing, there is low surface energy, improve the pollution resistance of coating, containing soft section of polytetrahydrofuran in polyfunctionality urethane acrylate, thus improve the fungus resistance of the paint film after solidification, make coating anti-soil persistence long; In addition, anti-pollution paint of the present invention using polyfunctional acrylic ester thinner as thinner, ensure paint film mechanical property basis on, due to the high crosslink density of interlaminar resin, make paint film have excellent compactness, can effectively stop greasy dirt to permeate, improve the pollution resistance of coating further;
(3) existing anti-pollution paint is all as matrix resin with pure fluorine-containing or siliceous acrylate unsaturated polyester, present invention uses poly-(carbonic ether-ether) dibasic alcohol and polytetrahydrofuran has prepared unsaturated polyester as matrix resin as soft section, form fine and close paint film, a small amount of fluorine-containing and siliceous group is introduced in binding resin structure, reach desirable antifouling property, compared to business-like anti-pollution paint, cost have dropped 80%.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum figure of polyfunctionality fluorine silicon urethane acrylate prepared by the embodiment of the present invention 1;
Fig. 2 is polyfunctionality urethane acrylate nucleus magnetic hydrogen spectrum figure prepared by the embodiment of the present invention 6.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just as further illustrating the features and advantages of the present invention instead of the restriction to patent requirements of the present invention.
Ultraviolet light polymerization anti-pollution paint of the present invention, comprise the polyfunctionality fluorine silicon urethane acrylate of 38-116 weight part, the polyfunctionality urethane acrylate of 3-8 weight part, 12-18 weight part polyfunctional acrylic ester thinner, the light trigger of 0.4-1.5 weight part, the flow agent of 0.15-0.55 weight part and the defoamer of 0.1-0.7 weight part.
The preparation method of polyfunctionality fluorine silicon urethane acrylate of the present invention (structural formula is formula I):
(1) in reaction vessel, add poly-(carbonic ether-ether) dibasic alcohol of 150-700 weight part, after dehydration, cooling, under inert atmosphere protection, add 12.4-14.5 weight part TriMethylolPropane(TMP) and 87-158 weight part vulcabond, 75-80 DEG C of reaction 2.5-4h, obtains the first intermediate;
(2) at 70-75 DEG C, add the catalyzer of 0.09-0.47 weight part and the hydroxyl polydimethylsiloxane of 8-17 weight part in the first intermediate, reaction 0.5-2h, obtains the second intermediate;
(3) in the second intermediate, add the trifluoroethanol of 12.6-18.7 weight part, be warmed up to 80-85 DEG C, reaction 2-3h, add the stopper of 0.57-0.82 weight part and the polyfunctionality hydroxy-acrylate monomer of 113-235 weight part, continue reaction 2-4h, obtain polyfunctionality fluorine silicon urethane acrylate.
In above-mentioned preparation method, the described dehydration temperature-fall period of step (1) is: will gather (carbonic ether-ether) dibasic alcohol and be heated to 110-120 DEG C, dewater 1-3h under-0.98MPa, then cools to 75-80 DEG C.
In above-mentioned preparation method, vulcabond is added drop-wise in reaction system with the speed of 5-12ml/min by step (1).
In above-mentioned preparation method, step (3) with the speed of 8-13ml/min by polyfunctionality hydroxy-acrylate monomer dropwise reaction system.
In above-mentioned preparation method, the molecular weight of poly-(carbonic ether-ether) dibasic alcohol of lower molecular weight is 1500-7000 dalton, is more preferably 2000-5000 dalton, prepares according to CN102432857; Vulcabond is one or more mixtures in hexamethylene diisocyanate, isophorone diisocyanate, 2,4 toluene diisocyanate, ditan-4,4-vulcabond; Catalyzer is dibutyl tin laurate or stannous octoate; The molecular weight of hydroxyl polydimethylsiloxane is 1000-4000 dalton, is more preferably 2000-3000 dalton; Stopper is Resorcinol or MEHQ; Polyfunctionality hydroxy-acrylate monomer is trimethylolpropane diacrylate, pentaerythritol triacrylate or double pentaerythritol C5 methacrylate.
The preparation method of polyfunctionality urethane acrylate of the present invention (structural formula is formula II):
(1) in reaction vessel, add the polytetrahydrofuran dibasic alcohol of 100-300 weight part, after dehydration, cooling, under inert atmosphere protection, add the catalyzer of 0.09-0.47 weight part and the vulcabond of 62-116 weight part, 75-80 DEG C of reaction 2.5-4h, obtains the first intermediate;
(2) be warmed up to 80-85 DEG C, add the stopper of 0.42-0.57 weight part and the polyfunctionality hydroxy-acrylate monomer of 87-180 weight part, continue reaction 2-4h, obtain polyfunctionality urethane acrylate.
In above-mentioned preparation method, the described dehydration temperature-fall period of step (1) is: polytetrahydrofuran dibasic alcohol is heated to 110-120 DEG C, and dewater 1-3h under-0.98MPa, then cools to 75-80 DEG C.
In above-mentioned preparation method, vulcabond is added drop-wise in reaction system with the speed of 5-12ml/min by step (1).
In above-mentioned preparation method, step (2) with the speed of 5-9ml/min by polyfunctionality hydroxy-acrylate monomer dropwise reaction system.
In above-mentioned preparation method, the molecular weight of polytetrahydrofuran dibasic alcohol is 1000-5000 dalton, is more preferably 2000-4000 dalton; Vulcabond is one or more mixtures in hexamethylene diisocyanate, isophorone diisocyanate, 2,4 toluene diisocyanate, ditan-4,4-vulcabond; Catalyzer is dibutyl tin laurate or stannous octoate; The molecular weight of hydroxyl polydimethylsiloxane is 1000-4000 dalton, is more preferably 2000-3000 dalton; Stopper is Resorcinol or MEHQ; Polyfunctionality hydroxy-acrylate monomer is trimethylolpropane diacrylate, pentaerythritol triacrylate or double pentaerythritol C5 methacrylate.
The polyfunctionality fluorine silicon urethane acrylate used in anti-pollution paint of the present invention is as film forming matrix resin, owing to containing fluorine and silicon group in this matrix resin, thus, after solidification, the surface energy of paint film is lower, there is excellent pollution resistance, the content of polyfunctionality fluorine silicon urethane acrylate is preferably 45-102 weight part, is more preferably 54-86 weight part.
The polyfunctionality urethane acrylate used in anti-pollution paint of the present invention is as matrix resin, using polytetrahydrofuran as soft section, due to the hydrolytic resistance of polytetrahydrofuran excellence, this resin is made to have excellent fungus resistance, thus, make the ultraviolet light polymerization anti-pollution paint obtained have excellent fungus resistance, polyfunctionality urethane acrylate content is preferably 4-7.5 weight part, is more preferably 4.5-6 weight part.
The polyfunctional acrylic ester thinner used in anti-pollution paint of the present invention, contribute to the cross-linking density improving paint film, thus, improve the pollution resistance of paint film, be preferably tetramethylol methane tetraacrylate, dipentaerythritol acrylate, one or more in Viscoat 295, its content is preferably 13-17 weight part, is more preferably 14-16 weight part.
The effect of the light trigger in anti-pollution paint of the present invention produces free radical under UV-irradiation, thus initiation urethane acrylate unsaturated double-bond carries out radical polymerization, described light trigger is preferably Irfacure 184, Darocure 1173, Irfacure 2959 or Irfacure 819, is more preferably Irfacure 184, Darocure 1173 or Irfacure 819.The content of light trigger is preferably 0.7-1.3.
The effect of the flow agent in anti-pollution paint of the present invention makes anti-pollution paint in film process, has good levelling effect, form smooth, smooth, even, transparent paint film at substrate surface.Described flow agent is preferably silicone based flow agent, and the model being more preferably the production of BYK company is BYK-300, BYK-301, BYK-306, BYK-331 or BYK-310.The content of flow agent is preferably 0.25-0.45 weight part.
The effect of the defoamer in anti-pollution paint of the present invention is in anti-pollution paint coating process, eliminates at the bubble used or produce in whipping process, thus, decrease the defect of the paint film generation that paint film causes due to the bubble produced.Described defoamer is preferably organic silicon type defoamer, and the model being more preferably the production of BYK company is BYK-065, BYK-066, BYK-070, BYK-088, BYK-141BYK-020 or BYK-080.The content of defoamer is preferably 0.2-0.5 weight part.
The preparation method of ultraviolet light polymerization anti-pollution paint of the present invention, comprises the following steps:
(1) polyfunctionality fluorine silicon urethane acrylate, polyfunctionality urethane acrylate, flow agent, defoamer are added high-speed mixer, stir 1-3h with 800-1300rpm, preferred 900-1200rpm stirs 1.5-2h, obtains mixture;
(2) mixture, light trigger, polyfunctional acrylic ester thinner are added high-speed mixer, stir 10-45min with 1100-1500rpm, preferred 1200-1400rpm stirs 25-35min mixing, obtains ultraviolet light polymerization anti-pollution paint.
Below in conjunction with embodiment and accompanying drawing, the invention will be further described.
Embodiment 1
Composition graphs 1 illustrates embodiment 1
Polyfunctionality fluorine silicon urethane acrylate preparation method:
(1) poly-(carbonic ether-ether) dibasic alcohol (molecular weight 1500 dalton) of 150g lower molecular weight is added in there-necked flask, be heated to 110 DEG C, dewater 1h under-0.98MPa, cools to 75 DEG C, under nitrogen protection, add 12.4g TriMethylolPropane(TMP), the 2,4 toluene diisocyanate of 87g is dripped, after dropwising with 5ml/min speed, reaction 2.5h, obtains the first intermediate;
(2) greenhouse cooling is to 70 DEG C, adds 0.09g dibutyl tin laurate and drip 8g hydroxyl polydimethylsiloxane (molecular weight 1000 dalton) in the first intermediate, and after adding, reaction 0.5h, obtains the second intermediate;
(3) in the second intermediate, add 12.6g trifluoroethanol, be warmed up to 80 DEG C, reaction 2h; Then, add 0.57g MEHQ, drip 113g pentaerythritol triacrylate with the speed of 8ml/min, after dropwising, continue reaction 2h, obtain polyfunctionality fluorine silicon urethane acrylate.
Carry out magnetic resonance detection to polyfunctionality fluorine silicon urethane acrylate prepared by embodiment 1, result as shown in Figure 1.Its nucleus magnetic hydrogen spectrum data (deuterochloroform is deuterated reagent): 1.10ppm, 1.28ppm, 1.47ppm, 1.56ppm, 2.05ppm, 2.16ppm, 2.30ppm, 3.52ppm, 4.29ppm, 4.53ppm, 4.86ppm, 5.00ppm, 5.87ppm, 6.08ppm, 6.41ppm and 7.03ppm.Prove the polyfunctionality fluorine silicon urethane acrylate really having prepared formula I structure.
Embodiment 2
Polyfunctionality fluorine silicon urethane acrylate preparation method:
(1) poly-(carbonic ether-ether) dibasic alcohol (molecular weight is 7000 dalton) of 700g lower molecular weight is added in there-necked flask, be heated to 120 DEG C, dewater 3h under-0.98MPa, cools to 80 DEG C, under nitrogen protection, add 14.5g TriMethylolPropane(TMP), 158g ditan-4,4-vulcabond is dripped, after dropwising with 12ml/min speed, reaction 4h, obtains the first intermediate;
(2) greenhouse cooling is to 75 DEG C, adds 0.47g stannous octoate and drip 17g hydroxyl polydimethylsiloxane (molecular weight 4000 dalton) in the first intermediate, and after adding, reaction 2h, obtains the second intermediate;
(3) in the second intermediate, add 18.7g trifluoroethanol, be warmed up to 85 DEG C, reaction 3h; Then, add 0.82g Resorcinol, drip 235g double pentaerythritol C5 methacrylate with the speed of 13ml/min, after dropwising, continue reaction 4h, obtain polyfunctionality fluorine silicon urethane acrylate.
Embodiment 3
Polyfunctionality fluorine silicon urethane acrylate preparation method:
(1) poly-(carbonic ether-ether) dibasic alcohol (molecular weight is 2000 dalton) of 200 lower molecular weights is added in there-necked flask, be heated to 115 DEG C, dewater 2h under-0.98MPa, cool to 78 DEG C, under nitrogen protection, add 13.6g TriMethylolPropane(TMP), 96g isophorone diisocyanate is dripped with 8ml/min speed, after dropwising, reaction 3h, obtains the first intermediate;
(2) greenhouse cooling is to 73 DEG C, adds 0.23g dibutyl tin laurate and drip 10g hydroxyl polydimethylsiloxane (2000 dalton) in the first intermediate, and after adding, reaction 1.5h, obtains the second intermediate;
(3) in the second intermediate, add 14.5g trifluoroethanol, be warmed up to 82 DEG C, reaction 2.5h; Then, add 0.67g Resorcinol, drip 165g trimethylolpropane diacrylate with the speed of 10ml/min, after dropwising, continue reaction 3h, obtain polyfunctionality fluorine silicon urethane acrylate.
Embodiment 4
Polyfunctionality fluorine silicon urethane acrylate preparation method:
(1) poly-(carbonic ether-ether) dibasic alcohol (molecular weight is 3500 dalton) of 350 lower molecular weights is added in there-necked flask, be heated to 120 DEG C, dewater 1.5h under-0.98MPa, cool to 80 DEG C, under nitrogen protection, add 13.8g TriMethylolPropane(TMP), 118g hexamethylene diisocyanate is dripped with 9ml/min speed, after dropwising, reaction 3.5h, obtains the first intermediate;
(2) greenhouse cooling is to 75 DEG C, adds 0.28g dibutyl tin laurate and drip 13g hydroxyl polydimethylsiloxane (molecular weight 3000 dalton) in the first intermediate, and after adding, reaction 1.5h, obtains the second intermediate;
(3) in the second intermediate, add 15.8g trifluoroethanol, be warmed up to 85 DEG C, reaction 2h; Then, add 0.63g MEHQ, drip 206g double pentaerythritol C5 methacrylate with the speed of 11ml/min, after dropwising, continue reaction 2.5h, obtain polyfunctionality fluorine silicon urethane acrylate.
Embodiment 5
Polyfunctionality fluorine silicon urethane acrylate preparation method:
(1) poly-(carbonic ether-ether) dibasic alcohol (molecular weight is 4000 dalton) of 380g lower molecular weight is added in there-necked flask, be heated to 118 DEG C, dewater 2.5h under-0.98MPa, cool to 78 DEG C, under nitrogen protection, add 14.2g TriMethylolPropane(TMP), 132g isophorone diisocyanate is dripped with 10.5ml/min speed, after dropwising, reaction 3h, obtains the first intermediate;
(2) greenhouse cooling is to 70 DEG C, adds 0.37g stannous octoate and drip 14g hydroxyl polydimethylsiloxane (molecular weight 3500 dalton) in the first intermediate, and after adding, reaction 1.5h, obtains the second intermediate;
(3) in the second intermediate, add 15.0g trifluoroethanol, be warmed up to 85 DEG C, reaction 2h; Then, add 0.77g Resorcinol, drip 161g polyfunctionality hydroxy-acrylate monomer with the speed of 12ml/min, after dropwising, continue reaction 3.5h, obtain polyfunctionality fluorine silicon urethane acrylate.
Embodiment 6
Prepared by polyfunctionality urethane acrylate:
(1) 100g polytetrahydrofuran dibasic alcohol (molecular weight 1000 dalton) is added in there-necked flask, be heated to 110 DEG C, dewater 1h under-0.98MPa, cools to 75 DEG C, under nitrogen protection, add 0.09g dibutyl tin laurate, the 2,4 toluene diisocyanate of 62g is dripped, after dropwising with 5ml/min speed, reaction 2.5h, obtains the first intermediate;
(2) be warmed up to 80 DEG C, add 0.42g Resorcinol, drip 87g pentaerythritol triacrylate with the speed of 5ml/min, after dropwising, continue reaction 2h, obtain polyfunctionality urethane acrylate.
Carry out magnetic resonance detection to polyfunctionality urethane acrylate prepared by embodiment 6, result as shown in Figure 2.Its nucleus magnetic hydrogen spectrum data (deuterochloroform is deuterated reagent): 1.63ppm, 2.15ppm, 2.21ppm, 3.43ppm, 3.59ppm, 4.19ppm, 4.28ppm, 4.31ppm, 5.87ppm, 5.90ppm, 6.07ppm, 6.13ppm, 6.17ppm, 6.41ppm, 6.46ppm and 7.13ppm.Prove the polyfunctionality urethane acrylate really having prepared formula II structure.
Embodiment 7
Prepared by polyfunctionality urethane acrylate:
(1) 300g polytetrahydrofuran dibasic alcohol (molecular weight 5000 dalton) is added in there-necked flask, be heated to 120 DEG C, dewater 3h under-0.98MPa, cools to 80 DEG C, under nitrogen protection, add 0.47g stannous octoate, 116g ditan-4,4-vulcabond is dripped, after dropwising with 12ml/min speed, reaction 4h, obtains the first intermediate;
(2) be warmed up to 85 DEG C, add 0.57g MEHQ, drip 180g double pentaerythritol C5 methacrylate with the speed of 9ml/min, after dropwising, continue reaction 4h, obtain polyfunctionality urethane acrylate.
Embodiment 8
Prepared by polyfunctionality urethane acrylate:
(1) 200g polytetrahydrofuran dibasic alcohol (molecular weight 2000 dalton) is added in there-necked flask, be heated to 115 DEG C, dewater 2h under-0.98MPa, cool to 78 DEG C, under nitrogen protection, add 0.21g stannous octoate, 84g isophorone diisocyanate is dripped with 8ml/min speed, after dropwising, reaction 3.5h, obtains the first intermediate;
(2) be warmed up to 85 DEG C, add 0.49g stopper, drip 120g trimethylolpropane diacrylate with the speed of 7ml/min, after dropwising, continue reaction 3h, obtain polyfunctionality urethane acrylate.
Embodiment 9
Prepared by polyfunctionality urethane acrylate:
(1) 240g polytetrahydrofuran dibasic alcohol (molecular weight 4000 dalton) is added in there-necked flask, be heated to 110 DEG C, dewater 2.5h under-0.98MPa, cool to 75 DEG C, under nitrogen protection, add 0.38g catalyzer, 93g hexamethylene diisocyanate is dripped with 10ml/min speed, after dropwising, reaction 3h, obtains the first intermediate;
(2) be warmed up to 85 DEG C, add 0.51g stopper, drip 147g double pentaerythritol C5 methacrylate with the speed of 8ml/min, after dropwising, continue reaction 2.5h, obtain polyfunctionality urethane acrylate.
Embodiment 10
Prepared by ultraviolet light polymerization anti-pollution paint
According to table 1 ratio (unit is g), prepares ultraviolet light polymerization anti-pollution paint in accordance with the following methods:
(1) 38-116g polyfunctionality fluorine silicon urethane acrylate, 3-8g polyfunctionality urethane acrylate, 0.15-0.55g flow agent, 0.1-0.7g defoamer are stirred 1-3h with 800-1300rpm, obtain mixture;
(2) mixture, 0.4-1.5g light trigger, 12-18g polyfunctional acrylic ester thinner are stirred 10-45min with 1100-1500rpm, the ultraviolet light polymerization anti-pollution paint obtained, is labeled as UVA01, UVA02, UVA03, UVA04, UVA05, UVA06 and UVA07 respectively.
Ultraviolet light polymerization anti-pollution paint UVA01 ~ UVA07 material ratio prepared by table 1
Respectively ultraviolet light polymerization anti-pollution paint UVA01 ~ UVA07 is coated on PU leather, at 330-450mJ/cm
2solidify under UV energy, the paint film after solidification is tested.Pollution resistance 3M permanent pen test, concrete testing method is, write word with oil pen on paint film after, after 10min, use absorbent cotton wiping, see whether leave the marking, without any the marking, shows that antifouling property is excellent.Pollution resistance (first wiping) for pollution resistance after absorbent cotton wiping first time, pollution resistance (wiping 30 times) be with absorbent cotton repeatedly wiping 30 times after pollution resistance; After wiping 30 times, still without any the marking, indicate paint film and there is lasting pollution resistance.Carry out performance test to described paint film, test result is in table 2.
Table 2 ultraviolet light polymerization anti-pollution paint obtains the performance test results of film
Obviously, the explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that the those of ordinary skill for described technical field, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (10)
1. polyfunctionality fluorine silicon urethane acrylate, is characterized in that, structure is such as formula shown in I:
In formula, m, n, p are integer, 10≤m≤70,10≤n≤70,12≤p≤53;
R
1-be the one in following structure:
-R
2-be the one in following structure:
2. the preparation method of polyfunctionality fluorine silicon urethane acrylate according to claim 1, is characterized in that, comprise the following steps:
(1) in reaction vessel, add poly-(carbonic ether-ether) dibasic alcohol, after dehydration, under inert atmosphere protection, add TriMethylolPropane(TMP) and vulcabond, reaction, obtains the first intermediate;
Described vulcabond is one or more mixtures in hexamethylene diisocyanate, isophorone diisocyanate, 2,4 toluene diisocyanate, ditan-4,4-vulcabond;
(2) in the first intermediate, add catalyzer and hydroxyl polydimethylsiloxane, reaction, obtains the second intermediate;
(3) in the second intermediate, add trifluoroethanol, after reaction, add stopper and polyfunctionality hydroxy-acrylate monomer, continue reaction, obtain polyfunctionality fluorine silicon urethane acrylate;
Described polyfunctionality hydroxy-acrylate monomer is trimethylolpropane diacrylate, pentaerythritol triacrylate or double pentaerythritol C5 methacrylate.
3. the ultraviolet light polymerization anti-pollution paint containing polyfunctionality fluorine silicon urethane acrylate according to claim 1, is characterized in that, comprising:
The polyfunctionality fluorine silicon urethane acrylate of 38-116 weight part;
The polyfunctionality urethane acrylate of 3-8 weight part;
The polyfunctional acrylic ester thinner of 12-18 weight part;
The light trigger of 0.4-1.5 weight part;
The flow agent of 0.15-0.55 weight part;
The defoamer of 0.1-0.7 weight part;
Described polyfunctionality urethane acrylate structure is such as formula shown in II:
In formula, q is integer, 15≤q≤78;
R
1-be the one in following structure:
-R
2-be the one in following structure:
4. ultraviolet light polymerization anti-pollution paint according to claim 3, it is characterized in that, the weight part of described polyfunctionality fluorine silicon urethane acrylate is 45-102, the weight part of polyfunctionality urethane acrylate is 4-7.5, the weight part of polyfunctional acrylic ester thinner is 13-17, the weight part of light trigger is 0.7-1.3, and the weight part of flow agent is 0.25-0.45, and the weight part of defoamer is 0.2-0.5.
5. ultraviolet light polymerization anti-pollution paint according to claim 4, it is characterized in that, the weight part of described polyfunctionality fluorine silicon urethane acrylate is 54-86, and the weight part of polyfunctionality urethane acrylate is 4.5-6, and the weight part of polyfunctional acrylic ester thinner is 14-16.
6. ultraviolet light polymerization anti-pollution paint according to claim 3, is characterized in that, described polyfunctionality urethane acrylate adopts following methods preparation:
(1) in reaction vessel, add polytetrahydrofuran dibasic alcohol, after dehydration, under inert atmosphere protection, add catalyzer and vulcabond, be obtained by reacting the first intermediate;
(2) in the first intermediate, add stopper and polyfunctionality hydroxy-acrylate monomer, after reaction, obtain polyfunctionality urethane acrylate.
7. ultraviolet light polymerization anti-pollution paint according to claim 3, is characterized in that, described polyfunctional acrylic ester thinner is one or more in tetramethylol methane tetraacrylate, dipentaerythritol acrylate, Viscoat 295.
8. ultraviolet light polymerization anti-pollution paint according to claim 3, it is characterized in that, described light trigger is Irfacure184, Darocure 1173, Irfacure 2959 or Irfacure 819, described flow agent is BYK-300, BYK-301, BYK-306, BYK-331 or BYK-310, and described defoamer is BYK-065, BYK-066, BYK-070, BYK-088, BYK-141BYK-020 or BYK-080.
9. the preparation method of ultraviolet light polymerization anti-pollution paint according to claim 3, is characterized in that, comprise the following steps:
(1) polyfunctionality fluorine silicon urethane acrylate, polyfunctionality urethane acrylate, flow agent and defoamer are uniformly mixed, obtain mixture;
(2) mixture, light trigger and polyfunctional acrylic ester thinner are uniformly mixed, obtain ultraviolet light polymerization anti-pollution paint.
10. the preparation method of ultraviolet light polymerization anti-pollution paint according to claim 9, it is characterized in that, the stirring velocity be uniformly mixed of described step (1) is 800-1300rpm, churning time is 1-3h, the stirring velocity be uniformly mixed of described step (2) is 1100-1500rpm, and churning time is 10-45min.
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