CN100503757C - Ultraviolet light solidifying paint containing POSS and its preparation method - Google Patents
Ultraviolet light solidifying paint containing POSS and its preparation method Download PDFInfo
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- CN100503757C CN100503757C CNB2005100282545A CN200510028254A CN100503757C CN 100503757 C CN100503757 C CN 100503757C CN B2005100282545 A CNB2005100282545 A CN B2005100282545A CN 200510028254 A CN200510028254 A CN 200510028254A CN 100503757 C CN100503757 C CN 100503757C
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Abstract
An ultraviolet solidified paint containing POSS is prepared through preparing the POSS with double bond from organic siloxane, proportionally mixing diisocyanate, polyol, catalyst and active diluent, stirring, heating while reacting to obtain the PUA prepolymer containing POSS, mixing it with catalyst, optical trigger, active diluent and other assistants, and stirring.
Description
Technical field
The invention belongs to the functional high molecule material technical field, be specifically related to ultraviolet-curing paint of a kind of POSS of containing and preparation method thereof.
Background technology
Along with the continuous pursuit of people to the high-quality product of high-performance, and to the growing interest of energy consumption and problem of environmental pollution, coating will more and more develop to directions such as high-performance, low cost, less energy-consumption and non-environmental-pollutions.Occurred in recent years with radiation curable coating, water-borne coatings, high solid coating and powder coating is the novel environment-friendly coating of representative, radiation-curable coating wherein, because of it does not contain volatile organic solvent, environmentally safe is filmed and is done back noresidue solvent and excellent application performance and be pushed to first of the environment-friendly type coating.UV-light (UV) is solidified and electron beam (EB) solidifies the general designation radiation curing, because electron beam curing apparatus is comparatively complicated, so the cost height is UV-curing technology being most widely used in radiation curable coating.
Nineteen forty-six, American I nmomt company has at first obtained first patent of unsaturated polyester/vinylbenzene uv curing ink.Germany makes particle board coating ultra-violet curing enter commercialization in the sixties first, first applying electronic beam radiation curing automobile component of U.S. Ford and instrument top coat.Afterwards, the ultraviolet-curing paint technology has experienced fast development in developed country, and average growth rate per annum has now become the big industry that annual value of production reaches multi-million dollar more than 10%.China just began photo-cured coating is researched and developed in earlier 1970s, and ultraviolet-curing paint is very rapid in China's development at present.And a kind of new ultra-violet photo-cured coating that POSS (polyhedral oligomeric position half siloxanes) the coating material solidified conduct of base ultraviolet light develops rapidly in recent years, its application in every respect more and more receives publicity.Domestic research in this respect at present still is in the starting stage, and mostly existing literature is the structural performance of relevant POSS and preparation thereof to relate to also relatively more rare that POSS uses in ultraviolet-curing paint.The present invention prepares the novel ultraviolet light photo-cured coating of a kind of POSS of containing, investigates the nanometer reinforcing effect of POSS in ultraviolet-curing paint is used, and the modification that also can be ultraviolet-curing paint provides a kind of new thinking.
Summary of the invention
The objective of the invention is to ultraviolet-curing paint that proposes a kind of POSS of containing and preparation method thereof.
The ultraviolet-curing paint that contains POSS that the present invention proposes is to be mixed by following weight proportion 200-500:0.5-20:80-120:0.1-2:10-30 after reaction obtains to contain the polyurethane acroleic acid prepolymer of POSS by vulcabond, double bond containing POSS, polyvalent alcohol, catalyzer and reactive thinner; Wherein, double bond containing POSS adopts organo-siloxane partial hydrolysis-envelope angle method to prepare.
Before the use, with above-mentioned polyurethane acroleic acid prepolymer, catalyzer, light trigger, the reactive thinner that contains POSS, and other auxiliary agent (as defoamer, flow agent etc.) promptly obtains UV light solidifying polyurethane acrylic acid paint by following weight proportion uniform mixing.Wherein:
Said organo-siloxane is methyl trichlorine siloxanes, ethyl trichloro silicane oxygen alkane, propyl-trichlorosilicane oxygen alkane, phenyl trichlorine siloxanes, vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, methyl ethylene trichlorine siloxanes, γ-chloropropyl trichlorine siloxanes, acryloxy Trimethoxy silane or acryloxy triethoxyl silane;
Said vulcabond is aromatic diisocyanate such as Toluene-2,4-diisocyanate, the 4-vulcabond, Toluene-2,4-diisocyanate, the 6-vulcabond, 4,4 '-diphenylmethanediisocyanate, 1, the 5-naphthalene diisocyanate, the ethylbenzene vulcabond, 4, the 6-Xylene Diisocyanate, 3,3 '-dimethyl diphenyl-4,4 '-vulcabond or 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, perhaps aliphatic diisocyanate such as hexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate or isophorone diisocyanate;
Said polyvalent alcohol is polyether glycol or polyester polyol.For example: polyethylene oxide polyvalent alcohol, poly(propylene oxide) polyvalent alcohol, polytetrahydrofuran polyvalent alcohol or pla-pcl polyvalent alcohol.As polyoxyethylene glycol (PEG), propylene oxide polyether Glycols (PPG), tetrahydrofuran (THF) polyether Glycols (PTMG), polyoxytrimethylene ether (PPO), poly-tetrahydrofuran ether (PTMO) and poly-butanediol (PBD), Viscotrol C (CO) etc.
Said catalyzer can be dibutyltin dilaurate, stannous octoate, N-methylmorpholine or triethylenediamine.
Said reactive thinner can be acrylate, methacrylic ester or vinylbenzene, and employed epoxide of cationoid polymerisation and vinyl ether etc. all are common employed reactive monomers in the radiation curing prescription.
Said light trigger can be benzophenone, α-hydroxyl isopropyl benzene ketone, α-hydroxy cyclohexyl phenylketone, benzoin methyl ether, Alpha-hydroxy Benzoin ethyl ether, isopropyl thioxanthone, two (4-methylthio phenyl formyl radical)-2-morpholinyl propane or 4-morpholinyl A acyl group-1-Bian Ji-1-(dimethylin) propane etc.
The preparation method of the above-mentioned ultraviolet-curing paint that contains POSS is as follows:
(1) in the there-necked flask that reflux condensate device and agitator are housed, adds the total machine solvent of 5～25mL organosilane monomer, 5～50mL distilled water and 25～150mL, 30～80 ℃ stirred in water bath 12～72 hours, collection obtains white solid, filter with total machine solvent wash, vacuum-drying is more than 12 hours under 30～60 ℃ of conditions, product is handled with the alkali organic solvent of 5～30 times of weight, again it is poured in the mixture of isopyknic hydrochloric acid and ice, filter and be washed to neutrality then, vacuum-drying is more than 12 hours under 40～80 ℃ of conditions.Thoroughly extract with ether again, can obtain unmodified POSS;
(2) be that dropwise Dropwise 5～25ml concentration is the active organosilicon monomer solution of 0.025g/ml, reacts 12～72 hours in 30～50 ℃ of water-baths in the mixed organic solvents of above-mentioned POSS of 0.025g/ml in 5～50ml concentration.Product poured in 5～20 times frozen water and the hydrochloric acid mixed solution leaves standstill more than 12 hours, the throw out that obtains with deionized water wash till filtrate is neutrality.Filter the white solid of collecting, vacuum-drying promptly obtained the POSS with two key groups more than 12 hours under 30～60 ℃ of conditions;
(3) P0SS, polyvalent alcohol, catalyzer and the reactive thinner of vulcabond, the two keys of band is even with the mixed of 200～500:0.5-20:80～120:0.1～2:10～30 (weight), be warming up to 60-80 ℃, reacted 3-6 hour, make reaction be tending towards finishing, promptly get the polyurethane acroleic acid prepolymer that contains POSS;
(4) before the use, that above-mentioned prepolymer, light trigger, reactive thinner and other auxiliary agent that contains POSS is even with the mixed of 100:0.1-2:5-10:1-5 (weight), promptly get UV light solidifying polyurethane acrylic acid paint.
Among the present invention, organosilane monomer can be methyl trichlorine siloxanes, ethyl trichloro silicane oxygen alkane, propyl-trichlorosilicane oxygen alkane, phenyl trichlorine siloxanes, vinyl trichloro silane, methyl ethylene trichlorine siloxanes or γ-chloropropyl trichlorine siloxanes etc.
Among the present invention, the active organosilicon monomer can be vinyl trichloro silane, methyl ethylene trichlorine siloxanes, γ-chloropropyl trichlorine siloxanes, vinyltrimethoxy silane, vinyltriethoxysilane, acryloxy Trimethoxy silane or acryloxy triethoxyl silane etc.
Among the present invention, total machine solvent can be ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, 1,2-propylene glycol, 1,3-propylene glycol, propylene-glycol ethyl ether, propylene glycol butyl ether, butanols, 1,3-butyleneglycol, 1,4-butyleneglycol, dioxane and glycerine etc.
Among the present invention, alkali organic solvent can be pyridine, picoline, ethylpyridine, ethamine, diethylamine, triethylamine, dimethyl formamide or N,N-DIMETHYLACETAMIDE etc.
Among the present invention, mixed organic solvents can be two kinds or the mixture of above solvent in tetrahydrofuran (THF), trichloromethane, methylene dichloride, dioxane, acetone, butanone, pimelinketone, benzene,toluene,xylene, pyridine, picoline, ethylpyridine, ethamine, diethylamine, triethylamine, dimethyl formamide or the N,N-DIMETHYLACETAMIDE.
Among the present invention, vulcabond can be aromatic diisocyanate such as Toluene-2,4-diisocyanate, the 4-vulcabond, Toluene-2,4-diisocyanate, the 6-vulcabond, 4,4 '-diphenylmethanediisocyanate, 1, the 5-naphthalene diisocyanate, the ethylbenzene vulcabond, 4, the 6-Xylene Diisocyanate, 3,3 '-dimethyl diphenyl-4,4 '-vulcabond or 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, perhaps aliphatic diisocyanate such as hexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate or different Buddhist ketone vulcabond etc.
Among the present invention, polyvalent alcohol can be polyether glycol, polyester polyol, polyacrylic ester or urethane.For example: polyethylene oxide polyvalent alcohol, poly(propylene oxide) polyvalent alcohol, polytetrahydrofuran polyvalent alcohol or pla-pcl polyvalent alcohol.As polyoxyethylene glycol (PEG), propylene oxide polyether Glycols (PPG), tetrahydrofuran (THF) polyether Glycols (PTMG), polyoxytrimethylene ether (PP0), poly-tetrahydrofuran ether (PTMO) and poly-butanediol (PBD), Viscotrol C (C0) etc.
Among the present invention, said catalyzer can be dibutyltin dilaurate, stannous octoate, N-methylmorpholine or triethylenediamine.
Among the present invention, said reactive thinner can be acrylate, methacrylic ester or vinylbenzene, and employed oxide compound and the vinyl ether etc. gone back of cationoid polymerisation all are common employed reactive monomers in the radiation curing prescription.
Among the present invention, said light trigger can be benzophenone, α-hydroxyl isopropyl benzene ketone, α-hydroxy cyclohexyl phenylketone, benzoin methyl ether, Alpha-hydroxy Benzoin ethyl ether, isopropyl thioxanthone, 2 (4-methylthio phenyl formyl radical)-2-morpholinyl propane or 4-morpholinyl A acyl group-1-Bian Ji-1-(dimethylin) propane etc.
Among the present invention, adjuvant used flow agent commonly used in the coating, defoamer, tensio-active agent, the filler etc. of comprising.
Advantage of the present invention is: by the synthetic class POSS of the hydrolysis of organo-siloxane, then with its functionalization, make it have reactive group, promptly synthesize and can participate in the POSS that polyreaction has two keys.Then utilize vulcabond and Propylene glycol monoacrylate and polyol reaction, prepare the urethane acrylate ultraviolet-curing paint of a kind of POSS of containing.The present invention has that technology is simple, little to the pollution of environment, cost is low and advantage such as curing of coating is fast, can satisfy coating and develop desired multiple needs, and the nanometer reinforcing effect of POSS in coating, the modification that also can be ultraviolet-curing paint provides a kind of new thinking, has bigger development prospect and application widely.
Description of drawings
Fig. 1 is the POSS molecular structure.
Fig. 2 contains the field emission scanning electron microscope figure that the urethane acrylate ultraviolet light polymerization of POSS is filmed.
Fig. 3 contains TG-DSC curve (containing 2%POSS) that the urethane acrylate ultraviolet light polymerization of POSS is filmed.
Fig. 4 contains TG-DSC curve (containing 5%POSS) that the urethane acrylate ultraviolet light polymerization of POSS is filmed.
Fig. 5 does not contain TG-DSC curve that the urethane acrylate ultraviolet light polymerization of POSS is filmed.
Table 1 is to contain the performance that the urethane acrylate ultraviolet light polymerization of POSS is filmed.
Embodiment
Above-mentioned a kind of ultraviolet-curing paint that contains POSS, its preparation method is at first carefully to add 5～25mL organosilane monomer in the there-necked flask that reflux condensate device and agitator are housed, 5～50mL distilled water and 25～150mL have the machine solvent, 30～80 ℃ stirred in water bath after 12～72 hours, the white solid that collection is obtained spends the night with total machine solvent wash filtration back vacuum-drying under 30～60 ℃ of conditions, after product is handled with the alkali organic solvent of 5～30 times of weight, it is poured in the mixture of isopyknic concentrated hydrochloric acid and ice, filter and be washed to neutrality then, vacuum-drying is spent the night under 40～80 ℃ of conditions.Thoroughly extract with ether again, can obtain unmodified POSS.
Be that dropwise Dropwise 5～25ml concentration is the active organosilicon monomer solution of 0.025g/ml, reacts 12～72 hours in 30～50 ℃ of water-baths in the mixed organic solvents of above-mentioned POSS of 0.025g/ml in 5～50ml concentration then.Pour product in 5～20 times frozen water and concentrated hydrochloric acid mixing solutions standing over night, the precipitate with deionized water that obtains is washed till filtrate is neutrality.Filter white solid vacuum-drying under 30～60 ℃ of conditions of collecting and promptly obtain POSS more than 12 hours with two key groups.
Then that POSS, polyvalent alcohol, catalyzer and the reactive thinner of vulcabond, the two keys of band is even with the mixed of 200～500:0.5-20:80～120:0.1～2:10～30 (weight), be warming up to 60-80 ℃ of reaction 3-6 hour, make reaction be tending towards finishing, promptly get the polyurethane acroleic acid prepolymer that contains POSS.
Before the use, above-mentioned prepolymer, light trigger, reactive thinner and other auxiliary agent that contains POSS is even with the mixed of 100:0.1-2:5-10:1-5 (weight), promptly get UV light solidifying polyurethane acrylic acid paint.
At last above-mentioned UV light solidifying polyurethane acrylic acid paint evenly is applied to matrix surface, directly places irradiation under the ultra-violet lamp, carry out ultraviolet light polymerization.Again this ultraviolet light polymerization film is carried out performance test.
Among the present invention, organosilane monomer can be methyl trichlorine siloxanes, ethyl trichloro silicane oxygen alkane, propyl-trichlorosilicane oxygen alkane, phenyl trichlorine siloxanes, vinyl trichloro silane, methyl ethylene trichlorine siloxanes or γ-chloropropyl trichlorine siloxanes etc.The active organosilicon monomer can be vinyl trichloro silane, methyl ethylene trichlorine siloxanes, γ-chloropropyl trichlorine siloxanes, vinyltrimethoxy silane, vinyltriethoxysilane, acryloxy Trimethoxy silane or acryloxy triethoxyl silane etc.Total machine solvent can be ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, 1,2-propylene glycol, 1,3-propylene glycol, propylene-glycol ethyl ether, propylene glycol butyl ether, butanols, 1,3-butyleneglycol, 1,4-butyleneglycol, dioxane and glycerine etc.Alkali organic solvent can be pyridine, picoline, ethylpyridine, ethamine, diethylamine, triethylamine, dimethyl formamide or N,N-DIMETHYLACETAMIDE etc.Mixed organic solvents can be two kinds or the mixture of above solvent in tetrahydrofuran (THF), trichloromethane, methylene dichloride, dioxane, acetone, butanone, pimelinketone, benzene,toluene,xylene, pyridine, picoline, ethylpyridine, ethamine, diethylamine, triethylamine, dimethyl formamide or the N,N-DIMETHYLACETAMIDE.Vulcabond can be aromatic diisocyanate such as Toluene-2,4-diisocyanate, the 4-vulcabond, Toluene-2,4-diisocyanate, the 6-vulcabond, 4,4 '-diphenylmethanediisocyanate, 1, the 5-naphthalene diisocyanate, the ethylbenzene vulcabond, 4, the 6-Xylene Diisocyanate, 3,3 '-dimethyl diphenyl-4,4 '-vulcabond or 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, perhaps aliphatic diisocyanate such as hexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate or different Buddhist ketone vulcabond etc.Polyvalent alcohol is polyether glycol, polyester polyol, polyacrylic ester or urethane.For example: polyethylene oxide polyvalent alcohol, poly(propylene oxide) polyvalent alcohol, polytetrahydrofuran polyvalent alcohol or pla-pcl polyvalent alcohol.As polyoxyethylene glycol (PEG), propylene oxide polyether Glycols (PPG), tetrahydrofuran (THF) polyether Glycols (PTMG), polyoxytrimethylene ether (PPO), poly-tetrahydrofuran ether (PTMO) and poly-butanediol (PBD), Viscotrol C (CO) etc.Catalyzer can be dibutyltin dilaurate, stannous octoate, N-methylmorpholine or triethylenediamine, and consumption is 0.1%-2% weight.Reactive thinner is acrylate, methacrylic ester or vinylbenzene, and employed oxide compound and the vinyl ether etc. gone back of cationoid polymerisation all are common employed reactive monomers in the radiation curing prescription.Light trigger is benzophenone, α-hydroxyl isopropyl benzene ketone, α-hydroxy cyclohexyl phenylketone, benzoin methyl ether, Alpha-hydroxy Benzoin ethyl ether, isopropyl thioxanthone, 2 (4-methylthio phenyl formyl radical)-2-morpholinyl propane or 4-morpholinyl A acyl group-1-Bian Ji-1-(dimethylin) propane etc.
The present invention will be described in detail below in conjunction with embodiment.Do not violating under the purport of the present invention, the present invention should be not limited to the content that following experimental example is specifically expressed.
Embodiment 1
In the there-necked flask that reflux condensate device and agitator are housed, careful 17.7mL distilled water is added in 10mL trichloromethyl siloxanes and the 60mL acetone under agitation condition, 50 ℃ stirred in water bath 48 hours, the white solid that after reaction finishes collection is obtained filters back vacuum-drying under 45 ℃ of conditions with washing with acetone and spends the night, product spends the night with the pyridine suspension and the stirring of 20 times of weight, pyridine solution is poured in the mixture of isopyknic concentrated hydrochloric acid and ice, collecting precipitation is washed with water to neutrality then, and vacuum-drying is spent the night under 60 ℃ of conditions.Thoroughly extract with ether again, can obtain unmodified POSS.Be triethylamine/tetrahydrofuran (THF) (1:100 of the above-mentioned POSS of 0.025g/ml then in 15ml concentration, volume ratio) in the mixing solutions, dropwise dripping 20ml concentration is the tetrahydrofuran solution of γ-acryloxy Trimethoxy silane (KH-570) of 0.025g/ml, and reaction is 72 hours in 35 ℃ of water-baths.Pour product in 10 times frozen water and concentrated hydrochloric acid mixing solutions standing over night, the precipitate with deionized water that obtains washing several times are till filtrate is neutrality.It is dry more than 12 hours under 60 ℃ of vacuum to filter the white solid of collecting, and promptly obtains the POSS with two key active groups.POSS (0.4g), 5.95g (0.0238mol) modified diphenylmethane diisocyanate (MDI), the 3.57g (0.0079mol) of the two keys of band are contained modified polyalcohol, 0.1g Resorcinol, 1.3g (0.01mol) Propylene glycol monoacrylate and 0.1g dibutyl tin dilaurate, after stirring, be warming up to and continue stirring reaction 4h about 70 ℃, make reaction be tending towards finishing.Promptly get the polyurethane acrylate prepolymer that contains POSS.Before the use, this is contained the polyurethane acrylate prepolymer (10 gram) of POSS, butyl acrylate (10g), Alpha-hydroxy Benzoin ethyl ether (0.1g), flow agent BYK-300 (0.02g) and defoamer 5400-PII (0.008g), stir, promptly get UV light solidifying polyurethane acrylic acid paint, again above-mentioned ultraviolet-curing paint evenly is applied to matrix surface and (contains 2%POSS as sample 1, weight ratio), with the ultra-violet lamp of 500W as source of radiation, directly sample is placed irradiation completion of cure under the ultra-violet lamp, be sample 1, this urethane acrylate ultraviolet light polymerization film that contains POSS is carried out various performance tests.
Fig. 2 is the field emission scanning electron microscope figure that this urethane acrylate ultraviolet light polymerization that contains POSS is filmed, and Fig. 3 is TG-DSC curve (containing 2%POSS) that this urethane acrylate ultraviolet light polymerization that contains POSS is filmed.The results of property that this urethane acrylate ultraviolet light polymerization is filmed is as shown in table 1.
Embodiment 2
Adopt the preparation condition identical with embodiment 1, still the amount of double bond containing POSS changes 1.0g into.The prepared urethane acrylate ultraviolet curable coating that contains POSS is sample 2 (containing 5%POSS).
Fig. 4 is TG-DSC curve (containing 5%POSS) that this urethane acrylate ultraviolet light polymerization that contains POSS is filmed.The results of property that this urethane acrylate ultraviolet light polymerization that contains POSS is filmed is as shown in table 1.
Adopt the preparation condition identical, but thinner butyl acrylate (10g) changes butyl acrylate (5.0g) and Viscoat 295 (TMPTA) into (5.0g) with embodiment 1.The prepared urethane acrylate ultraviolet curable coating that contains POSS is sample 3.
The results of property that this urethane acrylate ultraviolet light polymerization that contains POSS is filmed is as shown in table 1.
Embodiment 4
Adopt the preparation condition identical, but thinner butyl acrylate (10g) changes Viscoat 295 (TMPTA) into (10.0g) with embodiment 1.The prepared urethane acrylate ultraviolet curable coating that contains POSS is sample 4.
The results of property that this urethane acrylate ultraviolet light polymerization that contains POSS is filmed is as shown in table 1.
Adopt the preparation condition identical, still do not add double bond containing POSS with embodiment 1.Prepared urethane acrylate ultraviolet curable coating is sample 5.
Fig. 5 is TG-DSC curve (not containing POSS) that this urethane acrylate ultraviolet light polymerization is filmed.The results of property that this urethane acrylate ultraviolet light polymerization is filmed is as shown in table 1.
Embodiment 6
Adopt the preparation condition identical, but the ratio of modified diphenylmethane diisocyanate and modified polyalcohol becomes 5.95g (0.0238mol): 5.36g (0.0119mol) with embodiment 1.
Embodiment 7
Adopt the preparation condition identical, but the ratio of modified diphenylmethane diisocyanate and modified polyalcohol becomes 5.95g (0.0238mol): 2.68g (0.006mol) with embodiment 1.
Embodiment 8
Adopt the preparation condition identical, but modified diphenylmethane diisocyanate changes Toluene-2,4-diisocyanate into embodiment 1, the 4-vulcabond, modified polyalcohol becomes Viscotrol C.
Embodiment 9
Adopt the preparation condition identical, but modified diphenylmethane diisocyanate changes 3 into embodiment 1,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, modified polyalcohol become the tetrahydrofuran (THF) polyether Glycols.
Embodiment 10
Identical with embodiment 1, but the trichloromethyl siloxanes becomes the trichlorophenyl siloxanes, and its consumption becomes 15ml.γ-acryloxy Trimethoxy silane changes methyl ethylene trichlorine siloxanes into, and its concentration and consumption become 0.05g/ml and 30ml respectively.
Embodiment 11
Identical with embodiment 1, but the consumption of Alpha-hydroxy Benzoin ethyl ether (0.1g) becomes 0.05g.
Embodiment 12
Identical with embodiment 1, but the consumption of Alpha-hydroxy Benzoin ethyl ether (0.1g) becomes 0.15g.
Embodiment 13
Identical with embodiment 1, but the Alpha-hydroxy Benzoin ethyl ether becomes Alpha-hydroxy isopropyl benzene ketone, and consumption becomes 0.15g.
Embodiment 14
Identical with embodiment 1, but the Alpha-hydroxy Benzoin ethyl ether becomes α-hydroxy cyclohexyl phenylketone, and consumption becomes 0.15g.
The urethane acrylate ultraviolet-curing paint that contains POSS that the foregoing description 2-14 is prepared, its structure and performance and embodiment 1 come to the same thing or similar, have all that technology is simple, little to the pollution of environment, cost is low, good film-forming property, curing of coating is fast and advantage such as nanometer reinforcing effect, is a kind of good ultraviolet-curing paint.
Table 1
| Sample | Outward appearance | Pencil hardness | Water tolerance | Sticking power | Curing speed | Temperature of initial decomposition | |
| 1 | Simple is protruding, and glossiness is general | 4H | Very | 3 | In | 310℃ | |
| 2 | Surfacing, glossiness is general | 5H | Very | 2 | In | 311℃ | |
| 3 | Surfacing, glossiness is good | 5H | Very | 3 | Hurry up | 298℃ | |
| 4 | Surfacing, glossiness is good | 5H | Difference | 4 | Hurry up | 306 |
|
| 5 | The surface is more smooth, and glossiness is | 2H | Difference | 3 | Hurry up | 281℃ |
Claims (3)
1, a kind of ultraviolet-curing paint that contains POSS is characterized in that being mixed by following weight proportion 200-500:0.5-20:80-120:0.1-2:10-30 after reaction obtains to contain the polyurethane acroleic acid prepolymer of POSS by vulcabond, double bond containing POSS, polyvalent alcohol, catalyzer and reactive thinner; Mix by the polyurethane acroleic acid prepolymer, light trigger, reactive thinner and the auxiliary agent that contain POSS part by weight, promptly obtain the ultraviolet-curing paint of the required POSS of containing by 100:0.1-2:5-10:1-5; Wherein, double bond containing POSS adopts organo-siloxane partial hydrolysis-envelope angle method to prepare; Wherein:
Said organo-siloxane is methyl trichlorine siloxanes, ethyl trichloro silicane oxygen alkane, propyl-trichlorosilicane oxygen alkane, phenyl trichlorine siloxanes, vinyl trichloro silane, vinyltrimethoxy silane, vinyltriethoxysilane, methyl ethylene trichlorine siloxanes, γ-chloropropyl trichlorine siloxanes, acryloxy Trimethoxy silane or acryloxy triethoxyl silane;
Said vulcabond is a kind of of following aromatic diisocyanate: Toluene-2,4-diisocyanate, the 4-vulcabond, Toluene-2,4-diisocyanate, the 6-vulcabond, 4,4 '-diphenylmethanediisocyanate, 1, the 5-naphthalene diisocyanate, the ethylbenzene vulcabond, 4, the 6-Xylene Diisocyanate, 3,3 '-dimethyl diphenyl-4,4 '-vulcabond or 3,3 '-dimethyl-4,4 '-diphenylmethanediisocyanate, or following aliphatic diisocyanate is a kind of: hexamethylene diisocyanate, hexamethylene diisocyanate, cyclohexyl diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate or isophorone diisocyanate;
Said polyvalent alcohol is polyether glycol or polyester polyol;
Said catalyzer is dibutyltin dilaurate, stannous octoate, N-methylmorpholine or triethylenediamine;
Said reactive thinner is acrylate or methacrylic ester;
Said light trigger is benzophenone, benzoin methyl ether, Alpha-hydroxy Benzoin ethyl ether, Alpha-hydroxy isopropyl benzene ketone, Alpha-hydroxy phenylcyclohexane ketone, isopropyl thioxanthone or two (4-methylthio phenyl formyl radical)-2-morpholinyl propane;
Described auxiliary agent is defoamer and flow agent.
2, a kind of preparation method who contains the ultraviolet-curing paint of POSS as claimed in claim 1 is characterized in that concrete steps are:
(1) in the there-necked flask that reflux condensate device and agitator are housed, adds 5～25mL organosilane monomer, 5～50mL distilled water and 25～150mL have the machine solvent, 30～80 ℃ stirred in water bath 12～72 hours, collection obtains white solid, filter with total machine solvent wash, vacuum-drying is more than 12 hours under 30～60 ℃ of conditions, product is handled with the alkali organic solvent of 5～30 times of weight, it is poured in the mixture of isopyknic hydrochloric acid and ice, filter and be washed to neutrality then, vacuum-drying is more than 12 hours under 40～80 ℃ of conditions, thoroughly extract with ether again, obtain unmodified POSS;
(2) be that Dropwise 5～25ml concentration is the active organosilicon monomer solution of 0.025g/ml, reacts 12～72 hours in 30～50 ℃ of water-baths in the mixed organic solvents of above-mentioned POSS of 0.025g/ml in 5～50ml concentration; Product poured in 5～20 times frozen water and the hydrochloric acid mixed solution leaves standstill more than 12 hours, the throw out that obtains with deionized water wash till filtrate is neutrality; Filter the white solid of collecting, vacuum-drying promptly obtained the POSS with two key groups more than 12 hours under 30～60 ℃ of conditions;
(3) POSS, polyvalent alcohol, catalyzer and the reactive thinner of vulcabond, the two keys of the band part by weight with 200～500:0.5～20:80～120:0.1～2:10～30 is mixed, be warming up to 60-80 ℃, reacted 3-6 hour, make reaction be tending towards finishing, promptly get the polyurethane acroleic acid prepolymer that contains POSS;
(4) with resulting prepolymer and light trigger, reactive thinner and the auxiliary agent that contains the POSS polyurethane acroleic acid, mix, promptly get UV light solidifying polyurethane acrylic acid paint with the 100:0.1-2:5-10:1-5 part by weight;
Wherein, said organosilane monomer is methyl trichlorine siloxanes, ethyl trichloro silicane oxygen alkane, propyl-trichlorosilicane oxygen alkane, phenyl trichlorine siloxanes, vinyl trichloro silane, methyl ethylene trichlorine siloxanes or γ-chloropropyl trichlorine siloxanes;
Said active organosilicon monomer is vinyl trichloro silane, methyl ethylene trichlorine siloxanes, γ-chloropropyl trichlorine siloxanes, vinyltrimethoxy silane, vinyltriethoxysilane, acryloxy Trimethoxy silane or acryloxy triethoxyl silane.
3, the preparation method who contains the ultraviolet-curing paint of POSS according to claim 2, it is characterized in that said total machine solvent is ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, 1,2-propylene glycol, 1,3-propylene glycol, propylene-glycol ethyl ether, propylene glycol butyl ether, butanols, 1,3-butyleneglycol, 1,4-butyleneglycol, dioxane or glycerine;
Said alkali organic solvent is pyridine, picoline, ethylpyridine, ethamine, diethylamine, triethylamine, dimethyl formamide or N,N-DIMETHYLACETAMIDE;
Said mixed organic solvents is two kinds or the mixture of above solvent in tetrahydrofuran (THF), trichloromethane, methylene dichloride, dioxane, acetone, butanone, pimelinketone, benzene,toluene,xylene, pyridine, picoline, ethylpyridine, ethamine, diethylamine, triethylamine, dimethyl formamide or the N,N-DIMETHYLACETAMIDE.
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| CN101024751B (en) * | 2007-03-09 | 2010-04-21 | 厦门大学 | Coating material containing POSS acrylate copolymer and preparing method |
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| CN102782065A (en) * | 2010-02-26 | 2012-11-14 | 新日铁化学株式会社 | Coating agent composition |
| CN102174059B (en) * | 2011-02-23 | 2013-05-01 | 上海交通大学 | Sulfydryl-containing low polysiloxane compound, ultraviolet photoresist composition thereof, and impressing process |
| CN103396558B (en) * | 2013-07-01 | 2015-11-18 | 中科院广州化学有限公司 | End-vinyl fluorine silicon graftomer and its preparation method and application |
| US20160090504A1 (en) * | 2014-09-30 | 2016-03-31 | Fujifilm Corporation | Undercoat composition, composition set, inkjet recording method, and printed material |
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| CN105505192B (en) * | 2015-12-10 | 2018-02-06 | 兰州科天环保节能科技有限公司 | A kind of UV solidfication water polyurethane acrylate paints and preparation method thereof |
| CN108117624A (en) * | 2018-01-24 | 2018-06-05 | 中国科学院福建物质结构研究所 | A kind of preparation and application of the photosensitive resin of 3D printing containing POSS |
| CN111116915B (en) * | 2019-05-20 | 2022-05-27 | 杭州师范大学 | Liquid methacrylic acid functionalized POSS (polyhedral oligomeric silsesquioxane), photocuring acrylic resin modified by liquid methacrylic acid functionalized POSS and preparation method of photocuring acrylic resin |
| CN112225901B (en) * | 2020-09-30 | 2022-03-29 | 华南理工大学 | Modified castor oil based UV (ultraviolet) curing polyurethane acrylate and preparation method thereof |
| CN113185888B (en) * | 2021-05-31 | 2022-03-25 | 常州大学 | Preparation method of fluorosilicone coating with scratch resistance, fingerprint resistance and high light transmittance |
| CN114366851B (en) * | 2021-12-31 | 2022-09-02 | 江苏阳生生物股份有限公司 | Bone repair material for massive defects of mandible |
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