CN103265704A - Organic silicon modified acrylic ultraviolet curable water-based resin and preparation method thereof - Google Patents
Organic silicon modified acrylic ultraviolet curable water-based resin and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of an organic silicon modified acrylic ultraviolet curable water-based resin. The method comprises the following steps of: carrying out a hydrosilylation reaction between a hydrogen-containing silicone oil and glycidyl methacrylate so as to synthesize silicone oil containing a side epoxy group; then reacting the silicone oil containing the side epoxy group with an acrylic monomer to obtain a low-viscosity organic silicon acrylic prepolymer; and finally, performing grafting modification on the low-viscosity organic silicon acrylic prepolymer by using tetra-hydrophthalic anhydride and introducing a hydrophilic group to the molecular chain, thus obtaining the organic silicon modified acrylic ultraviolet curable water-based resin; besides, diluting the organic silicon modified acrylic ultraviolet curable water-based resin by adding water for efficient dispersion, thereby obtaining an ultraviolet curable organic silicon modified acrylic water-based emulsion. The product prepared by the method can be applied to technical fields of textile finishing, exterior wall coating, leather finishing and the like.
Description
Technical field
The present invention relates to a kind of organosilicon-modified acrylic UV-curable water-borne resin and preparation method thereof.
Background technology
UV-curing technology and coating thereof have obtained developing rapidly and using in recent years, but habitual esters of acrylic acid reactive thinner has stronger hormesis to people's skin and eyes in traditional oiliness curing system, influences the healthy of operator; Many reactive thinners are difficult to complete reaction in the ultraviolet light irradiation process in addition, and residual monomer directly has influence on the long-term behaviour of cured film, and have limited its application in the food sanitation industry.And aqueous solidified coating combines the advantage of traditional curing technology and water-borne coatings technology, and particularly environmentally safe does not have influence to HUMAN HEALTH, nonflammable, security is good, is developed fast over past ten years, and has become a main direction of coating development.
Acrylic resin itself has that look shallow, transparency is high, protects light, light is plentiful, absorb characteristics such as little at infrared region, and has advantage such as excellent erosion resistance, strong adhesion and monomer are numerous, synthetic easily, low price and be used widely.
The singularity of organosilicon polymer structure has been given its many excellent properties: ventilation property, snappiness, weathering resistance, water-repellancy and good physiology inertia, photocuring technology has fast setting, less energy-consumption, high-level efficiency, advantage such as pollution-free, the photocuring organosilicon material is extremely people's favor owing to the advantage that has both concurrently, and is used widely.
The photocuring organosilicon not only can be used as auxiliary agent and joins in the photocuring system, improves wettability, scratch resistance and the flow leveling of material, can also add photocuring system as reactive monomer, improves surface property, thermostability and the mechanical property of material.
In the prior art, adopt silicon hydrogen additive process to prepare organosilicon-modified acrylic, concrete grammar is: adopt the acrylic resin that contains organosilane or the organo-siloxane of reactive hydrogen and have a unsaturated link(age) to carry out the addition of silicon hydrogen and the organosilicon chain is incorporated in the acrylic resin.But existing organosilicon-modified acrylic adopts addition reaction of silicon with hydrogen, and the modified resin that is synthesized is a hydrophilic resin, has but lost the performance of ultraviolet light polymerization, and this severe reaction conditions, and productive rate is low, the cost height.
Summary of the invention
One of purpose of the present invention is to provide a kind of method of organosilicon-modified acrylic UV-curable water-borne resin, described method reaction conditions gentleness, the productive rate height, cost is low, and the photocuring water-base resin for preparing is both hydrophilic, simultaneously can ultraviolet light polymerization, have excellent surface property, thermostability and mechanical property.
In order to achieve the above object, the present invention has adopted following technical scheme:
A kind of method of organosilicon-modified acrylic UV-curable water-borne resin, described method comprises the steps:
(1) will contain pendant epoxies base silicone oil and stopper and add in the reaction vessel, under nitrogen protection, slowly dropwise addition of acrylic acid monomer and catalyzer in the reaction vessel, reaction, when pH in the reaction system was 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer;
(2) drip the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer in the acid-organosilicon crylic acid performed polymer that obtains to step (1), 60～70 ℃ of reactions, when acid number reaches theoretical value, be cooled to room temperature, obtain organosilicon-modified acrylic UV-curable water-borne resin.
Preferably, under nitrogen protection, stir be warming up to 80～90 ℃ after, slowly dropwise addition of acrylic acid monomer and catalyzer in the reaction vessel, the preferred stirring is warming up to 82～88 ℃, further preferred 83～87 ℃.Described intensification temperature for example is 81 ℃, 81.5 ℃, 82.5 ℃, 83.5 ℃, 84 ℃, 85 ℃, 86 ℃, 87.5 ℃, 88.5 ℃, 89.5 ℃.
Preferably, the dropping time of Acrylic Acid Monomer and catalyzer is 1～1.5 hour, for example 1.05 hours, 1.1 hours, 1.15 hours, 1.2 hours, 1.25 hours, 1.3 hours, 1.35 hours, 1.4 hours, 1.45 hours, preferred 1.06～1.47 hours, further preferred 1.12～1.42 hours.
Preferably, the described temperature of reaction of step (1) is 90～100 ℃, for example 91 ℃, 92 ℃, 93 ℃, 94 ℃, 95 ℃, 96 ℃, 97 ℃, 98 ℃, 99 ℃, and preferred 91.5～98.5 ℃, further preferred 92.5～97.5 ℃.
Preferably, the described reaction times of step (1) is 2～6 hours, for example 2.2 hours, 2.4 hours, 2.7 hours, 3.2 hours, 3.6 hours, 4 hours, 4.4 hours, 4.8 hours, 5.2 hours, 5.6 hours, preferred 2.5～5.5 hours, further preferred 3～5.5 hours.
In reaction process, the pH value of assaying reaction system at any time, when pH in the reaction system was 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer.
Preferably, the carboxyl molar mass of described Acrylic Acid Monomer is 1:1 with the ratio of the epoxy group(ing) molar mass that contains pendant epoxies base silicone oil, so that react completely.
Preferably, described stopper is selected from the mixture of any one or at least two kinds in MEHQ, p methoxy phenol, Resorcinol or the 2,6 ditertiary butyl p cresol.Described mixture for example 2, the mixture of 6-ditertbutylparacresol and Resorcinol, the mixture of Resorcinol and p methoxy phenol, the mixture of p methoxy phenol and MEHQ, 2, the mixture of 6-ditertbutylparacresol and p methoxy phenol, the mixture of Resorcinol and MEHQ, 2, the mixture of 6-ditertbutylparacresol, Resorcinol and p methoxy phenol, the mixture of Resorcinol, p methoxy phenol, MEHQ and 2,6 ditertiary butyl p cresol.
Preferably, the mass percent that the quality of the described stopper of step (1) accounts for the total mass of all raw materials of step (1) is 0.2～1.2wt%, for example 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, preferred 0.25～1.15wt%, further preferred 0.35～1.05wt%.All raw materials are namely: contain pendant epoxies base silicone oil, stopper, Acrylic Acid Monomer and catalyzer.
Preferably, described catalyzer is selected from triethylamine, Tetramethylammonium hydroxide, tetraethylammonium bromide or N, the mixture of any one in the N-dimethylbenzyl ammonium or at least two kinds.Described mixture is N for example, the mixture of N-dimethylbenzyl ammonium and tetraethylammonium bromide, the mixture of tetraethylammonium bromide and Tetramethylammonium hydroxide, the mixture of Tetramethylammonium hydroxide and triethylamine, N, the mixture of N-dimethylbenzyl ammonium and Tetramethylammonium hydroxide, the mixture of tetraethylammonium bromide and triethylamine, N, the mixture of N-dimethylbenzyl ammonium, tetraethylammonium bromide and Tetramethylammonium hydroxide, Tetramethylammonium hydroxide, triethylamine, N, the mixture of N-dimethylbenzyl ammonium and tetraethylammonium bromide.
Preferably, the mass percent that the quality of the described catalyzer of step (1) accounts for the total mass of all raw materials of step (1) is 0.4～1.5wt%, for example 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, preferred 0.45～1.45wt%, further preferred 0.55～1.35wt%.All raw materials are namely: contain pendant epoxies base silicone oil, stopper, Acrylic Acid Monomer and catalyzer.
Preferably, drip the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer during the acid-organosilicon crylic acid performed polymer that step (2) obtains step (1) is cooled to after 60～70 ℃, preferably be cooled to 61～69 ℃, further preferably be cooled to 62～68 ℃.Described cooling temperature for example is 60.5 ℃, 61.5 ℃, 62.5 ℃, 63 ℃, 64 ℃, 65 ℃, 66 ℃, 67 ℃, 68.5 ℃, 69.5 ℃.
In reaction process, acid number in the detection reaction system when acid number reaches theoretical value, is cooled to room temperature, and the side chain that obtains the tetrahydrophthalic anhydride modification has the organosilicon-modified acrylic UV-curable water-borne resin of hydrophilic radical carboxyl.Described theoretical value can obtain by following principle: in theory, the tetrahydrophthalic anhydride that adds 1 mole generates 1 mole carboxyl, according to the amount of the tetrahydrophthalic anhydride that adds, calculates the growing amount of theoretical carboxyl, and then determines theoretical acid number amount.
Preferably, described stopper is selected from the mixture of any one or at least two kinds in MEHQ, p methoxy phenol, Resorcinol or the 2,6 ditertiary butyl p cresol.Described mixture for example 2, the mixture of 6-ditertbutylparacresol and Resorcinol, the mixture of Resorcinol and p methoxy phenol, the mixture of p methoxy phenol and MEHQ, 2, the mixture of 6-ditertbutylparacresol and p methoxy phenol, the mixture of Resorcinol and MEHQ, 2, the mixture of 6-ditertbutylparacresol, Resorcinol and p methoxy phenol, the mixture of Resorcinol, p methoxy phenol, MEHQ and 2,6 ditertiary butyl p cresol.
Preferably, the mass percent that the quality of the described stopper of step (2) accounts for the total mass of all raw materials of step (2) is 0.2～1.2wt%, for example 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, preferred 0.25～1.15wt%, further preferred 0.35～1.05wt%.All raw materials are namely: acid-organosilicon crylic acid performed polymer, tetrahydrophthalic anhydride, stopper and catalyzer.
Preferably, described catalyzer is selected from triethylamine, Tetramethylammonium hydroxide, tetraethylammonium bromide or N, the mixture of any one in the N-dimethylbenzyl ammonium or at least two kinds.Described mixture is N for example, the mixture of N-dimethylbenzyl ammonium and tetraethylammonium bromide, the mixture of tetraethylammonium bromide and Tetramethylammonium hydroxide, the mixture of Tetramethylammonium hydroxide and triethylamine, N, the mixture of N-dimethylbenzyl ammonium and Tetramethylammonium hydroxide, the mixture of tetraethylammonium bromide and triethylamine, N, the mixture of N-dimethylbenzyl ammonium, tetraethylammonium bromide and Tetramethylammonium hydroxide, Tetramethylammonium hydroxide, triethylamine, N, the mixture of N-dimethylbenzyl ammonium and tetraethylammonium bromide.
Preferably, the mass percent that the quality of the described catalyzer of step (2) accounts for the total mass of all raw materials of step (2) is 0.4～1.5wt%, for example 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, preferred 0.45～1.45wt%, further preferred 0.55～1.35wt%.All raw materials are namely: acid-organosilicon crylic acid performed polymer, tetrahydrophthalic anhydride, stopper and catalyzer.
Preferably, the molar mass of described tetrahydrophthalic anhydride is 1:1 with the ratio of the molar mass of acid-organosilicon crylic acid performed polymer hydroxyl.
Preferably, the described pendant epoxies base silicone oil that contains is prepared by following method:
Add 100 parts of containing hydrogen silicone oils, 10～20 parts of glycidyl methacrylate, 0.1～5 part of isopropyl alcohol solution of chloroplatinic acid and 30～100 parts of solvents in container, 90～110 ℃ by silicon hydrogen addition isothermal reaction discharging in 6～12 hours; Do precipitation agent with methyl alcohol reaction product be precipitated out, and with methyl alcohol repetitive scrubbing throw out, removing unreacted monomer and catalyzer Platinic chloride, after the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil.
Described temperature of reaction is 90～110 ℃, and for example 92 ℃, 94 ℃, 96 ℃, 98 ℃, 102 ℃, 104 ℃, 106 ℃, 108 ℃, the described reaction times is 6～12 hours, for example 7 hours, 8 hours, 9 hours, 10 hours, 11 hours.
The massfraction of the reactive hydrogen of described containing hydrogen silicone oil is 0.06～0.2wt%, for example 0.08wt%, 0.1wt%, 0.12wt%, 0.14wt%, 0.16wt%, 0.18wt%, 0.19wt%, preferred 0.07～0.17wt%, further preferred 0.08～0.15wt%.
The massfraction of Platinic chloride is 1～3wt% in the described isopropyl alcohol solution of chloroplatinic acid, for example 1.2wt%, 1.4wt%, 1.6wt%, 1.8wt%, 2.1wt%, 2.3wt%, 2.5wt%, 2.7wt%, 2.9wt%, preferred 1.1～2.8wt%, further preferred 1.3～2.6wt%.
Described solvent is selected from the mixture of any one or at least two kinds in toluene, dimethylbenzene, ethyl glycollate, ethyl acetate, acetone, butanone, diacetylmethane, Virahol, butanols, diacetone alcohol, ether, sherwood oil, glycerine or the aromatic alcohol.Described mixture is the mixture of toluene and dimethylbenzene for example, the mixture of ethyl acetate and acetone, the mixture of butanone and diacetylmethane, the mixture of Virahol and butanols, the mixture of diacetone alcohol and ether, the mixture of sherwood oil and aromatic alcohol.
A kind of method of organosilicon-modified acrylic UV-curable water-borne resin, described method comprises the steps:
(1 ') adds 100 parts of containing hydrogen silicone oils, 10～20 parts of glycidyl methacrylate, 0.1～5 part of isopropyl alcohol solution of chloroplatinic acid and 30～100 parts of solvents in container, 90～110 ℃ by silicon hydrogen addition isothermal reaction discharging in 6～12 hours; Do precipitation agent with methyl alcohol reaction product be precipitated out, and with methyl alcohol repetitive scrubbing throw out, removing unreacted monomer and catalyzer Platinic chloride, after the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil;
(1) will contain pendant epoxies base silicone oil and stopper and add in the reaction vessel, under nitrogen protection, slowly dropwise addition of acrylic acid monomer and catalyzer in the reaction vessel, reaction, when pH in the reaction system was 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer;
(2) drip the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer in the acid-organosilicon crylic acid performed polymer that obtains to step (1), reaction is cooled to room temperature when acid number reaches theoretical value, obtain organosilicon-modified acrylic UV-curable water-borne resin.
A kind of method of organosilicon-modified acrylic UV-curable water-borne resin, described method comprises the steps:
(1 ' ') in container, add 100 parts of containing hydrogen silicone oils, 10～20 parts of glycidyl methacrylate, 0.1～5 parts of isopropyl alcohol solution of chloroplatinic acid and 30～100 parts of solvents, wherein, the massfraction of this containing hydrogen silicone oil reactive hydrogen is 0.06～0.2wt%, the Platinic chloride massfraction of isopropyl alcohol solution of chloroplatinic acid is 2wt%, 90～110 ℃ by silicon hydrogen addition isothermal reaction discharging in 6～12 hours, doing precipitation agent with methyl alcohol is precipitated out reaction product, and with methyl alcohol repetitive scrubbing throw out, removing unreacted monomer and catalyzer Platinic chloride, after the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil;
(2 ' ') with above-mentioned make contain pendant epoxies base silicone oil, stopper adds in the container, N
2Protection is stirred and is warming up to 80～90 ℃ down, and slowly dropwise addition of acrylic acid monomer and catalyzer dripped off in 1～1.5 hour, be warming up to 90～100 ℃ subsequently, reacted 2～6 hours, at any time the assaying reaction system pH, when the pH value equaled 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer;
(3 ' ') above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 60～70 ℃, drip the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer in the system, after dropwising, insulation reaction, when reaching theoretical value, acid number is cooled to room temperature,, the side chain that obtains the tetrahydrophthalic anhydride modification has the organosilicon-modified acrylic UV-curable water-borne resin of hydrophilic radical carboxyl.
Exemplary reaction principle of the present invention is as follows:
Two of purpose of the present invention is to provide a kind of organosilicon-modified acrylic UV-curable water-borne resin, and described organosilicon-modified acrylic UV-curable water-borne resin is prepared by method as mentioned above.The organosilicon-modified acrylic UV-curable water-borne resin that adopts the method for the invention to obtain is both hydrophilic, and having simultaneously can ultraviolet light polymerization, has excellent surface property, thermostability and mechanical property.
With organosilicon-modified acrylic UV-curable water-borne resin, thin up, obtain uV curable organosilicon-modified acrylic water-based emulsion efficient the dispersion, can be applicable to technical fields such as textile finishing, exterior coating, leather finish.
Compared with prior art, the present invention has following beneficial effect: reaction conditions gentleness, productive rate height, cost is low, and the photocuring water-base resin for preparing is both hydrophilic, and having simultaneously can ultraviolet light polymerization, has excellent surface property, thermostability and mechanical property.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
(1) add 100g containing hydrogen silicone oil (the reactive hydrogen massfraction is 0.1%), 14g glycidyl methacrylate, 0.2g isopropyl alcohol solution of chloroplatinic acid and 30g solvent in the 250ml four-hole boiling flask, 90 ℃ by silicon hydrogen addition isothermal reaction discharging in 6 hours.Do precipitation agent with methyl alcohol reaction product is precipitated out, and with methyl alcohol repetitive scrubbing throw out for several times, to remove unreacted monomer and catalyzer Platinic chloride.After the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil.
(2) add above-mentioned gained in the 250ml four-hole boiling flask and contain pendant epoxies base silicone oil, 0.4g MEHQ, logical N
2Protection; stirring is warming up to 80 ℃; slowly drip an amount of Acrylic Acid Monomer 8g and catalyst of triethylamine 0.5g according to the silicone oil oxirane value; dripped off in 1～1.5 hour, and be warming up to 90 ℃ subsequently, reacted 2～6 hours; at any time measure system pH; when the pH value equaled 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer.
(3) above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 60 ℃, drip the mixing solutions of 15g tetrahydrophthalic anhydride, 0.4g MEHQ and 0.5g triethylamine, after dropwising, insulation reaction, be cooled to room temperature until detecting when acid number reaches theoretical value (1 mole of tetrahydrophthalic anhydride produces 1 mole of carboxyl in theory), the side chain that obtains the tetrahydrophthalic anhydride modification has the organosilicon-modified acrylic UV-curable water-borne resin of hydrophilic radical carboxyl.
Embodiment 2
(1) add 100g containing hydrogen silicone oil (the reactive hydrogen massfraction is 0.1%), 17g glycidyl methacrylate, 0.4g isopropyl alcohol solution of chloroplatinic acid and 30g solvent in the 500ml four-hole boiling flask, 100 ℃ by silicon hydrogen addition isothermal reaction discharging in 10 hours.Do precipitation agent with methyl alcohol reaction product is precipitated out, and with methyl alcohol repetitive scrubbing throw out for several times, to remove unreacted monomer and catalyzer Platinic chloride.After the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil.
(2) in four-hole boiling flask, add the 0.7g MEHQ, logical N
2Protection; stirring is warming up to 85 ℃; slowly drip an amount of Acrylic Acid Monomer 8g and catalyst of triethylamine 0.8g according to the silicone oil oxirane value; dripped off in 1～1.5 hour, and be warming up to 95 ℃ subsequently, reacted 2～6 hours; at any time measure system pH; when the pH value equaled 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer.
(3) above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 60 ℃, drip the mixing solutions of 15g tetrahydrophthalic anhydride, 0.7g MEHQ and 0.8g triethylamine, after dropwising, insulation reaction, be cooled to room temperature until detecting when acid number reaches theoretical value (1 mole of tetrahydrophthalic anhydride produces 1 mole of carboxyl in theory), the side chain that obtains the tetrahydrophthalic anhydride modification has the organosilicon-modified acrylic UV-curable water-borne resin of hydrophilic radical carboxyl.
Embodiment 3
(1) add 100g containing hydrogen silicone oil (the reactive hydrogen massfraction is 0.1%), 20g glycidyl methacrylate, 0.8g isopropyl alcohol solution of chloroplatinic acid and 60g solvent in the 250ml four-hole boiling flask, 110 ℃ by silicon hydrogen addition isothermal reaction discharging in 12 hours.Do precipitation agent with methyl alcohol reaction product is precipitated out, and with methyl alcohol repetitive scrubbing throw out for several times, to remove unreacted monomer and catalyzer Platinic chloride.After the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil.
(2) in four-hole boiling flask, add the 1g MEHQ, logical N
2Protection; stirring is warming up to 90 ℃; slowly drip an amount of Acrylic Acid Monomer 8g and catalyst of triethylamine 1g according to the silicone oil oxirane value; dripped off in 1～1.5 hour, and be warming up to 100 ℃ subsequently, reacted 2～6 hours; at any time measure system pH; when the pH value equaled 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer.
(3) above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 70 ℃, drip the mixing solutions of 15g tetrahydrophthalic anhydride, 1g MEHQ and 1g triethylamine, after dropwising, insulation reaction, be cooled to room temperature until detecting when acid number reaches theoretical value (1 mole of tetrahydrophthalic anhydride produces 1 mole of carboxyl in theory), the side chain that obtains the tetrahydrophthalic anhydride modification has the organosilicon-modified acrylic UV-curable water-borne resin of hydrophilic radical carboxyl.
Embodiment 4
(1) in the 250ml four-hole boiling flask, adds 100g containing hydrogen silicone oil (the reactive hydrogen massfraction is 0.06wt%), 10g glycidyl methacrylate, 0.1g isopropyl alcohol solution of chloroplatinic acid and 30g solvent toluene, the massfraction of Platinic chloride is 1wt% in the described isopropyl alcohol solution of chloroplatinic acid, and 90 ℃ by silicon hydrogen addition isothermal reaction discharging in 12 hours.Do precipitation agent with methyl alcohol reaction product is precipitated out, and with methyl alcohol repetitive scrubbing throw out for several times, to remove unreacted monomer and catalyzer Platinic chloride.After the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil.
(2) add above-mentioned gained in the 250ml four-hole boiling flask and contain pendant epoxies base silicone oil, Resorcinol, logical N
2Protection; stirring is warming up to 90 ℃; slow dropwise addition of acrylic acid monomer and catalyzer Tetramethylammonium hydroxide; dripped off in 1～1.5 hour; the mass percent that the quality of described Resorcinol accounts for the total mass of all raw materials in this step (2) is 0.2wt%; the mass percent that the quality of described Tetramethylammonium hydroxide accounts for the total mass of all raw materials in this step (2) is 0.4wt%; the carboxyl molar mass of described Acrylic Acid Monomer is 1:1 with the ratio of the epoxy group(ing) molar mass that contains pendant epoxies base silicone oil; be warming up to 100 ℃ subsequently; reacted 2～6 hours, and measured system pH at any time, when the pH value equals 7.0; stopped reaction obtains the acid-organosilicon crylic acid performed polymer.
(3) above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 70 ℃, drip tetrahydrophthalic anhydride, the mixing solutions of MEHQ and triethylamine, the mass percent that the quality of described MEHQ accounts for the total mass of all raw materials in this step (3) is 0.2wt%, the mass percent that the quality of described triethylamine accounts for the total mass of all raw materials in this step (3) is 0.4wt%, the molar mass of described tetrahydrophthalic anhydride is 1:1 with the ratio of the molar mass of acid-organosilicon crylic acid performed polymer hydroxyl, insulation reaction, be cooled to room temperature until detecting when acid number reaches theoretical value (1 mole of tetrahydrophthalic anhydride produces 1 mole of carboxyl in theory), the side chain that obtains the tetrahydrophthalic anhydride modification has the organosilicon-modified acrylic UV-curable water-borne resin of hydrophilic radical carboxyl.
Embodiment 5
(1) in the 500ml four-hole boiling flask, adds 100g containing hydrogen silicone oil (the reactive hydrogen massfraction is 0.2wt%), 20g glycidyl methacrylate, 5g isopropyl alcohol solution of chloroplatinic acid and 100g solvent butanone, the massfraction of Platinic chloride is 3wt% in the described isopropyl alcohol solution of chloroplatinic acid, and 110 ℃ by silicon hydrogen addition isothermal reaction discharging in 6 hours.Do precipitation agent with methyl alcohol reaction product is precipitated out, and with methyl alcohol repetitive scrubbing throw out for several times, to remove unreacted monomer and catalyzer Platinic chloride.After the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil.
(2) add above-mentioned gained in the 250ml four-hole boiling flask and contain pendant epoxies base silicone oil, p methoxy phenol, slow dropwise addition of acrylic acid monomer and catalyzer Tetramethylammonium hydroxide, dripped off in 1～1.5 hour, the mass percent that the quality of described p methoxy phenol accounts for the total mass of all raw materials of this step (2) is 1.2wt%, the mass percent that the quality of Tetramethylammonium hydroxide accounts for the total mass of all raw materials of this step (2) is 1.5wt%, the carboxyl molar mass of Acrylic Acid Monomer is 1:1 with the ratio of the epoxy group(ing) molar mass that contains pendant epoxies base silicone oil, be warming up to 95 ℃ subsequently, reacted 2～6 hours, at any time measure system pH, when the pH value equals 7.0, stopped reaction obtains the acid-organosilicon crylic acid performed polymer.
(3) above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 60 ℃, drip tetrahydrophthalic anhydride, the mixing solutions of MEHQ and triethylamine, the mass percent that the quality of described MEHQ accounts for the total mass of all raw materials in this step (3) is 1.2wt%, the mass percent that the quality of described triethylamine accounts for the total mass of all raw materials in this step (3) is 1.5wt%, the molar mass of described tetrahydrophthalic anhydride is 1:1 with the ratio of the molar mass of acid-organosilicon crylic acid performed polymer hydroxyl, after dropwising, insulation reaction, be cooled to room temperature until detecting when acid number reaches theoretical value (1 mole of tetrahydrophthalic anhydride produces 1 mole of carboxyl in theory), the side chain that obtains the tetrahydrophthalic anhydride modification has the organosilicon-modified acrylic UV-curable water-borne resin of hydrophilic radical carboxyl.
Should be noted that and understand, under the situation that does not break away from the desired the spirit and scope of the present invention of accompanying Claim, can make various modifications and improvement to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not subjected to the restriction of given any specific exemplary teachings.
Applicant's statement, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not mean that namely the present invention must rely on above-mentioned method detailed and could implement.The person of ordinary skill in the field should understand, any improvement in the present invention to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the method for an organosilicon-modified acrylic UV-curable water-borne resin is characterized in that, described method comprises the steps:
(1) will contain pendant epoxies base silicone oil and stopper and add in the reaction vessel, under nitrogen protection, slowly dropwise addition of acrylic acid monomer and catalyzer in the reaction vessel, reaction, when pH in the reaction system was 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer;
(2) drip the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer in the acid-organosilicon crylic acid performed polymer that obtains to step (1), 60～70 ℃ of reactions, when acid number reaches theoretical value, be cooled to room temperature, obtain organosilicon-modified acrylic UV-curable water-borne resin.
2. the method for claim 1 is characterized in that, under nitrogen protection, stir be warming up to 80～90 ℃ after, slowly dropwise addition of acrylic acid monomer and catalyzer in the reaction vessel, the preferred stirring is warming up to 82～88 ℃, further preferred 83～87 ℃;
Preferably, the dropping time of Acrylic Acid Monomer and catalyzer is 1～1.5 hour, preferred 1.06～1.47 hours, and further preferred 1.12～1.42 hours;
Preferably, the described temperature of reaction of step (1) is 90～100 ℃, preferred 91.5～98.5 ℃, and further preferred 92.5～97.5 ℃.
3. method as claimed in claim 1 or 2 is characterized in that, the described reaction times of step (1) is 2～6 hours, preferred 2.5～5.5 hours, and further preferred 3～5.5 hours;
Preferably, the carboxyl molar mass of described Acrylic Acid Monomer is 1:1 with the ratio of the epoxy group(ing) molar mass that contains pendant epoxies base silicone oil;
Preferably, the described stopper of step (1) is selected from the mixture of any one or at least two kinds in MEHQ, p methoxy phenol, Resorcinol or the 2,6 ditertiary butyl p cresol.
4. as the described method of one of claim 1-3, it is characterized in that, the mass percent that the quality of the described stopper of step (1) accounts for the total mass of all raw materials of step (1) is 0.2～1.2wt%, preferred 0.25～1.15wt%, further preferred 0.35～1.05wt%;
Preferably, the described catalyzer of step (1) is selected from triethylamine, Tetramethylammonium hydroxide, tetraethylammonium bromide or N, the mixture of any one in the N-dimethylbenzyl ammonium or at least two kinds;
Preferably, the mass percent that the quality of the described catalyzer of step (1) accounts for the total mass of all raw materials of step (1) is 0.4～1.5wt%, preferred 0.45～1.45wt%, further preferred 0.55～1.35wt%.
5. as the described method of one of claim 1-4, it is characterized in that, during being cooled to after 60～70 ℃, the acid-organosilicon crylic acid performed polymer that step (2) obtains step (1) drips the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer, preferably be cooled to 61～69 ℃, further preferably be cooled to 62～68 ℃;
Preferably, the described stopper of step (2) is selected from the mixture of any one or at least two kinds in MEHQ, p methoxy phenol, Resorcinol or the 2,6 ditertiary butyl p cresol.
6. as the described method of one of claim 1-5, it is characterized in that, the mass percent that the quality of the described stopper of step (2) accounts for the total mass of all raw materials of step (2) is 0.2～1.2wt%, preferred 0.25～1.15wt%, further preferred 0.35～1.05wt%;
Preferably, the described catalyzer of step (2) is selected from triethylamine, Tetramethylammonium hydroxide, tetraethylammonium bromide or N, the mixture of any one in the N-dimethylbenzyl ammonium or at least two kinds;
Preferably, the mass percent that the quality of the described catalyzer of step (2) accounts for the total mass of all raw materials of step (2) is 0.4～1.5wt%, preferred 0.45～1.45wt%, further preferred 0.55～1.35wt%.
7. as the described method of one of claim 1-6, it is characterized in that the molar mass of described tetrahydrophthalic anhydride is 1:1 with the ratio of the molar mass of acid-organosilicon crylic acid performed polymer hydroxyl;
Preferably, the described pendant epoxies base silicone oil that contains is prepared by following method:
Add 100 parts of containing hydrogen silicone oils, 10～20 parts of glycidyl methacrylate, 0.1～5 part of isopropyl alcohol solution of chloroplatinic acid and 30～100 parts of solvents in container, 90～110 ℃ by silicon hydrogen addition isothermal reaction discharging in 6～12 hours; Do precipitation agent with methyl alcohol reaction product be precipitated out, and with methyl alcohol repetitive scrubbing throw out, removing unreacted monomer and catalyzer Platinic chloride, after the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil.
8. method as claimed in claim 7 is characterized in that, the massfraction of the reactive hydrogen of described containing hydrogen silicone oil is 0.06～0.2wt%, preferred 0.07～0.17wt%, further preferred 0.08～0.15wt%;
Preferably, the massfraction of Platinic chloride is 1～3wt% in the described isopropyl alcohol solution of chloroplatinic acid, preferred 1.1～2.8wt%, further preferred 1.3～2.6wt%;
Described solvent is selected from the mixture of any one or at least two kinds in toluene, dimethylbenzene, ethyl glycollate, ethyl acetate, acetone, butanone, diacetylmethane, Virahol, butanols, diacetone alcohol, ether, sherwood oil, glycerine or the aromatic alcohol.
9. as the described method of one of claim 1-8, it is characterized in that described method comprises the steps:
(1 ') adds 100 parts of containing hydrogen silicone oils, 10～20 parts of glycidyl methacrylate, 0.1～5 part of isopropyl alcohol solution of chloroplatinic acid and 30～100 parts of solvents in container, 90～110 ℃ by silicon hydrogen addition isothermal reaction discharging in 6～12 hours; Do precipitation agent with methyl alcohol reaction product be precipitated out, and with methyl alcohol repetitive scrubbing throw out, removing unreacted monomer and catalyzer Platinic chloride, after the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil;
(1) will contain pendant epoxies base silicone oil and stopper and add in the reaction vessel, under nitrogen protection, slowly dropwise addition of acrylic acid monomer and catalyzer in the reaction vessel, reaction, when pH in the reaction system was 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer;
(2) drip the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer in the acid-organosilicon crylic acid performed polymer that obtains to step (1), reaction is cooled to room temperature when acid number reaches theoretical value, obtain organosilicon-modified acrylic UV-curable water-borne resin;
Preferably, described method comprises the steps:
(1 ' ') in container, add 100 parts of containing hydrogen silicone oils, 10～20 parts of glycidyl methacrylate, 0.1～5 parts of isopropyl alcohol solution of chloroplatinic acid and 30～100 parts of solvents, wherein, the massfraction of this containing hydrogen silicone oil reactive hydrogen is 0.06～0.2wt%, the Platinic chloride massfraction of isopropyl alcohol solution of chloroplatinic acid is 2wt%, 90～110 ℃ by silicon hydrogen addition isothermal reaction discharging in 6～12 hours, doing precipitation agent with methyl alcohol is precipitated out reaction product, and with methyl alcohol repetitive scrubbing throw out, removing unreacted monomer and catalyzer Platinic chloride, after the vacuum-drying faint yellow transparent side base band epoxide group arranged contain pendant epoxies base silicone oil;
(2 ' ') with above-mentioned make contain pendant epoxies base silicone oil, stopper adds in the container, N
2Protection is stirred and is warming up to 80～90 ℃ down, and slowly dropwise addition of acrylic acid monomer and catalyzer dripped off in 1～1.5 hour, be warming up to 90～100 ℃ subsequently, reacted 2～6 hours, at any time the assaying reaction system pH, when the pH value equaled 7.0, stopped reaction obtained the acid-organosilicon crylic acid performed polymer;
(3 ' ') above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 60～70 ℃, drip the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer, after dropwising, reaction, be cooled to room temperature when acid number reaches theoretical value, the side chain that obtains the tetrahydrophthalic anhydride modification has the organosilicon-modified acrylic UV-curable water-borne resin of hydrophilic radical carboxyl.
10. an organosilicon-modified acrylic UV-curable water-borne resin is characterized in that, described organosilicon-modified acrylic UV-curable water-borne resin is prepared by the described method of one of claim 1-9.
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| CN110790936A (en) * | 2019-11-24 | 2020-02-14 | 邵美忠 | Dual-curing organic silicon resin and preparation method thereof |
| CN112574418A (en) * | 2020-12-07 | 2021-03-30 | 万华化学集团股份有限公司 | Organic silicon compound containing epoxy group and preparation method thereof, epoxy resin composition and preparation method thereof |
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| CN110790936A (en) * | 2019-11-24 | 2020-02-14 | 邵美忠 | Dual-curing organic silicon resin and preparation method thereof |
| CN112574418A (en) * | 2020-12-07 | 2021-03-30 | 万华化学集团股份有限公司 | Organic silicon compound containing epoxy group and preparation method thereof, epoxy resin composition and preparation method thereof |
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