CN103265704B - A kind of organosilicon-modified acrylic UV-Curing Waterborne Resin and preparation method thereof - Google Patents
A kind of organosilicon-modified acrylic UV-Curing Waterborne Resin and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of organosilicon-modified acrylic UV-Curing Waterborne Resin, the method first carries out addition reaction of silicon with hydrogen by containing hydrogen silicone oil and glycidyl methacrylate, synthesis is containing pendant epoxies base silicone oil, then low viscosity acid-organosilicon crylic acid performed polymer will be obtained by reacting containing pendant epoxies base silicone oil and Acrylic Acid Monomer, finally by tetrahydrophthalic anhydride, graft modification is carried out to it, molecular chain introduces hydrophilic radical, obtain organosilicon-modified acrylic UV-Curing Waterborne Resin, thin up, high efficiency dispersion obtains uV curable organosilicon-modified acrylic water-based emulsion.Product of the present invention can be applicable to the technical fields such as textile finishing, exterior coating, leather finish.
Description
Technical field
The present invention relates to a kind of organosilicon-modified acrylic UV-Curing Waterborne Resin and preparation method thereof.
Background technology
UV-curing technology and coating thereof obtain in recent years and develop rapidly and apply, but esters of acrylic acid reactive thinner usual in conventional oil-based curing system has stronger hormesis to the skin of people and eyes, affects the healthy of operator; In addition many reactive thinners are difficult to complete reaction in ultraviolet light irradiation process, and residual monomer directly has influence on the long-term behaviour of cured film, and limit its application in Food industry.And aqueous solidified coating combines the advantage of traditional curing technology and water-borne coatings technology, particularly environmentally safe, on HUMAN HEALTH without impact, nonflammable, security is good, is developed fast nearly ten years, and has become a Main way of paint development.
Acrylic resin itself has that look shallow, transparency is high, protects light, light is plentiful, absorb the features such as little in infrared region, and there is excellent erosion resistance, strong adhesion and monomer is numerous, synthesis easily, the advantage such as low price and being used widely.
The singularity of organosilicon polymer structure imparts its many excellent properties: ventilation property, snappiness, weathering resistance, water-repellancy and good physiological inertia, photocuring technology has fast setting, less energy-consumption, high-level efficiency, the advantage such as pollution-free, Photocurable Silicone Material, owing to having both advantage and extremely people's favor concurrently, and to be used widely.
Photo-curable silicone not only can join in photocuring system as auxiliary agent, improves the wettability of material, scratch resistance and flow leveling, can also add photocuring system, improve the surface property of material, thermostability and mechanical property as reactive monomer.
In prior art, adopt Si―H addition reaction legal system for organosilicon-modified acrylic, concrete grammar is: employing contains organosilane or the organo-siloxane of reactive hydrogen and is incorporated in acrylic resin by organosilicon chain with the acrylic resin of unsaturated link(age) carries out Si―H addition reaction.But existing organosilicon-modified acrylic adopts addition reaction of silicon with hydrogen, and the modified resin be synthesized is a hydrophilic resin, but loses the performance of ultraviolet light polymerization, and this severe reaction conditions, and productive rate is low, and cost is high.
Summary of the invention
An object of the present invention is a kind of method providing organosilicon-modified acrylic UV-Curing Waterborne Resin, described method reaction conditions is gentle, productive rate is high, cost is low, and the photocuring water-base resin prepared is both hydrophilic, simultaneously can ultraviolet light polymerization, there is excellent surface property, thermostability and mechanical property.
In order to achieve the above object, present invention employs following technical scheme:
A method for organosilicon-modified acrylic UV-Curing Waterborne Resin, described method comprises the steps:
(1) will add in reaction vessel containing pendant epoxies base silicone oil and stopper, under nitrogen protection, in reaction vessel, slowly drip Acrylic Acid Monomer and catalyzer, reaction, when pH in reaction system is 7.0, stopped reaction, obtains acid-organosilicon crylic acid performed polymer;
(2) mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer is dripped in the acid-organosilicon crylic acid performed polymer obtained to step (1), 60 ~ 70 DEG C of reactions, be cooled to room temperature when acid number reaches theoretical value, obtain organosilicon-modified acrylic UV-Curing Waterborne Resin.
Preferably, under nitrogen protection, stir after being warming up to 80 ~ 90 DEG C, in reaction vessel, slowly drip Acrylic Acid Monomer and catalyzer, preferably stir and be warming up to 82 ~ 88 DEG C, preferably 83 ~ 87 DEG C further.Described warming temperature is such as 81 DEG C, 81.5 DEG C, 82.5 DEG C, 83.5 DEG C, 84 DEG C, 85 DEG C, 86 DEG C, 87.5 DEG C, 88.5 DEG C, 89.5 DEG C.
Preferably, the time for adding of Acrylic Acid Monomer and catalyzer is 1 ~ 1.5 hour, such as 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, preferably 1.06 ~ 1.47 hours, preferably 1.12 ~ 1.42 hours further.
Preferably, step (1) described temperature of reaction is 90 ~ 100 DEG C, such as 91 DEG C, 92 DEG C, 93 DEG C, 94 DEG C, 95 DEG C, 96 DEG C, 97 DEG C, 98 DEG C, 99 DEG C, preferably 91.5 ~ 98.5 DEG C, preferably 92.5 ~ 97.5 DEG C further.
Preferably, step (1) the described reaction times is 2 ~ 6 hours, such as 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, preferably 2.5 ~ 5.5 hours, preferably 3 ~ 5.5 hours further.
In reaction process, the pH value of assaying reaction system at any time, when pH in reaction system is 7.0, stopped reaction, obtains 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 containing pendant epoxies base silicone oil, to make to 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 2,6 ditertiary butyl p cresol.Described mixture such as 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 step (1) described stopper accounts for the total mass of step (1) all raw materials is 0.2 ~ 1.2wt%, such as 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, preferably 0.25 ~ 1.15wt%, further preferred 0.35 ~ 1.05wt%.All raw materials are namely: containing pendant epoxies base silicone oil, stopper, Acrylic Acid Monomer and catalyzer.
Preferably, described catalyzer is selected from the mixture of any one or at least two kinds in triethylamine, Tetramethylammonium hydroxide, tetraethylammonium bromide or N, N-dimethylbenzyl ammonium.Described mixture such as N, 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, the mixture of Tetramethylammonium hydroxide, triethylamine, N, N-dimethylbenzyl ammonium and tetraethylammonium bromide.
Preferably, the mass percent that the quality of step (1) described catalyzer accounts for the total mass of step (1) all raw materials is 0.4 ~ 1.5wt%, such as 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, preferably 0.45 ~ 1.45wt%, further preferred 0.55 ~ 1.35wt%.All raw materials are namely: containing pendant epoxies base silicone oil, stopper, Acrylic Acid Monomer and catalyzer.
Preferably, the acid-organosilicon crylic acid performed polymer that step (1) obtains is cooled to the mixing solutions dripping tetrahydrophthalic anhydride, stopper and catalyzer in after 60 ~ 70 DEG C by step (2), is preferably cooled to 61 ~ 69 DEG C, is preferably cooled to 62 ~ 68 DEG C further.Described cooling temperature is such as 60.5 DEG C, 61.5 DEG C, 62.5 DEG C, 63 DEG C, 64 DEG C, 65 DEG C, 66 DEG C, 67 DEG C, 68.5 DEG C, 69.5 DEG C.
In reaction process, acid number in detection reaction system, when acid number reaches theoretical value, is cooled to room temperature, obtains the organosilicon-modified acrylic UV-Curing Waterborne Resin of side chain with hydrophilic radical carboxyl of tetrahydrophthalic anhydride modification.Described theoretical value obtains by following principle: in theory, and the tetrahydrophthalic anhydride adding 1 mole generates the carboxyl of 1 mole, according to the amount of added tetrahydrophthalic anhydride, 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 2,6 ditertiary butyl p cresol.Described mixture such as 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 step (2) described stopper accounts for the total mass of step (2) all raw materials is 0.2 ~ 1.2wt%, such as 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, preferably 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 the mixture of any one or at least two kinds in triethylamine, Tetramethylammonium hydroxide, tetraethylammonium bromide or N, N-dimethylbenzyl ammonium.Described mixture such as N, 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, the mixture of Tetramethylammonium hydroxide, triethylamine, N, N-dimethylbenzyl ammonium and tetraethylammonium bromide.
Preferably, the mass percent that the quality of step (2) described catalyzer accounts for the total mass of step (2) all raw materials is 0.4 ~ 1.5wt%, such as 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1.0wt%, 1.1wt%, 1.2wt%, 1.3wt%, 1.4wt%, preferably 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 prepares by the following method:
In container, 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, 90 ~ 110 DEG C by Si―H addition reaction isothermal reaction discharging in 6 ~ 12 hours; Do precipitation agent with methyl alcohol reaction product is precipitated out, and with methyl alcohol repetitive scrubbing throw out, to remove unreacted monomer and catalyzer Platinic chloride, after vacuum-drying pale yellow transparent side base band have epoxide group containing pendant epoxies base silicone oil.
Described temperature of reaction is 90 ~ 110 DEG C, such as 92 DEG C, 94 DEG C, 96 DEG C, 98 DEG C, 102 DEG C, 104 DEG C, 106 DEG C, 108 DEG C, and the described reaction times is 6 ~ 12 hours, such as 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%, such as 0.08wt%, 0.1wt%, 0.12wt%, 0.14wt%, 0.16wt%, 0.18wt%, 0.19wt%, preferably 0.07 ~ 0.17wt%, further preferred 0.08 ~ 0.15wt%.
In described isopropyl alcohol solution of chloroplatinic acid, the massfraction of Platinic chloride is 1 ~ 3wt%, such as 1.2wt%, 1.4wt%, 1.6wt%, 1.8wt%, 2.1wt%, 2.3wt%, 2.5wt%, 2.7wt%, 2.9wt%, preferably 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 aromatic alcohol.The mixture of described mixture such as toluene and dimethylbenzene, 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 method for organosilicon-modified acrylic UV-Curing Waterborne 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, and 90 ~ 110 DEG C by Si―H addition reaction isothermal reaction discharging in 6 ~ 12 hours; Do precipitation agent with methyl alcohol reaction product is precipitated out, and with methyl alcohol repetitive scrubbing throw out, to remove unreacted monomer and catalyzer Platinic chloride, after vacuum-drying pale yellow transparent side base band have epoxide group containing pendant epoxies base silicone oil;
(1) will add in reaction vessel containing pendant epoxies base silicone oil and stopper, under nitrogen protection, in reaction vessel, slowly drip Acrylic Acid Monomer and catalyzer, reaction, when pH in reaction system is 7.0, stopped reaction, obtains 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 obtained to step (1), reaction, is cooled to room temperature when acid number reaches theoretical value, obtains organosilicon-modified acrylic UV-Curing Waterborne Resin.
A method for organosilicon-modified acrylic UV-Curing Waterborne 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 part 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 DEG C by Si―H addition reaction isothermal reaction discharging in 6 ~ 12 hours, do precipitation agent with methyl alcohol reaction product is precipitated out, and with methyl alcohol repetitive scrubbing throw out, to remove unreacted monomer and catalyzer Platinic chloride, after vacuum-drying pale yellow transparent side base band have epoxide group containing pendant epoxies base silicone oil,
(2 ' '), stopper added in container, N by above-mentioned obtained containing pendant epoxies base silicone oil
2under protection, stir and be warming up to 80 ~ 90 DEG C, slowly drip Acrylic Acid Monomer and catalyzer, within 1 ~ 1.5 hour, drip off, be warming up to 90 ~ 100 DEG C subsequently, react 2 ~ 6 hours, assaying reaction system pH at any time, when pH value equals 7.0, stopped reaction, obtains acid-organosilicon crylic acid performed polymer;
(3 ' ') above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 60 ~ 70 DEG C, the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer is dripped in system, after dropwising, insulation reaction, room temperature is cooled to when acid number reaches theoretical value,, obtain the organosilicon-modified acrylic UV-Curing Waterborne Resin of side chain with hydrophilic radical carboxyl of tetrahydrophthalic anhydride modification.
Exemplary reaction principle of the present invention is as follows:
Two of object of the present invention is to provide a kind of organosilicon-modified acrylic UV-Curing Waterborne Resin, and described organosilicon-modified acrylic UV-Curing Waterborne Resin is prepared by method described above.Adopt the organosilicon-modified acrylic UV-Curing Waterborne Resin that obtains of the method for the invention both hydrophilic, have can ultraviolet light polymerization simultaneously, has excellent surface property, thermostability and mechanical property.
By organosilicon-modified acrylic UV-Curing Waterborne Resin, thin up, high efficiency dispersion obtains uV curable organosilicon-modified acrylic water-based emulsion, can be applicable to the technical fields such as textile finishing, exterior coating, leather finish.
Compared with prior art, the present invention has following beneficial effect: reaction conditions is gentle, and productive rate is high, cost is low, and the photocuring water-base resin prepared is both hydrophilic, have can ultraviolet light polymerization simultaneously, has excellent surface property, thermostability and mechanical property.
Embodiment
For better the present invention being described, 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) in 250ml four-hole boiling flask, add 100g containing hydrogen silicone oil (reactive hydrogen massfraction is 0.1%), 14g glycidyl methacrylate, 0.2g isopropyl alcohol solution of chloroplatinic acid and 30g solvent, 90 DEG C by Si―H addition reaction 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 several, to remove unreacted monomer and catalyzer Platinic chloride.After vacuum-drying pale yellow transparent side base band have epoxide group containing pendant epoxies base silicone oil.
(2) in 250ml four-hole boiling flask, above-mentioned gained is added containing pendant epoxies base silicone oil, 0.4g MEHQ, logical N
2protection; stirring is warming up to 80 DEG C; appropriate Acrylic Acid Monomer 8g and catalyst of triethylamine 0.5g is slowly dripped according to silicone oil oxirane value; within 1 ~ 1.5 hour, drip off, be warming up to 90 DEG C subsequently, react 2 ~ 6 hours; measure system pH at any time; when pH value equals 7.0, stopped reaction, obtains acid-organosilicon crylic acid performed polymer.
(3) above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 60 DEG C, drip the mixing solutions of 15g tetrahydrophthalic anhydride, 0.4g MEHQ and 0.5g triethylamine, after dropwising, insulation reaction, until detect that acid number is cooled to room temperature when reaching theoretical value (1 mole of tetrahydrophthalic anhydride produces 1 mole of carboxyl in theory), obtain the organosilicon-modified acrylic UV-Curing Waterborne Resin of side chain with hydrophilic radical carboxyl of tetrahydrophthalic anhydride modification.
Embodiment 2
(1) in 500ml four-hole boiling flask, add 100g containing hydrogen silicone oil (reactive hydrogen massfraction is 0.1%), 17g glycidyl methacrylate, 0.4g isopropyl alcohol solution of chloroplatinic acid and 30g solvent, 100 DEG C by Si―H addition reaction 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 several, to remove unreacted monomer and catalyzer Platinic chloride.After vacuum-drying pale yellow transparent side base band have epoxide group containing pendant epoxies base silicone oil.
(2) in four-hole boiling flask, 0.7g MEHQ is added, logical N
2protection; stirring is warming up to 85 DEG C; appropriate Acrylic Acid Monomer 8g and catalyst of triethylamine 0.8g is slowly dripped according to silicone oil oxirane value; within 1 ~ 1.5 hour, drip off, be warming up to 95 DEG C subsequently, react 2 ~ 6 hours; measure system pH at any time; when pH value equals 7.0, stopped reaction, obtains acid-organosilicon crylic acid performed polymer.
(3) above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 60 DEG C, drip the mixing solutions of 15g tetrahydrophthalic anhydride, 0.7g MEHQ and 0.8g triethylamine, after dropwising, insulation reaction, until detect that acid number is cooled to room temperature when reaching theoretical value (1 mole of tetrahydrophthalic anhydride produces 1 mole of carboxyl in theory), obtain the organosilicon-modified acrylic UV-Curing Waterborne Resin of side chain with hydrophilic radical carboxyl of tetrahydrophthalic anhydride modification.
Embodiment 3
(1) in 250ml four-hole boiling flask, add 100g containing hydrogen silicone oil (reactive hydrogen massfraction is 0.1%), 20g glycidyl methacrylate, 0.8g isopropyl alcohol solution of chloroplatinic acid and 60g solvent, 110 DEG C by Si―H addition reaction 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 several, to remove unreacted monomer and catalyzer Platinic chloride.After vacuum-drying pale yellow transparent side base band have epoxide group containing pendant epoxies base silicone oil.
(2) in four-hole boiling flask, 1g MEHQ is added, logical N
2protection; stirring is warming up to 90 DEG C; appropriate Acrylic Acid Monomer 8g and catalyst of triethylamine 1g is slowly dripped according to silicone oil oxirane value; within 1 ~ 1.5 hour, drip off, be warming up to 100 DEG C subsequently, react 2 ~ 6 hours; measure system pH at any time; when pH value equals 7.0, stopped reaction, obtains acid-organosilicon crylic acid performed polymer.
(3) above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 70 DEG C, drip the mixing solutions of 15g tetrahydrophthalic anhydride, 1g MEHQ and 1g triethylamine, after dropwising, insulation reaction, until detect that acid number is cooled to room temperature when reaching theoretical value (1 mole of tetrahydrophthalic anhydride produces 1 mole of carboxyl in theory), obtain the organosilicon-modified acrylic UV-Curing Waterborne Resin of side chain with hydrophilic radical carboxyl of tetrahydrophthalic anhydride modification.
Embodiment 4
(1) in 250ml four-hole boiling flask, add 100g containing hydrogen silicone oil (reactive hydrogen massfraction is 0.06wt%), 10g glycidyl methacrylate, 0.1g isopropyl alcohol solution of chloroplatinic acid and 30g solvent toluene, in described isopropyl alcohol solution of chloroplatinic acid, the massfraction of Platinic chloride is 1wt%, and 90 DEG C by Si―H addition reaction 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 several, to remove unreacted monomer and catalyzer Platinic chloride.After vacuum-drying pale yellow transparent side base band have epoxide group containing pendant epoxies base silicone oil.
(2) in 250ml four-hole boiling flask, above-mentioned gained is added containing pendant epoxies base silicone oil, Resorcinol, logical N
2protection, stirring is warming up to 90 DEG C, slow dropping Acrylic Acid Monomer and catalyzer Tetramethylammonium hydroxide, within 1 ~ 1.5 hour, drip off, 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 containing pendant epoxies base silicone oil, be warming up to 100 DEG C subsequently, react 2 ~ 6 hours, measure system pH at any time, when pH value equals 7.0, stopped reaction, obtain acid-organosilicon crylic acid performed polymer.
(3) above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 70 DEG C, 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, until detect that acid number is cooled to room temperature when reaching theoretical value (1 mole of tetrahydrophthalic anhydride produces 1 mole of carboxyl in theory), obtain the organosilicon-modified acrylic UV-Curing Waterborne Resin of side chain with hydrophilic radical carboxyl of tetrahydrophthalic anhydride modification.
Embodiment 5
(1) in 500ml four-hole boiling flask, add 100g containing hydrogen silicone oil (reactive hydrogen massfraction is 0.2wt%), 20g glycidyl methacrylate, 5g isopropyl alcohol solution of chloroplatinic acid and 100g solvent butanone, in described isopropyl alcohol solution of chloroplatinic acid, the massfraction of Platinic chloride is 3wt%, and 110 DEG C by Si―H addition reaction 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 several, to remove unreacted monomer and catalyzer Platinic chloride.After vacuum-drying pale yellow transparent side base band have epoxide group containing pendant epoxies base silicone oil.
(2) in 250ml four-hole boiling flask, above-mentioned gained is added containing pendant epoxies base silicone oil, p methoxy phenol, slow dropping Acrylic Acid Monomer and catalyzer Tetramethylammonium hydroxide, within 1 ~ 1.5 hour, drip off, the mass percent that the quality of described p methoxy phenol accounts for the total mass of this step (2) all raw materials is 1.2wt%, the mass percent that the quality of Tetramethylammonium hydroxide accounts for the total mass of this step (2) all raw materials is 1.5wt%, the carboxyl molar mass of Acrylic Acid Monomer is 1:1 with the ratio of the epoxy group(ing) molar mass containing pendant epoxies base silicone oil, be warming up to 95 DEG C subsequently, react 2 ~ 6 hours, measure system pH at any time, when pH value equals 7.0, stopped reaction, obtain acid-organosilicon crylic acid performed polymer.
(3) above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 60 DEG C, 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, until detect that acid number is cooled to room temperature when reaching theoretical value (1 mole of tetrahydrophthalic anhydride produces 1 mole of carboxyl in theory), obtain the organosilicon-modified acrylic UV-Curing Waterborne Resin of side chain with hydrophilic radical carboxyl of tetrahydrophthalic anhydride modification.
It should be noted that and understand, when not departing from the spirit and scope of the present invention required by accompanying claim, various amendment and improvement can be made to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not by the restriction of given any specific exemplary teachings.
Applicant states, 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 namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (44)
1. a method for organosilicon-modified acrylic UV-Curing Waterborne Resin, is characterized in that, described method comprises the steps:
(1) will add in reaction vessel containing pendant epoxies base silicone oil and stopper, under nitrogen protection, in reaction vessel, slowly drip Acrylic Acid Monomer and catalyzer, reaction, when pH in reaction system is 7.0, stopped reaction, obtains acid-organosilicon crylic acid performed polymer;
(2) mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer is dripped in the acid-organosilicon crylic acid performed polymer obtained to step (1), 60 ~ 70 DEG C of reactions, be cooled to room temperature when acid number reaches theoretical value, obtain organosilicon-modified acrylic UV-Curing Waterborne Resin.
2. the method for claim 1, is characterized in that, under nitrogen protection, stirs after being warming up to 80 ~ 90 DEG C, in reaction vessel, slowly drips Acrylic Acid Monomer and catalyzer.
3. method as claimed in claim 2, is characterized in that, under nitrogen protection, stirs and is warming up to 82 ~ 88 DEG C, in reaction vessel, slowly drip Acrylic Acid Monomer and catalyzer.
4. method as claimed in claim 3, is characterized in that, under nitrogen protection, stirs and is warming up to 83 ~ 87 DEG C, in reaction vessel, slowly drip Acrylic Acid Monomer and catalyzer.
5. the method for claim 1, is characterized in that, the time for adding of Acrylic Acid Monomer and catalyzer is 1 ~ 1.5 hour.
6. method as claimed in claim 5, it is characterized in that, the time for adding of Acrylic Acid Monomer and catalyzer is 1.06 ~ 1.47 hours.
7. method as claimed in claim 6, it is characterized in that, the time for adding of Acrylic Acid Monomer and catalyzer is 1.12 ~ 1.42 hours.
8. the method for claim 1, is characterized in that, step (1) described temperature of reaction is 90 ~ 100 DEG C.
9. method as claimed in claim 8, it is characterized in that, step (1) described temperature of reaction is 91.5 ~ 98.5 DEG C.
10. method as claimed in claim 9, it is characterized in that, step (1) described temperature of reaction is 92.5 ~ 97.5 DEG C.
11. methods as claimed in claim 1 or 2, it is characterized in that, step (1) the described reaction times is 2 ~ 6 hours.
12. methods as claimed in claim 11, it is characterized in that, step (1) the described reaction times is 2.5 ~ 5.5 hours.
13. methods as claimed in claim 12, it is characterized in that, step (1) the described reaction times is 3 ~ 5.5 hours.
14. methods as claimed in claim 1 or 2, is characterized in that, the carboxyl molar mass of described Acrylic Acid Monomer is 1:1 with the ratio of the epoxy group(ing) molar mass containing pendant epoxies base silicone oil.
15. methods as claimed in claim 1 or 2, is characterized in that, step (1) described stopper is selected from the mixture of any one or at least two kinds in MEHQ, p methoxy phenol, Resorcinol or 2,6 ditertiary butyl p cresol.
16. methods as described in one of claim 1-3, is characterized in that, the mass percent that the quality of step (1) described stopper accounts for the total mass of step (1) all raw materials is 0.2 ~ 1.2wt%.
17. methods as claimed in claim 16, is characterized in that, the mass percent that the quality of step (1) described stopper accounts for the total mass of step (1) all raw materials is 0.25 ~ 1.15wt%.
18. methods as claimed in claim 17, is characterized in that, the mass percent that the quality of step (1) described stopper accounts for the total mass of step (1) all raw materials is 0.35 ~ 1.05wt%.
19. methods as described in one of claim 1-3, is characterized in that, step (1) described catalyzer is selected from the mixture of any one or at least two kinds in triethylamine, Tetramethylammonium hydroxide, tetraethylammonium bromide or N, N-dimethylbenzyl ammonium.
20. methods as described in one of claim 1-3, is characterized in that, the mass percent that the quality of step (1) described catalyzer accounts for the total mass of step (1) all raw materials is 0.4 ~ 1.5wt%.
21. methods as claimed in claim 20, is characterized in that, the mass percent that the quality of step (1) described catalyzer accounts for the total mass of step (1) all raw materials is 0.45 ~ 1.45wt%.
22. methods as claimed in claim 21, is characterized in that, the mass percent that the quality of step (1) described catalyzer accounts for the total mass of step (1) all raw materials is 0.55 ~ 1.35wt%.
23. methods as described in one of claim 1-4, is characterized in that, the acid-organosilicon crylic acid performed polymer that step (1) obtains is cooled to the mixing solutions dripping tetrahydrophthalic anhydride, stopper and catalyzer in after 60 ~ 70 DEG C by step (2).
24. methods as claimed in claim 23, is characterized in that, the acid-organosilicon crylic acid performed polymer that step (1) obtains is cooled to the mixing solutions dripping tetrahydrophthalic anhydride, stopper and catalyzer in after 61 ~ 69 DEG C by step (2).
25. methods as claimed in claim 24, is characterized in that, the acid-organosilicon crylic acid performed polymer that step (1) obtains is cooled to the mixing solutions dripping tetrahydrophthalic anhydride, stopper and catalyzer in after 62 ~ 68 DEG C by step (2).
26. methods as described in one of claim 1-4, is characterized in that, step (2) described stopper is selected from the mixture of any one or at least two kinds in MEHQ, p methoxy phenol, Resorcinol or 2,6 ditertiary butyl p cresol.
27. methods as described in one of claim 1-5, is characterized in that, the mass percent that the quality of step (2) described stopper accounts for the total mass of step (2) all raw materials is 0.2 ~ 1.2wt%.
28. methods as claimed in claim 27, is characterized in that, the mass percent that the quality of step (2) described stopper accounts for the total mass of step (2) all raw materials is 0.25 ~ 1.15wt%.
29. methods as claimed in claim 28, is characterized in that, the mass percent that the quality of step (2) described stopper accounts for the total mass of step (2) all raw materials is 0.35 ~ 1.05wt%.
30. methods as described in one of claim 1-5, is characterized in that, step (2) described catalyzer is selected from the mixture of any one or at least two kinds in triethylamine, Tetramethylammonium hydroxide, tetraethylammonium bromide or N, N-dimethylbenzyl ammonium.
31. methods as described in one of claim 1-5, is characterized in that, the mass percent that the quality of step (2) described catalyzer accounts for the total mass of step (2) all raw materials is 0.4 ~ 1.5wt%.
32. methods as claimed in claim 31, is characterized in that, the mass percent that the quality of step (2) described catalyzer accounts for the total mass of step (2) all raw materials is 0.45 ~ 1.45wt%.
33. methods as claimed in claim 32, is characterized in that, the mass percent that the quality of step (2) described catalyzer accounts for the total mass of step (2) all raw materials is 0.55 ~ 1.35wt%.
34. methods as described in 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.
35. methods as described in one of claim 1-6, is characterized in that, describedly prepare by the following method containing pendant epoxies base silicone oil:
In container, 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, 90 ~ 110 DEG C by Si―H addition reaction isothermal reaction discharging in 6 ~ 12 hours; Do precipitation agent with methyl alcohol reaction product is precipitated out, and with methyl alcohol repetitive scrubbing throw out, to remove unreacted monomer and catalyzer Platinic chloride, after vacuum-drying pale yellow transparent side base band have epoxide group containing pendant epoxies base silicone oil.
36. methods as claimed in claim 35, is characterized in that, the massfraction of the reactive hydrogen of described containing hydrogen silicone oil is 0.06 ~ 0.2wt%.
37. methods as claimed in claim 36, is characterized in that, the massfraction of the reactive hydrogen of described containing hydrogen silicone oil is 0.07 ~ 0.17wt%.
38. methods as claimed in claim 37, is characterized in that, the massfraction of the reactive hydrogen of described containing hydrogen silicone oil is 0.08 ~ 0.15wt%.
39. methods as claimed in claim 35, it is characterized in that, in described isopropyl alcohol solution of chloroplatinic acid, the massfraction of Platinic chloride is 1 ~ 3wt%.
40. methods as claimed in claim 39, it is characterized in that, in described isopropyl alcohol solution of chloroplatinic acid, the massfraction of Platinic chloride is 1.1 ~ 2.8wt%.
41. methods as claimed in claim 40, it is characterized in that, in described isopropyl alcohol solution of chloroplatinic acid, the massfraction of Platinic chloride is 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 aromatic alcohol.
42. methods as described in 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, and 90 ~ 110 DEG C by Si―H addition reaction isothermal reaction discharging in 6 ~ 12 hours; Do precipitation agent with methyl alcohol reaction product is precipitated out, and with methyl alcohol repetitive scrubbing throw out, to remove unreacted monomer and catalyzer Platinic chloride, after vacuum-drying pale yellow transparent side base band have epoxide group containing pendant epoxies base silicone oil;
(1) will add in reaction vessel containing pendant epoxies base silicone oil and stopper, under nitrogen protection, in reaction vessel, slowly drip Acrylic Acid Monomer and catalyzer, reaction, when pH in reaction system is 7.0, stopped reaction, obtains 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 obtained to step (1), reaction, is cooled to room temperature when acid number reaches theoretical value, obtains organosilicon-modified acrylic UV-Curing Waterborne Resin.
43. methods as described in one of claim 1-2, it is characterized in that, 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 part 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 DEG C by Si―H addition reaction isothermal reaction discharging in 6 ~ 12 hours, do precipitation agent with methyl alcohol reaction product is precipitated out, and with methyl alcohol repetitive scrubbing throw out, to remove unreacted monomer and catalyzer Platinic chloride, after vacuum-drying pale yellow transparent side base band have epoxide group containing pendant epoxies base silicone oil,
(2 "), by above-mentioned obtained containing pendant epoxies base silicone oil, stopper adds in container, N
2under protection, stir and be warming up to 80 ~ 90 DEG C, slowly drip Acrylic Acid Monomer and catalyzer, within 1 ~ 1.5 hour, drip off, be warming up to 90 ~ 100 DEG C subsequently, react 2 ~ 6 hours, assaying reaction system pH at any time, when pH value equals 7.0, stopped reaction, obtains acid-organosilicon crylic acid performed polymer;
(3 ") above-mentioned acid-organosilicon crylic acid performed polymer is cooled to 60 ~ 70 DEG C; drip the mixing solutions of tetrahydrophthalic anhydride, stopper and catalyzer; after dropwising; reaction; be cooled to room temperature when acid number reaches theoretical value, obtain the organosilicon-modified acrylic UV-Curing Waterborne Resin of side chain with hydrophilic radical carboxyl of tetrahydrophthalic anhydride modification.
44. 1 kinds of organosilicon-modified acrylic UV-Curing Waterborne Resins, is characterized in that, described organosilicon-modified acrylic UV-Curing Waterborne Resin is prepared by the described method of one of claim 1-43.
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| CN110183664B (en) * | 2019-04-30 | 2021-09-28 | 常州大学 | Preparation method and application of ultraviolet-curing methacrylate-containing silicone oil |
| CN110760260A (en) * | 2019-11-24 | 2020-02-07 | 邵美忠 | Dual-curing vacuum coating primer and preparation method thereof |
| CN110790936A (en) * | 2019-11-24 | 2020-02-14 | 邵美忠 | Dual-curing organic silicon resin and preparation method thereof |
| CN110698911A (en) * | 2019-11-24 | 2020-01-17 | 邵美忠 | Double-curing glass printing ink and preparation method thereof |
| CN112574418B (en) * | 2020-12-07 | 2022-08-05 | 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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