CN104447325A - Ultraviolet-curable yellowing-resistant epoxy acrylate and preparation method thereof - Google Patents
Ultraviolet-curable yellowing-resistant epoxy acrylate and preparation method thereof Download PDFInfo
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- CN104447325A CN104447325A CN201410632414.6A CN201410632414A CN104447325A CN 104447325 A CN104447325 A CN 104447325A CN 201410632414 A CN201410632414 A CN 201410632414A CN 104447325 A CN104447325 A CN 104447325A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/10—Epoxy resins modified by unsaturated compounds
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Abstract
The invention relates to ultraviolet-curable yellowing-resistant epoxy acrylate and a preparation method thereof. The preparation method comprises the following steps: adding dicarboxylic anhydride, hydroxyethyl acrylate or hydroxyethyl methacrylate, a catalyst, an antioxidant and a polymerization inhibitor into a reactor, starting stirring and heating, controlling the temperature of the materials in the reactor to be 95-100 DEG C, and cooling when the acid value of the materials in the reactor meets a requirement; when the temperature of the materials in the reactor is lowered to 80 DEG C, stopping cooling, then adding glycidyl acrylate or glycidyl methacrylate and a catalyst; continuously heating the materials in the reactor, controlling the temperature to be 108-112 DEG C, and vacuumizing for 30 minutes when the acid value of the materials in the reactor is less than or equal to 5mgKOH/g, cooling and adding the polymerization inhibitor; and when the temperature of the materials in the reactor is lowered to 70 DEG C, filtering and discharging. The ultraviolet-curable yellowing-resistant epoxy acrylate provided by the invention has the advantages that the synthetic method is simple, the used raw materials are low in price, the product is good in weathering resistance and appropriate in price, and the viscosity of a finished product is low.
Description
Technical field
The present invention relates to a kind of uV curable color inhibition epoxy acrylate and preparation method thereof.
Background technology
UV-cured resin is the relatively low photoresist of a kind of molecular weight, has the group that can carry out photocuring reaction, as all kinds of unsaturated double-bond or epoxy group(ing) etc.In the product compositions that photocuring is final, UV-cured resin is the main body of photocuring, its performance determines the salient features of the rear material of solidification substantially, and therefore, the synthesis of UV-cured resin and selection are undoubtedly the important step of photocuring formula for a product design.
Begin one's study since China's ultraviolet photo-curing at the beginning of the eighties (UV), just really entered China by 95 years, all products and starting material all rely on import.But in the time of this recent two decades; Ultraviolet photo-curing industry is developed rapidly, according to the incomplete statistics of Chinese radiation curing association, to the annual rate of increase of 2012 China's ultraviolet photo-curing output value in the end of the year all more than 20%.Because the scope of this ultraviolet photo-curing sector application in several years is constantly being widened, technology is in continuous maturation, and personages of various circles of society are to the pay attention to day by day of environmental protection, to the concern of economic benefit, to the saving of the energy, makes the advantage of photocuring be able to obvious embodiment.There is the annual growth minimum 15% of scholarly forecast UV industry in these several years from now on.Because resin is the most important composition affecting the final performance of product, therefore greatly developing of this industry naturally can be more from requirement quantity and kind to light-cured resin.Existing light-cured resin kind mainly contains epoxy acrylate, polyurethane acroleic acid, polyester acrylate etc., polyether acrylate, acroleic acid esterification polyacrylic ester etc., these some outdoor weatherabilitys of existing UV-cured resin are poor, easy xanthochromia, non-refractory, limit its use range, there is the epoxy resin with benzene ring structure in raw materials used in building-up reactions, have the cycloaliphatic epoxy resin that price is very expensive.
Summary of the invention
The present invention is directed to above problem, a kind of uV curable color inhibition epoxy acrylate and preparation method thereof is provided.
Goal of the invention of the present invention is realized by following scheme:
A kind of uV curable color inhibition epoxy acrylate, prepares by the following method:
Dibasic acid anhydride, crylic acid hydroxy ester or methacrylic acid hydroxyl ester, catalyzer, oxidation inhibitor and stopper are added in reactor by the first step, start stirring heating to heat up, in reactor, temperature of charge controls at 95 ~ 100 DEG C, until when in reactor, the acid number of material reaches requirement, and cooling.
Second step, when the temperature of reactor content drops to 80 DEG C, stops cooling, after add glycidyl acrylate ester or glycidyl methacrylate and catalyzer; Continue the material in reactor heating, temperature controls at 108 ~ 112 DEG C, until during the acid number≤5mgKOH/g of reactor content, vacuumize 30 minutes, lower the temperature and add stopper.
3rd step, when temperature of charge in reactor drops to 70 DEG C, filters discharging.
A kind of uV curable color inhibition epoxy acrylate, dibasic acid anhydride is one or both in Succinic anhydried, Pyroglutaric acid; Described crylic acid hydroxy ester is one or more in Hydroxyethyl acrylate, Propylene glycol monoacrylate, trimethylol propane diacrylate, pentaerythritol triacrylate; Described methacrylic acid hydroxyl ester is one or more in hydroxyethyl methylacrylate, Rocryl 410, trimethylol propane dimethacrylate, pentaerythritol acrylate trimethyl; Described glycidyl acrylate also known as vinylformic acid-2,3-epoxypropyl ester, glycidyl methacrylate also known as methacrylic acid-2,3-epoxypropyl ester; Described catalyzer is one or more in triethylamine, N, N-dimethyl benzylamine, benzyl three second ammonia chloride, four butyl bromation amine, triphenyl phosphorus; Described stopper is one or more in Resorcinol, MEHQ, tertiarybutylhydroquinone, p-ten.-butylcatechol; Described oxidation inhibitor is one or more in antioxidant 1010, antioxidant 1076, antioxidant 264, triphenyl phosphite, Hypophosporous Acid, 50.
A kind of uV curable color inhibition epoxy acrylate, the amount of the catalyzer that the first step is added is consistent with the amount of the catalyzer that second step adds.
A preparation method for uV curable color inhibition epoxy acrylate,
Dibasic acid anhydride, crylic acid hydroxy ester or methacrylic acid hydroxyl ester, catalyzer, oxidation inhibitor and stopper are added in reactor by the first step, start stirring heating to heat up, in reactor, temperature of charge controls at 95 ~ 100 DEG C, until when in reactor, the acid number of material reaches design requirements, and cooling.
Second step, when the temperature of reactor content drops to 80 DEG C, stops cooling, after add glycidyl acrylate ester or glycidyl methacrylate and catalyzer; Continue the material in reactor heating, temperature controls at 108 ~ 112 DEG C, until during the acid number≤5mgKOH/g of reactor content, vacuumize 30 minutes, lower the temperature and add stopper.
3rd step, when temperature of charge in reactor drops to 70 DEG C, filters discharging.
A preparation method for uV curable color inhibition epoxy acrylate, dibasic acid anhydride is one or both in Succinic anhydried, Pyroglutaric acid; Described crylic acid hydroxy ester is one or more in Hydroxyethyl acrylate, Propylene glycol monoacrylate, trimethylol propane diacrylate, pentaerythritol triacrylate; Described methacrylic acid hydroxyl ester is one or more in hydroxyethyl methylacrylate, Rocryl 410, trimethylol propane dimethacrylate, pentaerythritol acrylate trimethyl; Described glycidyl acrylate also known as vinylformic acid-2,3-epoxypropyl ester, glycidyl methacrylate also known as methacrylic acid-2,3-epoxypropyl ester; Described catalyzer is one or more in triethylamine, N, N-dimethyl benzylamine, benzyl three second ammonia chloride, four butyl bromation amine, triphenyl phosphorus; Described stopper is one or more in Resorcinol, MEHQ, tertiarybutylhydroquinone, p-ten.-butylcatechol; Described oxidation inhibitor is one or more in antioxidant 1010, antioxidant 1076, antioxidant 264, triphenyl phosphite, Hypophosporous Acid, 50.
A preparation method for uV curable color inhibition epoxy acrylate, the amount of the catalyzer that the first step is added is consistent with the amount of the catalyzer that second step adds.
A preparation method for uV curable color inhibition epoxy acrylate,
The first step is by 100g Succinic anhydried, 130g Propylene glycol monoacrylate, 0.9g triphenyl phosphorus, 0.7g antioxidant 264,0.8g MEHQ is added in reactor, and start stirring heating and heat up, in reactor, temperature of charge controls at 95 ~ 100 DEG C, until in reactor during material acid number≤250mgKOH/g, cooling.
Second step is when reactor content temperature is 80 DEG C, add 145g glycidyl methacrylate and 0.9g triphenyl phosphorus, temperature controls at 108 ~ 112 DEG C, until during the acid number≤5mgKOH/g of reactor content, vacuumize 30 minutes, lower the temperature and add 0.1g MEHQ.
3rd step, when temperature of charge in reactor drops to 70 DEG C, filters discharging.
A preparation method for uV curable color inhibition epoxy acrylate,
The first step is by 100g Succinic anhydried, 300g pentaerythritol triacrylate, 2g four butyl bromation amine, 1.4g oxidation inhibitor triphenyl phosphite, 0.7g Hypophosporous Acid, 50,1.2g MEHQ is added in reactor, start stirring heating to heat up, in reactor, temperature of charge controls at 95 ~ 100 DEG C, until in reactor during material acid number≤100mgKOH/g, and cooling.
Second step is when reactor content temperature is 80 DEG C, add 145g glycidyl methacrylate and 2g four butyl bromation amine, temperature controls at 108 ~ 112 DEG C, until during the acid number≤5mgKOH/g of reactor content, vacuumize 30 minutes, lower the temperature and add 0.2g MEHQ.
3rd step, when temperature of charge in reactor drops to 70 DEG C, filters discharging.
A preparation method for uV curable color inhibition epoxy acrylate,
The first step is by 100g Succinic anhydried, the mixture of 500g pentaerythritol triacrylate and tetramethylol methane tetraacrylate, 2g four butyl bromation amine, 1.4g oxidation inhibitor triphenyl phosphite, 0.7g Hypophosporous Acid, 50,1.2g MEHQ is added in reactor, start stirring heating to heat up, in reactor, temperature of charge controls at 95 ~ 100 DEG C, until in reactor during material acid number≤100mgKOH/g, and cooling.
Second step is when reactor content temperature is 80 DEG C, add 145g glycidyl methacrylate and 2g four butyl bromation amine, temperature controls at 108 ~ 112 DEG C, until during the acid number≤5mgKOH/g of reactor content, vacuumize 30 minutes, lower the temperature and add 0.2g MEHQ.
3rd step, when temperature of charge in reactor drops to 70 DEG C, filters discharging.
A preparation method for uV curable color inhibition epoxy acrylate, the mixture of pentaerythritol triacrylate and tetramethylol methane tetraacrylate be pentaerythritol triacrylate content 60 ~ 65% and tetramethylol methane tetraacrylate content 35 ~ 40% a kind of mixture.
A kind of uV curable color inhibition epoxy acrylate provided by the invention and preparation method thereof, synthetic method is simple, and raw materials used cheap, finished product weathering resistance is excellent, affordable, and yellowing resistance is good, and the viscosity of finished product is low.Solve that epoxy acrylate xanthochromia is obvious, viscosity is high, the shortcoming that alicyclic epoxy acrylate is expensive He aliphatic urethane acrylate viscosity is high, price is high, industrially be with a wide range of applications, glycidyl acrylate or glycidyl methacrylate replace epoxy resin.
Embodiment
Embodiment 1: a kind of uV curable color inhibition epoxy acrylate, prepares by the following method:
Dibasic acid anhydride, crylic acid hydroxy ester or methacrylic acid hydroxyl ester, catalyzer, oxidation inhibitor and stopper are added in reactor by the first step, start stirring heating to heat up, in reactor, temperature of charge controls at 95 ~ 100 DEG C, until when in reactor, the acid number of material reaches requirement, and cooling.
Second step, when the temperature of reactor content drops to 80 DEG C, stops cooling, after add glycidyl acrylate ester or glycidyl methacrylate and catalyzer; Continue the material in reactor heating, temperature controls at 108 ~ 112 DEG C, until during the acid number≤5mgKOH/g of reactor content, vacuumize 30 minutes, lower the temperature and add stopper.
3rd step, when temperature of charge in reactor drops to 70 DEG C, filters discharging.
A kind of uV curable color inhibition epoxy acrylate, wherein the mass values of dibasic acid anhydride, crylic acid hydroxy ester, catalyzer, oxidation inhibitor, stopper, glycidyl methacrylate is 1000: 1300: 18: 7: 9: 1450.
A kind of uV curable color inhibition epoxy acrylate, wherein the mass values of dibasic acid anhydride, pentaerythritol triacrylate, catalyzer, oxidation inhibitor, stopper, glycidyl methacrylate is 1000: 3000: 40: 21: 14: 1450.
A kind of uV curable color inhibition epoxy acrylate, the mass ratio of the stopper that the quality of the stopper that the first step is added and second step add is 8: 1 ~ 6: 1.
A kind of uV curable color inhibition epoxy acrylate, in the first step reactor, the acid number of material is≤250mgKOH/g.
A kind of uV curable color inhibition epoxy acrylate, in the first step reactor, the acid number of material is≤100mgKOH/g.
A kind of uV curable color inhibition epoxy acrylate, described dibasic acid anhydride is one or both in Succinic anhydried, Pyroglutaric acid; Described crylic acid hydroxy ester is one or more in Hydroxyethyl acrylate, Propylene glycol monoacrylate, trimethylol propane diacrylate, pentaerythritol triacrylate; Described methacrylic acid hydroxyl ester is one or more in hydroxyethyl methylacrylate, Rocryl 410, trimethylol propane dimethacrylate, pentaerythritol acrylate trimethyl; Described glycidyl acrylate also known as vinylformic acid-2,3-epoxypropyl ester, glycidyl methacrylate also known as methacrylic acid-2,3-epoxypropyl ester; Described catalyzer is one or more in triethylamine, N, N-dimethyl benzylamine, benzyl three second ammonia chloride, four butyl bromation amine, triphenyl phosphorus; Described stopper is one or more in Resorcinol, MEHQ, tertiarybutylhydroquinone, p-ten.-butylcatechol; Described oxidation inhibitor is one or more in antioxidant 1010, antioxidant 1076, antioxidant 264, triphenyl phosphite, Hypophosporous Acid, 50.
A kind of uV curable color inhibition epoxy acrylate, the amount of the catalyzer that the first step is added is consistent with the amount of the catalyzer that second step adds.
A kind of uV curable color inhibition epoxy acrylate, glycidyl acrylate is also known as vinylformic acid-2,3-epoxypropyl ester, and glycidyl methacrylate is also known as methacrylic acid-2,3-epoxypropyl ester.
A kind of uV curable color inhibition epoxy acrylate, during the beginning stirring heating in the described the first step heats up, mixing speed is 90-300 rev/min, preference 90-150 rev/min and 200-300 rev/min; Heat temperature raising mode is the outside oil bath heating of reactor.
Embodiment 2: a kind of preparation method of uV curable color inhibition epoxy acrylate,
Dibasic acid anhydride, crylic acid hydroxy ester or methacrylic acid hydroxyl ester, catalyzer, oxidation inhibitor and stopper are added in reactor by the first step, start stirring heating to heat up, in reactor, temperature of charge controls at 95 ~ 100 DEG C, until when in reactor, the acid number of material reaches design requirements, and cooling.
Second step, when the temperature of reactor content drops to 80 DEG C, stops cooling, after add glycidyl acrylate ester or glycidyl methacrylate and catalyzer; Continue the material in reactor heating, temperature controls at 108 ~ 112 DEG C, until during the acid number≤5mgKOH/g of reactor content, vacuumize 30 minutes, lower the temperature and add stopper.
3rd step, when temperature of charge in reactor drops to 70 DEG C, filters discharging.
A preparation method for uV curable color inhibition epoxy acrylate, described dibasic acid anhydride is one or both in Succinic anhydried, Pyroglutaric acid; Described crylic acid hydroxy ester is one or more in Hydroxyethyl acrylate, Propylene glycol monoacrylate, trimethylol propane diacrylate, pentaerythritol triacrylate; Described methacrylic acid hydroxyl ester is one or more in hydroxyethyl methylacrylate, Rocryl 410, trimethylol propane dimethacrylate, pentaerythritol acrylate trimethyl; Described glycidyl acrylate also known as vinylformic acid-2,3-epoxypropyl ester, glycidyl methacrylate also known as methacrylic acid-2,3-epoxypropyl ester; Described catalyzer is one or more in triethylamine, N, N-dimethyl benzylamine, benzyl three second ammonia chloride, four butyl bromation amine, triphenyl phosphorus; Described stopper is one or more in Resorcinol, MEHQ, tertiarybutylhydroquinone, p-ten.-butylcatechol; Described oxidation inhibitor is one or more in antioxidant 1010, antioxidant 1076, antioxidant 264, triphenyl phosphite, Hypophosporous Acid, 50.
A kind of uV curable color inhibition epoxy acrylate, wherein the mass values of dibasic acid anhydride, crylic acid hydroxy ester, catalyzer, oxidation inhibitor, stopper, glycidyl methacrylate is 1000: 1300: 18: 7: 9: 1450.
A kind of uV curable color inhibition epoxy acrylate, wherein the mass values of dibasic acid anhydride, pentaerythritol triacrylate, catalyzer, oxidation inhibitor, stopper, glycidyl methacrylate is 1000: 3000: 40: 21: 14: 1450.
A kind of uV curable color inhibition epoxy acrylate, the mass ratio of the stopper that the quality of the stopper that the first step is added and second step add is 8: 1 ~ 6: 1.
A kind of uV curable color inhibition epoxy acrylate, the amount of the catalyzer that the first step is added is consistent with the amount of the catalyzer that second step adds.
A preparation method for uV curable color inhibition epoxy acrylate, during the beginning stirring heating in the described the first step heats up, mixing speed is 90-300 rev/min, preference 90-150 rev/min and 200-300 rev/min; Heat temperature raising mode is the outside oil bath heating of reactor.
A kind of uV curable color inhibition epoxy acrylate, in the first step reactor, the acid number of material is≤250mgKOH/g.
A kind of uV curable color inhibition epoxy acrylate, in the first step reactor, the acid number of material is≤100mgKOH/g.
Embodiment 3: a kind of preparation method of uV curable color inhibition epoxy acrylate,
The first step is by 100g Succinic anhydried, 130g Propylene glycol monoacrylate, 0.9g triphenyl phosphorus, 0.7g antioxidant 264,0.8g MEHQ is all added in reactor, then starts stirring heating and heats up, controlled by temperature of charge in reactor at 95 ~ 100 DEG C, until in reactor during material acid number≤250mgKOH/g, cooling.
Second step when reactor content temperature reduce to be 80 DEG C time, add 145g glycidyl methacrylate and 0.9g triphenyl phosphorus, then material in reactor heating, temperature is controlled at 108 ~ 112 DEG C, until during the acid number≤5mgKOH/g of reactor content, reactor is vacuumized 30 minutes, lower the temperature and add 0.1g MEHQ.
3rd step, when temperature of charge in reactor drops to 70 DEG C, filters discharging.
The molecular formula of described product is: C17H24O9.
The structural formula of described product is:
。
A preparation method for uV curable color inhibition epoxy acrylate, the chemical reaction of the first step:
。
A preparation method for uV curable color inhibition epoxy acrylate, the chemical reaction of second step:
。
A preparation method for uV curable color inhibition epoxy acrylate, the beginning stirring heating in the described the first step heats up, and mixing speed is 90-300 rev/min, preference 90-150 rev/min and 200-300 rev/min; Type of heating is the outside oil bath heating of reactor.
Embodiment 4: a kind of preparation method of uV curable color inhibition epoxy acrylate,
The first step is by 100g Succinic anhydried, 300g pentaerythritol triacrylate, 2g four butyl bromation amine, 1.4g oxidation inhibitor triphenyl phosphite, 0.7g Hypophosporous Acid, 50,1.2g MEHQ is added in reactor, start stirring heating to heat up, in reactor, temperature of charge controls at 95 ~ 100 DEG C, until in reactor during material acid number≤100mgKOH/g, and cooling.
Second step is when reactor content temperature is 80 DEG C, add 145g glycidyl methacrylate and 2g four butyl bromation amine, temperature controls at 108 ~ 112 DEG C, until during the acid number≤5mgKOH/g of reactor content, vacuumize 30 minutes, lower the temperature and add 0.2g MEHQ.
3rd step, when temperature of charge in reactor drops to 70 DEG C, filters discharging.
The molecular formula of described product is: C25H32O13.
The structural formula of described product is:
。
A preparation method for uV curable color inhibition epoxy acrylate, the beginning stirring heating in the described the first step heats up, and mixing speed is 90-300 rev/min, preference 90-150 rev/min and 200-300 rev/min; Type of heating is the outside oil bath heating of reactor.
A preparation method for uV curable color inhibition epoxy acrylate, the chemical reaction of the first step:
。
A preparation method for uV curable color inhibition epoxy acrylate, the chemical reaction of second step:
。
Embodiment 5: a kind of preparation method of uV curable color inhibition epoxy acrylate,
The first step is by 100g Succinic anhydried, the mixture of 500g pentaerythritol triacrylate and tetramethylol methane tetraacrylate, 2g four butyl bromation amine, 1.4g oxidation inhibitor triphenyl phosphite, 0.7g Hypophosporous Acid, 50,1.2g MEHQ is added in reactor, start stirring heating to heat up, in reactor, temperature of charge controls at 95 ~ 100 DEG C, until in reactor during material acid number≤100mgKOH/g, and cooling.
Second step is when reactor content temperature is 80 DEG C, add 145g glycidyl methacrylate and 2g four butyl bromation amine, temperature controls at 108 ~ 112 DEG C, until during the acid number≤5mgKOH/g of reactor content, vacuumize 30 minutes, lower the temperature and add 0.2g MEHQ.
3rd step, when temperature of charge in reactor drops to 70 DEG C, filters discharging.
A preparation method for uV curable color inhibition epoxy acrylate, the mixture of pentaerythritol triacrylate and tetramethylol methane tetraacrylate be pentaerythritol triacrylate content 60 ~ 65% and tetramethylol methane tetraacrylate content 35 ~ 40% a kind of mixture.
A preparation method for uV curable color inhibition epoxy acrylate, the beginning stirring heating in the described the first step heats up, and mixing speed is 90-300 rev/min, preference 90-150 rev/min and 200-300 rev/min; Type of heating is the outside oil bath heating of reactor.
Embodiment 6: a kind of uV curable color inhibition epoxy acrylate, the epoxy resin do not used with benzene ring structure raw materials used in building-up reactions, also not with the cycloaliphatic epoxy resin that price is very expensive, therefore product weathering resistance is excellent, affordable, and the viscosity of finished product is low.Solve that epoxy acrylate xanthochromia is obvious, viscosity is high, alicyclic epoxy acrylate is expensive and aliphatic urethane acrylate viscosity is high, price high shortcoming.
Embodiment 7: a kind of preparation method of uV curable color inhibition epoxy acrylate, the mass ratio of the stopper that the quality of the stopper that the first step is added and second step add is 8: 1 ~ 6: 1.
Embodiment 8: the application of a kind of uV curable color inhibition epoxy acrylate in preparation UV coating, ink or tackiness agent.
It is to be understood that: although above-described embodiment to be contrasted simple text description to mentality of designing of the present invention; but these text descriptions; just the simple text of mentality of designing of the present invention is described; instead of the restriction to mentality of designing of the present invention; any do not exceed mentality of designing of the present invention combination, increase or amendment, all fall within the scope of protection of the present invention.
Claims (10)
1. a uV curable color inhibition epoxy acrylate, is characterized in that preparing by the following method:
Dibasic acid anhydride, crylic acid hydroxy ester or methacrylic acid hydroxyl ester, catalyzer, oxidation inhibitor and stopper are added in reactor by the first step, start stirring heating to heat up, in reactor, temperature of charge controls at 95 ~ 100 DEG C, until when in reactor, the acid number of material reaches requirement, and cooling;
Second step, when the temperature of reactor content drops to 80 DEG C, stops cooling, after add glycidyl acrylate ester or glycidyl methacrylate and catalyzer; Continue the material in reactor heating, temperature controls at 108 ~ 112 DEG C, until during the acid number≤5mgKOH/g of reactor content, vacuumize 30 minutes, lower the temperature and add stopper;
3rd step, when temperature of charge in reactor drops to 70 DEG C, filters discharging.
2. a kind of uV curable color inhibition epoxy acrylate according to claim 1, is characterized in that: described dibasic acid anhydride is one or both in Succinic anhydried, Pyroglutaric acid; Described crylic acid hydroxy ester is one or more in Hydroxyethyl acrylate, Propylene glycol monoacrylate, trimethylol propane diacrylate, pentaerythritol triacrylate; Described methacrylic acid hydroxyl ester is one or more in hydroxyethyl methylacrylate, Rocryl 410, trimethylol propane dimethacrylate, pentaerythritol acrylate trimethyl; Described glycidyl acrylate also known as vinylformic acid-2,3-epoxypropyl ester, glycidyl methacrylate also known as methacrylic acid-2,3-epoxypropyl ester; Described catalyzer is one or more in triethylamine, N, N-dimethyl benzylamine, benzyl three second ammonia chloride, four butyl bromation amine, triphenyl phosphorus; Described stopper is one or more in Resorcinol, MEHQ, tertiarybutylhydroquinone, p-ten.-butylcatechol; Described oxidation inhibitor is one or more in antioxidant 1010, antioxidant 1076, antioxidant 264, triphenyl phosphite, Hypophosporous Acid, 50.
3. a kind of uV curable color inhibition epoxy acrylate according to claim 1, is characterized in that: the amount of the catalyzer that the described the first step is added is consistent with the amount of the catalyzer that second step adds.
4. the preparation method of a kind of uV curable color inhibition epoxy acrylate according to claim 1, is characterized in that:
Dibasic acid anhydride, crylic acid hydroxy ester or methacrylic acid hydroxyl ester, catalyzer, oxidation inhibitor and stopper are added in reactor by the first step, start stirring heating to heat up, in reactor, temperature of charge controls at 95 ~ 100 DEG C, until when in reactor, the acid number of material reaches design requirements, and cooling;
Second step, when the temperature of reactor content drops to 80 DEG C, stops cooling, after add glycidyl acrylate ester or glycidyl methacrylate and catalyzer; Continue the material in reactor heating, temperature controls at 108 ~ 112 DEG C, until during the acid number≤5mgKOH/g of reactor content, vacuumize 30 minutes, lower the temperature and add stopper;
3rd step, when temperature of charge in reactor drops to 70 DEG C, filters discharging.
5. the preparation method of a kind of uV curable color inhibition epoxy acrylate according to claim 4, is characterized in that: described dibasic acid anhydride is one or both in Succinic anhydried, Pyroglutaric acid; Described crylic acid hydroxy ester is one or more in Hydroxyethyl acrylate, Propylene glycol monoacrylate, trimethylol propane diacrylate, pentaerythritol triacrylate; Described methacrylic acid hydroxyl ester is one or more in hydroxyethyl methylacrylate, Rocryl 410, trimethylol propane dimethacrylate, pentaerythritol acrylate trimethyl; Described glycidyl acrylate also known as vinylformic acid-2,3-epoxypropyl ester, glycidyl methacrylate also known as methacrylic acid-2,3-epoxypropyl ester; Described catalyzer is one or more in triethylamine, N, N-dimethyl benzylamine, benzyl three second ammonia chloride, four butyl bromation amine, triphenyl phosphorus; Described stopper is one or more in Resorcinol, MEHQ, tertiarybutylhydroquinone, p-ten.-butylcatechol; Described oxidation inhibitor is one or more in antioxidant 1010, antioxidant 1076, antioxidant 264, triphenyl phosphite, Hypophosporous Acid, 50.
6. the preparation method of a kind of uV curable color inhibition epoxy acrylate according to claim 4, is characterized in that: the amount of the catalyzer that the described the first step is added is consistent with the amount of the catalyzer that second step adds.
7. the preparation method of a kind of uV curable color inhibition epoxy acrylate according to claim 4, is characterized in that:
The first step is by 100g Succinic anhydried, 130g Propylene glycol monoacrylate, 0.9g triphenyl phosphorus, 0.7g antioxidant 264,0.8g MEHQ is added in reactor, and start stirring heating and heat up, in reactor, temperature of charge controls at 95 ~ 100 DEG C, until in reactor during material acid number≤250mgKOH/g, cooling;
Second step is when reactor content temperature is 80 DEG C, add 145g glycidyl methacrylate and 0.9g triphenyl phosphorus, temperature controls at 108 ~ 112 DEG C, until during the acid number≤5mgKOH/g of reactor content, vacuumize 30 minutes, lower the temperature and add 0.1g MEHQ;
3rd step, when temperature of charge in reactor drops to 70 DEG C, filters discharging.
8. the preparation method of a kind of uV curable color inhibition epoxy acrylate according to claim 4, is characterized in that:
The first step is by 100g Succinic anhydried, 300g pentaerythritol triacrylate, 2g four butyl bromation amine, 1.4g oxidation inhibitor triphenyl phosphite, 0.7g Hypophosporous Acid, 50,1.2g MEHQ is added in reactor, start stirring heating to heat up, in reactor, temperature of charge controls at 95 ~ 100 DEG C, until in reactor during material acid number≤100mgKOH/g, and cooling;
Second step is when reactor content temperature is 80 DEG C, add 145g glycidyl methacrylate and 2g four butyl bromation amine, temperature controls at 108 ~ 112 DEG C, until during the acid number≤5mgKOH/g of reactor content, vacuumize 30 minutes, lower the temperature and add 0.2g MEHQ;
3rd step, when temperature of charge in reactor drops to 70 DEG C, filters discharging.
9. the preparation method of a kind of uV curable color inhibition epoxy acrylate according to claim 4, is characterized in that:
The first step is by 100g Succinic anhydried, the mixture of 500g pentaerythritol triacrylate and tetramethylol methane tetraacrylate, 2g four butyl bromation amine, 1.4g oxidation inhibitor triphenyl phosphite, 0.7g Hypophosporous Acid, 50,1.2g MEHQ is added in reactor, start stirring heating to heat up, in reactor, temperature of charge controls at 95 ~ 100 DEG C, until in reactor during material acid number≤100mgKOH/g, and cooling;
Second step is when reactor content temperature is 80 DEG C, add 145g glycidyl methacrylate and 2g four butyl bromation amine, temperature controls at 108 ~ 112 DEG C, until during the acid number≤5mgKOH/g of reactor content, vacuumize 30 minutes, lower the temperature and add 0.2g MEHQ;
3rd step, when temperature of charge in reactor drops to 70 DEG C, filters discharging.
10. the preparation method of a kind of uV curable color inhibition epoxy acrylate according to claim 9, is characterized in that: the mixture of described pentaerythritol triacrylate and tetramethylol methane tetraacrylate be pentaerythritol triacrylate content 60 ~ 65% and tetramethylol methane tetraacrylate content 35 ~ 40% a kind of mixture.
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| CN111285764A (en) * | 2019-01-14 | 2020-06-16 | 广东博兴新材料科技有限公司 | Treatment method for recycling (methyl) acrylic acid in esterification reaction system |
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