CN109867743B - Room-temperature self-crosslinking water-based acrylic resin dispersion and preparation method thereof - Google Patents
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Abstract
The invention discloses a room-temperature self-crosslinking aqueous acrylic resin dispersion and a preparation method thereof, belonging to the field of synthesis of high polymer materials. The room-temperature self-crosslinking water-based acrylic resin dispersion is prepared from the following raw materials in parts by weight: 30-57 parts of vinyl soft monomer, 15-35 parts of vinyl hard monomer, 15-43 parts of functional monomer, 0.5-15 parts of crosslinking monomer, 0.5-9 parts of crosslinking agent, 0.5-4 parts of initiator, 4-15 parts of neutralizer, 70-200 parts of deionized water, 1-3 parts of pH buffer and 0.05-0.2 part of chain transfer agent. The room-temperature self-crosslinking aqueous acrylic resin dispersoid is prepared by a semi-continuous-seed free radical polymerization method. The invention has the advantages that: the coating film has the advantages of high drying speed, good water resistance, high hardness, low-temperature crosslinking film forming, safety, environmental protection, accordance with the industry development trend and wide application field.
Description
Technical Field
The invention relates to the technical field of high polymer material synthesis, in particular to a room-temperature self-crosslinking aqueous acrylic resin dispersion and a preparation method thereof.
Background
Environmental friendliness has been the subject of development in the 21 st century, and solvent-based coatings with high VOC content have been challenged unprecedentedly as the awareness of environmental protection has increased and associated legal policies have been imposed to limit Volatile Organic Compound (VOC) emissions. Compared with the traditional solvent-based paint, the water-based paint takes water as a main solvent, only contains a very small amount of VOC, is a novel environment-friendly paint, and has the advantages of no toxicity, no harm, safe use, convenient storage and transportation and the like.
The water-based acrylic coating has the advantages of short drying time, good flexibility, light color, low cost, excellent light and color retention, outdoor weather resistance and the like, and is widely applied to the fields of machine manufacturing, transportation, light industry, chemical industry, buildings and the like. However, most of the water-based acrylic resins in the domestic market are thermoplastic, only hydrogen bonds and van der waals force exist among molecules, stable chemical bonds cannot be formed, the defects of poor water resistance, low-temperature brittleness, high-temperature after-tack and the like generally exist, and the application of the water-based acrylic resins in the high and new technology fields is severely limited.
Disclosure of Invention
The invention provides a room temperature self-crosslinking aqueous acrylic resin dispersion and a preparation method thereof, which overcome the defects and shortcomings of the prior art, and a copolymerization method is adopted to introduce a ketone-hydrazine normal temperature crosslinking system into aqueous acrylic resin to modify the acrylic resin.
The technical scheme for realizing the invention is as follows: the room-temperature self-crosslinking aqueous acrylic resin dispersion comprises the following raw materials in parts by weight: 31-57 parts of vinyl soft monomer, 16-35 parts of vinyl hard monomer, 15-43 parts of functional monomer, 0.5-15 parts of crosslinking monomer, 0.5-9 parts of crosslinking agent, 0.5-4 parts of initiator, 4-15 parts of neutralizer, 40-80 parts of solvent, 70-200 parts of deionized water, 1-3 parts of pH buffer and 0.02-0.2 part of chain transfer agent.
The vinyl soft monomer is selected from one or the combination of any more of butyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, sec-butyl acrylate, n-octyl acrylate, lauryl acrylate, isooctyl acrylate, vinyl acetate, isooctyl methacrylate and n-octyl methacrylate; the vinyl hard monomer is selected from one or the combination of any more of methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, styrene, divinyl benzene and acrylonitrile.
The functional monomer is a mixture of acid and hydroxyl monomer, the acid is selected from at least one of acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and itaconic acid, and the hydroxyl monomer is selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate.
The crosslinking monomer is diacetone acrylamide, and the crosslinking agent is at least one of adipic acid dihydrazide, succinic acid dihydrazide and carbonic acid dihydrazide.
The initiator is at least one of benzoyl peroxide, azodiisobutyronitrile, tert-butyl hydroperoxide, di-tert-butyl peroxide and di-tert-amyl peroxide; the solvent is one or the combination of any more of n-butyl alcohol, isopropanol, isobutanol and n-butyl ether.
The neutralizing agent is at least one of ammonia water, triethylamine, 2-amino-2-methyl-1-propanol, N, N-dimethylethanolamine and tetramethylammonium hydroxide; the pH buffer is one or the combination of two of sodium bicarbonate and ammonium bicarbonate; the chain transfer agent is n-dodecyl mercaptan.
The preparation method of the room-temperature self-crosslinking aqueous acrylic resin dispersion comprises the following steps:
(1) weighing and mixing vinyl soft monomers, vinyl hard monomers, functional monomers, crosslinking monomers, chain transfer agents and pH buffering agents according to a formula to form monomer mixed liquid; weighing initiator according to the formula amount and dissolving the initiator in a proper amount of solvent for later use;
(2) adding the residual solvent and the monomer mixed solution into a reaction kettle provided with a condenser pipe, a stirring rod and a thermometer, keeping the temperature at 80-88 ℃, adding 1/3 initiator dissolved in the step (1) and reacting for 25-40 minutes; adding 1/3 the initiator dissolved in the step (1), then adding the rest mixed monomer at a constant speed, keeping the temperature for 1 hour, adding the initiator dissolved in the rest step (1), heating to 90-95 ℃, keeping the temperature for 2-3 hours, and obtaining the water-based acrylic resin;
(3) Adjusting the temperature to 50 ℃, adding a neutralizing agent, adjusting the pH value to 7.0-9.0, adding deionized water for high-speed dispersion to form a water-based acrylic resin dispersion, finally adding a cross-linking agent, filtering and discharging to obtain the room-temperature self-crosslinking water-based acrylic resin dispersion.
The mass fraction of the monomer mixed liquor in the step (1) is 10-25%.
The adding mode of the residual mixed monomer in the step (2) is dropwise adding, and the total dropwise adding time is controlled to be 2-3 h.
The solid content of the room-temperature self-crosslinking aqueous acrylic resin dispersoid in the step (3) is 30-50%.
The invention has the beneficial effects that: the invention achieves the purpose of crosslinking and curing by introducing a ketone hydrazine crosslinking system capable of crosslinking and curing at room temperature during the preparation of the resin and controlling the pH of the system during the film formation of the resin. The ketone hydrazine crosslinking system does not react under the alkaline condition, can react under the weakly acidic condition at room temperature to achieve the purpose of crosslinking modification, the modification method is energy-saving and environment-friendly, has low cost and simple and convenient production and preparation, can simultaneously improve the defects of poor water resistance, poor salt fog resistance, low-temperature brittleness, high-temperature tack and low coating hardness of the water-based acrylic coating, can greatly improve the mechanical property of the coating, and has wide application prospect.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to embodiments of the present invention, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art based on the embodiments of the present invention without inventive step, are within the scope of the present invention.
Example 1
The room-temperature self-crosslinking aqueous acrylic resin dispersion comprises the following components in parts by weight:
vinyl soft monomer: 31 parts of butyl acrylate;
vinyl hard monomer: methyl methacrylate and styrene respectively account for 10 parts and 6 parts;
functional monomer: acrylic acid, hydroxypropyl acrylate, 11, 4 portions;
crosslinking monomer: 2 parts of diacetone acrylamide;
a crosslinking agent: 1.5 parts of succinic dihydrazide;
initiator: 0.5 part of azodiisobutyronitrile;
buffering agent: 1 part of sodium bicarbonate;
solvent: 44 parts of n-butanol;
dispersing agent: 112 parts of deionized water;
chain transfer agent: 0.02 portion of n-dodecyl mercaptan;
neutralizing agent: triethylamine in proper amount.
The preparation process of the room-temperature self-crosslinking water-based acrylic resin dispersion comprises the following steps:
(1) Weighing and mixing vinyl soft monomers, vinyl hard monomers, functional monomers, crosslinking monomers, chain transfer agents and pH buffering agents according to a formula to form monomer mixed liquid; weighing initiator according to the formula amount and dissolving the initiator in a proper amount of solvent for later use;
(2) adding the residual solvent and the monomer mixed solution with the mass fraction of 15% into a reaction kettle provided with a condenser pipe, a stirring rod and a thermometer, keeping the temperature at 85 ℃, adding 1/3 initiator and reacting for 30 minutes; adding 1/3 initiator, adding the rest mixed monomer at constant speed, keeping the temperature constant for 1 hour, adding the rest initiator, heating to 93 ℃, keeping the temperature constant for 2 hours, and obtaining the water-based acrylic resin;
(3) adjusting the temperature to 50 ℃, adding a proper amount of neutralizing agent, adjusting the pH value to 8.0, adding deionized water for high-speed dispersion to form a water-based acrylic resin dispersion, finally adding a cross-linking agent, filtering and discharging to obtain the room-temperature self-crosslinking water-based acrylic resin dispersion.
Example 2
The room-temperature self-crosslinking aqueous acrylic resin dispersion comprises the following components in parts by weight:
vinyl soft monomer: 26 parts of butyl acrylate and 11 parts of 2-ethylhexyl acrylate;
vinyl hard monomer: methyl methacrylate and styrene accounting for 10.6 parts and 13.9 parts respectively;
Functional monomer: acrylic acid and hydroxypropyl acrylate accounting for 12 parts and 11 parts respectively;
crosslinking monomer: 6 parts of diacetone acrylamide;
a crosslinking agent: adipic dihydrazide and succinic dihydrazide accounting for 2.5 parts and 1 part respectively;
initiator: azodiisobutyronitrile, tert-butyl hydroperoxide, 0.3, 0.75 parts;
buffering agent: 2.5 parts of sodium bicarbonate;
solvent: n-butyl alcohol and n-butyl ether in 52-6 weight portions;
dispersing agent: 125 parts of deionized water;
chain transfer agent: 0.02 portion of n-dodecyl mercaptan;
neutralizing agent: triethylamine in proper amount.
The preparation process of the room-temperature self-crosslinking water-based acrylic resin dispersion comprises the following steps:
(1) weighing and mixing vinyl soft monomers, vinyl hard monomers, functional monomers, crosslinking monomers, chain transfer agents and pH buffering agents according to a formula to form monomer mixed liquid; weighing initiator according to the formula amount and dissolving the initiator in a proper amount of solvent for later use;
(2) adding the residual solvent and the monomer mixed solution with the mass fraction of 15% into a reaction kettle provided with a condenser pipe, a stirring rod and a thermometer, keeping the temperature at 85 ℃, adding 1/3 initiator and reacting for 30 minutes; adding 1/3 initiator, adding the rest mixed monomer at constant speed, keeping the temperature constant for 1 hour, adding the rest initiator, heating to 93 ℃, keeping the temperature constant for 2 hours, and obtaining the water-based acrylic resin;
(3) Adjusting the temperature to 50 ℃, adding a proper amount of neutralizing agent, adjusting the pH value to 7.5, adding deionized water for high-speed dispersion to form a water-based acrylic resin dispersion, finally adding a cross-linking agent, filtering and discharging to obtain the room-temperature self-crosslinking water-based acrylic resin dispersion.
Example 3
The room-temperature self-crosslinking aqueous acrylic resin dispersion comprises the following components in parts by weight:
vinyl soft monomer: butyl acrylate, 2-ethylhexyl acrylate and isooctyl methacrylate which respectively account for 31.5, 9.5 and 16 parts;
vinyl hard monomer: 11.5 parts of methyl methacrylate, 16.5 parts of styrene and 7 parts of acrylonitrile;
functional monomer: acrylic acid and hydroxypropyl acrylate accounting for 12 parts and 31 parts respectively;
crosslinking monomer: diacetone acrylamide, 15 parts;
a crosslinking agent: adipic dihydrazide and succinic dihydrazide accounting for 6 parts and 3 parts respectively;
initiator: azodiisobutyronitrile, mono-tert-butyl hydroperoxide, 1.5, 2.5 parts;
buffering agent: 3 parts of sodium bicarbonate;
solvent: n-butyl alcohol and n-butyl ether accounting for 65 parts and 6 parts respectively;
dispersing agent: 180 parts of deionized water;
chain transfer agent: 0.15 part of n-dodecyl mercaptan;
neutralizing agent: triethylamine, N-dimethylethanolamine and proper amount.
The preparation process of the room-temperature self-crosslinking water-based acrylic resin dispersion comprises the following steps:
(1) weighing and mixing vinyl soft monomers, vinyl hard monomers, functional monomers, crosslinking monomers, chain transfer agents and pH buffering agents according to a formula to form monomer mixed liquid; weighing initiator according to the formula amount and dissolving the initiator in a proper amount of solvent for later use;
(2) adding the residual solvent and the monomer mixed solution with the mass fraction of 20% into a reaction kettle provided with a condenser pipe, a stirring rod and a thermometer, keeping the temperature at 85 ℃, adding 1/3 initiator and reacting for 40 minutes; adding 1/3 initiator, adding the rest mixed monomer at constant speed, keeping the temperature for 1 hour, adding the rest initiator, heating to 95 ℃, keeping the temperature for 2 hours to obtain the water-based acrylic resin;
(3) adjusting the temperature to 50 ℃, adding a proper amount of neutralizing agent, adjusting the pH value to 8.0, adding deionized water for high-speed dispersion to form a water-based acrylic resin dispersion, finally adding a cross-linking agent, filtering and discharging to obtain the room-temperature self-crosslinking water-based acrylic resin dispersion.
Example 4
The room-temperature self-crosslinking aqueous acrylic resin dispersion comprises the following components in parts by weight:
vinyl soft monomer: 28 parts of butyl acrylate and 14 parts of isooctyl methacrylate;
Vinyl hard monomer: methyl methacrylate, styrene and acrylonitrile accounting for 9 parts, 12 parts and 5 parts respectively;
functional monomer: methacrylic acid, crotonic acid, maleic anhydride, hydroxypropyl acrylate and hydroxyethyl methacrylate in 8, 4, 5, 15 and 6 weight portions separately;
crosslinking monomer: diacetone acrylamide, 7 parts;
a crosslinking agent: 2 parts and 3 parts of carbonic acid dihydrazide and succinic acid dihydrazide respectively;
initiator: benzoyl peroxide, tert-butyl hydroperoxide, 0.6 and 0.4 parts;
buffering agent: 1.5 parts of sodium bicarbonate;
solvent: 48 parts of isopropanol and 6 parts of n-butyl ether;
dispersing agent: 140 parts of deionized water;
chain transfer agent: 0.1 part of n-dodecyl mercaptan;
neutralizing agent: triethylamine, N-dimethylethanolamine and proper amount.
The preparation process of the room-temperature self-crosslinking water-based acrylic resin dispersion comprises the following steps:
(1) weighing and mixing vinyl soft monomers, vinyl hard monomers, functional monomers, crosslinking monomers, chain transfer agents and pH buffering agents according to a formula to form monomer mixed liquid; weighing initiator according to the formula amount and dissolving the initiator in a proper amount of solvent for later use;
(2) adding the residual solvent and the monomer mixed solution with the mass fraction of 10% into a reaction kettle provided with a condenser pipe, a stirring rod and a thermometer, keeping the temperature at 85 ℃, adding 1/3 initiator and reacting for 25 minutes; adding 1/3 initiator, adding the rest mixed monomer at constant speed, keeping the temperature for 1 hour, adding the rest initiator, heating to 90 ℃, keeping the temperature for 2 hours to obtain the water-based acrylic resin;
(3) Adjusting the temperature to 50 ℃, adding a proper amount of neutralizing agent, adjusting the pH value to 7.5, adding deionized water for high-speed dispersion to form a water-based acrylic resin dispersion, finally adding a cross-linking agent, filtering and discharging to obtain the room-temperature self-crosslinking water-based acrylic resin dispersion.
Example 5
The room-temperature self-crosslinking aqueous acrylic resin dispersion comprises the following components in parts by weight:
vinyl soft monomer: 21 parts of butyl acrylate and 9 parts of butyl methacrylate;
vinyl hard monomer: 17 parts and 13 parts of methyl methacrylate and 13 parts of styrene respectively;
functional monomer: methacrylic acid, maleic anhydride and hydroxyethyl methacrylate accounting for 14 parts, 2 parts and 21 parts respectively;
crosslinking monomer: 5 parts of diacetone acrylamide;
a crosslinking agent: 3 parts of adipic dihydrazide and 1 part of succinic dihydrazide;
initiator: benzoyl peroxide, di-tert-butyl peroxide, 0.3, 0.5 parts;
buffering agent: 1 part of sodium bicarbonate;
solvent: 60 parts of isopropanol and 11 parts of n-butyl ether;
dispersing agent: 146 parts of deionized water;
chain transfer agent: 0.05 part of n-dodecyl mercaptan;
neutralizing agent: triethylamine, tetramethyl ammonium hydroxide and proper amount.
The preparation process of the room-temperature self-crosslinking water-based acrylic resin dispersion comprises the following steps:
(1) weighing and mixing vinyl soft monomers, vinyl hard monomers, functional monomers, crosslinking monomers, chain transfer agents and pH buffering agents according to a formula to form monomer mixed liquid; weighing initiator according to the formula amount and dissolving the initiator in a proper amount of solvent for later use;
(2) adding the residual solvent and the monomer mixed solution with the mass fraction of 15% into a reaction kettle provided with a condenser pipe, a stirring rod and a thermometer, keeping the temperature at 88 ℃, adding 1/3 initiator and reacting for 30 minutes; adding 1/3 initiator, adding the rest mixed monomer at constant speed, keeping the temperature for 1 hour, adding the rest initiator, heating to 90 ℃, keeping the temperature for 2 hours to obtain the water-based acrylic resin;
(3) adjusting the temperature to 50 ℃, adding a proper amount of neutralizing agent, adjusting the pH value to 9, adding deionized water for high-speed dispersion to form a water-based acrylic resin dispersion, finally adding a cross-linking agent, filtering and discharging to obtain the room-temperature self-crosslinking water-based acrylic resin dispersion.
Example 6
The room-temperature self-crosslinking aqueous acrylic resin dispersion comprises the following components in parts by weight:
vinyl soft monomer: 31 parts of butyl acrylate;
Vinyl hard monomer: 35 parts of methyl methacrylate;
functional monomer: acrylic acid, hydroxypropyl acrylate, 12, 21 portions;
crosslinking monomer: 0.5 part of diacetone acrylamide;
a crosslinking agent: succinic dihydrazide, 0.5 part;
initiator: 0.5 part of azodiisobutyronitrile;
buffering agent: 1 part of sodium bicarbonate;
solvent: isopropyl alcohol, 65 parts;
dispersing agent: 100 parts of deionized water;
chain transfer agent: 0.02 portion of n-dodecyl mercaptan;
neutralizing agent: triethylamine in proper amount.
The preparation process of the room-temperature self-crosslinking water-based acrylic resin dispersion comprises the following steps:
(1) weighing and mixing vinyl soft monomers, vinyl hard monomers, functional monomers, crosslinking monomers, chain transfer agents and pH buffering agents according to a formula to form monomer mixed liquid; weighing initiator according to the formula amount and dissolving the initiator in a proper amount of solvent for later use;
(2) adding the residual solvent and the monomer mixed solution with the mass fraction of 17% into a reaction kettle provided with a condenser pipe, a stirring rod and a thermometer, keeping the temperature at 88 ℃, adding 1/3 initiator and reacting for 30 minutes; adding 1/3 initiator, adding the rest mixed monomer at constant speed, keeping the temperature for 1 hour, adding the rest initiator, heating to 95 ℃, keeping the temperature for 2 hours to obtain the water-based acrylic resin;
(3) Adjusting the temperature to 50 ℃, adding a proper amount of neutralizing agent, adjusting the pH value to 8.0, adding deionized water for high-speed dispersion to form a water-based acrylic resin dispersion, finally adding a cross-linking agent, filtering and discharging to obtain the room-temperature self-crosslinking water-based acrylic resin dispersion.
Example 7
The room-temperature self-crosslinking aqueous acrylic resin dispersion comprises the following components in parts by weight:
vinyl soft monomer: butyl acrylate and 2-ethylhexyl acrylate accounting for 41 parts and 16 parts respectively;
vinyl hard monomer: 30 parts of methyl methacrylate and 5 parts of acrylonitrile;
functional monomer: acrylic acid, hydroxypropyl acrylate, 14.5 parts and 28.5 parts;
crosslinking monomer: diacetone acrylamide, 15 parts;
a crosslinking agent: succinic dihydrazide, 9 parts;
initiator: 4 parts of azodiisobutyronitrile;
buffering agent: 3 parts of sodium bicarbonate;
solvent: isopropyl alcohol, n-butyl ether, 65 parts, 24 parts;
dispersing agent: 160 parts of deionized water;
chain transfer agent: 0.2 part of n-dodecyl mercaptan;
neutralizing agent: triethylamine, N-dimethylethanolamine and proper amount.
The preparation process of the room-temperature self-crosslinking water-based acrylic resin dispersion comprises the following steps:
(1) weighing and mixing vinyl soft monomers, vinyl hard monomers, functional monomers, crosslinking monomers, chain transfer agents and pH buffering agents according to a formula to form monomer mixed liquid; weighing initiator according to the formula amount and dissolving the initiator in a proper amount of solvent for later use;
(2) Adding the residual solvent and monomer mixed solution with the mass fraction of 25% into a reaction kettle provided with a condenser pipe, a stirring rod and a thermometer, keeping the temperature at 85 ℃, adding 1/3 initiator and reacting for 40 minutes; adding 1/3 initiator, adding the rest mixed monomer at constant speed, keeping the temperature for 1 hour, adding the rest initiator, heating to 95 ℃, keeping the temperature for 2 hours to obtain the water-based acrylic resin;
(3) adjusting the temperature to 50 ℃, adding a proper amount of neutralizing agent, adjusting the pH value to 7.5, adding deionized water for high-speed dispersion to form a water-based acrylic resin dispersion, finally adding a cross-linking agent, filtering and discharging to obtain the room-temperature self-crosslinking water-based acrylic resin dispersion.
In order to further illustrate the room temperature self-crosslinking aqueous acrylic resin dispersion disclosed by the invention, the room temperature self-crosslinking aqueous acrylic resin dispersion and the coating film performance of the embodiments 1-7 are correspondingly tested, and the test method comprises the following steps:
(1) testing storage and transportation stability: and (3) putting the acrylic resin dispersion sample into a 50 ℃ oven, standing at a constant temperature for 2 weeks, taking out, and standing in a room temperature environment for observation, wherein if no gel exists or separation occurs, the test is passed.
(2) And (3) testing the water absorption of the coating film: the water absorption of the acrylic resin dispersion coating film is tested by the method of GB/T1733-93. Firstly, a certain mass (W) is weighed 0 ) The coating film is soaked in water, taken out at intervals, quickly wiped off surface water by filter paper and immediately weighed (W) 1 ) Continuously testing for a period of time until the sampleThe product tends to be in swelling balance, and the water absorption (P) is calculated by the formula:
(3) and (3) testing the hardness of the coating film: the hardness of the resulting acrylic resin dispersion coating film was measured according to the method of GB/T6739-1996.
(4) And (3) adhesive force determination: the adhesion of the coating films of the dispersions obtained in the examples was determined according to the method of GB/T9286-1998.
(5) Surface dry time test: the room temperature self-crosslinking aqueous acrylic resin dispersion prepared in the example was uniformly applied to a polytetrafluoroethylene plate, dried at a constant temperature of 25 ℃ and the tack-free time of the coating film was measured according to the method of GB 1728-79.
(6) And (3) testing the crosslinking degree of the coating film: coating the emulsion, drying at 25 deg.C for 7 days, and weighing a certain mass M 0 The coating film is put into a Soxhlet extractor filled with ethyl acetate for extraction for 24 hours, then taken out and dried at the constant temperature of 25 ℃ for 2 days, and the mass M of the coating film is weighed 1 The degree of crosslinking F of the coating film is calculated according to the following formula:
(1) and (3) measuring the mechanical property: the mechanical properties of the coating were measured according to the method of GB13022-91 using a UTM4204 universal material tensile machine, the test results are shown in the following table:
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (5)
1. The preparation method of the room-temperature self-crosslinking aqueous acrylic resin dispersion is characterized by comprising the following raw materials in parts by weight: 31-57 parts of vinyl soft monomer, 16-35 parts of vinyl hard monomer, 15-43 parts of functional monomer, 0.5-15 parts of crosslinking monomer, 0.5-9 parts of crosslinking agent, 0.5-4 parts of initiator, 4-15 parts of neutralizer, 40-80 parts of solvent, 70-200 parts of deionized water, 1-3 parts of pH buffer and 0.02-0.2 part of chain transfer agent;
the solvent is one or the combination of any more of n-butyl alcohol and isopropanol;
the vinyl hard monomer is the combination of one or more of divinylbenzene, acrylonitrile and methyl methacrylate and styrene;
the functional monomer is a mixture of acid and hydroxyl monomer, the acid is selected from at least one of acrylic acid, methacrylic acid, crotonic acid, maleic anhydride and itaconic acid, and the hydroxyl monomer is selected from at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl methacrylate;
The crosslinking monomer is diacetone acrylamide, and the crosslinking agent is at least one of adipic acid dihydrazide, succinic acid dihydrazide and carbonic acid dihydrazide;
the room-temperature self-crosslinking aqueous acrylic resin dispersion is prepared by the following method, comprising the following steps:
(1) weighing and mixing vinyl soft monomers, vinyl hard monomers, functional monomers, crosslinking monomers, chain transfer agents and pH buffering agents according to a formula to form monomer mixed liquid; weighing initiator according to the formula amount and dissolving the initiator in a proper amount of solvent for later use;
(2) adding the residual solvent and 10-25% of monomer mixed solution into a reaction kettle provided with a condenser pipe, a stirring rod and a thermometer, keeping the temperature at 80-88 ℃, adding 1/3 initiator dissolved in the step (1) and reacting for 25-40 min; adding 1/3 the initiator dissolved in the step (1), then adding the rest mixed monomer at a constant speed, keeping the temperature for 1 hour, adding the initiator dissolved in the rest step (1), heating to 90-95 ℃, keeping the temperature for 2-3 hours, and obtaining the water-based acrylic resin;
(3) adjusting the temperature to 50 ℃, adding a neutralizing agent, adjusting the pH value to 7.0-9.0, adding deionized water for high-speed dispersion to form an aqueous acrylic acid dispersion, finally adding a cross-linking agent, filtering and discharging to obtain the room-temperature self-crosslinking aqueous acrylic resin dispersion, wherein the solid content of the room-temperature self-crosslinking aqueous acrylic resin dispersion is 30-50%.
2. The method for preparing room temperature self-crosslinking aqueous acrylic resin dispersion according to claim 1, wherein: the vinyl soft monomer is selected from one or any combination of butyl methacrylate, butyl acrylate, 2-ethylhexyl acrylate, sec-butyl acrylate, n-octyl acrylate, lauryl acrylate, vinyl acetate, isooctyl methacrylate and n-octyl methacrylate.
3. The method for preparing room temperature self-crosslinking aqueous acrylic resin dispersion according to claim 1, wherein: the initiator is at least one of benzoyl peroxide, azodiisobutyronitrile, tert-butyl hydroperoxide, di-tert-butyl peroxide and di-tert-amyl peroxide.
4. The method for preparing room temperature self-crosslinking aqueous acrylic resin dispersion according to claim 1, wherein: the neutralizing agent is at least one of ammonia water, triethylamine, 2-amino-2-methyl-1-propanol, N, N-dimethylethanolamine and tetramethylammonium hydroxide; the pH buffer is one or the combination of two of sodium bicarbonate and ammonium bicarbonate; the chain transfer agent is n-dodecyl mercaptan.
5. The method for preparing room temperature self-crosslinking aqueous acrylic resin dispersion according to claim 1, wherein: the adding mode of the residual mixed monomer in the step (2) is dropwise adding, and the total dropwise adding time is controlled to be 2-3 h.
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| CN111848878A (en) * | 2020-07-27 | 2020-10-30 | 中国科学院化学研究所 | Aqueous acrylic acid dispersion and preparation method and application thereof |
| CN112608406A (en) * | 2020-11-27 | 2021-04-06 | 浙江可思克高新材料股份有限公司 | Heavy calcium carbonate grinding dispersant and preparation method thereof |
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