CN112778472B - Polyaryletherketone modified core-shell structure acrylic acid water-based resin emulsion - Google Patents
Polyaryletherketone modified core-shell structure acrylic acid water-based resin emulsion Download PDFInfo
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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
- 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
- C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D151/08—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
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Abstract
The invention relates to a polyaryletherketone modified core-shell structure acrylic waterborne resin emulsion which is prepared by the steps of firstly, controlling the proportion of binary substituted phenol and difluoro aromatic hydrocarbon, adopting stepwise polymerization to synthesize hydroxyl terminated low molecular weight linear polyaryletherketone, then obtaining acrylic terminated linear polyaryletherketone through esterification reaction, and then using the acrylic terminated linear polyaryletherketone to participate in seed emulsion polymerization to prepare the polyaryletherketone modified core-shell structure acrylic resin emulsion. The emulsion curing coating has the characteristics of good chemical stability, high hardness and excellent mechanical property, and has the advantages of lower viscosity and more stable emulsion at the same mass fraction compared with common emulsion polymerization.
Description
Technical Field
The invention relates to a water-based resin, in particular to a polyaryletherketone modified core-shell structure acrylic water-based resin emulsion, and belongs to the technical field of environmental protection.
Background
The water-based paint is the main direction of the development of the paint in the world. With the continuous advance of industrialization and urbanization, people gradually realize that economic development cannot be achieved at the cost of environmental sacrifice, and begin to seek an industrial development mode with low pollution or even no pollution. In order to meet the requirements of environmental protection and energy conservation, the development of low-VOC environment-friendly water-based paint is a necessary trend for the development of the paint industry. In recent years, the development speed of domestic water-based coatings is fast, and particularly the demand of industrial water-based coatings is the most urgent. The annual demand of industrial paint in China is about 190 ten thousand tons, wherein 120 ten thousand tons can be replaced by water-based industrial paint, so that the paint has huge potential market, and the development of the water-based industrial paint can be expected to bring great economic and social benefits.
In the industry, development of high-performance environment-friendly water-based industrial coatings is urgently needed, but in the current domestic industrial field, as the country has no special policy on the environment-friendly property of paint and the environment-friendly requirement of the used place is not as high as that of home decoration, the traditional solvent-based coatings are mostly used in the fields of automobile paint, mechanical equipment paint, special anticorrosive paint, plastic paint, glass paint and the like.
CN201710517322.7 discloses a preparation method of a mesoporous molecular sieve/waterborne polyurethane composite emulsion for metal paint, which comprises the following steps of weighing 13-24 parts by mass of oligomer dihydric alcohol, 12-22 parts by mass of diisocyanate compound, 0.05-0.5 part by mass of SBA-15 mesoporous molecular sieve, 3-10 parts by mass of chain extender, 2-5 parts by mass of salt former and 40-60 parts by mass of deionized water; and (2) dehydrating the oligomer dihydric alcohol in vacuum, adding a diisocyanate compound and an SBA-15 mesoporous molecular sieve, heating to 75-95 ℃, reacting for 2-4 h, adding a chain extender, a catalyst and an organic solvent, reacting for 4-6 h at 58-80 ℃, adding a salt forming agent and ionized water for emulsification, and finally removing the organic solvent in vacuum to obtain the mesoporous molecular sieve/waterborne polyurethane composite emulsion for the metal paint. The composite emulsion prepared by the invention takes water as a solvent, has the advantages of large binding power, good heat resistance, no toxicity, no smell, greenness and environmental protection, and can be widely applied to water-based metal paint. But the hardness, wear resistance and high temperature resistance of the alloy material still need to be improved.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a polyaryletherketone modified acrylic resin emulsion with a core-shell structure and a preparation method thereof.
The invention adopts the following technical scheme that polyaryletherketone modified core-shell structure acrylic resin emulsion is characterized in that a molecular structure of the acrylic resin emulsion contains linear polyaryletherketone branched chains; firstly, polyaryletherketone with acrylic acid end capping is synthesized, and then the polyaryletherketone participates in seed polymerization of acrylic emulsion to prepare acrylic resin emulsion with a core-shell structure.
A preparation method of polyaryletherketone modified core-shell structure acrylic resin emulsion comprises the following steps:
preparation of acrylic acid end-capped linear polyaryletherketone: by controlling the proportion of binary substituted phenol and difluoro aromatic hydrocarbon, adopting step-by-step polymerization to synthesize hydroxyl-terminated low-molecular-weight linear polyaryletherketone, and then obtaining acrylic acid-terminated linear polyaryletherketone through esterification reaction;
II, aqueous acrylic acid seed emulsion polymerization: acrylic acid end-capped linear polyaryletherketone participates in seed emulsion polymerization to prepare polyaryletherketone modified core-shell structure acrylic resin emulsion.
Furthermore, the preparation method of the polyaryletherketone modified core-shell structure acrylic resin emulsion comprises the following steps in parts by weight:
preparation of acrylic acid terminated linear polyaryletherketone: under the condition of introducing nitrogen, adding 22-30 parts of binary substituted phenol, 9-13 parts of difluoroaromatic hydrocarbon, 5-8 parts of weak base and 40-50 parts of inert solvent into a reactor provided with a water distribution device, a heating device and a stirring device, heating to 130-150 ℃ under stirring, continuously removing water generated in the reaction through the water distribution device, carrying out heat preservation reaction at the temperature of 130-150 ℃ for 3-4h, then heating to 190-200 ℃ at the temperature rise speed of 5 ℃/h, and then cooling to 180 ℃ for heat preservation polymerization for 6-8 h; then cooling to 120 ℃ of 100-;
II, water-based acrylic acid seed emulsion polymerization:
a. a pre-emulsion stage: adding 30-40 parts of deionized water, 2-4 parts of emulsifier, 0.2-0.5 part of acrylic acid, 3-5 parts of hard monomer, 4-6 parts of soft monomer, 0.5-1 part of acrylic acid modified polyaryletherketone, 0.2-1 part of cross-linking agent monomer and 1-2 parts of pH buffer solution into a four-opening reaction container provided with a speed-regulating stirrer, a reflux pipe, a dropping funnel and a thermometer, and emulsifying under high-speed stirring of 1200 plus 1500r/min to obtain milky pre-emulsified mixed monomer emulsion;
b. a seed emulsion stage: heating the milky pre-emulsified mixed monomer emulsion prepared in the stage a to 75-90 ℃, simultaneously reducing the rotating speed to 800-900r/min, dropwise adding 0.05-0.1 part of initiator solution to initiate reaction at 75-90 ℃, and preserving the heat for 1-2h when blue light appears to obtain seed emulsion;
c. an emulsion polymerization stage: reacting 0.5-2 parts of acrylic acid, 12-15 parts of hard monomer, 15-25 parts of soft monomer, 8-12 parts of acrylic acid modified polyaryletherketone, 1-2 parts of cross-linking agent monomer, 0.2-0.5 part of initiator and 20-35 parts of water to prepare dropping liquid; slowly dripping the dripping liquid into the seed emulsion at the temperature of between 75 and 90 ℃, finishing dripping within 1 to 2 hours, heating to 100 and 105 ℃ after finishing dripping, and carrying out heat preservation reaction for 0.5 hour; and (3) adding alkali to adjust the pH value of the system to 8-9, cooling to room temperature, discharging, and filtering to obtain milky white liquid with the solid content of about 50%, namely the polyaryletherketone modified core-shell structure acrylic resin emulsion.
In the step I, the weight parts of the binary substituted phenol, the difluoro aromatic hydrocarbon, the weak base, the inert solvent, the acrylic acid and the methacrylic acid are (22-30): (9-13): (5-8): (40-50): (1-2): (2-3).
In the step II, the weight part ratio of acrylic acid, hard monomer, soft monomer, acrylic acid modified polyaryletherketone, cross-linking agent monomer, initiator and water is (0.5-2): (12-15): (15-25): (8-12): (1-2): (0.2-0.5): (20-35).
The binary substituted phenol is at least one of 1-hydroxy-4- (4-hydroxybenzene) -naphthyridine, 4' -dihydroxybiphenyl, 4- (2-methyl-4-hydroxyphenyl) naphthyridine, 1, 5-dihydroxyanthraquinone, 4- (3-phenyl-4-hydroxyphenyl) -2, 3-naphthyridine-1-ketone and 4- (4-hydroxyphenyl) -2, 3-naphthyridine-1-ketone.
The difluoro aromatic hydrocarbon is at least one of 4,4 '-difluorobenzophenone, 1, 4-di- (4' -fluorobenzoyl) benzene and 1, 3-di (4-fluorobenzoyl) benzene.
The weak base is at least one of sodium carbonate and potassium carbonate.
The inert solvent is at least one of dimethylbenzene, trimethylbenzene, ethylbenzene, methyl ethylbenzene and diethylbenzene.
The hard monomer is at least one of methyl methacrylate and styrene; the soft monomer is one or a combination of more of butyl acrylate, ethyl acrylate, isobutyl acrylate, methyl acrylate and butyl methacrylate.
The emulsifier is at least one of dodecyl benzene sulfonate, allyloxy fatty alcohol polyoxyethylene ether sulfate and acrylamide isopropyl sodium sulfonate; the cross-linking agent monomer is one or a combination of beta-hydroxyethyl acrylate, beta-hydroxypropyl methacrylate and methacrylic acid amine.
The initiator is at least one of potassium persulfate, benzoyl peroxide, tert-butyl peroxybenzoate, azobisisobutyronitrile, azobisisoheptonitrile, peroxybenzoic acid and ammonium persulfate.
The water-based resin is prepared by the preparation method of the polyaryletherketone modified core-shell structure acrylic resin emulsion.
Compared with the prior art, the invention has the following advantages or beneficial results:
(1) the method comprises the steps of synthesizing hydroxyl-terminated low-molecular-weight linear polyaryletherketone by stepwise polymerization by controlling the proportion of binary substituted phenol and difluoroaromatic hydrocarbon, obtaining acrylic acid-terminated linear polyaryletherketone by esterification, and preparing polyaryletherketone modified core-shell structure acrylic resin emulsion by the participation of the acrylic acid-terminated linear polyaryletherketone in seed emulsion polymerization, wherein the emulsion curing coating film has the characteristics of good chemical stability, high hardness and excellent mechanical property;
(2) microscopically, the acrylic resin has a structure with polyaryletherketone as a branch chain and acrylic resin as a main chain, and has high flexibility and low glass transition temperature when the addition amount of a soft monomer is relatively small;
(3) compared with common emulsion polymerization, the acrylic resin emulsion with the core-shell structure has the advantages of lower viscosity and more stable emulsion at the same mass fraction.
Detailed Description
The polyaryletherketone modified core-shell acrylic resin emulsion and the preparation method thereof according to the present invention are further described with reference to the following examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
Example 1
A polyaryletherketone modified core-shell structure acrylic resin emulsion is characterized in that the molecular structure of the acrylic resin emulsion contains linear polyaryletherketone branched chains; the invention firstly synthesizes polyaryletherketone with acrylic acid end capping, and then the polyaryletherketone participates in the seed polymerization of acrylic emulsion to prepare the acrylic resin emulsion with the core-shell structure, and the preparation method comprises the following steps in parts by weight:
preparation of acrylic acid terminated linear polyaryletherketone: adding 30 parts of 1, 5-dihydroxyanthraquinone, 13 parts of 1, 3-bis (4-fluorobenzoyl) benzene, 5 parts of potassium carbonate and 40 parts of trimethylbenzene into a reactor provided with a water distribution device, a heating device and a stirring device under the condition of introducing nitrogen, heating to 150 ℃ under stirring, continuously removing water generated in the reaction through the water distribution device, carrying out heat preservation reaction at 150 ℃ for 3h, then heating to 190 ℃ at the heating rate of 5 ℃/h, and carrying out heat preservation polymerization at 180 ℃ for 8 h; then cooling to 120 ℃, adding 1 part of acrylic acid and 2 parts of methacrylic acid, heating to 190 ℃ at the heating rate of 10 ℃/h, reacting for 8h, and removing the inert solvent through reduced pressure distillation to obtain acrylic acid modified polyaryletherketone;
II, aqueous acrylic acid seed emulsion polymerization: a. a pre-emulsion stage: adding 40 parts of deionized water, 4 parts of allyloxy fatty alcohol oxyethylene ether sulfate, 0.5 part of acrylic acid, 3 parts of methyl methacrylate, 6 parts of isobutyl acrylate, 1 part of acrylic acid modified polyaryletherketone, 1 part of beta-hydroxypropyl methacrylate and 2 parts of pH buffer solution into a four-opening reaction container with a speed-regulating stirrer, a reflux pipe, a dropping funnel and a thermometer; emulsifying under high-speed stirring at 1500r/min to obtain milky pre-emulsified mixed monomer emulsion; b. a seed emulsion stage: heating to 90 ℃, simultaneously reducing the rotating speed to 900r/min, dropwise adding 0.1 part of potassium persulfate solution to initiate reaction at 90 ℃, and preserving heat for 2 hours when blue light appears; c. an emulsion polymerization stage: 2 parts of acrylic acid, 15 parts of methyl methacrylate, 25 parts of isobutyl acrylate, 12 parts of acrylic acid modified polyaryletherketone, 2 parts of beta-hydroxypropyl methacrylate, 0.5 part of potassium persulfate and 35 parts of water are added to obtain a dropping liquid; slowly dripping the dripping liquid into the seed emulsion within 2h at 90 ℃, heating to 105 ℃ after finishing dripping, and carrying out heat preservation reaction for 0.5 h; adding alkali to adjust the pH value of the system to 8, cooling to room temperature, discharging, and filtering to obtain milky white liquid with solid content of about 50%, namely the polyaryletherketone modified core-shell structure acrylic resin emulsion.
Example 2
A polyaryletherketone modified core-shell structure acrylic resin emulsion is characterized in that the molecular structure of the acrylic resin emulsion contains linear polyaryletherketone branched chains; the invention firstly synthesizes polyaryletherketone with acrylic acid end capping, and then polyaryletherketone participates in seed polymerization of acrylic emulsion to prepare acrylic resin emulsion with a core-shell structure, wherein the preparation method comprises the following steps in parts by weight:
preparation of acrylic acid terminated linear polyaryletherketone: under the condition of introducing nitrogen, adding 22 parts of 4- (4-hydroxyphenyl) -2, 3-naphthyridine-1-one, 9 parts of 4,4' -difluorobenzophenone, 8 parts of sodium carbonate and 50 parts of ethylbenzene into a reactor provided with a water distribution device, a heating device and a stirring device, heating to 130 ℃ under stirring, continuously removing water generated in the reaction through the water distribution device, carrying out heat preservation reaction at 130 ℃ for 4 hours, then heating to 200 ℃ at the heating rate of 5 ℃/h, and carrying out heat preservation polymerization at 180 ℃ for 6 hours; then cooling to 100 ℃, adding 2 parts of acrylic acid and 3 parts of methacrylic acid, heating to 180 ℃ at a heating rate of 10 ℃/h for reaction for 5h, and removing the inert solvent through reduced pressure distillation to obtain acrylic acid modified polyaryletherketone;
II, aqueous acrylic acid seed emulsion polymerization: a. a pre-emulsion stage: adding 30 parts of deionized water, 2 parts of dodecyl benzene sulfonate, 0.2 part of acrylic acid, 5 parts of styrene, 4 parts of butyl acrylate, 0.5 part of acrylic acid modified polyaryletherketone, 0.2 part of amine methacrylate and 1 part of pH buffer solution into a four-opening reaction container with a speed-regulating stirrer, a reflux pipe, a dropping funnel and a thermometer; emulsifying under high-speed stirring at 1200r/min to obtain milky pre-emulsified mixed monomer emulsion; b. a seed emulsion stage: heating to 75 ℃, simultaneously reducing the rotating speed to 800r/min, dropwise adding 0.05 part of a benzoic peroxide solution to initiate reaction at 75 ℃, and preserving heat for 1h when blue light appears; c. an emulsion polymerization stage: 0.5 part of acrylic acid, 12 parts of styrene, 15 parts of butyl acrylate, 8 parts of acrylic acid modified polyaryletherketone, 1 part of methacrylic acid amine, 0.2 part of peroxybenzoic acid and 20 parts of water are added to obtain a dropping liquid; slowly dripping the dripping liquid into the seed emulsion within 1h at 75 ℃, heating to 100 ℃ after finishing dripping, and carrying out heat preservation reaction for 0.5 h; adding alkali to adjust the pH value of the system to 8, cooling to room temperature, discharging, and filtering to obtain milky white liquid with the solid content of about 50%, namely the polyaryletherketone modified core-shell structure acrylic resin emulsion.
Example 3
A polyaryletherketone modified core-shell structure acrylic resin emulsion is characterized in that the molecular structure of the acrylic resin emulsion contains linear polyaryletherketone branched chains; the invention firstly synthesizes polyaryletherketone with acrylic acid end capping, and then the polyaryletherketone participates in the seed polymerization of acrylic emulsion to prepare the acrylic resin emulsion with the core-shell structure, and the preparation method comprises the following steps in parts by weight:
preparation of acrylic acid terminated linear polyaryletherketone: adding 24 parts of 4,4 '-dihydroxybiphenyl, 10 parts of 1, 4-bis- (4' -fluorobenzoyl) benzene, 6 parts of potassium carbonate and 43 parts of dimethylbenzene into a reactor provided with a water distribution device, a heating device and a stirring device under the condition of introducing nitrogen, heating to 141 ℃ under stirring, continuously removing water generated in the reaction by the water distribution device, carrying out heat preservation reaction at 141 ℃ for 3.3h, then heating to 195 ℃ at the heating rate of 5 ℃/h, and carrying out heat preservation polymerization at 180 ℃ for 7 h; then cooling to 110 ℃, adding 1.4 parts of acrylic acid and 2.5 parts of methacrylic acid, heating to 185 ℃ at the heating rate of 10 ℃/h for reaction for 6h, and removing the inert solvent through reduced pressure distillation to obtain acrylic acid modified polyaryletherketone;
II, aqueous acrylic acid seed emulsion polymerization: a. a pre-emulsion stage: 36 parts of deionized water, 3 parts of acrylamide isopropyl sodium sulfonate, 0.4 part of acrylic acid, 4 parts of methyl methacrylate, 5 parts of butyl methacrylate, 0.9 part of acrylic acid modified polyaryletherketone, 0.4 part of beta-hydroxyethyl acrylate and 1.6 parts of pH buffer solution are added into a four-opening reaction container provided with a speed-regulating stirrer, a reflux pipe, a dropping funnel and a thermometer; emulsifying under high-speed stirring at 1300r/min to obtain milky pre-emulsified mixed monomer emulsion; b. a seed emulsion stage: heating to 78 ℃, simultaneously reducing the rotating speed to 850r/min, dropwise adding 0.07 part of tert-butyl peroxybenzoate solution to initiate reaction at 78 ℃, and preserving heat for 1.5h when blue light appears; c. an emulsion polymerization stage: 0.8 part of acrylic acid, 14 parts of methyl methacrylate, 20 parts of butyl methacrylate, 9 parts of acrylic acid modified polyaryletherketone, 1.6 parts of beta-hydroxyethyl acrylate, 0.3 part of tert-butyl peroxybenzoate and 28 parts of water are added to obtain dropping liquid; slowly dripping the dripping liquid into the seed emulsion within 1.6h at 78 ℃, heating to 102 ℃ after finishing dripping, and carrying out heat preservation reaction for 0.5 h; adding alkali to adjust the pH value of the system to 9, cooling to room temperature, discharging, and filtering to obtain milky white liquid with solid content of about 50%, namely the polyaryletherketone modified core-shell structure acrylic resin emulsion.
And (4) testing the storage stability: 0.5L of the polyaryletherketone modified core-shell acrylic resin emulsion sample of examples 1-3 was placed in a suitable plastic container, and taken out after 180 days, and no agglomeration, precipitation, or gelation occurred upon stirring.
And (3) testing the performance of the paint film: the polyaryletherketone modified core-shell acrylic resin emulsion embodiment of the invention is compared with a competitive product acrylic emulsion (comparative example) purchased on the market for testing application performance, industrial paint is prepared according to the same formula by selecting the embodiment and the comparative example, and the impact resistance, water resistance, adhesive force, hardness, salt spray resistance and stability of a paint film after the tinplate is completely cured and the performance after the paint film is prepared into finish paint are tested, wherein the test results are as follows:
as can be seen from the table above, the polyaryletherketone modified core-shell structure acrylic resin emulsion has high water resistance, salt spray resistance, hardness and wear resistance.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the following claims.
Claims (5)
1. The polyaryletherketone modified core-shell structure acrylic acid water-based resin emulsion is characterized in that the preparation method comprises the following steps:
preparation of acrylic acid terminated linear polyaryletherketone: by controlling the proportion of binary substituted phenol and difluoro aromatic hydrocarbon, adopting stepwise polymerization to synthesize hydroxyl-terminated low-molecular-weight linear polyaryletherketone, and then obtaining acrylic acid-terminated linear polyaryletherketone through esterification reaction;
the preparation process of the acrylic acid terminated linear polyaryletherketone in the step I comprises the following steps: adding binary substituted phenol, difluoroaromatic hydrocarbon, weak base and an inert solvent into a reactor under the condition of introducing nitrogen, heating to 150 ℃ with stirring, continuously removing water generated in the reaction through a water distribution device, carrying out heat preservation reaction at 150 ℃ for 3-4h, then heating to 200 ℃ with the heating speed of 5 ℃/h, and then cooling to 180 ℃ for heat preservation polymerization for 6-8 h; then cooling to 120 ℃ for 100 plus, adding acrylic acid and methacrylic acid, heating to 190 ℃ for reaction for 5-8h at the heating rate of 10 ℃/h, and removing the inert solvent through reduced pressure distillation to obtain acrylic acid terminated linear polyaryletherketone;
in the step I, the weight part ratio of the binary substituted phenol, the difluoro aromatic hydrocarbon, the weak base, the inert solvent, the acrylic acid and the methacrylic acid is (22-30): (9-13): (5-8): (40-50): (1-2): (2-3);
the binary substituted phenol is at least one of 1-hydroxy-4- (4-hydroxybenzene) -naphthyridine, 4' -dihydroxybiphenyl and 1, 5-dihydroxyanthraquinone; the difluoro aromatic hydrocarbon is at least one of 4,4 '-difluorobenzophenone, 1, 4-bis- (4' -fluorobenzoyl) benzene and 1, 3-bis (4-fluorobenzoyl) benzene;
II, water-based acrylic acid seed emulsion polymerization: acrylic acid end-capped linear polyaryletherketone participates in seeded emulsion polymerization to prepare polyaryletherketone modified core-shell structure acrylic resin emulsion;
the step II of the polymerization reaction process of the water-based acrylic acid seed emulsion comprises the following steps: reacting acrylic acid, a hard monomer, a soft monomer, acrylic acid-terminated linear polyaryletherketone, a cross-linking agent monomer, an initiator and water to prepare a dropping liquid; slowly dripping the dripping liquid into the seed emulsion at the temperature of between 75 and 90 ℃, finishing dripping within 1 to 2 hours, heating the reactor to 100-105 ℃ after finishing dripping, and carrying out heat preservation reaction for 0.5 hour; adding alkali to adjust the pH value of the system to 8-9, cooling to room temperature, discharging, and filtering to obtain milky liquid with the solid content of 50%, namely the polyaryletherketone modified core-shell structure acrylic resin emulsion;
in the step II, the weight parts of acrylic acid, hard monomers, soft monomers, acrylic acid-terminated linear polyaryletherketone, cross-linking agent monomers, initiator and water are (0.5-2): (12-15): (15-25): (8-12): (1-2): (0.2-0.5): (20-35);
the hard monomer is at least one of methyl methacrylate and styrene.
2. The polyaryletherketone modified core-shell acrylic acid aqueous resin emulsion of claim 1, wherein the weak base is at least one of sodium carbonate and potassium carbonate; the inert solvent is at least one of dimethylbenzene, trimethylbenzene, ethylbenzene, methyl ethylbenzene and diethylbenzene.
3. The polyaryletherketone modified core-shell acrylic waterborne resin emulsion of claim 1, wherein the preparation process of the seed emulsion comprises the following steps:
a. a pre-emulsion stage: adding 30-40 parts of deionized water, 2-4 parts of emulsifier, 0.2-0.5 part of acrylic acid, 3-5 parts of hard monomer, 4-6 parts of soft monomer, 0.5-1 part of acrylic acid-terminated linear polyaryletherketone, 0.2-1 part of cross-linking agent monomer and 1-2 parts of pH value buffer solution into a reaction vessel, and emulsifying under high-speed stirring at 1200-1500r/min to obtain milky pre-emulsified mixed monomer emulsion;
b. a seed emulsion stage: heating the milky pre-emulsified mixed monomer emulsion prepared in the stage a to 75-90 ℃, simultaneously reducing the rotating speed to 800-900r/min, dropwise adding 0.05-0.1 part of initiator solution to initiate reaction at 75-90 ℃, and preserving the heat for 1-2h when blue light appears to obtain the seed emulsion.
4. The polyaryletherketone modified core-shell acrylic acid aqueous resin emulsion of claim 1, wherein the soft monomer is one or a combination of acrylic ester butyl ester, ethyl acrylate, isobutyl acrylate, acrylic ester methyl ester and methacrylic ester butyl ester; the cross-linking agent monomer is one or a combination of more of beta-hydroxyethyl acrylate, beta-hydroxypropyl methacrylate and methacrylic acid amine; the initiator is at least one of potassium persulfate, benzoyl peroxide, tert-butyl peroxybenzoate, azobisisobutyronitrile, azobisisoheptonitrile, peroxybenzoic acid and ammonium persulfate.
5. The polyaryletherketone modified core-shell acrylic acid aqueous resin emulsion of claim 3, wherein the emulsifier is at least one of dodecylbenzene sulfonate and acrylamido isopropyl sodium sulfonate.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02229132A (en) * | 1989-03-01 | 1990-09-11 | Mitsubishi Petrochem Co Ltd | Aromatic diol and production thereof |
| CN102199239A (en) * | 2010-03-24 | 2011-09-28 | 东莞大宝化工制品有限公司 | Preparation method for acrylic acid microemulsion with self-crosslinking core-shell structure |
| CN102627907A (en) * | 2012-03-28 | 2012-08-08 | 中国科学院长春应用化学研究所 | Ultraviolet-cured coating composition |
| CN105237675A (en) * | 2015-10-15 | 2016-01-13 | 三棵树涂料股份有限公司 | Polyacrylic woodware emulsion with core-shell bi-crosslinking structure and preparation method thereof |
| JP2016145327A (en) * | 2015-02-02 | 2016-08-12 | 株式会社トクヤマデンタル | Adhesive composition for polyaryletherketone resin composite material |
| CN106398171A (en) * | 2016-08-31 | 2017-02-15 | 中国科学院长春应用化学研究所 | High-strength polyaryletherketone material with stable size and preparation method thereof |
| CN106866869A (en) * | 2017-02-23 | 2017-06-20 | 同光（江苏）新材料科技有限公司 | A kind of preparation method of core shell structure hydroxyl acrylic emulsion |
| CN107434842A (en) * | 2016-05-26 | 2017-12-05 | 万华化学集团股份有限公司 | A kind of core shell structure Hydroxylated acrylic resin emulsion and its preparation method and application |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4148843A (en) * | 1977-12-23 | 1979-04-10 | General Electric Company | Compositions of capped polyphenylene oxides and alkenyl aromatic resins |
| JP5206066B2 (en) * | 2007-03-28 | 2013-06-12 | Ｊｎｃ株式会社 | Polymerizable liquid crystal composition |
| JP2010231957A (en) * | 2009-03-26 | 2010-10-14 | Mitsubishi Paper Mills Ltd | Separator integrated electrode, manufacturing method for the same, and electrochemical element |
| CN103555167A (en) * | 2013-11-05 | 2014-02-05 | 北京理工大学 | High-temperature-resisting lacquered wire lacquer composition based on modified polyaryletherketone and preparation method thereof |
| CN103819977B (en) * | 2013-12-23 | 2016-04-27 | 杭州吉华高分子材料股份有限公司 | A kind of non-viscous paint and preparation method thereof |
| CN104059328B (en) * | 2014-04-23 | 2016-05-04 | 天津大学 | Polymethylacrylic acid is filled imidazoles micro-capsule-sulfonated polyether-ether-ketone composite membrane and preparation |
| CN104761717B (en) * | 2015-04-17 | 2018-03-20 | 中国科学院长春应用化学研究所 | A kind of PAEK quadripolymer and preparation method thereof |
| CN105567076B (en) * | 2016-03-04 | 2018-06-15 | 北京理工大学 | High temperature-resistant wire lacquer composition based on fluorinated poly arylene ether ketone modification by copolymerization polyimides and preparation method thereof |
| CN105968255B (en) * | 2016-06-28 | 2018-03-09 | 合众（佛山）化工有限公司 | A kind of self-flame-retardant acrylic emulsion and preparation method thereof |
| KR101969775B1 (en) * | 2017-02-21 | 2019-04-17 | 이동우 | Method of manufacturing for Thermoplastic film and Method of manufacturing for prepreg the same |
| CN106928659A (en) * | 2017-03-15 | 2017-07-07 | 中南大学 | A kind of high wear resistant photo-cured aryl oxide based epoxy acrylate/nanometer silicon dioxide composite material and preparation method thereof |
| CN106947075B (en) * | 2017-03-24 | 2019-06-07 | 福州通尔达电线电缆有限公司 | A kind of poly(aryl ether ketone) CABLE MATERIALS resin and its synthetic method |
| CN108164666B (en) * | 2017-12-12 | 2020-08-11 | 中国科学院兰州化学物理研究所 | Light-curable polyether-ether-ketone oligomer and preparation method thereof |
-
2018
- 2018-10-09 CN CN202110027166.2A patent/CN112778472B/en active Active
- 2018-10-09 CN CN202110027165.8A patent/CN112778866B/en active Active
- 2018-10-09 CN CN201811175032.XA patent/CN109456452B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02229132A (en) * | 1989-03-01 | 1990-09-11 | Mitsubishi Petrochem Co Ltd | Aromatic diol and production thereof |
| CN102199239A (en) * | 2010-03-24 | 2011-09-28 | 东莞大宝化工制品有限公司 | Preparation method for acrylic acid microemulsion with self-crosslinking core-shell structure |
| CN102627907A (en) * | 2012-03-28 | 2012-08-08 | 中国科学院长春应用化学研究所 | Ultraviolet-cured coating composition |
| JP2016145327A (en) * | 2015-02-02 | 2016-08-12 | 株式会社トクヤマデンタル | Adhesive composition for polyaryletherketone resin composite material |
| CN105237675A (en) * | 2015-10-15 | 2016-01-13 | 三棵树涂料股份有限公司 | Polyacrylic woodware emulsion with core-shell bi-crosslinking structure and preparation method thereof |
| CN107434842A (en) * | 2016-05-26 | 2017-12-05 | 万华化学集团股份有限公司 | A kind of core shell structure Hydroxylated acrylic resin emulsion and its preparation method and application |
| CN106398171A (en) * | 2016-08-31 | 2017-02-15 | 中国科学院长春应用化学研究所 | High-strength polyaryletherketone material with stable size and preparation method thereof |
| CN106866869A (en) * | 2017-02-23 | 2017-06-20 | 同光（江苏）新材料科技有限公司 | A kind of preparation method of core shell structure hydroxyl acrylic emulsion |
Non-Patent Citations (2)
| Title |
|---|
| 含二氮杂萘酮结构聚芳醚酮和聚芳醚砜研究进展;蹇锡高等;《中国塑料》;20020430;第16卷(第4期);第11-15页 * |
| 新一代耐高温多功能重防腐涂料用树脂──聚芳醚酮的国内外发展历程及现状;吴忠文;《电镀与涂饰》;20101115;第29卷(第11期);第21-55页 * |
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| CN109456452A (en) | 2019-03-12 |
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