CN109456452A - A kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion and preparation method thereof - Google Patents

A kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion and preparation method thereof Download PDF

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CN109456452A
CN109456452A CN201811175032.XA CN201811175032A CN109456452A CN 109456452 A CN109456452 A CN 109456452A CN 201811175032 A CN201811175032 A CN 201811175032A CN 109456452 A CN109456452 A CN 109456452A
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ether ketone
aryl ether
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CN109456452B (en
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刘鹏
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Guangdong Jiayuan New Material Co ltd
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D151/00Coating 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
    • C09D151/08Coating 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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    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02Macromolecular 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
    • C08F290/06Polymers provided for in subclass C08G
    • C08F290/062Polyethers
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    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The present invention relates to a kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsions and preparation method thereof, pass through the ratio of control binary substituted phenol, two fluorinated aromatic hydrocarbons first, using the linear poly(aryl ether ketone) of the gradually low molecular weight of polymerization synthesis of hydroxy sealing end, then the linear poly(aryl ether ketone) of propylene acid blocked is obtained by esterification, then seeded emulsion polymerization is participated in by the linear poly(aryl ether ketone) of propylene acid blocked and prepares poly(aryl ether ketone) modified core shell structural acrylic resin emulsion.Lotion cured coating film made from the preparation method has the characteristics that chemical stability is good, hardness is high, mechanical property is excellent, relative to general emulsion polymerization, has the advantages that its viscosity is lower in identical mass fraction, lotion is more stable.

Description

A kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion and preparation method thereof
Technical field
The present invention relates to a kind of water-base resin more particularly to a kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsions And preparation method thereof, belong to environmental technology field.
Background technique
Coating Water-borne modification is the main flow direction of world's paint development.With industrialization, the continuous propulsion of urbanization process, people Gradually recognize that economic development cannot start to pursue low pollution even free of contamination industrial development mould at the cost of the environment Formula.To adapt to environmental protection and energy-efficient requirement, the environment protecting water-based paint for developing low VOC becomes the inexorable trend of coating industry development. The development speed of domestic water paint is very fast in recent years, and especially industrial water paint demand is the most urgent.China's industry applies The annual requirement of material is at 1,900,000 tons or so, wherein can possess huge potential with aqueous industrial coating substitution up to 1,200,000 tons Market, it is contemplated that the development of water-based industrial paint will bring huge economic benefit and social benefit.
High-performance environmentally-friendly aqueous industrial coating is urgently developed in the industry, but in current domestic industrial field, since country is right Paint environmental protection characteristic does not have special coercion policy, and the place used is also so high to environmental requirement unlike house decoration, therefore, The fields overwhelming majority such as automobile coating, mechanized equipment paint, special anticorrosive paint, plastic paint, glass lacquer are also applied using traditional solvent type Material.
CN201710517322.7 discloses a kind of preparation of metallic paint mesopore molecular sieve/aqueous polyurethane multiple emulsion Method weighs 13~24 parts of oligomer dihydric alcohol, 12~22 parts of diisocyanate cpd, SBA-15 is situated between according to the mass fraction 0.05~0.5 part of porous molecular sieve, 3~10 parts of chain extender, 2~5 parts of salt forming agent and 40~60 parts of deionized water;By oligomer two Diisocyanate cpd and SBA-15 mesopore molecular sieve are added after first alcohol vacuum dehydration, is warming up to 75~95 DEG C, reaction 2~ 4h after chain extender, catalyst and organic solvent then is added, reacts 4~6h, then addition salts agent, ionized water at 58~80 DEG C Emulsification, last vacuum removal organic solvent obtain metallic paint mesopore molecular sieve/aqueous polyurethane multiple emulsion.The invention institute The multiple emulsion of preparation takes water as a solvent, can be extensive with big, heat-resist, non-toxic and tasteless, the environmentally protective advantage of cohesive force Applied to aqueous metallic paint.But its hardness, wearability, high temperature resistance need to be improved.
Summary of the invention
It is in order to overcome the shortcomings of the prior art and insufficient, the present invention is intended to provide a kind of poly(aryl ether ketone) modified core shell structure propylene Acid resin lotion and preparation method thereof.
The present invention takes following technical scheme, a kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion, feature It is, linear poly(aryl ether ketone) branch is contained in molecular structure;The present invention has synthesized the polyarylether with propylene acid blocked first Ketone, then poly(aryl ether ketone) participates in the seeding polymerization of acrylic emulsion, prepares core-shell structure emulsion acrylic resin.
A kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion, includes the following steps:
The preparation of the linear poly(aryl ether ketone) of I, propylene acid blocked: the ratio by controlling binary substituted phenol, two fluorinated aromatic hydrocarbons, Using the linear poly(aryl ether ketone) of the gradually low molecular weight of polymerization synthesis of hydroxy sealing end, propylene acid seal is then obtained by esterification The linear poly(aryl ether ketone) at end;
The reaction of II, water soluble acrylic acid seeded emulsion polymerization: seed emulsion is participated in by the linear poly(aryl ether ketone) of propylene acid blocked Polymerization preparation poly(aryl ether ketone) modified core shell structural acrylic resin emulsion.
Further, a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion, by weight Number meter, includes the following steps:
The preparation of the linear poly(aryl ether ketone) of I, propylene acid blocked: under logical condition of nitrogen gas, equipped with division box, heating dress It sets, 22-30 parts of binary substituted phenols, two fluorinated aromatic hydrocarbon of 9-13 part, 5-8 parts of weak base, 40-50 parts is added in the reactor of agitating device Atent solvent is heated to 130-150 DEG C under stirring, and the water generated in dereaction, 130-150 DEG C of guarantor are constantly removed by division box Temperature reaction 3-4h, is then warming up to 190-200 DEG C with the heating rate of 5 DEG C/h, then is down to 180 DEG C of heat preservation polymerization 6-8h;Then It is cooled to 100-120 DEG C, 1-2 parts of acrylic acid, 2-3 parts of methacrylic acids are added, 180- is warming up to the heating rate of 10 DEG C/h 190 DEG C of reaction 5-8h remove atent solvent by vacuum distillation, obtain acrylic acid modified poly(aryl ether ketone);
The reaction of II, water soluble acrylic acid seeded emulsion polymerization:
A, the pre-emulsion stage: in four mouthfuls of reaction vessels for being furnished with speed-adjustable stir device, return pipe, dropping funel and thermometer In, be added 30-40 parts of deionized waters, 2-4 parts of emulsifiers, 0.2-0.5 parts of acrylic acid, 3-5 parts of hard monomers, 4-6 parts of soft monomers, 0.5-1 parts of acrylic acid modified poly(aryl ether ketone), 0.2-1 parts of crosslinkers monomers, 1-2 portions of pH value buffers, in 1200-1500r/min High-speed stirred is emulsified, obtains milky pre-emulsification mix monomer lotion;
B, milky pre-emulsification mix monomer lotion made from a stage seed emulsion stage: is heated to 75-90 DEG C, while revolving speed is turned down to 800-900r/min, 0.05-0.1 parts of initiator solution initiation reactions at 75-90 DEG C are added dropwise, out Existing blue light heat preservation 1-2h is to get seed emulsion;
C, the emulsion polymerization stage: by 0.5-2 parts of acrylic acid, 12-15 parts of hard monomers, 15-25 parts of soft monomers, 8-12 parts of propylene Sour modified polyarylether ketone, 1-2 parts of crosslinkers monomers, 0.2-0.5 parts of initiators, 20-35 parts of water reactions, are made dropping liquid;75-90 DEG C dropping liquid is slowly added dropwise into seed emulsion, is dripped off in 1-2h, 100-105 DEG C is warming up to after being added dropwise, heat preservation is anti- Answer 0.5h;Add alkali regulation system pH value to be discharged after being cooled to room temperature to 8~9, be obtained by filtration solid content be 50% or so it is milky white Color liquid, as poly(aryl ether ketone) modified core shell structural acrylic resin emulsion.
Binary substituted phenol in the step I, two fluorinated aromatic hydrocarbons, weak base, atent solvent, acrylic acid, methacrylic acid Weight fraction ratio is (22-30): (9-13): (5-8): (40-50): (1-2): (2-3).
Acrylic acid, hard monomer, soft monomer, acrylic acid modified poly(aryl ether ketone), crosslinkers monomers, initiation in the step II Agent, water weight fraction ratio be (0.5-2): (12-15): (15-25): (8-12): (1-2): (0.2-0.5): (20-35).
The binary substituted phenol is 1- hydroxyl -4- (4- hydroxy benzenes)-benzodiazine, 4,4' dihydroxy diphenyl, 4- (2- Methyl -4- hydroxy phenyl) benzodiazine, 1,5- dihydroxy anthraquinone, 4- (3- phenyl -4- hydroxy phenyl) -2,3- benzodiazine -1- At least one of ketone, 4- (4- hydroxy phenyl) -2,3- benzodiazine -1- ketone.
Two fluorinated aromatic hydrocarbons are 4,4 '-difluoro benzophenones, 1,4- bis--(4 '-fluoro benzoyl) benzene, bis- (4- of 1,3- At least one of fluorobenzoyl) benzene.
The weak base is at least one of sodium carbonate, potassium carbonate.
The atent solvent is at least one of dimethylbenzene, trimethylbenzene, ethylbenzene, methyl-ethyl benzene, diethylbenzene.
The hard monomer is at least one of methyl methacrylate, styrene;The soft monomer is acrylic ester The combination of one or more of butyl ester, ethyl acrylate, isobutyl acrylate, propylene ester methyl ester, butyl methacrylate.
The emulsifier is dodecyl benzene sulfonate, allyloxy fatty alcohol ethylene oxide ether sulfate, propylene At least one of amide groups sodium isopropyl xanthate;The crosslinkers monomers are β-hydroxy-ethyl acrylate, Beta-methyl acrylic acid The combination of one or more of hydroxypropyl acrylate, methacrylic acid amino.
The initiator be potassium peroxydisulfate, benzoyl peroxide, peroxidized t-butyl perbenzoate, azodiisobutyronitrile, Azobisisoheptonitrile, perbenzoic acid, ammonium persulfate, at least one of.
A kind of water-base resin, using the preparation method system of above-mentioned poly(aryl ether ketone) modified core shell structural acrylic resin emulsion Standby gained.
Compared with the existing technology, the present invention has the following advantages that or beneficial outcomes:
(1) hydroxy-end capped low using gradually having synthesized by the ratio of control binary substituted phenol, two fluorinated aromatic hydrocarbons Then the linear poly(aryl ether ketone) of molecular weight obtains the linear poly(aryl ether ketone) of propylene acid blocked, propylene acid blocked by esterification Linear poly(aryl ether ketone) participate in seeded emulsion polymerization prepare poly(aryl ether ketone) modified core shell structural acrylic resin emulsion, the lotion Cured coating film protects the feature that the chemical stability having is good, hardness is high, mechanical property is excellent;
(2) on microcosmic, acrylic resin of the present invention has using poly(aryl ether ketone) as branch, using acrylic resin as the knot of main chain Structure has when soft monomer additional amount is relatively small compared with high-flexibility, and glass transition temperature is not high;
(3) present invention is core-shell structure emulsion acrylic resin, relative to general emulsion polymerization, is had in phase homogenous quantities point The advantage that its viscosity is lower, lotion is more stable when number.
Specific embodiment
Below with reference to embodiment to a kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion of the invention and its system Preparation Method is further described.It is understood that specific embodiment described herein is used only for explaining related invention, Rather than the restriction to the invention.
Embodiment 1
A kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion, which is characterized in that containing wired in its molecular structure Property poly(aryl ether ketone) branch;The present invention has synthesized the poly(aryl ether ketone) with propylene acid blocked first, and then poly(aryl ether ketone) participates in propylene The seeding polymerization of yogurt liquid prepares core-shell structure emulsion acrylic resin, and according to parts by weight, preparation method includes following step It is rapid:
The preparation of the linear poly(aryl ether ketone) of I, propylene acid blocked: under logical condition of nitrogen gas, equipped with division box, heating dress It sets, 30 parts of 1,5- dihydroxy anthraquinones, 13 parts of 1,3- bis- (4- fluorobenzoyl) benzene, 5 parts of carbonic acid is added in the reactor of agitating device Potassium, 40 parts of trimethylbenzenes, are heated to 150 DEG C under stirring, the water generated in dereaction, 150 DEG C of heat preservations are constantly removed by division box 3h is reacted, is then warming up to 190 DEG C with the heating rate of 5 DEG C/h, 180 DEG C of heat preservations polymerize 8h;Then 120 DEG C are cooled to, is added 1 Part acrylic acid, 2 parts of methacrylic acids, are warming up to 190 DEG C of reaction 8h with the heating rate of 10 DEG C/h, are removed by vacuum distillation lazy Property solvent, obtains acrylic acid modified poly(aryl ether ketone);
The reaction of II, water soluble acrylic acid seeded emulsion polymerization: a, pre-emulsion stage: it be furnished with speed-adjustable stir device, return pipe, drop In four mouthfuls of reaction vessels of liquid funnel and thermometer, 40 parts of deionized waters, 4 parts of allyloxy fatty alcohol ethylene oxide ether sulfuric acid are added Salt, 0.5 part of acrylic acid, 3 parts of methyl methacrylates, 6 parts of isobutyl acrylates, 1 part of acrylic acid modified poly(aryl ether ketone), 1 part of β- Hydroxy propyl methacrylate, 2 portions of pH value buffers;It is emulsified in 1500r/min high-speed stirred, obtain the mixing of milky pre-emulsification Monomer emulsions;B, the seed emulsion stage: being heated to 90 DEG C, while turning down revolving speed to 900r/min, and 0.1 part of persulfuric acid is added dropwise There is blue light heat preservation 2h in potassium solution initiation reaction at 90 DEG C;C, the emulsion polymerization stage: by 2 parts of acrylic acid, 15 parts of metering systems Sour methyl esters, 25 parts of isobutyl acrylates, 12 parts of acrylic acid modified poly(aryl ether ketone), 2 parts of Beta-methyl hydroxypropyl acrylates, 0.5 part of mistake Potassium sulfate, 35 parts of water obtain dropping liquid;90 DEG C dropping liquid is slowly added dropwise into seed emulsion, drips off in 2h, after being added dropwise 105 DEG C are warming up to, insulation reaction 0.5h;Add alkali regulation system pH value to 8, discharges after being cooled to room temperature, solid content is obtained by filtration For 50% or so milky white liquid, as poly(aryl ether ketone) modified core shell structural acrylic resin emulsion.
Embodiment 2
A kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion, which is characterized in that containing wired in its molecular structure Property poly(aryl ether ketone) branch;The present invention has synthesized the poly(aryl ether ketone) with propylene acid blocked first, and then poly(aryl ether ketone) participates in propylene The seeding polymerization of yogurt liquid prepares core-shell structure emulsion acrylic resin, and according to parts by weight, preparation method includes following step It is rapid:
The preparation of the linear poly(aryl ether ketone) of I, propylene acid blocked: under logical condition of nitrogen gas, equipped with division box, heating dress It sets, 22 parts of 4- (4- hydroxy phenyl) -2,3- benzodiazine -1- ketone, 9 part of 4,4 '-difluoro two is added in the reactor of agitating device Benzophenone, 8 parts of sodium carbonate, 50 parts of ethylbenzene, are heated to 130 DEG C, the water generated in dereaction are constantly removed by division box under stirring, Then 130 DEG C of insulation reaction 4h are warming up to 200 DEG C with the heating rate of 5 DEG C/h, 180 DEG C of heat preservations polymerize 6h;Then it is cooled to 100 DEG C, 2 parts of acrylic acid, 3 parts of methacrylic acids are added, 180 DEG C of reaction 5h are warming up to the heating rate of 10 DEG C/h, by subtracting Atent solvent is distilled off in pressure, obtains acrylic acid modified poly(aryl ether ketone);
The reaction of II, water soluble acrylic acid seeded emulsion polymerization: a, pre-emulsion stage: it be furnished with speed-adjustable stir device, return pipe, drop In four mouthfuls of reaction vessels of liquid funnel and thermometer, 30 parts of deionized waters, 2 parts of dodecyl benzene sulfonates, 0.2 part of propylene is added Acid, 5 parts of styrene, 4 parts of acrylic ester butyl esters, 0.5 part of acrylic acid modified poly(aryl ether ketone), 0.2 part of methacrylic acid amino, 1 part of pH value Buffer;It is emulsified in 1200r/min high-speed stirred, obtain milky pre-emulsification mix monomer lotion;B, the seed emulsion stage: 75 DEG C are heated to, while turning down revolving speed to 800r/min, 0.05 part of perbenzoic acid solution is added dropwise and causes at 75 DEG C There is blue light heat preservation 1h in reaction;C, the emulsion polymerization stage: by 0.5 part of acrylic acid, 12 parts of styrene, 15 parts of acrylic ester butyl esters, 8 The acrylic acid modified poly(aryl ether ketone) of part, 1 part of methacrylic acid amino, 0.2 part of perbenzoic acid, 20 parts of water obtain dropping liquid;75 DEG C will Dropping liquid is slowly added dropwise into seed emulsion, drips off in 1h, 100 DEG C is warming up to after being added dropwise, insulation reaction 0.5h;Add alkali Regulation system pH value discharges after being cooled to room temperature to 8, the milky white liquid that solid content is 50% or so is obtained by filtration, as gathers Aryl ether ketone modified core shell structural acrylic resin emulsion.
Embodiment 3
A kind of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion, which is characterized in that containing wired in its molecular structure Property poly(aryl ether ketone) branch;The present invention has synthesized the poly(aryl ether ketone) with propylene acid blocked first, and then poly(aryl ether ketone) participates in propylene The seeding polymerization of yogurt liquid prepares core-shell structure emulsion acrylic resin, and according to parts by weight, preparation method includes following step It is rapid:
The preparation of the linear poly(aryl ether ketone) of I, propylene acid blocked: under logical condition of nitrogen gas, equipped with division box, heating dress It sets, 24 parts of 4,4' dihydroxy diphenyls, 10 parts of 1,4- bis--(4 '-fluoro benzoyl) benzene, 6 parts is added in the reactor of agitating device Potassium carbonate, 43 parts of dimethylbenzene, are heated to 141 DEG C under stirring, constantly remove the water generated in dereaction by division box, and 141 DEG C Then insulation reaction 3.3h is warming up to 195 DEG C with the heating rate of 5 DEG C/h, 180 DEG C of heat preservation polymerase 17 h;Then 110 are cooled to DEG C, 1.4 parts of acrylic acid, 2.5 parts of methacrylic acids are added, 185 DEG C of reaction 6h are warming up to the heating rate of 10 DEG C/h, by subtracting Atent solvent is distilled off in pressure, obtains acrylic acid modified poly(aryl ether ketone);
The reaction of II, water soluble acrylic acid seeded emulsion polymerization: a, pre-emulsion stage: it be furnished with speed-adjustable stir device, return pipe, drop In four mouthfuls of reaction vessels of liquid funnel and thermometer, 36 parts of deionized waters, 3 parts of acrylamido sodium isopropyl xanthates, 0.4 are added Part acrylic acid, 4 parts of methyl methacrylates, 5 parts of butyl methacrylates, 0.9 part of acrylic acid modified poly(aryl ether ketone), 0.4 part of β- Hydroxy-ethyl acrylate, 1.6 portions of pH value buffers;It is emulsified in 1300r/min high-speed stirred, it is single to obtain the mixing of milky pre-emulsification Precursor emulsion;B, the seed emulsion stage: being heated to 78 DEG C, while turning down revolving speed to 850r/min, and 0.07 part of peroxidating is added dropwise There is blue light heat preservation 1.5h in the initiation reaction at 78 DEG C of t-butyl perbenzoate solution;C, the emulsion polymerization stage: by 0.8 part of propylene Acid, 14 parts of methyl methacrylates, 20 parts of butyl methacrylates, 9 parts of acrylic acid modified poly(aryl ether ketone), 1.6 parts of β-acrylic acid Hydroxyl ethyl ester, 0.3 part of peroxidized t-butyl perbenzoate, 28 parts of water obtain dropping liquid;78 DEG C dropping liquid is slowly added dropwise to seed emulsion In, it is dripped off in 1.6h, 102 DEG C is warming up to after being added dropwise, insulation reaction 0.5h;Add alkali regulation system pH value to 9, is cooled to It discharges after room temperature, the milky white liquid that solid content is 50% or so, as poly(aryl ether ketone) modified core shell structure propylene is obtained by filtration Acid resin lotion.
Storage stability test: by the poly(aryl ether ketone) modified core shell structural acrylic resin emulsion sample of 0.5L embodiment 1-3 Product are fitted into suitable plastic containers, are taken out after 180 days, are stirred without agglomeration, precipitating, gelatinization phenomenon.
Paint film property test: by poly(aryl ether ketone) modified core shell structural acrylic resin emulsion embodiment of the invention and market The competing product acrylic emulsion (comparative example) of upper purchase carries out the test comparison of application performance, and selection example and comparative example are according to phase Industrial paint is prepared with formula, tests impact resistance of the paint film after tinplate is fully cured, water resistance, adhesive force, hardness and resistance to Salt fog, stability, the performance being prepared into after finishing coat, test result is as follows table:
As can be seen from the above table, poly(aryl ether ketone) modified core shell structural acrylic resin emulsion of the invention is with higher resistance to Aqueous, salt fog resistance, and hardness is higher, wearability is preferable.
Although the present invention has been explained in detail and has referred to embodiment, for those of ordinary skill in the art, show Various schemes, modification and the change that can so make as specified above, should be construed as being included within the scope of the claims.

Claims (10)

1. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion, which is characterized in that including walking as follows It is rapid:
The preparation of the linear poly(aryl ether ketone) of I, propylene acid blocked: it by the ratio of control binary substituted phenol, two fluorinated aromatic hydrocarbons, uses The gradually linear poly(aryl ether ketone) of the low molecular weight of polymerization synthesis of hydroxy sealing end, then obtains propylene acid blocked by esterification Linear poly(aryl ether ketone);
The reaction of II, water soluble acrylic acid seeded emulsion polymerization: seeded emulsion polymerization is participated in by the linear poly(aryl ether ketone) of propylene acid blocked Prepare poly(aryl ether ketone) modified core shell structural acrylic resin emulsion.
2. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion according to claim 1, It is characterized in that, the preparation process of the linear poly(aryl ether ketone) of the step I propylene acid blocked are as follows: under logical condition of nitrogen gas, reacting Binary substituted phenol, two fluorinated aromatic hydrocarbons, weak base, atent solvent are added in device, 130-150 DEG C is heated under stirring, by dividing water to fill It sets constantly except the water generated in dereaction, then 130-150 DEG C of insulation reaction 3-4h is warming up to the heating rate of 5 DEG C/h 190-200 DEG C, then it is down to 180 DEG C of heat preservation polymerization 6-8h;Then it is cooled to 100-120 DEG C, acrylic acid, methacrylic acid is added, It is warming up to 180-190 DEG C of reaction 5-8h with the heating rate of 10 DEG C/h, atent solvent is removed by vacuum distillation, acrylic acid is obtained and changes Property poly(aryl ether ketone).
3. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion according to claim 2, It is characterized in that, binary substituted phenol in the step I, two fluorinated aromatic hydrocarbons, weak base, atent solvent, acrylic acid, methacrylic acid Weight fraction ratio is (22-30): (9-13): (5-8): (40-50): (1-2): (2-3).
4. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion according to claim 2, It is characterized in that, binary substituted phenol is 1- hydroxyl -4- (4- hydroxy benzenes)-benzodiazine, 4,4'- dihydroxybiphenyl, 4- (2- methyl - 4- hydroxy phenyl) benzodiazine, 1,5- dihydroxy anthraquinone, 4- (3- phenyl -4- hydroxy phenyl) -2,3- benzodiazine -1- ketone, 4- At least one of (4- hydroxy phenyl) -2,3- benzodiazine -1- ketone;Two fluorinated aromatic hydrocarbons be 4,4 '-difluoro benzophenones, At least one of 1,4- bis--(4 '-fluoro benzoyl) benzene, 1,3- bis- (4- fluorobenzoyl) benzene;The weak base be sodium carbonate, At least one of potassium carbonate;The atent solvent be dimethylbenzene, trimethylbenzene, ethylbenzene, methyl-ethyl benzene, in diethylbenzene at least It is a kind of.
5. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion according to claim 1, Be characterized in that, the step II water soluble acrylic acid seeded emulsion polymerization reaction process are as follows: by acrylic acid, hard monomer, soft monomer, Acrylic acid modified poly(aryl ether ketone), crosslinkers monomers, initiator, water reaction, are made dropping liquid;It will drop under conditions of 75-90 DEG C Liquid feeding is slowly added dropwise into seed emulsion, drips off in 1-2h, and post-reactor is added dropwise and is warming up to 100-105 DEG C, heat preservation is anti- Answer 0.5h;Add alkali regulation system pH value to be discharged after being cooled to room temperature to 8~9, be obtained by filtration solid content be 50% or so it is milky white Color liquid, as poly(aryl ether ketone) modified core shell structural acrylic resin emulsion.
6. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion according to claim 5, It is characterized in that, acrylic acid in the step II, soft monomer, acrylic acid modified poly(aryl ether ketone), crosslinkers monomers, draws hard monomer Send out agent, the weight fraction ratio of water is (0.5-2): (12-15): (15-25): (8-12): (1-2): (0.2-0.5): (20-35).
7. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion according to claim 5, It is characterized in that, according to parts by weight, the preparation process of the seed emulsion are as follows:
A, the pre-emulsion stage: in the reaction vessel be added 30-40 parts of deionized waters, 2-4 parts of emulsifiers, 0.2-0.5 parts of acrylic acid, 3-5 parts of hard monomers, 4-6 parts of soft monomers, 0.5-1 parts of acrylic acid modified poly(aryl ether ketone), 0.2-1 parts of crosslinkers monomers, 1-2 parts of pH value Buffer, it is emulsified in 1200-1500r/min high-speed stirred, obtain milky pre-emulsification mix monomer lotion;
B, the seed emulsion stage: milky pre-emulsification mix monomer lotion made from a stage is heated to 75-90 DEG C, together When turn down revolving speed to 800-900r/min, 0.05-0.1 parts of initiator solution initiation reactions at 75-90 DEG C are added dropwise, blue light occur 1-2h is kept the temperature to get seed emulsion.
8. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion according to claim 5, It is characterized in that, the hard monomer is at least one of methyl methacrylate, styrene;The soft monomer is acrylic ester The combination of one or more of butyl ester, ethyl acrylate, isobutyl acrylate, propylene ester methyl ester, butyl methacrylate;Institute The crosslinkers monomers stated are one or more of β-hydroxy-ethyl acrylate, Beta-methyl hydroxypropyl acrylate, methacrylic acid amino Combination;The initiator is potassium peroxydisulfate, benzoyl peroxide, peroxidized t-butyl perbenzoate, azodiisobutyronitrile, idol At least one of the different heptonitrile of nitrogen two, perbenzoic acid, ammonium persulfate.
9. a kind of preparation method of poly(aryl ether ketone) modified core shell structural acrylic resin emulsion according to claim 7, It is characterized in that, the emulsifier is dodecyl benzene sulfonate, allyloxy fatty alcohol ethylene oxide ether sulfate, acrylamide At least one of base sodium isopropyl xanthate.
10. a kind of preparation of such as described in any item poly(aryl ether ketone) modified core shell structural acrylic resin emulsions of claim 1-9 Method prepares resulting water-base resin.
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