CN106243273B - A kind of hydroxyl acrylic emulsion and the preparation method and application thereof with core-shell structure - Google Patents
A kind of hydroxyl acrylic emulsion and the preparation method and application thereof with core-shell structure Download PDFInfo
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- CN106243273B CN106243273B CN201610616909.9A CN201610616909A CN106243273B CN 106243273 B CN106243273 B CN 106243273B CN 201610616909 A CN201610616909 A CN 201610616909A CN 106243273 B CN106243273 B CN 106243273B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
- C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
Abstract
The invention discloses a kind of hydroxyl acrylic emulsion and the preparation method and application thereof with core-shell structure, the lotion be in following five kinds of vinyl monomers in the presence of initiator and emulsifier, made of emulsion polymerization, the dosage of the type of monomer and each monomer percentage shared in monomer total amount is as follows: the vinyl monomer 40-65% 1. without other functional functional groups；2. the vinyl monomer 5-30% of hydroxyl；3. the vinyl monomer 2-5% containing epoxy group；4. carboxylic vinyl monomer 1-7%；5. containing the vinyl monomer 1-3% of polyfunctionality (>=2)；The initiator amount is the 0.2-1.5% of monomer total amount；The total dosage of emulsifier is the 1-5% of monomer total amount；The above percentage is weight percentage.The aqueous double-component coating that the hydroxyl acrylic emulsion and water cross-linking agent are prepared, VOC content is low, and amount of solid content is high, is formed by hardness of film, flexibility has both, and has excellent various patience, is used for coatings of the aluminium profiles, alternative traditional solvent based coating.
Description
Technical field
The present invention relates to paint field, more specifically to a kind of hydroxyl acrylic emulsion with core-shell structure and
Preparation method and application.
Background technique
Aluminium and its alloy have many advantages, such as good corrosion resistance, electrical and thermal conductivity and easily processed into type, so aluminium closes
Gold is widely used in national defence, aerospace, traffic instrument, both mechanically and electrically device, the fields such as home decoration.But due to gold
Belong to aluminium to be easily oxidized and black dimmed, influence its beautiful and service life, therefore protection to Al alloy parts and decoration are non-
It is often necessary.
The effect that aluminium shape surface plays protection and decoration is coated in usually using solvent based coating and powdery paints in industry
Fruit, but oil paint often discharges the poisonous and hazardous organic matter of benzene class, aldehydes (VOC) in production, allotment and work progress,
People's health and ecological environment are seriously affected, is added in recent years, with increasingly strict, the water of environmental requirement in global range
Property coating obtain very fast development.The advantages that water paint is nontoxic with its, free from extraneous odour, non-ignitable and easy cleaning, has become tradition
The main substitute of solvent based coating, but restricted by itself preparating mechanism, the resistance to medium and hardness of film are according to routine
Method is difficult to be effectively improved, and in the case, people have started the water-based hydroxyl that can be crosslinked to the curing agent of addition
The research of resin.Hydroxy resin that latex type hydroxy acryl acid resin is synthesized with solvent method, being neutralized into salt, water-dispersion type
And water soluble hydroxy resin is compared, at low cost, solid content is higher, it is important to which volatile organic compounds (VOC) content is few,
It obtains the extensive concern of domestic and international research unit and coating producer and plays an active part in research and development.
Chinese patent CN 105038426A discloses a kind of Gao Gu, low VOC non-toluene solvent type acrylic resin, the resin
Polymerization is carried out as solvent using butyl acetate and propylene glycol methyl ether acetate and prepares resin, although the resin is no benzene system,
Possess lower VOC, but compared with using water as the lotion of medium, VOC emission or larger.Chinese patent 104194440A is disclosed
A kind of normal temperature solidified water resistant coating, the resin using Diacetone Acrylamide and acrylic acid series raw material initiator work
It with lower polymerization, is crosslinked using adipic dihydrazide, and is finally made with diacetone stable emulsion.Although the lotion energy room temperature is solid
Change, various patience have also obtained certain improvement, but comprehensive performance is poorer than heat curing type lotion, and are not used to metal baking finish
On, Chinese patent CN104293047A discloses a kind of acrylic-amino baking vanish, which is solidified using amino resins
Make paint film that there is good hardness, adhesive force, impact resistance and weatherability, but the cured paint film of amino is compared with urethane cures
Paint film richness, flexibility want poor, and urethane cures temperature is lower.Chinese patent CN200510134997.0 discloses one
Kind has the emulsion-type Hydroxylated acrylic resin of core-shell configuration, which, which introduces hydroxyl group, can be used as the hydroxyl of dual-component coating
Resin, but since its patience that limits of polymerization technique and raw material selection cannot get higher improvement, family higher for patience
The more difficult satisfaction of rustproof lacquer.
Summary of the invention
The technical problem to be solved in the present invention is that in view of the above drawbacks of the prior art, providing a kind of with nucleocapsid knot
Hydroxyl acrylic emulsion of structure and the preparation method and application thereof.The hydroxyl acrylic emulsion and water cross-linking agent are prepared aqueous double
Component coating, VOC content is low, and amount of solid content is high, is formed by hardness of film, flexibility has both, with excellent various resistance to
Property, it is used for coatings of the aluminium profiles, alternative traditional solvent based coating.
The technical solution adopted by the present invention to solve the technical problems is: providing a kind of hydroxy with core-shell structure
Yogurt liquid, it be in following five kinds of vinyl monomers in the presence of initiator and emulsifier, made of emulsion polymerization, the kind of monomer
Class and the dosage of each monomer percentage shared in monomer total amount are as follows: alkenes 1., without other functional functional groups
Monomer 40-65%；2., the vinyl monomer 5-30% of hydroxyl；3., the vinyl monomer 2-5% containing epoxy group；4., it is carboxylic
Vinyl monomer 1-7%；5., contain polyfunctionality (>=2) vinyl monomer 1-3%；
The initiator amount is the 0.2-1.5% of monomer total amount；
The emulsifier is nonionic emulsifier, anionic and nonionic type emulsifier and anionic emulsifier, the use of three
Amount ratio is (1.0-1.5): (0.8-1.0): 0.3；The total dosage of emulsifier is the 1-5% of monomer total amount；
The above percentage is weight percentage.
Hydroxyl acrylic emulsion of the present invention with core-shell structure, wherein following monomer dosages are in monomer total amount
In shared percentage it is preferred are as follows: the vinyl monomer of hydroxyl 2. 10-20%；Vinyl monomer containing epoxy group 3. 3-5%；Containing carboxylic
The vinyl monomer of base 4. 1-2%；Vinyl monomer containing polyfunctionality (>=2) 5. 1-3%.
Hydroxyl acrylic emulsion of the present invention with core-shell structure, wherein described without other functional functions
1. the vinyl monomer of group is (methyl) esters of acrylic acid class monomer, two or more in aromatic series vinyl monomer；
2. the vinyl monomer of the hydroxyl is (methyl) hydroxy-ethyl acrylate, any in (methyl) hydroxypropyl acrylate
It is one or more kinds of.
Hydroxyl acrylic emulsion of the present invention with core-shell structure, wherein the vinyl monomer containing epoxy group
3. being (methyl) glycidyl acrylate, any one or more than one in allyl glycidyl ester.
Hydroxyl acrylic emulsion of the present invention with core-shell structure, wherein the carboxylic vinyl monomer is 4.
It is acrylic acid, methacrylic acid, butenoic acid, maleic acid, fumaric acid, any one or more than one in itaconic acid.
Hydroxyl acrylic emulsion of the present invention with core-shell structure, wherein the alkene containing polyfunctionality (>=2)
5. class monomer is glycol diacrylate, 1,4-butanediol diacrylate, 1,6- hexanediyl ester, neopentyl glycol
Diacrylate, trimethylolpropane trimethacrylate, ethoxyquin (N=3,9,15,21) trimethylolpropane trimethacrylate,
Any one or more than one in third oxidation (N=3,4,5) trimethylolpropane trimethacrylate.
Hydroxyl acrylic emulsion of the present invention with core-shell structure, wherein in the hydroxyl acrylic emulsion, institute
It is any one or more than one in persulfate or azo compound for stating initiator；The emulsifier is non-ionic anti-
Answering property emulsifier, without APEO nonionic emulsifier, without APEO anionic and nonionic type emulsifier, anionic reactive emulsifier, alkane
Base sulfonate, alkyl sulfate, three kinds or three kinds or more in alkylbenzene sulfonate, alkyl succinate.
Hydroxyl acrylic emulsion of the present invention with core-shell structure, wherein its appearance is milky white sub-translucent indigo plant
Light liquid, viscosity 100-2000mPa.s, solid content 42-44%, pH value 7.0-8.5,0.05-0.2 μm of partial size, volatility has
Machine compound VOC content < 0.1%, hydroxyl value 10-100mgKOH/g, storage period 6 months or more.
The present invention also provides a kind of preparation methods of hydroxyl acrylic emulsion with core-shell structure as described above, first by
Stratum nucleare pre-emulsion is made in the partial monosomy and emulsifier for forming emulsion particle stratum nucleare, polymerize in the presence of initiator and stratum nucleare is made
Then lotion drops evenly shell mix monomer, polymerize in the presence of initiator, neutralized, and filtering, discharging are to have core
The hydroxyl acrylic emulsion of shell structure, the specific steps are as follows:
(1) preparation of stratum nucleare pre-emulsion: by partial monosomy 1., partial monosomy 4. and whole monomer 5., in emulsifier
Under the action of it is evenly dispersed in water, obtain stratum nucleare pre-emulsification monomer mixture；
(2) preparation of shell pre-emulsion: by remaining monomer 1., 4. and whole monomer 2., 3., in the work of emulsifier
Under it is evenly dispersed in water, obtain shell pre-emulsification monomer mixture；
(3) emulsifier and initiator are added in reaction medium water, are placed in 500ml flask and stir evenly, and heats up
To 75~80 DEG C, the stratum nucleare pre-emulsion of 1%-10% weight ratio is added dropwise, rotation speed maintains 100-300rpm, lasting to stir
0.5-1 hours, becomes blue phase to lotion, obtain seed emulsion；
(4) remaining stratum nucleare pre-emulsion and initiator solution, after being added dropwise, heat preservation 75~80 are then added dropwise into flask
DEG C, it maintains 0.5-1.0 hours；
(5) shell pre-emulsion and initiator solution are then added dropwise into flask, after dripping off, keeps the temperature 75-80 DEG C of maintenance
2.0-2.5 hour；
(6) 40 DEG C are cooled to, the ammonium hydroxide of 1.0-2.5g is blended into the lotion in flask until by the pH value of liquid in beaker
It is modulated to 7.5-8.0, filtering, discharging are the hydroxyl acrylic emulsion with core-shell structure.
The present invention also provides a kind of applications of hydroxyl acrylic emulsion with core-shell structure as described above, are applied to aluminium
Material incrustation coating.
Implement the hydroxyl acrylic emulsion and the preparation method and application thereof with core-shell structure of the invention, has with following
Beneficial effect:
(1) present invention has the hydroxyl acrylic emulsion of core-shell structure, and unique core-shell structure makes it have following excellent
Point: the core part of lotion will be introduced with multi-functional alkene, make its core that there is microgel structure, improve core part resin
Molecular weight, while semi-intercrossing network lotion (semi-LIPN) is also obtained, during emulsion film forming, with the diffusion of strand
A big semi-intercrossing network is formed, with the addition of curing agent, cross-linking reaction gradually occurs, and forms second network, obtains
The full interpenetrating networks film of thermosetting property, and then greatly improve the hardness and patience of resin；Hydroxyl, ring will be contained consciously simultaneously
The composition of oxygroup (methyl) acrylic monomers or both introduces the shell parts of lotion, active group can be made sufficiently to be distributed in this way
On the surface of lotion, increase reaction probabilities, effectively improve the use rate of group, improves water resistance, the comprehensive performances such as adhesive force；
(2) having hydroxy functional group both in the water paint prepared by the above-mentioned hydroxyl acrylic emulsion of the present invention can toast
Solidification can also be from solidization, and introduces epoxy functionality, the patience of resin is greatly improved, especially suitable for aluminium
On, its VOC content is extremely low (<0.1), and it is formed by hardness of film (2H), flexibility and improves for weatherability (>1000 hours),
Alternative traditional solvent based coating.
Specific embodiment
In the following, being described further in conjunction with specific embodiment to the present invention:
In the present invention, if not refering in particular to, all parts, percentage are unit of weight, used equipment and raw material etc.
It is commercially available or commonly used in the art.Method in following embodiments is unless otherwise instructed the normal of this field
Rule method.
A kind of hydroxyl acrylic emulsion with core-shell structure, it is in following five kinds of vinyl monomers in initiator and emulsification
In the presence of agent, made of emulsion polymerization, the dosage of the type of monomer and each monomer percentage shared in monomer total amount is such as
Under: vinyl monomer 40-65% 1., without other functional functional groups；2., the vinyl monomer 5-30% of hydroxyl；3., contain
The vinyl monomer 2-5% of epoxy group；4., carboxylic vinyl monomer 1-7%；5., contain polyfunctionality (>=2) vinyl monomer 1-
3%；Preferably, following monomer dosages percentage shared in monomer total amount is preferred are as follows: the vinyl monomer of hydroxyl 2. 10-
20%；Vinyl monomer containing epoxy group 3. 3-5%；Carboxylic vinyl monomer 4. 1-2%；, contain polyfunctionality (>=2) alkenes
Monomer 5. 1-3%.
The initiator amount is the 0.2-1.5% of monomer total amount；The initiator is persulfate or azo chemical combination
It is any one or more than one in object；
The emulsifier is nonionic emulsifier, anionic and nonionic type emulsifier and anionic emulsifier, the use of three
Amount ratio is (1.0-1.5): (0.8-1.0): 0.3；The total dosage of emulsifier is the 1-5% of monomer total amount；The emulsifier right and wrong
Reaction of ionic type emulsifier, without APEO nonionic emulsifier, without APEO anionic and nonionic type emulsifier, anionic reactivity cream
Agent, alkylsulfonate, alkyl sulfate, three kinds or three kinds or more in alkylbenzene sulfonate, alkyl succinate.
The monomer be 1. (methyl) esters of acrylic acid class monomer, two kinds or two kinds in aromatic series vinyl monomer with
On；
2. the vinyl monomer of the hydroxyl is (methyl) hydroxy-ethyl acrylate, any in (methyl) hydroxypropyl acrylate
It is one or more kinds of.
3. the vinyl monomer containing epoxy group is (methyl) glycidyl acrylate, in allyl glycidyl ester
It is any one or more than one.
4. the carboxylic vinyl monomer is acrylic acid, methacrylic acid, butenoic acid, maleic acid, fumaric acid, itaconic acid
In any one or more than one.
5. the vinyl monomer containing polyfunctionality (>=2) is glycol diacrylate, 1,4-butanediol diacrylate
Ester, 1,6- hexanediyl ester, neopentylglycol diacrylate, trimethylolpropane trimethacrylate, ethoxyquin (N=
3,9,15,21) trimethylolpropane trimethacrylate, third aoxidizes appointing in (N=3,4,5) trimethylolpropane trimethacrylate
One or more than one kinds of meaning.
Its appearance is milky white sub-translucent blue light liquid, viscosity 100-2000mPa.s, solid content 42-44%, pH value
7.0-8.5,0.05-0.2 μm of partial size, volatile organic compounds VOC content < 0.1%, hydroxyl value 10-100mgKOH/g, storage
It deposits the phase 6 months or more.
The present invention also provides a kind of preparation methods of hydroxyl acrylic emulsion with core-shell structure as described above, first by
Stratum nucleare pre-emulsion is made in the partial monosomy and emulsifier for forming emulsion particle stratum nucleare, polymerize in the presence of initiator and stratum nucleare is made
Then lotion drops evenly shell mix monomer, polymerize in the presence of initiator, neutralized, and filtering, discharging are to have core
The hydroxyl acrylic emulsion of shell structure, the specific steps are as follows:
(1) preparation of stratum nucleare pre-emulsion: by partial monosomy 1., partial monosomy 4. and whole monomer 5., in emulsifier
Under the action of it is evenly dispersed in water, obtain stratum nucleare pre-emulsification monomer mixture；
(2) preparation of shell pre-emulsion: by remaining monomer 1., 4. and whole monomer 2., 3., in the work of emulsifier
Under it is evenly dispersed in water, obtain shell pre-emulsification monomer mixture；
(3) emulsifier and initiator are added in reaction medium water, are placed in 500ml flask and stir evenly, and heats up
To 75~80 DEG C, the stratum nucleare pre-emulsion of 1%-10% weight ratio is added dropwise, rotation speed maintains 100-300rpm, lasting to stir
0.5-1 hours, becomes blue phase to lotion, obtain seed emulsion；
(4) remaining stratum nucleare pre-emulsion and initiator solution, after being added dropwise, heat preservation 75~80 are then added dropwise into flask
DEG C, it maintains 0.5-1.0 hours；
(5) shell pre-emulsion and initiator solution are then added dropwise into flask, after dripping off, keeps the temperature 75-80 DEG C of maintenance
2.0-2.5 hour；
(6) 40 DEG C are cooled to, the ammonium hydroxide of 1.0-2.5g is blended into the lotion in flask until by the pH value of liquid in beaker
It is modulated to 7.5-8.0, filtering, discharging are the hydroxyl acrylic emulsion with core-shell structure.
The present invention also provides a kind of applications of hydroxyl acrylic emulsion with core-shell structure as described above, are applied to
Aluminium material surface decorative paint.
Embodiment 1-3
Formula is shown in Table 1
Table 1 is the composition and dosage of the required material of embodiment 1-3
Embodiment 1-3 synthesis technology:
Material (1) and 30% material (2) are added in 500ml four-hole boiling flask, 80 DEG C is warming up to, 10% material is added
(3) it obtains seed emulsion within polymerase 10 .5 hours, the mixed liquor of remaining material (2) Yu material (3) is then added dropwise in 1 hour, keep the temperature
0.5 hour, the mixed liquor of material (4) and material (5) is then added dropwise, drips off within 2 hours, drips off heat preservation 2 hours, be then cooled to 40
DEG C, material (6) are added and neutralize, stir evenly, filtering and discharging.
Comparative example
Comparative example 1 is the hydroxy acryl acid lotion that routinely prepared by emulsion polymerization technique with conventional emulsifier, and is not added
Enter the vinyl monomer containing polyfunctionality (>=2) and the acrylic monomers with epoxy group.
Table 2 is the composition and dosage of the required material of comparative example 1
Comparative example 2 is the hydroxy acryl acid resin prepared with solution polymerization process, and the propylene for having epoxy group is added
Acid monomers.
Table 3 is the composition and dosage of the required material of comparative example 2
In the following, the performance parameter of the comparing embodiment 1-3 and comparative example 1-2 hydroxyl acrylic emulsion being prepared is seen below
Table:
Table 4 is the performance parameter of the hydroxyl acrylic emulsion of embodiment 1-3 and comparative example 1-2
In the following, decorative paint is made in the obtained hydroxyl acrylic emulsion of above-described embodiment 1-3 and comparative example 1-2, apply
Material formula is as follows:
1. above-mentioned hydroxyl acrylic emulsion, dosage is 40-60 parts；
2. water cross-linking agent, dosage is 6-15 parts；
3. cosolvent, dosage is 0.1-0.5 parts
4. aqueous adhesive force promotor, dosage is 0.1-0.3 parts；
5. neutralizer, dosage is 0.1-0.4 parts；
6. catalyst, dosage is 0.2-0.6 parts；
7. titanium dioxide, R-902, dosage are 10-20 parts；
8. water, surplus；
The water cross-linking agent can be one of amino resins, watersoluble closed type isocyanates or two kinds of mixture,
It is preferred that the two mixture.
The catalyst can be p-methyl benzenesulfonic acid, dinonylnaphthalene disulfonic acid, phosphoric acid, dodecyl benzene sulfonic acid, two laurels
Sour dibutyl tin, zinc naphthenate etc..
The cosolvent can be ethylene glycol monobutyl ether, glycol monoethyl ether, n-butanol, isobutanol, propylene glycol monobutyl ether, two
One of ethylene glycol monobutyl ether or more than one, preferred propylene glycol monobutyl ether.
The aqueous adhesive force promotor can be the A-1600 of Foshan He Mu Si resin Co., Ltd.
The neutralizer can be ammonium hydroxide, N, N- dimethylethanolamine, diethanol amine, triethanolamine, 2- methyl 2- aminopropan
Alcohol, preferably N, N- dimethylethanolamine.
In the following, by its paint film property of the coating of the above-mentioned hydroxyl acrylic emulsion containing embodiment 1-3 and comparative example 1-2
It is tested, test result such as table 5:
The gloss of paint film is tested using 60 ° of Glossmeter of Guangzhou style up to Co., Ltd's production；
The method that paint film impact property presses GB/T 1732-1993, using BGD302 paint film shock-testing；
Film thickness presses original GB 1764-1979 method, is measured using 4500 type boomerang of QUANIX；
Hardness of paint film presses GB/T 6739-2006 method；It is tested using pencil hardness method；
Paint film corrosion resistance presses GB T1771-2007 method, using Heng Yu Instrument Ltd. HY-952A series salt water
The measurement of nanospray experiment machine；
Paint film adhesion is measured by GB/T 9286-1998 method.It is tested using cross-hatching；
The method of the wet attachment of paint film, using HWS12 type electric-heated thermostatic water bath, temperature is set as 100 DEG C and boils test board, then
It is tested with cross-hatching.
Table 5 is its paint film property of the coating of the hydroxyl acrylic emulsion containing embodiment 1-3 and comparative example 1-2
The result shows that: it is described containing hydroxyl acrylic emulsion coating produced by the present invention in hardness, flexibility, adhesive force and resistance to
In time property with it is almost the same in the performance of traditional solvent-borne hydroxy acryl acid resin coating, but in VOC emission, environmental protection
Aspect has huge advantage, and having compared with traditional hydroxy acryl acid emulsion coatings properties significantly improves.
6 curing agent of table/resin is with the influence for comparing hardness of paint film
| M (curing agent)/m (resin) | 1:2 | 1:3 | 1:4 |
| Pencil hardness >=H | 2H | 2H | H |
The result shows that: in above-mentioned hydroxy acrylic acid formulation for coating material, the additive amount of curing agent is bigger, the pencil hardness of paint film
It is bigger.
7 curing agent of table/resin is with the influence for comparing paint film water boiling resistance performance
| M (curing agent)/m (resin) | 1:2 | 1:3 | 1:4 |
| The water boiling resistance time/hour >= | 2 | 3 | 1 |
The result shows that: in above-mentioned hydroxy acrylic acid formulation for coating material, the additive amount of curing agent is bigger, paint film water boiling resistance when
Between it is longer, however, the excessive flexibility that will greatly affect paint film of the hardness of paint film, is unfavorable for the bending process of aluminium later period, makes
The quick-fried paint of bending part is detached from, and Comprehensive Experiment result: the preferred 1:3's of the mass ratio of curing agent and resin is advisable.
It will be apparent to those skilled in the art that can make various other according to the above description of the technical scheme and ideas
Corresponding change and deformation, and all these changes and deformation all should belong to the protection scope of the claims in the present invention
Within.
Claims (7)
1. a kind of preparation method of the hydroxyl acrylic emulsion with core-shell structure, which is characterized in that hydroxyl acrylic emulsion is
In following five kinds of vinyl monomers in the presence of initiator and emulsifier, made of emulsion polymerization, the type of monomer and each monomer
Dosage it is shared in monomer total amount percentage it is as follows: vinyl monomer 40- 1., without other functional functional groups
65%；2., the vinyl monomer 5-30% of hydroxyl；3., the vinyl monomer 2-5% containing epoxy group；4., carboxylic vinyl monomer 1-
7%；5., the vinyl monomer 1-3% containing polyfunctionality >=2；
5. the vinyl monomer containing polyfunctionality >=2 is glycol diacrylate, 1,4-butanediol diacrylate, 1,6-
Hexanediyl ester, neopentylglycol diacrylate, trimethylolpropane trimethacrylate, ethoxyquin trimethylolpropane
Triacrylate, any one or more than one in the third oxidation trimethylolpropane trimethacrylate；
The initiator amount is the 0.2-1.5% of monomer total amount；
The emulsifier is nonionic emulsifier, anionic and nonionic type emulsifier and anionic emulsifier, the amount ratio of three
Example is (1.0-1.5): (0.8-1.0): 0.3；The total dosage of emulsifier is the 1-5% of monomer total amount；
The above percentage is weight percentage；
First stratum nucleare pre-emulsion is made by the partial monosomy and emulsifier of formation emulsion particle stratum nucleare in hydroxyl acrylic emulsion, is drawing
Stratum nucleare lotion is made in polymerization in the presence of sending out agent, then drops evenly shell mix monomer, polymerize in the presence of initiator, in
With, filtering, discharging be with core-shell structure hydroxyl acrylic emulsion, the specific steps are as follows:
(1) preparation of stratum nucleare pre-emulsion: by partial monosomy 1., partial monosomy 4. and whole monomer 5., in the work of emulsifier
Under it is evenly dispersed in water, obtain stratum nucleare pre-emulsification monomer mixture；
(2) preparation of shell pre-emulsion: by remaining monomer 1., 4. and whole monomer 2., 3., under the action of emulsifier
It is evenly dispersed in water, obtain shell pre-emulsification monomer mixture；
(3) emulsifier and initiator are added in reaction medium water, are placed in 500ml flask and stir evenly, and is warming up to 75
~80 DEG C, the stratum nucleare pre-emulsion of 1%-10% weight ratio is added dropwise, rotation speed maintains 100-300rpm, persistently stirs 0.5-1
Hour, become blue phase to lotion, obtains seed emulsion；
(4) remaining stratum nucleare pre-emulsion and initiator solution are then added dropwise into flask, after being added dropwise, keeps the temperature 75~80 DEG C,
It maintains 0.5-1.0 hours；
(5) shell pre-emulsion and initiator solution are then added dropwise into flask, after dripping off, keeps the temperature 75-80 DEG C of maintenance 2.0-
2.5 hour；
(6) 40 DEG C are cooled to, the ammonium hydroxide of 1.0-2.5g is blended into the lotion in flask until the pH value of liquid in beaker is modulated
For 7.5-8.0, filtering, discharging are the hydroxyl acrylic emulsion with core-shell structure.
2. the preparation method of the hydroxyl acrylic emulsion according to claim 1 with core-shell structure, which is characterized in that institute
1. stating the vinyl monomer without other functional functional groups is (methyl) acrylic ester monomer, in aromatic series vinyl monomer
Two or more；
2. the vinyl monomer of the hydroxyl is (methyl) hydroxy-ethyl acrylate, any one in (methyl) hydroxypropyl acrylate
Or more than one.
3. the preparation method of the hydroxyl acrylic emulsion according to claim 1 with core-shell structure, which is characterized in that institute
State the vinyl monomer containing epoxy group 3. and be (methyl) glycidyl acrylate, in allyl glycidyl ester any one or
More than one.
4. the preparation method of the hydroxyl acrylic emulsion according to claim 1 with core-shell structure, which is characterized in that institute
State carboxylic vinyl monomer be 4. acrylic acid, it is methacrylic acid, butenoic acid, maleic acid, fumaric acid, any one in itaconic acid
Kind or more than one.
5. the preparation method of the hydroxyl acrylic emulsion according to claim 1 with core-shell structure, which is characterized in that institute
It states in hydroxyl acrylic emulsion, the initiator is any one or more than one in persulfate or azo compound；
The emulsifier be non-reaction of ionic type emulsifier, without APEO nonionic emulsifier, without APEO anionic and nonionic type emulsifier, yin
Reaction of ionic type emulsifier, alkylsulfonate, alkyl sulfate, alkylbenzene sulfonate, three kinds in alkyl succinate or
Three kinds of person or more.
6. the preparation method of the hydroxyl acrylic emulsion according to claim 1 with core-shell structure, which is characterized in that hydroxyl
The appearance of base acrylic emulsion is milky white sub-translucent blue light liquid, viscosity 100-2000mPa.s, solid content 42-44%, pH value
7.0-8.5,0.05-0.2 μm of partial size, volatile organic compounds VOC content < 0.1%, hydroxyl value is 10-100mgKOH/g, storage
It deposits the phase 6 months or more.
7. a kind of application of the hydroxyl acrylic emulsion with core-shell structure as described in claim 1, which is characterized in that application
In aluminium material surface decorative paint.
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| CN109929067B (en) * | 2017-12-16 | 2021-07-23 | 万华化学（宁波）有限公司 | Acrylate emulsion with core-shell structure and preparation method and application thereof |
| CN109810219A (en) * | 2019-01-28 | 2019-05-28 | 宝骏新兴建材（天津）有限公司 | Lotion and preparation method thereof based on hydroxy acrylate |
| CN109970905B (en) * | 2019-03-12 | 2021-07-13 | 中煤科工集团杭州研究院有限公司 | Water-based polymer emulsion for integrated ceiling finishing coating and preparation method thereof |
| CN110511388B (en) * | 2019-08-23 | 2021-04-27 | 湖北双键精细化工有限公司 | Modified hydroxyl acrylic emulsion for water-based metal decorating paint and preparation method thereof |
| CN111116831B (en) * | 2020-01-07 | 2022-08-23 | 黄禹 | Preparation method of hydroxyl acrylic emulsion |
| CN111807961B (en) * | 2020-07-17 | 2023-05-30 | 万华化学集团股份有限公司 | High-hydroxyl acrylic emulsion with quick drying and long pot life and synthesis method thereof |
| CN113956731B (en) * | 2021-11-22 | 2022-05-13 | 浙江优艺雅涂料有限公司 | Primer for aluminum plate curtain wall, preparation method of primer, composite paint for aluminum plate curtain wall and preparation method of aluminum plate curtain wall |
| CN114716696B (en) * | 2022-04-06 | 2023-04-25 | 深圳市德立新材料科技有限公司 | Core-shell resin material, preparation method thereof, water-based polymer coating, battery diaphragm and secondary battery |
| CN114591470A (en) * | 2022-04-13 | 2022-06-07 | 广东华润涂料有限公司 | Waterborne emulsion for woodware, preparation method thereof, coating composition and product |
| CN115010867B (en) * | 2022-07-12 | 2023-05-23 | 亚士生态工业(滁州)有限公司 | Water-based wood lacquer emulsion and preparation method thereof |
| CN115894774A (en) * | 2022-12-16 | 2023-04-04 | 嘉宝莉化工集团股份有限公司 | Bio-based hydroxyl polyacrylate emulsion and preparation method and application thereof |
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