CN110172121A - A kind of water soluble acrylic acid ontology matting resin and preparation method thereof - Google Patents
A kind of water soluble acrylic acid ontology matting resin and preparation method thereof Download PDFInfo
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- CN110172121A CN110172121A CN201910447554.9A CN201910447554A CN110172121A CN 110172121 A CN110172121 A CN 110172121A CN 201910447554 A CN201910447554 A CN 201910447554A CN 110172121 A CN110172121 A CN 110172121A
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- acrylic acid
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- C—CHEMISTRY; METALLURGY
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- 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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- 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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- 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
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/068—Copolymers with monomers not covered by C09D133/06 containing glycidyl groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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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- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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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
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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
- C08F220/1812—C12-(meth)acrylate, e.g. lauryl (meth)acrylate
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Abstract
The invention discloses a kind of water soluble acrylic acid ontology matting resins and preparation method thereof, by using seeded emulsion polymerization and multi-stage emulsion polymerization technology collective effect, using multi-ethylenical unsaturation acrylate as crosslinking agent, stable water-based acrylic resin of the average grain diameter in 0.5~20 micron range is prepared.Resin larger particles in film forming procedure be neatly closely arranged in surface of the paint film formed it is micro-coarse structured, thus make resin body generate extinction effect.Water soluble acrylic acid ontology matting resin prepared by the present invention has the features such as hardness is high, and sense of touch is good, and scratch resistance, water resistance and thermal stability are good, and surface gloss is low.
Description
Technical field
The invention belongs to water paint field, in particular to a kind of water soluble acrylic acid ontology matting resin and its preparation side
Method.
Technical background
Matting resin, be exactly paint film surface gloss it is very low, be that our sense organ is formed by a kind of subjective impression.Essence
Really say, when a branch of light source (sunlight, light etc.) is radiated on paint film at an angle, most incident rays according to
Absorption, refraction, scattering etc. mainly has occurred in surface of the paint film characteristic, and only few some light is reflected away to be received by human eye,
People, which go out this paint film further according to subjective judgement, has extinction effect.Researchers are also according to experience, by different gloss
Intensity is divided into bloom (90 ° of gloss >), semi-matte (60 ° of 90 ° >=glossiness >), dumb light (30 ° of 60 ° >=glossiness >), eggshell
Light (6 ° of 30 ° >=glossiness >) and zero diopter (6 ° >=glossiness >=0 °) this Series grades.And " matting resin " mentioned here
From the point of view of specific gloss value, refer to surface gloss≤30 ° of the resin after film-forming, that is, includes the model of egg-shell gloss and zero diopter
Farmland.
In large quantities studies have shown that light reflected intensity depends on the flatness of body surface.Such as mirror, it is known that its
Surface is very moist, high to light reflectance, has high gloss.On the contrary, the surface of the paint film of micro-rough dissipates
Light is penetrated, repellel small part light, realizing has the appearance of extinction effect.According to this experience, researcher passes through various
Approach constructs coarse surface of the paint film to realize good extinction effect.Initial people are polished or are manually etched smooth using tool
Extinction effect is realized on the surface of paint film, and this method undoubtedly will lead to cost substantial increase, cumbersome and time consuming；Then study again
Pigments and fillers are added in various coating out or special delustering agent realizes the micro- coarse delustring of surface of the paint film.
Chinese patent CN103613702A discloses a kind of water-soluble multifunctional acrylic matting resin and preparation method thereof, adopts
It uses improved silica and the poly- methyl carbamide resin of organic thermosetting property as additional delustering agent, has obtained that there is flatting efficiency height, it is resistance to
It is aqueous, resistance to acid and alkali water-soluble multifunctional acrylic matting resin outstanding.But this method and process step is various, delustering agent and tree
Rouge ontology poor compatibility, the problems such as being easy to produce flocculation, precipitate.With making rapid progress for science and technology, led in photocureable coating
Domain, researchers develop using dual UV-curing technology, use low-energy light first, make it that can only radiate paint film table
Face generates fold, then it is fully cured using high-energy light irradiation paint film, and film formation surface reaches delustring because generating fold
Purpose.But this technology needs specific solidification equipment, and is only applicable to the acrylic monomer raw material of light sensitivity, raw material sources
It is limited.In art of powder coatings, researchers utilize the powdex blending extrusion with different hydroxyl values or acid value, have obtained powder
The ontology matting resin of last type.Chinese patent CN101735543A discloses a kind of preparation side of multifunctional acrylic matting resin
Method, the present invention passes through the matting resin homopolymer of synthesis low molecular weight first, then shrinks with hydroxyalkyl amide or isocyanuric acid three
Glyceride blending grinds to obtain.But this method is only applicable to the preparation of powdery paints, and solid content is 100%, raw material at
This is excessively high.In water paint field, researchers' discovery keeps generation partial size micro- in 0.5-20 by the partial size of control lotion synthesis
Latex particle in rice range, particle is arranged closely in surface of the paint film after film forming, forms micro-rough table after film curing is dry
Face and reach extinction effect.Chinese patent CN104974324A provide a kind of reaction from extinction type waterborne polyurethane resin and its
Preparation method, by being chemically reacted simultaneously using two kinds of hydrophilic chain extenders of sulfonic acid type-carboxylic acid type, to synthesis emulsion particle diameter into
Row control, has obtained the aqueous polyurethane of one-component from matting resin, glossiness is low, and synthesis technology is simple, but hardness of paint film
Not enough, it easily scratches, water resistance and thermal stability are poor.
Summary of the invention
The shortcomings that in order to overcome above-mentioned technology and deficiency, the primary purpose of the present invention is that providing a kind of water soluble acrylic acid sheet
Body matting resin.Extinction effect caused by the resin forms micro-coarse structured cause in film-forming rear surface by resin itself
's.Paint film has the features such as hardness is high, and sense of touch is good, and scratch resistance, water resistance and thermal stability are good, and lustrous surface is low.
Another object of the present invention is to provide a kind of preparation methods of above-mentioned water soluble acrylic acid ontology matting resin.The system
Preparation Method realizes emulsion particle diameter control in 0.5- by using seeded emulsion polymerization and multi-stage emulsion polymerization technology collective effect
20 microns of scope, the particle of larger particle is arranged closely in surface of the paint film and forms micro-rough structure in film forming procedure, from
And generate extinction effect.
In order to achieve the above technical purposes, the present invention is realized especially by following technical scheme:
A kind of water soluble acrylic acid ontology matting resin, includes following components according to mass parts:
1) seeded emulsion polymerization: 4~10 parts of I class of Mono-olefinic unsaturation acrylate, multi-ethylenical unsaturation acrylic acid
0.4~2 part of ester, 0.02-0.1 parts of initiator, 0.1-0.3 parts of emulsifier, 50-100 parts of deionized water；
2) level-one emulsion polymerization: 20~50 parts of I class of Mono-olefinic unsaturation acrylate, multi-ethylenical unsaturation acrylic acid
2~10 parts of ester, 0.1-0.5 parts of initiator, 50-150 parts of deionized water；
3) second level emulsion polymerization: 0.1-1 parts of I class of Mono-olefinic unsaturation acrylate, Mono-olefinic unsaturation acrylic acid
5-10 parts, 0.1-0.2 parts of initiator of II class of ester.
I class of Mono-olefinic unsaturation acrylate is selected from methyl acrylate, ethyl acrylate, the positive fourth of acrylic acid
One of ester, isobutyl acrylate, n-octyl, lauryl acrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate or
It is a variety of.
The multi-ethylenical unsaturation acrylate is selected from allyl acrylate, allyl methacrylate, cinnamic acid
One of allyl ester is a variety of.
The initiator is selected from one of ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate, it is preferred that the initiation
Agent is ammonium persulfate.
The emulsifier is selected from dodecyl sodium sulfate, neopelex, and one in lauryl sodium sulfate
Kind, it is preferred that the emulsifier is dodecyl sodium sulfate.
II class of Mono-olefinic unsaturation acrylate is selected from Tert-butyl Methacrylate, methacrylic acid isoborneol
One of ester, methyl methacrylate, ethyl methacrylate, glycidyl methacrylate are a variety of.
The glass transition temperature of I class of Mono-olefinic unsaturation acrylate should control within the scope of -70~50 DEG C, institute
The glass transition temperature for II class of Mono-olefinic unsaturation acrylate stated should control within the scope of -20~150 DEG C.
Can be added as needed pigment, dyestuff, crosslinking agent, each analog assistant etc. of matting resin of the present invention are adjusted
Section, advanced optimizes the performance of film.
The solid content of matting resin of the present invention is preferably between 20~40%, more preferably between 25~30%.
A kind of emulsion particle diameter of water soluble acrylic acid ontology matting resin of the present invention be preferably 0.5~20 micron it
Between, more preferably between 0.5~10 micron.
In another aspect of this invention, the preparation method of the water soluble acrylic acid ontology matting resin is provided, including
Following steps:
1) water soluble acrylic acid seed emulsion is prepared
In a nitrogen environment, monomer needed for seed emulsion is added in reactor, in the revolving speed of 500~2000r/min
10~30min of lower stirring, reduction revolving speed to 200~300r/min, then initiator is added dropwise dropwise and is controlled in 30~60min drop
It is complete, obtain water soluble acrylic acid seed emulsion；
2) level-one emulsion polymer is prepared
Deionized water is added into seed emulsion, monomer needed for being respectively dropped into level-one emulsion polymerization and initiator, and control
It is dripped off in 30~60min, level-one emulsion polymer is made；
3) second level emulsion polymer is prepared
It is respectively dropped into monomer and initiator needed for secondary polymerization into level-one emulsion polymer, and controls in 30~60min
It inside drips off, 1~2h of insulation reaction, cooling discharging is up to water soluble acrylic acid ontology matting resin.
The invention has the benefit that
(1) a kind of water soluble acrylic acid ontology matting resin that the present invention prepares, extinction effect is by resin body
Micro-rough structure is formed in film forming rear surface and is generated, and thoroughly solves past water soluble acrylic acid delustring from essential technique
Resin system needs the problem of additional delustering agent, can greatly reduce production cost.
(2) preparation process of the present invention controls the glass transition temperature of polymer by the ratio between soft or hard monomer；Pass through
Reasonable hydroxy radical content is designed, to provide suitable hydroxyl value；By introducing the unsaturated acrylate monomer of multi-ethylenical, to increase
Add crosslink density and hardness of paint film；Stablized and with preparing with larger grain by seeded emulsion polymerization and multi-stage emulsion polymerization technology
The lotion of diameter；By Molecular Design, the aqueous acrylic emulsion of synthesis is made to have hardness high, sense of touch is good, scratch resistance, resistance to
The features such as aqueous and thermal stability is good, and lustrous surface is low.
(3) a kind of water soluble acrylic acid ontology matting resin that the present invention prepares, preparation method are simply controllable.It compares
Have from matting resin that cost of material is low, source is wide in the aqueous polyurethane of one-component, experimental repeatability is good, the cream being prepared
The features such as liquid is more stable.
Specific embodiment
Below in conjunction with specific embodiment of the present invention, technical solution of the present invention is clearly and completely described, is shown
So, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the reality in the present invention
Example is applied, every other embodiment obtained by those of ordinary skill in the art without making creative efforts all belongs to
In the scope of protection of the invention.
The present invention utilizes seeded emulsion polymerization and multi-stage emulsion polymerization technology, prepares average grain diameter at 0.5~20 micron
Between emulsion particle.In film forming procedure, larger particles particle mutually melts lotion at surface of the paint film proper alignment, particle edge
It closes, but still remains the spherical morphology of particle, formation surface of the paint film is micro-coarse structured, to realize the purpose of delustring.Using kind
Sub- emulsion polymerization is to provide good polymeric rings to obtain stable emulsion particle early period for the reaction of later period multi-stage emulsion polymerization
Border.Using multi-ethylenical unsaturation acrylate, makes it after level-one emulsion polymerization, still retain double bond, it is poly- as second level lotion
The crosslinking points of conjunction, are polymerize once again, to increase emulsion particle diameter, obtain stable water-and acrylate ontology matting resin.
Embodiment 1
A kind of preparation method of water soluble acrylic acid ontology matting resin, comprising the following steps:
1) it prepares water soluble acrylic acid seed emulsion: deionized water 50ml and emulsifier dodecyl being added into reaction vessel
Sodium sulphate 0.15g is heated with stirring to 60~80 DEG C of constant temperature and stablizes.Air is substituted with nitrogen in reactor.It will be needed for seed emulsion
Monomer (10g butyl acrylate and 0.5g allyl methacrylate) is added in reactor, and 500~2000r/min's
10~30min is vigorously stirred under revolving speed.Revolving speed is reduced to drip dropwise to 200~300r/min, then by initiator ammonium persulfate 0.1g
Adduction control is dripped off in 30~60min.Lotion obtains water soluble acrylic acid seed emulsion in shallow white, blueing light.
2) it prepares level-one emulsion polymer: deionized water 50ml being added in Xiang Shangshu seed emulsion, then is respectively dropped into level-one
Monomer (30g butyl acrylate and 1.5g allyl methacrylate) needed for polymerizeing and initiator ammonium persulfate 0.2g, and control
It is dripped off in 30~60min.Lotion is creamy white, and obtains level-one emulsion polymer.
3) it prepares second level emulsion polymer: being respectively dropped into monomer needed for secondary polymerization in Xiang Shangshu level-one emulsion polymer
(0.5g ethyl acrylate and 9.5g Tert-butyl Methacrylate) and initiator ammonium persulfate 0.1g, and control in 30~60min
Inside drip off.A small amount of initiator 0.05g is added, 1~2h of insulation reaction, cooling discharging is up to water soluble acrylic acid ontology matting resin.
Embodiment 2
A kind of preparation method of water soluble acrylic acid ontology matting resin, comprising the following steps:
1) it prepares water soluble acrylic acid seed emulsion: deionized water 50ml and emulsifier dodecyl being added into reaction vessel
Sodium sulfonate 0.15g is heated with stirring to 60~80 DEG C of constant temperature and stablizes.Air is substituted with nitrogen in reactor.It will be needed for seed emulsion
Monomer (8g ethyl acrylate, 0.5g allyl methacrylate and 2g hydroxypropyl acrylate) is added in reactor, and 500
10~30min is vigorously stirred under the revolving speed of~2000r/min.Revolving speed is reduced to 200~300r/min, then by initiator persulfuric acid
Potassium 0.1g is added dropwise dropwise and controls and drips off in 30~60min.Lotion obtains water soluble acrylic acid seed in shallow white, blueing light
Lotion.
2) it prepares level-one emulsion polymer: deionized water 50ml being added in Xiang Shangshu seed emulsion, then is respectively dropped into level-one
Monomer (30g ethyl acrylate, 1.5g allyl methacrylate and 2g hydroxypropyl acrylate) needed for polymerizeing and initiator over cure
Sour potassium 0.2g, and control and dripped off in 30~60min.Lotion is creamy white, and obtains level-one emulsion polymer.
3) it prepares second level emulsion polymer: being respectively dropped into monomer needed for secondary polymerization in Xiang Shangshu level-one emulsion polymer
(0.5g ethyl acrylate and 10g isobornyl methacrylate) and initiator potassium persulfate 0.1g, and control in 30~60min
Inside drip off.A small amount of initiator 0.05g is added, 1~2h of insulation reaction, cooling discharging is up to water soluble acrylic acid ontology matting resin.
Embodiment 3
A kind of preparation method of water soluble acrylic acid ontology matting resin, comprising the following steps:
1) it prepares water soluble acrylic acid seed emulsion: deionized water 40ml and emulsifier dodecyl being added into reaction vessel
Sodium sulphate 0.15g is heated with stirring to 60~80 DEG C of constant temperature and stablizes.Air is substituted with nitrogen in reactor.It will be needed for seed emulsion
Monomer (10g n-butyl acrylate and 0.5g allyl acrylate) is added in reactor, and is turned in 500~2000r/min
10~30min is vigorously stirred under speed.Revolving speed is reduced to be added dropwise dropwise to 200~300r/min, then by initiator ammonium persulfate 0.05g
And it controls and is dripped off in 30~60min.Lotion obtains water soluble acrylic acid seed emulsion in shallow white, blueing light.
2) it prepares level-one emulsion polymer: deionized water 70ml being added in Xiang Shangshu seed emulsion, then is respectively dropped into level-one
Monomer (20g n-butyl acrylate, 2.5g allyl acrylate, 10g ethyl acrylate) needed for polymerizeing and initiator ammonium persulfate
0.2g, and control and dripped off in 30~60min.Lotion is creamy white, and obtains level-one emulsion polymer.
3) it prepares second level emulsion polymer: being respectively dropped into monomer needed for secondary polymerization in Xiang Shangshu level-one emulsion polymer
(0.5g n-butyl acrylate and 9.5g methyl methacrylate) and initiator ammonium persulfate 0.15g, and control in 30~60min
Inside drip off.A small amount of initiator 0.05g is added, 1~2h of insulation reaction, cooling discharging is up to water soluble acrylic acid ontology matting resin.
Embodiment 4
A kind of preparation method of water soluble acrylic acid ontology matting resin, comprising the following steps:
1) it prepares water soluble acrylic acid seed emulsion: deionized water 80ml and emulsifier dodecyl being added into reaction vessel
Benzene sulfonic acid sodium salt 0.2g is heated with stirring to 60~80 DEG C of constant temperature and stablizes.Air is substituted with nitrogen in reactor.It will be needed for seed emulsion
Monomer (9g lauryl acrylate and 1.0g allyl cinnamate) is added in reactor, and in the revolving speed of 500~2000r/min
Under be vigorously stirred 10~30min.Revolving speed is reduced to be added dropwise dropwise simultaneously to 200~300r/min, then by initiator sodium peroxydisulfate 0.15g
Control is dripped off in 30~60min.Lotion obtains water soluble acrylic acid seed emulsion in shallow white, blueing light.
2) it prepares level-one emulsion polymer: deionized water 50ml being added in Xiang Shangshu seed emulsion, then is respectively dropped into level-one
Monomer (20g lauryl acrylate, 1.5g allyl cinnamate, 10g hydroxypropyl acrylate) needed for polymerizeing and initiator persulfuric acid
Sodium 0.2g, and control and dripped off in 30~60min.Lotion is creamy white, and obtains level-one emulsion polymer.
3) it prepares second level emulsion polymer: being respectively dropped into monomer needed for secondary polymerization in Xiang Shangshu level-one emulsion polymer
(0.5g methyl acrylate and 9.5g glycidyl methacrylate) and initiator sodium peroxydisulfate 0.1g, and control 30~
It is dripped off in 60min.A small amount of initiator 0.05g is added, 1~2h of insulation reaction, cooling discharging is up to water soluble acrylic acid ontology delustring
Resin.
Embodiment 5
A kind of preparation method of water soluble acrylic acid ontology matting resin, comprising the following steps:
1) it prepares water soluble acrylic acid seed emulsion: deionized water 80ml and emulsifier dodecyl being added into reaction vessel
Sodium sulfonate 0.2g is heated with stirring to 60~80 DEG C of constant temperature and stablizes.Air is substituted with nitrogen in reactor.It will be single needed for seed emulsion
Body (9g isobutyl acrylate and 1.0g allyl methacrylate) is added in reactor, and is turned in 500~2000r/min
10~30min is vigorously stirred under speed.Revolving speed is reduced to be added dropwise dropwise to 200~300r/min, then by initiator sodium peroxydisulfate 0.15g
And it controls and is dripped off in 30~60min.Lotion obtains water soluble acrylic acid seed emulsion in shallow white, blueing light.
2) it prepares level-one emulsion polymer: deionized water 50ml being added in Xiang Shangshu seed emulsion, then is respectively dropped into level-one
Monomer (30g isobutyl acrylate and 1.5g methylpropanoic acid allyl ester) needed for polymerizeing and initiator sodium peroxydisulfate 0.2g, and control
It is dripped off in 30~60min.Lotion is creamy white, and obtains level-one emulsion polymer.
3) it prepares second level emulsion polymer: being respectively dropped into monomer needed for secondary polymerization in Xiang Shangshu level-one emulsion polymer
(0.5g isobutyl acrylate and 15g ethyl methacrylate) and initiator sodium peroxydisulfate 0.1g, and control in 30~60min
It drips off.A small amount of initiator 0.05g is added, 1~2h of insulation reaction, cooling discharging is up to water soluble acrylic acid ontology matting resin.
Embodiment 6
The water soluble acrylic acid ontology matting resin of embodiment 1-5 is placed in glassware and is spontaneously dried 3 days, then at 50 DEG C
Vacuum drying oven in it is dry for 24 hours.Film performance is as shown in table 1:
1 water soluble acrylic acid ontology matting resin film performance of table
As shown in Table 1, the embodiment of the present invention 1-5 has excellent low gloss effect, and gloss value is at 5 ° or less.This master
If because preparing emulsion-stabilizing, and average grain diameter is again 0.5 by using seeded emulsion polymerization and multi-stage polymerization techniques
Emulsion particle between~20 microns.During emulsion film forming, larger particles particle is on surface of the paint film proper alignment, particle side
Edge mutually merges, but still remains the spherical morphology of particle, and formation surface of the paint film is micro-coarse structured, to realize the mesh of delustring
's.Again due to there is the introducing of multi-ethylenical unsaturation acrylate monomer in monomer polymerization, it is close to substantially increase molecule cross-link
Degree and network structure make water soluble acrylic acid ontology matting resin prepared by the present invention have excellent impact resistance, water resistance, resistance to
The performances such as acid-base property, scratch-resistant.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understand without departing from the principles and spirit of the present invention can to these examples carry out it is a variety of variation, modification, replacement and
Modification, the scope of the present invention is defined by the appended.
Claims (10)
1. a kind of water soluble acrylic acid ontology matting resin, which is characterized in that according to mass parts include following components:
1) seeded emulsion polymerization: 4~10 parts of I class of Mono-olefinic unsaturation acrylate, multi-ethylenical unsaturation acrylate 0.4
~2 parts, 0.02-0.1 parts of initiator, 0.1-0.3 parts of emulsifier, 50-100 parts of deionized water；
2) level-one emulsion polymerization: 20~50 parts of I class of Mono-olefinic unsaturation acrylate, multi-ethylenical unsaturation acrylate 2
~10 parts, 0.1-0.5 parts of initiator, 50-150 parts of deionized water；
3) second level emulsion polymerization: 0.1-1 parts of I class of Mono-olefinic unsaturation acrylate, Mono-olefinic unsaturation acrylate II
5-10 parts of class, 0.1-0.2 parts of initiator.
2. a kind of water soluble acrylic acid ontology matting resin according to claim 1, which is characterized in that the Mono-olefinic
Unsaturated I class of acrylate is being selected from methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid just
One of monooctyl ester, lauryl acrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate are a variety of.
3. a kind of water soluble acrylic acid ontology matting resin according to claim 1, which is characterized in that the multi-ethylenical
Unsaturated acrylate is selected from allyl acrylate, allyl methacrylate, one of allyl cinnamate or a variety of.
4. a kind of water soluble acrylic acid ontology matting resin according to claim 1, which is characterized in that the initiator choosing
From one of ammonium persulfate, potassium peroxydisulfate or sodium peroxydisulfate.
5. a kind of water soluble acrylic acid ontology matting resin according to claim 1, which is characterized in that the emulsifier choosing
From dodecyl sodium sulfate, neopelex, one of lauryl sodium sulfate.
6. a kind of water soluble acrylic acid ontology matting resin according to claim 1, which is characterized in that the Mono-olefinic
Unsaturated II class of acrylate is selected from Tert-butyl Methacrylate, isobornyl methacrylate, methyl methacrylate, methyl
One of ethyl acrylate, glycidyl methacrylate are a variety of.
7. a kind of water soluble acrylic acid ontology matting resin according to claim 1, which is characterized in that the Mono-olefinic
The glass transition temperature of unsaturated I class of acrylate should control within the scope of -70~50 DEG C, the Mono-olefinic unsaturation propylene
The glass transition temperature of II class of acid esters should control within the scope of -20~150 DEG C.
8. a kind of water soluble acrylic acid ontology matting resin according to claim 1, which is characterized in that the matting resin
Solid content between 20~40%.
9. a kind of water soluble acrylic acid ontology matting resin according to claim 1, which is characterized in that the matting resin
Emulsion particle diameter between 0.5~20 micron.
10. the preparation method of water soluble acrylic acid ontology matting resin described in claim 1, which is characterized in that including following step
It is rapid:
1) water soluble acrylic acid seed emulsion is prepared
In a nitrogen environment, monomer needed for seed emulsion is added in reactor, is stirred under the revolving speed of 500~2000r/min
10~30min, reduction revolving speed to 200~300r/min are mixed, then initiator is added dropwise dropwise and is controlled and is dripped off in 30~60min,
Obtain water soluble acrylic acid seed emulsion；
2) level-one emulsion polymer is prepared
Deionized water is added into seed emulsion, monomer needed for being respectively dropped into level-one emulsion polymerization and initiator, and control 30
It is dripped off in~60min, level-one emulsion polymer is made；
3) second level emulsion polymer is prepared
It is respectively dropped into monomer and initiator needed for secondary polymerization into level-one emulsion polymer, and controls and is dripped in 30~60min
Complete, 1~2h of insulation reaction, cooling discharging is up to water soluble acrylic acid ontology matting resin.
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| CN112266714A (en) * | 2020-10-29 | 2021-01-26 | 浩力森化学科技（江苏）有限公司 | Preparation method of epoxy modified super-matte acrylic coating |
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| CN112266714A (en) * | 2020-10-29 | 2021-01-26 | 浩力森化学科技（江苏）有限公司 | Preparation method of epoxy modified super-matte acrylic coating |
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