CN109762425A - A kind of acrylic emulsion and its preparation method and application with core-shell structure and high thixotropic - Google Patents

A kind of acrylic emulsion and its preparation method and application with core-shell structure and high thixotropic Download PDF

Info

Publication number
CN109762425A
CN109762425A CN201811627849.6A CN201811627849A CN109762425A CN 109762425 A CN109762425 A CN 109762425A CN 201811627849 A CN201811627849 A CN 201811627849A CN 109762425 A CN109762425 A CN 109762425A
Authority
CN
China
Prior art keywords
monomer
emulsion
acrylic emulsion
core
methacrylate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201811627849.6A
Other languages
Chinese (zh)
Inventor
隆美林
徐延明
王泽群
蒋红娟
陶威
林杨
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CHANGZHOU HUAKE RESIN Co Ltd
Original Assignee
CHANGZHOU HUAKE RESIN Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by CHANGZHOU HUAKE RESIN Co Ltd filed Critical CHANGZHOU HUAKE RESIN Co Ltd
Priority to CN201811627849.6A priority Critical patent/CN109762425A/en
Publication of CN109762425A publication Critical patent/CN109762425A/en
Pending legal-status Critical Current

Links

Landscapes

  • Graft Or Block Polymers (AREA)

Abstract

The present invention relates to a kind of acrylic emulsion with core-shell structure and high thixotropic and its preparation method and applications;The first step prepares stratum nucleare part by emulsion polymerization, does not contain carboxylic monomer in the monomer of use, contains a small amount of cross-linking monomer;Second step prepares shell by emulsion polymerization, into the reaction mixture of the first step, the monomer of second step and the mixture of initiator is added dropwise, the monomer of second step contains monomer and cross-linking monomer with carboxyl, after the reaction was completed, it is cooled to specific temperature, the PH that a certain amount of amine adjusts lotion is added, the acrylic emulsion with core-shell structure and high thixotropic can be obtained.Acrylic emulsion prepared by the present invention can be used in aluminum powder baking varnish coating, can be reduced using silver powder directing agent and thickener in Design of Coatings Formulation, improve the gloss and patience of paint film, reduce the cost of coating, improve the applicability and construction tolerance of formulation for coating material.

Description

A kind of acrylic emulsion and its preparation method and application with core-shell structure and high thixotropic
Technical field
The present invention relates to technical field of coatings more particularly to a kind of acrylic emulsions with core-shell structure and high thixotropic And its preparation method and application.
Background technique
Aluminium silver paint is a kind of industrial widely used coating, is that aluminium silver powder is dispersed in paint, allows paint after spraying Film has very strong metallic travel, and cardinal principle is that the aluminium silver powder of sheet aligns in film, and light shines It can be appreciated that the flash effect of metallic luster, changeable colors along with angle by various regular reflections, transmission or interference, last people afterwards. If it is desired that film has very strong metallic travel, it is necessary to which the aluminium silver powder of sheet is in paint film as many face small mirrors one Sample tiles to reflect external light.The aluminium powder of sheet inside paint film it is as much as possible in tiling posture can have it is stronger Flash effect, it is opposite if the aluminium powder of sheet be erect arrangement it is excessive if, aluminium silver paint paint film can be more dull and blacks.Cause This, coating selected by aluminium silver paint and formula just have the higher requirement of relative requirement.
Application number CN201310206750.X, entitled a kind of exterior wall metallic travel aqueous fluorocarbon coating and its system Preparation Method, the coating are made of following components and its weight percent: water 32~36%, fluorin modified crylic acid ester lotion 38~ 42%, pure acrylate lotion 4~6%, water aluminum-silver slurry 10~15%, hydroxyethylcellulose thickener 0.1~0.15%, aluminium Pigment directing agent A0.4~0.6%, aluminium pigment directing agent B0.2~0.3%, defoaming agent 0.4~0.5%, polycarboxylate sodium's dispersion Agent 0.2~0.3%, pH adjusting agent 0.1~0.2%, wetting agent 0.25~0.30%, hydrophobically-modified alkali swollen thickener 0.3~ 0.5%, polyurethane associative thickener 0.3~0.5%, polyether-polyurethane association type rheology modifier 0.2~0.3%, preservative 0.15~0.25%, mould inhibitor 0.3~0.4%, ethylene glycol 1.0~1.4%, coalescing agent 3.7~4.3% and adhesive force are promoted Agent 0.2~0.3%;Wherein, the water aluminum-silver slurry is starched using the flake aluminum effect pigment of silica coating, the aluminium The content of flake aluminum is 64~66% in powder effect pigment slurry, and solvent is water;The aluminium pigment directing agent A is oxirane ring The block copolymer polyether nonionic surfactant of Ethylene Oxide, the aluminium pigment directing agent B are fatty acid modified polyester-type Wetting agent, weight ratio 2:1.
The invention is in order to obtain good aluminium silver powder arrangement effect, and addition can enhance low-shear viscosity in aluminium silver paint Aluminium pigment directing agent A and aluminium pigment directing agent B adjusts the pseudoplastic behavior of aluminium silverware, to enhance the row of the aluminium silver powder tiling of sheet Column effect.But aluminium silver paint made of the invention still will appear aluminium when paint film is thicker when air humidity is big or spraying The case where silver powder dimness and nigrescence;In addition, some auxiliary agents additionally added can also reduce the gloss and patience of aluminium silver paint coating, increase Add the cost of formula.
Summary of the invention
The purpose of the present invention is overcoming the deficiencies of existing technologies, provide a kind of with core-shell structure and high thixotropic acrylic acid The preparation method and application of lotion.
Realizing the technical solution of the object of the invention is: a kind of system of the acrylic emulsion with core-shell structure and high thixotropic Method;The acrylic emulsion with core-shell structure and high thixotropic is obtained by following two steps:
Step 1, stratum nucleare pre-emulsion is prepared using monomer, emulsifier, deionized water, does not contain carboxyl list in the monomer of use Body contains a small amount of cross-linking monomer;Stratum nucleare pre-emulsion, which instills in initiator solution, causes emulsion polymerization;
By the nuclear layer monomer mixture of design flow, deionized water, emulsifier is added to the container, after nitrogen is bubbled 30 minutes, High-speed stirred (100-120rpm) disperses 30min, and stratum nucleare pre-emulsion is prepared.Deionized water and emulsification are added into reaction kettle Agent composition leads to nitrogen protection, is heated to after reaction temperature, and the initiator solution that design flow is added causes emulsion polymerization, Later slowly to the stratum nucleare pre-emulsion being added dropwise in reaction kettle, 120-150min is dripped off, and keeps the temperature 60min after dripping off.
The monomer that stratum nucleare pre-emulsion is prepared in step 1 described in above-mentioned technical proposal is vinylacetate, vinyl chloride, dichloro- Ethylene, methyl methacrylate, hydroxyethyl methacrylate, n-BMA, isooctyl methacrylate, methyl-prop Olefin(e) acid hydroxypropyl acrylate, octadecyl methacrylate, lauryl methacrylate, isobornyl methacrylate, metering system Sour dodecyl ester, styrene, acrylonitrile, acrylamide, N- methylol methacrylamide, N- n-butoxy methacryl Amine, N- isobutoxymethyl acrylamide, glycidyl methacrylate, dimethylaminoethyl methacrylate, methyl-prop Olefin(e) acid dimethylamino propyl ester, divinylbenzene, ethylene glycol dimethacrylate, 1,4-butanediol dimethylacrylate, 1, 6- hexanediol dimethacrylate, polyethylene glycol dimethacrylate, trimethylol-propane trimethacrylate, methyl Two or more in allyl acrylate, the part resin contain carboxylic monomer, and hydroxyl solid weight ratio is 1-3%, stratum nucleare The glass transition temperature of polymer is 20-50 DEG C.
Initiator described in above-mentioned technical proposal is potassium peroxydisulfate, and ammonium persulfate, one or more of sodium peroxydisulfate draws Sending out agent dosage is the 0.2-0.5% for preparing the monomer mass of shell pre-emulsion.
Emulsifier described in above-mentioned technical proposal is the mixing of anionic emulsifier and nonionic emulsifier, anionic The ratio of emulsifier and nonionic emulsifier is 3:1-1:1.
Temperature used by emulsion polymerization described in above-mentioned technical proposal is 75-95 DEG C, and specific reaction temperature is according to initiator Type and dosage determine.
Step 2, shell pre-emulsion is prepared using monomer, emulsifier and deionized water, the monomer of use contains with carboxyl Monomer and cross-linking monomer;To having instilled in the initiator solution of stratum nucleare pre-emulsion for step 1, the shell of a dropping step 2 is pre- Lotion carries out emulsion polymerization and obtains core-shell emulsion, after the reaction was completed, is cooled to design temperature, a certain amount of PH is added Regulator adjusts PH, obtains the acrylic emulsion with core-shell structure and high thixotropic.
By the shell monomers mixture of design flow, deionized water, emulsifier is added to the container, after nitrogen is bubbled 30 minutes, High-speed stirred (100-120rpm) disperses 30min, and shell pre-emulsion is prepared.The shell being prepared is added dropwise into reaction kettle Pre-emulsion drips off in 30-50min, after dripping off, keeps the temperature 1h.After cooling to design temperature, PH regulator, which is added, and can be obtained has Core-shell structure, the acrylic emulsion for thickening property certainly.
The monomer that shell pre-emulsion is prepared in step 2 described in above-mentioned technical proposal is vinylacetate, vinyl chloride, dichloro- Ethylene, methyl methacrylate, hydroxyethyl methacrylate, methacrylic acid, n-BMA, methacrylic acid are different Monooctyl ester, hydroxy propyl methacrylate, octadecyl methacrylate, lauryl methacrylate, methacrylic acid isoborneol The positive fourth oxygen of ester, lauryl methacrylate, styrene, acrylonitrile, acrylamide, N- methylol methacrylamide, N- Butylmethacrylamide, N- isobutoxymethyl acrylamide, glycidyl methacrylate, dimethylaminoethyl Ethyl ester, dimethylaminoethyl propyl ester, divinylbenzene, ethylene glycol dimethacrylate, 1,4-butanediol dimethyl Acrylate, 1,6-Hexanediol dimethacrylate, polyethylene glycol dimethacrylate, trimethylol propane trimethyl third Three kinds or more in olefin(e) acid ester, allyl methacrylate, which contains carboxylic monomer and carboxylic monomer, hydroxyl solid Weight ratio is 1-3%;Carboxyl solid weight ratio is 10-15%, and the glass transition temperature of sheath polymers is 5-40 DEG C.
Cross-linking monomer described in above-mentioned technical proposal is divinylbenzene, ethylene glycol dimethacrylate, 1,4-butanediol Dimethylacrylate, 1,6-Hexanediol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane tris Methacrylate, it is a kind of in allyl methacrylate.
Initiator described in above-mentioned technical proposal is potassium peroxydisulfate, and ammonium persulfate, one or more of sodium peroxydisulfate draws Sending out agent dosage is the 0.2-0.5% for preparing the monomer mass of shell pre-emulsion.
Emulsifier described in above-mentioned technical proposal is the mixing of anionic emulsifier and nonionic emulsifier, anionic The ratio of emulsifier and nonionic emulsifier is 3:1-1:1.
Temperature used by emulsion polymerization described in above-mentioned technical proposal is 75-95 DEG C, and specific reaction temperature is according to initiator Type and dosage determine.
PH regulator described in above-mentioned technical proposal is triethylamine, N, N- dimethylethanolamine, triethanolamine, one in ammonium hydroxide Kind, degree of neutralization 5-10%.
In step 1 described in above-mentioned technical proposal, the weight accounting of cross-linking monomer is 0.5-1.5%;In step 2, crosslinking is single The weight ratio of body is 1.0-2.0%.
The mass ratio of acrylic emulsion stratum nucleare and shell that above-mentioned technical proposal is prepared is 4:1-9:1, stratum nucleare polymerization The glass transition temperature of object is 20-50 DEG C, and the glass transition temperatures of sheath polymers is 5-40 DEG C, acrylic emulsion it is whole Body solid content is 25-50%.
The acrylic emulsion of above-mentioned technical proposal preparation can be to prepare aluminium silver baking vanish.
After adopting the above technical scheme, the present invention have the effect of it is following positive:
In the acrylic emulsion of preparation of the invention, contains hydrophobic stratum nucleare part and be wrapped in outer hydrophilic Stratum nucleare.The glass transition temperature of hydrophobicity stratum nucleare is higher, can promote coating rapid draing.Include inside hydrophilic shell Polymer chain containing a large amount of carboxyls adds after PH regulator adjusts, and is changed into carboxylate radical and band since carboxyl is neutralized Negative electrical charge is gone up, mutually exclusive between like charges and long-chain polymer is caused to extend in the water phase of lotion, emulsion particle Son is accumulated mutually and forms ordered structure, and the polymer of the shell of latex particle is mutually wound, to increase the viscous of lotion Degree, shows as the high viscosity under low sheraing;And when at lotion under high shear conditions, biggish shearing force destroys emulsion particle The ordered structure that son accumulation is formed, thus also can not mutually be wound between sheath polymers chain, thus low under showing high shear Viscosity.Appropriate crosslinking limits moveing freely for molecular resin chain in core-shell structure, improves the rigidity of latex particle, enhancing The quick-drying and thixotropy of lotion.Exactly there is quick-drying core high thixotropic, acrylic emulsion provided by the invention is very suitable Together in the matrix resin of aluminium silver paint.It can be reduced in Design of Coatings Formulation using silver powder directing agent and thickener, improve paint film Gloss and patience, reduce the cost of coating, improve formulation for coating material applicability and construction tolerance.The aluminium silver paint of production, aluminium Silver powder orientation is outstanding, and paint film silvery white is glittering, and the gloss of silver powder paint film itself is higher.
Specific embodiment
(embodiment 1)
The present embodiment is a kind of preparation side for acrylic emulsion with core-shell structure and high thixotropic that the present invention is shown Method is as follows:
(1) by 232g deionized water, round-bottomed bottle is added in 6g anionic emulsifier SDS, 3g nonionic emulsifier NP-10 In, 14g acrylamide, 158g methyl methacrylate, 56g butyl acrylate, 24g acrylic acid hydroxyl are continuously added after mixing evenly Ethyl ester, 2g allyl methacrylate, 0.4g ammonium persulfate, 1000rpm is dispersed with stirring half an hour under room temperature, and stratum nucleare is prepared The pre-emulsion of polymer;
(2) 397g deionized water is added into reaction flask, 0.2g SDS, 0.1g NP-10 stirs evenly dissolution, leads to nitrogen 30min is added the pre-emulsion 20g that the first step is prepared, is stirring evenly and then adding into and draws after being heated to 78-80 DEG C of holding stabilization Agent ammonium persulfate 0.4g is sent out, 15min is kept the temperature, after system has blue light in observing response bottle, continues the pre-emulsion that the first step is added dropwise, control Time processed in 100-120min, in 78-80 DEG C of heat preservation 60min after dripping off;
(3) by 80g deionized water, 1.6g SDS, 0.8g NP-10 is added in round-bottomed bottle, continuously adds after mixing evenly, 13g methyl methacrylate, 15g butyl acrylate, 4g hydroxy-ethyl acrylate, 12g methacrylic acid, 0.8g methacrylic acid alkene Propyl ester, 0.3g ammonium persulfate, 1000rpm is dispersed with stirring half an hour under room temperature, and the pre-emulsion of sheath polymers is prepared;
(4) sheath polymers that step 3 obtains are added dropwise to reaction flask, control dropping temperature is 78-80 DEG C, and time for adding exists 50-60min, after being added dropwise, reaction flask is warming up to 90-92 DEG C and keeps the temperature 1 hour, and reaction terminates.
(5) it cooling to 60 DEG C, 1.2g N is added, N- dimethylethanolamine stirs 30min, continue to cool to 40 DEG C, 300 The discharging of mesh sock filtration, can be obtained product.
The acrylic acid solid content is 29-31%, and viscosity is in 120-300cps, 50 DEG C of storages, 30 days stabilizations, hard resin acid Value is 24.6mg KOH/g, and hard resin hydroxy radical content is 1.2%, and the glass transition temperature of sheath polymers is 51 DEG C, shell The glass transition temperature of layer resin is 37 DEG C, and the mass ratio of nucleocapsid is 5.6:1.The acrylic emulsion and Qing Te company The amino resins such as Cmyel 303, Cymel325 cooperation system aluminium silver baking vanish, 140-150 DEG C of baking 20-30min can be complete White drying, silver powder orientation is outstanding, and paint film silvery white is glittering, is suitable as aluminium silver priming paint.
(embodiment 2)
The present embodiment is the acrylic acid with core-shell structure and high thixotropic for another different acidity that the present invention is shown The preparation method of lotion is as follows:
(1) by 232g deionized water, round-bottomed bottle is added in 6g anionic emulsifier SDS, 3g nonionic emulsifier NP-10 In, 14g acrylamide, 158g methyl methacrylate, 56g butyl acrylate, 24g acrylic acid hydroxyl are continuously added after mixing evenly Ethyl ester, 2.2g 1,6- hexanediyl ester, 0.4g ammonium persulfate, 1000rpm is dispersed with stirring half an hour under room temperature, prepares Obtain the pre-emulsion of stratum nucleare polymer;
(2) 397g deionized water is added into reaction flask, 0.2g SDS, 0.1g NP-10 stirs evenly dissolution, leads to nitrogen 30min is added the pre-emulsion 20g that the first step is prepared, is stirring evenly and then adding into and draws after being heated to 78-80 DEG C of holding stabilization Agent ammonium persulfate 0.4g is sent out, 15min is kept the temperature, after system has blue light in observing response bottle, continues the pre-emulsion that the first step is added dropwise, control Time processed in 100-120min, in 78-80 DEG C of heat preservation 60min after dripping off;
(3) by 80g deionized water, 1.6g SDS, 0.8g NP-10 is added in round-bottomed bottle, continuously adds after mixing evenly, 20g methyl methacrylate, 14g butyl acrylate, 4g hydroxy-ethyl acrylate, 6g methacrylic acid, 1g 1,6- hexylene glycol dipropyl Olefin(e) acid ester, 0.4g ammonium persulfate, 1000rpm is dispersed with stirring half an hour under room temperature, and the pre-emulsion of sheath polymers is prepared;
(4) sheath polymers that step 3 obtains are added dropwise to reaction flask, control dropping temperature is 78-80 DEG C, and time for adding exists 50-60min, after being added dropwise, reaction flask is warming up to 90-92 DEG C and keeps the temperature 1 hour, and reaction terminates.
(5) it cooling to 60 DEG C, 1.2g N is added, N- dimethylethanolamine stirs 30min, continue to cool to 40 DEG C, 300 The discharging of mesh sock filtration, can be obtained product.
The acrylic acid solid content is 29-31%, and viscosity is in 5-50cps, 50 DEG C of storages, 30 days stabilizations, hard resin acid value 12.3mg KOH/g, hard resin hydroxy radical content are 1.2%, and the glass transition temperature of sheath polymers is 51 DEG C, shell tree The glass transition temperature of rouge is 37 DEG C, and the mass ratio of nucleocapsid is 5.6:1.The Cmyel of the acrylic emulsion and Qing Te company The aluminium silver baking vanish of the cooperation system of the amino resins such as 303, Cymel325, can be completely dried in 140-150 DEG C of baking 20-30min, Silver powder orientation is outstanding, and paint film silvery white is glittering, is suitable as aluminium silver priming paint.And the viscosity of resin is lower, prepares the viscosity for claiming coating Also very low, it is suitble to some special construction sites.
(embodiment 3)
The present embodiment is the higher different acidity of another glossiness that the present invention is shown with core-shell structure and high thixotroping The preparation method of the acrylic emulsion of property is as follows:
(1) by 232g deionized water, 6g SDS, 3g NP-10 is added in round-bottomed bottle, continuously adds 14g third after mixing evenly Acrylamide, 88g methyl methacrylate, 70g styrene, 56g butyl acrylate, 24g hydroxy-ethyl acrylate, 2g Isosorbide-5-Nitrae-fourth two Alcohol diacrylate, 1000rpm is dispersed with stirring half an hour under room temperature, and the pre-emulsion of stratum nucleare polymer is prepared;
(2) 212g deionized water is added into reaction flask, 0.2g SDS, 0.1g NP-10 stirs evenly dissolution, leads to nitrogen 30min is added the pre-emulsion 20g that the first step is prepared, is stirring evenly and then adding into and draws after being heated to 78-80 DEG C of holding stabilization Agent ammonium persulfate 0.4g is sent out, 15min is kept the temperature, after system has blue light in observing response bottle, continues the pre-emulsion that the first step is added dropwise, control Time processed in 100-120min, in 78-80 DEG C of heat preservation 60min after dripping off;
(3) by 80g deionized water, 1.6g SDS, 0.8g NP-10 is added in round-bottomed bottle, continuously adds after mixing evenly, 20g styrene, 14g butyl acrylate, 4g hydroxy-ethyl acrylate, 6g methacrylic acid, 0.6g 1,4-butanediol diacrylate Ester, 1000rpm is dispersed with stirring half an hour under room temperature, and the pre-emulsion of sheath polymers is prepared;
(4) sheath polymers that step 3 obtains are added dropwise to reaction flask, control dropping temperature is 78-80 DEG C, and time for adding exists 50-60min, after being added dropwise, reaction flask is warming up to 90-92 DEG C and keeps the temperature 1 hour, and reaction terminates.
(5) it cooling to 60 DEG C, 1.2g N is added, N- dimethylethanolamine stirs 30min, continue to cool to 40 DEG C, 300 The discharging of mesh sock filtration, can be obtained product.
The acrylic acid solid content is 44-47%, and viscosity is in 50-150cps, 50 DEG C of storages, 30 days stabilizations, hard resin acid value For 12.3mg KOH/g, hard resin hydroxy radical content is 1.2%, and the glass transition temperature of sheath polymers is 51 DEG C, shell The glass transition temperature of resin is 37 DEG C, and the mass ratio of nucleocapsid is 5.6:1.In acrylic acid formula, styrene is increased Content increases the index of refraction of resin entirety.The Cmyel 303 of the acrylic emulsion and Qing Te company, Cymel325 etc. amino The aluminium silver baking vanish of resin complex, surface drying speed are exceedingly fast, and surface drying can be realized in 3-5min at room temperature.It is toasted at 140-150 DEG C 20-30min can be completely dried, and silver powder orientation is outstanding, and paint film silvery white is glittering, and the gloss of silver powder paint film itself is higher, is suitble to do Aluminium silver priming paint and paint for priming paint and top lacquer.
(embodiment 4)
The present embodiment is that the present invention shows the step of being applied to aluminium silver baking vanish of acrylic emulsion:
(1) aluminium silver powder JCS-110 (fine horse speeds) 12.5g, dispersant B YK 192 (Bi Ke chemistry) is added in high speed dispersion agent 0.8g adds suitable cosolvent butyl glycol ether and water, obtains aluminium paste after high speed dispersion;
(2) the aluminium paste 31.5g for obtaining the first step, acrylic emulsion 46g obtained in example 1, water-compatible amino resin Cymel 325 (cyanogen specialization) 3.7g, adds suitable defoaming agent, levelling agent, other auxiliary agents such as PH regulator are added appropriate Water be adjusted to working viscosity, aluminium silver baking vanish can be obtained;
(3) by obtained aluminium silver baking vanish in 150 DEG C of baking 20min, the aluminium silver paint core paint film property tested is as follows:
Test item As a result
Aluminium silver paint thixotropic index 7.7
Film thickness < 15um
Aluminium silver powder orientation Well, no floating, nigrescence phenomenon
Anti-sag, stream pendant No sag, stream pendant, paint film is smooth, and edge does not collect paint
Gloss 76 (20 °), 90 (60 °)
According to acrylic emulsion prepared by the present invention, viscosity is low, stable storing, and preparation method is simple, and thixotropy is strong, answers Used in aluminium silver baking vanish field, can to avoid using thickener and orientation auxiliary agent, improve the gloss and patience of paint film, reduce coating Cost, improve formulation for coating material applicability and construction tolerance.
Particular embodiments described above has carried out further in detail the purpose of the present invention, technical scheme and beneficial effects It describes in detail bright, it should be understood that the above is only a specific embodiment of the present invention, is not intended to restrict the invention, it is all Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention Within the scope of shield.

Claims (10)

1. a kind of preparation method of the acrylic emulsion with core-shell structure and high thixotropic;It is characterized in that, passing through following two steps Suddenly the acrylic emulsion with core-shell structure and high thixotropic is obtained:
Step 1, stratum nucleare pre-emulsion is prepared using monomer, emulsifier, deionized water, does not contain carboxylic monomer in the monomer of use, Contain a small amount of cross-linking monomer;Stratum nucleare pre-emulsion, which instills in initiator solution, causes emulsion polymerization.
Step 2, shell pre-emulsion is prepared using monomer, emulsifier and deionized water, the monomer of use contains the list with carboxyl Body and cross-linking monomer;To having instilled in the initiator solution of stratum nucleare pre-emulsion for step 1, the shell pre-emulsion of a dropping step 2 It carries out emulsion polymerization and obtains core-shell emulsion, after the reaction was completed, be cooled to design temperature, a certain amount of PH is added and adjusts Agent adjusts PH, obtains the acrylic emulsion with core-shell structure and high thixotropic.
2. a kind of preparation method of acrylic emulsion with core-shell structure and high thixotropic according to claim 1, feature Be: the monomer that stratum nucleare pre-emulsion is prepared in step 1 is vinylacetate, vinyl chloride, dichloro- ethylene, methyl methacrylate Ester, hydroxyethyl methacrylate, n-BMA, isooctyl methacrylate, hydroxy propyl methacrylate, methyl-prop Olefin(e) acid stearyl, lauryl methacrylate, isobornyl methacrylate, lauryl methacrylate, benzene second Alkene, acrylonitrile, acrylamide, N- methylol methacrylamide, N- n-butoxy methyl acrylamide, N- isobutoxymethyl Acrylamide, glycidyl methacrylate, dimethylaminoethyl methacrylate, dimethylaminoethyl propyl ester, Divinylbenzene, ethylene glycol dimethacrylate, 1,4-butanediol dimethylacrylate, 1,6- hexylene glycol dimethyl allene Acid esters, polyethylene glycol dimethacrylate, trimethylol-propane trimethacrylate, two in allyl methacrylate Kind is a variety of, which contains carboxylic monomer, and hydroxyl solid weight ratio is 1-3%.
3. a kind of preparation method of acrylic emulsion with core-shell structure and high thixotropic according to claim 1, feature Be: the monomer that shell pre-emulsion is prepared in step 2 is vinylacetate, vinyl chloride, dichloro- ethylene, methyl methacrylate Ester, hydroxyethyl methacrylate, methacrylic acid, n-BMA, isooctyl methacrylate, hydroxyethyl methacrylate Propyl ester, octadecyl methacrylate, lauryl methacrylate, isobornyl methacrylate, methacrylic acid 12 Arrcostab, styrene, acrylonitrile, acrylamide, N- methylol methacrylamide, N- n-butoxy methyl acrylamide, N- Isobutoxymethyl acrylamide, glycidyl methacrylate, dimethylaminoethyl methacrylate, methacrylic acid two Methylamino propyl ester, divinylbenzene, ethylene glycol dimethacrylate, 1,4-butanediol dimethylacrylate, 1,6- oneself two Alcohol dimethylacrylate, polyethylene glycol dimethacrylate, trimethylol-propane trimethacrylate, methacrylic acid Three kinds or more in allyl ester, which contains carboxylic monomer and carboxylic monomer, and hydroxyl solid weight ratio is 1-3%;Carboxylic Base solid weight ratio is 10-15%.
4. a kind of preparation method of acrylic emulsion with core-shell structure and high thixotropic according to claim 1, feature Be: in step 1, the weight accounting of cross-linking monomer is 0.5-1.5%;In step 2, the weight ratio of cross-linking monomer is 1.0- 2.0%.
5. a kind of preparation method of acrylic emulsion with core-shell structure and high thixotropic according to claim 4, feature Be: the cross-linking monomer be divinylbenzene, ethylene glycol dimethacrylate, 1,4-butanediol dimethylacrylate, 1,6-Hexanediol dimethacrylate, polyethylene glycol dimethacrylate, trimethylol-propane trimethacrylate, first It is a kind of in base allyl acrylate.
6. a kind of preparation method of acrylic emulsion with core-shell structure and high thixotropic according to claim 1, feature Be: the initiator is potassium peroxydisulfate, and ammonium persulfate, one or more of sodium peroxydisulfate, initiator amount is to prepare The 0.2-0.5% of the monomer mass of shell pre-emulsion.
7. a kind of preparation method of acrylic emulsion with core-shell structure and high thixotropic according to claim 1, feature Be: the PH regulator is triethylamine, N, one of N- dimethylethanolamine, triethanolamine, ammonium hydroxide, degree of neutralization 5- 10%.
8. a kind of preparation method of acrylic emulsion with core-shell structure and high thixotropic according to claim 1, feature Be: the emulsifier is the mixing of anionic emulsifier and nonionic emulsifier, anionic emulsifier and nonionic The ratio of type emulsifier is 3:1-1:1.
9. a kind of acrylic emulsion with core-shell structure and high thixotropic, it is characterised in that: such as any power in claim 1-8 The acrylic emulsion that benefit requires a kind of preparation method of acrylic emulsion with core-shell structure and high thixotropic to be prepared, The mass ratio of the acrylic emulsion stratum nucleare and shell is 4:1-9:1, and the glass transition temperature of stratum nucleare polymer is 20-50 DEG C, The glass transition temperature of sheath polymers is 5-40 DEG C, and the whole solid content of acrylic emulsion is 25-50%.
10. a kind of application of the acrylic emulsion with core-shell structure and high thixotropic, it is characterised in that: using such as claim A kind of preparation method of the acrylic emulsion with core-shell structure and high thixotropic described in any claim is prepared in 1-8 Acrylic emulsion prepares aluminium silver baking vanish.
CN201811627849.6A 2018-12-28 2018-12-28 A kind of acrylic emulsion and its preparation method and application with core-shell structure and high thixotropic Pending CN109762425A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811627849.6A CN109762425A (en) 2018-12-28 2018-12-28 A kind of acrylic emulsion and its preparation method and application with core-shell structure and high thixotropic

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811627849.6A CN109762425A (en) 2018-12-28 2018-12-28 A kind of acrylic emulsion and its preparation method and application with core-shell structure and high thixotropic

Publications (1)

Publication Number Publication Date
CN109762425A true CN109762425A (en) 2019-05-17

Family

ID=66452192

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811627849.6A Pending CN109762425A (en) 2018-12-28 2018-12-28 A kind of acrylic emulsion and its preparation method and application with core-shell structure and high thixotropic

Country Status (1)

Country Link
CN (1) CN109762425A (en)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110405200A (en) * 2019-06-18 2019-11-05 华南农业大学 A kind of yolk-eggshell structure noble metal@hollow Nano carbon balls composite material and preparation method and application
CN110885406A (en) * 2019-12-06 2020-03-17 万华化学(宁波)有限公司 Preparation method of acrylic emulsion, acrylic emulsion and application thereof
CN111019052A (en) * 2019-12-05 2020-04-17 上海金力泰化工股份有限公司 Low-thixotropic acrylic emulsion for water-based automobile paint and preparation method and application thereof
CN111848876A (en) * 2020-07-28 2020-10-30 万华化学集团股份有限公司 Preparation method of acrylic emulsion, prepared acrylic emulsion and application thereof
CN112063243A (en) * 2020-08-11 2020-12-11 擎天材料科技有限公司 Anti-sagging water-based varnish and preparation method and application thereof
CN112390913A (en) * 2020-10-15 2021-02-23 天津中油渤星工程科技有限公司 Self-healing material for well cementation and preparation method thereof
CN113583154A (en) * 2021-09-07 2021-11-02 河北工业大学 Preparation method of polyacrylate latex particles with large particle size
CN113980587A (en) * 2021-12-03 2022-01-28 深圳市科泰顺科技有限公司 Pure adhesive film with core-shell structure and preparation method thereof
CN114456670A (en) * 2021-03-02 2022-05-10 海南赛诺实业有限公司 Acrylic acid coating silicon oxide plating film and manufacturing method thereof
CN115093735A (en) * 2022-07-21 2022-09-23 安徽尚德轨道设备制造有限公司 Cold spray multi-element alloy anticorrosive material and preparation method thereof
CN115746651A (en) * 2022-11-08 2023-03-07 广东西顿新材料科技有限公司 Water-based acrylic resin for water-based single-component plastic silver paint and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005232297A (en) * 2004-02-19 2005-09-02 Mitsubishi Rayon Co Ltd Acrylic polymer fine particle and plastisol composition
CN101273103A (en) * 2005-07-27 2008-09-24 日本油漆株式会社 Water-based metallic coating composition and method of forming multilayered coating film
CN101283063A (en) * 2005-10-11 2008-10-08 关西涂料株式会社 Effect pigment-containing, water-borne base coating compositions
CN102604497A (en) * 2012-02-15 2012-07-25 上海天地涂料有限公司 Water-based metallic flashing paint and preparation method of the flashing paint
CN105670427A (en) * 2014-11-21 2016-06-15 沈阳顺风新城建筑材料有限公司 Metal flashing paint

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005232297A (en) * 2004-02-19 2005-09-02 Mitsubishi Rayon Co Ltd Acrylic polymer fine particle and plastisol composition
CN101273103A (en) * 2005-07-27 2008-09-24 日本油漆株式会社 Water-based metallic coating composition and method of forming multilayered coating film
CN101283063A (en) * 2005-10-11 2008-10-08 关西涂料株式会社 Effect pigment-containing, water-borne base coating compositions
CN102604497A (en) * 2012-02-15 2012-07-25 上海天地涂料有限公司 Water-based metallic flashing paint and preparation method of the flashing paint
CN105670427A (en) * 2014-11-21 2016-06-15 沈阳顺风新城建筑材料有限公司 Metal flashing paint

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110405200A (en) * 2019-06-18 2019-11-05 华南农业大学 A kind of yolk-eggshell structure noble metal@hollow Nano carbon balls composite material and preparation method and application
CN111019052A (en) * 2019-12-05 2020-04-17 上海金力泰化工股份有限公司 Low-thixotropic acrylic emulsion for water-based automobile paint and preparation method and application thereof
CN110885406A (en) * 2019-12-06 2020-03-17 万华化学(宁波)有限公司 Preparation method of acrylic emulsion, acrylic emulsion and application thereof
CN111848876B (en) * 2020-07-28 2022-07-12 万华化学集团股份有限公司 Preparation method of acrylic emulsion, prepared acrylic emulsion and application thereof
CN111848876A (en) * 2020-07-28 2020-10-30 万华化学集团股份有限公司 Preparation method of acrylic emulsion, prepared acrylic emulsion and application thereof
CN112063243A (en) * 2020-08-11 2020-12-11 擎天材料科技有限公司 Anti-sagging water-based varnish and preparation method and application thereof
CN112390913A (en) * 2020-10-15 2021-02-23 天津中油渤星工程科技有限公司 Self-healing material for well cementation and preparation method thereof
CN112390913B (en) * 2020-10-15 2023-03-07 天津中油渤星工程科技有限公司 Self-healing material for well cementation and preparation method thereof
CN114456670A (en) * 2021-03-02 2022-05-10 海南赛诺实业有限公司 Acrylic acid coating silicon oxide plating film and manufacturing method thereof
CN113583154A (en) * 2021-09-07 2021-11-02 河北工业大学 Preparation method of polyacrylate latex particles with large particle size
CN113980587A (en) * 2021-12-03 2022-01-28 深圳市科泰顺科技有限公司 Pure adhesive film with core-shell structure and preparation method thereof
CN113980587B (en) * 2021-12-03 2023-10-03 深圳市科泰顺科技有限公司 Pure adhesive film with core-shell structure and preparation method thereof
CN115093735A (en) * 2022-07-21 2022-09-23 安徽尚德轨道设备制造有限公司 Cold spray multi-element alloy anticorrosive material and preparation method thereof
CN115746651A (en) * 2022-11-08 2023-03-07 广东西顿新材料科技有限公司 Water-based acrylic resin for water-based single-component plastic silver paint and preparation method thereof
CN115746651B (en) * 2022-11-08 2024-03-19 广东西顿新材料科技有限公司 Water-based acrylic resin for water-based single-component plastic silver powder paint and preparation method thereof

Similar Documents

Publication Publication Date Title
CN109762425A (en) A kind of acrylic emulsion and its preparation method and application with core-shell structure and high thixotropic
Chen et al. Emulsifier-free latex of fluorinated acrylate copolymer
JPH0819201B2 (en) Amphiphilic copolymer, method for producing the same, and colored aqueous coating composition
CN106565893B (en) A kind of bottom surface unification metallic paint waterborne styrene-acrylic emulsion and preparation method thereof
CN104277172A (en) Water-based waterproof acrylate emulsion and preparation method thereof
CN1345900A (en) Levelling agent for surface paint
CN106243272B (en) A kind of high adhesion force aqueous thermosetting acrylic resin and preparation method and application
CN109722154A (en) A kind of car repair aqueous polyurethane metal flash paint and preparation method thereof
CN105254904A (en) Fluorinated hydroxy acrylic resin aqueous dispersion and preparation method thereof
CN1175963A (en) Finely particulate composite latices and use thereof in solvent-free paints
CN105669915A (en) Water-soluble epoxy silicone acrylic resin and preparation method thereof
US10696850B2 (en) Ethylenically crosslinkable fluorinated polymer additives for architectural coatings
CN115433492A (en) Water-based fluorocarbon coating for spraying and preparation method and application thereof
CN109021761B (en) Glazing oil and preparation method thereof
KR20120008322A (en) Acrylic emulsion resin having high weather resistance and paint composition comprising the same
CN108977035A (en) Low-VOC aqueous polyurethane floor coatings and preparation method thereof
CN105400385B (en) A kind of photocuring wear-resistant paint and preparation method thereof with anti-microbial property
CN112745740B (en) Extinction scratch-resistant powder coating composition, preparation method thereof and extinction scratch-resistant coating
CN108359338A (en) A kind of Self-leveling varnish and preparation method thereof that high can glue spraying
US6281280B1 (en) Low-gloss paints including polyvinylidene fluoride having a high melt viscosity
JP6981963B2 (en) Gel composition, cosmetics, and method for producing gel composition
CN106349416A (en) Modified waterborne acrylic emulsion and preparation method thereof
CN109354645A (en) A kind of acrylic resin of self-crosslinking
CN105885598A (en) Environment-friendly high-water-resistance glazing paint
CN110105500A (en) A kind of preparation method of super-hydrophobic paper surface treating agent

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20190517

RJ01 Rejection of invention patent application after publication