CN107840919A - A kind of hud typed tertiary acrylate and vinyl acetate emulsion and preparation method and application - Google Patents
A kind of hud typed tertiary acrylate and vinyl acetate emulsion and preparation method and application Download PDFInfo
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- CN107840919A CN107840919A CN201711156830.3A CN201711156830A CN107840919A CN 107840919 A CN107840919 A CN 107840919A CN 201711156830 A CN201711156830 A CN 201711156830A CN 107840919 A CN107840919 A CN 107840919A
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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
- C08F218/00—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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2331/00—Characterised by the use of 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 an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
- C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
- C08J2331/04—Homopolymers or copolymers of vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Abstract
The invention discloses a kind of hud typed tertiary acrylate and vinyl acetate emulsion and preparation method and application, the hud typed tertiary acrylate and vinyl acetate emulsion includes stratum nucleare emulsion monomer and shell emulsion monomer, stratum nucleare emulsion monomer is made up of mass ratio for 95 99.5% vinylacetate and 0.5 5% cross-linking monomer, shell emulsion monomer is made up of mass ratio for 60 80% vinylacetate, 10 25% tertiary ethylene carbonate, 8 20% acrylic ester monomer, 1 5% function monomer, and the mass ratio of stratum nucleare emulsion monomer and shell emulsion monomer is 12:1‑2.The present invention does stone to be crosslinked vinyl acetate, intensity is provided, tertiary ethylene carbonate, acrylic ester monomer and function monomer are modified to shell vinylacetate jointly simultaneously, pliability, cementability and the water resistance on polymer are added, solves the technology barrier that polymer glue powder intensity, pliability, water resistance, cementability can not have concurrently simultaneously.
Description
Technical field
The present invention relates to a kind of emulsion and its redispersable latex powder, and in particular to a kind of hud typed tertiary acrylate and vinyl acetate emulsion and its
Preparation method and application.
Background technology
Redispersible latex powder is one of important component in building field dry-mixed mortar, redispersible in dry-mixed mortar
The addition of property latex powder, significantly improves tensile strength, cracking resistance and the deformability of cement mortar, compensate for ordinary mortar
Performance deficiency and deficiency.With the fast development of social economy, energy-conserving and environment-protective theory is widelyd popularize, and polymer emulsion powder exists
The application of building trade is more and more wider, and performance requirement also improves constantly.Therefore traditional rubber powder it is water-fast, weather-proof the problems such as it is increasingly aobvious
Write, and the contradiction of water resistance, adhesion strength and flexility is difficult to balance during performance is improved.
Nowadays, in the market is used to prepare the emulsion of redispersible latex powder, mainly using ethylene-vinyl acetate emulsion as
Main, tertiary vinegar milk liquid, acrylate and vinyl acetate emulsion, acrylic acid ester emulsion etc. also have certain share, the weather-proof alkali resistance of ethylene-vinyl acetate class rubber powder
Can it is poor, by tertiary ethylene carbonate, acrylate etc. modification tertiary vinegar milk liquid, although water-fast weather resistance has necessarily acrylate and vinyl acetate emulsion
Improvement, but still can not meet the requirement of some application fields.Although rubber powder water resistance prepared by acrylic acid ester emulsion is excellent
Different, but adhesive strength can not birds of the same feather flock together with vinyl acetate, compound emulsion compares favourably.
Pliability, cementability and water resistance are difficult existing for the emulsion of the re-dispersible glue powder for building prepared in the prior art
How the problem of being balanced with compatibility, therefore, on the premise of vinyl acetate is as main body raw material, is improved and balanced and be redispersible
Property the pliability of emulsion, water resistance and adhesive strength used in latex powder into where problem and study hotspot.
The content of the invention
In order to solve the above technical problems, it is an object of the invention to provide a kind of hud typed tertiary acrylate and vinyl acetate emulsion and its preparation
Redispersible latex powder prepared by method and the application hud typed tertiary acrylate and vinyl acetate emulsion.
Specifically, the invention provides a kind of hud typed tertiary acrylate and vinyl acetate emulsion, the hud typed tertiary acrylate and vinyl acetate emulsion includes stratum nucleare breast
Liquid monomer and shell emulsion monomer, friendship of the stratum nucleare emulsion monomer by mass ratio for 95-99.5% vinylacetate and 0.5-5%
Join monomer composition, shell emulsion monomer is 60-80% vinylacetate, 10-25% tertiary ethylene carbonate, 8- by mass ratio
20% acrylic ester monomer, 1-5% function monomer form, and the mass ratio of stratum nucleare emulsion monomer and shell emulsion monomer is
1-2:1-2.
Preferably, cross-linking monomer is ethylene glycol dimethacrylate, propylene glycol diacrylate, BDO two
At least one of acrylate, diallyl phthalate, trimethylol-propane trimethacrylate.
Preferably, at least one of tertiary ethylene carbonate Veova-9, Veova-10, VEH.
Preferably, acrylic ester monomer is ethyl acrylate, n-butyl acrylate, acrylic acid-2-ethyl caproite, methyl
At least one of n-octyl.
Preferably, function monomer is methacrylic acid, GMA, lauryl acrylate, acrylic acid
At least one of organic silicone grease of stearyl, methacrylic acid.
Present invention also offers a kind of preparation method of described hud typed tertiary acrylate and vinyl acetate emulsion, this method includes following step
Suddenly:
1) preparation of pre-emulsion:Weigh protecting colloid, emulsifying agent and deionized water to be placed in emulsion tank, after stirring and evenly mixing
It is slowly added to stratum nucleare emulsion monomer/shell emulsion monomer and carries out pre-emulsification, forms stratum nucleare/shell pre-emulsion of stable homogeneous;
2) preparation of seed emulsion:Buffer and deionized water are added in reactor, opens and stirs and be warming up to 60-80
DEG C, the redox initiator of the stratum nucleare pre-emulsion and 10-15% that add total monomer amount 3-10% carries out reaction and prepares seed
Emulsion;
3) preparation of stratum nucleare emulsion:The redox of remaining stratum nucleare pre-emulsion and 30-35% is added dropwise in seed liquor
Initiator, controlling reaction temperature are 60-80 DEG C, time for adding 1-2h, 0.5-1h are incubated after completion of dropwise addition;
4) preparation of Structure of Core/shell Emulsion:Shell pre-emulsion and 45-50% redox initiator are at the uniform velocity added drop-wise to
In stratum nucleare emulsion, controlling reaction temperature is 60-80 DEG C, time for adding 1.5-2.5h, and 0.5-1.5h is incubated after completion of dropwise addition, is dropped
Remaining redox initiator is added after temperature, is produced after insulation.
Wherein, in step (1), one in the polyvinyl alcohol that protecting colloid is alcoholysis degree 88% and the degree of polymerization is 500-1700
Kind.Emulsifying agent is AEO, APES, alkyl polyoxyethylene ether, NPE
In one kind.
In step (4), the emulsion after insulation is cooled to 50-60 DEG C, remaining redox initiator solution is divided into
Two equal portions, first part drips and is added dropwise second part after 0.5h, second part drip after be incubated 1h, be cooled to room temperature afterwards, filter
After obtain hud typed tertiary acrylate and vinyl acetate emulsion.
Invention further provides a kind of described hud typed tertiary acrylate and vinyl acetate emulsion answering in redispersible latex powder is prepared
With by hud typed tertiary 100 parts of the acrylate and vinyl acetate emulsion, inorganic anti-caking agent 5-10 parts, the poly-vinyl alcohol solution that concentration is 10-30%
7-16 parts are mixed to prepare redispersible latex powder.
Beneficial effects of the present invention:The hud typed tertiary acrylate and vinyl acetate emulsion of the present invention is designed by latex ionic structure, well
Application field is balanced to intensity, water-fast, flexible demand, wherein doing stone to be crosslinked vinyl acetate, there is provided intensity, simultaneously
Tertiary ethylene carbonate, acrylic ester monomer and function monomer are modified to shell vinylacetate jointly, added
Pliability, cementability and water resistance on polymer, solve polymer glue powder intensity, pliability, water resistance, cementability not
The technology barrier that can be had concurrently simultaneously, promote redispersible latex powder answering in application fields such as building mortar, building coatings
Use performance.
Embodiment
Technical solution of the present invention is illustrated to be clearer, the skill below in conjunction with embodiment to the present invention
Art scheme is further elaborated:
One of technical scheme provided by the invention is:
The invention provides a kind of hud typed tertiary acrylate and vinyl acetate emulsion, the hud typed tertiary acrylate and vinyl acetate emulsion include stratum nucleare emulsion monomer and
Shell emulsion monomer, stratum nucleare emulsion monomer are 95-99.5% vinylacetate and 0.5-5% cross-linking monomer group by mass ratio
Into, shell emulsion monomer by mass ratio be 60-80% vinylacetate, 10-25% tertiary ethylene carbonate, 8-20% third
The mass ratio of the function monomer composition of olefin(e) acid esters monomer, 1-5%, stratum nucleare emulsion monomer and shell emulsion monomer is 1-2:1-2.
In order to solve the conventional water resistance for improving EVA emulsions, to influence material former strong, such as ensures former strong and emulsion minimum
Film-forming temperature higher contradiction again, the present invention using the method for latex particle structure design balance product to intensity, pliability,
Water-fast and low film formation temperature requirement.The hud typed tertiary acrylate and vinyl acetate emulsion of the present invention forms stone with vinylacetate and cross-linking monomer
There is provided intensity for emulsion, then be copolymerized with vinylacetate, tertiary ethylene carbonate, acrylic ester monomer and function monomer to be formed it is soft
Water-fast shell be wrapped on stratum nucleare, acquisition has hud typed emulsion, by adjusting nucleocapsid than, stratum nucleare and the glass of shell
Change the monomer ratio of transition temperature and shell, make intensity, pliability, water resistance and the MFT of emulsion greatly
The demand of application is met, the intensity of great raising degree cement system, cementability, water resistance etc. after film forming in cement, gram
The low adhesive strength of tertiary vinegar or acrylate and vinyl acetate emulsion in cement mortar in the prior art, poor water resistance are taken and have occurred being cracked
Problem.
Wherein, in stratum nucleare emulsion cross-linking monomer introducing, improve the glass transition temperature of vinylacetate, ensure that emulsion
Intensity, be also beneficial to the hud typed formation of rule, and the highly branched side base of tertiary ethylene carbonate and acrylic acid alkyl
The hydrophobicity of ester is protected to adjacent vinylacetate side base ester group, effectively raises the water resistance of emulsion, reduced TG
The addition of transition temperature acrylic ester monomer improves the pliability and water resistance of emulsion after emulsion film forming, greatly improves
Application of the emulsion in mortar, while improve the cohesive force and bonding force of blending base material.
Preferably, cross-linking monomer is ethylene glycol dimethacrylate, propylene glycol diacrylate, BDO two
At least one of acrylate, diallyl phthalate, trimethylol-propane trimethacrylate.Above-mentioned crosslinking list
The presence of body, the glass transition temperature of stratum nucleare emulsion is improved, make the intensity of stratum nucleare emulsion increase, while also promote the stone of rule
The formation of the coreshell type structure of soft shell.
Preferably, at least one of tertiary ethylene carbonate Veova-9, Veova-10, VEH.Above-mentioned tertiary carbon acid monomers
Introducing add the pliability and water resistance of polymer latex particles.
Preferably, acrylic ester monomer is ethyl acrylate, n-butyl acrylate, acrylic acid-2-ethyl caproite, methyl
At least one of n-octyl.The hydrophobic acrylic monomer of lower glass transition temperatures impart polymer emulsion and
Pliability, cementability and the water resistance of latex powder.
Preferably, function monomer is methacrylic acid, GMA, lauryl acrylate, acrylic acid
At least one of organic silicone grease of stearyl, methacrylic acid.Above-mentioned function monomer and tertiary ethylene carbonate, acrylate
The common Dichlorodiphenyl Acetate vinyl acetate of class monomer is modified, and drastically increases water resistance, the pliability of emulsion and rubber powder.
The two of technical scheme provided by the invention are:
Present invention also offers a kind of preparation method of described hud typed tertiary acrylate and vinyl acetate emulsion, this method includes following step
Suddenly:
1) preparation of pre-emulsion:Weigh protecting colloid, emulsifying agent and deionized water to be placed in emulsion tank, after stirring and evenly mixing
It is slowly added to stratum nucleare emulsion monomer/shell emulsion monomer and carries out pre-emulsification, forms stratum nucleare/shell pre-emulsion of stable homogeneous;
2) preparation of seed emulsion:Buffer and deionized water are added in reactor, opens and stirs and be warming up to 60-80
DEG C, the redox initiator of the stratum nucleare pre-emulsion and 10-15% that add total monomer amount 3-10% carries out reaction and prepares seed
Emulsion;
3) preparation of stratum nucleare emulsion:The redox of remaining stratum nucleare pre-emulsion and 30-35% is added dropwise in seed liquor
Initiator, controlling reaction temperature are 60-80 DEG C, time for adding 1-2h, 0.5-1h are incubated after completion of dropwise addition;
4) preparation of Structure of Core/shell Emulsion:Shell pre-emulsion and 45-50% redox initiator are at the uniform velocity added drop-wise to
In stratum nucleare emulsion, controlling reaction temperature is 60-80 DEG C, time for adding 1.5-2.5h, and 0.5-1.5h is incubated after completion of dropwise addition, is dropped
Remaining redox initiator is added after temperature, is produced after insulation.
The method that the hud typed tertiary acrylate and vinyl acetate emulsion of the present invention uses semi-continuous emulsion polymerizing, pre-emulsification is first carried out by monomer,
Seeding polymerization is carried out afterwards, pre-emulsion is slowly then being added dropwise to carry out polymerisation, the polymerization technique, which improves, to be polymerize
Emulsion intercalation method in journey, while also improve the success rate of emulsion preparation.The hud typed tertiary acrylate and vinyl acetate emulsion of the present invention passes through core
Layer crosslinking provides excellent intensity, and by tertiary ethylene carbonate, acrylic ester monomer and function monomer Dichlorodiphenyl Acetate vinyl acetate
Be modified as shell, improve the pliability and water resistance of polymer, and by nucleocapsid than regulation and shell list
The regulation of body ratio, a series of emulsions for meeting different application demand can be produced, greatly improve emulsion practicality and
Application, while raising conversion ratio is advantageous to using redox initiator, polymerisation can be carried out at a lower temperature,
Energy consumption can be reduced, reduces production cost.Therefore it is resistance to that high-performance, high flexibility, height are createed on the basis of hud typed tertiary acrylate and vinyl acetate emulsion
The redispersible latex powder of water has important application prospect and industrial value.
Wherein, in step (1), one in the polyvinyl alcohol that protecting colloid is alcoholysis degree 88% and the degree of polymerization is 500-1700
Kind.The protecting colloid of low polymerization degree makes emulsion viscosity in polymerization process moderate, is advantageous to being smoothed out for polymerization, obtained emulsion
Viscosity is also corresponding moderate, is advantageous to dust and improves production efficiency.
The emulsifying agent is AEO, APES, alkyl polyoxyethylene ether, nonyl phenol gather
One kind in oxygen vinethene.The emulsifying agent is nonionic emulsifier, compared with using anion emulsifier in the prior art
Compared with only using nonionic emulsifier improving emulsion intercalation method and water resistance in the present invention, while production can be avoided to dust
During latex powder static electrification effect cause effectively to collect, the use of nonionic emulsifier effectively overcomes this and asked
The presence of topic, improve the efficiency of production.
The redox initiator is hydrogen peroxide/rongalite, TBHP/rongalite, ammonium persulfate/Asia
Niter cake, hydrogen peroxide/sulfuric acid ferrous iron, hydrogen peroxide/frerrous chloride, hydrogen peroxide/tartaric acid, ammonium persulfate/sulfuric acid are sub-
Iron, persulfate/mercaptan, isopropyl benzene hydroperoxide/frerrous chloride, potassium peroxydisulfate/frerrous chloride, potassium peroxydisulfate/silver nitrate, uncle
One kind in butylhydroperoxide/sodium pyrosulfite, potassium peroxydisulfate/sodium hydrogensulfite combination.Had using redox initiator
Beneficial to raising conversion ratio, while polymerisation can be carried out at a lower temperature, can reduce energy consumption, reduce production cost.
The buffer is anhydrous sodium acetate.Buffer can adjust the pH value of emulsion in reaction system, make in course of reaction
Emulsion pH is in suitable scope, is advantageous to progress and the stabilization of emulsion of polymerisation.
In step (4), the emulsion after insulation is cooled to 50-60 DEG C, remaining redox initiator solution is divided into
Two equal portions, first part drips and is added dropwise second part after 0.5h, second part drip after be incubated 1h, be cooled to room temperature afterwards, filter
After obtain hud typed tertiary acrylate and vinyl acetate emulsion.
The three of technical scheme provided by the invention are:
Invention further provides a kind of application of hud typed tertiary acrylate and vinyl acetate emulsion in redispersible latex powder is prepared,
By hud typed tertiary 100 parts of the acrylate and vinyl acetate emulsion, inorganic anti-caking agent 5-10 parts, the poly-vinyl alcohol solution 7- that concentration is 10-30%
16 parts are mixed to prepare redispersible latex powder.Specifically preparation method is:By hud typed tertiary acrylate and vinyl acetate emulsion and defoamer, protection
The function additives such as colloid are well mixed and are preheated to 40-70 DEG C, are at the uniform velocity pumped to 130-160 with together with inorganic anti-caking agent respectively
DEG C spray drying tower in be spray-dried, it is redispersible latex powder to collect solid powder in tower.
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the implementation
Among example scope.The experimental method of unreceipted actual conditions in the following example, conventionally and condition, or according to commodity
Specification selects.
In following embodiments, if not otherwise indicated, agents useful for same and material are that conventional commercial can obtain, used in raw material
Food additives dosage be no more than national Specification scope.
Embodiment 1
A kind of hud typed tertiary acrylate and vinyl acetate emulsion includes:
Stratum nucleare emulsion monomer by following mass ratio monomer composition:Vinylacetate 176.4g, dimethacrylate second two
Alcohol ester 3.6g.
Shell emulsion monomer by following mass ratio monomer composition:Vinylacetate 162g, tertiary ethylene carbonate 67.5g,
Butyl acrylate 27g, GMA 13.5g.
In the present embodiment, latex particle nucleocapsid ratio is 1:1.5, protecting colloid is the degree of polymerization 800 and alcoholysis degree is 88%
Polyvinyl alcohol;Emulsifying agent is NPE;Buffer is anhydrous sodium acetate;Redox initiator is tert-butyl group mistake
Hydrogen oxide/rongalite.Redox initiator is dissolved in water, and the redox initiator solution that mass concentration is 5% is made.
The preparation method of the hud typed tertiary acrylate and vinyl acetate emulsion comprises the following steps:
(1) homogeneous mixture solotion is made in deionized water 95g, polyvinyl alcohol 12g and emulsifying agent 1.25g blending and stirrings;Will
Vinylacetate 176.4g, cross-linking monomer 3.6g, after being mixed evenly, it is slowly added in the mixed solution with stirring,
Stratum nucleare pre-emulsion is made;
By deionized water 155g, emulsifying agent 1.88g and polyvinyl alcohol 18g blending and stirrings, homogeneous mixture solotion is made;By vinegar
Vinyl acetate 162g, tertiary ethylene carbonate 67.5g, butyl acrylate 27g, GMA 13.5g mixing are equal
After even, it is slowly added in the mixed solution with stirring, shell pre-emulsion is made;
(2) deionized water 110g and buffer 2.25g is mixed after being heated to 65 DEG C, adds the 6% pre- breast of stratum nucleare
Change liquid, 15% redox initiator solution, seed emulsion is formed after reacting 30min;
(3) 65 DEG C are maintained the temperature at, starts that remaining pre-emulsion and 30% oxidation is slowly added dropwise into seed emulsion
Initiator solution is reduced, after pre-emulsion is added dropwise, is incubated 0.5h, prepared by stratum nucleare emulsion completes;
(4) keep the temperature of stratum nucleare emulsion at 65 DEG C, start slowly to be added dropwise into stratum nucleare emulsion shell pre-emulsion and
45% redox initiator solution, after shell pre-emulsion is added dropwise, by 5% redox initiator solution to
Continue to be added dropwise in emulsion, be incubated 1h;Prepared by emulsion shell structurre completes;
Emulsion after insulation is cooled to 55 DEG C, remaining redox initiator solution is divided into two equal portions, first part
Drip and be added dropwise second part after 0.5h, second part drip after be incubated 1h, be cooled to room temperature afterwards, hud typed uncle obtained after filtering
Acrylate and vinyl acetate emulsion.
Embodiment 2
A kind of hud typed tertiary acrylate and vinyl acetate emulsion includes:
Stratum nucleare emulsion monomer by following mass ratio monomer composition:Vinylacetate 199g, 1,4- butanediol diacrylate
Ester 1g.
Shell emulsion monomer by following mass ratio monomer composition:Vinylacetate 160g, tertiary ethylene carbonate
VV1020g, Isooctyl acrylate monomer 16g, octadecyl acrylate 4g.
In the present embodiment, nucleocapsid ratio is 1:1, the polyvinyl alcohol that protecting colloid is the degree of polymerization 500 and alcoholysis degree is 88%;Breast
Agent is NPE;Buffer is anhydrous sodium acetate;Redox initiator is hydrogen peroxide/frerrous chloride.
Redox initiator is dissolved in water, and the redox initiator solution that mass concentration is 6% is made.
The preparation method of the hud typed tertiary acrylate and vinyl acetate emulsion comprises the following steps:
(1) homogeneous mixture solotion is made in deionized water 120g, polyvinyl alcohol 16g and emulsifying agent 1.25g blending and stirrings;Will
Vinylacetate 199g, BDO diacrylate 1g, after being mixed evenly, it is slowly added to the mixing with stirring
In solution, stratum nucleare pre-emulsion is made;
By deionized water 120g, emulsifying agent 1.25g and polyvinyl alcohol 16g blending and stirrings, homogeneous mixture solotion is made;By vinegar
Vinyl acetate 160g, tertiary ethylene carbonate VV1020g, Isooctyl acrylate monomer 16g, octadecyl acrylate 4g are well mixed
Afterwards, it is slowly added to, with being stirred in solution, shell pre-emulsion be made;
(2) deionized water 110g and buffer 2.25g is mixed after being heated to 60 DEG C, adds the 10% pre- breast of stratum nucleare
Change liquid, 10% redox initiator solution, seed emulsion is formed after reacting 30min;
(3) 60 DEG C are maintained the temperature at, starts that remaining pre-emulsion and 35% oxidation is slowly added dropwise into seed emulsion
Initiator solution is reduced, after pre-emulsion is added dropwise, is incubated 0.5h;Prepared by stratum nucleare emulsion completes;
(4) keep the temperature of stratum nucleare emulsion at 60 DEG C, start slowly to be added dropwise into stratum nucleare emulsion shell pre-emulsion and
40% redox initiator solution, after shell pre-emulsion is added dropwise, by 10% redox initiator solution
Continue to be added dropwise into emulsion, be incubated 1h;Prepared by emulsion shell structurre completes;
Emulsion after insulation is cooled to 50 DEG C, remaining redox initiator solution is divided into two equal portions, first part
Drip and be added dropwise second part after 0.5h, second part drip after be incubated 1h, be cooled to room temperature afterwards, hud typed uncle obtained after filtering
Acrylate and vinyl acetate emulsion.
Embodiment 3
A kind of hud typed tertiary acrylate and vinyl acetate emulsion includes:
Stratum nucleare emulsion monomer by following mass ratio monomer composition:Vinylacetate 145.5g, diallyl phthalate third
Ester 4.5g.
Shell emulsion monomer by following mass ratio monomer composition:Vinylacetate 180g, tertiary ethylene carbonate VV972g,
Butyl acrylate type 45g, methacrylic acid organo-silicon ester 3g.
In the present embodiment, latex particle nucleocapsid ratio is 1:2, protecting colloid be the degree of polymerization 1200 and alcoholysis degree be 88% it is poly-
Vinyl alcohol;Emulsifying agent is APES;Buffer is anhydrous sodium acetate;Redox initiator be ammonium persulfate/
Sodium hydrogensulfite.Redox initiator is dissolved in water, and the redox initiator solution that mass concentration is 8% is made.
The preparation method of the hud typed tertiary acrylate and vinyl acetate emulsion comprises the following steps:
(1) deionized water 80g, polyvinyl alcohol 12g and emulsifying agent 1.0g blending and stirrings are made uniform;By vinylacetate
After 145.5g, diallyl phthalate 4.5g are mixed evenly, it is slowly added in the mixed solution with stirring, system
Obtain stratum nucleare pre-emulsion;
By deionized water 160g, emulsifying agent 2.0g and polyvinyl alcohol 24g blending and stirrings, homogeneous mixture solotion is made;By vinegar
Vinyl acetate 180g, tertiary ethylene carbonate VV972g, butyl acrylate type 45g, methacrylic acid organo-silicon ester 3g are well mixed
Afterwards, it is slowly added in (5) mixed solution with stirring, shell pre-emulsion is made;
(2) deionized water 110g and buffer 2.25g is mixed after being heated to 70 DEG C, adds the 5% pre- breast of stratum nucleare
Change liquid, 15% redox initiator solution, seed emulsion is formed after reacting 30min;
(3) 70 DEG C are maintained the temperature at, starts that remaining pre-emulsion and 35% oxidation is slowly added dropwise into seed emulsion
Initiator solution is reduced, after pre-emulsion is added dropwise, is incubated 0.5h;Prepared by stratum nucleare emulsion completes;
(4) keep the temperature of stratum nucleare emulsion at 70 DEG C, start slowly to be added dropwise into stratum nucleare emulsion shell pre-emulsion and
40% redox initiator solution, after shell pre-emulsion is added dropwise, by 5% redox initiator solution to
Continue to be added dropwise in emulsion, be incubated 1h;Prepared by emulsion shell structurre completes;
Emulsion after insulation is cooled to 60 DEG C, remaining redox initiator solution is divided into two equal portions, first part
Drip and be added dropwise second part after 0.5h, second part drip after be incubated 1h, be cooled to room temperature afterwards, hud typed uncle obtained after filtering
Acrylate and vinyl acetate emulsion.
Embodiment 4
A kind of hud typed tertiary acrylate and vinyl acetate emulsion includes:
Stratum nucleare emulsion monomer by following mass ratio monomer composition:Vinylacetate 475g, 1,4- butanediol diacrylate
Ester 25g.
Shell emulsion monomer by following mass ratio monomer composition:Vinylacetate 150g, tertiary ethylene carbonate
VV1050g, Isooctyl acrylate monomer 40g, octadecyl acrylate 10g.
In the present embodiment, nucleocapsid ratio is 2:1, the polyvinyl alcohol that protecting colloid is the degree of polymerization 500 and alcoholysis degree is 88%;Breast
Agent is NPE;Buffer is anhydrous sodium acetate;Redox initiator is hydrogen peroxide/frerrous chloride.
Redox initiator is dissolved in water, and the redox initiator solution that mass concentration is 10% is made.
The preparation method of the hud typed tertiary acrylate and vinyl acetate emulsion comprises the following steps:
(1) homogeneous mixture solotion is made in deionized water 240g, polyvinyl alcohol 32g and emulsifying agent 2.5g blending and stirrings;Will
After vinylacetate 475g, BDO diacrylate 25g are mixed evenly, the mixing with stirring is slowly added to
In solution, stratum nucleare pre-emulsion is made;
By deionized water 120g, emulsifying agent 1.25g and polyvinyl alcohol 16g blending and stirrings, homogeneous mixture solotion is made;By vinegar
Vinyl acetate 150g, tertiary ethylene carbonate VV1050g, Isooctyl acrylate monomer 40g, octadecyl acrylate 10g are well mixed
Afterwards, it is slowly added to, with being stirred in solution, shell pre-emulsion be made;
(2) deionized water 200g and buffer 3g is mixed after being heated to 80 DEG C, adds 10% stratum nucleare pre-emulsification
Liquid, 10% redox initiator solution, seed emulsion is formed after reacting 30min;
(3) 80 DEG C are maintained the temperature at, starts that remaining pre-emulsion and 35% oxidation is slowly added dropwise into seed emulsion
Initiator solution is reduced, after pre-emulsion is added dropwise, is incubated 1h;Prepared by stratum nucleare emulsion completes;
(4) keep the temperature of stratum nucleare emulsion at 80 DEG C, start slowly to be added dropwise into stratum nucleare emulsion shell pre-emulsion and
40% redox initiator solution, after shell pre-emulsion is added dropwise, by 10% redox initiator solution
Continue to be added dropwise into emulsion, be incubated 1h;Prepared by emulsion shell structurre completes;
Emulsion after insulation is cooled to 50 DEG C, remaining redox initiator solution is divided into two equal portions, first part
Drip and be added dropwise second part after 0.5h, second part drip after be incubated 1h, be cooled to room temperature afterwards, hud typed uncle obtained after filtering
Acrylate and vinyl acetate emulsion.
Comparative example 1
The comparative example provides a kind of tertiary acrylate and vinyl acetate emulsion without hud typed design, and the emulsion includes:Vinylacetate
330g, tertiary ethylene carbonate VV1045g, butyl acrylate 60g, GMA 5g, protecting colloid 36g, breast
Agent 2.2g, buffer 2.25g, redox initiator 2.15g, water 450g protecting colloids are the degree of polymerization 500 and alcoholysis degree is
88% polyvinyl alcohol;Emulsifying agent is alkyl alcohol ethoxylates;Buffer is anhydrous sodium acetate;Redox initiator is uncle
Butylhydroperoxide/rongalite.Latex ion is without hud typed design in the emulsion components.
The preparation method of the hud typed tertiary acrylate and vinyl acetate emulsion comprises the following steps:
(1) water 225g, protecting colloid 36g, emulsifying agent 2.2g are mixed, mixed solution is made;
(2) vinylacetate 330g is slowly added in (1) mixed solution with stirring, pre-emulsion is made.
(3) water 225g and buffer 2.25g are mixed after being heated to 65 DEG C, add 5% pre-emulsion, 10%
Redox initiator solution, seed emulsion is formed after stirring reaction 30min;
(4) 65 DEG C are maintained the temperature at, starts that remaining pre-emulsion and 75% oxidation is slowly added dropwise into seed emulsion
Initiator solution is reduced, after pre-emulsion is added dropwise, 10% redox initiator solution is continued to drip into emulsion
Add, be incubated 1h afterwards;
Emulsion after insulation is cooled to 55 DEG C, remaining 5% redox initiator solution is divided into two equal portions, first part
Drip and be added dropwise second part after 0.5h, second part drip after be incubated 1h, be cooled to room temperature afterwards, obtained after filtering described common
Tertiary acrylate and vinyl acetate emulsion.
Embodiment 5
Redispersible latex powder is prepared using the emulsion prepared in embodiment 1-4 and comparative example, preparation method is as follows:
The emulsion 1000g being prepared, defoamer 2g, mass concentration in embodiment 1-4 and comparative example 1 be 20% it is poly-
Glycohol solution 100g, 60 DEG C are preheated to after being mixed evenly, measuring pump is pumped to inlet temperature and entered by spray drying tower
Row spray drying obtains latex powder, then crosses 50 mesh sieves, is spray-dried in 150 DEG C of spray drying tower, while adds 1000 mesh
Anti-caking agent 140g, through the isolated redispersible latex powder of cyclone separator.
It is right respectively with Malvern particle instrument, Brookfield viscosity testers, PHS-03C types pH meter and DSC thermal analyzers
The glass transition temperature that emulsion and redispersible latex powder solution carry out particle diameter, emulsion viscosity, emulsion pH and emulsion is carried out
Test;The dry film that emulsion and latex powder are made to certain area and thickness carries out water absorption rate test;And by rubber powder according to national standard GB/
T 29906-2013 carry out the application performance test of external wall outer insulation;Test result is as shown in table 1:
The performance test results are characterized in the embodiment of the present invention of table 1 and comparative example
As shown in table 1, compared with comparative example, the water absorption rate of emulsion and latex powder dry film significantly reduces embodiment 1-4,
Water-fast intensity in application performance experiment also improves nearly 20% compared with comparative example, illustrates that water resistance lifting is notable;Apply simultaneously
The intensity of performance is also obviously improved compared with comparative example;Showed in the MFT of embodiment compared with comparative example low combination intensity,
Illustrate that hud typed its pliability of design is greatly improved.
Using the rubber powder prepared in the embodiment of the present invention and comparative example, the basic components configuration dry powder according to dry powder emulsion paint
Emulsion paint, using the external wall emulsion paint of GB/T 9755-2001 standard to water resistance, washability, resistant be stained with, resistance to artificial climate
Ageing properties are tested, and test result is shown in Table 2, as shown in table 2, the latex powder after coreshell type structure of the present invention design,
Glue film strength is balanced very well with pliability, therefore is better than comparative example on wash-resistant property;It is additionally due to hud typed
Formula design hydrophobic monomer is enriched with outer shell, and the water resistance of embodiment, resistant are stained with obvious in performance and ageing-resistant performance
Better than comparative example.
The test result of the emulsion paint of table 2
The invention provides the preparation method of a kind of hud typed tertiary acrylate and vinyl acetate emulsion and its redispersible latex powder, by hard
The hud typed design of core soft shell, solve adhesive strength and water resistance during polyvinyl acetate hydrophobically modified and be difficult to take into account
Contradiction, and by introducing tertiary ethylene carbonate in latex particle shell, acrylate Arrcostab and some function monomers enter
Row is modified, and improves water resistance, the pliability of emulsion and rubber powder, cement system is greatly improved to non-after film forming in cement
The adhesive strength of polar material, water resistance, solves cement system cracking etc..Through hud typed design and tertiary ethylene carbonate, third
Olefin(e) acid esters monomer and the common Dichlorodiphenyl Acetate vinyl acetate of function monomer are modified jointly, greatly improve polymer emulsion and rubber powder exists
Application in mortar, while the cohesive force and bonding force of blending base material are improved, further promote redispersible
Application performance of the property latex powder in application fields such as building mortar, building coatings.
Described above is presently preferred embodiments of the present invention, is not intended to limit the invention, all in substantive content of the present invention
Any modification, equivalent substitution and simple modifications for being made etc., should be included in the scope of the protection.
Claims (10)
1. a kind of hud typed tertiary acrylate and vinyl acetate emulsion, it is characterised in that the hud typed tertiary acrylate and vinyl acetate emulsion includes stratum nucleare emulsion monomer and shell
Layer emulsion monomer, stratum nucleare emulsion monomer are 95-99.5% vinylacetate and 0.5-5% cross-linking monomer group by mass ratio
Into, shell emulsion monomer by mass ratio be 60-80% vinylacetate, 10-25% tertiary ethylene carbonate, 8-20% third
The mass ratio of the function monomer composition of olefin(e) acid esters monomer, 1-5%, stratum nucleare emulsion monomer and shell emulsion monomer is 1-2:1-2.
2. hud typed tertiary acrylate and vinyl acetate emulsion according to claim 1, it is characterised in that cross-linking monomer is ethylene glycol dimethyl third
Olefin(e) acid ester, propylene glycol diacrylate, 1,4 butanediol diacrylate, diallyl phthalate, trihydroxy methyl third
At least one of alkane trimethyl acrylic ester.
3. hud typed tertiary acrylate and vinyl acetate emulsion according to claim 1, it is characterised in that tertiary ethylene carbonate Veova-9,
At least one of Veova-10, VEH.
4. hud typed tertiary acrylate and vinyl acetate emulsion according to claim 1, it is characterised in that acrylic ester monomer is acrylic acid second
At least one of ester, n-butyl acrylate, acrylic acid-2-ethyl caproite, n octyl methacrylate.
5. hud typed tertiary acrylate and vinyl acetate emulsion according to claim 1, it is characterised in that function monomer is methacrylic acid, first
At least one in the organic silicone grease of base glycidyl acrylate, lauryl acrylate, octadecyl acrylate, methacrylic acid
Kind.
A kind of 6. method for preparing the hud typed tertiary acrylate and vinyl acetate emulsion described in claim 1, it is characterised in that this method includes following
Step:
1) preparation of pre-emulsion:Weigh protecting colloid, emulsifying agent and deionized water to be placed in emulsion tank, after stirring and evenly mixing slowly
Add stratum nucleare emulsion monomer/shell emulsion monomer and carry out pre-emulsification, form stratum nucleare/shell pre-emulsion of stable homogeneous;
2) preparation of seed emulsion:Buffer and deionized water are added in reactor, opens and stirs and be warming up to 60-80 DEG C,
The redox initiator of the stratum nucleare pre-emulsion and 10-15% that add total monomer amount 3-10% carries out reaction and prepares seed breast
Liquid;
3) preparation of stratum nucleare emulsion:The Redox Initiator of remaining stratum nucleare pre-emulsion and 30-35% is added dropwise in seed liquor
Agent, controlling reaction temperature are 60-80 DEG C, time for adding 1-2h, 0.5-1h are incubated after completion of dropwise addition;
4) preparation of Structure of Core/shell Emulsion:The redox initiator of shell pre-emulsion and 45-50% is at the uniform velocity added drop-wise to stratum nucleare
In emulsion, controlling reaction temperature is 60-80 DEG C, time for adding 1.5-2.5h, 0.5-1.5h is incubated after completion of dropwise addition, after cooling
Remaining redox initiator is added, is produced after insulation.
7. the preparation method of hud typed tertiary acrylate and vinyl acetate emulsion according to claim 6, it is characterised in that in step (1), protection
One kind in the polyvinyl alcohol that colloid is alcoholysis degree 88% and the degree of polymerization is 500-1700.
8. the preparation method of hud typed tertiary acrylate and vinyl acetate emulsion according to claim 6, it is characterised in that in step (1), emulsification
Agent is one in AEO, APES, alkyl polyoxyethylene ether, NPE
Kind.
9. the preparation method of hud typed tertiary acrylate and vinyl acetate emulsion according to claim 6, it is characterised in that in step (4), will protect
Emulsion after temperature is cooled to 50-60 DEG C, remaining redox initiator solution is divided into two equal portions, first part drips 0.5h
Afterwards be added dropwise second part, second part drip after be incubated 1h, be cooled to room temperature afterwards, hud typed tertiary acrylate and vinyl acetate emulsion obtained after filtering.
10. application of the hud typed tertiary acrylate and vinyl acetate emulsion in redispersible latex powder is prepared described in claim 1, its feature exist
In by hud typed tertiary 100 parts of the acrylate and vinyl acetate emulsion, inorganic anti-caking agent 5-10 parts, the poly-vinyl alcohol solution that concentration is 10-30%
7-16 parts are mixed to prepare redispersible latex powder.
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CN109180854A (en) * | 2018-08-07 | 2019-01-11 | 东莞大宝化工制品有限公司 | A kind of aqueous acrylic resin and preparation method thereof from the controllable gloss of delustring |
CN110294825A (en) * | 2019-05-08 | 2019-10-01 | 河北四友卓越科技有限公司 | A kind of hud typed tertiary carbon redispersable latex powder and preparation method thereof |
CN111072840A (en) * | 2019-12-16 | 2020-04-28 | 广东海特高新材料有限公司 | High-elasticity building waterproof emulsion and preparation method thereof |
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CN104610487A (en) * | 2014-12-31 | 2015-05-13 | 北京天维宝辰化学产品有限公司 | Vac-veova emulsion, preparation method of vac-veova emulsion and redispersible latex powder |
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CN109180854A (en) * | 2018-08-07 | 2019-01-11 | 东莞大宝化工制品有限公司 | A kind of aqueous acrylic resin and preparation method thereof from the controllable gloss of delustring |
CN110294825A (en) * | 2019-05-08 | 2019-10-01 | 河北四友卓越科技有限公司 | A kind of hud typed tertiary carbon redispersable latex powder and preparation method thereof |
CN110294825B (en) * | 2019-05-08 | 2021-03-23 | 河北四友卓越科技有限公司 | Core-shell type tertiary carbon redispersible latex powder and preparation method thereof |
CN111072840A (en) * | 2019-12-16 | 2020-04-28 | 广东海特高新材料有限公司 | High-elasticity building waterproof emulsion and preparation method thereof |
CN111978454A (en) * | 2020-08-26 | 2020-11-24 | 东莞市宜人包装材料有限公司 | Tertiary carbon emulsion for bonding UV (ultraviolet) glazing paper products and preparation method thereof |
CN115260402B (en) * | 2022-07-01 | 2024-01-26 | 东北林业大学 | Core polymer TAIC crosslinked PVAc/PS core-shell emulsion and preparation method thereof |
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