CN102190754B - Acrylate emulsion, waterproof acrylate re-dispersible latex powder prepared from same, and preparation method for latex powder - Google Patents
Acrylate emulsion, waterproof acrylate re-dispersible latex powder prepared from same, and preparation method for latex powder Download PDFInfo
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Abstract
The invention relates to acrylate emulsion, waterproof acrylate re-dispersible latex powder prepared from same, and a preparation method for the latex powder, in particular to acrylate polymer, waterproof acrylate re-dispersible latex powder with excellent waterproofness prepared from the same, and a preparation method for the latex powder. The acrylate has high stability in the polymerization process, and the re-dispersible latex powder prepared from the same has excellent waterproofness.
Description
Technical field
The present invention relates to a kind of acrylic ester emulsion, and redispersible latex powder prepared therefrom and the preparation method of this latex powder, more specifically, the present invention relates to a kind of acrylate, prepared therefrom have the acrylate redispersable latex powder of excellent in water resistance and a preparation method of this rubber powder, described acrylate has satisfactory stability in polymerization process, and redispersion latex powder prepared therefrom has excellent in water resistance.
Background technology
Redispersable latex powder is a kind of free flowable polymer powder that obtains after the efflorescence of polymer emulsion drying.After adding water therein, latex powder can be distributed to the stable dispersion liquid of generation in the water again, forms and the original regeneration emulsion that the polymer emulsion performance is identical, purposes is similar.Redispersible polymer latex powder adhesion under normal condition also can keep good flowability, has good stability in storage; In use, be conducive to reduce dust and organism volatile matter to the pollution of environment, and can improve construction quality and shorten construction period, thus very popular in building trade.
The research of redispersable latex powder starts from 1934, and at first the I.G FarbenindustrieA.C. company by Germany develops vinyl acetate (PVAc) class redispersable latex powder.After this, for overcoming PVAc class redispersable latex powder redispersible, film-forming properties, cohesiveness, the characteristics of poor performance such as physical strength are developed vinyl acetate-ethene (VAc/E) again in succession, acrylate-vinyl acetate (A/VAc), pure acrylic acid ester (PA), cinnamic acrylic ester (St/A), styrene butadiene polymeric systems such as (St/BR) is for the preparation of redispersible latex powder, and the use range of latex powder also is extended to structure and unstructuredness building adhesive gradually, dry-mixed mortar, wall thermal insulating and facing system, body of wall levelling glue and sealing emplaster, powder coating, fields such as building putties.
At present increasing building structure requires building materials that good water-repellancy is arranged.As the redispersable latex powder that building materials use, its water resistance also more and more receives publicity, yet requires development product less relatively at this respect specially.As in patents such as USP5872189, USP6224981, USP705553, CN200780042954, CN200910093334, preparing redispersable latex powder by designing the specific latexes kernel structure or introducing functional comonomer or adopt new modes such as emulsion polymerization technique to synthesize new polymeric system, the latex powder water tolerance obtains certain raising, but actual effect is very little, can not well solve the waterproof problem in the material of construction application process.In preparation water tolerance polymkeric substance, selected hydrophobic acrylic acid's ester monomer ratio will increase usually in addition, and this can make the stability decreases of letex polymerization again, and this also is the restraining factors of preparation water tolerance acrylate latex powder.
Summary of the invention
[technical problem]
The present invention is designed to address the above problem.The purpose of this invention is to provide a kind of acrylic ester emulsion, acrylate redispersable latex powder prepared therefrom and this latex powder preparation method, this acrylate redispersable latex powder has excellent in water resistance, thereby can solve the waterproof problem in the material of construction application process.
[technical scheme]
To achieve these goals, one aspect of the present invention provides a kind of acrylic ester emulsion, and it has nucleocapsid structure, wherein nuclear layer monomer: the weight ratio of shell monomers is 8: 2.
Another aspect of the present invention provides the acrylate redispersable latex powder by the preparation of aforesaid propylene acid esters.
Another aspect of the present invention provides the preparation method of described acrylate redispersable latex powder.
[beneficial effect]
Propylene ester emulsion of the present invention has satisfactory stability at emulsion polymerization process; Acrylate redispersable latex powder by this acrylic ester emulsion preparation can form the little regeneration emulsion of more former emulsion particle diameter variation behind the redispersion in water; And the prepared excellent in water resistance of having filmed of the emulsion of regenerating thus.
Embodiment
One aspect of the present invention provides a kind of acrylic ester emulsion, and it has nucleocapsid structure, and control in the stratum nucleare monomer and the weight ratio of the monomer in the shell be 8: 2, wherein the composition of this acrylic ester emulsion is as shown in table 1:
Table 1
Wherein, the consumption in the table 1 is the percentage ratio that accounts for total monomer weight, and described hard monomer is alkyl methacrylate or vinylbenzene.
The solid content control of final prepared acrylic ester emulsion is 40～45%.
Emulsifier type and concentration are with molecular weight and the molecular weight distribution of impact polymer, and influence determines emulsion particle number, latex particle size and the size distribution of polymer performance.Whether emulsifying agent uses reasonable, will be referred to whether emulsion system is stable, can polymerization process normally carry out with and subsequent whether store and use the problem of safety, also relates to the cost of polymkeric substance finished product.
The described emulsifying agent compound emulsifying agent that to be anionic emulsifier and nonionic emulsifier be mixed with in 1: 1～1: 3 ratio in the present invention, these two kinds of emulsifying agent performance complements, the two can alternately be adsorbed on the emulsion particle surface, has increased the interionic distance of emulsifying agent on the emulsion particle surface on the one hand; Because the electrostatic shielding effect of nonionic emulsifier greatly reduces the lip-deep static tension force of emulsion particle, increased emulsifying agent in the emulsion particle adsorption on the other hand, STABILITY OF POLYMER EMULSION is improved.
Described anionic emulsifier is to be selected from dodecyl phenyl ether disodium sulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, perfluoro-pelargonic acid ammonium, perfluor oxygen in the last of the ten Heavenly stems base benzene sulfonic acid sodium salt one or more; Described nonionic emulsifier is for being selected from polyoxyethylene octylphenol ether, high-carbon fatty alcohol polyoxyethylene ether, the polyoxyethylene amine one or more.
Employed emulsifying agent part by weight control is at 2～5% of total monomer weight among the present invention.When emulsifier concentration be lower than total monomer weight 2% the time, only the emulsified agent molecule in part emulsion particle surface covers, and condensing of emulsion particle easily taken place, and reduces polymerization stability; When the concentration of emulsifying agent be higher than total monomer weight 5% the time, the hydrophilic radical of emulsifying agent makes the water tolerance behind the polymer film forming be affected in the letex polymerization, and more emulsifying agent consumption can make and has more hydrophilic radical on the emulsion particle, difficult dehydration in spray-drying process, correspondingly need higher drying temperature, emulsion particle is bondd easily, influence the redispersibility of latex powder; In the use, free emulsifying agent also can be introduced a large amount of bubbles, the mechanical property of infringement polymkeric substance.
Ionic emulsifying agent only just can play effective emulsifying effect under certain pH value condition, wherein anionic emulsifier need use in alkaline medium, and buffer reagent can make the control of pH value in desired scope.Described buffer reagent can be selected from one or more in sodium-acetate, sodium bicarbonate, Sodium phosphate dibasic, the sodium sulfate, and consumption is about total monomer weight 0.2～0.5%.
The selection of the kind of monomer and copolymerization determination of ratio generally go to consider from the angle of glass transition temperature of polymer, latex powder use properties and cost.There is minimum film-forming temperature (MFT) in polymer emulsion, be that emulsion particle is assembled the minimum temperature that forms continuous film mutually, the only construction of the temperature more than minimum film-forming temperature, could guarantee even compact and the cohesiveness of film, and the glass transition temperature Tg of polymkeric substance becomes positive correlation with the polymer film forming temperature.If second-order transition temperature is too high, the hardness height of film, (construction temperature is normal temperature even lower) polymer film forming difficulty at normal temperatures, polymkeric substance will be affected for the modified effect of mortar, if but the second-order transition temperature of polymkeric substance is too low, the polymer particles intergranular condenses again easily in spray process, influences the redispersion of latex powder.On the contrary, if Tg is too low, the storage stability in storage of latex powder also can reduce.Therefore the second-order transition temperature of telomerized polymer is very important, specifically can be by the additional proportion design redispersible polymer latex powder second-order transition temperature of selecting suitable monomers and regulating the soft or hard monomer.
In order to prevent the bonding between the emulsion particle in the high temperature drying process, the present invention is designed to the nucleocapsid structure that stratum nucleare is softer, shell is harder with emulsion particle, make the higher shell of Tg become the sealing coat of emulsion particle in spraying drying, make on the one hand and be difficult between the micelle merge fully, when in water, disperseing again, be separated into emulsion with less granularity; On the other hand, in spray and preservation process, can reduce the possibility of the adhesion caking between the rubber powder.
Alkyl methacrylate described in the present invention is to be selected from methyl methacrylate, Jia Jibingxisuanyizhi and the methacrylic tert-butyl acrylate one or more; Using hard monomer in the present invention is in order to improve the water tolerance of polymkeric substance.
Described alkyl acrylate is to be selected from the just own ester of ethyl propenoate, n-butyl acrylate, vinylformic acid n-pentyl ester and propylene ester one or more, and it can guarantee that emulsion polymer has good film-forming properties.
The oleophylic long-chain that many carbon of described (methyl) vinylformic acid ester comprises can strengthen the hydrophobicity of the polymkeric substance that forms, and the existing in polymkeric substance inside and can play self-plasticizing action of these oleophylic chains, is used for the second-order transition temperature of telomerized polymer.Many carbon of vinylformic acid ester of the present invention is for being selected from (methyl) stearyl acrylate alcohol ester, (methyl) lauryl acrylate, methacrylic acid tridecyl ester and (methyl) Isooctyl acrylate monomer one or more, and its consumption is controlled to be 1～10% of acrylate monomer gross weight.
The described polymkeric substance that contains silicon, fluorine element has low surface tension, and contain the segment of these elements behind the polymer film forming can be to the film surface transport, form the film surface of water-tolerant, improve the water resistance of material.Preferred employing in the present invention is siliceous, propylene ester monomer and the propylene ester monomer copolymerization of using always of fluorine element, thereby improves the water tolerance of prepared latex powder.Described monomer siliceous, fluorine element is to be selected from methyl ethylene dichlorosilane, vinyltriethoxysilane, methyl allyl acyloxypropyl trimethoxysilane, vinylformic acid hexafluoro butyl ester, trifluoroethyl methacrylate and the methacrylic acid ten difluoro heptyl esters one or more.This class monomer has good effect to improving prepared latex powder water tolerance, just can achieve the goal with a spot of monomer, and controlling its consumption is 1～10% of total monomer weight.
Described (methyl) acrylic acid hydroxy alkyl ester and unsaturated alkyl carboxylic acid can be used as the wetting ability function monomer, make the acrylic ester polymer of gained that good dispersiveness be arranged in water; Yet the hydrophilic radical that comprises on this class monomer can make the emulsion spray-drying process become difficult again, so their consumption will be controlled proper.Described (methyl) acrylic acid hydroxy alkyl ester is for being selected from (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-3-hydroxy propyl ester, vinylformic acid-4-hydroxyl butyl ester and vinylformic acid-5-hydroxyl pentyl ester one or more, and controlling these monomer consumptions is 1～5% of total monomer weight.
Described alkyl carboxylic acid is acrylic or methacrylic acid, and consumption is controlled at 1～5% of total monomer weight.
Adopt oil-soluble initiator in the present invention, oil-soluble initiator can be dissolved in the acrylate monomer, and emulsification can avoid water soluble starter to cause the monomer formation oligopolymer that is dissolved in the water and the problem that polymerization stability is descended at aqueous phase to it is entered in micella or the monomer droplet so together.Oil-soluble initiator among the present invention can be selected from least a in the following material: benzoyl peroxide, lauryl peroxide, succinyl-superoxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), tertbutyl peroxide; The consumption control of initiator is at 0.5～1.0% of total monomer weight.
Method of emulsion polymerization has intermittent type emulsion polymerization, semi-continuous emulsion polymerizing method, continuous emulsion polymerization, pre-emulsion polymerization method, seed emulsion polymerization etc. several.Wherein semi-continuous emulsion polymerizing adds components such as partial monosomy and initiator, emulsifying agent, dispersion medium in the reactor earlier, after being aggregated to a certain degree, again residual monomers, or on the initiator, reductive agent etc. joins continuously according to certain step at certain time intervals and proceeds polyreaction in the reactor, until reaching desired transformation efficiency, reaction namely comes to an end.Semi-continuous emulsion polymerizing can be divided into hunger, semistarvation, three kinds of states of exuberant attitude again according to the speed of monomer dropping speed, control polymerization rate and rate of heat release by reinforced speed, guarantee system homo(io)thermism and polyreaction balance are carried out, the peak heat release of avoiding other polymerization methods to occur; Monomer just reacts in the middle of in a single day entering system, and it is identical with reinforced middle monomer composition that monomer-free accumulation in the system, the copolymerization of the polymkeric substance that generates are formed, and can control the copolymerization of emulsion polymer effectively and form.
The present invention realizes the free-radical emulsion polymerization of acrylate monomer by the semi-continuous emulsion polymerizing method, but is not limited to this method, and the step that the present invention prepares described acrylic ester emulsion is as follows:
A, in the ratio in the table 1 each component under agitation to be made the stratum nucleare, the shell monomers mixed solution that are dissolved with initiator uniformly respectively standby;
B, Jiang Shui, emulsifying agent, buffer reagent is disposable joins in the reactor that has thermometer, whipping appts, balance dropping funnel, mixes; Add the nuclear layer monomer that accounts for nuclear layer monomer weight 20～30% then, stir after 20～30 minutes, make it be distributed to aqueous phase equably; Then heat to about 30 minutes of 75 ℃～80 ℃ insulations, become the blue stratum nucleare seed emulsion that forms until reactant;
C, keep this temperature, drip remaining nuclear layer monomer in the stratum nucleare seed emulsion, the control rate of addition dropwised in 2.5～3.5 hours, continued insulation and formed the stratum nucleare emulsion in 0.5～1 hour;
D, drip the shell monomers mixed solution in the reaction system, the dropping time is controlled at 1～1.5h; After dropwising, temperature of reaction is raised to 90 ± 5 ℃, continues insulation 1～1.5 hour;
E, cool to room temperature gradually filter with 100 order steel meshes, and discharging obtains the acrylic ester emulsion that solid content is 40～45wt%.
Another aspect of the present invention provides the acrylate redispersable latex powder by the preparation of aforesaid propylene acid esters.
Adopted the described acrylate redispersable latex powder of spray drying method for preparation among the present invention.
Spraying drying is to utilize spraying gun that stock liquid is separated into droplet, and utilizes the hot-air dry droplet and obtain a kind of drying means of product.Stock liquid can be that solution, emulsion, suspension, fused solution or cream are stuck with paste liquid.Drying products can be made powdery, particulate state, hollow ball or a shape according to production requirement.
Redispersible latex powder of the present invention is by add other auxiliary agent in the gained acrylic ester emulsion of above-mentioned preparation, as anti-caking agent, protective colloid, defoamer, sterilant etc., and form by atomization drying dehydration efflorescence.The component of composition for preparing renewable dispersed latex powder of the present invention is as shown in table 2:
Table 2
Latex particle taking place along with the vaporization of moisture in the droplet, droplet volumetric shrinkage in spray process pile up even merge, makes numerous emulsion particle pile up and form rubber powder.At this moment only under the situation that original emulsifying agent exists, emulsion particle will be piled up formation can't the rubber powder of redispersion in water, needs to add protective colloid, inorganic anti condensing agent etc.The common provide protection of protective colloid, emulsifying agent and inorganic anti condensing agent is arranged between the particle; can make between the latex particle and be spaced from each other; the factor coexistence of merging between emulsion particle and separating; the latex powder granularity of Xing Chenging can maintain in certain scope like this, to guarantee the redispersible of latex powder in water.
Protective colloid commonly used comprises silicon sol, ether of cellulose, polyvinyl alcohol, polyacrylamide, polyvinylpyrrolidone, ethers modified polyvinyl alcohol, modified polyacrylic acid, starch and derivative thereof.Protective colloid of the present invention be alcoholysis degree more than 90%, the polymerization degree is 300～1200 polyvinyl alcohol (PVA).The polymerization degree is lower than 300 PVA, can not play a very good protection to colloid, and the polymerization degree is excessive, and emulsion viscosity is increased, and influences the carrying out of atomization process.It is standby that PVA is mixed with 20% the aqueous solution, and consumption is controlled in 5～20% of acrylic ester polymer gross weight.
Inorganic coagulation-prevention agent of the present invention is to be selected from calcium carbonate, clay, silicon-dioxide, pure aluminium silicate, talcum powder and the kaolin one or more, and consumption is 5%～20% of acrylic ester polymer weight.
According to the needs of dry pulverizing process or latex powder performance, can also further add some functional aids, mainly comprise defoamer, sterilant etc., its consumption is decided according to the actual requirements.
Another aspect of the present invention provides the preparation method of acrylate latex powder, and it is to obtain by the spray method that adopts rotary atomizer, and this method comprises the steps:
The composition that spraying drying is shown in Table 2;
Latex powder forms by cyclonic separator separates, and collects powder in the tower exit with stainless steel storage tank;
Obtain latex powder with the filtration of 200 mesh filter screens.
Spraying drying can make material realize dry nebulization in the short time (several seconds to 30 seconds), higher heat utilization efficiency is arranged, be easy to regulate or control the quality index of product by changing operational condition, in addition can be according to processing requirement, make Powdered, hollow ball-shape or a loose shape product, and need not pulverize, simplified technical process, realize mechanize, automatization easily, can also alleviate dust from flying, improve work situation, be easy to realize operate continuously and full automatic control.
The product of the handled raw material of spray drying unit and gained also has a great difference, and their flow process is substantially the same.Because it is very big, particularly particularly important to the drying of heat-sensitive material for quality product and technico-economical comparison influence that the material atomizing obtains size and the degree of uniformity of droplet, therefore making the used spraying gun of feed liquid atomizing is the key part of spray-dryer.Used spraying gun has following three kinds at present: pneumatic atomizer, pressure atomizer, rotary atomizer.Use rotary atomizer to prepare redispersible latex powder among the present invention.
For obtaining even, the stay-in-grade latex powder of outward appearance, spray art condition optimization of the present invention is: atomizing wheel rotating speed 200～500r/min, and 100～150 ℃ of drying tower inlet temperature, drying tower temperature out are 70～90 ℃, input speed is 30～80mL.min
-1Spray-drying tower is furnished with the exhausting negative pressure device, and latex powder forms by cyclonic separator separates, and collects powder in the tower exit with stainless steel storage tank, after 200 mesh filter screens filter, places loft drier to preserve with the bag sealing.
Embodiment
Hereinafter, will describe in further detail preferred embodiment of the present invention.Before being described, should be appreciated that the term that uses in specification sheets and appending claims should not be construed to only limits to general or literal connotation, but is allowing the contriver to be used for making an explanation based on correspondence technical elements of the present invention on the basis of principle that best interpretations ground suitably limits term.Therefore, the description that proposes in specification sheets is only for being used for explaining the object of the invention preferred embodiment, but not be intended to limit the scope of the invention, thereby be appreciated that under the situation that does not depart from the spirit and scope of the invention, can make being equal to substituting and revising it.
Embodiment 1:
1, the preparation of acrylate core-shell polymer emulsion
Table 3
Prepare as follows according to the prescription shown in the table 3:
A, the prescription of pressing in the table 3 mix nuclear layer monomer and shell monomers respectively with separately initiator, form uniform nuclear layer monomer solution and shell monomers solution for standby;
B, with the polyoxyethylene octylphenol ether in the starting raw material, dodecyl phenyl ether disodium sulfonate and anhydrous Na HC0
3Join in the four-hole bottle that has thermometer, whipping appts, balance dropping funnel, condensing reflux pipe, under stirring action, add the deionized water of amount described in the table 3, stirred 30 minutes;
C, the nuclear layer monomer that adding 25wt% measures in reaction flask stirred after 20～30 minutes, made it be distributed to aqueous phase equably; Heat to 80 ℃ then, be incubated about 30 minutes and become blue until reactant, restir namely formed transparent stratum nucleare seed emulsion in 20 minutes;
C, keep this temperature, in formed stratum nucleare seed emulsion, drip remaining nuclear layer monomer, remain in 3～3.5 hours monomer dropping is intact, continue insulation then and formed the stratum nucleare polymer emulsion in 1 hour;
D, drip the shell monomers mixed solution in this temperature downhill reaction system, the dropping time is controlled at 1～1.5h; After dropwising, temperature of reaction is raised to 90 ℃, continues insulation 1～1.5 hour;
E, cool to room temperature gradually filter formed emulsion with 100 order steel meshes, it is 45% siliceous polyacrylate dispersion that discharging obtains solid content.
2, the preparation of redispersible latex powder
Table 4
Choose prepared acrylic ester emulsion 100 grams, regulate pH value to 9 with the NaOH dilute solution of 0.2 gram 5%.In emulsion, add the polymerization degree and be 400, alcoholysis degree is 90% the PVA aqueous solution, calcium carbonate and defoamer BYK-088 disperse to be formed for spray-dired feed liquid under the violent stirring effect.Setting atomizer rotating disk rotating speed is 300r.min
-1, inlet temperature is 120 ℃, temperature out is 80 ℃, input speed 50ml.min
-1Carry out spraying drying under the condition.Spray-drying tower is furnished with the exhausting negative pressure device, and latex powder forms by cyclonic separator separates, and collects powder in the tower exit with stainless steel tubbiness storage tank, after 200 mesh filter screens filter, places loft drier to preserve with the bag sealing.
Embodiment 2:
1, preparing acrylate emulsion
Except being prepared the acrylic ester emulsion according to the component shown in the table 5, prepare acrylic ester emulsion in the mode identical with embodiment 1.
Table 5
2, the preparation of redispersable latex powder
Except in the acrylic ester emulsion of above-mentioned condition preparation, adding outside the component shown in the table 6 (wherein, the described PVA polymerization degree is 800, alcoholysis degree be 98%), prepare redispersable latex powder in the mode identical with embodiment 1.
Table 6
Embodiment 3:
1, preparing acrylate emulsion
Except being prepared the acrylic ester emulsion according to the component shown in the table 7, prepare acrylic ester emulsion in the mode identical with embodiment 1.
Table 7
2, redispersable latex powder
Except in the acrylic ester emulsion of above-mentioned condition preparation, adding outside the component shown in the table 8 (wherein, the described PVA polymerization degree is 1000, alcoholysis degree be 95%), prepare redispersable latex powder in the mode identical with embodiment 1.
Table 8
Embodiment 4:
1, preparing acrylate emulsion
Except being prepared the acrylic ester emulsion according to the component shown in the table 9, prepare acrylic ester emulsion in the mode identical with embodiment 1.
Table 9
2, the preparation of redispersible latex powder
Except in the acrylic ester emulsion of above-mentioned condition preparation, adding outside the component shown in the table 10 (wherein, the described PVA polymerization degree is 1200, alcoholysis degree be 95%), prepare redispersable latex powder in the mode identical with embodiment 1.
Table 10
Comparative Examples 1:
Except initiator being replaced by the water-based initiator, all the other are to finish letex polymerization with the identical preparation method of embodiment 1.The more oil-soluble initiator of this polymerization process stability is poor, and gained emulsion film forming water tolerance is relatively poor.
Comparative Examples 2:
Except the methyl allyl acyloxypropyl trimethoxysilane among the embodiment 1 is replaced by the n-butyl acrylate, all the other prepare acrylic ester emulsion in the mode identical with embodiment 1.The emulsion water tolerance of gained is relatively poor.
Comparative Examples 3:
Be 1400 polymkeric substance except PVA required in the spray process among the embodiment 1 being replaced with the polymerization degree, all the other components are finished by the 1 described mode of enforcement.The PVA of this polymerization degree makes and sticks together in the stock liquid spray process of gained, is difficult to make the powder of even particle size.
Comparative Examples 4:
Be 250 polymkeric substance except PVA required in the spray process among the embodiment 1 being replaced with the polymerization degree, all the other components are finished by the 1 described mode of enforcement.The PVA of this polymerization degree makes the stock liquid of the gained formed latex powder of spraying, and is scattered in to be difficult to form the regeneration emulsion in the water.
Testing method:
1, stability of emulsion and cohesion rate:
The stability of emulsion polymerization is represented with the cohesion rate, is obtained by weighting method.Polyreaction finishes, and emulsion is filtered with 100 order filtering nets, and the condensation product on collection filter residue and reactor, the agitator is dried about 120 ℃ to constant weight and weighed, according to formula 1 calculating cohesion rate:
Formula 1
Cohesion rate=m
1/ m
2* 100%
Wherein: m
1Weight for condensation product;
m
2Gross weight for nuclear layer monomer and shell monomers.
The stability of the more little expression emulsion polymerization process of the value of cohesion rate is just more good.
2, the particle diameter of emulsion particle and Determination of distribution thereof
The particle diameter that the emulsion particle of ACRYLIC EMULSION reaches lactiferous emulsion particle is again obtained by ZEN3600 type nanometer laser particle size analyzer (Britain Ma Erwen company) test, and measuring process is as follows:
Get 1～2 emulsion with the dilution of 20mL deionized water, leave standstill after stirring until bubble and eliminate fully; Emulsion after the dilution is poured in the polystyrene sample pond, and liquid level is about 1-1.5cm height apart from the sample pool bottom, puts into instrument and tests.
3, the mensuration of regeneration emulsion film water-intake rate
A certain amount of regeneration emulsion places the mould of tetrafluoroethylene, at room temperature dry 3 days; Then with the film of moulding under 50 ℃ vacuum condition dry a day again, obtain the film that thickness is 0.2mm;
Prepared film is cut into the sample that size is 0.2 * 4 * 4mm, places the distilled water of certain temperature to soak, and regularly takes out, and weighs after blotting the film coated surface washmarking with filter paper, by formula 2 calculates the water-intake rate of filming:
Formula 2
Water-intake rate=(m
3-m
0)/m
0* 100%
In the formula: m
0Be the weight after the constant weight of filming;
m
3Be the weight behind the suction 24h that films.
The results are shown in the table 11 of test:
Table 11
Claims (5)
1. an acrylic ester emulsion is characterized in that, emulsion particle wherein has nucleocapsid structure, and this acrylic ester emulsion is prepared by following component polymerization:
Starting raw material, based on the gross weight of stratum nucleare and shell monomers, this starting raw material comprises the emulsifying agent of 2～5wt%, the buffer reagent of 0.2～0.5wt%, the water of 120～150wt%;
Stratum nucleare, based on the gross weight of stratum nucleare and shell monomers, this stratum nucleare comprises the initiator of 0.4～0.6wt%, the hard monomer of 20～40wt%, the alkyl acrylate of 30～50wt%, the monomer of siliceous, the fluorine element of 1～10wt%, and many carbon of (methyl) vinylformic acid ester of 1～10wt%;
Shell, based on the gross weight of stratum nucleare and shell monomers, this shell comprises the initiator of 0.1～0.2wt%, the hard monomer of 10～15wt%, the alkyl acrylate of 1～5wt%, (methyl) acrylic acid hydroxy alkyl ester of 1～5wt%, and the alkyl carboxylic acid of 1～5wt%;
Wherein, described hard monomer is alkyl methacrylate or vinylbenzene, and the weight ratio of nuclear layer monomer and shell monomers is 80: 20, and the solid content of this acrylic ester emulsion is 40～45wt%;
Wherein, the described emulsifying agent compound emulsifying agent that to be anionic emulsifier and nonionic emulsifier be mixed with by 1: 1～1: 3 weight ratio; Described buffer reagent is to be selected from sodium-acetate, sodium bicarbonate, Sodium phosphate dibasic, the sodium sulfate one or more; Described initiator is oil-soluble initiator; Described alkyl methacrylate is to be selected from methyl methacrylate, Jia Jibingxisuanyizhi and the methacrylic tert-butyl acrylate one or more; Described alkyl acrylate is for for being selected from ethyl propenoate, n-butyl acrylate, vinylformic acid n-pentyl ester and propylene ester one or more in the ester just; Described monomer siliceous, fluorine element is to be selected from methyl ethylene dichlorosilane, vinyltriethoxysilane, methyl allyl acyloxypropyl trimethoxysilane, vinylformic acid hexafluoro butyl ester, trifluoroethyl methacrylate and the methacrylic acid ten difluoro heptyl esters one or more; Described many carbon of vinylformic acid ester is for being selected from (methyl) stearyl acrylate alcohol ester, (methyl) lauryl acrylate, methacrylic acid tridecyl ester and (methyl) Isooctyl acrylate monomer one or more; Described (methyl) acrylic acid hydroxy alkyl ester is for being selected from (methyl) 2-Hydroxy ethyl acrylate, (methyl) vinylformic acid-3-hydroxy propyl ester, vinylformic acid-4-hydroxyl butyl ester and vinylformic acid-5-hydroxyl pentyl ester one or more; And described alkyl carboxylic acid is acrylic or methacrylic acid;
Wherein, described anionic emulsifier is to be selected from dodecyl phenyl ether disodium sulfonate, Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, perfluoro-pelargonic acid ammonium, perfluor oxygen in the last of the ten Heavenly stems base benzene sulfonic acid sodium salt one or more; Described nonionic emulsifier is to be selected from polyoxyethylene octylphenol ether, high-carbon fatty alcohol polyoxyethylene ether, the polyoxyethylene amine one or more.
Wherein, described initiator is to be selected from least a in the following material: benzoyl peroxide, lauryl peroxide, succinyl-superoxide, Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile) and tertbutyl peroxide;
Wherein, described acrylic ester emulsion prepares as follows:
A, in nuclear layer monomer and shell monomers, add initiator, and under agitation evenly mixing to make the stratum nucleare, the shell monomers mixed solution that are dissolved with initiator uniformly respectively standby;
B, Jiang Shui, emulsifying agent, buffer reagent is disposable joins in the reactor that has thermometer, whipping appts, balance dropping funnel, mixes; Add 20～30% the nuclear layer monomer mixed solution account for nuclear layer monomer weight then, stir after 20～30 minutes, make it be distributed to aqueous phase equably; Then heat to 75 ℃～80 ℃ insulations 30 minutes, become the blue stratum nucleare seed emulsion that forms until reactant;
C, keep this temperature, drip remaining nuclear layer monomer mixed solution in the stratum nucleare seed emulsion, the control rate of addition dropwised in 2.5～3.5 hours, continued insulation and formed the stratum nucleare emulsion in 0.5～1 hour;
D, drip the shell monomers mixed solution in the reaction system, the dropping time is controlled at 1～1.5h; After dropwising, temperature of reaction is raised to 90 ± 5 ℃, continues insulation 1～1.5 hour;
E, cool to room temperature gradually filter with 100 order steel meshes, and discharging obtains acrylic ester emulsion.
2. a water-fast acrylate redispersable latex powder is characterized in that, it is obtained by the composition spray drying that comprises following component:
The described acrylic ester emulsion of the claim 1 of 100 weight parts, its solid content are 40wt%;
Based on the described acrylic ester emulsion of 100 weight parts, the inorganic coagulation-prevention agent of 2～8 weight parts;
Based on the described acrylic ester emulsion of 100 weight parts, the PVA aqueous solution of 10～50 weight parts, wherein, the content of the PVA of the PVA aqueous solution is 20wt%;
Based on the described acrylic ester emulsion of 100 weight parts, 0.2～0.5 weight part concentration is the NaOH aqueous solution of 5wt%;
Based on the described acrylic ester emulsion of 100 weight parts, other auxiliary agent of 0.05～0.1 weight part;
Described inorganic coagulation-prevention agent is to be selected from calcium carbonate, clay, silicon-dioxide, pure aluminium silicate, talcum powder and the kaolin one or more; Described other auxiliary agent is defoamer or sterilant.
3. latex powder according to claim 2 is characterized in that, wherein, the alcoholysis degree of described PVA is more than 90%, and the polymerization degree is 300～1200.
4. according to the preparation method of claim 2 or 3 described latex powder, it is characterized in that it is to obtain by the spray method that adopts rotary atomizer, this method comprises the steps:
Spraying drying claim 2 or 3 described compositions;
Latex powder forms by cyclonic separator separates, and collects powder in the tower exit with stainless steel storage tank;
Obtain latex powder with the filtration of 200 mesh filter screens.
5. preparation method according to claim 4 is characterized in that, wherein, the spray art condition is: atomizing wheel rotating speed 200～500r/min, and 100～150 ℃ of drying tower inlet temperature, drying tower temperature out are 70～90 ℃, input speed is 30～80mLmin
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| CN106543374A (en) * | 2016-10-13 | 2017-03-29 | 四川大学 | Fluoro-acrylate copolymer emulsion and preparation method thereof and prepare latex film method |
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| CN111072862B (en) * | 2019-12-31 | 2022-09-20 | 长兴化学工业(中国)有限公司 | Acrylate polymer microsphere, preparation method and application thereof |
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Denomination of invention: Acrylate emulsion, waterproof acrylate re-dispersible latex powder prepared from same, and preparation method for latex powder Effective date of registration: 20160902 Granted publication date: 20130911 Pledgee: Chuzhou credit Company limited by guarantee Pledgor: Wang Xiaodi|Beijing Tianwei Paragon chemical products Ltd. Registration number: 2016990000762 |
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