CN102464754B - Emulsifier-free acrylic ester emulsion polymerization method - Google Patents
Emulsifier-free acrylic ester emulsion polymerization method Download PDFInfo
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Abstract
The invention relates to an emulsifier-free acrylic ester emulsion polymerization method. For a reaction system comprising 40-60 wt% of purified water, 2-9 wt% of a carboxylic acid monomer (A) with a polymerizable functional group of a carbon-carbon double bond and 40-50 wt% of a methyl acrylicylester monomer or an acrylic ester monomer ( B ), 0.2-2.0 wt% of an inorganic alkali liquid is adopted to adjust the pH value of the reaction to 9.0-13.0, 0.2-1.0 wt% of a peroxide initiator of a sulfate is adopted to carry out emulsion polymerization, and an organic amine compound is adopted to adjustthe pH value of the resulting aqueous resin emulsion to 7.0-9.5 at the terminal stage of the reaction. The prepared aqueous resin emulsion has characteristics of particle size of about 100-130 nm, uniform distribution, good appearance, low acid value of 3.5-6.5 mgKOH/g, specific gravity of about 1.07, excellent storage stability, good permeability and easy construction, wherein the specific gravity of the prepared aqueous resin emulsion is slightly larger than the specific gravity of the water. The dry coating film by the emulsion has characteristics of good water resistance, excellent tensile strength and excellent wear resistance.
Description
Technical field
The present invention relates to the water-and acrylate emulsion polymerisation process, the acrylic ester emulsion polymerization method that particularly relates to a kind of emulsifier-free, the water dispersible acrylic ester emulsion of environmental protection and public nuisance free can be provided, its resin emulsion particle diameter is little and the outward appearance that is evenly distributed is good, proportion is a bit larger tham water, low acid value, the storage stability is superior, and permeate well is easily constructed.The water tolerance of its dry coating is good, and tensile strength is good and wear resistant is superior.
Background technology
Traditionally, acrylic ester emulsion be with acrylic monomer in the aqueous solution, adopt low molecular weight emulsifier to react through emulsion polymerization, to monomer, water and/or solvent, initiator, emulsifying agent, under the effect and mechanical stirring of emulsifying agent, make monomer in water or other solvents, be dispersed into milk sap and carry out radical polymerization and get.If but in the time of need to making polymer solids, then must breakdown of emulsion, the multistep formality such as washing, dehydration, drying, production cost is high; And the impurity such as emulsifying agent is difficult for eliminating in the polymeric articles of gained, and affects electric property etc., and improper.
Resulting emulsion is when drying, and emulsifying agent easily oozes out in polymkeric substance, and pollute the surface of acrylic ester emulsion and reduce and other materials between Bonding strength, also inapplicable.
React caused problem for solving emulsifying agent participation emulsion polymerization, in patent documentation 1 (TOHKEMY 2006-206907 number), putting down in writing the non-ionic surfactant acrylic ester synthesizing emulsions such as use Triton X-100 (polyethyleneglycol octyl phenyl ether), polyethylene glycol nonylphenyl ether, polyoxyethylene glycol decyl phenyl ether, though help anti-environmental pollution processed, but the compound of these Environmental Hormones is harmful, and is restricted in the use.
When usually carrying out emulsion polymerization, monomer is less in the solubleness of aqueous phase, be difficult for making drop to migrate to micella (micelle), give hydrotropy and need to add the organic solvents such as acetone or Virahol, also someone attempts adding co-emulsifier and under high-speed stirring, makes monomer be dispersed into the micron order monomer droplet in water and be made for main locus of polymerization.That is so-called mini-emulsion polymerization, to solve the problem of monomer indissoluble.
Above-mentioned fine emulsion polymerization can solve the problem of monomer indissoluble preferably, someone adopts oil-soluble initiator to make directly initiated polymerization in drop of monomer, monomer does not need by the transition process of drop to micella, and directly droplet nucleation is avoided the undissolved problem of monomer.
Adopt the compound emulsifying agent that is formed by ionogenic surfactant and long chain aliphatic alcohol or long chain alkane by the people, make monomer in miniemulsion, form stable nano-liquid droplet (30～500nm).Because the pressure difference between the large small droplets of the osmotic pressure that ionogenic surfactant and compound emulsifying agent produce counteracting monomer, reduce the monomer diffusion between the different size drop, thereby greatly improve the stability of small droplets, make miniemulsion obtain enough kinetic stabilities.Make by water, oil, tensio-active agent and auxiliary agent, can the thermodynamically stable milk sap of spontaneous formation.
But in polymerization process, change along with the water in the composing system, solvent, emulsifying agent and assistant for emulsifying agent or polymeric reaction temperature, can make surfactant molecule in solution, mutually be transformed into the structure of oil O/W, water W/O and doubly-linked ideotype (bicontinue) B.C three types in oil in water owing to the micella hydrophilic, that lipophilic group produces, form that median size is little, surface tension is low, the wettability perviousness is extremely strong, the better polymer micro-emulsion of stability.
In patent documentation 2 (Japanese kokai publication hei 7-331208 communique), in the presence of the macromolecule emulsifier of pointing out to consist of for principal constituent at reactive emulsifier, with styrenic and/or (methyl) alkyl acrylate (B) and vinylformic acid and/or methacrylic acid anionic property monomer (C), emulsification is composed glutinous agent resin and must be composed glutinous agent resin emulsion, with the water-based adhesive composition that contains acrylic ester polymer emulsion and/or sticking agent and form with latex.
But previous reaction emulsifying agent (A) refers to the usage ratio that has carbon-to-carbon double bond to have the interfacial agent of hydrophilic group and hydrophobic group in the molecule and accounts for the formation monomer component up to 10～50wt%, and needs in addition to compose glutinous agent resin participation reaction.
How to avoid emulsifying agent to participate in the problem points that reaction causes, the emulsion polymerization process or the part of resulting polymers that do not add emulsifying agent in the reaction process fully or only add micro-emulsifying agent (its concentration is less than critical micella concentration C MC) have the feature of macromolecule emulsifier, are the trend of the times of emulsion polymerization.This is the emulsifier-free emulsion polymerization that does not add conventional emulsifier, can get the emulsion particle of surface cleaning, single dispersion, avoids simultaneously emulsifying agent on the impact of environment.
In addition, in patent documentation 1, when pointing out the acrylic ester synthesizing emulsion, water-solublely increase glutinous resin and do not use emulsifying agent to carry out letex polymerization by using, can improve the stability of freezing of acrylic ester emulsion, and can be after freezing thaw the time can re-use, satisfy these physical property fully with synthetic can making once, though the effect that shortens the operation stage is arranged.But adopt to increase glutinous resin be water-soluble, make the latex film shortcoming water tolerance of gained, and be not suitable for the coating aspect.
Wish solves the problem points of water tolerance, should from latex film in ionogen and the relevant latex colloidal particle stability of other low molecular content set about.And the latex colloidal particle stability is mainly determined by the surfactivity oligomer, and latex micelle surface charge density is larger, and then stability is better; The micelle surface stability still depends on the wetting ability of latex micelle particle surface, and wetting ability is larger, and then stability is better; This is that polarity because of the latex micelle causes particle surface and aqueous phase interface to interact reducing the Gibbs free energy at interface, enables to improve due to the stability of emulsion micelle particle.
Therefore avoiding adopting the pollution of non-ionic surfactant generation and the problem that co-emulsifier solves the monomer indissoluble, and do not add the emulsifier-free emulsion polymerization of conventional emulsifier, and when improving emulsion polymerization small droplets stability and improved the stability of latex micelle by the surfactivity oligomer, and the emulsion particle of surface cleaning, single dispersion, avoid simultaneously emulsifying agent on the impact of environment, be the problem that the present invention needs to be resolved hurrily.
Summary of the invention
The object of the present invention is to provide a kind of acrylic ester emulsion polymerization method of emulsifier-free, median size is even, the wettability perviousness is extremely strong to synthesize, the better polymer micro-emulsion of stability.
For achieving the above object, the acrylic ester emulsion polymerization method of emulsifier-free provided by the invention comprises following operation:
1) preparation is the reaction system that principal constituent forms by the carboxylic acid monomer A2～9wt% of pure water 40～60wt%, tool carbon-to-carbon double bond polymerizable functionalities base and alkyl methacrylate or alkyl acrylate monomer B 40～50wt%;
2) react in the scope of pH9.0～13.0 with the inorganic alkali lye adjustment of 0.2～2wt%;
3) keep this to react on 70～95 ℃ of temperature and stirred 30 minutes with rotating speed 150～300rpm, adopt the Sodium Persulfate of 0.2～1.0wt%, the colony that Potassium Persulphate, ammonium persulphate form select one or more give Initiation as initiator, carry out emulsion polymerization;
4) the pH value of adjusting resulting water-base resin emulsion with the organic amine of selecting one or more in by ammoniacal liquor, Trimethylamine 99, monoethanolamine, dimethylethanolamine, dimethylethanolamine, colony that the 2-amido-the 2-methylpropanol forms in last stage reaction obtains the narrow water-based acryl polymer of particle diameter 100～130nm homogeneous and distributed pole in 7.0～9.5 scope.
Described polymerization process, wherein to state the carboxylic acid monomer A of carbon-to-carbon double bond polymerizable functionalities base be one or more that selected by vinylformic acid, methacrylic acid, itaconicacid and β-crotonic acid colony to tool
Described polymerization process, wherein alkyl methacrylate or alkyl acrylate monomer B be methyl methacrylate, methacrylic acid ethyl ester, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid tri-n-butyl, methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, vinylformic acid tri-n-butyl, vinylformic acid 2-b hexyl, methacrylic acid 2-b hexyl, lauryl methacrylate(LMA), vinyl cyanide, vinyl cyanide colony select one or more.
Described polymerization process, wherein inorganic alkali lye is one or more that selected by sodium hydroxide, potassium hydroxide, tertiary sodium phosphate colony.
By the inventive method emulsion polymerization preparation and surperficial latex micelle particle with larger wetting ability and better stability, synthesize median size evenly, the better polymer micro-emulsion of extremely strong, the stability of wettability perviousness.
Description of drawings
Fig. 1 is the polymerization process of the acrylic ester emulsion of a kind of emulsifier-free relevant with the present invention, by the microspherulite diameter distribution curve of the emulsion polymer of embodiment 1～5 gained wherein and directly draw the distribution situation of microspherulite diameter.
Fig. 2 is the polymerization process of the acrylic ester emulsion of a kind of emulsifier-free relevant with the present invention, utilizes the measured Tg point of METTLER-TOLEDO Differentialscanning calorimeters (DSC) by the emulsion polymer of embodiment 1 gained wherein.
The drawing reference numeral explanation:
Ordinate zou: volume (%);
X-coordinate: particle diameter (μ m).
Embodiment
The present invention is to by pure water 40～60wt%, carboxylic acid monomer A2～the 9wt% of tool carbon-to-carbon double bond polymerizable functionalities base, reaching alkyl methacrylate or alkyl acrylate monomer B 40～50wt% is the reaction that principal constituent forms, do not adopt organic solvent or solubility promoter or amphoteric solvent, adjusting reaction with inorganic alkali lye 0.2～2.0wt% first (is advisable with pH 9.0～13.0 in suitable pH value scope, wherein again take 11.0～13.0 as should) the lower initiator that adds gives the emulsion polymerization reaction that Initiation carries out emulsifier-free, add the organic amine of an amount of pH adjusting agent (is advisable with 8.0～9.0) in 7.0～9.5 scope to adjust pH in the reaction latter end, can be made into that particle diameter 100～130nm is evenly distributed and extremely narrow polymer emulsion, so that finish the present invention.The water dispersible acrylic ester emulsion of environmental protection and public nuisance free can be provided, and its resin emulsion particle diameter is little and the outward appearance that is evenly distributed is good, and proportion is a bit larger tham water, low acid value, and the storage stability is superior, the good easy construction of perviousness.The water tolerance of its dry coating is good, and tensile strength is good and wear resistant is superior.
The present invention is when letex polymerization, make the carboxylic acid monomer of apparatus carbon-to-carbon double bond polymerizable functionalities base in water, making carboxylic acid monomer's dissolving of carbon-to-carbon double bond polymerizable functionalities base form alkaline aqueous solution with inorganic base dissolving Acrylic Acid Monomer makes the end group at polymer molecular chain (oleophylic) form hydrophilic ionic group,, form charged layer at microsphere surface and can make emulsion-stabilizing as initiator with the superoxide of Sulfates.
Usually the Acrylic Acid Monomer of adopting in the emulsification method is too little in the solubleness of aqueous phase, be difficult for being moved to micella by monomer droplet, as adopt traditional emulsion polymerisation process, wish to get relatively difficulty of stable acrylic ester emulsion, the mode that need adopt the organic solvent (such as acetone or Virahol etc.) of industrial normal adding gives solubilising.And the present invention does not namely adopt organic solvent when the film performance of the water-and acrylate emulsion of considering gained.
Initiator of the present invention, although the colony that can adopt the superoxide of conventional benzoyl peroxide (BPO), azo isobutyronitrile (AIBN), Sodium Persulfate, ammonium persulphate, Potassium Persulphate, hydrogen peroxide to form select one or more give Initiation as initiator.But be preferably employing vitriol superoxide in the present invention, for example can enumerate Sodium Persulfate and (be designated hereinafter simply as Na
2S
2O
8), Potassium Persulphate (is designated hereinafter simply as K
2S
2O
8), ammonium persulphate (is designated hereinafter simply as (NH
4)
2S
2O
8).
By the initiator initiated polymerization,, namely separate out from aqueous phase when the polymericular weight that generates reaches a certain threshold value than very fast, forms initial latex particle by chain growth speed in water for monomer molecule.Because these particle surface electric density are lower, electrostatic repulsion forces is not enough and make particle-stabilised between the particle, can mutually assemble, until generate stable latex particle, radical ion (hydrophilic) on polymer molecular chain (oleophylic) and terminal group thereof, the ester class that generates has the characteristic of anionic emulsifier-contain hydrophilic and oleophilic base, and reach the emulsifying effectiveness of emulsifier-free, the polymer esters class that makes polymerization and get has the characteristic of anionic emulsifier, and reaches the emulsifying effectiveness that emulsifier-free carries out letex polymerization.
The present invention is by adding mineral alkali, makes the monomer polarization group that participates in the emulsion polymerization reaction and forms charged layer in microsphere surface, can make emulsion-stabilizing make the latex micelle particle surface of gained have hydrophilic group, to replace conventional emulsifier.
In reaction process, do not add emulsifying agent fully, make (methyl) alkyl acrylate (B), carry out emulsion polymerization with the carboxylic acid monomer (A) of tool carbon-to-carbon double bond polymerizable functionalities base for principal constituent, make the part of resulting polymers have the feature of macromolecule emulsifier, select pH value that organic amine adjusts gained water-base resin emulsion in the scope of pH 7.0～9.5 in the reaction latter end, and the acid value of the water-base resin emulsion of gained is low to moderate 3.5～6.5mgKOH/g.When carrying out the emulsion polymerization of emulsifier-free again, make the terminal group at the polymer molecular chain of oleophylic form hydrophilic ionic group, form charged layer at the microsphere surface of the latex micelle of gained and can make emulsion-stabilizing.
Mineral alkali of the present invention, although can adopt one or more that the colony that formed by sodium hydroxide, potassium hydroxide, calcium hydroxide, yellow soda ash, salt of wormwood, hydrolith, sodium hydride, potassium hydride KH, tertiary sodium phosphate selects, be preferably in sodium hydroxide, potassium hydroxide, the tertiary sodium phosphate one or more.This kind mineral alkali can make wetting ability and the anion characteristic that height is arranged in the pH of broadness scope with the carboxylic acid monomer of the tool carbon-to-carbon double bond polymerizable functionalities base of its reaction, make the hydrophilic ionic group of terminal group formation at the polymer molecular chain of oleophylic, so that the microsphere surface of the latex micelle of gained forms charged layer, and emulsion that must be stable.
In the present invention, the carboxylic acid monomer of the tool carbon-to-carbon double bond polymerizable functionalities base of Yu Shuizhong, the monocarboxylic acid such as vinylformic acid, methacrylic acid, β-crotonic acid (maleic acid) or Malin's acid, Malin's acid anhydrides, fumaric acid, Yi Kang are sour such as enumerating, muconic acid (2, the 4-muconic acid) carboxylic acid of omega-dicarboxylic acids such as,, make with mineral alkali as initiator with the superoxide of vitriol
CarboxylicAcid mono dissolves and the hydrophilic resin of the son that secures satisfactory grades, and the part of resulting polymers has the feature of macromolecule emulsifier, can replace conventional interfacial agent, does not add emulsifying agent fully and make in reaction process
CarboxylicAcid mono carries out the emulsion polymerization of emulsifier-free in water, make terminal group at the oleophylic of polymer molecular chain form hydrophilic ionic group and form charged layer at microsphere surface and make emulsion-stabilizing.
Carboxylic acid monomer (A) as for institute of the present invention apparatus carbon-to-carbon double bond polymerizable functionalities base, the usage ratio that accounts for reaction refers to 2～9wt%, if its usage ratio is during less than 2wt%, then the emulsifying property of this multipolymer of gained reduces, more easy to foaming, when surpassing again 9wt%, then the hydrophobicity of this multipolymer become excessive, and emulsifying property variation.The usage ratio of monomers B refers to 40～50wt%, if its usage ratio is during less than 40wt%, then the emulsifying property of this multipolymer of gained reduces when surpassing 50wt% again, and then the wetting ability of this multipolymer becomes excessive, the performance of the resin emulsion of gained reduces, and especially water tolerance reduces.
In mineral alkali of the present invention, can make wetting ability and anion characteristic that height is arranged in the pH of broadness scope with the carboxylic acid monomer of the tool carbon-to-carbon double bond polymerizable functionalities base of its reaction, make the hydrophilic ionic group of terminal group formation at the polymer molecular chain of oleophylic, so that the microsphere surface of the latex micelle of gained forms charged layer, and emulsion that must be stable, has superior emulsifying property, though its acid value is not given special restriction, with in the warp and the time the acid value of multipolymer solid usually be advisable to be set as about 3.5～6.5mg KOH/g.
As for the used acryl monomer of the present invention, determined by the viscosity of the tackyness of the water-and acrylate emulsion of considering gained, this emulsion or stability etc., needing respectively, this glass tansition temperature (Tg) is set in the specified range.The Tg of acryl monomer component is set in-20～20 ℃, is preferably-5～10 ℃.
The solid of water-and acrylate emulsion is divided to set for 40～50% and is advisable, the viscosity in the time of can easily suppressing to make water-based emulsion, and the intensity of agglutination is improved.And the form of the water-and acrylate emulsion of gained does not contain organic solvent.
Be applicable to the acryl monomer of the inventive method, though do not give special restriction, wherein have a carboxylic acid A monomer of carbon-to-carbon double bond polymerizable functionalities base, for example can enumerate by vinylformic acid (acrylic acid; Be designated hereinafter simply as AAc), methacrylic acid (methacrylic acid; Be designated hereinafter simply as MAAc), fumaric acid (fumaric acid), itaconicacid (itaconic acid; Be designated hereinafter simply as ITA) and β-crotonic acid (crotonicacid; Be designated hereinafter simply as CTA) colony that forms select one or more.
As for alkyl methacrylate or alkyl acrylate monomer B, for example can enumerate by methyl methacrylate (methyl methacrylate; Be designated hereinafter simply as MMA), methacrylic acid ethyl ester (ethylmethacrylate; EMA), n-BMA (n-butyl methacrylate; N-BMA), Propenoic acid, 2-methyl, isobutyl ester (i-butyl methacrylate; I-BMA), methacrylic acid tri-n-butyl (t-butyl methacrylate; T-BMA), methyl acrylate (methyl acrylate; MA), ethyl propenoate (ethyl acrylate; EA), n-butyl acrylate (n-butyl acrylate; Be designated hereinafter simply as n-BA), isobutyl acrylate (i-butyl acrylate; Be designated hereinafter simply as i-BA), vinylformic acid tri-n-butyl (t-butyl acrylate; T-BA), vinylformic acid 2-b hexyl (2-ethyl hexyl scrylate; Be designated hereinafter simply as 2-EHA), methacrylic acid 2-b hexyl (2-ethyl hexyl methylacrylate; 2-EHMA), lauryl methacrylate(LMA) (lauric methyl acrylate; LMA); Vinyl cyanide (acrylnitrile; AN), vinyl cyanide (methyl acrylnitrile; MAN) one or more that the colony that forms selects.And depending in case of necessity, also can merge the monomer in addition such as the acrylic ester monomer that uses vinyl acetate, vinylbenzene.
By the inventive method the acryl resin emulsion, its storage stability is good, with traditional way person relatively the time, because it is good aspect thermotolerance, tack strength, the intensity of agglutination, coating.And because not containing organic solvent in this resin emulsion, for making as the coating person, aspect safety and sanitation, be more suitable.Especially optimum uses the strict building materials of standard of residual solvent in requiring the higher goods of thermotolerance, tack strength, the intensity of agglutination.
Monomer molecule by the initiator initiated polymerization, so chain growth speed, is namely separated out from aqueous phase than very fast, forms initial latex particle in the inventive method when the polymericular weight that generates reaches a certain threshold value in water.Because these particle surface electric density are lower, electrostatic repulsion forces is not enough and make particle-stabilised between the particle, can mutually assemble, form hydrophilic ionic group until generate stable latex particle in the terminal group of the polymer molecular chain of oleophylic, the ester class of its generation has the characteristic of anionic emulsifier, and reach the emulsifying effectiveness of emulsifier-free, make polymerization and the polymer esters class have the characteristic of anionic emulsifier, and reach the emulsifying effectiveness that emulsifier-free carries out letex polymerization.
Adopt the organic amine of making the pH adjusting agent in the inventive method, can enumerate: ammoniacal liquor (ammonia; Be designated hereinafter simply as NH
4OH), Trimethylamine 99 (trimethyl amine; Be designated hereinafter simply as TMA), diethylamide (Diethylamine; DEA), triethylamine (triethylamine; TEA), monoethanolamine (monoethanolamine; Be designated hereinafter simply as META), diethanolamine diethanolamine; DETA), dimethylethanolamine (dimethyl ethanolamine; Be designated hereinafter simply as DMEA), diethylethanolamine (dimethyl ethanolamine; DEEA), isopropyl alcohol amine (isopropyl ethanolamine; Be designated hereinafter simply as IPEA), 2-amido-2-methylpropanol (2-amino-2-methyl propanol, AMP), 2-dimethylin-2-methylpropanol (2-dimethylamino-2-methyl propanol; DMAMP), morpholine (morpholine, MOR), n-methylmorpholine (n-methyl morpholine; NMR), n ethyl morpholine (morpholine; NEM) etc.That wherein should use is ammoniacal liquor, Trimethylamine 99, dimethylethanolamine, 2-amido-2-methylpropanol etc.
By the inventive method emulsion polymerization preparation and surperficial latex micelle particle with larger wetting ability and better stability, synthesize that median size is little, surface tension is low, the wettability perviousness is extremely strong, the better polymer emulsion of stability.
The polymerization process of the acrylic ester emulsion of a kind of emulsifier-free that the present invention is relevant, in reactive tank, to add by to carboxylic acid monomer (A) 2～9wt% by pure water 40～60wt% and tool carbon-to-carbon double bond polymerizable functionalities base, the reaction that alkyl methacrylate or alkyl acrylate monomer (B) 40～50wt% forms, adjust reaction in the scope of pH value 9.0～13.0 with inorganic alkali lye 0.2～2.0wt% first, then adopt the superoxide initiator 0.2～1.0wt% by vitriol, carry out emulsion polymerization, adjust the pH value of water-base resin emulsion of gained with organic amine compound in the reaction latter end in 7.0～9.5 scope.The water-base resin emulsion that makes, particle diameter approximately 100～130nm and the outward appearance that is evenly distributed are good, low acid value 3.5～6.5mgKOH/g, and its proportion is about 1.07 and is a bit larger tham water, and the storage stability is superior, the good easy construction of perviousness.The water tolerance of its dry coating is good, and tensile strength is good and wear resistant is superior.
At first weigh distilled water (distilled water that adds first the 40～60wt% that accounts for the reactant that participates in polyreaction), beginning is with approximately 150～300RPM stirring of rotating speed, after being maintained at 70～95 ℃, add the carboxylic acid monomer of tool carbon-to-carbon double bond polymerizable functionalities base and inorganic alkali lye, add initiator after arriving design temperature in 20～30 minutes, beginning slowly drips alkyl acrylate or alkyl methacrylate monomer and finished dropping in 2.0～4.5 hours, and keeps continuing under temperature and the rotating speed reaction approximately 2～3 hours.Closing well heater but continuing to stir lowers the temperature it naturally.After dropping to 40 ℃, behind the organic amine with water dilution pH adjusting agent, slowly added approximately 15 minutes, make the pH value reach 8.0～9.0, finish polyreaction.The median size of the water-and acrylate emulsion of gained is little, and (microspherulite diameter d is 100～130nm).
By the inventive method emulsion polymerization preparation and surperficial latex micelle particle with larger wetting ability and better stability, synthesize median size evenly, the better polymer micro-emulsion of extremely strong, the stability of wettability perviousness.
Probe into the inventive method and how can reach emulsifier-free and carry out letex polymerization, roughly being attributable to is the effectively synthetic uniform polymer particle of particle diameter, usually applicable out-phase system polymerization.Out-phase is that polymerization has employing water as the emulsion polymerization of solvent or adopts organic liquid as the dispersion polymerization of solvent.Any situation is because all being to add in a large number the dispersion agents such as soap class or polymer tranquilizer, the problem that has aftertreatment problem after synthetic or impurity to residue in resultant.The feature that synthesis method separately also has his method to be difficult to substitute, the exploitation of bringing into play this feature namely belongs to essential.Avoid the participation of emulsifying agent to react the problem points that causes, the present invention does not add emulsifying agent fully in reaction process, to carboxylic acid monomer (A) 2～9wt% by pure water 40～60wt% and tool carbon-to-carbon double bond polymerizable functionalities base, the reaction system that alkyl methacrylate or alkyl acrylate monomer (B) 40～50wt% forms, adjust reaction with inorganic alkali lye 0.2～2wt% first and in the scope of pH value 9.0～13.0, make the feature with macromolecule emulsifier, then adopt the superoxide initiator by vitriol, carry out emulsion polymerization, adjust the pH value of water-base resin emulsion of gained with organic amine compound in the reaction latter end in 7.0～9.5 scope.And get the emulsion particle of surface cleaning, single dispersion, avoid simultaneously emulsifying agent on the impact of environment.
In recent years surging environmental problem or from the viewpoint of the exploitation of the application of medical biotechnology relation or various functional materials is just being given the exploitation of the synthesis method of the exploitation of the friendly type technique of environment that waits in expectation or high-purity polymer particle.
The particle of the uniform so-called monodispersity of particle diameter synthesizes the aspect, and the emulsion polymerization of emulsifier-free is arranged, and this polymerization is take water as solvent, also have concurrently do not add the soap class cleaning technique as feature.Therefore polymerization becomes merely, in the simplest situation namely for to be made of monomer/initiator/water.Usually problem of maximum of particle synthesis method, the scope of the particle diameter of the Yu Keyu that is everlasting control, along with the got particle diameter 100～130nm of the emulsifier-free polymerization process of the inventive method and the emulsion that is evenly distributed, particle diameter can give the scope of control and also expanded by expectation.
The emulsifier-free polymerization is namely attempted to be applied to the application of bonding agent, tamanori, printing ink industry of nuisanceless type etc. for a long time.The monodispersity particle at peace and quiet interface system just is being used the standard particle of the correction of the model particle of doing colloid research or electron microscope etc. again.Precisely because the field of particle diameter applicatory is below inferior micron.The synthetic of particle that surpasses this particle diameter is difficult.On the other hand, along with the expansion of its purposes, can have been enumerated liquid crystal distance piece, electroconductive particle, medical examination carrier, analyzed with high additive value goods such as weighting agent, duplicating machine toning agents in recent years by its purposes for micron-sized monodispersity particle.The emulsion polymerization with emulsifier-free of the inventive method, but the also monodisperse particle of synthesis nano, the median size of the water-and acrylate emulsion of gained is little, and (microspherulite diameter d is 100～130nm), is expected to be applied to above-mentioned field.
Test method
The emulsion physical property:
1, median size d, size distribution and standard deviation (sd). dispersion coefficient D.
Emulsion polymer to gained, the MASTERSIZER-2000 that makes with MANERN company gets the microspherulite diameter distribution curve according to the laser diffraction method, measure median size d, size distribution and standard deviation (sd). and dispersion coefficient D is calculated as follows: D=sd/d. can directly be drawn the distribution situation of microspherulite diameter by the microspherulite diameter distribution curve of the emulsion polymer of gained.
2, glass tansition temperature Tg (℃)
The differential of utilizing METTLER-TOLEDO instrument company to make scans calorimeter (Differential scanning calorimeters; DSC) measured Tg point.
3, acid value
Take the emulsion that makes, tested according to the method for the 2nd one the 1st joint regulation of JIS (JIS) K5601.
4, proportion
Take the emulsion that makes, the method for stipulating according to JIS (JIS) K7232 prepares sample and gives test.
5, pH value
Take the emulsion that makes, the method for stipulating according to the 12nd one the 10th joint of JIS (JIS) K0400 prepares sample and gives test.
6, stability in storage
Take the emulsion that makes, the method for stipulating according to the 2nd one the 7th joint of JIS (JIS) K5600 prepares sample and gives test.
7, freeze stability
Take the emulsion that makes, prepare sample and give test according to Japan's the 2nd one the 6th method that saves regulation of lower industry specification (JIS) K5600.
The emulsion film physical property:
1, tensile strength
Take the emulsion that makes, the method for stipulating according to JIS (JIS) K6251 prepares sample and gives test.
2, tear strength
Take the emulsion that makes, the method for stipulating according to JIS (JIS) K6252 prepares sample and gives test.
3, elongation
Take the emulsion that makes, the method for stipulating according to JIS (JIS) K6251 prepares sample and gives test.
The hardness of 4, filming
Take the emulsion that makes, the method for stipulating according to JIS (JIS) K6253 prepares sample and gives test.
5, water-intake rate on the three
Take the emulsion that makes, the method for stipulating according to JIS (JIS) K7112 prepares sample and gives test.
The emulsion workability:
Take the emulsion that makes, according to the method for JIS (JIS) A1181 regulation, observe Combination, adherence, the recoatability of itself and aggregate (CA-400), it is good that ◎ represents its result, and X to represent its result be bad.
As for the ionogen stability, then tested according to the method for JIS (JIS) K6935 the 2nd joint regulation.
Described in detail the polymerization process of the acrylic ester emulsion of a kind of emulsifier-free relevant with the present invention with following example, do not meaned that only the present invention only is confined to the content that these examples disclose.
About embodiment 1～5
The carboxylic acid monomer that embodiment 1～3 adopts is the monocarboxylic acid of tool carbon-to-carbon double bond polymerizable functionalities base, but adopts different mineral alkalis.
The mixture of the monocarboxylic acid that 4～5 of embodiment adopt tool carbon-to-carbon double bond polymerizable functionalities base and the dicarboxylic acid of different tool carbon-to-carbon double bond polymerizable functionalities bases.
The water-and acrylate emulsion of gained, essentially consist and emulsion physical property, Physical properties of coating film and emulsion workability, as shown in table 1.
About comparative example 1～4
Water-and acrylate emulsion traditionally, its acid value is often high than gained person of the present invention, even or its acid value be low to moderate as gained of the present invention, but it is to adopt emulsifying agent in letex polymerization.Be for relatively, with acid value than the high water-and acrylate emulsion of the present invention as a comparative example 1～2 and acid value be low to moderate and adopt conventional emulsifier CMC (12R) to carry out letex polymerization person as a comparative example 3～4 as gained of the present invention.Its sill forms and emulsion physical property, Physical properties of coating film and emulsion workability, and is as shown in table 2.
(1) in reactive tank, add inorganic alkali lye 0.2～2.0wt% and weigh distilled water (distilled water that adds first the 40～60wt% that accounts for the reactant that participates in polyreaction), beginning is maintained at 70～95 ℃ with approximately 150～300RPM stirring of rotating speed.
(2) add carboxylic-acid monomer (A) and (account for approximately 2～9wt%) of whole monomers such as vinylformic acid, methacrylic acid or β-crotonic acid and itaconicacid monomer.
(3) in approximately arriving design temperature in 20 minutes, after adding the superoxide initiator 0.2～1.0wt% of vitriol, beginning slowly drips alkyl acrylate monomer (B) and (accounts for approximately 40～50wt%) and finished dropping in 2.0～4.5 hours of whole monomers, and keep temperature and rotating speed to continue reaction approximately 2～3 hours such as methyl methacrylate, methacrylic acid ethyl ester, Propenoic acid, 2-methyl, isobutyl ester, methacrylic acid tri-n-butyl, methyl acrylate, n-butyl acrylate, vinylformic acid 2-b hexyl.
(4) close well heater but continue to stir it is lowered the temperature naturally.After temperature is down to 40 ℃, after water dilution pH adjusting agent, slowly added approximately 15 minutes, make the pH value reach 8～9.Finish reaction and get the water-and acrylate emulsion.It forms and divides and the acryl water-and acrylate emulsion of gained and the physical property of dry coating, and is as shown in table 1.And can directly draw the distribution situation of microspherulite diameter from resulting polyalcohol microspherulite diameter distribution curve, its representative graph as shown in Figure 1.
The emulsion workability:
To by embodiment 1～5 the acryl resin 68.2wt% of emulsifier-free, collocation is such as aggregate 11.4wt% such as concrete, silica sands, make the flooring board product with various powder filler 11.4wt%, colorant 6.8wt%, check these Combination, adherence, recoatability.
Comparative example 1～4
Shown in the essentially consist in the table 2, synthesize the water-based acrylic ester emulsion with embodiment 1～5 with method.It forms and divides and the acryl water-and acrylate emulsion of gained and the physical property of dry coating, and is as shown in table 2.
Emulsion composition, emulsion physical property, emulsion workability and the Physical properties of coating film of table 1: embodiment
Table 2: water-and acrylate emulsion for comparison forms a minute transitivity
The water-and acrylate emulsion that makes of the inventive method as shown in Table 1, glass tansition temperature such as embodiment 5 lower (9.00 ℃), the difference of the glass tansition temperature of embodiment 3 higher (8.48 ℃), but can in response to the physical property requirement that is coated with membrane product, be concocted use.And the dry film of the water-and acrylate emulsion of embodiment 3, its hardness is harder, then can should be applicable to the painting coating aspect.The higher physical property of filming of the water-and acrylate emulsion that the inventive method makes reaches lower water-intake rate applicable to the waterproofing work of all kinds of buildings.
The water-based acryl resin emulsion that is got by the inventive method, no matter the carboxylic acid monomer who adopts (A) is monocarboxylic acid and/or the dicarboxylic acid of tool carbon-to-carbon double bond polymerizable functionalities base, can adopt different inorganic alkali lye to carry out the letex polymerization of emulsifier-free, the stability in storage of the water-and acrylate emulsion that makes, to freeze stability good, and applicable various operating environments use.And because not containing organic solvent, for making as the coating person, aspect safety and sanitation, be more suitable.Especially optimum uses the strict building materials of standard of residual solvent in requiring the higher goods of tack strength, physical strength.
And adopt excessive carboxylic acid by comparative example 1～2, the acid value of resulting emulsion is high, and water-intake rate is risen, although comparative example 1～2 can get the emulsion of median size 115nm, but its stability in storage and to freeze stability poor, although the Combination of itself and aggregate is good, its adherence and recoatability are not good, and are not suitable for various operating environments.And the acid value of comparative example 3～4 is low to moderate as gained of the present invention, although the stability in storage of resulting emulsion and to freeze stability good, but adopt conventional emulsifier CMC (12R) to carry out letex polymerization, the particle diameter of gained emulsion becomes large and the water-intake rate on the three of filming rises, and Combination, adherence and the recoatability of itself and aggregate are also not good, and are not suitable for various operating environments.
Claims (2)
1. the acrylic ester emulsion polymerization method of an emulsifier-free is characterized in that, comprises following operation:
1) preparation is the reaction system that principal constituent forms by the carboxylic acid monomer A2～9wt% of pure water 40～60wt%, tool carbon-to-carbon double bond polymerizable functionalities base and alkyl methacrylate or alkyl acrylate monomer B40～50wt%;
2) react in the scope of pH9.0～13.0 with the inorganic alkali lye adjustment of 0.2～2wt%;
3) keep this to react on 70～95 ℃ of temperature and stirred 30 minutes with rotating speed 150～300rpm, the colony that adopts Sodium Persulfate, Potassium Persulphate, the ammonium persulphate of 0.2～1.0wt% to form select one or more give Initiation as initiator, carry out emulsion polymerization;
4) the pH value of adjusting resulting water-base resin emulsion with the organic amine of selecting one or more in by Trimethylamine 99, monoethanolamine, dimethylethanolamine, colony that the 2-amido-the 2-methylpropanol forms in last stage reaction obtains the narrow water-based acryl polymer of particle diameter 100～130nm homogeneous and distributed pole in 7.0～9.5 scope;
The consumption sum of described raw material is 100wt%;
The carboxylic acid monomer A of described tool carbon-to-carbon double bond polymerizable functionalities base is one or more that selected by vinylformic acid, methacrylic acid, methylene-succinic acid and β-crotonic acid colony;
Described alkyl methacrylate or alkyl acrylate monomer B be methyl methacrylate, methacrylic acid ethyl ester, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, Tert-butyl Methacrylate, methyl acrylate, ethyl propenoate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, vinylformic acid 2-b hexyl, methacrylic acid 2-b hexyl, lauryl methacrylate(LMA) colony select one or more.
2. polymerization process according to claim 1, wherein, described inorganic alkali lye is one or more that selected by sodium hydroxide, potassium hydroxide, tertiary sodium phosphate colony.
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| CN103709303B (en) * | 2014-01-13 | 2016-06-22 | 张家港保税区康得菲尔实业有限公司 | A kind of preparation method of coating water-and acrylate emulsion |
| CN108948236B (en) * | 2018-06-27 | 2020-02-14 | 天津大学 | Polystyrene macroscopic molding block and preparation method thereof |
| CN111269349B (en) * | 2020-01-23 | 2022-04-05 | 中化化工科学技术研究总院有限公司 | Polycarboxylic acid polymer emulsifier and preparation method thereof |
| CN114230691A (en) * | 2021-12-31 | 2022-03-25 | 湖南高瑞电源材料有限公司 | Micro-precipitation polymerization preparation method and application of water-based resin |
| CN115286967B (en) * | 2022-07-07 | 2023-11-21 | 江苏景宏新材料科技有限公司 | Water-based acrylate binder, water-based matte gloss oil and preparation method thereof |
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