CN111072862B - Acrylate polymer microsphere, preparation method and application thereof - Google Patents

Acrylate polymer microsphere, preparation method and application thereof Download PDF

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CN111072862B
CN111072862B CN201911406827.1A CN201911406827A CN111072862B CN 111072862 B CN111072862 B CN 111072862B CN 201911406827 A CN201911406827 A CN 201911406827A CN 111072862 B CN111072862 B CN 111072862B
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CN111072862A (en
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孟祥伟
苏郁蕙
陆敏军
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Eternal Chemical China Co Ltd
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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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • 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
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/42—Gloss-reducing agents

Abstract

The invention provides an acrylate polymer microsphere, a preparation method and application thereof. The acrylate polymer microspheres sequentially comprise a hard core, a soft core and a hard shell from inside to outside, the Tg of the hard core is at least 50 ℃ higher than that of the soft core, and the hard shell comprises an acrylic acid protective colloid. The acrylic ester polymer microsphere is suitable for the water-based self-extinction acrylic ester polymer emulsion, does not contain the traditional extinction agent, has low cost, and has good extinction effect, stability, tolerance and thick coating transparency.

Description

Acrylate polymer microsphere, preparation method and application thereof
Technical Field
The invention belongs to the field of water-based paint, and particularly relates to water-based self-extinction acrylate polymer emulsion containing acrylate polymer microspheres and a preparation method thereof.
Background
The matte coating with soft color is very popular with consumers because the coating film has strong texture and gives people an elegant and comfortable feeling. Compared with high-gloss paint, the preparation of surface-matting paint is difficult. The matting is usually carried out by imparting a certain degree of microroughness to the surface of the coating film, and can be achieved by adding a coating matting agent. The matting principle of a coating film is considered to be that when the coating film is dried, the surface shrinks due to the volatilization of a solvent, particles of a matting agent uniformly distributed therein are gradually accumulated and float on the surface of the coating film, minute concavities and convexities are formed on the surface, and the surface diffusely reflects incident light to achieve a matting effect.
The addition of certain amounts of matting agents, such as silicon-containing compounds and polymers (e.g. silica, silicates, silanes, wax-treated silica) and fillers (e.g. diatomaceous earth, clays, zeolites) to resins is the most common way of obtaining matt coatings in the last decades. However, in order to avoid precipitation problems caused by incompatibility between the resin and the matting agent, it is important to select an appropriate matting agent for different kinds of resins. Post-treatment of the coated surface, such as etching or polishing, is another conventional method of producing low gloss surfaces. However, this is very time consuming and expensive.
The micron-sized silicon dioxide has the characteristics of easy dispersion, good racemization optical property, good suspension property in liquid coating, long-time storage, small influence on the rheological property of the coating, high chemical inertness and the like, thereby being the most used coating matting agent. However, the silica matting agent still has some application disadvantages, such as repeated work-returning on the production line of furniture factories, poor transparency of thick coating; the thick dry film is coated on the dark color plate to be white and blue; the use of more silica in low gloss products leads to increased porosity and poor coating resistance.
The matte resin compositions appearing on the market comprise traditional resin compositions added with matte additives (such as matte powder, micro-powder wax and the like) and also comprise polyurethane dispersion resin compositions without the matte additives; the existing preparation of the water-based matte coating adopts a method of physically adding a flatting agent, the prepared matte coating is poor in brittleness, and the addition of the flatting agent can cause the performance reduction of the coating, such as poor storage stability of the precipitated coating, poor polishing resistance of the coating, reduced transparency of a coating film and the like; meanwhile, the matte polyurethane dispersion has a great problem in the aspect of temperature resistance, and due to the structural limitation of the polyurethane material, the polyurethane dispersion also has a great defect in the aspect of temperature resistance, so that the coating structure of the matte touch resin coating is easy to collapse after hot pressing or high-temperature drying after coating, and the whole matte coating is no longer matt or the coating surface has uneven gloss because the original matte structure is not resistant to temperature, and the manufacturing cost is high.
In recent years, studies have been made on self-matting coatings which can provide a low-gloss effect after coating without adding a matting agent. Chinese patent application CN109180854A discloses a water-based self-extinction gloss-controllable acrylic resin, which controls the content of an organic polymeric flocculant by controlling the ratio of carboxyl in acrylic acid and acrylic acid derivatives, thereby controlling the glossiness of a coating film. This patent results in matting by adjusting the ratio of carboxyl groups, but this leads to an excessively high acid value of the resin as a whole, and ultimately affects the resistance of the dried coating film. Chinese patent application CN105968253A discloses a water-based self-extinction acrylic emulsion, which realizes extinction by preparing the water-based self-extinction acrylic emulsion through organosiloxane block graft modification, but the cost is higher. Chinese patent CN104193946B discloses a self-extinction polyurethane resin prepared mainly from polyether polyol, isocyanate, diol, acrylic acid grafted substances, hydrophilic chain extender, cross-linking agent, amine chain extender, etc., wherein the self-extinction polyurethane resin introduces acrylic acid grafted substances capable of absorbing light, which belongs to chemical extinction, but the manufacturing cost of the polyurethane extinction resin is relatively high.
Therefore, there are various technical solutions for the self-extinction resin compositions on the market, including physical extinction and chemical extinction (polyurethanes and siloxanes), but the cost is generally high. For matt coatings for woodware and paper, the physical property requirements such as strict weather resistance, solvent resistance and the like do not exist mostly, and consumers are sensitive to cost, pay more attention to cost performance, and the cost is equivalent to that of common matt powder matt coatings.
Therefore, there is a need in the art for a water-based self-flatting acrylate polymer coating with low cost, good light-eliminating effect, stability, resistance (including water resistance, boiling water resistance, alkali resistance, alcohol resistance, stain resistance), and thick coating transparency.
Disclosure of Invention
The application aims to provide a water-based self-extinction acrylic ester polymer coating which is low in cost and has good extinction effect, stability, resistance and thick coating transparency. The coating can be coated on metal, wood, paper and plastic parts, is widely applied to water-based industrial paint, water-based wood paint and water-based ink, and has wide market prospect.
In order to achieve the purpose, the invention provides acrylate polymer microspheres which sequentially comprise a hard core, a soft core and a hard shell from inside to outside, wherein the Tg of the hard core is at least 50 ℃ higher than that of the soft core, and the hard shell comprises an acrylic acid protective colloid.
In one or more embodiments, the hard core has a Tg of 95 ℃ to 120 ℃ and the soft core has a Tg of-45 ℃ to 38 ℃.
In one or more embodiments, the starting materials for the acrylate polymeric microspheres include an acrylic protective colloid, a hard monomer, a soft monomer, a functional monomer, and a crosslinking monomer.
In one or more embodiments, the monomers of the hard core include hard monomers, functional monomers, and optionally soft monomers, and the monomers of the soft core include soft monomers, crosslinking monomers, and optionally hard monomers.
In one or more embodiments, the hard monomer is a combination of one or more of methyl methacrylate, styrene, acrylonitrile, acrylamide, methyl styrene, acrylic acid, methacrylic acid.
In one or more embodiments, the soft monomer is a combination of one or more of ethyl acrylate, butyl acrylate, n-octyl acrylate, isooctyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, vinyl versatate.
In one or more embodiments, the functional monomer is a combination of one or more of isobornyl methacrylate, glycidyl methacrylate, acetoacetoxyethyl methacrylate, hydroxyethyl methacrylate, and vinyl versatate.
In one or more embodiments, the crosslinking monomer is an alkenyl silicone monomer; preferably, the alkenyl silicone monomer is (R) 3 ) c Si(OR 1 ) 4-c Wherein R is 1 Is C1-C3 alkyl, R 3 Is an unsaturated group having an alkenyl group, and c is an integer of 1 to 3; preferably, the alkenyl silicone monomer is methacryloxypropyltrimethoxysilane.
In one or more embodiments, the acrylic protective colloid is an oligomer comprising one or a combination of two of the monomers of acrylic and methacrylic acid, the oligomer having a weight average molecular weight of 2000 to 45000, a polydispersity index (PDI) of 1.5 to 9, a Tg of 30 to 130 ℃, the weight of acrylic and methacrylic acid comprising 5 to 30% of the total monomer weight of the acrylic protective colloid.
In one or more embodiments, the monomers of the acrylic protective colloid include (a) a combination of one or more selected from the group consisting of styrenic monomers, acrylate esters, and methacrylate esters, (b) acrylic acid and/or methacrylic acid, and (c) functional monomers.
In one or more embodiments, the monomers of the acrylic protective colloid comprise (a)60 to 90% of a combination of one or more selected from the group consisting of styrenic monomers, acrylates and methacrylates, (b)5 to 30% of acrylic acid and/or methacrylic acid, and (c)2.5 to 10% of a functional monomer, based on the total weight of the monomers of the acrylic protective colloid.
In one or more embodiments, the raw materials of the acrylate polymer microspheres comprise 30 to 70 parts by weight of acrylic protective colloid, 100 to 200 parts by weight of hard monomer, 20 to 100 parts by weight of soft monomer, 1 to 30 parts by weight of functional monomer and 1 to 10 parts by weight of crosslinking monomer.
In one or more embodiments, the mass ratio of the hard core, the soft core and the hard shell is 100 to 150: 100: 30-70 parts.
In one or more embodiments, the feedstock for the hard core comprises, by mass, 100: 5-50 of hard monomer and functional monomer.
In one or more embodiments, the soft core raw material comprises the following components in a mass ratio of 90-10: 10-90 of hard monomer and soft monomer, and 1-10% of crosslinking monomer by mass of the total mass of the hard monomer and the soft monomer.
The present invention also provides an aqueous dispersion of acrylate polymer microspheres according to any one of the embodiments of the present invention.
The invention also provides a method for preparing the acrylate polymer microspheres of any embodiment of the invention, which comprises the following steps:
(1) dispersing acrylic acid protective colloid in water to obtain aqueous dispersion of acrylic acid protective colloid;
(2) adding a monomer and an initiator of a hard core into the aqueous dispersion of the acrylic acid protective colloid in the step (1) to react to generate the hard core of the acrylate polymer microsphere; and
(3) and (3) adding a soft-core monomer into the product obtained in the step (2) to react to obtain the acrylate polymer microsphere.
The invention also provides an acrylate polymer emulsion containing (a) the acrylate polymer microspheres of any embodiment of the invention and (B) cellulose ether and/or starch ether.
In one or more embodiments, the cellulose ether and/or starch ether is a cellulose ether that is a combination of one or more of methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, and hydroxyethyl methyl cellulose, or a starch ether, or a mixture of both; the starch ether is one or more of hydroxyethyl starch ether, hydroxypropyl starch ether and carboxymethyl starch ether.
In one or more embodiments, the acrylate polymer microspheres comprise 35 to 45% of the total weight of the acrylate polymer emulsion.
In one or more embodiments, the cellulose ether and/or starch ether comprises from 0.08 to 0.8%, preferably from 0.1 to 0.6% by weight of the total acrylate polymer emulsion.
In one or more embodiments, the mass ratio of the cellulose ether and/or starch ether to the acrylate polymer microspheres is from 0.2 to 1.5: 100.
in one or more embodiments, the acrylate polymer emulsion contains the following raw materials in parts by weight:
Figure BDA0002348872340000051
in one or more embodiments, the acrylate polymer emulsion comprises the following raw materials in parts by weight:
Figure BDA0002348872340000052
Figure BDA0002348872340000061
in one or more embodiments, the pH adjusting agent is preferably aqueous ammonia.
In one or more embodiments, the additive preferably includes an antifoaming agent and/or a biocide.
The present invention also provides a method of making the acrylate polymer emulsion of any of the embodiments of the present invention comprising the step of dispersing the cellulose ether and/or starch ether in an aqueous dispersion of the acrylate polymer microspheres.
The invention also provides application of the acrylate polymer microspheres or the aqueous dispersion thereof or the acrylate polymer emulsion in any embodiment of the invention in preparation of an aqueous extinction coating.
The invention also provides a coating with 60 DEG angle gloss of less than or equal to 55 or an article with the coating, wherein the coating is formed by aqueous extinction coating containing the acrylate polymer microspheres or the aqueous dispersion thereof or the acrylate polymer emulsion of any embodiment of the invention; preferably, the substrate of the article is metal, wood, paper or plastic.
Drawings
FIG. 1 is a schematic structural diagram of an acrylate polymer microsphere of the present invention.
FIG. 2 is a schematic diagram of the preparation process of the acrylate polymer microspheres of the invention.
FIG. 3 is a particle size distribution curve of the acrylate polymer microspheres prepared in example 1.
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as amounts, amounts and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
Herein, unless otherwise specified, the ratio refers to a mass ratio, and the percentage refers to a mass percentage.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, as long as there is no contradiction between combinations of these technical features, any combinations of the technical features in the respective embodiments or examples may be made, and all possible combinations should be considered as the scope of the present specification.
The acrylic ester polymer emulsion of the invention utilizes the characteristics that acrylic ester polymer microspheres and cellulose ether or starch ether have good compatibility in an aqueous medium (the aqueous medium is water, deionized water and hydrophilic solvent according to needs), the compatibility is poor in a drying film-forming process, the Tg difference between hard cores and soft cores of the acrylic ester polymer microspheres is large, and the shrinkage rate is obviously different in the drying film-forming process, so that a micro-rough coating film surface is formed, the self-extinction effect is generated, and the permeability is not influenced. In addition, the acrylate polymer microsphere is prepared by adopting a Rheology Control technology (RC) and taking acrylic acid protective colloid as an emulsifier, has the characteristic of small particle size, and improves the transparency of dry film thick coating. The invention can produce the self-extinction acrylic ester polymer emulsion with low cost in mass production on the premise of not increasing the manufacturing difficulty and the cost.
According to the invention, through the special design of the resin particle structure (shrinkage difference caused by double Tg formed by a hard core-soft core structure) and the introduction of special raw materials (cellulose ether and starch ether have good compatibility with resin in emulsion but have reduced compatibility during film forming), the self-extinction resin composition with high cost performance is obtained, and the cost can be obviously reduced.
Herein, the microsphere refers to a microspherical particle having a particle size in the nanometer and micrometer scale range; the polymer microspheres refer to microspheres containing a polymer as a main component (for example, 80% or more, 90% or more) or as a whole; the acrylate polymer refers to a polymer in which monomers forming the polymer are mainly (for example, 50% or more, 60% or more, 80% or more, 90% or more) or entirely selected from one or more of acrylic acid, methacrylic acid, acrylate monomers, and methacrylate monomers.
Herein, the polymer and the resin have the same meaning. Herein, the aqueous dispersion of the polymer or the polymer microspheres refers to a substance obtained by dispersing the polymer or the polymer microspheres in water, and is also referred to as a polymer emulsion (abbreviated as emulsion); the aqueous dispersion of polymer or polymeric microspheres may include other ingredients in addition to the polymer and water. The resin composition herein refers to a composition of a resin and other substances except the resin, and may be, for example, an aqueous dispersion of polymer microspheres, or a polymer coating obtained by drying an aqueous dispersion of polymer microspheres to form a film.
Herein, the coating layer and the coating film have the same meaning, and refer to a solid continuous film obtained by applying and drying the coating material. Herein, coating is used in the meaning well known in the art and generally refers to a liquid that is applied to the surface of an object to be protected or decorated and forms a firmly attached continuous film with the object to be coated, including but not limited to paints, inks. The coating may be an aqueous dispersion of a polymer or polymeric microspheres. Herein, self-matting means that a matte effect (i.e., matting effect) of a coating film can be obtained without adding a conventional matting agent (e.g., silica, silicate, silane, wax-treated silica, diatomaceous earth, clay, zeolite, etc.). Herein, an aqueous coating (i.e., a coating of an aqueous system) refers to a coating using water as a solvent or dispersion medium.
As shown in figure 1, the acrylate polymer microsphere has a three-layer structure, namely a hard core, a soft core and a hard shell from inside to outside. In the present invention, the microspheres have a multilayer structure means that the microspheres may be divided into multiple layers having different physical or chemical properties as a whole. In certain embodiments, the acrylate polymer microspheres consist of a hard core, a soft core, and a hard shell.
In the invention, the hard core of the acrylate polymer microsphere has higher glass transition temperature (Tg), and the soft core of the acrylate polymer microsphere has lower Tg, so that the hard core and the soft core have different shrinkage rates in the film forming process by drying. The invention discovers that when the Tg of the hard core is higher than that of the soft core by at least 50 ℃, the extinction effect can be obtained by utilizing the shrinkage rate difference of the hard core and the soft core in the drying film-forming process; if the Tg of the hard core is higher than that of the soft core by less than 50 ℃, the shrinkage difference between the hard core and the soft core is too small, the surface roughness of the microsphere is insufficient, and the extinction effect is poor. Therefore, for the acrylate polymer microspheres of the present invention, the monomer composition and the amount ratio of the hard core and the soft core are not particularly limited as long as the Tg of the hard core and the soft core obtained by polymerization satisfies the requirements of the present invention. In certain embodiments, the Tg of the hard core of the polyacrylate polymeric microspheres is at least 80 ℃ higher than the Tg of the soft core, e.g., at least 100 ℃ higher.
In certain embodiments, the hard core has a Tg of 95 ℃ to 120 ℃ and the soft core has a Tg of-45 ℃ to 38 ℃.
In some embodiments, the mass ratio of hard core, soft core and hard shell is 100-150: 100: 30 to 70, for example 120 to 140: 100: 50-70.
The hard shell of the present invention comprises or consists of an acrylic protective colloid.
The acrylate polymer microsphere can be prepared by adopting a rheological control technology. The rheological control technology is that when polymer microspheres are prepared by emulsion polymerization, protective colloid is used for replacing conventional micromolecular emulsifier and used for stabilizing the polymer microspheres formed in the polymerization process, so that the rheological property of the emulsion is controlled.
Acrylate polymer emulsions are typically made by stabilizing polymeric microspheres formed during the polymerization process using conventional small molecule emulsifiers. According to the invention, the acrylate polymer microspheres with good monodispersity and good stability can be obtained by using the protective colloid as an emulsifier to carry out soap-free emulsion polymerization.
Herein, protective colloids have the meaning well known in the art and generally refer to water soluble polymers used to stabilize emulsion systems, including but not limited to gelatin, polyvinyl alcohol and its modifications, polyvinyl pyrrolidone, cellulose derivatives, acrylic protective colloids. In the present invention, acrylic protective colloids have the meaning well known in the art and generally refer to water-soluble oligomers obtained by polymerization of monomers comprising acrylic acid and/or methacrylic acid which can be used to stabilize emulsion systems. In the acrylic protective colloids, the weight of the monomers of acrylic acid and methacrylic acid is generally from 5 to 30% by weight of the total weight of the monomers of the acrylic protective colloids. The acrylic protective colloids suitable for use in the present invention preferably have a weight average molecular weight of from 2000 to 45000, more preferably from 5000 to 20000, a polydispersity index of from 1.5 to 9, more preferably from 2 to 5, a Tg of from 30 to 130 ℃ and more preferably from 50 to 100 ℃. Methods for preparing acrylic protective colloids are known in the art and include, but are not limited to, bulk polymerization, solution polymerization, and emulsion polymerization. The protective colloids prepared by the above method are all suitable for the present invention. In certain embodiments, the acrylic protective colloids used in the present invention are prepared using bulk polymerization.
In certain embodiments, the monomers of the acrylic protective colloid comprise: (a) one or more of acrylic acid, methacrylic acid, acrylate monomer, methacrylate monomer and styrene monomer, and (b) functional monomer. In the present invention, the acrylate monomer, the methacrylate monomer and the styrene monomer have meanings well known in the art.
In certain embodiments, the monomers of the acrylic protective colloid include: (a) one or more of styrene monomer, acrylate monomer and methacrylate monomer, (b) acrylic acid and/or methacrylic acid and (c) functional monomer, or the combination of the monomers. In certain embodiments, the monomers of the acrylic protective colloid comprise, based on the total monomer weight of the acrylic protective colloid: (a) 60-90% of one or more of styrene monomers, acrylate monomers and methacrylate monomers, (b) 5-30% of acrylic acid and/or methacrylic acid and (c) 2.5-10% of functional monomers.
In certain embodiments, the monomers of the acrylic protective colloid include: (a) styrene monomer, (b) one or more of acrylate and methacrylate monomer, (c) acrylic acid and/or methacrylic acid and (d) functional monomer, or the composition of the monomers. In certain embodiments, the monomers of the acrylic protective colloid comprise, based on the total monomer weight of the acrylic protective colloid: (a) 15-60% of styrene monomer, (b) 20-50% of one or more of acrylic ester and methacrylate ester monomers, (c) 5-30% of acrylic acid and/or methacrylic acid and (d) 2.5-10% of functional monomer, or consists of the monomers.
In the present invention, the functional monomer refers to a hydrophobic functional monomer (also referred to as a hydrophobic monomer). Hydrophobic functional monomers have meanings well known in the art. The addition of the hydrophobic functional monomer can provide hydrophobicity, so that the microphase separation phenomenon of the acrylate polymer microspheres (more hydrophobic) and the cellulose ether/starch ether (more hydrophilic) is more obvious, the extinction effect is better, and the water resistance and the solvent resistance of the resin after being dried into a film are provided. The hydrophobic functional monomer suitable for use in the present invention may be a hydrophobic functional monomer conventionally used in the art for preparing acrylate polymers, for example, including but not limited to isobornyl methacrylate, glycidyl methacrylate, acetoacetoxyethyl methacrylate, hydroxyethyl methacrylate, and vinyl versatate. It will be understood by those skilled in the art that the acrylate-based monomers, methacrylate-based monomers, hard monomers and soft monomers do not include the above hydrophobic functional monomers unless otherwise specified herein.
The raw materials of the acrylate polymer microsphere comprise acrylic acid protective colloid, hard monomer, soft monomer, optional functional monomer and optional crosslinking monomer.
In the present invention, the hard monomer refers to a vinyl group-containing monomer having a relatively high Tg value of the polymerized polymer, and includes, but is not limited to, methacrylate monomers (such as methyl methacrylate), styrene monomers (such as styrene and methyl styrene), acrylic acid, methacrylic acid, acrylonitrile and acrylamide having a relatively high Tg value of the polymerized polymer. As will be understood by those skilled in the art, a higher Tg value generally means a Tg of 95 ℃ to 120 ℃.
In the present invention, the soft monomer refers to a vinyl group-containing monomer having a low Tg value of the polymerized polymer, and includes, but is not limited to, an acrylate monomer having a low Tg value of the polymerized polymer (such as ethyl acrylate, butyl acrylate, n-octyl acrylate, isooctyl acrylate, 2-ethylhexyl acrylate), a methacrylate monomer having a low Tg value of the polymerized polymer (such as butyl methacrylate), and vinyl versatate. As will be understood by those skilled in the art, a lower Tg value generally means a Tg of-45 deg.C to 38 deg.C.
In a preferred embodiment, the raw materials of the acrylate polymer microspheres of the present invention include an acrylic protective colloid, a hard monomer, a soft monomer, a functional monomer, and a crosslinking monomer. The amount ratio of the acrylic protective colloid, the hard monomer, the soft monomer, the functional monomer and the crosslinking monomer is not particularly limited as long as the Tg of the hard core and the soft core obtained by polymerization satisfies the requirements of the present invention, and preferably the mass ratio of the hard core, the soft core and the hard shell also satisfies the requirements of the present invention. In certain embodiments, the raw material of the acrylate polymer microspheres of the present invention comprises 30 to 70 parts by weight (e.g., 35 to 65 parts by weight) of the acrylic protective colloid, 100 to 200 parts by weight (e.g., 120 to 200 parts by weight) of the hard monomer, 20 to 100 parts by weight (e.g., 25 to 90 parts by weight) of the soft monomer, 1 to 30 parts by weight (e.g., 10 to 20 parts by weight) of the functional monomer, and 1 to 10 parts by weight (e.g., 5 to 10 parts by weight) of the crosslinking monomer.
It will be appreciated by those skilled in the art that the starting material for the acrylate polymer microspheres of the present invention includes an initiator. The initiator suitable for use in the present invention is not particularly limited, and may be an initiator commonly used in the art for initiating a radical emulsion polymerization, such as ammonium persulfate. In the present invention, the amount of the initiator may be an amount conventionally used in the art, and for example, the amount of the initiator may be 0.5 to 5 parts by weight, preferably 1 to 2 parts by weight, for 100 parts by weight of the total monomers.
In the present invention, the monomers of the hard core generally include hard monomers and optionally may further include soft monomers and functional monomers. Functional monomers suitable for the hard core of the present invention are the aforementioned hydrophobic functional monomers including, but not limited to, isobornyl methacrylate, glycidyl methacrylate, acetoacetoxyethyl methacrylate, hydroxyethyl methacrylate, and vinyl versatate.
In certain embodiments, the monomers of the hard core include hard monomers and functional monomers. In certain embodiments, the feedstock for the hard cores comprises, in a mass ratio of 100: 5-50 of hard monomer and functional monomer.
The monomers of the hard core may also optionally include soft monomers. In embodiments where the monomers of the hard shell comprise soft monomers, the limitation on the amount of soft monomers in the hard core only requires that the Tg of the hard core obtained by polymerisation be at least 50 ℃ higher than the Tg of the soft core.
In the present invention, the monomers of the soft core generally include soft monomers and optionally may also include hard monomers and crosslinking monomers. The crosslinking monomer suitable for use in the present invention may be a monomer conventionally used for crosslinking acrylate polymers. The crosslinking monomer contains two or more vinyl groups. In certain embodiments, the crosslinking monomer is an alkenyl silicone monomer, preferably (R) 3 ) c Si(OR 1 ) 4-c Wherein R is 1 Is C1-C3 alkyl, R 3 Is an unsaturated group having an alkenyl group, and c is an integer of 1 to 3. Preferably, R 3 Is a group containing 6 to 10 carbon atoms. Preferably, R 3 Is a group containing an ester group. Preferably, R 3 Is methacryloxypropyl. The alkenyl silicone monomer may be, for example, methacryloxypropyltrimethoxysilaneAn alkane.
In certain embodiments, the monomers of the soft core include soft monomers and crosslinking monomers, and optionally may also include hard monomers. Of the monomers of the soft core, the mass of crosslinking monomers is generally from 1 to 10% of the total mass of soft monomers and optionally hard monomers. In embodiments where the monomers of the soft core comprise hard monomers, the limitation on the amount of hard monomers in the soft core only requires that the Tg of the soft core as polymerized be at least 50 ℃ lower than the Tg of the hard core.
In certain embodiments, the monomers of the soft core include hard monomers, soft monomers, and crosslinking monomers. In certain embodiments, the soft shell comprises the following raw materials in a mass ratio of 90-10: 10-90 of hard monomer and soft monomer, and crosslinking monomer with the mass of 1-10% of the total mass of the hard monomer and the soft monomer.
The acrylate polymer microsphere is dispersed in water to obtain the water dispersion of the acrylate polymer microsphere. The content of the acrylic acid ester polymer microspheres in the aqueous dispersion of acrylic acid ester polymer microspheres of the present invention is not particularly limited, and may be, for example, 20 to 50%, 30 to 50%, 35 to 50%, 40 to 50%, 35 to 45% of the total weight of the aqueous dispersion of acrylic acid ester polymer microspheres.
The preparation process of the acrylic ester polymer microsphere is shown in figure 2, firstly, providing an aqueous dispersion of acrylic acid protective colloid, then adding a monomer and an initiator of a hard core into the aqueous dispersion of the acrylic acid protective colloid, carrying out first-step emulsion polymerization to generate the hard core of the acrylic ester polymer microsphere, then adding a monomer and an initiator of a soft core, carrying out second-step emulsion polymerization to generate a soft core on the surface of the hard core of the acrylic ester polymer microsphere, and coating the surface of the soft core with the acrylic acid protective colloid to form a hard shell, thereby obtaining the acrylic ester polymer microsphere.
Specifically, the method for preparing the acrylate polymer microspheres comprises the following steps:
(1) dispersing acrylic acid protective colloid in water to obtain aqueous dispersion of acrylic acid protective colloid;
(2) adding a monomer of a hard core and an initiator into the aqueous dispersion of the acrylic acid protective colloid in the step (1) to react to generate the hard core of the acrylate polymer microsphere; and
(3) and (3) adding a monomer with a soft core and an initiator into the reaction system after the reaction in the step (2) to react to obtain the emulsion containing the acrylate polymer microspheres.
Aqueous dispersions of acrylic protective colloids can be obtained by dispersing an acrylic protective colloid (usually a solid) in water. Before adding the acrylic acid protective colloid to water, a pH regulator (such as ammonia water) may be added to water to adjust the pH of water to 5-9, and then the acrylic acid protective colloid may be added. The pH regulator suitable for use in the present invention may be a weak base such as aqueous ammonia (the concentration of aqueous ammonia may be from 15 wt% to 30 wt%). In the preparation of the aqueous dispersion of the acrylic protective colloid, the amount of the pH adjusting agent may be an amount conventionally used in the art, and in the case of aqueous ammonia having a concentration of 25% by weight, 5 to 10 parts by weight of aqueous ammonia having a concentration of 25% by weight may be added per 100 parts by weight of water. When the aqueous dispersion of the acrylic protective colloid is prepared, the dispersion system may be suitably heated (for example, to 60 to 90 ℃ C.) to facilitate dispersion. The concentration of the aqueous dispersion of the acrylic protective colloid is not particularly limited as long as the acrylic protective colloid can be uniformly dispersed in water, and for example, in the aqueous dispersion of the acrylic protective colloid, the mass ratio of the acrylic protective colloid to water may be 15 to 30: 100, e.g. 20-25: 100.
in the present invention, the reaction temperature of step (2) and step (3) may be an emulsion polymerization reaction temperature which is conventional in the art. In certain embodiments, the reaction temperature of step (2) and step (3) is from 60 ℃ to 90 ℃, e.g., from 70 ℃ to 90 ℃, about 80 ℃.
In step (2), the initiator may be added at a timing conventional in the art, and preferably, the initiator is added at the same time as the initiation of the addition of the hard core monomer. The reaction time of step (2) may be determined according to the actual reaction rate, and may be, for example, 0.5 to 2 hours. In certain embodiments, during the reaction of step (2), the sclerosant monomer and initiator are added slowly to the aqueous dispersion of acrylic protective colloid until the reaction of step (2) is complete.
In step (3), the timing of adding the initiator may be conventional in the art, and it is preferable to start adding the initiator at the same time as starting adding the soft core monomer. The reaction time of step (3) may be determined based on the actual reaction rate. In certain embodiments, the reaction of step (3) is divided into step (3a) and step (3b), wherein step (3a) comprises: adding a soft core monomer and an initiator into the reaction system after the reaction in the step (2) to perform a reaction, wherein the reaction time can be determined according to the actual reaction rate and can be, for example, 0.5-2h, and in the step (3a), the soft core monomer is added; the step (3b) includes: adding the rest of the initiator into the reaction system after the reaction in the step (3a) to perform the reaction, wherein the reaction time can be determined according to the actual reaction rate, and can be 1-5h, for example. In certain embodiments, during the reaction of step (3a), the soft core monomer and initiator are added slowly until the end of the step (3a) reaction. In certain embodiments, during the reaction of step (3b), the remainder of the initiator is added slowly over a period of 0.25 to 1 hour, and after the addition of the initiator is complete, the reaction is continued for a further period of 0.75 to 4 hours.
In the process of the present invention, the amount of the initiator may be an amount conventionally used in the art, as described above, and for example, the total amount of the initiator used in the step (2) and the step (3) may be 0.5 to 5 parts by weight, preferably 1 to 2 parts by weight, for 100 parts by weight of the total of the monomers (the total amount of the hard core monomer and the soft core monomer). It will be understood by those skilled in the art that, in the step (2) and the step (3), the initiator is generally added to the reaction system at a relatively uniform rate when the initiator is added. For a water-soluble initiator (such as ammonium persulfate), the initiator can be dissolved in water (the mass ratio of the initiator to the water can be 5-10: 100) and then added into a reaction system.
The aqueous dispersion of the acrylate polymer microspheres of the invention may be an emulsion containing the acrylate polymer microspheres of the invention prepared by the above-described method for preparing acrylate polymer microspheres.
The acrylic ester polymer emulsion of the present invention contains (a) the acrylic ester polymer microspheres of the present invention and (B) cellulose ether and/or starch ether.
In the present invention, because the acrylate polymer microspheres are (more hydrophobic) and the cellulose ether/starch ether are (more hydrophilic), in order to make the microphase separation phenomenon more pronounced and the matting effect better, the cellulose ether and/or starch ether preferably constitutes 0.08 to 0.8%, more preferably 0.1 to 0.6%, of the total weight of the acrylate polymer emulsion. If the weight percentage of the cellulose ether and/or the starch ether in the acrylate polymer emulsion is less than 0.08 percent, the extinction effect is poor; if the cellulose ether and/or starch ether accounts for more than 0.8% by weight of the acrylate polymer emulsion, the introduction of too many hydrophilic groups deteriorates the resistance of the coating film.
In the present invention, cellulose ether and starch ether have their ordinary meanings. Cellulose ether is a high molecular compound having an ether structure made of cellulose. Starch ethers are a generic term for modified starches which contain ether linkages in the molecule, also known as etherified starches.
The cellulose ether suitable for the present invention is not particularly limited, and may be an ionic cellulose ether, a nonionic cellulose ether, or an ionic-nonionic cellulose mixed ether, for example, including, but not limited to, carboxymethyl cellulose (CMC), polyanionic cellulose (PAC), Methyl Cellulose (MC), Ethyl Cellulose (EC), hydroxypropyl cellulose (HPC), hydroxyethyl cellulose (HEC), cyanoethyl cellulose (CEC), Ethyl Methyl Cellulose (EMC), hydroxypropyl methyl cellulose (HPMC), hydroxyethyl methyl cellulose (HEMC), methyl cyanoethyl cellulose (MCEC), carboxymethyl hydroxyethyl cellulose (CMHEC), carboxymethyl hydroxypropyl cellulose (CMHPC), carboxymethyl methyl cellulose (CMMC), and carboxymethyl ethyl cellulose (CMEC). In a preferred embodiment, the cellulose ether is a water-soluble cellulose ether, including but not limited to CMC, MC, HEC, HEMC, HPC, and HPMC. In certain embodiments, the cellulose ether is hydroxypropyl methylcellulose, preferably hydroxypropyl methylcellulose having a hydroxypropoxyl content of 4 to 12 percent.
The starch ether suitable for use in the present invention is not particularly limited and may be an ionic starch ether, a nonionic starch or a mixture of ionic and nonionic starch ethers, including, for example, but not limited to, hydroxyalkyl starch (e.g., hydroxyethyl starch ether, hydroxypropyl starch ether), hydroxypropyl distarch phosphate, hydroxypropyl distarch glyceride and carboxymethyl starch ether. In certain embodiments, the starch ether is a water-soluble starch ether, including but not limited to hydroxyethyl starch ether, hydroxypropyl starch ether, and carboxymethyl starch ether, preferably hydroxyethyl starch ether (HES).
In certain embodiments, the acrylate polymer microspheres comprise 35 to 45% of the total weight of the acrylate polymer emulsion.
In certain embodiments, the mass ratio of cellulose ether and/or starch ether to acrylate polymer microspheres in the acrylate polymer emulsion of the present invention is from 0.2 to 1.5: 100.
in certain embodiments, the acrylate polymer emulsions of the present invention further contain additives. Herein, the additive is an additive commonly used in the art for aqueous emulsions, and may be, for example, an antifoaming agent, a bactericide. The acrylate polymer emulsions of the present invention may contain various additives as is conventional in the art, for example, the total weight of the additives is generally less than 0.5% (e.g., 0.1% to 0.2%) of the total weight of the acrylate polymer emulsion, the weight of the biocide is generally less than 0.3% (e.g., 0.05% to 0.1%) of the total weight of the acrylate polymer emulsion, and the weight of the defoamer is generally less than 0.2% (e.g., 0.05% to 0.1%) of the total weight of the acrylate polymer emulsion.
In certain embodiments, the acrylate polymer emulsions of the present invention further comprise a pH adjuster. The pH adjusting agent suitable for the acrylate polymer emulsion of the present invention may be a weak base such as aqueous ammonia (the concentration of aqueous ammonia may be 15 wt% to 30 wt%). The content of the pH adjustor in the acrylate polymer emulsion of the present invention is not particularly limited as long as the pH of the acrylate polymer emulsion is 5 to 9. In the case of 25 wt% aqueous ammonia as the pH regulator, the mass of the 25 wt% aqueous ammonia is usually 1-5%, preferably 2-4% of the total weight of the acrylate polymer emulsion.
It will be understood by those skilled in the art that the acrylate polymer emulsion of the present invention may further contain a compound (also referred to as initiator residual compound) converted from the initiator used in the preparation of the acrylate polymer microspheres of the present invention by emulsion polymerization, and the content of the acrylate polymer emulsion of the present invention can be determined by the amount of the initiator used in the preparation of the acrylate polymer microspheres and the content of the acrylate polymer microspheres in the acrylate polymer emulsion of the present invention, and is usually less than 1%, for example, 0.2 to 0.5% of the total weight of the acrylate polymer emulsion.
It will be understood by those skilled in the art that the acrylate polymer emulsions of the present invention contain water. In certain embodiments, water comprises 50-65%, such as 50-60%, 55-65%, 55-60% of the total weight of the acrylate polymer emulsion.
In certain embodiments, the acrylate polymer emulsions of the present invention comprise acrylate polymer microspheres, cellulose ether and/or starch ether, optional additives, optional pH adjusters and optional initiator residual compounds, and water; preferably, the acrylate polymer emulsion of the present invention comprises the acrylate polymer microspheres, cellulose ether and/or starch ether, optional additives, optional pH adjuster and optional initiator residual compound in amounts as described above, with the balance being water.
In certain embodiments, the acrylate polymer emulsions of the present invention comprise the following raw materials in parts by weight:
Figure BDA0002348872340000161
in certain embodiments, the acrylate polymer emulsion of the present invention comprises the following raw materials in parts by weight:
Figure BDA0002348872340000171
the acrylic ester polymer emulsion of the present invention can be prepared by dispersing the acrylic ester polymer microspheres of the present invention, cellulose ether and/or starch ether, optional additives, and optional pH adjusting agent in water. The acrylate polymer emulsion of the present invention may also be prepared by dispersing cellulose ether and/or starch ether, optional additives and optional pH adjusting agents in an aqueous dispersion of the acrylate polymer microspheres of the present invention.
In certain embodiments, the method of making the acrylate polymer emulsion of the present invention comprises:
(1) adding a pH regulator into the aqueous dispersion of the acrylate polymer microspheres, and regulating the pH to 5-9;
(2) dispersing cellulose ether and/or starch ether in water to obtain an aqueous dispersion of the cellulose ether and/or starch ether, adding the aqueous dispersion of the cellulose ether and/or starch ether and optional additives into the aqueous dispersion of the acrylate polymer microspheres of the invention with the pH adjusted in the step (1), and uniformly dispersing to obtain the acrylate polymer emulsion of the invention.
In the step (2), the concentration of the aqueous dispersion of the cellulose ether and/or the starch ether is not particularly limited as long as the cellulose ether and/or the starch ether can be uniformly dispersed in water, and for example, in the aqueous dispersion of the cellulose ether and/or the starch ether, the ratio of the mass of water to the total mass of the cellulose ether and the starch ether may be 100: 1 to 20.
The extinction effect can be obtained by utilizing the shrinkage difference of the hard core and the soft core of the acrylate polymer microsphere in the drying film-forming process. Therefore, the acrylate polymer microspheres or the aqueous dispersion thereof can be used for preparing an aqueous extinction coating, and the aqueous dispersion of the acrylate polymer microspheres can also be directly used as an aqueous self-extinction acrylate polymer coating. The method for preparing the water-based system matting coating by using the acrylate polymer microspheres or the water dispersion thereof of the invention can be a conventional method in the field, for example, a person skilled in the art can add a matting agent or other auxiliary agents known in the art to the water dispersion of the acrylate polymer microspheres of the invention according to actual needs, thereby preparing the water-based system matting coating. The extinction coating of the aqueous system prepared from the aqueous dispersion of the acrylate polymer microspheres is coated on a metal, wood, paper or plastic substrate, and a coating with 60-degree angle gloss below 55 can be obtained. Generally, when the 60 ° gloss of the coating film is more than 55, the gloss is significant, and therefore, when the 60 ° gloss of the coating film is 55 or less, the corresponding coating is considered as a matte coating.
The acrylic ester polymer emulsion can be directly used as a water-based self-extinction acrylic ester polymer coating and can also be used for preparing a water-based extinction coating. The method for preparing the matting coating agent of the aqueous system using the acrylate polymer emulsion of the present invention may be a conventional method in the art, for example, a person skilled in the art may conventionally add an auxiliary agent known in the art to the acrylate polymer emulsion of the present invention according to actual needs to prepare a matting coating agent to obtain a desired aqueous system. The aqueous system extinction coating prepared from the acrylate polymer emulsion is coated on a substrate such as metal, wood, paper or plastic parts, and the surface of a coating film with 60-degree angle gloss below 55 can be obtained.
Thus, the present invention also includes a coating having a 60 ℃ gloss of 55 or less formed from an aqueous matte finish containing the acrylate polymer microspheres or aqueous dispersion thereof, or acrylate polymer emulsion of the present invention, or an article having such a coating. Substrates of the articles of the present invention include, but are not limited to, metal, wood, paper, and plastic.
The water-based self-extinction acrylic ester polymer coating has the following advantages:
(1) the water-based self-extinction acrylic ester polymer coating does not need to use SiO 2 The matting agent has good matting effect, storage stability, freeze-thaw stability, adhesion, water resistance, boiling water resistance, alkali resistance, alcohol resistance, stain resistance and dry film appearance;
(2) the paint film clarity and the resistance of the water-based self-extinction acrylic ester polymer paint are superior to those of silicon dioxide extinction powder, and the cost of the paint film is obviously lower than that of the silicon dioxide extinction powder.
The invention will now be described by way of specific examples, which are intended to provide a better understanding of the contents of the invention. It is to be understood that these examples are illustrative only and not limiting. The starting materials and reagents used in the examples were, unless otherwise specified, those conventionally available on the market. The experimental methods, preparation methods and detection methods used in the examples are all conventional methods unless otherwise specified. The instruments used in the examples are conventional in the art unless otherwise specified.
The acrylic protective colloids used in the examples were prepared from 40% styrene, 20% methyl methacrylate, 10% ethyl acrylate, 25% acrylic acid and 5% isobornyl methacrylate, based on the total mass of the monomers, by mass polymerization, and had a weight average molecular weight of about 7500, a polymer dispersibility index of 2.4, and a Tg of 85 ℃.
The hydroxypropyl methylcellulose used in the examples was purchased from Hebei Chengning cellulose, Inc. and had a hydroxypropoxyl content of 8.3%; hydroxyethyl starch ether was purchased from Shandong West Asia chemical industry Co., Ltd and had a purity of 98%; SiO 2 2 The delusterant is TS100 produced by Yingchuang Degussa; the concentration of ammonia water is 25 wt%; the bactericide is LEX series produced by Rohm and Haas; the defoamer is TEGO810 series produced by Digao.
Example 1: preparation of acrylic ester Polymer emulsion
(1) Providing an aqueous dispersion of an acrylic protective colloid: under the condition of stirring, 270 parts by weight of deionized water, 20 parts by weight of ammonia water and 60 parts by weight of acrylic acid protective colloid (solid) are sequentially added into a reaction bottle, the temperature is raised to 80 ℃, and the aqueous dispersion of the acrylic acid protective colloid is obtained by stirring and dispersing.
(2) The reaction temperature was maintained at 80 ℃ all the time, 3 parts by weight of ammonium persulfate was dissolved in 40 parts by weight of deionized water, and when dropping of the sclerosant monomer was started, the aqueous solution of ammonium persulfate was slowly dropped into the reaction flask.
(3) Synthesizing a hard core: uniformly mixing 35 parts by weight of methyl methacrylate, 80 parts by weight of styrene and 15 parts by weight of isobornyl methacrylate, dropwise adding the mixture into a reaction bottle, simultaneously dropwise adding an ammonium persulfate solution for 1h, and carrying out free radical emulsion polymerization to generate a hard core of the acrylate polymer microsphere.
(4) Synthesizing a soft core: uniformly mixing 70 parts by weight of butyl acrylate, 20 parts by weight of styrene and 6 parts by weight of methacryloxypropyltrimethoxysilane, dropwise adding the mixture into a reaction bottle, simultaneously dropwise adding an ammonium persulfate solution for 1h, and carrying out free radical emulsion polymerization to generate a soft core of the acrylate polymer microsphere.
(5) And (3) continuing to dropwise add the initiator for 0.5h, keeping the temperature at 80 ℃ for 2h after the aqueous solution of ammonium persulfate prepared in the step (2) is just dropwise added, and obtaining the emulsion containing the acrylate polymer microspheres with the hard core-soft core-hard shell three-layer structure.
(6) Neutralizing: the temperature of the reaction bottle is reduced to 40 ℃, 5 parts by weight of ammonia water and 40 parts by weight of deionized water are uniformly mixed, and the mixture is dripped into the reaction bottle.
(7) 4 parts by weight of hydroxypropylmethylcellulose was dispersed in 35 parts by weight of deionized water to obtain an aqueous dispersion of hydroxypropylmethylcellulose. This aqueous dispersion of hydroxypropylmethylcellulose, 0.6 part by weight of a bactericide and 0.4 part by weight of a defoaming agent were sequentially added to a reaction flask and uniformly mixed to obtain an acrylic ester polymer emulsion of example 1.
The particle size distribution of the acrylate polymer microspheres obtained in example 1 is shown in FIG. 3, where the Average particle size (Z-Average diameter) of the microspheres is about 71.07nm, the polydispersity index (PDI) is 0.041, and the microspheres have high transparency and are easily dispersed. The particle size analysis was carried out using a laser particle size analyzer (Brookhaven BI-DCP) to determine the mean particle size, attenuator (attorneter): 8.
examples 2 to 6: preparation of acrylic ester Polymer emulsion
The acrylate polymer emulsions of examples 2-6 were prepared according to the raw material formulation given in table 1 using the method of example 1, wherein hydroxyethyl starch ether was used instead of hydroxypropyl methylcellulose in example 6. The amounts of deionized water listed in Table 1 were used as the total amount, wherein the amounts of deionized water used for preparing the aqueous dispersion of an acrylic protective colloid, the aqueous solution of ammonium persulfate and the mixture of aqueous ammonia and deionized water were the same as in example 1, respectively, and the balance of deionized water was used for preparing the aqueous dispersion of hydroxypropylmethylcellulose or hydroxyethyl starch ether. The amounts of aqueous ammonia listed in Table 1 were the same as those of example 1, respectively, for the preparation of the aqueous dispersion of an acrylic protective colloid and for the preparation of a mixture of aqueous ammonia and deionized water, based on the total amount of aqueous ammonia.
Table 1: raw material formulations for the acrylate Polymer emulsions of examples 1-6
Figure BDA0002348872340000201
Figure BDA0002348872340000211
Comparative example 1: preparation of acrylic ester Polymer emulsion
(1) Providing an aqueous dispersion of an acrylic protective colloid: under the stirring condition, adding 20 parts by weight of ammonia water into 270 parts by weight of deionized water, adding 60 parts by weight of acrylic acid protective colloid (solid), heating to 80 ℃, and uniformly dispersing to obtain the aqueous dispersion of the acrylic acid protective colloid.
(2) Synthesizing microspheres: and (2) keeping the constant temperature of 80 ℃ during the reaction, dissolving 3 parts by weight of ammonium persulfate in 40 parts by weight of deionized water, adding an aqueous solution of the ammonium persulfate, 35 parts by weight of methyl methacrylate, 80 parts by weight of styrene, 15 parts by weight of isobornyl methacrylate, 70 parts by weight of butyl acrylate, 20 parts by weight of styrene and 6 parts by weight of methacryloxypropyltrimethoxysilane into the aqueous dispersion of the acrylic protective colloid obtained in the step (1), carrying out emulsion polymerization to obtain an emulsion containing acrylic ester polymer microspheres, and cooling to 40 ℃.
(3) Preparing an emulsion: 5 parts by weight of ammonia water and 40 parts by weight of deionized water were mixed to obtain a mixture of ammonia water and water, and the mixture of ammonia water and water, 38 parts by weight of deionized water, 0.6 part by weight of a bactericide and 0.4 part by weight of a defoaming agent were added to the emulsion containing acrylic ester polymer microspheres obtained in step (2) and mixed uniformly to obtain the acrylic ester polymer emulsion of comparative example 1.
Comparative example 2: preparation of acrylic ester Polymer emulsion
(1) Providing an aqueous dispersion of an acrylic protective colloid: under the condition of stirring, 270 parts by weight of deionized water, 20 parts by weight of ammonia water and 60 parts by weight of acrylic acid protective colloid (solid) are sequentially added into a reaction bottle, the temperature is raised to 80 ℃, and the aqueous dispersion of the acrylic acid protective colloid is obtained by stirring and dispersing.
(2) The reaction temperature was maintained at 80 ℃ all the time, 3 parts by weight of ammonium persulfate was dissolved in 40 parts by weight of deionized water, and when dropping of the sclerosant monomer was started, the aqueous solution of ammonium persulfate was slowly dropped into the reaction flask.
(3) Synthesizing a hard core: uniformly mixing 35 parts by weight of methyl methacrylate, 80 parts by weight of styrene and 15 parts by weight of isobornyl methacrylate, dropwise adding into a reaction bottle, simultaneously dropwise adding an ammonium persulfate solution for 1h, and carrying out free radical emulsion polymerization to generate a hard core of the acrylate polymer microsphere.
(4) Synthesizing a soft core: uniformly mixing 70 parts by weight of butyl acrylate, 20 parts by weight of styrene and 6 parts by weight of methacryloxypropyltrimethoxysilane, dropwise adding the mixture into a reaction bottle, simultaneously dropwise adding an ammonium persulfate solution for 1h, and carrying out free radical emulsion polymerization to generate a soft core of the acrylate polymer microsphere.
(5) And (3) continuing to dropwise add the initiator for 0.5h, keeping the temperature at 80 ℃ for 2h until the aqueous solution of ammonium persulfate prepared in the step (2) is completely dropwise added, and obtaining the emulsion containing the acrylate polymer microspheres with the hard core-soft core-hard shell three-layer structure.
(6) Neutralizing: reducing the temperature of the reaction bottle to 40 ℃, and mixing 5 parts by weight of ammonia water and 40 parts by weight of deionized water to obtain a mixture of the ammonia water and the water; to the emulsion containing acrylic ester polymer microspheres obtained in step (5), 45 parts by weight of a mixture of ammonia water and water, 38 parts by weight of deionized water, 0.6 parts by weight of a bactericide, and 0.4 parts by weight of an antifoaming agent were added to obtain an acrylic ester polymer emulsion of comparative example 2.
Comparative examples 3 to 5: preparation of acrylic ester Polymer emulsion
The acrylic ester polymer emulsions of comparative examples 3-5 were prepared according to the raw material formulation given in Table 2 using the method of example 1, wherein the silica matting agent was used in place of hydroxypropyl methylcellulose in comparative example 5. The amounts of deionized water listed in Table 2 were used as the total amount, wherein the amounts of deionized water used for preparing the aqueous dispersion of the acrylic protective colloid, the aqueous solution of ammonium persulfate and the mixture of aqueous ammonia and deionized water were the same as those used in example 1, respectively, and the balance of deionized water was used for preparing the aqueous dispersion of hydroxypropylmethylcellulose or TS100 (comparative examples 3-5). The amounts of aqueous ammonia listed in Table 2 were the same as those in example 1, respectively, as the total amount of aqueous ammonia used for preparing the aqueous dispersion of the acrylic protective colloid and the amount of aqueous ammonia used for preparing the mixture of aqueous ammonia and deionized water.
Table 2: raw material formulation of acrylic ester polymer emulsion of comparative examples 1 to 5
Figure BDA0002348872340000231
Figure BDA0002348872340000241
Test example
The acrylic ester polymer emulsions of examples 1 to 6 and comparative examples 1 to 5 were measured for their properties by the following methods, and the results are shown in tables 4 and 5.
(1) Calculation method of Tg:
the glass transition temperature was calculated according to the following formula (FOX formula):
1/Tg＝W 1 /Tg 1 +W 2 /Tg 2 +W 3 /Tg 3 +…+W n /Tg n
wherein Tg (in K) is the glass transition temperature of the copolymer, Tg i (in K) is the glass transition temperature of the homopolymer of the i-th monomer, W i The mass fraction of the ith monomer in all the monomers is shown.
(2) Method for measuring gloss: the test is carried out according to the GB/T9754 specification, and a triangular gloss meter is adopted, and the test result is carried out at an angle of 60 degrees.
(3) Evaluation method of storage stability: about 0.5L of the sample was sealed, placed in a 50 ℃ constant temperature oven after sealing, taken out after 7 days and placed at 23 ℃ for 3 hours, and the state in the container was checked, and if the sample was uniformly stirred without hard lumps, it was recorded as "not deteriorated".
(4) Evaluation method of freeze-thaw stability: the test was carried out according to the specification of 5.5 in GB/T9755-2001, and the presence or absence of hard lumps, agglomeration and separation was observed after the test, and if no hard lumps, agglomeration and separation were observed, it was recorded as "no deterioration".
(5) Evaluation method of adhesion: according to the GB/T9286-1998 specification.
(6) Evaluation method of Water resistance: the test solution is purified water with the temperature of 23 +/-2 ℃, the test is carried out according to the GB/T4893.1-2005, the appearance of the coating film is observed after the test, and the judgment standard is shown in the table 3.
(7) Evaluation method of boiling water resistance: the test solution was boiled water and tested according to the GB/T4893.1-2005, and the appearance of the coating film was observed after the test, and the criteria for the determination are shown in Table 3.
(8) Evaluation method of alkali resistance: the acrylic ester polymer emulsion was uniformly coated on the surface of wood (coated with a layer of the acrylic ester polymer emulsion of comparative example 1 as a primer) with a 100 μm wire bar, dried at 50 ℃ for 4 hours to form a film, the film was immersed in 50g/L sodium bicarbonate solution for an experimental time of 1 hour, and after the test, the film was taken out and left for 1 hour to observe the appearance of the film, and the criteria were as shown in Table 3.
(9) Evaluation method of alcohol resistance: the acrylic ester polymer emulsion is uniformly coated on the surface of wood (a layer of acrylic ester polymer emulsion of comparative example 1 is coated as a primer) by a 100-micron wire rod, the coating is dried at 50 ℃ for 4 hours to form a film, the coating is immersed in 50 percent (volume fraction) of ethanol solution, the experimental time is 1 hour, the coating is taken out after the test and placed for 1 hour, the appearance of the coating is observed, and the judgment standard is shown in table 3.
(10) Evaluation method of stain resistance: the acrylic ester polymer emulsion was uniformly coated on the surface of wood with a 100 μm wire bar (a layer of the acrylic ester polymer emulsion of comparative example 1 was coated as a primer), dried at 50 ℃ for 4 hours to form a film, subjected to a vinegar resistance and tea resistance test, and observed before and after the test for the appearance of the coating film, and the criteria were as shown in table 3.
The vinegar resistance test is as follows: the test solution is brewed vinegar (acidity 5g/100ml), the coating film is immersed in the test solution for 1h, and the test solution is taken out after the test and is placed for 1h, and then the appearance of the coating film is observed.
The tea-resistance test is as follows: the test solution is green tea water (2g of green tea powder added with 250ml of boiling water, and placed at room temperature for 5min), the coating film is immersed in the test solution for 1h, and the appearance of the coating film is observed after the test is taken out and placed for 1 h.
(11) Evaluation method of dry film appearance: the acrylic ester polymer emulsion was uniformly applied to the surface of wood with a 100 μm wire bar (the bottom of which was coated with a layer of the acrylic ester polymer emulsion of comparative example 1 as a primer), dried at 50 ℃ for 4 hours to form a film, and the change in the appearance of the coating film was visually observed, and the criteria for the determination are shown in table 3.
Table 3: coating film appearance judgment standard
Appearance of the coating film after the test Determination result
Transparent and unchanged No abnormality
The white fog area of the coating film is less than or equal to 15 percent Slight whitening
15％<The white fog area of the coating is less than or equal to 85 percent Whitening of the skin
85％<White fog area of coating film White fog
Table 4: properties of the acrylate Polymer emulsions of examples 1-6
Figure BDA0002348872340000261
Figure BDA0002348872340000271
Table 5: properties of the acrylate Polymer emulsions of comparative examples 1-5
Performance of Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative example 5
Hard core Tg (. degree.C.) - 105 105 105 105
Soft core Tg (. degree. C.) - -26 -26 -26 -26
Tg(℃) 33 - - - -
Gloss (60 degree) 91 60 65 5 25
Storage stability No deterioration No deterioration No deterioration No deterioration No deterioration
Freeze thaw stability No deterioration No deterioration No deterioration No deterioration No deterioration
Attachment of 1 1 1 1 1
Water-resistant (24h) No abnormality No abnormality No abnormality Whitening of the skin No abnormality
Boiling resistant water (15min) No abnormality No abnormality No abnormality Whitening of the skin Slight whitening
Alkali resistance No abnormality No abnormality No abnormality Slight whitening No abnormality
Alcohol resistance No abnormality No abnormality No abnormality Slight whitening Slight whitening
Vinegar-resistant vinegar No abnormality No abnormality No abnormality Slight whitening No abnormality
Tea for resisting diseases No abnormality No abnormality No abnormality Slight whitening No abnormality
Appearance of Dry film Is transparent Is transparent Is transparent Is transparent White fog

Claims (10)

1. A method of making acrylate polymer microspheres, the method comprising:
(1) dispersing acrylic acid protective colloid in water to obtain aqueous dispersion of acrylic acid protective colloid;
(2) adding a monomer and an initiator of a hard core into the aqueous dispersion of the acrylic acid protective colloid in the step (1) to react to generate the hard core of the acrylate polymer microsphere; and
(3) adding a monomer with a soft core and an initiator into the reaction system after the reaction in the step (2) to react to obtain the acrylate polymer microspheres;
the acrylate polymer microspheres sequentially comprise a hard core, a soft core and a hard shell from inside to outside, the Tg of the hard core is higher than that of the soft core by at least 50 ℃, the monomer of the hard core consists of a hard monomer and a functional monomer, and the monomer of the soft core consists of a soft monomer, a crosslinking monomer and a hard monomer;
the hard monomer is one or a combination of methyl methacrylate, styrene, acrylonitrile, acrylamide, methyl styrene, acrylic acid and methacrylic acid;
the soft monomer is one or a combination of more of ethyl acrylate, butyl acrylate, n-octyl acrylate, isooctyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate and vinyl versatate;
the functional monomer is one or a combination of more of isobornyl methacrylate, glycidyl methacrylate, acetoacetoxyethyl methacrylate, hydroxyethyl methacrylate and vinyl versatate;
the crosslinking monomer is an alkenyl organosilicon monomer;
the hard shell comprises an acrylic protective colloid;
the acrylic protective colloid is an oligomer comprising a combination of one or more of acrylic monomers and methacrylic monomers, the oligomer having a Tg of 30 ℃ to 130 ℃.
2. The method of claim 1, wherein the hard core has a Tg of 95 ℃ to 120 ℃ and the soft core has a Tg of-45 ℃ to 38 ℃.
3. The method of claim 1, wherein the acrylate polymer microspheres have at least one of the following characteristics:
(1) the alkenyl organosilicon monomer is (R) 3 ) c Si(OR 1 ) 4-c Wherein R is 1 Is C1-C3 alkyl, R 3 Is an unsaturated group having an alkenyl group, and c is an integer of 1 to 3;
(2) in the acrylic protective colloid, the weight of the acrylic monomer and the methacrylic monomer accounts for 5-30% of the total weight of the monomers of the acrylic protective colloid, the weight average molecular weight of the oligomer is 2000-45000, and the polydispersity index of the oligomer is 1.5-9;
(3) the raw materials of the acrylate polymer microspheres comprise 30-70 parts by weight of acrylic acid protective colloid, 100-200 parts by weight of hard monomer, 20-100 parts by weight of soft monomer, 1-30 parts by weight of functional monomer and 1-10 parts by weight of crosslinking monomer;
(4) the mass ratio of the hard core to the soft core to the hard shell is 100-150: 100: 30-70 parts of;
(5) the hard core comprises the following raw materials in a mass ratio of 100: 5-50 of hard monomers and functional monomers; and
(6) the soft core comprises the following raw materials in a mass ratio of 90-10: 10-90 of hard monomer and soft monomer, and 1-10% of crosslinking monomer by mass of the total mass of the hard monomer and the soft monomer.
4. The method of claim 1, wherein the alkenyl silicone monomer is methacryloxypropyltrimethoxysilane.
5. Acrylate polymer microspheres produced by the process according to any one of claims 1 to 4.
6. An acrylate polymer emulsion comprising (a) the acrylate polymer microspheres of claim 5 and (B) cellulose ether and/or starch ether; wherein the mass ratio of the cellulose ether and/or starch ether to the acrylate polymer microspheres is 0.2-1.5: 100.
7. the acrylate polymer emulsion of claim 6 wherein the cellulose ether and/or starch ether comprises from 0.08% to 0.8% by weight of the total acrylate polymer emulsion.
8. The acrylate polymer emulsion of claim 6, wherein said acrylate polymer emulsion has at least one characteristic:
(1) the cellulose ether is one or more of methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose, and the starch ether is one or more of hydroxyethyl starch ether, hydroxypropyl starch ether and carboxymethyl starch ether;
(2) the acrylate polymer microspheres account for 35-45% of the total weight of the acrylate polymer emulsion; and
(3) the acrylic ester polymer emulsion contains the following raw materials in parts by weight:
30 to 70 parts by weight of an acrylic acid protective colloid,
100 to 200 parts by weight of a hard monomer,
20 to 100 parts by weight of a soft monomer,
1 to 30 parts by weight of a functional monomer,
1 to 10 parts by weight of a crosslinking monomer, and
0.6-5 parts by weight of cellulose ether and/or starch ether.
9. Use of the acrylate polymer microspheres or the aqueous dispersion thereof according to claim 5 or the acrylate polymer emulsion according to any one of claims 6 to 8 for the preparation of an aqueous matting coating.
10. A coating having an angular gloss of 60 ° or less of 55, or an article having the coating, wherein the coating is formed from an aqueous matting coating comprising the acrylate polymer microspheres or aqueous dispersion thereof according to claim 5, or the acrylate polymer emulsion according to any one of claims 6 to 8.
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