CN112608415B - Nano zinc oxide/vinyl polymer composite microsphere and preparation method and application thereof - Google Patents

Nano zinc oxide/vinyl polymer composite microsphere and preparation method and application thereof Download PDF

Info

Publication number
CN112608415B
CN112608415B CN202011341959.3A CN202011341959A CN112608415B CN 112608415 B CN112608415 B CN 112608415B CN 202011341959 A CN202011341959 A CN 202011341959A CN 112608415 B CN112608415 B CN 112608415B
Authority
CN
China
Prior art keywords
zinc oxide
nano zinc
vinyl polymer
microsphere
polymer composite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202011341959.3A
Other languages
Chinese (zh)
Other versions
CN112608415A (en
Inventor
秦佃斌
陈涛
林争超
乔义涛
纪学顺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Group Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co Ltd filed Critical Wanhua Chemical Group Co Ltd
Priority to CN202011341959.3A priority Critical patent/CN112608415B/en
Publication of CN112608415A publication Critical patent/CN112608415A/en
Application granted granted Critical
Publication of CN112608415B publication Critical patent/CN112608415B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • 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
    • C09D7/65—Additives macromolecular
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention discloses a nano zinc oxide/vinyl polymer composite microsphere and a preparation method thereof, wherein the composite microsphere comprises: based on the total dry weight of the composite microsphere, 90-99.5 wt% of crosslinked or non-crosslinked vinyl polymer microsphere with Tg in the range of 80-150 ℃ and 0.5-10 wt% of nano zinc oxide, wherein the nano zinc oxide is loaded on the surface of the vinyl polymer microsphere. The composite microsphere can be used as a flatting agent for the anti-adhesion, stain resistance and chemical resistance of coating or adhesive; the composite microspheres have uniform particle size distribution, and can ensure stable glossiness; the composite microsphere is a powdery wet solid, is convenient to use, and can be stored and transported for a long time.

Description

Nano zinc oxide/vinyl polymer composite microsphere and preparation method and application thereof
Technical Field
The invention relates to a narrow-dispersion nano zinc oxide/vinyl polymer composite microsphere and a preparation method and application thereof. The composite microsphere plays a role in adjusting the glossiness and the transparency of a paint film and improving hand feeling in the preparation of paint or adhesive, and is particularly suitable for being used as a flatting agent with boiling water and scalding resistance, chemical resistance, adhesion resistance, stain resistance, scratch resistance, high transparency and high smoothness in water-based paint and adhesive.
Background
The matt or matte coating attracts the consumers due to nature, nobility and elegance. The surface of the matt or matte coating can also conceal slight film defects, so that the appearance is uniform and consistent. At present, the matt or matte coating is prepared mainly by directly adding a matting agent into the coating, wherein the matting agent can enable a paint film to form an uneven rough surface, diffuse reflection is formed when light is incident, and the paint film is in a matt or matte state, so that the aim of matting is fulfilled. The flatting agent can provide flatting and can also endow the paint film with good resistance, good hand feeling and other properties. The flatting agent is mainly divided into silicon dioxide or calcium carbonate inorganic flatting agent, polymethyl urea organic flatting agent and liquid or solid polyethylene wax. When a matt or matte coating is prepared, the silica or calcium carbonate inorganic flatting agent has poor compatibility with resin, and can provide good transparency of a paint film, but can also greatly reduce the performances of the paint film such as water resistance, alcohol resistance, wear resistance and the like. Although the polymethyl urea organic flatting agent has good compatibility with resin, the performances of water resistance, alcohol resistance, wear resistance and the like of a paint film cannot be greatly reduced, the paint film is hazy due to the larger difference of the refractive index of the polymethyl urea organic flatting agent and the resin forming the paint film, and the transmittance of the paint film is reduced. The polyethylene wax flatting agent is easy to migrate to the surface of the coating and easy to polish, and the problem of unstable delamination can be caused when the finished coating is prepared.
In order to solve these problems, in recent years, vinyl polymer microspheres have been used as matting agents in coating compositions to provide matt coatings, and due to the excellent compatibility between the vinyl polymer microspheres and film-forming resins, the water resistance, alcohol resistance, abrasion resistance, transparency and other properties of the paint film can be significantly improved, and a smooth special hand can be provided. For example, companies such AS japanese unexamined patent publication, japanese water accumulation chemical, microbeads AS provide single-size thermosetting PMMA microsphere solid powder AS products of various sizes, which can be used AS matting agents. CN101037558a relates to an aqueous coating composition containing a polymeric matting agent component having an average particle size of 1 to 20um and a binder component capable of providing a matte coating having transparency, abrasion resistance, flexibility and feel or touch properties and a coated article made therefrom. CN107531974a surprisingly found that by selecting the appropriate combination of stabilizer species and stabilizer concentration and initiator species, suspension polymerization can be allowed to produce storage stable aqueous dispersions containing particles having an average particle size diameter of 1 micron to 30 microns, can be used as matting agents. Because the vinyl polymer microspheres have very good compatibility with the resin for film formation, particularly polyacrylate type resin, the vinyl polymer microspheres have more excellent performance than inorganic flatting agents and organic flatting agents such as polyethylene wax, polymethyl urea and the like. However, the size of the microspheres is relatively large, generally in the range of 1-30um, and the resin has poor wrapping property, so that the scratch resistance, especially the chemical resistance of the microspheres is poor when the microspheres are used as a flatting agent on base materials such as plastics, metals, woodware, leather and the like. Furthermore, the general paint film is expected to have excellent anti-blocking and anti-staining properties, and the high Tg vinyl polymer microspheres at 80 ℃ or higher can be used for well meeting the properties, but the high Tg vinyl polymer microspheres are used, especially in a system compatible with the high Tg film-forming resin, because the high Tg vinyl polymer microspheres have poor deformation capability and the fusion deformation capability of latex particles in the high Tg film-forming resin is poor, the defect of scratch resistance or chemical resistance is particularly outstanding.
The thermosetting PMMA microspheres used as matting agents mentioned above, which are in the form of solid powders in appearance, present a great risk of dust explosion, especially in relatively confined production plants. Since these powders are light and easily inhaled into the body, there is a great occupational health risk. Because dry powders are difficult to disperse uniformly in a system in a formulation, it is generally necessary to carry out a filtration step after the paint has been dispensed or to add a certain amount of wetting dispersant to aid in its dispersion during industrial production. CN101037558a relates to an aqueous coating composition containing a polymeric matting agent component and a binder component, which greatly limits its range of application in view of compatibility issues with other binders, since it is a composition, including a binder component. CN107531974A is prepared by suspension polymerization to produce a storage stable aqueous dispersion containing particles having an average particle size diameter of 1 to 30 microns, and as is well known to those skilled in the art, microspheres prepared by suspension polymerization have a broad particle size distribution, poor stability of particle size from batch to batch, and their matting ability is completely dependent on the size and distribution of the particle size, and the different particle sizes and particle size distributions have different matting abilities, which means that the matting abilities of the particles prepared by suspension polymerization are not uniform from batch to batch. In view of the long term storage and shipping in containers, it is well known to those skilled in the art that the criterion for storage stability is generally the absence of caking or hard precipitates after storage at 50 ℃ for at least four weeks. At present, it is difficult to stably store an aqueous dispersion or aqueous composition containing vinyl polymer particles having an average diameter of more than 1um and a relatively large density without delamination and precipitation unless a thickening agent is added in an amount to increase the viscosity of the system or an anti-settling agent, such as CN102533040a, CN102952462A, CN105308131a, etc. However, it is disadvantageous to add thickeners and partially hydrolyzed ethyl acetate (co) polymer stabilizers, which are highly hydrophilic, to the coating systems with high requirements for water and chemical resistance, especially in the fields of aqueous leather finishes and aqueous wood paints.
We have unexpectedly found that these problems can be solved by loading a layer of nano-zinc oxide on vinyl polymer microspheres having a certain amount of amide and carboxyl groups on the surface and then preparing a wet powder of narrowly dispersed nano-zinc oxide/vinyl polymer composite microspheres. EP0373918, CN101665556A, US2009043043 and other patents describe that transition metal ions can form a complex with carboxyl functional groups on film-forming resin to generate postcrosslinking, and the performance of a paint film can be obviously improved. However, since the transition metal powder is not well dispersed uniformly, it cannot be added directly to the film-forming resin, but only under the conditions of a specific reaction degree, temperature and PH during the free-radical emulsion polymerization of the resin. The nano-zinc oxide/vinyl polymer composite microspheres prepared by the invention can uniformly distribute the nano-zinc oxide between the polymer microspheres and the film-forming resin, and the nano-zinc oxide reacts with carboxyl on the surfaces of the microspheres and carboxyl of the film-forming resin to generate crosslinking, so that the polymer microspheres are more firmly embedded in the film-forming resin, thereby improving the performances of scratch resistance, chemical resistance and the like, and having excellent anti-blocking and stain-resistant performances.
The nano zinc oxide is adsorbed on the surface of the polymer microsphere, can replace part of protective glue, plays a role in space isolation, prevents the microspheres from being mutually adhered when the gel effect is achieved, improves the stability of a system, and reduces the addition of the protective glue. Inorganic salts (activated calcium phosphate, magnesium carbonate, titanium dioxide, barium sulfate, etc.) are used as inorganic suspension stabilizers instead of organic polymers, and have been widely used in suspension polymerization processes for preparing particles having large particle diameters, such as ion exchange resin particles, polyvinyl chloride particles, etc. US2010062254 describes the preparation of a range of 4-15um polyurethane microspheres of different colors using inorganic suspension stabilizers. However, the use of inorganic suspension stabilizers to prepare micron-sized vinyl polymer microspheres has not been found. Since the smaller the particle size of the polymer microspheres, the more difficult the inorganic suspension stabilizer is to adsorb on the surface of the polymer microspheres, a large amount of organic suspension stabilizer is required to stabilize the system, especially vinyl polymer microspheres with Tg of 80 ℃ or higher, and due to the obvious gelation effect, when the conversion rate of the polymer reaches a certain value, the internal viscosity of the microspheres is very high, and the microspheres are easy to adhere. We have surprisingly found that amide functional groups are introduced on the surface of a vinyl polymer, and the amide functional groups and nano zinc oxide are coordinated to improve the affinity between the vinyl polymer and the nano zinc oxide, so that the vinyl polymer can be more firmly adsorbed on the surface of a microsphere. The nano zinc oxide can be used as an inorganic suspension stabilizer in the preparation process of the vinyl polymer microspheres with the Tg of 80 ℃ or higher to replace part of organic high polymer protective glue, so that the stability of the system is improved. The coordination can also prevent the nano zinc oxide from falling off from the surface of the microsphere in the subsequent post-treatment processes such as washing and the like.
Disclosure of Invention
The invention aims to provide a nano zinc oxide/vinyl polymer composite microsphere with narrow particle size distribution and a preparation method thereof. Because the nano zinc oxide and the carboxyl generate a crosslinking effect, the performances of the paint film such as anti-adhesion, stain resistance and the like are ensured, and the performances of scratch resistance and chemical resistance of the paint film can be obviously improved. Preferably, the composite microsphere moist powder is solid and can be stored and transported for a long time. Due to the characteristics of moist powder, the powder has no risk of dust explosion and human inhalation, and can be easily and uniformly dispersed in various water-based coating compositions. The narrow particle size distribution also ensures stable gloss.
The invention also aims to provide the application of the composite microspheres in preparing coatings or adhesives as an auxiliary agent for adjusting the glossiness and the transmittance of paint films and improving hand feeling, and preferably as a flatting agent.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a nano zinc oxide/vinyl polymer composite microsphere, comprising:
based on the total dry weight of the composite microsphere, 90-99.5 wt% of crosslinked or non-crosslinked vinyl polymer microsphere with Tg in the range of 80-150 ℃ and 0.5-10 wt% of nano zinc oxide, wherein the nano zinc oxide is loaded on the surface of the vinyl polymer microsphere.
As a preferred scheme, the polymer microsphere comprises the following raw materials by weight based on the total weight of the vinyl polymer microsphere: 1-5 wt% of hydrophilic monovinyl monomer containing amide group, 1-5 wt% of hydrophilic monovinyl monomer containing carboxyl group, 85-98 wt% of nonionic monovinyl monomer and 0-5 wt% of at least one polyethylenically unsaturated monomer selected from allyl methacrylate, diallyl phthalate, 1,4-butanediol dimethacrylate, 1,2-ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate or divinylbenzene.
The volume particle average diameter (D50) of the nano zinc oxide/vinyl polymer composite microsphere is in the range of 1-25um, and D50 is preferably equal to narrow-dispersion composite microspheres with different particle diameters of 3um, 5um and 10 um. The narrow particle size distribution can provide stable extinction capability. Preferably D50=5um, a better balance between extinction capability and performance can be maintained. The particle size is too small, the extinction capability is poor, and the excellent transparency and the fine surface effect can be maintained. Too large a particle size results in an increased matting effect, but a marked decrease in transparency and a marked loss in properties, in particular scratch resistance.
In the present invention, the hydrophilic monovinyl monomer containing an amide group is selected from one or more of acrylamide, methacrylamide, N-methylolacrylamide, N-dimethylacrylamide, diacetone acrylamide and methacrylamide ethyl ethylene urea, preferably methacrylamide ethyl ethylene urea. The hydrophilic monovinyl monomer having an amide group is preferably used in an amount ranging from 1 to 5% by weight based on the total weight of the vinyl polymer microspheres. The hydrophilic monovinyl monomer having amide groups is used in an amount of less than 1% by weight, the amount of the enriched amide groups on the surface of the microsphere is too small to provide a sufficient amount of ligands, the nano zinc oxide is not sufficiently adsorbed on the surface of the microsphere, and the polymerization stability may be deteriorated. The amount of amide group-containing hydrophilic monovinyl monomer used should not be too high, preferably not higher than 5% by weight, and it is well known to those skilled in the art that the introduction of both carboxyl and amide functional groups into the system results in an increase in the viscosity of the system. Too high a quantity of hydrophilic monomer is used, which leads to poor water and chemical resistance of the paint film.
In the present invention, the hydrophilic monovinyl monomer containing a carboxyl group is selected from one or more of methacrylic acid, acrylic acid, acryloxypropionic acid, methacryloxypropionic acid, itaconic acid, maleic acid or anhydride, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, and monomethyl itaconate, preferably one or more of methacrylic acid and acrylic acid, and more preferably methacrylic acid. The hydrophilic monovinyl monomer having a carboxyl group is preferably used in an amount ranging from 1 to 5% by weight based on the total weight of the vinyl polymer microspheres. The use amount of the hydrophilic monovinyl monomer containing carboxyl is less than 1 percent by weight, and the carboxyl enriched on the surface of the microsphere is too little to provide a sufficient amount of crosslinking points, so that the scratch resistance cannot be sufficiently realized. The amount of the hydrophilic monovinyl monomer containing carboxyl is not preferably too high, preferably not higher than 5% by weight, and too high an amount of the hydrophilic monovinyl monomer results in too many hydrophilic carboxyl functional groups on the surface of the microspheres, the water resistance and chemical resistance of the paint film may be poor, and too high an amount of the hydrophilic monovinyl monomer may result in a large amount of aqueous phase polymerization during the polymerization of the microspheres, and thus the yield of the microspheres may also be reduced.
In the present invention, the nonionic monovinyl monomer is selected from one or more of styrene, a-methylstyrene, p-methylstyrene, vinyltoluene, vinyl acetate, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, oleyl (meth) acrylate, palmityl (meth) acrylate, and stearyl (meth) acrylate. Styrene and methyl methacrylate are preferred. Preferably, the homopolymer and/or copolymer of the nonionic monovinyl monomer has a Tg in the range of 80 to 150 ℃, and a high Tg contributes to the improvement of the blocking and stain resistance of the paint film.
In the present invention, at least one polyethylenically unsaturated monomer selected from allyl methacrylate, diallyl phthalate, 1,4-butanediol dimethacrylate, 1,2-ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate or divinylbenzene may be used as a crosslinking agent, preferably a crosslinking agent, and the use of a crosslinking agent can improve the solvent resistance of the microspheres and prevent the gloss from increasing due to deformation in a coating formulation with a high film-forming aid. The chemical resistance of the paint film can be further improved by using high amount of the cross-linking agent.
In the invention, the particle size of the nano zinc oxide is in the range of 1-200nm, preferably in the range of 50-100 nm. Beyond the range, the adsorption amount of the nano zinc oxide on the surface of the microsphere is too small, the suspension stabilizing effect is not obvious, and the excellent scratch resistance can not be embodied in a paint film.
In the present invention, the nano zinc oxide is preferably added in an amount of 0.5 to 10% by weight, more preferably 1 to 8% by weight, based on the total weight of the vinyl polymer microspheres. Because the nano zinc oxide has smaller particle size and higher oil absorption, the addition amount of the nano zinc oxide is not too much, and after the nano zinc oxide is added too much, the zinc oxide cannot be well dispersed, and can adsorb a large amount of suspension stabilizer and co-stabilizer, so that the stability is deteriorated and the performance is reduced, and the use amount is preferably not more than 10 wt%, and more preferably not more than 8 wt%. The addition amount of the nano zinc oxide is not lower than 0.5 wt%, preferably not lower than 1 wt%, the addition amount is too small, the adsorption amount of the nano zinc oxide on the surfaces of the microspheres is too small, the suspension stabilizing effect is not obvious, and the excellent scratch resistance can not be embodied in a paint film.
The composite microsphere is prepared by a seed suspension polymerization method, and the method comprises the following steps:
1. preparing an oligomer-containing vinyl polymer seed emulsion, which is prepared by carrying out free radical emulsion polymerization on raw materials comprising or consisting of the following components in parts by mass:
a) 9 to 49 parts of at least one monovinyl monomer;
b) 0.5-20 parts of at least one molecular weight regulator;
c) 0.02-1.25 parts of at least one emulsifier;
d) 0 to 0.75 parts of at least one polyethylenically unsaturated crosslinking monomer;
e) 0.01-0.49 parts of water-soluble initiator;
f) 50-90 parts of deionized water;
2. (a) mixing 0.1-1.5 parts of oil-soluble free radical initiator and 9-79 parts of monomer mixed solution, wherein the monomer mixed solution comprises 1-5 wt% of hydrophilic monovinyl monomer containing amido, 1-5 wt% of hydrophilic monovinyl monomer containing carboxyl, 85-98 wt% of nonionic monovinyl monomer and 0-5 wt% of at least one multi-ethylenic unsaturated monomer to obtain mixed solution; (b) Adding the mixed solution into 20-90 parts of deionized water dissolved with 0.01-2 parts of emulsifier to carry out dispersion and emulsification so as to prepare pre-emulsion; (c) Adding a certain amount of the vinyl polymer seed emulsion in the step 1 into the pre-emulsion, and stirring and swelling; (d) Dispersing a certain amount of nano zinc oxide into deionized water to obtain a dispersion liquid containing the nano zinc oxide, and dissolving a certain amount of protective glue into the deionized water to obtain a deionized water solution in which the protective glue is dissolved; (e) After the vinyl monomer is completely swelled into the seed emulsion, adding a dispersion liquid containing nano zinc oxide and a deionized water solution dissolved with protective glue into the swelled seed emulsion; (f) Finally, heating to initiate free radical polymerization to prepare nano zinc oxide/vinyl polymer microsphere suspension;
3. carrying out solid-liquid separation treatment on the nano zinc oxide/vinyl polymer composite microsphere suspension obtained in the step 2 to obtain a filter cake with the water content of less than or equal to 35%;
4. and (3) transferring the filter cake obtained in the step (3) to mixing equipment with an atomizing nozzle to crush the filter cake into powder or small blocks, and adjusting the water content to be within the range of 15-35% to obtain the narrowly dispersed nano zinc oxide/vinyl polymer composite microsphere wet powder. The parts are weight parts.
Wherein, the monovinyl monomer in step 1 a) is selected from one or more of styrene, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, methacrylic acid and acrylic acid. The nonionic monovinyl monomer of (a) in step 2 is selected from one or more of styrene, a-methylstyrene, p-methylstyrene, vinyltoluene, vinyl acetate, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, oleyl (meth) acrylate, palmityl (meth) acrylate, and stearyl (meth) acrylate. Styrene and methyl methacrylate are preferred. Preferably, the homopolymer and/or copolymer of the nonionic monovinyl monomer has a Tg in the range of 80 to 150 ℃, and a high Tg contributes to the improvement of the blocking and stain resistance of the paint film.
In the preparation method of the vinyl polymer seed emulsion in the step 1, the molecular weight regulator is added into the mixture containing the monovinyl monomer, so that the vinyl polymer seed emulsion containing the oligomer can be obtained under the action of the initiator, and the oligomer can absorb the vinyl-containing polymerizable monomer more easily, so that the volume of the vinyl polymer seed emulsion can be swelled by several times or even dozens of times. Suitable molecular weight regulators may include one or more of tetrabromomethane, sodium methallylsulfonate, alkyl mercaptoalkanoates and mercaptans, preferably one or more of mercaptocatenary (C3-C8) alkanoic (C1-C8) alkyl esters and C4-C22 linear or branched alkyl mercaptans, more preferably one or more of methyl 3-mercaptopropionate, butyl 3-mercaptopropionate, n-hexyl mercaptan, n-dodecyl mercaptan.
The polyethylenically unsaturated crosslinking monomer described in step 1 is selected from one or more of allyl methacrylate, diallyl phthalate, 1,4-butanediol dimethacrylate, 1,2-ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, or divinylbenzene. The initiator in step 1 is selected from water-soluble peroxide initiators, preferably one or more of potassium persulfate, sodium persulfate and ammonium persulfate. The reaction temperature of the reaction of step 1 is preferably in the range of 75 to 95 ℃ and the monomer dropping time is preferably in the range of 1 to 4 hours.
In the vinyl polymer seed emulsion containing oligomer obtained by the method of step 1, the preparation steps can be referred to the description of preparing seed crystals in CN101037558 a. Contains at least one oligomer copolymerized with a vinyl group-containing polymerizable monomer, the oligomer being present in a proportion of 5 to 60% by weight, preferably 10 to 40% by weight, more preferably 15 to 25% by weight, based on the solids content of the vinyl polymer emulsion. The oligomer has a weight average molecular weight in the range of 200 to 10000, preferably in the range of 1000 to 8000, more preferably in the range of 2000 to 5000.
The average diameter of the oligomer-containing vinyl polymer seed emulsion obtained by the process of step 1 is in the range of 0.2 to 1.0. Mu.m, preferably in the range of 0.4 to 0.8. Mu.m.
The emulsifier in the step 1 is selected from anionic emulsifiers, such as sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium tridecyl sulfate, sodium 2-ethylhexyl sulfate, sodium alkyl sulfosuccinate, and disodium ethoxyethanol sulfosuccinate monoester; or nonionic emulsifiers such as one or more of tridecyl alcohol ethoxylate, oleic alcohol ethoxylate, octylphenol ethoxylate, nonylphenol ethoxylate; or anionic nonionic emulsifier, such as one or more of alkyl polyoxyethylene ether sulfate and alkyl polyoxyethylene ether; preferred are anionic emulsifiers such as one or more of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium tridecyl sulfate, sodium 2-ethylhexyl sulfate, sodium alkyl sulfosuccinate, more preferably one or more of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate and sodium tridecyl sulfate.
In the above step 2 preparation method, the pre-emulsion is preferably prepared in step 2 by using a high speed dispersing machine at 500-10000rpm, preferably 1000-5000rpm, and particularly preferably 2000-3000 rpm.
In the above step 2 preparation method, the dispersion time of the pre-emulsion is preferably controlled within 5 to 120 minutes, preferably within 10 to 60 minutes, and particularly preferably within 15 to 30 minutes.
In the preparation method of step 2, since the high-speed disperser generates a large amount of heat during the preparation of the pre-emulsion, which causes a certain increase in the temperature of the pre-emulsion, the pre-emulsion is prepared under the condition of controlling the temperature of the pre-emulsion, preferably, the pre-emulsion is prepared by the high-speed disperser within the range of 10 to 50 ℃, preferably, within the range of 20 to 40 ℃, and particularly preferably, the pre-emulsion is prepared under the room temperature condition.
In the preparation method of step 2, the temperature for swelling by stirring is not too high so as to prevent radical polymerization of a large amount of monomers in short of absorption by the oligomer-containing vinyl polymer seed emulsion. The swelling with stirring is preferably carried out at a temperature in the range from 10 to 80 ℃, preferably in the range from 20 to 60 ℃ and particularly preferably in the range from 30 to 40 ℃.
In the above preparation method, the nano zinc oxide in step 2 (d) is preferably dispersed in deionized water in advance, and a high speed dispersing machine is preferably used to prepare the zinc oxide dispersion at a rotation speed of 500-10000rpm, preferably 1000-5000rpm, and particularly preferably 2000-3000 rpm. It is preferred to add a small amount of the emulsifier described in step 1 to aid in its dispersion. The dispersion time of the nano zinc oxide is preferably not less than 30min, and more preferably not less than 60min.
In the preparation method, the nano zinc oxide dispersion liquid in the step 2 (d) is preferably prepared and is not suitable for overnight storage, and after long-term storage, the steps can be repeated by using a high-speed dispersion machine. And adding the nano zinc oxide dispersion liquid after the vinyl polymer seed emulsion containing the oligomer is completely swelled.
In the above preparation method, polyvinyl alcohol (PVA) is preferably used as the protective glue, and the molecular weight of the PVA is preferably 1-10W dalton. Polyvinyl alcohol (PVA) is solid powder, and needs to be dissolved in hot water in advance before use to prepare an aqueous solution with a certain proportion for use. The nano zinc oxide dispersion liquid is added into the swelled seed emulsion before the polyvinyl alcohol aqueous solution. Polyvinyl alcohol (PVA) is preferably added in an amount of 0.1 to 1% by weight, more preferably 0.3 to 0.7% by weight, based on the total weight of the vinyl polymer microspheres.
In the above production process, the temperature at which the radical polymerization is initiated in step (f) is preferably in the range of 40 to 90 ℃ and particularly preferably in the range of 50 to 80 ℃. The reaction time is preferably from 1 to 10 hours, particularly preferably from 4 to 6 hours.
As a preferable embodiment, in the swelling step 2, when the oligomer-containing vinyl polymer seed emulsion is swollen, the swollen monomer is preferably made into an emulsion form (i.e., an emulsifier is added), and more preferably, the monomer is dispersed into small droplets by a high-speed dispersing machine in the presence of the emulsifier and water. The amount of emulsifier used should not exceed its Critical Micelle Concentration (CMC) in the system water to prevent secondary balling reactions from occurring. The emulsifier is selected from anionic emulsifiers such as sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium tridecyl sulfate, sodium 2-ethylhexyl sulfate, sodium alkyl succinate sulfonate, or nonionic emulsifiers such as one or more of tridecyl alcohol ethoxylate, oleic alcohol ethoxylate, octylphenol ethoxylate, nonylphenol ethoxylate, preferably anionic emulsifiers such as one or more of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium tridecyl sulfate, sodium 2-ethylhexyl sulfate, sodium alkyl succinate sulfonate, more preferably one or more of sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, and sodium tridecyl sulfate. The emulsifier is preferably added in an amount of 0.1 to 2% by weight, more preferably 0.4 to 1.2% by weight, based on the total weight of the vinyl polymer microspheres.
The polyethylenically unsaturated crosslinking monomer described in step 2 is selected from one or more of allyl methacrylate, diallyl phthalate, 1,4-butanediol dimethacrylate, 1,2-ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, or divinylbenzene.
In the preparation method of the narrow-dispersion nano zinc oxide/vinyl polymer composite microsphere suspension of the step 2, the free radical initiator is selected from one or more of azo compound initiator, peroxide initiator and redox initiator, preferably azo compound initiator and peroxide initiator, such as one or more of azobisisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide, tert-butyl hydroperoxide, lauroyl peroxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate, more preferably one or more of azobisisobutyronitrile, lauroyl peroxide, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate and benzoyl peroxide. The free radical initiator is preferably added in an amount of 0.1 to 1.5% by weight, based on the total weight of the vinyl polymer microspheres.
In the preparation method of the narrow-dispersion nano zinc oxide/vinyl polymer composite microsphere suspension, the stirring swelling time in the step (c) is 10 to 600 minutes, preferably 30 to 300 minutes, and more preferably 60 to 120 minutes.
In a preferred embodiment, the solids weight ratio of the swelling monomers used (vinyl-containing polymerizable monomers, i.e. amide-containing hydrophilic monovinyl monomer + carboxyl-containing hydrophilic monovinyl monomer + nonionic monovinyl monomer + polyethylenically unsaturated monomer total) to the vinyl polymer emulsion (i.e. oligomer-containing vinyl polymer seed emulsion) is preferably from 10 to 3375, particularly preferably from 100.
The narrow-dispersion nano zinc oxide/vinyl polymer composite microsphere suspension prepared by the method is preferably prepared by one-step swelling, and D50 is preferably in the range of 2-25 microns, and more preferably the narrow-dispersion vinyl polymer microsphere suspension with different particle sizes, wherein D50 is equal to 3um, 5um and 10 um.
The vinyl polymers prepared by the process of the invention have a glass transition temperature of 80 ℃ or higher, preferably in the range of 100 to 150 ℃. The method for performing solid-liquid separation treatment on the narrow-dispersion nano zinc oxide/vinyl polymer composite microsphere suspension in the step 3 comprises but is not limited to sedimentation, filtration, membrane filtration, filter pressing and vacuum modes, and equipment used comprises but is not limited to a plate and frame filter press, a belt filter press, a centrifugal machine, a ceramic filter, a stacked spiral dehydrator and a drum filter. Because the vinyl polymer microspheres are narrowly distributed and the particles are easily arranged regularly, we have found that when the thickness of the filter cake layer is greater than 1 cm, water is difficult to permeate, and therefore the separation equipment is preferably a centrifuge that provides a high separation factor, more preferably a scraped-blade automatic discharge centrifuge. The separation factor is preferably equal to or greater than 700. The centrifugation time is preferably more than 30 minutes, more preferably more than 1 hour, the solid content is preferably more than or equal to 65%, the solid content is related to the centrifugation time, the solid content is higher as the centrifugation time is longer, but the centrifugation time is preferably 30-120 minutes because the particles are distributed narrowly and hydrophilic carboxyl groups in the particles can generate water cooperation with water, have a certain water locking function, and the filter cake can hardly reach a lower water content, and the water content of the filter cake is preferably in a range of 15-35%. When the water content is more than 40%, a filter cake cannot be formed, and a filter cake layer on a rotary drum of the centrifuge falls off after the centrifugation is finished, and the state is similar to a slurry state.
The centrifuge is preferably provided with a spraying system, a small amount of deionized water can be used for washing a filter cake, and hot water with the temperature of more than or equal to 80 ℃ is preferably used for washing the filter cake so as to remove substances such as an emulsifier, a hydrophilic stabilizer and the like to the maximum extent. Although the migration of the hydrophilic stabilizer, especially partially hydrolyzed vinyl acetate polymer having a large number of hydroxyl groups is poor, it may participate in film formation, so that the coating contains a large number of polar functional groups such as hydroxyl groups, which results in poor chemical resistance of the coating to alcohol, acid, and the like. The hydrophilic substances can be basically centrifuged along with the mother liquor by a centrifugal mode, and a filter cake contains a small amount of hydrophilic substances after being rinsed by a small amount of water. As is well known to those skilled in the art, the centrifuged mother liquor and the rinse water can be reused as reaction water.
The mixing equipment with the atomizing spray head in the step 4 can select a double-cone mixer, a single-cone double-helix mixer, a horizontal helical ribbon mixer, a horizontal coulter mixer, a gravity-free mixer and a continuous mixer. The material after centrifugation forms a large filter cake which needs to be crushed into powder or fine particles for convenient use by customers, and the water content of the filter cake after each centrifugation has certain deviation, particularly when the filter cake is thick, the water content of the outer layer of the filter cake is smaller than the solid content of the inner layer, preferably a horizontal colter mixer with an atomizing nozzle, and the water content can be adjusted in a spraying manner while mixing and crushing, so that the solid content of each batch is stabilized at a certain value, and the batch stability of the filter cake is improved. After spray adjustment, the water content is preferably in the range of 15% to 35%, more preferably 25. + -. 1 ℃.
In yet another aspect, the invention relates to the use of the above-mentioned narrow-dispersion nano zinc oxide/vinyl polymer composite microsphere wet powder in the preparation of coating or adhesive as an aid for regulating the gloss and transparency of paint film and improving hand feeling. In this aspect, the narrow-dispersion nano zinc oxide/vinyl polymer composite microsphere wet powder is preferably used as a delustering agent in coatings or adhesives used in woodware, synthetic leather coated products, paper and plastics. More preferably, it is used for woodware coated articles. The proper amount of the gloss reducing agent can be selected according to the needed gloss reducing agent, and when the gloss reducing agent is used for woodware coating products, the gloss reducing agent is usually added into 5-30% of the coating composition by weight.
The narrowly dispersed nano zinc oxide/vinyl polymer composite microsphere wet powder can be used as a flatting agent, so that the scratch resistance and chemical resistance of a paint film can be remarkably improved on the premise of not reducing the water resistance, wear resistance, adhesion resistance, stain resistance and the like of the paint film.
Interpretation of terms:
"copolymer" means a polymer polymerized from at least two different monomers.
"oligomer" means a polymer of controlled number and molecular structure consisting of multiple repeating units and having a weight average molecular weight of 200 to 10000. The oligomer copolymerized by the vinyl-containing polymerizable monomer is a polymer with the weight-average molecular weight of 200-10000, which is obtained by polymerizing the polymerizable vinyl monomer under the action of a molecular chain regulator.
The "mean particle diameter" is the value of d50 measured on a HELOS/SUCELL (from Newcastle GmbH, germany) wet laser particle sizer.
"molecular weight" or "Mw" refers to the weight average molecular weight of a polymer as determined by Gel Permeation Chromatography (GPC) against polyacrylic acid standards.
"swelling" refers to a process in which the polymerizable vinyl group-containing monomer continuously permeates into the oligomer-containing seed emulsion and the particle size thereof is continuously increased.
"wt%" means weight percent.
"60 ° gloss" refers to the gloss of the coating as measured using a MN268 gloss meter (from tsumadzu corporation) at a 60 ° viewing angle.
"glass transition temperature" refers to a glass transition temperature measured by a Differential Scanning Calorimetry (DSC) method, and is a value at which the inflection point on a differential analysis chart shows no glass transition.
The high-speed dispersion machine is a multifunctional experimental machine for JFS-2200/T of Shanghai Sejie chemical equipment Co.
Evaluation of the coating Properties:
boiling water scalding resistance: beech board, spraying, first and second pass
Figure BDA0002796916550000161
4400 (Vanhua chemical group Co., ltd.) varnish, 80g/m 2 The third pass is coated with matte finish paint of 80g/m 2 Drying at 35 deg.C for 1h, and curing at 23 deg.C for 7 days. The boiling water was poured into a 200ml glass beaker, and after pouring some boiling water over the beech board coated with the matte finish, a 200ml glass beaker with boiling water was placed directly on top. And after the glass beaker is cooled to room temperature by water and then is kept stand for 2 hours, the beaker is moved away to observe whether the water-white phenomenon exists or not, and the water-white recovery condition is observed after 16 hours. Reference can be made to the national standard GB/T4893.1 method for measuring the cold liquid resistance of furniture surfaces.
Chemical resistance: beech board, spraying, first and second pass
Figure BDA0002796916550000171
4400 (Vanhua chemical group Co., ltd.) varnish, 80g/m 2 The third pass is coated with matte finish paint of 80g/m 2 Drying at 35 deg.C for 1h, and curing at 23 deg.C for 7 days. Placing a plurality of layers of filter paper soaked with 50% ethanol, 3% acetic acid and 5% sodium bicarbonate on a beech board coated with the matte finish paint, covering the filter paper with a glass cup to prevent volatilization, and observing whether a trace is left after the filter paper is placed for 1 hour. Reference can be made to the national standard GB/T4893.1 "furniture surface cold liquid resistance determination method".
Stain resistance: refer to national standard GB/T4893.1 "furniture surface Cold tolerance determination method" for resisting contamination resistance of coffee, mustard oil, vinegar or green tea.
Anti-adhesion: 1. base material: MDF density board 2. Test method: spraying the prepared paint twice, spraying 1.5 g/twice on the density board, maintaining the first at 50 deg.C for 0.5 hr, maintaining the second at 50 deg.C for 6 hr, standing at room temperature overnight, overlapping two boards, and standing at 55 deg.C for 2t/m 2 The test is carried out after 5h, and reference can be made to GB/T23982-2009 determination method for blocking resistance of wood coatings.
Scratch resistance: 1. base material: bai Feng panel 2. Test method: two 80g/m spraying passes of the prepared varnish or colored paint 2 The scratch test can be carried out by a scratch tester at room temperature at night after the first time of baking at 50 ℃ for 30min and the second time of baking at 50 ℃ for 30min, and the national standard GB/T9279-2007 scratch test of colored paint and varnish can be referred to.
All temperature and pressure units are Standard Temperature and Pressure (STP) unless otherwise indicated. Optionally added means added or not added.
Detailed Description
The present invention will be further described in detail with reference to the following examples. The examples are not intended to limit the invention. Parts are by weight unless otherwise specified.
Example 1:
adding 5.5 parts of DES-30 (disodium ethoxyethanol sulfosuccinate monoester, solvay) and 220 parts of deionized water into a pre-emulsification kettle, stirring and dissolving, adding 96 parts of styrene, 410 parts of isooctyl acrylate, 3 parts of 1,6-hexanediol diacrylate, 4 parts of butyl acrylate, 0.3 part of acrylic acid and 90 parts of n-dodecyl mercaptan, and stirring to obtain a stable pre-emulsion; (2) Adding 1.35 parts of SDS (sodium dodecyl sulfate), 17 parts of methyl methacrylate, 1 part of acrylic acid and 980 parts of deionized water into a reaction kettle, starting stirring and heating, heating to 85 ℃, adding a solution formed by 0.03 part of APS (ammonium persulfate) and 1 part of deionized water, and continuing to react for 15min after blue light appears to prepare a seed emulsion; (4) And after the preparation of the seed emulsion is finished, dropwise adding a solution formed by the prepared pre-emulsion, 1.2 parts of APS and 12 parts of deionized water into the reaction kettle for 4 hours, preserving heat for 1 hour after dropwise adding is finished, then cooling to 45 ℃, adding 0.15 part of ammonia water, and filtering to obtain the oligomer-containing vinyl polymer emulsion with the average particle size of about 0.45 um. The solid content was 33wt%. The proportion of oligomer to the solids content of the vinyl polymer emulsion is about 13%. The oligomer has a weight average molecular weight of about 3200 to 5700.
Example 2:
adding 5.5 parts of emulsifier CM-30 (ethoxylated alkyl sodium sulfate, solvay) and 220 parts of deionized water into a pre-emulsification kettle, stirring and dissolving, adding 96 parts of methyl methacrylate, 414 parts of butyl acrylate, 0.3 part of acrylic acid, 1.2 parts of diallyl phthalate and 100 parts of n-dodecyl mercaptan, and stirring to obtain stable pre-emulsion; (2) Adding 1.35 parts of SDS, 25 parts of butyl acrylate, 1 part of acrylic acid and 980 parts of deionized water into a reaction kettle, starting stirring and heating, heating to 85 ℃, adding a solution formed by 0.03 part of APS and 1 part of deionized water, and continuing to react for 15min after blue light appears to prepare a seed emulsion; (4) After the preparation of the seed emulsion is finished, dropwise adding a solution formed by the preparation number pre-emulsion and 1.2 parts of APS and 11 parts of deionized water into the reaction kettle for 4 hours, after the dropwise adding is finished, keeping the temperature for 1 hour, then cooling to 45 ℃, adding 0.18 part of ammonia water, and then filtering to obtain the oligomer-containing vinyl polymer emulsion with the average particle size of about 0.65 mu m, wherein the solid content is 34wt%. The proportion of oligomer to the solids content of the vinyl polymer emulsion is about 16%. The oligomer has a weight average molecular weight of about 1500 to 3600.
Example 3:
adding 5.5 parts of SDBS (sodium dodecyl benzene sulfonate) and 220 parts of deionized water into a pre-emulsification kettle, stirring and dissolving, adding 96 parts of styrene, 410 parts of butyl acrylate, 4 parts of isooctyl acrylate, 0.3 part of acrylic acid, 3 parts of divinylbenzene and 80 parts of n-dodecyl mercaptan, and stirring to obtain a stable pre-emulsion; (2) Adding 1.35 parts of SDBS, 30 parts of methyl methacrylate, 1.5 parts of acrylic acid and 980 parts of deionized water into a reaction kettle, starting stirring and heating, heating to 85 ℃, adding a solution formed by 0.03 part of APS and 1 part of deionized water, and continuing to react for 15min after blue light appears to prepare a seed emulsion; (4) And after the preparation of the seed emulsion is finished, dropwise adding a solution formed by the prepared pre-emulsion, 1.2 parts of APS and 12 parts of deionized water into the reaction kettle for 4 hours, preserving heat for 1 hour after dropwise adding is finished, then cooling to 45 ℃, adding 0.2 part of ammonia water, and filtering to obtain the oligomer-containing vinyl polymer emulsion with the average particle size of about 0.78 um. The solid content was 33wt%. The proportion of oligomer to the solids content of the vinyl polymer emulsion is about 14%. The oligomer has a weight average molecular weight of about 2200 to 4300.
Comparative example 1:
adding 5.5 parts of CM-30 and 220 parts of deionized water into a pre-emulsification kettle, stirring and dissolving, adding 146 parts of methyl methacrylate, 464 parts of butyl acrylate and 0.3 part of acrylic acid, and stirring to obtain a stable pre-emulsion; (2) Adding 1.35 parts of SDS, 25 parts of butyl acrylate, 1 part of acrylic acid and 980 parts of deionized water into a reaction kettle, starting stirring and heating, heating to 85 ℃, adding a solution formed by 0.03 part of APS and 1 part of deionized water, and continuing to react for 15min after blue light appears to prepare a seed emulsion; (4) And after the preparation of the seed emulsion is finished, dropwise adding a solution formed by the prepared pre-emulsion, 1.2 parts of APS and 12 parts of deionized water into the reaction kettle for 4 hours, preserving heat for 1 hour after dropwise adding is finished, then cooling to 45 ℃, adding 0.18 part of ammonia water, and filtering to obtain the vinyl polymer emulsion which has the average particle size of about 0.63um and does not contain the oligomer.
Example 4:
adding 18 parts by weight of methyl methacrylate, 0.5 part by weight of methacrylamide ethyl ethylene urea, 1 part by weight of methacrylic acid, 1 part by weight of 1,6-hexanediol diacrylate and 0.2 part by weight of lauroyl peroxide into a monomer batching kettle, completely dissolving the lauroyl peroxide into the monomers by ultrasonic or magnetic stirring, then pouring the monomer mixture into a dispersing kettle containing 0.1 part by weight of sodium dodecyl benzene sulfonate and 60 parts by weight of water, controlling the temperature to be about 30 ℃, and dispersing for 15 minutes at the rotating speed of 1000rpm by a high-speed dispersing machine. The dispersed monomer emulsion was poured into a polymerization vessel containing 0.1 part by weight of the oligomer-containing vinyl polymer emulsion of example 2, a stirrer, a condenser and a nitrogen blanket, and the emulsion was allowed to swell for 1 hour at 25 ℃ and 180rpm stirring speed, while 0.5 part of nano zinc oxide was added to 10 parts of deionized water and dispersed for 30 minutes at 2500rpm using a high speed disperser, and 0.1 part of PVA was dissolved in 10 parts of deionized water at 85 ℃. After the monomer is completely absorbed by the vinyl polymer emulsion containing oligomer, adding the prepared nano zinc oxide dispersion and PVA aqueous solution into a polymerization kettle, heating to 80 ℃ to initiate polymerization, polymerizing for 2 hours at the temperature, curing for 1 hour at 93 ℃, and finally cooling to room temperature to obtain suspension containing the nano zinc oxide/polymethyl methacrylate composite microspheres, wherein the D50 particle size is 5.1 microns. The suspension was poured into a baghouse centrifuge and centrifuged at 3000rpm for 30min. Then, the filter cake is rinsed by hot water with the mass of 85 ℃ which is half of that of the suspension, the rinsing is carried out for 1-2min, and the centrifugation is continued for 30min after the rinsing is finished. And finally, filling the centrifuged filter cake into a coulter type mixer, mixing and crushing for 10min, adjusting the water content to 25 +/-1 ℃, and packaging.
Comparative example 2:
adding 18 parts by weight of methyl methacrylate, 0.5 part by weight of methacrylamide ethyl ethylene urea, 1 part by weight of methacrylic acid, 1 part by weight of 1,6-hexanediol diacrylate and 0.2 part by weight of lauroyl peroxide into a monomer compounding kettle, completely dissolving the lauroyl peroxide into the monomers by ultrasonic or magnetic stirring, subsequently pouring the monomer mixture into a dispersion kettle containing 0.1 part by weight of sodium dodecyl benzene sulfonate and 60 parts by weight of water, and dispersing for 15 minutes at the rotating speed of 1000rpm by a high-speed dispersion machine at the temperature of about 30 ℃. The dispersed monomer emulsion was poured into a polymerization vessel containing 0.5 part by weight of the oligomer-free alkenyl polymer emulsion of comparative example 1, a stirrer, a condenser and a nitrogen blanket, and the emulsion was allowed to swell at 25 ℃ and 180rpm stirring speed for 1 hour, 0.5 part of nano zinc oxide was added to 10 parts of deionized water and dispersed at 3500rpm for 30 minutes using a high speed dispersing machine, and 0.1 part of PVA was dissolved in 10 parts of deionized water at 85 ℃. Adding the prepared nano zinc oxide dispersion liquid and PVA aqueous solution into a polymerization kettle, heating to 80 ℃ to initiate polymerization, polymerizing for 2 hours at the temperature, curing for 1 hour at 93 ℃, finally cooling to room temperature, and filtering to obtain the polydisperse nano zinc oxide/polymethyl methacrylate composite microsphere suspension, wherein the particle size is in the range of dozens to hundreds of micrometers, and more coagula are formed. The suspension was poured into a baghouse centrifuge and centrifuged at 3000rpm for 30min. Then leaching the filter cake with 85 ℃ hot water of half the mass of the suspension for 1-2min, and continuing to centrifuge for 30min after leaching. And finally, filling the centrifuged filter cake into a coulter type mixer, mixing and crushing for 10min, adjusting the water content to 25 +/-1 ℃, and packaging.
Comparative example 3:
adding 18 parts by weight of methyl methacrylate, 0.5 part by weight of methacrylamide ethyl ethylene urea, 1 part by weight of methacrylic acid, 1 part by weight of 1,6-hexanediol diacrylate and 0.2 part by weight of lauroyl peroxide into a monomer compounding kettle, completely dissolving the lauroyl peroxide into the monomers by ultrasonic or magnetic stirring, subsequently pouring the monomer mixture into a dispersing kettle containing 0.1 part by weight of sodium dodecyl benzene sulfonate and 60 parts by weight of water, controlling the temperature at about 30 ℃, and dispersing for 15 minutes at the rotating speed of 1000rpm by a high-speed dispersing machine. The dispersed monomer emulsion is poured into a polymerization kettle which is provided with a stirrer and a condenser and is protected by nitrogen, the mixture is stirred for 1 hour at the temperature of 25 ℃ and the stirring speed of 180rpm, 0.5 part of nano zinc oxide is added into 10 parts of deionized water, the mixture is dispersed for 30 minutes at the rotating speed of 2500rpm by a high-speed dispersion machine, and 0.1 part of PVA is dissolved in 10 parts of deionized water at the temperature of 85 ℃. Adding the prepared nano zinc oxide dispersion liquid and PVA aqueous solution into a polymerization kettle, heating to 80 ℃ to initiate polymerization, polymerizing for 2 hours at the temperature, curing for 1 hour at 93 ℃, finally cooling to room temperature, and filtering to obtain the polydisperse nano zinc oxide/polymethyl methacrylate composite microsphere suspension, wherein the particle size is in the range of dozens to hundreds of micrometers, and a large amount of coagula is formed. The suspension was poured into a baghouse centrifuge and centrifuged at 3000rpm for 30min. Then, the filter cake is rinsed by hot water with the mass of 85 ℃ which is half of that of the suspension, the rinsing is carried out for 1-2min, and the centrifugation is continued for 30min after the rinsing is finished. And finally, filling the centrifuged filter cake into a coulter type mixer, mixing and crushing for 10min, adjusting the water content to 25 +/-1 ℃, and packaging.
Comparative example 4:
according to the method of patent CN107531974a, example 7, the starting material composition is 44.66 parts of partially hydrolyzed vinyl acetate polymer PVOH (HD =88%/Mw =160 KDa), 253.44 parts of methyl methacrylate, 1.9 parts of lauroyl, 700 parts of deionized water by suspension polymerization to prepare a polymethyl methacrylate dispersion with a D50 particle size of about 3.9 microns, and 500 grams are stored in a thermostat at 65 ℃.
Comparative example 5:
the polymethyl methacrylate dispersion prepared in ratio 4 was poured into a baghouse centrifuge and centrifuged at 3000rpm for 30min. Only a small amount of filter cake was formed and a large amount of particles were not separated.
Comparative example 6:
the polymethyl methacrylate dispersion prepared in comparative example 4 was poured into a baghouse centrifuge and centrifuged at 12000rpm for 120min. Then leaching the filter cake with 85 ℃ hot water of half the mass of the suspension for 1-2min, and continuing to centrifuge for 60min after leaching. . And finally, filling the centrifuged filter cake into a coulter type mixer, mixing and crushing for 10min, adjusting the water content to 25 +/-1 ℃, and packaging.
Example 5:
to a monomer compounding kettle, 73 parts by weight of styrene, 3 parts by weight of diacetone acrylamide, 3 parts by weight of acrylic acid, 1 part by weight of divinylbenzene, and 0.8 part by weight of azobisisoheptonitrile were added, and the azobisisoheptonitrile was completely dissolved in the monomers by ultrasonic or magnetic stirring, and then the monomer mixture was poured into a dispersion tank containing 0.9 part by weight of sodium dodecyl sulfate and 95 parts by weight of water, and dispersed for 20 minutes at 1500rpm using a high-speed disperser. The dispersed monomer emulsion was poured into a polymerization vessel containing 1.3 parts by weight of the oligomer-containing vinyl polymer emulsion of example 1, a stirrer, a condenser and a nitrogen blanket, and the emulsion was allowed to swell for 5 hours at 25 ℃ and 180rpm stirring speed, 6 parts of nano zinc oxide was added to 200 parts of deionized water and dispersed for 30 minutes at 3500rpm using a high speed dispersing machine, and 0.5 part of PVA was dissolved in 200 parts of deionized water at 85 ℃. Adding the prepared nano zinc oxide dispersion liquid and PVA aqueous solution into a polymerization kettle, heating to 80 ℃ to initiate polymerization after the monomers are completely absorbed by the alkenyl polymer emulsion containing oligomer, polymerizing for 2 hours at the temperature, curing for 1 hour at 93 ℃, and finally cooling to room temperature to obtain suspension containing the nano zinc oxide/polystyrene composite microspheres, wherein the D50 particle size is 3.0 micrometers. The suspension was poured into a baghouse centrifuge and centrifuged at 3000rpm for 30min. Then leaching the filter cake with 85 ℃ hot water of half the mass of the suspension for 1-2min, and continuing to centrifuge for 30min after leaching. And finally, filling the centrifuged filter cake into a coulter type mixer, mixing and crushing for 10min, adjusting the water content to 25 +/-1 ℃, and packaging.
Example 6:
adding 4 parts by weight of n-butyl acrylate, 1 part by weight of methacrylamide ethyl ethylene urea, 1 part by weight of methacrylic acid, 32 parts by weight of methyl methacrylate, 2 parts by weight of allyl methacrylate and 0.4 part by weight of azobisisobutyronitrile into a monomer batching kettle, completely dissolving the azobisisobutyronitrile into the monomers by ultrasonic or magnetic stirring, subsequently pouring the monomer mixture into a dispersion tank containing 0.4 part by weight of sodium dodecyl sulfate and 80 parts by weight of water, and dispersing for 15 minutes at 2000rpm by a high-speed dispersion machine, wherein the temperature is controlled at about 30 ℃. The dispersed monomer emulsion was poured into a polymerization vessel containing 0.1 part by weight of the oligomer-containing alkenyl polymer emulsion of example 3, a stirrer, a condenser and a nitrogen blanket, and the emulsion was allowed to swell for 2 hours at 25 ℃ and 180rpm stirring speed, 0.6 part of nano zinc oxide was added to 100 parts of deionized water and dispersed for 30 minutes at 3500rpm using a high speed dispersing machine, and 0.25 part of PVA was dissolved in 100 parts of deionized water at 85 ℃. Adding the prepared nano zinc oxide dispersion liquid and PVA aqueous solution into a polymerization kettle, heating to 80 ℃ to initiate polymerization after the monomers are completely absorbed by the alkenyl polymer emulsion containing oligomer, polymerizing for 2 hours at the temperature, curing for 1 hour at 93 ℃, and finally cooling to room temperature to obtain suspension containing the nano zinc oxide/vinyl polymer composite microspheres, wherein the D50 particle size is 12.3 microns. The suspension was poured into a baghouse centrifuge and centrifuged at 3000rpm for 30min. Then leaching the filter cake with 85 ℃ hot water of half the mass of the suspension for 1-2min, and continuing to centrifuge for 30min after leaching. And finally, filling the centrifuged filter cake into a coulter type mixer, mixing and crushing for 10min, adjusting the water content to 25 +/-1 ℃, and packaging.
Comparative example 7:
76 parts by weight of styrene, 3 parts by weight of methacrylamidoethylethyleneurea, 1 part by weight of divinylbenzene, and 0.8 part by weight of azobisisoheptonitrile were charged into a monomer compounding tank, and the azobisisoheptonitrile was completely dissolved in the monomers by ultrasonic or magnetic stirring, and then the monomer mixture was poured into a dispersion tank containing 0.9 part by weight of sodium lauryl sulfate and 95 parts by weight of water, and dispersed for 20 minutes at 1500rpm by a high-speed disperser. The dispersed monomer emulsion was poured into a polymerization vessel containing 1.3 parts by weight of the oligomer-containing vinyl polymer emulsion of example 2, a stirrer and a condenser and protected with nitrogen, the emulsion was allowed to swell for 5 hours at 25 ℃ and 180rpm stirring speed, 6 parts of nano zinc oxide was added to 200 parts of deionized water and dispersed for 30 minutes at 3500rpm using a high speed dispersing machine, and 0.5 part of PVA was dissolved in 200 parts of deionized water at 85 ℃. Adding the prepared nano zinc oxide dispersion liquid and PVA aqueous solution into a polymerization kettle, heating to 80 ℃ to initiate polymerization after the monomers are completely absorbed by the alkenyl polymer emulsion containing oligomer, polymerizing for 2 hours at the temperature, curing for 1 hour at 93 ℃, and finally cooling to room temperature to obtain suspension containing the nano zinc oxide/polystyrene composite microspheres, wherein the D50 particle size is 3.0 micrometers. The suspension was poured into a baghouse centrifuge and centrifuged at 3000rpm for 30min. Then leaching the filter cake with 85 ℃ hot water of half the mass of the suspension for 1-2min, and continuing to centrifuge for 30min after leaching. And finally, filling the centrifuged filter cake into a coulter type mixer, mixing and crushing for 10min, adjusting the water content to 25 +/-1 ℃, and packaging. Because the polymer microsphere prepared in the comparative example 7 has no carboxyl functional group on the surface, the polymer microsphere can not effectively form crosslinking with the nano zinc oxide after being added into a formula to form a film, and the scratch resistance and the chemical resistance are low.
Comparative example 8:
76 parts by weight of styrene, 3 parts by weight of methacrylic acid, 1 part by weight of divinylbenzene, and 0.8 part by weight of azobisisoheptonitrile were charged into a monomer compounding tank, and azobisisoheptonitrile was completely dissolved in the above monomers by ultrasonic or magnetic stirring, and then the monomer mixture was poured into a dispersion tank containing 0.9 part by weight of sodium lauryl sulfate and 95 parts by weight of water, and dispersed for 20 minutes at 1500rpm using a high-speed disperser. The dispersed monomer emulsion was poured into a polymerization vessel containing 1.3 parts by weight of the oligomer-containing vinyl polymer emulsion of example 2, a stirrer, a condenser and a nitrogen blanket, and the emulsion was allowed to swell for 5 hours at 25 ℃ and 180rpm stirring speed, 6 parts of nano zinc oxide was added to 200 parts of deionized water and dispersed for 30 minutes at 3500rpm using a high speed dispersing machine, and 0.5 part of PVA was dissolved in 200 parts of deionized water at 85 ℃. Adding the prepared nano zinc oxide dispersion liquid and PVA aqueous solution into a polymerization kettle, heating to 80 ℃ to initiate polymerization after monomers are completely absorbed by alkenyl polymer emulsion containing oligomer, polymerizing for 2 hours at the temperature, curing for 1 hour at 93 ℃, and finally cooling to room temperature, wherein a large amount of agglomeration is generated in the suspension, a pipeline is blocked, and discharging is difficult. Because the surface of the polymer microsphere has no amino functional group and cannot form coordination with the nano zinc oxide, the nano zinc oxide is only adsorbed to the surface of the microsphere in a pure physical way, the adsorption quantity is small, the space interval stabilizing effect is not enough under the same condition, and the polymer microsphere is unstable in the preparation process, is agglomerated into slag and is easy to block a pipeline.
Example 7:
the formula of the matte finish paint for the water-based wood paint comprises the following components:
lacper 4500 (Vanhua Chemicals group Ltd.) 67% by weight
Anti-settling agent, laponite RD (Rockwood additives USA) 0.2 wt%
Base wetting agent Tego 245 (Yingchuang Industrial group-di Gao Chuji) 0.2% by weight
Leveling agent BYK 348 (Bi Kehua science, ltd.) 0.4% by weight
film-Forming aid DOWDPM + DPNB (Dow chemical Co.) 9% by weight
Antifoam BYK 024 (Bi Kehua, inc.) 0.2% by weight
Matting agent hybrid Polymer particles (each of examples 4-5 and comparative examples 2-4,6-7 added at the same solids mass) 15% by weight
Thickener Vesmody U902 (Van chemical group Co., ltd.) 1% by weight
7% by weight of pure water
Preparing the coating for the water-based wood paint: and (3) uniformly mixing the raw materials in the formula under stirring by a dispersion machine at room temperature to obtain the coating for the water-based wood lacquer. The prepared coating was coated on a panel and then subjected to performance evaluation as shown in table 1 below:
table 1: basic properties of the coating
Figure BDA0002796916550000271
The above data (excluding gloss) is best at 5 and worst at 1. Transparency a Test method the transparency of the same dark panel (such as black walnut) is compared by applying the same thickness of paint film. Degree of smoothness b The test method comprises the following steps: find 5 different people to rub the paint surface with the back of the hand, feel the smoothness and score it.
The comparison shows that the invention can provide excellent performances of scratch resistance, chemical resistance and the like of the paint film on the premise of not reducing the performances of boiling water and scalding resistance, transparency, adhesion resistance, stain resistance and the like of the paint film.

Claims (14)

1. A nano zinc oxide/vinyl polymer composite microsphere, comprising:
based on the total dry weight of the composite microsphere, 90-99.5 wt% of crosslinked or non-crosslinked vinyl polymer microsphere with Tg in the range of 80-150 ℃ and 0.5-10 wt% of nano zinc oxide, wherein the nano zinc oxide is loaded on the surface of the vinyl polymer microsphere; the polymeric microspheres are formed by polymerizing monomers comprising from 1 to 5 weight percent of a hydrophilic monovinyl monomer containing an amide group, from 1 to 5 weight percent of a hydrophilic monovinyl monomer containing a carboxyl group, from 85 to 98 weight percent of a nonionic monovinyl monomer, and from 0 to 5 weight percent of at least one polyethylenically unsaturated monomer selected from allyl methacrylate, diallyl phthalate, 1,4-butanediol dimethacrylate, 1,2-ethylene glycol dimethacrylate, 1,6-hexanediol diacrylate, or divinylbenzene, based on the total weight of the vinyl polymeric microspheres;
the preparation method of the nano zinc oxide/vinyl polymer composite microsphere comprises the following steps:
(1) Preparing a vinyl polymer seed emulsion containing an oligomer by free radical emulsion polymerization;
(2) (a) uniformly mixing an oil-soluble radical initiator, 1-5 wt% of hydrophilic monovinyl monomer containing an amido group, 1-5 wt% of hydrophilic monovinyl monomer containing a carboxyl group, 85-98 wt% of nonionic monovinyl monomer and 0-5 wt% of multi-ethylenically unsaturated monomer; (b) Adding the mixed solution of the step (a) into water dissolved with an emulsifier for high-speed dispersion and emulsification to prepare pre-emulsion; (c) Adding the vinyl polymer seed emulsion containing the oligomer in the step (1), stirring and swelling to obtain a swollen suspension; (d) Dispersing nano zinc oxide into water to obtain a dispersion liquid containing the nano zinc oxide, and dissolving a protective adhesive into the water to obtain an aqueous solution in which the protective adhesive is dissolved; (e) Adding a dispersion liquid containing nano zinc oxide and an aqueous solution dissolved with protective glue into the swelled suspension liquid; (f) Finally, heating to initiate free radical polymerization to prepare nano zinc oxide/vinyl polymer microsphere suspension;
(3) Carrying out solid-liquid separation treatment on the nano zinc oxide/vinyl polymer microsphere suspension liquid in the step (2) to obtain a filter cake with the water content of less than or equal to 35 wt%;
(4) And (4) transferring the filter cake obtained in the step (3) to mixing equipment with an atomizing nozzle, crushing the filter cake into powder, and adjusting the water content to be within the range of 15-35% to obtain the wet powder of the composite microspheres.
2. The nano zinc oxide/vinyl polymer composite microspheres of claim 1, wherein the amide group-containing hydrophilic monovinyl monomer is selected from one or more of acrylamide, methacrylamide, N-methylolacrylamide, N-dimethylacrylamide, diacetone acrylamide, and methacrylamide ethylethylene urea.
3. The nano zinc oxide/vinyl polymer composite microsphere according to claim 2, wherein the hydrophilic monovinyl monomer containing amide group is methacrylamide ethyl ethylene urea.
4. The nano zinc oxide/vinyl polymer composite microsphere according to any one of claims 1 to 3, wherein the hydrophilic monovinyl monomer containing carboxyl is selected from one or more of methacrylic acid, acrylic acid, acryloxypropionic acid, methacryloxypropionic acid, itaconic acid, maleic acid or anhydride, fumaric acid, crotonic acid, monomethyl maleate, monomethyl fumarate, and monomethyl itaconate.
5. The nano zinc oxide/vinyl polymer composite microsphere according to claim 4, wherein the hydrophilic monovinyl monomer containing carboxyl is selected from one or more of methacrylic acid and acrylic acid.
6. The nano zinc oxide/vinyl polymer composite microspheres of any one of claims 1 to 3, wherein the non-ionic mono vinyl monomer is selected from one or more of styrene, a-methyl styrene, vinyl toluene, vinyl acetate, acrylonitrile, methacrylonitrile, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, lauryl (meth) acrylate, palmityl (meth) acrylate, and stearyl (meth) acrylate.
7. The nano zinc oxide/vinyl polymer composite microspheres of any one of claims 1 to 3, wherein the nano zinc oxide particle size is in the range of 1-200 nm.
8. The nano zinc oxide/vinyl polymer composite microsphere according to claim 7, wherein the nano zinc oxide particle size is in the range of 50-100 nm.
9. The nano zinc oxide/vinyl polymer composite microsphere according to any one of claims 1 to 3, wherein the volume particle average diameter D50 of the composite microsphere is in the range of 1-25 um.
10. The nano zinc oxide/vinyl polymer composite microsphere according to claim 9, wherein the composite microsphere is a narrow-dispersion composite microsphere with different particle diameters, the volume particle average diameter D50 of which is equal to 3um, 5um and 10 um.
11. Use of the nano zinc oxide/vinyl polymer composite microspheres according to any one of claims 1 to 10 as an aid for adjusting the gloss, the transparency and the improved hand of a paint film in the preparation of a coating or an adhesive.
12. Use of the nano zinc oxide/vinyl polymer composite microspheres according to any one of claims 1 to 10 as matting agent in the preparation of coatings or adhesives.
13. A suspension obtained by open-dispersing the nano zinc oxide/vinyl polymer composite microspheres according to any one of claims 1 to 10 by ethanol, glycerol, propylene glycol methyl ether acetate, ethylene glycol butyl ether, diethylene glycol butyl ether, dipropylene glycol methyl ether.
14. A solid particle composition obtained by spray and/or microwave drying the nano zinc oxide/vinyl polymer composite microspheres according to any one of claims 1 to 10.
CN202011341959.3A 2020-11-25 2020-11-25 Nano zinc oxide/vinyl polymer composite microsphere and preparation method and application thereof Active CN112608415B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011341959.3A CN112608415B (en) 2020-11-25 2020-11-25 Nano zinc oxide/vinyl polymer composite microsphere and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011341959.3A CN112608415B (en) 2020-11-25 2020-11-25 Nano zinc oxide/vinyl polymer composite microsphere and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN112608415A CN112608415A (en) 2021-04-06
CN112608415B true CN112608415B (en) 2022-11-08

Family

ID=75225251

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011341959.3A Active CN112608415B (en) 2020-11-25 2020-11-25 Nano zinc oxide/vinyl polymer composite microsphere and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN112608415B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116622172B (en) * 2023-06-07 2024-03-12 海安浩驰科技有限公司 Corrosion-resistant ultraviolet-resistant film and preparation method and application thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317328C (en) * 2000-09-21 2007-05-23 罗姆和哈斯公司 Aqueous nanocomposite dispersions: processes, compositions, and uses thereof
US7829626B2 (en) * 2006-03-15 2010-11-09 Rohm And Haas Company Aqueous compositions comprising polymeric duller particle
CN101885905B (en) * 2009-05-12 2013-08-21 无锡纳奥新材料科技有限公司 Polymer/ inorganic nano particle composite nano-particle and preparation method thereof and uses
ES2768232T3 (en) * 2012-07-06 2020-06-22 Akzo Nobel Coatings Int Bv Method for producing a dispersion of nanocomposites comprising particles of inorganic nanoparticle compounds and organic polymers
US10174190B2 (en) * 2014-04-25 2019-01-08 Sekisui Plastics Co., Ltd. Composite particles, method for producing composite particles, and use thereof
CN109401511A (en) * 2018-10-29 2019-03-01 成都新柯力化工科技有限公司 A kind of self-cleaning external wall of building water paint and preparation method
CN110387008B (en) * 2019-07-17 2022-07-15 广州市侗富贵化工原材料有限公司 Preparation method of silicon dioxide coated PMMA microsphere flatting agent

Also Published As

Publication number Publication date
CN112608415A (en) 2021-04-06

Similar Documents

Publication Publication Date Title
CA2377306C (en) Bimodal poly(meth)acrylate plastisols and process for producing same
US4970241A (en) Multi-stage opacifying polymer particles containing non-polymeric acid absorbed therein
CA2605009C (en) Process for the production of aqueous binder latices
TWI487754B (en) Aqueous coating composition and coating formed therefrom having a particular gloss profile
CN109476789B (en) Aqueous dispersion and use thereof
JPH01213371A (en) Aqueous coating composition having sweeping mechanism of anionic seed
CA3032277A1 (en) Ambient self-crosslinkable latex
CN112608415B (en) Nano zinc oxide/vinyl polymer composite microsphere and preparation method and application thereof
US9453133B2 (en) Additives for improved hiding and paint compositions containing same
NO314310B1 (en) plastisol
JPH0692566B2 (en) Dispersion type paint resin composition
JPS60223873A (en) Water based paint composition
WO2020130994A2 (en) Polymodal and alkali soluble resin supported emulsion polymers
JP6874154B2 (en) Vinyl chloride resin latex composition and its manufacturing method
CN107531974B (en) Aqueous dispersion and use thereof
JPS6166710A (en) Production of non-film-forming vinyl resin emulsion and method of powdering same
EP3215577B1 (en) Additives for improved hiding and paint compositions containing same
US10954370B2 (en) Emulsion and preparing method therefor
US5492944A (en) Pure-aliphatic compound-soluble powdery bonding agent for paints
JPH02140271A (en) Hollow polymer pigment and coating composition using the pigment
CN116410394A (en) Water-based poly (methyl) acrylic acid self-extinction resin and finish-free self-extinction multicolor paint
JP5570132B2 (en) Cationic colored sealer composition
JP2008208181A (en) Fine polymer particles for structural viscosity-imparting agent
JP4398080B2 (en) Paint composition
JPS6281461A (en) Non-dispersion type resin composition

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant