CN110387008B - Preparation method of silicon dioxide coated PMMA microsphere flatting agent - Google Patents
Preparation method of silicon dioxide coated PMMA microsphere flatting agent Download PDFInfo
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- CN110387008B CN110387008B CN201910648395.9A CN201910648395A CN110387008B CN 110387008 B CN110387008 B CN 110387008B CN 201910648395 A CN201910648395 A CN 201910648395A CN 110387008 B CN110387008 B CN 110387008B
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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
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
- 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
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- 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
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- 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 discloses a preparation method of a silicon dioxide coated PMMA microsphere flatting agent. The silicon dioxide coated PMMA microsphere flatting agent provided by the invention is prepared from methyl methacrylate, a cross-linking agent, silica sol and the like through a suspension polymerization method, the PMMA microsphere is internally provided with a high cross-linking structure, the PMMA microsphere is externally coated with a layer of nano silicon dioxide particles, the average particle size of the microsphere is 0.1-12 mu m, the high cross-linking structure ensures that the microsphere is good in rigidity and difficult to deform, the outer layer of silicon dioxide particles endows the microsphere with good heat resistance and wear resistance, the scanning electron microscope picture can observe that the surface of the microsphere is rough because of being coated with a layer of silicon dioxide particles, the silicon dioxide coated PMMA microsphere is good in sphericity, good in handfeel when being used as a flatting agent and low in coating glossiness.
Description
Technical Field
The invention relates to the technical field of high-molecular functional materials, in particular to a preparation method of a silicon dioxide coated PMMA (polymethyl methacrylate) microsphere matting agent.
Background
Silica is generally used as a flatting agent in the fields of coatings and ink flatting, and at present, the silica powder is generally crushed and ground by a physical method in industrial production, and the prepared powder is non-spherical particles. The non-spherical structure causes poor extinction effect and touch feeling of the coating, and the coating cannot be applied to products with higher requirements. The invention patent with publication number CN107922203A discloses a method for preparing spherical silica aerogel particles, but the process is complicated, and a large amount of organic solvent is consumed, which is high in cost. The invention with the publication number of CN101054427B discloses a preparation method of micron-sized PMMA microspheres, but the PMMA microspheres have poor wear resistance and cannot be applied to products with higher requirements on wear resistance.
In order to overcome the respective defects of the silicon dioxide and the PMMA microspheres, the advantages of the silicon dioxide and the PMMA microspheres are combined: the PMMA microspheres have good sphericity and good wear resistance of silicon dioxide, and the silicon dioxide coated PMMA microspheres are prepared by using a suspension polymerization method, and the microspheres with the structure of PMMA coated by the silicon dioxide are not reported.
Disclosure of Invention
The invention aims to provide a preparation method of a silica-coated PMMA (polymethyl methacrylate) microsphere matting agent, so as to solve the technical problems.
In order to realize the purpose, the technical scheme of the invention is as follows:
a preparation method of a silica-coated PMMA microsphere matting agent comprises the following steps:
(1) mixing methyl methacrylate, a cross-linking agent, an initiator, an emulsifier, silica sol and water, and homogenizing at room temperature for 5-10 min to prepare a monomer pre-emulsion;
(2) and (2) heating the monomer pre-emulsion obtained in the step (1) to 60-80 ℃ under the protection of nitrogen, stirring at a constant temperature for 4-5 hours, filtering, drying and crushing to obtain the silica-coated PMMA microsphere matting agent.
Preferably, the cross-linking agent is selected from one or more of allyl acrylate, allyl methacrylate and trimethylolpropane triacrylate.
Preferably, the amount of the cross-linking agent is 1-30% of the total weight of the methyl methacrylate and the cross-linking agent.
Preferably, the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, lauroyl peroxide and benzoyl peroxide.
Preferably, the amount of the initiator is 0.2-1% of the total weight of the monomer pre-emulsion.
Preferably, the emulsifier is selected from one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
Preferably, the amount of the emulsifier is 0.1-1% of the total weight of the methyl methacrylate and the cross-linking agent.
Preferably, the solid content of the silica sol is 10-30%.
Preferably, the average particle size of the silicon dioxide in the silica sol is 1-10 nm.
Preferably, the amount of the silica sol is 1-15% of the total weight of the methyl methacrylate and the cross-linking agent.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method for preparing the silica-coated PMMA microspheres by the suspension polymerization method through one-step synthesis has the advantages of simple process and low cost; the existing conventional emulsion polymerization method is suitable for synthesizing microspheres with the particle size of less than 500nm, and although the dispersion polymerization method, the precipitation polymerization method and the like can synthesize large-particle-size micron-sized spherical products, a large amount of organic solvents are consumed, the cost is high, and the yield is small. The invention uses the suspension polymerization method, utilizes the homogeneous emulsifier to directly disperse the monomers, oil solubility and initiator into micron-sized suspension liquid drops under the action of the emulsifier, then initiates polymerization at high temperature, directly forms micron-sized spherical particles in the liquid drops, and forms the silica-coated PMMA microspheres by adsorbing silica sol on the surfaces of the microspheres, thus being suitable for industrial production;
(2) the average particle size of the silicon dioxide coated PMMA microsphere flatting agent provided by the invention is 0.1-12 mu m, the high cross-linking structure ensures that the microsphere has good rigidity and is not easy to deform, the outer layer silicon dioxide particles endow the microsphere with good heat resistance and wear resistance, the surface of the microsphere becomes rough due to the coating of a layer of silicon dioxide particles can be observed from a scanning electron microscope picture, and the synthesized coated structure microsphere has good sphericity.
(2) The silica-coated PMMA microspheres provided by the invention have the advantages of both silica and PMMA microspheres, have good sphericity of PMMA microspheres, and have high heat resistance and wear resistance of silica;
(3) the microspheres synthesized by the invention are added into paint and ink, so that the extinction effect is good, the coating is endowed with excellent hand feeling, wear resistance and heat resistance, and the glossiness of the coating is low.
Drawings
FIG. 1 is an electron microscope scanning picture of silica-coated PMMA microsphere powder provided by example 1 of the present invention;
FIG. 2 is an SEM image of PMMA microspheres prepared by comparative example 1 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a preparation method of a silica-coated PMMA microsphere flatting agent, which comprises the following steps:
(1) mixing methyl methacrylate, a cross-linking agent, an initiator, an emulsifier, silica sol and water, and homogenizing at room temperature for 5-10 min to prepare a monomer pre-emulsion;
(2) and (2) heating the monomer pre-emulsion obtained in the step (1) to 60-80 ℃ under the protection of nitrogen, stirring at a constant temperature for 4-5 hours, filtering, drying and crushing to obtain the silica-coated PMMA microsphere matting agent.
In an embodiment of the present invention, the crosslinking agent is selected from one or more of allyl acrylate, allyl methacrylate, trimethylolpropane triacrylate.
In an embodiment of the present invention, the amount of the crosslinking agent is 1 to 30% by weight based on the total weight of the methyl methacrylate and the crosslinking agent.
Further, the amount of the cross-linking agent is 20-30% of the total weight of the methyl methacrylate and the cross-linking agent.
In an embodiment of the present invention, the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, lauroyl peroxide, benzoyl peroxide.
In an embodiment of the present invention, the amount of the initiator is 0.2 to 1% of the total weight of the monomer pre-emulsion.
Further, the use amount of the initiator is 0.2-0.5% of the total weight of the methyl methacrylate and the cross-linking agent.
In an embodiment of the present invention, the emulsifier is selected from one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, and sodium dodecyl sulfonate.
In an embodiment of the present invention, the emulsifier is used in an amount of 0.1 to 1% by weight based on the total weight of the methyl methacrylate and the crosslinking agent.
Further, the using amount of the emulsifier is 0.5-1% of the total weight of the methyl methacrylate and the cross-linking agent.
In an embodiment of the present invention, the solid content of the silica sol is 10 to 30%.
In an embodiment of the present invention, the silica sol has an average particle diameter of 1 to 10 nm.
In an embodiment of the present invention, the amount of the silica sol is 1 to 15% by weight of the total weight of the methyl methacrylate and the crosslinking agent.
Further, the amount of the silica sol is 5-15% of the total weight of the methyl methacrylate and the cross-linking agent.
In an embodiment of the present invention, the average particle diameter of the suspended droplets of the monomer pre-emulsion is 0.1 to 10 μm.
In the embodiment of the invention, the average particle size of the silica-coated PMMA microsphere matting agent is 0.1-12 μm.
The following description will further describe embodiments of the present invention with reference to the accompanying drawings.
Example 1
The preparation method of the silica-coated PMMA microsphere matting agent provided by the embodiment comprises the following steps:
(1) weighing 240g of methyl methacrylate, 60g of trimethylolpropane triacrylate, 0.9g of azodiisobutyronitrile, 1.5g of sodium dodecyl sulfate, 15g of silica sol and 200g of distilled water, adding the raw materials into a homogenizing dispersion machine at room temperature, mixing, and homogenizing at the rotation speed of 10000r/min for 15min to prepare a monomer pre-emulsion for later use, wherein the solid content of the silica sol is 20%, and the average particle size of silicon dioxide in the silica sol is 5 nm;
(2) adding 500g of distilled water into a 2L flask, stirring and heating to 65 ℃ under the protection of nitrogen, continuing to stir the monomer pre-emulsion at the constant temperature (65 ℃) for 5 hours to prepare a microsphere suspension, and filtering, drying, crushing and grinding to obtain the silicon dioxide coated PMMA microsphere powder.
In this embodiment, the obtained silica-coated PMMA microsphere powder is subjected to an electron microscope scanning test, and the test result is shown in fig. 1, where the surface of the PMMA microsphere becomes rough due to coating of a layer of silica particles, and the sphericity of the silica-coated PMMA microsphere is good.
Examples 2 to 7
To further illustrate the beneficial effects of the present invention, the preparation method similar to that in example 1 is adopted to prepare the silica-coated PMMA microsphere powder, examples 2-7 are different from example 1 only in the homogenization rate in step (1), and the rotation speed of homogenization in examples 2-7 is shown in table 1.
In order to further illustrate the beneficial effects of the invention, the average particle size of the suspension droplets of the monomer pre-emulsion in the above examples 1-7 is tested, and the performance of the silica-coated PMMA microsphere powder obtained in the above examples is also tested, and the test results are shown in table 1.
Table 1 results of performance testing
Example 8
The preparation method of the silica-coated PMMA microsphere matting agent provided by the embodiment comprises the following steps:
(1) weighing 240g of methyl methacrylate, 20g of allyl methacrylate, 40g of trimethylolpropane triacrylate, 0.9g of benzoyl peroxide, 1.5g of sodium dodecyl sulfate, 15g of silica sol and 200g of distilled water, adding the raw materials into a homogenizing dispersion machine at room temperature, mixing, and homogenizing for 15min at the rotation speed of 10000r/min to prepare a monomer pre-emulsion for later use;
(2) adding 500g of distilled water into a 2L flask, stirring and heating to 75 ℃ under the protection of nitrogen, continuously stirring the monomer pre-emulsion at a constant temperature (65 ℃) for 5 hours to prepare a microsphere suspension, and filtering, drying, crushing and grinding the microsphere suspension to obtain the silica-coated PMMA microsphere powder.
The test shows that the average grain diameter of the silicon dioxide coated PMMA microsphere powder in the step (2) is 3.6 mu m.
Example 9
The preparation method of the silica-coated PMMA microsphere matting agent provided by the embodiment comprises the following steps:
(1) weighing 220g of methyl methacrylate, 80g of trimethylolpropane triacrylate, 1.5g of benzoyl peroxide, 3g of sodium dodecyl sulfate, 45g of silica sol and 200g of distilled water, adding the raw materials into a homogenizing dispersion machine at room temperature, mixing, and homogenizing at the rotation speed of 10000r/min for 15min to obtain a monomer pre-emulsion for later use;
(2) adding 500g of distilled water into a 2L flask, stirring and heating to 75 ℃ under the protection of nitrogen, continuously stirring the monomer pre-emulsion at a constant temperature (65 ℃) for 5 hours to prepare a microsphere suspension, and filtering, drying, crushing and grinding the microsphere suspension to obtain the silica-coated PMMA microsphere powder.
The average particle size of the silica-coated PMMA microsphere powder in the step (2) is 3.6 μm.
Example 10
The preparation method of the silica-coated PMMA microsphere matting agent provided by the embodiment comprises the following steps:
(1) weighing 210g of methyl methacrylate, 90g of trimethylolpropane triacrylate, 1.2g of benzoyl peroxide, 1.8g of sodium dodecyl sulfate, 30g of silica sol and 200g of distilled water, adding the raw materials into a homogenizing dispersion machine at room temperature, mixing, and homogenizing at the rotation speed of 10000r/min for 15min to prepare a monomer pre-emulsion for later use;
(2) adding 500g of distilled water into a 2L flask, stirring and heating to 75 ℃ under the protection of nitrogen, continuously stirring the monomer pre-emulsion at a constant temperature (65 ℃) for 5 hours to prepare a microsphere suspension, and filtering, drying, crushing and grinding the microsphere suspension to obtain the silica-coated PMMA microsphere powder.
The test shows that the average grain diameter of the silicon dioxide coated PMMA microsphere powder in the step (2) is 4.3 mu m.
Comparative example 1
(1) Weighing 240g of methyl methacrylate, 60g of trimethylolpropane triacrylate, 0.9g of azodiisobutyronitrile, 1.5g of sodium dodecyl sulfate and 200g of distilled water, adding the raw materials into a homogenizing dispersion machine at room temperature, mixing, and homogenizing at the rotation speed of 10000r/min for 15min to obtain a monomer pre-emulsion for later use;
(2) adding 500g of distilled water into a 2L flask, stirring and heating to 65 ℃ under the protection of nitrogen, continuously stirring the monomer pre-emulsion at a constant temperature (65 ℃) for 5 hours to prepare microsphere suspension, and filtering, drying, crushing and grinding the microsphere suspension to obtain PMMA microsphere powder.
The comparative example also performs an electron microscope scanning test on the obtained PMMA microsphere powder, and the test result is shown in fig. 2, the surface of the PMMA microsphere powder is smooth, and compared with the silica-coated PMMA microsphere powder shown in fig. 1, the PMMA microsphere powder of the comparative example has poorer sphericity.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in the embodiments without departing from the principles and spirit of the invention, and these embodiments are still within the scope of the invention.
Claims (5)
1. The preparation method of the silica-coated PMMA microsphere matting agent is characterized by comprising the following steps of
(1) Mixing methyl methacrylate, a cross-linking agent, an initiator, an emulsifier, silica sol and water, and homogenizing at room temperature for 5-10 min to prepare a monomer pre-emulsion;
(2) heating the monomer pre-emulsion obtained in the step (1) to 60-80 ℃ under the protection of nitrogen, stirring for 4-5 h at constant temperature, filtering, drying and crushing to obtain a silica-coated PMMA microsphere matting agent;
the dosage of the cross-linking agent is 1 to 30 percent of the total weight of the methyl methacrylate and the cross-linking agent;
the dosage of the initiator is 0.2 to 1 percent of the total weight of the monomer pre-emulsion;
the dosage of the emulsifier is 0.1 to 1 percent of the total weight of the methyl methacrylate and the cross-linking agent;
the amount of the silica sol is 1 to 15 percent of the total weight of the methyl methacrylate and the cross-linking agent;
the average grain diameter of the silicon dioxide in the silica sol is 1 nm-10 nm.
2. A method of preparing a silica-coated PMMA microsphere matting agent according to claim 1, wherein the cross-linking agent is selected from one or more of allyl acrylate, allyl methacrylate and trimethylolpropane triacrylate.
3. A method for preparing a silica-coated PMMA microsphere matting agent according to claim 1, wherein the initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, lauroyl peroxide, benzoyl peroxide.
4. A method for preparing a silica-coated PMMA microsphere matting agent according to claim 1 characterized in that the emulsifier is selected from one or more of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and sodium dodecyl sulfate.
5. A method for preparing a silica-coated PMMA microsphere matting agent according to any one of claims 1 to 4 characterized in that the solid content of the silica sol is 10% to 30%.
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