JPS60229959A - Preparation of coated inorganic solid material - Google Patents

Abstract

PURPOSE:To prepare the titled substance, easily, by homopolymerizing a cationic surfactant monomer capable of forming a micelle, or copolymerizing the monomer with other monomer, thereby enabling the rapid and uniform polymerization. CONSTITUTION:The objective substance can be prepared by polymerizing a cationic surfactant monomer of preferably the formula (R1 is H or CH3; R2 is lower alkyl; R3 is 6-24C long-chain alkyl; Y is -O- or -NH-; n is 2-8; X is halogen) [e.g. (meth)acryloyloxythyl diethyl dodocyl ammonium bromide, etc.] or copolymerizing the monomer with other monomer having radically polymerizable unsaturated bond (e.g. styrene), in a liquid medium in the presence of an inorganic solid material to be coated.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD This invention relates to a method for making inorganic solid materials coated with polymers.

[Prior art]

Inorganic solid materials coated with polymers are considered to have a wide variety of applications depending on the type of polymer and the type of solid material coated. For example, fillers such as calcium carbonate, silica, and clay are used in large quantities as fillers in rubber, plastics, paints, paper, and the like. At this time, since these fillers are inorganic substances, they have a low affinity with organic substances such as rubber and plastics to be kneaded, and for this reason, various measures have been taken. Torera no 1
One method is to make the filler surface lipophilic.
In reality, surface treatment is performed using a silane coupling agent or the like. However, the reality is that even with such processing, satisfactory results have not been obtained. Also,
Further developing the above ideas, we will further enhance the functions of these fillers by developing plastic beads with fillers as the core, molding by integrating plastic and filler, or developing polymer emulsions with fillers as the core. Attempts are being made to do so.

On the other hand, by focusing on the excellent properties of inorganic powder as a substrate, such as porosity, pressure resistance, and chemical resistance, we can coat these substrates with polymers with special functions, thereby creating new functionalities. The idea of developing materials has also been proposed, and attempts have also been made to produce molded bodies or emulsions with functions that cannot be obtained by conventional methods by coating the surface of certain polymer particles with different types of polymers.

In recent years, a method of coating a solid substance by bringing into contact a monomer having an unsaturated bond capable of radical polymerization and a polymerization initiator in the coexistence of an organic sulfonic acid having a vinyl group or a salt thereof has been proposed in Japanese Patent Publication No. 54-8548 and Japanese Patent Publication No. 57-115412
has been disclosed.

However, in those methods, the monomer actually used is mainly limited to methyl methacrylate (hereinafter abbreviated as MMA), and the solid materials to which it is applied are also not versatile, so they are not fully practical. It's not sexualized.

In view of the above points, the inventors of the present invention have conducted extensive studies, and as a result,
By polymerizing a cationic monomer, especially a cationic monomer having surface-active ability, alone or with a monomer having a radically polymerizable unsaturated bond in suspension of an inorganic solid substance in a liquid medium. The present invention was achieved by discovering that an inorganic solid material coated with a polymer can be easily obtained.

[Purpose of the invention]

An object of the present invention is to provide a method for easily obtaining an inorganic solid material coated with a polymer using a surfactant type monomer capable of forming micelles.

[Disclosure of the invention]

The above objects of the present invention are achieved by the following method for producing a coated inorganic solid material.

A coating characterized in that a cationic surfactant type monomer is polymerized or copolymerized alone or together with a monomer having a radically polymerizable unsaturated bond in the presence of an inorganic solid substance to be coated in a liquid medium. A method for producing inorganic solid substances.

[Best mode for carrying out the invention]

The present invention is characterized in that, among cationic monomers, a surfactant-type monomer having a micelle-forming ability is homopolymerized or copolymerized with other monomers. By varying the type of polymer used and the type of inorganic solid material coated, a variety of polymer-coated inorganic solid materials can be obtained.

Various types of monomers can be used as the cationic surfactant type monomer used in the present invention, but preferably the following general formula 2 (wherein R1 is a hydrogen atom or a methyl group, R2 is a lower alkyl group, R3 is a long-chain alkyl group with 6 to 24 carbon atoms, Y is a 10-group or -NH- group, n is a positive integer of 2 to 8, and X is a halogen.) acrylate or methacrylate type (hereinafter abbreviated as (meth)acrylate type)
The cationic monomer and acrylamide are one or more quaternary salts of long-chain alkyl cationic monomers of the methacrylamide type (hereinafter abbreviated as (meth)acrylamide type).

First, the above monomer is exemplified as a tertiary amine type. (
For meth)acrylate L, for example, dimethylamine ethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, propylaminoethyl (meth)acrylate, dimethylaminepropyl (meth)acrylate, dimethylaminobutyl (meth)acrylate, dimethylaminohexyl (meth)acrylate, dimethylaminooctyl (meth)acrylate, dimethylaminopropyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide, and the like. These tertiary amine monomers are quaternized with long-chain alkyl halides and used as cationic surfactant type monomers.
The long-chain alkyl halide used for quaternization is preferably a straight button-like argylnolide having 6 to 24 carbon atoms. of·
As the loge/atom, any of chloride, bromide, and iodide can be used, but bromide and iodide are preferable for carrying out the reaction. A conventional method can be used for quaternization, for example, a tertiary amine type monomer and a long-chain alkyl halide may be mixed and reacted in a solvent such as water, alcohol, or acetone. Temperature is 0~50°C, time is 5~
It is 40 hours.

The cationic surfactant type monomers produced by the above method have a long chain alkyl group having 6 to 24 carbon atoms, so for the sake of simplification, examples of these compounds are given by replacing It3 with a dodecyl group. An example is shown in which X is fixed to bromine. For example, (meth)acryloyloxyethyldimethyldodecylammonium bromide, (meth)acryloyloxyethyldiethyldobufluammonium bromide, (
(meth)acryloyloxyethyldipropyldodecylammonium bromide, (meth)acryloyloxypropyldimethyldodecylammonium bromide, (meth)acryloyloxybutyldimethyldodecylammonium bromide, (meth)acryloyloxyhexyldimethyldodecylammonium bromide, (meth)
Acryloyloxyoctyldimethyldodecylammonium bromide, (meth)acrylamidopropyldimethyldodecylammonium bromide, (meth)acrylamidopropyldiethyldodecylammonyl Monomers having polymerizable unsaturated bonds include hydrophobic monomers and hydrophilic monomers. Can be used on any part of the body.

Examples of hydrophobic monomers include styrene, α-methylstyrene, vinyl acetate, vinyl chloride, acrylonitrile,
Ethyl acrylate, butyl acrylate, glycidyl acrylate, MMA butyl methacrylate, glycidyl methacrylate, N-propylacrylamide, n-butylacrylamide.

n-octylacrylamide, N-ethylmethacrylamide, N-butylacrylamide, N, I'q-digly7ylacrylamide, N-acryloylpyrrolitine, N-acryloylpiperidene, N-methacryloylpyrrolidine, ethylene, propylene, divinyl Benzene, ethylene glycol dimethacrylate, divinyl ether, butadiene.

Such as taloloprene. Specific examples of the hydrophilic monomer include hydroxyethyl methacrylate, N-vinylpyrrolidone, acrylamide, N,N-dimethylacrylamide, N-ethylacrylamide, methacrylamide, acrylic acid, or a salt thereof.

Such as methacrylic acid or its salt.

The inorganic solid substance to be coated can have various shapes such as spherical, powder, fibrous, plate, and scale. Specifically, simple metals and oxides.

Sulfides, nitrides, carbides, silicides, borides.

Chlorides, phosphates, sulfates, sulfites, carbonates.

Silicates, hydroxides and mixtures thereof, double salts.

There are intermolecular compounds, etc. Specifically, iron and copper.

Aluminum, alumina, red iron, ferrite.

Cadmium sulfide, carbon nitride, boron carbide, zirconium silicide, calcium boride, silver chloride, aluminum phosphate, ceracola, calcium sulfite.

These include calcium carbonate, aluminum hydroxide, and silica gel, as well as titanium white, zinc white, and yellow lead.

Inorganic pigments such as cobalt blue, chrome green, and white carbon,
Clays such as perlite, asbestos, sand, mica, shirasu balloon, zeolite, talc, bentonite, and other natural minerals can be applied.

The amount of monomer added to the inorganic solid substance is 0.05 to 1,
000% by weight or 0.1 to 500% by weight.

The reason why the amount added varies over such a wide range is that there are various cases, such as when a solid substance is coated with an extremely thin polymer, or when plastic beads having a solid substance as a core are manufactured.

When initiating polymerization, it can be carried out only by heating, but
Usually, better results are obtained by using a polymerization initiator. The polymerization initiator is not limited as long as it has the ability to initiate radical polymerization, and examples thereof include inorganic peroxides, organic peroxides, combinations of these peroxides and reducing agents, and azo compounds. Specifically ammonium persulfate.

Examples include potassium persulfate, hydrogen peroxide, t-butyl peroxide, penzoyl peroxide, and cumene hydroxy peroxide. Reducing agents that can be combined with these include sulfites, hydrogen sulfites, and lower-order substances such as iron, copper, and cobalt. Examples include ionic salts, organic amines such as aniline, and reducing sugars such as aldoses and ketoses. Examples of azo compounds include azobisisoprotinitrile, 2,2'-azobis-2-amidinopropane hydrochloride, 2,2'-7zobis-2,4-dimethylvaleronitrile, and 4,4'-azobis-4-one azovaleric acid. etc. can be applied.

It is also possible to use two or more of these initiators in combination. The amount added is based on normal polymerization conditions! For example, it may be 0, 1 to 5 parts by weight, preferably 0,805 to 2 parts by weight per monomer.

Water is generally used as the liquid medium in which the polymerization or copolymerization takes place in the presence of solid substances. P I-1 of the aqueous medium needs to be controlled depending on the type of inorganic solid substance. That is, silica, titanium dioxide, etc., which have a low isoelectric point, may be in an acidic, neutral, or basic state, but iron oxide, which has a high isoelectric point.

For alumina, etc., better results can often be obtained by polymerizing with a basic aqueous solution.

Alcohols and ketones other than wood can also be used, as well as mixed solvents of these with water.

The amount of liquid medium added is usually 0.2 to the volume of solid material.
~1,000 times, preferably 05 to 500 times.

Furthermore, in order to improve the dispersion of these solid substances and monomers, it is also possible to use surfactants, and various types of surfactants such as anionic, nonionic, and cationic surfactants can be used.

There is no particular restriction on the order in which the monomer and solid substance are added to the liquid medium, and they may be added in any order.

Usually, an inorganic solid substance is placed in a liquid medium, a monomer is added thereto, and the monomer is thoroughly mixed with the inorganic solid substance, and then a polymerization initiator is added to initiate polymerization.

The polymerization initiator may be added before the monomer is added.

Although it is still preferable to replace the atmosphere in the polymerization vessel with an inert gas such as nitrogen gas, polymerization is also possible in an atmosphere of oxygen-containing gas such as air. The progress of polymerization can be confirmed by a change in the appearance of the dispersed solid substance or by quantitative determination of the remaining monomer by gas chromatography or the like. After polymerization for a predetermined period of time, the reaction mixture can be separated by a method such as filtration or centrifugation to obtain a solid material coated with the polymer.

On the other hand, the filtrate can be discarded or recycled.

〔Effect of the invention〕

According to the present invention, since a surfactant type monomer capable of forming micelles is used, in the presence of a solid substance in a liquid medium, the monomer is adsorbed to the surface of the solid substance, and as a result, the surface of the solid substance is It is necessary for the development of new functional materials by combining different materials because the polymerization can proceed quickly and uniformly, and the ratio of polymer coating the solid substance can be easily controlled. It becomes a technology.

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited only to these Examples.

Example 1 Distilled water 25n+l! Silicage # (150-200 mesh) for column chromatography 8. After adding Qf and stirring thoroughly, 0.508 f of methacryloyloxyethyldimethyldodecylammonium promite (hereinafter referred to as Cx2Br, !: abbreviation f) and 2.2'-7 zobis(2
-amidinopropane) hydrochloride (hereinafter abbreviated as ■-50) 14rr++F was added. The reaction solution was freeze degassed and replaced with a nitrogen atmosphere, and then polymerized at 5°C for 24 hours in a constant temperature bath with stirring. After polymerization, a small amount of hydroquinone was added to the polymerization mixture to stop the polymerization, and the polymerization mixture was heated at 8,000 rpm.

After centrifugation for 10 minutes, the precipitate and supernatant were separated, and the precipitate was further mixed with water and washed by repeating centrifugation several times. The supernatant liquid and the washing liquid were combined, and an aqueous sodium bromide solution of Part 10 was added thereto to salt out the latex-like polymer. The precipitated polymer was separated by filtration, washed with water, dried, and weighed. The yield was 0.068 # (yield: 13.3 cm). When the precipitate was dried and weighed, it was found to be 3.367F, and the coated polymer yield was 0.36JF (yield 70.9
% )Met.

When we observed the surface of this object with a scanning electron microscope, we found that
It was confirmed that the surface was uniformly coated with the polymer.

Examples 2 to 9 A solid substance was coated with a polymer in exactly the same manner as in Example 1 except for the combinations of solid substances, monomers, and polymerization initiators shown in Table 1 and the amount of added IJ [+]. I did it. The product was analyzed in exactly the same manner as in Example 1, and the results are shown in Table 2.

Example 10 1 25 ml of distilled water as reaction solvent! to l/20 normal sodium hydroxide aqueous solution 2.1rr+l! by adding
was adjusted to 8.0, and γ-
Iron oxide 1.00#% C12Br 1.01 as monomer
A solid substance was coated with a polymer in exactly the same manner as in Example 1 except that V 50 28rr+f was used as the 921 polymerization initiator. The product was analyzed in exactly the same manner as in Example 1, and the results were that the yield of precipitate was 1, the yield of 03t1 coating polymer was 3.1%, and the yield of latex polymer was 91.6%.

Example 11 25 ml of an aqueous solution prepared with PI-1 of 988 using sodium hydroxide and sodium hydrogen carbonate was used as a reaction solvent, and C1zBr 1.0131? as a monomer. A solid substance was coated with a polymer in exactly the same manner as in Example 10 except that . However, the polymerization time was 16 hours. The product was analyzed in exactly the same manner as in Example 1, and the yield of precipitate was 1.041? , coated polymer yield 3.9%
A latex polymer yield of 55.6 was obtained.

Reference Example The critical micelle concentrations (hereinafter referred to as c, m, c, ) of various cationic surfactant type monomers were measured by a dye solubilization method using azobenzene and an electrical conductivity method, and the results are shown in Table 3.

Table 8 Wood Compounds having the following structure are expressed as CnBr (where n is 6, 8, 10, 12.14.16 or 1
8) H3 Patent applicant Mitsui Toatsu Chemical Co., Ltd.

Claims (1)

[Claims] 1. In a liquid medium, in the presence of an inorganic solid substance to be coated, a cationic surfactant type monomer is polymerized or co-polymerized alone or together with a monomer having a radically polymerizable unsaturated bond. A method for producing a coated inorganic solid material characterized by polymerization. 2. The cationic surfactant type monomer has the general formula (wherein Rx is hydrogen or a methyl group, R2 is a lower alkyl group,
R3 is a long-chain alkyl group having 6 to 24 carbon atoms, Y is a 10-group or -NH- group, n is a positive integer of 2 to 8, and X is a halogen. ) Claim 1
The method described in section.