JPS59230008A - Production of globular polymer - Google Patents

Abstract

PURPOSE:To provide the titled polymer having reactivity and useful as a raw material of ion exchange resin, etc., by the aqueous suspension polymerization of a monomer mixture containing glycidyl acrylate, etc. in the presence of a water- soluble polymer containing unsaturated carboxylic acid and unsaturated sulfonic acid in a chemically bonded form. CONSTITUTION:The objective polymer is obtained by the aqueous suspension polymerization of (A) glycidyl (meth)acrylate or a monomer mixture composed of >=50wt% of said acrylate and the remaining part of one or more other monomers in the presence of (B) a water-soluble polymer containing (i) a monomer unit comprising an ethylenic unsaturated carboxylic acid or its salt and (ii) a monomer unit comprising an ethylenic unsaturated sulfonic acid or its salt in a chemically bonded form and (C) an oil-soluble radical polymerization initiator, 2-9pH and a stirring speed of 50-500r.p.m.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a spherical polymer, and more specifically, the present invention relates to a method for producing a spherical polymer, and more specifically, the present invention relates to a method for producing a spherical polymer. The present invention relates to a method for producing a spherical monomer having an epoxy group and a bonded metal by carrying out aqueous suspension polymerization under specific conditions in the presence of the present invention.

Traditionally, pellet-like and flake-like materials have been used as raw materials for molding.
There are cases where it is convenient to prepare granular polymers from the beginning because they are easy to handle, such as small spheres or fine particles. There are many application fields where this is required.

Polymers with bonded epoxy groups have the potential to be applied to various fields of use by introducing various functional groups depending on their reactivity.
Publication No. 96261 discloses a technique for producing immunoactive fine particles by reacting G Oil A M combined fine particles with an immunoactive substance having an amino group. According to this publication, polymerization is carried out in a medium that dissolves the monomer but precipitates the produced polymer, and that depending on the monomer composition and the selection of the polymerization medium, fine particulate G (5 octapolymer) of 006 to 10μ is produced. However, since such means use organic solvents for polymerization medium, washing, etc.,
On an industrial scale, there are many points that need to be taken into account in terms of work environment and safety, such as odors, and in application fields such as ion exchange resins (for example, gels for liquid chromatography), there are usually 20
Particles with a particle size of ~1000μ are used (power)
There is a need for an industrial means for producing spherical polymers with a particle size of

Also, Journal of the Chemical Society of Japan, 1979, (12), p. 17
56-1759 discloses a method for producing a GMA spherical polymer as a substrate for producing a chelating ion exchange resin, in which a large amount of sodium sulfate and calcium carbonate are used as dispersants together with gelatin to obtain a spherical polymer. In order to decompose and decenter calcium carbonate from the produced polymer, complicated operations such as addition of hydrochloric acid and washing with hot water are required.

Here, the present inventors have discovered that EBOKI 7 has various reactivities derived from epoxy groups, and in general, the generated polymer particles are highly adhesive and easily cause agglomeration and coalescence to form a sticky mass. It is possible to produce spherical particles of group-containing East coalescence in an industrially advantageous manner (as a result of intensive studies,
Using a specific water-soluble polymer as a dispersant and at a specific pH.
The inventors have discovered that a spherical polymer having a desired particle size can be produced by industrial means by carrying out aqueous suspension polymerization under stirring conditions, and have thus arrived at the present invention.

That is, an object of the present invention is to provide an industrial method for producing a spherical polymer having epoxy groups bound thereto and having various reactivities.

The purpose of this first explanation is to add GA or GMA alone or a monomer mixture consisting of 0% by weight or more of the above monomer and the balance consisting of at least one other monomer to form a material that is substantially ethylenically unsaturated. A water-soluble polymer and an oil-soluble radical having a monomer unit consisting of a carboxylic acid or a salt thereof and a monomer unit consisting of an ethylenically unsaturated diurephonic acid or a salt thereof.
In the presence of a polymerization initiator, pH 2~^, stirring speed 50~50
This can be achieved by aqueous suspension polymerization under Qr, p, nh conditions.

The present invention will be explained in detail below.

First, as a monomer, G%) A alone or 50i amount%
As mentioned above, it is necessary to use a monomer mixture consisting of preferably 60% or more of G (MJ A and the balance being at least one other monomer. As the other monomer, G (MI
As long as it is a monomer that can be copolymerized with A, it can be employed without any limitation, such as vinyl halides and vinylidene halides such as vinyl chloride, vinyl bromide, vinyl fluoride, and vinylidene chloride; acrylics; acids, unsaturated carboxylic acids such as methacrylic acid, maleic acid, itaconic acid, and their salts; methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methoxyethyl acrylate, phenyl acrylate, cyclohexyl acrylate, etc. Enether acrylates; Methyl methacrylate, Ethyl methacrylate) Butyl methacrylate, Octyl methacrylate, Methoxyethyl methacrylate, Phenyl methacrylate, Cyclohexy meccrylate, etc. Methyl vinyl t-ton 1
Unsaturated ketones such as methyl isoprohebenyl ketones; B/R ethers such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; Methyl vinyl ether ethers; acriframide and its alkyl/L
7M conversion; unsaturated hydrocarbons such as vinyl/l/,'/lephonic acid, ali/l/nurphonic acid, methallyl 7-sulfonic acid, and their salts; Rukyl or halogen substitute;
Allyl alcohol and its esters or ethers; basic vinyl compounds such as vinylpyridine 1 vinylimidazo-I and dimethyl rareminoethyl meccrylate; vinyl compounds such as acrolein, methacrolein, vinylidene cyanide) methacrylonitrile I can list various types. In addition, if necessary, divinylbenzene, ethylene glycol 2, dimecacrylate, diethylene glyconocataacrylate, polyethylene glycol dimethacrylic acid, triallyl cyanurate), etc. may be added. By using a crosslinkable monomer, the polymer can also be actively crosslinked.

Next, a method for polymerizing the monomer will be described.

First, the water-soluble polymer to be present in the polymerization system, which is a particularly important structural component for achieving the purpose of the present invention, includes a monomer unit (component A) consisting essentially of an ethylenically unsaturated carboxylic acid or a salt thereof. Any water-soluble polymer made of ethylenically unsaturated fluoronic acid or a salt thereof and containing the same components can be effectively used in the present invention, but in general, components A and B can be used effectively in the present invention. It can be produced by copolymerizing the components with a well-known method (solution polymerization using special KS water as a polymerization medium). It goes without saying that methods such as hydrolyzing the polymerized copolymer to introduce component A into the polymer, or introducing component B by fluorinating the polymer can also be employed.

In addition, the composition ratio of component A and component B in such a water-soluble polymer is difficult to limit to G (which varies slightly depending on the copolymerization ratio of MIA and the type of other monomers, but Generally A component/B component = 60-80% 770-20%
There is no particular restriction on the degree of polymerization of such a polymer, but in a practical molecular weight range, it is better to use a polymer with a small molecular weight to reduce the opening force and the effect of preventing coalescence of dispersed particles. Rakoichi Uderu. Depending on the type of other monomers, a water-soluble polymer prepared by copolymerizing or graft-polymerizing a small amount of a hydrophobic monomer such as vinylidene chloride in addition to components A and B may be used. In some cases, a better spherical polymer can be obtained, and therefore, such a polymer is also included in the scope of the water-soluble polymer used in the present invention.

In addition, the A component introduced into such water-soluble polymers includes unsaturated colored carboxylic acids such as acrylic acid, methacrylic acid, vinyl acetic acid and crotonic acid, and salts thereof; maleic acid, fumaric acid, and iconic acid. (1) Unsaturated polyhydric carboxylic acids such as aconitic acid, citraconic acid, and mesaconic acid, and their salts, etc.) In particular, from the viewpoint of forming spherical polymers, monomer units consisting of methacrylic acid and its salts are preferred. Introduction is recommended.

In addition, as the B component, nulphonated unsaturated hydrocarbons such as nuthylene, allylsulfonic acid, methallyl nulphonic acid, and salts thereof; acrylic acids such as nulphoethyl methacrylate, nurfoglovir enether methacrylate, etc. Alternatively, sulfoalkyl nuethers of methacrylic acid and salts thereof can be mentioned.

Note that the amount of water-soluble polymer used is preferably 5% by weight or more based on the monomer. polyvinyl alcohol)v (PV A
) in an amount of 0.1 to 5 times the weight of the monomer gives particularly good results.

Further, examples of the oil-soluble radical polymerization initiator include the following azo compounds or organic peroxides. For example, examples of azo compounds include 2,2' di-monoazobinuisoptilonitrile, 2,2-azo(2-1
Tyl-valeronitrile (2,4-dimethylbutyronitrile), 2,2-azobis(2-methylbutyronitrile), 2,2'-azobis(2,3,3-)dimethylbutyronitrile], 2,
2'-Azobis(2,4,4-)limethylvaleronitrile), 2,2'-Azobis(2,4-X-methylvaleronitrile), 2,2'-Azobia(2,4-
dimethyl-4-ethoxyvaleronitrile/l/), 2.
2'-azobis(2,4-dimethyl-4-n-butoxyvaleronitrile) and the like can be used. Examples of organic peroxides include acetyl peroxide, glopionyl oxide, imbutyryl peroxide, Diacyl peroxides such as octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,5,5-trimethyfurehexanoyl peroxide, penzoyl peroxide, di-2-ethylhexyl silver'oxydicarbonate, etc. Class; t-butyl peroxyisobutyrate, t-butyl peroxypivalate, t-buty/L'perone neodocanoate V1
Peroxyenethers such as t-butyl peroxylaurate and the like can be used. Of course, two or more of the above oil-soluble radical polymerization initiators can also be used in appropriate combination. Among them, azo compounds are preferred from the viewpoint of handling safety and performance, and 2,2'-azobinisobutyronitrile or 2,2'-azobinui(2,4-dimethylvaleronitrile) is particularly preferred.

Although it is difficult to specify the amount of the initiator to be used, it is generally used within the range of 02 to 2.0% based on the monomer weight.

In addition, regarding the pH of the polymerized thread, if the acidity is too strong, ring opening of the epoxy group will occur during polymerization, and if the pH is too strong, the generated polymer σ) will be hydrolyzed, so the PH2
It is necessary to set it within the range of 9 to 9, preferably 2 to 7.

Furthermore, the stirring conditions, which play an important role in adjusting the particle size, need to be ashed depending on the shape of one blade, the presence or absence of baffle plate σ), the desired particle size, etc., and are difficult to define unambiguously. However, the stirring speed is approximately 50 to 500 r, p, m,
It is necessary to set it within the range of . In addition, as for the shape of the blade, a turbine blade is suitable for the paddle-shaped blade because it is easy to obtain a uniform particle size distribution.

Although the polymerization temperature depends on the type of initiator, the higher the humidity, the more likely the ring-opening reaction of the epoxy group will occur, or a portion of the epoxy resin will be emulsified and undergo emulsion polymerization, resulting in a latex-shaped fine polymer. To avoid problems such as formation, a temperature range of approximately 80° C. or lower, preferably 40 to 70° C., is recommended.

t) It is desirable to use industrial tap water as the polymerization medium, but there is no problem in coexisting with a water-miscible organic solvent or with a 1M delyte salt.

By adopting the method of the present invention described above, the diameter of one particle is approximately 10μ.
The above-mentioned spherical polymer can be selectively formed, and although the polymer has a gel moisture content of 20% or less, since it is insoluble in solvents, some of the epoxy groups are ring-opened and the parent wood group is It is presumed that a cross-linked structure has been introduced along with the
As mentioned above, although it has a variety of reactivities derived from epoxy groups and can be applied to a reasonable number of industrial fields, the sticky lumps of polymer particles that are produced generally tend to aggregate strongly and coalesce, resulting in a chip-like structure. A noteworthy effect of the present invention is that spherical particles of an epoxy group-containing polymer that are easily agglomerated can be manufactured by industrial means.

EXAMPLES The present invention will be described in more detail by way of Examples below, but the scope of the present invention is not limited in any way by the description of these Examples.

In the examples, parts and percentages are expressed on a vehicle weight basis unless otherwise specified. The gel moisture content is determined by placing polymer particles sufficiently equilibrated with deionized water in a centrifugal separator with a centrifugal effect of 2000 G. After removing the water adhering to the particle surface, its weight (Wl) was measured, and then the polymer particles were dried to measure the dry weight (w2J), which was determined by the following formula.

1-W2 Gel moisture content = -□ x i o o (%) 2 Example 1 Methacrylic acid/p-nuthylene sulfonate sodium 707
20 parts of a water-soluble polymer of No. 30 and pvA (degree of polymerization 1ooo
, saponification degree 87%) was dissolved in 778 parts of water and charged into a polymerization tank equipped with a paddle-type stirrer. Dissolve 2 parts and charge into a polymerization tank, 50 Or, p
, m.

Polymerization was carried out at 60°C for 2 hours under stirring conditions (polymerized yarn p
H = 3) However, no aggregation or coalescence of the produced polymer was observed, and a spherical polymer with an average particle diameter of 70μ (gel moisture content: 11%) was observed.
) was able to be formed.

Example 2 Same as Example 1 except that 180 parts of GMA and 20 parts of triethylene glyco-dimethacrylate were used instead of 200 parts of GMA, and 1 part of benzoyl peroxide was used as a radical polymerization initiator, and the polymerization humidity was adjusted to 70°C. When polymerization was carried out in the same manner, a spherical polymer (gel moisture content: 13%) with an average particle diameter of 55 μm was produced.

Example 6 Polymerization was carried out according to the recipe described in Example 1, except that the stirring speed was changed as shown in the table below.

The results of measuring the particle diameter of the produced polymer are also shown in the table below.

From the above table, even if the remaining constituent requirements satisfy the means of the present invention, it is not possible to form a good spherical polymer when the stirring conditions are outside the recommended range of the present invention (Ya 1 and V). is clearly understood.

Procedural amendment C method) % formula % 1. Indication of the case Patent Application No. 104785 of 1982 2. Name of the invention Method for producing spherical polymer 3. Person making the amendment Relationship with the case Patent applicant address Osaka, Osaka Prefecture 2-2-8 Dojimahama, Kita-ku, Ichikita-ku Name
(405) Nippon Exlan Kogyo Co., Ltd. September 7, 1982 (Shipping date: September 27, 1982) 5, Subject of amendment 4

Claims (1)

[Scope of Claims] 1. Glycidinorea acrylate or glycidyl methacrylate alone or a monomer mixture consisting of 50% by weight or more of the above monomer and the balance consisting of at least one other monomer, substantially ethylene In the presence of a water-soluble polymer and an oil-soluble radical polymerization initiator having a monomer unit consisting of an unsaturated carboxylic acid or a salt thereof and a monomer unit consisting of an ethylenically unsaturated sulfonic acid or a salt thereof, A method for producing a spherical polymer, characterized by carrying out aqueous suspension polymerization under conditions of pH 2 to 9 and stirring intensity of 50 to 500 r, p, m. 2. The manufacturing method according to claim 1, wherein the water-soluble polymer is used in an amount of 5% by weight or more based on the monomer. 3, 31 degree 500-2000 and saponification degree 85-95
% of polyvinyl alcohol is present. The manufacturing method according to claim 1, wherein the polymerization is carried out under a temperature condition of 480° C. or lower.