JPS59232104A - Bead polymer and production thereof - Google Patents

Abstract

PURPOSE:To obtain an inexpensive bead polymer excellent in separation performance and suitable as a packing for liquid chromatography, by suspension-polymerizing glycidyl (meth)-acrylate in an aqueous medium in the presence of a specified water-soluble polymer and heat-treating the produced polymer. CONSTITUTION:To an aqueous medium are added (A) glycidyl (meth)acrylate or a monomer mixture containing at least 50wt% this monomer and the balance of other monomers (e.g., vinyl chloride), (B) a dispersant comprising a water-soluble polymer obtained by copolymerizing an ethylenically unsaturated carboxylic acid (salt) with an ethylenically unsaturated sulfonic acid (salt), and (C) an oil-soluble radical polymerization initiator (e.g., 2,2'-azobisisobutyronitrile). This mixture is suspension-polymerized under a condition including a pH of 2-9 and an agitator speed of 50-500rpm. The product is heat-treated under a condition including a pH <=3 and a temperature >=70 deg.C to obtain the purpose bead polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a bead-shaped polymer made by the present invention and a method for producing the same. Polymers that have epoxy groups bound to them have the potential to be applied in a variety of fields by introducing various functional groups due to their reactivity (3). discloses a technique for producing immunoactive fine particles by reacting heglycidyl acrylate (GA) or hagelicidyl methacrylate (IMA) polymer fine particles with an immunoactive substance having an amino group. According to the authors, polymerization is carried out in a medium in which the monomer is dissolved but the resulting polymer is precipitated, and the polymer composition and the selection of the polymerization medium can be used to
Although it is described that a particulate GA or I'iG MA polymer having a particle size of 0.03 to 10% can be obtained, such a method uses an organic solvent for the polymerization medium, washing, etc., and therefore cannot be used on an industrial scale. There are many points to keep in mind regarding the working environment and overall environment, such as odors. Also, Journal of the Chemical Society of Japan, 197
9, (12), p. 1756-1759 discloses a method for producing a GM octohedral polymer as a substrate for producing a chelating ion exchange resin. Sodium sulfate and calcium carbonate are used as dispersants, and complicated operations such as addition of hydrochloric acid and washing with hot water are required to decompose and remove calcium carbonate from the resulting polymer.

91 In recent years, liquid chromatography has become just one of the analytical tools and 1. In addition to being used as an industrial separation method, it is increasingly being used as an industrial separation method in many fields such as the food industry, pharmaceutical industry, synthesis and purification of chemical industry product intermediates, inorganic industry, and textile industry. As such a gel for liquid chromatography, dequinutran crosslinked polymer gel, Acrylic/l/
A wide variety of products have been developed, including cross-linked polymer-based gels, cross-linked polynutylene gels, cross-linked polyvinyl acetate/l/gels, cross-linked polyethylene glycol dimethacrylate thread gels, and silanol/polyoxyethylene thread gels.

However, gels with high separation performance and high throughput are generally expensive;
i a Fine chemical company 1 etc. Sephadectic Nuge) l/(Dequinutran cross-linked polymer system gel) is,
Although the performance is excellent, it is very expensive, and it is a problem in industrial applications where huge columns are packed with large amounts of thi.
By the way (5) Yes.

Here, as a result of intensive research to provide a bead-like polymer that is inexpensive and has high separation performance, the present inventors used a specific water-soluble polymer as a dispersant and
An epoxy group-containing spherical polymer having a desired particle size can be produced by aqueous suspension polymerization under H and stirring conditions, and the epoxy group can be removed by acidic heat treatment of the thus obtained polymer under specific conditions. The present invention was achieved based on the discovery that a hydroxyl group is introduced by ring opening and a bead-shaped polymer having high separation ability can be provided industrially advantageously.

That is, the object of the present invention is to provide a hydrophilic and solvent-insoluble bead-shaped polymer into which a large amount of hydroxyl groups are introduced by modifying the epoxy group without the problems of aggregation and coalescence that are peculiar to epoxy group-containing polymers, and the production thereof. The purpose of mah% is to provide a bead-shaped polymer that is inexpensive and has high separation performance. A further different objective will become clear from the present invention σ)J(weight theory (6) described below).

The bead-shaped polymer according to the present invention for achieving this purpose is GA or GMA (hereinafter referred to as G (M) A
G (M) is made by polymerizing a monomer mixture consisting of A and the balance consisting of at least one other monomer, and a hydroxyl group is introduced by ring opening of an epoxy group. The bead-like polymer has a gel moisture content of 60% or more and is insoluble in solvents, and the G(M)A alone contains 50% by weight or more of the monomer and the remainder. is a monomer mixture consisting of at least one other monomer, a monomer unit consisting essentially of an ethylenically unsaturated carboxylic acid or a salt thereof, and a monomer unit consisting essentially of an ethylenically unsaturated nurphonic acid or a salt thereof. In the presence of a water-soluble polymer and an oil-soluble radical polymerization initiator, P
After aqueous suspension polymerization at pH 2 to 9 and stirring speed 50 to 5 oor, p, m, Ph 3 or more and temperature 70
It can be advantageously produced by heat treatment at a temperature of .degree. C. or higher.

(7) Hereinafter, the present invention will be described in detail. First, the epoxy group-containing spherical polymer which is a component of the first stage is G (ltQA alone or 50 weight 1i% or more), preferably 60 weight % or more. G(
M) It is necessary to produce a mono- and ti-1 monomer mixture consisting of A and the remainder of at least one other monomer. In addition, other monomers to be copolymerized with G(M)A include GQ
tq) Known single π-isomers that can be copolymerized with A, such as vinyl chloride, vinyl bromide, vinyl halides and halogenated hinylidene such as hinyl fluoride/I/1 hnyritene chloride; acrylic acid, methacrylic acid, maleic acid , itaconic acid and other unsaturated carboxylic acids and their salts; methyl acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, methoxyethyl acrylate, phenyl acrylate,
Entel acrylates such as cyclohexyl acrylate;
Methyl methacrylate, ethyl methacrylate, butyl methacrylate) methacrylic acid enethers such as octyl methacrylate, methoxyethyl meccrylate, phenyl methacrylate, cyclohexyl methacrylate; methyl vinyl ketone, phenyl vinyl ketone\methyl isopropenyl t
unsaturated ketones such as vinyl formate, vinyl acetate, vinyl fluoropionate, vinyl butyrate, vinyl benzoate, etc.; vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; acrylamide and its alkyl substituted products; vinyl nulphonic acid , allylnulfonic acid, methallylnulfonic acid, p-nutylenesulfonic acid, and other unsaturated hydrocarbon nulfonic acids and their salts] 1; Nutylene, α-methylnuthylene, chloro7thylene, and other alkyl- or halogen-substituted products thereof; allyl alcohol; Enthers or ethers; basic vinyl compounds such as vinylpyridine, vinylimidasol, dimethylaminoethyl meccrylate; vinyl compounds such as acrolein, methacrolein, vinylithine cyanide, meccrylonitrile, etc. I can do it. In addition, if necessary, Nhinylbenzene, ethylene glycol dimethacrylate, siethi(9), polyethylene glycol dimethacrylate, N,N'-methylenevinucrylamide, divinyl succinate, diaryl succinate) vs. hibinyl meccrylate 1 Allyl triallyl cyanurate methacrylate 1 The horse-riding compound can also be positively crosslinked by using a crosslinking monomer such as triallyl isocyanurate.

The polymerization method employed in the present invention using such monomers is as follows:
It is characterized in that suspension polymerization is essentially carried out under specific pH and stirring conditions in the presence of an O-oil-soluble radical polymerization initiator in a specific water-soluble polymer. That is, in general, when an epoxy group-containing monomer is added to an aqueous system, in the case of the method of the present invention, a specific water-soluble polymer present in the polymerization system and the action of stirring etc. combine to form 1.
This prevents the agglomeration of the polymer and makes it possible to obtain uniform spherical polymer particles.

The water-soluble polymer present in the polymer thread, which is a particularly important component (lO) in this polymerization method, includes single 3f units [component A] consisting essentially of an ethylenically unsaturated carboxylic acid or a salt thereof. It is necessary to use a water-soluble polymer containing a monomer unit (component B) consisting of ethylenically unsaturated nurphonic acid or its salt, and finally the above-mentioned A
Although any water-soluble polymer obtained by any method can be effectively used in the present invention as long as it has both components A and B, in general, an ether of acrylic acid or methacrylic acid is used. There are also methods such as hydrolyzing a copolymer made by copolymerizing unsaturated ethyl carboxylates such as the above to introduce component A into the polymer, or introducing component B by nurphonization of the polymer. Needless to say, I can be hired.

In addition, the composition ratio of component A and component B in such a water-soluble polymer varies slightly depending on the copolymerization ratio of G (M) A and the types of other monomers, and cannot be uniquely limited (11). Although it is difficult, generally A component/B component = 60
It is desirable that it is in the range of ~80%/70~20%,
Although there is no particular restriction on the degree of polymerization of such a polymer, in the practical molecular M range, it is more advantageous to use one with a small molecular weight in terms of handling and to prevent the coalescence of the spherical polymer produced. effective against moreover,
Depending on the type of other monomers, A
A better spherical polymer may be obtained by using a water-soluble polymer obtained by copolymerizing or graft polymerizing a small amount of a hydrophobic monomer such as vinylidene chloride in addition to component B and component B.) Therefore, such polymers may also be used as component A in the present invention, such as unsaturated luponic acids such as acrylic acid, methacrylic acid, vinyl acetic acid, and crotonic acid, and their salts; maleic acid, fumaric acid, itaconic acid, and aconite. Examples include unsaturated polycarboxylic acids such as citraconic acid and mesaconic acid, and their salts, but monomer units consisting of methacrylic acid and its salts are particularly preferred from the viewpoint of forming spherical polymers. In addition, as component B, sulfonated unsaturated hydrocarbons such as nuthyrene, methacrylic acid, methacrylic acid, and salts thereof; ≠
Nurphoalkylene ethers of acrylic acid or methacrylic acid and salts thereof, such as nurfoglovir methacrylate, can be mentioned.

Note) Although it is difficult to specify the amount of water-soluble polymer used, it is 5% by weight based on the monolithic polymer.
It is desirable to use the above. In addition, 1. Particularly good results can be obtained by using the above-mentioned water-soluble polymer in combination with a polymerization degree of 500 to 2% by weight.

The oil-soluble radical polymerization initiator (13) can be employed without any limitation as long as the object of the present invention is achieved, but the following azo compounds or organic polymers are preferred. Examples include oxides. For example, as an azo compound, 2,2'-azobifisoptilonitrile, 2.2'-azobinu (2,4-dimethylvaleronitrile), 2.2 '-azobis(2-methylcapronitrile), 2,2'-azobis(2,3,3-)limethylputyronitrile], 2,2'-azobis(214+
4-trimethylvaleronitrile), 2,2-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-ethoxyvaleronitrile)
), 2,2'-azobinu (2,4-dimethyl-4-
Examples of organic peroxides include acetyl peroxide, globionyl peroxide, imbutyryl peroxide, octanoyl peroxide, and decanoyl peroxide. , lauroyl peroxide, 3,
5゜(14) Diacyl peroxides such as 5-trimethylhexanoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, di-2-functional f/l/hexyl oxydicarbonate; t-butyl peroxide Peroquinene ethers such as oxyisobutyrate, t-butylperoxypiparate, t-butylperoxydisodocaate, and 7-butylperoxylaurate can be used. Of course, two or more of the above oil-soluble radical polymerization initiators can also be used in appropriate combination. Although it is difficult to define the amount of the initiator to be used, it is generally 0.2 to 2
．． It is used within the range of 0% by weight.

Regarding the pH of the polymerization system, if the pH is too strong, it will cause ring opening of the Epoquin group during the polymerization reaction, and if the pH is too strong, it will cause hydrolysis of the produced polymer.
It is necessary to set it within the range of 2 to 9, preferably 2 to 7.

In addition, the (15) particle size of the final bead-like polymer is almost uniquely determined by the size of the epoxy group-containing spherical polymer, and plays an important role in adjusting the particle size of the spherical polymer. The stirring conditions need to be changed depending on the shape of the blades, the presence or absence of baffles, the desired particle size, etc., and are difficult to define unambiguously, but the stirring speed is approximately 50 to 500 r, p, m, etc. It is necessary to set it within the range. In addition, as for the shape of the blade, a paddle shape or a Coupin blade is suitable because it is easy to obtain a uniform particle size distribution.

Note that the polymerization temperature depends on the type of opening agent, but the higher the temperature, the ring-opening reaction of the epoxy group or a part of the monomer will be emulsified and cause emulsion polymerization, resulting in a latex-like polymer. In order to avoid problems such as formation of fine polymers, a temperature range of approximately 80°C or lower, preferably 40 to 70°C is recommended.

In addition, as the polymerization medium, it is desirable to use industrial water, but if desired, a water-miscible organic solvent may also be coexisted.
It does not depart from the present invention to coexist electrolyte salts.

The a(M)A-based spherical polymer thus obtained has a particle size of approximately 10μ or more, and although the polymer has a gel moisture content of 20% or less, it is insoluble in solvents. It is presumed that some of them are ring-opened and intramolecular or intermolecular crosslinks are introduced together with hydrophilic groups.

Approximately 10μ produced according to such polymerization method is then
A spherical polymer having a particle size of 20% or less and a gel moisture content of 20% or less has a pH of 3 or less, preferably 25 or less, and a temperature of 7oC.
By heat-treating under conditions of 80 C or higher, preferably 80 C or higher, hydroxyl groups are industrially introduced by ring opening of epoxy groups, and the gel moisture content is 30% or higher, preferably 50% or higher. modified into bead-like polymers.

Any of organic acids such as acid and citric acid and malic acid can be used without any limitation.

In addition, the heat treatment time is determined by heat treatment conditions (PH, temperature) (1
7] It is difficult to define it unambiguously, but
It is preferable to keep the amount of residual epoxy groups as small as possible, and it is generally set within the range of 0, T3 to 5 hours.

Furthermore, as an aspect of such heat treatment operation, G(M) A
A method in which the spherical polymer is once separated from an aqueous suspension, washed, dehydrated, and then reslurried in water. 1) A method in which a predetermined amount of acid is directly added to the polymer suspension after polymerization. is also possible.

In this manner, the present invention is capable of providing a hydrophilic (gel moisture content ≧30%) and solvent-insoluble bead-shaped polymer without causing problems in the working environment or safety, and without requiring complicated steps. This is a noteworthy effect.

The bead-shaped polymer according to the present invention can be widely used for various purposes such as a modifier for bookmarks, fibers, films, etc. Among these, the bead-shaped polymer can be used by acylating or modifying a part of the hydroxyl groups. Liquid Chroma (18) can be suitably used as a gel for tofuphy after alkylation.

EXAMPLES The present invention will be described below in more detail with reference to Examples, but the scope of the present invention is not limited in any way by the description of these Examples. In the examples, parts and ladle fractions are expressed on a weight basis unless otherwise specified. In addition, after removing the gel moisture content, the weight (Wl) was measured,
Next, the polymer particles were dried and the weight after drying (W2) was measured, and was determined by the following formula.

2 Example 1 Methacrylic acid/py sodium tyrene sulfonate = 707
20 parts of a water-soluble polymer of No. 30 and pvA (degree of polymerization 1000
, degree of tenization: 87%) was dissolved in 778 parts of water, and the solution was charged into a polymerization tank (19) equipped with a paddle-type stirrer. 2.2-Azobinu (2,4-dimethylvaleroni) will be added to 200 copies of VC and GMA next! J/l/)
2 parts were dissolved and charged into a polymerization tank, and the stirring conditions were changed as shown in Table 1 below to polymerize at 60'C x 2 hours (PH
=3).

The gel moisture content of each of the spherical polymers (A II to ■) was measured and found to be 11%.

Next, the spherical polymer of jllllIll was filtered and washed, re-nullified in water adjusted to P1 (= 1.5) with nitric acid, and heated at 80°C for 3 hours. As a result, water-swollen bead-shaped polymer (A) was obtained.

The gel moisture content of this polymer (A) was 83%. In addition, since neither of the polymers (black and A) dissolves in hot water at 130°C, nor does it dissolve in organic solvents such as methyl ethyl chloride, which is the solvent for GMA.
The cross-linked intermediates of 150 mesh and 650 mesh were taken out and packed into a glass column with an inner diameter of 15 (7) x height of 30 mm, and their performance as gels for liquid chromatography was evaluated. When 0.5 cc of an aqueous solution containing 5% each of NaC and Na5CN was loaded into the column as a sample, and deionized water was used as the eluent and the elution rate was 60 cc/hour, 1L + acl was 22.5 acs N.
a5CN showed a concentration peak at an elution volume of 3600, and was almost completely separated.

Example 2 The spherical polymer (Ill) produced in Example 1 was dispersed in a formic acid aqueous solution, and the acidic heat treatment conditions (PH1 temperature, time) were changed as shown in Table 2 below to form four types of beads. Polymer (B-E) was produced. The results of measuring the gel moisture content are also listed in Table 2 (2).

From the above table of Table 2, it is understood that by employing the acidic heat treatment conditions according to the present invention, the desired bead-shaped polymer can be advantageously provided.

In addition, polyethylene glycol (average molecular J
i12000), using an aqueous solution containing 5% each of ammonium sulfate,
When the gel performance of the bead-shaped polymer (D) was evaluated in the same manner as in Example 1, polyethylene glycol was 16.
50 parts% ammonium sulfate showed a concentration peak at a position of 29 cc, and separation was almost complete.

Example 3 (22) Same as Example 1 (All) except that 20 parts of triethylene glycol dimethacrylate and 1 part of benzoyl peroxide were used as an oil-soluble radical polymerization initiator, and the polymerization degree was set to 70'C. When polymerized, a spherical polymer with an average particle size of 55μ (1'l, gel moisture content: 16%) was obtained.
was generated.

Next, 80 parts of formic acid was added to the polymerization solution (PH = 16).
After heat treatment at 95° C. for 3 hours, a water-swollen bead-like polymer (F, gel moisture content: 65%) was obtained.

Separation ability was evaluated in the same manner as in Example 1 for an aqueous solution sample containing 5% each of macho acid, common salt, sodium nitrate, and soda rhodin, and the elution curve shown in FIG. 1 was created.

[Brief explanation of the drawing]

FIG. 1 shows the elution curve determined from Example 3. Liang 1 Ranji San Hong) No. ([procedural amendment (method) % formula % ■, case description 1988 Patent M No. 108422-2, title of invention Bead-shaped polymer and method for producing the same 3, amendment Relationship with the case of the person who filed the patent application Address of the patent applicant: 2-2-8 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture 1982
September 7, 2016 (Delivery date: September 27, 1982) 5. Subject of amendment (1) Application (2) Full text of specification (no amendments to drawings) (2) 6. Contents of amendment

Claims (1)

[Claims] 21. Polymerizing glycidyl acrylate or glycidimethacrylate alone or 1'i a monomer mixture consisting of 50% by weight or more of the above monomer and the balance consisting of at least one other monomer. A bead-shaped polymer having a gel moisture content of 60% or more and having a hydroxyl group introduced by ring-opening of an epoxy group, and being insoluble in solvents. 2. The bead-shaped polymer according to claim 1, wherein the particle size of the polymer is 10 μm or more. 3. Glycidyl acrylate or glycidyl acrylate 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 ethylenically unsaturated carboxylic acid or a salt thereof and a monomer unit consisting of an ethylenically unsaturated nurphonic acid or a salt thereof, in the presence of a water-soluble polymer (2) and an oil-soluble radical polymerization initiator, at a pH of 2 to 9, and A method for producing a bead-shaped polymer, which comprises carrying out aqueous suspension polymerization at a stirring rate of 50 to 500 r, p, m, followed by heat treatment at a pH of 3 or lower and a temperature of 70° C. or higher. 41. - The manufacturing method according to claim 3, wherein the water-soluble polymer is used in an amount of 5% by weight or more based on the monomer. 5. The polymerization system has a polymerization degree of 500 to 2000 and a Nan preparation of 85.
4. The method of claim 3, wherein ~95% polyvinyl alcohol is present. 6. The manufacturing method according to claim 3, wherein the polymerization is carried out at a temperature of 80° C. or lower. The manufacturing method according to claim 3, wherein the heat treatment is performed for 1019 to 5 hours.