JPS6197301A - Production of spherical hydrophilic resin having porous surface - Google Patents

Abstract

PURPOSE:To obtain the titled resin useful as, e.g., a support for immobilizing enzymes or a hydroscopic material stably in good efficiency, by polymerizing an aqueous solution of a water-soluble ethylenically unsaturated monomer suspended by dispersion in a hydrophobic solvent inert to polymerization in the presence of a specified dispersant. CONSTITUTION:A dispersant mixture (B) is obtained by adding a polyoxyalkyl ene monoether-type hydrophobic group-containing oil-soluble noionic surfactant to a sorbitan fatty acid ester of a HLB of 3nu9 so that the resultant HLB may be adjusted to 6-10. 1pt.wt. 15-80wt% aqueous solution of a water-soluble ethylenically unsaturated monomer (A) [e.g., (meth)acrylic acid] is suspended by dispersing in 1-4pts.wt. hydrophobic solvent inert to polymerization such as an aliphatic or alicyclic hydrocarbon of a b.p. of30-200 deg.C in the presence of 0.05-10wt%, based on component A, component B. A water-soluble radical polymerization initiator (e.g., potassium persulfate) is added to the dispersion and dissolved and this dispersion is subjected to W/O suspension polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a spherical hydrophilic resin. More specifically, W1011 in the presence of a specific dispersant
The present invention relates to a manufacturing method capable of stably obtaining a spherical hydrophilic resin with a porous resin surface by triturbid polymerization.

[Conventional technology]

Conventionally, a method using W10 suspension polymerization has been known as a method for producing hydrophilic resins from water-soluble ethylenically unsaturated monomers (Japanese Patent Publication No. 34-10644).
/ 0111 In order to stably obtain a hydrophilic resin by turbid polymerization, the type of dispersant to be selected is an important factor. That is, the function of the dispersant during W10 suspension polymerization 1iW1
Since the effect is to make the type 0 suspension Yasuo, the particle size and morphology of the resulting resin are affected by the type of dispersant.Many proposals have been made regarding the type 0 dispersant. Examples of dispersants for suspension polymerization of water-soluble ethylenically unsaturated monomers such as sorbitan fatty acid esters, fatty acid monoglycerides, cellulose esters, and cellulose ethers have been proposed (
Tokuko Sho 54-30710. Japanese Patent Publication No. 55-7825).

[Problem that the invention seeks to solve]

The above dispersants can provide a stable W10 suspension, therefore all the obtained hydrophilic resins have a spherical morphology with a smooth surface.

The main uses of hydrophilic resins obtained from water-soluble ethylenically unsaturated monomers include water-absorbing or hygroscopic materials, enzyme-immobilized supports, chelate resins, and packing materials for powder chromatography. In this case, a resin having a large surface area and a porous surface is preferable from a resin having a spherical smooth surface in terms of absorbency and the like.

Considering these circumstances, a hydrophilic resin with a smooth surface and spherical morphology manufactured using a dispersant that provides stable W10 suspension fully meets the requirements for achieving the original purpose. It's hard to say.

As a method for obtaining a hydrophilic porous resin, an ethylenically unsaturated monomer is polymerized in the presence of a polymerization-inactive, easily volatile or easily eluted compound using a water-soluble polymerization method or a bulk polymerization method. However, a method has been proposed in which easily volatile or easily leached compounds are removed after drying and pulverization.

This method involves complicated steps such as pulverization and removal of easily eluted compounds, and cannot be said to be an industrially efficient manufacturing method. Therefore, the development of an industrially efficient method for producing a single-surface porous hydrophilic resin is eagerly awaited.

[Means for solving problems]

In order to solve the above problems, the present inventors conducted intensive studies to stably and efficiently obtain a surface-porous spherical hydrophilic resin. By using a mixed dispersant that is a mixture of sorbitan fatty acid ester and an oil-soluble nonionic surfactant,
The present invention was completed by discovering that a hydrophilic resin having a spherical shape and a porous resin surface can be stably obtained. As a dispersant in W10@turbidity polymerization in which an aqueous solution of a water-soluble ethylenically unsaturated monomer is suspended and dispersed, and the ethylenically unsaturated monomer is polymerized using a water-soluble radical polymerization initiator. Provided is a method for producing a superficially porous spherical hydrophilic resin characterized by using a mixed dispersant containing a sorbitan fat having an HLB of 3 to 9 and a bo-11 oxyalkylene monoether type nonionic surfactant added thereto. It is something.

Polymerization-inert and hydrophobic solvents that can be used in the present invention include those that do not inhibit radical polymerization and are immiscible with water.

All organic solvents are used. Considering the removal of polymerization heat and drying of the obtained resin, the boiling point is 30 to 20.
Aliphatic hydrocarbons or alicyclic hydrocarbons at 0°C are preferred. Special K, normal hexane or cyclohexane are preferably used.

The dispersant used in the present invention is a sorbitan fatty acid ester with a good dispersibility of Hr, +B3 to +9, mixed with a polyoxyalkylene monoether type (dispersible nonionic surfactant), and the HLB of the mixed dispersant is Any combination of surfactants may be used as long as the number is in the range of 6 to 10. The nonionic surfactants used in the present invention include surfactants having a hydrophobic group with a polyoxyalkylene monoether structure. Any oil-soluble one may be used.For example, polyoxyalkylene monononylphenol ether, polyoxyalkylene monolacrylate, etc. may be used.Polyoxyalkylene may be derived from different types of oxyalkylene even if it has a single composition. The composition may be a mixed composition, and the structure may be random or block-like.

A feature of the present invention is that, in W10 suspension polymerization, sorbitan fatty acid ester with good dispersibility is used in combination with a nonionic surfactant that has an aggregating effect. A resin having a spherical morphology with a porous surface can be obtained. When only sorbitan fatty acid ester is used as a dispersant, only a resin with one surface is clear can be obtained, whereas when only an oil-soluble nonionic surfactant is used, the polymerized system aggregates and forms a gel. It turns into Stable suspension can be achieved by using a mixed dispersant in which an oil-soluble nonionic surfactant is mixed with sorbitan fatty acid ester, which has a good dispersing power of HLB 3 to 9, and the HLB of the mixed system is 6 to 10. A dispersed state is obtained, and 1
A resin with a porous surface can be obtained.

The appropriate amount of the mixed dispersant to be used is usually 0.03 to 10% by weight, preferably 0.03 to 5% by weight, based on the monomer.
The amount is 0% by weight.

According to the method of the present invention, no matter what kind of water-soluble ethylenically unsaturated monomer is used, a spherical resin with a porous surface can be produced by W10% turbid polymerization using the mixed dispersant of the present invention. Obtainable.

Examples of water-soluble ethylenically unsaturated monomers include (meth)acrylic acid, alkali metal salts of (meth)acrylic acid,
Ammonium salts, (meth)acrylamide and N-substituted (
meth)acrylamide M, 2-(meth)acryloylethanesulfone and its derivatives, styrene sulfonic acid and its salts, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and their 4
Examples include grade ammonium salts. One or more of these monomers can be used in any combination. Further, other water-soluble monomers can be copolymerized within a range that does not impair hydrophilicity.

Furthermore, if necessary, a water-soluble crosslinking agent having two or more polymerizable unsaturated groups, such as methylene bisacrylamide, or two or more that can react with the functional group of the ethylenically unsaturated monomer. It is also possible to carry out a crosslinking reaction during or after the (co)polymerization of the monomers using a water-soluble crosslinking agent 1 having a functional group such as ethylene glycol diglycidyl ether.

What is the monomer concentration of the monomer aqueous solution in the present invention?

It can be changed within a wide range, but generally 13 to 80
% by weight is preferred.

Further, the ratio of the above monomer aqueous solution to the amount of the polymerization-inactive and hydrophobic bath medium can be varied over a wide range, but is usually in the range of 1:1 to 1:4 in terms of volume ratio. is suitable.

For monomer polymerization, a water-centered radical polymerization initiator 1
For example, peroxides, hydroperoxides, or azo compounds are used in known amounts. These polymerization initiators can be used in combination of two or more types, and furthermore, chromium ions, sulfites, hydroxylamine,
It is also possible to add hydrazine or the like and use it as a redox polymerization initiator.

[Effect]

Although the mechanism of action in the production method of the present invention is not necessarily clear, the polymer dissolving power of the oil-soluble nonionic surfactant dissolves a portion of the polymer particles produced by polymerization, and the minute polymer particles are fused. , due to the balance between the agglomeration action and the dispersion power of the highly dispersible sorbitan fatty acid ester, which provides stable particles, or the oil-soluble nonionic surfactant forms a monomer sorbitan protective layer of the sorbitan fatty acid ester. It is surmised that the effect of partially collapsing and dissolving a portion of the monomer in the oil layer provides a resin with a spherical shape and a porous surface.

〔Example〕

The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 In a 500 AT 4-neck round bottom flask equipped with a stirrer, a reflux condenser, 1 dropping door, and a nitrogen gas inlet tube, 7250 ml of n-hex, HL B 4.7 (nosorbitan monostearate) 0.4 y and HL B Polyoxyethylene monononylphenol ether of 7.6 (KO average number of added moles: 3 moles) O, a mixed dispersant of t (HL
B6.6) was charged, nitrogen gas was blown in to drive out dissolved oxygen, and the temperature was raised to 75°C.

Separately, in a flask, add 98% caustic soda to 40 tons of ion-exchanged water while cooling the acrylic d30F from the outside.
．． It was neutralized with a solution of 4F. Next, 0.11 of potassium persulfate was added and dissolved, and then hydrogen gas was blown into the aqueous solution to remove oxygen present in the aqueous solution. This solution was added dropwise to the above-mentioned 4-hole flask over 30 minutes to polymerize. After the polymerization was completed, the temperature was maintained at 75°C and the reaction was continued for an additional 1 hour. After that, n-hexane as a heating medium is distilled off under reduced pressure, and a portion of the remaining swollen polymer is transferred to a vacuum line at 80 to 100°C.
A spherical hydrophilic resin with a porous surface and a center particle size of 70 to 200 pm□ was obtained. The amount of deposits in the reaction tank was 0.14 v.

Example 2 In place of the mixed dispersant of nrubitan monostearate and polyoxyethylene monononylphenol ether in Example 1, solpitan monolacrate of HLB 8.6 was used.
6f and HL B 5.8 polyoxyethylene monononylphenol ether (go average added mole number 2 moles)
Polymerization was carried out in the same manner as in Example 1 except that a mixed dispersant (HLB 7.7) with 0.3 Ta. The amount of deposits in the reaction tank was 0.32.0 Example 3 The same procedure as in Example 2 was carried out. However, since it is an ethylenically unsaturated monomer water bath, sodium vinyl sulfonate 251 was used instead of sodium acrylate, and this was mixed with ion-exchanged water 75
When a water-soluble monomer dissolved in F was used, a surface-porous spherical hydrophilic resin with a center particle diameter of 8 to 200 μm was obtained.

The amount of deposits in the reaction tank was 0.8r.

Example 4 Polymerization was carried out according to Example 1. However, as a mixed dispersant, sorbitan monopalmitate (1iL B6.
7) o, at and polyoxyethylene monolawallyl ether (HLB 9.7. KO average added mole number 5 moles)
Mixed dispersant (HL B 7.
5), the monomer was dimethylaminoethylmethacryle) 20% water-soluble d85F, and the polymerization initiator was 2,2'-azobis(2,4-dimethylvaleronitrile) (M product name V- 65, manufactured by Wako Tsumugi Co., Ltd.)
When polymerization was carried out using o.1st, the center particle size was 7.
A spherical hydrophilic resin with surface porosity of 0 to 150 μm was obtained.

The amount of deposits in the reaction tank was 0.72.

Comparative Example 1 Polymerization was carried out in the same manner as in Example 1. However, as a dispersant, sorbitan monostearate (HL B 4.7) 0.
When only 6f was used, a fine hydrophilic resin with a center particle size of 3° to 70 μm and a smooth surface and a spherical shape was obtained. The amount of deposits in the reaction tank was 1.3r.

Comparative Example 2 Polymerization was carried out according to Example 1. However, in addition to the dispersant, 0.6 t of sorbitan monostearate with an HLB of 4.7 is used.
and polyoxyethylene monononylphenol ether with HL B 7.6 (IO average added mole number 5.0 moles)
When polymerization was carried out using a mixed dispersant (HLB5.4) mixed with 0.2 t, the center particle size was 50 to 80 μm.
A fine hydrophilic resin with a smooth surface and a spherical shape was obtained. 2. Proteins in the reaction tank. It was Of.

Comparative Example 3 Polymerization was carried out according to Example 1. However, when only polyoxyethylene monononyl phenol ether (50 average addition -ryl number 3.0 mol) with HL B 7.6 was used as a dispersant, the 1-polymerization system gelled.

〔Effect of the invention〕

In the present invention, W/'O&? "FTI polymerization method is adopted. Using this method, an ethylenically unsaturated monomer is polymerized into minute droplets in an inert and hydrophobic bath medium using a mixed dispersant. When polymerizing by dispersing and suspending, the heat generated during one polymerization can be removed by refluxing the solvent, and furthermore, when stirring is stopped after the polymerization is completed, the 9 water-containing resin that is formed precipitates, which can be removed by decantation, filtration, or centrifugation. There is an advantage that the resin can be easily separated by means such as separation.

The hydrophilic resin produced according to the present invention has a spherical shape with one surface porosity, and can be easily separated, so that it can be used in a wide variety of applications.

For example, it can be widely used as an enzyme-immobilized support, a chelate resin, and a water-absorbing or moisture-absorbing material.

Furthermore, as in the present invention, a mixed dispersant prepared by adding a polyoxyalkylene monoether type nonionic surfactant to a sorbitan fatty acid ester with an HLB of 3 to 9 so that the HLB becomes 6 to 10 may be used. In particular, 1
There is also the advantage that the amount of polymerized material adhering to the polymerization apparatus, stirrer, etc. can be kept to an extremely small amount, and the polymerization apparatus can be used continuously.

Applicant's agent: Kaoru Furuya Procedural amendment (spontaneous) December 5, 1980 1, Case indication Japanese Patent Application No. 59-218146 2, Name of the invention Method for manufacturing surface-porous spherical hydrophilic resin 3, Relationship with the case of the person making the amendment Patent applicant (091) Kao Soap Co., Ltd. 4, agent 1-3 Nihonbashi Yokoyama-cho, Chuo-ku, Tokyo Nakai Building Detailed explanation of the invention column 6 of the specification, contents of the amendment ( 1) Change “75°C” to “65°C” on page 11, line 6 of the specification.
” and corrected / :shi (1)
Page 11, line 14, “75℃” was corrected to “65℃” (1) Page 13, lines 8-9 “2,2°-Azobis (2
, 4-dimethylvaleronitrile)" was corrected to "2,2°-azobis(2-amidinopropane) hydrochloride" (1) p. 13, line 10, rV-65J was corrected to "ry-50".

Claims (1)

[Claims] 1. A water-soluble ethylenically unsaturated monomer aqueous solution is suspended and dispersed in a polymerization-inert and hydrophobic solvent in the presence of a dispersant, and a water-soluble radical polymerization initiator is used. In W/O suspension polymerization in which ethylenically unsaturated monomers are polymerized, a mixed dispersant is used as a dispersant, in which a polyoxyalkylene monoether type nonionic surfactant is added to a sorbitan fatty acid ester with an HLB of 3 to 9. A method for producing a surface-porous spherical hydrophilic resin, characterized by using the following. 2. Production of a superficially porous spherical hydrophilic resin according to claim 1, wherein the polymerization inert and hydrophobic solvent is an aliphatic or alicyclic hydrocarbon having a boiling point in the range of 30 to 200°C. Method. 3. The method for producing a surface porous spherical hydrophilic resin according to claim 1, wherein the mixed dispersant has an HLB in the range of 6 to 10.