JPH11158230A - Manufacture of hydroxyl-containing porous resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a porous resin having a narrow particle size distribution of secondary particles by introducing with pressure a monomer solution comprising divinylbenzene and a certain vinylbenzyl oxyalkanol derivative, a polymerization initiator and an organic solvent into an aqueous medium containing a surfactant through a porous glass membrane having a uniform pore size, and then carrying out a polymerization. SOLUTION: A monomer mixture comprising 15-97 wt.% of divinylbenzene and 3-30 wt.% of a vinylbenzyl oxyalkanol derivative represented by the formula (wherein (n) is 2-16), 5-50 wt.% of a polymerization initiator and an organic solvent which is hardly water-soluble, does not involve the polymerization, dissolves the monomer mixture but dose not dissolve a copolymer to be formed are mixed to obtain a monomer solution. The monomer solution is introduced with pressure and dispersed or suspended into, an aqueous medium containing an anionic or a nonionic surfactant through a group glass membrane, and then polymerized.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a hydroxyl group-containing porous resin. The hydroxyl group-containing porous resin obtained by the present invention is a material useful as a column filler, various adsorbents, a carrier, and the like. obtain.

[0002]

2. Description of the Related Art Hitherto, a divinylbenzene-styrene-based porous resin has been used as a filler for analytical and preparative columns, a carrier for enzymes and catalysts, taking advantage of its excellent mechanical strength and chemical stability. Alternatively, it is researched, developed, and used in various applications and fields, such as adsorption carriers for various useful substances. Divinylbenzene-styrene porous resin is usually obtained by suspension polymerization, and when observing the surface or inside of apparent particles (hereinafter, referred to as secondary particles) of the obtained resin using an electron microscope or the like, It can be seen that fine particles (hereinafter, referred to as primary particles) having a size of about 10 to 100 nm are strongly aggregated. In other words, the gap between the aggregated primary particles and the primary particles is a space in which the organic solvent was present during the polymerization, and when the primary particles themselves are a high-order cross-linked resin, almost no space exists. Is insoluble in organic solvents and basically hardly swells.

As a specific method for producing such a divinylbenzene-styrene-based porous resin, for example, a monomer mixture containing divinylbenzene and styrene, a polymerization initiator, and a hardly water-soluble resin which does not participate in the polymerization reaction. In addition, a method is known in which a monomer solution mixed with an organic solvent in which the monomer mixture dissolves but a copolymer obtained therefrom does not dissolve is subjected to suspension polymerization in an aqueous medium [for example, Journal of Applied Polymer Science]. (J. Appl. Polym. Sci.) Vol. 23, 92
7 (1979), Angewant. Makromol. Chem.
80, 31 (1979)]. Generally, in this type of conventional suspension polymerization, the diameter of the secondary particles is usually 50 μm.
A porous resin of about m to 2 mm is obtained. Before the polymerization, as a step of dispersing or suspending the monomer solution in an aqueous medium, a step of performing the step under high-speed stirring using a homogenizer or a homomixer (hereinafter, referred to as a microsuspension step) is employed. In this case, a porous resin having a secondary particle diameter of usually about 0.5 to 50 μm is obtained. However, since the secondary particles obtained by these methods do not have a uniform particle diameter, they have a wide particle size distribution, and a classification operation is required to provide them for various uses.

A divinylbenzene-styrene-based porous resin utilizes the excellent mechanical strength and chemical stability of the resin matrix to introduce a functional group on the surface of the primary particles or in the vicinity thereof, and to use useful substances. Has attracted attention in various applications and fields as a so-called functional porous resin obtained by imparting new functionality by chemically modifying. Conventionally, there are basically two known methods for introducing a functional group: (i) an aromatic ring site of a synthesized divinylbenzene-styrene-based porous resin and a residual vinyl group; (Ii) In addition to divinylbenzene and styrene monomer, a monomer having a desired functional group (hereinafter referred to as a functional group-containing monomer) is previously mixed. , A method of polymerizing this. However, in the method (i), the chemical reaction is essentially solid-
Since the reaction is carried out between liquids, there are various disadvantages that the reaction conditions are often severe, the conversion of the reaction is extremely poor, and the secondary particles are destroyed during the reaction. Also in the method (ii), it is difficult to efficiently arrange and orient the functional group site of the used functional group-containing monomer on or near the surface of the primary particle.
With the disadvantage that most of the functional group-containing monomers are present inside the area of the monomer mixture, and as a result, the functional group sites are buried inside the cross-linked resin matrix, and their functions cannot be sufficiently performed. I have. That is, the higher the degree of crosslinking with divinylbenzene, the more the swellability of the primary particles in the solvent is extremely reduced. Therefore, this drawback is a serious problem in designing and synthesizing a functional porous resin. I have.

[0005]

Accordingly, the present invention provides a method for efficiently arranging hydroxyl groups on or near the surface of primary particles.
An object of the present invention is to provide a method for producing a porous resin which can be oriented and has a narrow particle size distribution of secondary particles.

[0006]

In view of the importance in the technical development of a functional porous resin or a functional group-containing porous resin, the present inventors have attempted to overcome the above-mentioned drawbacks in the conventional production method. , Diligently studied. as a result,
As the functional group-containing monomer used in the polymerization method (ii), a vinylbenzyloxyalkanol derivative represented by the following general formula (1) having a strong or strong affinity for an organic solvent is used. The monomer solution containing divinylbenzene is dispersed or suspended in an aqueous medium by pressing it into an aqueous medium containing an anionic or nonionic surfactant through a porous glass membrane having a uniform pore size. (Hereinafter referred to as a membrane emulsification step), when the polymerization is carried out, during the polymerization, the derivative is "polymer + monomer" and "organic solvent"
Are predominantly present near the interface between the two regions, and the hydroxyl groups derived from the derivative are arranged and oriented on or near the surface of the primary particles of the resulting resin, and the particle size distribution of the secondary particles The inventors have found that a narrow porous resin can be obtained, and have reached the present invention.

That is, the present invention relates to divinylbenzene and a compound represented by the general formula (1):

[0008]

Embedded image

(Wherein, n represents an integer of 2 to 16), a monomer mixture containing a vinylbenzyloxyalkanol derivative represented by the formula (I), a polymerization initiator, A monomer solution obtained by mixing an organic solvent in which a monomer mixture dissolves but a copolymer obtained therefrom does not dissolve is passed through a porous glass membrane having a uniform pore size to an anionic or nonionic interface. The present invention relates to a method for producing a hydroxyl group-containing porous resin, which comprises polymerizing after being dispersed or suspended by being pressed into an aqueous medium containing an activator.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, raw materials and a polymerization step will be described in detail with respect to a method for producing a hydroxyl group-containing porous resin of the present invention.

The monomer mixture used in the polymerization of the present invention is
It comprises divinylbenzene and a vinylbenzyloxyalkanol derivative represented by the general formula (1).

As divinylbenzene, generally available commercially available divinylbenzene having a purity of about 50 to 60% may be used as it is, or may be used after being purified by distillation. Contains about 50-40% ethylvinylbenzene as an impurity. Of course, if available, high purity ones can be used. In addition, divinylbenzene mainly has meta and para isomers, and in the present invention, a mixture of these isomers may be used, or each isomer may be used alone.

The vinylbenzyloxyalkanol derivative represented by the general formula (1) may be a mixture of meta and para isomers, or each isomer alone. Further, n in the formula is an integer of 2 to 16.
When n is less than 2, the arrangement of hydroxyl groups on the resin surface
When the orientation is reduced and n is larger than 16, the polymerization rate is decreased and the specific surface area of the obtained resin is undesirably decreased. From these points, n is preferably an integer of 4 or more, and more preferably 12 or less. The portion of the alkylene chain of the vinylbenzyloxyalkanol derivative represented by the general formula (1) is generally called a spacer, and plays an important role in affinity with an organic solvent such as a hydrocarbon solvent or an alkanol solvent. I am carrying it.

The vinylbenzyloxyalkanol derivative represented by the general formula (1) can be produced by a known method [for example, Journal of American Chemical Society (J. Am. Chem. So.)
c. ) 112, 6723 (1990)]. That is, the general formula (2):

[0015]

Embedded image

(Wherein n represents an integer of 2 to 16), which is obtained by treating an alkyl diol represented by the formula (1) with sodium hydride or the like to form an alkoxide, and subsequently reacting the alkoxide with vinylbenzyl chloride. it can. In addition, vinylbenzyl chloride is generally available as a mixture of meta and para isomers, but in the present invention, it can be used as a mixture as it is. Of course, the meta or para isomers may be used alone. Further, the vinylbenzylalkanol represented by the general formula (1) improves the reaction selectivity to the target product by appropriately selecting the molar stoichiometric ratio of the alkyl diol, sodium hydride, and vinylbenzyl chloride. be able to.

The contents of divinylbenzene and the vinylbenzyloxyalkanol derivative represented by the general formula (1) contained in the monomer mixture are determined based on the total weight of the monomers of 100% by weight. Usually, the content of the vinylbenzyloxyalkanol derivative represented by the general formula (1) in the monomer mixture is about 3 to 30% by weight, and the remainder contains divinylbenzene and the like. Since the vinylbenzyloxyalkanol derivative represented by the general formula (1) introduces a hydroxyl group on or near the resin surface, its content is usually 3% by weight or more based on the total weight of the monomers. In particular, it is preferably at least 5% by weight. Also,
The content of the derivative is preferably set to 30% by weight or less of the total weight of the monomers, since the reduction in the polymerization rate and the decrease in the surface area of the obtained resin can be suppressed.

According to the production method of the present invention, 75% or more of the used vinylbenzyloxyalkanol derivative represented by the general formula (1) can be arranged and oriented on the surface of or near the primary particles of the resin. Yes (n in general formula (1)
Is a vinylbenzyloxyalkanol derivative of 4 or more). In other words, the amount that can be arranged and oriented on or near the primary particle surface is limited in space,
It can be said that it is sufficient to use up to 30% by weight of the total weight of the monomers in order to obtain the desired hydroxyl group-containing porous resin.

The monomer mixture may contain an aromatic monovinyl monomer. As the aromatic monovinyl monomer, styrene, methylstyrene, ethylvinylbenzene and the like can be used.
Use more than seeds. As these, commercially available products may be used as they are, or those purified by distillation may be used. Methylstyrene is meta-, para-, α- and β-
In the present invention, a mixture of these isomers may be used, or each isomer may be used alone. In addition, ethyl vinyl benzene
Although there are meta and para isomers, in the present invention,
A mixture of these isomers may be used, or each isomer may be used alone. Further, in the case of ethylvinylbenzene, since a predetermined amount is contained in commercially available divinylbenzene, it is usually used as it is. Of course, if it is available, it is newly added and used. Is also good.

Even when an aromatic monovinyl monomer is contained in the monomer mixture, the content of the vinylbenzyloxyalkanol derivative represented by the general formula (1) is 3%.
To about 30% by weight, and the balance includes about 15 to 97% by weight of divinylbenzene and about 0 to 82% by weight of an aromatic monovinyl monomer. 1 divinylbenzene
If the amount is less than 5% by weight, the specific surface area of the obtained resin is undesirably reduced. From these points, the content of divinylbenzene is preferably at least 20% by weight. Further, the content of the aromatic monovinyl monomer is not more than 82% by weight from the viewpoint of the mechanical strength of the obtained resin. Usually,
In the monomer mixture, 5 aromatic monovinyl monomers were added.
In many cases, the content of divinylbenzene is 92% by weight or more.

The polymerization initiator is not particularly limited as long as it is soluble in the above monomer mixture. Examples include organic peroxides such as benzoyl peroxide and lauryl peroxide, and azo compounds such as azobisisobutyronitrile. The amount of the polymerization initiator to be used is in an arbitrary range depending on the required physical properties of the obtained porous resin and the like, but is usually preferably about 0.5 to 5% by weight of the total weight of the monomers.

The organic solvent to be mixed with the above-mentioned monomer mixture does not participate in the polymerization reaction, is hardly soluble in water, and dissolves the monomer mixture but does not dissolve the copolymer obtained therefrom. With such an organic solvent, the function as a so-called porous solvent can be sufficiently exhibited.

In order to make the arrangement and orientation of the hydroxyl groups on the surface of the primary particles of the porous resin or in the vicinity thereof more effective, the organic solvent is preferably represented by the formula (1). Organic solvents having a good affinity for the vinylbenzyloxyalkanol derivative to be used are preferred. For example, a hydrocarbon solvent having 6 to 12 carbon atoms or an alkanol solvent having 3 to 12 carbon atoms can be used. Specific examples include aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane, decane and dodecane, and alkanol solvents such as butanol, pentanol, hexanol, heptanol, octanol and decanol. Of course, the aliphatic hydrocarbon portion or the like of the organic solvent described above may be of a linear type or a branched type. Further, these organic solvents may be used alone or in combination of two or more. The mixing ratio of the organic solvent and the monomer mixture can be mixed in any range depending on the required physical properties of the obtained porous resin,
Usually, the volume ratio of the organic solvent / monomer mixture is 70 /
It is preferred to mix within the range of 30 to 25/75.

In the present invention, a monomer solution obtained by uniformly mixing the monomer mixture, the polymerization initiator and the organic solvent is mixed with an anionic or nonionic surfactant through a porous glass membrane having a uniform pore diameter. The polymerization is carried out after the step of dispersing or suspending in the aqueous medium by press-injecting it into the aqueous medium containing, that is, the step of emulsifying the membrane of the monomer solution.

The porous glass membrane used in the membrane emulsification step may be any glass membrane having uniform pores with an average pore diameter of about 0.1 to 10 μm. In particular, a glass film prepared from shirasu porous glass is excellent in terms of uniformity of pores and is preferable in the present invention. When a porous glass membrane having an average pore diameter of less than 0.1 is used, it takes a long time to emulsify the membrane, which is not preferable from the viewpoint of industrial production. In addition, the average pore diameter is 10μ
When a glass film having a diameter of more than m is used, it is very difficult to obtain emulsified droplets having a uniform particle size. That is, if the average pore diameter of the glass membrane is about 0.1 to 10 μm, the emulsified droplet obtained by membrane emulsification usually has a particle diameter of about 3 to 10 times the pore diameter of the glass membrane. Moreover, the particle size distribution is very sharp.

As the surfactant contained in the aqueous medium,
Anionic surfactants such as sodium alkylsulfate, sodium alkylbenzenesulfonate and sodium alkylsulfosuccinate, polyoxyethylene alkyl ethers, nonionic surfactants such as polyethylene glycol fatty acid esters, and the like can be used. In the membrane emulsification step, the monomer solution may be in an amount capable of stably existing as emulsified droplets in the aqueous medium, but is usually preferably about 0.05 to 2% by weight in the aqueous medium. The amount of the monomer solution and the aqueous medium is usually from an industrial point of view, and the monomer solution / aqueous medium = 1/10 to 10 by volume ratio.
It is better to carry out in a range of 1/2.

In the membrane emulsification step, the pressure at which the organic phase composed of the monomer solution is pressed into the aqueous phase of the aqueous medium via the glass membrane is such that the desired emulsified droplets are obtained, and are deformed or broken. There is no particular limitation as long as it is within a range that does not cause a drop. Usually, a critical pressure (here, a minimum pressure at which the organic phase can permeate the pores of the glass membrane) is set to 1.
When the pressure is about 0.5 to 1.5 times, emulsified droplets having a very sharp particle size distribution can be obtained stably and with good operability. The temperature at the time of film emulsification is not particularly limited, as long as the temperature at which film emulsification is stable and polymerization does not start is not particularly limited, but the temperature is usually preferably 0 to 60 ° C.

The polymerization conditions and the like after the membrane emulsification step are not different from the conventionally known suspension polymerization. For example, the dispersion or suspension obtained in the membrane emulsification step is heated. The polymerization can be carried out by a general suspension polymerization method. Therefore, a dispersion stabilizer such as a water-soluble polymer often used in ordinary suspension polymerization can be used in order to prevent the emulsion droplets from uniting and aggregating during the polymerization. Of course, during the polymerization, when the reaction proceeds stably without emulsified droplets coalescing or aggregating, it is not necessary to use a dispersion stabilizer such as a water-soluble polymer in combination. When a dispersion stabilizer is used, it may be contained in the aqueous phase from the time of the membrane emulsification step or may be added during the polymerization step. Examples of the water-soluble polymer include generally well-known polyvinyl alcohol, polyacrylamide, polyacrylic acid, gelatin, and the like. There is no particular limitation as long as the amount can be dispersed.

There are no particular restrictions on the polymerization temperature or the polymerization time in the polymerization step, but appropriate conditions may be selected in consideration of the decomposition temperature and half-life of the polymerization initiator, the boiling point of the organic solvent, and the like. Also, the type of polymerization reaction vessel and stirring method,
There is no particular limitation as long as the polymerization can proceed stably without the monomer droplets coalescing or aggregating.
In addition, an inorganic dispersant such as the above-described water-soluble polymer or colloidal silica may be added to suppress coalescence and aggregation of monomer droplets during polymerization, and the type and amount used are not particularly limited. .

The method of isolating, washing and drying the resin obtained by the above polymerization is not particularly limited, and can be carried out, for example, as follows. The resin obtained by polymerization is filtered off by an appropriate method, washed well with hot water to remove a surfactant and a dispersion stabilizer attached to the resin, and further, an unreacted monomer and an organic solvent which is a porous solvent. Washing is sufficiently carried out with acetone, methanol or the like in order to remove water, followed by heating and drying under reduced pressure to obtain a hydroxyl group-containing porous resin.

The hydroxyl group-containing porous resin thus obtained can be evaluated not only for its general physical properties such as specific surface area, primary and secondary particle diameters, but also for its hydroxyl value and functional group orientation ratio (%). It can be characterized by performing physical property evaluation. That is, the amount of the reactive hydroxyl group in the resin can be known from the hydroxyl value. The functional group orientation rate (%) is
The ratio of "the amount of hydroxyl groups existing on or near the surface of the primary particles" to "the amount of hydroxyl groups based on vinylbenzyloxyalkanol represented by the general formula (1) used in the polymerization" is shown.

The hydroxyl group-containing porous resin obtained by the production method of the present invention usually has a high specific surface area of 50 m ² / g or more, a functional group orientation ratio of 75% or more, and 5 to 60 mgK.
It has a hydroxyl value of OH / g. In addition, the hydroxyl group-containing porous resin of the present invention has a spherical and opaque appearance of secondary particles, and the particle diameter thereof is 50 when ordinary suspension polymerization is performed.
In the case of suspension polymerization including a micro-suspension step, it is about 0.5 to 50 μm, and in the case of suspension polymerization including a membrane emulsification step, it is about 0.3 to 100 μm. The size of the primary particles is usually 10 to 10 in any case.
It is about 100 nm.

Further, the hydroxyl group-containing porous resin obtained by the production method of the present invention has a resin matrix of divinylbenzene-
Since it is a styrene-based resin, it has excellent mechanical strength and chemical stability.Of course, it is a useful material as a column filler and various adsorbents, and a carrier by itself. It is possible to chemically secondary-modify with various functional groups and functional substances using a hydroxyl group, and it is very useful as a functional porous resin. Furthermore, since the hydroxyl group is present from the polymer main chain via the alkyl spacer, it is considered that the reactivity inherent to hydroxyl can be sufficiently exhibited, and this secondary modification can be easily performed.

[0034]

According to the production method of the present invention, hydroxyl groups are efficiently arranged and oriented on or near the surface of primary particles,
Moreover, a porous resin having a narrow particle size distribution of the secondary particles can be obtained.

[0035]

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 (suspension polymerization including membrane emulsification step) Divinylbenzene (content (purity) 55%, remaining 45%
Is ethyl vinyl benzene) 51.38 g, styrene 2
5.69 g, 8.56 g of vinylbenzyloxyhexanol (compound of general formula (1) where n is 6), 42.68 g of n-heptane, and 1.71 of azobisisobutyronitrile
An organic phase 1 consisting of a monomer solution in which 3 g (2% by weight of the total amount of monomers) was uniformly mixed was prepared. In addition, polyvinyl alcohol (Poval-2) was added to 630 ml of ion exchange water.
24: Kuraray Co., Ltd.) (12.6 g) and sodium dodecyl sulfate (1.26 g) were added and dissolved to prepare an aqueous phase 2 composed of an aqueous medium. The prepared organic phase 1 and aqueous phase 2 were respectively charged into the organic phase tank 3 and the aqueous phase tank 4 of the membrane emulsification apparatus (manufactured by Ise Chemical Industry Co., Ltd.) shown in FIG. The aqueous phase 2 is circulated through the aqueous phase line 6 by using the circulation pump 11, and then the organic phase 1 is circulated to 0.66 kgf / c using nitrogen gas.
At a pressure of m ² , pressure is applied to the aqueous phase 2 through a porous glass membrane 8 having an average pore diameter of 0.70 μm in a double tube module 7 provided in a circulating aqueous phase line 6 to perform membrane emulsification, An emulsion was obtained. The membrane emulsification was carried out by injecting 120 ml (100 g) of the organic phase 1 over about two and a half hours, and was terminated there. The membrane emulsification was performed while maintaining the temperatures of the organic phase 1 and the aqueous phase 2 at 25 to 30 ° C.

Next, 740 g of the emulsion obtained above
Was charged into a 1 L separable flask, and a stirrer, a thermometer, a nitrogen inlet tube and a cooling tube were set, and the mixture was stirred at about 400 to 500 rpm under a nitrogen gas stream, and the mixture was stirred at 75 to 80 ° C.
The polymerization was carried out for 6 hours while maintaining this temperature. After the polymerization, the mixture was cooled to room temperature, and the obtained resin was separated by filtration, washed well with hot water, then with methanol and acetone, and heated under reduced pressure (about 1 mm / Hg) (7 mm).
(0-80 ° C.) to obtain 57.6 g (yield 86%) of a porous resin.

Examples 2 to 7 In the same manner as in Example 1, except that the charged amount of each monomer or the charged amount of the organic solvent was changed as shown in Table 1, and the film emulsification conditions were changed as shown in Table 2. Polymerization was carried out in exactly the same manner as in Example 1 to obtain a hydroxyl group-containing porous resin.

Comparative Examples 1-2 (Suspension polymerization including microsuspension step) A 1 L separable flask was charged with 600 ml of ion-exchanged water, and 1.50 g of polyvinyl alcohol (Poval-217: manufactured by Kuraray Co., Ltd.) was added thereto. Added and dissolved. Subsequently, 1.647 g of the monomer mixture, the organic solvent and azobisisobutyronitrile shown in Table 1 (2.
(0% by weight), and the mixture was dispersed for 5 minutes at a stirring speed of about 10,000 rpm using a homogenizer (manufactured by IKA). Then replace it with a regular stirrer,
A thermometer, a nitrogen inlet tube and a cooling tube were set, and the dispersion was heated to 75 to 80 ° C. while stirring at about 400 to 500 rpm under a nitrogen stream, and the polymerization was carried out for 6 hours while maintaining this temperature. Was performed. After the polymerization, the mixture was cooled to room temperature, and the obtained resin was separated by filtration. The resin was washed well with hot water, then with methanol and acetone, and reduced under reduced pressure (about 1 mm /
Hg) and dried (70-80 ° C.) to obtain 68.0 g (yield 81%) of a resin.

[0040]

[Table 1]

[0041]

[Table 2]

Tables 3 and 4 show the physical properties of the resins obtained in the examples and comparative examples.

[0043]

[Table 3]

[0044]

[Table 4]

The physical properties of the resins obtained in the respective examples were measured according to the following methods.

Primary particle diameter (nm): From a photograph of a scanning electron microscope (Hitachi, "S-2000"), an arbitrary 100
The size of at least one primary particle was measured, and the number average particle size was calculated.

Secondary particle size (μm): From a photograph of a scanning electron microscope (Hitachi, “S-2000”), an arbitrary 500
The size of at least two secondary particles is measured, and the volume average particle diameter d
v, number average particle diameter dn, dv / d as a measure of particle size distribution
n was calculated.

Specific surface area (m ² / g): Measured using a BET surface area measuring device (“NOVA1200” manufactured by Counterchrome).

Hydroxyl value (mgKOH / g): The neutralization titration method (JIS K0070) was modified as follows. In a flat bottom flask, weigh 1 g of the resin,
An acetylation reagent (25 g of acetic anhydride was placed in a 100 ml volumetric flask, and pyridine was added to make 100 ml.
2.5ml and pyridine 2.5
Then, the mixture was heated in an oil bath at 60 ° C. for 2 hours. next,
This was cooled to room temperature, 1 ml of water was added, and an ultrasonic bath 80
The solution was heated at ℃ for 1 hour to decompose acetic anhydride. After cooling, the inner wall of the flask was washed with 5 ml of ethanol, a few drops of a phenolphthalein solution were added as an indicator, and the hydroxyl value (mgK
OH / g) was calculated.

Incidentally, in the divinylbenzene-styrene resin such as the porous resin in the present invention, since the primary particles are cross-linked to a higher order, acetylation is carried out under the conditions under the conditions of acetylation on the surface of the primary particles or the same. It travels in the vicinity and hardly permeates and reacts inside the particles. Therefore, it can be assumed that the hydroxyl value measured above is based on the hydroxyl group existing on or near the resin (primary particle) surface.

Hydroxyl orientation ratio (%): Calculated by the following equation.

[0052]

(Equation 1)

Here, the amount of hydroxyl groups on and near the surface of the resin (primary particles) was calculated from the above hydroxyl value by the following equation.

[0054]

(Equation 2)

The theoretical hydroxyl group content based on the vinylbenzyloxyalkanol represented by the general formula (1) used was calculated by the following equation.

[0056]

(Equation 3)

[Brief description of the drawings]

FIG. 1 is a schematic view of a membrane emulsifying apparatus used in Examples 1 to 7.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Organic phase 2 ... Water phase 3 ... Organic phase tank 4 ... Water phase tank 5 ... Organic phase line 6 ... Water phase line 7 ... Double tube module 8 ... Porous glass membrane 9 ... ... nitrogen gas line 10 ... pressure gauge 11 ... circulation pump 12 ... nitrogen gas cylinder

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08F 212: 06)

Claims (3)

[Claims] 1. Divinylbenzene and general formula (1): (Wherein, n represents an integer of from 2 to 16), a monomer mixture containing a vinylbenzyloxyalkanol derivative represented by the following formula, a polymerization initiator, and a water-insoluble and non-soluble monomer mixture. The monomer solution obtained by mixing with an organic solvent that dissolves but does not dissolve the copolymer obtained therefrom is passed through a porous glass membrane having a uniform pore size to form an anionic or nonionic surfactant. A method for producing a hydroxyl group-containing porous resin, comprising polymerizing after dispersing or suspending by injecting into a water-based medium containing the polymer. 2. The monomer mixture according to claim 1, further comprising an aromatic monovinyl monomer.
The manufacturing method as described. 3. The method according to claim 1, wherein the organic solvent is at least one of a hydrocarbon solvent having 6 to 12 carbon atoms and an alkanol solvent having 4 to 12 carbon atoms. .