JPH11193310A - Alkyl-group-containing porous polymer, manufacture thereof and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a porous polymer which has an excellent mechanical strength and chemical stability and is useful for a column filler by polymerizing a monomer mixture containing a divinylbenzene and an alkylstyrene derivative. SOLUTION: A monomer solution is obtained by mixing a monomer mixture containing a divinylbenzene and an alkylstyrene derivative represented by the formula (n is an integer of 3-18), an initiator of polymerization and an organic solvent which is insoluble in water and dissolves the monomer mixture but does not dissolve the copolymer produced therefrom. The monomer solution is then dispersed or suspended in water for polymerization. The alkyl chain- containing porous polymer has a specific surface area of 50-600 m<2> /g. The content of the alkylstyrene derivative represented by the formula in the monomer mixture is about 3-50 wt.%. And the monomer solution may further contain an aromatic monivinyl monomer (e.g. styrene).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel alkyl group-containing porous polymer, a method for producing the same and a use thereof.

[0002]

2. Description of the Related Art Conventionally, porous materials have been developed by utilizing their structural and chemical properties to make use of packing materials for analytical and preparative columns, carriers for enzymes and catalysts, and various other useful materials. It is researched, developed, and used in various applications and fields, such as a substance adsorption carrier. Typical examples thereof include inorganic materials such as porous silica gel and alumina, and synthetic polymer materials such as divinylbenzene-styrene porous polymer and divinylbenzene-methacrylate porous polymer.

[0003] Porous silica gel has excellent mechanical strength, and as such, is mainly used as a column packing of a normal layer system.
Alternatively, a form in which an alkyl long chain is introduced using the surface silanol group is widely used mainly as a column packing material of an inverse layer system. However, there are problems due to the inherent chemical stability of silica gel, such as the stability in basic media and the effect of residual silanol groups [see, for example, Journal of Chromatographic Science (J.
Chromatogr. Sci. Vol. 22, p. 386 (1984), Journal of Chromatography (J. Chromatogr.) Vol. 149, p. 199 (1978)].

[0004] On the other hand, divinylbenzene-styrene porous polymers are excellent in both mechanical strength and chemical stability, and many researches and developments have been made in applications and fields of column packings [for example, Journal of the
Chromatographic Science (J. Chroma
togr. Sci. 22: 386 (1984)
Year), Journal of Chromatography (JC)
Chromatogr. 442: 97 (1988)
)], And a considerable variety of polymer-based reversed-phase columns are commercially available. Such divinylbenzene-
The basic method for producing a styrene-based porous polymer has been known for a long time, and includes, for example, a monomer mixture of divinylbenzene and styrene, a polymerization initiator, and a monomer which is hardly soluble in water and does not participate in polymerization. A monomer solution obtained by mixing an organic solvent (usually called a porous solvent) in which a mixture dissolves but a copolymer obtained by polymerization does not dissolve is obtained by suspension polymerization in an aqueous medium. [For example, Journal of Applied Polymer Science (J. Appl. Polym. Sci.)
23, p. 927 (1979), Angewante Macromolecule Chemi (Angew. Makromol.
Chem. ) 80, 31 (1979)]. This kind of porous polymer obtained by a suspension polymerization method usually has an apparent particle (hereinafter referred to as a secondary particle) having a diameter of μ.
Observation of the surface or inside of the secondary particles with an electron microscope or the like shows that finer particles having a size of the order of nm (hereinafter referred to as primary particles) are strongly aggregated. Recognize. That is, the aggregated 1
The space between the primary particles and the primary particles is the space where the organic solvent was present during the polymerization, and when the primary particles themselves are cross-linked to a higher order by divinylbenzene, the space between the primary particles and most of the organic solvent is reduced. It is insoluble and hardly swells. The porous polymer obtained by this method has a large specific surface area, is excellent in mechanical strength and chemical stability, and is widely used, including fillers for analytical and preparative columns and various carriers.

[0005] However, at present, the column performance when using a divinylbenzene-styrene-based porous polymer filler is generally inferior when compared comprehensively with the case using a silica gel-based filler. In other words, when the performance of an alkyl group-modified silica gel-based filler and that of a divinylbenzene-styrene-based porous polymer filler are compared in terms of the number of theoretical columns as a reversed-phase column-based filler, the silica gel-based filler is usually higher in theory. Give the number of steps. The cause of the low theoretical plate number of the polymer filler is pointed out by a wide pore distribution of the porous polymer and a polymer surface characteristic caused by aromatics, but there are many unclear details. In addition, the chemical and structural environment (for example, control of hydrophobicity / hydrophilicity, control of three-dimensional structure, etc.) of the polymer surface of the divinylbenzene-styrene-based polymer filler has few variations, and it is used as a filler or an adsorption carrier. Has a problem that it lacks versatility.

In order to solve the above-mentioned problems of the divinylbenzene-styrene-based porous polymer, the present inventors have first prepared an alkyl chain-containing porous polymer obtained by using a vinylbenzyloxyalkane derivative and divinylbenzene as essential monomers. Polymer (WO / 9 / WO
No. 73695). The present inventors have found that this alkyl chain-containing porous polymer has better performance as a column packing material than a general divinylbenzene-styrene-based porous polymer, and the chain length and chain structure of the alkyl chain portion ( By changing the type (linear type or branched type), there is also a chemical / structural variation as a filler, and it has been found that this is a very useful porous polymer. However, since this porous polymer has an ether bond at the link between the alkyl chain and the polymer matrix, it may be used as a filler under severe analysis conditions (for example, pH 3 or less, pH 12 or less).
Considering the long-term use under the above conditions or under high temperature conditions, there is still a concern about the chemical stability of the polymer (of course, under normal analysis conditions (eg, pH 3 to pH 1).
(2, analysis conditions at 0 to 50 ° C.), the chemical stability of the alkyl chain-containing polymer is not a problem at all).

[0007]

SUMMARY OF THE INVENTION The present invention has been made in consideration of the above-mentioned problems of the porous polymer in view of the importance and future of the column filler and the adsorbent for the divinylbenzene-styrene porous resin in the field of the porous resin. In order to overcome this, intensive studies have been made on further improvement of the alkyl chain-containing porous polymer described in the above-mentioned International Publication WO / 973690. As a result, by using an alkylstyrene derivative represented by the following general formula (1) as an alkyl chain-containing monomer derivative used in the production of a porous polymer, an alkyl group having excellent chemical stability is contained. A divinylbenzene-styrene-based porous polymer was obtained, and the present inventors have found that the porous polymer has good performance as a column filler, and have reached the present invention.

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

[0009]

Embedded image (Wherein, n represents an integer of 3 to 18) An alkyl chain-containing porous polymer having a specific surface area of 50 to 600 m ² / g obtained by polymerizing a monomer mixture containing an alkylstyrene derivative represented by the following formula: About.

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

[0011]

Embedded image (Where n represents an integer of 3 to 18), a monomer mixture containing an alkylstyrene derivative represented by the following formula, a polymerization initiator, and a water-insoluble and water-insoluble monomer mixture that does not participate in polymerization. Is a method for producing an alkyl chain-containing porous polymer, which comprises dispersing or suspending a monomer solution obtained by mixing an organic solvent in which a copolymer obtained by polymerization with an organic solvent does not dissolve in an aqueous medium and polymerizing the monomer solution. About the method.

Furthermore, the present invention relates to a packing material for liquid chromatography comprising the above-mentioned porous polymer containing an alkyl chain.

[0013]

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

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

As divinylbenzene, commercially available divinylbenzene having a purity of about 50 to 60%, which is generally available, 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 alkylstyrene derivative represented by the general formula (1) may be a mixture of meta and para isomers, or may be each isomer alone. Further, n in the formula is an integer of 3 to 18. It is preferable that the lower limit of n is 6 and the upper limit is an integer of 16. When n is less than 3, the effect of the alkyl chain on the surface of the secondary particles of the obtained porous polymer is not exerted, and the alkyl chain-containing porous polymer intended in the present invention does not make sense. When n is larger than 18, the polymerizability is reduced,
It is not preferable because the specific surface area of the obtained porous polymer is reduced.

The synthesis of the alkylstyrene derivative represented by the general formula (1) can be carried out by various methods, and the present invention is not limited at all. For example, Journal of American Chemical Society (J. Am. Chem. Soc.) Vol. 75, No. 3326
P (1953), p.
An alkylstyrene derivative can be synthesized. That is, the general formula (2):

[0018]

Embedded image (Wherein n represents an integer of 3 to 18) from the alkylbenzene represented by the general formula (3) by Friedel-Crafts acylation reaction:

[0019]

Embedded image (In the formula, n represents an integer of 3 to 18.)
To give an alkyl acetophenone which is subsequently reduced with aluminum isopropoxide to give a compound of general formula (4):

[0020]

Embedded image (In the formula, n represents an integer of 3 to 18.)
After the conversion into -alkylphenylmethylcarbinol, the desired alkylstyrene derivative represented by the general formula (1) can be obtained by a dehydration reaction.

The contents of divinylbenzene and the alkylstyrene derivative represented by the general formula (1) contained in the monomer mixture can be used in the following ranges based on the total weight of the monomers of 100% by weight. Usually, the content of the alkylstyrene derivative represented by the general formula (1) in the monomer mixture is 3 to 50% by weight.
And the balance contains divinylbenzene and the like. The alkylstyrene derivative represented by the general formula (1) is particularly preferably contained in an amount of 5% by weight or more in order to sufficiently exert its effect. In order not to cause a decrease in the polymerization rate or a decrease in the specific surface area of the obtained porous polymer, the content of the derivative is preferably 50% by weight or less based on the total weight of the monomers.

The monomer mixture may contain an aromatic monovinyl monomer. As the aromatic monovinyl monomer, styrene, methylstyrene, ethylvinylbenzene, and the like can be used, and one or more of these can be used as a mixture. As these, commercially available products may be used as they are, or those purified by distillation may be used. Methylstyrene is meta-, para-, α
There are isomers such as-and-, but in the present invention, a mixture of these isomers may be used, or each isomer may be used alone. In addition, ethyl vinylbenzene has meta and para isomers, and in the present invention, a mixture of these isomers may be used.
Alternatively, 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.

When an aromatic monovinyl monomer is contained in the monomer mixture, the content of the alkylstyrene derivative represented by the general formula (1) is about 3 to 50% by weight, and the remainder is divinylbenzene 15 to 97%. % By weight and 0 to 82% by weight of an aromatic monovinyl monomer
Including degree. If the content of divinylbenzene is less than 15% by weight, the specific surface area of the obtained porous polymer is undesirably reduced. Further, the content of the aromatic monovinyl monomer is preferably 82% by weight or less from the viewpoint of the mechanical strength of the obtained porous polymer.
In general, the monomer mixture often contains 5% by weight or more of an aromatic monovinyl monomer. In this case, the upper limit of the content of divinylbenzene is 92% by weight.

The polymerization initiator is not particularly limited as long as it is soluble in the above-mentioned monomers, but organic peroxides such as benzoyl peroxide and lauryl peroxide, and azo compounds such as azobisisobutyronitrile can be used. No. The amount of the catalyst used may be any range depending on the required physical properties of the obtained porous polymer 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 a solvent, a function as a so-called porous solvent can be exhibited. Among them, an organic solvent having a high affinity for the alkylstyrene derivative is preferable, and a hydrocarbon solvent having 6 to 12 carbon atoms is particularly preferable. Specific examples include hexane, heptane, octane, nonane, decane, undecane, dodecane and the like.
Further, the hydrocarbon portion of the hydrocarbon solvent may be linear or branched. These organic solvents may be used alone or as a mixture of two or more.
The mixing ratio of the organic solvent and the monomer mixture can be mixed in an arbitrary range depending on the required physical properties of the obtained porous polymer and the like. However, usually, the volume ratio of the organic solvent / monomer mixture is from 70/30 to 15 It is better to mix within the range of / 85. Outside this range, a polymer having a good porous structure cannot be obtained in most cases.

The process itself in the suspension polymerization of the present invention is not different from the conventional suspension polymerization, and can be carried out by a known method. For example, a monomer solution obtained by uniformly mixing the monomer mixture, a polymerization initiator and an organic solvent,
Dispersion or suspension in an aqueous medium with stirring can be carried out by a general suspension polymerization method in which polymerization is carried out by heating. The aqueous medium may contain a suitable dispersion stabilizer. The dispersion stabilizer is not particularly limited as long as it can stably disperse the monomer solution as droplets in an aqueous medium, but generally well-known polyvinyl alcohol, polyacrylamide, polyacrylic acid, gelatin and the like. Of water-soluble polymers. The amount used is not particularly limited as long as monomer droplets having a target particle diameter can be stably obtained. In addition, a sufficient amount of the dispersion stabilizer to prevent coalescence and aggregation of the monomer droplets during the polymerization can be adjusted in advance at the stage of dispersion and suspension.

The ratio of the monomer solution to the aqueous medium is not particularly limited as long as the dispersion / suspension step and the polymerization step can be carried out without any problem. / Aqueous medium = 1/10 to 1 /
It is better to carry out in the range of 1.

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. In addition, the type of the polymerization reactor and the stirring method are not particularly limited as long as the polymerization can proceed stably without the coalescence and aggregation of the monomer droplets. In addition, as in general suspension polymerization, an inorganic dispersant such as the above-described water-soluble polymer or colloidal silica may be added to prevent coalescence and aggregation of monomer droplets during polymerization. The amount used is not particularly limited. This general suspension polymerization method is effective when the secondary particle diameter of the target porous polymer needs to be about 50 μm to 2 mm.

When the secondary particle diameter of the target porous polymer needs to be about 0.5 to 100 μm, a suspension polymerization method including a microsuspension step before polymerization is effective. The micro-suspension process, for example,
A monomer solution obtained by uniformly mixing the monomer mixture, the polymerization initiator, and the organic solvent is dispersed in an aqueous medium containing a suitable dispersion stabilizer by a method of once finely dispersing while stirring at high speed using a homomixer or a homogenizer. be able to.

The stirring speed in the microsuspension step depends on various conditions such as the ratio of the organic phase composed of the monomer solution to the aqueous phase containing the dispersion stabilizer, and the type and concentration of the dispersion stabilizer. 1-1 using a homogenizer
When preparing on a 5 L scale, 1000 to 30000 r
When it is performed in the range of pm, the characteristics of the homogenizer can be sufficiently exhibited. When the micro-suspension step is included before the polymerization, the same conditions as in the conventionally known suspension polymerization method can be applied and applied as the conditions in the polymerization step.

The secondary particle size of the obtained porous polymer is
When it is required that the particle size distribution is about 0.3 to 100 μm and the particle size distribution is very sharp, a suspension polymerization method including a film emulsification step before polymerization is extremely effective. That is,
Prior to the polymerization, a suspension comprising a step of dispersing or suspending the monomer solution by pressing it into an aqueous medium containing an anionic or nonionic surfactant through a porous glass membrane having a uniform pore size. It is a turbid polymerization. A conventionally known method can be applied and applied to the membrane emulsification step itself before the polymerization.

As the porous glass membrane used in this membrane emulsification step, any glass membrane having a uniform pore diameter with an average pore diameter in the range of about 0.1 to 10 μm may be used. 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 μm is used, it takes a long time to emulsify the membrane, which is not preferable from the viewpoint of industrial production. Further, when a glass membrane having an average pore diameter of more than 10 μm is used, it is extremely difficult to obtain emulsified (dispersed) droplets having a uniform particle diameter. Not preferred. That is, the average pore diameter of the glass membrane is 0.1
When a particle having a diameter of about 10 to 10 μm is used, the emulsified (dispersed) droplet obtained by membrane emulsification usually has a pore diameter of 3 to 1 of the glass membrane.
It has a particle size of about 0 times and its particle size distribution is very sharp.

In the membrane emulsification step, the pressure at which the organic phase composed of the monomer solution is injected into the aqueous phase through the glass membrane is such that the desired emulsified (dispersed) 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 0.5 to 1.5 times, emulsified (dispersed) droplets having a very sharp particle size distribution can be obtained stably and with good operability. Also, regarding the temperature at the time of membrane emulsification, if the temperature at which membrane emulsification can be performed stably and polymerization does not start, an organic phase,
The aqueous phase is not particularly limited, but it is usually preferable to carry out at 0 to 60 ° C.

Examples of the surfactant used in the aqueous phase at the time of membrane emulsification include anionic surfactants such as sodium alkyl sulfate, sodium alkylbenzene sulfonate and sodium alkyl sulfosuccinate; polyoxyethylene alkyl ether; polyethylene glycol fatty acid ester; Non-ionic surfactants and the like can be used, and the amount of the organic phase used during the membrane emulsification step may be an amount capable of stably presenting an organic phase as emulsified droplets. 0.
It is preferable to set it to about 05 to 2% by weight.

After the membrane emulsification step, the process proceeds to the polymerization step. In order to prevent the emulsified (dispersed) droplets from coalescing and coagulating during the polymerization, a water-soluble polymer such as a water-soluble polymer often used in ordinary suspension polymerization is used. A dispersion stabilizer may be used in combination. Of course, during the polymerization, when the reaction proceeds stably without the coalescence and aggregation of the emulsified (dispersed) droplets, it is not necessary to use a dispersion stabilizer such as a water-soluble polymer. 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 water-soluble polymers such as polyvinyl alcohol, polyacrylamide, polyacrylic acid, and gelatin, as in the case of ordinary suspension polymerization. Its usage is
There is no particular limitation as long as the emulsified (dispersed) droplets can be stably dispersed with a required particle diameter. The amount of water used as the aqueous phase in the present invention is not particularly limited as long as the process of membrane emulsification and polymerization can be carried out smoothly, and may be the same as in the case of ordinary suspension polymerization. Further, the same polymerization conditions as those of conventionally known suspension polymerization can be applied and applied.

In any of the above-mentioned general suspension polymerization, suspension polymerization including a microsuspension step before polymerization, and suspension polymerization including a membrane emulsification step prior to polymerization, the porous polymer obtained by polymerization may be used. The method for isolating, washing and drying the polymer is not limited at all, and can be carried out, for example, as follows. The porous polymer obtained by the polymerization is filtered off by an appropriate method, washed well with hot water to remove the dispersion stabilizer and the surfactant attached to the polymer, and further washed with an unreacted monomer or a porous solvent. Washing with acetone, methanol or the like to remove a certain organic solvent is sufficient, followed by heating and drying under reduced pressure to obtain the desired alkyl chain-containing porous polymer.

The alkyl chain-containing porous polymer of the present invention usually has a high specific surface area of 50 to 600 m ² / g,
The appearance of the secondary particles is spherical and opaque. The secondary particle size is
Usually, 50 μm to 2 mm in the case of general suspension incorporation,
In the case of suspension polymerization including a microsuspension step before polymerization, the thickness is about 0.5 to 100 μm, and in the case of suspension polymerization including a membrane emulsification step before polymerization, about 0.3 to 100 μm. Furthermore, in the case of polymerization including a membrane emulsification step,
As a measure of the particle size distribution of the secondary particles, the volume average particle diameter (d
When the ratio (dv / dn) between v) and the number average particle diameter (dn) is calculated, dv / dn = 1.005 to 1.050 is very close to 1 and the particle size distribution is sharp. In addition, the size of the primary particles is usually 10 to 100 n in any case.
m.

Such an alkyl chain-containing porous polymer of the present invention is excellent in mechanical strength and chemical stability because the polymer matrix is a divinylbenzene-styrene polymer, and as such, can be used as a column filler or various adsorbents. It can exhibit excellent performance for applications such as agents and carriers. In particular, n in the alkylstyrene derivative represented by the general formula (1)
By appropriately selecting the value of and the amount used, it is possible to variously control the chemical environment and the structural environment of the surface of the obtained porous polymer, and to enhance the utility in the above various applications. it can.

The alkyl chain-containing porous polymer of the present invention is particularly useful as a filler for liquid chromatography based on the above-mentioned properties. When used for this purpose, the particle size distribution of the polymer particles needs to be narrow from the viewpoint of column performance. When used as a filler for liquid chromatography for analysis, a polymer particle having a particle diameter of about 3 to 10 μm is extremely useful. In the present invention, a porous polymer obtained by suspension polymerization including a microsuspension step before polymerization has a wide particle size distribution, and thus can be generally used as the filler by classifying to a desired particle size. On the other hand, a porous polymer obtained by suspension polymerization including a membrane emulsification step before polymerization can be used as the filler without classification because of its narrow particle size distribution as described above.

As described above, the packing material for liquid chromatography of the present invention has excellent chemical stability and can be used for analysis in a wide pH range. Furthermore, in liquid chromatography using the alkyl chain-containing porous polymer of the present invention as a filler, better separation performance (for example, higher theoretical performance) than in the case where a conventional divinylbenzene-styrene-based porous polymer is used as a filler. (Number of stages) to perform highly accurate analysis.

[0041]

According to the present invention, 50 to 600 m ² / g
Thus, an alkyl chain-containing porous polymer having a high surface area can be obtained. The porous polymer has an appearance of secondary particles (apparent particles) which is spherical and opaque, and has a particle diameter of 50 μm to 2 mm in the case of ordinary suspension polymerization, and in the case of suspension polymerization including a microsuspension step. Is 0.5
To 100 μm, and about 0.3 to 100 μm in the case of suspension polymerization including a membrane emulsification step. The size of the primary particles is usually about 10 to 100 nm in any case. Such an alkyl group-containing porous resin of the present invention can control the chemical environment and the three-dimensional environment of the surface of the obtained porous polymer by changing the amount and the alkyl chain length of the alkyl chain-containing monomer used for polymerization. Is possible,
It is very useful as a column filler, various adsorbents, and carriers. In particular, the porous polymer obtained by the suspension polymerization including the microsuspension process is classified into the desired particle size, and the porous polymer obtained by the suspension polymerization including the membrane emulsification process. Can be used as it is as a packing material for liquid chromatography without classification, and shows high separation performance. Also, because of its excellent chemical stability, it can be used in a wide range of pH and temperature conditions.
Hereinafter, it can be used even under a pH condition of 12 or more or a temperature condition exceeding 50 ° C.

[0042]

The present invention will be described more specifically below with reference to examples and comparative examples.

(1) Examples and Comparative Examples of Alkyl Chain-Containing Porous Polymer

Example 1 A 100 equipped with a stirrer, thermometer, nitrogen inlet tube and cooling tube
540 ml of ion-exchanged water in a separable flask of 0 ml
And polyvinyl alcohol (“Poval 2”)
17 ", manufactured by Kuraray Co., Ltd.) and dissolved.
Subsequently, divinylbenzene (content (purity) 55%, remaining 45% ethylvinylbenzene) 58.63 g, styrene 24.43 g, p-hexylstyrene 14.66
g, n-heptane 49.25 g and azobisisobutyronitrile 1.954 g (2.0% by weight of the total amount of monomers)
, And stirred under a nitrogen stream at a stirring speed of about 400 to 500 rpm for 10 minutes. The temperature is raised to 75 to 80 ° C., and the polymerization is performed for 6 hours while maintaining the temperature. Was performed. After the polymerization, the mixture was cooled to room temperature, and the obtained polymer was separated by filtration. The polymer was washed well with hot water and then with acetone, and reduced under reduced pressure (about 1 mm /
Hg) and dried by heating (70-80 ° C.), and 92.8 g (9
4%) of an alkyl chain-containing porous polymer was obtained. The apparent particle size (secondary particle size) of this polymer is 195 μm in volume average particle size (dv) and 1 in number average particle size (dn).
It was 69 μm and dv / dn = 1.1541.
The primary particle diameter is 43 nm on average, and the specific surface area is 22 nm.
It was 5 m ² / g.

Example 2 Polymerization was carried out in the same manner as in Example 1 except that the types and charged amounts of each monomer and the charged amount of the organic solvent were changed as shown in Table 1. The resulting porous polymer was obtained.

Example 3 Ion-exchanged water 60 was placed in a 1000 ml separable flask.
Then, 2.10 g of polyvinyl alcohol (“Poval 210”, manufactured by Kuraray Co., Ltd.) was added and dissolved therein. Subsequently, divinylbenzene (content (purity) 55
%, The remaining 45% is ethylvinylbenzene) 48.86
g, styrene 20.36 g, p-hexylstyrene 1
2.22 g, n-heptane 41.04 g and azobisisobutyronitrile 1.629 g (2.0
% By weight) and dispersed with a homogenizer (manufactured by IKA) at a stirring speed of about 13000 rpm for 10 minutes. Next, it was replaced with a normal stirrer, a thermometer, a nitrogen inlet pipe and a cooling pipe were set, and the dispersion was heated to 75 to 80 ° C. while stirring at about 400 to 500 rpm under a nitrogen stream. The polymerization was carried out for 6 hours while maintaining the temperature. After the polymerization, the mixture was cooled to room temperature, and the obtained polymer was separated by filtration, washed well with hot water, then with methanol and acetone, and heated under reduced pressure (about 1 mm / Hg) (70 to 80 ° C.). ) Dried, 7
7.3 g (94% yield) of an alkyl chain-containing porous polymer was obtained. The apparent particle size (secondary particle size) of this polymer is 3.89 μm in volume average particle size (dv), 3.48 μm in number average particle size (dn), and dv / dn =
1.118. The average primary particle diameter is 41n.
m and specific surface area were 221 m ² / g.

Examples 4 to 8 and Comparative Examples 1 and 2 The procedure of Example 3 was the same as Example 3 except that the types and the amounts of the monomers and the amounts of the organic solvents were changed as shown in Table 1. Polymerization is carried out in the same manner, and the alkyl chain-containing porous polymer (Example) or divinylbenzene-
A styrene porous polymer (comparative example) was obtained.

Example 9 Divinylbenzene (content (purity) 55%, remaining 45%
Is ethyl vinyl benzene) 50.82 g, styrene 2
1.17 g, p-hexylstyrene 12.70 g, n-
Organic phase 1 consisting of a monomer solution in which 42.68 g of heptane and 1.694 g of azobisisobutyronitrile (2.0% by weight of the total amount of monomers) were uniformly mixed was prepared. Further, 12.6 g of polyvinyl alcohol (“Poval 224”, manufactured by Kuraray Co., Ltd.) and 1.26 g of sodium dodecyl sulfate were added to 630 ml of ion-exchanged water to prepare an aqueous phase 2 composed of an aqueous medium dissolved therein. 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 connected to the aqueous phase line 6 using the circulation pump 11.
And subsequently the organic phase 1 is washed with nitrogen gas at 0.
At a pressure of 64 kgf / cm ² , an average pore diameter of 0.7 in the double tube module 7 provided in the circulating aqueous phase line 6
The emulsion was obtained by press-fitting into the aqueous phase 2 via the 0 μm porous glass membrane 8 to emulsify the membrane. 120ml membrane emulsification
(99.3 g) of the organic phase 1 was injected over about two and a half hours, and the reaction was terminated. In addition, membrane emulsification is performed using the organic phase
And while maintaining the temperature of 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 59.1 g (yield 90%) of an alkyl chain-containing porous polymer. The apparent particle size (secondary particle size) of this polymer is represented by the volume average particle size (dv)
5.04 μm, 4.96 μm in number average particle diameter (dn)
And dv / dn = 1.016. The average primary particle diameter is 41 nm, and the specific surface area is 235 m ² / g.
Met.

Examples 10 to 12 and Comparative Example 3 In Example 9, the type and charge amount of each monomer or the charge amount of the organic solvent were changed as shown in Table 1, and the film emulsification conditions were as shown in Table 2. Polymerization was carried out in exactly the same manner as in Example 9 except for changing, to obtain an alkyl chain-containing porous polymer (Example) or a divinylbenzene-styrene porous polymer (Comparative Example).

[0051]

[Table 1]

[0052]

[Table 2]

Table 3 shows the physical properties of the polymers obtained in the examples.

[0054]

[Table 3]

(2) Examples and Comparative Examples of Packing Materials for Liquid Chromatography

Example 13 Preparation of filler: The polymer obtained in Example 3 was subjected to a gas flow classifier (“MDS-II”, Nippon Pneumatic Co., Ltd.)
Was used for classification. The apparent particle size (secondary particle size) of the polymer after classification is expressed as a volume average particle size (dv) of 5.
13 μm, the number average particle diameter (dn) was 4.94 μm, and dv / dn was 1.038. The primary particle diameter was 41 nm on average, and the specific surface area was 222 m ² / g. The polymer obtained after this classification was used as a filler. Column packing: 4.6 m inner diameter of the packing material obtained above
m, a packing column of 150 mm in length using “Packing Solvent R-5” (manufactured by GL Sciences) and isopropyl alcohol with a packing pressure of 80 to 1
Low pressure packing was performed at 50 kg / cm ² to obtain a column for liquid chromatography. Liquid chromatography analysis: The column obtained above was connected to a high performance liquid chromatography system ("HPLC610 Isocratec", manufactured by Waters), eluent acetonitrile / water = 50/50, flow rate 1.0 ml / mi.
n, temperature 25 ° C., detection UV 254 nm, pyridine, 2-ethylpyridine, N, N-dimethylaniline, phenol, methyl salicylate, 3-pentanone,
The test compound of 3-hexanone was analyzed. As the performance of the column, the retention time and the number of theoretical plates were examined.

Examples 14 to 15 and Comparative Examples 4 to 5 Classification and classification were performed in the same manner as in Example 13 except that the polymers used were changed to those shown in Table 4.
Column packing and liquid chromatography analysis were performed.

Examples 16 to 18 and Comparative Example 6 The procedure of Example 13 was repeated, except that the polymer shown in Table 4 was used as a filler without classification, and the column packing and liquid application were performed in the same manner as in Example 13. Chromatographic analysis was performed.

Table 4 shows the polymers used as fillers in the above Examples and Comparative Examples and their physical properties.

[0060]

[Table 4]

Table 5 shows the results of liquid chromatography in the above Examples and Comparative Examples.

[0062]

[Table 5]

The properties of the polymers obtained in the examples and comparative examples were measured according to the following methods.

Primary particle diameter (nm): From a photograph of a scanning electron microscope (“S-2000”, manufactured by Hitachi), the size of 100 or more primary particles is measured, and the number average particle diameter is calculated. did.

Secondary particle diameter (μm): From a photograph of a scanning electron microscope (“S-2000”, manufactured by Hitachi), the size of arbitrary 500 or more secondary particles was measured, and the volume average particle diameter (d) was measured.
v) and the number average particle diameter (dn) was calculated. In addition, dv / dn was calculated as a standard of the particle size distribution.

Specific surface area (m ² / g) and average pore radius (Å): BET surface area measuring device (“NOVA1200”,
Counter chrome).

[Brief description of the drawings]

FIG. 1 is a schematic view of a membrane emulsifying apparatus used in Examples 9 to 12 and Comparative Example 3. 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 pipe module 8 ... Porous glass membrane 9 ... ... nitrogen gas line 10 ... pressure gauge 11 ... circulation pump 12 ... nitrogen gas cylinder

Claims (10)

[Claims] 1. Divinylbenzene and general formula (1): (Wherein, n represents an integer of 3 to 18) An alkyl chain-containing porous polymer having a specific surface area of 50 to 600 m ² / g obtained by polymerizing a monomer mixture containing an alkylstyrene derivative represented by the following formula: . 2. The alkyl chain-containing porous polymer according to claim 1, wherein the monomer mixture further contains an aromatic monovinyl monomer. 3. The method according to claim 1, wherein the monomer mixture has the general formula (1): 3. The alkyl chain-containing porous polymer according to claim 1, comprising an alkylstyrene derivative represented by the formula: wherein n is an integer of 3 to 18. 3. 4. Divinylbenzene and general formula (1): (Where n represents an integer of 3 to 18), a monomer mixture containing an alkylstyrene derivative represented by the following formula, a polymerization initiator, and a water-insoluble and water-insoluble monomer mixture that does not participate in polymerization. Is a method for producing an alkyl chain-containing porous polymer, which comprises dispersing or suspending a monomer solution obtained by mixing an organic solvent in which a copolymer obtained by polymerization with an organic solvent does not dissolve in an aqueous medium and polymerizing the monomer solution. Method. 5. The method according to claim 4, wherein the monomer mixture further contains an aromatic monovinyl monomer. 6. The method according to claim 4, wherein the organic solvent is at least one kind of a hydrocarbon solvent having 6 to 12 carbon atoms, which is used alone or in combination. 7. The method according to claim 4, wherein the step of dispersing or suspending the monomer solution in the aqueous medium is performed by high-speed stirring using a homogenizer or a homomixer. 8. The method of dispersing or suspending a monomer solution in an aqueous medium, the aqueous medium containing an anionic or nonionic surfactant through a porous glass membrane having a uniform pore size. The method according to claim 4, wherein the method is performed by press-fitting the inside. 9. The porous glass membrane having an average pore diameter of 0.1
The method according to claim 8, wherein the thickness is from 10 to 10 m. 10. A packing material for liquid chromatography containing the alkyl chain-containing porous polymer according to claim 1 or 2.