JPS5923563B2 - Molding composition for porous tertiary crosslinked polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a composition for molding a porous three-dimensionally crosslinked polymer.

Porous three-dimensional crosslinked polymers with a network structure are widely used as base materials for ion exchange resins, but in recent years, their characteristics of large pore volume and specific surface area have attracted attention, and they have been used under the name porous polymers for liquid chromatography. Water is becoming increasingly popular as a filler, and is also used as a catalyst carrier.
It exhibits excellent performance as a support for hydrophobic catalysts for hydrogen exchange reactions.

It is also being used as an adsorbent for organic gases and liquids. However, the conventional method for producing the resin is suspension polymerization in an aqueous suspension.

In this manufacturing method, most of the particles of the raw material mixture suspended in the suspension are small particles with a diameter of 1 mm or less due to the physical properties of the raw material mixture, and it is difficult to economically produce particles with a diameter of 1 mm or more. For this reason, there are restrictions on the use of this resin. If the resin is produced using a molding composition according to the present invention, the shape and size of the resin can be freely changed. It was also found that the pore volume and specific surface area, which are the characteristics of this resin, are the same as those of products made by suspension polymerization, and that the range of use of this resin can be further expanded. The composition of the present invention uses the same raw materials as conventional porous three-dimensional crosslinked polymers, and its main raw materials are a monovinyl monomer, a polyvinyl monomer as a crosslinking agent, and a diluent.

The monovinyl monomer may be any organic compound having one vinyl group, and a typical example is styrene, but other aromatic compounds include methylstyrene, ethylstyrene, vinylnaphthalene, etc. Examples of the acrylic type include methacrylic acid and acrylic ester. Polyvinyl monomer is
Any organic compound may be used as long as it has two or more vinyl groups; styrenic compounds include divinylbenzene, divinylstyrene, divinyltoluene, divinylxylene,
Examples include trivinylbenzene, and examples of acrylic acid include trimethylolmethane trimethacrylate and tetramethylolmethanetetramethacrylate. The diluent may be any organic compound that is not reactive with monovinyl monomers and polyvinyl monomers and is compatible with the monomers.
Although one type may be used, two types having different properties are usually mixed as appropriate depending on the desired physical properties of the resin. One is called a precipitant, which has good compatibility with monomers but has no affinity with the polymer formed after polymerization.
Examples include natural oils and fats, higher alcohols, paraffins, linear polymers with a low degree of polymerization, and rogen compounds of these. The other one is called a swelling agent, which is compatible with monomers, has a good affinity with the polymer formed after polymerization, and causes the polymer to swell. Specifically, many of them are called high boiling point organic solvents, such as rogenated ethane, aromatic solvents, and logonides of aromatic solvents, such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, trichlorobenzene, etc. It is. However, it is not possible to clearly distinguish between precipitants and swelling agents.
There are also diluents with intermediate physical properties, and this can be said in terms of comparison. The composition of the present invention is prepared by mixing the above-mentioned monovinyl monomer, polyvinyl monomer, precipitant, swelling agent, and, if necessary, a polymerization initiator such as benzoyl peroxide, butyl peroxide, azobisisobutyl nitrile, etc., to form a homogeneous liquid mixture. The mixed solution is heated to 60°C to 110°C to carry out a polymerization reaction, and when the rate of increase in viscosity of the liquid becomes rapid,
The mixture is quenched with cold water to a temperature below 40°C to form a jelly-like product, but the blending ratio of the mixture before polymerization can be varied over a wide range.

Practically, the ratio of monovinyl monomer to polyvinyl monomer is 100 parts (by weight) of monovinyl monomer, 5 to 200 parts (by weight) of polyvinyl monomer,
The diluent is 20 to 300 parts (by weight) when the total of monovinyl monomer and polyvinyl monomer is 100 parts (by weight).
It may be determined according to the physical properties required of the product. If there is a large amount of diluent, the pore volume will increase, but the strength will decrease. The composition of this invention is prepared by placing these raw material monovinyl monomer, polyvinyl monomer, and diluent in a reactor, placing the reactor in a constant temperature bath, and maintaining the temperature at 60 to 110°C, the temperature at which the monomer polymerizes. are superimposed.

The viscosity of the raw material mixture differs depending on the raw material, but once the monomers begin to polymerize, the viscosity gradually increases. After a certain point, the rate of increase in viscosity becomes rapid. Once it is confirmed that the viscosity has increased rapidly, the raw material mixture is rapidly cooled down to 40° C. or lower to stop the polymerization reaction, resulting in a jelly-like mass. The details of the state of the substance inside this jelly-like substance are unknown, but it is thought that the gel effect caused by the polyvinyl monomer sharpens as the viscosity increases, and that once the polymerization acceleration effect begins to appear, the temperature should be lowered. That's fine. The time required from placing the raw material mixture in a constant temperature bath to start polymerization and cooling it varies depending on the polymerization temperature, but in the case of 90°C to 100°C, it takes about 20 to 60 minutes.

If the temperature is low, the time can be longer than this, and if the temperature is high, the time can be shorter than this. However, an additional 8 to 10 hours are required to complete monomer polymerization. From the above, this jelly-like content is a mixture of a monomer, an oligomer formed by partially polymerizing the monomer, a partially gelled polymer, and a diluent.

When this jelly-like substance is ground well, it becomes a sticky powder. When this is kneaded into a clay-like substance, it becomes a highly plastic clay-like substance. This is the composition of this invention. When heated, this material becomes a completely solid porous polymer. This composition has caking properties and can be kneaded well by kneading, but it hardly adheres to the materials that make up the molding machine, such as wood, glass, metal, and plastic, and when extruded, It has the characteristic that it can be molded very easily.

In addition, this molding material has a
It can maintain its original physical properties for more than several months, and does not deteriorate for 3 to 4 months even when maintained at 30°C.

To make a porous resin from this molded product, heat it again in a constant temperature bath and keep it at 60 to 110°C. After 8 to 10 hours, you can obtain a porous three-dimensional crosslinked polymer with a network structure. I can do it. Furthermore, this repolymerization maintains the shape of the molded polymer, and if the diluent is washed away with a solvent in the same manner as when manufacturing by suspension polymerization, the pore volume of this molded polymer can be reduced. The specific surface area is comparable to that of three-dimensional crosslinked polymers obtained by suspension polymerization, and it can be used satisfactorily for conventional purposes. Next, typical embodiments of this invention will be shown to clarify the effects.

Example 1 Raw material mixture This raw material mixture was placed in a 1000 ml beaker and heated at a temperature of 90°C for 30 minutes. When the viscosity reached 100 centipoise using a rotational viscometer, the beaker was immersed in cold water of 20°C or lower and heated at 30°C. After cooling, a jelly-like semi-polymer was obtained.

This jelly-like material was crushed in an experimental crusher for 2 hours and 30 minutes, and the resulting powder was kneaded with an experimental kneader to obtain a clay-like composition. An appropriate amount of this composition is put into a cylindrical container with a 4 mm diameter nozzle and extruded with an extrusion rod to form a 4 mm diameter rod, which is then cut into 4 mm length to create a 4 mm diameter x 4 mm L column. Ivy.

The molding rate at this time was 100%, and the extrusion molding was extremely good. A predetermined number of the above-mentioned cylindrical materials were placed in a 50 mm diameter beaker, and the beaker was immersed in a bath at 90° C. to start polymerization again, and the polymerization was completed after 11 hours. During this period, the cylindrical object maintained its original shape and did not lose its shape at all. After thoroughly washing the polymerized cylinder with hexane and acetone to remove the diluent and other unpolymerized substances, the pore volume and specific surface area of the cylinder were measured, and the results were as follows. .

Pore volume 2.1CC/7 (by mercury intrusion method) Specific surface area 260m2/7 (by B.E.T method) Example 2
The above raw material mixture was prepared in the same manner as in Example 1, and heated to 90°C for 30 minutes.
Heat for 2 minutes, and when the viscosity reaches 90 centipoise,
The mixture was cooled with cold water at 5° C. to obtain a jelly-like semi-polymer.

This was crushed using a crusher in the same manner as in Example 1, and kneaded to form a clay-like composition. Shape this into a cross (the diameter of the cross is 3mm)
, a cylindrical container with a nozzle having a hole with a width of 1 mm) and extruded to form a rod-shaped body with a cross-shaped cross section, and cut it into a length of 4 mm to have a length with a cross-shaped cross-section. A 4 mm molded product was made. There was almost no difference in moldability and yield from Example 1 at this time. This molded product is 50mm
A predetermined amount of the solution was poured into a φ beaker, placed in a 90° C. bath, and polymerization started again and was completed in 10 hours.

During this time, the molded product with a cruciform cross section did not lose its shape, and the polymerization was completed in its original shape. This was washed with acetone and hexane and dried in the same manner as in Example 1, and its physical properties were measured, and the results were as follows. Pore volume: 2.6 CC/y Specific surface area: 320 d/7 Example 3 Raw material mixture A jelly-like material was prepared from the above raw material mixture in the same manner as in Example 1, and the jelly-like material was crushed to form a cylindrical material, and repolymerization was also carried out. The polymer obtained by polymerization in the same manner as in Example 1 was washed with acetone and hexane, and after drying, its physical properties were measured, and the results were as follows.

Pore volume 1.5CC/t Specific surface area 220i/y

Claims (1)

[Claims] 1 Monovinyl monomer 100 selected from styrene aromatic compounds or acrylic aliphatic compounds as raw materials (
5 to 200 (by weight) parts of a polyvinyl monomer selected from the above compounds as a crosslinking agent, and 20 to 200 parts (by weight) of an organic compound that does not react with the monovinyl monomer and polyvinyl monomer and is compatible with the monomer as a diluent.
A diluent, monomer, oligomer, obtained by heating and polymerizing a solution (hereinafter referred to as raw material mixture) mixed in the range of 300 (weight) parts, and cooling it at the point when the polyvinyl monomer starts to partially crosslink. A composition for molding a porous three-dimensionally crosslinked polymer, which is obtained by grinding and kneading a jelly-like mixture containing gelled polymers to obtain a clay-like plastic material.