KR0138709B1 - Mothod for the preparation of porous exchange resin with high density - Google Patents

Abstract

The present invention relates to a method for producing a high density porous ion exchange resin, and more particularly, to a method for producing a high density porous ion exchange resin suitable for ion exchange treatment of a highly viscous fluid.

The present invention improves the dispersibility of a density increasing agent in a method of preparing a polymer matrix by suspending and polymerizing a monomer, a crosslinking agent, a polymerization initiator, a polymerization stabilizer, a pore-forming agent, and introducing ion groups thereto. In order to prepare a high-density porous ion exchange resin, the insoluble inorganic compound is added as a density increasing agent when the suspension polymerization proceeds about 1 to 30%.

According to the present invention, the dispersibility of an insoluble inorganic compound which is a density increasing agent is increased, and the inorganic compound can penetrate deep into the polymer matrix to reduce the leakage of the inorganic material.

Description

Manufacturing method of high density porous ion exchange resin

The present invention relates to a method for producing a high density porous ion exchange resin, and more particularly, to a method for preparing a high density porous ion exchange resin suitable for ion exchange treatment of a highly viscous fluid.

Ion-exchange resins are separated into gel-type ion exchange resins and porous ion-exchange resins by the presence or absence of pores or voids through which molecules can freely pass within the base polymer matrix. 2,960,480, 2,788,331, 2,641,417, 2,614,099 and 2,591,573, and the synthesis of porous polymer resins is disclosed in US Pat.

The gel ion exchange resin is a pore-free resin, and the apparent density is generally 1.2 g / cc or more, so there is no big problem in the process, but in a dry state, molecules cannot penetrate into the resin. However, in solvents with high affinity, the polymer swells in the solvent, making the polymer flexible, allowing molecules to penetrate into the gel. At this time, the penetration rate of molecules is greatly affected by the degree of swelling of the polymer matrix. Therefore, the gel ion exchange resin can exert an ion exchange capacity under a good solvent having a high affinity for the resin.

In addition, porous ion exchange resin has pore or pore so that molecules can easily penetrate into the resin because various cationic or anionic groups are bonded to the basic polymer matrix, but it can be easily applied regardless of the characteristics of the solvent. There is a serious problem when the apparent density is less than 1 g / cc in the dry state and lower to about 1 g / cc in the hydrous state so that the upstream of the liquid flows upward from the bottom of the resin tube.

Therefore, many studies have been conducted to increase the density of the porous ion exchange resin, and representative techniques thereof include a halogen introduction method or an inorganic oxide penetration method. In particular, U.S. Patent No. 4,399,235 synthesizes a basic matrix applicable to a porous ion exchange resin, and then increases the density by introducing a part of the position where the ionic group is introduced, by introducing halogen atoms such as bromine, chlorine, iodine, etc. The method is described. However, in this method, the addition of a polymer matrix halogenation reaction process is not only expensive in terms of the process but also reduces the ion exchange capacity due to the halogenation reaction.

And US Pat. No. 4,477,597 and US Pat. No. 4,724,082 describe methods for increasing the density by infiltrating insoluble inorganic materials into the polymer matrix. This method solves the problem of reducing the ion exchange capacity, but there is a problem that some of the insoluble minerals leak continuously causing secondary pollution.

In general, the expansion rate of the ion exchange resin layer required or recommended in the ion exchange process is 50% or less, and when the expansion rate exceeds 50%, the density of the ion exchange active point is lowered, thereby decreasing the ion exchange efficiency. Therefore, in order to avoid excessive expansion of the resin layer due to the resistance generated by the flow of fluid in the application of porous ion exchange resin, the flow rate must be slowed down. However, when the flow rate is slowed, a thick liquid film is formed on the outer surface of the resin particles, which causes a large external material transfer resistance, thereby causing a slow ion exchange rate.

Therefore, in order to solve this problem, a study to increase the density of the porous ion exchange resin is required, and it is generally advantageous to treat liquids or viscous liquids having a relatively high specific gravity of the high density ion exchange resin. In other words, the high density ion exchange resin can reduce the expansion of the resin layer and increase the flow rate of the fluid in the upflow stream.

Accordingly, the inventors of the present invention have made research efforts to increase the density of porous ion exchange resins, thereby preparing a polymer matrix by suspending polymerization of hydrophobic and high specific gravity inorganic compounds such as monomers and introducing ionic groups therein.

It is an object of the present invention to prepare a high density porous ion exchange resin useful for ion exchange of highly viscous liquids.

Hereinafter, the present invention will be described in detail.

The present invention improves the dispersibility of a density increasing agent in a method of preparing a polymer matrix by suspending and polymerizing a monomer, a crosslinking agent, a polymerization initiator, a polymerization stabilizer, a pore-forming agent, and introducing ion groups thereto. In order to proceed with the suspension polymerization of about 1 to 30%, the insoluble inorganic compound is added as a density increasing agent.

Hereinafter, the present invention will be described in more detail.

In other words, the present invention provides the above-mentioned suspension polymerization in order to increase the dispersibility of the density increasing agent which is added during the preparation of the polymer matrix by the usual suspension polymerization method by adding and mixing a monomer, a crosslinking agent, a polymerization initiator, a polymerization stabilizer, a pore-forming agent and the like. When the polymerization of the polymer matrix by about 1 to 30% was carried out, a porous polymer matrix was prepared by adding an insoluble inorganic compound as a density increasing agent, and then a cation or anion exchange resin was prepared by a conventional ion introduction method for the obtained polymer matrix. .

The monomer is an aromatic compound having a substituent containing an alkyl group containing one double bond, for example, styrene, monovinyl toluene, ethylvinyl toluene or vinyl naphthalene, and particularly preferably styrene.

In addition, the cross-linking agent is an aromatic compound having two or more substituents of an alkyl group having a double bond, for example, divinylbenzene, trivinylbenzene, divinyl toluene, divinyl xylene, divinyl naphthalene, trivinyl naphthalene or diisop Rotenyl benzene and the like, particularly preferably divinylbenzene.

As the polymerization initiator, 2,2-azobisisobutyronitrile (hereinafter referred to as AIBN) or 2- (3-biphenylyl) -5-phenyloxazole (hereinafter referred to as BPO) is dissolved in an organic phase. use.

In addition, polydimethyldiarylammonium chloride, gelatin, boric acid, or polyvinyl alcohol may be used as a polymerization stabilizer in order to protect the oil residue from the beginning to the end of the polymerization in suspension polymerization. The volume of the aqueous phase at the time of suspension polymerization is 2 to 8 times, more preferably 3 to 5 times the organic phase.

As a pore-forming agent for synthesizing the porous polymer matrix, a solvent having a high affinity with the polymer matrix or a good affinity with the monomer and a solvent having a low affinity with the polymer matrix are used. In particular, toluene is preferably used as a solvent having a high affinity and normal heptane is used as a solvent having a small affinity.

It is also possible to add plastirene, which has also been used in conventional manufacturing methods, to form a relatively large specific surface area. At this time, by adding 0 to 20 parts by weight of polystyrene with respect to 100 parts by weight of monomer, the specific surface area of the synthesized porous polymer matrix is adjusted to 100 to 600 m ² / g.

In addition, the insoluble inorganic compound, which is the density increasing agent, is mixed with the monomer, the crosslinking agent, the polymerization initiator, the polymerization stabilizer, the pore-forming agent, and the like to proceed with the reaction at about 70 ° C. for about 2 to 3 hours. About 1 to 10 parts by weight of the solution was added, followed by 7 to 10 hours at about 80 ° C. by a conventional suspension polymerization reaction, followed by further reaction at about 90 ° C. for 1 to 2 hours to completely react the unreacted material. Let's do it.

Examples of the insoluble inorganic compound as the density increasing agent include inorganic substances such as silica or alumina, or copper oxides such as cuprous oxide (CuO ₂ ) and cuprous oxide (CuO), and mercury oxide (HgO). Metal oxides such as titanium oxide (TiO ₂ ), lead oxide (PbO) or nickel oxide (NiO).

The amount of the insoluble inorganic compound according to the present invention is about 1 to 10 parts by weight based on 100 parts by weight of the monomer. If the amount is less than 1 part by weight, the density is low, which is not suitable for the application of viscous fluid and is 10 parts by weight. If the amount is exceeded, there is a problem that the mechanical strength is lowered.

By the method as described above, a porous polymer matrix having an average diameter of 0.1 mm to 1.2 mm is synthesized. Polymer matrices applied to conventional ion exchange resins must not be dissolved in water. Various polymers such as phenol resins, polyethylene resins, styrene resins and acrylic resins are applied to such polymers, and among them, styrene-based resins in which the basic repeating unit of the polymer matrix is composed of styrene derivatives are used.

Subsequently, ion exchange resins are prepared by introducing cationic or anionic groups into the porous polymer matrix obtained by a general iontophoretic method.

As the general ion group introduction method, a cation exchange resin is prepared by introducing a sulfone group by reacting concentrated sulfuric acid in a nitrobenzene solvent, and an anion exchange resin is prepared by introducing a chloromethyl group into a polymer matrix and then reacting with a trialkylamine.

The conventional method for preparing a high density porous ion exchange resin is to increase the density of the polymer matrix by starting the polymerization reaction by infiltration of the insoluble inorganic compound before starting the polymerization of the polymer matrix. 30% to 30% of the polymerization was carried out, and an insoluble inorganic compound was added to disperse the polymer matrix in good dispersibility and then disperse the polymer matrix in good dispersibility and then complete the polymerization of the polymer matrix.

The polymer matrix prepared by the above-described manufacturing method according to the present invention can further increase the density of the polymer matrix by infiltrating the insoluble inorganic material deep inside, and also reduce the inorganic leakage in the polymer matrix.

Hereinafter, the present invention will be described in detail with reference to Examples.

Example 1

Into a cylindrical four-necked reactor equipped with a cooler, a nitrogen injector, a stirrer, a monomer injector, and a baffle, 700 ml of pure water prepared by secondary distillation and ion exchange was added, and 0.5 g of polyvinyl alcohol as a suspension polymerization stabilizer was added thereto. After stirring for 30 minutes, polyvinyl alcohol was completely dissolved to prepare an aqueous phase. At this time, nitrogen was spread to 20 ml / min to remove dissolved oxygen.

Subsequently, 100 ml of normal heptane, 70 ml of divinylbenzene solution (divinyl benzene 55%: 45% ethyl styrene), 30 ml of styrene, and 0.5 g of benzoyl peroxide as a polymerization initiator were mixed and reacted at 70 ° C. for 2 hours and 30 minutes. After the addition of 3g of titanium oxide as a density increasing agent was mixed thoroughly to prepare an organic phase.

The prepared organic phase was introduced into a four-necked reactor containing an aqueous phase, followed by stirring for about 40 minutes to form oil droplets. When the remnants of a constant size were formed, the temperature was raised to 80 ° C. at a rate of 0.5 ° C./min, and the reaction was maintained for about 8 hours to allow the reaction to proceed sufficiently. In addition, the temperature of the reactor was maintained at 90 ° C. for about 2 hours to completely remove some unreacted material. After the reaction was cooled, the polymer matrix was separated by a filter, washed several times with pure water and acetone, and then vacuum dried.

50 g of the polymer matrix prepared above and 100 g of nitrobenzene were added to a round two-necked reactor, followed by swelling for about 1 hour at 50 ° C. by mechanical stirring. Then, 300 g of concentrated sulfuric acid was slowly added, and the temperature was raised to 90 ° C. Mad. After the sulfidation reaction, pure water was added at a rate of about 0.5ml / min for 3 hours, followed by 4 hours at 3ml / min, followed by dilution. The sulfated ion exchange resin was separated, washed with pure water, and dried under vacuum to obtain high density. Porous cation exchange resin was synthesized. The specific surface area of the synthesized resin was about 130 m ² / g, and the apparent density in the aqueous state was about 1.14 g / cc.

Example 2

The polymer matrix was prepared by suspension polymerization under the same production apparatus and polymerization conditions as in Example 1, and introduced into a spatula group to prepare a cation exchange resin, but 10 g of titanium dioxide was used as a density increasing agent. The specific surface area of the resin thus synthesized was about 110 m ² / g and the apparent density in the aqueous state was about 1.16 g / cc.

Example 3

Suspension polymerization was prepared by the same production apparatus and polymerization conditions as in Example 1 to prepare a polymer matrix, and a sulfone group was introduced thereto to prepare a cation exchange resin, except 100 mL of normal heptane and a divinylbenzene solution (divinylbenzene 55%: ethyl 70 ml of styrene (45%), 30 ml of styrene, and 0.5 g of benzoyl peroxide were mixed and reacted at 70 ° C. for 2 hours and 30 minutes. Then, 10 g of polystyrene and 3 g of titanium dioxide were added thereto to prepare an organic phase, followed by general polymerization. The apparatus was used to extract the polystyrene polymer matrix using a toluene solvent. As a result, the specific surface area of the synthesized resin was 450 m ² / g, and the apparent density of the water-containing state was about 1.11 g / cc. An ion exchange resin having a relatively large specific surface area was prepared as compared to the resin synthesized in Example 1.

Example 4

A cation exchange resin was prepared in the same manner as in Example 3, but 5 g of silica was used as a density increasing agent. The specific surface area of the synthesized cation exchange resin was 430 m 2 / g, and the apparent density was about 1.12 g / cc.

Example 5

Polymer matrix was prepared in the same manner as in Example 1, but 5 g of copper oxide was used as a density increasing agent. 50 g of dried polymer matrix resin, 5 g of zinc chloride and 100 g of dichloroethane were introduced into a conventional round two-necked reactor, and mechanical stirring was performed at 25 ° C. for about 1 hour, and then 200 g of chloromethyl ester was slowly added, followed by chloromethylation for about 8 hours. It was. After swelling 20 g of chloromethylated resin in 100 ml of toluene, 30 ml of triethylamine was added and reacted at 70 ° C. for about 10 hours to prepare a strong base anion exchange resin. The specific surface area of the prepared anion exchange resin was 92 m ² / g, and the apparent density was about 1.12 g / cc.

Example 6

An anion exchange resin was prepared in the same manner as in Example 5, except that 100 ml of normal heptane, 70 ml of divinylbenzene solution (55% divinylbenzene: 45% ethyl styrene), 30 ml of styrene, and 0.5 g of benzoyl peroxide were mixed to 70 ° C. After reacting for 3 hours at 7 g of titanium dioxide, the mixture was sufficiently mixed to prepare an organic phase. The specific surface area of the prepared anion exchange resin was about 90 m ² / g and the apparent density was about 1.13 g / cc.

Comparative Example 2

The polymer matrix was prepared by suspension polymerization in the same manner as in Example 3, and a strong basic anion exchange resin was prepared by introducing a chloromethyl group thereto, but without adding a density increasing agent.

As a result, the specific surface area of the synthesized resin was about 490m ² / g and the apparent density in the aqueous state was about 1.02g / cc.

Comparative Example 3

The polymer matrix was prepared by suspension polymerization in the same manner as in Example 5, and a quaternary ammonium salt was introduced thereto to prepare a strong basic anion exchange resin, but no density increasing agent was added. As a result, the specific surface area of the synthesized resin was about 90 m ² / g and the apparent density of the hydrous state was about 1.01 g / cc.

Claims (4)

In the method of preparing a polymer matrix by suspending and polymerizing a monomer, a crosslinking agent, a polymerization initiator, a polymerization stabilizer and a pore-forming agent, and introducing ion groups therein to increase the dispersibility of the density increasing agent, A method for producing a high density porous ion exchange resin, characterized in that suspension polymerization adds an insoluble inorganic compound as a 1 to 30% progress paper density increasing agent. The method for producing a high density porous ion exchange resin according to claim 1, wherein the amount of the insoluble inorganic compound is 1 to 10 parts by weight based on 100 parts by weight of the monomer. The method of claim 1, wherein the insoluble inorganic compound is silica, alumina or metal oxide. The method of claim 3, wherein the metal oxide is copper oxide, mercury oxide, titanium oxide, lead oxide or nickel oxide.