JPH074532B2 - Sulfonic acid type cation exchange resin for catalysts - Google Patents

Description

The present invention relates to a sulfonic acid type cation exchange resin for catalysts.

The catalyst resin of the present invention is particularly effective as a reaction catalyst in a solvent containing no water, and is effective, for example, in ester synthesis from alcohol and carboxylic acid and alkylation reaction of phenol and the like.

[Prior art]

Conventionally, cation exchange resins have been widely used not only for water treatment but also as reaction reagents and reaction catalysts because of their chemical and physical stability. Particularly, a styrene-divinylbenzene-based strongly acidic cation exchange resin having a sulfonic acid group as a functional group is widely used as a catalyst.

By the way, in a cation exchange resin having a sulfonic acid group as a functional group, the resin is sufficiently swollen by the water solvent in the water solvent system, and the diffusion of the reaction substrate in the resin particles through the network is relatively quick. It has high activity because it is carried out in the sea. However, in a solvent that does not contain water, the resin network is contracted, which prevents the diffusion of the reaction substrate into the resin particles and sterically blocks the surroundings of the sulfonic acid groups with other polymer chains. Therefore, there was a problem that the catalytic activity did not appear.

In order to overcome such drawbacks, so-called porous resins have been developed in which physical pores are added to the resin and only the surface of the pores is used, but these resins are used to increase the porosity. Not only has the drawback that the degree of cross-linking must be relatively high, and that the inside of the resin is not used except for the surface, and the higher degree of cross-linking also lowers the heat stability in the H form. It had drawbacks.

[Object of the Invention]

The present invention has been made in view of such circumstances, and an object thereof is to provide a sulfonic acid type cation exchange resin for a catalyst having high activity in a non-aqueous solvent.

[Structure of Invention]

The gist of the present invention is to crosslink a copolymer of a divinyl compound and an aromatic monovinyl compound having a degree of crosslinking of 2 to 40% by sulfonation of 5 to 40 mol% of all aromatic rings present in the crosslinked copolymer. The sulfonic acid type cation exchange resin for a reaction catalyst in a non-aqueous solvent thus obtained.

The cation exchange resin for catalyst produced in the present invention has 5 to 40 mol% of the total aromatic rings (exchange capacity 0.4 to 2.5 me).
q / g), preferably 10 to 40 mol% and particularly preferably 10 to 3
It is required that 0 mol% be sulfonated. The sulfonation rate is a fairly low value because the usual homogenous resin is 90 mol% or more. The production of such a resin is basically carried out by sulfonating a crosslinked copolymer composed of a monovinyl compound and a polyvinyl compound.

As the aromatic monovinyl compound used in the present invention, known compounds such as styrene, vinyltoluene and vinylnaphthalene can be used. From the industrial viewpoint, styrene is particularly useful.

Divinylbenzene, trivinylbenzene, trimethylolpropane trimethacrylate, etc. are useful as the polyvinyl compound, but divinylbenzene is particularly useful from an industrial viewpoint. In the case of using divinylbenzene, industrially usable divinylbenzene contains impurities such as ethylvinylbenzene, but the incorporation of such impurities does not affect the effect of the present invention. Further, if necessary, it is possible to include a monovinyl aliphatic compound such as acrylonitrile or methyl methacrylate.

The amount of polyvinylbenzene to styrene can be varied arbitrarily, but generally it is used in an amount corresponding to between about 2 to 40% by weight, preferably 5 to 20% by weight of the total amount of polyvinylbenzene and styrene. Therefore, the degree of cross-linking (% by weight of polyvinylbenzene based on all charged monomers) is 2-40
%, Preferably 5 to 20%.

Polymerization of a mixture of styrene and a polyvinyl compound is carried out by a known method. For the purpose of imparting porosity to the resin or adjusting the entanglement of the polymer chains, a solvent inert to the polymerization such as toluene, ethylbenzene or n-hexane, or a linear polymer such as polystyrene is added to the mixture. It is also possible to carry out polymerization.

Polymerization is preferably gelatin, polyvinyl alcohol as a dispersion stabilizer, in an aqueous solution containing a dispersion stabilizer such as magnesium silicate, benzoyl peroxide, a radical polymerization initiator such as azobisisobutyronitrile to the monomer, Add 0.05 to 10% by weight, and add 6 at 60 to 100 ℃ under nitrogen.
It is preferably carried out for about 20 hours in suspension with water as a medium, and the so-called pearl polymerization method is preferably adopted.

The spherical gel or porous copolymer obtained by the above polymerization method is sulfonated by adding a required amount of sulfonating agent in the presence of a swelling agent. As the swelling agent, an organic solvent which swells the crosslinked copolymer well and is inert to the sulfonation agent is preferable, and examples thereof include halogenated solvents such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride and trichloroethylene, nitromethane and nitro. Nitro solvents such as propane and nitrobenzene are particularly useful. The amount of such a solvent used is preferably such that the crosslinked copolymer is sufficiently swollen and the sulfonation reaction is smoothly carried out. Generally, it is 3 to 10 relative to the crosslinked copolymer.
Used by weight.

Chlorsulfonic acid, olium,
Sulfuric acid or the like can be used, but from the viewpoint of uniformly introducing sulfonic acid groups into the crosslinked copolymer, chlorosulfonic acid or olium is preferable, and from the viewpoint of keeping the introduction ratio of sulfonic acid groups constant, chlorosulfonic acid. Sulfonic acid is preferred.

The amount of chlorosulfonic acid used is defined by the amount of sulfonic acid groups to be introduced, but for the purpose of the present invention, it is preferable to use 5 to 40 mol% of all aromatic rings. If the amount of chlorosulfonic acid used is 5 mol% or less, the required introduction amount of sulfonic acid groups is insufficient, and if it is 40 mol% or more, the introduction rate of sulfonic acid groups is too high. It is preferably 10 to 40 mol%, particularly preferably 10 to 30 mol%.

The conditions of the sulfonation reaction vary depending on the degree of cross-linking of the cross-linked aromatic copolymer to be used, etc., but at room temperature to 120 ° C, 2 to 15
It's time.

After the reaction, the sulfonated resin is thoroughly washed with water after removing the swelling agent by a method such as azeotropic distillation.

The cation exchange resin of the present invention thus obtained is a high porous resin having a pore volume of 0.1 ml / g or more, preferably 0.2 ml / g or more as determined by the mercury method.

The resin of the present invention produced as described above is useful as a catalyst, particularly as a catalyst in an organic solvent that does not easily swell a usual ion exchange resin. For example, esterification, alkylation, dehydration condensation, addition It is useful for reactions such as reactions.

Although the conditions when used as a catalyst vary depending on the reaction, for example, in the esterification reaction from a carboxylic acid and an alcohol, 0.01 to 0.5 mol% of the resin of the present invention is used as the amount of the sulfonic acid group based on the carboxylic acid. Add room temperature to 1
It is desirable to perform the heating at 20 ° C. At this time, when the boiling points of the carboxylic acid and the alcohol are 100 ° C. or higher, it is also preferable to carry out while azeotropically expelling water.

The reaction may be either batch-wise or continuous.

[Example-1] Synthesis of resin Styrene-divinylbenzene copolymer having a crosslinking degree of 10%, a pore volume of 0.2 ml / g by a mercury method, and a toluene swelling degree of 5.2 ml / gr.
100 gr was suspended in 600 ml of 1,2-dichloroethane and left for 4 hours. Then, 23 g of chlorosulfonic acid dissolved in 50 ml of 1,2-dichloroethane was added, and the mixture was allowed to stand at room temperature for 4 hours,
Sulfonation was carried out by stirring.

After completion of the reaction, water 1 was added to the reaction mixture and heated to 95 ° C. to remove 1,2-dichloroethane by azeotropic distillation. Then, the resin was washed with a sufficient amount of water to obtain 334 ml of a sulfonated resin. The performance of the obtained resin is shown in Table-1.

[Example-2] Synthesis of resin Resin was prepared in the same manner as in Example-1 except that 100 gr of the same cross-linked copolymer as used in Example-1 was used and 14 gr of chlorosulfonic acid was used as a sulfonating agent. 246 ml was obtained.
The performance of the obtained resin is shown in Table-1.

Example-3 Synthesis of Resin Using the same cross-linked copolymer 100 gr as used in Example 1,
Resin 469 ml was obtained in the same manner as in Example 1 except that chlorosulfonic acid 50 gr was used as the sulfonating agent. The performance of the obtained resin is shown in Table-1.

[Example-4] Synthesis of resin The same treatment as in Example-1 was carried out except that the same cross-linked copolymer 100 gr as used in Example-1 was used and 30% oleum 43 gr was used as a sulfonating agent. , 360 ml of resin was obtained.
The performance of the obtained resin is shown in Table-1.

[Application Example] An esterification reaction was performed using the resin of the present invention. For comparison, the same reaction was carried out using a commercially available sulfonic acid type resin, the reaction rate constant was determined, and the performance was compared.

1 Experimental Method The completely regenerated (H-type) sulfonic acid type cation exchange resin sieved in a dry state to 420 to 590 μm was dried again in a vacuum dryer at 105 ° C. for 8 hours. A predetermined amount of the dry resin was placed in a round bottom flask equipped with a cooling tube, a motor and a thermometer, and n-
After adding a certain amount of butanol and heating to 80 ° C., the mixture was allowed to stand for 1 hour, and a predetermined amount of carboxylic acid separately heated to 80 ° C. was added to start the reaction. The reaction solution is sampled at regular intervals,
The residual carboxylic acid or the ester formed was quantified by the neutralization titration method or the gas chromatograph, and the change with time of the conversion rate was traced.

2 The esterification reaction was performed under the following three conditions.

(Condition-A) n-Butanol: 89 ml Acetic acid: 11 ml Catalyst resin: Add in an absolutely dry state so that the amount of sulfonic acid groups in the system is 0.1 equivalent / -solution Temperature: 80 ° ± 0.5 ° C Stirring speed: 200 rpm Round Bottom flask capacity: 200 ml (Condition-B) Same as Condition-A except that the catalyst resin was added so that the amount of sulfonic acid groups in the system was 0.02 equivalent / -solution (Condition-C) n-Butanol: 37 ml n -Caprylic acid: 13 ml Catalyst resin: The amount of sulfonic acid groups in the system is 0.1 equivalent /-Add in an absolutely dry state so as to be a solution Temperature: 80 ° ± 0.5 ° C Stirring speed: 200 rpm Round bottom flask capacity: 100 ml 1 The following irreversible reaction rate constant k ₁ (Hr ⁻¹ ) was calculated by the following method.

Where, t: reaction time (Hr) x: conversion k ₁ is Was plotted against t and calculated from the slope of the straight line. It was confirmed that there was a clear linear relationship up to a conversion rate of around 50%.

[Application Example 1] An esterification reaction was carried out using the condition-A. The catalyst ion-exchange resin used was one synthesized in Example-1 and Example-3.

Amberlite as an ion exchange resin for catalysts 1R-12
0B, Amberlyst 15 (Rohm & Haas)
Yaion SK1B, PK216 (Made by Mitsubishi Kasei Co., Ltd.)
The same operation was performed using.

The reaction rate number k ₁ when each resin is used is as shown in Table 2, and it can be seen that the resin of the present invention has a high reaction rate.

[Application Example 2] An esterification reaction was carried out using the condition-B. The catalyst resin used was one synthesized in Example-1 and Example-2.

The same operation was performed using DIAION PK208 (manufactured by Mitsubishi Kasei Co., Ltd.) as the ion exchange resin for the catalyst.

The reaction rate constant k ₁ when each resin is used is shown in Table 3.

[Application Example 3] An esterification reaction was carried out using the condition-C. The resin used is the one synthesized in Example-1.

DIAION PK208, an ion exchange resin for catalysts
Bar list The same operation was performed using 15.

The reaction rate constant k ₁ when each resin is used is shown in Table 4.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number in the agency FI Technical indication location // C07B 61/00 300 (72) Inventor Eiji Miyata 1000 Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Shigenori Wada, 1000, Kamoshida-cho, Midori-ku, Yokohama-shi, Kanagawa San Ryo Kasei Co., Ltd. (56) Reference JP-A-51-59089 (JP, A) JP-A-59-93042 (JP, A)

Claims (4)

[Claims] 1. A crosslinked copolymer of a divinyl compound and an aromatic monovinyl compound having a degree of crosslinking of 2 to 40% is sulfonated by 5 to 40 mol% of all aromatic rings present in the crosslinked copolymer. Obtained sulfonic acid type cation exchange resin for reaction catalyst in non-aqueous solvent 2. The cross-linked copolymer has a pore volume of 0.1 m as determined by the mercury method.
The cation exchange resin according to claim 1, which is a high-porous resin having a l / g or more. 3. A cation exchange resin according to claim 1, which has a degree of crosslinking of 5 to 20%. 4. 10 to 10 of the wholly aromatic rings present in the crosslinked copolymer
The cation exchange resin according to claim 1, wherein 30% is sulfonated.