JP2012081440A - Vinylpyridine resin for catalyst carrier and method of producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vinylpyridine resin, which is hard to powder and thermally decompose, contains many pores of a small size such that deterioration of carbonylation catalyst activity of methanol by thermal decomposition is suppressed, and has a pore capacity and a specific surface area which can provide sufficient catalyst activity.SOLUTION: The vinylpyridine resin has a capacity ratio of pores having pore a diameter of 3-5 nm to all pores of 4% or more and 60% or less, an overall pore capacity of 0.15 cc/g or more and 0.35 cc/g or less, and a specific surface area of 20 m/g or more and 100 m/g or less. The method of producing the vinylpyridine resin includes using a poor solvent and a good solvent in combination as porous agents, the amount of the good solvent being 50 wt.% or more and less than 90 wt.% relative to the total weight of the porous agents.

Description

  The present invention relates to a vinylpyridine resin used as a catalyst carrier in the production of acetic acid by methanol carbonylation reaction and a method for producing the same.

  Acetic acid is a basic chemical with a wide range of uses, such as raw materials for polyvinyl acetate, acetylcellulose and acetates, and solvents for terephthalic acid production plants.

  As methods for producing acetic acid used in the chemical industry, methods using carbonylation of methanol, partial oxidation of acetaldehyde, oxidation of butane, propane and the like are known, but most of them are currently produced by carbonylation of methanol. Has been made.

  As a method for producing acetic acid by carbonylation of methanol, “Monsanto method” (Patent Document 1) in which methanol and carbon monoxide are reacted in a water-containing acetic acid solvent in which a rhodium compound and methyl iodide are uniformly dissolved is often used. Are known. Further, in recent years, as an improved method of the Monsanto method, a technique in which the reaction proceeds in a heterogeneous system using a catalyst in which rhodium is supported on a porous vinylpyridine resin carrier (Patent Document 2, Patent Document 3, Patent Document 4). Patent Document 5) has been proposed and put to practical use.

  In these improved methods, in addition to the advantage of the Monsanto method that acetic acid can be produced from methanol in high yields, hydroiodic acid is produced by hydrolysis of methyl iodide by reducing the water concentration in the reaction product solution. By reducing the amount, the corrosion of the equipment system and the load of the separation and purification process of product acetic acid can be suppressed, and the reaction rate increases by immobilizing the rhodium complex to achieve a high concentration of the catalyst, and the catalyst is converted into the reactor. It has the further advantage that the cost and load required for separation and recovery can be reduced by reducing the deposition of the catalyst by enclosing the catalyst inside.

  As a porous vinylpyridine resin that can be used in these technologies, Patent Document 6 adds divinylbenzene as a crosslinking agent, isooctane as a porous agent, and benzoyl peroxide as a polymerization initiator to a vinylpyridine monomer. Oil phase, sodium chloride added to adjust density and prevent dissolution of vinylpyridine in the aqueous phase, sodium nitrite added to prevent polymerization of vinylpyridine monomer dissolved in the aqueous phase, and cellulosic suspension A vinyl pyridine resin produced by mixing an aqueous phase containing a turbid stabilizer in a polymerization reactor, dispersing the oil phase and polymerizing at 80 ° C. for 2 hours, followed by heat treatment at 95 ° C. for 5 hours. It is disclosed.

Japanese Patent Publication No.47-3334 JP-A-63-253047 JP-A-5-306253 JP-A-5-306254 JP-A-6-315637 Japanese Patent Publication No. 61-25731

  However, in the vinyl pyridine resin obtained by the conventional method described in Patent Document 6 and the like, the resin is easily pulverized or thermally decomposed, and the pores are blocked by the detachment generated by pulverization or thermal decomposition. As a result, there is a problem that the deterioration of the catalyst activity is accelerated.

  In view of the above problems, an object of the present invention is to provide a vinyl pyridine resin that is difficult to be pulverized and thermally decomposed and that has a reduced catalytic activity due to thermal decomposition and has sufficient catalytic activity, and a method for producing the same. And

As a result of intensive studies, the present inventors have found that the proportion of the volume of pores having a pore diameter of 3 to 5 nm in the total pores is 4% or more and 60% or less, and the total pore volume is 0.15 cc / g or more and 0.0. It has been found that the above problems can be solved by a vinylpyridine resin having a surface area of 35 cc / g or less and a specific surface area of 20 m ² / g or more and 100 m ² / g or less.

  Further, by using a poor solvent and a good solvent as the porous agent in combination such that the amount of the good solvent is 50 wt% or more and less than 90 wt% with respect to the total weight of the porous agent, the vinylpyridine resin according to the present invention is used. As a result, the present invention was completed.

  The catalyst in which the rhodium complex is supported on the vinylpyridine resin of the present invention has sufficient catalytic activity for the carbonylation reaction of methanol, is not easily pulverized or thermally decomposed, and is lost to a higher thermal decomposition rate. I do not live.

The figure which shows the typical pore diameter distribution of resin obtained by the Example of this invention. The figure which shows the relationship between the ratio of the volume which the pore which has a 3-5 nm pore diameter with respect to the total pore volume of resin occupies for all the pores, and the powdering speed | rate. The figure which shows the relationship between the total pore volume of resin, and carbonylation reaction catalytic activity. The figure which shows the relationship between the thermal decomposition time and catalyst decomposition rate in Example 1 and Comparative Example 1 of the present invention. The figure which shows the relationship between the catalyst decomposition rate and carbonylation reaction catalytic activity in Example 1 and Comparative Example 1 of the present invention.

The vinylpyridine resin according to the present invention is produced in the form of particles, and the particle diameter is 50 μm or more and 1500 μm or less, preferably 200 μm or more and 1000 μm or less. The vinyl pyridine resin according to the present invention has a volume ratio (hereinafter referred to as 3 to 5 nm pore volume ratio) of pores having a pore diameter of 3 to 5 nm of 4 to 60%, Preferably, it is 4% or more and 50% or less. Furthermore, the vinylpyridine resin according to the present invention has a total pore volume of 0.15 cc / g or more and 0.35 cc / g or less, preferably 0.15 cc / g or more and 0.25 cc / g or less, and a specific surface area of 20 m. ² / g or more and 100 m ² / g or less, preferably 30 m ² / g or more and 80 m ² / g or less.

  According to the studies by the present inventors, the 3-5 nm pore volume ratio is 4% or more, so that the catalyst powdering rate and the thermal decomposition rate are significantly lower than those of conventional vinylpyridine resins. Have.

  The vinylpyridine resin particles used for the catalyst are composed of a number of microgels having a size of 0.10 to 100 μm and crosslinked in a network form. Here, in order to increase the proportion of pores having a small pore diameter of 3 to 5 nm, it is necessary to reduce the size of the microgels constituting the resin and appropriately control the fusion of the microgels. Therefore, in the vinylpyridine resin of the present invention in which the volume ratio of the pores having a pore diameter of 3 to 5 nm is 4% or more, the microgels constituting the resin are uniformly and densely bonded to each other. Microgel separation due to thermal decomposition is less likely to occur. Furthermore, since the size of the microgel is small, the clogging of the pores due to the detached microgel hardly occurs, and the decrease in the catalytic activity due to the clogging of the pores is suppressed.

  On the other hand, when the 3-5 nm pore volume ratio exceeds 60%, the diffusion of the reactant becomes rate-limiting and the catalytic activity is lowered.

Further, if the total pore volume is less than 0.15 cc / g or the specific surface area is less than 20 m ² / g, sufficient catalytic activity cannot be obtained, and conversely, the total pore volume exceeds 0.35 cc / g. When the specific surface area is 100 m ² / g or more, a weak portion is generated in the resin structure, and the powder is easily pulverized or thermally decomposed.

  The method for producing the vinylpyridine resin of the present invention is not particularly limited. For example, an oily medium containing a vinylpyridine monomer, a crosslinking agent, a porous agent, and a polymerization initiator is mixed with an aqueous medium, and the vinylpyridine monomer is subjected to suspension polymerization. Can be manufactured by a method.

  At this time, the aqueous medium may contain an appropriate amount of a dispersant (suspension stabilizer), a surfactant, a deradical radical agent, a specific gravity adjuster, a pH adjuster, and the like as required. By mixing these oily medium and aqueous medium in a polymerization reactor, gradually raising the temperature to polymerize the polymer at 50 ° C. to 80 ° C., further raising the temperature and applying heat treatment at 85 ° C. to 95 ° C. The vinylpyridine resin of the present invention can be produced.

  The porous agent in the present invention refers to a solvent that dissolves a monomer but hardly dissolves a polymer formed by polymerization of the monomer. For example, an organic solvent having a property of swelling a crosslinked copolymer, a non-swellable organic solvent, etc. Can be used.

  When vinylpyridine resin particles are synthesized by the suspension polymerization method, the porous agent charged together with the monomer is phase-separated to crosslink into a large number of networks having a size of 0.10 to 100 μm. A microgel is generated. The size of the microgel, the fusion between the microgels, or the distribution of the organic solvent in the gap between the microgels is significantly affected by the compatibility between the microgel and the porous agent.

  Here, the method for producing a vinyl pyridine resin according to the present invention adjusts the compatibility of the vinyl pyridine polymer and the solvent by using a poor solvent and a good solvent for the vinyl pyridine polymer in combination as a porous agent. It is characterized by controlling the precipitation and fusion of the precipitated microgels via monomers in a solvent.

  The compatibility between the polymer and the solvent used as the porous agent depends on the polarities of the two, and the closer the polarity is, the higher the compatibility is. As a measure of solubility, a solubility parameter (SP) represented by the square root of the cohesive energy density representing intermolecular bonding force is used. In the present invention, a solvent having an SP whose absolute value of the difference from the SP of the vinylpyridine polymer is less than 2 is defined as a good solvent, and a solvent having an SP greater than 2 is defined as a poor solvent.

  As such a good solvent, for example, trimethylbenzene, toluene, xylene, 2-ethylhexanol and the like can be used. Moreover, as such a poor solvent, dioctyl phthalate, octane, nonane, etc. can be used, for example.

  In the present invention, “combined” means that two or more porous agents are mixed and suspended when used for a porous agent, and two or more polymerization initiators are mixed and used when used for a polymerization initiator. This is used for polymerization. These two or more types of porous agents or polymerization initiators may be prepared by mixing in advance, or may be mixed by stirring or the like in a reaction vessel.

According to the study by the present inventors, it is considered that the method of the present invention can provide a vinylpyridine resin having desired characteristics by the following actions.
When only the poor solvent is used as the porous agent, the polymer produced by the polymerization of the monomer is immediately phase-separated from the solvent, so that relatively small microgels are precipitated first. These precipitated microgels take in unreacted monomers exhibiting high compatibility and fuse with each other to grow into relatively large microgels. At this time, since the gap between the microgels is closed by the incorporated monomer, large pores derived from the gaps between the large microgels develop in the final resin. In the resin made in this way, the joint surface between the microgels becomes small due to the developed large-sized pores, and the microgels are easily detached by pulverization or thermal decomposition. Further, the pores are easily blocked by the released microgel, and the catalytic activity is likely to be lowered.

  On the other hand, when only a good solvent is used as a porous agent, the polymer and the solvent are difficult to phase-separate, and the microgel begins to precipitate after growing to a certain size. At this time, the monomer remaining in the solvent is reduced. Furthermore, since the monomers are evenly distributed between the good solvent and the microgels, the fusion of the precipitated microgels via the monomers is hardly performed, and as a result, the good dispersion is evenly distributed in the gaps between the microgels. Only minute pores derived from the solvent are formed. For this reason, the resin finally obtained has a small pore size, and sufficient catalytic activity cannot be obtained.

  On the other hand, the method for producing a vinylpyridine resin according to the present invention is characterized in that phase separation between a polymer and a solvent is adjusted by using a poor solvent and a good solvent in combination. Therefore, the size of the precipitated microgel and the fusion of the microgels after precipitation via the monomer in the solvent are controlled, and the microgel of a large size like when using only a poor solvent does not develop, A resin in which small microgels are closely joined can be obtained. At this time, the good solvent is highly compatible with the microgel, and a part of the good solvent solvates the skeleton inside the microgel. The remaining mixture of the good solvent and the poor solvent is uniformly dispersed in the gaps between the microgels. Therefore, the gap between the microgels is not completely blocked by the monomer, and the pores having a pore diameter of 3 to 5 nm are formed by removing the good solvent and the poor solvent after the resin is formed. Are uniformly formed.

  In this way, it is possible to obtain a macroporous resin in which microgels are closely joined to each other while leaving pores of appropriate sizes derived from the gaps. In this resin, since the microgels having relatively small sizes are densely bonded to each other, powdering and thermal decomposition of the resin due to separation of the microgel can be suppressed. Further, since the microgel constituting the vinylpyridine resin is small, the pores are not easily blocked by the microgel released by pulverization or thermal decomposition, and the catalytic activity is not easily lowered.

  The composition of the porous agent used in the present invention varies depending on the properties of the good solvent and the poor solvent used, but the good solvent is 50 wt% or more and less than 90 wt%, preferably 60 wt% or more and 85 wt% or less with respect to the total weight of the porous agent. Is preferred.

  When the proportion of the good solvent is less than 50 wt%, the precipitated microgel grows while taking in the monomer in the solvent and finally becomes a large microgel, and the pores derived from the gaps also become large. Further, the necessary number of pores having a pore diameter of 3 to 5 nm are not formed.

  In addition, as a good solvent, what has benzene rings, such as a trimethylbenzene, toluene, xylene, is preferable. 3-5 nm because the good solvent is uniformly distributed in the skeleton in the microgel and the gaps between the microgels due to the high compatibility between the benzene ring of the good solvent and the aromatic ring of the copolymer composed of vinylpyridine and divinylbenzene. This is because it is possible to distribute more and more uniformly the pores having the above pore diameters, and further, it is possible to make the powder structure and thermal decomposition difficult to occur without unevenness of the resin structure.

  Examples of the vinylpyridine monomer include, but are not limited to, 2-vinylpyridine, 3-vinylpyridine, 4-vinylpyridine, 4-vinylpyridine derivatives or 2-vinylpyridine having a lower alkyl group such as a methyl group or an ethyl group in the pyridine ring. Derivatives and the like can be used.

  2-methyl-5-vinylpyridine, 2-ethyl-5-vinylpyridine, 3-methyl-5-vinylpyridine, 2,3-dimethyl-5-vinylpyridine, 2-methyl-3-ethyl-5-vinylpyridine Etc. can be used. These monomers may be used alone, or two or more monomers may be combined.

  As the crosslinking agent, a compound having two or more vinyl groups can be used. Aromatic polyvinyl compounds such as divinylbenzene, divinyltoluene, divinylnaphthalene, or trivinylbenzene, aliphatic polyvinyl compounds such as butadiene, diallyl phthalate, ethylene glycol diacrylate, or ethylene glycol dimethacrylate, or divinylpyridine, trivinylpyridine Polyvinyl nitrogen-containing heterocyclic compounds such as divinylquinoline or divinylisoquinoline can be used. Moreover, it is preferable to use a crosslinking agent in the ratio of 20-60 wt% with respect to a monomer, Preferably it is 25-35 wt%.

  The polymerization initiator used in the present invention is not particularly limited, and any of those conventionally used for initiating the reaction of vinyl compounds such as benzoyl peroxide, lauroyl peroxide, and azobisisobutyronitrile. Can also be used. A preferable use amount of the polymerization initiator is 0.5 to 5.0 wt%, preferably 0.7 to 2.0 wt% with respect to the monomer mixture.

  Furthermore, in this invention, it is preferable to use the said polymerization initiator as a main polymerization initiator, and to use this in combination with the auxiliary polymerization initiator which has a half temperature lower than a main polymerization initiator.

  When the reaction temperature approaches 100 ° C. due to the reaction heat generated when the monomers are polymerized, the aqueous phase boils and the dispersed oil droplets coalesce. When only the main polymerization initiator is used, it is necessary to reduce the oil phase / water phase ratio in order to remove this heat of reaction and control the reaction temperature to 100 ° C. or less, and the amount of resin obtained per batch is small. There was a problem.

  In contrast, by using a combination of the main polymerization initiator and the auxiliary polymerization initiator, the polymerization temperature can be lowered while maintaining the polymerization rate. This facilitates the removal of the heat of polymerization reaction, and the oil phase / water phase ratio can be increased, so that the production amount per batch can be increased.

  As such an auxiliary polymerization initiator, for example, 2,2′-Azobis (2,4-dimethylvaleronitrile), 2,2′-Azobis (2-methylbutyronitrile), or the like can be used. The ratio of the polymerization initiator to the auxiliary polymerization initiator depends on the types of the polymerization initiator and auxiliary polymerization initiator used, but is, for example, 1: 0.2 to 1.0, preferably 1: 0.3 to 0.00. 5 is preferable.

  The dispersant used in the present invention is not particularly limited, and conventionally used polyvinyl alcohol, hydroxyethyl cellulose, carboxymethyl cellulose, sodium polymethacrylate, sodium polyacrylate, starch, gelatin, styrene / maleic anhydride copolymer Water-soluble polymers such as a combined ammonium salt, and inorganic salts such as calcium carbonate, calcium sulfate, bentonite, and magnesium silicate can be used.

  There are no particular limitations on the surfactant, deradical agent, specific gravity adjusting agent, and pH adjusting agent used in the present invention, and any conventionally used one can be used. For example, dodecylbenzenesulfonic acid or the like can be used as the surfactant, sodium nitrite or the like can be used as the deradical agent, sodium chloride or the like can be used as the specific gravity adjusting agent, and sodium hydroxide or the like can be used as the pH adjusting agent. .

  The vinylpyridine resin of the present invention can be suitably used for production of acetic acid by heterogeneous system by supporting a rhodium complex.

1. Preparation of vinylpyridine resin [Example 1]
As an aqueous phase, 10 wt% NaCl (specific gravity adjusting agent), 0.3 wt% NaNO ₂ (detergent), 0.064 wt% gelatin (dispersing agent) and 0.009 wt% sodium dodecylbenzenesulfonate (surfactant) 6250 g of a solution in which was dissolved in ion exchange water was prepared.

  As oil phase, 36.4 wt% 4-vinylpyridine (vinylpyridine monomer), 43.6 wt% divinylbenzene (purity: 55 wt%) (crosslinking agent), 15 wt% 1,2,4-trimethylbenzene (good solvent) 3750 g of a liquid containing 5 wt% dioctyl phthalate (poor solvent) was prepared.

  Furthermore, 0.84wt% benzoyl peroxide (polymerization agent) and 0.34wt% 2,2'-Azobis (2,4-dimethylvaleronitrile) (auxiliary polymerization initiator) are dissolved in the oil phase, and 10L suspension with jacket is added. Placed in a turbid polymerization reactor. The aqueous phase prepared from the lower part of the reactor was supplied thereto and gently stirred.

  After stirring until the oil droplets were uniformly dispersed, the temperature of the liquid in the reactor was increased by flowing warm water of 65 ° C. through the jacket of the reactor, and the monomer was polymerized in the reactor. After the temperature of the liquid in the reactor rose to 60 ° C, the rate of increase increased, and after rising to 80 ° C, it gradually decreased. After confirming that the liquid in the reactor had fallen to 60 ° C., the liquid in the reactor was further heated to 90 ° C. and held there for 4 hours. Thereafter, the liquid in the reactor was cooled to room temperature, solid-liquid separation was performed by filtration, and the resin was recovered. The recovered resin was further extracted and washed to remove porous agents 1,2,4-trimethylbenzene and dioctyl phthalate, and classified with a sieve to obtain the final 4-vinylpyridine resin for catalyst.

[Example 2]
A 4-vinylpyridine resin for a catalyst was obtained in the same manner as in Example 1 except that 5 wt% octane was used as a poor solvent and 15 wt% toluene was used as a good solvent.

[Example 3]
A 4-vinylpyridine resin for a catalyst was obtained in the same manner as in Example 1 except that 6 wt% octane was used as a poor solvent and 14 wt% toluene was used as a good solvent.

[Example 4]
A 4-vinylpyridine resin for a catalyst was obtained in the same manner as in Example 1 except that a 3 m ³ suspension polymerization reactor with a jacket (aqueous phase: 1650 kg, oil phase: 990 kg) was used.

[Comparative Example 1]
A 4-vinylpyridine resin for a catalyst was obtained in the same manner as in Example 1 except that only 20 wt% isooctane was used as a solvent.

[Comparative Example 2]
A 4-vinylpyridine resin for a catalyst was obtained in the same manner as in Example 1 except that 10 wt% octane was used as the poor solvent and 10 wt% toluene was used as the good solvent.

[Comparative Example 3]
As in Example 1, except that 0.91 wt% benzoyl peroxide was used as the polymerization initiator and 0.27 wt% 2,2′-Azobis (2,4-dimethylvaleronitrile) was used as the auxiliary polymerization initiator, 4- A vinylpyridine resin was obtained.

[Comparative Example 4]
A 4-vinylpyridine resin for a catalyst was obtained in the same manner as in Example 1 except that the temperature of warm water flowing through the jacket was raised to 65 ° C at 10 ° C / hr.

2. Measurement of physical properties The physical properties of the obtained 4-vinylpyridine resin for catalyst support were measured by the following methods.

(1) Measurement of resin specific surface area, pore volume, average pore diameter Specific surface area, pore volume (total pore volume, 3-5 nm pore volume), average of obtained 4-vinylpyridine resin for catalyst carrier The pore diameter was measured by a nitrogen adsorption method (Yuasa Ionics Co., Ltd. AUTOSORB-1).

(2) Measurement of pulverization rate 17 g (dry) of the obtained 4-vinylpyridine resin for catalyst support was taken, 100 g of methyl iodide 17 wt% methanol solution was added, and the mixture was shaken for 18 hours. Classification was performed.

  The quaternized 4-vinylpyridine resin for catalyst carrier was placed in a 300 ml cylindrical separable flask (with 4 baffles), and stirred for 40, 72 and 144 hours at 1000 rpm with a 40 mm desk turbine stirring blade.

  After stirring, solid-liquid separation was performed with a sieve having an opening of 90 μm. The pulverization rate was determined by the ratio between the weight of the obtained pulverized product and the weight of the charged 4-vinylpyridine resin for the catalyst carrier. Moreover, the pulverization rate was calculated | required from the pulverization rate (%) after 72 hours and 144 hours, and stirring time, and the average value was made into the pulverization rate in each Example and a comparative example.

(3) Measurement of catalytic activity (i) Catalysis The obtained 4-vinylpyridine resin for catalyst carrier 8.5g (dry basis) and reaction solution 79.7g (methanol 31.3wt%, methyl iodide 21.6wt%, acetic acid 47.1wt% ) And a predetermined amount of rhodium acetate were charged into a 200 ml zirconium autoclave and reacted at a reaction temperature of 180 ° C. and a CO pressure of 5.0 MPaG for 1 hour to catalyze.

(Ii) Reaction test A total amount of the above catalyst and 80 g of the reaction solution (methanol 25 wt%, acetic acid 62.5 wt%, methyl iodide 12.5 wt%) were charged into a 200 ml zirconium autoclave and reacted at a reaction temperature of 180 ° C. and a CO pressure of 5.0 MPaG for 1 hour. The carbonylation reaction rate was determined from the CO consumption and the amount of acetic acid produced.

  Table 1 shows the physical properties of the resulting 4-vinylpyridine resin for catalyst support, and FIG. 1 shows a typical pore size distribution.

＊カルボニル化活性の一番低い比較例３の活性を１とした。

* The activity of Comparative Example 3 having the lowest carbonylation activity was set to 1.

  The relationship between the volume ratio occupied by pores having a pore diameter of 3 to 5 nm with respect to the total pore volume and the powdering rate is shown in FIG. It can be seen that the powdering rate decreases as the volume ratio occupied by pores having a pore diameter of 3 to 5 nm increases.

  FIG. 3 shows the relationship between the pore volume and the carbonylation reaction catalytic activity. It can be seen that the catalytic activity of the carbonylation reaction is constant when the pore volume is 0.15 cc / g or more.

(4) Measurement of thermal decomposition rate and relationship between decomposition rate and catalytic activity The 4-vinylpyridine resin obtained in Example 1 and Comparative Example 1 was catalyzed, and the thermal decomposition rate, decomposition rate and carbonylation reaction were carried out by the following method. The relationship of catalyst activity was investigated.

(I) Thermal decomposition acceleration test The obtained 4-vinylpyridine resin for a catalyst support was catalyzed by the above-described method, charged with 200 ml of acetic acid in a 200 ml zirconium autoclave, and heated to 220 ° C. with stirring. Thereafter, the liquid was sampled every 24 hours, the nitrogen concentration was measured, and the amount of detached pyridine groups was determined. Further, the nitrogen concentration in the 4-vinylpyridine resin was separately measured, and the decomposition rate was determined from the ratio with the leaving pyridine group.

  FIG. 4 shows the relationship between the thermal decomposition time and the catalyst decomposition rate. It turns out that the thermal decomposition rate of Example 1 (2) is small compared with the comparative example 1 (4).

  Next, the relationship between the catalytic decomposition rate and the catalytic activity of the carbonylation reaction is shown in FIG. In FIG. 5, the catalyst activity ratio is expressed with the activity of the untreated catalyst as 1. In Comparative Example 1 (4), the activity of the untreated catalyst is lower than the decomposition rate of about 20%, whereas in Example 1 (2), the activity of the untreated catalyst is maintained up to the decomposition rate of about 30%. It was.

  In addition, both Example 1 and Comparative Example 1 exceeded the initial activity when the decomposition rate was low, but this caused the distance between the microgel or the fusion thereof to be increased by heat, and the diffusion rate of the reactant was improved. It is thought that it was because.

Claims (4)

The ratio of the volume of pores having a pore diameter of 3 to 5 nm to the total pores is 4% to 60%, the total pore volume is 0.15 cc / g to 0.35 cc / g, and the specific surface area is 20 m ^2. A vinyl pyridine resin for a catalyst carrier, wherein the vinyl pyridine resin is / g or more and 100 m ² / g or less. A method for producing a vinylpyridine resin for a catalyst carrier by mixing an oily medium containing a vinylpyridine monomer, a crosslinking agent, a porous agent and a polymerization initiator with an aqueous medium, and subjecting the oily medium to suspension polymerization.
A porous agent is a combination of a good solvent and a poor solvent,
The method for producing a vinyl pyridine resin for a catalyst carrier, wherein the amount of the good solvent used is 50 wt% or more and less than 90 wt% with respect to the total weight of the porous agent.   The method for producing a vinyl pyridine resin for a catalyst carrier according to claim 2, wherein the good solvent has a benzene ring.   The vinyl pyridine for a catalyst carrier according to claim 2 or 3, wherein the polymerization initiator is a combination of the main polymerization initiator and an auxiliary polymerization initiator having a half-temperature lower than that of the main polymerization initiator. Manufacturing method of resin.

Images