JPH0539315A - Production of hydrogenated aromatic resin - Google Patents

Abstract

PURPOSE:To produce a hydrogenated aromatic resin by hydrogenating an aromatic resin such as a coumarone-indene resin especially under industrially practicable conditions. CONSTITUTION:A process for producing a hydrogenated aromatic resin by hydrogenating an aromatic resin containing 50wt.% or above indene as a monomer component constituting the resin, wherein the hydrogenation is performed in the presence of a catalyst prepared by infiltrating 0.5-3.0wt.% platinum into an alumina support having a pore volume of 0.5cc/g or above and an average pore diameter of 100280Angstrom . A high-indene aromatic resin such as a difficultly hydrogenatable coumarone-indene resin can be hydrogenated easily under industrially and easily practicable gentle conditions. Further, the catalyst life can be prolonged.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a hydrogenated aromatic resin. More specifically, it relates to a method for producing a hydrogenated aromatic resin obtained by hydrogenating an aromatic resin containing 50 wt% or more of indene as a polymerization component.

[0002]

2. Description of the Related Art So-called coumarone-indene resin obtained by polymerizing a distillate obtained by distilling gas oil recovered from coal tar and coke oven gas in the presence of Friedel-Crafts catalyst is mainly an adhesive agent. , Which are used as coating resins, these hydrogenated products are being developed for new applications by taking advantage of their weather resistance, color tone and excellent adhesive properties. For example, JP-A-2-14742
And Japanese Patent Laid-Open No. 2-866455, its characteristics are described.

However, the above-mentioned coumarone-indene resin used for hydrogenation is much less susceptible to hydrogenation than the raw material monomer, and further, the thermal decomposition product of petroleum naphtha is polymerized in the presence of Friedel-Crafts catalyst. It is much less susceptible to hydrogenation than the so-called petroleum resin obtained. This is probably because petroleum resins have styrene and methylstyrene as the main components which are relatively susceptible to hydrogenation, whereas coumarone-indene resins have indene which is difficult to be hydrogenated as a main component. For example, in an experiment conducted by the present inventor, when hydrogenating a styrene oligomer and an indene oligomer having the same molecular weight using a stabilized nickel catalyst under the same reaction conditions, the former hydrogenation rate was 100%. In contrast, that of the latter was 40%. The method for producing a hydrogenated petroleum resin is described in, for example, JP-A-59-75904, JP-A-59-136312 and JP-A-1-190704.
In these methods, 50% by weight of indene is used as a polymerization component.
It is impossible to economically hydrogenate the aromatic resin containing the above.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for hydrogenating an aromatic resin containing indene in an amount of 50 wt% or more as a polymerization component. Another object of the present invention is to provide a method for producing the hydrogenated aromatic resin.

[0005]

In order to solve the above problems, the present inventor has conducted diligent research focusing on hydrogenation catalysts, and if a specific platinum catalyst is used, it is economical to use hydrogenated resins. The present invention has been completed by finding out that can be manufactured. That is, according to the present invention, when hydrogenating an aromatic resin containing 50 wt% or more of indene as a polymerization component, the pore volume of 0.
5 cc / g or more, preferably 0.5 cc / g or more 0.7
A method for producing a hydrogenated aromatic resin, which comprises using a catalyst in which platinum is supported in an amount of 0.5 to 3.0 wt% on an alumina carrier having a cc / g or less and an average pore diameter of 100 to 280Å. is there.

The aromatic resin to be used in the present invention is obtained by polymerizing an aromatic oil containing indene in an amount of 50 wt% or more based on the total polymerization components in the presence of a Friedel-Crafts catalyst such as boron trifluoride or aluminum chloride. It is obtained by doing. At this time, other polymer components of indene include coumarone, styrene, α-methylstyrene, p-methylstyrene, methylindene, and the like, and in addition to these, phenol and alkylphenol may be contained.

The catalyst used in the present invention must have a specific metal supported on a specific carrier. When hydrogenating an aromatic resin targeted by the present invention, it goes without saying that the catalyst has a high hydrogenation ability for an aromatic ring, but it is adsorbed at an active site on the catalyst as compared with hydrogenation of a monomer component. Since the steric hindrance during the treatment is large, it is necessary to have a structure in which the resin is easily adsorbed. That is, it is possible to obtain a large reaction rate by rapidly executing the steps of diffusion of resin into catalyst pores-adsorption at active sites-hydrogenation-desorption from active sites-desorption from catalyst pores. You can This can be realized only by controlling the hydrogenation activity of the catalytic metal species, the interaction between the metal and the carrier, the catalyst pore structure, and the like. As a result of diligently searching for metals and carriers and studying the carrier structure, the present inventors have surprisingly found that platinum has a pore volume of 0.5 cc / g or more and an average pore diameter of 1
0.5-3.0wt% on an alumina carrier of 00-280Å
It was found that by using the catalyst supported in the above range, a reaction rate that is industrially sufficiently feasible can be obtained.

In addition to platinum, noble metals such as rhodium, palladium and ruthenium or inexpensive nickel catalysts are usually used industrially for hydrogenating aromatic rings, but the aromatic resin of the present invention usually contains 10 to 10 parts. Nickel catalysts that are permanently poisoned by sulfur are not preferred because they contain 2000 ppm of sulfur. Further, rhodium, palladium, and ruthenium do not show high activity in hydrogenation of the aromatic resin of the present invention, and only platinum shows high activity.

As the carriers used industrially, silica, titania, boria, magnesia, carbon, activated clay, etc. are available in addition to alumina, but high activity can be obtained only when alumina, especially γ-alumina is used. Be done. Although the reason for this has not been clarified, it is presumed that the interaction between alumina and platinum, the surface acidity, etc. are influencing. The alumina used for the carrier has a pore volume of 0.5 cc / g or more, preferably 0.5 cc / g or more and 0.7 cc / g or less, and an average pore diameter of 100 to 280 Å, preferably 15
It must be in the range of 0 to 250Å. The pore volume referred to here is the pore diameter measured by the gas adsorption method 600Å
It represents the sum of the following volumes. The average pore diameter is calculated by the following formula from the values of specific surface area and pore volume. Here, the specific surface area is preferably in the range of 50 to 250 m ² / g. Average pore diameter = 4 * (pore volume) / (specific surface area) The reason why a satisfactory hydrogenation rate cannot be obtained when the average pore diameter is smaller than 100Å is that the diffusion of the resin in the catalyst pores is smooth. It is considered that it is not done in. Further, if it is larger than 300Å, it is advantageous for diffusion, but it is considered that the specific surface area becomes small, so that the number of active sites becomes small and the activity is lowered. If the pore volume is smaller than 0.5 cc / g, the number of active sites is also small, which is disadvantageous.

The amount of platinum supported is 0.5 to 3.0 wt%, preferably 1.0 to 2.0 wt%. 0.5
When it is less than wt%, satisfactory activity cannot be obtained, and 3.0
Even if it is more than wt%, the activity is not improved in proportion to the amount of metal and it is economically disadvantageous.

The catalyst used in the present invention can be prepared by a general impregnation method. That is, the carrier alumina is dispersed in water, and a platinum compound such as H ₂ Pt
Cl ₆ , [Pt (NH ₃ ) ₄ ] Cl ₂ , Pt (NO ₂ )
An aqueous solution of ₂ (NH ₃ ) ₂ or the like is dropped to impregnate it. After evaporation of water and drying, reduction treatment is performed in a hydrogen atmosphere. If necessary, firing treatment may be performed before the reduction treatment.

The reaction may be carried out batchwise or continuously. Since the catalyst of the present invention is hardly poisoned by the resin and impurities in the resin, continuous operation can be easily performed. The reaction conditions include a temperature of 200 to 350 ° C. and a pressure of 50 to
It is preferably in the range of 150 kg / cm ² , and the solvent may or may not be used. If a solvent is used,
Cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, decalin and the like are preferable.

[0013]

EXAMPLES The present invention will be described in detail below with reference to examples. Example 1 1 wt% Pt / alumina prepared by an impregnation method from γ-alumina and chloroplatinic acid (H ₂ PtCl ₆ ) (pore volume: 0.605 cc / g, specific surface area: 105.9 m ² / g, average pore diameter) 228Å) 5g was charged, reaction pressure 100k
The reaction was carried out under the conditions of g / cm ² and a temperature of 280 ° C. for 6 hours. As a result of taking out the product and performing ¹ H-NMR analysis,
The amount of aromatic hydrogen was 2.5%. Table 1 shows the monomer composition and aromatic hydrogen content of the coumarone-indene resin used as the raw material.

[0014]

[Table 1] ─────────────────────── Component ratio (wt%) ──────────────── ───────── Indene 74 Coumaron 3 Styrene 14 p-Methylstyrene 3 Phenol 6 ──────────────────────── Aromatic hydrogen content 48% ─────────────────────── Sulfur content 50ppm ────────────────────────

Example 2 Five coumarone-indene resins were added to a 0.2 l autoclave.
0 g, 1 wt% Pt / alumina (pore volume 0.590 m
1 / g, specific surface area 129.7 m ² / g, average pore diameter 1
82 Å) 5 g was charged and hydrogenation was carried out under the same conditions as in Example 1. The amount of aromatic hydrogen in the product was 2.1%. The composition of the raw material resin and the amount of aromatic hydrogen are shown in Table 2.

[0016]

[Table 2] ─────────────────────── Component ratio (wt%) ──────────────── ───────── Indene 59 Coumaron 6 Styrene 18 p-Methylstyrene 9 Phenol 8 ─────────────────────── Aromatic hydrogen content 46% ─────────────────────── Sulfur content 70ppm ────────────────────────

Example 3 The same operation as in Example 2 was carried out except that the amount of metal in the catalyst of Example 2 was changed to 2 wt%. The amount of aromatic hydrogen in the product is 1.
It was 9%.

Example 4 1 wt% Pt / alumina prepared by impregnating spherical γ-alumina having a diameter of 1 mm with chloroplatinic acid (pore volume 0.605 ml / g, specific surface area 105.9 m ² / g,
The average pore diameter 228Å) 50ml was packed into a fixed bed reactor, the raw material was 50 wt% solution by dissolving the resin of Example 1 in ethyl cyclohexane, the reaction temperature 300 ° C., a pressure 100kg / cm ^2, LHSV0.3h ^-1 , oil was passed under the condition of gas / liquid ratio of 2500 (v / v) to carry out hydrogenation.
Ethylcyclohexane was removed by evaporation from the produced oil after passing for 200 hours, and the amount of aromatic hydrogen in the resin component was measured and found to be 0.9%. The operation was continued for 2500 hours continuously, but during this period, the catalyst activity did not change.

Comparative Example 1 The same operation as in Example 1 was carried out except that Rh was used instead of Pt in Example 1. The amount of aromatic hydrogen in the product is 6.3%
Met.

Comparative Example 2 The same operation as in Example 1 was carried out except that Ru was used instead of Pt in Example 1. The amount of aromatic hydrogen in the product is 32.1
%Met.

Comparative Example 3 The same operation as in Example 1 was carried out except that Pd was used instead of Pt in Example 1. The amount of aromatic hydrogen in the product is 19.0
%Met.

Comparative Example 4 0.5 wt% Ru-0.5 wt in place of Pt in Example 1
The same operation as in Example 1 was performed except that% Rh was used.
The amount of aromatic hydrogen in the product was 19.3%.

Comparative Example 5 The same operation as in Example 1 was carried out except that zirconia was used in place of the alumina of Example 1. The amount of aromatic hydrogen in the product was 28.2%.

Comparative Example 6 In place of the catalyst of Example 1, 1 wt% Pt / alumina (pore volume 0.580 ml / g, specific surface area 277.5 m ² /
g, average pore diameter 84Å) was used, and the same operation as in Example 1 was performed. The amount of aromatic hydrogen in the product was 6.0%. 1

Comparative Example 7 In place of the catalyst of Example 1, 1 wt% Pt / alumina (pore volume 0.537 ml / g, specific surface area 71.6 m ² / g,
The same operation as in Example 1 was performed except that an average pore diameter of 300Å) was used. The amount of aromatic hydrogen in the product was 6.5%.

Comparative Example 8 Pt in Example 1 was replaced with Rh, and the reaction temperature was 32.
The same operation as in Example 1 was performed except that the temperature was 0 ° C. The aromatic hydrogen content of the product was 4.1%, which was improved as compared with Comparative Example 1, but the softening point of the product was lowered by 20 ° C. as compared with Example 1 due to the decomposition reaction.

[0027]

Industrial Applicability According to the present invention, aromatic resins such as coumarone-indene resin, which are difficult to hydrogenate, can be easily hydrogenated under mild conditions that are industrially easy to carry out. In addition, the catalyst life can be extended.

Claims (1)

[Claims] 1. A pore volume of 0.5 when hydrogenating an aromatic resin containing 50 wt% or more of indene as a polymerization component.
A method for producing a hydrogenated aromatic resin, which comprises using a catalyst in which platinum is supported on an alumina carrier having a cc / g or more and an average pore diameter of 100 to 280Å in a range of 0.5 to 3.0 wt%.