JP2002275212A - Method for producing hydrogenated petroleum resin and hydrogenation catalyst used for the production method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst having high hydrogenation activity and a proper hydrogenolysis property, and to provide a method for producing a hydrogenated petroleum resin. SOLUTION: This method for producing the hydrogenated petroleum resin, comprising hydrogenating a petroleum resin in the presence of a hydrogenation catalyst, is characterized by using a catalyst comprising nickel and synthetic silica alumina and satisfying conditions comprising a nickel content of 50 to 65 wt.%, a catalyst surface area of 300 to 400 m<2> /g and a bulk density of 0.22 to 0.50 g/cm<3> ; the hydrogenation catalyst for the petroleum resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a hydrogenated petroleum resin. The hydrogenated petroleum resin obtained by the present invention has good color tone and thermal stability, and is a tackifier such as a tacky / adhesive, a paint, a printing ink, a traffic paint, a sealant for a semiconductor, and a water-resistance imparting agent. Further, it can be used as a plastic modifier.

[0002]

2. Description of the Related Art Hydrogenation of petroleum resin using a hydrogenation catalyst comprising a metal such as cobalt, copper, nickel, palladium, platinum, ruthenium and rhodium supported on a carrier such as diatomaceous earth, silica, alumina and silica-alumina. By doing
It is known that a hydrogenated petroleum resin having excellent color tone, heat stability, weather resistance and the like can be obtained.

[0003] As the hydrogenation catalyst used in the hydrogenation reaction, those having higher hydrogenation activity are suitable in order to be advantageous in terms of cost and to reduce industrial waste and reduce the impact on the environment. I have. In addition, it is necessary to control the molecular weight, softening point, and the like of such a hydrogenated petroleum resin in order to improve the compatibility with various elastomers according to the use.
Since this is performed by controlling the hydrocracking reaction when hydrogenating the raw petroleum resin, it is necessary to select a catalyst having an optimum hydrocracking property. Further, from the viewpoint of workability in refining the obtained hydrogenated petroleum resin, a material having excellent handling properties such as little scattering of the hydrogenation catalyst and easy filtration is suitable.

[0004] The active metal species, which is the main component of the hydrogenation catalyst used in such a hydrogenation reaction, has a great influence on the hydrogenation activity and hydrogenolysis. For example, when using a hydrogenation catalyst that uses cobalt, copper, etc. as the active metal species, the hydrogenation activity is insufficient, so use a large amount of the catalyst or perform the hydrogenation reaction under extremely severe high-temperature and high-pressure conditions. Must be performed, which is disadvantageous in terms of raw materials and production costs. A hydrogenation catalyst using a noble metal such as palladium, platinum, ruthenium or rhodium as an active metal species has a high hydrogenation activity but is expensive and disadvantageous in terms of cost. In order to alleviate this, there arises a problem that a facility for recovering the catalyst is required and a reaction form is restricted.

[0005] A carrier, which is another main component of the hydrogenation catalyst, also has a significant effect on hydrogenation activity and hydrocracking. In the hydrogenation reaction of petroleum resins, diatomaceous earth, silica, alumina and other carriers have a surface area that affects the hydrogenation activity,
No knowledge has been found regarding the balance with specific gravity that affects workability and dispersibility.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for inexpensively producing a hydrogenated petroleum resin using a catalyst having a high hydrogenation activity and an appropriate hydrocracking property.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, the catalyst containing a specific amount of nickel among the catalysts containing nickel and synthetic silica alumina, In addition, it has been found that when a hydrogenation catalyst having a specific catalyst surface area and a bulk specific gravity is used, petroleum resins exhibit high hydrogenation activity and moderate hydrocracking properties. The present invention has been completed based on such new findings.

That is, the present invention relates to a method for producing a hydrogenated petroleum resin by hydrogenating a petroleum resin in the presence of a hydrogenation catalyst, comprising nickel and synthetic silica alumina as a hydrogenation catalyst; Content 50 ~
A method for producing a hydrogenated petroleum resin, characterized by using a material satisfying the conditions of 65% by weight, a catalyst surface area of 300 to 400 m ² / g and a bulk specific gravity of 0.22 to 0.50 g / cm ³ ; Catalyst.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The petroleum resin used in the present invention is not particularly limited, and known petroleum resins can be used. In general, petroleum resins are roughly classified into aliphatic petroleum resins, aromatic petroleum resins, and cyclopentadiene-based petroleum resins according to the type of the raw material monomer (fraction). C5 petroleum resin as aliphatic petroleum resin as aliphatic petroleum resin,
C5-C9 petroleum resins and the like, and aromatic petroleum resins include C9-based petroleum resins. The C5 petroleum resin is a C5 petroleum fraction (for example, pentene, methylbutene,
Isoprene, cyclopentene, etc.) by cationic polymerization. The C9 petroleum resin is not particularly limited, but is generally C9 obtained by cracking naphtha.
Ninth petroleum fraction (for example, styrene, vinyltoluene, α
-Methylstyrene, indene, etc.) can be used. The C5-C9 petroleum resin is obtained by copolymerizing the C5 fraction and the C9 fraction in the same manner as in the production of the C5 petroleum resin. The dicyclopentadiene-based petroleum resin is obtained by thermally or cationically polymerizing dicyclopentadiene. These petroleum resins may be those modified with a polar group such as a hydroxyl group or an ester group by a generally known method. The color tone of the petroleum resin is usually about 5 to 15 Gardner.

The softening point and molecular weight of the petroleum resin are not particularly limited, but the softening point is preferably about 50 ° C. to 200 ° C. (the lower limit is more preferably 70 ° C. and the upper limit is more preferably 150 ° C.), and the number average molecular weight is It is preferably about 200 to 3000 (more preferably, 250 as the lower limit and 2500 as the upper limit). Softening point of 50 ° C or more,
When the number average molecular weight is 200 or more, workability is improved, which is preferable. On the other hand, setting the softening point to 200 ° C. or lower and the number average molecular weight to 3000 or lower is preferable because the hydrogenation reaction easily proceeds and the workability is improved.

The method for producing a hydrogenated petroleum resin according to the present invention is to hydrogenate the petroleum resin as a raw material by appropriately adjusting the hydrogenation conditions in the presence of the following specific hydrogenation catalyst. Usually, all of the olefinic double bonds of the petroleum resin and more than 1% of the aromatic ring are hydrogenated. In particular, if the hydrogenated petroleum resin is used as a tackifier resin for rubber-based hot-melt adhesives or ethylene-vinyl acetate copolymer-based hot-melt adhesives, which are practical applications, the compatibility with the adhesive's base resin From the viewpoint, the hydrogenation rate of the aromatic ring is preferably set to 40 to 80%. In addition, if it is used as a modifier for thermoplastics such as polyethylene and polypropylene,
It is preferable to set the hydrogenation ratio of the aromatic ring to 80 to 100%.

The hydrogenation catalyst contains nickel and synthetic silica alumina and has a nickel content of 5%.
0 to 65% by weight, catalyst surface area 300 to 400 m ² / g,
The catalyst satisfies the condition of a bulk specific gravity of 0.22 to 0.50 g / cm ³ . A catalyst that satisfies the specific conditions can exhibit both high hydrogenation activity and moderate hydrocracking properties for petroleum resins.

That is, the nickel content in the catalyst is determined in order to develop a high hydrogenation activity.
When the nickel content is 50% by weight or more, it is preferable because the amount is sufficient to express a high hydrogenation activity, and when the nickel content is 65% by weight or less, the activity reduction due to excessive loading of nickel and the production cost are reduced. This is preferable because there is no adverse effect such as increase.

The catalyst surface area is determined in order to sufficiently disperse nickel in the catalyst and sufficiently exhibit hydrogenation activity. The catalyst surface area should be not less than 300 m ² / g and not less than 40 m ² / g.
When the content is 0 m ² / g or less, high hydrogenation activity and appropriate hydrodegradability are exhibited, which is preferable.

The bulk specific gravity of the catalyst is determined in order to improve workability and dispersibility in the reaction system. By setting the bulk specific gravity to 0.22 g / cm ³ or more, scattering is reduced. 0.50 g /
When the molecular weight is not more than ³ cm ³ , the dispersibility of the catalyst in the reaction system becomes good, and high hydrogenation activity and appropriate hydrogenolyticity are exhibited.

As the carrier of the catalyst, synthetic silica alumina is suitable because the surface area, solid acidity and specific gravity can be freely controlled. That is, the hydrogenation activity is controlled by controlling the surface area, and the hydrogenolyticity is controlled by controlling the solid acidity.
Further, by controlling the specific gravity, hydrocracking property and workability can be made favorable.

The amount of the solid acid in the catalyst is not particularly limited, but is not less than 0.75 mmol / g and not more than 0.90 mmol.
/ G or less is preferable because appropriate hydrogenolytic properties can be exhibited.

The hydrogenation catalyst of the present invention comprises nickel and synthetic silica alumina as main components. If necessary, a group 1 metal such as sodium and potassium, magnesium, calcium, and the like may be used as a promoter. Group 2 metals such as barium; Group 3 metals such as aluminum; Group 4 metals such as titanium and zirconium; Group 6 metals such as chromium and molybdenum; Group 7 metals such as manganese; Group 8 metals such as iron; Group 10 metals, such as palladium, and Group 1 metals, such as copper
Group 12 metals, Group 12 metals such as zinc or oxides thereof,
Various compounds such as metal compounds such as sulfides can be added and used to the extent that the performance of the catalyst is not impaired. The cocatalyst contributes to trapping of catalyst poisons and regulation of solid acidity, and as a result, has a role in controlling the hydrocracking reaction.

The method for preparing the hydrogenation catalyst is not particularly limited, and a known method can be employed. As a specific example of the preparation method, nickel nitrate, by adding an alkaline solution such as sodium carbonate to a nickel salt solution such as nickel sulfate, precipitated on the carrier as basic nickel carbonate,
Then, the nickel catalyst is subjected to a precipitation method of thermally decomposing to nickel oxide after washing and drying, and an impregnation method of impregnating the carrier with a nickel salt solution such as nickel nitrate which is easily dried and roasting to obtain nickel oxide. Obtain the oxide. Further, a method of heating the catalyst oxide under a hydrogen gas stream to reduce and activate nickel oxide may be used. To prepare the catalyst of the present invention, for example, in the case of the precipitation method, the temperature, pH, stirring, etc. may be appropriately adjusted.

The conditions of the hydrogenation reaction are not particularly limited, but it is preferable to appropriately adjust the hydrogen partial pressure in the range of about 2.9 to 29.4 MPa and the reaction temperature in the range of about 200 to 350 ° C. . Hydrogen partial pressure is 14.7 MPa or more, 2
The pressure is more preferably 4.5 MPa or less, and the reaction temperature is more preferably 250 ° C. or more and 300 ° C. or less.
When the hydrogen partial pressure is less than 2.9 MPa or when the reaction temperature is less than 200 ° C., the hydrogenation reaction does not easily proceed.
On the other hand, when the hydrogen partial pressure exceeds 29.4 MPa or when the reaction temperature exceeds 320 ° C., the hydrocracking reaction takes precedence, lowering the softening point of the obtained hydrogenated petroleum resin and reducing the hydrogenated petroleum resin Not only does the yield tend to decrease, but there is also a problem in terms of equipment safety.

The hydrogenation reaction may be performed in a molten state of the raw petroleum resin, or may be performed by dissolving the raw petroleum resin in a solvent. The solvent that can be used is not particularly limited. For example, cyclohexane, decalin, n-hexane,
n-heptane and the like.

The amount of the catalyst in the hydrogenation reaction is usually about 0.1 to 4% by weight, preferably 0.2 to 3% by weight or less based on the petroleum resin as the raw material. When the amount of the catalyst used is less than 0.1%, the hydrogenation reaction does not easily proceed, and when it exceeds 4% by weight, there is a disadvantage in cost. The reaction time is about 1 to 10 hours, preferably 2 hours or more and 8 hours or less. If the reaction time is less than 1 hour, it is difficult to control the hydrogenation reaction, and if it exceeds 10 hours, the production cost is disadvantageous.

The reaction type of the hydrogenation reaction is a batch type,
Both distribution type can be adopted. Especially when using a continuous reactor of a fluidized bed such as a suspension bubble column, productivity is improved,
Further, the reaction conditions such as the amount of the catalyst can be freely changed, which is preferable. Further, by setting the bulk specific gravity of the hydrogenation catalyst within the range of the present invention, the dispersibility in the reactor can be kept good, so that it is suitable for the reaction of hydrogenating petroleum resin in a fluidized bed continuous reactor. ing.

The hydrogenated petroleum resin thus obtained has a softening point of usually about 60 to 170 ° C., preferably 65 ° C.
The temperature is at most 145 ° C. The number average molecular weight is usually about 200 to 3000, preferably 500 or more,
2000 or less.

[0025]

According to the present invention, the amount of catalyst used in producing a hydrogenated petroleum resin can be reduced, so that the catalyst cost and the amount of industrial waste can be reduced at the same time.

[0026]

The present invention will be described in more detail with reference to examples and comparative examples below, but the present invention is not limited to these examples. In each example, all parts are on a weight basis.

Example 1 C9 petroleum resin (trade name “Petrogin 120”, color tone 1)
0 Gardner, softening point 120 ° C, 100 parts of Mitsui Chemicals, Inc. containing 30% vinyltoluene and 30% indene as main components) and nickel-synthetic silica-alumina catalyst oxide prepared by a precipitation method in a hydrogen stream. At 400
° C, hydrogen reduced catalyst for 1 hour (nickel content 55% by weight, catalyst surface area 350 m ² / g, bulk specific gravity 0.30 g /
cm ³ ) A hydrogenation reaction was performed in a shaking autoclave under the conditions of a partial pressure of hydrogen of 19.6 MPa, a reaction temperature of 295 ° C. and a reaction time of 5 hours in a shaking autoclave. After completion of the reaction, the obtained resin was dissolved in 400 parts of cyclohexane, and the catalyst was removed by filtration. After that, the stirring blade, condenser, thermometer, temperature controller and pressure indicator were attached.
Put the filtrate in a liter separable flask and add 200
C9-based hydrogenated petroleum with a olefin hydrogenation rate of 100%, an aromatic ring hydrogenation rate of 60%, a softening point of 100 ° C, and a color tone of 20 Hazen. 99 parts of resin were obtained. Table 1 shows the results.

The hydrogenation rate was determined based on the H-spectral area of the olefin appearing in the vicinity of 5 to 6 ppm in ¹ H-NMR of the starting resin and the obtained hydrogenated resin, and 7 pp.
It was calculated based on the following formula from the H-spectral area of the aromatic ring appearing near m. Hydrogenation rate = {1− (spectral area of hydrogenated resin / spectral area of raw material resin)} × 10
0 (%). The softening point is based on the ring and ball method of JIS K 2531.

Example 2 In Example 1, C9-based petroleum resin (trade name)
"Neopolymer 120", color tone 10 Gardner, softening point
120 ° C, vinyl toluene 30% as main component
Containing 30% dendene, manufactured by Nippon Synthetic Resins Co., Ltd.)
Nickel-synthetic silica prepared by a precipitation method as a catalyst
Alumina catalyst oxide in water at 400 ° C for 1 hour under hydrogen stream
Element-reduced catalyst (nickel content 54% by weight, catalyst surface
Product 380m ²/ G, bulk specific gravity 0.30 g / ml).
The same operation as in Example 1 was performed except that 6 parts were used.
100% hydrogenation rate, 98% hydrogenation rate of aromatic ring, soft
C9-based hydrogenated petroleum with a transition point of 100 ° C and a color tone of 20 Hazen
This gave 101 parts of a fat. Table 1 shows the results.

Example 3 A C9 petroleum resin (trade name "Petrogin 120", manufactured by Mitsui Chemicals, Inc.) melted at 200 ° C. from a bottom of a reactor into a hydrogenation reactor of a suspension bubble column having a diameter of 2 inches and a height of 1 m. )
And 10% catalyst slurry (decalin 69%, petroleum resin 2
1%, a catalyst 10%, and a catalyst prepared by reducing a nickel-synthetic silica alumina catalyst oxide prepared by a precipitation method at 400 ° C. for 1 hour under a hydrogen stream (nickel content 55% by weight, catalyst surface area 350 m) ² / g, bulk specific gravity 0.
30 g / cm3). ) Was fed by a plunger pump. The speed was 360 g / hour each,
2.0 g catalyst / hour. The reaction conditions are hydrogen pressure 1
9.6 MPa, a hydrogen gas flow rate of 165 NL / hour, and a reaction temperature of 280 ° C. were set. The reaction time (resin residence time) was about 5.5 hours. 100 g of the obtained C9-based hydrogenated petroleum resin was dissolved in 300 ml of cyclohexane, and the catalyst was removed by filtration. The obtained C9-based hydrogenated petroleum resin varnish was distilled under reduced pressure to remove cyclohexane and decalin. As a result, 100 g of a colorless and transparent C9-based hydrogenated petroleum resin was obtained. The final decompression condition is 240
C, 1.3 kPa for 20 minutes. The hydrogenation rate of the olefin of the obtained resin is 100%, and the hydrogenation rate of the aromatic ring is 65.
%, Softening point 101 ° C. and color tone 20 Hazen. Table 1 shows the results.

Example 4 In Example 1, a petroleum resin (trade name “High Resin # 120”, color tone 8 Gardner, softening point 120 ° C.,
The same operation as in Example 1 was performed except that C5-C9 copolymer resin (manufactured by Toho Chemical Industry Co., Ltd.) was used, and the hydrogenation rate of olefin was 100%, the hydrogenation rate of aromatic ring was 98%, and the softening point was 10
101 parts of hydrogenated petroleum resin having a color tone of 20 Hazen at 0 ° C. were obtained. Table 1 shows the results.

Example 5 In Example 1, a petroleum resin (trade name “Quinton 1325”, color tone 5 Gardner, softening point 125 ° C.,
The same operation as in Example 1 was performed except that cyclopentadiene resin (manufactured by Nippon Zeon Co., Ltd.) was used, and 101 parts of a hydrogenated petroleum resin having a olefin hydrogenation rate of 100%, a softening point of 100 ° C. and a color tone of 20 Hazen was used. Obtained. Table 1 shows the results.

Comparative Example 1 In Example 1, a nickel-diatomaceous earth catalyst was prepared by subjecting a nickel diatomaceous earth catalyst oxide prepared by a precipitation method to hydrogen reduction at 400 ° C. for 1 hour in a hydrogen stream (nickel content: 51% by weight, catalyst: Example 1 except that 0.9 part of a surface area of 270 m ² / g and a bulk density of 0.30 g / cm 3 was used.
The same operation as described above was performed, and the hydrogenation rate of the olefin was 100%.
101 parts of a C9 hydrogenated petroleum resin having an aromatic ring hydrogenation rate of 60%, a softening point of 100 ° C. and a color tone of 20 Hazen was obtained. Table 1 shows the results.

Comparative Example 2 In Example 3, a nickel diatomaceous earth catalyst oxide prepared by a precipitation method was used as a catalyst at 400 ° C. in a hydrogen atmosphere.
1 hour hydrogen reduced catalyst (nickel content 48% by weight,
Catalyst surface area 290 m ² / g, bulk specific gravity 0.30 g / m
l) The same operation as in Example 3 was carried out except that the 15% catalyst slurry liquid was used and 3.6 g / hour was fed, and the hydrogenation rate of the olefin was 100%, the hydrogenation rate of the aromatic ring was 65%, and the softening point was 101 parts of a C9 hydrogenated petroleum resin having a color tone of 20 Hazen at 102 ° C. were obtained. Table 1 shows the results.

[0035]

[Table 1]

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G069 AA03 AA12 BA03A BA03B BB02A BB02B BC68A BC68B CC02 EC03X EC03Y EC21X EC21Y FC08 4J100 AU01P CA31 DA01 DA23 HA03 HB02 HB17 HB61 JA01 JA03 JA05 JA07 JA46

Claims (5)

[Claims] 1. A method for producing a hydrogenated petroleum resin by hydrogenating a petroleum resin in the presence of a hydrogenation catalyst, comprising nickel and synthetic silica alumina as a hydrogenation catalyst, and having a nickel content of 50 to 50%. 65% by weight, catalyst surface area 300-400 m ² / g and bulk specific gravity 0.22-
A method for producing a hydrogenated petroleum resin, characterized by using a material satisfying a condition of 0.50 g / cm ³ . 2. The petroleum resin having a number average molecular weight of 200 to 30.
2. The production method according to claim 1, wherein the range is 00. 3. The method according to claim 1, wherein the petroleum resin has a softening point in the range of 50 to 200 ° C. 4. The production method according to claim 1, wherein the hydrogenation reaction is performed using a fluidized bed continuous reactor. 5. The method according to claim 1, wherein
It contains nickel and synthetic silica alumina, and has a nickel content of 50 to 65% by weight and a catalyst surface area of 300.
４００400 m ² / g and bulk specific gravity 0.22 to 0.50 g
/ Cm ² hydrogenation catalyst for petroleum resins.