JP3687079B2 - Phenol-modified C9 hydrogenated petroleum resin and process for producing the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing a phenol-modified C9 hydrogenated petroleum resin. The phenol-modified C9 hydrogenated petroleum resin obtained by the production method of the present invention is a tackifier such as an adhesive / adhesive, paint, printing ink, traffic paint or semiconductor sealant, water resistance imparting agent or plastic modification. It can be used for agents.
[0002]
[Prior art]
Phenol-modified C9 petroleum resin is a thermoplastic resin obtained by polymerizing C8 or higher aromatic hydrocarbons having an olefinic unsaturated bond in the cracked oil fraction of petroleum naphtha in the presence of phenols. Therefore, it has a high polarity and excellent compatibility with an elastomer such as an acrylic resin. However, phenol-modified C9-based petroleum resins have the disadvantages of poor color tone and inferior thermal stability and weather resistance compared to ordinary C9-based petroleum resins.
[0003]
The disadvantages of such phenol-modified C9 petroleum resin can be improved by hydrogenating the resin. However, when the hydrogenation rate of the aromatic ring of the phenol-modified C9 petroleum resin is set high (90% or more) in order to improve the above disadvantages, elimination of the phenolic hydroxyl group occurs and the ratio of the aromatic ring is Decrease. As a result, there is a problem that the polarity, which is a characteristic of the phenol-modified C9 petroleum resin, is lowered, and the compatibility with a highly polar elastomer such as an acrylic resin is deteriorated. On the other hand, when the hydrogenation rate of the aromatic ring of the phenol-modified C9 petroleum resin is set low, the elimination of phenolic hydroxyl groups is less than when the hydrogenation rate is high. However, the above disadvantages cannot be sufficiently improved.
[0004]
[Problems to be solved by the invention]
An object of the present invention is to provide a phenol-modified C9-based hydrogenated petroleum resin excellent in color tone, thermal stability, weather resistance and excellent in compatibility with highly polar elastomers such as acrylic resins, and a method for producing the same. To do.
[0005]
[Means for Solving the Problems]
As a result of intensive studies to solve the above-mentioned problems of the prior art, the inventors of the present invention contain a phenol-modified C9 petroleum resin having a specific hydroxyl value and containing an alkaline earth metal as a promoter. using a specific amount of hydrogenation catalyst containing group metal as the main catalyst at specific reaction conditions, the hydrogenation from 0 to 50% of total and an aromatic ring of olefinic double bonds of the phenol-modified C9 petroleum resins them if, without impairing the most phenol-modified C9 petroleum resin as a raw material of the hydroxyl group, the color tone was found that phenol-modified C9-based hydrogenated petroleum resin having a specific hydroxyl value is 1 Gardner or less is obtained. The present invention has been completed based on such new findings.
[0006]
DETAILED DESCRIPTION OF THE INVENTION
Examples of the phenol-modified C9 petroleum resin used as a raw material of the present invention, C9 fraction obtained by cracking of naphtha (e.g., styrene, vinyl toluene, alpha-methyl styrene, indene, etc.), in the presence of phenols , be one obtained by cationic polymerization, the hydroxyl value Ru used as in the range of 10~120mgKOH / g.
[0007]
As phenols, alkylphenols such as phenol or cresol, xylenol, pt-butylphenol, p-octylphenol, and p-nonylphenol can be used. Of these, phenol is preferred. These phenols may be used independently and may use 2 or more types together. The amount of phenol used is determined to be within the range of the hydroxyl value of the phenol-modified C9 petroleum resin , and is usually about 5 to 40 parts by weight, preferably 10 to 10 parts by weight with respect to 100 parts by weight of the C9 fraction. 30 parts by weight.
[0008]
Phenol-modified C9-based hydrogenated petroleum resin according to the present invention, the presence of a particular hydrogenation catalyst showing a phenol-modified C9 petroleum resins are the raw material, the following, in particular hydrogenation conditions, the raw material phenol It can be produced by hydrogenating all of the olefinic double bonds of the modified C9 petroleum resin and 0 to 50% of the aromatic ring.
[0009]
As the hydrogenation catalyst, a catalyst containing an alkaline earth metal as a promoter and a group 8 metal as a main catalyst is used. The ▲ 8 ▼ group metal nickel as a main catalyst, palladium, platinum, cobalt, rhodium or ruthenium beam of metal or oxides thereof, can be used and various metal compounds such as sulfides, and a cocatalyst As the alkaline earth metal, various kinds of alkaline earth metals such as magnesium, calcium and barium or metal compounds such as oxides and sulfides thereof can be used. Here, the group 8 metal acts as a hydrogenation catalyst for olefinic double bonds and aromatic nuclei, and the alkaline earth metal acts mainly as a co-catalyst for suppressing decomposition of the hydroxyl group. The alkaline earth metal also has an action of preventing the main catalyst Group 8 metal from being eroded by the phenolic hydroxyl group in the raw material resin. Accordingly, when a hydrogenation catalyst containing no alkaline earth metal is used, the hydroxyl group of the raw material phenol-modified C9 petroleum resin is eliminated. The ratio of the alkaline earth metal to the Group 8 metal is not particularly limited, but is usually about 1 to 15% by weight with respect to the Group 8 metal.
[0010]
Such a hydrogenation catalyst used in the present invention may be used by being supported on a support such as alumina, silica (diatomaceous earth), carbon, and titania having a large porous surface area. In the present invention, among these catalysts, a nickel-diatomaceous earth catalyst containing an alkaline earth metal (especially calcium or magnesium) is preferable from the viewpoint of easy adjustment of the hydrogenation rate within the above range and cost. Examples of such a hydrogenation catalyst include a stabilized nickel-diatomaceous earth catalyst (“SN-250”, manufactured by Sakai Chemical Co., Ltd.).
[0011]
In addition, the raw material phenol-modified C9 petroleum resin needs to hydrogenate at least all of the olefinic double bonds. Hydrogenation to such an extent that olefinic double bonds remain is not preferable in terms of thermal stability and weather resistance. On the other hand, the hydrogenation rate of the aromatic ring is 0 to 50% from the viewpoint of compatibility with highly polar elastomers such as acrylic resins and the suppression of elimination of phenolic hydroxyl groups. resulting elimination of the phenolic hydroxyl groups, also the ratio of the aromatic ring is reduced, there is a tendency that the polarity of the obtained phenol-modified C9-based hydrogenated petroleum resin is lowered. In addition, since the hydrogenation rate of an aromatic ring is so small that it has polarity, the hydrogenation rate of an aromatic ring may be 0%.
[0012]
The conditions for the hydrogenation reaction are appropriately adjusted within the range where the hydrogen partial pressure is usually about 30 to 300 kg / cm ² and the reaction temperature is usually about 240 to 300 ° C. Preferably, the hydrogen partial pressure is 150 to 250 Kg / cm ² and the reaction temperature is 260 to 290 ° C. When the hydrogen partial pressure is less than 30 kg / cm ² or when the reaction temperature is less than 240 ° C., hydrogenation is difficult to proceed. When the hydrogen partial pressure exceeds 300 Kg / cm ² or when the reaction temperature exceeds 300 ° C., hydrogenation tends to proceed excessively, and there is also a problem in terms of equipment safety. The hydrogenation reaction is performed in a state where the raw material phenol-modified C9 petroleum resin is melted or dissolved in a solvent. Examples of the solvent that can be used include cyclohexane, n-hexane, n-heptane, decalin and the like.
[0013]
In such a hydrogenation reaction, when the hydrogenation catalyst is employed in a batch system as a reaction form, the amount used is the ratio of the main catalyst in the hydrogenation catalyst to the raw material phenol-modified C9 petroleum resin. The amount is usually about 0.1 to 2% by weight, preferably 0.1 to 1% by weight. When the amount is less than 0.1% by weight, the hydrogenation is difficult to proceed. When the amount exceeds 2% by weight, the hydrogenation tends to proceed excessively. The reaction time is usually about 1 to 10 hours, preferably 2 to 8 hours. If the reaction time is less than 1 hour, the hydrogenation is difficult to proceed, and if it exceeds 10 hours, the hydrogenation tends to proceed too much, which is disadvantageous in terms of cost.
[0014]
In addition, about the usage-amount and reaction time of a catalyst, although the case where a batch type was employ | adopted as a reaction format was demonstrated, a flow type (a fixed bed type, a fluidized bed type etc.) can also be employ | adopted as a reaction format.
[0015]
Phenol-modified C9-based hydrogenated petroleum resins obtained in this way, despite the hydrogenation rate of the aromatic rings are 50% or less, the color tone is 1 Gardner or less. Moreover, the hydroxyl value of the obtained phenol-modified C9-based hydrogenated petroleum resin is 10 to 120 mgKOH / g, which is almost the same as the hydroxyl value of the raw material phenol-modified C9-based petroleum resin, and does not decrease due to hydrogenation. When the hydroxyl value is less than 10 mgKOH / g, the polarity of the phenol-modified C9-based hydrogenated petroleum resin becomes small, causing problems such as poor compatibility with highly polar elastomers such as acrylic resins. On the other hand, if the hydroxyl value exceeds 120 mgKOH / g, the color tone, thermal stability and weather resistance deteriorate, which is not preferable.
[0016]
The softening point of the phenol-modified C9 hydrogenated petroleum resin is usually about 70 to 150 ° C., preferably 80 to 120 ° C., and the number average molecular weight is usually about 500 to 1600, preferably 500 to 900. The raw material (unhydrogenated product) also has the same softening point and number average molecular weight as the hydride product.
[0017]
【Example】
EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In each example, both parts and% are based on weight.
[0018]
Example 1
Phenol-modified C9 petroleum resin “High Resin PM-90” (color 11 Gardner, hydroxyl value 32 mg KOH / g, softening point 89.5 ° C., manufactured by Toho Chemical Co., Ltd.) 100 parts and nickel-diatomaceous earth catalyst prepared by precipitation method ( 0.5 parts of nickel (containing 50% nickel and 5% calcium) was charged into an autoclave, and a hydrogenation reaction was carried out under conditions of a hydrogen partial pressure of 200 kg / cm ² , a reaction temperature of 275 ° C., and a reaction time of 5 hours. After completion of the reaction, the obtained resin was dissolved in 300 parts of cyclohexane, and the catalyst was removed by filtration. Then, put the filtrate into a 1-liter separable flask equipped with a stirring blade, condenser, thermometer, temperature controller and pressure indicator, and gradually elevate and reduce pressure to 200 ° C and 20 torr to remove the solvent. 99 parts of phenol-modified C9 hydrogenated petroleum resin having an olefin hydrogenation rate of 100%, an aromatic ring hydrogenation rate of 0 %, a color tone of 1 Gardner or less (100 Hazen) , a hydroxyl value of 35 mgKOH / g, and a softening point of 90 ° C. Got.
[0019]
The hydrogenation rate is calculated from the following formula based on the H-spectral area of the olefin appearing near 5.6 ppm and the H-spectral area of the aromatic ring appearing near 7 ppm in ¹ H-NMR of the raw resin and the obtained hydrogenated resin. Calculated based on Hydrogenation rate = {1− (spectral area of hydrogenated resin / spectral area of raw resin)} × 100 (%). Further, the hydroxyl value is according to the ring and ball method of JIS K 0070 and the softening point is according to JIS K 2531.
[0021]
Comparative Example 1
Phenol-modified C9 petroleum resin “Neopolymer E-100” (color tone 15 Gardner, hydroxyl value 68 mg KOH / g, softening point 90 ° C., Nippon Petrochemical Co., Ltd.) 100 parts and nickel-diatomite catalyst prepared by precipitation method ( (Containing nickel 50%, calcium 0%) 0.5 parts was charged in an autoclave and the hydrogen partial pressure was 200 kg / cm ² The hydrogenation reaction was carried out under the conditions of a reaction temperature of 275 ° C. and a reaction time of 5 hours. After completion of the reaction, the obtained resin was dissolved in 300 parts of cyclohexane, and the catalyst was removed by filtration. Then, the filtrate is put into a 1 liter separable flask equipped with a stirring blade, condenser, thermometer, temperature controller and pressure indicator, and the solvent is removed by gradually raising and lowering the pressure to 200 ° C. and 20 torr. Thus, 99 parts of a phenol-modified C9 hydrogenated petroleum resin having an olefin hydrogenation rate of 100%, an aromatic ring hydrogenation rate of 21%, a color tone of 3 Gardner, a hydroxyl value of 42 mgKOH / g, and a softening point of 90 ° C. were obtained.
[0022]
Comparative Example 2
In Example 1, except for changing the charged amount of the catalyst to 5.0 parts performs same as operation as in Example 1, hydrogenation of 100% olefins, the hydrogenation rate of 95% of the aromatic ring, tone 1 Gardner In the following (100 Hazen) , 97 parts of a phenol-modified C9 hydrogenated petroleum resin having a hydroxyl value of 15 mgKOH / g and a softening point of 85 ° C. was obtained.

Claims (1)

0.1-2% by weight of a hydrogenation catalyst containing a phenol-modified C9 petroleum resin having a hydroxyl value of 10-120 mgKOH / g and containing an alkaline earth metal as a co-catalyst and a group 8 metal as a main catalyst In the presence of (in terms of the amount of main catalyst used in the catalyst) , the hydrogen partial pressure is 30 to 300 kg / cm ^2. And wherein the temperature of 240 to 300 ° C., under the conditions of the reaction time to 10 hours, hydrogenating 0-5 0% total and the aromatic ring of the olefinic double bond of the phenol-modified C9 petroleum resins A method for producing a phenol-modified C9 hydrogenated petroleum resin having a color tone of 1 Gardner or less and a hydroxyl value of 10 to 120 mgKOH / g .