JPH09268209A - Phenol-modified 9c-based hydrogenated petroleum resin and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin excellent in color tone, heat stability, compatibility, etc., by hydrogenating all of an olefinic double bond of a phenol- modified 9C-based petroleum resin which is a raw material and a specific ratio of an aromatic ring or below. SOLUTION: This petroleum resin comprises a phenol-modified 9C-based petroleum resin in which all of olefinic double bond and 0-80% aromatic ring are hydrogenated and has <=1 Gardner color tone and further preferably has 10-120mg KOH hydroxyl value. The petroleum resin is obtained by hydrogenating (A) a phenol-modified 9C-based petroleum resin in the presence of (B) a hydrogenation catalyst containing the group VIII metal as a main catalyst and containing an alkaline earth metal as a cocatalyst, preferably under hydrogenation conditions at 30-300kg/cm<2> hydrogen partial pressure and 240-300 deg.C for 1-10hr. The catalyst of the component B includes e.g. a nickel-diatomaceous earth catalyst (containing 50% nickel and 5% calcium) prepared by precipitation method.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a phenol-modified C
It relates to a method for producing a 9-based hydrogenated petroleum resin. The phenol-modified C9 hydrogenated petroleum resin obtained by the production method of the present invention is a tackifier such as tackiness / adhesives, paints, printing inks, traffic paints or semiconductor encapsulants, water resistance imparting agents or plastic modifiers. It can be used as an agent.

[0002]

Phenol-modified C9 petroleum resin is a thermoplastic resin obtained by polymerizing C8 or more aromatic hydrocarbons having an olefinic unsaturated bond in a cracked oil fraction of petroleum naphtha in the presence of phenols. Since it is a resin and has a hydroxyl group, it has a high polarity and is excellent in compatibility with an elastomer such as an acrylic resin. However, the phenol-modified C9-based petroleum resin has the drawbacks that it has a poorer color tone than conventional C9-based petroleum resins and is inferior in terms of thermal stability and weather resistance.

The drawbacks of the 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-mentioned drawback, elimination of the phenolic hydroxyl group occurs, and the ratio of the aromatic ring is reduced. Decrease. As a result, phenol modified C
The 9-type petroleum resin has a problem in that the polarity is low and the compatibility with a highly polar elastomer such as an acrylic resin is poor. On the other hand, when the hydrogenation rate of the aromatic ring of the phenol-modified C9 petroleum resin is set low, the desorption of the phenolic hydroxyl group is less than that when the hydrogenation rate is high. However, the above-mentioned drawbacks cannot be sufficiently improved.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a phenol-modified C which is excellent in color tone, thermal stability, weather resistance and compatibility with highly polar elastomers such as acrylic resins.
It is an object to provide a 9-based hydrogenated petroleum resin and a method for producing the same.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems of the prior art, the present inventors have found that a phenol-modified C9 petroleum resin contains an alkaline earth metal as a cocatalyst. (8) In the presence of a hydrogenation catalyst containing a group metal as a main catalyst, all of the olefinic double bonds of the phenol-modified C9 petroleum resin and 0 to 8 of the aromatic ring are contained.
It has been found that by hydrogenating 0%, a phenol-modified C9-based hydrogenated petroleum resin having a color tone of 1 Gardner or less can be obtained without substantially deteriorating the hydroxyl groups of the raw material phenol-modified C9-based petroleum resin. The present invention has been completed based on this new finding.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The phenol-modified C9 petroleum resin which is a raw material of the present invention is not particularly limited, but generally, a C9 fraction obtained by cracking naphtha (for example, styrene, vinyltoluene, α-methylstyrene,
Indenes and the like) obtained by cationic polymerization in the presence of phenols can be used.

As the phenols, phenol or alkylphenols such as cresol, xylenol, pt-butylphenol, p-octylphenol and p-nonylphenol can be used. Of these, phenol is preferred. These phenols may be used alone or in combination of two or more. The amount of phenols used is not particularly limited, but the hydroxyl value of the phenol-modified C9 petroleum resin is 10 to 120 mg KO.
Phenols are preferably blended so as to be in the range of H / g. The amount used is usually about 5 to 40 parts by weight, preferably 10 to 100 parts by weight of the C9 fraction.
30 parts by weight.

The phenol-modified C9-based hydrogenated petroleum resin of the present invention is prepared by adjusting the hydrogenation conditions of the above-mentioned raw material phenol-modified C9-based petroleum resin in the presence of the following specific hydrogenation catalyst. 0-80% of all olefinic double bonds and aromatic rings of the raw material phenol-modified C9 petroleum resin
It can be produced by hydrogenating to a degree.

As the hydrogenation catalyst, one containing an alkaline earth metal as a promoter and a Group 8 metal as a main catalyst is used. As the Group 8 metal serving as the main catalyst, various metals such as nickel, palladium, platinum, cobalt, rhodium, ruthenium, rhenium, molybdenum and the like or metal compounds such as oxides and sulfides thereof can be used. As the alkaline earth metal serving as a cocatalyst, various materials such as 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 the decomposition of hydroxyl groups. The alkaline earth metal also has a function of preventing the Group 8 metal of the main catalyst from being corroded by the phenolic hydroxyl group in the raw material resin. Therefore, when a hydrogenation catalyst containing no alkaline earth metal is used, the hydroxyl groups of the raw material phenol-modified C9 petroleum resin are desorbed. The use 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.

The hydrogenation catalyst used in the present invention may be used by supporting it on a carrier such as alumina, silica (diatomaceous earth), carbon or titania, which is porous and has a large surface area.
In the present invention, among these catalysts, the nickel-diatomaceous earth catalyst containing an alkaline earth metal (especially calcium and magnesium) is preferable from the viewpoint of easy adjustment of the hydrogenation ratio within the above range and cost. As such a hydrogenation catalyst, for example, a stabilized nickel-diatomaceous earth catalyst (“SN-25
0 ”, manufactured by Sakai Chemical Co., Ltd., and the like.

The phenol-modified C9 petroleum resin used as a raw material is required to hydrogenate at least all olefinic double bonds. Hydrogenation to the extent that olefinic double bonds remain is not preferable in terms of thermal stability and weather resistance. On the other hand, when the hydrogenation rate of the aromatic ring exceeds 80%, desorption of the phenolic hydroxyl group occurs, and the proportion of the aromatic ring decreases, so that the polarity of the obtained phenol-modified C9 hydrogenated petroleum resin becomes low. There is a tendency and it is not preferable. From the viewpoint of compatibility with highly polar elastomers such as acrylic resins, the hydrogenation rate of aromatic rings is preferably 0 to 50%. Note that the hydrogenation rate of the aromatic ring may be 0% because the lower the hydrogenation rate of the aromatic ring is, the more polar it is.

The hydrogenation reaction is usually carried out at a hydrogen partial pressure of 30.
~ 300 Kg / cm ² range, reaction temperature is usually 24
The temperature is adjusted appropriately in the range of 0 to 300 ° C. The hydrogen partial pressure is preferably 150 to 250 Kg / cm ² , and the reaction temperature is 260 to 290 ° C. Hydrogen partial pressure is 30 kg
If the reaction temperature is less than / cm ² or the reaction temperature is less than 240 ° C., hydrogenation is difficult to proceed. Hydrogen partial pressure is 300K
If it exceeds g / cm ² or if the reaction temperature exceeds 300 ° C., hydrogenation tends to proceed too much, which is problematic in terms of equipment safety. Further, 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.

In such a hydrogenation reaction, when the above-mentioned hydrogenation catalyst is batchwise adopted as a reaction form, the amount of the hydrogenation catalyst used is the main catalyst in the hydrogenation catalyst with respect to the phenol-modified C9 petroleum resin as a raw material. Is usually 0.1 to 2% by weight, preferably 0.1 to 1% by weight. If it is less than 0.1% by weight, hydrogenation is difficult to proceed, and if it exceeds 2% by weight, hydrogenation tends to proceed too much. The reaction time is usually about 1 to 10 hours, preferably 2 to 8 hours. If the reaction time is less than 1 hour, hydrogenation is difficult to proceed, and if it exceeds 10 hours, hydrogenation tends to proceed too much, which is also disadvantageous in terms of cost.

The use amount of the catalyst and the reaction time have been described in the case where a batch system is employed as the reaction system. However, a flow system (fixed bed system, fluidized bed system, etc.) may be employed as the reaction system. it can.

The thus obtained phenol-modified C9 hydrogenated petroleum resin has a color tone of 1 Gardner or less, even though the hydrogenation rate of the aromatic ring is 80% or less. 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 is not lowered by hydrogenation. The hydroxyl value is 10mgKO
If it is less than H / g, the polarity of the phenol-modified C9 hydrogenated petroleum resin becomes small and the compatibility with the highly polar elastomer such as acrylic resin becomes poor. If the hydroxyl value exceeds 120 mgKOH / g, the color tone, thermal stability and weather resistance will deteriorate, which is not preferable.

The softening point of the phenol-modified C9 hydrogenated petroleum resin is usually about 70 to 150 ° C., preferably 8
0 to 120 ° C., and the number average molecular weight is usually 500 to 1
It is about 600, preferably 500 to 900. In addition,
The raw material (unhydrogenated material) also has a softening point and a number average molecular weight similar to those of hydrides.

[0017]

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

Example 1 Phenol-modified C9 petroleum resin "Neopolymer E-10"
0 "(color tone 15 Gardner, hydroxyl value 68 mgKOH /
g, a softening point of 90 ° C., 100 parts of Nippon Petrochemical Co., Ltd., and 0.5 parts of a nickel-diatomaceous earth catalyst (containing 50% nickel and 5% calcium) prepared by a precipitation method were charged into an autoclave, and a hydrogen partial pressure was 200 kg. / Cm ² , reaction temperature 2
The hydrogenation reaction was carried out under the conditions of 75 ° C. and a reaction time of 5 hours. After the reaction was completed, the obtained resin was added to cyclohexane 300.
Part, and the catalyst was removed by filtration. Then, put the filtrate into a 1 liter separable flask equipped with a stirring blade, a condenser, a thermometer, a temperature controller and a pressure indicator, and gradually elevate the temperature to 200 ° C and reduce the pressure to 20 torr to remove the solvent. And the olefin hydrogenation rate is 10
0%, aromatic ring hydrogenation rate 15%, color tone 300 Hazen,
98 parts of a phenol-modified C9 hydrogenated petroleum resin having a hydroxyl value of 69 mgKOH / g and a softening point of 92.0 ° C. were obtained.

The hydrogenation rate is determined from the H-spectral area of the olefin which appears in the vicinity of 5.6 ppm and the H-spectral area of the aromatic ring which appears in the vicinity of 7 ppm of ¹ H-NMR of the raw material resin and the obtained hydrogenated resin. It was calculated based on the following formula. Hydrogenation rate = {1- (spectral area of hydrogenated resin / spectral area of raw material resin)} × 100
(%). The hydroxyl value is measured by JIS K 0070, and the softening point is measured by the ring and ball method of JIS K 2531.

Example 2 In Example 1, as the phenol-modified C9 petroleum resin, "HIRESIN PM-90" (color tone 11 Gardner,
Hydroxyl value 32 mgKOH / g, softening point 89.5 ° C, manufactured by Toho Kagaku Co., Ltd. was used, and the same operation as in Example 1 was carried out to obtain 100% olefin hydrogenation ratio and 0 aromatic ring hydrogenation ratio. %, Color tone 100 Hazen, hydroxyl value 35 mg KOH
/ G, 99 parts of phenol-modified C9-based hydrogenated petroleum resin having a softening point of 90 ° C was obtained.

Comparative Example 1 The same procedure as in Example 1 was carried out except that the nickel-diatomaceous earth catalyst prepared by the precipitation method (containing 50% nickel and 0% calcium) was used as the catalyst in Comparative Example 1. Hydrogenation rate 100%, aromatic ring hydrogenation rate 21%,
99 parts of a phenol-modified C9 hydrogenated petroleum resin having a color tone of 3 Gardner, a hydroxyl value of 42 mgKOH / g and a softening point of 90 ° C. was obtained.

Comparative Example 2 The same operation as in Example 2 was carried out except that the charged amount of the catalyst was changed to 5.0 parts in Example 2, and the olefin hydrogenation rate was 100% and the aromatic ring hydrogenation rate was 100%. 97 parts of a phenol-modified C9 hydrogenated petroleum resin having 95%, a color tone of 100 Hazen, a hydroxyl value of 15 mgKOH / g and a softening point of 85 ° C. was obtained.

Claims (4)

[Claims] 1. A phenol-modified C9-based hydrogenated petroleum resin having 0 to 80% of all of the olefinic double bonds and aromatic rings of the phenol-modified C9-based petroleum resin and having a color tone of 1 Gardner or less. 2. A hydroxyl value of 10 to 120 mg KOH / g
The phenol-modified C9 hydrogenated petroleum resin according to claim 1. 3. A phenol-modified C9 petroleum resin containing a phenol-modified C9 petroleum resin in the presence of a hydrogenation catalyst containing an alkaline earth metal as a promoter and a Group 8 metal as a main catalyst. The method for producing a phenol-modified C9-based hydrogenated petroleum resin according to claim 1 or 2, wherein 0 to 80% of all of the olefinic double bonds and the aromatic ring are hydrogenated. 4. The hydrogenation condition is a hydrogen partial pressure of 30 to 300 k.
g / cm ² , temperature 240 to 300 ° C., reaction time 1 to 10
The manufacturing method according to claim 3, which is time.