JP2001172323A - Hydrogenation method of hydroxyl group-containing petroleum resin and hydroxyl group-containing petroleum resin hydride obtained by the method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a petroleum resin hydride having a good color tone and a high hydroxyl value by hydrogenating a hydroxyl group-containing petroleum resin without decomposing too many hydroxyl groups in the hydroxyl group- containing petroleum resin. SOLUTION: The hydrogenation method of a hydroxyl group-containing petroleum resin comprises hydrogenation of the hydroxyl group-containing petroleum resin in the presence of a hydrogenation catalyst having at least one metal element selected from the group consisting of a group VIII metal, copper, chromium, gold and rhenium and a compound of formula (1): R-O-R' (wherein R and R' are each a hydrogen atom, an alkyl group, an alcohol, or an ether or R and R' together form a cyclic structure).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for hydrogenating a hydroxyl group-containing petroleum resin. The hydride of the hydroxyl group-containing petroleum resin obtained by the hydrogenation method of the present invention has a light color and appropriate polarity and compatibility, so that it can be used for adhesives, adhesives, paints, printing inks, traffic paints, semiconductor sealants, plastics and the like. It is used as an additive having various functions for various compositions such as films.

[0002]

2. Description of the Related Art A hydroxyl group-containing petroleum resin is a thermoplastic resin obtained by polymerizing a hydrocarbon having an olefinic unsaturated bond in a petroleum naphtha cracked oil fraction in the presence of alcohols, phenols and the like. Since the resin structure contains a large number of hydroxyl groups, it is known that the resin structure has a high polarity and is excellent in compatibility with plastics such as an acrylic polymer and a polycarbonate having a relatively high polarity. However, the initial color tone of the hydroxyl group-containing petroleum resin is yellow or brown, so it has been difficult to apply it to applications where color tone is important (for example, tackifiers for acrylic adhesives for transparent labels).

[0003] The hydroxyl group-containing petroleum resin also contains an olefinic double bond and, in some cases, an aromatic double bond. In addition, various kinds of impurities are slightly contained. Therefore, the heating induces the Diels-Alder reaction, the retro Diels-Alder reaction, the depolymerization reaction, the oxidation reaction, and other various reactions relatively easily, and has a disadvantage that light stability, heat stability, and weather resistance are poor. .
As a means for overcoming such disadvantages relating to color tone, light stability, heat stability, and weather resistance, a method of hydrogenating the hydroxyl group-containing petroleum resin is known.
7, No. 4, pp. 290-295 (1984).

According to the method described in the above-mentioned literature, a resin having a light color and improved stability can be obtained, but hydroxyl groups are decomposed and the inherent high-polarity characteristic of the hydroxyl group-containing petroleum resin is lost. There was a tendency.

More specifically, according to the above-mentioned paper, when a nickel-containing dicyclopentadiene resin is subjected to a hydrogenation reaction using a nickel catalyst, the decomposition of hydroxyl groups is remarkable, the amount of the catalyst is 2.0 parts by weight, the reaction temperature is 240 ° C. and the reaction temperature is 240 ° C. Under a condition of a pressure of 1.96 MPa, the hydroxyl value of a hydroxyl group-containing dicyclopentadiene resin, which is a raw material to be hydrogenated, is reduced from 216 mgKOH / g to 90 mgKOH / g after hydrogenation, and about 60% of hydroxyl groups are decomposed. Have been.

[0006] Further, in the same document, a hydroxyl value of 70 mgK
In the case of hydrogenating an OH / g hydroxyl-containing dicyclopentadiene resin, it has been reported that when palladium is used as a catalyst, the decomposition of hydroxyl groups hardly occurs, but a high hydroxyl value such as 100 mgKOH / g or more is obtained. No application examples have been reported for a hydroxyl-containing dicyclopentadiene resin having

[0007] When the present inventors hydrogenated a hydroxyl-containing dicyclopentadiene resin having a high hydroxyl value (217 mgKOH / g) using a palladium catalyst, it was confirmed that about 23% of the hydroxyl groups were decomposed.

Incidentally, as a basic idea for suppressing the decomposition of hydroxyl groups, a method of reducing the reaction temperature and reaction pressure and employing mild reaction conditions is also one option. However, in this case, the decoloring property is poor, and a light-colored resin having a color tone of less than 400 Hazen cannot be obtained.

From the viewpoint of high polarity (that is, high hydroxyl value) and light color, even if based on the prior art, for example, some decomposition of the hydroxyl group is expected, and a high hydroxyl value (3
Hydrogenation of petroleum resin (more than 00mgKOH / g)
It is expected that a hydride of petroleum resin having a hydroxyl value of 200 mgKOH / g or more will be obtained. However, in practice, a petroleum resin having a very high hydroxyl value usually has an excessively low softening point, so that the hydrogenated resin using this as a raw material to be hydrogenated naturally has a low softening point, A hydrogenated resin having a practical softening point cannot be obtained. Generally, in the case of a hydroxyl group-containing dicyclopentadiene resin, the softening point is 1
In order to obtain a hydrogenated resin at about 00 ° C., the hydroxyl value of the hydroxyl group-containing petroleum resin, which is a raw material to be hydrogenated, is 2
It is limited to about 40 mgKOH / g. In addition, in order to obtain a resin having a softening point of 125 ° C., the hydroxyl value of the petroleum resin as the raw material to be hydrogenated is limited to about 150 mg KOH / g. For this reason, it is not realistic to employ a petroleum resin value having too high a hydroxyl value as a starting material.

As described above, according to the prior art, it was difficult to obtain a light-colored, high-hydroxyl-value petroleum resin hydride having a practical softening point.

[0011]

DISCLOSURE OF THE INVENTION The present invention provides a method for hydrogenating a hydroxyl group-containing petroleum resin without decomposing the hydroxyl group much.
It is an object of the present invention to provide a petroleum resin hydride having a good color tone and a high hydroxyl value.

[0012]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems of the prior art, and as a result, in the presence of a specific hydrogenation catalyst and a specific compound, a hydroxyl group, which is a raw material to be hydrogenated, It has been found that the above object can be achieved by hydrogenating the contained petroleum resin. The present invention has been completed based on such new knowledge.

That is, the present invention relates to a group 8 metal,
A hydrogenation catalyst having at least one metal element selected from the group consisting of copper, chromium, gold, and rhenium, and a general formula (1): R—O—R ′ (R and R ′ are each a hydrogen atom, A hydroxyl group-containing petroleum resin in the presence of a compound represented by an alkyl group, an alcohol, an ether, or a ring structure in which R and R 'are bonded to each other. The present invention relates to a method for hydrogenating petroleum resins. Further, the present invention relates to a hydrogenated petroleum resin containing a hydroxyl group obtained by the hydrogenation method.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The hydrogenation method of the present invention is to hydrogenate a hydroxyl group-containing petroleum resin as a raw material in the presence of a specific hydrogenation catalyst and a specific compound shown below. Further, the present invention relates to a hydrogenated petroleum resin containing a hydroxyl group obtained by the hydrogenation method.

[0015] The hydrogenation catalyst used in the present invention includes ▲
And those having at least one metal element selected from the group consisting of Group 8 metals, copper, chromium, gold and rhenium. As the hydrogenation catalyst having such a metal element, various types of the metal, metal compounds such as oxides and sulfides of the metal, and the like can be used. Among them, the Group VIII metals include metals such as cobalt, nickel, ruthenium, rhodium, palladium, platinum and the like, and metal compounds such as oxides and sulfides thereof.

The above-mentioned hydrogenation catalyst may be used by being supported on a carrier such as alumina, silica (diatomaceous earth), carbon, titania and the like having a large surface area. In the present invention, among these catalysts, palladium / carbon, palladium /
Alumina, nickel / diatomaceous earth, nickel / silica, nickel / silica alumina, platinum / carbon, platinum / alumina, copper-chromium oxide catalyst and the like are preferred. Among such hydrogenation catalysts, as a palladium / carbon catalyst, 5C-50W (trade name, manufactured by NEC Chemcat Corporation)
However, as a palladium / alumina catalyst, 5% Pd-alumina powder catalyst manufactured by NE Chemcat Co., Ltd., and as a nickel-diatomaceous earth catalyst, manufactured by Nissan Gardler Catalyst Co., Ltd., trade name G-96DRS, Nikki Chemical Manufactured by
N-113 is Pt / C as a platinum / carbon catalyst manufactured by NEC Chemcat Co., Ltd., and C-900 is a copper-chromium oxide catalyst manufactured by Sakai Chemical Co., Ltd.
Etc. can be exemplified.

In the present invention, it is essential that a specific compound be used together with the catalyst during the hydrogenation. As the compound, a compound represented by the general formula R-O-R '(R, R' represents a hydrogen atom, an alkyl group, an alcohol, an ether,
Or a ring structure in which R and R 'are bonded. )), And specifically, water, alcohols, ethers, alicyclic ethers and the like can be used. More specifically, water, methanol, ethanol, n-propanol,
Use isopropanol, 2-methyl-2-propanol, cyclohexanol, 2-ethylhexyl alcohol, ethylene glycol, glycerin, diethyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane, etc. it can. Among them, water is most suitable in terms of the effect of suppressing the decomposition of hydroxyl groups. These compounds may be used alone,
Also, two or more kinds may be used in combination. The amount of the compound to be used is generally 40 parts by weight or less, preferably 5 to 20 parts by weight, based on 100 parts by weight of the hydroxyl group-containing petroleum resin.

The hydroxyl group-containing petroleum resin used as the raw material to be hydrogenated used in the present invention is not particularly limited. For example, alcohol-modified dicyclopentadiene resin, alcohol-modified C9-dicyclopentadiene resin, phenol-dicyclopentadiene resin, phenol Modified C9 petroleum resin and the like. More specifically, a thermal polymer of dicyclopentadiene and allyl alcohol, a thermal polymer of dicyclopentadiene and C9 fraction and allyl alcohol, a thermal polymer of phenol and dicyclopentadiene, and a cationic polymer of C9 fraction and phenol Things and the like. Among these hydroxyl group-containing petroleum resins, alcohol-modified dicyclopentadiene resins are particularly preferred because many hydroxyl groups can be imparted. The C9 fraction is not particularly limited, but refers to a so-called aromatic vinyl compound. Specifically, it refers to styrene, vinyl toluene, α-methyl styrene, β-methyl styrene, indene, isopropenyl toluene, methyl indene, ethyl styrene, dimethyl styrene and the like. These C9 fractions may be used alone or as a mixture of two or more.

The above-mentioned dicyclopentadiene does not necessarily have to be pure dicyclopentadiene, but includes, for example, a dicyclopentadiene fraction obtained by a known industrial technique. The above-mentioned phenol does not necessarily need to be pure phenol, and includes, for example, alkyl-substituted phenols. Specific examples include methylphenol, ethylphenol, dimethylphenol, octylphenol, nonylphenol and the like. Further, the above-mentioned allyl alcohol is not limited to allyl alcohol, and a part of the structure may be substituted with a substituent.

Among the above hydroxyl-containing petroleum resins, examples of the alcohol-modified dicyclopentadiene resin include Quinton 1700 (trade name, manufactured by Nippon Zeon Co., Ltd.) and Neolesin NB-90 (trade name, manufactured by Nippon Petrochemical Co., Ltd.). it can. As a phenol-dicyclopentadiene resin,
Made by Nippon Petrochemical Co., Ltd., trade name: Neolesin PH-105
Etc. can be exemplified. Also, as the phenol-modified C9 petroleum resin, Nippon Petrochemical Co., Ltd., trade name Neopolymer E
-100 or the like.

The softening point of the hydroxyl group-containing petroleum resin is not particularly limited, but is preferably about 70 to 160 ° C, more preferably 80 to 150 ° C. It is preferable that the number average molecular weight of the hydroxyl group-containing petroleum resin is usually about 200 to 3000. When the number average molecular weight is less than 200, the heat resistance is poor, and when it is more than 3000, the compatibility with other mixed resins used in the composition for the use tends to be poor.

The conditions of the hydrogenation reaction are such that the hydrogenation pressure is usually in the range of about 0.49 to 29.4 MPa, and the reaction temperature is usually in the range of about 80 to 300 ° C. Preferably, the hydrogenation pressure is between 9.8 and 19.6 MPa, and the reaction temperature is between 200 and 280 ° C. Hydrogenation pressure is 0.49MPa
If the reaction temperature is less than 80 ° C., or if the reaction temperature is less than 80 ° C., hydrogenation is difficult to proceed. When the hydrogen partial pressure exceeds 29.4 MPa or when the reaction temperature exceeds 300 ° C., the resin chains are decomposed, and the softening point of the formed resin tends to decrease. There is.

When such a hydrogenation reaction is employed, for example, in a batch reaction mode, the ratio of the hydrogenation catalyst to the hydroxyl group-containing petroleum resin is about 0.01 to 10 parts by weight, preferably 0.02 parts by weight. -5 parts by weight. 0.0
If the amount is less than 1 part by weight, the hydrogenation hardly proceeds, and
If the amount exceeds the weight part, the hydrogenation tends to proceed too much. The reaction time is generally about 10 minutes to 10 hours, preferably 20 minutes to 8 hours. If the reaction time is less than 10 minutes, it is difficult to exhibit sufficient decolorization, and the hydrogenation of the double bond may be insufficient. If the time exceeds 10 hours, the decomposition of the resin chain is accelerated, and the softening point tends to be remarkably lowered, and the cost is disadvantageous.

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. In the hydrogenation reaction, the use of a solvent may or may not be used. The solvent is not particularly limited as long as it is inert to the reaction, and is a solvent in which raw materials and products are easily dissolved or dispersed. For example, n-hexane, cyclohexane, n-heptane, methylcyclohexane, dimethylcyclohexane, decalin and the like can be used alone or in combination of two or more. The amount of the solvent used is not particularly limited, but is usually 5 parts by weight or more, preferably 10 to 70 parts by weight, based on the raw material resin.

On the basis of the above hydrogenation reaction conditions, the decomposition of hydroxyl groups can be suppressed as much as possible despite the fact that the double bonds in the hydroxyl group-containing petroleum resin as the raw material to be hydrogenated are sufficiently hydrogenated. Moreover, a light-colored hydrogenated petroleum resin hydride can be easily obtained. The hydroxyl value, color tone, and softening point of the hydride of a hydroxyl group-containing petroleum resin obtained in the present invention vary depending on the type of the hydroxyl group-containing petroleum resin used as the raw material to be hydrogenated, but usually fall within the following range. The hydroxyl value of the hydride is a value that holds 65% or more, preferably 85% or more, of the hydroxyl value of the hydroxyl-containing petroleum resin as the raw material to be hydrogenated, and is usually 80 mgKOH / g.
At least 250 mgKOH / g, preferably 10 mgKOH / g or less.
0 mgKOH / g or more and 200 mgKOH / g or less. The color tone of the hydride is usually 350 Hazen or less, preferably 200 Hazen or less. The softening point is usually from 80 ° C to 170 ° C, preferably from 100 ° C to 150 ° C.

[0026]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In addition, in each example, all parts are parts by weight.

Example 1 Hydroxy group-containing dicyclopentadiene resin (manufactured by Zeon Corporation, trade name "Quinton-1700", color tone 10)
Gardner, hydroxyl value 217 mgKOH / g) 100
Parts, a palladium / carbon catalyst (manufactured by NE Chemcat Co., Ltd., trade name "5C-50W") (1.0 part) and pure water (15 parts) were charged into an autoclave, and a hydrogen partial pressure of 1 was added.
The hydrogenation reaction was performed under the conditions of 9.6 MPa, a reaction temperature of 270 ° C., and a reaction time of 5 hours. After completion of the reaction, the obtained hydrogenated resin was dissolved in 300 parts of toluene, and the catalyst was removed by filtration. Thereafter, a filtrate and an antioxidant (Ciba Specialty Chemicals Co., Ltd.), trade name “Irganox 101” were placed in a reaction vessel equipped with a stirring blade, a reflux condenser, a thermometer, a temperature controller and a pressure indicator.
0 ") 0.35 part, and the temperature was gradually increased and reduced to 2.67 kPa at 200 ° C. to remove the solvent, and 98 parts of a hydrogenated dicyclopentadiene resin hydride having a color tone of 200 Hazen and a hydroxyl value of 217 mgKOH / g were added. I got

Example 2 A hydrogen-containing dicyclopentadiene resin having a color tone of 150 Hazen and a hydroxyl value of 205 mg KOH / g was prepared in the same manner as in Example 1 except that the amount of pure water was changed to 10 parts. 98 parts were obtained.

Example 3 A hydrogen-containing dicyclopentadiene resin having a color tone of 50 Hazen and a hydroxyl value of 198 mgKOH / g was prepared in the same manner as in Example 1 except that the amount of pure water was changed to 5 parts. 98 parts were obtained.

Comparative Example 1 Example 1 was the same as Example 1 except that pure water was not used.
The same operation as described above was carried out to obtain a color tone of 250 Hazen and a hydroxyl value of 1
98 parts of a hydrogenated dicyclopentadiene resin hydride containing 68 mg KOH / g were obtained.

Comparative Example 2 The same operation as in Example 1 was carried out except that the reaction temperature was 250 ° C., the amount of the catalyst was 5.0 parts without using pure water, and the color tone 2 was Gardner, and the hydroxyl value was 2. 207mgKOH /
g of hydroxy-containing dicyclopentadiene resin hydride 98
Got a part.

Example 4 The procedure of Example 1 was repeated, except that methanol was used instead of pure water, to obtain a color tone of 150 Hazen.
98 parts of a hydrogenated dicyclopentadiene resin having a hydroxyl value of 190 mgKOH / g were obtained.

Example 5 A hydrogen-containing dicyclopentadiene resin having a color tone of 250 Hazen and a hydroxyl value of 202 mgKOH / g was prepared in the same manner as in Example 1 except that cyclohexanol was used in place of pure water. 98 parts were obtained.

Example 6 A hydrogenated dicyclopentadiene resin hydride having a color tone of 200 Hazen and a hydroxyl value of 210 mgKOH / g was prepared in the same manner as in Example 1 except that tetrahydrofuran was used instead of pure water. I got

Example 7 In Example 1, nickel-diatomaceous earth ("G-96DRS", Nissan Gardler Catalyst Co., Ltd.) was used as a catalyst.
The same operation as in Example 1 was carried out except for using the above, to obtain 98 parts of a hydrogenated dicyclopentadiene resin hydride having a color tone of 150 Hazen and a hydroxyl value of 152 mgKOH / g.

Comparative Example 3 Example 7 was the same as Example 7 except that pure water was not used.
The same operation as described above was carried out to obtain a color tone of 200 Hazen and a hydroxyl value of 8
98 parts of a hydrogenated dicyclopentadiene resin containing 7 mgKOH / g hydroxyl group were obtained.

Example 8 In Example 1, platinum / carbon (“P
t / C "(manufactured by NE Chemcat Corporation) except that the same operation as in Example 1 was carried out, and 98 parts of a hydroxyl-containing dicyclopentadiene resin hydride having a color tone of 200 Hazen and a hydroxyl value of 194 mgKOH / g were used. I got

Comparative Example 4 Example 8 was the same as Example 8 except that pure water was not used.
The same operation as described above was carried out to obtain a color tone of 300 Hazen and a hydroxyl value of 1
98 parts of a hydrogenated dicyclopentadiene resin containing 50 mg KOH / g of hydroxyl group was obtained.

Example 9 The procedure of Example 1 was repeated, except that copper / chromium oxide (“C-900”, manufactured by Sakai Chemical Co., Ltd.) was used as the catalyst. This gave 98 parts of a hydrogenated dicyclopentadiene resin having a hydroxyl value of 210 mgKOH / g in 250 Hazen.

Comparative Example 5 Example 9 was repeated except that pure water was not used.
The same operation as described above was carried out to obtain a color tone of 250 Hazen and a hydroxyl value of 1
98 parts of a hydrogenated dicyclopentadiene resin hydride of 65 mgKOH / g were obtained.

[0041]

[Table 1]

In Table 1, only the reaction temperature of Comparative Example 2 was 2
The conditions were 50 ° C. and the amount of catalyst used was 5.0 parts.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J100 AU01P AU02P AU03P CA01 HA03 HB02 HB16 HB17 HB36 HB50 HD22 JA01 JA03

Claims (10)

[Claims] 1. A hydrogenation catalyst having at least one metal element selected from the group consisting of Group VIII metals, copper, chromium, gold and rhenium, and a general formula (1): R
In the presence of a compound represented by -OR '(R and R' each represent a hydrogen atom, an alkyl group, an alcohol or an ether, or a ring structure in which R and R 'are bonded). A method for hydrogenating a hydroxyl group-containing petroleum resin, comprising hydrogenating a hydroxyl group-containing petroleum resin. 2. The hydrogenation method according to claim 1, wherein the hydrogenation catalyst has at least one metal element selected from the group consisting of nickel, palladium, platinum, copper and chromium. 3. The hydrogenation method according to claim 2, wherein the hydrogenation catalyst has at least one metal element selected from the group consisting of palladium, platinum, copper and chromium. 4. The hydrogenation method according to claim 1, wherein the amount of the compound represented by the general formula (1) is 40 parts by weight or less based on 100 parts by weight of the hydroxyl group-containing petroleum resin. 5. The hydrogenation method according to claim 4, wherein the amount of the compound represented by the general formula (1) is 5 to 20 parts by weight. 6. The hydrogenation method according to claim 1, wherein the compound represented by the general formula (1) is water. 7. The hydrogenation method according to claim 1, wherein the hydrogenation is carried out in the presence or absence of an organic solvent other than the compound represented by the general formula (1). 8. The hydrogenation method according to claim 1, wherein the hydroxyl group-containing petroleum resin is an alcohol-modified dicyclopentadiene resin. 9. A hydrogenated hydroxyl group-containing petroleum resin obtained by the hydrogenation method according to claim 1. Description: 10. A hydride of a hydroxyl group-containing petroleum resin having a hydroxyl value of 65% of a hydroxyl group-containing petroleum resin as a raw material before hydrogenation.
% Or more and 80 mgKOH / g or more and 250 mg
The hydroxyl group-containing petroleum resin hydride according to claim 9, which has a value of KOH / g or less, a color tone of 350 Hazen or less, and a softening point of 80C or more and 170C or less.