JPH03106905A - Production of hydrogenated hydrocarbon resin - Google Patents

Abstract

PURPOSE:To produce a hydrogenated hydrocarbon resin within a short hydrogenation time while preventing the resin from being decomposed or lowering in its softening point during the hydrogenation reaction by hydrogenating the resin in the presence of a ketone or a phenol. CONSTITUTION:A hydrocarbon resin (e.g. coumarone/indene resin) is hydrogenated in the presence of 1-15wt.%, based on the resin, ketone (e.g. methyl isobutyl ketone) or phenol (e.g. cresol) at a temperature of ordinary temperature to 300 deg.C under a pressure of hydrogen of ordinary pressure to 350kg/cm<2>G.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is a colorless and transparent tackifier with good heat resistance and weather resistance for use in adhesives, adhesives, rubber, paints, inks, vibration damping materials, etc. The present invention relates to a method for producing hydrogenated hydrocarbon resins useful as adhesives, adhesion promoters, vibration damping agents, etc.

[Prior art] When producing a hydrogenated hydrocarbon resin, a method of carrying out a hydrogenation reaction by adding a substance other than a solvent into the reaction system involves adding alcohols to prevent the resin from decomposing and lowering its softening point. The method of adding alcohols,
A method of adding one or more selected from ethers, lactones, esters and amides is disclosed in JP-A-64-62.
Each of these is disclosed in Publication No. 307 and is already known. [Problems to be Solved by the Invention] However, with these conventional techniques, the reaction rate and reaction activity often decrease, and the disadvantage is that the desired hydrogenation rate cannot be obtained or it takes a long time to obtain it. Ta. Taking these drawbacks of the prior art into consideration, the present invention not only does not cause decomposition of the resin or decrease in the softening point during the hydrogenation reaction, but also actively increases the reaction activity and reaction rate, thereby achieving the target. The purpose of this study is to develop a new method for producing hydrogenated hydrocarbon resins that achieves the same hydrogenation rate within a short reaction time.

[Means for Solving the Problems] The present inventor conducted research to solve the above-mentioned problems, and found that hydrogenation of hydrocarbon resins in the presence of ketones or phenols causes decomposition of the resin. It was discovered that the reaction activity and reaction rate were increased without lowering the softening point, and the desired hydrogenation rate could be obtained within a short reaction time, that is, ketones or phenols act as hydrogenation reaction promoters. The invention has been completed. The ketones used in the present invention are compounds having a chemical structure as shown in formula (1), for example, methyl O 11 R1-C-R, ......
(1) (where R1 and R are alkyl groups) Examples include ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, and the like. Although the addition rate varies depending on the type of ketone, it is preferably in the range of 1-15% by weight based on the hydrocarbon resin. Furthermore, the phenols used in the present invention are compounds having a chemical structure as shown in formula (2), and examples thereof include phenol, cresol, xylenol, etc. (where R is hydrogen or an alkyl group). ．． Similarly, although the addition rate differs depending on the type of phenol, it is 1 to 1% per hydrocarbon resin.
A range of 5% by weight is preferred.

Examples of the hydrocarbon resin include coal-based coumaron-indene resin, petroleum-based 09 petroleum resin, C, petroleum resin, styrene-based resin, natural rosin-based resin, and terpene-based resin. Among them, it is particularly effective for coumaron-indene resin, which has a slow hydrogenation reaction rate. This resin has a higher sulfur content than other hydrocarbon resins, which poisons the hydrogenation catalyst and inhibits the reaction.
It is preferable to use a resin reduced in sulfur by the method described in Japanese Patent Application No. 092, ie, by distillation of raw material oil and light polymerization treatment, as the raw material for hydrogenation.

The hydrogenation reaction can be carried out by charging a hydrocarbon resin and 1 to 15% by weight of ketones or phenols (based on the resin) together in a reactor, and then dissolving the resin in a solvent such as cyclohexane, methylcyclohexane, or ethylcyclohexane. Alternatively, the resin may be melted as is and heated at room temperature to 300°C and normal pressure to 35°C in the presence of a catalyst containing a metal such as nickel, palladium, platinum, cobalt, ruthenium, or rhodium or an oxide of the metal.
Hydrogenation is carried out by a conventional method under a hydrogen pressure of 0 kg/c+a"G. Normal temperature and normal pressure are used for special high activity cases such as Raney nickel, and usually 150 to 300°C and 100 to 1
Hydrogenation is carried out under conditions of approximately 50 kg/cm"G. After separating and washing decomposed products such as hydrogen sulfide, the solvent and ketones are distilled off by evaporation treatment of hydrogenated oil to produce hydrogenated hydrocarbon resin. As the solvent, saturated hydrocarbons such as cyclohexane are preferable because they consume less hydrogen.

[Function] The exact mechanism of why the ketones or phenols used in the present invention act as promoters of hydrogenation reactions is unknown, but in hydrogenation reactions, they usually act as promoters of hydrogenation reactions.
Since the rate-determining step is the adsorption of the hydride onto the catalyst, we hypothesized that the adsorption of the hydride onto the catalyst may act to accelerate this process.

[Examples] Examples of the present invention will be described below, but the present invention is not limited to these Examples in any way.

Example 1 25 g of low sulfur coumaron-indene resin having the properties shown in Table 1 as the hydrocarbon resin, 2.18 g of methyl isobutyl ketone (8.7 weight percent relative to the resin) as the ketone, and 25 g of ethylcyclohexane as the solvent. and nickel-diatomaceous earth catalyst (Ni content 45%) 8.2g (3.3% by weight based on resin) with pressure resistance 300kg/am”G, capacity 2
Charge into a ゜00IIQ electromagnetic stirring autoclave, hydrogen pressure 30-100kg/cm''G, reaction temperature 250
'C, the hydrogenation reaction was carried out under the conditions of a reaction time of 8 hours and a stirrer rotation speed of 60 rpm. After the reaction, the catalyst and resin solution were separated by filtration, and the filtrate oil was charged into a rotary evaporator at 150°C and 5mmHg.
The temperature was gradually increased and the pressure was reduced to distill off ethylcyclohexane and methyl isobutyl, thereby obtaining 22 g of hydrogenated coumaron-indene resin.

The properties of the obtained hydrogenated coumaron-indene resin are also listed in Table 1. The nuclear hydrogenation rate was high, and the hydrogenation reaction was almost completed within the predetermined reaction time. Therefore, the heat discoloration resistance was also very good. In addition, there is no change in the softening point before and after hydrogenation,
No resin decomposition occurred.

<Examples 2 to 5> Methyl ethyl ketone instead of methyl isobutyl ketone,
Hydrogenation was carried out under the same conditions as in Example 1, except that 2.18 g (8.7% by weight of the resin) of one of diisobutyl ketone, phenol, and 0-cresol was added to obtain a hydrogenated coumaron-indene resin. 22g was obtained.

Properties are shown in Table 1. Similarly, the nuclear hydrogenation rate was high, and the hydrogenation reaction was almost completed within the specified reaction time. It also had excellent heat discoloration resistance. There was no change in the softening point, and no decomposition of the resin occurred.

<Example 6> Hydrogenation was carried out under the same conditions as in Example 1, except that a commercially available C, petroleum resin (manufactured by Nippon Petrochemical Co., Ltd., Nisseki Neopolymer 100) was used as the raw material hydrocarbon resin. 22g of fossil petroleum resin was obtained. The properties are shown in Table I. Similarly, the nuclear hydrogenation rate was high. Comparative Example 1> Example 1 except that methyl isobutyl ketone was not added.
A hydrogenation reaction was carried out under the same conditions as above to obtain 22 g of hydrogenated coumaron-indene resin.

The properties of the obtained hydrogenated coumaron-indene resin are also listed in Table 1. The nuclear hydrogenation rate was low, the hydrogenation reaction was not completed within a predetermined reaction time, and the hue and heat discoloration resistance were also poor.

Comparative Examples 2 and 3 A hydrogenation reaction was carried out under the same conditions as in Example 1, except that benzaldehyde or ethanol was added instead of methyl isobutyl ketone, to obtain 22 g each of hydrogenated coumaron-indene resins.

The properties are also listed in Table 1. Similarly, the nuclear hydrogenation rate was low, and the hue and heat discoloration resistance were also poor.

<Comparative Example 4> A hydrogenation reaction was carried out under the same conditions as in Example 6, except that methyl isobutyl ketone was not added, and 22 g of hydrogenated petroleum resin was obtained. Similarly, the nuclear hydrogenation rate was low. [Effects of the Invention] According to the present invention, the reaction time in hydrogenation of hydrocarbon resins can be shortened and productivity can be improved. It becomes possible to produce a resin with a high hydrogenation rate in a relatively short time.

Claims (1)

[Claims] A method for producing a hydrogenated hydrocarbon resin, which comprises hydrogenating a hydrocarbon resin in the presence of ketones or phenols.