JPH05155918A - Production of hydrogenated hydrocarbon resin - Google Patents

Abstract

PURPOSE:To economically obtain a hydrogenated hydrocarbon resin on an industrial scale by hydrogenating a hydrocarbon resin in the presence of an alkaline earth metal oxide or hydroxide using, as a catalyst, Ni metal supported on a carrier. CONSTITUTION:A hydrocarbon resin is hydrogenated in the presence of a hydroxide and/or oxide of an alkaline earth metal using, as a catalyst, nickel metal supported on a carrier. This process is significantly effective particularly when the resin to be hydrogenated is an aliphatic hydrocarbon resin. The alkaline earth metal is preferably magnesium or calcium. The amount of the hydroxide and/or oxide is 5-100 pts.wt. per 100 pts.wt. nickel metal catalyst.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for hydrogenating a hydrocarbon resin. More specifically, the hydrocarbon resin, when using a nickel metal supported on a carrier as a catalyst for hydrogenation, by coexisting with a specific component, the hydrolytic decomposition of the hydrocarbon resin is suppressed and the softening point, The present invention relates to a method for producing a hydrogenated hydrocarbon resin capable of efficiently improving hydrogenation and coloring without lowering a flash point and a yield.

[0002]

2. Description of the Related Art Conventionally, in the fields of pressure-sensitive adhesives, hot melt adhesives, printing inks, paints, paper and fiber treatment agents, rosin-based and terpene-based materials are naturally used as tackifiers. However, there are drawbacks such as unstable supply and large price fluctuations, and in recent years synthetic hydrocarbon resins have come to be used as substitutes. More recently, with the advancement of technology in each field and the development of new applications, tackifiers are required to have higher performance than before, and have excellent heat stability under severe conditions, weather resistance, and polar polymers. In order to improve the compatibility of the above and further reduce the hue and odor on the appearance, a hydrogenated hydrocarbon resin as described in, for example, JP-A-64-33105 is developed and utilized. Has reached.

The method for producing the hydrogenated hydrocarbon resin is as follows:
For example, by dissolving the hydrocarbon resin in a suitable solvent, or by melting the hydrocarbon resin as it is, nickel, palladium,
A method of hydrogenating in the presence of a metal such as platinum, cobalt, ruthenium, or an oxide catalyst at room temperature to 350 ° C. and atmospheric pressure to 300 kg / cm ² under hydrogen pressure is known. Since it is carried out under relatively mild conditions sufficient to improve only the appearance hue, the hue of the product is unstable, poor in persistence, inferior in heat resistance, weather resistance and odor.

On the other hand, in order to obtain a sufficient degree of hydrogenation, a large amount of expensive metal catalyst is required and it is necessary to carry out the reaction under more severe hydrogenation conditions. However, under such conditions, the hydrocarbon resin undergoes hydrogenolysis as well as hydrogenation reaction, and a low molecular weight product is generated by the breaking of the molecular chain, so that the softening point and flash point of the hydrogenated resin are significantly lowered. Furthermore, it has been widely known that an extremely unfavorable phenomenon that the yield of hydrogenated resin is reduced is recognized.

As another method, Japanese Patent Publication No. 45-70.
In JP-A-64-64, a two-stage hydrogenation method was proposed, but this method involves hydrogenation at a low temperature of 180 to 230 ° C. in the first stage, and subsequently at a high temperature of 200 to 260 ° C. in the second stage. Was required and was industrially uneconomical.

In view of these problems, the inventors of the present invention previously found that in order to selectively suppress only the hydrogenolysis reaction without lowering the hydrogenation activity of the hydrogenation catalyst, nickel metal on the carrier is used. It was found that a method using a catalyst in which an oxide of alkaline earth metal and that of alkaline earth metal are simultaneously supported is effective (Japanese Patent Application No. 3-177592).

[0007]

However, in this method, although a binary element-supported catalyst must be used, the production of this catalyst requires a complicated operation, and the catalyst is not a general-purpose product. Therefore, there is a drawback that the cost becomes high.

The present invention overcomes the above-mentioned drawbacks of the prior art, and provides a catalyst that selectively suppresses only the hydrocracking reaction while maintaining the hydrogenation activity and that can be obtained at a low cost. It is an object of the present invention to provide a method for economically producing a hydrogenated hydrocarbon resin by using it on an industrial scale.

[0009]

DISCLOSURE OF THE INVENTION As a result of intensive efforts to solve the above problems, the present inventors have found that at least a hydroxide or oxide of an alkaline earth metal is selected for an inexpensive and versatile nickel catalyst. A method of effectively producing a hydrogenated hydrocarbon resin without causing a decrease in molecular weight due to hydrogenolysis by coexisting one or two or more species has been found.

That is, the gist of the present invention is that, when hydrogenating a hydrocarbon resin using nickel metal supported on a carrier as a catalyst, a hydroxide or / and an oxide of an alkaline earth metal is made to coexist. And a method for producing a hydrogenated hydrocarbon resin.

The present invention will be described in more detail. As the hydrocarbon resin, C _{4 to} C ₁₀ olefins, diolefins, aromatic olefin derivatives, and other polymerizable unsaturated compounds may be used alone or in combination of two or more. Obtained by polymerizing a mixture in the presence of a Friedel-Crafts catalyst such as aluminum trichloride, boron trifluoride or a complex thereof,
Solid with a softening point of 30 to 140 ° C and a pour point of 30 ° C
A liquid aliphatic hydrocarbon resin having a viscosity of 50 to 10,000 cSt / 50 ° C. and a derivative thereof, or a cyclopentadiene or an alkyl-substituted cyclopentadiene, alone or in a mixture, or a cyclopentadiene-based resin having the following viscosity. A mixture of a monomer and a polymerizable unsaturated compound capable of copolymerization in an arbitrary ratio, polymerized by heat or a radical initiator, a Friedel-Crafts catalyst, or the like, and having a softening point of 30 to 180 ° C. The point is 30 ° C or less, and the viscosity is 5 to 10,000 cSt /
A cyclopentadiene resin and a derivative thereof which are liquid at 50 ° C. are used.

In the present invention, it has been found that particularly remarkable effects are exhibited in hydrogenation of an aliphatic hydrocarbon resin.

As the catalyst, a hydroxide or / and an oxide of an alkaline earth metal is used together with a nickel metal catalyst (hereinafter referred to as a nickel metal catalyst) supported on a carrier. The nickel metal catalyst is generally industrially available and may be in a reduced state or a stabilized state and is not particularly limited. As the carrier, a porous carrier having a large surface area, such as diatomaceous earth, alumina, or silica, is generally used. The amount of nickel and nickel oxide supported on the carrier is 10 to 70% by weight, preferably 30 to 60% by weight. The shape of the catalyst can be selected according to the reaction type. That is, it may be in the form of powder, pellet, extrudate, cylinder or sphere.

The alkaline earth metal hydroxides or oxides include magnesium, calcium, strontium,
Examples thereof include hydroxides and oxides such as barium, and preferred examples include hydroxides or oxides of magnesium or calcium. Industrially, calcium hydroxide or calcium oxide that can be obtained at low cost is selected, but the shape thereof is more preferably a fine powder having a large surface area.

The coexistence ratio of the nickel metal catalyst and the alkaline earth metal hydroxide and / or oxide is
5 to 100 parts by weight of an alkaline earth metal hydroxide or / and oxide per 100 parts by weight of the nickel metal catalyst,
It is preferably 10 to 75 parts by weight. When this ratio is less than 5 parts by weight, it is difficult to suppress the hydrocracking, and when it exceeds 100 parts by weight, the hydrogenation activity is suppressed, which is effective under normal hydrogenation conditions. Hydrogenation becomes difficult, which is not preferable.

The amount of the nickel metal catalyst used in the present invention is not particularly limited, but is 0.3 to 1 relative to the hydrocarbon resin.
It is 0% by weight, preferably 0.3 to 5% by weight. In addition,
Although the reason has not been clarified yet, surprisingly, the coexistence of a hydroxide or / and an oxide of an alkaline earth metal significantly promotes the hydrogenation reaction, and makes the amount of the nickel metal catalyst used more remarkably than ever before. Because you can save
Its industrial value is extremely high.

In the hydrogenation reaction of the present invention, the temperature is from room temperature to 35.
0 ° C., preferably 150 to 250 ° C., hydrogen pressure is atmospheric pressure to 3
The reaction is carried out under the conditions of 00 kg / cm ² , preferably 30 to 150 kg / cm ² , and a reaction time of usually 0.5 to 10 hours. The reaction system may be a batch system or a continuous system and is not particularly limited.

Depending on the hydrocarbon resin used, hydrogenation may be carried out in the presence of a solvent or without solvent. Examples of the solvent include hexane, heptane, octane, cyclohexane, methylcyclohexane, dimethylcyclohexane, benzene, toluene, xylene and the like, and these can be used alone or in combination.

The hydrogenated hydrocarbon resin obtained by the present invention is, as described above, a pressure-sensitive adhesive, a hot melt adhesive, a printing ink, a paint, etc., which are the usual uses of the hydrogenated hydrocarbon resin, and a modified polyolefin etc. It can be used for the purpose of a substance.

[0020]

EXAMPLES In order to further clarify the content of the present invention, examples and comparative examples are shown below, but the present invention is not limited to these examples.

The measuring methods relating to the evaluation of the properties of the raw material resin and hydrogenated resin were carried out according to the following methods.

Softening point: JIS K-2207 (ring and ball method), iodine value: JIS K-0070, hue: JIS
K-5400 (Gardner) and JIS K-24
21 (Hazen), viscosity: JIS K-2283, flash point: JIS K-2265 (COC method)

Comparative Example 1 An iodine value of 155, a Gardner color of 8, and a softening point of 105 were placed in an autoclave having an internal capacity of 1 liter.
℃ aliphatic hydrocarbon resin (Marukalets S-105
A: A solution of 250 g of Maruzen Petrochemical Co., Ltd. and 250 g of dimethylcyclohexane, and 6.3 g of a powdery nickel catalyst (Nissan Gardler Catalyst Co., Ltd.) composed of 55% by weight of nickel and 45% by weight of diatomaceous earth. ,
The hydrogenation reaction was carried out while stirring at 200 ° C. for 5 hours at a hydrogen pressure of 60 kg / cm ² . After the reaction was completed, the resin solution obtained by separating the catalyst by filtration was filtered with a rotary evaporator to 200
After removing the solvent under the conditions of 30 ° C. and 30 Torr, it was cooled and solidified, and the hydrogenated resin 24 had a softening point of 94.5 ° C. and was almost colorless and transparent.
5 g was obtained.

As a measure of the degree of hydrogenation, a 50% by weight solution of hydrogenated resin in toluene was prepared and the hue was measured with a Hazen colorimeter. As a result, the number of hues was 10.

The obtained hydrogenated resin has a significantly lower softening point than that of the raw material resin, and it is clear that hydrogenolysis has occurred. In order to raise the softening point of this hydrogenated resin, the rotary evaporator was used again to
As a result of further distilling off the low molecular weight resin, the softening point of the hydrogenated resin was 102 ° C under the conditions of ℃, 15 Torr and 1 hour.
However, the yield was reduced to 237 g.

(Comparative Example 2) Hydrogenation was performed in the same manner as in Comparative Example 1 except that 3.2 g of the nickel catalyst was used to obtain 246 g of hydrogenated resin. The softening point of the obtained hydrogenated resin is 98 ° C.
However, the Hazen hue number was 50, and the coloration was slightly pale yellow, and hydrogenation was insufficient.

Comparative Example 3 Comparative Example 1 was repeated except that hydrogenation was carried out in the presence of 6.3 g of nickel catalyst and 0.2 g of powdered commercial calcium hydroxide.

The obtained hydrogenated resin weighed 244 g and had a softening point of 97 ° C. and a Hazen hue number of 10. Although the hydrocracking is slightly suppressed as compared with Comparative Example 1, it cannot be said to be sufficient.

(Comparative Example 4) The same procedure as in Comparative Example 1 was carried out except that hydrogenation was carried out in the presence of 3.2 g of nickel catalyst and 3.5 g of calcium hydroxide to obtain 245 g of hydrogenated resin.

The softening point of the obtained hydrogenated resin was 105 ° C., but the Hazen hue number was remarkably inferior at 60, and although hydrogenolysis was suppressed, adverse effects on the hydrogenation reaction were observed, which is not preferred. ..

Example 1 Comparative Example 1 except that hydrogenation was carried out in the coexistence of 6.3 g of nickel catalyst and 1 g of calcium hydroxide.
The same procedure as above was performed to obtain 246 g of a hydrogenated resin.

The softening point of the obtained hydrogenated resin was 105 ° C., the Hazen hue number was 5, and it was clear that the hydrogenolysis was completely suppressed and the hydrogenation reaction was promoted.

Example 2 Comparative Example 1 except that hydrogenation was carried out in the coexistence of 3.2 g of nickel catalyst and 1 g of calcium hydroxide.
In the same manner as in (2) above, 247 g of hydrogenated resin was obtained.

The softening point of the obtained hydrogenated resin is 104.5.
However, the Hazen hue number was 10, and Comparative Example 1
On the other hand, it can be seen that even with half the amount of the nickel catalyst, the hydrogenation reaction proceeds sufficiently and the hydrogenolysis is also suppressed.

(Example 3) Instead of calcium hydroxide,
245 g of hydrogenated resin was obtained in the same manner as in Example 2 except that 1 g of powdered commercially available calcium oxide was used.

The softening point of the obtained hydrogenated resin is 104 ° C.,
The Hazen hue number is 10, and it can be seen that calcium oxide is also effective.

Example 4 A hydrogenated resin of 246 g was obtained in the same manner as in Comparative Example 1 except that hydrogenation was carried out in the presence of 3.2 g of nickel catalyst and 1 g of powdered commercially available magnesium hydroxide.

The obtained hydrogenated resin has a softening point of 105 ° C., a Hazen hue number of 10, and it is apparent that the hydrogenolysis was completely suppressed and the hydrogenation reaction was promoted.

(Comparative Example 5) Iodine value 240, Gardner hue 8, viscosity 1,050 cSt / 50 ° C, flash point 202
C., 500 g of an aliphatic liquid hydrocarbon resin (Marcaclear V: Maruzen Petrochemical Co., Ltd.) having a pour point of + 9.degree. 3 at 200 ℃ in cm ²
The hydrogenation reaction was carried out for an hour. After the reaction, the catalyst was separated by filtration to obtain 490 g of a nearly colorless and transparent hydrogenated liquid resin having a viscosity of 810 cSt / 50 ° C. and a flash point of 165 ° C.

As an index of the degree of hydrogenation, the hue of the hydrogenated liquid resin was measured with a Hazen colorimeter as it was, and the number of hues was 5.

It is clear that the obtained hydrogenated liquid resin has much lower viscosity and flash point than the raw material resin and undergoes severe hydrocracking.

In order to raise the viscosity and flash point of this hydrogenated liquid resin, vacuum distillation was carried out to distill off the light components, and as a result, a product having a viscosity of 1,040 cSt / 50 ° C. and a flash point of 201 ° C. was obtained. Yield dropped to 476 g.

Comparative Example 6 A hydrogenated liquid resin 49 was prepared in the same manner as in Comparative Example 5 except that 3.8 g of nickel catalyst was used.
2 g was obtained. The viscosity of the hydrogenated liquid resin obtained is 870 cS.
The flash point was t / 50 ° C., the flash point was 168 ° C., and the Hazen hue number was 40, which is a very poor result.

(Example 5) 220g in the coexistence of 3.8g of nickel catalyst and 2.5g of commercially available powdery calcium hydroxide.
The same procedure as in Comparative Example 5 was carried out except that hydrogenation was carried out at 0 ° C to obtain 493 g of hydrogenated liquid resin.

The viscosity of the obtained hydrogenated liquid resin is 1,05
0cSt / 50 ℃, flash point 202 ℃, Hazen hue is 5
It is clear that the hydrocracking was completely suppressed and the hydrogenation reaction was further promoted.

Example 6 Hydrogenated liquid resin 4 was prepared in the same manner as in Comparative Example 5 except that hydrogenation was carried out in the presence of 3.8 g of a nickel catalyst and 1.9 g of powdered commercially available magnesium hydroxide.
91 g were obtained.

The viscosity of the resulting hydrogenated liquid resin is 1,03
0cSt / 50 ℃, flash point 201 ℃, Hazen hue is 5
Met.

[0048]

The method for producing a hydrogenated hydrocarbon resin of the present invention comprises:
By using a hydroxide or / and an oxide of an alkaline earth metal together with a nickel metal catalyst as a catalyst, hydrogenation can be sufficiently performed and hydrocracking can be selectively suppressed, so that the softening point and the flash point are lowered. The effect is that the hue can be improved within a short time without causing the above phenomenon.
In addition, regardless of the solid or liquid form of the raw material hydrocarbon resin,
Compared with conventional expensive catalysts, a small amount of inexpensive nickel metal catalyst is used, so the hydrogenation catalyst cost can be significantly saved, and the yield is almost quantitative, so it is an industrially very economical method. is there. In addition, even when hydrogenating a liquid hydrocarbon resin, no decrease in viscosity or flash point is observed, so a product can be obtained only by going through a decatalyzing step after hydrogenation. A post-process such as distillation, which has been adopted to adjust the properties, is unnecessary, and the product can be easily adjusted.

Claims (4)

[Claims] 1. A hydrogenated hydrocarbon characterized in that, when hydrogenating a hydrocarbon resin using nickel metal supported on a carrier as a catalyst, a hydroxide or / and an oxide of an alkaline earth metal is allowed to coexist. Resin manufacturing method. 2. Per 100 parts by weight of nickel metal catalyst,
5 alkaline earth metal hydroxides and / or oxides
The manufacturing method according to claim 1, wherein -100 parts by weight are made to coexist. 3. The method according to claim 1, wherein the alkaline earth metal is calcium or magnesium. 4. The production method according to claim 1, wherein the hydrocarbon resin is an aliphatic hydrocarbon resin.