JPH04372606A - Production of hydrogenated petroleum resin - Google Patents

Abstract

PURPOSE:To produce a resin which is colorless, transparent and odorless, excels in heat stability and has a high commercial value in high yields and good workability without lowering the softening point, viscosity and flash point by selectively and effectively hydrogenating the unsaturated bonds without causing hydrogenolysis. CONSTITUTION:A process for producing a hydrogenated petroleum resin by using a nickel catalyst prepared by impregnating a carrier with nickel and at least one member selected between an alkali metal oxide and an alkaline earth metal oxide in such amounts that 3-30 pts.wt. (in terms of the metal) the oxide is present per 100 pts.wt. of the nickel.

Description

[Detailed description of the invention]

0001

FIELD OF THE INVENTION This invention relates to a method for hydrogenating petroleum resins. More specifically, when petroleum resins are hydrogenated using a nickel catalyst, by using a nickel catalyst containing a certain specific component, hydrogenolysis of petroleum resins can be suppressed, that is, the softening point and flash point can be lowered, and The present invention relates to a method for producing hydrogenated petroleum resin that can efficiently perform hydrogenation and improve coloration without causing a decrease in yield.

0002

[Prior Art and Problems] Conventionally, in the fields of pressure sensitive adhesives, hot melt adhesives, printing inks, paints, paper and fiber treatment agents, etc., natural tackifiers such as rosin and terpene have been used as tackifiers. Resins that rely on raw materials have been used for a long time, but they have drawbacks such as unstable supply and large price fluctuations, so in recent years petroleum resins have come to be used as substitutes. Furthermore, in recent years, with the advancement of technology in various fields and the development of new applications, tackifiers are required to have better performance than ever before, with excellent thermal stability and weather resistance under harsh conditions, and polar polymers. In order to improve the compatibility, as well as the appearance hue and odor,
For example, hydrogenated petroleum resins as described in JP-A-64-33105 have been developed and are now in use.

[0003] As a method for producing the hydrogenated petroleum resin, for example, petroleum resin is mixed with hexane, heptane, octane, cyclohexane, methylcyclohexane, benzene, toluene,
It is dissolved in a single or mixed solvent such as xylene, or by melting the petroleum resin as it is, and is heated at room temperature to 350°C in the presence of Raney nickel or a metal or oxide catalyst such as nickel or palladium, platinum, cobalt, or ruthenium supported on a carrier. ℃ under hydrogen pressure of normal pressure to 300 kg/cm2, but under relatively mild hydrogenation conditions sufficient to improve only the visual hue, the product shows a temporary improvement in hue. However, it is known to be unstable, to recolor after a long period of time, and to have poor heat resistance, weather resistance, and odor. On the other hand, in order to obtain a more sufficient degree of hydrogenation to overcome these drawbacks, it is necessary to carry out the reaction under severe hydrogenation conditions. However, under such conditions, petroleum resin undergoes hydrogenolysis as well as hydrogenation reaction, and low molecular weight products are produced due to molecular chain scission, resulting in a significant drop in the softening point and flash point of the hydrogenated resin. It is also widely known that an extremely undesirable phenomenon occurs in which the yield of hydrogenated resin decreases.

As a method for solving these problems, Japanese Patent Publication No. 7064/1983 proposes a two-stage hydrogenation method. That is, 180-230℃ in the first stage
Hydrogenation is carried out at a low temperature of 20
Although it has been disclosed that hydrogenation is carried out at a high temperature of 0 to 260°C, this method requires an extra step of reacting at a different temperature, and can hardly be called an economical method from an industrial perspective.

On the other hand, Japanese Patent Publication No. 57-47681 proposes a method in which 0.05 to 50 wt% of alcohol is added to the hydrocarbon solvent during hydrogenation in the hydrocarbon solvent. However, since the solubility of petroleum resin in alcohol is very low, the viscosity of the reaction liquid itself becomes high, resulting in a decrease in the contact efficiency with the hydrogenation catalyst and making it difficult for the hydrogenation reaction to proceed efficiently, which is not necessarily desirable. It's hard to call it a method. Further, even if all the problems could be solved by adding a special solvent, it would still be difficult to say that it is a preferable method from the economical and workability standpoints, and a solution method from a different perspective has been desired.

[0006]

[Problem to be Solved by the Invention] It is already a well-known fact that the problems with hydrocracking of petroleum resins are caused by the thermal decomposition of the resin at high temperatures or the hydrocracking characteristics of the hydrogenation catalyst. . However, if mild reaction conditions are used to solve the former factor, as mentioned above, the degree of hydrogenation of the resulting resin will be insufficient, and its heat resistance, weather resistance, etc. will be unsatisfactory as a product. However, as a method to solve the latter factor, for example, reducing the amount of metal supported on the hydrogenation catalyst,
On the other hand, since the hydrogenation activity is insufficient, a larger amount of catalyst is required to be added, which inevitably leads to an economical problem of increasing production costs.

The present invention relates to the hydrogenation of petroleum resins, and provides a method for effectively producing hydrogenated resins without causing a decrease in molecular weight due to hydrogenolysis while using an inexpensive nickel catalyst. It is something to do.

[0008]

[Means for Solving the Problems] The present inventors conducted extensive research in order to make it possible to selectively suppress only the hydrogenolysis reaction without reducing the hydrogenation activity of the hydrogenation catalyst. As a result, instead of the Raney nickel or nickel supported on a carrier catalyst that has been conventionally used for the hydrogenation of petroleum resins, a catalyst with a specific ratio of alkali metal or alkaline earth metal oxides and nickel supported on a carrier has been used. The present inventors have found that this object can be achieved and have completed the present invention.

That is, the gist of the present invention is to combine nickel and at least one of the oxides of alkali metals and alkaline earth metals in a ratio of 3 to 30 parts by weight in terms of metal per 100 parts by weight of nickel. There is a method for producing hydrogenated petroleum resin, which is characterized by carrying out a hydrogenation reaction of petroleum resin in the presence of a nickel-based catalyst supported on a carrier.

To explain the present invention in more detail, the petroleum resin in the present invention includes C4 to C10 olefins,
A mixture containing an appropriate proportion of at least one selected from diolefins, aromatic olefin derivatives, and other polymerizable unsaturated compounds is mixed with aluminum trichloride, boron trifluoride, or complexes thereof, etc. Softening point: 40 obtained by polymerization in the presence of a Friedel-Crafts catalyst
~120℃ solid resin and pour point below room temperature,
and liquid petroleum resins with a viscosity of 50 to 10,000 cSt/50°C and derivatives thereof, cyclopentadiene, alkyl-substituted cyclopentadiene alone or as a mixture, or polymers copolymerizable with these cyclopentadiene monomers. Softening point 4 obtained by polymerizing a mixture containing a sexually unsaturated compound in any proportion with heat or a radical initiator or a Friedel-Crafts catalyst, etc.
These are solid resins having a temperature of 0 to 180°C, and liquid cyclopentadiene resins having a pour point below room temperature and a viscosity of 5 to 10,000 cSt/50°C, and derivatives thereof.

[0011] As the hydrogenation conditions for these petroleum resins, the conditions of the conventional methods as described above can be adopted, but conditions of a temperature of 150 to 250°C and a hydrogen pressure of 30 to 150 kg/cm2 are preferred. The reaction format may be batchwise or continuous and is not particularly limited.

[0012] As described above, the present invention is characterized by the use of a nickel-based catalyst containing at least one selected from oxides of alkali metals and alkaline earth metals. In addition, in the present invention, the term nickel refers to reduced nickel,
The term nickel is used to include not only metallic nickel but also those with a protective film formed by surface oxidation, sulfidation, etc. to prevent risks such as spontaneous combustion and improve the shelf life of the catalyst. In short, any material that can be converted into metallic nickel under the conditions of use is sufficient. The amount of nickel supported on the carrier is 10
~70% by weight (value calculated by converting the total amount into metal, the same applies hereinafter),
Preferably it is 30 to 60% by weight. Further, the proportion of the alkali metal and alkaline earth metal oxides is 3 to 30 parts by weight (the value calculated by converting the total amount into metal, the same applies hereinafter) to 100 parts by weight of nickel supported on the carrier, more preferably It is 10 to 25 parts by weight. If this ratio is less than 3 parts by weight, it will be difficult to suppress hydrogenolysis, and if it exceeds 30 parts by weight, the hydrogenation activity will drop significantly and effective hydrogenation will become difficult. Undesirable.

[0013] Oxides of alkali metals and alkaline earth metals generally include oxides of potassium, sodium, magnesium, calcium, barium, etc., and preferably oxides of magnesium, calcium, and potassium. . These oxides can be easily prepared from the above-mentioned oxygenated compounds of alkali metals and alkaline earth metals, such as hydroxides, carbonates, nitrates, and the like.

The carrier is not particularly limited, but may be a porous carrier with a large surface area, such as alumina, diatomaceous earth,
Examples include silica, preferably alumina or diatomaceous earth, and more preferably alumina, which has a low solid acidity that is thought to affect hydrogenolysis.

The shape of the catalyst can be selected depending on the type of reaction. That is, they are in powder form, pellet form, extrudate, cylindrical shape, spherical shape, etc.

The hydrogenated petroleum resin obtained by the present invention can be used for pressure sensitive adhesives, hot melt adhesives, printing inks, paints, paper and fiber treatment agents, etc., which are the usual uses of hydrogenated petroleum resins as described above. It can be used for various purposes.

[0017]

[Examples] In order to make it easier to understand the contents of the present invention, Examples and Comparative Examples are shown below, but the present invention is not limited thereto. (Comparative Example 1) In an autoclave with an internal capacity of 1 liter, a solution of 250 g of C5 petroleum resin (Marukarez S-105A: manufactured by Maruzen Petrochemical Co., Ltd.) with an iodine value of 155, a Gardner hue of 8, and a softening point of 105°C and 250 g of methylcyclohexane was added. Its main component composition is nickel/diatomaceous earth (55/
Powdered hydrogenation catalyst (G-4) composed of a ratio of
9B (manufactured by Nissan Girdler Catalyst Co., Ltd.) was charged, and a hydrogenation reaction was carried out at 200° C. for 5 hours at a hydrogen pressure of 60 kg/cm 2 . After the reaction, the catalyst was separated by filtration and the resulting resin was heated at 200°C and 30°C in a rotary evaporator.
After removing the solvent under rr conditions, it is cooled and solidified to a softening point of 9.
245 g of hydrogenated petroleum resin at 2.5°C was obtained. Table 1 shows the properties of the resin.

The obtained hydrogenated petroleum resin has a softening point significantly lower than that of the raw resin, and it is clear that hydrogenolysis has occurred. In order to raise the softening point of this hydrogenated petroleum resin, low molecular weight substances were distilled off again using a rotary evaporator at 260°C, 15 Torr, and for 1 hour. is 1
Although the temperature increased to 0.01°C, the yield decreased to 236g.

(Comparative Example 2) 200g of nickel nitrate [N
i(NO3)2.6H2O] and 105 g of calcium nitrate [Ca(NO3)2.4H2O] were dissolved in 1.5 liters of ion-exchanged water, and 31.4 g of diatomaceous earth was added thereto, and 10 wt. % sodium carbonate [Na2CO
3] Approximately 1.5 liters of aqueous solution and 1 liter of ion-exchanged water at 80°C
The solution was added dropwise over about 1 hour while maintaining the pH at 8. After dropping, the mixture was aged for about 1 hour, resulting in a precipitate (a mixture of basic nickel carbonate, calcium carbonate, and diatomaceous earth).
After filtering and washing with water, it was dried at 105°C. 400 dry items
After baking at ℃ to form an oxide, pulverize and heat the pulverized product to 430℃.
The catalyst was reduced in a hydrogen stream for 2 hours to bring the nickel into a metallic state, and then surface oxidized with 1% by volume of oxygen (balance nitrogen) to produce a catalyst with a nickel/calcium/diatomaceous earth composition ratio of 45/20/35. I got it. A resin was hydrogenated in the same manner as in Comparative Example 1 except that this catalyst was used as a hydrogenation catalyst. Although the softening point of the obtained hydrogenated resin was small and hydrogenolysis was suppressed, the degree of hydrogenation was low and the hue was pale yellow. Table 1 shows the properties of the resin.

(Example 1) 12.8g of calcium nitrate
A mixture of nickel/magnesium/diatomaceous earth was prepared in the same manner as in Comparative Example 2, except that the amount of sodium carbonate aqueous solution was changed to about 1 liter, and the amount of diatomaceous earth was changed to 39.2 g. Composition ratio is 50/
After obtaining a catalyst with a ratio of 1.5/48.5, a hydrogenation reaction of the resin was carried out in the same manner as in Comparative Example 1. 247 g of hydrogenated petroleum resin with a softening point of 102°C was obtained. Table 1 shows the properties of the resin. It is clear that this catalyst system has high hydrogenation activity and suppresses hydrogenolysis.

(Example 2) The amount of magnesium nitrate was 42
．． Comparative Example 1 The hydrogenation reaction of the resin was carried out in the same manner as described above. 244 g of hydrogenated petroleum resin with a softening point of 103° C. was obtained. Table 1 shows the properties of the resin. It is clear that this catalyst system has high hydrogenation activity and suppresses hydrogenolysis.

(Example 3) 100 g of nickel oxide powder, 19.7 g of anhydrous calcium carbonate powder and 62.9 g of nickel oxide powder
After dry mixing 1 g of alumina powder, about 70 g of ion-exchanged water was added and wet kneading was performed. Kneaded material at 130℃
The composition ratio of nickel / calcium / alumina was 50 /
A catalyst with a ratio of 10/40 was obtained. Using this catalyst, a resin hydrogenation reaction was carried out in the same manner as in Comparative Example 1. Softening point 10
243 g of hydrogenated petroleum resin at 5° C. was obtained. Table 1 shows the properties of the resin. It is clear that this catalyst system has high hydrogenation activity and suppresses hydrogenolysis.

(Example 4) Except that 13.9 g of anhydrous potassium carbonate powder was used instead of anhydrous calcium carbonate,
In the same manner as in Example 3, a catalyst having a nickel/potassium/alumina composition ratio of 53/5/42 was obtained. Using this catalyst, a resin hydrogenation reaction was carried out in the same manner as in Comparative Example 1. 245 g of hydrogenated petroleum resin with a softening point of 105° C. was obtained. Table 1 shows the properties of the resin. It is clear that this catalyst system has high hydrogenation activity and suppresses hydrogenolysis.

[0024]

[Table 1]

(Comparative Example 3) Iodine number 240, Gardner hue 8, viscosity 1,070 cSt/50°C, flash point 202
℃, 500 g of C5 liquid petroleum resin (Maruka Clear V: manufactured by Maruzen Petrochemical Co., Ltd.) with a pour point of +9℃, and 15 g of the nickel catalyst used in Comparative Example 1 were placed in a 1L autoclave, and the mixture was heated at 200℃ under a hydrogen pressure of 60 kg/cm2. The hydrogenation reaction was carried out for 3 hours. After the reaction, the catalyst was separated by filtration and the viscosity was 74.
Hydrogenated liquid resin 4 with 5cSt/50℃ and flash point 152℃
90g was obtained. Table 2 shows the properties of the resin.

The obtained hydrogenated liquid resin has a significantly lower viscosity and flash point than the raw material resin, and it is clear that hydrogenolysis is severe.

In order to increase the viscosity and flash point of this hydrogenated liquid resin, vacuum distillation was carried out to remove light components, resulting in a viscosity of 1.
, 030 cSt/50° C. and a flash point of 201° C. were obtained, but the yield was reduced to 475 g.

(Comparative Example 4) A hydrogenation reaction of a resin was carried out in the same manner as in Comparative Example 3, except that the same hydrogenation catalyst as in Comparative Example 2 was used. Although the obtained hydrogenated liquid resin showed no decrease in viscosity at all, the degree of hydrogenation was low and the hue was pale yellow. Table 2 shows the properties of the resin.

(Examples 5 to 8) A hydrogenation reaction of a resin was carried out in the same manner as in Comparative Example 3, except that the catalyst used in Examples 1 to 4 was changed. Approximately 490 g of hydrogenated liquid resin which was sufficiently hydrogenated was obtained using either catalyst system. Table 2 shows the properties of the resin. It is clear that hydrogenolysis hardly occurs or its degree is small.

[0030]

[Table 2]

[0031]

[Effects of the Invention] The hydrogenated petroleum resin manufacturing method of the present invention can be applied to solid and liquid petroleum resins, and can selectively and efficiently hydrogenate only unsaturated bonds without causing hydrogenolysis. Therefore, hydrogenated petroleum resin can be obtained in high yield without causing a decrease in softening point, viscosity, or flash point. In addition, conventionally, the softening point or viscosity of hydrogenated products
Post-processes such as distillation that were used to adjust the flash point are no longer necessary, and the product can be obtained by simply going through a decatalyst process after hydrogenation, and if a solvent is used, simply removing the solvent. This improves work efficiency. Furthermore, the obtained hydrogenated petroleum resin is colorless, transparent, odorless, has excellent thermal stability, and has high product value.

Claims (3)

[Claims] Claim 1: Nickel and at least one oxide of an alkali metal or an alkaline earth metal are combined into nickel 1
In the presence of a nickel-based catalyst in which the oxide is supported on a carrier at a ratio of 3 to 30 parts by weight in terms of metal per 00 parts by weight,
A method for producing hydrogenated petroleum resin, characterized by carrying out a hydrogenation reaction of petroleum resin. 2. The method for producing a hydrogenated petroleum resin according to claim 1, wherein the carrier is diatomaceous earth and/or alumina. 3. The method for producing a hydrogenated petroleum resin according to claim 1 or 2, wherein the carrier is alumina.