JPH04110304A - Preparation of hydrogenated petroleum resin - Google Patents

Abstract

PURPOSE:To obtain a hydrogenation product of an arom. ring-contg. petroleum resin highly selectively at a high yield by catalytically reducing an arom. ring- contg. petroleum resin with hydrogen in the presence of a catalyst comprising specific metals and platinum. CONSTITUTION:An arom. ring-contg. petroleum resin [e.g. a homopolymer of an arom. hydrocarbon having a double bond in the side chain (e.g. styrene) or a homopolymer of an arom. hydrocarbon having a double bond in the ring (e.g. indene)] is hydrogenated by catalytic reduction with hydrogen in the pres ence of a catalyst comprising metals of the group I and/or II and platinum (pref. platinum and the metals of the group I and/or II are supported on a carrier, the ant. carried of platinum is 0.1-10wt.% of the total catalyst wt., and the atomic ratio of the total amt. carried of the metals of the group I and/or II to platinum is 0.08-5). Thus the hydrogenation is carried out effectively, and undesirable side reactions are satisfactorily suppressed.

Description

[Detailed description of the invention] “Industrial application field” The present invention relates to a method for producing hydrogenated petroleum resins.

[Prior Art] The so-called petroleum resin obtained by polymerizing the thermal decomposition product of petroleum naphtha in the presence of a Friedel-Crafts catalyst is mainly used as a tackifier for pressure-sensitive adhesives or adhesives, and as a modifier for plastic compounding. However, resins suitable for these uses usually have a softening point of 60 to 140°C and a molecular weight of about 600 to 10,000. These hydrogenated petroleum resins have good weather resistance, color tone, stability, and compatibility with rubber, polyolefin, or ethylene-vinyl acetate copolymer, etc.
It is particularly excellent as a resin for use in the above applications. However, the petroleum resin subjected to the hydrogenation reaction is far less likely to be hydrogenated than its raw material monomer. Although the reason for this is not fully understood, there is a general tendency that hydrogenation becomes more difficult as the degree of polymerization increases. In particular, when converting the benzene ring of petroleum resin, which has an aromatic ring, to a cyclohexane ring, a large amount of a catalyst such as a nickel catalyst or a platinum catalyst is added, and hydrogenation is carried out under severe conditions such as high temperature, high pressure, and long time. The reaction is difficult to proceed.

Moreover, if the hydrogenation activity of the catalyst used is insufficient, side reactions such as unfavorable decomposition reactions often occur due to high temperature and high pressure conditions (the softening point and yield of hydrogenated petroleum resins may decrease). There was a disadvantage.

[Problems to be Solved by the Invention] The present invention provides that when a petroleum resin having an aromatic ring is hydrogenated using a conventional hydrogenation catalyst, a relatively large amount of catalyst is required; The object of the present invention is to solve the aforementioned problems of requiring harsh hydrogenation conditions and causing undesired side reactions. That is, the present invention provides a method for producing hydrides of aromatic petroleum resins in high yield and high selectivity by suppressing side reactions such as decomposition reactions by finding a more highly active hydrogenation catalyst. The purpose is to

[Means for Solving the Problems] In order to achieve the above-mentioned object, the present inventors conducted extensive studies on hydrogenation catalysts, and unexpectedly found that a hydrogenation catalyst supported on platinum and other specific metals was used. By doing so,
discovered for the first time that the object of the present invention can be achieved,
The present invention has now been completed. The present invention has been completed based on this fact.

That is, the present invention is characterized in that when hydrogenating a petroleum resin having an aromatic ring, catalytic reduction is carried out with hydrogen in the presence of a catalyst consisting of a metal element of Group 1 and/or Group 2 of the Periodic Table and platinum. The present invention relates to a method for producing a hydride of a petroleum resin having an aromatic ring.

[Function] As mentioned above, a catalyst containing only platinum, which is a metal of group 8 of the periodic table, as an active species is known as a hydrogenation catalyst for aromatic hydrocarbon compounds and petroleum resins having an aromatic ring. However, Group 1 of the periodic table and/or
Alternatively, a catalyst consisting of a Group 2 metal element and platinum is completely unknown.

Although it is not yet clear why adding metal elements from Group 1 and/or Group 2 of the periodic table improves the hydrogenation activity of platinum catalysts and suppresses side reactions such as decomposition. , is estimated as follows.

In other words, by adding metal elements from Group 1 and/or Group 2 of the periodic table, the interaction between the aromatic ring in the petroleum resin undergoing hydrogenation and platinum, which is an active site, changes to an appropriate strength. ■ It is activated by the adsorption and dissociation process of hydrogen molecules; ■ It becomes possible to use platinum more efficiently by improving the dispersibility of platinum, which is an active site, and suppressing aggregation. ■ Furthermore, it is presumed that the addition of these basic metals neutralizes the acid sites of the carrier and suppresses side reactions such as decomposition, increasing the hydrogenation rate and suppressing side reactions. .

In the present invention, the petroleum resin having an aromatic ring used as a raw material is not particularly limited, but it is usually a homopolymer of an aromatic hydrocarbon having a double bond in the side chain, or a petroleum resin having a double bond in the fused ring. Examples include at least one polymer selected from the group consisting of a homopolymer of an aromatic hydrocarbon and a polymer of a mixture of the aromatic hydrocarbon and other olefins. These polymers can be obtained by polymerizing monomer components exemplified below in the presence of a Friedel-Crafts catalyst such as aluminum chloride or boron trifluoride. The petroleum resin has a number average molecular weight of 600 to 1
It is about 0000.

Among the monomer components constituting the raw petroleum resin, aromatic hydrocarbons having double bonds in their side chains include, for example, styrene, α-methylstyrene, vinyltoluene, vinylgysylene, propenylbenzene, etc., and the double bonds are condensed. Examples of the aromatic hydrocarbon in the ring include indene, methylindene, and ethylindene. Other primary nophines include butene,
Examples include pentene, hexene, heptene, octene, butadiene, pentadiene, cyclopentadiene, dicyclopentadiene, and octadiene.

The catalyst used in the present invention is a catalyst comprising platinum and a metal element of Group 1 and/or Group 2 of the periodic table supported on various known carriers, t=-L. The carrier to be used is not particularly limited, and conventionally known carriers can be used, but carbon, alumina, silica, titania, etc. are usually used. The shape of the carrier may be normal, such as powder, spherical, pellet, or ready-to-use molded product, and the size may be from 0 to
There is no particular restriction as to whether it is preferable to have a diameter of about mm. The amount of platinum 1 supported on the carrier is not particularly limited, but is usually about 0.1 to 10% by weight, preferably 0.5 to 5% by weight. If it is less than 0.1% by weight, the platinum content is small and the activity is low, so the amount of catalyst used increases. Moreover, when it exceeds 10% by weight, the dispersion of platinum becomes poor and the hydrogenation efficiency of platinum decreases. Therefore, anything outside the above range is economically disadvantageous.

In the present invention, the conventionally known platinum catalyst is
It is essential to add metal elements of group 2 and/or group 2 by the method described below.

In the present invention, metal elements of Group 1 and/or Group 2 of the periodic table are included as metal elements used in combination with platinum, but thorium, potassium, rubidium, etc. are particularly effective in improving hydrogenation activity. cesium, magnesium,
Calcium or barium is preferred. The first of these periodic table
The method for preparing a catalyst comprising a group metal element and/or group 2 metal element and platinum is not particularly limited, and any of various known methods can be employed. For example, a method of impregnating and adding metal elements of Group 1 and/or Group 2 of the periodic table to a platinum catalyst (Sequential 1mp
regnation), a method of simultaneously supporting a platinum salt such as chloroplatinic acid and a metal element of Group 1 and/or Group 2 of the periodic table (co-1mprcgnation), N
A method of supporting a luster compound such as a2[Pt 12 (CO'ha ) from an organic solvent can be adopted.In the case of the former two, when added, The form of the Group 2 metal element is not particularly limited, but it is best to use one that does not leave impurities after the catalyst is prepared, and generally nitrates,
Added in carbonate form.

There is no particular limitation on the amount of the metal element in Group 1 and/or Group 2 of the periodic table, but usually the atomic ratio of metal element in Group 1 and/or Group 2 of the periodic table/platinum is 0 or 0. .03～
5, preferably in a supported amount in the range of 01 to 1.5. In addition, when metal elements of Group 1 and/or Group 2 of the periodic table are used together, the picture metal/
It is preferable to add platinum so that the atomic ratio of platinum falls within the range of the supported amount. If the supported amount is less than the above atomic ratio of 0.08, the effect of adding metal elements of Group 1 and/or Group 2 of the periodic table, that is, the effect of catalytic hydrogenation activity, tends to decrease. In addition, if it is used in excess of 5, the metal elements of Group 1 of the periodic table will cover the platinum particles, which are active sites for hydrogenation, which may cause a decrease in hydrogenation activity.

The obtained catalyst consisting of a metal element of Group 1 and/or Group 2 of the periodic table and platinum can be activated by a general method and subjected to a hydrogenation reaction. For example, about 500°
Activation is achieved by calcining at C for about 2 hours under air flow, followed by reduction at about 400°C for about 2 hours in hydrogen flow.

There are no particular restrictions on the method for hydrogenating the petroleum resin, and conventionally known methods such as a batch suspended bed method, a flow suspended bubble method, a fixed bed method, etc. may be appropriately selected and employed. can.

When a suspended bed method or a flow-through suspended bubble method is adopted, the raw petroleum resin is melted and heated, or diluted with a saturated hydrocarbon solvent such as cyclohexane and heated, for the subsequent hydrogenation reaction. can be provided. The fixed bed method has the advantage of eliminating the need for filtering the catalyst, removing the solvent used, etc., thereby simplifying the process.

The reaction conditions of the present invention are appropriately determined in consideration of the physical properties of the raw material petroleum resin, the reaction method to be adopted, the hydrogenation rate of the target hydrogenated petroleum resin, etc.; However, it is desirable to conduct the hydrogenation reaction at a reaction temperature and hydrogen pressure such that a sufficient reaction rate can be increased and side reactions such as decomposition can be sufficiently suppressed for the desired hydrogenation reaction. Usually, the reaction temperature is about 200 to 300°C and the hydrogen pressure is about 10 to 200 atm. The amount of hydrogen supplied is about 2 to 50 times the theoretical absorption amount of petroleum resin.

In addition, when using the fixed bed method, the supply amount of petroleum resin is W
H3V(weight l1ourlySpace V
Elocity % (weight of petroleum resin supplied per hour/catalyst filling weight) is preferably about 0.01 m10.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 0.377g of H2PtC#s 61120 was added to 5
7.1 g of granular γ-
Alumina (average particle size 3'') was added and impregnated for 30 minutes.

Thereafter, water was distilled off at 40°C using a low evaporator. The resulting platinum-impregnated alumina was heated to 115°C1
After drying in an oven for 5 hours, it was air-calcined at 500°C for 2 hours, and further reduced with hydrogen at 400°C for 2 hours to obtain a 2% by weight platinum-supported alumina catalyst.

The platinum-supported alumina catalyst was placed in a solution of 13.1 mg of NaNO3 dissolved in 50 ml of distilled water, and impregnated for 30 minutes. Then, using a rotary evaporator,
Water was distilled off at 0°C. The obtained platinum-supported catalyst impregnated with sodium nitrate was dried in an oven at 11°C for 5 hours, air-calcined at 500°C for 2 hours, and further heated at 400°C.
After hydrogen reduction for 2 hours, the sodium/lium-platinum supported catalyst (,N
The a/pt atomic ratio was 0.21).

The obtained sodium-platinum supported catalyst was packed into a flow-type reactor with an internal volume of 1Ω, and the reaction temperature was 280°C, the reaction hydrogen pressure was 100kg/cl, and the hydrogen flow rate was 50ONΩ/11. #120 J
, polymer of C9 fraction, softening point 120°C1 sulfur content 150 ppm, aromatic ring content 54%, manufactured by Mikata Petrochemical ■)
was supplied at a rate of 400 ml/h to carry out the hydrogenation reaction continuously. The hydrogenation rate of the sub-ringed reaction product after 24 hours from the start of operation was 78%, and the softening point was 119°C.
Met. Note that the hydrogenation rate of the reaction product was determined by the following measurement method.

That is, the absorbance at 274.5 nm was measured using an ultraviolet spectrometer and calculated using the following formula.

A−B×”00 (wherein, A indicates the absorbance of the raw petroleum resin, and B indicates the absorbance of the hydrogenated petroleum resin).

The softening point was measured according to the ring and ball method specified in JIS-253.

Example 2 The metal added to the platinum supported catalyst was changed from sodium to cesium (
C8NO3 = 82f, 4mg, Cs/Pt -f
The catalyst was prepared in the same manner as in Example 1, except that 1 and 26) were changed, and the hydrogenation was carried out under the same reaction conditions as in Example 1. As a result, the hydrogenation rate of the reaction product was 81%, and the softening point was 81%. is 1
It was 20°C.

Example 3 The metal added to the platinum supported catalyst was changed from sodium to calcium (Ca(NO3)2 4H20 = 43.0mg5C
The catalyst was prepared in the same manner as in Example 1, except that a/Pt = 0.24), and the hydrogenation was carried out under the same reaction conditions as in Example 1. As a result, the hydrogenation rate of the reaction product was 79 %
, the softening point was 119°C.

Comparative Example 1 0377 g of H2PtC (c.[1t120
71 g of granular γ-alumina (average particle size: 3 mm) was added to a solution dissolved in distilled water and soaked for 30 minutes. Thereafter, water was distilled off at 40°C using a rotary evaporator. The obtained platinum-impregnated alumina was dried in an oven at 115°C for 5 hours, air-calcined at 500°C for 12 hours, and further hydrogenated at 400°C for 2 hours to obtain a 7.2% by weight platinum-supported alumina catalyst. Thereafter, hydrogenation was carried out under the same reaction conditions as in Example 1. As a result, the hydrogenation rate of the reaction product was 66%, and the softening point was 1''5°C.

[Effects of the Invention] According to the present invention, by using a highly active hydrogenation catalyst consisting of a metal element of Group 1 and/or Group 2 of the periodic table and platinum, petroleum resins having an aromatic ring can be hydrogenated. Hydrogenation can be carried out efficiently, and undesired side reactions can be sufficiently suppressed.

Therefore, by using the method of the present invention, a great effect can be achieved in that a hydride of a petroleum resin having an L1-like aromatic ring can be obtained in high yield and with high selectivity.

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Claims (1)

[Claims] 1. Catalytic reduction with hydrogen in the presence of a catalyst consisting of a metal element of Group 1 and/or Group 2 of the Periodic Table and platinum when hydrogenating a petroleum resin having an aromatic ring. A method for producing a petroleum resin hydride having an aromatic ring, characterized by: 2. The petroleum resin having an aromatic ring is a homopolymer of an aromatic hydrocarbon having a double bond in a side chain, a homopolymer of an aromatic hydrocarbon having a double bond in a condensed ring, and the aromatic carbon. 2. The method according to claim 1, wherein the polymer is at least one polymer selected from the group consisting of polymers of mixtures of hydrogen and other olefins. 3. The production method according to claim 1 or 2, wherein the catalyst is formed by supporting platinum and a metal element of Group 1 and/or Group 2 of the periodic table on a carrier. 4. The catalyst supports platinum in an amount of 0.1 to 10% by weight based on the total weight of the catalyst, and the total amount of metal elements of Group 1 and/or Group 2 of the periodic table is atomic relative to platinum. Claim 1, wherein the supported amount is adjusted to a ratio of 0.03 to 5.
The manufacturing method described in 2 or 3.