JPH05331241A - Hydroxyl group-containing hydrogenated petroleum resin and its production - Google Patents

Abstract

PURPOSE:To obtain a large amount of a hydroxyl group-containing hydrogenated petroleum resin having a stable high-quality without taking care of the aspect of the raw material by polymerizing a C9 fraction of petroleum in the presence of phenols and hydrogenating the resultant polymer in the presence of a hydro- genating catalyst. CONSTITUTION:A C9 fraction whose boiling point under ordinary pressure is 140-280 deg.C in cracked petroleum fractions obtained by thermal cracking of petroleums or catalytic cracking thereof using a catalyst is polymerized in the presence of phenols (preferably phenol) using a Friedel-Crafts type catalyst. Then, a petroleum resin which is the polymerization product is hydrogenated under pressure in the presence of a hydrogenation catalyst to provide the objective resin having 0.2-2meq./g hydroxyl content, >=90% hydrogenation ratio of ring, <=100 APHA hue and <=1 bromine value and consisting of a C9 based petroleum fraction and phenols. As the hydrogenation catalyst, a hydrogenation catalyst consisting essentially of Ni metal, containing a carbonic acid salt of Mg as a cocatalyst and supported on a diatomaceous earth carrier is preferably used.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel hydrogenated petroleum resin and a method for producing the same. More specifically, a high-quality hydrogenated petroleum resin having limited constituents and physical properties and a C9 fraction are polymerized in the presence of phenols, and the polymer is further hydrogenated under pressure in the presence of a catalyst. A method for producing a quality hydrogenated petroleum resin.

[0002]

BACKGROUND OF THE INVENTION Petroleum resins are spent fractions of C4 to C6 aliphatic olefins obtained by pyrolysis of petroleum naphtha or catalytic cracking using a catalyst, and aromatic carbonization of C8 or more having an olefinic unsaturated bond. C5 obtained by homopolymerizing or copolymerizing one or more polymerizable substances contained in the spent fraction of hydrogen with a Friedel-Crafts type catalyst or heat.
, C9 and C5-C9 copolymerized petroleum resins, as well as terpene resins and natural rosins.

Since these petroleum resins have tackiness, adhesiveness, and compatibility with other resins, they are mixed with various plastics, rubbers, and oily substances to form paints, printing inks,
Used for adhesives, adhesives, traffic paints, etc.

However, petroleum resins are generally colored yellow to light brown, have a peculiar odor, have low thermal stability, and have low weather resistance.

As a solution to this problem, there is a method of hydrogenating a petroleum resin in the presence of a catalyst, and the resin obtained by this method is a hydrogenated petroleum resin. This hydrogenated petroleum resin is usually colorless and transparent to white, has no odor, has excellent heat stability and weather resistance, and has high adhesiveness and tackiness. Further, it has excellent compatibility with various plastics such as rubber, polyolefin, and ethylene-vinyl acetate copolymer. Therefore, it is widely used not only in the fields of food and sanitary but also in fields requiring high quality such as hot melt adhesives, printing applications and various plastic modifiers.

By the way, although hydrogenated petroleum resins are used for various purposes, their physical properties are various and they are properly used for each grade. For example, C5 hydrogenated petroleum resin has abundant raw materials and its manufacturing conditions are relatively mild.
Therefore, although it is manufactured in large quantities and at low cost, it has thermal stability,
There is a problem with tackiness. Further, the C9-based hydrogenated petroleum resin is superior in thermal stability and tackiness to the C5-based hydrogenated petroleum resin, but is not satisfactory.

On the other hand, rosin and terpene-based hydrogenated resins derived from natural products are excellent in thermal stability, adhesiveness and tackiness,
Among them, the adhesive property, which is an important property, is remarkably excellent. Therefore, it is used in fields where high quality is required.
However, since it is derived from a natural product, it is expensive and has a resource problem. Furthermore, although it is excellent in physical properties, it has not reached a satisfactory range.

Further, in Japanese Patent Laid-Open No. 57-16015,
Pyrolysis fraction of petroleum fraction with boiling point of 140-280 ℃ 1
0.1 to 3.0 parts by weight of phenols are added to 00 parts by weight,
It has been proposed to polymerize with a Friedel-Crafts type catalyst, neutralize the polymer, and treat with activated clay to hydrogenate it. The hydrogenated petroleum resin produced by this method has improved thermal stability, weather resistance, hue, and adhesiveness and tackiness, but is not satisfactory. It is inferior to the hydrogenated resin of.

Further, in Japanese Patent Laid-Open No. 1-210409,
A liquid petroleum resin obtained by polymerizing a fraction having 5 carbon atoms obtained by thermally decomposing naphtha by using a polymerization initiator having a hydroxyl group, and a liquid petroleum resin obtained by hydrogenating the resin are proposed. Although the physical properties of the liquid resin obtained by hydrogenation are improved, neither thermal stability, adhesiveness nor tackiness is satisfactory.

[0010]

As described above, among the petroleum resins, hydrogenated petroleum resins have excellent physical properties, and particularly natural rosin and terpene-based hydrogenated resins have excellent physical properties. However, these have merits and demerits in terms of required characteristics, resources, and price, and none of them can satisfy all from a wide range of applications. The present invention solves this problem and provides a stable, high-quality hydrogenated petroleum resin.

[0011]

[Means for Solving the Problems] The present inventors diligently studied a hydrogenated petroleum resin which is stable and of high quality and which has no fear of resources. As a result, they found a hydrogenated petroleum resin having limited constituent components and physical property values, and found that the hydrogenated petroleum resin can satisfy the required performance and, in addition, there is no resource concern from the raw material side, and it can be provided in a large amount. Then, the present invention has been completed.

That is, the present invention has a hydroxyl group content of 0.2 to 2
meq. / G, ring hydrogenation rate is 90% or more, hue is APHA
And a bromine number of 1 or less and a C9 petroleum fraction and phenols as main constituents, and a hydrogenated hydroxylated petroleum resin, and a method for producing the same. Hereinafter, the present invention will be described in detail.

The skeleton of the hydrogenated petroleum resin containing hydroxyl groups of the present invention has a hydroxyl group content of 0.2 to 2 meq. / G, and C9 petroleum fraction and phenols are the main constituents.

The present inventors have made detailed studies on the adhesiveness and tackiness, which are the greatest features of petroleum resins. as a result,
Hydroxyl content, hydroxyl-imparting substance, and resin main constituents are extremely important. Only when these are strictly limited, the targeted adhesion and tackiness of rosin-based and terpene-based hydrogenated resins derived from natural products can be achieved. I figured out what I could achieve. That is, the hydroxyl group content is 0.2 to 2 meq. / G.
0.2 meq. If it is less than / g, the adhesiveness and tackiness will be
Falls sharply. Also, 2 meq. If it is more than / g, not only the adhesiveness and tackiness are hardly improved, but also the properties such as thermal stability and weather resistance of the petroleum resin are deteriorated. 0.2-2 meq.
/ G, the adhesiveness and tackiness are high, and the thermal stability and weather resistance are also high.

Alcohols and hydrogen peroxide as a polymerization initiator have hitherto been proposed as a hydroxyl group-providing substance, but these hydroxyl group-providing substances cannot achieve the object of the present invention. The object of the present invention can be achieved only when the hydroxyl group-imparting substance is a phenol. Also, the main constituent material of the resin is C9
Consist of petroleum fractions. If the main constituent is a C5 petroleum fraction, the adhesiveness and tackiness will not be satisfactory, and the thermal stability and weather resistance will not be satisfactory. The object of the present invention can be achieved only when the main constituent is a C9 petroleum fraction. Here, the hydroxyl group content can be analyzed and measured by an infrared absorptiometry (IR method) nuclear magnetic resonance spectroscopy (NMR) or the like.

Further, in the present invention, the main constituent may be in a range in which the performance is not deteriorated even if it contains a small amount of substances other than phenols and C9 petroleum fraction. Specific examples include C5 petroleum fractions, rosin series, and terpene series. The range depends on the substance to be added, but usually 5
It is within 0% by weight. It is also essential that the hydrogenated petroleum resin has a ring hydrogenation rate of 90% or more, a hue of APHA of 100 or less, and a bromine number of 1 or less. These are related to heat stability, weather resistance, hue, odor, and the above-mentioned adhesiveness and tackiness. That is, when the ring hydrogenation rate is less than 90%,
Since it has many ring double bonds unstable to heat, light, etc., the thermal stability and weather resistance are drastically reduced. In addition, coloring and odor also occur. Therefore, it is not suitable for long-term storage,
In addition, it deteriorates during use and cannot exhibit its original performance.
Also, because of its color and odor, it cannot be used for hygiene purposes.
The use will be limited. This ring hydrogenation rate can be measured by an ultraviolet absorptiometry (UV). Further, when the hue exceeds 100 in APHA, not only the commercial value is lowered, but also the thermal stability and weather resistance of the resin, which are presumed to be caused by the coloring substance (due to a trace amount, makes identification difficult), are observed. This hue can be measured based on JIS-K0101. or,
When the bromine number is more than 1, it has a large number of chain double bonds, and the thermal stability and weather resistance are drastically reduced. Therefore, in the field of hot melt, etc., it deteriorates during heating and melting, resulting in deterioration of characteristics, deterioration during long-term use and storage,
It deteriorates. Also, coloring and odor, which are important as a product, will occur. In addition, it cannot be used for hygiene, and the application is limited. This bromine number is J
It can be measured based on IS-K2543.

In addition, various physical properties such as molecular weight and molecular weight distribution have been studied in detail. Important properties of hydrogenated petroleum resin to be possessed, especially natural product-derived rosin-based and terpene-based water It was concluded that the above-mentioned constitutional requirements are necessary and sufficient to exceed the characteristics of the additive resin.

The hydrogenated petroleum resin shown in the present invention is a high quality hydrogenated petroleum resin having constitutional requirements and characteristics which have not been hitherto obtained.
Further, from its constituents, a large amount of inexpensive petrochemicals that are not derived from natural products can be used as a raw material, which is highly useful.

The hydroxylated hydrogenated petroleum resin of the present invention is a C9 fraction having a boiling point of 140 to 280 ° C. at atmospheric pressure among cracked oil fractions obtained by thermal decomposition of petroleum or catalytic cracking using a catalyst. It can be produced by polymerizing the components in the presence of phenols using a Friedel-Crafts type catalyst, and hydrogenating the petroleum resin as the polymerization product under pressure in the presence of a hydrogenation catalyst.

Of the cracked oil fractions obtained by thermal cracking or catalytic cracking using a catalyst, the boiling point at atmospheric pressure is 140 to 28.
C9 fraction at 0 ° C means styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, indene,
Alkylindene, dicyclopentadiene, ethylbenzene, trimethylbenzene, naphthalene, etc. are mainly contained, and these have a polymerizing property and are usually obtained as a mixture.

The phenols include phenol or cresol, xylenol, P-tert-butylphenol, p-octylphenol, nonylphenol and other alkyl-substituted phenols having a phenolic hydroxyl group in the molecule, usually having 6 carbon atoms. ~ 20 phenols can be used. These may be used alone or in combination. Of these, phenol is particularly preferable, and hydrogenated petroleum having high adhesiveness and tackiness can be obtained. The amount of phenols present during the polymerization reaction is such that the hydroxyl group content of the hydrogenated petroleum resin is 0.2 to 2 meq. / G, but usually 4 to 100 parts by weight of raw oil
It is 30 parts by weight, preferably 5 to 20 parts by weight. The amount of phenolic compound is small and the hydroxyl group content is 0.2 meq. /
When it is less than g, the compatibility between the hydrogenated petroleum resin and various polymers is lowered, and the adhesiveness is rapidly lowered. Further, the hydroxyl group content is 2 meq. If it exceeds / g, not only the adhesion cannot be improved, but also the physical properties such as heat stability and weather resistance deteriorate. In addition,
The addition amount of the phenol compound of the present invention does not include the addition amount of phenol or the like added as a part of the Friedel-Crafts type catalyst. Here, the feed oil is the above-mentioned C9 fraction, but C5 petroleum fraction, rosin-based resin and terpene-based resin may be added as long as the characteristics of the hydrogenated petroleum resin are not deteriorated. This raw material oil and phenols are polymerized using a Friedel-Crafts type catalyst.

Examples of Friedel-Crafts type catalysts include boron trifluoride, aluminum chloride and the like, but complex catalysts using boron trifluoride ethyl ether, phenol, butyl ether, butyl alcohol, methyl alcohol and the like are preferable. As polymerization conditions, in the presence of a phenol compound, 0.05 to 5 wt% of Friedel-Crafts type catalyst with respect to the raw material oil is used, and the polymerization temperature is 0 to 60 ° C.
Is.

Then, the petroleum resin obtained by polymerization is separated and removed by a Friedel-Crafts type catalyst and unpolymerized substances by a conventional method. Then, the petroleum resin is hydrogenated under pressure in the presence of a hydrogenation catalyst.

As the hydrogenation catalyst, any catalyst having hydrogenation ability can be used without any particular limitation. For example, a Group 8 metal, that is, a metal such as nickel, palladium, platinum, cobalt, rhodium, or ruthenium may be used alone or in combination with one or more of metals 1a, 2a, 1b, 4a or oxides. It is possible to use a combination of these, such as alumina, silica, diatomaceous earth, activated carbon,
Those supported on a carrier such as titania are used. Particularly preferably, hydrogen containing nickel metal as a main component and at least one oxide, hydroxide or carbonate selected from alkaline earth metals of Mg, Ca, Ba and Sr as a cocatalyst component on a diatomaceous earth carrier. Chemical conversion catalyst (Japanese Patent Application No. 3-156053)
issue). The catalyst suppresses sintering of nickel particles due to heat, and also suppresses poisoning of the catalyst by sulfur compounds usually contained in petroleum resins. As a result, the life of the catalyst is improved, the catalyst can be repeatedly used, and the economical efficiency is remarkably improved. or,
It is preferable to use Cu metal instead of the alkaline earth metal as a co-catalyst, since the same effect is exhibited. The amount of hydrogenation catalyst used is not particularly limited. This is because the specific surface area of the catalyst, the amount of metal and its degree of dispersion, the type and content of co-catalyst, the hydrogenation rate, the type of petroleum resin, the content of its sulfur compounds, the hydrogenation conditions, etc. are greatly different. However, usually petroleum resin 10
It is 0.1 to 30 parts by weight with respect to 0 parts by weight, and is appropriately determined. The shape of the catalyst is also not limited, and either powder or pellets can be used.

The hydrogenation reaction conditions should be determined according to the type of petroleum resin, the sulfur compound content, the type and amount of hydrogenation catalyst, or the desired properties of the hydrogenated petroleum resin, but in general The reaction temperature is 150 to 320 ° C., the reaction pressure is 30 to 300 Kg / cm ² , and the reaction time is 1 to 10 hours.

In the present invention, hydrogenation in the absence of a solvent is possible, but a higher quality hydrogenated petroleum resin can be obtained under a milder condition in the presence of a solvent, which is effective and efficient. is there. Hydrocarbons, ethers, alcohols, esters, ketones, amides, etc. can be used as this solvent, but considering the stability of the solvent, price, hydrogenation rate, quality of hydrogenated petroleum resin, etc. Hydrogen is more preferred. A more preferable solvent is at least one solvent selected from saturated hydrocarbons, saturated cyclic hydrocarbons, and aromatic hydrocarbons having a boiling point of 140 to 280 ° C. under normal pressure.

Specific solvents include saturated chain hydrocarbons such as n-nonane, 2-methyl-nonane and 3-methyl-
Nonane, 4-methyl-nonane, n-decane, iso-decane, 2-methyldecane, 3-methyldecane, 4-methyldecane, n-undecane, 2-methylundecane, 3-
Methylundecane, 4-methylundecane, n-dodecane, iso-dodecane, 2-methyldodecane, 3-methyldodecane, 4-methyldodecane, 5-methyldodecane,
2,3-dimethyldodecane, 2,3,4-trimethyldodecane, 2,3,4,5-tetramethyldodecane, n-
Tridecane, methyltridecane, dimethyltridecane,
Trimethyltridecane, n-tetradecane, methyltetradecane, dimethyltetradecane, trimethyltetradecane, pentadecane, alkylpentadecane, hexadecane, alkylhexadecane, heptadecane, alkylheptadecane, octadecane, alkyloctadecane, alkyloctadecane, nonadecane, alkylnonadecane, eicosane, alkyl Eikosan etc. can be mentioned. Examples of the saturated cyclic hydrocarbon include trimethylcyclohexane, tetramethylcyclohexane, methylethylcyclohexane, bicyclohexane, methylbicyclohexane, dimethylbicyclohexane, ethylbicyclohexane, methylethylbicyclohexane, diethylbicyclohexane and the like. As aromatic hydrocarbons, diethylbenzene, trimethylbenzene, tetramethylbenzene, methylethylbenzene, isopropylbenzene, P-cymene, amylbenzene, naphthalene,
Examples thereof include alkylnaphthalene, cyclohexylbenzene, alkylcyclohexylbenzene, fluorene and alkylfluorene. These may be one kind or a mixture of two or more kinds.

A solvent having a boiling point of less than 140 ° C. at atmospheric pressure increases the pressure during hydrogenation and requires high-pressure operation, which makes the equipment complicated and expensive. Further, a solvent having a boiling point of more than 280 ° C. at atmospheric pressure is good in terms of pressure, but the hydrogen addition rate, which is the first purpose, becomes small and the efficiency is lowered. Further, it becomes difficult to separate the product from the hydrogenated petroleum resin. The preferable addition amount of the solvent is 10 to 15 with respect to 100 parts by weight of the petroleum resin.
The amount is 0 parts by weight, more preferably 20 to 100 parts by weight. After completion of the hydrogenation reaction, usually by separating the catalyst by filtration, and usually by separating the solvent by distillation,
The intended hydrogenated petroleum resin can be obtained. At the time of separating the catalyst, the catalyst may be washed with the same solvent. Also, the recovered solvent is easy to reuse.

The form of the hydrogenation reaction is not particularly limited and can be carried out by a usual method. For example, a batch type suspension bed system, a flow type fixed bed system, a flow type suspension bubble column system and the like can be implemented.

The hydrogenated petroleum resin obtained by the present invention has excellent adhesiveness and adhesiveness, is colorless and transparent and has no odor, and is also excellent in heat resistance and weather resistance. As an adhesive, an adhesive, a rubber, a paint. It is useful and effective as an additive for plastics, inks, etc.

[0031]

The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited thereto.

Example 1 Of the cracked oil fraction obtained by the thermal cracking of petroleum, 6 parts by weight of phenol was added to 100 parts by weight of a fraction having a boiling point of 140 to 220 ° C. under normal pressure, and trifluorocarbon was added. After adding 0.5 wt% of borohydride phenol and polymerizing at 30 ° C for 3 hours, the catalyst is removed with an aqueous solution of caustic soda, followed by washing with water to remove unreacted oil and low-polymerized substances and petroleum resin having a softening point of 122 ° C. (A) was obtained. Add a resin (A) to a stainless steel pressure vessel with an internal volume of 300 ml equipped with an electromagnetic stirrer and a heater.
70 g, Ni / diatomaceous earth catalyst [Ni (5
0 wt% content] 3.5 g, 21 g of commercially available paraffinic hydrocarbon (made by Idemitsu Co., bp: 160-200 ° C.) as a solvent
Was charged, the atmosphere was replaced with nitrogen gas and then with hydrogen gas, and then pressurized with hydrogen. Next, the mixture is stirred and heated to a temperature of 250 ° C. and a pressure of 100.
It was kept at Kg / cm ² · G for 4 hours. Then let it cool down,
The catalyst and the solvent were separated from the reaction product to obtain a hydrogenated petroleum resin. When the hydrogenated petroleum resin was analyzed, the hydrogenation rate was 95.4.
%, Bromine number 1 or less, hue APHA 20 or less, colorless and transparent,
Odorless, softening point 124 ° C, hydroxyl group content 0.3 meq./g
Met. 40 parts by weight of the hydroxyl group-containing hydrogenated petroleum resin (A-1) thus obtained, 40 parts by weight of an ethylene-vinyl acetate copolymer (Tosoh Corporation: Ultracene 720, vinyl acetate-containing 28% MI 150) , Microcrystalline Wax (manufactured by Nippon Seiro Co., Ltd .: Hi-M
ic1080, melting point 183 ° F) 20 parts by weight 180 ° C
The results are shown in Table 1.

Example 2 A resin (B) having a softening point of 120 ° C. was obtained in the same manner as in Example 1 except that 7 parts by weight of phenol was added and the polymerization was carried out. Using this resin (B) as a hydrogenation catalyst, Ni (47 wt.
%)-Mg (wt%)-diatomaceous earth (50 wt%) catalyst 3.
A hydrogenated petroleum resin (B-1) was obtained in the same manner as in Example 1 except that 5 g was added and hydrogenated. The hydrogenated petroleum resin obtained had a hydrogenation rate of 94.6%, a bromine number of 1 or less, and a hue of 20 or less.
Colorless and transparent, odorless, softening point 123 ° C, hydroxyl group content 0.4m
eq. / G. This hydroxylated hydrogenated petroleum resin (B
A hot melt composition was prepared in the same manner as in Example 1 using -1), and the evaluation results are shown in Table 1.

Comparative Example 1 Of the cracked oil fractions obtained by the thermal cracking of petroleum, 0.5 wt% of boron trifluoride phenol was added to 100 parts by weight of a fraction having a boiling point of 140 to 220 ° C. under normal pressure. The same treatment as in Example 1 was carried out except that the polymerization was carried out at 40 ° C. to obtain a resin (C). This resin (C) was hydrotreated under the same conditions as in Example 1 to obtain a hydrogenated petroleum resin (C-1). The hydrogenated petroleum resin (C-1) thus obtained had a hydrogenation ratio of 98.2% and a hue of 2
0 or less, colorless and transparent, odorless, softening point 123 ° C, hydroxyl group content 0.1 meq. / G or less. Then, a hot melt composition was prepared in the same manner as in Example 1, and the evaluation results are shown in Table 1.

Comparative Example 2 A commercial C9 hydrogenated petroleum resin (Arakawa Chemical Co., Ltd., Alcon P-125, softening point 122 ° C., hydrogenation rate of about 98%) was used, and the hot melt composition was the same as in Example 1. Prepare things,
The evaluation results are shown in Table 1.

Comparative Example 3 Commercial terpene resin (Clearon P manufactured by Yasuhara Yushi Co., Ltd.)
A hot melt composition was prepared in the same manner as in Example 1 using −125, softening point 125 ° C.), and the evaluation results are shown in Table 1.

[0037]

[Table 1]

[0038]

INDUSTRIAL APPLICABILITY According to the present invention, a novel hydrogenated petroleum resin of high quality, specifically, colorless and odorless hydrogenated petroleum excellent in adhesiveness, tackiness, heat resistance and weather resistance is provided. A resin and a method for producing the resin can be provided. Also, this hydrogenated petroleum resin is abundant in terms of resources and can be provided in large quantities at low cost. Further, as a method for producing the hydrogenated petroleum resin, a method of adding a solvent and hydrogenating can efficiently provide the hydrogenated petroleum resin under milder conditions.

Claims (3)

[Claims] 1. A hydroxyl group content of 0.2 to 2 meq. / G, the ring hydrogenation rate is 90% or more, the hue is APHA 100 or less, the bromine number is 1 or less, and a C9 petroleum fraction and phenols are the main constituents. Added petroleum resin. 2. A cracked oil fraction obtained by thermal cracking of petroleum or catalytic cracking using a catalyst has a boiling point of 14 at atmospheric pressure.
A C9 fraction at 0 to 280 ° C is polymerized in the presence of phenols using a Friedel-Crafts type catalyst, and the petroleum resin as the polymerization product is hydrogenated under pressure in the presence of a hydrogenation catalyst. And the hydroxyl group content is 0.2-2 me
q. / G, ring hydrogenation rate is 90% or more, hue is APHA 1
A process for producing a hydroxylated hydrogenated petroleum resin having a bromine number of 00 or less, a bromine number of 1 or less, and a C9 petroleum fraction and phenols as main constituents. 3. The hydrogenation of petroleum resin is selected from saturated chain hydrocarbons, saturated cyclic hydrocarbons and aromatic hydrocarbons having a boiling point of 140 to 280 ° C. at normal pressure with respect to 100 parts by weight of petroleum resin. The manufacturing method according to claim 2, which is carried out by mixing 10 parts by weight or more of one or more kinds of solvents.