JPH0153288B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing hydrocarbon resins. In detail, it has excellent compatibility with polymeric substances, heat resistance,
This invention relates to a method for producing hydrocarbon resin with excellent hue. Hydrocarbon resins are used as tackifying resins in adhesives, pressure-sensitive adhesives, etc. for the purpose of imparting adhesiveness and tackiness to various polymeric substances, such as rubbers such as natural rubber, SBR, and chloroprene rubber.
It is used together with ethylene copolymers or waxes. Generally, tackifying resins include natural resins such as rosin and terpene resins,
Various petroleum resins are used. Among these, rosin resins are widely used because they have excellent adhesive strength, adhesive strength, and flexibility at low temperatures, and terpene resins also have excellent heat resistance stability, but both are made from natural products. It is expensive because it is
There is also a problem in terms of resources. On the other hand, relatively inexpensive petroleum resins have been proposed as tackifying resins to replace natural resins, but none have been developed that have performance comparable to rosin and terpene resins. In other words, petroleum resins are generally obtained by polymerizing cracked oil fractions obtained by thermal decomposition of petroleum.
The raw material oil is a fraction having a boiling point in a wide range of 170°C to 170°C and 140°C to 280°C. When a cracked oil fraction having a boiling point range of about 20° C. to 140° C. is used as a raw material, the resulting resin becomes a so-called aliphatic hydrocarbon resin containing no aromatic nucleus. In this case, the raw material oil contains a large amount of conjugated diolefin and non-conjugated diolefin, so the resin has a high degree of unsaturation.
It has poor hue and heat stability. On the other hand, when a cracked oil fraction with a boiling point range of 140°C to 280°C is used as a raw material, the resin obtained is an aromatic hydrocarbon resin, although in this case also the heat resistance stability and hue are sufficient. Furthermore, when used in adhesives and pressure-sensitive adhesives, the adhesiveness and tackiness are also poor. An object of the present invention is to provide a method for producing a tackifier resin that is synthesized from abundant and inexpensive industrial raw materials and has performance equivalent to or better than conventional rosin or terpene resins, It is an object of the present invention to provide a method for producing hydrocarbon resins suitable for use as resins for use in rubber compounding, tackifiers for rubber compounding, resins for modifying polyolefin resins and polyester resins, and the like. The present inventors have developed an aromatic hydrocarbon resin obtained by polymerizing a specific fraction of cracked oil obtained by thermal decomposition of petroleum as a tackifying resin (Japanese Patent Application Laid-Open No.
45635), an aromatic hydrocarbon resin obtained by copolymerizing a specified fraction of cracked oil and propylene trimer in the presence of phenols (Japanese Unexamined Patent Publication No. 131634/1983), and a specified distillate of cracked oil. Although a patent has already been filed for an aromatic hydrocarbon resin obtained by polymerizing turpentine and turpentine in the presence of phenols (Japanese Patent Application No. 138590/1983), the production of hydrocarbon resin according to the present invention The method achieves the above objectives and has performance equivalent to or better than the above application. That is, the object of the present invention is (A) (a) A conjugated diolefin-containing product obtained by distilling a fraction having a boiling point range of 140 to 220°C among cracked oil fractions obtained by thermal decomposition of petroleum. The total content of indene and its alkyl derivatives is 2 wt% or less, the indene content is 8% or less, and the vinyltoluene content is 60% or less. 100 parts by weight of ~90% fraction, or 2 to 30 parts by weight of (b) propylene trimer added to 100 parts by weight of the above fraction (a) as feedstock oil, 0.01 parts by weight relative to the feedstock oil.
Polymerize at -30 to 60°C using ~5.0wt% Friedel-Crafts catalyst, (B) neutralize the resulting polymerized oil, and (C) neutralize the polymerized oil during or after the neutralization reaction.
A method for producing a hydrocarbon resin characterized by using 0.1 to 20 parts by weight of activated clay per 100 parts by weight and carrying out clay treatment at 10 to 100°C, and if necessary, (D) This is achieved by a method for producing a hydrocarbon resin characterized by hydrogenation treatment. Hereinafter, the method for producing a hydrocarbon resin according to the present invention will be described in more detail. (A) Polymerization The raw material oil (a) in the present invention is a conjugated diolefin obtained by distilling a fraction having a boiling point range of 140 to 220°C among cracked oil fractions obtained by thermal decomposition of petroleum. The content is 0.7wt% or less, the conjugated diolefin content is 3% or less, and the total content of indene and its alkyl derivatives is 2wt% or less, the indene content is 8% or less, and the vinyltoluene content is 3% or less. It is a distillate of 60-90%. More specifically, the raw material oil (a) must satisfy the following conditions. (a) The total content of cyclopentadiene and methylcyclopentadiene in the feedstock oil (a) separated from the above starting feedstock oil, that is, the conjugated diolefin content, is 0.7wt% or less, and the conjugated diolefin content is defined by formula (1). Reduce the rate to 3% or less. Conjugated diolefin content (%) = Conjugated diolefin content (wt%) in feedstock oil (a) ^(1)* /Polymerizable component (wt%) in feedstock oil (a) ^(2)* ×100... (1) *Note 1 Conjugated diolefin content refers to the total content of cyclopentadiene and methylcyclopentadiene. *Note 2 This is the total amount of polymerizable components, such as styrene and its alkyl derivatives, indene and its alkyl derivatives, and cyclopentadiene and methylcyclopentadiene. (b) The total content of indene and its alkyl derivatives in the raw material oil (a) separated from the starting raw material oil is 2 wt% or less, and the indene content defined by formula (2) is 8% or less. Indene content (%) = indene and alkyl derivative content (wt%) in feedstock oil (a) / polymerizable component (wt%) in feedstock oil (a) x 100...(2) (c) ( 3) Vinyl toluene content defined by formula 60~
90%, preferably 70-85%. Vinyltoluene content (%) = Vinyltoluene content (wt%) in feedstock oil (a) / Polymerizable components (wt%) in feedstock oil (a)
) x 100...(3) If the composition of the raw material oil (a) exceeds the range of conditions (a) to (c) above, the hue and heat resistance stability of the resulting hydrocarbon resin will decrease, especially The discoloration becomes significant and, for example, when used as a hot-melt adhesive, the adhesiveness, flexibility, and heat resistance stability deteriorate, resulting in insufficient performance as an adhesive. Each component of the starting stock oil and stock oil (a) is analyzed by gas chromatography under the following conditions. (i) Styrene, allylbenzene, 1,3,5-trimethylbenzene and o-ethyltoluene are
20wt% Apiezon L Grease (Associated Electrical Industries)
Celite (a product of John Manville Corporation) containing Celite (a product of John Manville Corporation) was packed into a 3 m long column and analyzed at 100°C and a helium flow rate of 60 ml/min. (ii) Each component other than those shown in (i) is analyzed using a 3 m long column filled with Celite containing 20 wt% polyethylene glycol 4000 at 125°C and a helium flow rate of 60 ml/min. The starting raw materials used in the present invention include by-products obtained when producing ethylene, propylene, butenes, and butadienes by thermal decomposition such as steam cracking from petroleum fractions such as naphtha, kerosene, or light oil. A cracked oil fraction having a boiling point range of 140-220°C can be used. Its representative components are shown in Table 1. On the other hand, as feedstock oil (a), for example, the starting feedstock oil is poured into a rectification column, rectified from the top of the column under conditions that satisfy the above condition (b), and the top of the column is distilled. The bottom oil obtained by charging the output fraction again into another rectification column and rectifying it under conditions that allow a fraction satisfying the above condition (a) to be obtained from the bottom of the column can be used.

【table】

[Table] In the present invention, 2 to 30 parts by weight of the propylene trimer (b) added to 100 parts by weight of the fraction (a) can be used as the raw material oil. The propylene trimer referred to herein is nonene (C ₉ olefin) obtained by oligomerization of propylene, and is usually synthesized using an acid catalyst such as phosphoric acid. Further, from an industrial perspective, it is advantageous to use a fraction whose main component is _C9 olefin, which is produced as a by-product during the synthesis of propylene oligomers (mainly tetramers) for the production of synthetic detergents. In this case, it is preferable to use highly pure nonene, but it is preferable to use a mixture in which nonene is the main component and other olefins, especially C ₇ to C ₁₁ olefins or paraffins, which are simultaneously produced during propylene oligomerization, coexist. It is also possible to use However, when this mixture is to be used in the present invention, it is preferable that the nonene content is 60% or more, particularly 70% or more. When raw material oil (b) is used as a polymerization raw material together with raw material oil (a), the amount added is 2 to 30 parts by weight, preferably 5 to 25 parts by weight, per 100 parts by weight of raw material oil (a). When the raw material oil (b) is added within the above range, a tackifying resin with even better compatibility with other polymeric substances can be obtained, and when used as a component of an adhesive, it can also provide excellent adhesion. You can get sex. In the polymerization reaction, boron trifluoride, aluminum chloride, and the like are typically used as Friedel-Crafts type catalysts, and various complexes thereof, such as ether complexes and lower alcohol complexes, are used. Among these, a methanol complex of boron trifluoride is particularly preferred, and when this is used, a hydrocarbon resin particularly excellent in heat resistance can be obtained. Further, for the purpose of controlling the molecular weight, a molecular weight regulator can be added to the reaction system in an amount of 0.1 to 10 parts by weight, preferably 0.5 to 5.0 parts by weight, per 100 parts by weight of the raw oil. As the molecular weight modifier, phenols, alcohols, esters, acetic acid, etc. can be used.
Examples of phenols include phenol or alkyl-substituted phenols such as cresol, xylenol, p-tert-butylphenol, p-octylphenol, and nonyl-phenol, which usually have a phenolic -OH group in the molecule and have a carbon number of 6.
Examples include ~20 phenols, and examples of alcohols include methanol, ethanol, propanol, and the like. These molecular weight regulators can also be supplied as complexes of Friedel-Crafts type catalysts. Although it is not advantageous to supply all the necessary amount of the molecular weight regulator as a complex because the amount of catalyst is too large, supplying a part of the molecular weight regulator as a complex,
The other part is preferably added to the polymerization system as it is. These polymerization raw materials, catalysts, and the like are placed in a polymerization reactor, and the polymerization reaction can be carried out continuously or batchwise at a reaction temperature of -30 to 60°C, preferably 0 to 60°C. (B) Neutralization Neutralize the polymerized oil obtained by the polymerization reaction. As a neutralizing agent, an aqueous solution of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia aqueous solution, etc. can be used in a proportion of 0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of polymerized oil. ,
Among them, calcium hydroxide is preferred. After washing with these neutralizing agents, washing with water is performed as necessary, but when using calcium hydroxide, filtration is only necessary after contacting the polymerized oil with the neutralizing agent, or after the clay treatment described below. is sufficient. Neutralization is carried out at 10-80°C for 10-180 minutes, preferably
It is desirable to do this for 30 to 120 minutes. (C) Clay treatment During or after the neutralization reaction, 100% of the polymerized oil
0.1 to 20 parts by weight, preferably 0.5 to 20 parts by weight
Using 10 parts by weight of activated clay, clay treatment is carried out at 10 to 100°C, preferably 20 to 80°C, for 2 minutes to 2 hours. For white clay treatment, the techniques used in the white clay treatment of petroleum products can be applied as they are. It is disclosed in "Clay Handbook" (Gihodo), edited by Japan Clay Society, from page 382 (Saiwai Shobo), and from page 768 (Gihodo). Activated clay and unreacted substances can be removed from the clay-treated polymerized oil by filtration, distillation, etc. (D) Hydrogenation The polymerized oil after clay treatment can be subjected to hydrogenation treatment if necessary. The hydrogenation treatment is carried out by using a conventionally known catalyst and conditions in a continuous or batch manner using the polymerized oil as it is or by dissolving it in a solvent after removing unreacted substances. To give a specific example, the catalysts can be group metals and group metals such as nickel, palladium, platinum, cobalt, ruthenium, rhodium, or their oxides and sulfides. Those supported on a carrier are also preferred. The reaction temperature is 40 to 400C, preferably 150 to 300C, and the reaction pressure is 10 to 400Kg/ ^cm2 , preferably 30 to 250Kg/ ^cm2 . In addition, as a solvent, cyclohexane, n-
Hexane, n-heptane, etc. can be used. The degree of hydrogenation depends on the required properties such as the hue of the hydrocarbon resin, tackifying effect, and compatibility with other resins. It is selected as appropriate, such as hydrogenating part or all of it. In the present invention, it is extremely important to perform the clay treatment (C) after the polymerization reaction. Of course, the effects of the present invention cannot be obtained even if clay treatment is not performed on the raw material oil before the polymerization reaction, and hydrocarbons with excellent compatibility with polymeric substances, heat resistance, and color are not obtained. No resin is obtained. In addition, by performing clay treatment after the polymerization reaction, hydrogenation treatment
In (D), substances that have a poisoning effect on the catalyst can be removed, and the activity and life of the catalyst can be significantly extended. Hereinafter, the present invention will be specifically explained with reference to Examples and Comparative Examples. The test methods for various physical properties and properties are as follows. Test method (1) Softening point (ring and ball method) According to JISK-2531. [°C] (2) Melting hue of resin According to the Gardner method (ASTM D-1544-68). (3) Bromine number According to ASTM D-1158-59T. [g/100
g] (4) Heat resistance The melting hue after treatment at 250°C for 3 hours was measured by the Gardner method described in item (2). (5) Adhesive strength Press between 0.1 mm thick and 25 mm wide aluminum plates at 180℃ for 3 minutes so that the adhesive layer becomes 0.2 mm.
After being left at 20±1°C and 60% humidity for 24 hours, T-peeling was performed using a Tensilon tensile tester (peeling speed 150 mm/min). [g/25mm] (6) Evaluation of hue of hot melt adhesive After blending, the hue of the hardened hot melt adhesive was evaluated according to the following criteria. White: 〇 Pale yellow: △ Yellow to brown: × Example 1 140 produced by steam cracking of naphtha
The cracked oil fraction F having a boiling point range of .degree. C. to 220.degree. C. showed the following composition from the results of gas chromatography analysis.

[Table] This cracked oil fraction F is charged into the rectification column A-1 under the operating conditions shown in Table 3 via a heater, and the indensified oil fraction F, which is one of the regulatory conditions for feedstock oil of the present invention, is charged from the top of the column to the rectification column A-1 under the operating conditions shown in Table 3. and its alkyl derivatives total content is 2wt
% or less, and a fraction with an indene content of 8% or less was obtained.

[Table] Next, the fraction distilled from the top of the A-1 column was charged into the rectification column C-1 under the operating conditions shown in Table 3 above, and the total content of cyclopentadiene and methylcyclopentadiene was 0.7 wt% or less. A feedstock oil (a) satisfying the feedstock oil regulations of the present invention with a conjugated diolefin content of 3% or less was obtained from the bottom of the C-1 column. Conjugated diolefins are distilled from the top of the C-1 column. Through this operation, from 100 parts by weight of starting stock oil F,
54 parts by weight of the raw material oil (a) of the present invention was obtained. The composition of this raw material oil (a) was as follows.

[Table] For 100 parts by weight of the raw material oil (a) obtained in this way,
Add 2 parts by weight of para-cresol, add 0.5 wt% boron trifluoride methanol complex compound catalyst, and heat at 30°C.
Polymerization was carried out for 3 hours. Next, 2 parts by weight of calcium hydroxide was added to 100 parts by weight of the polymerized oil, and after neutralization by stirring at 70°C for 1 hour, 5 parts by weight of activated clay [Galleon Earth NS manufactured by Mizusawa Chemical Co., Ltd.] was added. , and 30 at the same temperature.
The white clay treatment was performed by stirring for a minute. Thereafter, unreacted oil and low polymers were removed by distillation to obtain hydrocarbon resin-A. Example 2 10 parts by weight of propylene trimer (90% nonene) was added to 100 parts by weight of raw material oil (a), and para-cresol was added.
Polymerization was carried out in the same manner as in Example 1 at 30°C in the presence of 1.0 parts by weight to obtain hydrocarbon resin-A. Comparative Example 1 Polymerization and neutralization were carried out in the same manner as in Example 1, and unreacted oil and low polymers were removed by distillation to obtain a hydrocarbon resin F-. Comparative Example 2 Polymerization and neutralization were carried out in the same manner as in Example 2, and unreacted oil and low polymers were removed by distillation to obtain a hydrocarbon resin F-. Table 5 shows various properties of hydrocarbon resins -A, -A produced in Examples 1 and 2 and hydrocarbon resins F-, F- produced in Comparative Examples 1 and 2.
Shown below. As is clear from Table 5, the hydrocarbon resins produced by the production method of the present invention were excellent in hue and heat resistance, and these resins also showed excellent compatibility with other polymeric substances. . Next, in order to examine the performance when the hydrocarbon resins produced in Examples 1 and 2 and Comparative Examples 1 and 2 were used as hot melt adhesives, 40 parts by weight of the hydrocarbon resin and ethylene-vinyl acetate were combined. 40 parts by weight of polymer (manufactured by Mitsui Polychemical Co., Ltd.: Evaflex #220, vinyl acetate content 28%, melt index 150) and 20 parts by weight of paraffin wax (manufactured by Nippon Oil Co., Ltd.: melting point 145〓) at approximately 180°C.
A hot melt adhesive composition was prepared by melt-mixing, and its various properties were measured. The results are summarized in Table 5. From Table 5, according to the method of the present invention, the hue is good;
It is clear that a resin with excellent hot melt adhesive properties is obtained. Example 3 Resin obtained in Example 1 - 300 g, cyclohexane 300 g, nickel-diatomaceous earth catalyst 2 g
was charged into an autoclave, heated to 230 to 260°C, and reacted for 4 hours at a hydrogen pressure of 40 kg/cm ² . After the reaction, the reaction mixture was cooled, the catalyst was filtered, and cyclohexane and low polymers were removed by vacuum distillation to obtain hydrogenated resin-B. Example 4 Resin-A obtained in Example 2 was hydrogenated in the same manner as in Example 3 to obtain hydrogenated resin-B. Comparative Example 3 The hydrocarbon resin F-1 obtained in Comparative Example 1 was used in Example 3.
Hydrogenation was carried out in the same manner as above to obtain hydrogenated resin F-. Comparative Example 4 The hydrocarbon resin F- obtained in Comparative Example 2 was used in Example 3.
Hydrogenation was carried out in the same manner as above to obtain hydrogenated resin F-. Hydrogenated resin produced according to Examples 3 and 4
Table 6 shows various properties of hydrocarbon resins F- and F- produced in B and -B and Comparative Examples 3 and 4. As is clear from Table 6, the hydrogenated resins produced by the production method of the present invention were excellent in hue and heat resistance, and these resins also showed excellent compatibility with other polymeric substances.

【table】

【table】

Claims (1)

[Claims] 1 (A) (a) A conjugated diolefin content obtained by distilling a fraction having a boiling point range of 140 to 220°C among cracked oil fractions obtained by thermal decomposition of petroleum. The conjugated diolefin content is 3% or less, and the total content of indene and its alkyl derivatives is 2wt% or less.
% or less, the indene content is 8% or less, and the vinyl toluene content is 60 to 90%.
100 parts by weight, or 2 to 30 parts by weight of (b) propylene trimer added to 100 parts by weight of the above fraction (a) as a feedstock oil, based on the feedstock oil.
Polymerize at -30 to 60°C using 0.01 to 5.0 wt% Friedel-Crafts catalyst, (B) neutralize the obtained polymerized oil, and (C) carry out polymerization during or after the neutralization reaction. oil
A modified method for producing a hydrocarbon resin, characterized in that 0.1 to 20 parts by weight of activated clay is used per 100 parts by weight, and clay treatment is carried out at 10 to 100°C. 2 (A) (a) Conjugated diolefin content of 0.7 wt% or less obtained by distilling a fraction having a boiling point range of 140 to 220°C among cracked oil fractions obtained by thermal decomposition of petroleum. The diolefin content is 3% or less, and the total content of indene and its alkyl derivatives is 2wt.
% or less, the indene content is 8% or less, and the vinyl toluene content is 60 to 90%.
100 parts by weight, or 2 to 30 parts by weight of (b) propylene trimer added to 100 parts by weight of the above fraction (a) as a feedstock oil, based on the feedstock oil.
Polymerize at -30 to 60°C using 0.01 to 5.0 wt% Friedel-Crafts catalyst, (B) neutralize the obtained polymerized oil, and (C) carry out polymerization during or after the neutralization reaction. oil
An improved method for producing a hydrocarbon resin characterized by using 0.1 to 20 parts by weight of activated clay per 100 parts by weight, performing clay treatment at 10 to 100°C, and (D) hydrogenating the same. .