JPH0153287B2 - - 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, but even in this case, although 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. To 100 parts by weight of ~90% fraction, (b) 5 to 50 parts by weight of turpentine oil or a branched aliphatic olefin fraction having 10 to 20 carbon atoms is added as a raw material oil, and 0.1 part of phenols is added.
0.01 to feedstock oil in the presence of ~3.0 parts by weight
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 In the present invention, first, 5 to 50 parts by weight of the raw material oil (b) is added to 100 parts by weight of the raw material oil (a) to obtain the raw material oil, and in the presence of 0.1 to 3.0 parts by weight of phenols. Then, polymerization is carried out at -30 to 60°C using a Friedel-Crafts type catalyst of 0.01 to 5.0 wt% based on the raw material oil. The raw material oil (a) in the present invention is 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, and has a conjugated diolefin content of 0.7. 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 to 90%. It is a fraction of More specifically, the raw material oil (a) must satisfy the following conditions. (a) The total content of cyclopentadiene and methylcyclopentanediene in the feedstock oil (a) separated from the starting feedstock oil, that is, the conjugated diolefin content, is 0.7wt% or less, and the conjugated diolefin defined by formula (1) Keep the content below 3%. 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 (a) / Polymerizable component (wt%) in feedstock (a) x 100...(3) Feedstock (a) If the composition exceeds the range of conditions (a) to (c) above, the hue and heat resistance stability of the resulting hydrocarbon resin will decrease, and the coloration will be particularly marked, for example, when used as a hot melt adhesive. The adhesion, flexibility, and heat resistance stability of the adhesive deteriorates, 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 (product of John Manville Corporation) containing Celite (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. In the present invention, starting oils 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. A column 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 column bottom can be used.

【table】

[Table] The raw material oil (b) in the present invention is turpentine oil or a branched aliphatic olefin fraction having 10 to 20 carbon atoms. Here, turpentine oil is volatile, and refers to a portion of raw pine resin or terpenes that is distilled out by contacting with water vapor. Further, α-pinene, β-pinene, dipentene, etc., which are the main components contained in turpentine oil, can be used alone or as a mixture thereof. On the other hand, the branched aliphatic olefin fraction is a branched aliphatic olefin fraction having 10 to ₂₀ carbon atoms, preferably 12 to 17 carbon atoms. butadiene is removed from the
Carbon number 10 obtained by oligomerization of so-called spent B-B (butane-butene) fraction
~20 components can be preferably used. For oligomerization, a conventionally known method can be used, for example, a Friedel-Crafts type catalyst, such as aluminum chloride, titanium tetrachloride, boron triborode, etc., is used for 100 parts by weight of the spent B-B fraction. The reaction can be carried out using 0.01 to 10 parts by weight at -20 to +30°C. If the carbon number of the branched aliphatic olefin fraction is less than the above range, it is unfavorable from a safety standpoint such as a low flash point, while if it exceeds the above range, it will not be compatible with feedstock (a). Since it has poor copolymerization reactivity, it does not become a hydrocarbon resin as defined in the present invention and is not preferred. In the present invention, raw material oil (b) is added to the above-mentioned raw material oil (a) as an essential component. If raw material oil (b) is not added or if the amount added is less than 5 parts by weight per 100 parts by weight of raw material oil (a), the compatibility with other polymeric substances will be poor, such as hot melt adhesives. In this case, the clouding point becomes high and a hot melt adhesive with excellent adhesiveness cannot be obtained. Also raw material oil (a)
Even if more than 50 parts by weight of raw material oil (b) is added to 100 parts by weight, a hot melt adhesive with excellent adhesiveness cannot be obtained. Therefore, the raw material oil (b) is used in an amount of 5 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the raw material oil (a). Details of the polymerization reaction are disclosed in, for example, US Pat. No. 3,778,421, and are specifically as follows. The phenols present during the polymerization reaction include phenol, cresol, xylenol, p
Phenols having a phenolic -OH group in the molecule and usually having a carbon number of 6 to 20 can be used, such as alkyl-substituted phenols such as -tert-butylphenol, p-octylphenol, and nonyl-phenol. (a) 0.1 to 100 parts by weight
Polymerization is carried out in the presence of 3.0 parts by weight, preferably 0.5 to 2 parts by weight. As the Friedel-Crafts type catalyst, boron trifluoride, aluminum chloride, etc. are typically used, and various complexes thereof, such as ether complexes and lower alcohol complexes, are used.
These catalysts are usually 0.01-5wt% based on the feedstock oil.
Preferably it is used in an amount of 0.1 to 3 wt%. Phenols can also be supplied as phenol complexes of Friedel-Crafts type catalysts.
Although it is not advantageous to supply all the necessary amount of phenols as a phenol complex because the amount of catalyst is too large, it is possible to supply a part of the phenols as a phenol complex and add the other part as is to the polymerization system. This is preferably adopted. These polymerization raw materials, catalysts, etc. 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. However, when calcium hydroxide is used, filtration is only performed after contacting the polymerized oil with the neutralizing agent or after the clay treatment described below. It is enough. Neutralization is
At 10-80℃, 10-180 minutes, preferably 30-180 minutes
It is recommended to do this for 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. ``Process'' (Saiwai Shobo) from page 382, or ``Clay Handbook'' edited by the Japan Clay Society (Gihodo) from page 768. 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 dissolving the polymerized oil as it is or after removing unreacted substances in a solvent and using a conventionally known catalyst and conditions in a continuous or batchwise manner. 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 250C/ ^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 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,
Commercially available turpentine oil (analysis results α-pinene 90wt
%, β-pinene 5wt%, and other components 5wt%. ) and 2 parts by weight of phenol to prepare boron trifluoride phenolate.
0.6wt% was added and polymerized at 30°C 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 2 500 g of a spent butane-butene fraction having the composition shown in Table 5 was placed in a No. 2 autoclave equipped with a stirrer, a thermometer, and a catalyst addition port, and the temperature was kept at 10°C. After that, 5 g of aluminum chloride was added to 20 g of hexane.
was added little by little as a catalyst and allowed to react for 2 hours. After filtering the catalyst in this reaction solution and passing it through a layer of activated clay to remove unreacted substances, vacuum distillation was performed to obtain a branched aliphatic compound with a boiling point of 171 to 262°C, a bromine number of 89, and an average molecular weight of 193. Olefin distillate feedstock oil (b) was obtained.

[Table] For 100 parts by weight of raw material oil (a) in Example 1,
20 parts by weight of the above raw material oil (b) was added, and polymerization, neutralization, and clay treatment were performed in the same manner as in Example 1 to obtain hydrocarbon resin-A. Example 3 Hydrocarbon resin-A was obtained in the same manner as in Example 1 except that 10 parts by weight of activated clay was used for treatment. Comparative Example 1 For 100 parts by weight of the cracked oil fraction F in Example 1, 10 parts by weight of turpentine oil and 2 parts by weight of phenol
Parts by weight were added and polymerized and neutralized in the same manner as in Example 1 to obtain hydrocarbon resin F-1 without activated clay treatment. Comparative Example 2 10 parts by weight of turpentine oil was added to 100 parts by weight of the raw material oil (a) in Example 1, and polymerization and neutralization were carried out in the same manner as in Example 1 to produce hydrocarbon resin F- without activated clay treatment. I got 2. Comparative Example 3 20 parts by weight of the branched aliphatic olefin fraction used in Example 2 was added to 100 parts by weight of the raw material oil (a) in Example 1, and polymerized and neutralized in the same manner as in Example 1.
Hydrocarbon resin F-3 was obtained without activated clay treatment. Table 6 shows various properties of hydrocarbon resins -A to -A produced in Examples 1 to 3 and hydrocarbon resins F-1 to F-3 produced in Comparative Examples 1 to 3. As is clear from Table 6, 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 to 3 and Comparative Examples 1 to 3 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 (Mitsui Polychemical Co., Ltd.: Evaflex #220, vinyl acetate content 28% MI150), paraffin wax (Nippon Oil Co., Ltd.:
A hot-melt adhesive composition was prepared by melting and mixing 20 parts by weight (melting point: 145) at about 180°C, and its various properties were measured. The results are summarized in Table 6. From Table 6, 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.

[Table] Example 4 Resin obtained in Example 1 - 300g, cyclohexane 300g, nickel-diatomaceous earth catalyst 2g
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 5 Resin-A obtained in Example 2 was hydrogenated in the same manner as in Example 4 to obtain hydrogenated resin-B. Comparative Example 4 Resin F-1 obtained in Comparative Example 1 was hydrogenated in the same manner as in Example 4 to obtain hydrogenated resin F-4. Hydrogenated resins produced according to Examples 4 and 5 -
Table 7 shows various properties of the hydrocarbon resin F-4 produced in B to -B and Comparative Example 4. As is clear from Table 7, 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】

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%.
To 100 parts by weight, (b) 5 to 50 parts by weight of turpentine oil or a branched aliphatic olefin fraction having 10 to 20 carbon atoms is added as a raw material oil, and 0.1 part of phenols is added.
For feedstock oil in the presence of ~3.0 parts by weight
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 method for producing a hydrocarbon resin, which comprises 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. 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 particle conductor is 2wt.
% or less, the indene content is 8% or less, and the vinyl toluene content is 60 to 90%.
To 100 parts by weight, (b) 5 to 50 parts by weight of turpentine oil or a branched aliphatic olefin fraction having 10 to 20 carbon atoms is added as a raw material oil, and 0.1 part of phenols is added.
For feedstock oil in the presence of ~3.0 parts by weight
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 method for producing a hydrocarbon resin, which comprises 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.