JPS626570B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a hydrocarbon resin with improved hue and heat resistance stability. More specifically, the boiling point range obtained during thermal decomposition of petroleum is
It relates to a method in which a fraction at 140 to 280°C is contacted with an unsaturated polar compound and then polymerized. The unsaturated hydrocarbon-containing fraction obtained during the thermal decomposition of petroleum is polymerized using a Friedel-Crafts type catalyst,
Methods of producing hydrocarbon resins are well known. Hydrocarbon resins primarily have a boiling point range of −20
Aliphatic hydrocarbon resin obtained by polymerizing an unsaturated hydrocarbon-containing fraction with a boiling point range of 140 to +100℃ and an aromatic resin obtained by polymerizing an unsaturated hydrocarbon-containing fraction with a boiling point range of 140 to 280℃. There are two types of hydrocarbon resins. Among these hydrocarbon resins, aromatic hydrocarbon resins have particularly poor hue and heat resistance stability, and are also inferior in odor compared to aliphatic hydrocarbon resins. Therefore, it is difficult to use it in applications that require excellent hue, heat stability, or odor, such as hot melt adhesives, pressure-sensitive adhesives, or hot-melt traffic paints. Conventionally, in the production method of hydrocarbon resin, _{cyclopentadiene} or As a method for removing cyclopentadiene components such as methylcyclopentadiene by pretreatment before polymerization, Japanese Patent Publication No. 1983-5442 describes a method for removing cyclopentadiene components such as methylcyclopentadiene by dimerizing the cyclopentadiene components by preheating treatment. A method of removing the maleic anhydride and a method of forming an addition product with maleic anhydride at room temperature in Japanese Patent Publication No. 43-21737 are proposed, and these methods are known as methods for improving the hue of hydrocarbon resins. Among these methods, the former method requires complicated processing operations and also produces addition products of unsaturated hydrocarbon components in the unsaturated hydrocarbon-containing fraction of the polymerization raw material with cyclopentadiene components. When this method is applied to the polymerization of aliphatic unsaturated hydrocarbon-containing fractions, the loss of unsaturated hydrocarbon components other than the cyclopentadiene components is large.
A certain degree of hue improvement effect is recognized, but the boiling point range is 140 to
Even if this method is applied to the polymerization of a fraction containing aromatic unsaturated hydrocarbons at 280°C, a hydrocarbon resin that is excellent in hue, heat resistance stability, and odor cannot be obtained. In addition, in the latter method, as described in the same publication, an unsaturated hydrocarbon-containing fraction containing a large amount of cyclopentadiene components is used as the unsaturated hydrocarbon-containing fraction of the raw material. In order to form an addition product with the pentadiene component, a large amount of maleic anhydride must be used, and as a result, a large amount of the addition product must be removed by distillation, which requires complicated operations. In addition, this method has disadvantages in that it uses a large amount of maleic anhydride, which tends to cause corrosion of the equipment, and is also less economical. In addition, in the latter method, as is clear from the examples in the same publication, the boiling point range is 20 to 100.
Aliphatic hydrocarbon resins obtained from unsaturated hydrocarbon-containing fractions with a boiling point range of 100 to 200°C
The hue (Gardner) of the aromatic hydrocarbon resins obtained from the unsaturated hydrocarbon-containing fractions was not good, being 9 to 12 and 14 to 18, respectively. However, even if this method is applied to the polymerization of , a hydrocarbon resin having excellent hue, particularly heat stability and odor cannot be obtained. Furthermore, in the latter method, an addition product of cyclopentadiene and maleic anhydride produced by treating an unsaturated hydrocarbon-containing fraction of the raw material containing a large amount of cyclopentadiene components with maleic anhydride is used. Even if the polymer is directly polymerized without being separated and removed by distillation or the like, a hydrocarbon resin that is excellent in hue, heat resistance stability, and odor cannot be obtained. In addition, Japanese Patent Publication No. 36-19287 states that the boiling point range obtained during thermal decomposition of petroleum is 20 to 280℃.
A method has been proposed for producing a hydrocarbon resin with a high acid value and saponification value by copolymerizing an unsaturated hydrocarbon-containing fraction with an α/β-unsaturated carboxylic acid or its anhydride. It is described that the hue of the hydrocarbon resin used is light in color. However, as in this method, α-· β−
Even when polymerized in the coexistence of an unsaturated carboxylic acid or its anhydride, the obtained hydrocarbon resin is not sufficiently good in terms of hue, as is clear from the description of the examples in the same publication. Therefore, it is difficult to produce a hydrocarbon resin that is excellent in terms of heat resistance stability and odor. In general, the unsaturated hydrocarbon-containing fraction that is the polymerization raw material in the method for producing aromatic hydrocarbon resins is unsaturated hydrocarbons with a boiling point range of -20 to +280°C that are produced during thermal decomposition of petroleum. The boiling point range obtained by distilling the contained fraction is
Any unsaturated hydrocarbon-containing fraction between 140 and 280°C can be used. The unsaturated hydrocarbon-containing fraction produced during thermal decomposition of petroleum contains cyclopentadiene components such as cyclopentadiene, methylcyclopentadiene, fulvene, methylfulvene, and dimethylfulvene, as well as dicyclopentadiene and methyldicyclopentadiene. , dicyclopentadiene components such as dimethyldicyclopentadiene are included along with other unsaturated hydrocarbon components.
When distilling this unsaturated hydrocarbon-containing fraction to obtain an unsaturated hydrocarbon-containing fraction with a boiling point range of 140 to 280°C, the dicyclopentadiene component is gradually removed during distillation. In addition to cyclopentadiene and methylcyclopentadiene produced by decomposition, cyclopentadiene components such as fulvene, methylfulvene, and dimethylfulvene are distilled out. The cyclopentadiene component is usually contained in the unsaturated hydrocarbon-containing fraction within the range of about 1 to 7% by weight. The present inventors have developed a method for producing high-grade hot melt adhesives and pressure-sensitive adhesives from unsaturated hydrocarbon-containing fractions with a boiling point ranging from 140 to 280°C, which contain a fairly large amount of cyclopentadiene components. The present invention was arrived at as a result of extensive research into a method for producing an aromatic hydrocarbon resin that can be used as a tackifier resin for adhesives, etc., and has improved hue, heat resistance stability, and odor. . The present invention provides any aromatic unsaturated hydrocarbon-containing fraction with a boiling point range of 140 to 280°C containing cyclopentadiene components such as cyclopentadiene, methylcyclopentadiene, fulvene, methylfulvene, and dimethylfulvene. The unsaturated hydrocarbon-containing fraction obtained by adjusting the content of the cyclopentadiene component to a specific range through operations such as distillation is subjected to a contact treatment with a specific unsaturated polar compound for the cyclopentadiene component. This is based on the discovery that a hydrocarbon resin that satisfies the above objectives can be produced by polymerizing the hydrocarbon resin. That is, the present invention provides cyclopentadienes in an unsaturated hydrocarbon-containing fraction obtained during thermal decomposition of petroleum, which has a boiling point in any range of 140 to 280°C and contains a cyclopentadiene component. The unsaturated hydrocarbon-containing fraction with the boiling point range adjusted to a range of 0.01 to 0.7% by weight is converted into unsaturated carboxylic acid ester, α/β-unsaturated carboxylic acid imide, α/β-unsaturated It is characterized by polymerization using a Friedel-Crafts type catalyst after contact treatment with an unsaturated polar compound selected from the group consisting of carboxylic acid nitriles and quinones, or in the coexistence of both, with improved hue and heat resistance stability. This is a method for producing a hydrocarbon resin. In the method of the present invention, the unsaturated hydrocarbon-containing fraction used as a raw material for producing hydrocarbon resin is
Unsaturated hydrocarbons with a boiling point within any range of 140 to 280°C and containing cyclopentadiene components, which are produced as by-products during thermal decomposition of petroleum, such as steam cracking, gas phase cracking, sand cracking, and hydroforming. Containing fraction, preferably 140 to 240°C
It is an unsaturated hydrocarbon-containing fraction that is within an arbitrary range of and contains a cyclopentadiene component. Here, the cyclopentadiene component is a compound having a cyclopentadiene ring, such as cyclopentadiene, methylcyclopentadiene, fulvene, methylfulvene, and dimethylfulvene, as described above. The unsaturated hydrocarbon-containing fraction, which is used as a production raw material and has a boiling point within the range of 140 to 280°C and contains cyclopentadiene components, is usually used during the thermal decomposition of petroleum as mentioned above. The boiling point range obtained is -20 to +280℃
It is obtained by distilling a fraction containing unsaturated hydrocarbons. During the distillation operation, dicyclopentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, etc. contained in the unsaturated hydrocarbon-containing fraction of the raw material are decomposed and distilled out. Although cyclopentadiene components such as cyclopentadiene and fulvene have low boiling points, their boiling point range is
It is contained in fractions containing unsaturated hydrocarbons at temperatures between 140 and 280°C. Further, methylfulvene, dimethylfulvene, etc. are essentially contained in the unsaturated hydrocarbon-containing fraction having the boiling point range mentioned above. The unsaturated hydrocarbon-containing fraction with a boiling point range of 140 to 280°C thus obtained usually contains the cyclopentadiene component in an amount of 1 to 7% by weight, particularly 1.5 to 3% by weight. It is often included in the range of %. The unsaturated hydrocarbon-containing fraction, which has a boiling point range of 140 to 280°C and contains cyclopentadiene components, is treated by distillation or the like to reduce the content of cyclopentadiene components in the low-boiling pre-fraction to 0.01 to 280°C.
It is necessary to adjust to a range of 0.7% by weight,
In particular, it is preferable to adjust the content to a range of 0.05 to 0.5% by weight. Since the content of cyclopentadiene components is more than 0.7% by weight and the amount of unsaturated polar compounds used increases, it becomes less economical, and carbonization is superior in terms of hue, heat resistance stability, and odor. Hydrogen resin will no longer be obtained. In addition, reducing the content of cyclopentadiene components to less than 0.01% by weight by distillation etc. means that the dicyclopentadiene components present in the raw material fraction supplied to the distillation column are always decomposed during distillation. This is difficult because cyclopentadiene components are produced, and other polymerizable unsaturated components in the unsaturated hydrocarbon-containing fraction disappear. As mentioned above, the unsaturated hydrocarbon-containing fraction with a boiling point range of 140 to 280°C, which has been adjusted to have a content of cyclopentadiene components in the range of 0.01 to 0.7% by weight, mainly contains a hydrocarbon fraction with a carbon number of 9. However, it may also contain hydrocarbon fractions having 10 or more carbon atoms or hydrocarbon fractions having 7 and 8 carbon atoms. This unsaturated hydrocarbon-containing fraction includes styrene, α-methylstyrene, β
-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, indene,
Aromatic unsaturated hydrocarbons such as methylindene,
It contains components such as aromatic saturated hydrocarbons such as xylene, ethylbenzene, cumene, ethyltoluene, n-propylbenzene, trimethylbenzene, indane, methylindane, naphthalene, methylnaphthalene, and dimethylnaphthalene. In addition, xylene,
It is also possible to use a fraction from which specific components such as ethylbenzene or styrene have been removed, or an unsaturated hydrocarbon-containing fraction that does not contain these specific components. In the method of the present invention, the unsaturated hydrocarbon-containing fraction whose content of cyclopentadiene components has been adjusted is subjected to a contact treatment in the presence of an unsaturated polar compound before being subjected to polymerization. Alternatively, the unsaturated hydrocarbon-containing fraction in which the content of the cyclopentadiene components is adjusted is polymerized in the coexistence of an unsaturated polar compound. Among these methods, a method in which a contact treatment is performed in advance in the presence of an unsaturated polar compound before polymerization and then polymerization is preferred. The unsaturated polar compounds used in the method of the present invention include α/β-unsaturated carboxylic acid esters,
It is an unsaturated polar compound selected from the group consisting of α/β-unsaturated carboxylic acid imide, α/β-unsaturated carboxylic acid nitrile, and quinones. α・β−
Examples of unsaturated carboxylic acid esters include methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl crotonate, dimethyl maleate, diethyl maleate, dimethyl itaconate, diisopropyl citraconate, diethyl tetrahydrophthalate, etc. , α/β-unsaturated carboxylic acid imides include, for example, maleimide, itaconimide, citraconimide, tetrahydrophthalimide, N-substituted imides of these imides, and α/β-unsaturated carboxylic acid nitriles include, for example, acrylonitrile, methacrylonitrile. , crotonitrile, maleic acid dinitrile, citraconic acid dinitrile, tetracyanoethylene, etc. Further, examples of quinones include benzoquinone, naphthoquinone, etc. Among these unsaturated polar compounds, α・β-unsaturated carboxylic acid imides or α・β-
Preference is given to using unsaturated carboxylic acid nitriles. The amount of these unsaturated polar compounds to be used is not particularly limited, but from 0.8 to 1 mole of the cyclopentadiene component in the polymerization raw material in which the content of the cyclopentadiene component has been adjusted by the above-mentioned operation such as distillation. It is preferably in the range of 3.0 mol, particularly preferably in the range of 1.0 to 2.0 mol. These unsaturated polar compounds can be supplied to the unsaturated hydrocarbon-containing fraction in which the content of the cyclopentadiene component has been adjusted in any of the solid state, molten state, or solution state. The contact treatment of the unsaturated hydrocarbon-containing fraction with an adjusted content of cyclopentadiene components and the unsaturated polar compound is sufficient if the unsaturated polar compound is dissolved in the unsaturated hydrocarbon-containing fraction, The temperature during the contact treatment is not particularly limited, but is usually in the range of 10 to 80°C, preferably in the range of 20 to 60°C. The time for contact treatment varies depending on the contact temperature, but is usually 1 minute to 2 minutes.
The time period is preferably in the range of 2 minutes to 1 hour. The unsaturated hydrocarbon-containing fraction subjected to the coupling treatment in the presence of an unsaturated polar compound by the above method is subjected to a polymerization reaction. The unsaturated hydrocarbon-containing fraction subjected to the above contact treatment can be polymerized alone, or the unsaturated hydrocarbon-containing fraction subjected to the above contact treatment may be polymerized, if necessary, with a boiling point range of -20
An aliphatic unsaturated hydrocarbon-containing fraction having a boiling point within this range and not substantially containing cyclopenta components, or an aliphatic unsaturated hydrocarbon component other than cyclopentadiene components having a boiling point within this range A mixed unsaturated hydrocarbon-containing fraction blended with can also be used as a polymerization raw material. Examples of aliphatic unsaturated hydrocarbon-containing fractions that can be used as copolymerization raw materials and have a boiling point in any range from -20 to +100°C and do not substantially contain cyclopentadiene components include, for example,
De-butadiene C ₄ fraction, de-cyclopentadienes
_C5 fraction, isoprene _- free _C5 fraction and does not contain cyclopentadiene components, _C4C5
Examples include fractions that do not contain cyclopentadiene components. The unsaturated hydrocarbon-containing fraction that has been subjected to the contact treatment with an unsaturated polar compound by the method described above can be treated by a conventional method such as boron trifluoride or its complex, aluminum trichloride, aluminum tribromide,
The polymerization is carried out in the presence of a Friedel-Crafts type catalyst such as tin tetrachloride or titanium tetrachloride at a temperature of usually 0 to 80°C, preferably 20 to 50°C. The hydrocarbon resin of the present invention can be obtained by treating the reaction mixture after the polymerization reaction by a conventional method.
Furthermore, when an unsaturated hydrocarbon-containing fraction having an adjusted boiling point range and having an adjusted content of dicyclopentadiene components is polymerized in the coexistence of an unsaturated polar compound, the present invention can be carried out using the same treatment method. A hydrocarbon resin is obtained. By employing the method of the present invention, not only the hue and heat stability, which were considered to be the biggest drawbacks of conventional aromatic hydrocarbon resins, are greatly improved, but also the odor is also improved. Furthermore, by treating the unsaturated hydrocarbon-containing fraction of the raw material with the method of the present invention, catalyst poison components in the raw material are removed, so the amount of catalyst used can be reduced compared to conventional methods. It also has the advantage of being able to The hydrocarbon resin produced by the method of the present invention has excellent hue, heat resistance stability, and odor.
It is used for applications such as hot melt adhesives, pressure sensitive adhesives, and hot melt traffic paints. Next, the method of the present invention will be specifically explained using examples. In addition, in the examples and comparative examples,
The hydrocarbon resin was evaluated by the following method. (1) Hue Take 10g of hydrocarbon resin in a test tube (inner diameter 16mm), immerse it in a constant temperature bath kept at 150℃,
Immediately after heating and melting, it was compared with a Gardner standard color and expressed as a Gardner value. (2) Heat resistance stability 5 g of hydrocarbon resin was placed in a test tube (inner diameter 16 mm), and after immersing it in a constant temperature bath kept at 200°C for 3 hours, the test tube was compared with the Gardner standard color and expressed as a Gardner value. (3) Odor The odor was divided into three grades, A, B, and C, ranging from weak odor to strong irritating odor when heated and melted (200°C). Example 1 Naphtha cracking fraction (A) with a boiling point range of 140 to 240°C
has the following composition: Polymerizable component: 46.3% by weight Cyclopentadiene component: 1.8% by weight This cracked fraction (A) was used as a starting material oil, and it was summarized in Table 1.
The feed is fed to the distillation column shown in Table 1, and distillation is carried out under the operating conditions listed in Table 1. A low boiling point fraction containing cyclopentadiene components is removed from the top of the column, and a high boiling point fraction is removed from the bottom of the column. The main fraction with a low content of similar components was taken out from the seventh stage.

[Table] Through this distillation, 8% by weight of the low boiling point fraction and 21% by weight of the high boiling point fraction of the starting material oil (A) were removed to obtain a main fraction having the following composition. Polymerizable component: 41.5% by weight Cyclopentadiene component: 0.2% by weight Next, 0.4% by weight of maleimide is added to this main fraction.
(1.5 molar equivalent of cyclopentadiene component) was added and treated at 40°C for 30 minutes with stirring. This treated fraction was then treated with 0.5 boron trifluoride phenol complex catalyst.
% by weight and polymerized at 35°C for 2 hours, the catalyst was decomposed with an aqueous solution of caustic soda, washed with water, unreacted oil and low polymers were distilled off, and a hydrocarbon having the properties shown in Table 2 was obtained. Resin was obtained. Examples 2 to 4, Comparative Example 1 The naphtha cracked fraction (A) used in Example 1 is shown in Table 2.
Distillation was carried out under the same conditions as in Example 1, except that the distillation conditions were changed to those described in Table 2, to obtain a main fraction having the composition shown in Table 2. Next, the main fraction was treated with maleimide under the conditions listed in Table 2, and then polymerized and post-treated in the same manner as in Example 1 to obtain a hydrocarbon resin having the properties listed in Table 2. Examples 5 and 6 The main fraction used in Example 1 was treated under the conditions listed in Table 2, and then polymerized and post-treated in the same manner as in Example 1 to form a carbonized product having the properties listed in Table 2. A hydrogen resin was obtained. Examples 7 to 9 The main fraction obtained in Example 1 was treated with the unsaturated polar compound listed in Table 2, and polymerized and post-treated in the same manner as in Example 1 to form a carbonized product having the properties listed in Table 2. A hydrogen resin was obtained. Examples 10 and 11 The main fraction obtained in Example 1 was treated with maleimide under the conditions listed in Table 2, and then polymerized and post-treated in the same manner as in Example 1 to obtain the properties listed in Table 2. A hydrocarbon resin having the following properties was obtained.

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Claims (1)

[Claims] 1. The boiling point range obtained during thermal decomposition of petroleum is
The content of cyclopentadiene components in an unsaturated hydrocarbon-containing fraction that is within the arbitrary range of 140 to 280°C and contains cyclopentadiene components.
The unsaturated hydrocarbon-containing fraction in the boiling point range adjusted to 0.01 to 0.7% by weight is converted into α/β-unsaturated carboxylic acid ester, α/β-unsaturated carboxylic acid imide, α/β-unsaturated carboxylic acid, etc. Polymerization with a Friedel-Crafts type catalyst after contact treatment with an unsaturated polar compound selected from the group consisting of acid nitriles and quinones, or in the coexistence of both, with improved hue and heat resistance stability. Method for producing hydrocarbon resin. 2 As a fraction containing unsaturated hydrocarbons, the boiling point range is
The method according to claim 1, which uses an unsaturated hydrocarbon-containing fraction whose temperature is in an arbitrary range of 140 to 280°C and whose content of cyclopentadiene components is adjusted to a range of 0.05 to 0.5% by weight. Method. 3 Unsaturated polar compound per mole of cyclopentadiene component in the unsaturated hydrocarbon-containing fraction
The method according to claim 1 or 2, wherein the amount is used in the range of 0.8 to 3.0 mol. 4. The method according to any one of claims 1 to 3, wherein an α/β-unsaturated carboxylic acid imide or an α/β-unsaturated carboxylic acid nitrile is used as the unsaturated polar compound.