JPS5916564B2 - Method for producing hydrocarbon resin - Google Patents

Description

[Detailed description of the invention] The present invention relates to a method for producing a hydrocarbon resin.

More specifically, the present invention relates to a method for producing a hydrocarbon resin that has excellent compatibility with resins having polar groups such as rosin-based resins such as rosin-modified products and alkyd-based resins. A method for producing hydrocarbon resins by polymerizing unsaturated hydrocarbon-containing fractions obtained during thermal decomposition of petroleum products in the presence of a Friedel-Crafts type catalyst is well known. Hydrocarbon resins include aliphatic hydrocarbon resins obtained by polymerizing unsaturated hydrocarbon-containing fractions with a boiling point range of -20 to +100°C, and unsaturated hydrocarbon-containing fractions with a boiling point range of 140 to 280°C. They are classified into three types: aromatic hydrocarbon resins obtained by polymerization and aliphatic aromatic copolymerized hydrocarbon resins obtained by copolymerizing both unsaturated hydrocarbon-containing fractions. Among these hydrocarbon resins, aliphatic hydrocarbon resins have excellent hue and heat resistance stability, but rosin resins and alkyd resins are used in traffic paints, hot melt adhesives, adhesive tapes, printing inks, etc. When used in combination with resins having polar groups such as, aliphatic hydrocarbon resins have the disadvantage of poor compatibility with these resins. In addition, aromatic hydrocarbon resins generally have a high softening point and are excellent in compatibility with resins having polar groups, but they have the drawbacks of poor hue, heat stability, and weather resistance.
After all, it is difficult to use it for applications such as traffic paint, hot melt adhesives, pressure sensitive adhesives, adhesive tapes, and printing inks. Also, Special Publication No. 38-3590, Special Publication No. 4
Publication No. 0-29024 or JP-A-48-60789
In the aliphatic aromatic copolymerized hydrocarbon resin proposed in the above publication, the drawbacks of aliphatic hydrocarbon resin and aromatic hydrocarbon resin are improved to some extent, but at the same time, the disadvantages of both resins are improved. It is inevitable that the strengths of each will be diminished. For example, this aliphatic aromatic copolymerized hydrocarbon resin in particular does not have sufficient compatibility with other resins having polar groups and has insufficient heat resistance stability, making it insufficient for use in the above-mentioned applications that require these physical properties. performance cannot be demonstrated. In addition, this aliphatic aromatic copolymerized hydrocarbon resin generally has a low softening point, and in order to produce a resin with a high softening point, the polymerization operation must be carried out at a low temperature, which consumes a lot of utility. There is also the disadvantage of doing so. On the other hand, a method in which a fraction containing an aliphatic unsaturated hydrocarbon is heat-treated to cyclize and dimerize dienes or cyclodienes to convert them into, for example, synchropentadienes, which are then polymerized, is disclosed in JP-A No. 481. Publication No. 90383, Japanese Unexamined Patent Publication No. 4
These methods are well known and have been proposed in Japanese Patent Application Laid-open No. 9-107394 and Japanese Patent Application Laid-open No. 48-28591. However, although the hydrocarbon resins obtained by these methods have a high softening point and excellent heat resistance stability, they do not have sufficient compatibility with other resins having polar groups. The present inventors have discovered that 6 heat-melting traffic paints and hot-melt adhesives have excellent hue, heat stability, compatibility with other resins having polar groups, and weather resistance, and the softening point can be easily adjusted. As a result of studying methods for producing hydrocarbon resins that can be used for applications such as pressure-sensitive adhesives and printing inks, we found that aliphatic unsaturated hydrocarbon-containing fractions, synchropentadiene components, and aromatic unsaturated hydrocarbon components were It has been discovered that the above object can be achieved by polymerizing unsaturated hydrocarbon-containing fractions each containing a specific proportion, and the present invention has been achieved.

That is, the present invention provides a linear aliphatic unsaturated hydrocarbon component in the aliphatic unsaturated hydrocarbon-containing fraction (a) with a boiling point range of -20 to +100°C produced during thermal decomposition of petroleum. in a range of 30 to 90% by weight, a synchropentadiene component in a range of 5 to 30% by weight, and an arbitrary aromatic unsaturated hydrocarbon component (c) having a boiling point range of 140 to 240°C in a range of 5 to 40% by weight. Contains within the range of
The method for producing a hydrocarbon resin is characterized in that an unsaturated hydrocarbon-containing fraction in which the cyclopentadiene component is adjusted to about 1% by weight or less is polymerized in the presence of a Friedel-Crafts type catalyst.

The aliphatic unsaturated hydrocarbon-containing fraction (a) used as a polymerization raw material in the method for producing a hydrocarbon resin of the present invention is a product of thermal decomposition such as steam cracking of petroleum, sand cracking, and hydroreforming. When the boiling point range of the product is −
It is a fraction containing aliphatic unsaturated hydrocarbons at a temperature of 20 to +100°C.

This aliphatic unsaturated hydrocarbon-containing fraction includes C5, such as 2-methyl-1-butene, 2-methyl-2-butene, 1-benzene, 2-benzene, 1-butene, 2-butene, isobutylene, etc. C4-based alkenes; C5- and C4-based dienes such as piperylene, isoprene, cyclopentadiene, methylcyclopentadiene, butadiene; 2-methylbutane, 2,2-dimethylpropane, cyclopropane, cyclopentane , butane and other aliphatic saturated hydrocarbon components whose main components are C5 and C4. It is also possible to use a fraction obtained by removing specific unsaturated hydrocarbon components such as isoprene or butadiene from these aliphatic unsaturated hydrocarbon-containing fractions. Of the aliphatic unsaturated hydrocarbon-containing fractions having a boiling point range of 20 to 100° C., aliphatic unsaturated hydrocarbon-containing fractions having a boiling point range of 20 to 100°C may be used. Particular preference is given to using a fraction in the method of the invention. The amount of the aliphatic unsaturated hydrocarbon-containing fraction (a) with a boiling point range of -20 to +100°C produced during the thermal decomposition of petroleum used in the method of the present invention is determined by The content of chain aliphatic unsaturated hydrocarbon components in all unsaturated hydrocarbon components of the hydrocarbon-containing fraction must be in the range of 30 to 90% by weight,
A range of 40 to 80% by weight is particularly preferred.

When the content of the aliphatic hydrocarbon component in all unsaturated hydrocarbon components is less than 30% by weight, the heat stability and weather resistance of the resulting hydrocarbon resin deteriorate. When the content of the aliphatic hydrocarbon component exceeds 90% by weight, the compatibility of the resulting hydrocarbon resin with other resins having polar groups deteriorates significantly. The aliphatic unsaturated hydrocarbon containing a) having the boiling point range used in the method of the present invention contains a cyclopentadiene component such as cyclopentadiene or methylcyclopentadiene. In this method, in order to prevent the production of insoluble gel as a by-product during the polymerization step, it is necessary that these cyclopentadiene components be approximately 1% by weight or less,
In particular, it is preferable to use a fraction containing no aliphatic unsaturated hydrocarbons. For this purpose, it is preferable to use an unsaturated hydrocarbon-containing fraction in which these cyclopentadiene components are converted into synchropentadienes by heat treatment before polymerization. When the cyclopentadiene component is converted into synchropentadiene by heat treatment of the aliphatic unsaturated hydrocarbon-containing fraction as described above, the unsaturated hydrocarbon-containing fraction produced by this operation is The synchropentadiene compounds contained in the solution are synchropentadiene components (
b). Examples of the dicyclopentadiene class 7 component (b) used as a polymerization raw material in the method for producing a hydrocarbon resin of the present invention include syncropentadiene, methyldicyclopentadiene, dimethyldicyclopentadiene, and other syncropentadiene derivatives.

One or two of these synchropentadiene components
Mixtures of more than one species are used; it is also possible to use mixed fractions containing these synchropentadiene components. Among these synchropentadiene components, it is preferable to use synchropentadiene or a mixed fraction containing synchropentadiene in the method of the present invention. The content of the synchropentadiene component (b) in the total unsaturated hydrocarbon components of the unsaturated hydrocarbon-containing fraction of the polymerization raw material must be in the range of 5 to 30% by weight, and 10 to 25% by weight. Particularly preferred is a range of % by weight. If the content of the synchropentadiene component in the total unsaturated hydrocarbon component is less than 5% by weight, the resulting hydrocarbon resin will have poor heat resistance stability and a lower softening point. If the content of the synchropentadiene component exceeds 30% by weight, the softening point of the resulting hydrocarbon resin will be too high and its adjustment will be difficult, and not only will many gels form, but the resulting resin will have a softening point. Since the molecular weight distribution becomes broader, a drawback arises in that the compatibility with resins having polar groups decreases. As mentioned above, a mixed fraction containing a synchlopentadiene component can be used as the dicyclopentadiene class 7 component (b).

For example, as a mixed fraction of an aliphatic unsaturated hydrocarbon-containing fraction (a) and a synchropentadiene-containing fraction b),
A distillate containing aliphatic unsaturated hydrocarbons with a boiling point range of -20 to +100°C and containing cyclopentadiene components produced during thermal decomposition of petroleum is subjected to heat treatment at a temperature of 50 to 250°C. By converting the cyclopentadiene component into a dicyclopentadiene class 7 component, and further adding the syncropentadiene component as necessary, the content of the syncropentadiene component in the total unsaturated hydrocarbon component can be reduced. It is preferable to use an unsaturated hydrocarbon-containing fraction whose ratio is adjusted to fall within the above range. The aromatic unsaturated hydrocarbon component (c
) is any aromatic unsaturated hydrocarbon component having a boiling point range of 140 to 240°C.

More specifically, examples include styrene, α-methylstyrene, β-methylstyrene, vinyltoluene, isopropenyltoluene, allylbenzene, allyltoluene, 1-propenyltoluene, indene, and methylindene. Not only one kind of these aromatic unsaturated hydrocarbon components but also a mixture of two or more kinds can be used. In addition, as this aromatic unsaturated hydrocarbon component, aromatic unsaturated hydrocarbons with a boiling point range of 140 to 240°C are produced during thermal decomposition such as steam cracking, sand cracking, and hydroreforming of petroleum. It is also possible to use containing fractions. When using an aromatic unsaturated hydrocarbon-containing fraction with a boiling point range of 140 to 240°C produced by thermal decomposition of petroleum, this fraction must be mixed with maleic anhydride, itaconic anhydride, etc. before polymerization. α of
- It is preferable to use a fraction purified by heat treatment at a temperature of 50° C. or higher in the presence of a β-monounsaturated dicarboxylic acid anhydride. Among these aromatic unsaturated hydrocarbon components (c), aromatic vinyl compounds having a boiling point range of 140 to 200°C, such as styrene, α-methylstyrene, vinyltoluene, and isopropenyltoluene, are used. It is particularly preferred to use at least one selected from the group consisting of styrene, α-methylstyrene and isopropenyltoluene in the method of the present invention. When any of the above-mentioned aromatic unsaturated hydrocarbon components is used, the content of c) in the aromatic unsaturated hydrocarbon component in all unsaturated hydrocarbon components of the unsaturated hydrocarbon-containing fraction. The proportion should be in the range 5 to 40% by weight, preferably in the range 10 to 35% by weight. When the content of aromatic unsaturated hydrocarbon components in all unsaturated hydrocarbon components exceeds 40% by weight, the resulting hydrocarbon resin will have poor heat stability and weather resistance. When the content of the aromatic unsaturated hydrocarbon component is less than 5% by weight, the compatibility of the resulting hydrocarbon resin with resins having polar groups decreases. In the process of the invention, the boiling point range is -20 to +1
00°C aliphatic unsaturated hydrocarbon-containing fraction (a), synchropentadiene component (b) and boiling point range of 140°C
An unsaturated hydrocarbon-containing fraction containing any aromatic unsaturated hydrocarbon component (c) in a specific range as described above at a temperature of The hydrocarbon resin of the present invention can be produced by polymerizing by a batch polymerization method or a continuous polymerization method.

Friedel-Crafts type catalysts include boron trifluoride or its complexes, aluminum trichloride, aluminum tribromide, tin tetrachloride, titanium tetrachloride, etc.
Preference is given to using aluminum trichloride as polymerization catalyst in the process of the invention. In the method of the present invention, the polymerization reaction is
Preferably it is carried out at a temperature of 0 to 120°C. The reaction mixture after the polymerization reaction is deactivated by adding water, steam, alkaline aqueous solution, ammonia, etc. to the reaction mixture after the polymerization reaction is completed, and the unreacted hydrocarbon oil is distilled off after deashing by washing with water etc. , the hydrocarbon resin of the present invention is obtained. The hydrocarbon resin produced by the method of the present invention has excellent hue and heat resistance stability, and is also excellent in compatibility with other trees having polar groups such as rosin resins and alkyd resins. The resin can be used in its unmodified state or modified with unsaturated carboxylic acids, their anhydrides, or their esters as needed to produce hot-melt traffic paints, hot-melt adhesives, pressure-sensitive adhesives, adhesive tapes, printing inks, etc. Served for a purpose.

In addition, the method of the present invention has the advantage that the softening point of the hydrocarbon resin can be easily adjusted. Next, the method of the present invention will be specifically explained using Examples.

In addition, in the Examples and Comparative Examples, evaluation of the hydrocarbon resin was performed by the following method. (1) Hue (Cardner color) Hydrocarbon resin 107 was placed in a test tube (inner diameter 161 Lm), immersed in a constant temperature bath kept at 150°C, heated and melted, and immediately compared with the standard color of Cardner. , expressed as Cardner value.

(2) Heat-resistant stable hydrocarbon resin 57 was placed in a test tube (inner diameter 16) equipped with a vertical stirrer, and placed in a constant temperature bath maintained at 240°C.
．． After being immersed under stirring for 5 hours, the color was compared with a cardner standard color and expressed as a cardner value.

(3) Softening point It was measured by the ring and ball method according to JIS K253l.

(4) A mixture of a compatible hydrocarbon resin and a partner resin at a predetermined ratio is placed in a beaker, melted and stirred at 200°C for 15 minutes, and transferred to a test tube with an inner diameter of 16 mm while hot.

Compatibility was determined by the transparency of the mixture phase when cooled to room temperature θ, and the results were ranked in descending order of A. B. C, D,. E
It is divided into five stages. A indicates complete or almost complete compatibility, and D indicates non-compatibility. The mixing ratio with the other resin is shown in Table 1. (5) A 50% by weight benzene solution of the weather-resistant resin is applied onto a white aluminum plate using an applicator and dried.

The coating thickness when dry is 35±2μ. This coated plate was measured using a sash yarn type weatherometer (black panel temperature 63
Weather resistance was determined by the yellowness of the resin surface after irradiation for 80 hours using a spray cycle of 9 minutes/1 hour). Ratings are from best to A. B.. C. D. ．． Set it to 5 stages of E.
The closer to E, the greater the yellowing. In the following examples, as the aliphatic unsaturated hydrocarbon-containing fraction, a fraction having the composition shown in Table 2, which produced O by thermal decomposition of naphtha, was used.

Examples 1 to 3 A slurry of anhydrous aluminum chloride dispersed in mixed xylene was placed in a pressure-resistant polymerization vessel with an actual internal volume of 1e, and Table 3
The aliphatic unsaturated hydrocarbon-containing fraction, synchropentadiene fraction and isopropenyltoluene (m-/p
- = 81/19) is continuously fed at a flow rate such that the residence time is 2 hours.

The schematic composition and polymerization temperature of each component are shown in Table 3. The cyclopene 2''*tadiene components in the polymerization component compositions of Examples 1 to 3 are about 0.5, about 0.6, and about 0.8% by weight, respectively. Mix with an equal volume of hot water, stir at 95°C for 1 hour, and then wash with hot water until the washing liquid becomes neutral.
After normal pressure stripping at 200℃, 51
A resin was obtained by stripping under reduced pressure at 1 LmHg. Table 3 shows the yield and physical properties of the resin. Examples 4 to 7 Mixed xylene used as the catalyst dispersion medium in Example 1 and isopropenyltoluene (m-/p-=81/19) as the aromatic unsaturated hydrocarbon component (c) Polymerization and post-treatment were carried out in the same manner as in Example 1, except that the Kobi Sangtan 1tS water hook component (C) was changed to the compound listed in Table 4 (the weight parts were the same), and the results shown in Table 4 were obtained. Obtained.

Ren l styrene I?・-7, 7? 7 ma. /． Iisogropenyl α-methyls Example 8 Raw material C shown in Table 2 was selected as the aliphatic unsaturated hydrocarbon-containing fraction, and raw material C was heated and stirred under pressure at 130° C. for 2 hours.

By this operation, the content of cyclopentadiene is 0.8
The content of synchropentadiene was 14.4% by weight, and the content of chain aliphatic unsaturated hydrocarbon components was 43.0% by weight. 21.5 parts by weight of α-methylstyrene was mixed with 100 parts by weight of this treated fraction, and the chain aliphatic unsaturated hydrocarbon component (a), synchropentadiene component (5) and α - Polymerization feed raw materials containing 54, 18 and 27% by weight of each polymerization component of methylstyrene (c) were prepared. In addition,
The cyclopentadiene component in the polymerization component composition is approximately 1% by weight.
It is. Actual internal volume 1f! 488 ml/hour of the above prepared raw material was added to an autoclave, and 0.8 ml of anhydrous aluminum chloride was added to the autoclave.
A slurry in which parts by weight were dispersed in 3 parts by weight of mixed xylene was supplied at a flow rate of 3.3 ml per hour, polymerization was carried out at 50°C, and post-treatment was carried out by the method described in Example 1.

Resin yield is 42% by weight, resin softening point is 88°C, hue is Cardner number 7, heat resistance stability is Cardner number 12,
The compatibility with the rosin resin and the alkyd resin was both A, and the weather resistance was also A. Example 9 Fraction 100 with a boiling point of 140°C to 240°C produced by thermal decomposition of naphtha
3 parts by weight of maleic anhydride and 0.0 parts by weight of anhydrous ferric chloride.
After reacting with 2 parts by weight at 100° C. for 2 hours with stirring, distillation was performed under reduced pressure (151 LmHg, bottom temperature 150° C.) to obtain a purified aromatic unsaturated hydrocarbon-containing fraction.

Its composition is shown in Table 5. 21.4 parts by weight of this purified fraction, 58.7 parts by weight of raw material D shown in Table 2 as the aliphatic unsaturated hydrocarbon-containing fraction, and 19.8 parts by weight of the synchropentadiene fraction were mixed. Therefore, the compositions of the chain aliphatic unsaturated hydrocarbon component (a), the synchropentadiene component (b), and the aromatic unsaturated hydrocarbon component (c) are about 64, about 22, and about 14% by weight, respectively. A raw material for polymerization feed was prepared. Note that the composition of the cyclopentadiene component is approximately 0.7% by weight. The above-mentioned prepared raw material was supplied to an autoclave having an actual internal volume of 11 at a flow rate of 500 ml per hour, and a slurry of 0.75 parts by weight of anhydrous aluminum chloride dispersed in 20 parts by weight of n-hexane was supplied at a flow rate of 12 ml per hour,
Polymerization was carried out at 45°C, and post-treatment was carried out by the method described in Example 1. The resin yield is 46%, the softening point of the resin is 91℃, the hue is Cardner number 9, and the heat resistance stability is Cardner number 14.
The compatibility with , rosin resin, and alkyd resin was A and B1, respectively, and the weather resistance was C. Example 10 In Example 1, 58 parts by weight of the aliphatic unsaturated hydrocarbon-containing fraction (B) whose raw material supply composition is shown in Table 2, purity 9
18 parts by weight of 9.7% synchropentadiene and α-
By adding 24 parts by weight of methylstyrene, the polymer component compositions of the chain aliphatic unsaturated hydrocarbon component (a), the synchropentadiene component (b), and the α-methylstyrene (c) were the same as in Example 1. Polymerization feedstocks of about 45, about 23, and about 32 weight percent, respectively, were similarly prepared.

The composition of the cyclopentadiene component is approximately 0.5% by weight.
It is. Polymerization and post-treatment were carried out in the same manner as described in Example 1, except that this polymerization feed material was used. Resin yield is 49
weight%, the softening point of the resin is 90°C, the hue is Cardner number 6, the heat resistance stability is Cardner number 11, the compatibility with rosin resins and alkyd resins is A1, and the weather resistance is B (' Comparative Examples 1 to 5 In Example 1, the feed compositions of the aliphatic unsaturated hydrocarbon-containing fraction (8), synchropentadiene fraction, and isopropenyltoluene shown in Table 2 were changed to the quantities shown in Table 6. Accordingly, a polymer feed raw material having the polymerization component composition shown in Table 6 was prepared, and the polymerization and post-treatment were carried out in the same manner as described in Example 1, except that the polymerization temperature was set to the temperature shown in Table 5.

Claims (1)

[Claims] 1. An aliphatic unsaturated hydrocarbon-containing fraction (a
) in which the chain aliphatic unsaturated hydrocarbon component is 30 to 9
0% by weight, dicyclopentadiene component (b) in the range of 5 to 30% by weight, and any aromatic unsaturated hydrocarbon component having a boiling point range of 140 to 240°C (
c) in the range of 5 to 40% by weight, and the cyclopentadiene component is adjusted to about 1% by weight or less, is polymerized in the presence of a Friedel-Crafts type catalyst. Characteristic method for producing hydrocarbon resin. 2 The chain aliphatic unsaturated hydrocarbon component in the aliphatic unsaturated hydrocarbon-containing fraction (a) is in the range of 40 to 80% by weight, and the dicyclopentadiene component (b) is in the range of 10 to 2% by weight.
5% by weight and an optional aromatic unsaturated hydrocarbon component (c) having a boiling point range of 140 to 240°C in the range of 10 to 35% by weight. The method of claim 1. 3 The aliphatic unsaturated hydrocarbon-containing fraction (a) has a boiling point range of 20 to 10 obtained during thermal decomposition of petroleum.
3. The method according to claim 1, characterized in that an aliphatic unsaturated hydrocarbon-containing fraction at 0° C. is used. 4. Any one of claims 1 to 3, characterized in that an aliphatic unsaturated hydrocarbon-containing fraction that does not contain a cyclopentadiene component is used as the aliphatic unsaturated hydrocarbon-containing fraction (a). That method. 5. As a mixed fraction of the aliphatic unsaturated hydrocarbon-containing fraction (a) and the dicyclopentadiene component (b), 50 to 250% of the aliphatic unsaturated hydrocarbon-containing fraction containing the cyclopentadiene component The cyclopentadiene component is converted into a dicyclopentadiene component by heat treatment at a temperature of ℃, and the content of the dicyclopentadiene component is adjusted by adding dicyclopentadiene as necessary. The method according to any one of claims 1 to 4, characterized in that the unsaturated hydrocarbon-containing fraction is used. 6. The method according to any one of claims 1 to 5, characterized in that dicyclopentadiene or a mixed fraction containing dicyclopentadiene is used as the dicyclopentadiene component (b). 7 The aromatic unsaturated hydrocarbon component (c) is produced during thermal decomposition of petroleum and has a boiling point range of 140 to 240.
7. The method according to any one of claims 1 to 6, characterized in that a fraction containing aromatic unsaturated hydrocarbons at a temperature of .degree. C. is used. 8 The aromatic unsaturated hydrocarbon component (c) is produced during thermal decomposition of petroleum and has a boiling point range of 140 to 240.
Claims characterized in that a fraction purified by heat-treating a fraction containing an aromatic unsaturated hydrocarbon at ℃ in the presence of an α/β-unsaturated dicarboxylic acid anhydride is used. Any method from 1 to 7. 9. The method according to claim 8, characterized in that an aromatic vinyl compound having a boiling point range of 140 to 200° C. is used as the aromatic unsaturated hydrocarbon component (c). 10. Claims 1 to 9 characterized in that at least one member selected from the group consisting of styrene, α-methylstyrene, and isopropenyltoluene is used as the aromatic unsaturated hydrocarbon component (c). Either way. 11. The method according to any one of claims 1 to 10, characterized in that aluminum trichloride is used as the Friedel-Crafts catalyst. 12. The method according to any one of claims 1 to 11, characterized in that the polymerization reaction is carried out at a temperature of 10 to 120°C.