JPH0834824A - Hydrocarbon resin - Google Patents

Abstract

PURPOSE:To provide a hydrocarbon resin well soluble in an aliphatic solvent such as hexane and highly reactive with another monomer or the like. CONSTITUTION:This resin is one prepared by polymerizing a fraction (A) containing an aliphatic unsaturated hydrocarbon of a boiling point of -20 to 100 deg.C and formed when petroleum or the like is cracked and refined and a dicyclopentadiene (B) in the presence of a Friedel-Crafts catalyst, containing 5-50 pts.wt. component B and 95-50 pts. wt. aliphatic unsaturated hydrocarbon of component A and having an iodine value of 100(g/100g) or above.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrocarbon resin, and more particularly to a hydrocarbon resin which is easily soluble in an aliphatic hydrocarbon solvent without impairing the characteristics of dicyclopentadiene resin.

[0002]

2. Description of the Related Art A method for producing a hydrocarbon resin by polymerizing an unsaturated hydrocarbon-containing fraction obtained at the time of decomposing and refining petroleum in the presence of a Friedel-Crafts type catalyst is well known. The hydrocarbon resin obtained by this method is an aliphatic hydrocarbon resin obtained by polymerizing an unsaturated hydrocarbon-containing fraction having a boiling range of −20 ° C. to 100 ° C., and a boiling range of 140.
To 280 ° C., an aromatic hydrocarbon resin obtained by polymerizing an unsaturated hydrocarbon-containing fraction, an aliphatic aromatic copolymerized hydrocarbon resin obtained by copolymerizing both unsaturated hydrocarbon-containing fractions, and Aliphatic carbonization obtained by subjecting an aliphatic unsaturated hydrocarbon-containing fraction to heat treatment to cyclize and diene the diene or cyclodiene, for example, converting to dicyclopentadiene, and then polymerizing Classified as hydrogen resin.

Among these petroleum-based hydrocarbon resins, dicyclopentadiene-based resins, which belong to alicyclic hydrocarbon resins, are characterized by their high reactivity as compared with other hydrocarbon resins. There is. It is believed that this is due to the presence of unsaturated bonds in the side chains, as compared with other hydrocarbon resins having unsaturated bonds in the main chain. Therefore, the dicyclopentadiene unit is
It can be said to have an extremely important meaning.

These petroleum hydrocarbon resins have hitherto been used for various purposes, but when used, they are often used by dissolving them in a solvent. For example, the above-mentioned dicyclopentadiene resin is usually obtained by thermally polymerizing dicyclopentadiene. This hydrocarbon resin is easily dissolved in an aromatic solvent such as toluene and xylene, but resins other than the aliphatic hydrocarbon resin are hardly soluble or insoluble in the aliphatic solvent.

[0005]

However, in recent years, the use of aromatic solvents is being regulated from the standpoint of environmental protection. For this reason, it is difficult to use a conventional hydrocarbon resin that is soluble only in an aromatic solvent.

Therefore, an object of the present invention is to provide a resin that is easily soluble in an aliphatic solvent without impairing the characteristics of the dicyclopentadiene resin.

[0007]

In order to solve the above problems, the present invention provides (A) an aliphatic unsaturated hydrocarbon having a boiling point of -20 ° C to 100 ° C, which is produced during the decomposition and refining of petroleum. A fraction containing (B) dicyclopentadiene,
Polymerized in the presence of a Friedel-Crafts type catalyst, containing 5 to 50 parts by weight of (B) with respect to 95 to 50 parts by weight of the aliphatic unsaturated hydrocarbon of (A), and having an iodine value of A hydrocarbon resin having a weight of 100 (g / 100 g) or more is provided.

The hydrocarbon resin of the present invention will be described in detail below.

Fraction (A) containing an aliphatic unsaturated hydrocarbon used as a main raw material of the hydrocarbon resin of the present invention.
Is a boiling point of -20 to 1 generated during the decomposition and refining of petroleum
It is a fraction at 00 ° C. The fraction (A) containing the aliphatic unsaturated hydrocarbon usually contains alkenes having 4 to 5 carbon atoms, dienes, and saturated aliphatic hydrocarbons. Examples of alkenes having 4 to 5 carbon atoms include 2
-Methyl-1-butene, 2-methyl-2-butene, 1-
Pentene, 2-pentene, 1-butene, 2-butene, isobutene and the like can be mentioned. Examples of dienes having 4 to 5 carbon atoms include piperylene, isoprene, cyclopentadiene, butadiene and the like. In addition, carbon number 4 ~
Examples of the saturated aliphatic hydrocarbon of 5 include 2-methylbutane, 2,2-dimethylpropane, cyclopropane, cyclopentane, butane and the like. In such a fraction, the aliphatic unsaturated hydrocarbon is usually contained in an amount of 30 to 60% by weight. Further, in the present invention, from the fraction produced during the decomposition and refinement of petroleum,
Furthermore, it is also possible to use a fraction from which a specific unsaturated hydrocarbon component such as isoprene or butadiene has been removed.

The dicyclopentadiene (B) used as another main raw material of the hydrocarbon resin of the present invention.
Examples thereof include dicyclopentadiene derivatives such as dicyclopentadiene, methyldicyclopentadiene and dimethyldicyclopentadiene. In the present invention, one kind or a mixture of two or more kinds of these dicyclopentadiene is used, and a mixed fraction containing these dicyclopentadiene can also be used. Among these dicyclopentadiene components, it is preferable to use dicyclopentadiene or a mixed fraction containing dicyclopentadiene.

The content ratio of the above-mentioned fraction (A) and dicyclopentadiene (B) in the hydrocarbon resin of the present invention is
The reactivity of the dicyclopentadiene resin is fully exhibited, the solubility in the aliphatic solvent is high, the molecular weight distribution is wide, and the hydrocarbon resin excellent in compatibility with other resins is obtained. The proportion of 5 to 50 parts by weight of (B) relative to 95 to 50 parts by weight of the fraction (A),
The proportion of (B) 7 to 40 parts by weight is preferable with respect to (A) 93 to 60 parts by weight. When the proportion of the fraction (A) is high, the reactivity of the cyclopentadiene resin is low. When the ratio of the component (B) is higher than this, the solubility of the resin in the aliphatic solvent decreases. Furthermore, since the molecular weight distribution of the resin produced is wide, the compatibility with other resins is also reduced.

The hydrocarbon resin of the present invention has an iodine value of 10
It is 0 or more (g / 100g). The iodine value is a numerical value showing the reactivity of a hydrocarbon resin, and is defined by JIS
It is a numerical value measured by the method described in K0700.

The softening point of the hydrocarbon resin of the present invention is usually
It is preferably in the range of 80 to 140 ° C. The molecular weight is usually 1000 to 70000 in terms of weight average molecular weight.
The range of is preferable.

The hydrocarbon resin of the present invention comprises the above-mentioned fraction (A).
And (B) dicyclopentadiene are polymerized in the presence of a Friedel-Crafts type catalyst. For example, the above-mentioned fraction (A) and dixylopentadiene (B)
And may be separately supplied to the reactor at a predetermined ratio to be subjected to the polymerization reaction, or a mixed fraction containing the above-mentioned fraction (A) and dicyclopentadiene (B) may be subjected to the polymerization reaction. May be. As a specific example of the mixed fraction containing the dicyclopentadiene component, a mixed fraction of the aliphatic unsaturated hydrocarbon-containing fraction (A) and the dicyclopentadiene component (B) may be used for the thermal decomposition of petroleum. A boiling point range of −20 to 100 ° C., which is generated at this time, is 50 to 50 in the aliphatic unsaturated hydrocarbon fraction containing a cyclopentadiene component.
Conversion of cyclopentadiene to dicyclopentadiene by heat treatment at a temperature of 250 ° C.,
Further, an unsaturated hydrocarbon-containing fraction in which the proportion of the dicyclopentadiene component in the total unsaturated hydrocarbon component is adjusted so as to fall within the above range by adding dicyclopentadiene compounds as needed is mentioned. .

In the present invention, the Friedel-Crafts type catalyst used in the polymerization reaction includes, for example, aluminum chloride, aluminum bromide, boron trifluoride, various complexes of boron acid fluoride, stannic chloride and stannic bromide. Examples thereof include tin, antimony chloride, antimony bromide, and titanium chloride. Among these, aluminum chloride is
It is preferable because the hydrocarbon resin can be obtained in a high yield. The ratio of the Friedel-Crafts type catalyst used is such that the fraction (A) as a polymerization raw material and the dicyclopentadiene (B) are
For all unsaturated components in the mixture consisting of 0.
It is in the range of 01 to 1.00 mol / kg-unsaturated component, preferably 0.05 to 0.50 mol / kg-unsaturated component.

In the present invention, the prepolymerization reaction can be carried out in the absence of a solvent or in the presence of a solvent. Examples of the solvent used when carried out in the presence of a solvent include, butane, pentane, hexane, heptane, aliphatic hydrocarbons such as octane, benzene, toluene, xylene, ethylbenzene, cumene,
Aromatic hydrocarbons such as cymene and diisopropylbenzene can be exemplified. When a solvent is used, its usage ratio varies depending on the ratio of the components (A) / (B),
The weight ratio to all unsaturated components in the mixed fraction is preferably in the range of 0.10 to 1.00.

In the present invention, the polymerization reaction is usually 0 to
It is performed at 120 ° C, preferably in the range of 30 to 100 ° C. The time required for the polymerization reaction varies depending on the catalyst used, the reaction temperature and other conditions, but it is usually in the range of 1 to 5 hours.

The hydrocarbon resin can be obtained by treating the reaction mixture after completion of the polymerization reaction by a conventional method such as decomposition treatment of catalyst, washing with water, distillation of solvent and the like.

The hydrocarbon resin obtained in the present invention can be used as it is or after being modified by utilizing the unsaturated bond contained therein, for various purposes. For example, it can be used for applications such as traffic paints, hot melt adhesives, pressure sensitive adhesives, adhesive tapes and printing inks.

[0020]

EXAMPLES Next, the present invention will be specifically described with reference to examples.

The compositions of the aliphatic unsaturated hydrocarbon-containing fraction having a boiling point of -7 to 69 ° C. and the dicyclopentadiene fraction used in the following Examples and Comparative Examples are shown in Tables 1-1 to 1-2.
As shown in.

[0022]

[0023]

In addition, the following Examples 1-3 and Comparative Example 1
The softening point, hue, iodine value and molecular weight of the resin obtained in any one of Examples 3 to 3 were measured according to the following methods.

Softening point The softening point was measured by the ring and ball method according to JIS K2207.

Hue: Gardner No. was determined according to JIS K5400.

Iodine value: Measured according to JIS K0700.

Molecular weight Measured by gel permeation chromatography.

Acid value Measured according to JIS K0070.

Example 1 A glass autoclave having an internal volume of 2 l was charged with 45 ml of dehydrated and purified xylene,
The volume of the reaction mixture in the autoclave was adjusted to 50 ml by adding n-octane. Next, 3.0 g of aluminum chloride was added, and the mixture was heated to 70 ° C. while stirring in a nitrogen atmosphere. While maintaining the temperature at 70 ° C., the aliphatic unsaturated hydrocarbon fraction having the composition shown in Table 1-1 and the dicyclopentadiene fraction having the composition shown in Table 1-2 were adjusted to have a weight ratio of 85/15. 150g of prepared mixture
Was added dropwise over 15 minutes. After completion of the dropping, stirring was continued for 2 hours to carry out the reaction while maintaining the temperature. Then, 100 times mole of methanol was added to aluminum chloride to stop the polymerization reaction. The obtained polymerization reaction mixture was washed with a large amount of water 5 times, and then the solvent and the unreacted monomer were distilled off under reduced pressure using an evaporator to obtain a hydrocarbon resin.

The polymerization conditions in this polymerization reaction are shown in Table 2.
In addition, Table 3 shows the measurement results of the physical properties of the obtained hydrocarbon resin. The resin composition (the ratio of the aliphatic unsaturated hydrocarbon component and the dicyclopentadiene component) in Table 3 was calculated by measuring the respective reaction rates by gas chromatography.

(Examples 2 to 3) As shown in Table 2, the procedure of Example 1 was repeated except that the ratio of the aliphatic unsaturated hydrocarbon-containing fraction / dicyclopentadiene fraction and the amount of xylene were changed. , Was polymerized to produce a hydrocarbon resin. If the amount of xylene is 50 ml or more, 50 ml is
The mixture was placed in a toclave, the rest was mixed with the monomer, and the mixture was added dropwise. Table 2 shows the polymerization conditions in the polymerization reaction, and 3 shows the measurement results of the physical properties of the obtained hydrocarbon resin.

(Comparative Examples 1 and 2) Polymerization was carried out by carrying out polymerization in the same manner as in Example 1 except that the ratio of the aliphatic unsaturated hydrocarbon-containing fraction / dicyclopentadiene fraction and the amount of xylene were changed. A hydrogen resin was produced. Table 2 shows the polymerization conditions in the polymerization reaction, and 3 shows the measurement results of the physical properties of the obtained hydrocarbon resin.

(Comparative Example 3) A glass autoclave having an internal volume of 2 l was charged with 150 g of dicyclopentadiene fraction and 100 ml of xylene, and the atmosphere was replaced with nitrogen. The temperature was raised to 90 ° C. and polymerization was performed for 90 minutes. Xylene was distilled off from the obtained product by vacuum distillation to obtain a resin. Table 3 shows the physical properties of the obtained resin.

[0035] (* 1) Aliphatic unsaturated hydrocarbon-containing fraction / dicyclopentadiene (weight ratio) (converted to unsaturated hydrocarbon component) (* 2) Xylene / reaction component (weight ratio) (* 3) mol / kg monomer

[0036] (* 1) Aliphatic unsaturated hydrocarbon unit / dicyclopentadiene unit (% by weight) (* 2) Gardner-No

(Examples 4 and 5) When 50 g of the hydrocarbon resin obtained in Examples 1 and 3 was dissolved in 50 g of n-hexane, it was easily dissolved at room temperature.

Comparative Examples 4 and 5 When 50 g of the resin obtained in Comparative Examples 1 and 3 was dissolved in 50 g of n-hexane, the resin of Comparative Example 1 was left at room temperature and dissolved for one day and night. The resin of Comparative Example 3 did not dissolve.

Example 6 500 g of the hydrocarbon resin obtained in Example 1 was melted at 210 ° C., and maleic anhydride 10 was added.
g was added with stirring and the reaction was carried out for 1 hour. After the reaction,
The resin obtained was dissolved in toluene, washed with water, and the acid value of the resin was measured. As a result, it was 8.8 mgKOH / g.

(Comparative Example 6) Using the resin obtained in Comparative Example 2, the acid value was measured in the same manner as in Example 6. The acid value of the obtained resin was measured and found to be 4.5 mgKOH / g.

[0041]

The hydrocarbon resin of the present invention is a resin that is easily soluble in an aliphatic solvent without impairing the characteristics of the dicyclopentadiene resin. For example, traffic paints, hot melt adhesives and adhesives. Pressure adhesive, adhesive tape
It can be suitably used for applications such as printing and printing ink.

Claims (2)

[Claims] 1. A fraction containing (A) an aliphatic unsaturated hydrocarbon having a boiling point of −20 ° C. to 100 ° C., which is produced during decomposition and refining of petroleum, and (B) dicyclopentadiene. Is polymerized in the presence of a Friedel-Crafts type catalyst, and contains 95 to 50 parts by weight of the aliphatic unsaturated hydrocarbon of (A), 5 to 50 parts by weight of (B), and iodine. Value is 100 (g /
Hydrocarbon resin of 100 g) or more. 2. The hydrocarbon resin according to claim 1, wherein the fraction containing an aliphatic unsaturated hydrocarbon is a fraction containing an aliphatic unsaturated hydrocarbon having 4 to 5 carbon atoms.