JPS61185516A - Production of hydrocarbon resin - Google Patents

Abstract

PURPOSE:To prevent the formation of gel and to improve the color tone and tackifying property of a hydrocarbon resin, by using a homogeneous catalyst composed of aluminum halide, etc. in the production of the hydrocarbon resin by the cationic polymerization of a monomer mixture containing conjugated chain diolefin. CONSTITUTION:The objective hydrocarbon resin can be produced by the cationic polymerization of a monomer mixture containing a 4-5C conjugated chain diolefin (e.g. 1,3-pentadiene), using a homogeneous catalyst obtained by compounding (A) an aluminum halide (preferably aluminum chloride), (B) an unsaturated polymer having low molecular weight (preferably a hydrocarbon resin or an oily polymer produced in the production of the hydrocarbon resin), (C) an aromatic hydrocarbon (e.g. benzene) and (D) an oxygen-containing organic compound (e.g. alcohol). The amounts of the components B and C are 0.5-10 pts.(wt.) and 1-10pts. per 1pt. of the component A, and that of the component D is 0.2-0.8mol per 1mol of the component A. USE:Useful as a tackifying agent of a pressure-sensitive adhesive type by mixing with natural rubber or synthetic rubber.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing hydrocarbon resins, and more specifically, to an industrially useful carbonization method with excellent hue by using a novel homogeneous catalyst. The present invention relates to a method for producing hydrogen resin.

(Prior art) Chain conjugated diolefins such as 1.3-pentadiene, isogrene, 1.3-tutadiene, etc., or these, latins, d-butenes, methylbutenes, diisobutylene, cyclopentene, styrene, methylstyrenes, etc. carbon number 4
It is known that polymers with various properties can be obtained by cationic polymerization of monomer mixtures consisting of ~10 monoolefinically unsaturated hydrocarbons. Examples of such monomer mixtures include fractions with a boiling point of -20 to 60°C produced by naphtha decomposition, and fractions in which various monoolefinic unsaturated hydrocarbons are combined with these fractions. Aluminum halides, particularly aluminum chloride, are generally preferred as catalysts for polymerization. However, since aluminum halide is generally a powdered solid, there are problems in handling it, and when polymerization is carried out using aluminum halide powder,
Attempts have been made to use aluminum halides in combination with various compounds because they tend to be accompanied by the formation of undesirable high molecular weight polymers in the production of aluminum halides and in industrial use.

For example, t) A method in which aluminum halide is dispersed in aromatic hydrocarbons such as xylene and mesitylene, and hydrogen halides such as hydrogen chloride are absorbed and used as a homogeneous complex (Japanese Patent Publication No. 45-7307 ) is known, but although this method allows resin to be produced without producing dullness, it has the disadvantage that the hue of the produced resin is poor.

Attempts have also been made to use oxygen-containing organic compounds such as mata alcohol, phenol, ether, ketone, aldehyde, calgenic acid, and carboxylic acid ester in combination with aluminum chloride (Japanese Patent Publication No. 18241/1983). However, this method was still not sufficient in terms of prevention of gluing and tackifying properties.

(Problems to be Solved by the Invention) Therefore, the present inventors have conducted extensive studies to solve the drawbacks of the conventional method for producing hydrocarbon resins that uses aluminum halide complexes as catalysts, and have found that Using a homogeneous complex catalyst obtained by dispersing aluminum halide in a solution obtained by dissolving a molecular weight unsaturated polymer in an aromatic hydrocarbon solvent and further adding an oxygen-containing organic compound, it is possible to It has been discovered that an industrially useful hydrocarbon resin with excellent tackifying properties and hue can be obtained without any formation, and the present invention has been completed.

(Means for Solving the Problems) An object of the present invention is to provide a method for producing a hydrocarbon resin that prevents the formation of glue and has excellent tackifying properties and hue; In producing a hydrocarbon resin by cationically polymerizing a monomer mixture containing a chain conjugated diolefin having 4 to 5 carbon atoms, (A) an aluminum halide, (B) a low molecular weight unsaturated polymer as a catalyst. This is achieved by using a homogeneous catalyst composed of (C) an aromatic hydrocarbon and (2) an oxygen-containing organic compound.

The monomer mixture used in the present invention includes a4-5 carbon chain conjugated diolefin alone or together with these conjugated diolefins, butenes, Contains a monoolefinic unsaturated hydrocarbon having 4 to 10 carbon atoms such as pentenes, methylbutenes, diiso-ff-lene, cyclopentene, styrene, methylstyrene, etc., and the content of conjugated diolefin is usually 30 ~85% by weight.

Such monomer mixtures are generally obtained from a naphtha cracking fraction at -20 DEG to 60 DEG C., or optionally by combining this fraction with various monoolefinically unsaturated hydrocarbon fractions. Such industrially available monomer mixtures usually contain significant amounts of saturated hydrocarbons, such as butanes, potassium, cyclopentane, etc., but the presence of these components is not considered for the purposes of the present invention. It does not prevent In addition, if it is within a range that does not essentially impede the effects of the present invention, Schiff O
It may contain a dimer of ia p diene, a dimer of so, a co-dimer of cyclointadiene and a linear conjugated diene, and the like.

In the present invention, a homogeneous complex mainly composed of aluminum halide is used as a catalyst.

Examples of aluminum halides used as the first component include aluminum chloride, aluminum bromide, aluminum iodide, and aluminum fluoride.
Among them, aluminum chloride and aluminum bromide are preferred, and aluminum chloride is particularly preferred. Aluminum halide is usually used in the form of particles having a mesh size of 5 to 200, but is not limited thereto and can be used in the form of larger or smaller particles.

The low molecular weight unsaturated polymer used as the second component is
Usually number average molecular weight 100-10,000, bromine number 10
Specific examples thereof include resinous or liquid aliphatic hydrocarbon resins produced by cationic polymerization, oily polymers produced as by-products during their production, liquid polybutene, liquid polybutadiene, etc. Among them, hydrocarbon resins and oily polymers produced as by-products during their production are preferred. The low molecular weight polymer is an essential component for obtaining a homogeneous complex catalyst, and is usually used in a proportion of 0.1 times or more by weight, preferably 0.5 to 10 times by weight, relative to aluminum rodanide. It will be done.

The aromatic hydrocarbons used as the third component are:
Examples include evabenzene, toluene, xylene, mesitylene, ethylbenzene, and are usually 0.5 times or more by weight, preferably 1 to 1 times the weight of aluminum norodanide.
It is used at a ratio of 10 times the weight.

Examples of the oxygen-containing organic compound used as the fourth component include alcohols, phenols, ethers, ketones, calgenic acids, and cardanic acid esters. A specific example is methanol.

Ethanol, butanol, ethylene glycol, cyclopentanol, benzyl alcohol, phenol, cresol, catechol, dimethyl ether, diethyl ether, diphenyl ether.

Examples include acetone, methyl ethyl ketone, cyclohexanone, formic acid, acetic acid, butyric acid, maleic acid, benzoic acid, phthalic acid, ethyl acetate, butyl acetate, and methyl zolopionate.

If the amount of the oxygen-containing organic compound is small, it is difficult to obtain a completely homogeneous complex, and if the amount is too large, the activity of the catalyst tends to be impaired.
It is preferable to use it at a ratio of 1 to 1 mole, more preferably 0.2 to 0.8 mole.

Although the method for preparing the catalyst is not particularly limited, a method in which an oxygen-containing organic compound is dropped into an aromatic hydrocarbon solution containing a low molecular weight polymer in which aluminum halide is dispersed is preferred. Since heat is generated when adding the oxygen-containing organic compound in this method, it is preferable to add the oxygen-containing organic compound gradually and to cool it. The polymerization reaction can be carried out by adding the monomer mixture to the catalyst, or vice versa. If desired, both can be introduced into the reactor at the same time. The reaction is carried out according to known methods, whether patch or continuous.

Since the reaction is usually exothermic, the polymerization temperature can be advantageously controlled by the presence of a diluent.

Examples of the diluent include aliphatic hydrocarbons such as pentane and hexannatate, and aromatic hydrocarbons such as benzene, toluene and xylene, and any of them can be used in the present invention.

Polymerization is usually carried out at -20 to 100°C, preferably 0 to 80°C.
The pressure of one reaction system may be above or below atmospheric pressure. Reaction time is also not important;
Generally, it can vary from a few seconds to 12 hours or more. The polymer thus obtained is treated and dried according to conventional methods.

(Effects of the Invention) According to the present invention, a catalyst can be easily introduced into a reactor during production of a hydrocarbon resin, and formation of dull particles during the polymerization reaction can be prevented.

The hydrocarbon resin obtained by the present invention has excellent hue,
That is, it has a Gardner chromaticity of 5 or less as measured by ASTM-D-1544-68T, and a temperature of 60 to 130°C.
Preferably, those having a softening point defined in JIS K-2531 of 70 to 120° C. are aliphatic such as pentane, hexane, benzene, toluene, xylene, chloroform, and carbon tetrachloride.

Soluble in aromatic or halogenated hydrocarbon solvents,
It is a resinous polymer that exhibits low melt viscosity.

This hydrocarbon resin is also compatible with natural resins such as natural resins, various synthetic resins including SBR, polyethylene, ethylene-vinyl acetate copolymers, polyterpenes, and rosins, and various waxes. This hydrocarbon resin is water-repellent,
Because it exhibits excellent properties such as adhesiveness, holding power, and peeling power,
It is useful as an adhesive for adhesive tapes when mixed with natural plums and various synthetic plums, and is also useful as a tackifier for imparting tackiness to unvulcanized plums.

(Example) The present invention will be described in more detail with reference to Examples below. In addition, the parts and parts in the examples and reference side are based on the weight of a continuous hook.

Example 1 100 parts of benzene and 1.5 parts of aluminum chloride as a catalyst were placed in a glass flask and stirred to maintain the temperature of the system at 40°C. Next, in the above liquid, 1.3 pentadiene 58.7%, cyclopentene 16.1%, diisobutylene 8.4%, unsaturated hydrocarbon having 4 to 5 carbon atoms 1.6%,
120 parts of a monomer mixture consisting of 15.2* saturated hydrocarbons having 4 to 5 carbon atoms (100 parts in total of 1,3 pentadiene, cyclopentene, and diisobutylene) are continuously added to 90
It was added slowly over a period of minutes. The system was cooled and maintained at 65°C since the temperature would rise due to heat generated by the reaction. After the addition was completed, the polymerization system was maintained at 65° C. and stirred for an additional 30 minutes, and then an equal mixture of methanol and 28% aqueous ammonia was added to decompose the aluminum chloride.

The catalyst particles inactivated by decomposition were removed by filtration, and the F solution was transferred to a glass flask and heated while blowing nitrogen to distill off unreacted hydrocarbons and solvent, and then heated to 230°C.
The temperature was raised to. Next, saturated steam was blown into the system to remove the oily polymer produced by the polymerization reaction and the remaining solvent, and after confirming that almost no oil layer existed in the distillate, the steam injection was stopped. The molten residue was filtered out and allowed to cool to room temperature, yielding a yellow resinous substance.

For each of the obtained hydrocarbon resins, the resin yield, softening point (measured by the ring and ball method specified by JIS K-2531), weight average molecular weight, and number average molecular weight (HLC
standard), Gardner chromaticity (ASTMD-1544
-63T) was measured. The results are shown in Table 1.

The method for preparing the catalyst used in the experiment is as follows.

A solution of a low molecular weight unsaturated polymer dissolved in twice the amount of aromatic hydrocarbon was charged into a corrugated Erlenmeyer flask sealed with nitrogen and equipped with a condenser. Furthermore, aluminum chloride in an amount equal to the amount of the low molecular weight unsaturated polymer was charged, and the mixture was stirred using a magnetic stirrer in a hot water bath at 30°C. Next, an oxygen-containing organic compound in an amount of 0.5 moles per 9 mm of aluminum chloride was gradually added dropwise, and stirring was continued for 30 to 60 minutes to obtain a reddish-brown, completely uniform complex catalyst.

Example 2 47.4 1,3-pentadiene as a monomer mixture,
Cyclopentene 13.01 diisobutylene 25.9%,
1.4 unsaturated hydrocarbons with 4 to 5 carbon atoms, 4 to 5 carbon atoms
A polymerization experiment was carried out in the same manner as in Example 1, except that a monomer mixture containing 12.3% of saturated hydrocarbons was used, hexane was used as the solvent, and the reaction temperature was 50°C. The results are shown in Table 2.

From the results in Table 2, it can be seen that when a low molecular weight unsaturated polymer is not used (Experiment No. 2-3), the prevention of gluing is insufficient.

Reference Example To evaluate the usefulness of the hydrocarbon resin obtained in Example 1 as an adhesive for adhesive tape, natural comb (Beer crepe, Mooney viscosity ML, + 100°C = 6 (
A test was conducted using B) as follows.

First, 100 parts of hydrocarbon resin and 1 part of antioxidant are mixed with 100 parts of rubber, then toluene is added to make a solution with a solid content concentration of 16.7%, and this is made into a 1 mil thick solution. An adhesive tape was prepared by applying the adhesive tape to a thickness of 25 μm on a diester film, and its tackiness, adhesive strength, and holding power were measured. The results are shown in Table 3.

The adhesive tape test was conducted in accordance with the method specified in JIS Z-0237, and the tackiness was determined by pasting a 10 cln long adhesive tape on the slope of a 30' stainless steel plate, and placing the tape at a position 10 m above the slope. Steel balls of 30 sizes ranging from 3,732 inches in diameter to 1 inch are rolled at an initial speed of O, and the size of the largest diameter ball that stops on the adhesive tape is indicated, and the adhesive strength is measured using No. 280 water-resistant abrasive paper. The adhesive tape was attached to a polished stainless steel plate with a width of 10 m x length of 100 mm, and the adhesive tape was peeled off at a speed of 200 m+/min at 23°C in the 1800 direction. Adhesive tape was pasted so that the areas were in contact with each other, a load of 1 kII was applied at 40° C., and the time until the adhesive tape fell off was measured. ``From these results, according to the method of the present invention, it is possible to produce a hydrocarbon resin without producing resin, and the resin obtained by the method of the present invention has excellent hue and is also excellent as a tackifier. It can be seen that it imparts tackiness.

Claims (1)

[Claims] 1. In producing a hydrocarbon resin by cationically polymerizing a monomer mixture containing a chain conjugated diolefin having 4 to 5 carbon atoms, (A) aluminum halide and (B) low molecular weight polymers are used as polymerization catalysts. A method for producing a hydrocarbon resin, comprising using a homogeneous catalyst comprising a saturated polymer, (C) an aromatic hydrocarbon, and (D) an oxygen-containing organic compound.