JPH0655773B2 - Preparation of cyclic olefin-based random copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a cyclic olefin random copolymer. More specifically, it has excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and various mechanical properties, and has a narrow molecular weight distribution and composition distribution. The present invention provides a method for producing a cyclic olefin-based random copolymer having a low content of a polymer and a low molecular weight polymer.

[Conventional technology]

Polycarbonate, polymethylmethacrylate, polyethylene terephthalate, and the like are known as synthetic resins having excellent transparency. For example, polycarbonate is a resin that is excellent in transparency, heat resistance, heat aging resistance, and impact resistance. However, there is a problem that it is easily attacked by a strong alkali and has poor chemical resistance. Polymethylmethacrylate is apt to be attacked by ethyl acetate, acetone, toluene, etc., swells in ether, and has a problem of low heat resistance. Further, although polyethylene terephthalate has excellent heat resistance and mechanical properties, it has a problem that it is weak against strong acids and alkalis and is easily hydrolyzed.

On the other hand, polyolefin, which is widely used as a general-purpose resin, has many excellent chemical resistance, solvent resistance, and mechanical properties, but many have poor heat resistance. Inferior in transparency. In general, in order to improve the transparency of polyolefin, a method of adding a nucleating agent to refine the crystal structure or quenching to stop the crystal growth is used, but the effect cannot be said to be sufficient. Rather, the addition of a third component such as a nucleating agent may impair the excellent properties inherent to polyolefin, and the quenching method requires a large amount of equipment and reduces the crystallinity. As a result, heat resistance and rigidity may be reduced.

For a copolymer of ethylene and a bulky comonomer,
For example, in US Pat. No. 2,883,372, ethylene and 2.3-
Copolymers with dihydrodicyclopentadiene are disclosed. However, although this copolymer has an excellent balance of rigidity and transparency, it has a glass transition temperature of around 100 ° C. and is poor in heat resistance. Also, ethylene and 5-ethylidene-2
Norbornene copolymers have similar drawbacks.

Further, Japanese Patent Publication No. 46-14910 proposes a homopolymer of 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a, -octahydronaphthalene. However, the polymer is inferior in heat resistance and heat aging resistance. Furthermore, in Japanese Patent Laid-Open No. 58-127728, 1,
A homopolymer of 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a, -octahydronaphthalene or a copolymer of the cyclic olefin and a norbornene-type comonomer has been proposed. However, it is clear from the description in the above publication that all the polymers are ring-opening polymers. Since such a ring-opening polymer has an unsaturated bond in the polymer main chain, it has the drawback of being poor in heat resistance and heat aging resistance.

Further, the present applicant is a cyclic olefin-based random copolymer consisting of ethylene and a specific bulky cyclic olefin, while having transparency heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, It has been discovered that it is a synthetic resin with well-balanced mechanical properties and that it exhibits excellent performance in the field of optical materials such as optical memory disks and optical fibers. Sho 59
-220550, Japanese Patent Application No. 59-236828, Japanese Patent Application No. 59-236829,
Proposed to Japanese Patent Application No. 59-242336. Although the cyclic olefin-based random copolymers proposed to these have the above-mentioned excellent performance, it is easy to contain an unreacted cyclic olefin monomer and a low molecular weight polymer in the copolymer. When the cyclic olefin-based random copolymer is used for the above-mentioned applications in the field of optical materials, particularly for optical memory disks, birefringence due to the unreacted cyclic olefin monomer or low molecular weight polymer, noise due to irregular reflection, etc. There was a problem that it was the cause. Accordingly, there is a demand for a cyclic olefin-based random copolymer having a low content of these cyclic olefin monomers or low molecular weight polymers.

[Problems to be solved by the invention]

The inventors of the present invention have excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and various mechanical properties, and have a narrow molecular weight distribution and composition distribution. As a result of examining the method for producing a cyclic olefin-based random copolymer having a low content of the polymer and the low molecular weight polymer, a specific precipitation treatment and an extraction treatment were performed on the solution of the cyclic olefin-based random copolymer obtained by the polymerization. The inventors have found that the above-mentioned objects can be achieved by carrying out, and have reached the present invention. The cyclic olefin-based random copolymer obtained by the method of the present invention has a small content of the unreacted cyclic olefin monomer and the low molecular weight polymer and is excellent in the above-mentioned performance, and therefore, in the field of optical materials, particularly When it is used for optical memory disk applications, it is characterized in that noise due to birefringence or diffuse reflection is reduced.

[Action for Solving Problems] and [Action] The present invention provides ethylene and the following general formula in a liquid phase consisting of a hydrocarbon medium in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound. I] and a cyclic olefin-based random copolymer solution by copolymerizing at least one cyclic olefin selected from the group consisting of unsaturated monomers represented by the general formula [II], A cyclic olefin-based random copolymer characterized in that the resulting copolymer solution is contacted with a ketone or an alcohol to precipitate the copolymer, and the precipitated copolymer is separated and then contacted with a ketone. A manufacturing method is provided.

General formula [In the formula, n and m are both positive integers, l is a positive number of 3 or more, R ¹ to R ¹⁰ are each a hydrogen atom,
Represents a halogen atom or a hydrocarbon group].

In the method of the present invention, the soluble vanadium compound component used as the catalyst component is a vanadium compound component soluble in the hydrocarbon medium of the polymerization reaction system, and specifically, it has the general formula VO (OR) aXb or VO (OR). cXd (where R is a hydrocarbon group, 0 ≦ a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3,
A vanadium compound represented by 0 ≦ c ≦ 4, 0 ≦ d ≦ 4, 3 ≦ c + d ≦ 4) or an electron donor adduct thereof can be mentioned as a typical example. More specifically
VOCl ₃ , VO (OC ₂ H ₅ ) Cl ₂ , VO (OC ₂ H ₅ ) ₂ Cl, VO (O-iso-C ₃ H ₇ ) C
l ₂ , VO (OnC ₄ H ₉ ) Cl ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₂ , VCl ₄ , VOCl
₄ , VO (OnC ₄ H ₉ ) ₃ , VCl ₃ · 20C ₈ H ₁₇ OH and the like can be exemplified.

Examples of the electron donor that may be used for preparing the soluble vanadium catalyst component include alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid or inorganic acid esters, ethers, acid amides, and acid anhydrides. , Oxygen-containing electron donors such as alkoxysilane, nitrogen-containing electron donors such as ammonia, amine, nitrile and isocyanate can be used. More specifically, methanol, ethanol, propanol, pentanol, hexanol, octanol, dodecanol, octadecyl alcohol, oleyl alcohol, benzine alcohol, phenylethyl alcohol, cumyl alcohol, isopropyl alcohol, cumyl alcohol, isopropylbenzyl alcohol, etc. C1-C18 alcohols; C6-C20 phenols which may have a lower alkyl group such as phenol, cresol, xylenol, ethylphenol, propylphenol, nonylphenol, cumylphenol, naphthol; acetone; , C3 to C15 ketones such as methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone and benzoquinone; acetoaldehyde , Aldehydes having 2 to 15 carbon atoms such as propionaldehyde, octylaldehyde, benzaldehyde, tolualdehyde, naphthaldehyde; methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cyclohexyl acetate, ethyl propionacetate, Methyl butyrate, ethyl valerate, methyl chloroacetate, ethyl dichloroacetate, methyl methacrylate, ethyl crotonic acid, ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, benzoic acid Cyclohexyl, phenyl benzoate, benzyl benzoate, methyl toluate,
Ethyl toluate, aluminum toluate, ethyl ethyl benzoate, methyl anisate, n-butyl maleate, diisobutyl methylmalonate, di-n-hexyl cyclohexenecarboxylate, diethyl nadi succinate, diisopropyl tetrahydrophthalate, diethyl phthalate, phthalate. Diisobutyl acid salt, di-n-butyl phthalate, di2-ethylhexyl phthalate, γ-butyrolactone, δ-valerolactone, coumarin, phthalide, ethylene carbonate and other carbon atoms 2
To 30 organic acid esters; C2 to C15 acid halides such as acetyl chloride, benzoyl chloride, toluic acid chloride, and anisic acid chloride; methyl ether, ethyl ether, isopropyl ether, butyl ether, amyl ether, tetrahydrolane, 2 to 2 carbon atoms such as anisole and diphenyl ether
Ethers of 0; acid amides such as acetic acid amide, benzoic acid amide, toluic acid amide; amines such as methylamine, ethylamine, diethylamine, tributylamine, piperidine, tribenzylamine, aniline, pyridine, picoline, tetramethylenediamine Nitriles such as acetonitrile, benzonitrile and tolunitrile; alkoxysilanes such as ethyl silicate and diphenyldimethoxysilane. Two or more kinds of these electron donors can be used.

As the organoaluminum compound catalyst component used in the present invention, a compound having at least one Al-carbon bond in the molecule can be used. For example, (i) the general formula R ¹ _m Al (OR ² ) _n H _p X _q (where R ¹ and R ² are usually 1 to 15 carbon atoms)
Hydrocarbon groups, including one, preferably one to four, may be the same or different from each other. X is halogen, m is 0 ≦
m ≦ 3, n is 0 ≦ n <3, p is 0 ≦ n <3, and q is 0 ≦ q
<A number of 3 and m + n + p + q = 3)
An organoaluminum compound represented by: (ii) a Group 1 metal represented by the general formula M ¹ Al ▲ R ¹ ₄ ▼ (wherein M ¹ is Li, Na, K and R ¹ is the same as above) and aluminum And complex alkylated products thereof.

The organoaluminum compound belonging to (i) above,
The following can be illustrated.

The general formula R ¹ _m Al (OR ² ) _3-m (wherein R ¹ and R ² are the same as above. M is preferably 1.
5 ≦ m ≦ 3).

General formula R ¹ _m AlX _3-m (where R ¹ is the same as above. M is preferably 0 <m
<3).

The general formula R ¹ _m AlH _3-m (where R ¹ is the same as above. M is preferably 2 ≦ m <
3).

General formula R ¹ _m Al (OR ² ) _n Xq (wherein R ¹ and R ² are the same as above. X is halogen, 0
<M ≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3
And the like can be exemplified.

In the aluminum compound belonging to (i), more specifically, trialkyl aluminum such as triethyl aluminum and tributyl aluminum; trialkyl aluminum such as triisopropyl aluminum; dialkyl aluminum alkoxide such as diethyl aluminum ethoxide and dibutyl aluminum butoxide;
In addition to alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide, partially alkoxylated alkylaluminum having an average composition represented by ▲ R ¹ _0.5 ▼ Al (OR ² ) _0.5 ; diethyl Dialkyl aluminum halides such as aluminum chloride, dibutyl aluminum chloride and diethyl aluminum bromide; alkyl aluminum sesquichlorides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum Partially halogenated alkyls such as alkyl aluminum dihalides such as dibromide Luminium; Dialkyl aluminum hydride such as diethyl aluminum hydride and dibutyl aluminum hydride; Partially hydrogenated alkyl aluminum such as alkyl aluminum dihydride such as ethyl aluminum dihydride and propyl aluminum dihydride; Ethyl aluminum ethoxy chloride, Butyl aluminum butoxy Partially alkoxylated and halogenated alkyl aluminums such as chloride and ethyl aluminum ethoxy bromide can be exemplified. Further, the compound similar to (i) may be an organoaluminum compound in which two or more aluminums are bound via an oxygen atom or a nitrogen atom. Examples of such compounds include (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ and (C ₄ H ₉ ) ₂ AlOAl.
(C ₄ H ₉ ) ₂ , Can be exemplified.

Examples of the compound belonging to (ii) include LiAl (C ₂ H ₅ ) ₄ and LiAl
(C ₇ H _{15) 4} etc. can be exemplified. Among these, it is particularly preferable to use an alkylaluminum halide, an alkylaluminum dihalide or a mixture thereof.

In the method of the present invention, the cyclic olefin used as a polymerization raw material is represented by the general formula [I] and the general formula [II]. [Wherein, n and m are both positive integers, l is a positive integer of 3 or more, and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group] It is at least one cyclic olefin selected from the group consisting of saturated monomers. The cyclic olefin represented by the general formula [I] can be easily produced by condensing cyclopentadiene and the corresponding olefin by the Diels-Alder reaction, and the cyclic olefin represented by the general formula [II] is also Similarly, it can be easily produced by condensing cyclopentadiene and the corresponding cyclic olefin by the Diels-Alder reaction. Specific examples of the cyclic olefin represented by the general formula [I] include 1,4,5,8-dimethano-1,2,3,
In addition to 4,4a, 5,8,8a-octahydronaphthalene, 2-
Methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2, 3,4,4a, 5,8,8a-octahydronaphthalene, 2-
Propyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-hexyl-1,4,5,8-dimethano-1,2, 3,4,4a, 5,8,8a-octahydronaphthalene,
2-stearyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,
8a-octahydronaphthalene, 2,3-dimethyl-1,4,5,8
-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-chloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 2-bromo-1,4,5,8-dimethano-
1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Octahydronaphthalene, 2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2
-Cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,
8,8a-octahydronaphthalene, 2-n-butyl-1,4,
5,8-Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,
Examples include octahydronaphthalene such as 4,4a, 5,8,8a-octahydronaphthalene, and the compounds shown in Table 1.

Specific examples of the cyclic olefin represented by the general formula [II] include the compounds shown in Table 2.

Further, in the method of the present invention, the ethylene and the cyclic olefin are copolymerized, but in addition to the essential two components, other copolymers may be copolymerized as necessary within the range not impairing the object of the present invention. It is also possible to copolymerize unsaturated monomer components.
Specific examples of the copolymerizable unsaturated monomer include propylene, 1-butene-4-methyl-1-pentene, and 1 in the range of less than the equimolar amount with the ethylene component unit in the random copolymer to be produced. -Hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-octadecene, 1-eicocene 2-olefins having 3 to 20 carbon atoms are produced. Cyclopentene, cyclohexene, 3-methylcyclohexene, cyclooctene, 3a, which is less than the equimolar amount of the cyclic olefin component unit in the random copolymer,
5,6,7a-Tetrahydro-4,7-methano-1H-indene (general formula: ) Such as cycloolefin, 1,4-hexadiene, 4-
Methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene,
5-ethylidene-2-norbornene, 5-vinyl-2-
Non-conjugated dienes such as norbornene, norbornene-
2,5-Methylnorbornene-2,5-ethylnorbornene-2,5-isopropylnorbornene-2,5-n
-Butylnorbornene-2,5-i-butylnorbornene-2,5,6-dimethylnorbornene-2,5-chloronorbornene-2,2-fluoronorbornene-2,5,
Examples thereof include norbornenes such as 6-dichloronorbornene-2.

The copolymerization reaction according to the method of the present invention is carried out in a hydrocarbon medium. Examples of the hydrocarbon medium include aliphatic hydrocarbons such as hexane, heptane, octane and kerosene, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, aromatic hydrocarbons such as benzene, toluene and xylene, and the above-mentioned polymerization. Examples thereof include a polyunsaturated monomer, and a mixed medium of two or more of these may be used. In the method of the present invention, the copolymerization reaction is carried out in a continuous manner. The concentration of the soluble vanadium compound supplied to the polymerization reaction system at that time is usually 10 times or less, preferably 7 to 1 times, more preferably 5 to 1 times the concentration of the soluble vanadium compound in the polymerization reaction system. is there. The ratio of aluminum atoms to vanadium atoms (Al / V) in the polymerization reaction system is 2 or more, preferably 2 to 50,
Particularly preferably, it is in the range of 3 to 20. The soluble vanadium compound and the organoaluminum compound are usually supplied after being diluted with the hydrocarbon medium. Here, it is desirable to dilute the soluble vanadium compound within the above concentration range, but a method of adjusting the organoaluminum compound to an arbitrary concentration of, for example, 50 times or less the concentration in the polymerization reaction system and supplying it to the polymerization reaction system is adopted. To be done. In the method of the present invention, the concentration of the soluble vanadium compound in the copolymerization reaction system is usually 0.01 to 5 gram atom / l as vanadium atom, preferably 0.05 to 3 gram atom / l.

In the method of the present invention, the copolymerization reaction is -50 to
It is carried out at a temperature of 100 ° C, preferably -30 to 80 ° C, more preferably -20 to 60 ° C. In the method of the present invention, the copolymerization reaction is usually carried out in a continuous manner. In that case, ethylene as a polymerization raw material, a cyclic olefin, a copolymerizable component to be copolymerized as required, a soluble vanadium compound component as a catalyst component, an organoaluminum compound component and a hydrocarbon medium are continuously supplied to the polymerization reaction system. The polymerization reaction mixture is continuously withdrawn from the polymerization reaction system. Further, in the method of the present invention, the copolymerization reaction can be carried out by the batch method. The average distillation time in the copolymerization reaction varies depending on the kind of the polymerization raw material, the concentration of the catalyst component and the temperature, but is usually 5 minutes to 5 hours, preferably 10 minutes to 3
It is a range of time. The pressure during the copolymerization reaction is usually maintained at more than 0 and 50 kg / cm ² , preferably more than 0 and 20 kg / cm ² , depending on the case, in the presence of an inert gas such as nitrogen or argon. Good. Further, in order to adjust the molecular weight of the copolymer, a molecular weight modifier such as hydrogen can be appropriately present.

The ethylene / cyclic olefin molar ratio fed to the copolymerization reaction in the process of the present invention is usually 99/1 to 1/9.
The range is 9, preferably 98/2 to 2/98.

The resulting copolymer solution obtained by the copolymerization reaction in the method of the present invention is a hydrocarbon medium solution of a cyclic olefin-based random copolymer. The concentration of the cyclic olefin-based random copolymer contained in the produced copolymer solution is usually 2.
It is in the range of 0 to 100% by weight, preferably 40 to 60% by weight, and the resulting copolymer solution also contains a soluble vanadium compound component and an organoaluminum compound component which are catalyst components. The cyclic olefin-based random copolymer is deposited by bringing the produced copolymer solution into contact with a ketone or an alcohol. The proportion of the ketone or alcohol used is usually 200 to 1000 parts by weight, preferably 300 to 1000 parts by weight per 100 parts by weight of the polymer solution for the formation.
It is in the range of 500 parts by weight. As the ketone, acetone,
Examples thereof include ketones having 3 to 7 carbon atoms such as methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, dipropyl ketone and acetylacetone. Alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, sec-butanol and tert-butanol.
Examples of alcohols are: The ketone or alcohol may contain a small amount of water. When a mixed solution containing the ketone or alcohol in an amount of 0.1 to 10% by weight, preferably 1 to 5% by weight, is used, the content of unreacted cyclic olefin monomer and low molecular weight polymer is low and It is preferable because the copolymer powder having a large bulk density can be obtained. The contact of the resulting copolymer solution with the ketone or alcohol is usually carried out at 0 to 100 ° C., preferably 10 to 70 ° C., particularly preferably at a temperature in the vicinity of the boiling point of the ketone or alcohol under stirring conditions. It is carried out using a tank-type mixer equipped with stirring blades such as turbine blades and comb teeth blades, and the stirring speed at that time is usually 200 to 2000, preferably 800 to 15
It is 00r.pm.

By the catalytic treatment, the cyclic olefin-based random copolymer is usually precipitated in the form of powder to form a suspension. The suspension containing the copolymer is separated into the mother liquor and the copolymer by a separation means such as centrifugation or filtration. The separated copolymer is further contacted with a ketone to reduce the content of unreacted cyclic olefin monomer and low molecular weight polymer. In this case, the ratio of the ketone is such that the concentration of the copolymer in the ketone is usually 10 to 100 g / l, preferably 30 to 60.
g / l range, contact temperature is usually 10 to 85
℃, preferably 50 to 80 ℃. The contact treatment between the copolymer and the ketone is usually carried out under stirring conditions, for example, usually using a tank mixer equipped with stirring blades such as turbine blades and comb teeth blades, and the stirring rotational speed at that time. Is usually 50 to 400 rpm, preferably 100 to 200 rpm. The time required for contact is usually 1 to 8 hours, preferably 2 to 5 hours. As the ketone used, the ketone exemplified in the precipitation treatment can be similarly exemplified. The copolymer which has been subjected to contact treatment with a ketone can be separated by a separation means such as centrifugation or filtration. If necessary, the separated copolymer may be further washed with a ketone under the same conditions as the contact treatment with the ketone.

Further, the cyclic olefin-based random copolymer obtained by the method of the present invention is amorphous or crystalline, but among the cyclic olefin-based random copolymers, it does not have a DSC melting point and is obtained by X-ray diffraction. From the measurement results, the amorphous copolymer is suitable. Further, the ethylene / cyclic olefin molar ratio of the cyclic olefin-based random copolymer obtained by the method of the present invention is usually 99/1 to 1/9.
It is in the range of 9, preferably 98/2 to 2/98. The glass transition point (Tg) of the cyclic olefin-based random copolymer is usually 10 to 240 ° C., preferably 20 to 200.
It is in the range of ° C.

The cyclic olefin-based random copolymer obtained by the method of the present invention has a bulk density of usually 0.05 to 0.3, preferably 0.1.
To 0.25, the bulk density is higher than that of the copolymer obtained by the method proposed in the above-mentioned prior art, so that the handling during molding is easy. Further, since the copolymer obtained by the method of the present invention has a small content of unreacted cyclic olefin monomer and low molecular weight polymer contained in the copolymer, it is in the field of optical materials, particularly optical memory. It is characterized in that when it is molded for disk use, noise due to birefringence, irregular reflection, etc. will be reduced.

〔Example〕

Next, the method of the present invention will be specifically described with reference to examples.
The physical properties of the cyclic olefin based random copolymers obtained in Examples and Comparative Examples were determined by the methods described below.

[Method of measuring basic physical properties of polymer]

 MFR: Measured at 260 ° C and a load of 2160 g.

[Η]: The intrinsic viscosity was measured at 135 ° C using an Atlantic viscometer.

Bulk density [AD]; determined according to JIS 6721.

Copolymer composition [mol%]; The peak height of the absorption band (1026 cm _{sealed -1} ) based on the cyclic olefin component was measured by infrared spectroscopy, and the content of the cyclic olefin component was determined. The content of the ethylene component was calculated as the residual amount of the cyclic olefin component.

Ash content [AshV, Al, Cl]; determined by X-ray diffraction method.

Volatile component [VM]: Weight change was measured under the conditions of 300 ° C., 1 Torr, and 1 Hr, and shown in% by weight.

Unreacted cyclic olefin content: The polymer was dissolved in cyclohexane and quantified by gas chromatography.

Softening point [TMA]; Penetration test Ingredient of Du pont, 5 with thermomechanical analyzer
Measure the softening point temperature at a heating rate of ° C / min.

Molecular weight distribution [M / Mn]; by GPC method.

Diluted Example 1 VO (OC ₂ H ₅₎ as [Catalyst Preparation] Catalyst Cl ₂ hexane, vanadium concentration 6.7 mmol / - was prepared as to be in hexane.

Organoaluminum compound catalyst as ethylaluminum sesquichloride the _{(Al (C 2 H 5)} 1.5 Cl 1.5) was diluted with hexane aluminum concentration is 107 mmol / - was prepared as to be in hexane.

〔polymerization〕

Copolymerization reaction of ethylene and cyclic olefin (tetracyclododecene) was continuously carried out using a polymerization tank equipped with a stirrer and having an inner diameter of 500 mm and a reaction volume of 100. That is, the vanadium catalyst prepared by the above-mentioned method was supplied at a V catalyst concentration of 0.6 mMol / ratio to the polymerization solvent (cyclohexane) in the polymerization tank, and the V catalyst immediately before being supplied to the polymerization tank.
The catalyst concentration is a dilution ratio of 2 with respect to the catalyst concentration in the polymerization tank.
Dilute with cyclohexane as a polymerization solvent so that it becomes less than twice,
Supplied. Ethyl aluminum sesquichloride, which is an organoaluminum compound, was supplied at a ratio of Al / V = 8.0. Cyclohexane used as a polymerization solvent was supplied in such a proportion that the reaction time was 1 hour. Ethylene and the molecular weight modifier H ₂ were supplied from the gas phase part in the polymerization tank, and tetracyclododecene was supplied to the liquid phase part in the polymerization tank. Polymerization temperature 11
A continuous solution polymerization reaction was carried out at ℃ and polymerization pressure of 1.8 kg / cm ² G. N ₂ gas was introduced to maintain the polymerization pressure. The polymerization temperature was controlled by circulating a refrigerant through a jacket attached outside the polymerization vessel. When the copolymerization reaction is performed under the above conditions, an ethylene / tetracyclododecene copolymer is obtained.

[Decalcification]

Add methanol and boiler water to the polymerization solution extracted from the bottom of the polymerization tank, and add 25% NaOH solution as a PH regulator,
The polymerization reaction was stopped and the catalyst residue remaining in the polymer was removed.

The polymerization solution after deashing should have an inner diameter of 10 mm before the precipitation operation.
00mm Effective Volume 1000 Stored in a drum with a jacket. The temperature inside the drum was adjusted to 50 to 55 ° C by passing warm water through the inside of the jacket.

[Deposition]

Inner diameter 400mm, inner volume 80, baffle plate and polymerization drum 160 / hr using precipitation drum with stirrer, precipitation solvent (acetin +
Water) 480 / hr, that is, ethylene at a ratio such that the supply ratio of the precipitation solvent to the supply ratio of the polymerization solution is tripled.
The precipitation operation of the tetracyclododecene copolymer was performed. As the deposition solvent, a mixed solvent prepared by adding 2 wt% of water to acetone was used. A four-blade turbine blade was used as the stirrer during the deposition operation, and the rotation speed was 1000 rpm. Liquid temperature during precipitation is 50 to 5
It was 5 ° C. The precipitated suspension containing the copolymer was supplied to a precipitating drum, which was provided with a baffle having an inner diameter of 550 mm and an inner volume of 360 and a stirrer by overflow, and then precipitated. The residence time of the post-deposition drum was 40 min to 60 min. The rotation speed is
200 rpm. [Centrifugation] A tank-type centrifuge [manufactured by Tanabe Iron Works (Type 0 30)] was used, and a suspension containing the copolymer was prepared with a copolymer having a wetness of 300 to 350% at a rotation speed of 1250 rpm. And filtrate.

[Extraction]

The wetness of 300 to 350% of the copolymer is 1000 mm in inner diameter.
Then, the mixture was put into an extraction tank with a finger baffle having an internal volume of 1000 l and a stirrer and supplied with acetone as an extraction solvent. The supply amount was converted to the copolymer dry polymer so that the polymer concentration in the extraction tank would be 40 g /. Hot water was passed through the jacket to control the extraction temperature to 75-80 ° C. The extraction time was 3 hours at the above temperature. The stirring was performed with a turbine blade at 150 rpm.

(Centrifugation)

The suspension containing the copolymer after extraction using the centrifuge at a rotation speed of 1250 rpm was separated into the copolymer having a wetness of 250 to 300% and the filtrate.

[Dry]

The final product was obtained by drying the copolymer having a wetness of 250 to 300% using a tray vacuum dryer.

The drying conditions are 105 to 106 ° C and 24 hours. Table 1 shows the polymerization conditions and basic polymer physical properties.

Examples 2 to 4 The procedure of Example 1 was repeated, except that the polymerization conditions, precipitation conditions and extraction conditions were changed as shown in Table 1. The results are shown in Table 1.

(Effect of the invention) The cyclic olefin-based random copolymer obtained by the method of the present invention is excellent in transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and various mechanical properties, and It has a feature that the molecular weight distribution and composition distribution are narrow and excellent in uniformity. Further, the cyclic olefin-based random copolymer obtained by the method of the present invention has a feature that it has a large bulk density and is excellent in handling at the time of molding, and also the unreacted cyclic olefin monomer and low molecular weight contained in the copolymer. Since the content of the polymer is small, it has a feature that noise due to birefringence, irregular reflection, etc. is reduced when it is molded in the field of optical materials, particularly optical memory disks.

Claims (2)

[Claims] 1. Unsaturation represented by the following general formula [I] and general formula [II] in a liquid phase consisting of a hydrocarbon medium in the presence of a catalyst formed of a soluble vanadium compound and an organoaluminum compound. A solution of a cyclic olefin-based random copolymer is produced by copolymerizing at least one cyclic olefin selected from the group consisting of monomers, and a ketone or alcohol is contacted with the produced copolymer solution. A method for producing a cyclic olefin-based random copolymer, characterized in that the copolymer is deposited by the above process, and the deposited copolymer is separated and then brought into contact with a ketone. [In the formula, n and m are both positive integers, l is an integer of 3 or more, R ¹ to R ¹⁰ are each a hydrogen atom,
Represents a halogen atom or a hydrocarbon group]. 2. The method according to claim 1, wherein the ketone or alcohol is a ketone or alcohol containing 0.1 to 10% by weight of water.