JPH0780973B2 - Cyclic olefin-based random copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a cyclic olefin-based random copolymer. More specifically, it is excellent in 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, and particularly contains a low molecular weight polymer. A cyclic olefin-based random copolymer having a low rate is provided.

[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 easily 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.

Regarding the copolymerization of ethylene and a bulky comonomer, a copolymer of ethylene and 2.3-dihydrodicyclopentadiene is disclosed in, for example, US Pat. No. 2,883,372. However, although this copolymer has an excellent balance of rigidity and transparency, it has a glass transition temperature around 100 ° C and is poor in heat resistance. Further, a copolymer of ethylene and 5-ethylidene-2-norbornene has the same drawback.

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 JP-A-58-127728,
A homopolymer of 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene or a copolymer of the cyclic olefin and a norbornene-type comonomer is 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 found that it is a synthetic resin with well-balanced mechanical properties and exhibits excellent performance in applications in the field of optical materials such as optical memory disks and optical fibers, and it has already been disclosed in JP-A-60-168708. Japanese Patent Application No. 59-220550, Japanese Patent Application No. 59-236828, Japanese Application No. 59-23682
No. 9 and Japanese Patent Application No. 59-242336. The cyclic olefin-based random copolymers proposed in these have the above-mentioned excellent performance, but the copolymer easily contains a low molecular weight polymer, and the cyclic olefin-based random copolymer containing them is included. When used in the above-mentioned applications in the field of optical materials, particularly in the applications of optical memory disks, there is a problem in that it causes poor surface smoothness, surface tackiness, and decrease in disk strength, which are considered to be caused by a low molecular weight polymer. Therefore, there is a demand for a cyclic olefin-based random copolymer having a low content of these low molecular weight polymers and a narrow molecular weight distribution.

[Problems to be solved by the invention]

The present inventors are excellent in transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and various mechanical properties, have a narrow molecular weight distribution and composition distribution, and particularly contain a low molecular weight polymer. As a result of investigating a small amount of cyclic olefin-based random copolymer, ethylene and cyclic olefin monomer are copolymerized under specific conditions in the presence of a catalyst formed from a soluble vanadium compound component and an organoaluminum compound component. As a result, they have found that a novel cyclic olefin-based random in which the above-mentioned object is achieved can be obtained, and arrived at the present invention. The cyclic olefin-based random copolymer according to the present invention has a small amount of the unreacted cyclic olefin monomer and is excellent in the above-mentioned performance. Therefore, when it is used for an optical memory disk, noise due to diffused reflection is reduced. There is a feature that becomes.

[Means for Solving Problems] and [Operation] According to the present invention, a cyclic olefin-based random copolymerization obtained by polymerizing ethylene and a cyclic olefin represented by the following general formula [I] by a continuous polymerization method (I) 40 to 97 mol% of the repeating unit (a) derived from ethylene and 3 to 60 mol% of the repeating unit (b) derived from the cyclic olefin, and (ii) Repeating unit (b) derived from cyclic olefin
Form a structure represented by the following general formula [II], and (iii) the intrinsic viscosity [η] measured in decalin at 135 ° C.
It is in the range of 0.01 to 20 dl / g, (iv) the molecular weight distribution (w / n) measured by gel permeation chromatography is 4 or less, and (v) the glass transition temperature (Tg) is 10 to In the range of 240 ° C., (vi) the crystallinity measured by X-ray diffraction is 0 to
A cyclic olefin-based random copolymer characterized by being in the range of 10% is provided.

General formula [In the formula, n is 1 or 2, and R ¹ to R ¹⁰ each represent a hydrogen atom or an alkyl group].

General formula [In the formula, n and R ¹ to R ¹⁰ are the same as defined above. The cyclic olefin-based random copolymer of the present invention is a cyclic olefin-based random copolymer composed of an ethylene component and a specific cyclic olefin component. The cyclic olefin component is a cyclic olefin component represented by the following general formula [I], and in the cyclic olefin-based random copolymer of the present invention, the cyclic olefin component is the general formula [II].
Form a structure represented by.

General formula [In the formula, n is 1 or 2, and R ¹ to R ¹⁰ each represent a hydrogen atom or an alkyl group].

General formula [In the formula, n and R ¹ to R ¹⁰ are the same as defined above. ] In the cyclic olefin-based random copolymer of the present invention,
The repeating unit (a) derived from the ethylene component is 40 to
97 mol%, preferably in the range of 50 to 95 mol%,
The repeating unit (b) derived from the cyclic olefin is in the range of 3 to 60 mol%, preferably 5 to 50 mol%, the repeating unit (a) derived from the ethylene component and the repeating unit derived from the cyclic olefin component. (B) forms a substantially linear cyclic olefin-based random copolymer that is randomly arranged. The fact that the cyclic olefin-based random copolymer of the present invention is substantially linear and does not have a gel-like crosslinked structure is confirmed by the fact that the copolymer is completely dissolved in decalin at 135 ° C. it can.

The cyclic olefin-based random copolymer of the present invention has an intrinsic viscosity [η] of 0.01 to 20 dl measured in decalin at 135 ° C.
/ g, preferably 0.05 to 10 dl / g.

The molecular weight distribution (w / n) of the cyclic olefin-based random copolymer of the present invention measured by gel permeation chromatography (GPC) is 4 or less, preferably 3.5.
The range is particularly preferably 3 or less. When the molecular weight distribution (W / n) is greater than 4, the content of low molecular weight copolymer increases, and when molded in the field of optical materials such as optical memory disks and optical fibers, noise increases due to poor surface smoothness. In addition, the surface tackiness is increased and the mechanical strength is decreased.

The glass transition temperature (Tg) of the cyclic olefin-based random copolymer of the present invention is 10 to 240 ° C., preferably 20 to 200.
It is in the range of ° C and melting points are usually not observed.

The crystallinity of the cyclic olefin-based random copolymer of the present invention measured by X-ray diffractometry is 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%. When the crystallinity of the copolymer is more than 10%, noise due to birefringence, irregular reflection and the like will increase when molded in the field of optical materials such as optical memory disks and optical fibers.

The cyclic olefin-based random copolymer of the present invention can be produced by the following method. That is, it is selected from the group consisting of ethylene and an unsaturated monomer represented by the following general formula [I] 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. In the method of copolymerizing at least one cyclic olefin, the concentration of the soluble vanadium compound supplied into the polymerization reaction system is continuously maintained while maintaining the concentration of the soluble vanadium compound within the polymerization reaction system at 10 times or less. The ratio of aluminum atoms to vanadium atoms (Al / V) in the liquid phase of the polymerization reaction system is kept at 2 or more, and the repeating unit (a) derived from the ethylene component in the copolymer is 40 to 97 mol% and Repeating unit (b) derived from cyclic olefin component is 3 to 60 mol%
The ethylene and the cyclic olefin are continuously supplied so as to be in the range of 10 and the copolymerization is carried out continuously to achieve a cyclic olefin-based random copolymer.

General formula [In the formula, n is 1 or 2, and R ¹ to R ¹⁰ each represent a hydrogen atom or an alkyl group].

In the method for producing a cyclic olefin-based random copolymer of the present invention, the soluble vanadium compound component used as a catalyst component is a vanadium compound component soluble in the hydrocarbon medium of the polymerization reaction system, and specifically, the general formula VO
(OR) aXb or V (OR) cXd (where R is a hydrocarbon group, 0 ≦
a ≦ 3, 0 ≦ b ≦ 3, 2 ≦ a + b ≦ 3, 0 ≦ c ≦ 4, 0
Representative examples include vanadium compounds represented by ≦ d ≦ 4, 3 ≦ c + d ≦ 4) or electron donor adducts thereof. 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 ) Cl ₂ , VO (OnC
₄ H ₉ ) Cl ₂ , VO (OC ₂ H ₅ ) ₃ , VOBr ₂ , VCl ₄ , VOCl ₂ , VO (OnC ₄ H ₉ ) ₃ ,
Examples thereof include VCl ₃ · 20C ₈ H ₁₇ OH.

As the organoaluminum compound catalyst component used in the production of the cyclic olefin random copolymer of 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 (wherein R ¹ and R ² are hydrocarbon groups having usually 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, which 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 <3
And (m + n + p + q = 3), (ii) the general formula M ¹ Al ▲ R ¹ ₄ ▼ (where M ¹ is Li, Na, K, and R ¹ is The same as the above), a complex alkylated product of a Group 1 metal and aluminum.

Examples of the organoaluminum compound belonging to (i) above include the following.

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).

The general formula R ¹ _m AlX _3-m (where R ¹ is as defined above, X is halogen, and m is preferably 0 <m <3).

General formula R ¹ _m AlH _3-m (wherein R ¹ is the same as above, m is preferably 2 ≦ m <3).

The general formula R ¹ _m Al (OR ² ) _n Xq (where R ¹ and R ² are the same as before. X is halogen, 0 <m
≦ 3, 0 ≦ n <3, 0 ≦ q <3, and m + n + q = 3).

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, diethyl aluminum bromide; ethyl aluminum Um sesquichloride, butyl aluminum sesquichloride, alkylaluminum sesquihalide such as ethylaluminum sesquichloride bromide,
Partially halogenated alkyl aluminum such as alkyl aluminum dihalide such as ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dibromide, etc .; Dialkyl aluminum hydride such as diethyl aluminum hydride, dibutyl aluminum hydride, ethyl aluminum dihydride, Partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as propylaluminum dihydride; Partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxy chloride, butylaluminum butoxycyclolide, ethylaluminum ethoxybromide. Can be illustrated. 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. Such compounds for _{example, (C 2 H 5) 2} AlOAl (C 2 H 5) 2, (C 4 H 9) 2 AlO
Al (C ₄ H ₉ ) ₂ , Can be exemplified. Examples of the compound belonging to (ii) above include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ . Among these, it is particularly preferable to use an alkylaluminum halide, an alkylaluminum dihalide or a mixture thereof.

In the method for producing a cyclic olefin random copolymer of the present invention, the cyclic olefin used as a polymerization raw material is at least one kind selected from the group consisting of unsaturated monomers represented by the general formula [I]. It is a cyclic olefin. 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. Specific examples of the cyclic olefin represented by the general formula [I] include, for example, 1,4,5,8-dimethano-
In addition to 1,2,3,4,4a, 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-octahydro Naphthalene, 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-1,2,3,4,4
a, 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-octahydro Naphthalene, 2-cyclohexyl-1,4,5,8-
Dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-n-butyl-1,4,5,8-dimethano-1,2,3,4,4
Octahydronaphthalene such as a, 5,8,8a-octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene And the compounds listed in Table 1 can be exemplified.

Further, in the method for producing a cyclic olefin-based random copolymer of the present invention, the ethylene and the cyclic olefin are copolymerized, but it is necessary within a range that does not impair the object of the present invention in addition to the two essential components. According to the requirement, other copolymerizable unsaturated monomer components can be copolymerized. Specific examples of the copolymerizable unsaturated monomer include, for example, propylene, 1-butene, and 4-methyl-1- in a range of less than equimolar to the ethylene component unit in the random copolymer to be produced.
Pentene, 1-hexene, 1-octene, 1-decene,
1-dodecene, 1-tetradecene, 1-hexadecene,
It is possible to copolymerize 1-octadecene, 1-eicosene and the like α-olefin having 3 to 20 carbon atoms.

The copolymerization reaction 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 for producing the cyclic olefin-based random copolymer of the present invention, the copolymerization reaction is carried out by a continuous method. At that time, the concentration of the soluble vanadium compound supplied to the polymerization reaction system is 10 times the concentration of the soluble vanadium compound of the polymerization reaction system.
Up to 2 times, preferably 7 to 1 times, more preferably 5 times
It is in the range of 1 to 1, and preferably 3 to 1. 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 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 that the soluble vanadium compound is diluted within the above concentration range, but the 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.
Is the range.

In the method for producing a cyclic olefin-based random copolymer of the present invention, in addition to the catalyst components of the soluble vanadium compound and the organoaluminum compound, a copolymerization reaction is optionally performed in the presence of an electron donor in the polymerization reaction system. You can also do it. Examples of the electron donor include alcohols, phenols, ketones, aldehydes, carboxylic acids, esters of organic acids or inorganic acids, ethers, acid amides, acid anhydrides, oxygen-containing electron donors such as alkoxysilanes, ammonia, amines, nitriles. , A nitrogen-containing electron donor such as isocyanate, and the like can be used.

The copolymerization reaction is −50 to 100 ° C., preferably −30
To 80 ° C, more preferably -20 to 60 ° C. The copolymerization reaction is usually carried out by a continuous method.
In that case, ethylene as a raw material for polymerization, a cyclic olefin, a copolymerizable component to be copolymerized as necessary, a soluble vanadium compound component as a catalyst component, an organoaluminum compound component and a hydrocarbon medium are continuously supplied to a polymerization reaction system. Is
The polymerization reaction mixture is continuously withdrawn from the polymerization reaction system.
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 hours. The pressure during the copolymerization reaction usually exceeds 0 and is 50 kg / c.
It is maintained at 20 kg / cm ² above m ² , preferably above 0 and optionally an inert gas such as nitrogen, argon may be present. 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 is usually 99/1 to 1/99, preferably 98/2 to 2 /.
The range is 98.

The resulting copolymer solution obtained by the copolymerization reaction is a hydrocarbon medium solution of a cyclic olefin-based random copolymer. The concentration of the cyclic olefin-based random copolymer contained in the resulting copolymer solution is usually 2.0 to 20.0% by weight, preferably 2.0 to 10.0% by weight. The cyclic olefin-based random copolymer is deposited by bringing the produced copolymer solution into contact with a ketone or an alcohol. By separating the precipitated copolymer by a separation means such as filtration or centrifugation, the cyclic olefin-based random copolymer of the present invention can be obtained. The amount of the ketone or alcohol used is usually 200 to 1000 parts by weight, preferably 300 to 1000 parts by weight, based on 100 parts by weight of the resulting copolymer solution.
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. Examples of alcohols include alcohols having 1 to 4 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, and tert-butanol. The ketone or alcohol may contain a small amount of water. When a mixed solution containing the ketone or alcohol in an amount of usually 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 small and the bulk density is low. It is preferable because the copolymer powder having a large value 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 00 rpm.

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. By subjecting the copolymer separated and separated to a further extraction treatment with a ketone, the content of unreacted cyclic olefin monomer and low molecular weight polymer is small, the molecular weight distribution and composition distribution are narrow, and the cyclic glass transition temperature is high. It is preferable because an olefin-based random copolymer can be obtained. The ratio of the ketone at that time is such that the concentration of the copolymer in the ketone is usually 10 to 100 g / l, preferably 30 to 60 g / l, and the temperature at the time of contact is usually 1
The temperature is 0 to 85 ° C, preferably 15 to 80 ° C. 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, and the washing condition at that time is the same as the contact treatment condition with the ketone.

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 of the present invention has a small content of unreacted cyclic olefin monomer and low molecular weight polymer contained in the copolymer, it was molded in the field of optical materials, particularly for use in optical memory disks. In this case, there is a feature that noise due to irregular reflection is reduced.

On the other hand, the cyclic olefin-based random copolymer obtained by the method of the present invention has transparency, heat resistance, heat aging resistance, chemical resistance,
Since it has excellent solvent resistance, dielectric properties and various mechanical properties, and has a narrow molecular weight distribution and composition distribution and excellent uniformity, for example, its low molecular weight product is used as a synthetic wax for candles, pine wood shaft impregnating agents, and paper. Processing agent, sizing agent, rubber anti-aging agent, corrugated cardboard waterproofing agent, chemical fertilizer retarding agent,
Heat storage agents, ceramic binders, paper capacitors, electrical insulation materials such as electric wires and cables, neutron moderators, fiber processing aids, water repellent materials for building materials, paint protection agents, polish agents, thixotropic agents, pencil / crayon core hardening agents. It can be used in the fields of agents, carbon ink substrates, electrostatic copying toners, synthetic resin molding lubricants, release agents, resin colorants, hot melt adhesives, lubricating greases, and the like. In addition, its high molecular weight products are used in optical fields such as optical lenses, optical disks, optical fibers, glass windows, electric iron water tanks, microwave oven products, liquid crystal display substrates, printed circuit boards, high frequency circuit boards, and transparent conductive materials. Electrical fields such as sheets and films, medical fields such as syringes, pipettes and animal gauges, chemical fields, camera bodies, various instrument housings, films,
It can be used in various fields such as Hermet.

On the other hand, when the cyclic olefin content is about 20 mol% or less, it can be used in a field utilizing shape memory, a vibration damping material, or a tube. Concretely, it is a vibration damping material as a laminate with joints of irregularly shaped pipes, laminate materials inside and outside pipes and rods, optical fiber connector tightening pins, casts, containers, automobile bumpers, various gap prevention materials, metal surface materials ( It can be used in various fields such as soundproofing materials) or medical tubes.

〔Example〕

Next, the cyclic olefin-based random copolymer 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]

Copolymer composition [mol%]; based on the content of the cyclic olefin component units of the cyclic olefin-based random copolymer previously determined by ¹³ C-MNR (200 MHz), by infrared spectroscopy A calibration curve was prepared between the peak height of the absorption band based on the cyclic olefin component unit and the content of the cyclic olefin component unit. The peak height of the absorption band in the infrared absorption spectrum of the cyclic olefin-based random copolymer was measured to determine the content of the cyclic olefin component. When the cyclic olefin-based random copolymer is a copolymer of ethylene and cyclic olefin, the content of the ethylene component unit was determined as the balance of the cyclic olefin component unit.

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

Molecular weight distribution [w / n]; by GPC method.

Glass transition temperature [Tg]; Dynamic Mechanic manufactured by Dupont
It was determined by al Analyser (DMA).

Crystallinity; 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.

Example 1 Using a 2 liter polymerization vessel equipped with a stirring blade, ethylene was continuously added.
A copolymerization reaction of 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene (Table 3) (a): DMON hereinafter was carried out. . That is, a cyclohexane solution of DMON from the upper part of the polymerization vessel, 0.4 l / h so that the DMON concentration in the polymerization vessel was 60 g / l, and a cyclohexane solution of VO (OC ₂ H ₅ ) Cl ₂ as a catalyst in the polymerization vessel. Of vanadium to 0.7 mmol / l per hour (the concentration of vanadium supplied at this time is 2.86 times the concentration in the polymerization vessel), ethylaluminum sesquichloride (Al (C ₂ H ₅ ) ₁₅ Cl ₁₅ The cyclohexane solution of) was continuously fed into the polymerization vessel at a rate of 0.4 l / hr and cyclohexane at a rate of 0.5 l / hr so that the aluminum concentration in the polymerization vessel was 5.6 mmol / l. Withdrawing continuously so that the polymerization liquid in the polymerization vessel is always 1. In addition, ethylene is fed from the top of the polymerization vessel every hour.
80 liters, 80 liters of nitrogen per hour, and 0.2 liters of hydrogen per hour are supplied. The copolymerization reaction was carried out at 10 ° C. by circulating a refrigerant in a jacket attached outside the polymerization vessel. When the copolymerization reaction is carried out under the above conditions, a polymerization reaction mixture containing an ethylene / DMON random copolymer is obtained. A cyclohexane / isopropyl alcohol (1/1) mixed liquid was added to the polymerization liquid extracted from the lower part of the polymerization reactor to stop the polymerization reaction. Then, an aqueous solution prepared by adding 5 ml of concentrated hydrochloric acid to 1 part of water was brought into contact with the polymerization solution at a ratio of 1: 1 using a homomixer under strong stirring to transfer the catalyst residue to a water tank. The above-mentioned mixed solution was allowed to stand still, the water tank was removed, and further washed twice with distilled water to purify and separate the polymerization solution.

The obtained polymerization liquid was brought into contact with 3-fold amount of acetone under vigorous stirring, and the solid portion was collected by filtration and thoroughly washed with acetone. Then, the obtained solid part was put into acetone so as to be 40 g / l, and a reaction treatment was carried out at 60 ° C. for 2 hours. afterwards,
Collect the solid part by filtration, under nitrogen flow, 130 ℃, 350mm
It was dried with Hg for 24 hours.

As described above, the ethylene / DMON copolymer is 94 g / hr.
Obtained at the speed of. The ethylene content of the obtained copolymer is
61.3 mol%, intrinsic viscosity [η] is 0.85, measured by GPC w
/ n was 2.50, the crystallinity by X-ray diffraction was 0%, and the glass transition temperature Tg was 143 ° C. The volatile component is 0.4wt
%, And the unreacted monomer content was 0.13 wt%.

Examples 2 to 14 Copolymerization was continuously carried out in the same manner as in Example 1 except that the copolymerization conditions were as shown in Table 2. The physical properties obtained are shown in Table 2.

[Effect of the Invention] The cyclic olefin-based random copolymer of the present invention is transparent,
It has excellent 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 and excellent uniformity. Further, the cyclic olefin-based random copolymer 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 since the content of the low molecular weight polymer contained in the copolymer is small, it is in the field of optical materials. In particular, when it is molded for use as an optical memory disk, the surface smoothness and the disk strength are improved, and the surface tackiness is reduced.

Claims (1)

[Claims] 1. A cyclic olefin-based random copolymer obtained by polymerizing ethylene and a cyclic olefin represented by the following general formula [I] by a continuous polymerization method, wherein: (i) a repeating unit derived from ethylene. 40 to 97 mol% of (a) and 3 to 60 mol% of the repeating unit (b) derived from the cyclic olefin, and (ii) repeating unit (b) derived from the cyclic olefin.
Form a structure represented by the following general formula [II], and (iii) the intrinsic viscosity [η] measured in decalin at 135 ° C is
In the range of 0.01 to 20 dl / g, (iv) the molecular weight distribution (w / n) measured by gel permeation chromatography is 4 or less, and (v) the glass transition temperature [Tg] is 10 to 240 ° C. And (vi) the crystallinity measured by X-ray diffraction is 0 to
A cyclic olefin-based random copolymer characterized by being in the range of 10%. General formula [In the formula, n is 1 or 2, and R ¹ to R ¹⁰ each represent a hydrogen atom or an alkyl group]. General formula [In the formula, n and R ¹ to R ¹⁰ are the same as defined above. ]