JPH0655797B2 - Preparation of cyclic olefin-based random copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a cyclic olefin-based random copolymer. More specifically, a cyclic olefin-based random copolymer having excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties, and having a narrow molecular weight distribution and composition distribution is provided. It is intended to provide a method which can be produced in high yield.

[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. Although polyethylene terephthalate is still excellent in 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, U.S. Pat.No. 2,883,372 describes 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 apparent 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, heat resistance,
It has the drawback of being poor in 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 characteristics 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. 59-226828, Japanese Application No. 59-22682
No. 9 and Japanese Patent Application No. 59-242336. The cyclic olefin-based random copolymers proposed in these have the above-mentioned excellent performances, but in any of the methods for producing the copolymer, a catalyst formed from a soluble vanadium compound and an organoaluminum compound is used. Although the copolymerization reaction is carried out in the presence of, the yield of the copolymer per unit amount of the catalyst is low in any of the methods, and as a result, a large amount of the polymerization catalyst must be used. There is also a problem that the treatment becomes complicated when removing the catalyst component remaining in the copolymer. Therefore, in the production of the cyclic olefin-based random copolymer, it is desired to improve the copolymer yield per unit amount of catalyst.

[Problems to be solved by the invention]

The present inventors have developed a cyclic olefin-based random copolymer having excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties and various mechanical properties, and a narrow molecular weight distribution and composition distribution. As a result of examining a method that can be produced in high yield, it was found that the above-mentioned object can be achieved,
The present invention has been reached. According to the method of the present invention, the yield per unit amount of catalyst is improved, so that the amount of catalyst used can be reduced and, in addition, the catalyst component remaining in the produced polymer can be easily removed.

[Action for Solving Problems] and [Action] According to the present invention, it is composed of an unsaturated monomer represented by the following general formula [I] and general formula [II], which is pre-contacted with a soluble vanadium compound. A ring characterized by copolymerizing at least one cyclic olefin and ethylene selected from the group in the liquid phase consisting of a hydrocarbon medium in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound. A method for producing an olefin-based random copolymer is provided.

General formula [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].

In the method of the present invention, the soluble vanadium compound component used as a catalyst constituent is a vanadium compound component soluble in a hydrocarbon catalyst of a polymerization reaction system, 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 ≦
Representative examples are vanadium compounds represented by 4, 0 ≦ 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 ), V
Examples include Cl ₃ .20C ₈ H ₁₇ OH.

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,
Preferably, the hydrocarbon groups containing 1 to 4 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.

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).

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).

The general formula R ¹ _m AlH ₃ -m (wherein R ¹ is as defined 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, 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 sesquichloride, butyl aluminum sesquichloride, alkyl aluminum sesquihalides such as ethyl aluminum sesquibromide, ethyl aluminum dichloride, propyl aluminum dichloride, butyl aluminum dichloride Partially halogenated alkyl such as alkyl aluminum dihalides such as bromide 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 AlOA.
l (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 _{5) 4} and the like 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-under reaction, and the cyclic olefin represented by the general formula [II] is also available. Similarly, it can be easily prepared by condensing cyclopentadiene and the corresponding cyclic olefin by the Diels-under reaction. Specific examples of the cyclic olefin represented by the general formula [I] include 1,4,5,8-dimethano-1,2,3,4,4
In addition to a, 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-octahydro Naphthalene, 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-octahydro Naphthalene, 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-octahydro Naphthalene, 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-1,2,3,4,4
Examples include octahydronaphthalene such as a, 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.

In the method of the present invention, the cyclic olefin monomer is subjected to a pre-contact treatment with a soluble vanadium compound and then fed to a copolymerization reaction with ethylene. As the soluble vanadium compound used in the pre-contact treatment, the above-exemplified compounds can be similarly mentioned as the catalyst component, and a mixture of two or more thereof can also be used. The ratio of the soluble vanadium compound used is the cyclic olefin monomer 10
It is usually 0.05 to 50 mol, preferably 0.5 to 00 mol.
To 5 moles. The pre-contact treatment of the cyclic olefin monomer and the soluble vanadium compound can be carried out in the absence of a solvent, or can be carried out in the presence of a hydrocarbon medium. As the hydrocarbon medium, the hydrocarbon medium exemplified as the medium for the copolymerization reaction can be similarly mentioned. The temperature at the time of contact is usually -50 to 100 ° C, preferably 0 to 50 ° C, and the time required for contact is usually 0.01 to 20 min, preferably 0.05 to 5
It is in the range of min.

Examples of the method of the pre-contact treatment include a method of mixing both components in a tank-type mixing tank in the presence of a hydrocarbon medium, if necessary, and then contacting the mixture, and then supplying the mixture to a copolymerization reaction tank. Can be line-mixed in the presence of a hydrocarbon medium, if necessary, and contacted, and then the mixture is fed to a copolymerization reaction tank.

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 can also be copolymerized with an unsaturated monomer component.
Specific examples of the copolymerizable unsaturated monomer include propylene, 1-butene, and 4-methyl-1-pentene in a range of less than equimolar to the ethylene component unit in the random copolymer to be produced, 1-hexene, 1-octene, 1-
Examples thereof include α-olefin having 3 to 20 carbon atoms such as decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-octadecene and 1-eicosene.

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 by a continuous method or a batch method. The concentration of the soluble vanadium compound supplied to the polymerization reaction system at that time is usually 10 times or less, preferably 7 times the concentration of the soluble vanadium compound in the polymerization reaction system.
To 1 time, more preferably 5 to 1 time. 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 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 as vanadium atom.
0.01 to 5 gram atom / l, preferably 0.05 to 3
It is in the range of gram atom / l.

Further, in the method of the present invention, in addition to the soluble vanadium compound and the organoaluminum compound, it is also possible to carry out the copolymerization in the presence of other components such as an electron donor in the polymerization reaction system. 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.

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 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. The polymerization reaction mixture is continuously withdrawn from the polymerization reaction system. Also,
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 specific polymerization reaction is usually maintained above 0 and 50 kg / cm ² , preferably above 0 and 20 kg / cm ² , and an inert gas such as nitrogen or argon may be optionally 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 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 reaction mixture obtained by the copolymerization reaction in the method of the present invention is a solution of cyclic olefin-based random copolymer in a hydrocarbon medium, and the reaction mixture contains a soluble vanadium compound component and an organoaluminum compound component which are catalyst components. Also includes. The cyclic olefin-based random copolymer is obtained by contacting the polymerization reaction mixture with a poor solvent such as ketone or alcohol. If necessary, the separated copolymer may be subjected to treatment such as washing with a solvent or extraction.

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 has no DSC melting point and is measured by X-ray diffraction. From the results, the non-crystalline 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 temperature (Tg) of the cyclic olefin random copolymer is usually 10 to 240 ° C, preferably 20 to 2
It is in the range of 00 ° C.

〔Example〕

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

Examples 1-2, Comparative Examples 1-2 Using 10 polymerization vessels equipped with stirring blades, ethylene and 1,4,5,8-dimethano-1,2,3,4,4a, 5, were continuously fed. 8,8a-octahydronaphthalene Hereinafter, a copolymerization reaction of TCD) was performed. That is, a cyclohexane solution of TCD was introduced from the upper part of the polymerization vessel at a rate of 1.0 per hour so that the TCD concentration in the polymerization vessel was as shown in Table 3, and a cyclohexane solution of VO (OC ₂ H ₅ ) Cl ₂ was used as a catalyst in the polymerization vessel. So that the vanadium concentration at
Ethylaluminum sesquichloride _{(Al (C 2 H 5)} 1.5 Cl 1.5)
The cyclohexane solution of was continuously fed into the polymerization vessel at a rate of 3.0 so that the aluminum concentration in the polymerization vessel was in the condition shown in Table 3.

At this time, in Examples 1 and 2, the cyclohexane solution of TDC and the cyclohexane solution of vanadium were continuously fed into the polymerization vessel while being in contact with each other for about 1 minute by line mixing.
In Comparative Examples 1 and 2, the TCD cyclohexane solution and the vanadium cyclohexane solution were continuously supplied to the polymerization reactor through separate lines.

On the other hand, the polymerization liquid in the polymerization vessel was continuously discharged from the lower portion of the polymerization vessel so that the polymerization liquid was always 5. Further, 70 g of ethylene was continuously supplied from the upper portion of the polymerization vessel, and hydrogen was continuously supplied so that the concentration of hydrogen in the gas phase in the polymerization vessel was about 3 to 4%. Also, nitrogen was supplied at a rate of 400 per hour.

The copolymerization reaction was carried out at 13 ° C by circulating a refrigerant through a jacket attached outside the polymerization vessel. When the copolymerization reaction was carried out under the above conditions, a polymerization reaction mixture containing an ethylene / TCD random copolymer was obtained. To the polymerization liquid extracted from the lower part of the polymerization vessel, a small amount of methanol was added to stop the polymerization reaction, and the mixture was poured into a large amount of acetone / methanol,
The produced polymer was precipitated. The copolymer was thoroughly washed with acetone and then dried under reduced pressure at 80 ° C for 24 hours. Through the above operation, an ethylene / TCD random copolymer was obtained in a yield shown in Table 3. Ethylene composition of copolymer measured by ¹³ C-NMR analysis, 135 ° C
The intrinsic viscosity [η] measured in a decalin solvent is shown in Table 3.

[Effect of the Invention] According to the method of the present invention, the yield of the cyclic olefin-based random copolymer per unit amount of the catalyst is improved, so that it is possible to reduce the amount of the catalyst used. Is characterized in that it is easy to remove the remaining catalyst component. Further, 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 a molecular weight distribution and It is characterized by a narrow composition distribution and excellent uniformity.

Claims (1)

[Claims] 1. At least one cyclic olefin and ethylene selected from the group consisting of unsaturated monomers represented by the following general formulas [I] and [II], which have been pre-contacted with a soluble vanadium compound, A process for producing a cyclic olefin-based random copolymer, which comprises copolymerizing in a liquid phase composed of a hydrocarbon medium in the presence of a catalyst formed from a soluble vanadium compound and an organoaluminum compound. General formula [In the formula, n and m are both positive integers, l is an integer of 3 or more, and R ¹ to R each represent a hydrogen atom, a halogen atom, or a hydrocarbon group].