JP2528488B2 - Method for producing cyclic olefin 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 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 It is intended to provide a manufacturing method.

[Prior Art] A binary copolymer of ethylene and a cyclic olefin, or an α-olefin and a cyclic olefin such as ethylene and propylene or 1-butene is generally used by a Ziegler type catalyst in which a titanium compound or a vanadium compound is combined with an organoaluminum compound. It is already known that a terpolymer can be obtained. However, there is no example in which a C3-C20 α-olefin is copolymerized with a cyclic olefin in the absence of ethylene in the form of a Ziegler type copolymer, and there is no report on such copolymers.

Further, as synthetic resins having excellent transparency, polycarbonate, polymethyl methacrylate, polyethylene terephthalate, and the like are known. For example, polycarbonate is a resin having excellent heat resistance, heat aging resistance and impact resistance as well as transparency. However, there is a problem that it is easily attacked by a strong alkali and has poor chemical resistance. Polymethyl methacrylate has a problem that it is easily attacked by ethyl acetate, acetone, toluene, etc., swells in ether, and has low heat resistance. Polyethylene terephthalate has excellent heat resistance and mechanical properties, but is susceptible to strong acids and alkalis, and is susceptible to hydrolysis.

On the other hand, polyolefins that are widely used as general-purpose resins are excellent in chemical resistance and solvent resistance, and also have many excellent mechanical properties, but many have poor heat resistance and are crystalline resins. Therefore, it is inferior in transparency. In general, to improve the transparency of polyolefin, a method of adding a nucleating agent to refine the crystal structure or quenching to stop crystal growth is used, but its effect is hardly 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-scale apparatus and is accompanied by a decrease in crystallinity. Therefore, heat resistance and rigidity may be reduced.

For the copolymerization of ethylene and bulky comonomers,
For example, U.S. Pat.No. 2,883,372 discloses 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 around 100 ° C and is poor in heat resistance. Also, ethylene and 5-ethylidene-2-
Norbornene copolymers have similar disadvantages.

JP-B-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. Further, JP-A-58-127728 discloses that
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 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 a drawback of poor heat aging resistance. In addition, a cyclic olefin random copolymer composed of ethylene and a specific bulky cyclic olefin has transparency while maintaining a balance of heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and mechanical properties. It is a well-developed synthetic resin and has excellent performance in the field of optical materials such as optical memory disks and optical fibers.
168708, JP-A-61-98780, JP-A-61-115
912, JP 61-115916, JP 61-12081
No. 6, Japanese Patent Application No. 61-95906 and Japanese Patent Application No. 61-95905. As described above, all of the copolymers proposed in these have copolymerized ethylene, and in particular, there has been a problem that a large amount of cyclic olefin must be copolymerized in order to impart heat resistance.

Therefore, there is a demand for a cyclic olefin-based random copolymer excellent in heat resistance even with a small cyclic olefin content.

[Problems to be solved by the invention]

The present inventors have excellent 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 have a particularly low cyclic olefin content. As a result of examining a new cyclic olefin-based random copolymer excellent in heat resistance, the number of carbon atoms was 3
A novel cyclic olefin-based random copolymer having the above objects achieved by copolymerizing α-olefin and cyclic olefin of 20 to 20 in the presence of a zirconium catalyst and a catalyst formed from alumoxane under specific conditions. The inventors have found that they can be obtained and reached the present invention.

[Means for Solving the Problems] and [Action] According to the present invention, (A) at least two indenyl groups, a substituted indenyl group or a substituted indenyl group, or an α-olefin having 3 to 20 carbon atoms and a cyclic olefin. Polymerization is carried out in the presence of a catalyst formed from a zirconium compound having a ligand whose partial hydride is bonded via an alkylene group such as ethylene group, and (B) aluminoxane. A cyclic olefin-based random copolymer comprising an α-olefin component having 3 to 20 carbon atoms and a cyclic olefin component, which is characterized in that: (i) Repeats derived from the α-olefin component having 3 to 20 carbon atoms 5 to 99 mol% of units and 1 to 95 mol% of repeating units derived from the cyclic olefin component
(Ii) Intrinsic viscosity [η] measured in decalin at 135 ° C
Is provided in the range of 0.01 to 10 dl / g.

The cyclic olefin random copolymer according to the present invention is a cyclic olefin random copolymer composed of an α-olefin component having 3 to 20 carbon atoms and a cyclic olefin component. The cyclic olefin component is a cyclic olefin component represented by the following general formulas [I], [II] and [III], and in the cyclic olefin random copolymer according to the present invention, the cyclic olefin component has the general formula A structure represented by [IV], [V] or [VI] is formed.

General formula Wherein a and b are each an integer of 0 or more, c and d are each an integer of 3 or more, and R ¹ to R ¹⁰ each represent a hydrogen atom, a halogen atom or a hydrocarbon group. ] General formula Wherein a, b, c, d and R ¹ to R ¹⁰ are the same as described above. In the method for producing a cyclic olefin random copolymer of the present invention, specific examples of the α-olefin used as a polymerization raw material include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1 Examples thereof include α-olefins having 3 to 20 carbon atoms such as octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

Further, in the method for producing a cyclic olefin random copolymer of the present invention, the cyclic olefin used as a polymerization raw material is an unsaturated monomer represented by the general formulas [I], [II] and [III]. It is at least one cyclic olefin selected from the group consisting of: 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] can also be produced. Similarly, cyclopentadiene and a corresponding cyclic olefin
It can be easily produced by condensation by 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, 2,3-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,
Octahydronaphthalenes such as 4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, and Table 1
The compounds described in 1 can be exemplified.

Specific examples of the cyclic olefin represented by the general formula (II) include the compounds shown in Table 2 and the like.

Further, as the cyclic olefin represented by the general formula [III], specifically, for example, cyclopentene, 3-methylcyclopentene, 4-methylmethylcyclopentene, 3,
4-dimethylcyclopentene, 3,5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene, 3
-Methylcyclohexene, 4-methylcyclohexene,
Examples thereof include 3,4-dimethylcyclohexene, 3-chlorocyclohexene and cycloheptene.

In the cyclic olefin random copolymer according to the present invention, the repeating unit derived from the α-olefin component having 3 to 20 carbon atoms is 5 to 99 mol%, preferably 15 to 95 mol%, particularly preferably 30 to 90 mol%. Mol%, the repeating unit derived from the cyclic olefin component is 1 to 95 mol%, preferably 5 to 85 mol%, particularly preferably 10 to 70 mol%, and the carbon number is 3 to 20. The repeating units derived from the α-olefin component and the repeating units derived from the cyclic olefin component form a substantially linear cyclic olefin-based random copolymer randomly arranged. The fact that the cyclic olefin random copolymer according to the present invention is substantially linear and does not have a gel-like crosslinked structure can be confirmed by completely dissolving the copolymer in decalin at 135 ° C.

13 of the cyclic olefin random copolymer according to the present invention
The intrinsic viscosity [η] measured in decalin at 5 ° C is in the range of 0.01 to 10 dl / g, preferably 0.05 to 7 dl / g, particularly preferably 0.1 to 5 dl / g.

The molecular weight distribution (▲ ▼ / ▲ ▼) of the cyclic olefin random copolymer according to the present invention measured by gel permeation chromatography (GPC) is usually 4 or less, preferably 3.5 or less, and particularly preferably 3 or less. .

The glass transition temperature (Tg) of the cyclic olefin random copolymer according to the present invention is in the range of 10 to 240 ° C, preferably 20 to 200 ° C.

The cyclic olefin random copolymer according to the present invention,
(A) At least two indenyl groups, substituted indenyl groups or partial hydrides thereof are bonded to an α-olefin having 3 to 20 carbon atoms and a predetermined amount of the cyclic olefin via an alkylene group such as an ethylene group. It can be produced by polymerizing in the presence of a zirconium compound having a form of a ligand as a ligand and (B) an aluminoxane.

The zirconium compound has two or more indenyl groups,
It may have a substituted indenyl group or a partial hydride thereof, but one having two indenyl groups, a substituted indenyl group or a partial hydride thereof is preferable.

Examples of the zirconium compound include ethylene bis (indenyl) zirconium dichloride, ethylene bis (indenyl) zirconium monochloride monohydride, ethylene bis (indenyl) ethoxy zirconium chloride, ethylene bis (4,5,6,7-tetrahydro-1-) (Indenyl) ethoxy zirconium chloride, ethylene bis (indenyl) dimethyl zirconium, ethylene bis (indenyl) diethyl zirconium, ethylene bis (indenyl) diphenyl zirconium, ethylene bis (indenyl) dibenzyl zirconium, ethylene bis (indenyl) methyl zirconium monobromide, ethylene Bis (indenyl) ethyl zirconium monochloride, ethylenebis (indenyl) benzyl zirconium monochloride Ethylene bis (indenyl) methyl zirconium monochloride, ethylene bis (indenyl) zirconium dichloride, ethylene bis (indenyl) zirconium dibromide, ethylene bis (4,5,6,7-tetrahydro-1-indenyl) dimethyl zirconium, ethylene bis ( 4,5,6,7-tetrahydro-1-indenyl) ethyl zirconium ethoxide, ethylenebis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, ethylenebis (4,5,6,7- Tetrahydro-1-indenyl) zirconium dibromide, ethylenebis (4-methyl-1-indenyl) zirconium dichloride, ethylenebis (5-methyl-1-indenyl) zirconium dichloride, ethylenebis (6-methyl-1-indenyl) zirconium Dichloride, Ethylenebis (7-methyl-1-indenyl) zirconium dichloride, ethylenebis (2,3-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4,7-dimethyl-1-indenyl) zirconium dichloride, ethylenebis (4 , 7-Dimethoxy-1-indenyl)
Zirconium dichloride, and the like.

The aluminoxane used as the catalyst component (B) is represented by the general formula [VII] and the general formula [VIII] The organoaluminum compound represented by can be exemplified. In the aluminoxane, R is a methyl group,
Ethyl group, n-propyl group, isopropyl group, n-butyl group, hydrocarbon groups such as isobutyl group, preferably methyl group, ethyl group, isobutyl group, particularly preferably methyl group, m is 2 or more, It is preferably an integer of 5 or more. The following method can be exemplified as a method for producing the aluminoxane.

(1) Compounds containing adsorbed water, salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, primary chloride
A method in which a trialkylaluminum is added to a hydrocarbon medium suspension such as cerium hydrate and reacted.

(2) A method in which water is allowed to act directly on a trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.

Among these methods, the method (1) is preferably adopted. The aluminoxane may contain a small amount of organic metal component.

The catalyst components (A) and (B) may be used as they are or supported on a carrier. Examples of the carrier include inorganic compounds such as silica and alumina, and organic high molecular compounds such as polyethylene and polypropylene.

In the present invention, it has never been proposed by producing a copolymer of an α-olefin having a carbon number in the range of 3 to 20 and the cyclic olefin in a specific ratio using the above catalyst system. It was found that a copolymer having properties can be obtained. The copolymerization of the α-olefin having 3 to 20 carbon atoms with the cyclic olefin can be carried out in either the liquid phase or the gas phase, but is particularly preferably carried out in the liquid phase. In the liquid phase,
It is usually carried out in a hydrocarbon medium. Specific examples of the hydrocarbon medium include aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, and octadecane; alicyclics such as cyclopentane, methylcyclopentane, cyclohexane, and cyclooctane. In addition to hydrocarbons, aromatic hydrocarbons such as benzene, toluene, and xylene, petroleum fractions such as gasoline, kerosene, and gas oil, olefins as raw materials can be mentioned as the hydrocarbon medium. Of these hydrocarbon media, aromatic hydrocarbons are preferred.

In the method of the present invention, the temperature during the polymerization reaction is usually −
It is in the range of 50 to 230 ° C, preferably -30 to 200 ° C.

The ratio of the zirconium compound used when the method of the present invention is carried out by the liquid phase polymerization method is usually 10 ⁻⁸ to 10 ⁻² g atom / as the concentration of zirconium metal atom in the polymerization reaction system.
l, preferably in the range of 10 ⁻⁷ to 10 ⁻³ gram atom / l. The aluminoxane content is usually 10 ^-4 to 10 as the concentration of aluminum atoms in the polymerization reaction system.
^-1 gram atom / l, preferably in the range of 10 ^-3 to 5 × 10 ^-2 gram atom / l, and the ratio of aluminum atom to transition metal atom in the polymerization reaction system is usually 4 to 10
⁷ , preferably in the range 10 to 10 ⁶ . The molecular weight of the copolymer can be adjusted by hydrogen and / or polymerization temperature.

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 With a narrow composition distribution and excellent uniformity,
For example, its low molecular weight is used as a synthetic wax for candles, match stem impregnating agents, paper processing agents, sizing agents, rubber anti-aging agents, corrugated water resistance agents, chemical fertilizer retarding agents, heat storage agents, ceramic binders, paper capacitors, Electric insulation materials such as electric wires and cables, neutron moderators, fiber processing aids,
Building material water repellent material, paint protective agent, polishing agent, thixotropy imparting agent, pencil / crayon core curing imparting agent, carbon ink base material, electrostatic copying toner, synthetic resin molding lubricant, mold release agent, resin colorant, It can be used in fields such as hot melt adhesives and lubricating greases. In addition, the high molecular weight material is used in optical fields such as optical lenses, optical disks, optical fibers, and glass windows, water tanks for electric irons, microwave oven supplies, liquid crystal display substrates, printed circuit boards, high frequency circuit boards,
Electric fields such as transparent conductive sheets and films, syringes,
It can be used in various fields such as medical fields such as pipettes and animal gauges, chemical fields, camera bodies, housings for various instruments, films and helmets.

On the other hand, when the content of the cyclic olefin component is about 20 mol% or less, it can be used as a field utilizing shape memory, as a vibration damping material or as a tube. Concretely, vibration damping material (sound proofing material) as a laminate with deformed pipe joints, inner and outer laminating materials of pipes and rods, optical fiber connector tightening pins, casts, containers, automobile bumpers, various gap preventing materials, metal surface materials Materials) or medical tubes.

〔Example〕

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

[Polymer physical property measurement method]

Copolymer composition [mol%]; Content of cyclic olefin component unit of cyclic olefin random copolymer was determined by 13 C-NMR (200 MHz).

[Η]; Intrinsic viscosity was measured at 135 ° C. using an Ubelode viscometer.

Molecular weight distribution [▲ ▼ / ▲ ▼]; by GPC method.

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

Example 1 [Preparation of ethylene bis (indenyl) zirconium dichloride] A 200 ml glass flask sufficiently purged with nitrogen was charged with 60 ml of tetrahydrofuran, and then cooled to -78 ° C. Then, 4.9 g of zirconium tetrachloride was added, the temperature was gradually raised to 60 ° C, and stirring was continued at 60 ° C for 1 hour to form a solution. Continued,
Bis (indenyl) dissolved in 50 ml of tetrahydrofuran
21 mmol of a lithium salt of ethane was added, and the mixture was stirred at 60 ° C for 1 hour and then at 25 ° C for 12 hours. Then, tetrahydrofuran was removed under reduced pressure to obtain a solid. The solid was washed with methanol and dried under reduced pressure. 2.1 g of ethylenebis (indenyl) zirconium dichloride were obtained.

(Preparation of aluminoxane)

Al ₂ (SO ₄ ) _{3 is} placed in a 400 ml flask which is sufficiently purged with nitrogen.
・ Charge 37g of 14H ₂ O and 125ml of toluene, cool to 0 ℃,
Trimethylaluminum diluted with 125 ml of toluene 500 mm
ol was added dropwise. Next, the temperature was raised to 40 ° C., and the reaction was continued at that temperature for 10 hours. After the reaction, solid-liquid separation is performed by excess,
Further, toluene was removed from the liquid to obtain 13 g of a white solid aluminoxane. The molecular weight determined by freezing point depression in benzene is 930, and the catalyst component (B)
The m value shown therein was 14. It was redissolved in toluene and used for the polymerization.

(Conjugation)

After charging 500 ml of purified toluene and 15 g of tetracyclododecene into a 1000 ml glass autoclave sufficiently replaced with nitrogen, propylene gas was passed at 60 l / h and kept at 20 ° C for 10 minutes. Then, aluminoxane corresponding to 5 mg of aluminum atom and ethylenebis (indenyl) zirconium dichloride dissolved in toluene corresponding to 0.5 × 10 ^-2 mg of zirconium atom were charged to initiate polymerization. . After carrying out the polymerization at 20 ° C. for 2 hours under normal pressure, the polymerization was stopped with isopropanol. The polymerization proceeded in a uniform solution state, and absorption of propylene was observed even after 2 hours of polymerization. The polymer solution was added to a large amount of a mixed solution of methanol / acetone to precipitate a polymer, which was dried overnight at 120 ° C. under reduced pressure. The polymer yield after drying is
It was 6.1 g and the activity per unit zirconium was 60 g polymer / milligram atom Zr · hr. The propylene content of the obtained copolymer was 75 mol% and the intrinsic viscosity [η] was 0.09.
dl / g, G / PCG ▲ ▼ / ▲ ▼ was 1.48, and glass transition temperature Tg was 78 ° C.

Examples 2 to 9 Copolymerization was carried out in the same manner as in Example 1 except that the copolymerization conditions were as shown in Table 3. Table 3 shows the obtained physical properties.

 ─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-51-149391 (JP, A) JP-A-61-221206 (JP, A) JP-A-61-272216 (JP, A) JP-A-60- 168708 (JP, A) JP 61-115916 (JP, A) JP 61-115912 (JP, A) JP 61-98780 (JP, A)

Claims (1)

(57) [Claims] 1. An α-olefin having 3 to 20 carbon atoms and a cyclic olefin are bonded to each other by (A) at least two indenyl groups, a substituted indenyl group or a partial hydride thereof are bonded via an alkylene group such as an ethylene group. Zinc compound having the above-mentioned form as a ligand, and (B) aluminoxane, are polymerized in the presence of a catalyst to form an α-olefin component having 3 to 20 carbon atoms. A cyclic olefin-based random copolymer comprising a cyclic olefin component, and (i) 5 to 99 mol% of repeating units derived from the α-olefin component having 3 to 20 carbon atoms and repeating units derived from the cyclic olefin component. Unit is 1 to 95 mol%
(Ii) Intrinsic viscosity [η] measured in decalin at 135 ° C
Is in the range of 0.01 to 10 dl / g, and a method for producing a cyclic olefin-based random copolymer.