JPH01156308A - Novel cyclic olefin random copolymer - Google Patents

Abstract

PURPOSE:To obtain the title copolymer having excellent transparency, heat (aging) resistance, chemical resistance, solvent resistance, dielectric characteristics, etc. and narrow molecular weight distribution and composition distribution, by polymerizing an alpha-olefin and a cyclic olefin in the presence of a specified catalyst. CONSTITUTION:A 3-20C alpha-olefin (A) (e.g., 4-methyl-1-pentene) and a cyclic olefin (B) (e.g., tetracyclododecene) are polymerized at -50-230 deg.C in the presence of a catalyst (C) consisting of a Zr compound (a) having a ligand in which two or more (substituted) indenyl groups or said groups partially hydrogenated are bound to one another through an alkylene group such as an ethylene group, and aluminooxane (b), thus giving the title copolymer which consists of 5-99mol.% repeating units derived from component A and 1-95mol.% repeating units derived from component B and has an intrinsic viscosity (at 135 deg.C, in decalin) of 0.01-10dl/g, a molecular weight distribution (by gel permeation chromatography) of 4 or greater, and a glass transition temperature of 10-240 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel cyclic olefin random copolymer. More specifically, we are developing a cyclic olefin random copolymer that 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 purpose is to provide.

[Conventional technology]

Generally, a Ziegler type catalyst combining a titanium compound or a vanadium compound and an organoaluminum compound is used to produce a binary copolymer of ethylene and a cyclic olefin, or a ternary copolymer of ethylene and an α-olefin such as propylene or 1-butene and a cyclic olefin. It is already known that it can be obtained. However, there is no example of Ziegler-type copolymerization of an α-olefin having 3 to 20 carbon atoms with a cyclic olefin in the absence of ethylene, and naturally there are no reports on such copolymers.

Also, known synthetic resins with excellent transparency include polycarbonate, polymethyl methacrylate, and polyethylene terephthalate.

For example, polycarbonate is a resin that has excellent heat resistance, heat aging resistance, and impact resistance as well as transparency. However, there is a problem that it is easily attacked by strong alkalis and has poor chemical resistance. Polymethyl methacrylate has problems in that it is easily attacked by ethyl acetate, acetone, toluene, etc., swells in ether, and has low heat resistance. Furthermore, although polyethylene terephthalate has excellent heat resistance and mechanical properties, it is susceptible to strong acids and alkalis and is susceptible to hydrolysis.

On the other hand, polyolefins, which are widely used as general-purpose resins, have excellent chemical resistance, solvent resistance, and mechanical properties, but many have poor heat resistance, and because they are crystalline resins, Less transparent. Generally, to improve the transparency of polyolefins, methods are used to refine the crystal structure by adding a nucleating agent, or to stop crystal growth by rapid cooling, but these methods are not very effective. Adding a third component such as a nucleating agent may impair the excellent properties originally possessed by polyolefins, and the rapid cooling method requires large-scale equipment, and the heat resistance decreases as the degree of crystallinity decreases. There is a possibility that the strength and rigidity may also decrease.

Regarding the copolymerization of ethylene and bulky comonomers, for example, U.S. Pat. No. 2,883,372 discloses a copolymer of ethylene and 2,3-dihydrodicyclopentadiene. However, although this copolymer has an excellent balance of rigidity and transparency, its glass transition temperature is 100°C.
It is close to that and has poor heat resistance. Also, copolymers of ethylene and 5-ethylidene-2-norbornene have similar drawbacks.

In addition, 1.4.5.
8-dimethano-1,2,3,4,4a, 5.8.8a
- A homopolymer of octahydronaphthalene has been proposed, but this polymer has poor heat resistance and heat aging resistance. Seri et al., JP-A-58-127728, 1, 4, 5
．． 8-dimethano-1,2,3,4゜4a, 5.8.8
Although a homopolymer of a-octahydronaphthalene or a copolymer of the cyclic olefin and a norbornene type comonomer has been proposed, it is clear from the description in the above publication that these polymers are ring-opening polymers. It is. Since such ring-opened polymers have unsaturated bonds in the polymer main chain, they have the disadvantage of poor heat resistance and heat aging resistance. In addition, the cyclic olefin-based random copolymer consisting of ethylene and a specific bulky cyclic olefin has a balance of heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and mechanical properties while maintaining transparency. JP-A-60-168708 and JP-A-6
1-98780, JP-A-61-115912, JP-A-61-115916, JP-A-61-1
This is proposed in Japanese Patent Application No. 20816, Japanese Patent Application No. 61-95906, and Japanese Patent Application No. 61-95905. As mentioned above, all of these proposed copolymers are copolymerized with ethylene, and in particular, they have the disadvantage that a large amount of cyclic olefin must be copolymerized in order to provide them with heat resistance.

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

[Problem that the invention seeks to solve]

The present inventors have demonstrated excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties.
As a result of investigating a new cyclic olefin-based random copolymer with a narrow molecular weight distribution and composition distribution and excellent heat resistance even with a particularly low cyclic olefin content, we found that α-olefins and cyclic olefins having 3 to 20 carbon atoms were combined with zirconium The present invention was accomplished by discovering that a novel cyclic olefin random copolymer that achieves the above object can be obtained by copolymerizing under specific conditions in the presence of a catalyst and a catalyst formed from alumoxane.

[Means for Solving the Problems] and [Operation] According to the present invention, there is provided a cyclic olefin-based random copolymer comprising an α-olefin component having 3 to 20 carbon atoms and a cyclic olefin component, ) 5 to 99 mol% of repeating units derived from an α-olefin component having 3 to 20 carbon atoms; and 1 to 95 mol% of repeating units derived from the cyclic olefin component, (i
i) Intrinsic viscosity [η] measured in decalin at 135°C
Provided is a cyclic olefin random copolymer characterized in that the amount of dIl/g is in the range of 0.01 to 10 dIl/g.

The cyclic olefin random copolymer of the present invention has 3 carbon atoms.
It is a cyclic olefin-based random copolymer composed of an α-olefin component and a cyclic olefin component of from 1 to 20. The components of the cyclic olefin are represented by the following general formula [1],
The cyclic olefin component is represented by [II] and [m], and in the cyclic olefin random copolymer of the present invention, the cyclic olefin component has the general formula [■],
It forms a structure represented by ['V] or [VI].

General formula [wherein a and b are both integers of 0 or more, C and d are integers of 3 or more, and R1 to R18 each represent a hydrogen atom, a halogen atom, or a hydrocarbon group. ] General formula [wherein a, b, C, d and R1 to R111 are the same as above. ] In the method for producing the cyclic olefin random copolymer of the present invention, the α-olefins used as polymerization raw materials are specifically propylene, ■-butene, 1-
hexene, 4-methyl-1-pentene, 1-octene,
Examples include α-olefins having 3 to 20 carbon atoms such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

Furthermore, in the method for producing the cyclic olefin random copolymer of the present invention, the cyclic olefins used as polymerization raw materials are represented by general formulas [1], [■] and general formula [m]. At least one cyclic olefin selected from the group consisting of unsaturated monomers. The cyclic olefin represented by the general formula [1] can be easily produced by condensing cyclopentadiene and the corresponding olefin in a Diels-Alder reaction, and the cyclic olefin represented by the general formula [11] Similarly, cyclic olefins can be easily produced by condensing cyclopentadiene and a corresponding cyclic olefin in a Diels-Alder reaction. Specifically, the cyclic olefin represented by the general formula [1] includes, for example, 1.4.
5.8-dimethano-1,2,3,4,4a, 5.8.
In addition to 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
,4,4&, 5.8.8a-octahydronaphthalene, 2-methyl-3-ethyl-1,4,5,8-dimethano-1,2,3°4,4a, 5.8.8a-octa Hydronaphthalene, 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 1.2.3-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,"Lt,
5.8.8a-Octahydronaphthalene, 2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a
, octahydronaphthalenes such as 5.8.8a-octahydronaphthalene, and the compounds listed in Table 1.

Further, specific examples of the cyclic olefin represented by the general formula (m) include cyclopentene, 3-methylcyclopentene, 4-methylmethylcyclopentene, 3.4
-dimethylcyclopentene, 3.5-dimethylcyclopentene, 3-chlorocyclopentene, cyclohexene,
Examples include 3-methylcyclohexene, 4-methylcyclohexene, 3,4-dimethylcyclohexene, 3-chlorocyclohexene, and cycloheptene.

In the cyclic olefin random copolymer of the present invention,
5 to 99 mol% of repeating units derived from an α-olefin component having 3 to 20 carbon atoms, preferably 15 to 95 mol%, particularly preferably 30 to 90 mol%
1 to 95 mol%, preferably 5 to 85 mol% of repeating units derived from the cyclic olefin component.
The repeating units derived from the α-olefin component having 3 to 20 carbon atoms and the repeating units derived from the cyclic olefin component are arranged randomly, preferably in the range of 10 to 70 mol%. - Forms a substantially linear cyclic olefin random copolymer. The fact that the cyclic olefin random copolymer of 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.

135°C of the cyclic olefin random copolymer of the present invention
The intrinsic viscosity [η] measured in decalin is 0.01 to 10 dl/g, preferably 0.05 to 7 a/g.
g, particularly preferably from 0.1 to 5 dl! / g
within the range of

The molecular weight distribution (!11"i/1Jii) of the cyclic olefin random copolymer of the present invention measured by gel perminiscence chromatography (GPC) is usually 4 or less, preferably 3.5 or less, particularly preferably 3 or less It is.

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

The cyclic olefin random copolymer of the present invention comprises an α-olefin having 3 to 20 carbon atoms and a predetermined amount of the cyclic olefin, (A) at least two indenyl groups, substituted indenyl groups, or partially hydrogenated indenyl groups thereof; can be produced by polymerization in the presence of a catalyst formed from a zirconium compound having as a ligand a compound in which is bonded via an alkylene group such as an ethylene group, and (B) an aluminoxane. can.

The above-mentioned zirconium compound can have two or more indenyl groups, substituted indenyl groups, or partially hydrogenated products thereof, and preferably has two indenyl groups, substituted indenyl groups, or partially hydrogenated products thereof.

Examples of the above zirconium compounds include ethylenebis(indenyl)zirconium dichloride, ethylenebis(indenyl)zirconium monochloride monohydride, ethylenebis(indenyl)ethoxyzirconium chloride, ethylenebis(4,5,6,7-tetrahydro-1- indenyl)ethoxyzirconium chloride, ethylenebis(indenyl)dimethylzirconium, ethylenebis(indenyl)diethylzirconium, ethylenebis(indenyl)diphenylzirconium, ethylenebis(indenyl)dibenzylzirconium, ethylenebis(indenyl)methylzirconium monopromide, Ethylene bis (indenyl) ethyl zirconium monochloride, ethylene bis (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)dimethylzirconium, ethylenebis(4,5,6,7-tetrahydro-1-indenyl)ethylzirconium 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-Simethyl-1-indenyl) zirconium dichloride, ethylenebis(4,7-simethoxy-1-indenyl)
Examples include zirconium dichloride.

The aluminoxane used as the catalyst component (B) has the general formula [■] and the general formula [■] R, AI-(-0-A
t), -0-AIR, [■]■ Organoaluminum compounds represented by the following can be exemplified. In the aluminoxane, R is a methyl group,
Hydrocarbon groups such as ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, preferably methyl group, ethyl group, isobutyl group, particularly preferably methyl group, m is 2 or more, Preferably it is 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 crystal water, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which trialkylaluminum is added to a suspension in a hydrocarbon medium and reacted.

(2) A method in which water is directly applied to trialkylaluminium in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran.

Among these methods, method (1) is preferably employed. Note that the aluminoxane may contain a small amount of organometallic 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 polymer compounds such as polyethylene and polypropylene. be able to.

In the present invention, a copolymer of a specific ratio of an α-olefin having 3 to 20 carbon atoms and the cyclic olefin is produced using the catalyst system as described above, which has not been previously proposed. It has been discovered that a copolymer having the following properties can be obtained. Carbon number is 3 to 20
The copolymerization of the cyclic olefin and the α-olefin within the above range can be carried out in either the liquid phase or the gas phase, but it is particularly preferable to carry out the copolymerization in the liquid phase. When carried out in the liquid phase, it is usually carried out in a hydrocarbon medium. Specifically, the hydrocarbon medium includes aliphatic hydrocarbons such as butane, isobutane, pentane, hexane, octane, decane, dodecane, hexadecane, and octadecane, cyclopenkune,
In addition to alicyclic hydrocarbons such as methylcyclopentane, cyclohexane, and cyclooctane, aromatic hydrocarbons such as benzene, toluene, and xylene, and petroleum fractions such as gasoline, kerosene, and light oil, raw material olefins are also carbonized. It can be used as a hydrogen medium. Among these hydrocarbon media, aromatic hydrocarbons are preferred.

In the method of the present invention, the temperature during the polymerization reaction is usually -5
The temperature range is from 0 to 230°C, preferably from -30 to 200°C.

When carrying out the method of the present invention by liquid phase polymerization, the proportion of the zirconium compound used is usually 10-8 to 10-2 gram atom/Q, preferably 10-2 as the concentration of zirconium metal atoms in the polymerization reaction system. It ranges from 7 to 10-3 gram atoms/Q. The proportion of aluminoxane to be used is usually in the range of 10-4 to 10-1 gram atom/Q, preferably 10-3 to 5X 10-2 gram atom/Q as the concentration of aluminum atoms in the polymerization reaction system. and the ratio of aluminum atoms to transition metal atoms in the polymerization reaction system is usually 4 to 107, preferably l
< is in the range of 10 to 106. The molecular weight of the copolymer can be adjusted by hydrogen and/or polymerization temperature.

The cyclic olefin random copolymer obtained by the method of the present invention has excellent transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, and various mechanical properties, and has excellent molecular weight distribution and Because of its narrow compositional distribution and excellent uniformity, its low molecular weight product can be used as a synthetic wax for waxing, pine wood impregnating agent, paper processing agent, sizing agent, rubber anti-aging agent, cardboard waterproofing agent, and slow-acting chemical fertilizer. heat storage agents, ceramic binders, paper capacitors, electrical insulation materials such as electric wires and cables, neutron moderators, textile processing aids, water-resistant building materials, paint protection agents, polishing agents, thixotropy imparting agents, pencils and crayons. It can be used in fields such as core hardening agents, carbon ink base materials, toners for electrostatic copying, lubricants for synthetic resin molding, mold release agents, resin colorants, hot melt adhesives, and lubricating greases. In addition, the polymer lid body is used in optical fields such as optical lenses, optical discs, optical fibers, and glass windows, water tanks for electric irons, microwave oven supplies, etc.
Liquid crystal display substrates, printed circuit boards, high frequency circuit boards, electrical fields such as transparent conductive sheets and films, medical fields such as syringes, pipettes, animal gauges, chemical fields, camera bodies, housings for various instruments, films, helmets, etc. It can be used in various fields.

On the other hand, when the cyclic olefin component content is about 20 mol % or less, it can be used in fields utilizing shape memory, vibration damping materials, or tubes. Specifically, fittings for odd-shaped pipes, laminate materials for the inside and outside of pipes and rods,
Optical fiber connectors can be tightened on bottles, casts, containers, etc.
It can be used in various fields such as automobile bumpers, various gap prevention materials, vibration damping materials (soundproofing materials) as laminates with metal surface materials, and medical tubes.

〔Example〕

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

[Polymer basic physical property measurement method]

Copolymer composition [mol%]; 13cm NMR (20
Calculate the content of cyclic olefin component units in the cyclic olefin random copolymer by [η); 1
The intrinsic viscosity was measured at 35°C using an Ubbelod viscometer.

Molecule jL distribution (!iri/M”ii): GPC
Law Niyor.

Glass transition temperature (Tg); Dyna manufactured by DuPont
mic mechanical analyzer (D
MA).

Example 1 [Preparation of ethylene bis(indenyl) zirconium dichloride] Tetrahydrofuran 60- was charged into a 200 m9 glass flask which was sufficiently purged with nitrogen, and then cooled to -78°C. Add 4.9g of zirconium tetrachloride to it, and add 60g of zirconium tetrachloride.
The temperature was gradually raised to .degree. C., and the mixture was stirred at 60.degree. C. for 1 hour to form a solution. Subsequently, 21 mmol of a lithium salt of bis(indenyl)ethane dissolved in 50 mmol of tetrahydrofuran was added, and the mixture was stirred at 60°C for 1 hour and then continued at 25°C for 12 hours. Thereafter, 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 was obtained.

[Preparation of aluminoxane]

A12 (300ml) was added to a 400ml flask that was sufficiently purged with nitrogen
4) Charge 2037 g of 3.14H and 125-g of toluene, and after cooling to 0°C, drop 500 mmol of trimethylaluminum diluted with 125- toluene. next,
- Shoichi The temperature was raised to 40°C, and the reaction was continued at that temperature for 10 hours.

After the reaction, solid-liquid separation was performed by filtration, and toluene was further removed from the furnace solution to obtain 13 g of white solid aluminoxane. The molecular weight determined by freezing point depression in benzene was 930, and the m
The value was 14. For polymerization, it was used after being redissolved in toluene.

[Overlapping]

After charging 500 g of purified toluene and 15 g of tetracyclododecene into a 1000+nlQ glass autoclave which had been sufficiently purged with nitrogen, propylene gas was passed through the autoclave at 60 g of the autoclave, and the autoclave was kept at 20° C. for 10 minutes. Next, aluminoxane equivalent to 5 milligram atoms in terms of aluminum atoms and ethylene bis(indenyl>zirconium dichloride) dissolved in toluene corresponding to 0.5X 10-2 milligram atoms in terms of zirconium atoms were charged to start polymerization. After polymerization was carried out at 20°C for 2 hours at normal pressure, the polymerization was stopped using an inproper tool.The polymerization proceeded in a homogeneous solution state, and absorption of propylene was observed even after 2 hours of polymerization. The polymer solution was added to a large amount of methanol/acetone mixture to precipitate the polymer and dried under reduced pressure at 120'C overnight.The polymer yield after drying was 6.1 g.
The activity per unit zirconium was 60 g polymer/milligram atom.hr. The propylene content of the obtained copolymer was 75 mol%, and the intrinsic viscosity [η] was 0.0.
9 dl/g - 57 anus by GPC measurement is 1. The 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 changed as shown in Table 3. The obtained physical properties are shown in Table 3.

death 'C 3) J'X

Claims (1)

[Claims] (1) A cyclic olefin random copolymer consisting of an α-olefin component having 3 to 20 carbon atoms and a cyclic olefin component, wherein (i) a repeating unit derived from the α-olefin component having 3 to 20 carbon atoms; 5 to 99 mol% and 1 to 95 repeating units derived from the cyclic olefin component.
(ii) the intrinsic viscosity [η
] is in the range of 0.01 to 10 dl/g.