JP2647409B2 - New olefin random copolymer - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a novel olefin-based random copolymer. More specifically, transparency, heat resistance, heat aging resistance,
To provide an olefin-based random copolymer having excellent chemical resistance, solvent resistance, dielectric properties and various mechanical properties, narrow molecular weight distribution and composition distribution, and having a carbon-carbon unsaturated bond in a side chain. Aim.

[Conventional technology]

Generally, a binary copolymer of ethylene and a cyclic olefin, or a terpolymer of an ethylene and a α-olefin such as propylene or 1-butene and a cyclic olefin by a Ziegler catalyst combining a titanium compound or a vanadium compound with an organoaluminum compound Is already known. 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 strong alkalis 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 widely used as general-purpose resins are excellent in chemical resistance, solvent resistance, and also excellent in mechanical properties, but many are poor in heat resistance, and because they are crystalline resins Poor 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, this copolymer has an excellent balance between rigidity and transparency, but has a glass transition temperature of around 100 ° C. and is inferior 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 with a norbornene-type comonomer has been proposed. However, it is clear from the above-mentioned publication that all of the polymers are ring-opening polymers. Since such a ring-opened polymer has an unsaturated bond in the polymer main chain, heat resistance,
It has a drawback of poor heat aging resistance. In addition, while the olefin random copolymer comprising ethylene and a specific bulky cyclic olefin has transparency, heat resistance, heat aging resistance, chemical resistance, solvent resistance, dielectric properties, balance of mechanical properties. Japanese Patent Application Laid-Open No. 60-168708 discloses that the synthetic resin is excellent in performance in the field of optical materials such as optical memory disks and optical fibers.
JP-A-61-98780, JP-A-61-115912, JP-A-61-115916, JP-A-61-120816, Japanese Patent Application No. 61-95906, Japanese Patent Application No. 61-95905. As described above, all of the copolymers proposed therein are copolymerized with ethylene. In particular, a large amount of cyclic olefin must be copolymerized in order to impart heat resistance.

Further, in order to impart polarity to the copolymer, it is usually necessary to use a peroxide to react with maleic anhydride or the like, and in this case, the molecular weight is reduced due to cleavage of the main chain.

Therefore, there is a demand for an olefin random copolymer which is excellent in heat resistance even with a small content of cyclic olefin and which can be modified without using peroxide.

[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, narrow molecular weight distribution and composition distribution, low cyclic olefin content. Studies on novel olefin-based random copolymers that have excellent heat resistance and have a carbon-carbon unsaturated bond in the side chain that can react with maleic anhydride, etc., and therefore can be easily modified for various purposes. As a result, the above object was achieved by copolymerizing an α-olefin having 3 to 20 carbon atoms, a cyclic polyene and a cyclic olefin under specific conditions in the presence of a catalyst formed from a zirconium catalyst and an aluminoxane. The present inventors have found that a novel olefin-based random copolymer can be obtained and arrived at the present invention.

According to the present invention, a linear or branched α-olefin component having 3 to 20 carbon atoms (A), 1,3-cyclopentadiene, 3-cyclohexadiene, 5-ethyl-1,3-
Cyclohexadiene, 1,3-cycloheptadiene, dicyclopentadiene, dicyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5-isopropylidene-2- Norbornene, methylhydroindene, 2,
At least one cyclic polyene component (B) selected from the group consisting of 3-diisopropylidene-5-norbornene, 2-ethyledene-3-isopropylidene-5-norbornene and 2-propenyl-2,5-norbornadiene; Formulas [I], [II] and [II]
I] [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. An olefin random copolymer comprising a cyclic olefin component (C) represented by at least one formula selected from the group consisting of: (i) 30 units of a repeating unit derived from the α-olefin component (A). To 90 mol% of the cyclic polyene component (B)
5 to 85 mol% of the repeating unit derived from the cyclic olefin component (C);
(Ii) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is in the range of 0.05 to 10 dl / g, and an olefin random copolymer is provided.

The olefin random copolymer of the present invention is an olefin random copolymer composed of an α-olefin component (A) having 3 to 20 carbon atoms, a cyclic polyene (B), and a cyclic olefin component (C). The components of the cyclic olefin are represented by the following general formulas [I], [II] and [III]
Wherein the cyclic olefin component forms a structure represented by the general formula [IV], [V] or [VI] in the olefin random copolymer of the present invention.

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 an olefin random copolymer of the present invention, specifically, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-hexene, -Octene, 1-
Examples thereof include α-olefins having 3 to 20 carbon atoms, such as decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

In addition, in the method for producing an olefin random copolymer of the present invention, specific examples of the cyclic polyene used as a polymerization raw material include 1,3-cyclopentadiene and 1,3
-Cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, dicyclopentadiene, dicyclohexadiene, 5-ethylidene-2-
Norbornene, 5-methylene-2-norbornene, 5-
Vinyl-2-norbornene, 5-isopropylidene-2
-Norbornene, methylhydroindene, 2,3-diisopropylidene-5-norbornene, 2-ethyledene-3
-Isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene and the like.

In the method for producing an olefin random copolymer of the present invention, the cyclic olefin used as a polymerization raw material, if necessary, may be any of the cyclic olefins represented by the general formulas [I], [II] and [III]. It is at least one type of 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 a cyclopentadiene and a corresponding olefin by a Diels-Alder reaction, and the cyclic olefin represented by the general formula [II] is also usable. Similarly, it can be easily produced by condensing cyclopentadiene and a corresponding cyclic olefin by a Diels-Alder reaction. Specific examples of the cyclic olefin represented by the general formula [I] include, in addition to 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4
a, 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-1,2,3,4,4
a, 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-1,2,3,4,4a, 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-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a- Examples include octahydronaphthalenes such as octahydronaphthalene and the compounds described in Table 1.

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

In the olefin random copolymer of the present invention, the repeating unit derived from the α-olefin component (A) having 3 to 20 carbon atoms has 5 to 99 mol%, preferably 15 to 95 mol%, particularly preferably 30 to 95 mol%. In the range of 90 mol%, and 1 to 95 mol%, preferably 5 to 85 mol% of the repeating unit derived from the cyclic polyene component (B);
Particularly preferably, it is in the range of 10 to 70 mol%, and the repeating unit derived from the cyclic olefin component (C) is in the range of 0 to 90 mol%, preferably 2 to 80 mol%, particularly preferably 5 to 70 mol%. And has 3 to 3 carbon atoms
20 repeating units derived from the α-olefin component (A), the cyclic polyene component (B) and the repeating unit derived from the cyclic olefin component (C) are randomly arranged substantially linear olefin random copolymers. Is formed. That the olefin random copolymer of the present invention is substantially linear and does not have a gel-like crosslinked structure,
This can be confirmed by the complete dissolution of the copolymer in decalin at 135 ° C.

The intrinsic viscosity [η] of the olefin random copolymer of the present invention measured in decalin at 135 ° C. is 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 olefin random copolymer of the present invention measured by gel permeation chromatography (GPC) is usually 4 or less, preferably 3.5 or less, particularly preferably 3 or less.

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

The zirconium compound has two or more indenyl groups,
It can have a substituted indenyl group or a partially hydride thereof, but preferably has two indenyl groups, a substituted indenyl group or a partially hydride thereof.

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.

As the aluminoxane used as the catalyst component (B), general formulas [VII] and [VIII] The organic aluminum compound represented by these can be illustrated. 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 suspension of a hydrocarbon medium such as cerium hydrate to cause a reaction.

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

Among these methods, it is preferable to adopt the method (1). The aluminoxane may contain a small amount of an 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 been conventionally proposed to produce a copolymer of α-olefin having 3 to 20 carbon atoms, a cyclic polyene and a cyclic olefin at a specific ratio by using the above catalyst system. It has been found that a copolymer having unprecedented properties can be obtained.
The copolymerization of the α-olefin having 3 to 20 carbon atoms with the cyclic polyene and the cyclic olefin is carried out in a liquid phase,
Although it can be carried out in any of the gas phase, it is particularly preferred to carry out in the liquid phase. When carried out 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. Among 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.

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

The olefin 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 has a molecular weight distribution and a composition distribution. Since it is narrow and excellent in uniformity, for example, its low molecular weight compound is used as a synthetic wax for candles, matchwood impregnating agents, paper processing agents, sizing agents, rubber antioxidants, corrugated cardboard waterproofing agents, chemical fertilizer retarders, 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.

Furthermore, since the novel random olefin copolymer of the present invention has a carbon-carbon unsaturated bond in the side chain, vulcanization and modification are easy.

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

[Polymer physical property measurement method]

Copolymer composition [mol%]; The content of the cyclic olefin component unit of the 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.

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
After adding 21 mmol of a lithium salt of ethane, the mixture was stirred at 60 ° C. for 1 hour, and then stirred 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 ° C,
Trimethylaluminum 500mm diluted with 125ml of toluene
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 aluminoxane as a white solid. The molecular weight determined by freezing point depression in benzene is 930, and the catalyst component (B)
The m value shown therein was 14. For polymerization, it was redissolved in toluene before use.

〔polymerization〕

After 500 ml of purified toluene and 15 g of 5-ethyledene-2-norbornene were charged into a 1000 ml glass autoclave sufficiently purged with nitrogen, propylene gas was passed at 60 / h, and the mixture was kept at 20 ° C. for 10 minutes. Subsequently, aluminoxane equivalent to 5 milligram atoms in terms of aluminum atoms,
Ethylene bis (indenyl) dissolved in toluene equivalent to 0.5 × 10 ^-2 milligram atoms in terms of zirconium atoms
The polymerization was initiated by charging zirconium dichloride. 20 ℃
For 4 hours under normal pressure, and then terminated with isopropanol. Polymerization proceeds in a homogeneous solution state,
Even after 4 hours of polymerization, absorption of propylene was observed. 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 was 2.2 g, the propylene content of the obtained copolymer was 66 mol%, the intrinsic viscosity [η] was 0.16 dl / g, and the GPC
▲ ▼ / ▲ ▼ by measurement was 1.41.

Examples 2 to 8 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 the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location C08F 232/08 C08F 232/08 (56) References JP-A-61-148211 (JP, A) JP-A Sho51 -149391 (JP, A) JP-A-61-221206 (JP, A)

Claims (1)

(57) [Claims] 1. A linear or branched α-olefin component having 3 to 20 carbon atoms (A), 1,3-cyclopentadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene. 1,3-cycloheptadiene, dicyclopentadiene, dicyclohexadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 5-isopropylidene-2-norbornene, Methylhydroindene, 2,3
At least one cyclic polyene component (B) selected from the group consisting of -diisopropylidene-5-norbornene, 2-ethyledene-3-isopropylidene-5-norbornene and 2-propenyl-2,5-norbornadiene;
And the following general formulas [I], [II] and [III] [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. An olefin random copolymer comprising a cyclic olefin component (C) represented by at least one formula selected from the group consisting of: (i) 30 units of a repeating unit derived from the α-olefin component (A). To 90 mol% of the cyclic polyene component (B)
5 to 85 mol% of the repeating unit derived from the cyclic olefin component (C);
(Ii) intrinsic viscosity [η] measured in decalin at 135 ° C.
Is in the range of 0.05 to 10 dl / g, the olefin-based random copolymer.