WO2018186619A1

WO2018186619A1 - Copolymer and method for manufacturing same

Info

Publication number: WO2018186619A1
Application number: PCT/KR2018/003648
Authority: WO
Inventors: 박소영; 수데반수지스
Original assignee: 에스케이이노베이션 주식회사; 에스케이종합화학 주식회사
Priority date: 2017-04-06
Filing date: 2018-03-28
Publication date: 2018-10-11
Also published as: KR102282288B1; KR20180113248A

Abstract

Disclosed are a copolymer and a method for manufacturing same, the copolymer improving in processability in accordance with lowered Mooney viscosity, and assuring elongation rate of 250% or greater. The copolymer according to the present invention is characterized by comprising ethylene, propylene, alpha-olefin having six or more carbons, and diene.

Description

Copolymer and its manufacturing method

FIELD OF THE INVENTION The present invention relates to copolymers and methods for their preparation, and more particularly, to quaternary copolymers comprising ethylene, alpha-olefins and dienes and methods for their preparation.

Ternary copolymers of ethylene, alpha-olefins and dienes have a molecular structure that does not have an unsaturated bond in the main chain, and weather resistance, chemical resistance and heat resistance, etc., are superior to common conjugated diene rubbers. Due to these characteristics, ternary elastic copolymers are widely used in various automotive parts materials, electric wire materials, construction and industrial materials such as hoses, gaskets, belts, bumpers or blends with plastics.

Such terpolymers have been prepared by copolymerizing three monomers using a catalyst mainly comprising a vanadium compound, for example, a vanadium-based Ziegler-Natta catalyst or a metallocene catalyst.

Currently, EPDM (ethylene-propylene-diolefin ternary copolymer), which is a ternary copolymer using propylene as an alpha-olefin, is mainly used in the industry. However, in recent years, there is an increasing demand for rubber using ternary copolymers having better mechanical properties and more advantageous in terms of productivity.

In particular, in the automotive industry, which occupies half of rubber applications using ternary copolymers, the demand for mechanical properties, heat resistance, and the like is increasing due to the weight reduction and luxury of automobiles.

Related prior art documents are Korean Patent Publication No. 10-1660480 (September 27, 2016), which discloses a ternary elastic copolymer including a diene and a method of manufacturing the same.

It is an object of the present invention to provide a copolymer having a low pattern viscosity, which has good processability, and which can secure an excellent elongation and a method of producing the same.

Copolymer according to an embodiment of the present invention for achieving the above object is characterized in that it comprises ethylene, propylene, alpha-olefin having 6 or more carbons and dienes.

The copolymer production method according to an embodiment of the present invention for achieving the above object comprises the step of polymerizing an ethylene monomer, a propylene monomer, an alpha-olefin monomer having 6 or more carbon atoms and a diene monomer in the presence of a catalyst composition. It is done.

The copolymer according to the present invention and a method for producing the same have a low pattern viscosity (1 + 4 to 125 ° C.) and diene is added in a high content ratio, such as roll, calendering, and extrusion. The workability is improved, which results in an increase in elongation.

As a result, the copolymer according to the present invention and the manufacturing method thereof can not only be excellent in workability but also can secure a high elongation. Therefore, it is easy to mold into a complicated shape, so that rubber parts such as automobiles and industrial products, wires, roofing sheets, etc. It is suitable for application to (roofing sheet).

Advantages and features of the present invention, and methods for achieving them will be apparent with reference to the embodiments described below. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various forms, and only the present embodiments are intended to complete the disclosure of the present invention, and the general knowledge in the art to which the present invention pertains. It is provided to fully inform the person of the scope of the invention and the invention is defined only by the scope of the claims.

Hereinafter, a copolymer according to an embodiment of the present invention and a manufacturing method thereof will be described in detail.

Copolymer according to an embodiment of the present invention comprises 30 to 80% by weight ethylene monomer, 1 to 50% by weight propylene monomer, 1 to 40% by weight alpha-olefin monomer and 1 to 10% by weight diene monomer, alpha-olefin Includes alpha-olefins having 6 or more carbon atoms.

Here, the copolymer according to the embodiment of the present invention has a weight average molecular weight of 100,000 to 300,000. As such, the copolymer according to the embodiment of the present invention may exhibit excellent mechanical properties as it has a weight average molecular weight of 100,000 to 300,000, more specifically 100,000 to 150,000.

Ethylene may be included in an amount ratio of 30 to 80% by weight, more specifically 45 to 70% by weight of the total weight of the copolymer, in order to impart suitable properties to the rubber parts of the complex form produced in the extrusion form. If the content of the ethylene monomer is less than 30% by weight, the strength is low, there is a problem that the extrusion processability is lowered or the physical properties such as tensile strength is weakened. On the contrary, when the content of the ethylene monomer exceeds 80% by weight, there is a problem that the generation of gel (Gel) during the polymerization is intensified.

Propylene lowers the pattern viscosity. The propylene monomer may be included in an amount ratio of 1 to 50% by weight, more specifically 5 to 20% by weight of the total weight of the copolymer. When the content of the propylene monomer is less than 1% by weight, it may be difficult to properly exert the above effects. On the contrary, when the content of the propylene monomer exceeds 50% by weight, the workability is improved as the elongation is increased, but there is a problem in that physical properties such as tensile strength are lowered due to a decrease in the amount of ethylene added.

Alpha-olefins are added to improve the physical properties such as mechanical properties, heat resistance. Such alpha-olefins may comprise alpha-olefins having 6 or more carbon atoms. More specifically, the alpha-olefin may include any one or more of alpha-olefins having 6 and 8 carbon atoms. More specifically, 1-hexene may be used as the alpha-olefin as an alpha-olefin having 6 carbon atoms, and 1-octene may be used as the alpha-olefin having 8 carbon atoms.

Such alpha-olefin monomer may be included in an amount ratio of 1 to 40% by weight, more specifically 15 to 35% by weight of the total weight of the copolymer. When the content of the alpha-olefin monomer is less than 1% by weight, it may be difficult to properly exert the above effects. On the contrary, when the content of the alpha-olefin monomer exceeds 40% by weight, there is a problem in that physical properties such as tensile strength are lowered due to a decrease in the amount of ethylene added.

In addition, the diene included in the copolymer according to the embodiment of the present invention may use a non-conjugated diene monomer.

Here, the diene may be added in a content ratio of 1 to 10% by weight, more specifically 3 to 7% by weight of the total weight of the copolymer according to the embodiment of the present invention.

Specific examples of such dienes include 5-1,4-hexadiene, 1,5-heptadiene, 1,6-octadiene, 1,7-nonadiene, 1,8-decadiene, 1,12-tetradeca Dienes, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4-ethyl-1,4-hexadiene, 3,3- Dimethyl-1,4-hexadiene, 5-methyl-1,4-heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5 -Heptadiene, 5-ethyl-1,5-heptadiene, 4-methyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4-ethyl-1,4-octadiene, 5- Ethyl-1,4-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene, 5-ethyl-1,5-octadiene, 6-ethyl-1,5- Octadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 6-ethyl-1,6-octadiene, 6-propyl-1,6-octadiene, 6-butyl -1,6-octadiene, 7-methyl-1,6-octadiene, 4-methyl-1,4-nonadiene, ethylidene-2-norbornene, 5-methylene-2-norbornene, 5- ( 2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5 -(4-pentenyl) -2-norbornene, 5- (1-methyl-3-butenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (1- Methyl-4-pentenyl) -2-norbornene, 5- (2,3-dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene , 5- (6-heptenyl) -2-norbornene, 5- (3-methyl-hexenyl) -2-norbornene, 5- (3,4-dimethyl-4-pentenyl) -2-norbornene , 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene , 5- (1,2-dimethyl-5-hexenyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2,3-trimethyl- 4-pentenyl) -2-norbornene, 5-propylidene-2-norbornene, 5-isopropylidene-2-norbornene, 5-butylidene-2-norbornene, 5-isobutylidene-2 -Norbornene, 2,3-diisopropylidene -5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, etc. are mentioned. And the diene selected from these can be used 1 or more types.

The copolymer according to the embodiment of the present invention described above has a high crystalline temperature due to the formation of ethylene blocks compared to the conventional terpolymer, and has the effect of having a high tensile strength even under the same pattern viscosity.

As described above, the copolymer according to the embodiment of the present invention uses an alpha-olefin having a relatively long chain compared to the conventional terpolymer, and is intentionally prepared so that a large number of C2 blocks are formed. The copolymer has a higher tensile strength than the conventional terpolymer.

In addition, the copolymer according to an embodiment of the present invention, as described above, any one or more of the alpha-olefin having 6 and 8 carbon atoms can be used as the alpha-olefin.

Here, the copolymer according to an embodiment of the present invention is a copolymerization of a monomer composition comprising ethylene, propylene, alpha-olefin and diene while continuously supplying a copolymer under a catalyst composition such as a Ziegler-Natta catalyst or a metallocene catalyst. It can be manufactured by.

However, the copolymer according to the embodiment of the present invention may be copolymerized in the presence of a Ziegler-Natta catalyst having a higher diene conversion rate (%) when considering the diene conversion rate (%) of evaluating the diene content of the copolymer relative to the diene injection amount. have. However, the present invention is not limited thereto, and other olefin polymerization catalysts such as metallocene may be used.

As the Ziegler-Natta catalyst, for example, VCl ₄ having a structure represented by Chemical Formula 1 may be used.

[Formula 1]

More specifically, the catalyst composition may include a Ziegler-Natta-based catalyst as a main catalyst and further include organoaluminum as a cocatalyst. Here, the organic aluminum cocatalyst may use ethyl aluminum sesquichloride having a structure of Formula 2 below.

[Formula 2]

In the present invention, the crystallization temperature is measured in a heating-cooling-heating step at a rate of 10 ° C./min from −100 ° C. to 200 ° C. in a nitrogen atmosphere using a differential scanning calorimeter. The peak of the exothermic curve is defined as the crystallization temperature in the cooling stage where the melt is recrystallized again. Conventional ternary copolymers have a crystallization temperature in a relatively low temperature range (less than 0 ° C.) to improve elasticity and flexibility.

On the other hand, the copolymer according to the embodiment of the present invention is prepared to have a low crystallization temperature (T _c ) compared to the conventional terpolymer. As a result, the copolymer according to the embodiment of the present invention has a low crystallization temperature (Tc) to improve oil blooming, high C. Set characteristics and roll processability. Copolymers according to embodiments of the invention have a crystallization temperature of, for example, 30 to 70 ° C, more specifically 40 to 50 ° C.

In addition, the copolymer according to an embodiment of the present invention has a pattern viscosity (1 + 4 125 ℃) of 30 to 45, it is possible to improve the processability such as roll (calendering) and extrusion (extrusion) This has the advantage of increasing elongation. The copolymer according to the embodiment of the present invention has an elongation of, for example, 250% to 300%.

As a result, the copolymer according to the embodiment of the present invention is not only excellent in workability, but also ensures high elongation. Therefore, the copolymer is easily molded into a complicated shape, and thus rubber parts, wires, roofing sheets (such as automobiles and industrial products) It is suitable for application to roofing sheet.

In addition, the copolymer according to the embodiment of the present invention, the molecular weight distribution of less than 2.0, Δtanδ of 1 or more, crosslink density of 25 lb · in or less, hardness of 75 or more (Shore A), 100% of 65 kgf / cm ² or less It can have a modulus.

Hereinafter, a copolymer production method according to an embodiment of the present invention will be described.

The copolymer production method according to an embodiment of the present invention comprises the step of polymerizing, in the presence of a catalyst composition, an ethylene monomer, a propylene monomer, an alpha-olefin monomer having 6 or more carbon atoms and a diene monomer.

As described above, the copolymer according to the embodiment of the present invention comprises 30 to 80% by weight of ethylene monomer, 1 to 50% by weight of propylene monomer, 1 to 40% by weight of alpha-olefin monomer and 1 to 10% by weight of diene monomer. In addition, the alpha-olefin may include an alpha-olefin having 6 or more carbon atoms.

In this case, the alpha-olefin may include one or more of 1-hexene and 1-octene.

In addition, the copolymer according to the embodiment of the present invention has a high crystallinity temperature due to the formation of ethylene block has the effect that can have a high tensile strength even under the same pattern viscosity.

As described above, the copolymer of the present invention uses an alpha-olefin having a relatively long chain compared to the conventional terpolymer, and also forms a large number of C2 blocks. It has a high tensile strength.

In addition, the copolymer of the present invention may have a crystallization temperature (T _c ) of 30 to 70 ℃, more specifically 40 to 50 ℃, the catalyst composition further comprises a Ziegler-Natta-based main catalyst and an organoaluminum promoter It may include.

Ziegler-Natta-based main catalyst may use a VCl ₄ having the formula (1).

[Formula 1]

For example, the organic aluminum promoter may use ethyl aluminum sesquechloride having the following Chemical Formula 2 structure.

[Formula 2]

실시예Example

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, this is presented as a preferred example of the present invention and in no sense can be construed as limiting the present invention.

Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

1. 공중합체 제조1. Copolymer Preparation

Table 1 shows the compositions of the copolymers prepared according to Examples 1 to 3 and 1 to 2 and the composition ratios thereof.

Here, the composition ratios of the copolymers prepared according to Examples 1 to 3 and Comparative Examples 1 to 2 were confirmed using 1 H NMR.

23 mg of sample and 0.7 mL of deuterated ortho-Diclorobenzene solvent were added to a 1 mL high temperature vial and dissolved at 120 ° C. for 3 hours to prepare a 2.5 wt% solution. The solution was transferred to an NMR tube of a 5 mm probe.

Next, using a 500MHz Bruker NMR instrument, the experiment was carried out at 120 ℃ under the following conditions.

1H NMR Condition: Pulse Program = zg30

Scan # = 64 scan

d1 = 10-20 sec

At this time, after integration of the width value of the peak corresponding to each ppm section, it was input to the calculation formula to calculate the result.

TABLE 1

Example One

The polymer polymerization proceeds in a 3 L reactor. 6.9 g of a solution of ethylaluminumsesquechloride in 1.3 L of normal hexane (solvent), 5,000 cc of propylene, 100 g of 1-octene (monomer) and 20 wt% dissolved in hexane 3.0 g of ethylidene-2-norbornene (monomer, diene) and 30,000 cc of ethylene (monomer) were added thereto. At this time, after the reaction temperature conditions were set to 30 ℃, 2.6g of vanadium catalyst (VCl ₄ ) dissolved at 5wt% concentration in hexane was added to the reactor. Next, the polymer polymerization reaction time was performed for 20 minutes, and 12.0 g of polypropylene glycol-400 (reaction terminator) dissolved in 20% by weight of hexane was added thereto. Next, the polymerization solution after the reaction was precipitated in ethanol and dried in a vacuum oven to prepare a copolymer.

Example 2

A copolymer was prepared in the same manner as in Example 1 except that 10,000 cc of propylene was added.

Example 3

A copolymer was prepared in the same manner as in Example 1 except that 15,000 cc of propylene was added.

Comparative example 1: ethylene- Dien Binary copolymer

The polymer polymerization proceeds in a 3 L reactor. 6.9 g of a solution of ethylaluminum sesquechloride (promoter, ethylaluminumsesquechloride) dissolved in 1.3 L of normal hexane (solvent), 100 g of 1-hexene (monomer) in hexane at a concentration of 20 wt% Liden-2-norbornene (monomer, diene) and 30,000 cc of ethylene (monomer) were added. At this time, after the reaction temperature conditions were set to 30 ℃, 2.6g of vanadium catalyst (VCl ₄ ) dissolved at 5wt% concentration in hexane was added to the reactor. Next, the polymer polymerization reaction time was performed for 20 minutes, and 12.0 g of polypropylene glycol-400 (reaction terminator) dissolved in 20% by weight of hexane was added thereto. Next, the polymerization solution after the reaction was precipitated in ethanol and dried in a vacuum oven to prepare a copolymer.

Comparative example 2: ethylene- Octene - Dien Quaternary copolymer

The polymer polymerization proceeds in a 3 L reactor. 6.9 g of a solution of ethylaluminum sesquechloride (ethylaluminumsesquechloride) dissolved in 1.3 L of normal hexane (solvent), 100 g of 1-octene (monomer) and 20 wt% in hexane, 3.0 g of ethyl Liden-2-norbornene (monomer, diene) and 30,000 cc of ethylene (monomer) were added. At this time, after the reaction temperature conditions were set to 30 ℃, 2.6g of vanadium catalyst (VCl ₄ ) dissolved at 5wt% concentration in hexane was added to the reactor. Next, the polymer polymerization reaction time was performed for 20 minutes, and 12.0 g of polypropylene glycol-400 (reaction terminator) dissolved in 20% by weight of hexane was added thereto. Next, the polymerization solution after the reaction was precipitated in ethanol and dried in a vacuum oven to prepare a copolymer.

2. 물성 평가2. Property evaluation

Table 2 shows the physical property evaluation results for Examples 1 to 3 and Comparative Examples 1 and 2.

TABLE 2

1) Molecular weight and molecular weight distribution

The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC), and the molecular weight distribution (MWD) was divided by the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC). Was calculated.

2) glass transition temperature (T _g ) and crystallization temperature (T _c )

The differential scanning calorimeter is used to measure the heating-cooling-heating step at a rate of 10 ° C./min from −100 ° C. to 200 ° C. in a nitrogen atmosphere. The peak of the exothermic curve is defined as the crystallization temperature in the cooling stage where the melt is recrystallized again.

3) Crosslinking density (lb · in)

Oscillation is applied to the sealed specimen by putting the specimen mixed in the mixing ratio (ASTM 3568) described in Table 3 below into a die of a moving die rheometer (MDR) device. Over time, the specimen is a bridge to check that the torque (Torque) increases, defines the difference value between the maximum torque (M _H) and the minimum torque by the cross-linking density.

TABLE 3

4) Pattern viscosity (1 + 4 125 ℃)

Fill the chamber of the Monet Viscosity instrument with the specimen and measure the torque while rotating the rotor. After preheating the specimen in the chamber at 125 ° C. for 1 minute, the torque value after the rotor was rotated at a speed of 2 rpm for 4 minutes was converted to define a pattern viscosity.

5) Tensile strength (kgf / cm ² )

After mixing the mixture in the mixing ratio of Table 3 (ASTM 3568) for 30 minutes at 160 ℃, after cutting the specimen according to the ASTM D412 test method, the tensile strength was measured through a UTM machine. At this time, the strength at the time of breaking the specimen was defined as tensile strength.

6) Δtanδ

Δtanδ was measured using a Rubber Process Analyzer according to ASTM D6204-01. The RPA2000 MV 2000E instrument model from Monsanto was used, and the measurement sample was prepared from a copolymer sample treated with an antioxidant (Irganox 1076) into a sheet using a press mold, which was 7% strain at 100 ° C and 0.1-210 rad. tan δ was measured in the frequency range of / s. At this time, Δtanδ represents the difference between tan delta values corresponding to the angular frequency of 104.7 and 0.2 rad / s.

7) elongation

The specimens are fabricated by pressing for 20 minutes at 160 and 250 bar to conform to the shapes specified in ASTM D412. Then, after aging in a thermo-hygrostat for 24 hours, using an Instron 3343 UTM instrument to measure the ASTM D412 test conditions to calculate the elongation through the formula below.

L ₀ : Length of fabricated specimen (length of first specimen before measurement)

L _b : specimen cutting length during measurement

Elongation (%) = {(L _b -L ₀ ) / L ₀ } × 100

8) Definition and measurement method of t90

When measured for 30 minutes at 160 ° C using an MDR (Moving Disk Rheometer) instrument, it will have a torque curve over time and t90 corresponds to 90% of the maximum torque value at the optimum vulcanization time. It is time and shows the crosslinking speed and productivity.

As shown in Tables 1 to 3, the copolymers prepared according to Examples 1 to 3 had mechanical properties (hardness, 100% modulus, tensile strength) when compared to the copolymers prepared according to Comparative Examples 1 to 2. ), The pattern viscosity (1 + 4 125 ℃) shows a very low value without significant change.

In addition, it can be seen that the copolymer prepared according to Examples 1 to 3 has an increased elongation as compared to the copolymer prepared according to Comparative Example 1.

Based on the above experimental results, in the case of the copolymer prepared according to Examples 1 to 3, it has a low pattern viscosity of 36.4 to 43.3, and thus workability such as roll, calendering, and extrusion It was confirmed that the elongation tends to increase as a result.

In addition, in the case of the copolymer prepared according to Examples 1 to 3, as the addition amount of ethylene decreases according to the low crystallization temperature has an oil blooming prevention effect, it was confirmed that the roll processability is improved.

In addition, in the case of the copolymer prepared according to Examples 1 to 3, it was confirmed that the crosslinking rate increases as the diene content increases, thereby improving productivity.

In addition, in the case of the copolymers prepared according to Examples 1 to 3, compared to the copolymers prepared according to Comparative Examples 1 to 2, the measured value of t90 was measured to be 6.5 to 8.2 min, indicating that the crosslinking time was significantly shortened. As a result, it was confirmed that the crosslinking speed and productivity can be improved.

Although the above has been described with reference to the embodiments of the present invention, various changes and modifications can be made at the level of those skilled in the art. Such changes and modifications can be said to belong to the present invention without departing from the scope of the technical idea provided by the present invention. Therefore, the scope of the present invention will be determined by the claims described below.

Claims

Copolymers comprising ethylene, propylene, alpha-olefins with 6 or more carbons and dienes.
The method of claim 1,

The alpha-olefin is

A copolymer comprising at least one of 1-hexene and 1-octene.
The method of claim 2,

Copolymer comprising 30 to 80% by weight of the ethylene monomer, 1 to 50% by weight of propylene monomer, 1 to 40% by weight of alpha-olefin monomer and 1 to 10% by weight of diene monomer.
The method of claim 3,

Copolymer comprising 45 to 70% by weight of the ethylene monomer, 5 to 20% by weight propylene monomer, 15 to 35% by weight alpha-olefin monomer and 3 to 7% by weight diene monomer.
The method of claim 1,

Copolymer having a pattern viscosity of 30 to 45 (1 + 4 125 ℃).
The method of claim 1,

Copolymer having a crystallization temperature (T c ) of 30 to 70 ° C.
The method of claim 1,

Copolymer having a crystallization temperature (T c ) of 40 to 50 ℃.
The method of claim 1,

Copolymers having a molecular weight distribution of less than 2.0.
The method of claim 1,

Copolymers having at least one Δtanδ.
The method of claim 1,

A copolymer having a crosslinking density of 25 lb · in or less.
The method of claim 1,

Copolymer having a hardness of at least 75 (Shore A).
The method of claim 1,

Copolymers having a 100% modulus of 65 kgf / cm 2 or less.
The method of claim 1,

Copolymers having an elongation of 250% to 300%.
The method of claim 1,

Copolymer having a weight average molecular weight (Mw) of 100,000 to 300,000.
A method of producing a copolymer comprising polymerizing an ethylene monomer, a propylene monomer, an alpha-olefin monomer having 6 or more carbon atoms and a diene monomer in the presence of a catalyst composition.
The method of claim 15,

The catalyst composition is

Method for producing a copolymer comprising a Ziegler-Natta-based main catalyst.
The method of claim 16,

The catalyst composition is

A method for producing a copolymer further comprising an organoaluminum promoter.
The method of claim 15,

The copolymer

30 to 80% by weight of the ethylene monomer, 1 to 50% by weight of propylene monomer, 1 to 40% by weight of alpha-olefin monomer and 1 to 10% by weight of diene monomer,

The alpha-olefin is a copolymer manufacturing method comprising an alpha-olefin having 6 or more carbon atoms.
The method of claim 18,

The alpha-olefin is

A method for producing a copolymer comprising at least one of 1-hexene and 1-octene.
The method of claim 18,

The copolymer

45 to 70 wt% of the ethylene monomer, 5 to 20 wt% of the propylene monomer, 15 to 35 wt% of the alpha-olefin monomer and 3 to 7 wt% of the diene monomer.