KR20160115700A

KR20160115700A - Olefin-based elastomer

Info

Publication number: KR20160115700A
Application number: KR1020160019825A
Authority: KR
Inventors: 우지윤; 김효주; 박상은; 최익제; 이충훈; 박해웅; 이영우
Original assignee: 주식회사 엘지화학
Priority date: 2015-03-26
Filing date: 2016-02-19
Publication date: 2016-10-06
Also published as: KR101792934B1

Abstract

The present invention includes Te1 (Elution temperature 1) and Te2 (Elution temperature 2), which are different from each other at a temperature range of -20 ° C to 130 ° C in the measurement of temperature rising elution fractionation (TREF) Wherein the elastomer has a density of 0.86 g / cc to 0.91 g / cc and a melt index (MI) of 0.1 g / 10 min to 50 g / 10 min, and the elastomer is measured according to ASTM D638 And a tensile strength at break of 20 kgf / cm ² to 400 kgf / cm ^{2. The} olefin elastomer according to the present invention has a narrow molecular weight distribution and a temperature rising elution fractionation (TREF) Since it contains an olefin polymer containing two Te1 (Elution temperature 1) and Te2 (Elution temperature 2) in measurement, it can exhibit excellent tensile strength and tensile elongation, It can be used in various fields and applications such as packaging, construction, household goods, and the like such as materials for shipbuilding, toy, textile, and medical use.

Description

Olefin elastomer {OLEFIN-BASED ELASTOMER}

The present invention relates to an olefin-based polymer and an olefin-based elastomer containing the olefin-based polymer. More particularly, the present invention relates to a thermoplastic elastomer composition comprising two different elution temperatures Te1 (Elution temperature 1) and Te2 (Elution temperature 2).

Dow has announced the early 1990s [Me ₂ Si (Me ₄ C ₅ ) NtBu] TiCl ₂ (hereinafter abbreviated as CGC) (U.S. Patent No. 5,064,802) In the copolymerization of olefins, the CGC is superior to conventional metallocene catalysts in two major ways:

(1) High molecular weight polymers are produced with high activity even at high polymerization temperatures,

(2) the copolymerization of alpha-olefins with large steric hindrance such as 1-hexene and 1-octene is also excellent.

On the other hand, the copolymer produced by the CGC catalyst has a lower content of the low molecular weight portion than the copolymer prepared by the conventional Ziegler-Natta catalyst, thereby improving physical properties such as strength.

However, in spite of these advantages, the copolymer prepared by CGC et al. Has a disadvantage in that the processability is lowered compared with the polymer produced by the conventional Ziegler-Natta catalysts.

U. S. Patent No. 5,539, 076 discloses a metallocene / non-metallocene mixed catalyst system for making specific point density high density copolymers. The catalyst system is supported on the inorganic carrier. The problem with the supported Ziegler-Natta and metallocene catalyst systems is that the supported hybrid catalysts are less active than homogeneous single catalysts, making it difficult to produce olefinic polymers having tailored properties. Further, since the olefin-based polymer is produced in a single reactor, there is a fear that the gel generated in the blending method is produced, the insertion of the comonomer into the high molecular weight portion is difficult, and the shape of the resulting polymer is poor. Further, the two polymer components are not uniformly mixed, and quality control may become difficult.

Therefore, development of an olefin-based polymer capable of overcoming the disadvantages of conventional olefin-based polymers and capable of providing improved physical properties is still required.

US Patent No. 5,064,802 US Patent No. 6,548,686

Chem. Rev. 2003, 103, 283 Organometallics 1997, 16, 5958 Organometallics 2004, 23, 540 Chem. Commun. 2003, 1034 Organometallics 1999, 18, 348 Organometallics 1998, 17, 1652 J. Organomet. Chem. 2000, 608, 71

The object of the present invention is to provide an olefin-based polymer having a narrow molecular weight distribution and having a Te1 (Elution temperature 1) and a Te2 (Elution temperature 2) in a specific temperature range when measuring a temperature rising elution fractionation (TREF) And an olefin elastomer excellent in tensile strength and tensile elongation.

In order to solve the above problems,

An olefinic system containing Te1 (Elution temperature 1) and Te2 (Elution temperature 2), which are different from each other in the temperature range of -20 ° C to 130 ° C in the measurement of temperature rising elution fractionation (TREF) As the olefin elastomer containing a polymer,

The composition had a density of 0.86 g / cc to about 0.90 g / cc, a melt index (MI) 0.1 g / 10 min to 50 g / 10 min, and the tensile strength when the rupture measured according to ASTM D638 20 kgf / cm ² to 400 kgf / cm < ² >.

The olefin-based elastomer according to the present invention includes an olefin-based polymer having a narrow molecular weight distribution and two Te1 (Elution temperature 1) and Te2 (Elution temperature 2) values when measuring temperature rising elution fractionation (TREF) It can exhibit excellent tensile strength and tensile elongation. Therefore, it can be used in various fields and applications such as various packing, construction, household goods such as materials for automobile, electric wire, toy, fiber, medical and the like.

1 is a graph showing a temperature rising elution fraction (TREF) of the olefinic polymer prepared in Example 1. Fig.
2 is a graph showing a temperature rising elution fraction (TREF) of the olefinic polymer prepared in Example 2. Fig.
3 is a graph showing a temperature rising elution fraction (TREF) of the olefin-based polymer prepared in Example 3. Fig.
4 is a graph showing a temperature rising elution fraction (TREF) of the olefinic polymer prepared in Example 4. Fig.
5 is a graph showing a temperature rising elution fraction (TREF) of the olefinic polymer prepared in Comparative Example 1. FIG.
6 is a graph showing a temperature rising elution fraction (TREF) of the olefinic polymer prepared in Comparative Example 2. Fig.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The terms and words used in the present specification and claims should not be construed as limited to ordinary or dictionary terms and the inventor may appropriately define the concept of the term in order to best describe its invention It should be construed as meaning and concept consistent with the technical idea of the present invention.

The olefin elastomer of the present invention has elution temperatures Te1 (Elution temperature 1) and Te2 (Elution temperature 1) which are different from each other in the temperature range of -20 ° C. to 130 ° C. when measuring the temperature rising elution fractionation (TREF) 2), wherein the elastomer has a density of 0.86 g / cc to 0.91 g / cc and a melt index (MI) of 0.1 g / 10 min to 50 g / 10 min. ASTM Tensile strength at break measured according to D638 is 20 kgf / cm ² to 400 kgf / cm ² .

As used herein, the term "polymer" means a polymeric compound prepared by polymerization of the same or different types of monomers. The generic term "polymer" includes the terms " homopolymer ", "copolymer "," terpolymer "

By "interpolymer" is meant a polymer made by polymerization of two or more different types of monomers. The generic term "interpolymer" refers to the term " copolymer "(commonly used to refer to a polymer made from two different monomers) Quot; terpolymer "). &Lt; / RTI > This includes polymers made by polymerization of four or more types of monomers.

As used herein, the term "quasi-crystalline" refers to a polymer having a primary transition temperature, a crystalline melting point (Tm), an elution point, etc. measured by temperature rising elution fractionation (TREF), differential scanning calorimetry (DSC) Quot; The density, Tm, elution point, etc. of quasicrystal vary depending on the crystallinity. The term "amorphous" refers to a polymer having no crystalline melting point as measured by temperature rising elution fractionation (TREF), differential scanning calorimetry (DSC) or equivalent techniques.

The olefin polymer according to the present invention has a narrow molecular weight distribution and includes two Te1 (Elution temperature 1) and Te2 (Elution temperature 2) in a specific temperature range when measuring TREF.

Generally, when two or more hybrid catalysts are used, there may be two Te which are TREF peaks. However, in this case, since it is difficult to predict and control the activity and copolymerization of each of the hybrid catalysts, it may be difficult to produce an olefin polymer having properties suitable for the application. Further, the two or more kinds of catalyst components are not uniformly mixed, and quality control may become difficult.

On the other hand, in general, when two Te's are measured in the TREF measurement, it may mean that two or more polymers having different branch branching contents of the polymer are mixed. At this time, the BGN constants vary depending on the side chain content distribution in the polymer, thereby changing the strength and physical properties of the base resin and the compound product.

In addition, the molecular weight distribution generally increases when two or more kinds of polymers are mixed. In this case, the impact strength, mechanical properties, and the like are decreased, and blocking phenomenon occurs.

Therefore, the olefin-based polymer has two Te1 (Elution temperature 1) and Te2 (Elution temperature 2) in the TREF measurement and a BGN (Branch Gradient Number) in the GPC FT-IR (Fourier transform infrared spectroscopy) 1.0 to -0.001.

The BGN of the olefin-based polymer may be in the range of -1.0 to -0.001, specifically -0.8 to -0.001, more specifically -0.5 to -0.001, more specifically -0.3 to -0.001 .

Depending on the BGN of the olefinic polymer, the strength and physical properties of the base resin and the compound product may vary. When the BGN has the above range, physical properties such as tensile strength and phosphorus of the base resin can be increased.

The term "BGN" used in the specification of the present invention is a scale showing how the content of comonomer such as alpha olefin is distributed according to the molecular weight.

[Formula 1]

In Equation (1)

The low molecular weight means the lower 10% molecular weight in the total molecular weight distribution, the higher molecular weight means the upper 10% molecular weight, and the side branch content means the branch content of 2 or more carbon atoms per 1,000 carbon atoms.

The branched branch in the BGN refers to a branched chain derived from the alpha olefin such as propylene, 1-butene, 1-hexene and 1-octene as comonomers in the olefinic polymer polymerization process. It means side branches attached.

The side branch may include both a short carbon branch (SCB) having 2 to 6 carbon atoms and an LCB (long carbon branch) having 7 or more carbon atoms.

When the BGN has a positive value, it means that the side chain content is low in the low molecular weight region and the side chain content is high in the high molecular weight region. On the contrary, when the BGN is a negative value, The side branch content is high and the side branch content is relatively low in the high molecular weight region.

Generally, when two peaks are observed in TREF measurement, it means that two or more polymers having different side chain content are mixed. At this time, the BGN constants vary depending on the side chain content distribution in the polymer, thereby changing the strength and physical properties of the base resin and the compound product. In addition, the molecular weight distribution generally increases when two or more kinds of polymers are mixed. In this case, the impact strength, mechanical properties, and the like are decreased, and blocking phenomenon occurs.

In the present invention, it is possible to provide a polymer having two peaks (Te1 and Te2) and a BGN value of -1.0 to -0.001 and a narrow molecular weight distribution in TREF measurement. The olefin polymer of the present invention having the physical properties described above can be improved in mechanical properties such as tensile strength and elongation.

In the present invention, molecular weight, molecular weight distribution and side-chain content can be continuously measured at the same time, for example, by using GPC-FTIR equipment (Cross-fractionation Chromatography) or CFC equipment (Cross-fractionation Chromatography) Respectively.

The olefin-based polymer contained in the olefin-based elastomer according to the present invention may include a first semi-crystalline olefin-based polymer and a second semi-crystalline olefin-based polymer. The temperature may be in the range of -20 ° C to And may have the first semi-crystalline olefinic polymer peak (P1) and the second semi-crystalline olefinic polymeric peak (P2) in the temperature range of 130 deg. At this time, Te (Elution temperature) of each peak is represented by Te1 and Te2, respectively.

The olefin-based polymer contained in the olefin-based elastomer according to an example of the present invention has one peak containing amorphous in the region of -20 ° C to -10 ° C which is the lowest temperature (cryogenic temperature) in addition to the two quasi-crystalline peaks Or more. In general, the olefinic polymer has one quasi-crystalline peak, whereas the olefinic polymer in the olefinic elastomer according to an example of the present invention has two quasicrystal peaks, which may increase the mechanical properties.

The measurement of the TREF used in the present specification can be performed using, for example, a TREF machine manufactured by PolymerChar, and measurement can be performed while raising the temperature from -20 ° C to 130 ° C with o-dichlorobenzene as a solvent.

In the olefinic polymer, Te1 may exist at a relatively lower temperature than Te2 in the TREF measurement, and the Te1 may be present in a range of -20 ° C to 100 ° C in the range of 0.86 to 0.91 g / cc of the olefin polymer And Te2 may be in the range of 0 占 폚 to 130 占 폚.

Wherein the first semi-crystalline olefinic polymer has a lower density and a lower elution temperature (Te1) than the second semi-crystalline olefinic polymer, and the second semi-crystalline olefinic polymer has a higher density than the first semi-crystalline olefinic polymer , And can exhibit a high elution temperature (Te2).

As used herein, the term "Te (Elution temperature)" refers to the peak temperature of each peak in the TREF elution curve expressed in terms of the elution amount with respect to temperature (dC / dT), and the fraction ratio can be calculated as an integral value of the temperature- have.

Specifically, the olefinic polymer included in the olefin elastomer according to an exemplary embodiment of the present invention has a density in the range of 0.86 g / cc to 0.87 g / cc, the Te1 is in the range of -20 ° C to 30 ° C, Te2 may range from 30 DEG C to 80 DEG C. [

In the olefin polymer according to another embodiment of the present invention, the Te1 is in the range of 10 to 50 占 폚 when the TREF is measured in the range of the density of 0.87 g / cc to 0.89 g / cc, Lt; 0 > C to 100 < 0 > C.

According to another embodiment of the present invention, when TFE is measured at a density of 0.89 g / cc to 0.91 g / cc of the olefinic polymer, Te1 ranges from 20 to 70 deg. C, Te2 ranges from 70 to 130 deg. have.

According to another example of the present invention, the fraction ratio of the first semi-crystalline olefinic polymer peak (P1) in the TREF measurement may be 5 to 95%, specifically 10 to 90%, more particularly 20 to 90%. Further, the fraction ratio of the second semi-crystalline olefinic polymer peak (P2) may be 5 to 95%, 10 to 90%, more specifically 10 to 80%.

Further, in calculating the fraction ratio, the starting point of each peak in the elution amount to temperature (dC / dT) graph is defined as the point where the polymer starts to elute based on the base line, and the end point of each peak is defined as a base line The polymer was defined as the point at which elution was terminated.

At this time, when the first semi-crystalline olefinic polymer peak (P1) and the second semi-crystalline olefinic polymeric peak (P2) partially overlap, the point at which the value of the elution amount (dC / DT) And the starting point of the P2 peak.

Further, since the peak represented at -20 캜 to -10 캜 is represented by a mixture of an amorphous polymer and a low-crystalline polymer, the peak appearing at this position can be treated in addition to the fraction ratio of the P1 peak.

The olefin polymer according to one embodiment of the present invention includes Tm1 and Tm2 which are the melting temperatures (Tm) obtained in the DSC curve, and the density of the olefin polymer is in the range of 0.86 to 0.91 g / cc, 30 deg. C to 120 deg. C, and Tm2 may be in the range of -10 deg. C to 140 deg.

There is one Tm when preparing a polymer with a common metallocene catalyst. However, when two Tm exist, the crystal is melted and crystallized at different temperatures, so that thermal stability and mechanical strength can be increased.

When two or more hybrid catalysts are used, two Tm may be present. However, in this case, since it is difficult to predict and control the activity and copolymerization of each of the hybrid catalysts, it may be difficult to produce an olefin polymer having properties suitable for the application. Further, the two or more kinds of catalyst components are not uniformly mixed, and quality control may become difficult.

Tm used herein means the temperature at the peak of each peak in the temperature-heat flow graph of a differential scanning calorimeter (DSC).

According to one example of the present invention, Tm1 may be from -30 deg. C to 45 deg. C and Tm2 may be from 45 deg. C to 110 deg. C in the range of the density of 0.86 g / cc to 0.87 g / cc.

According to another embodiment of the present invention, Tm1 may be 20 占 폚 to 75 占 폚 and Tm2 may be 75 占 폚 to 120 占 폚 in the range of the density of 0.87 g / cc to 0.89 g / cc.

According to another embodiment of the present invention, the Tm1 may be in the range of 30 占 폚 to 90 占 폚, and the Tm2 may be in the range of 90 占 폚 to 140 占 폚 in the range of the density of 0.89 g / cc to 0.91 g / cc.

On the other hand, the olefinic polymer included in the olefinic elastomer according to an exemplary embodiment of the present invention has a melt index (MI) of about 0.1 to about 2,000 g / 10 min measured at 190 DEG C under a load of 2.16 kg in accordance with ASTM D1238, About 0.1 to about 1,000 g / 10 min, more preferably about 0.1 to 500 g / 10 min, but is not limited thereto.

The weight average molecular weight of the olefinic polymer may be from about 10,000 to about 500,000 g / mol, preferably from about 20,000 to about 200,000 g / mol, but is not limited thereto.

The molecular weight distribution (MWD) of the olefin-based polymer may be about 1.0 to about 3.0, preferably about 1.5 to 3.0, and more preferably 2.2 to 2.9.

The olefin based elastomer according to the present invention can exhibit excellent tensile strength and tensile elongation and has a density of 0.86 g / cc to 0.90 g / cc and a melt index (MI) of 4 g / 10 min to 15 g / 10 min. A tensile strength at break of 20 kgf / cm ² to 200 kgf / cm ² measured according to D638, and a tensile elongation at 1500 to 2500%.

More specifically, the olefin elastomer according to an example of the present invention has a tensile strength at break measured according to ASTM D638 of 20 kgf / cm < ² > (measured at a density of 0.863 g / cc and a melt index kgf / cm < ² >, and the tensile elongation may be 1500% to 2500%.

The olefinic elastomer according to another embodiment of the present invention has a density of 0.872 g / cc to 0.873 g / cc and a melt index (MI) of 4.5 g / 10 min to 5.2 g / 10 min. The tensile strength may be 100 kgf / cm ² to 200 kgf / cm ² , and the tensile elongation may be 1500% to 2500%.

The olefinic elastomer can be used for blow molding, extrusion molding or injection molding. The olefinic elastomer satisfying the above physical properties has improved impact strength and processability, and can be used for automobile, electric wire, toy, And various other applications such as packaging, construction, household goods, and the like.

The olefinic polymer comprising the olefinic elastomer according to an example of the present invention, that is, the olefinic polymer having the above physical properties can be obtained by polymerizing an olefinic monomer using a catalyst composition comprising a transition metal compound represented by the following formula .

&Lt; Formula 1 >

In Formula 1,

M is a Group 4 transition metal,

Q ₁ and Q ₂ are the same or different from each other, and each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 6 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkylamido of 1 to 20 carbon atoms; Arylamido having 6 to 20 carbon atoms; Or an alkylidene of 1 to 20 carbon atoms,

R ₁ to R ₆ are the same or different and each independently hydrogen; Silyl; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl of 1 to 20 carbon atoms; R ₁ and R ₂ may be connected to each other or two or more of R ₃ to R ₆ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, or aryl of 6 to 20 carbon atoms,

R ₇ to R ₁₁ are the same or different from each other, and each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms; At least two adjacent to each other of R ₇ to R _{11 may} be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.

The transition metal compound of Formula 1 described in the present specification is structurally linked with a cyclopentadienyl ligand having an amido group linked to a phenylene bridge, so that the Cp-MN angle is narrow, The Q ₁ -MQ ₂ angle has the characteristic of keeping it wide. In addition, unlike the CGC structure connected by a silicon bridge, the cyclopentadiene, phenylene bridge, nitrogen and metal sites fused with benzothiophene are linked in the ring structure in the structure of the compound represented by the above formula (1) Thereby forming a more stable and rigid pentagonal ring structure.

Therefore, when these compounds are activated by reacting them with a promoter such as methylaluminoxane or B (C ₆ F ₅ ) ₃ and then applied to the olefin polymerization, characteristics such as high activity, high molecular weight and high- Lt; RTI ID = 0.0 > polyolefin < / RTI > Particularly, because of the structural characteristics of the catalyst, an ultra-low density polyolefin copolymer having a density of less than 0.910 g / cc can be produced because a large amount of alpha-olefin can be introduced as well as linear low density polyethylene having a density of 0.910 to 0.930 g / cc .

Particularly, it is possible to produce a polymer having a narrow MWD as compared to the CGC, excellent copolymerization, and a high molecular weight even in a low-density region by using the catalyst composition comprising the transition metal compound.

In addition, various substituents can be introduced into the cyclopentadienyl and quinoline system to which benzothiophene is fused, which ultimately controls the structure and physical properties of the polyolefin produced by easily controlling the electronic and stereoscopic environment around the metal . The compound of formula (1) is preferably used for preparing a catalyst for the polymerization of olefin monomers, but is not limited thereto and is applicable to all fields in which the transition metal compound can be used.

In the present specification, alkyl and alkenyl may each be linear or branched.

In the present specification, the silyl may be a silyl substituted with an alkyl having 1 to 20 carbon atoms, and may be, for example, trimethylsilyl or triethylsilyl.

In the present specification, aryl includes monocyclic or polycyclic aryl, and specifically includes phenyl, naphthyl, anthryl, phenanthryl, klycenyl, pyrenyl, and the like.

According to another embodiment of the present disclosure, R ₁ and R ₂ are alkyl of 1 to 20 carbon atoms.

According to another embodiment of the present disclosure, R ₁ and R ₂ are alkyl of 1 to 6 carbon atoms.

According to another embodiment of the present disclosure, R ₁ and R ₂ are methyl.

According to another embodiment of the present disclosure, R ₃ to R ₆ are the same or different and each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Or an alkenyl having 2 to 20 carbon atoms.

According to another embodiment of the present disclosure, R ₃ to R ₆ are the same or different and each independently hydrogen; Or an alkyl having 1 to 20 carbon atoms.

According to another embodiment of the present disclosure, R ₃ to R ₆ are the same or different and each independently hydrogen.

According to another embodiment of the present disclosure, M is Ti, Hf or Zr.

According to another embodiment of the present specification, R ₁₁ may be connected to R ₁₁ and adjacent R ₁₀ to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms. The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.

According to another embodiment of the disclosure, R ₁₁ is an unsubstituted or substituted C 1 -C 20 alkyl, C 6 -C 20 aryl; Alkylaryl having 7 to 20 carbon atoms.

Here, the substituent is halogen, alkyl having 1 to 20 carbon atoms, hydrocarbyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, or aryloxy having 6 to 20 carbon atoms.

According to another embodiment of the present disclosure, R ₇ to R ₁₀ are hydrogen.

According to another embodiment of the present invention, the compound represented by Formula 1 is a compound wherein R ₁₁ is unsubstituted or substituted C 1 -C 20 alkyl, C 6 -C 20 aryl; In the case of alkylaryl having 7 to 20 carbon atoms, it may be a transition metal compound, for example, any one selected from the group consisting of compounds represented by the following formulas, or two or more compounds thereof.

According to another embodiment of the present invention, the compound represented by Formula 1 is a compound wherein R ₁₁ is linked to R ₁₀ adjacent to R ₁₁ to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms , It can be represented by the following formula (2)

(2)

In Formula 2,

M, Q ₁ , Q ₂ , and R ₁ to R ₉ are the same as defined in Formula 1,

Cy is a 5-or 6-membered aliphatic ring,

R, R ₁₆ and R ₁₇ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms;

m is an integer of 0 to 2 when Cy is a 5-membered aliphatic ring, and an integer of 0 to 4 when Cy is a 6-membered aliphatic ring.

According to one embodiment of the present invention, the formula (2) may preferably be represented by the following formula (2-1) or (2-2).

&Lt; Formula (2-1)

In Formula 2-1, R ₁₂ to R ₁₇ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,

The remaining substituents are the same as in the formula (1).

&Lt; Formula (2-2)

In Formula 2-2,

R ₁₈ to R ₂₁ are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms,

The remaining substituents are the same as in the formula (1).

The compound of formula 1 may be prepared by the following steps a) to d):

a) reacting an amine compound represented by the following formula (5) with alkyl lithium, and then adding a compound containing a protecting group (-R ₀ , protecting group) to prepare a compound represented by the following formula ;

b) reacting the compound represented by Formula 6 with alkyllithium and then adding a ketone compound represented by Formula 7 below to prepare an amine compound represented by Formula 8;

c) reacting the compound represented by the formula (8) with n-butyllithium to prepare a di-lithium compound represented by the following formula (9); And

d) reacting a compound represented by the above formula (9) with MCl ₄ (M = Group 4 transition metal) and an organolithium compound to prepare a transition metal compound represented by the following formula

&Lt; Formula 1 >

&Lt; Formula 5 >

(6)

&Lt; Formula 7 >

(8)

&Lt; Formula 9 >

In Formulas 5 to 9,

R ' is hydrogen,

R ₀ is a protecting group,

And the other substituents are the same as defined in the above formula (1).

In the step a), the protecting group-containing compound may be selected from trimethylsilyl chloride, benzyl chloride, t-butoxycarbonyl chloride, benzyloxycarbonyl chloride and carbon dioxide.

When the protecting group-containing compound is carbon dioxide, the compound of Formula 6 may be a lithium carbamate compound represented by Formula 6a.

&Lt; Formula 6a &

The description of the substituent is the same as defined in formula (1).

According to one particular embodiment, the compound of formula 1 can be prepared by the following scheme 1.

In the above Reaction Scheme 1, the description of the substituent is as shown in Chemical Formula (1).

The present invention also provides a catalyst composition comprising the compound of formula (1).

The catalyst composition may further comprise a cocatalyst. As the cocatalyst, those known in the art can be used.

For example, the catalyst composition may further include at least one of the following formulas (10) to (12) as a cocatalyst.

&Lt; Formula 10 >

_{- [Al (R 22) -O} ] a-

Wherein each R < ₂₂ > is independently a halogen radical; A hydrocarbyl radical having from 1 to 20 carbon atoms; Or a hydrocarbyl radical having 1 to 20 carbon atoms substituted by halogen, a is an integer of 2 or more,

&Lt; Formula 11 >

D (R ₂₂₎ ₃

In the above formula, D is aluminum or boron, R ₂₂ is the same as in the above formula (10)

&Lt; Formula 12 >

[LH] + [Z (A) ₄ ] - or [L] + [Z (A) ₄ ]

Wherein L is a neutral or cationic Lewis acid, H is a hydrogen atom, Z is a Group 13 element, A is independently an aryl having 6 to 20 carbon atoms or an aryl having 1 to 6 carbon atoms in which at least one hydrogen atom can be substituted with a substituent And the substituent is halogen, hydrocarbyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, or aryloxy of 6 to 20 carbon atoms.

According to one embodiment of the present invention, there is provided a method for preparing the catalyst composition, comprising the steps of: first contacting the catalyst composition with the compound represented by Chemical Formula 10 or Chemical Formula 11 to obtain a mixture; And a step of adding the compound represented by the formula (12) to the mixture.

Secondly, a method for preparing a catalyst composition by contacting the catalyst composition with the compound represented by the general formula (12) is provided.

According to another embodiment of the present invention, in the case of the first method among the catalyst composition manufacturing methods according to the above-described embodiment, the molar ratio of the compound represented by Formula 10 or Formula 11 to the catalyst composition is 1 : 2 to 1: 5,000, more preferably 1:10 to 1: 1,000, and most preferably 1:20 to 1: 500.

The molar ratio of the compound represented by Formula 12 to the catalyst composition is preferably 1: 1 to 1:25, more preferably 1: 1 to 1:10, and most preferably 1: 1 to 1: 5.

When the molar ratio of the compound represented by the formula (10) or (11) to the catalyst composition is less than 1: 2, the alkylation of the metal compound may not proceed completely due to the low amount of the alkylating agent. The alkylation of the compound is carried out but there is a problem that activation of the alkylated metal compound can not be completely achieved due to the side reaction between the remaining excess alkylating agent and the activating agent of the above formula (12).

When the ratio of the compound represented by the general formula (12) to the compound represented by the general formula (12) is less than 1: 1, the amount of the activator is relatively small and the activation of the metal compound is not completely performed. If there is a problem and the ratio is more than 1:25, activation of the metal compound is completely performed, but there is a problem that the unit cost of the catalyst composition is insufficient due to the excess activator remaining or the purity of the produced polymer is low.

According to another embodiment of the present invention, in the case of the second method among the catalyst composition producing methods according to the above-mentioned one embodiment, the molar ratio of the compound represented by the formula (12) to the catalyst composition is 1: 1 to 1: 500 More preferably from 1: 1 to 1:50, and most preferably from 1: 2 to 1:25. When the molar ratio is less than 1: 1, the amount of the activating agent is relatively small and the activation of the metal compound is not completely performed. Thus, there is a problem that the activity of the resulting catalyst composition is low. However, there is a problem that the unit cost of the catalyst composition is economically undesirable due to an excess amount of the remaining activator, or the purity of the produced polymer is lowered.

According to another embodiment of the present invention, in the production of the catalyst composition described above, an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms such as pentane, hexane, heptane and the like, an aliphatic hydrocarbon solvent substituted with a chlorine atom such as dichloromethane and chlorobenzene Aromatic hydrocarbon solvents such as hydrocarbon solvents, benzene, toluene and the like may be used, but not always limited thereto, and any solvent available in the art may be used. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to use a further cocatalyst.

In addition, the composition may further comprise an additive. For example, a compound containing a hetero atom, and specifically, examples of the compound containing the hetero atom include a heterocyclic compound; Or an alkane containing a heteroatom.

Examples of the heterocyclic compound include an aromatic ring containing a hetero atom; A heterocycloalkane; Or heterocycloalkenes.

Examples of the hetero atom-containing alkane include an alkane containing an amine group or an ether group.

The heteroaromatic ring; A heterocycloalkane; Or the heterocycloalkene includes a 5-membered or 6-membered ring.

The heteroatom-containing compound may contain O, S, Se, N, P or Si as a heteroatom.

The heteroatom-containing compound may contain one heteroatom.

The heteroatom-containing compound may be substituted, and when the heteroatom-containing compound is substituted, one or two or more substituents may be substituted from the group consisting of hydrogen, methyl, phenyl, and benzyl.

Examples of the heteroatom-containing compound include pyridine, 3,5-dimethylpyridine, 2,4,6-trimethylpyridine, 2,6-dimethylpyridine, 2,4-dimethylpyridine, thiophene, , 2,3-dimethylthiophene, piperidine, phosphinene, pyrrole, 2-methylpyrrole, aniline, para-toluidine, tetrahydrofuran, 2,3-dimethyltetrahydrofuran, 2,5- Is selected from the group consisting of 3,4-dihydro-2H-pyrene, furan, 2-methylfuran, 2,3-dimethylfuran, 2,5-dimethylfuran, diethyl ether, methyltetobutyl ether and triethylamine One or more, but is not limited thereto.

The catalyst composition and the cocatalyst may also be used in the form of being supported on a carrier. The carrier may be silica-alumina or silica-magnesia, or any other carrier known in the art may be used. In addition, such a carrier can be used in a dried state at a high temperature, for example, the drying temperature may be not lower than 180 ° C and not higher than 800 ° C. If the drying temperature is lower than 180 ° C., the excess portion of the carrier may react with the cocatalyst to deteriorate the performance. If the drying temperature is excessively higher than 800 ° C., the content of the hydroxy group on the carrier surface is lowered, Can be reduced.

According to another embodiment of the present invention, the compound represented by the above formula (10) is not particularly limited as long as it is alkylaluminoxane. Preferred examples thereof include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane, and a particularly preferred compound is methylaluminoxane.

According to another embodiment of the present invention, the compound represented by the above formula (11) is not particularly limited, but preferable examples thereof include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum , Triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tripentylaluminum, triisopentylaluminum, trihexylaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, trimethylboron, triisobutylboron, tripropylboron, tributylboron and the like. Particularly preferred compounds include trimethylaluminum, triethylaluminum, trimethylaluminum, triethylaluminum, , And triisobutylaluminum.

According to another embodiment of the present invention, examples of the compound represented by the above-described formula (12) include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetra (P-toluyl) boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (p- N, N-diethylanilinium tetraphenylboron, N, N-diethyl (N, N-dimethylaminophenyl) boron, tributylammonium tetrapentafluorophenylboron, Anilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetra (P-tolyl) aluminum, trimethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, trimethylammonium tetra (p-tolyl) aluminum, Aluminum triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (ptrifluoromethylphenyl) aluminum, trimethylammoniumtetra (ptrifluoromethylphenyl) aluminum, tributylammonium tetrapentafluoro N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, Tetraphenyl aluminum, triphenyl phosphonium tetraphenyl aluminum, trimethyl phosphonium tetraphenyl aluminum, triethyl ammonium tetraphenyl (P-tolyl) boron, triethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammoniumtetra (p-tolyl) boron, tripropylammoniumtetra (O, p-dimethylphenyl) boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra Fluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylaniline (P-trifluoromethylphenyl) boron, triphenylcarboniumtetra (p-trifluoromethylphenyl) boron, triphenylphosphonium tetraphenylboron, triphenylphosphonium tetra Penta By Luo and the like phenylboronic.

According to another embodiment of the present invention, the olefin-based monomer is an alpha-olefin-based monomer, a cyclic olefin-based monomer, a dienolefin-based monomer, a triene olefin-based monomer, a styrene- Homopolymerization of one species, or copolymerization of two or more species.

The alpha-olefin-based monomer includes an aliphatic olefin having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms, and specifically includes ethylene, propylene, 1-butene, 1-pentene, Pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, Diethyl-1-hexene, 3,4-dimethyl-1-hexene, and the like. The alpha-olefins may also be homopolymerized or alternating, random, or block copolymerized. The copolymerization of the alpha-olefins may be carried out by copolymerization of ethylene and an alpha-olefin having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms (ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, 1-pentene, ethylene and 1-octene) and copolymers of propylene and an alpha-olefin having 2 to 12 carbon atoms, preferably 2 to 8 carbon atoms (propylene and 1-butene, propylene and 4-methyl- And 4-methyl-1-butene, propylene and 1-hexene, propylene and 1-octene).

In the copolymerization of ethylene or propylene with other alpha-olefins, the amount of the other alpha-olefin may be selected to be not more than 90% by weight of the total monomers, and usually not more than 70% by weight, preferably not more than 60% , More preferably 50 wt% or less, and in the case of the propylene copolymer, 1 to 90 wt%, preferably 5 to 90 wt%, and more preferably 10 to 70 wt%.

The cyclic olefins may have 3 to 24 carbon atoms, preferably 3 to 18 carbon atoms. Specific examples thereof include cyclopentene, cyclobutene, cyclohexene, 3-methylcyclohexene, cyclooctene, tetracyclodecene, Norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-norbornene, octylcyclodecene, dicyclopentadiene, 2-norbornene, 5,5,6-trimethyl-2-norbornene and ethylene norbornene. The cyclic olefins can be copolymerized with the above-mentioned alpha-olefins, wherein the amount of the cyclic olefin is from 1 to 50 mol%, preferably from 2 to 50 mol%, based on the copolymer.

The dienes and trienes are preferably polyenes having 4 to 26 carbon atoms and having 2 or 3 double bonds. Specific examples thereof include 1,3-butadiene, 1,4-pentadiene, 1,4-hexa Dienes, 1,5-hexadiene, 1,9-decadiene, 2-methyl-1,3-butadiene, etc. The styrenes include styrene or an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms An alkoxy group, a halogen group, an amine group, a silyl group, a halogenated alkyl group or the like.

According to another embodiment of the present disclosure, the polymerizing step may be carried out in a hydrocarbon-based solvent in a liquid phase, a slurry phase, a bulk phase, or a gas phase polymerization.

Slurry phase, bulk phase, or gas phase polymerization, since they exist in the form of carrier-borne or insoluble particles of the carrier as well as the catalyst composition in homogeneous solution state. Further, the respective polymerization conditions may be variously changed depending on the state of the catalyst used (homogeneous or heterogeneous phase (supported type)), polymerization method (solution polymerization, slurry polymerization, gas phase polymerization) . And the degree of modification thereof can be easily modified by anyone skilled in the art.

Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms such as pentane, hexane, heptane, nonane, decane and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, chlorine atoms such as dichloromethane and chlorobenzene A substituted hydrocarbon solvent, or the like can be mixed and injected. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to use a further cocatalyst.

Examples of the alkylaluminum include trialkylaluminum, dialkylaluminum halide, alkylaluminum halide, aluminum dialkylhydride or alkylaluminum sesquihalide, and more specific examples include Al (C ₂ H ₅ ) ₃ _{, Al (C 2 H 5)} 2 H, Al (C 3 H 7) 3, Al (C 3 H 7) 2 H, Al (iC 4 H 9) 2 H, Al (C 8 H 17) 3, Al _{(C 12 H 25) 3,} Al (C 2 H 5) (C 12 H 25) 2, Al (iC 4 H 9) (C 12 H 25) 2, Al (iC 4 H 9) 2 H, Al ( iC ₄ H ₉ ) ₃ , (C ₂ H ₅ ) ₂ AlCl, (iC ₃ H ₉ ) ₂ AlCl or (C ₂ H ₅ ) ₃ Al ₂ Cl ₃ . These organoaluminum compounds can be continuously introduced into each reactor and can be introduced at a rate of about 0.1 to 10 moles per kg of reaction medium introduced into the reactor for proper moisture removal.

In one example of the present invention, the polymerizing step may be carried out in a batch reactor or a continuous reactor, preferably in a continuous reactor.

In one example of the present invention, the polymerizing step may be carried out in the presence of an inert gas, for example, an argon or nitrogen gas.

The inert gas may be, for example, a nitrogen gas or a hydrogen gas alone, or a mixture of the gases.

The use of the inert gas serves to prevent moisture or impurities from entering the air and inhibit the catalytic activity. The inert gas may be added such that the mass ratio of the olefin monomer is about 1:10 to 1: 100 But is not limited thereto. If the amount of the inert gas used is too small, the catalytic composition reacts abruptly, making it difficult to produce an olefin polymer having a molecular weight and a molecular weight distribution. When an inert gas is introduced in an excessively large amount, .

The polymerization temperature in copolymerizing ethylene with an alpha olefin as a comonomer using the catalyst may range from about 130 to about 250 ° C, preferably from about 140 to about 200 ° C.

Also, the polymerization pressure is preferably carried out at about 1 to about 150 bar, more preferably about 1 to about 120 bar, most preferably about 10 to about 120 bar.

The present invention provides an olefin-based elastomer comprising the olefin-based polymer produced by the process for producing the olefin-based polymer, wherein the olefin-based polymer is a mixture of two or more polyolefin units having different crystallizabilities.

Example

Hereinafter, the present invention will be described more specifically based on the following examples. These examples are provided to aid understanding of the present invention and the scope of the present invention is not limited thereto.

Synthesis of ligands and transition metal compounds

Organic reagents and solvents were purchased from Aldrich unless otherwise noted and purified by standard methods. At every stage of the synthesis, the contact between air and moisture was blocked to improve the reproducibility of the experiment.

Production Example 1: Preparation of ligand

8- (l, 2-Dimethyl-lH- Benzo [b] cyclopenta [d] thiophene Yl) -2- methyl -1,2,3,4- Tetrahydroquinoline Preparation of 8- (1,2- dimethyl-1H-benzo [b] cyclopenta [d] thiophen-3-yl) -2-methyl-1,2,3,4-tetrahydroquinoline

NBuLi (14.9 mmol, 1.1 eq) was slowly added dropwise to a solution of 2-methyl-1,2,3,4-tetrahydroquinoline (2 g, 13.6 mmol) in ether (10 mL) at -40 ° C. After slowly raising the temperature to room temperature, the mixture was stirred at room temperature for 4 hours. The temperature was lowered to -40 ° C again, and CO ₂ (g) was injected, and the reaction was maintained at a low temperature for 0.5 hour. The temperature was gradually raised, and residual CO ₂ (g) was removed through a bubbler. THF (17.6 mmol, 1.4 mL, tBuLi (10.4 mmol, 1.3 eq) was added at -20 ° C and the mixture was aged for 2 hours at -20 ° C. The ketone (1.9 g, 8.8 mmol) was dissolved in diethyl ether The mixture was stirred at room temperature for 12 hours and then poured into 10 mL of water. The mixture was stirred for 2 minutes with hydrochloric acid (2 N, 60 mL), extracted with an organic solvent, neutralized with aqueous NaHCO ₃ solution, The solvent was extracted and the water was removed with MgSO4. A yellow oil was obtained via a silica gel column (1.83 g, 60% yield).

^{1 H NMR (C6D6): δ} 1.30 (s, 3H, CH3), 1.35 (s, 3H, CH3), 1.89 ~ 1.63 (m, 3H, Cp-H quinoline-CH2), 2.62 ~ 2.60 (m, 2H, 2H, quinoline-NCH2), 3.92 (broad, IH, quinoline-NCH2), 2.61-2.59 (m, 2H, quinoline- 2H), aromatic), 7.54-7.53 (m, 1H, aromatic), 7.62-7.60 (m, 2H) (m, 1H, aromatic) ppm

Preparation Example 2: Preparation of transition metal compound

8- (l, 2-Dimethyl-lH- Benzo [b] cyclopenta [d] thiophene Yl) -2- methyl -1,2,3,4- Tetrahydroquinoline Preparation of 8- (1,2-dimethyl-1H-benzo [b] cyclopenta [d] thiophen-3-yl) -2-methyl-1,2,3,4-tetrahydroquinoline-titanium dichloride

NBuLi (3.0 mmol, 2.1 eq) was slowly added dropwise to the above ligand (1.0 g, 2.89 mmol) at -20 ° C. Yellow slurry was observed to form and slowly warmed to room temperature and then stirred at room temperature for 12 hours. TiCl ₄ DME (806 mg, 2.89 mmol, 1.0 eq) was added dropwise and the mixture was stirred at room temperature for 12 hours. After removal of the solvent, it was extracted with toluene to give a red solid (700 mg, 52% yield).

^{1 H NMR (C6D6): δ} 1.46 ~ 1.467 (t, 2H, quinoline-NCH2), 1.85 (s, 3H, Cp-CH3), 1.79 (s, 3H, Cp-CH3), 2.39 (s, 3H, Cp 2H, quinoline-NCH2), 5.22-5.20 (m, 1H, N-CH), 5.26-5.25 (m, 1H, N 1H, aromatic), 7.19-7.08 (m, 2H, aromatic), 7.73-7.68 (m, 1H, aromatic)

&Lt; Preparation of olefin elastomer &

Example 1

A 1.5 L autoclave continuous reactor was charged with hexane solvent (5.1 kg / h) and 1-octene (1.04 kg / h), and the temperature at the top of the reactor was preheated to 160 ° C. (2.1 mol / min) of the triisobutyl aluminum compound (0.03 mmol / min), the metallocene compound (0.7 μmol / min) obtained above and the dimethylanilinium tetrakis (pentafluorophenyl) Lt; / RTI > Ethylene (0.87 kg / h) was then fed into the autoclave reactor and maintained at 160 캜 for 30 minutes or more at a pressure of 89 bar in a continuous process, followed by copolymerization to obtain a copolymer. Next, the remaining ethylene gas was taken out, and the polymer solution was dried in a vacuum oven for 12 hours or more, and the physical properties were measured.

Example 2

A 1.5 L autoclave continuous reactor was charged with a hexane solvent (5.1 kg / h) and 1-octene (0.92 kg / h), and the temperature at the top of the reactor was preheated to 160 ° C. (1.8 μmol / min) of the triisobutyl aluminum compound (0.03 mmol / min), the metallocene compound (0.6 μmol / min) obtained above and the dimethylanilinium tetrakis (pentafluorophenyl) Lt; / RTI > Ethylene (0.87 kg / h) was then fed into the autoclave reactor and maintained at 160 ° C for 30 minutes or more in a continuous process at a pressure of 89 bar, followed by copolymerization to obtain a copolymer. Next, the remaining ethylene gas was taken out, and the polymer solution was dried in a vacuum oven for 12 hours or more, and the physical properties were measured.

Example 3

A 1.5 L autoclave continuous reactor was filled with hexane solvent (5.1 kg / h) and 1-octene (0.8 kg / h), and the temperature at the top of the reactor was preheated to 160 ° C. (2.04 μmol / min) of the triisobutyl aluminum compound (0.03 mmol / min), the metallocene compound (0.68 μmol / min) obtained above and the dimethylanilinium tetrakis (pentafluorophenyl) Lt; / RTI > Ethylene (0.87 kg / h) was then fed into the autoclave reactor and maintained at 160 캜 for 30 minutes or more at a pressure of 89 bar in a continuous process, followed by copolymerization reaction to obtain a copolymer. Next, the remaining ethylene gas was taken out, and the polymer solution was dried in a vacuum oven for 12 hours or more, and the physical properties were measured.

Example 4

A 1.5 L autoclave continuous reactor was charged with a hexane solvent (5.1 kg / h) and 1-octene (1.2 kg / h), and then the temperature at the top of the reactor was preheated to 160 ° C. (1.8 μmol / min) of the triisobutyl aluminum compound (0.03 mmol / min), the metallocene compound (0.6 μmol / min) obtained above and the dimethylanilinium tetrakis (pentafluorophenyl) Lt; / RTI > Ethylene (0.87 kg / h) was then fed into the autoclave reactor and maintained at 160 캜 for 30 minutes or more at a pressure of 89 bar in a continuous process, followed by copolymerization to obtain a copolymer. Next, the remaining ethylene gas was taken out, and the polymer solution was dried in a vacuum oven for 12 hours or more, and the physical properties were measured.

Comparative Example 1

An ethylene-1-octene copolymer (product name: LC670) manufactured by LG Chemical Co., Ltd., which was produced using only one type of metallocene catalyst, was prepared.

Comparative Example 2

An ethylene-1-octene copolymer (product name: LC760) of LG Chem manufactured using only one type of metallocene catalyst was prepared.

Experimental Example 1: Measurement of temperature rising elution fractionation (TREF)

TREF is a PolymerChar TREF machine and can be measured in the range of -20 캜 to 130 캜 using o-dichlorobenzene as a solvent.

80 mg of the polymer sample was dissolved in 20 mL of o-dichlorobenzene solvent at 135 DEG C for 30 minutes and then stabilized at 95 DEG C for 30 minutes. This was introduced into a TREF column, cooled to -20 占 폚 at a cooling rate of 0.5 / min, and then held for 2 minutes. Then, o-dichlorobenzene as a solvent was passed through the column at a flow rate of 0.5 mL / min while heating at a rate of 1 / min from -20 ° C to 130 ° C to measure the concentration of the eluted polymer.

The TREF measurement results are shown in Figs. 1 to 6 and Tables 1 and 2 below.

Experimental Example 2: BGN (Branch gradient number) measurement

The BGN was obtained by continuously measuring the molecular weight, the molecular weight distribution, and the side-chain content continuously using GPC-FTIR equipment (Cross-fractionation Chromatography) or CFC equipment and calculating the value by the following formula 1.

The logarithm of the molecular weight (Mw) (log Mw) as the x-axis is measured by continuously measuring the molecular weight, the molecular weight distribution and the side chain content simultaneously using the GPC-FTIR equipment or the CFC equipment, (dwt / dlog Mw) is plotted on the y-axis, the side branch content of the low molecular weight side branch at the left boundary of 80% of the total area excluding 10% of the total area (unit: (C)), and the side chain content of the high molecular weight is calculated by calculating the value of the side chain content at the right border of the middle 80% as shown in the following formula (1).

[Formula 1]

In Equation (1)

Experimental Example 3: Measurement of other properties

The density of the polymer; ASTM D-792.

- molecular weight distribution (MWD); The number average molecular weight (Mn) and the weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC), and the weight average molecular weight was calculated by dividing by the number average molecular weight.

The melt index (MI) of the polymer was measured by ASTM D-1238 (condition E, 190 ° C, 2.16 Kg load).

Experimental Example 4: differential scanning calorimeter ( DSC ) Measure

(DSC: Differential Scanning Calorimeter 6000 manufactured by PerKinElmer). Specifically, the temperature was increased to 200 DEG C, held at that temperature for 1 minute, then decreased to -100 DEG C, and the temperature was increased again to obtain the melting point of the top of the DSC curve. At this time, the temperature rise and fall speed is 10 ° C / min, and the melting point is obtained during the second temperature rise. The results of DSC analysis of the polymer according to the present invention are shown in Table 1 below.

Experimental Example 5: Measurement of mechanical properties

The olefinic polymers prepared in Examples 1 to 4 and Comparative Examples 1 and 2 were extruded to prepare pellet-like olefinic elastomers. The olefinic elastomers were then extruded in accordance with ASTM D638 (50 mm / min) Elongation was measured. The results are shown in Table 2 below.

density
(g / cc) MI
(g / 10 min) Tm1 Tm2 Mw MWD BGN Example
One 0.873 5.2 59.4 90.2 88k 2.83 -0.042 Example
2 0.872 5.0 52.6 86.1 93k 2.77 -0.040 Example
3 0.872 4.5 19.3 83.1 96k 2.47 -0.043 Example
4 0.863 14.1 30.0 79.0 98k 2.21 -0.044 Comparative Example 1 0.869 5.1 56.9 - 90k 2.45 0.006 Comparative Example 2 0.862 11.0 48.9 - 98k 2.41 0.004

As can be seen in Table 1, the olefin polymers of Examples 1 to 4 using a single catalyst according to the present invention had BGN values in the range of -1.0 to -0.001 and values of BGN corresponding to negative values . &Lt; / RTI > If BGN has the above range as in the embodiment of the present invention, physical properties such as tensile strength and phosphorus of the base resin can be increased.

In addition, the olefin polymers of Examples 1 to 4 according to the present invention show two Tm's as a result of DSC analysis, unlike the olefin polymers of Comparative Examples 1 and 2.

The tensile strength
(kgf / cm ² ) Tensile elongation
(%) Te1 Te2 (° C) Fraction Ratio (%) (° C) Fraction Ratio (%) Example
One 133.8 1776.3 23.8 70 62.8 30 Example
2 127.1 1789.7 20.6 70 60.4 30 Example
3 140.7 1675.7 11.6 47 56.6 53 Example
4 27.7 2080.9 2.8 74 50.6 26 Comparative Example 1 86.4 886.3 26.2 100 - - Comparative Example 2 17.5 1331.6 15.6 100 - -

As shown in Table 2, unlike the olefin polymers of Comparative Example 1 and Comparative Example 2, the olefin polymer according to the present invention exhibited two peaks of P1 and P2 during TREF measurement, And Te2. In Examples 1 to 4, two Tes are observed in the TREF measurement, in the density range of about 0.863 to 0.873 g / cc, 2.8 to 23.8 DEG C for Te1, and 50.6 to 62.8 DEG C for Te2 The temperature range of.

In addition, as shown in Table 2, the pellet-like elastomer produced by using the olefin polymer in Examples 1 to 3 according to one embodiment of the present invention was produced using the olefin polymer of Comparative Example 1 It can be confirmed that the tensile strength and the tensile elongation are remarkably superior to those of the pellet-type allosteromers. In addition, it can be confirmed that the pellet-like elastomer of Example 4 exhibits significantly higher tensile strength and tensile elongation than the pellet-like elastomer of Comparative Example 2. [

Claims

An olefinic system containing Te1 (Elution temperature 1) and Te2 (Elution temperature 2), which are different from each other in the temperature range of -20 ° C to 130 ° C in the measurement of temperature rising elution fractionation (TREF) As the olefin elastomer containing a polymer,
The composition had a density of 0.86 g / cc to about 0.91 g / cc, a melt index (MI) 0.1 g / 10 min to 50 g / 10 min, and the tensile strength when the rupture measured according to ASTM D638 20 kgf / cm ² to 400 kgf / cm < ² >.

The method according to claim 1,
Wherein the olefinic polymer has a BGN (Branch Gradient Number) in the range of -1.0 to -0.001 measured by GPC FT-IR (chromatography Fourier transform infrared spectroscopy).

The method according to claim 1,
In the TREF measurement, the Te1 is present at a relatively lower temperature than Te2, the Te1 is in the range of -20 DEG C to 100 DEG C in the range of the density of the olefin polymer of 0.86 to 0.91 g / cc, Lt; RTI ID = 0.0 > 130 C. < / RTI >

The method according to claim 1,
Wherein the Te1 is in a range of -20 占 폚 to 30 占 폚, and the Te2 is in a range of 30 占 폚 to 80 占 폚, wherein the olefin polymer has a density of 0.86 to 0.87 g / cc.

The method according to claim 1,
Wherein the olefin polymer has a density of 0.87 to 0.89 g / cc, the Te1 is in a range of 10 DEG C to 50 DEG C, and the Te2 is in a range of 50 DEG C to 100 DEG C.

The method according to claim 1,
Wherein the olefin polymer has a density of 0.89 to 0.91 g / cc, the Te1 ranges from 20 DEG C to 70 DEG C, and the Te2 ranges from 70 DEG C to 120 DEG C.

The method according to claim 1,
The olefin-based polymer includes a first semi-crystalline olefin-based polymer and a second semi-crystalline olefin-based polymer,
Wherein the fraction of the first semi-crystalline olefinic polymer peak (P1) is from 5 to 95% and the fraction of the second semi-crystalline olefinic polymer peak (P2) is from 5 to 95% in the TREF measurement.

8. The method of claim 7,
Wherein the fraction of the first semi-crystalline olefinic polymer peak (P1) in the TREF measurement is 10 to 90%, and the fraction of the second semi-crystalline olefinic polymer peak (P2) is in the range of 10 to 90% .

The method according to claim 1,
Wherein the BGN is -0.8 to -0.001.

The method according to claim 1,
The olefinic polymer has a melt index (MI) of 0.1 to 2000 g / 10 min.

The method according to claim 1,
Wherein the olefinic polymer has a weight average molecular weight (Mw) of 10,000 to 500,000 g / mol.

The method according to claim 1,
Wherein the olefinic polymer has a molecular weight distribution (MWD) of 1.0 to 3.0.

The method according to claim 1,
Wherein the elastomer has a density of from 0.86 g / cc to 0.91 g / cc and a melt index (MI) of from 4 g / 10 min to 15 g / 10 min and a tensile elongation at break of 1200% to 2500% measured according to ASTM D638 Olefinic elastomer.

The method according to claim 1,
Wherein the olefin-based polymer is obtained by polymerizing an olefin-based monomer using a catalyst composition comprising a transition metal compound represented by the following formula (1):
&Lt; Formula 1 >

In Formula 1,
M is a Group 4 transition metal,
Q ₁ and Q ₂ are the same or different from each other, and each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 6 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkylamido of 1 to 20 carbon atoms; Arylamido having 6 to 20 carbon atoms; Or an alkylidene of 1 to 20 carbon atoms,
R ₁ to R ₆ are the same or different and each independently hydrogen; Silyl; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid radical of a Group 14 metal substituted with hydrocarbyl of 1 to 20 carbon atoms; R ₁ and R ₂ may be connected to each other or two or more of R ₃ to R ₆ may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, or aryl of 6 to 20 carbon atoms,
R ₇ to R ₁₁ are the same or different from each other, and each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Or arylalkyl having 7 to 20 carbon atoms; At least two adjacent to each other of R ₇ to R _{11 may} be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms; The aliphatic ring or aromatic ring may be substituted with halogen, alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.