KR20180074576A - Polyolefin-based resin composition and elastomer comprising the same - Google Patents

Abstract

The present invention relates to a polyolefin-based resin composition and a polyolefin-based elastomer containing the same. The polyolefin-based resin composition has low viscosity at a high shear rate, thereby enabling production of a polyolefin-based elastomer exhibiting excellent processability. To this end, the density of the polyolefin-based resin composition is 0.850-0.910 g/cc.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyolefin-based resin composition, and an elastomer containing the same. BACKGROUND ART [0002]

The present invention relates to a polyolefin-based resin composition and an elastomer containing the polyolefin-based resin composition, which have low viscosity at a high shear rate and can exhibit excellent processability.

Catalysts of the [Me ₂ Si (Me ₄ C ₅ ) NtBu] TiCl ₂ (Constrained-Geometry Catalyst, hereinafter abbreviated as CGC) catalysts developed in the early 1990s show a high activity even at a high polymerization temperature during the copolymerization reaction of ethylene and an α- And produces a polymer of high molecular weight, and the copolymerization of alpha-olefins having a large steric hindrance such as 1-hexene and 1-octene is also excellent. In addition, 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.

To this end, a metallocene / nonmetallocene mixed catalyst system has been proposed for the preparation of high purity high density copolymers. The catalyst system is supported on the inorganic carrier. However, the supported Ziegler-Natta and metallocene catalyst systems have a problem that the supported hybrid catalysts are less active than the homogeneous single catalysts, making it difficult to produce olefin-based polymers having properties suitable for their use. Further, since an olefin-based polymer is produced in a single reactor, there is a fear that a gel generated in the blending method is generated, insertion of a comonomer into a 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.

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

On the other hand, when molding with a polyolefin resin, excellent toughness, strength, environmental stress, crack resistance and the like are required for the polymer constituting the polyolefin resin. Normally, when the molecular weight of the polyolefin polymer is increased, these properties may be improved, but the workability of the resin is lowered when the molecular weight of the polymer is increased. Accordingly, a polyolefin polymer having different physical properties is used in combination, or a polyolefin polymer having a single physical property is used alone, but the structure of the polymer is appropriately adjusted or an appropriate processing aid is used.

However, the polyethylene polymers made of Ziegler-Natta and metallocene catalysts have a narrow molecular weight distribution and cause various problems when they are used alone.

Recently, polyolefin elastomer products have been developed variously, so that it is preferable to have good processability and fluidity even though they have the same melt index.

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

The present invention provides a polyolefin-based resin composition and an elastomer containing the polyolefin-based resin composition, which exhibit excellent workability because of low viscosity at a high shear rate.

According to one embodiment of the present invention, the cross-section chromatography (CFC) analysis at -20 ° C to 130 ° C after pretreatment with a density of 0.850 to 0.910 g / cc and under the following conditions There is provided a polyolefin-based resin composition wherein the cumulative elution line has a slope value of 2 or less when the cumulative elution amount of the olefin polymer is 20 to 80 wt% of the total elution amount:

<Pretreatment Condition>

1) Stabilized at 95 ° C for 45 minutes

2) cooled to -20 ° C at a rate of 0.5 ° C / min

3) Stabilization at -20 ° C for 10 minutes

In the polyolefin-based resin composition, the R ² value of the trend line in the cumulative dissolution line may be 0.997 or more and less than 1.

The polyolefin-based resin composition may have a molecular weight distribution of 3 or more.

The polyolefin-based resin composition may have a weight average molecular weight (Mw) of 50,000 to 120,000 Da.

The polyolefin resin composition preferably has a low density region of 0.80 g / cc or more and less than 0.860 g / cc and a high density region of 0.880 g / cc or more and 0.90 g / cc or less, and has a melt index (ASTM Measured under a load of 2.16 kg at a temperature of 190 占 폚 according to the D1238 standard); And at least one second olefin copolymer having a density of from 0.850 to 0.890 g / cc and a melt index of at least 300 g / 10 min (measured at a temperature of 190 DEG C and a load of 2.16 kg according to the ASTM D1238 standard) The first and second olefin copolymers may be contained in a content ratio such that the melt index measured under a load of 2.16 kg at a temperature of 190 캜 according to ASTM D1238 is 10 g / 10 min or less.

In the polyolefin-based resin composition, each of the first and second olefin copolymers may be independently a copolymer of ethylene and an alpha olefin comonomer having 4 to 8 carbon atoms.

According to another embodiment of the present invention, there is provided a polyolefin-based elastomer comprising the resin composition.

The polyolefin-based resin composition according to the present invention has a low viscosity at a high shear rate, thereby making it possible to provide a polyolefin-based elastomer capable of exhibiting excellent processability.

1 is a graph showing the results of CFC analysis of Example 1. Fig.
2 is a graph showing the results of CFC analysis of Comparative Example 1. Fig.
3 is a graph showing shear viscosities of Example 1 and Comparative Examples 1 and 2 at a high shear rate.

The terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises", "comprising", or "having" are used to designate the presence of stated features, steps, components, or combinations thereof, and are not intended to preclude the presence of one or more other features, Components, or combinations thereof, as a matter of convenience, without departing from the spirit and scope of the invention.

The invention is capable of various modifications and may take various forms, which illustrate specific embodiments and are described in detail below. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, a polyolefin-based resin composition according to a specific embodiment of the present invention and an elastomer containing the same will be described.

In the present invention, an olefin-based polymer having different densities and MI is used in the production of a polyolefin-based resin composition using two or more olefin-based polymers, and the crystallinity of the polymer in the resin composition is controlled, By making the slope value of the elution line 2 or less, the viscosity at a high shear rate is remarkably low as compared with the polyolefin-based resin composition having the same density and the melt index, so that excellent workability can be exhibited.

That is, the polyolefin-based resin composition according to one embodiment of the present invention

A density of 0.850 to 0.910 g / cc,

Cumulative elution when the cumulative elution amount of the olefin polymer eluted in the cross-fractionation chromatography (CFC) analysis in the range of -20 캜 to 130 캜 after pretreatment under the following conditions is 20% by weight to 80% by weight of the total elution amount The slope value of the line is 2 or less:

<Pretreatment Condition>

1) Stabilized at 95 ° C for 45 minutes

2) cooled to -20 ° C at a rate of 0.5 ° C / min

3) Stabilization at -20 ° C for 10 minutes

Here, the polyolefin-based resin composition or elastomer generally has a low degree of crystallinity, such as a few percent, so that it is difficult to measure properly, and it is difficult to obtain an effective measurement value because the error range is considerably large even when measured. Therefore, since it is general to approximate the degree of crystallization through the density of the resin, the following description assumes that the density of the resin is an alternative property to the degree of crystallization.

Cross fractionation chromatography (CFC) is a device in which gel permeation chromatography (GPC) for molecular weight fractionation is combined with temperature rising elution fractionation (TREF) for crystalline fractionation , The amount of the polymer eluted by the temperature section, the molecular weight of the polymer and the molecular weight distribution can be confirmed while increasing the temperature of the sample.

In the present invention, the CFC measurement is performed by completely dissolving the polyolefin resin composition sample in orthodichlorobenzene (ODCB) containing 0.5 mg / mL of BHT (butylated hydroxytoluene) at 140 占 폚, (A column packed with an inert glass bead carrier) maintained at 140 캜 through a sample loop of the sample holder and cooled gradually to a predetermined first elution temperature to crystallize the polymer sample, Thereafter, the ODCB is passed through the TREF column, and the eluted component is injected into the GPC portion to perform molecular weight fractionation, and a chromatogram can be obtained by an infrared detector. Meanwhile, in the TREF part, the temperature is raised to the next elution temperature, and a chromatogram of the first elution temperature is obtained, and eluted components at the second elution temperature are injected into the GPC part. By repeating this operation, a chromatogram of the eluted component at each elution temperature can be obtained. At this time, preprocessing as described above is performed on the polyolefin-based resin composition before measurement.

The chromatogram of the eluted component at each elution temperature obtained by the TREF measurement is processed by a data processing program attached to the apparatus and the elution amount (proportional to the area of the chromatogram) normalized so that the total is 100% is obtained. The integral elution curve for the elution temperature is also calculated. By differentiating the integral elution curve with temperature, the derivative elution curve can be obtained. In each chromatogram, the molecular weight distribution is obtained after conversion from the storage capacity to the molecular weight is carried out by using a standard curve prepared by using standard polystyrene prepared in advance.

The polyolefin-based resin composition according to one embodiment of the present invention is characterized in that the cumulative elution amount of the olefin polymer during the CFC analysis at a density of 0.850 to 0.910 g / cc at -20 to 130 ° C is 20% 80% by weight, the slope value of the cumulative dissolution line is 2 or less, more specifically 1.7 or less, more specifically 1.67 or less. The cumulative amount of elution of 20 to 80% by weight means a region excluding the high-density region excluding the low-density region eluted at -20 캜 to the maximum extent. The elution line slope value indicates a broader crystalline distribution than a conventional polyolefin elastomer, and as a result, excellent workability can be exhibited.

The polyolefin-based resin composition may have a high R ² value of the trend line of the cumulative dissolution line of 0.997 or more and less than 1, more specifically, 0.999 or more and less than 1. By having such a high R ² value, it has a wide crystalline distribution and a uniform distribution according to the degree of crystallinity, so that it can exhibit a low viscosity even at a high shear rate as compared with an olefinic polymer having the same density and MI.

The polyolefin-based resin composition has a melt index of 10 g / 10 min or less measured at 190 ° C and a load of 2.16 kg according to ASTM D1238 under conditions satisfying the above-mentioned physical properties, more specifically, 10 g / 10 min. By having such a melt index, the physical properties are more optimized and high impact strength and good mechanical properties can be achieved with excellent processability.

The polyolefin-based resin composition may have a molecular weight distribution (PDI) of 3 or more, more specifically 4 or more, and more specifically 4 to 5, under conditions that satisfy the above-mentioned physical properties. By having such a broad molecular weight distribution, the physical properties are more optimized and excellent workability can be exhibited.

The polyolefin resin composition may have a weight average molecular weight (Mw) of 50,000 to 120,000 Da, more specifically 70,000 to 100,000 Da under conditions satisfying the above physical property characteristics.

On the other hand, the polyolefin-based resin composition exhibiting the above-mentioned physical properties is preferably a polyolefin-based resin composition containing at least one of ethylene, propylene, 1-butene, 1-pentene, Dodecene, 1-hexadecene, 1-hexadecene, 1-hexadecene, Of an olefinic monomer selected from the group consisting of 4-butadiene, 1,5-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene and 3-chloromethylstyrene And may include homopolymers or copolymers.

The polyolefin resin composition is selected from the group consisting of ethylene, propylene, and mixtures thereof, and the remaining auxiliary components include 1-butene, 1-pentene, 4-methyl- -Olefins having 4 to 10 carbon atoms such as 6 to 8 carbon atoms, such as heptene, 1-octene, 1-decene, 1-undecene, 1-undecene, Two or more, specifically two or three, olefin polymers, including repeating units derived from comonomers. The content of the? -Olefin comonomer contained in the olefin polymer may be 35 to 40 mol%. At this time, the content of the comonomer (-olefin) can be calculated as the content (mol%) of the -olefin with respect to the molar amount of the entire copolymer by ¹ H-NMR or ¹³ C-NMR.

When the polyolefin-based resin composition contains two or three kinds of olefin polymers, the respective olefin polymers to be contained may be ones having different physical properties such as kind, density or MI of the monomers, and the polyolefin- The kind, the physical properties, and the mixing ratio can be appropriately adjusted so as to satisfy the physical property requirements of the resin composition.

More specifically, the polyolefin-based resin composition contains a low density region of 0.80 g / cc or more and less than 0.860 g / cc and a high density region of 0.880 g / cc or more and 0.90 g / cc or less, and has a melt index (Measured according to ASTM D1238 standard at a temperature of 190 DEG C and a load of 2.16 kg); And one or more second olefin copolymers having a density of from 0.850 to 0.890 g / cc and a melt index of at least 300 g / 10 min (measured at a temperature of 190 DEG C and a load of 2.16 kg according to the ASTM D1238 standard) have. The mixing ratio of the first and second olefin copolymers may be determined within a range that satisfies the physical properties of the polyolefin-based resin composition. More specifically, the mixing ratio of the first olefin copolymer and the second olefin copolymer may be determined according to ASTM D1238, And a melt index of the polyolefin-based resin composition measured under a load of 10 g / 10 min or less.

In the first and second olefin copolymers, the content ratio of the monomers constituting the respective copolymers may be adjusted in various ranges depending on the physical properties to be imparted to the polyolefin-based resin composition. By way of non-limiting example, the first olefin copolymer may have an ethylene content of 50 wt% or more, or 50 to 90 wt%, an alpha-olefin content of 50 wt% or less, or 10 to 50 wt% Olefin copolymer can exhibit appropriate elasticity as an elastomer.

The weight average molecular weight of the first and second olefin copolymers may be controlled in various ranges depending on physical properties to be imparted to the polyolefin elastomer. As a non-limiting example, the first olefin copolymer may have a weight average molecular weight of 50,000 to 200,000 g / mol, which may be advantageous for imparting appropriate physical properties as an elastomer.

On the other hand, it has been confirmed that in the polyolefin-based resin composition, the first olefin copolymer can be produced by a production method using a specific catalyst system described later. More specifically, the first olefin copolymer may be prepared by a process comprising the step of copolymerizing ethylene and an alpha-olefin in the presence of a catalyst composition comprising a transition metal compound of the formula

&Lt; Formula 1 >

In Formula 1,

Each M &_lt; _{1 &gt;} is independently a transition metal of Group 4,

Q ₁ and Q ₂ are each independently selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An aryl group, an arylalkyl group having 7 to 20 carbon atoms, an alkylamido group having 1 to 20 carbon atoms, an arylamido group having 6 to 20 carbon atoms, and an alkylidene group having 1 to 20 carbon atoms,

R ₁ to R ₆ are each independently selected from the group consisting of hydrogen, halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, An alkylaryl group, an arylalkyl group having 7 to 20 carbon atoms, and a metalloid radical of a Group 14 metal substituted with hydrocarbyl having 1 to 20 carbon atoms; Or at least two functional groups adjacent to each other of R ₁ to R ₆ are connected to each other to form a group selected from the group consisting of halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms An aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms, which is unsubstituted or substituted with one substituent;

R ₇ to R ₁₁ each independently represent a hydrogen atom, a halogen atom, an amino group, an amino group having 1 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, A metalloid radical of a Group 14 metal substituted with an aryl group having from 7 to 20 carbon atoms, an alkylaryl group having from 7 to 20 carbon atoms, an arylalkyl group having from 7 to 20 carbon atoms and a hydrocarbyl group having from 1 to 20 carbon atoms; Or at least one functional group selected from the group consisting of halogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms, wherein at least two functional groups adjacent to each other among R ₇ to R ₁₁ are connected to each other An aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms, which is unsubstituted or substituted with a substituent.

According to the structural characteristics of the transition metal compound of the above-mentioned formula (1), which are also confirmed in the following examples, by copolymerizing ethylene and an alpha-olefin using a catalyst composition containing them together, a first olefin copolymer Coalescence can be produced.

Specifically, in Formula 1, M ₁ may be Ti, Hf, or Zr.

In Formula 1, Q ₁ and Q ₂ are each independently selected from the group consisting of hydrogen, halogen, and an alkyl group having 1 to 6 carbon atoms.

In the above formula (1), R ₁ and R ₂ are each an alkyl group having 1 to 20 carbon atoms, more specifically an alkyl group having 1 to 6 carbon atoms, and still more specifically, a methyl group.

In Formula 1, R ₃ to R ₆ are each independently selected from the group consisting of hydrogen; An alkyl group having 1 to 20 carbon atoms; Or an alkenyl group having 2 to 20 carbon atoms, more specifically, hydrogen or an alkyl group having 1 to 20 carbon atoms, and more specifically, each of them may be a hydrogen atom.

In the above formula (1), R ₇ to R ₁₀ may each independently be hydrogen or an alkyl group having 1 to 6 carbon atoms.

In the above formula (1), R ₁₁ may be an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, May be any one or two or more selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an aryloxy group having 6 to 20 carbon atoms. In formula (1), 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 any one or two or more substituents selected from the group consisting of a halogen group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. have.

More specifically, the transition metal compound represented by the formula (1) is a transition metal compound represented by the formula (1) wherein R ₁₁ is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, May be a compound represented by the following formula, and any one or a mixture of two or more thereof may be used:

In the above formula, OMe means a methoxy group and Me means a methyl group.

The transition metal compound represented by the formula (1) may be a compound represented by the following formula (2) when R ₁₁ is connected to adjacent R ₁₀ to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms Can be:

(2)

In the above Formula _{2, M 1, Q 1,} Q 2, R 1 to R ₉ have the same meanings as defined in formula 1, Cy is nitrogen (N) containing a carbon number of 4 or 5 aliphatic cyclic group, R, R ₁₂ And R ₁₃ are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. An aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms;

m is an integer of 0 to 2 when Cy is an aliphatic cyclic group of 4 carbon atoms and may be an integer of 0 to 4 when Cy is an aliphatic cyclic group of 5 carbon atoms.

More specifically, the compound of Formula 2 may be a compound of Formula 2a or 2b:

&Lt; EMI ID =

In Formula 2a,

Ra to Rd each independently represent hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms And the remaining substituents are as defined in Formula 1,

(2b)

In Formula 2b,

Re and Rf are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms. An alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms, and the remaining substituents are the same as defined in formula (1).

Specific examples of the transition metal compound represented by the above formula (2) may be a compound represented by the following formula:

In the above formula, tBu means a tert-butyl group.

In addition, the catalyst composition used for producing the first olefin copolymer may further include a cocatalyst.

The cocatalyst can be used without particular limitation as long as it is known in the art, such as alkylaluminoxane, alkylaluminum or Lewis acid. Specifically, the cocatalyst may include any one or a mixture of two or more selected from the group consisting of compounds represented by the following formulas (3) to (6):

(3)

- [Al (R &lt; ₄₁ &gt;) - O] a-

In Formula 3, R ₄₁ is independently a halogen, a hydrocarbyl group having 1 to 20 carbon atoms or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen, a is an integer of 2 or more,

&Lt; Formula 4 >

D ( _R42 ) ₃

In Formula 4, D is aluminum or boron, and R ₄₂ is independently a halogen, a hydrocarbyl group having 1 to 20 carbon atoms, or a hydrocarbyl group having 1 to 20 carbon atoms substituted with halogen,

&Lt; Formula 5 >

[LH] + [Z (A) ₄ ] -

(6)

[L] + [Z (A) ₄ ] -

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

The compound represented by the above-described general formula (3) may be alkylaluminoxane, and specific examples thereof include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane and butylaluminoxane, and more specifically, methylaluminoxane.

The compound represented by the above-mentioned general formula (4) is specifically exemplified by trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, But are not limited to, cyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, For example, be selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, and the like, and more specifically may be selected from trimethylaluminum, triethylaluminum, triisobutylaluminum, and the like.

The compound of formula (5) or (6) is specifically exemplified by triethylammoniumtetraphenylboron, tributylammoniumtetraphenylboron, trimethylammoniumtetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra (p- Tolyl) boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl) boron, tributylammonium N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, Diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl (P-tolyl) aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra (p-tolyl) aluminum, tripropylammonium tetra (Dimethylphenyl) aluminum, tributylammoniumtetra (p-trifluoromethylphenyl) aluminum, trimethylammoniumtetra (ptrifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N, N- Diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetrapentafluorophenyl aluminum, diethylammonium tetrapentatetraphenyl aluminum, tri Phenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum (P-tolyl) boron, triethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammoniumtetra (p-tolyl) boron, tripropylammoniumtetra Dimethylphenyl) boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl) boron, tributyl N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron , Diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, triphenylcarboniumtetra (p-trifluoromethylphenyl) boron, or triphenylcarbonium tetrapentafluorophenylboron, etc. .

The addition amount of the above-described co-catalyst compound may be in a molar ratio of about 1: 1 to 1:20 based on the transition metal compound of the above formula (1). In order to exhibit the effect of the promoter compound above a certain level, the content of the promoter compound may be 1: 1 or more in a molar ratio with respect to the main catalyst compound of the transition metal compound of the formula (1). Further, for proper property control of the olefin copolymer to be produced and effective activation of the main catalyst compound, the promoter compound may be contained at a molar ratio of 1:20 or less with respect to the main catalyst compound.

 On the other hand, in the method for producing the first olefin copolymer, the olefin copolymer can be produced by a method comprising copolymerizing ethylene and an alpha-olefin-containing monomer in the presence of the catalyst composition described above. The alpha-olefin monomers that can be used here include 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-hexadecene, 1-hexadecene, and the like, more preferably 1-octene.

The copolymerization may be carried out at a temperature of 120 ° C. or higher, 120 ° C. to 180 ° C., or 120 ° C. to 160 ° C., and may be conducted at a pressure of 50 bar or more, 50 to 120 bar, or 70 to 100 bar.

The copolymerization step may be performed by a solution process using the catalyst composition described above, or the slurry process or the gas phase process may be performed using the catalyst composition together with an inorganic carrier such as silica. More specific progress conditions and methods of the copolymerization step will be described below, focusing on the continuous solution polymerization process.

In the copolymerization step, a scavenger may be charged at a rate of 0.4 to 5 times the total water content in the reactor. Such a scavenger serves to remove impurities such as moisture or air that may be contained in the reactant, and may be introduced before the copolymerization of the reactant occurs. The scavenger and the mixture of reactants may be mixed in a separate reactor other than the polymerization reactor and the scavenger and the reactant may be mixed and the reactants mixed with the scavenger for a sufficient time in the feed line where the reactants are fed to the polymerization reactor . Preferable examples of the scavenger include, but are not limited to, trialkylaluminum such as TiBAl (triisobutylaluminum) or TOA (trioctylaluminum).

In addition, the copolymerization step can be carried out by introducing the catalyst composition, the monomer and the scavenger mentioned above in the reactor.

The catalyst composition may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the olefin polymerization process, for example, pentane, hexane, heptane, nonane, decane, or an isomer thereof; Aromatic hydrocarbon solvents such as toluene or benzene; Or a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane or chlorobenzene, or may be injected by dilution.

And, in one embodiment proceeding the copolymerization step, the molar ratio of ethylene to the solvent needs to be a ratio suitable to dissolve the reactant and the resulting olefin copolymer. For example, the molar ratio of (ethylene / solvent) may be about 1 / 10,000 to 10, or about 1/100 to 5, or about 1/20 to 1. By appropriately setting such a molar ratio, the copolymerization step can be effectively carried out, and the amount of the solvent can be optimized, thereby making it possible to suppress the increase of the equipment and the increase of the energy cost due to the purification recycle of the solvent.

The solvent can be introduced into the reactor at a temperature of about -40 to 150 ° C. by using a heater or a freezer, and the polymerization reaction can be started together with the monomer and the catalyst composition.

In addition, a high-capacity pump can be used to increase the pressure above about 50 bar to provide feeds (solvent, monomers, catalyst composition, etc.), thereby avoiding additional pumping between the reactor arrangement, The mixture can be passed through.

The olefin copolymer produced in the reactor may then be maintained at a concentration of less than about 20% by weight in the solvent and may be transferred to a primary solvent separation process for solvent removal after a short residence time. The appropriate time for the olefin copolymer to stay in the reactor can be from about 1 minute to 10 hours, or from about 3 minutes to 1 hour, or from about 5 minutes to 30 minutes. As a result, the productivity can be reduced, the loss of the catalyst can be suppressed, and the size of the reactor can be optimized.

After the above-mentioned copolymerization step, the solvent separation step may be further performed by changing the solution temperature and pressure in order to remove the solvent present with the olefin copolymer exiting the reactor. At this time, the copolymer solution transferred from the reactor is maintained in a molten state through a heater, and the unreacted raw material solvent is vaporized in a separator, and the resulting copolymer can be granulated by an extruder or the like.

The first olefin copolymer produced according to the above production method has a low density region of 0.80 g / cc or more and less than 0.860 g / cc and a high density region of 0.880 g / cc or more and 0.90 g / cc or less, (Measured at a temperature of 190 캜 and a load of 2.16 kg according to the ASTM D1238 standard).

On the other hand, the second olefin copolymer to be mixed with the first olefin copolymer has a higher melt index together with the density of the middle region of the first olefin copolymer, specifically, a density of 0.850 to 0.890 g / cc And a melt index of 300 g / 10 min or more (measured at a temperature of 190 캜 and a load of 2.16 kg in accordance with ASTM D1238).

As a non-limiting example, the density of the second olefin copolymer may be 0.85 to 0.88 g / cc, or 0.86 to 0.88 g / cc. Also, as a non-limiting example, the melt index of the second olefin copolymer may have a melt index of 300 g / 10 min or more, or 300 to 700 g / 10 min under a load of 2.16 kg and a temperature of 190 ° C.

On the other hand, according to another embodiment of the present invention, there is provided a polyolefin-based elastomer comprising the above-mentioned resin composition.

According to one embodiment, the polyolefin-based elastomer is a mixture of the first and second olefin copolymers described above and exhibits the same physical properties as the polyolefin-based resin composition, and can exhibit excellent processability.

Best Mode for Carrying Out the Invention Hereinafter, preferred embodiments are described to facilitate understanding of the present invention. However, the following examples are intended to illustrate the present invention without limiting it thereto.

Preparation Example 1: Preparation of first olefin polymer A

A 1.5 L autoclave continuous reactor was charged with a hexane solvent (5.00 kg / h) and 1-octene (1.05 kg / h), and the temperature at the top of the reactor was preheated to 145 ° C. Benzo [b] cyclopenta [d] thiophen-3-yl) -2-methyl-1,2,3, -triisobutyl aluminum compound (0.045 mmol / 4-tetrahydroquinoline (0.42 占 퐉 ol) was obtained in the same manner as in Example 1, except that 4-tetrahydroquinoline (8- (1,2-dimethyl-1H-benzo [b] cyclopenta [d] thiophen- / min) and dimethylanilinium tetrakis (pentafluorophenyl) borate promoter (1.26 μmol / min) were simultaneously introduced into the reactor. Then, 0.87 kg / h of ethylene was fed into the autoclave reactor and maintained at 145 ° C. for one hour or more in a continuous process at a pressure of 89 bar, followed by copolymerization reaction to obtain a copolymer. The obtained copolymer was dried in a vacuum oven at 190 DEG C for at least 12 hours and then used.

As a result of the analysis using DSC (Differential Scanning Calorimetry), the prepared copolymer had a low density region at Tm 33 ° C and a high density region at Tm 80 ° C and showed a density of 0.861 g / cc. The melt index (MI _2.16 ) measured at a temperature of 190 캜 and a load of 2.16 kg according to ASTM D1238 was 0.24 g / 10 min.

In the Tm described above, Tm 33 ° C represents the Tm of the ethylene / 1-octene copolymer having a density of 0.850 g / cc and Tm 80 ° C represents the Tm of the ethylene / 1-octene copolymer having a density of 0.890 g / .

Preparation Example 2: Preparation of second olefin polymer B

Affinity (TM) GA1950 (Dow, density = 0.874 g / cc, MI _2.16 = 500 g / 10 min) was used as the olefin polymer.

Example 1

Polymer A prepared in Production Example 1 was blended as the first polyolefin polymer, and Affinity (TM) GA1950 (manufactured by Dow) prepared in Production Example 2 as the second polyolefin polymer was blended to prepare a polyolefin resin composition. At this time, the blending ratio was 50:50 by weight of the final polyolefin resin composition, and blending was performed at 200 ° C using a Twin Extruder.

Comparative Example 1

Lucene 占 LC670 (manufactured by LG Chemical) was used as the olefin polymer.

Comparative Example 2

As the olefin polymer, Engage (TM) 8407 (manufactured by Dow) was used.

Experimental Example 1

The properties of the polyolefin-based resin composition prepared in Example 1 and the polyolefin polymer prepared in Comparative Examples 1 and 2 were measured by the following methods, and the results are shown in Table 1 below.

(1) Density (g / cc): A sample was prepared by press molding a 180 ° C. sheet having a thickness of 3 mm and a radius of 2 cm, and measured on a Mettler scale at 23 ° C. in a buoyancy measuring manner.

(2) Melt index (g / 10 min): Melt index (MI) of the polymer was measured by ASTM D-1238 (condition E, 190 ° C, 2.16 kg load).

(3) Weight average molecular weight (Mw) and molecular weight distribution (PDI): Using a gel permeation chromatography (GPC) The number average molecular weight (Mn) was measured, and the weight average molecular weight was divided by the number average molecular weight to calculate a polydispersity index (PDI). At this time, the analysis temperature was 160 캜, trichlorobenzene was used as a solvent, and the molecular weight was measured by standardizing with polystyrene.

(4) 1-Octene content: The ¹ -octene content (mol%) based on the total molar amount of the copolymer was calculated by ¹ H-NMR.

density
(g / cc) MI _2.16
(g / 10 min) Mw
(Da, k = 10 ³ ) PDI 1-octene content
(mole%) Comparative Example 1 0.870 5.0 83k 2.29 35.5 Comparative Example 2 0.871 27.9 53k 1.98 37.7 Example 1 0.869 5.9 87k 4.55 37.5

Experimental Example  2

The polyolefin resin composition of Example 1 and the olefin polymer of Comparative Example 1 were subjected to CFC analysis under the following conditions using Cross fractionation chromathography (manufactured by polymer char), and the amount of cumulative elution ranged from 20 to 80% by weight The cumulative dissipation line slope and the R ² value of the trend line were calculated. The results are shown in Table 1 and FIGS. 1 and 2, respectively.

Eluent: 1,2-dichlorobenzene

Pre-treatment condition before CFC analysis

1) Stabilized at 95 ° C for 45 minutes

2) cooled to -20 ° C at a rate of 0.5 ° C / min

3) Stabilization at -20 ° C for 10 minutes

Elution temperature (占 폚): -20, -15, -10, 0, 5, 10, 13, 16, 19, 22, 25, 28, 31, 34, 37, 40, 43, 46, , 61, 64, 67, 70, 73, 76, 79, 82, 85, 88, 91, 94, 97, 100, 105, 115, 130

Cumulative elution The cumulative elution slope between 20 and 80 wt% R ^{2 of the} trend line Comparative Example 1 3.99 0.996 Comparative Example 2 2.22 0.987 Example 1 1.67 0.999

Experimental Example  3

The shear viscosity of the polyolefin resin composition of Example 1 and the olefin polymers of Comparative Examples 1 and 2 at high shear rates was measured. The results are shown in Fig.

As a result, the polyolefin-based resin composition of Example 1 significantly improved the shear viscosity at the high shear rate as compared with Comparative Example 1 having the same level of density, and compared with Comparative Example 2 having a melt index (MI _{2. 16} ) of about 30 The results were almost equal.

From this, it can be seen that the polyolefin-based resin composition of Example 1 has excellent processability.

Claims (7)

A density of 0.850 to 0.910 g / cc,
Cumulative elution when the cumulative elution amount of the olefin polymer eluted in the cross-fractionation chromatography (CFC) analysis in the range of -20 캜 to 130 캜 after pretreatment under the following conditions is 20% by weight to 80% by weight of the total elution amount And a tilt value of the line is not more than 2. The polyolefin-
<Pretreatment Condition>
1) Stabilized at 95 ° C for 45 minutes
2) cooled to -20 ° C at a rate of 0.5 ° C / min
3) Stabilization at -20 ° C for 10 minutes
The polyolefin-based resin composition according to claim 1, wherein the R ² value of the trend line in the cumulative dissolution line is 0.997 or more and less than 1.
The polyolefin-based resin composition according to claim 1, wherein the polyolefin-based resin composition has a molecular weight distribution of 3 or more.
The polyolefin-based resin composition according to claim 1, wherein the weight average molecular weight (Mw) is 50,000 to 120,000 Da.
The polyolefin-based resin composition according to claim 1, wherein the polyolefin-based resin composition has a low density region of 0.80 g / cc or more and less than 0.860 g / cc and a high density region of 0.880 g / cc or more and 0.90 g / cc or less, At least one first olefin copolymer having a melt index (measured under a load of 2.16 kg at a temperature of 190 占 폚 according to ASTM D1238 standard); And
At least one second olefin copolymer having a density of from 0.850 to 0.890 g / cc and a melt index of at least 300 g / 10 min (measured at a temperature of 190 DEG C and a load of 2.16 kg according to ASTM D1238)
Wherein said first and second olefin copolymers have a melt index of not more than 10 g / 10 min measured at a temperature of 190 캜 and a load of 2.16 kg according to ASTM D1238.
6. The polyolefin-based resin composition according to claim 5, wherein each of the first and second olefin copolymers is independently copolymerized with ethylene and an alpha-olefin comonomer having 4 to 8 carbon atoms.
A polyolefin-based elastomer comprising the polyolefin-based resin composition according to claim 1.

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