KR20160077642A - Ethylene-alphaolefin-styrene copolymers and method for preparing the same - Google Patents

Ethylene-alphaolefin-styrene copolymers and method for preparing the same Download PDF

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KR20160077642A
KR20160077642A KR1020140187784A KR20140187784A KR20160077642A KR 20160077642 A KR20160077642 A KR 20160077642A KR 1020140187784 A KR1020140187784 A KR 1020140187784A KR 20140187784 A KR20140187784 A KR 20140187784A KR 20160077642 A KR20160077642 A KR 20160077642A
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carbon atoms
radical
ethylene
styrene
alpha olefin
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KR1020140187784A
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Korean (ko)
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박해웅
조윤희
공진삼
이충훈
박상은
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주식회사 엘지화학
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Abstract

The present invention provides an ethylene-alpha olefin-styrene copolymer including 50-80 wt% of an ethylene derived monomer, 10-40 wt% of an alpha olefin-based compound derived monomer, and 10-40 wt% of a styrene-based compound derived monomer based on a copolymer total weight. In addition, a weight average molecular weight of the copolymer is 50,000-200,000, density thereof is 0.875-0.900 g/cc, and a melting point (Tm) thereof is 40.0-70.0°C. According to the present invention, the ethylene-alpha olefin-styrene copolymer can be prepared using a catalyst composition including a transition metal compound, and a copolymer having higher density and a lower melting point, than a conventional copolymer, is provided.

Description

TECHNICAL FIELD The present invention relates to an ethylene-alpha olefin-styrene copolymer, and an ethylene-alpha olefin-styrene copolymer and a method for producing the same. BACKGROUND ART < RTI ID =

The present invention relates to ethylene-alpha olefin-styrene copolymers and processes for their preparation. More specifically, the present invention relates to an ethylene-alpha olefin-styrene copolymer having a higher melting point and a lower melting point than conventional copolymers and a method for producing the same.

In the copolymerization reaction of ethylene and alpha olefins in the early 1990s, [Dow] [Me 2 Si (Me 4 C 5 ) NtBu] TiCl 2 (Constrained-Geometry Catalyst, hereinafter abbreviated as CGC) (1) high molecular weight copolymers with high activity at high polymerization temperatures, (2) copolymers of 1-hexene and 1- It is also excellent in the copolymerization of α-olefins with large steric hindrance such as octene. In addition, various characteristics of CGC were gradually known during the polymerization reaction, and efforts to synthesize the derivative and use it as a polymerization catalyst have actively been made in academia and industry.

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

The present invention relates to an ethylene-olefin-styrene copolymer having a high density and a low melting point as compared with conventional copolymers and a process for producing the same.

In order to solve the above problems, the present invention provides a thermoplastic resin composition comprising 50 to 80% by weight of an ethylene monomer, 10 to 40% by weight of an alpha olefin monomer, and 10 to 40% by weight of a styrene monomer, based on the total weight of the copolymer , The copolymer has a weight average molecular weight of 50,000 to 200,000, a density of 0.875 to 0.900 g / cc, and a melting point (Tm) of 40.0 to 70.0 ° C.

The ethylene-alpha olefin-styrene copolymer may be prepared by using a composition containing a transition metal compound represented by the following formula (1).

 [Chemical Formula 1]

Figure pat00001

In Formula 1,

R1 and R2 may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Silyl radical; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; Or a metalloid radical of a Group 4 metal substituted with hydrocarbyl; The R1 and R2 or two R2 may be linked to each other to form a ring by an alkylidene radical comprising an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms;

R3 may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical; Two or more of R3's may be linked to each other to form an aliphatic ring or an aromatic ring;

CY1 is a substituted or unsubstituted aliphatic or aromatic ring, the substituent on CY1 is a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical, and when the number of the substituents is plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring;

M is a Group 4 transition metal;

Q1 and Q2 may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms.

The ethylene-alpha olefin-styrene copolymer according to the present invention can be produced by using a catalyst composition containing a transition metal compound, and has a high density and a low melting point as compared with conventional copolymers.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other objects, features and advantages of the present invention will be more apparent from the following detailed description taken in conjunction with the accompanying drawings, in which: FIG.

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.

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 "

The term 'catalytic activity' used in the present invention means a value obtained by dividing the molar (mol) and the time (hr) of the catalyst using the yield (kg) of the finally obtained polymer through metallocene polymerization.

In order to solve the above-mentioned problems, one embodiment of the present invention is a method for producing a thermoplastic resin composition, comprising 50 to 80% by weight of an ethylene monomer, 10 to 40% by weight of an alpha olefin monomer, 10 to 40% by weight of a styrene monomer Styrene copolymer having a weight average molecular weight of 50,000 to 200,000, a density of 0.875 to 0.900 g / cc and a melting point (Tm) of 40.0 to 70.0 ° C. to provide.

The ethylene-alpha olefin-styrene copolymer may contain repeating units derived from the ethylene monomer, repeating units derived from the alpha olefin-based monomer, and repeating units derived from the styrene- As shown in FIG.

The alpha olefin-based compound which is a monomer of the ethylene-alpha olefin-styrene copolymer may be at least one selected from the group consisting of propylene, 1-butene, 1-pentene, 4- , 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-aidocene.

The styrene compound, which is a monomer of the ethylene-alpha olefin-styrene copolymer, may be at least one selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, Ethyl styrene, t-butyl styrene, and the like.

The ethylene-alpha olefin-styrene copolymer may have a weight average molecular weight of the copolymer of 50,000 to 200,000, preferably 70,000 to 150,000. The density of the copolymer is 0.875 to 0.900 g / cc, the melting point (Tm) is 40.0 to 70.0 ° C, the density is 0.88 to 0.90 g / cc and the melting point (Tm) have. Also, the crystallization temperature (Tc) of the copolymer according to an embodiment of the present invention may be 20 to 50 ° C, preferably 20 to 43 ° C.

The ethylene-alpha olefin-styrene copolymer may be prepared using a composition comprising a transition metal compound represented by the following formula (1).

 [Chemical Formula 1]

Figure pat00002

In Formula 1,

R1 and R2 may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Silyl radical; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; Or a metalloid radical of a Group 4 metal substituted with hydrocarbyl; The R1 and R2 or two R2 may be linked to each other to form a ring by an alkylidene radical comprising an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms;

R3 may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical; Two or more of R3's may be linked to each other to form an aliphatic ring or an aromatic ring;

CY1 is a substituted or unsubstituted aliphatic or aromatic ring, the substituent on CY1 is a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical, and when the number of the substituents is plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring;

M is a Group 4 transition metal;

Q1 and Q2 may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms.

Among the compounds of the formula (1), the transition metal compound is preferably a transition metal compound represented by the following formula (2) or (3) for controlling the electronic and stereoscopic environment around the metal.

(2)

Figure pat00003

(3)

Figure pat00004

In the general formulas (2) and (3)

R4 and R5 may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Or a silyl radical;

R6 may be the same or different and are each independently selected from the group consisting of hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical; Two or more R < 6 > among the R < 6 > may be linked to each other to form an aliphatic or aromatic ring;

Q3 and Q4 may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; Or an arylamido radical having 6 to 20 carbon atoms;

M is a Group 4 transition metal.

In the above formula (1), more preferred compounds for controlling the electronic stereoscopic environment around the metal are transition metal compounds having the following structures.

Figure pat00005

In the above formula,

R7, which may be the same or different, are each independently selected from hydrogen or a methyl radical,

Q5 and Q6 may be the same or different and are each independently selected from a methyl radical, a dimethylamido radical, or a chloride radical.

The catalyst composition comprising the transition metal compound may include at least one of the following promoter compounds represented by the following general formula (4), (5) or (6).

[Chemical Formula 4]

- [Al (R < 8 >) - O] n -

In Formula 4,

R8 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

n is an integer of 2 or more;

[Chemical Formula 5]

D (R 8) 3

In Formula 5,

R8 is as defined in Formula 4 above;

D is aluminum or boron;

[Chemical Formula 6]

[LH] + [ZA 4 ] - or [L] + [ZA 4 ] -

In Formula 6,

L is a neutral or cationic Lewis acid;

H is a hydrogen atom;

Z is a Group 13 element;

A may be the same as or different from each other, and independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy .

Examples of the compound represented by the general formula (4) include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane and the like. A more preferred compound is methylaluminoxane.

Examples of the compound represented by Formula 5 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

Examples of the compound represented by Formula 6 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p-tolyl) Boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (ptrifluoromethylphenyl) boron, trimethylammoniumtetra (ptrifluoromethylphenyl) boron, tributylammoniumtetra N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenylboron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammonium tributylammonium (P-trifluoromethylphenyl) aluminum, trimethylammonium tetra (p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N , N-diethylanilinium tetrapentafluorophenyl aluminum, diethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra (p-tolyl) Boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p -trifluoromethylphenyl) boron, triphenylcarboniumtetra -Phenyl) boron and the like, triphenylamine car I Titanium tetra-penta flow phenylboronic.

The catalyst composition comprising the transition metal compound usable in the present invention can be prepared by a first method

1) contacting the transition metal compound represented by Formula 1 with the compound represented by Formula 4 or 5 to obtain a mixture; And

2) adding the compound represented by Formula 6 to the mixture.

The catalyst composition comprising the transition metal compound that can be used in the present invention can be prepared by a method of contacting the transition metal compound represented by Formula 1 and the compound represented by Formula 4 as a second method.

In the first method of the above method for producing the catalyst composition, the molar ratio of (the transition metal compound represented by Formula 1 / the compound represented by Formula 4 or Formula 5) is preferably 1 / 5,000 to 1/2, , More preferably from 1/1000 to 1/10, and most preferably from 1/500 to 1/20. When the molar ratio of the transition metal compound represented by the formula (1) / the compound represented by the formula (4) or the formula (5) exceeds 1/2, the amount of the alkylating agent is so small that the alkylation of the metal compound can not proceed completely If the molar ratio is less than 1/5000, the alkylation of the metal compound is performed, but the alkylation of the alkylated metal compound due to the side reaction between the excess of the alkylating agent and the activating agent of the above formula (6) . The molar ratio of (transition metal compound represented by Formula 1 / compound represented by Formula 6) is preferably 1/25 to 1, more preferably 1/10 to 1, and most preferably 1 / 5 ~ 1. (The transition metal compound represented by the above formula (1) / the compound represented by the above formula (6)) exceeds 1, the amount of the activator is relatively small and the activation of the metal compound is not completely achieved. However, when the molar ratio is less than 1/25, the activation of the metal compound is completely performed. However, the problem is that the unit cost of the catalyst composition is not economical due to the excess activator remaining or the purity of the produced polymer is low have.

In the case of the second method among the above-mentioned methods for producing the catalyst composition, the molar ratio of (the transition metal compound represented by the formula (1) / the compound represented by the formula (4)) is preferably 1 / 10,000 to 1/10, Is 1 / 5,000 to 1/100, and most preferably 1 / 2,000 to 1/500. When the molar ratio is more than 1/10, the amount of the activator is relatively small and the activation of the metal compound is not achieved completely. Therefore, there is a problem in that the activity of the catalyst composition is decreased. Although the activation is completely performed, there is a problem that the unit cost of the catalyst composition is not economical due to the excess activator remaining or the purity of the produced polymer is low.

As the reaction solvent, hydrocarbon solvents such as pentane, hexane, heptane and the like, or aromatic solvents such as benzene, toluene and the like may be used in the preparation of the catalyst composition containing the transition metal compound. The transition metal compound and the cocatalyst can also be used in the form supported on silica or alumina.

The process for preparing an ethylene-alpha olefin copolymer of the present invention is a process for producing an ethylene-alpha olefin-styrene copolymer by a general method known in the art except for using a catalyst composition containing a transition metal represented by the above formula can do.

Hereinafter, the present invention will be described focusing on a continuous solution polymerization process. However, the scope of the present invention is not limited thereto.

Polymerization process

The polymerization process proceeds by the introduction of a catalyst composition comprising the above transition metal compound and cocatalyst, ethylene, alpha olefin, and styrene monomer on the reactor. In the case of polymerization in the form of a solution phase and a slurry, a solvent is injected onto the reactor. Therefore, in the case of solution polymerization, a mixture of a solvent, a catalyst composition, ethylene, an alpha olefin and a styrene monomer is present inside the reactor.

It is particularly preferable that the process for producing the copolymer is carried out in the presence of a solvent, the ethylene, the olefin monomer is 1-octene, the styrene monomer is styrene, and the solvent is n-hexane.

The process for preparing the ethylene-alpha olefin-styrene copolymer according to an embodiment of the present invention may be performed by a batch solution polymerization process.

The solvent may be one or more selected from the group consisting of an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, an aromatic hydrocarbon solvent, and a hydrocarbon solvent substituted with a chlorine atom, Specific examples of the solvent include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms such as pentane, hexane, heptane, nonane, decane, and isomers thereof; Aromatic hydrocarbon solvents such as toluene and benzene; Hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene; A mixture thereof, and the like may be used, but the present invention is not limited thereto.

The present invention relates to a process for producing a polyolefin having a weight average molecular weight of 50,000 to 200,000, a density of 0.875 to 0.900 g / cc, and a melting point (Tm) of 100,000 to 200,000 by performing polymerization of ethylene, an alpha olefin monomer and a styrene monomer under the conditions of a reaction temperature of 110 to 130 ° C. Ethylene-alpha olefin-styrene copolymer having an ethylene content of 40.0 to 70.0 ° C. Particularly, in the case of a ternary copolymer containing a styrene monomer according to an embodiment of the present invention, a conventional copolymer having a high melting point and a high density can be provided.

The ethylene-alpha olefin copolymer according to the present invention can be used for a variety of applications such as packaging, construction, household goods such as materials for automobile, electric wire, toy, fiber, medical and the like.

Hereinafter, the present invention will be described more specifically based on the following examples. It is to be understood, however, that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

< Example >

< Example  1 to 4> Ethylene- Alpha olefin  Copolymer production

The 2L batch reactor was charged with 1 liter of hexane solvent and 210 ml of 1-octene and the styrene content shown in Table 1 below. The reaction temperature was 120 ° C and the pressure of the reactor was maintained at 35 bar using ethylene gas.

Triisobutylaluminum was added as a scavenger in order to remove the poison of the reaction solution in the reactor, 20 mol of octadecylmethylammonium tetrakis (pentafluorophenyl) borate co-catalyst was diluted in toluene, and the catalyst Was dissolved in hexane treated with triisobutyl aluminum compound, and 2 탆 ol was added to the reactor to conduct the reaction. The catalyst was prepared by reacting [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-eta 5, [1,2,3,4- Tetrahydroquinolin-8 -yl] tetramethylcyclopentadienyl-eta 5, kappa-N)] titanium dimethyl) compound.

After 10 minutes, the polymerization was terminated, and the polymer was precipitated from the polymer solution produced from the polymerization reaction using methanol, and the physical properties thereof were measured. The results are shown in Table 1 below.

The specific conditions of Examples 1 to 3 are shown in Table 1 below.

< Comparative Example  1> Ethylene- Alpha olefin  Copolymer production

An ethylene-alpha olefin copolymer was prepared in the same manner as in Example 1 except that styrene monomer was not used as shown in Table 1 below.

< Experimental Example > Example  1 to 3 and Comparative Example  1 &lt; / RTI &gt;

The above embodiments 1-3 and the comparative example the density of a copolymer produced in the first, a melt index (MI 2 .16), glass transition temperature (Tg), melting temperature (Tm), crystallization temperature (Tc), such as by measuring The results are shown in Table 1 below.

SAMPLE polymerization
Condition Polymerization results Styrene
(ml) Yield
(g) Density
(g / cc) MI
(g /
10 min) Tc
℃ Tm
℃ Tg
℃ Wt% (1 to C8)
(/ 1000C) Wt% (S)
(/ 1000C) Comparative Example 1 0 96.7 0.879 0.59 44.4 /
62.5 61.8 -48.4 39.4 (31.5) 0 Example 1 10 90.4 0.882 0.69 41.8 /
64.8 60.8 -46.5 37.2 (29.8) 2.7 (2.0) Example 2 30 75.2 0.884 0.48 35.4 /
56.7 53.9 -45.3 35.7 (28.7) 7.6 (5.6) Example 3 50 44.3 0.886 0.17 27.0 47.8 -43.2 35.2 (28.3) 11.0 (8.2)

(1) Density: Measured by ASTM D792 analysis method

(2) a melt index (MI 2 .16): measured using the ASTM D1238 method

(3) Glass transition temperature (Tg), melting temperature (Tm), crystallization temperature (Tc): Measured using a differential scanning calorimeter (TA Instruments, DSC 2910)

From the results of Table 1, it can be seen that as the amount of styrene per 1000 carbon atoms in the ethylene-alpha olefin-styrene copolymer according to the present invention increases, the catalytic activity decreases, the density increases, and the melting point decreases .

Claims (12)

Based on the total weight of the copolymer,
50 to 80% by weight of an ethylene monomer,
10 to 40% by weight of an alpha olefinic compound monomer,
And 10 to 40% by weight of a styrene-based compound monomer,
Wherein the copolymer has a weight average molecular weight of 50,000 to 200,000, a density of 0.875 to 0.900 g / cc, and a melting point (Tm) of 40.0 to 70.0 ° C.
The method according to claim 1,
The alpha-olefin-based monomer of the ethylene-alpha olefin-styrene copolymer may be selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl- And at least one member selected from the group consisting of 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, and 1-aidocene.
The method according to claim 1,
The styrene-based compound monomer of the ethylene-alpha olefin-styrene copolymer is at least one member selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, Styrene, and t-butylstyrene. 2. The ethylene-alpha olefin-styrene copolymer according to claim 1,
The method according to claim 1,
The ethylene-alpha olefin-styrene copolymer may contain,
Wherein the copolymer has a weight average molecular weight of 70,000 to 150,000 densities of 0.875 to 0.900 g / cc and a melting point (Tm) of 40.0 to 70.0 ° C.
The method according to claim 1,
An ethylene-alpha olefin-styrene copolymer produced by using a composition comprising a transition metal compound represented by the following formula (1).
[Chemical Formula 1]
Figure pat00006

In Formula 1,
R1 and R2 may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Silyl radical; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; Or a metalloid radical of a Group 4 metal substituted with hydrocarbyl; The R1 and R2 or two R2 may be linked to each other to form a ring by an alkylidene radical comprising an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms;
R3 may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical; Two or more of R3's may be linked to each other to form an aliphatic ring or an aromatic ring;
CY1 is a substituted or unsubstituted aliphatic or aromatic ring, the substituent on CY1 is a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical, and when the number of the substituents is plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring;
M is a Group 4 transition metal;
Q1 and Q2 may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms.
A method for producing an ethylene-alpha olefin-styrene copolymer, which comprises polymerizing ethylene, an alpha olefin-based monomer, and a styrene-based monomer in the presence of a catalyst composition comprising a transition metal compound represented by the following formula
[Chemical Formula 1]
Figure pat00007

In Formula 1,
R1 and R2 may be the same or different from each other, and each independently hydrogen; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; Silyl radical; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; Or a metalloid radical of a Group 4 metal substituted with hydrocarbyl; The R1 and R2 or two R2 may be linked to each other to form a ring by an alkylidene radical comprising an alkyl having 1 to 20 carbon atoms or an aryl radical having 6 to 20 carbon atoms;
R3 may be the same or different from each other, and each independently hydrogen; Halogen radicals; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical; Two or more of R3's may be linked to each other to form an aliphatic ring or an aromatic ring;
CY1 is a substituted or unsubstituted aliphatic or aromatic ring, the substituent on CY1 is a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkoxy radical having 1 to 20 carbon atoms; An aryloxy radical having 6 to 20 carbon atoms; Or an amido radical, and when the number of the substituents is plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring;
M is a Group 4 transition metal;
Q1 and Q2 may be the same or different from each other and are each independently a halogen radical; An alkyl radical having 1 to 20 carbon atoms; An alkenyl radical having 2 to 20 carbon atoms; An aryl radical having 6 to 20 carbon atoms; An alkylaryl radical having 7 to 20 carbon atoms; An arylalkyl radical having 7 to 20 carbon atoms; An alkylamido radical having 1 to 20 carbon atoms; An arylamido radical having 6 to 20 carbon atoms; Or an alkylidene radical having 1 to 20 carbon atoms.
The method of claim 6,
Wherein the catalyst composition comprising the transition metal compound comprises at least one selected from the group consisting of the promoters represented by the following general formulas (4), (5) and (6)
[Chemical Formula 4]
- [Al (R8) -O] n-
In Formula 4,
R8 may be the same or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;
n is an integer of 2 or more;
[Chemical Formula 5]
D (R 8) 3
In Formula 5,
R8 is as defined in Formula 4 above;
D is aluminum or boron;
[Chemical Formula 6]
[LH] + [ZA4] - or [L] + [ZA4] -
In Formula 6,
L is a neutral or cationic Lewis acid;
H is a hydrogen atom;
Z is a Group 13 element;
A may be the same as or different from each other, and independently at least one hydrogen atom is an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms substituted or unsubstituted with halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or phenoxy .
The method of claim 6,
The alpha-olefin-based monomer of the ethylene-alpha olefin-styrene copolymer may be selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl- Wherein the ethylene-alpha olefin-styrene copolymer comprises at least one member selected from the group consisting of 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, Gt;
The method of claim 6,
The styrene-based compound monomer of the ethylene-alpha olefin-styrene copolymer is at least one member selected from the group consisting of styrene,? -Methylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, Styrene, and t-butylstyrene. The method of producing an ethylene-alpha olefin-styrene copolymer according to claim 1,
The method of claim 6,
Wherein the step of preparing the ethylene-alpha olefin-styrene copolymer is performed by a batch solution polymerization process.
The method of claim 6,
Wherein the solvent comprises at least one selected from the group consisting of an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, an aromatic hydrocarbon solvent, and a hydrocarbon solvent substituted with a chlorine atom. A process for producing an ethylene - alpha olefin - styrene copolymer.
The method of claim 6,
Wherein the polymerization of the ethylene alpha olefin monomer and the styrene monomer is carried out at 110 to 130 &lt; RTI ID = 0.0 &gt; C. &Lt; / RTI &gt;
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