KR20240079772A - Ethylene alpha-olefin copolymer with bimodal composition, method for preparing the same, resin composition and molded artivle comprising the same - Google Patents

Abstract

The present invention provides an olefin-based copolymer with controlled branch chain content, a method for producing the same, and a resin composition and molded article containing the olefin-based copolymer. The olefin-based copolymer of the present invention has an ethylene structural unit and an alpha-olefin structure. It is an ethylene alpha-olefin copolymer containing a unit, and includes two or more different elution peaks in the temperature range of 35 to 130 ° C when analyzed by TGIC (Thermal Gradient Interaction Chromatography). An ethylene alpha-olefin copolymer is provided. .

Description

Ethylene alpha-olefin copolymer having two types of chain distribution, method for producing the same, and resin composition and molded article containing the olefin copolymer {ETHYLENE ALPHA-OLEFIN COPOLYMER WITH BIMODAL COMPOSITION, METHOD FOR PREPARING THE SAME, RESIN COMPOSITION AND MOLDED ARTIVLE COMPRISING THE SAME}

The present invention relates to an ethylene alpha-olefin-based copolymer having two types of chain distribution, a method for producing the same, and a resin composition and molded article containing the olefin-based copolymer.

Dow Chemical's [Me ₂ Si(Me ₄ C ₅ )NtBu]TiCl ₂ (Constrained-Geometry Catalyst, 'CGC') catalyst used in the conventional ethylene alpha-olefin copolymerization reaction is 1-hexene and 1- It is known that copolymerization of alpha-olefins with high steric hindrance, such as octene, is excellent, and the polymerized olefin-based polymer not only has a narrow molecular weight distribution (MWD), but also has a single chain structure with a certain branched chain distribution.

Since these existing ethylene alpha-olefin copolymers basically have a single chain structure with uniform branched chain distribution, it is difficult to simultaneously achieve the required properties such as compatibility with other resins, processability, strength, and impact strength. It is known to be not easy.

For example, in order to improve low-temperature properties by compounding ethylene alpha-olefin copolymer and polypropylene, a relatively low density ethylene alpha-olefin copolymer must be used, and this low density ethylene alpha-olefin copolymer has low strength. There are disadvantages to this.

The purpose of the present invention is to provide an ethylene alpha olefin-based copolymer with a dual composition distribution and a method for producing the same using a metallocene catalyst in which R-type and S-type stereocompounds coexist.

Another object of the present invention is to provide an ethylene alpha-olefin copolymer with excellent tensile elongation, tensile strength, and shrinkage rate, and a method for producing the same.

The ethylene alpha-olefin copolymer according to the present invention is an ethylene alpha-olefin copolymer containing an ethylene structural unit and an alpha-olefin structural unit, and when analyzed by TGIC (Thermal Gradient Interaction Chromatography), the temperature range is 35 to 130°C. Contains two or more different elution peaks.

The ethylene alpha-olefin copolymer may have a density of 0.857 to 0.903 g/ml.

The method for producing an ethylene alpha-olefin copolymer of the present invention includes ethylene and It includes polymerizing at least one type of olefinic monomer.

[Formula 1]

(In Formula 1 above,

M is a group 4 transition metal;

Q ¹ and Q ² are each independently halogen, (C ₁ -C ₂₀ )alkyl, (C ₂ -C ₂₀ )alkenyl, (C ₂ -C ₂₀ )alkynyl, (C ₆ -C ₂₀ )aryl, ( C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkylamido, (C ₆ -C ₂₀ )arylamido or (C ₁ -C ₂₀ )alkylidene;

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently hydrogen; (C ₁ -C ₂₀ )alkyl with or without acetal, ketal or ether groups; (C ₂ -C ₂₀ )alkenyl with or without acetal, ketal or ether groups; (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl with or without an acetal, ketal or ether group; or (C ₁ -C ₂₀ )alkylsilyl with or without an acetal, ketal or ether group; R ¹ and R ² may be connected to each other to form a ring, R ³ and R ⁴ may be connected to each other to form a ring, and two or more of R ⁵ to R ¹⁰ may be connected to each other to form a ring. You can;

R ¹¹ , R ¹² and R ¹³ are each independently hydrogen; (C ₁ -C ₂₀ )alkyl with or without acetal, ketal or ether groups; (C ₂ -C ₂₀ )alkenyl with or without acetal, ketal or ether groups; (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl with or without an acetal, ketal or ether group; (C ₁ -C ₂₀ )alkylsilyl with or without acetal, ketal or ether groups; (C ₁ -C ₂₀ )alkoxy; or (C ₆ -C ₂₀ )aryloxy; R ¹¹ and R ¹² or R ¹² and R ¹³ may be connected to each other to form a ring.)

[Formula 2]

-[Al(Ra)-O] _n -

(In Formula 2 above,

Ra is each independently halogen; or a (C ₁ -C ₂₀ ) hydrocarbyl group substituted or unsubstituted with halogen,

n is an integer greater than or equal to 2),

[Formula 3]

Q(Rb) ₃

(In Formula 3 above,

Q is aluminum or boron,

Rb is each independently halogen; or a (C ₁ -C ₂₀ )hydrocarbyl group substituted or unsubstituted with halogen),

[Formula 4]

[W] ⁺ [Z(Rc) ₄ ] ^-

(In Formula 4 above,

[W] ⁺ is a cationic Lewis acid; or a cationic Lewis acid with a hydrogen atom bonded to it,

Z is a group 13 element,

Rc is each independently a (C ₆ -C ₂₀ )aryl group substituted with one or two or more substituents selected from the group consisting of halogen, (C ₁ -C ₂₀ )hydrocarbyl group, alkoxy group, and phenoxy group; It is a (C ₁ -C ₂₀ )alkyl group substituted with one or two or more substituents selected from the group consisting of halogen, (C ₁ -C ₂₀ )hydrocarbyl group, alkoxy group, and phenoxy group).

The transition metal compound may be one in which R-type and S-type steric compounds coexist.

The polypropylene resin composition of the present invention includes polypropylene; and the ethylene alpha-olefin copolymer.

The molded article of the present invention can be manufactured from the above resin composition.

The ethylene alpha-olefin-based copolymer composition having two chain structures with different comonomer contents using one type of metallocene catalyst of the present invention improves low-temperature impact strength and decreases it by increasing the amorphous or low-crystalline region. It is possible to simultaneously improve tensile elongation, tensile strength, and shrinkage rate.

Figure 1 is a graph showing the TGIC area ratio according to the catalyst composition ratio of the ethylene/1-octene copolymers prepared in Examples 1 to 3.

Hereinafter, preferred embodiments of the present invention will be described. However, the embodiments of the present invention may be modified into various other forms, and the scope of the present invention is not limited to the embodiments described below.

The term “alkyl” as used in the present invention refers to a monovalent straight-chain or branched saturated hydrocarbon radical consisting of only carbon and hydrogen atoms. Examples of such alkyl radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t- Including but not limited to butyl, pentyl, hexyl, octyl, dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc.

In addition, the term “alkenyl” as used in the present invention refers to a straight-chain or branched-chain hydrocarbon radical containing one or more carbon-carbon double bonds, and includes ethenyl, propenyl, butenyl, pentenyl, etc. It is not limited to this.

In addition, the term "alkynyl" as used in the present invention refers to a straight-chain or branched-chain hydrocarbon radical containing one or more carbon-carbon triple bonds, such as methynyl, ethynyl, propynyl, butynyl, pentynyl, and hexy. Includes, but is not limited to, nyl, heptinyl, octinyl, etc.

In addition, the term “aryl” described in the present invention is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes a single or fused ring system. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.

In addition, the term "alkylaryl" as used in the present invention refers to an organic group in which one or more hydrogens of an aryl group are replaced by an alkyl group, such as methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, isopropylphenyl, It includes, but is not limited to, butylphenyl, t-butylphenyl, etc.

Additionally, the term “arylalkyl” as used in the present invention refers to an organic group in which one or more hydrogens of an alkyl group are replaced by an aryl group, and includes, but is not limited to, phenylpropyl, phenylhexyl, etc.

In addition, the term `` Amido '' described in the present invention means an amino group (-NH ₂ ) coupled to the carbonyl group (C = O), and the alkylamido is at least one hydrogen in the -NH ₂ of the amido group. means an organic group substituted with, and "arylamido" means an organic group in which at least one hydrogen in -NH ₂ of the amido group is substituted with an aryl group, and the alkyl group in the alkylamido group and the aryl group in the arylamido group are It may be the same as the examples of the alkyl group and aryl group described above, but is not limited thereto.

In addition, the term "alkylidene" used in the present invention refers to a divalent aliphatic hydrocarbon group in which two hydrogen atoms are removed from the same carbon atom of the alkyl group, and includes ethylidene, propylidene, isopropylidene, butylidene, and pentylidene. It includes, but is not limited to, etc.

In addition, the term "acetal" as used in the present invention refers to an organic group formed by the combination of an alcohol and an aldehyde, that is, a substituent with two ether (-OR) bonds on one carbon, methoxymethoxy, 1-methoxy, Toxyethoxy, 1-methoxypropyloxy, 1-methoxybutyloxy, 1-ethoxyethoxy, 1-ethoxypropyloxy, 1-ethoxybutyloxy, 1-(n-butoxy)ethoxy, 1-(iso-butoxy)ethoxy, 1-(sec-butoxy)ethoxy, 1-(tertiary-butoxy)ethoxy, 1-(cyclohexyloxy)ethoxy, 1-methoxy -1-methylmethoxy, 1-methoxy-1-methylethoxy, etc., but not limited thereto.

In addition, the term "ether" as used in the present invention is an organic group having at least one ether bond (-O-), and includes 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, and 2-phenoxyethyl. , 2-(2-methoxyethoxy)ethyl, 3-methoxypropyl, 3-butoxypropyl, 3-phenoxypropyl, 2-methoxy-1-methylethyl, 2-methoxy-2-methylethyl , 2-methoxyethyl, 2-ethoxyethyl, 2-butoxyethyl, 2-phenoxyethyl, etc., but are not limited thereto.

In addition, the term "silyl" described in the present invention refers to a -SiH ₃ radical derived from silane, and at least one of the hydrogen atoms in the silyl group may be substituted with various organic groups such as alkyl and halogen, and may be substituted with various organic groups such as alkyl and halogen. trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, vinyldimethylsilyl, propyldimethylsilyl, Includes, but is not limited to, triphenylsilyl, diphenylsilyl, phenylsilyl, trimethoxysilyl, methyldimeroxysilyl, ethyldiethoxysilyl, triethoxysilyl, vinyldimethoxysilyl, triphenoxysilyl, etc.

Additionally, the term “alkoxy” described in the present invention refers to an -O-alkyl radical, where ‘alkyl’ is as defined above. Examples of such alkoxy radicals include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, etc.

Additionally, the term “halogen” used in the present invention means a fluorine, chlorine, bromine or iodine atom.

Additionally, the term “C _n ” described in the present invention means that the number of carbon atoms is n.

The present invention seeks to provide an ethylene alpha-olefin copolymer that uses one type of metallocene catalyst but has two chains with different branching content due to catalyst isomers.

The ethylene alpha-olefin copolymer prepared in the present invention is an ethylene alpha-olefin copolymer containing an ethylene structural unit and an alpha-olefin structural unit, and elutes at two different temperatures when analyzed by TGIC (Thermal Gradient Interaction Chromatography). Through this, it can be confirmed that two chain structures with different branch chain contents are created.

The present invention provides an olefin-based copolymer that includes two or more different elution peaks in the temperature range of 35 to 130°C when analyzed by TGIC (Thermal Gradient Interaction Chromatography).

In the present invention, the polymerization of ethylene and alpha-olefin can be carried out in a catalyst composition in which the R-type and S-type stereo compounds of the transition metal compound represented by the following formula (1) coexist.

[Formula 1]

In Formula 1,

M is a group 4 transition metal;

Q ¹ and Q ² are each independently halogen, (C ₁ -C ₂₀ )alkyl, (C ₂ -C ₂₀ )alkenyl, (C ₂ -C ₂₀ )alkynyl, (C ₆ -C ₂₀ )aryl, ( C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkylamido, (C ₆ -C ₂₀ )arylamido or (C ₁ -C ₂₀ )alkylidene;

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently hydrogen; (C ₁ -C ₂₀ )alkyl with or without acetal, ketal or ether groups; (C ₂ -C ₂₀ )alkenyl with or without acetal, ketal or ether groups; (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl with or without an acetal, ketal or ether group; or (C ₁ -C ₂₀ )alkylsilyl with or without an acetal, ketal or ether group; R ¹ and R ² may be connected to each other to form a ring, R ³ and R ⁴ may be connected to each other to form a ring, and two or more of R ⁵ to R ¹⁰ may be connected to each other to form a ring. You can;

R ¹¹ , R ¹² and R ¹³ are each independently hydrogen; (C ₁ -C ₂₀ )alkyl with or without acetal, ketal or ether groups; (C ₂ -C ₂₀ )alkenyl with or without acetal, ketal or ether groups; (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl with or without an acetal, ketal or ether group; (C ₁ -C ₂₀ )alkylsilyl with or without acetal, ketal or ether groups; (C ₁ -C ₂₀ )alkoxy; or (C ₆ -C ₂₀ )aryloxy; R ¹¹ and R ¹² or R ¹² and R ¹³ may be connected to each other to form a ring.

The transition metal compound represented by Formula 1 is a new compound in which the amido ligand and ortho-phenylene form a condensed ring, and the pentagonal pi-ligand bonded to the ortho-phenylene is fused by a thiophene heterocycle. Includes structural ligands. Accordingly, the transition metal compound has the advantage of having a higher copolymerization activity of ethylene alpha-olefin than a transition metal compound in which the thiophene hetero ring is not fused.

In the present invention, in the compound represented by Formula 1, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may each independently be substituted with a substituent including an acetal, ketal, or ether group. When substituted with such a substituent, it may be more advantageous for supporting the support on the surface of the carrier.

Additionally, in the compound represented by Formula 1, M is preferably titanium (Ti), zirconium (Zr), or hafnium (Hf).

Additionally, in the transition metal compound represented by Formula 1, Q ¹ and Q ² are each independently preferably halogen or (C ₁ -C ₂₀ )alkyl, and more preferably chlorine or methyl.

In addition, in the transition metal compound represented by Formula 1, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may each independently be hydrogen or (C ₁ -C ₂₀ )alkyl, preferably Each may independently be hydrogen or methyl. More preferably, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may each independently be hydrogen or methyl, provided that at least one of R ³ and R ⁴ is methyl and R ⁵ may be methyl. there is.

Additionally, in the transition metal compound represented by Formula 1, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each preferably hydrogen.

The transition metal compound represented by Formula 1 preferably contains the above substituents to control the electronic and steric environment around the metal.

Meanwhile, the transition metal compound represented by Formula 1 can be obtained from a transition metal compound precursor represented by Formula 5 below:

[Formula 5]

In Formula 5, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each defined in Formula 1 above. It's like a bar.

Here, the transition metal compound precursor represented by Formula 5 is prepared by (i) reacting a tetrahydroquinoline derivative represented by Formula 6 below with alkyl lithium and then adding carbon dioxide to prepare a compound represented by Formula 7 below; and (ii) reacting a compound represented by the following formula (7) with alkyl lithium, then adding a compound represented by the following formula (8) and treating with acid:

[Formula 6]

[Formula 7]

[Formula 8]

In Formula 6, Formula 7 and Formula 8, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are Each is as defined in Formula 1 above.

However, in Formulas 6, 7 and 8, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may each independently be hydrogen or (C ₁ -C ₂₀ )alkyl, preferably each It may independently be hydrogen or methyl. More preferably, R ¹ , R ² , R ³ , R ⁴ and R ⁵ may each independently be hydrogen or methyl, provided that at least one of R ³ and R ⁴ is methyl and R ⁵ may be methyl. there is. In addition, R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are each preferably hydrogen. Through this, the accessibility and reactivity of the starting material can be secured, and it is advantageous for controlling the electronic and steric environment of the transition metal compound of Formula 1 to be produced.

In the preparation of the precursor compound represented by Formula 5, step (i) is a reaction of reacting the tetrahydroquinoline derivative represented by Formula 6 with alkyl lithium and then adding carbon dioxide to convert it to the compound represented by Formula 5. This can be performed according to the method described in known literature (Tetrahedron Lett. 1985, 26, 5935; Tetrahedron 1986, 42, 2571; J. Chem. SC. Perkin Trans. 1989, 16.).

In addition, in step (ii), an ortho-lithium compound is generated by causing a deprotonation reaction by reacting alkyllithium with the compound represented by Formula 7, and then reacting with the compound represented by Formula 8 and treating it with acid. A transition metal compound precursor represented by Chemical Formula 5 can be obtained.

The reaction of producing an ortho-lithium compound by reacting alkyl lithium with the compound represented by Formula 7 is performed according to a method described in a known literature (Organometallics 2007, 27, 6685 or Korean Patent Publication No. 2008-0065868). In the present invention, a transition metal compound precursor represented by Formula 5 can be obtained by reacting the produced ortho-lithium compound with the compound represented by Formula 8 and treating it with acid.

Here, the compound represented by Formula 8 can be prepared through various known methods. Scheme 1 below shows an example, and not only can it be prepared in one step, but also the transition metal compound precursor of Formula 5 of the present invention can be easily and economically prepared using inexpensive starting materials. There is (J. Organomet. Chem., 2005, 690, 4213).

[Scheme 1]

Meanwhile, various known methods can be used to synthesize the transition metal compound represented by Formula 1 from the transition metal compound precursor represented by Formula 5 obtained through the above method. By adding about 2 equivalents of alkyllithium to the transition metal compound precursor represented by Formula 5 to induce a deprotonation reaction, a dilithium compound of cyclopentadienyl anion and amide anion was prepared, and then (Q ¹ ) (Q ² ) It can be prepared by adding MCl ₂ to remove about 2 equivalents of LiCl.

In addition, the compound represented by Formula 5 is reacted with the M(NMe ₂ ) ₄ compound to remove about 2 equivalents of HNMe ₂ to obtain a transition metal compound represented by Formula 1 where both Q ¹ and Q ² are NMe ₂ , The NMe ₂ ligand can be changed to a chlorine ligand by reacting Me ₃ SiCl or Me ₂ SiCl ₂ here.

When the transition metal compound represented by Formula 1 prepared through the above process is polymerized in a catalyst composition in which R-type and S-type steric compounds coexist, two types of polymers with different structures and physical properties can be formed.

This is believed to be due to the difference in ethylene conversion rates between R-type and S-type compounds. The comonomer conversion rates of R-type and S-type stereocompounds are similar, but may have different ethylene conversion rates due to differences in stereostructure. Specifically, the S-type stereocompound requires additional energy to form a specific arrangement for a polymerization reaction because the space into which ethylene can be inserted is wider than that of the R-type compound. Therefore, the S-type stereocompound exhibits a low ethylene conversion rate, and thus can form a polymer chain with a relatively high comonomer content and thin lamella thickness. On the other hand, the R-type stereocompound exhibits a high ethylene conversion rate and can form a polymer chain with a relatively low comonomer content and thick lamella thickness.

The transition metal compound, which is the main catalyst of the present invention, consists of two stereo compounds, R-type and S-type stereo compounds. As such, in the transition metal compound of the present invention, two steric compounds coexist, so that polymers with different structures can be produced despite using a single catalyst. As shown in the structural formula below, the transition metal compound of the present invention has two compounds, an R-type stereocompound (a) and an S-type stereocompound (b), and thus acts as two catalysts.

The R-type stereocompound (a) forms a low molecular weight polymer chain containing a low comonomer, and the S-type stereocompound (b) forms a high molecular weight polymer chain containing a high comonomer. The reason is that the comonomer conversion rate is similar for the R-type stereocompound (a) and the S-type stereocompound (b), but because the ethylene conversion rate is lower for the S-type stereocompound, the S-type stereocompound (b) has a relatively high content of comonomer. It is believed that it forms a polymer chain containing monomers.

When the catalyst changes into an active species, the methyl group of Ti is located on the opposite side due to steric hindrance caused by the sulfur (S) element of thiophene. Afterwards, in the case of the R-type compound (a), the space where ethylene is inserted is narrow and rotation is not possible, so ethylene lies on the same plane as the methyl group (Me), as shown in the structural formula below showing the insertion structure of the meso-active species ethylene. Thus, polymerization proceeds easily through migration.

On the other hand, as shown in the structural formula below showing the insertion structure of the racemic active species ethylene, the S-type stereocompound (b) has a large ethylene insertion space, so ethylene rotates and coordinates with Ti, and for polymerization, a methyl group ( In order to lie on the same plane as Me), rotation energy is required. Therefore, compared to the R-type compound (a), the S-type compound (b) has a lower ethylene conversion rate.

When a comonomer is inserted, since its molecular size is larger than that of ethylene, the S-type stereocompound also lies on the same plane as the methyl group (Me) due to ligand steric hindrance, and the comonomer conversion rate is similar to that of the R-type stereocompound (a). It is judged.

In order to produce an ethylene alpha-olefin copolymer containing two types of polymer chains with different comonomer contents under the above catalyst composition, the R-type stereocompound and the S-type stereocompound are present in a molar ratio of 1:0.1 to 1:1. It is desirable to do so. If the molar ratio is less than 1:0.1, a large amount of low-density polymer chains are formed due to the predominance of S-type steric compounds, which may cause stickiness of the product. If the molar ratio exceeds 1:1, high-density polymer chains become dominant, resulting in lower tensile elongation and low temperature. There is a lack of improvement in impact strength and shrinkage rate.

In the present invention, the catalyst composition may further include a cocatalyst compound. The co-catalyst compound activates the transition metal compound, and may be an aluminoxane compound, an organo-aluminum compound, or a bulky compound that activates the catalyst compound. Specifically, the cocatalyst compound may be selected from the group consisting of compounds represented by the following formulas 2 to 4.

[Formula 2]

-[Al(Ra)-O] _n -

In Formula 6 above,

Ra is each independently halogen; or a (C ₁ -C ₂₀ ) hydrocarbyl group substituted or unsubstituted with halogen,

n is an integer of 2 or more.

[Formula 3]

Q(Rb) ₃

In Formula 3 above,

Q is aluminum or boron,

Rb is each independently halogen; Or it is a (C ₁ -C ₂₀ ) hydrocarbyl group substituted or unsubstituted with halogen.

[Formula 4]

[W] ⁺ [Z(Rc) ₄ ] ^-

In Formula 4 above,

[W] ⁺ is a cationic Lewis acid; or a cationic Lewis acid with a hydrogen atom bonded to it,

Z is a group 13 element,

Rc is each independently a (C ₆ -C ₂₀ )aryl group substituted with one or two or more substituents selected from the group consisting of halogen, (C ₁ -C ₂₀ )hydrocarbyl group, alkoxy group, and phenoxy group; It is a (C ₁ -C ₂₀ )alkyl group substituted with one or two or more substituents selected from the group consisting of halogen, (C ₁ -C ₂₀ )hydrocarbyl group, alkoxy group, and phenoxy group.

The cocatalyst compound is included in a catalyst together with the transition metal compound represented by Formula 1 and serves to activate the transition metal compound. Specifically, in order for the transition metal compound to become an active catalyst component used in olefin polymerization, the ligand in the transition metal compound is extracted to cationize the central metal (M ¹ or M ² ) while generating a counter ion with a weak binding force, that is, an anion. A compound containing a unit represented by Formula 2, a compound represented by Formula 3, and a compound represented by Formula 4 that can act together act as cocatalysts.

The 'unit' represented by Formula 2 is a structure in which n structures within [ ] are connected in the compound. If it contains the unit represented by Formula 2, other structures in the compound are not particularly limited, and the repetition of Formula 2 It may be a cluster-type compound in which units are connected to each other, for example, a spherical compound.

In order for the co-catalyst compound to exhibit a better activation effect, the compound represented by Formula 2 is not particularly limited as long as it is alkylaluminoxane, but preferred examples include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, and butylaluminoxane. Oxylic acid and the like, and a particularly preferred compound is methylaluminoxane.

In addition, the compound represented by Formula 3 is not particularly limited as an alkyl metal compound, and non-limiting examples thereof include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloroaluminum, and triiso Propyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum, tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyldimethyl aluminum, methyldiethyl aluminum, triphenyl aluminum, tri-p-tolyl These include aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, triethyl boron, triisobutyl boron, tripropyl boron, and tributyl boron. Considering the activity of the transition metal compound, one or two or more types selected from the group consisting of trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum may be preferably used.

Considering the activity of the transition metal compound, the compound represented by Formula 4 is a dimethylanilinium cation when [W] ⁺ is a cationic Lewis acid to which a hydrogen atom is bonded, and when [W] ⁺ is a cationic Lewis acid, [ (C ₆ H ₅ ) ₃ C] ⁺ , and [Z(Rc) ₄ ] ^- may be preferably used as [B(C ₆ F ₅ ) ₄ ] ^- .

A compound represented by Formula 4, where [W] ⁺ is a cationic Lewis acid to which a hydrogen atom is bonded, non-limiting examples include trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl) )borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate, N,N-dimethylanilinium benzyltris(pentafluorophenyl) ) Borate, N,N-dimethylanilinium tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(4- (t-triisopropylsilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl)borate, N,N-di Ethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylammonium tetrakis(2,3 ,5,6-tetrafluorophenyl)borate, N,N-diethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate,tripropylammonium tetrakis(2,3,4,6 -Tetrafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, dimethyl(t-butyl)ammonium tetrakis(2,3,4,6) -tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate, N,N-diethylanilinium tetrakis(2,3,4, 6-tetrafluorophenyl)borate, N,N-dimethyl2,4,6-trimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl)borate and dialkylammonium. It is preferable that there is more than one type.

Non-limiting examples of the dialkylammonium include di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, or dicyclohexylammonium tetrakis(pentafluorophenyl)borate.

In addition, as a compound represented by Formula 4, non-limiting examples where [W] ⁺ is a cationic Lewis acid include a compound selected from the group consisting of trialkylphosphonium, dialkyloxonium, dialkylsulfonium, and carbonium salt. It is preferable to have at least one type.

The trialkylphosphonium includes, but is not limited to, triphenylphosphonium tetrakis(pentafluorophenyl)borate, tri(o-tolylphosphonium tetrakis(pentafluorophenyl)borate, or tri(2,6-dimethylphenyl). ) Phosphonium tetrakis (pentafluorophenyl) borate, etc. can be mentioned.

The dialkyloxonium includes, but is not limited to, diphenyloxonium tetrakis(pentafluorophenyl)borate, di(o-tolyl)oxonium tetrakis(pentafluorophenyl)borate, or di(2,6- Dimethylphenyl oxonium tetrakis(pentafluorophenyl)borate, etc. can be mentioned.

The dialkylsulfonium includes, but is not limited to, diphenylsulfonium tetrakis(pentafluorophenyl)borate, di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate, or bis(2,6- Dimethylphenyl)sulfonium tetrakis(pentafluorophenyl)borate, etc. can be mentioned.

The carbonium salt includes, but is not limited to, tropylium tetrakis(pentafluorophenyl)borate, triphenylmethyl carbenium tetrakis(pentafluorophenyl)borate, or benzene(diazonium)tetrakis(pentafluorophenyl)borate. ) Baurate, etc. can be mentioned.

A catalyst can be prepared using the compounds of Formula 1 to Formula 4. In this case, the method exemplified below can be used to prepare the catalyst.

First, when Q ¹ and Q ² of the transition metal compound represented by Formula 1 are halogens, there is a method of contacting the compound represented by Formula 2. Second, when Q ¹ and Q ² in Formula 1 are alkyl radicals, a catalyst can be prepared by contacting a mixture of a transition metal compound with a compound represented by Formulas 3 and 4, or the compounds represented by Formulas 3 and 4 They can also be manufactured by putting them directly into a polymerization reactor.

The amount of the co-catalyst compound added can be determined by considering the amount of the main catalyst compound added of the transition metal compound represented by Formula 1 and the amount necessary to sufficiently activate the main catalyst compound. According to the present invention, the cocatalyst compound is 1:1 to 100,000, based on the molar ratio of the metal contained in the cocatalyst compound to 1 mole of the transition metal contained in the main catalyst compound of the transition metal compound represented by Formula 1, It may be included in a molar ratio of preferably 1:1 to 10,000, more preferably 1:1 to 5,000.

More specifically, the compound represented by Formula 2 is preferably used at a molar ratio of 1:10 to 5,000, more preferably 1:50 to 1,000, and most preferably 1:100 to the transition metal compound represented by Formula 1. It may be included at a molar ratio of ~1,000. If the molar ratio of the compound represented by Formula 2 to the transition metal compound of Formula 1 is less than 1:10, the amount of aluminoxane is so small that a problem may occur in which activation of the transition metal compound cannot proceed completely, and 1:5,000 may occur. If it is exceeded, the excess aluminoxane may act as a catalyst poison and the polymer chain may not grow well.

When A of the cocatalyst compound represented by Formula 3 is boron, the ratio is 1:1 to 100, preferably 1:1 to 10, more preferably 1:1 to the transition metal compound represented by Formula 1. It may be included in a molar ratio of 3. In addition, when A of the cocatalyst compound represented by Formula 3 is aluminum, it may vary depending on the amount of water in the polymerization system, but is 1:1 to 1000, preferably 1:1, with respect to the transition metal compound represented by Formula 1. It may be included in a molar ratio of 1 to 500, more preferably 1:1 to 100.

The cocatalyst compound represented by Formula 4 may be included in a molar ratio of 1:1 to 100, preferably 1:1 to 10, and more preferably 1:1 to 4, with respect to the main catalyst compound represented by Formula 1. there is. If the ratio of the cocatalyst compound represented by Formula 4 is less than 1:1, the amount of activator is relatively small and the metal compound cannot be completely activated, which may cause a problem in that the activity of the resulting catalyst composition decreases. If it exceeds 100, the metal compound is completely activated, but the unit cost of the catalyst composition may not be economical due to the remaining excess activator, or the purity of the produced polymer may be low.

Meanwhile, the catalyst of the present invention including the main catalyst compound and the co-catalyst compound may further include a carrier. Here, as the carrier, any carrier made of inorganic or organic materials used in the production of catalysts in the technical field to which the present invention pertains may be used without limitation.

According to one embodiment of the present invention, the carrier is SiO ₂ , Al ₂ O ₃ , MgO, MgCl ₂ , CaCl ₂ , ZrO ₂ , TiO ₂ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ , SiO ₂ -Al ₂ O ₃ , SiO ₂ -MgO, SiO ₂ -TiO ₂ , SiO ₂ -V ₂ O ₅ , SiO ₂ -Cr ₂ O ₃ , SiO ₂ -TiO ₂ -MgO, bauxite, zeolite, starch ), cyclodextrin, or synthetic polymer.

Preferably, the carrier includes a hydroxy group on the surface, and is selected from the group consisting of silica (SiO ₂ ), silica-alumina (SiO ₂ -Al ₂ O ₃ ), and silica-magnesia (SiO ₂ -MgO). There may be more than one species.

Methods for supporting a catalyst containing the main catalyst compound and the co-catalyst compound on the carrier include directly supporting the main catalyst compound on a dehydrated carrier; A method of pretreating the carrier with the cocatalyst compound and then supporting the main catalyst compound; A method of supporting the main catalyst compound on the carrier and then post-treating it with the cocatalyst compound; A method of reacting the main catalyst compound with the co-catalyst compound and then adding the carrier for reaction may be used.

The solvent that can be used in the supporting method may be an aliphatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, a halogenated aliphatic hydrocarbon-based solvent, or a mixture thereof.

The aliphatic hydrocarbon-based solvent includes, but is not limited to, pentane, hexane, heptane, octane, nonane, decane, undecane, or dodecane ( dodecane), etc.

Non-limiting examples of the aromatic hydrocarbon solvent include benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, or toluene.

Non-limiting examples of the halogenated aliphatic hydrocarbon-based solvent include dichloromethane, trichloromethane, dichloroethane, or trichloroethane.

In addition, it is advantageous in terms of efficiency of the loading process to carry out the loading method at a temperature of -70 to 200°C, preferably -50 to 150°C, and more preferably 0 to 100°C.

Meanwhile, in the present invention, the ethylene alpha-olefin polymer produced through a polymerization process performed by directly contacting ethylene and alpha-olefin comonomer compounds has a relatively insoluble and/or fixed catalytic site, so that the polymer chain is formed according to this information. It can be prepared by polymerization of monomers under conditions that allow rapid immobilization. This immobilization can be accomplished, for example, by using a solid insoluble catalyst, by carrying out the polymerization in a medium in which the resulting polymer is generally insoluble, and by maintaining the polymerization reactants and products below the crystallization temperature (T _c ) of the polymer. .

The above-mentioned catalyst can be preferably applied to the copolymerization of ethylene and alpha-olefin. Hereinafter, a method for producing an ethylene alpha-olefin copolymer including the step of copolymerizing ethylene and alpha-olefin in the presence of the catalyst will be described.

Processes for the polymerization of ethylene and alpha-olefins are well known in the art and include bulk polymerization, solution polymerization, slurry polymerization and low pressure gas phase polymerization. Metallocene catalysts are particularly useful in known forms of operation using fixed bed, moving bed or slurry processes carried out in single, series or parallel reactors.

When the polymerization reaction is carried out in a liquid or slurry phase, a solvent, ethylene, or the alpha-olefin monomer itself can be used as a medium.

Since the catalyst presented in the present invention exists in a uniform form within the polymerization reactor, it is preferable to apply it to a solution polymerization process conducted at a temperature above the melting point of the polymer. However, as disclosed in U.S. Patent No. 4,752,597, a heterogeneous catalyst composition obtained by supporting the transition metal compound and cocatalyst on a porous metal oxide support may be used in slurry polymerization or gas phase polymerization processes. Therefore, if the catalyst of the present invention is used with an inorganic carrier or an organic polymer carrier, it can be applied to slurry or gas phase processes. That is, the transition metal compound and co-catalyst compound can be used in a form supported on an inorganic carrier or an organic polymer carrier.

The solvent that can be used during the polymerization reaction may be an aliphatic hydrocarbon-based solvent, an aromatic hydrocarbon-based solvent, a halogenated aliphatic hydrocarbon-based solvent, or a mixture thereof. The aliphatic hydrocarbon-based solvent includes, butane, isobutane, pentane, hexane, heptane, octane, nonane, and decane. ), undecane, dodecane, cyclopentane, methylcyclopentane, or cyclohexane. In addition, the aromatic hydrocarbon-based solvent includes, but is not limited to, benzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, toluene, xylene, or Examples include chlorobenzene. The halogenated aliphatic hydrocarbon solvent includes, but is not limited to, dichloromethane, trichloromethane, chloroethane, dichloroethane, trichloroethane, or 1,2-dichloroethane. (1,2-dichloroethane) and the like.

As described above, the ethylene alpha-olefin copolymer according to the present invention can be prepared by polymerizing ethylene and alpha-olefin comonomer in the presence of the catalyst composition. At this time, the transition metal compound and the cocatalyst component can be added separately into the reactor, or each component can be mixed in advance and then added to the reactor, and there are no restrictions on mixing conditions such as the order of addition, temperature, or concentration. For example, when producing a copolymer of ethylene and 1-octene, 1-octene may be included in an amount of 0.1 to 99.9% by weight, preferably 1 to 75% by weight, more preferably 5 to 50% by weight. may be included.

Meanwhile, the amount of the catalyst added in the polymerization reaction of the present invention is not particularly limited because it can be determined within a range where the polymerization reaction of the monomer can sufficiently occur depending on the slurry phase, liquid phase, gas phase, or bulk process.

However, according to the present invention, the amount of the catalyst added is 10 ^-8 to 1 mol/L, preferably 10 ^-7 to 10 based on the concentration of the central metal (M) in the main catalyst compound per unit volume (L) of monomer. It may be ^-1 mol/L, more preferably 10 ^-7 to 10 ^-2 mol/L.

Additionally, the polymerization reaction of the present invention may be a batch type, semi-continuous type, or continuous type reaction, and is preferably a continuous reaction.

*148 The temperature and pressure conditions for the polymerization reaction of the present invention can be determined considering the efficiency of the polymerization reaction depending on the type of reaction to be applied and the type of reactor, but the polymerization temperature is 100 to 200°C, preferably 120 to 160°C. It may be ℃, and the pressure may be 1 to 3000 atm, preferably 1 to 1000 atm.

<Ethylene alpha-olefin copolymer>

The ethylene alpha-olefin copolymer of the present invention is prepared by the above method for producing the ethylene alpha-olefin copolymer.

The ethylene alpha-olefin copolymer prepared by the above method uses one type of metallocene catalyst, but catalyst isomerism produces an ethylene alpha-olefin copolymer having two chains with different branch chain contents. As previously explained, the transition metal compound used as the main catalyst in the present invention is a transition metal compound of the R-type stereocompound by coexisting in one transition metal the two different stereocompounds of the R-type stereocompound and the S-type stereocompound. It is believed that this forms a polymer chain with a high branched chain content and high molecular weight, and the transition metal compound of the R-type stereocompound forms a polymer chain with a low branched chain content and low molecular weight.

Therefore, the ethylene alpha-olefin copolymer of the present invention has a two-chain structure with different branch chain content, which indicates the number of carbon atoms attached to the side chain, and has a high branch chain content in the amorphous or low crystalline region and a high molecular weight chain structure. It includes polymer chains with low branched chain content and low molecular weight. Low-temperature impact strength can be improved by the amorphous or low-crystalline branched chain content and high molecular weight polymer chain. On the other hand, as the amorphous or low-crystalline region increases, physical properties such as tensile elongation, tensile strength, and shrinkage may decrease. However, the presence of polymer chains with a low branch chain content and low molecular weight increases the tensile elongation and tensile strength as described above. It contributes to improving physical properties such as strength and shrinkage rate. Therefore, the ethylene alpha-olefin copolymer of the present invention has physical properties such as improved low-temperature impact strength and improved tensile elongation, tensile strength, and shrinkage rate.

When the ethylene alpha-olefin copolymer of the present invention was analyzed by TGIC (Thermal Gradient Interaction Chromatography), the elution temperature of the amorphous or low-crystalline polymer chain with high branched chain content and the polymer chain with low branched chain content were different, resulting in two different types. It elutes at different temperatures and has two peaks.

The ethylene alpha-olefin-based copolymer of the present invention has two or more clearly distinct elution peaks in the temperature range of 35 to 130°C when analyzed by TGIC (Thermal Gradient Interaction Chromatography).

The ethylene alpha-olefin copolymer can increase the polymerization activity of ethylene and alpha-olefin monomers and exhibit a high molecular weight by using a catalyst containing the main catalyst compound and the cocatalyst compound. At this time, the ethylene alpha-olefin copolymer may have a weight average molecular weight (Mw) of 10,000 to 1,000,000, preferably 50,000 to 800,000, and more preferably 100,000 to 300,000.

Additionally, the ethylene alpha-olefin copolymer may have a molecular weight distribution (Mw/Mn) of 1 to 10, preferably 1.5 to 8, and more preferably 1.5 to 3.

Additionally, the ethylene alpha-olefin copolymer may have a density of 0.857 to 0.903 g/ml.

A polypropylene resin composition can be prepared by mixing and blending the ethylene alpha-olefin copolymer of the present invention with a polypropylene resin, and when a molded article is manufactured using the resulting polypropylene resin composition, the molded article thus obtained is resistant to low-temperature impact. In addition to strength, it has excellent tensile elongation, tensile strength, and shrinkage properties.

Example

Hereinafter, the present invention will be described in detail through examples. However, the following examples are merely illustrative of the present invention and are not intended to limit the present invention to the following examples.

<Preparation of catalyst composition>

Synthesis of compound (2)

Transition metal compound (2), used as a main catalyst, was synthesized from compound (1) according to Scheme 2 below. The specific synthesis process is as follows.

[Scheme 2]

First, 1.63 g (3.55 mmol, 1.6 M diethyl ether solution) of methyl lithium was added dropwise to 10 mL of diethyl ether solution in which 0.58 g (1.79 mmol) of compound (1) was dissolved at -30°C (step i).

The solution obtained in step i) was stirred at room temperature overnight, then the temperature was lowered to -30°C, and 0.37 g (1.79 mmol) of Ti(NMe ₂ ) ₂ Cl ₂ was added at once to the solution (step ii).

The solution obtained in step ii) was stirred for 3 hours and then all solvent was removed using a vacuum pump to obtain a solid product. The obtained solid product was dissolved in 8 mL of toluene, and then 1.16 g (8.96 mmol) of Me ₂ SiCl ₂ was added (step iii).

The solution obtained in step iii) was stirred at 80°C for 3 days, and then the solvent was removed using a vacuum pump. As a result, 0.59 g of red solid compound (2) was obtained (75% yield).

The ¹ H NMR spectrum of the obtained red solid compound confirmed that two stereocompounds exist in a ratio of 2:1.

¹ H NMR (C ₆ D ₆ ): δ 7.10 (t, J = 4.4 Hz, 1H), 6.90 (d, J = 4.4 Hz, 2H), 5.27 and 5.22 (m, 1H, NCH), 2.54-2.38 ( m, 1H, CH ₂ ), 2.20-2.08 (m, 1H, CH ₂ ), 2.36 and 2.35 (s, 3H), 2.05 and 2.03 (s, 3H), 1.94 and 1.93 (s, 3H), 1.89 and 1.84 (s, 3H), 1.72-1.58 (m, 2H, CH ₂ ), 1.36-1.28 (m, 2H, CH ₂ ), 1.17 and 1.14 (d, J = 6.4, 3H, CH ₃ ) ppm.

¹³ C{ ¹ H} NMR (C ₆ D ₆ ): 162.78, 147.91, 142.45, 142.03, 136.91, 131.12, 130.70, 130.10, 128.90, 127.17, 123.39, 121.33, 119.87 , 54.18, 26.48, 21.74, 17.28, 14.46, 14.28, 13.80, 13.27 ppm.

<Physical property analysis>

1. Density (g/mL): The copolymer treated with antioxidants was manufactured into a specimen with a thickness of 3 mm and a radius of 2 cm using a compression mold at 180°C, cooled to room temperature, and measured using ASTM D-792. (Manufacturer: Toyoseiki, Model Name: T-001)

2. Melt index (MI): Measured with an instrument (manufacturer: Mirage, model name: SD-120L) by applying the ASTM D-1238 (condition E, 190°C, 2.16 kg load) method.

3. Molecular weight distribution (Mwd): Measured at 160°C using 1,2,4-trichlorobenzene solvent using GPC (Gel Permeation Chromatography, device name: PL-GPC220, manufacturer: Agilent) analysis method.

4. Melting point (Tm): Differential Scanning Calorimeter (DSC), device name: DSC 2920, manufacturer: TA) was used. DSC reaches equilibrium at a temperature of 0°C, then increases the temperature by 10°C per minute to 200°C, decreases it by 10°C per minute to -90°C, and then increases the temperature again by 10°C per minute to 200°C. It was measured using this method. The melting point is obtained by taking the area at the top of the endothermic curve during the second temperature rise.

5. Comonomer content (wt%): analyzed by ¹ H NMR (device name: Avance DRX400, manufacturer: Bruker).

6. Tensile elongation and tensile strength: Measured according to ASTM D638 using a universal testing machine (INSTRON 4466).

<TGIC analysis>

Polymer Char's CFC (Cross-Fractionation Chromatography) equipment was used, and the sample to be analyzed was stirred at 150°C for 60 minutes to dissolve 1,2,4-trichlorobenzene (2.5 mg/mL), and then the dissolved sample was It is introduced into a TGIC (Thermal Gradient Interaction Chromatography) column at 1ml/min and then stabilized at 150°C for 20 minutes. The TGIC column is then cooled to 35°C at a cooling rate of 20°C min. The temperature is raised from 35℃ to 130℃ in 5℃ increments and eluted with a GPC column at a flow rate of 1ml/min. The elution time at this time is 5 minutes, and the analysis time for each fraction is 20 minutes. After passing through the GPC column, an infrared detector (IR5) is used to determine the elution amount for each temperature fraction, the molecular weight and branched chain distribution of the polymer corresponding to each fraction. The peak area of each fraction is checked using the analysis software 'CFC calc', and n-heptane is used as an internal standard.

Examples 1 to 3

After purging the inside of a high-pressure reactor (internal capacity: 2L, stainless steel) with nitrogen at room temperature, 1L of normal hexane and 2mL of triisobutylaluminum were added. Next, after adjusting the input amount of 210 ml of 1-octene and ethylene gas, the reactor temperature was preheated to 140°C, and a mixed solution of 1.5 μmol of the synthesized transition metal compound (2) and 187.5 μmol of triisobutyl aluminum) was added. A solution of dimethylanilinium tetrakis (pentafluorophenyl)borate cocatalyst (45.0 μmol) was mixed and injected into the reactor, and then polymerization reaction was performed for 5 minutes.

After the polymerization reaction was completed, the reaction was terminated using ethanol diluted with 10% HCl, the temperature was lowered to room temperature, and excess gas was discharged. Next, the polymerization solution of the copolymer dispersed in the solvent was transferred to a container, dried in a vacuum oven at 80°C for more than 15 hours, and the S-type/R-type ratio was varied through catalytic recrystallization to form an ethylene/1-octene copolymer. The composite was prepared, and the results are shown in Table 1.

S-type/R-type ratio Area ratio of Te-1 (%) Area ratio of Te-2 (%) Density
(g/ml) 1-octene content
(wt%) Comonomer conversion rate (%) Example 1 0.57 55.2 41.8 0.871 37.3 22.9 Example 2 0.70 64.4 34.9 0.870 37.4 23.1 Example 3 0.91 84.7 11.7 0.861 43.0 32.1

As can be seen from Table 1, as the proportion of S-type steric compounds in the transition metal compound, which is the main catalyst used in Examples 1 to 3, increases, the area ratio of the first fraction (polymer chain with high branched chain content) increases. It can be seen that an ethylene-alpha olefin copolymer with an area ratio higher than that of the second fraction (polymer chain with a low branch chain content) was obtained.

Although this is a single catalyst, it is believed that the presence of isomers can control polymer physical properties by controlling the polymer structure produced by controlling the S/R type ratio.

Manufacturing examples and comparative manufacturing examples

Manufacturing Examples 1-2

After purging the inside of a high-pressure reactor (internal capacity: 2L, stainless steel) at room temperature with nitrogen, 1L of normal hexane and 2mL of triisobutylaluminum were added. Next, after adjusting the amount of 1-butene and ethylene gas, the reactor temperature was preheated to 140°C, and dimethyl was added to the mixed solution of 1.5 μmol of the synthesized transition metal compound (2) and 187.5 μmol of triisobutyl aluminum). A solution of anilinium tetrakis (pentafluorophenyl)borate cocatalyst (45.0 μmol) was mixed and injected into the reactor, and then polymerization reaction was performed for 5 minutes.

After the polymerization reaction was completed, the reaction was terminated using ethanol diluted with 10% HCl, the temperature was lowered to room temperature, and excess gas was discharged. Next, the polymerization solution of the copolymer dispersed in the solvent was transferred to a container and dried in a vacuum oven at 80°C for more than 15 hours to prepare ethylene/1-butene copolymers.

The physical properties of each ethylene/1-butene copolymer prepared above were measured, and the results are shown in Table 2.

Comparative Manufacturing Examples 1-2

Ethylene-1-butene copolymers (LC565, LC175) commercially produced by LG Chemical (LG) were purchased, their physical properties were measured, and the results are shown in Table 2.

Manufacturing Example 1 Production example 2 Comparative Manufacturing Example 1 Comparative Manufacturing Example 2 copolymer
Properties density
(g/mL) 0.865 0.870 0.865 0.870 MI
(g/10 min.) 5.0 1.1 5.0 1.1 Mwd 2.7 2.5 2.6 2.3 Tm-1
(℃) 52.5 58.4 31.6 43.1 Tm-2
(℃) 112.7 114.1 - - tensile elongation >1000% >1000% 583% 665% tensile strength
(MPa) 2.8 6.8 1.8 3.4 TGIC
Analysis Te-1
(℃) 45.7 50.2 57.5 63.8 Comonomer content
(wt%) 31.6 31.2 27.3 24.4 Te-2
(℃) 81.7 85.5 - - Comonomer content
(wt%) 16.4 20.1 - -

As can be seen from Table 2, the ethylene-alpha olefin copolymers of Preparation Examples 1 and 2 are a first fraction (polymer with a high branched chain content) defined by first and second peaks that are clearly distinguished from each other in the TGIC analysis results. chain) and a second fraction (polymer chain with low branched chain content).

In addition, the fraction ratio of the first peak area is larger than that of the second peak area, and the average SCB content is high, so it can be seen that more comonomers are introduced into the first peak area compared to the second peak area.

This is because the transition metal compound, which is the main catalyst used in Preparation Examples 1 and 2, contains an R-type stereo compound and an S-type compound in a ratio of 1:0.8, so the two stereo compounds serve as two catalysts with different structures. It is believed that a polymer chain with high branched chain content and high molecular weight with a low elution temperature and a polymer chain with low branched chain content and low molecular weight were formed.

This difference in branch chain content also causes differences in crystallinity. Polymer chains with high branched chain content are amorphous or have low crystallinity, while chains with low branched chain content have high crystallinity. This may mean that two types of chains with large differences in crystallinity due to differences in branch chain content are included together in the copolymer of the above example.

Claims (6)

In the ethylene alpha-olefin copolymer comprising an ethylene structural unit and an alpha-olefin structural unit,
When analyzing TGIC (Thermal Gradient Interaction Chromatography), it contains two or more different elution peaks in the temperature range of 35 to 130 ° C.
Ethylene alpha-olefin copolymer 2. The ethylene alpha-olefin copolymer according to claim 1, wherein the ethylene alpha-olefin copolymer has a density of 0.857 to 0.903 g/ml. A step of polymerizing ethylene and at least one olefinic monomer in the presence of a main catalyst compound containing a transition metal compound represented by the following formula (1) and one or more cocatalyst compounds selected from the compounds represented by the formulas (2) to (4) below. Includes,
Method for producing an ethylene alpha-olefin copolymer according to any one of claims 1 and 2:
[Formula 1]

(In Formula 1 above,
M is a group 4 transition metal;
Q ¹ and Q ² are each independently halogen, (C ₁ -C ₂₀ )alkyl, (C ₂ -C ₂₀ )alkenyl, (C ₂ -C ₂₀ )alkynyl, (C ₆ -C ₂₀ )aryl, ( C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl, (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl, (C ₁ -C ₂₀ )alkylamido, (C ₆ -C ₂₀ )arylamido or (C ₁ -C ₂₀ )alkylidene;
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently hydrogen; (C ₁ -C ₂₀ )alkyl with or without acetal, ketal or ether groups; (C ₂ -C ₂₀ )alkenyl with or without acetal, ketal or ether groups; (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl with or without an acetal, ketal or ether group; or (C ₁ -C ₂₀ )alkylsilyl with or without an acetal, ketal or ether group; R ¹ and R ² may be connected to each other to form a ring, R ³ and R ⁴ may be connected to each other to form a ring, and two or more of R ⁵ to R ¹⁰ may be connected to each other to form a ring. You can;
R ¹¹ , R ¹² and R ¹³ are each independently hydrogen; (C ₁ -C ₂₀ )alkyl with or without acetal, ketal or ether groups; (C ₂ -C ₂₀ )alkenyl with or without acetal, ketal or ether groups; (C ₁ -C ₂₀ )alkyl(C ₆ -C ₂₀ )aryl with or without an acetal, ketal or ether group; (C ₆ -C ₂₀ )aryl(C ₁ -C ₂₀ )alkyl with or without an acetal, ketal or ether group; (C ₁ -C ₂₀ )alkylsilyl with or without acetal, ketal or ether groups; (C ₁ -C ₂₀ )alkoxy; or (C ₆ -C ₂₀ )aryloxy; R ¹¹ and R ¹² or R ¹² and R ¹³ may be connected to each other to form a ring.)
[Formula 2]
-[Al(Ra)-O] _n -
(In Formula 2 above,
Ra is each independently halogen; or a (C ₁ -C ₂₀ ) hydrocarbyl group substituted or unsubstituted with halogen,
n is an integer greater than or equal to 2),
[Formula 3]
Q(Rb) ₃
(In Formula 3 above,
Q is aluminum or boron,
Rb is each independently halogen; or a (C ₁ -C ₂₀ )hydrocarbyl group substituted or unsubstituted with halogen),
[Formula 4]
[W] ⁺ [Z(Rc) ₄ ] ^-
(In Formula 4 above,
[W] ⁺ is a cationic Lewis acid; or a cationic Lewis acid with a hydrogen atom bonded to it,
Z is a group 13 element,
Rc is each independently a (C ₆ -C ₂₀ )aryl group substituted with one or two or more substituents selected from the group consisting of halogen, (C ₁ -C ₂₀ )hydrocarbyl group, alkoxy group, and phenoxy group; It is a (C ₁ -C ₂₀ )alkyl group substituted with one or two or more substituents selected from the group consisting of halogen, (C ₁ -C ₂₀ )hydrocarbyl group, alkoxy group, and phenoxy group). The method for producing an ethylene alpha-olefin copolymer according to claim 3, wherein the transition metal compound is a combination of R-type and S-type steric compounds. polypropylene; and
The ethylene alpha-olefin copolymer of any one of claims 1 and 2;
A polypropylene resin composition comprising. A molded article manufactured from the resin composition of claim 5.