WO2018117596A1 - Polyolefin and manufacturing method thereof - Google Patents

Abstract

A polyolefin and a manufacturing method thereof are provided. The polyolefin is formed by copolymerization of an olefin-based monomer and a comonomer, and satisfies the following characteristics (1) to (3): (1) a melting temperature (T_m) of 20 to 100 °C; (2) a number average comonomer length (n₀) of 1.0 to 1.1; and (3) a relation between melt temperature (T_m, °C) and density (a.g/㎤) of 1598.7a-1333.2 > T_m > 1796.3a-1513.4.

Description

Polyolefins and Methods for Making the Same

The present invention relates to a polyolefin and a method for producing the same.

Metallocene catalyst, one of the catalysts used to polymerize olefins, is a compound in which ligands such as cyclopentadienyl group, indenyl group, and cycloheptadienyl group are bonded to a transition metal or transition metal halogen compound in a basic form. Have

Olefin copolymers polymerized using such metallocene catalysts are known to have a narrower molecular weight distribution as well as a constant comonomer distribution as compared to copolymers polymerized with conventional Ziegler-Natta catalysts. In particular, the olefin content of ethylene / alpha-olefin copolymers and their distribution are one of the most important structural parameters because they affect the crystallization process and morphology, the structure and physical properties in the solid state.

The number average lengths (nO, nE) of the monomers, one of the major indices of the microchain structure of the copolymer, can be calculated from the following formula, Seger's method (Anal. Chem. 2004, 76, 5734-5747).

nO is the number average comonomer (alpha-olefin) length and the average number of comonomers repeated without the monomer (ethylene) intervening, nE is the number average monomer (ethylene) length and conversely the comonomer (alpha-olefin) It is the average number of monomers (ethylene) repeated without lifting. EOE is the mole% of the ethylene (monomer) -octene (comonomer) -ethylene (monomer) block of the copolymer chain, EOO is the ethylene (monomer) -octene (comonomer) -octene (comonomer) block of the copolymer chain Mole%, OOO is the mole% of the octene (comonomer) -octene (comonomer) -octene (comonomer) block of the copolymer chain, EEE is the ethylene (monomer) -ethylene (monomer) -ethylene (monomer) of the copolymer chain ) Mole% of the block, EEO is the mole% of the ethylene (monomer) -ethylene (monomer) -octene (comonomer) block of the copolymer chain, OEO is the octene (comonomer) -ethylene (monomer) -octene of the copolymer chain The mole percentage of the (comonomer) block. Each tri-element sequence sequence mole fraction of the above formula can be calculated using Randall's method (Macromol Sci, Part C: Polymer Reviews, 1989, 29, 2-3).

Since the number average length nO of the comonomer is a measure of how continuously the comonomer is present, it can be seen that in the copolymer having the same comonomer content, the smaller the nO, the more uniform the comonomer distribution. In general, as the comonomer is uniformly distributed throughout the chain, the melting temperature of the copolymer is lowered. Thus, even when the copolymer has the same comonomer content, the melting temperature is lower as the number average length nO of the comonomer is smaller.

On the other hand, since the copolymer may exhibit a heat sealing effect at a lower temperature as the melting temperature is lower, the heat sealing effect may be exerted at different temperatures even if the comonomer content is the same as described above.

The problem to be solved by the present invention is to provide a polyolefin that can exhibit a heat-sealing effect at a lower temperature than conventional polyolefin having the same density and comonomer content because the distribution of the comonomer is uniform and the melting temperature is low.

The objects of the present invention are not limited to the above-mentioned technical problem, and other technical problems not mentioned will be clearly understood by those skilled in the art from the following description.

Polyolefin according to an embodiment of the present invention for solving the above problems is formed by copolymerizing an olefin monomer and a comonomer, and satisfies the characteristics of the following (1) to (3).

(1) Melting temperature (T _m ): 20 ~ 100 ℃

(2) Number average comonomer length (n ₀ ): 1.0 to 1.1

(3) Relationship between melting temperature (T _m , ° C) and density (a, g / cm 3): 1598.7a-1333.2> T _m > 1796.3a-1513.4

At least one of the olefin monomer and the comonomer may include an alpha-olefin.

The olefinic monomer and the comonomer may be ethylene and 1-octene, respectively.

The polyolefin may be formed by copolymerization under an olefin polymerization catalyst including a transition metal compound represented by Chemical Formula B1.

<Formula B1>

In Formula B1, n is 1 to 4, X1 and X2 are each independently halogen, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C6-20 aryl, C1-20 alkyl C6-20 Aryl, C6-20 aryl C1-20 alkyl, C1-20 alkylamido, C6-20 arylamido or C1-20 alkylidene, R1 to R12 are each independently hydrogen, substituted or unsubstituted C1-20 alkyl , Substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C6-20 aryl, substituted or unsubstituted C1-20 alkyl C6-20 aryl, substituted or unsubstituted C6-20 aryl C1-20 alkyl, Substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C3-20 heteroaryl, or substituted or unsubstituted C1-20 silyl, and M is titanium (Ti), zirconium (Zr) or hafnium (Hf) Can be.

Formula B1 may be the following Formula B2.

<Formula B2>

In Formula B2, R1 and R2 are each independently hydrogen or methyl, and R3 is hydrogen, C1-20 alkyl, C6-20 aryl, C1-20 alkyl C6-20 aryl, C6-20 aryl C1-20 alkyl, C1 -20 alkylamido, C6-20 arylamido, C1-20 heteroalkyl or C3-20 heteroaryl, R4 to R10 are hydrogen, R13 to R15 are each independently hydrogen, substituted or unsubstituted C1-20 Alkyl, substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C6-20 aryl, substituted or unsubstituted C1-20 alkyl C6-20 aryl, substituted or unsubstituted C6-20 aryl C1-20 alkyl , Substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C3-20 heteroaryl, or substituted or unsubstituted C1-20 silyl, X1 and X2 are each independently halogen or C1-20 alkyl, M may be titanium (Ti), zirconium (Zr) or hafnium (Hf).

Formula B1 may be one of Formulas 57 to 112.

Method for producing a polyolefin according to an embodiment of the present invention for solving the other problem is to form a polyolefin by copolymerizing an olefin monomer and a comonomer under an olefin polymerization catalyst containing a transition metal compound represented by the formula (B1) Steps.

<Formula B1>

In Formula B1, n is 1 to 4, X1 and X2 are each independently halogen, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C6-20 aryl, C1-20 alkyl C6-20 Aryl, C6-20 aryl C1-20 alkyl, C1-20 alkylamido, C6-20 arylamido or C1-20 alkylidene, R1 to R12 are each independently hydrogen, substituted or unsubstituted C1-20 alkyl , Substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C6-20 aryl, substituted or unsubstituted C1-20 alkyl C6-20 aryl, substituted or unsubstituted C6-20 aryl C1-20 alkyl, Substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C3-20 heteroaryl, or substituted or unsubstituted C1-20 silyl, and M is titanium (Ti), zirconium (Zr) or hafnium (Hf) to be.

The polyolefin may satisfy the following properties (1) to (3).

(1) Melting temperature (Tm): 20 ~ 100 ℃

(2) Number average comonomer length (n0): 1.0 to 1.1

(3) Relationship between melting temperature (Tm, ℃) and density (a, g / cm 3): 1598.7a-1333.2> Tm> 1796.3a-1513.4

The olefinic monomer and the comonomer may be ethylene and 1-octene, respectively.

Specific details of other embodiments are included in the detailed description and drawings.

According to embodiments of the present invention has at least the following effects.

The polyolefin of the present invention is produced using an olefin polymerization catalyst containing a transition metal compound, so that the distribution of comonomers is uniform and the melting temperature is low, so that the heat sealing effect at a lower temperature than conventional polyolefins having the same density and comonomer content Can be represented.

Effects according to embodiments of the present invention are not limited by the contents exemplified above, and more various effects are included in the present specification.

1 is a schematic view showing a process for synthesizing an ethylene / 1-octene copolymer.

2 is a graph showing the relationship between density and Tm for the ethylene / 1-octene copolymers of each production example and comparative example.

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

In the present specification, the term "CA-B" means "carbon number A or more and B or less", the term "A to B" means "A or more and B or less", the term "substituted or unsubstituted" "Substituted" means that at least one hydrogen of the hydrocarbon compound or hydrocarbon derivative is halogen, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C6-20 aryl, C1-20 alkyl C6- Substituted with 20 aryl, C6-20 aryl C1-20 alkyl, C1-20 alkylamido, C6-20 arylamido or C1-20 alkylidene, and "unsubstituted" means "hydrocarbon compound or hydrocarbon" At least one hydrogen of the derivative is halogen, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C6-20 aryl, C1-20 alkyl C6-20 aryl, C6-20 aryl C1-20 alkyl, C1 Unsubstituted with -20 alkylamido, C6-20 arylamido or C1-20 alkylidene.

Polyolefin according to an embodiment of the present invention is a copolymer formed by polymerizing an olefin monomer and a comonomer, and has the following characteristics.

(1) Melting temperature (Tm): 20 ~ 100 ℃

(2) Number average comonomer length (n0): 1.0 to 1.1

(3) Relationship between melting temperature (Tm) and density (a): 1598.7a-1333.2> Tm> 1796.3a-1513.4

Since the polyolefin having such characteristics exhibits a uniform comonomer distribution and a low melting temperature, etc., compared to the conventional polyolefin having the same density and comonomer content, it may exhibit a heat sealing effect at a lower temperature.

Olefin monomers and comonomers consist of C2-20 alpha-olefins, C1-20 diolefins, C3-20 cycloolefins, and C3-20 cyclodiolefins. It may include one or more selected from the group.

Specifically, the olefinic monomers and comonomers are propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1 Alpha-olefins comprising at least one selected from the group consisting of dodecene, 1-tetradecene and 1-hexadecene.

Preferably, the polyolefin may be a copolymer in which ethylene, an olefinic monomer, is copolymerized with 1-octene, which is a comonomer, in which case the number average comonomer length may be a number average 1-octene length.

In an exemplary embodiment, the polyolefin may be polymerized by polymerization such as free radicals, cationics, coordination, condensation, addition, and the like.

In an exemplary embodiment, the polyolefin may be prepared by gas phase polymerization, solution polymerization or slurry polymerization. Examples of solvents that can be used when the polyolefin is prepared by solution polymerization or slurry polymerization include C5-12 aliphatic hydrocarbon solvents such as pentane, hexane, heptane, nonane, decane and isomers thereof; Aromatic hydrocarbon solvents such as toluene, benzene; Hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene; Although mixtures of these, etc. are mentioned, It is not limited only to these.

The polyolefin may be polymerized under an olefin polymerization catalyst including a transition metal compound for an olefin polymerization catalyst represented by the following formula B1. In addition, the transition metal compound for the olefin polymerization catalyst may be prepared from a transition metal compound precursor for the olefin polymerization catalyst represented by the general formula (A1).

<Formula A1>

In Formula A1, n may be 1 to 4, and R1 to R12 are each independently hydrogen, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C6 -20 aryl, substituted or unsubstituted C1-20 alkyl C6-20 aryl, substituted or unsubstituted C6-20 aryl C1-20 alkyl, substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C3- 20 heteroaryl, or substituted or unsubstituted C1-20 silyl. In addition, R11 and R12 may be connected to each other to form a substituted or unsubstituted C5-20 heterocycle including nitrogen (N).

<Formula B1>

In Formula B1, n is 1 to 4, X1 and X2 are each independently halogen, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C6-20 aryl, C1-20 alkyl C6-20 Aryl, C6-20 aryl C1-20 alkyl, C1-20 alkylamido, C6-20 arylamido or C1-20 alkylidene, R1 to R12 are each independently hydrogen, substituted or unsubstituted C1-20 alkyl , Substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C6-20 aryl, substituted or unsubstituted C1-20 alkyl C6-20 aryl, substituted or unsubstituted C6-20 aryl C1-20 alkyl, Substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C3-20 heteroaryl, or substituted or unsubstituted C1-20 silyl, and M is titanium (Ti), zirconium (Zr) or hafnium (Hf) Can be. In addition, R11 and R12 may be connected to each other to form a substituted or unsubstituted C5-20 heterocycle including nitrogen (N).

Specifically, the transition metal compound precursor for the olefin polymerization catalyst may be represented by the following Chemical Formula A2.

<Formula A2>

In Formula A2, R1 and R2 are each independently hydrogen or methyl, and R3 is hydrogen, C1-20 alkyl, C6-20 aryl, C1-20 alkyl C6-20 aryl, C6-20 aryl C1-20 alkyl, C1 -20 alkylamido, C6-20 arylamido, C1-20 heteroalkyl or C3-20 heteroaryl, R4 to R10 are hydrogen, R13 to R15 are each independently hydrogen, substituted or unsubstituted C1-20 Alkyl, substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C6-20 aryl, substituted or unsubstituted C1-20 alkyl C6-20 aryl, substituted or unsubstituted C6-20 aryl C1-20 alkyl , Substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C3-20 heteroaryl, or substituted or unsubstituted C1-20 silyl.

More specifically, the transition metal compound precursor for the olefin polymerization catalyst may be at least one of the following Chemical Formulas 1 to 56.

The transition metal compound for the olefin polymerization catalyst may be specifically represented by the following general formula (B2).

<Formula B2>

In Formula B2, R1 and R2 are each independently hydrogen or methyl, and R3 is hydrogen, C1-20 alkyl, C6-20 aryl, C1-20 alkyl C6-20 aryl, C6-20 aryl C1-20 alkyl, C1 -20 alkylamido, C6-20 arylamido, C1-20 heteroalkyl or C3-20 heteroaryl, R4 to R10 are hydrogen, R13 to R15 are each independently hydrogen, substituted or unsubstituted C1-20 Alkyl, substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C6-20 aryl, substituted or unsubstituted C1-20 alkyl C6-20 aryl, substituted or unsubstituted C6-20 aryl C1-20 alkyl , Substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C3-20 heteroaryl, or substituted or unsubstituted C1-20 silyl.

In addition, X1 and X2 are each independently halogen or C1-20 alkyl, M may be titanium (Ti), zirconium (Zr) or hafnium (Hf).

More specifically, the transition metal compound for the olefin polymerization catalyst may be at least one of the formulas (57) to (112).

The olefin polymerization catalyst described above may further include a cocatalyst compound together with a transition metal compound for the olefin polymerization catalyst.

The cocatalyst compound may include one or more of a compound represented by Formula A, a compound represented by Formula B, and a compound represented by Formula C.

<Formula A>

In Formula A, n is an integer of 2 or more, and Ra may be a halogen atom, a C1-20 hydrocarbon group, or a C1-20 hydrocarbon group substituted with halogen. Specifically, Ra may be methyl, ethyl, n-butyl or isobutyl, but is not limited thereto.

<Formula B>

In Formula B, D is aluminum (Al) or boron (B), and Rb, Rc and Rd are each independently a halogen atom, a C1-20 hydrocarbon group, a C1-20 hydrocarbon group substituted with halogen or a C1-20 alkoxy group Can be. Specifically, when D is aluminum, each of Rb, Rc, and Rd may be independently methyl or isobutyl, and when D is boron, Rb, Rc, and Rd may be pentafluorophenyl, respectively. It is not limited.

<Formula C>

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

In Formula C, L is a neutral or cationic Lewis base, [LH] ⁺ or [L] ⁺ is Bronsted acid, Z is a Group 13 element, and A is each independently substituted or unsubstituted C6-20. It may be an aryl group or a substituted or unsubstituted C1-20 alkyl group. Specifically, [LH] ⁺ may be a dimethylanilinium cation, [Z (A) ₄ ] ⁻ may be [B (C ₆ F ₅ ) ₄ ] ⁻ , and [L] ⁺ is [( C ₆ H ₅ ) ₃ C] ⁺ , but is not limited thereto.

The olefin polymerization catalyst may further include a carrier.

The carrier is not particularly limited as long as it can support the transition metal compound and the promoter compound for the olefin polymerization catalyst. In an exemplary embodiment, the carrier can be carbon, silica, alumina, zeolite, magnesium chloride, or the like.

As a method of supporting the transition metal compound and the promoter compound for the olefin polymerization catalyst on the carrier, a physical adsorption method or a chemical adsorption method may be used.

In an exemplary embodiment, the physical adsorption method is a method in which a solution containing a transition metal compound for an olefin polymerization catalyst is contacted with a carrier and dried, and a solution in which the transition metal compound and a promoter compound for an olefin polymerization catalyst is dissolved is contacted with a carrier. Or a method of drying and a solution in which a transition metal compound for an olefin polymerization catalyst is dissolved in contact with a carrier, followed by drying to prepare a carrier in which the transition metal compound for an olefin polymerization catalyst is supported, and separately a solution in which a promoter compound is dissolved. After contacting the carrier and dried to prepare a carrier on which the cocatalyst compound is loaded, and the like may be mixed.

In an exemplary embodiment, the chemical adsorption method first supports a promoter compound on the surface of the carrier, and then a transition metal compound for the olefin polymerization catalyst on the promoter compound, or a functional group (eg, In the case of silica, it may be a method of covalently bonding a hydroxyl group (-OH)) and a catalyst compound on the surface of silica.

The sum of the supported amount of the main catalyst compound including the transition metal compound may be 0.001 mmol to 1 mmol based on 1 g of the carrier, and the supported amount of the promoter catalyst may be 2 mmol to 15 mmol based on 1 g of the carrier.

However, such a carrier does not necessarily have to be included and can be appropriately selected depending on necessity.

Hereinafter, specific preparation examples of the compound represented by Chemical Formula 74 in the transition metal compound for olefin polymerization catalyst of the present invention, and specific experiments for evaluating the physical properties of the ethylene / 1-octene copolymer polymerized under the olefin polymerization catalyst including the same An example is described.

Preparation Example 1 Preparation of Transition Metal Compound for Olefin Polymerization Catalyst

Preparation Example 1-1: of 8- (2-methyl-4-phenyl-2,3,6,7-tetrahydro-s-indasenyl) -1,2,3,4-tetrahydroquinoline (Formula 1) Produce

1.0 g (5.37 mmol) of 2-methyl-3,5,6,7-tetrahydro-s-indacene-1 (2H) -one is dissolved in chloroform in which 1.65 g (12.4 mmol) of aluminum chloride (AlCl 3) is dispersed. Chloroform) solution was slowly added at 0 to 30 mL. After the addition was completed, the mixture was stirred for 1 hour. After 1 hour, Bromine (858 mg) (5.37 mmol) was slowly added to the solution at zero. After the addition was completed, the temperature was slowly raised to room temperature, followed by stirring for 12 hours or more. After stirring, 50 mL of water was added to terminate the reaction. The organic layer was extracted using dichloromethane and the solvent was removed under vacuum. Thereafter, 4-bromo-2-methyl-2,3,6,7-tetrahydro-s-indacene-1 (5H) -one having the following 1H-NMR spectrum was obtained by column chromatography ( Yield: 50%).

1 H NMR (CDCl 3): δ 7.51 (s, 1H), 3.30 (m, 1H), 3.02 (m, 4H), 2.75 (m, 1H), 2.60 (dd, 1H), 2.16 (m, 2H), 1.32 (d, 3H) ppm.

1.06 g (4.00 mmol) of 4-bromo-2-methyl-2,3,6,7-tetrahydro-s-indacene-1 (5H) -one and 634 mg (5.20 mmol) of phenylboronic acid ) And 230 mg (5 mol%) of tetrakis (triphenylphosphine) palladium (Pd (PPh3) 4) in 40 mL of tetrahydrofuran and 10 mL of methanol in a solution of potassium carbonate (K2CO3) 2.0 M ( 3.3 M equivalents) was added slowly. After the addition was completed, the temperature was raised to 80 ° C. and stirred for 12 hours or more. After stirring, 50 mL of water was added to terminate the reaction. The organic layer was extracted using ethyl acetate and the solvent was removed in vacuo. Thereafter, 2-methyl-4-phenyl-2,3,6,7-tetrahydro-s-indacene-1 (5H) -one having the following 1H-NMR spectrum was obtained by column chromatography (yield). : 77%).

1 H NMR (CDCl 3): δ 7.60 (s, 1H), 7.50 to 7.25 (m, 5H), 3.17 (m, 1H), 3.00 (t, 2H), 2.81 (t, 2H), 2.68 (m, 1H) , 2.51 (dd, 1H), 2.08 (m, 2H), 1.26 (d, 3H) ppm.

479 mg (3.60 mmol) of 1,2,3,4-tetrahydroquinoline (1,2,3,4-Tetrahydroquinoline) was dissolved in 10 mL of hexane, followed by n-butyllithium (n-BuLi) 1.6 M (3.78 mmol) was slowly added at -30 ° C. After the addition was completed, the temperature was slowly raised to room temperature, followed by stirring for 12 hours or more. After stirring, the resulting solid was filtered to remove the solvent, dissolved in 10 mL of diethyl ether, and carbon dioxide (CO 2) was added at -78 ° C. After slowly raising the temperature to room temperature, the mixture was stirred for 12 hours or more. Thereafter, 285 mg (3.95 mmol) of tetrahydrofuran and 1.7 M (3.95 mmol) of t-butyllithium (t-BuLi) were continuously added at −20 ° C. and stirred for 2 hours.

800 mg (3.05 mmol) of 2-methyl-4-phenyl-2,3,6,7-tetrahydro-s-indacene-1 (5H) -one and 260 mg (6.11 mmol) of lithium chloride (LiCl) were slowly added thereto. After raising the temperature slowly to room temperature, the mixture was stirred for 12 hours or more. After stirring, 20 mL of water was added to terminate the reaction. Thereafter, the organic layer was extracted using ethyl acetate, and the solvent was removed under vacuum, and the compound of formula 1 having a 1H-NMR spectrum as follows through column chromatography was subjected to 8- (2-methyl-4- Phenyl-2,3,6,7-tetrahydro-s-indasenyl) -1,2,3,4-tetrahydroquinoline was obtained (yield: 30%).

1 H NMR (CDCl 3): δ 7.50-7.31 (m, 5H), 7.00 (d, 1H), 6.95-6.89 (m, 2H), 6.69 (t, 1H), 3.33 (m, 2H), 3.24 (m, 2H), 2.96-2.83 (m, 4H), 2.79 (t, 2H), 2.03 (m, 2H), 1.98 (s, 3H) ppm.

<Formula 1>

Preparation Example 1-2: [1- (1,2,3,4-tetrahydroquinolin-8-yl) -2-methyl-4-phenyl-2,3,6,7-tetrahydro-s-indasenyl ] Dimethyl Titanium (Formula 74)

8- (2-methyl-4-phenyl-2,3,6,7-tetrahydro-s-indasenyl) -1,2,3,4- which is a compound of Formula 1 synthesized in Preparation Example 1-1 303 mg (0.80 mmol) of tetrahydroquinoline was dissolved in 10 mL of diethyl ether, and 1.6 M (3.21 mmol) of methyllithium (MeLi) was slowly added at -78 ° C. After the addition was completed, the temperature was slowly raised to room temperature. Then, 152 mg (0.80 mmol) of titanium chloride (TiCl 4) was slowly added at room temperature, followed by stirring for 4 hours. After the reaction was terminated, the solvent was removed in vacuo and then extracted using hexane (Hexane). Thereafter, the solvent was removed in vacuo to give [1- (1,2,3,4-tetrahydroquinolin-8-yl) -2-methyl-4-phenyl, which is a compound of formula 74 having the 1 H-NMR spectrum as follows. -2,3,6,7-tetrahydro-s-indacenyl] dimethyl titanium was obtained (yield: 55%).

1 H NMR (C6D6): δ 7.82 (d, 2H), 7.50 (t, 1H), 7.37 (t, 2H), 7.15 (d, 1H), 711-7.01 (m, 2H), 6.79 (s, 1H) , 4.61 (m, 2H), 2.88 (m, 2H), 2.63 (m, 4H), 1.95 (s, 3H), 1.82 (m, 4H), 0.93 (s, 3H), 0.28 (s, 3H) ppm .

<Formula 74>

Preparation Examples 2 to 4 Synthesis of Ethylene / 1-octene Copolymer Using an Olefin Polymerization Catalyst Containing a Transition Metal Compound

Ethylene and 1-octene were copolymerized using an olefin polymerization catalyst including the transition metal compound synthesized in Preparation Example 1, and polymerization conditions were changed as shown in Table 1 below for each Preparation Example.

Specifically, the compound of formula 74 synthesized in Preparation Example 1 [1- (1,2,3,4-tetrahydroquinolin-8-yl) -2-methyl-4-phenyl-2,3,6, 7-tetrahydro-s-indasenyl] dimethyl titanium was dissolved in an amount of hexane solvent and treated with triisobutylaluminum, followed by copolymerization of ethylene and 1-octene under a continuous solution process. As a specific polymerization method, a hexane solvent (1), 1-octene (2) and a scavenger (as shown in FIG. 1) are maintained by heating a 850 mL reactor to a constant temperature using a jacket for temperature control and maintaining a pressure of 90 bar. 3) and ethylene (4) were continuously fed directly into the reactor (5) and cocatalyst (6), respectively, continuously feeding the reactor (7) in a single stream. The molten polymer is passed through reactor outlet stream (8) into separator (9) to separate from unreacted ethylene, unreacted octene, hexane, and then finally through pelletizer 12 to be collected as solid pellets. It was. Dimethylanilinium tetrakis (pentafluorophenyl) borate was used as a cocatalyst and triisobutylaluminum was used as a scavenger.

Production Example	Temperature (℃)	Pressure (bar)	Hexane (g / min)	1-octene (g / min)	Catalyst (μmol / min)	Cocatalyst (μmol / min)	Scavenger (μmol / min)
2	154	90	46.7	10.0	0.18	1.1	18
3	150	90	46.7	6.0	0.16	0.9	18
4	145	90	46.7	6.0	0.13	0.8	18

Experimental Example 1 Measurement of Physical Properties of Ethylene / 1-Octene Copolymer

The physical properties of the ethylene / 1-octene copolymers polymerized in Preparation Examples 2 to 4 were measured by measuring ¹³ C NMR and melting temperature (T _m ) as follows, and the results are shown in Table 2 below.

Experimental Example 1-1: Measurement of ¹³ C NMR

About 2-3 ml of a solvent mixed with benzene-d6 and 1,2,4-Trichlorobenzene was placed in a 10 mm NMR tube, and then 0.3 to 0.4 g of the sample was added. This was dissolved in a solution state at 120 ° C. for 4 hours or more using an oven. After raising the temperature of the Agilent AS 400 NMR equipped with a 10 mm broad-band probe to 120 ℃, the sample tube was placed in the NMR apparatus. ¹³ C-NMR analysis of the conditions applying 90 ° pulse, 1.3s acquisition time, 10s relaxation delay to scan by 5,000 times to obtain a ¹³ C-NMR spectrum.

Experimental Example 1-2: Measurement of Melting Temperature (T _m )

Differential scanning calorimeter (DSC: Differential Scanning Calorimeter 2920) manufactured by TA was used for the measurement. Specifically, the temperature was increased to 200 ° C., then maintained at that temperature for 5 minutes, then lowered to 30 ° C., and the temperature increased again to bring the top of the DSC curve to the melting temperature. At this time, the rate of temperature rise and fall was 10 ° C./min, and the melting temperature was obtained while the second temperature was rising.

Production Example	Active (kg-PE / g-cat)	Density (g / cm 3 )	MI 2 (g / 10min)	1-octene (mol%)	Tm (℃)
2	82	0.857	7.64	13.8	25.5
3	85	0.868	1.18	10.7	47.1
4	130	0.877	0.28	9.1	61.3

Experimental Example 2 Comparison of Physical Properties of Ethylene / 1-Octene Copolymer

Properties of the ethylene / 1-octene copolymers of Preparation Examples 2 to 4 measured through Experimental Example 1 and the like and properties of Engage products (Comparative Examples 1 to 5) which are ethylene / 1-octene copolymers obtained from DOW It was compared as shown in Table 3. 2 is a graph showing the relationship between density and Tm for the ethylene / 1-octene copolymers of each production example and comparative example.

division	Density (g / cm 3 )	T m (℃)	1-octene (mol%)	Crystallinity (%)	Number average 1-octene length (n 0 )
Preparation Example 2	0.857	25.5	13.8	5.4	1.07
Preparation Example 3	0.868	47.1	10.7	12.6	1.05
Preparation Example 4	0.877	61.3	9.1	13.5	1.03
Comparative Example 1	0.857	36.9	11.7	18.3	1.18
Comparative Example 2	0.865	49.8	10.8	19.4	1.15
Comparative Example 3	0.867	54.0	11.1	16.9	1.14
Comparative Example 4	0.868	53.4	10.7	19.2	1.13
Comparative Example 5	0.877	69.0	9.0	20.5	1.16

As shown in Table 3 and FIG. 2, the ethylene / 1-octene copolymers of Preparation Examples 2 to 4 have a lower melting temperature (T _m ) than the ethylene / 1-octene copolymers of Comparative Examples 1, 4 and 5 having the same density. And it can be confirmed that the degree of crystallinity is significantly low.

In addition, the ethylene / 1-octene copolymer of the preparation example had a number average 1-octene length (n0) of 1.03 to 1.07, whereas the ethylene / 1-octene copolymer of the comparative example was 1.13 or more. It can be seen that the copolymer was more uniformly distributed in 1-octene than the ethylene / 1-octene copolymer of the comparative example.

From the difference in properties between the ethylene / 1-octene copolymers of the production examples and the comparative examples, it can be seen that the polyolefin of the present invention can be exhibited at a significantly lower temperature than the conventional polyolefin.

The embodiments belonging to the spirit of the present invention have been described in detail with reference to the illustrated chemical structural formulas and preparation examples. However, the spirit of the invention is not limited to the illustrated chemical structures and preparation examples, and the spirit of the invention may be variously modified based on the illustrated chemical structures and preparation examples. Exemplary chemical structural formulas and preparation examples are provided to completely inform those of ordinary skill in the art to the scope of the spirit of the invention, the scope of the spirit of the invention to the scope of the claims It is only defined by Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims (9)

1. Polyolefin which is formed by copolymerizing an olefin monomer and a comonomer and satisfying the following characteristics (1) to (3).

   (1) Melting temperature (Tm): 20 ~ 100 ℃

   (2) Number average comonomer length (n0): 1.0 to 1.1

   (3) Relationship between melting temperature (Tm, ℃) and density (a, g / cm 3): 1598.7a-1333.2> Tm> 1796.3a-1513.4
2. The method of claim 1,

   At least one of the olefin monomers and comonomers comprises an alpha-olefin.
3. The method of claim 1,

   The olefin monomer and the comonomer are ethylene and 1-octene, respectively.
4. The method of claim 1,

   Polyolefin formed by copolymerization under an olefin polymerization catalyst containing a transition metal compound represented by the following formula (B1).

   <Formula B1>

   

   (In Chemical Formula B1,

   n is 1 to 4,

   X1 and X2 are each independently halogen, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C6-20 aryl, C1-20 alkyl C6-20 aryl, C6-20 aryl C1-20 alkyl, C1 -20 alkylamido, C6-20 arylamido or C1-20 alkylidene,

   R1 to R12 are each independently hydrogen, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C6-20 aryl, substituted or unsubstituted C1-20 alkyl C6 -20 aryl, substituted or unsubstituted C6-20 aryl C1-20 alkyl, substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C3-20 heteroaryl, or substituted or unsubstituted C1-20 silyl ego,

   M is titanium (Ti), zirconium (Zr) or hafnium (Hf))
5. The method of claim 4, wherein

   Formula (B1) is a polyolefin of formula (B2).

   <Formula B2>

   

   (In Chemical Formula B2,

   R1 and R2 are each independently hydrogen or methyl,

   R3 is hydrogen, C1-20 alkyl, C6-20 aryl, C1-20 alkyl C6-20 aryl, C6-20 aryl C1-20 alkyl, C1-20 alkylamido, C6-20 arylamido, C1-20 hetero Alkyl or C3-20 heteroaryl,

   R4 to R10 are hydrogen,

   R13 to R15 are each independently hydrogen, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C6-20 aryl, substituted or unsubstituted C1-20 alkyl C6 -20 aryl, substituted or unsubstituted C6-20 aryl C1-20 alkyl, substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C3-20 heteroaryl, or substituted or unsubstituted C1-20 silyl Is,

   X 1 and X 2 are each independently halogen or C 1-20 alkyl,

   M is titanium (Ti), zirconium (Zr) or hafnium (Hf))
6. The method of claim 4, wherein

   Formula B1 is one of the following formulas 57 to 112 polyolefin.

   

   

   

   
7. A method for producing a polyolefin comprising copolymerizing an olefin monomer and a comonomer to form a polyolefin under an olefin polymerization catalyst including a transition metal compound represented by the following Formula B1.

   <Formula B1>

   

   (In Chemical Formula B1,

   n is 1 to 4,

   X1 and X2 are each independently halogen, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, C6-20 aryl, C1-20 alkyl C6-20 aryl, C6-20 aryl C1-20 alkyl, C1 -20 alkylamido, C6-20 arylamido or C1-20 alkylidene,

   R1 to R12 are each independently hydrogen, substituted or unsubstituted C1-20 alkyl, substituted or unsubstituted C2-20 alkenyl, substituted or unsubstituted C6-20 aryl, substituted or unsubstituted C1-20 alkyl C6 -20 aryl, substituted or unsubstituted C6-20 aryl C1-20 alkyl, substituted or unsubstituted C1-20 heteroalkyl, substituted or unsubstituted C3-20 heteroaryl, or substituted or unsubstituted C1-20 silyl ego,

   M is titanium (Ti), zirconium (Zr) or hafnium (Hf))
8. The method of claim 7, wherein

   The said polyolefin is a manufacturing method of the polyolefin which satisfy | fills the characteristic of following (1)-(3).

   (1) Melting temperature (Tm): 20 ~ 100 ℃

   (2) Number average comonomer length (n ₀ ): 1.0 to 1.1

   (3) Relationship between melting temperature (T _m , ° C) and density (a, g / cm 3): 1598.7a-1333.2> T _m > 1796.3a-1513.4
9. The method of claim 7, wherein

   Wherein said olefinic monomer and comonomer are ethylene and 1-octene, respectively.

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