KR20210059900A - Polyolefin and Process for Preparing the Same - Google Patents

Abstract

The present invention relates to an olefin-based polymer and to a manufacturing method thereof. The olefin-based polymer according to an embodiment of the present invention contains a large amount of unsaturated groups in the molecule to be easy to modify. The olefin-based polymer is prepared by polymerization of an olefinic monomer in the presence of a catalyst comprising at least one transition metal compound represented by chemical formula 1 and at least one co-catalyst compound, and has a density of 0.85 to 0.95 g/cm^3, and total amount of unsaturated groups of 0.5 mole% or more in the molecule.

Description

Olefin polymer and its manufacturing method {Polyolefin and Process for Preparing the Same}

The present invention relates to an olefin-based polymer and a method for producing the same. Specifically, the present invention relates to an olefin-based polymer that is easily modified by containing a large amount of unsaturated groups in a molecule and a method for producing the same.

Metallocene catalyst, one of the catalysts used to polymerize olefins, is coordination of ligands such as cyclopentadienyl, indenyl, and cycloheptadienyl to transition metals or transition metal halide compounds. As a bonded compound, it has a sandwich structure in its basic form.

Ziegler-Natta catalyst, which is another catalyst used to polymerize olefins, is dispersed on a solid surface in which the metal component as the active point is inert, and the properties of the active point are not uniform, whereas the metallocene catalyst has a certain structure. It is known as a single-site catalyst with all active sites having the same polymerization properties because it is a single compound with. Polymers polymerized with such a metallocene catalyst have a narrow molecular weight distribution, uniform distribution of comonomers, and higher copolymerization activity than Ziegler-Natta catalysts.

On the other hand, attempts have been made to modify the olefin-based polymer to improve its physical properties. For example, a method of improving the physical properties of an olefin-based polymer is known by adding an organic compound such as maleic anhydride to an ethylene-based polymer and grafting it. At this time, in order to grafting maleic anhydride to the ethylene-based polymer, peroxide is added to activate a hydrocarbon chain to react with an alkene.

If the content of unsaturated groups present in the molecule of the olefin-based polymer is relatively large, grafting of maleic anhydride may be possible even with a small amount of peroxide. In addition, since unsaturated groups in the olefin-based polymer molecule can be substituted with various functional groups, modification of the olefin-based polymer can be easily performed.

Accordingly, there is a demand for an olefin-based polymer containing a large amount of unsaturated groups in a molecule and a method for producing the same.

An object of the present invention is to provide an olefin-based polymer containing a large amount of unsaturated groups in the molecule.

Another object of the present invention is to provide a method for producing an olefin-based polymer containing a large amount of unsaturated groups in the molecule.

According to an embodiment of the present invention for achieving this object, an olefin-based monomer is polymerized in the presence of a catalyst including at least one transition metal compound and at least one cocatalyst compound represented by Formula 1 below. In addition, an olefin-based polymer having a density of 0.85 to 0.95 g/cm 3 and a total amount of unsaturated groups in the molecule of 0.5 mole% or more is provided.

[Formula 1]

In Formula 1 above, M is titanium (Ti), zirconium (Zr) or hafnium (Hf),

Each X is independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene,

Q is carbon (C), silicon (Si), germanium (Ge) or tin (Sn),

R ¹ to R ¹⁴ are each independently hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl , Substituted or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, or substituted or unsubstituted C _1-20 silyl Is,

R ¹ to R ¹² may each independently connect adjacent groups to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring.

Preferably, in Formula 1 above, M is zirconium or hafnium, X is each independently halogen or substituted or unsubstituted C _1-20 alkyl, Q is carbon or silicon, and R ¹ to R ¹² are each independently Hydrogen or substituted or unsubstituted C _1-20 alkyl, and R ¹³ and R ¹⁴ are each independently hydrogen, substituted or unsubstituted C _1-20 alkyl, or substituted or unsubstituted C _6-20 aryl.

Meanwhile, the cocatalyst compound may be selected from the group consisting of a compound represented by Formula 2 below, a compound represented by Formula 3, and a compound represented by Formula 4.

[Formula 2]

[Formula 3]

[Formula 4]

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

In Formula 2 above, n is an integer of 2 or more, and R _a is a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with a halogen,

In Formula 3 above, D is aluminum (Al) or boron (B), and R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, a C _1-20 hydrocarbon group substituted with a halogen Or a C _1-20 alkoxy group,

In Formula 4 above, L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Bronsted acid, Z is a Group 13 element, and A is each independently substituted or unsubstituted C _{6 It is a -20} aryl group or a substituted or unsubstituted C _1-20 alkyl group.

Specifically, the supercatalyst compound represented by Formula 4 may be a compound represented by Formula 4-1 below.

[Formula 4-1]

In Formula 4-1 above, R _e , R _f and R _g are each independently hydrogen, a substituted or unsubstituted C _1-20 alkyl group, a substituted or unsubstituted C _2-20 alkenyl group, a substituted or unsubstituted C _6-20 aryl group, substituted or unsubstituted C _1-20 alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 may be alkyl,

Y may be a group 13 element of the periodic table of the elements, for example, boron (B), aluminum (Al), gallium (Ga), or indium (In),

R _h may be a halogen-substituted or unsubstituted C _6-20 aryl group or a halogen-substituted or unsubstituted C _1-20 alkyl group.

Preferably, the supercatalyst compound represented by Formula 4 may be a compound represented by Formula 4-2 below.

[Formula 4-2]

In addition, the catalyst may further include a carrier supporting the transition metal compound and the cocatalyst compound.

Specifically, the carrier may include at least one selected from the group consisting of silica, alumina, and magnesia. Preferably, the carrier may be silica.

The carrier can support both the transition metal compound and the cocatalyst compound. At this time, the amount of the transition metal compound supported on the carrier may be 0.001 to 1 mmole based on 1 g of the carrier, and the amount of the cocatalyst compound supported on the carrier may be 2 to 15 mmole based on 1 g of the carrier.

According to another embodiment of the present invention, comprising the step of polymerizing an olefinic monomer in the presence of a catalyst including at least one transition metal compound and at least one cocatalyst compound represented by Formula 1 below, and the density is There is provided a method for producing an olefin-based polymer in which 0.85 to 0.95 g/cm 3 and the total amount of unsaturated groups in the molecule is 0.5 mole% or more.

[Formula 1]

In Formula 1 above, M, X, Q and R ¹ to R ¹⁴ are as defined above.

Specifically, the olefin-based polymer according to the present invention may be prepared by copolymerizing an olefin-based monomer and an olefin-based comonomer.

At this time, the olefinic monomer is ethylene, and the olefinic comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1- It may be one or more selected from the group consisting of undecene, 1-dodecene, 1-tetradecene and 1-hexadecene. Preferably, the olefinic monomer is ethylene and the olefinic comonomer is 1-octene.

The olefin-based polymer according to an embodiment of the present invention contains a large amount of unsaturated groups in the molecule, so that modification is easy.

Hereinafter, the present invention will be described in more detail.

The olefin-based polymer according to an embodiment of the present invention is prepared by polymerizing an olefin-based monomer in the presence of a catalyst including at least one transition metal compound and at least one cocatalyst compound represented by the following formula (1), and has a density Is 0.85 to 0.95 g/cm 3, and the total amount of unsaturated groups in the molecule is 0.5 mole% or more.

In addition, the method for producing an olefin-based polymer according to another embodiment of the present invention polymerizes an olefin-based monomer in the presence of a catalyst including at least one transition metal compound and at least one cocatalyst compound represented by the following formula (1). The olefin-based polymer has a density of 0.85 to 0.95 g/cm 3, and the total amount of unsaturated groups in the molecule is 0.5 mole% or more.

Catalyst for olefin polymerization

A catalyst for preparing an olefin-based polymer according to an embodiment of the present invention includes at least one transition metal compound and at least one cocatalyst compound represented by Formula 1 below.

[Formula 1]

In Formula 1 above, M is a Group 4 transition metal, and may be titanium (Ti), zirconium (Zr), or hafnium (Hf). Specifically, M may be zirconium or hafnium.

Each X is independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene. Specifically, each of X may independently be halogen or substituted or unsubstituted C _1-20 alkyl.

Q is carbon (C), silicon (Si), germanium (Ge) or tin (Sn). Specifically, Q may be carbon or silicon.

R ¹ to R ¹⁴ are each independently hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl , Substituted or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, or substituted or unsubstituted C _1-20 silyl to be. At this time, R ¹ to R ¹² may each independently connect adjacent groups to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring.

Specifically, R ¹ to R ¹² are each independently hydrogen or substituted or unsubstituted C _1-20 alkyl, and R ¹³ and R ¹⁴ are each independently hydrogen, substituted or unsubstituted C _1-20 alkyl, or substituted Or it may be _{unsubstituted C 6-20 aryl.}

Meanwhile, the cocatalyst compound may include at least one of a compound represented by Formula 2 below, a compound represented by Formula 3, and a compound represented by Formula 4.

[Formula 2]

In Formula 2 above, n is an integer of 2 or more, and R _a may be a halogen atom, a C _1-20 hydrocarbon, or a C _1-20 hydrocarbon substituted with a halogen. Specifically, R _a may be methyl, ethyl, n -butyl or isobutyl.

[Formula 3]

In Formula 3 above, D is aluminum (Al) or boron (B), and R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, a C _1-20 hydrocarbon group substituted with a halogen Or a C _1-20 alkoxy group. Specifically, when D is aluminum (Al), R _b , R _c and R _d may each independently be methyl or isobutyl, and when D is boron (B), R _b , R _c and R _d are Each may be pentafluorophenyl.

[Formula 4]

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

In Formula 4 above, L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Bronsted acid, Z is a Group 13 element, and A is each independently substituted or unsubstituted C _{6 It is a -20} aryl group or a substituted or unsubstituted C _1-20 alkyl group. Specifically, [LH] ⁺ may be a dimethylanilinium cation _{dimethyl, [Z (A) 4]} - is _{[B (C 6 F 5)} 4] - may be a, [L] ⁺ is [(C ₆ H ₅ ) ₃ C] ⁺ can be.

Specifically, examples of the compound represented by Formula 2 above include methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like, and methylaluminoxane is preferred, but is not limited thereto.

Examples of the compound represented by Formula 3 above include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethyl chloro aluminum, triisopropyl aluminum, tri- s -butyl aluminum, tricyclopentyl aluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri- p -tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, and trimethyl aluminum, triethyl aluminum and triisobutyl aluminum are preferred, but are not limited thereto.

Specifically, the supercatalyst compound represented by Formula 4 may be a compound represented by Formula 4-1 below.

[Formula 4-1]

In Formula 4-1 above, R _e , R _f and R _g are each independently hydrogen, a substituted or unsubstituted C _1-20 alkyl group, a substituted or unsubstituted C _2-20 alkenyl group, a substituted or unsubstituted C _{It may be a 6-20} aryl group, a substituted or unsubstituted C _1-20 alkyl C _6-20 aryl, a substituted or unsubstituted C _6-20 aryl C _1-20 alkyl.

Y may be an element of Group 13 of the periodic table of the elements, and may be, for example, boron (B), aluminum (Al), gallium (Ga), or indium (In).

R _h may be a halogen-substituted or unsubstituted C _6-20 aryl group or a halogen-substituted or unsubstituted C _1-20 alkyl group.

Examples of the compound represented by Formula 4 above include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra( p -tolyl) Boron, trimethylammonium tetra ( o , p -dimethylphenyl) boron, tributylammonium tetra ( p -trifluoromethylphenyl) boron, trimethylammonium tetra ( p -trifluoromethylphenyl) boron, tributylammonium tetra Pentafluorophenyl boron, N,N-diethylanilinium tetraphenyl boron, N,N-diethylanilinium tetrapentafluorophenyl boron, diethylammonium tetrapentafluorophenyl boron, triphenylphosphonium Tetraphenyl boron, trimethylphosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tripropyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra ( p -tolyl ) Aluminum, tripropylammonium tetra ( p -tolyl) aluminum, triethyl ammonium tetra ( o , p -dimethylphenyl) aluminum, tributyl ammonium tetra ( p -trifluoromethylphenyl) aluminum, trimethyl ammonium tetra ( p -trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, N,N-diethylanilinium tetraphenylaluminum, N,N-diethylanilinium tetrapentafluorophenylaluminum, di Ethyl ammonium tetrapenta tetraphenyl aluminum, triphenyl phosphonium tetraphenyl aluminum, trimethyl phosphonium tetraphenyl aluminum, tripropyl ammonium tetra ( p -tolyl) boron, triethyl ammonium tetra ( o , p -dimethylphenyl) boron , Tributylammonium tetra ( p -trifluoromethylphenyl) boron, triphenyl carbonium tetra ( p -trifluoromethylphenyl) boron, and liphenylcarbonium tetrapentafluorophenyl boron, etc., but these Is not limited to.

Preferably, the supercatalyst compound represented by Formula 4 above may be a compound represented by Formula 4-2 below.

[Formula 4-2]

In a preferred embodiment of the present invention, the catalyst for olefin polymerization may further include a carrier supporting a transition metal compound.

In this case, the carrier may include a material containing a hydroxy group on the surface, and preferably, a material having a highly reactive hydroxy group and a siloxane group, which is dried to remove moisture from the surface, may be used. For example, the carrier may include at least one selected from the group consisting of silica, alumina, and magnesia. Specifically, silica, silica-alumina, and silica-magnesia dried at high temperature may be used as a carrier, and these are usually oxides such _{as Na 2} O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ) ₂ , Carbonate, sulfate, and nitrate components. In addition, they may contain carbon, zeolite, magnesium chloride, and the like. However, the carrier is not limited thereto, and is not particularly limited as long as it can support the transition metal compound and the cocatalyst compound.

The carrier may have an average particle size of 10 to 250 µm, preferably an average particle size of 10 to 150 µm, and more preferably 20 to 100 µm.

The micropore volume of the carrier may be 0.1 to 10 cc/g, preferably 0.5 to 5 cc/g, and more preferably 1.0 to 3.0 cc/g.

The specific surface area of the carrier may be 1 to 1,000 m 2 /g, preferably 100 to 800 m 2 /g, more preferably 200 to 600 m 2 /g.

In a preferred embodiment, when the carrier is silica, the silica may have a drying temperature of 200 to 900°C. The drying temperature may be preferably 300 to 800°C, more preferably 400 to 700°C. When the drying temperature is less than 200°C, there is too much moisture so that the moisture on the surface and the cocatalyst compound react, and when it exceeds 900°C, the structure of the carrier may collapse.

The concentration of the hydroxy group in the dried silica may be 0.1 to 5 mmole/g, preferably 0.7 to 4 mmole/g, and more preferably 1.0 to 2 mmole/g. If the concentration of the hydroxy group is less than 0.1 mmole/g, the amount of the first cocatalyst compound is lowered, and if it exceeds 5 mmole/g, the catalyst component may be deactivated.

The amount of the transition metal compound supported on the carrier may be 0.001 to 1 mmole based on 1 g of the carrier. When the ratio between the transition metal compound and the carrier satisfies the above range, it exhibits an appropriate supported catalytic activity, which is advantageous in terms of maintaining catalyst activity and economic efficiency.

The amount of the cocatalyst compound supported on the carrier may be 2 to 15 mmole based on 1 g of the carrier. If the ratio of the cocatalyst compound and the carrier satisfies the above range, it is advantageous in terms of maintaining the activity of the catalyst and economical efficiency.

One or two or more carriers may be used. For example, both a transition metal compound and a cocatalyst compound may be supported on one carrier, or a transition metal compound and a cocatalyst compound may be supported on two or more carriers, respectively. In addition, only one of the transition metal compound and the cocatalyst compound may be supported on the carrier.

As a method of supporting a transition metal compound and/or a cocatalyst compound that can be used in a catalyst for olefin polymerization, a physical adsorption method or a chemical adsorption method may be used.

For example, the physical adsorption method is a method in which a solution in which a transition metal compound is dissolved is in contact with a carrier and then dried, a solution in which a transition metal compound and a cocatalyst compound are dissolved in contact with a carrier and then dried, or a transition metal compound This dissolved solution is brought into contact with a carrier and then dried to prepare a carrier carrying a transition metal compound. Separately, a solution in which the cocatalyst compound is dissolved is brought into contact with the carrier and dried to prepare a carrier carrying the cocatalyst compound. After that, it may be a method of mixing them, or the like.

In the chemical adsorption method, a cocatalyst compound is first supported on the surface of a carrier, and then a transition metal compound is supported on the cocatalyst compound, or a functional group on the surface of the carrier (e.g., in the case of silica, a hydroxy group (-OH )) and the catalyst compound may be covalently bonded.

Olefin polymerization

The olefin-based polymer according to an embodiment of the present invention is prepared by polymerizing an olefin-based monomer in the presence of a catalyst including at least one transition metal compound and at least one cocatalyst compound represented by Formula 1 below.

[Formula 1]

In Formula 1 above, M, X, Q and R ¹ to R ¹⁴ are as defined in the section of the catalyst for olefin polymerization above.

The cocatalyst compound is as described in the section of the catalyst for olefin polymerization above.

In a preferred embodiment of the present invention, the catalyst for olefin polymerization may further include a carrier supporting a transition metal compound. Here, the carrier is as described in the section of the catalyst for olefin polymerization above.

The olefin-based polymer according to the present invention may be prepared by polymerization of an olefin-based monomer alone or copolymerization of an olefin-based monomer and an olefin-based comonomer. In a preferred embodiment of the present invention, the olefin-based polymer may be prepared by copolymerizing an olefin-based monomer and an olefin-based comonomer.

For example, the olefinic monomer is ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1 -It may be dodecene, 1-tetradecene, 1-hexadecene, and the like, and the olefin-based polymer may be a homopolymer including only one olefinic monomer or a copolymer including two or more olefinic monomers exemplified above. In a preferred embodiment of the present invention, the olefinic monomer is ethylene, and the olefinic comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene. , 1-decene, 1-undecene, 1-dodecene, 1-tetradecene and 1-hexadecene may be one or more selected from the group consisting of. Preferably, the olefinic monomer may be ethylene and the olefinic comonomer may be 1-octene.

Here, the content of ethylene is preferably 55 to 99.9% by weight, more preferably 90 to 99.9% by weight. The content of the alpha-olefin comonomer is preferably 0.1 to 45% by weight, more preferably 0.1 to 10% by weight.

The olefin-based polymer according to an embodiment of the present invention may be polymerized by polymerization such as free radical, cationic, coordination, condensation, and addition. However, it is not limited to these.

As a preferred embodiment, the olefin-based polymer may be prepared by a gas phase polymerization method, a solution polymerization method, a slurry polymerization method, or a bulk polymerization method. At this time, the conditions of each polymerization reaction may be variously modified depending on the state of the catalyst for olefin polymerization used (homogeneous or heterogeneous (supported)), a polymerization method, a desired polymerization result, or a form of a polymer.

For example, when the olefin-based polymer is prepared by a solution polymerization method or a slurry polymerization method, as an example of a solvent that can be used, a C _5-12 aliphatic hydrocarbon solvent such as pentane, hexane, heptane, nonane, decane and isomers thereof ; Aromatic hydrocarbon solvents such as toluene and benzene; Hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene; And mixtures thereof, and the like, but are not limited thereto.

In the method for producing an olefin-based polymer according to an embodiment of the present invention, the amount of the catalyst for olefin polymerization is not particularly limited, but, for example, the central metal of the transition metal compound (ie, titanium, zirconium or hafnium) in the polymerization reaction system. ) May have a concentration of 1×10 ^-5 mole/l to 9×10 ^-5 mole/l.

For example, the polymerization of the olefin-based monomer may be carried out in a batch, semi-continuous or continuous manner. In addition, the polymerization of the olefinic monomer may be carried out in two or more stages having different reaction conditions, and the molecular weight of the final polymer may be controlled by changing the polymerization temperature or by injecting hydrogen into the reactor.

The olefin-based polymer according to an embodiment of the present invention prepared by the above-described manufacturing method has a density of 0.85 to 0.95 g/cm 3, and the total amount of unsaturated groups in the molecule is 0.5 mole% or more.

Specifically, the olefin-based polymer according to an embodiment of the present invention has a density of 0.85 to 0.95 g/cm 3. Preferably, the density of the olefin-based polymer may be 0.85 to 0.93 g/cm 3 or 0.85 to 0.92 g/cm 3.

In the olefin-based polymer according to an embodiment of the present invention, the total amount of unsaturated groups in the molecule is 0.5 mole% or more. Preferably, the total amount of unsaturated groups in the molecule of the olefin-based polymer may be 0.5 mole% to 1.3 mole%, 0.52 mole% to 1.3 mole%, or 0.55 mole% to 1.25 mole%.

Example

Hereinafter, the present invention will be described in more detail through examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example

(1) Synthesis of (3,6- di - t - butylfluorenyl) lithium

In a solution of 3,6-di- t -butylfluorene (3,6-di- t- butylfluorene; 5 g, 18 mmole) diluted in ether (75 mL), n -butyllithium (7.8 g, 18.3 mmole, 1.6 M hexane solution) was slowly added at 0°C, and the temperature was slowly raised to room temperature, followed by stirring for 12 hours or more. After completion of the reaction, all solvents were removed under vacuum, and 5.11 g (100%) of a yellow solid compound was obtained.

(2) 1-( cyclopentadienyl )-1-(3,6- di - t - butylfluorenyl )-1,1-diphenylmethane synthesis

(3,6-di- t -butylfluorenyl) lithium ((3,6-di- t -butylfluorenyl) lithium; 5.11 g, 18 mmole) was diluted in ether (50 ml) to diphenyl fulbene ( A solution obtained by diluting diphenylfulvene; 4.14 g, 18.0 mmole) in ether (25 ml) was slowly added at room temperature, followed by stirring for 12 hours. After adding 30 ml of distilled water, the resulting pale off-white solid was filtered and dried under vacuum to obtain 7.0 g (76%) of a compound.

¹ H-NMR (CDCl ₃ , 300 MHz): δ 8.40-8.00 (br, 3H), 7.49 (m, 4H), 7.21-6.80 (m, 9H), 6.65-5.82 (br, 3H), 5.47 (s , 1H), 1.30 (s, 18H).

(3) Synthesis of Diphenylmethylidene [( cyclopentadienyl )-(3,6- di - t - butylfluorenyl )] dilithium

1- (cyclopentadienyl) -1- (3,6-di - t - butyl-fluorenyl) diphenyl methane-1,1-di (1- (cyclopentadienyl) -1- (3,6-di-t -butylfluorenyl)-1,1-diphenylmethane; 5.08 g, 9.99 mmole) in ether (20 mL) was diluted with n -butyllithium (9.0 g, 21.1 mmole, 1.6 M hexane solution) at 0 ℃ slowly. After that, the temperature was gradually raised to room temperature and stirred for 18 hours. The produced fluorescent orange solid was filtered, washed with hexane, and dried under vacuum to obtain 5.17 g (100%) of a compound.

(4) Synthesis of Diphenylmethylidene [( cyclopentadienyl )-(3,6- di - t - butylfluorenyl )] zirconium dichloride

Diphenyl methylidene [(cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] dilithium (diphenylmethylidene [(cyclopentadienyl) - ( 3,6-di-t-butylfluorenyl)] dilithium; 1.0 g, 1.93 mmole) was diluted with hexane (30 ml) to a solution of zirconium chloride (ZrCl ₄ ; 450 mg, 1.93 mmole) diluted in hexane (3 ml) was slowly added at -30°C. Was gradually raised to room temperature and stirred for 12 hours. After completion of the reaction, the mixture was extracted with toluene and filtered. Toluene was removed under vacuum and washed with pentane to obtain 1.1 g (85%) of a red solid compound.

¹ H-NMR (C ₆ D ₆ , 300 MHz): δ 8.32 (s, 2H), 7.64 (t, 4H), 7.15-6.89 (m, 8H), 6.40 (d, 2H), 6.15 (t, 2H ), 5.55 (t, 2H), 1.35 (s, 18H).

(5) Synthesis of Diphenylmethylidene [( cyclopentadienyl )-(3,6- di - t - butylfluorenyl )] zirconium dimethyl

Diphenyl methylidene [(cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] zirconium dichloride (diphenylmethylidene [(cyclopentadienyl) - (3,6-di-t-butylfluorenyl) zirconium dichloride; 1.075 g, 1.607 mmole) was diluted in toluene (50 ml) and MeMgBr (1.386 mg, 4.018 mmole, 3.0 M diethyl ether solution) was diluted in toluene (10 ml) slowly at -30°C. After addition, the mixture was stirred for 1.5 hours while refluxing at 70°C. After completion of the reaction, the mixture was extracted with toluene and filtered. After removing the toluene under vacuum, washing with hexane to obtain a yellow solid compound, diphenylmethylidene [(cyclopentadienyl)-(3,6-di- t -butylfluorenyl)] zirconium dimethyl 737 mg (73%) Got it.

¹ H-NMR (C ₆ D ₆ , 300 MHz): δ 8.37 (s, 2H), 7.80 (d, 2H), 7.68 (d, 2H), 7.11-6.78 (m, 8H), 6.29 (d, 2H) ), 6.13 (t, 2H), 5.47 (t, 2H), 1.32 (s, 18H), -1.20 (s, 6H).

Example 1~11

An ethylene/1-octene copolymer was prepared using the transition metal compound catalyst obtained in Preparation Example above using a 2-liter autoclave reactor. First, moisture and impurities in the reactor were removed using a vacuum pump. The vacuum state was maintained to be at ^{least 3.0 × 10 -1 torr or less.} Thereafter, the temperature of the reactor was raised to 60°C while purging the reactor for at least 30 minutes using argon (Ar) gas. At the same time, the catalyst, cocatalyst, scavenger and 1-octene were quantified in a glove box.

Purified solvent (hexane) and copolymer (1-octene) were added to the reactor, and 0.95 ml of 1M triisobutyl aluminum (TiBAL) was added as a scavenger to remove oxygen, moisture, and impurities remaining in the solvent. Was put in. Thereafter, the stirrer of the reactor was set to 500 rpm, and when the reaction temperature was reached, the stirring was stopped, and a catalyst (Preparation Example) and a cocatalyst (a compound of Formula 4-2 above) were introduced into the reactor using argon gas. Then, ethylene was added at a pressure of about 30 bar, and the reaction was started while stirring. After ethylene was added, when the pressure in the reactor reached 25 bar, hydrogen was added. Ethylene was continuously added based on 30 bar to proceed in a semi-batch reaction. The reaction temperature was maintained in the range of 60 ~ 120 ℃.

When the reaction time reached 5 minutes, the addition of ethylene and stirring were stopped to terminate the reaction. The molten polymer in the reactor was transferred to a separator through the outlet of the reactor, unreacted ethylene and 1-octene were separated from the hexane solvent, and the polymer was dried in a vacuum oven at 80° C. for 12 hours or longer to obtain a polyolefin.

Specific polymerization conditions of each Example are as described in Table 1 below.

catalyst
(μmole) Cocatalyst
(μmole) Octen
(M) Temperature
(℃) Hydrogen
(g/min) polymer
(g) activation
(KgPE/gCat-hr) Example 1 4 24 0.4 90 - 141.91 677.9 Example 2 4 24 0.8 90 - 172.00 821.6 Example 3 2 12 1.2 65 0.1 219.68 2098.8 Example 4 2 12 1.6 90 0.1 309.91 2960.8 Example 5 3 18 1.6 65 0.1 227.81 1450.9 Example 6 3 18 1.2 65 0.1 219.68 1399.2 Example 7 3 18 1.2 65 0.5 239.11 1522.9 Example 8 2 12 1.2 90 0.2 236.91 2263.4 Example 9 3 18 1.2 90 0.2 227.83 1421.1 Example 10 3 18 1.6 90 0.2 237.74 2271.3 Example 11 2 12 1.6 90 0.2 234.20 1491.6

Comparative example 1~7

For comparison, seven commercially available linear low-density polyethylene resins (LC190 and LC170 from LG, Engage 8100, Engage 8842, Affinity 1900, Affinity 1950 and Affinity 1875 from Dow) were analyzed.

Test example

The physical properties of the olefin polymer obtained in the above example and the resin of the comparative example were measured according to the following methods and standards. The results are shown in Table 2 below.

(1) density

It was measured according to ASTM D1505.

(2) Unsaturated content in the molecule

After the polymer to prepare a specimen in a film form by melting at 190 ℃, it was analyzed using ethane -d ₂ (trichloroethane-d ₂₎ a solvent trichlorobenzene at a high temperature (120 ℃ by ¹ H-NMR (AS400 of Agilent). The content was calculated through section integration at the corresponding chemical shift of each unsaturated group.

density
(g/cm 3) Unsaturated group content (number/1000C) Vinylene Trisubstituted olefin vinyl Vinylidene Sum Sum
(mole%) Example 1 0.916 1.0651 1.1417 0.2725 0.2256 2.7049 0.54098 Example 2 0.894 1.3396 2.2480 0.3432 0.1616 4.0924 0.81848 Example 3 0.871 0.7463 2.0952 0.1674 0.4235 3.4325 0.68650 Example 4 0.865 1.2774 2.8073 0.2985 0.8778 5.2610 1.05220 Example 5 0.858 0.8935 2.0052 0.1981 0.5003 3.5970 0.71940 Example 6 0.858 1.2523 1.8906 0.2734 0.6752 4.0915 0.81830 Example 7 0.865 0.7463 0.7786 3.0692 0.4353 5.1732 1.03464 Example 8 0.878 0.7643 0.8791 2.5699 0.5776 4.7540 0.95080 Example 9 0.880 1.2774 0.9688 2.8564 0.7227 5.6067 1.12134 Example 10 0.865 0.8935 0.8002 3.8467 0.4827 6.0565 1.21130 Example 11 0.874 1.2523 0.8935 3.7812 0.5692 6.0634 1.21268 Comparative Example 1 0.890 0.2512 0.1882 0.0251 0.1228 0.5873 0.11746 Comparative Example 2 0.870 0.2835 - 0.0279 0.1013 0.4127 0.08254 Comparative Example 3 0.870 - - - 0.1504 0.1504 0.03008 Comparative Example 4 0.857 - 0.1555 0.0279 0.0460 0.2294 0.04588 Comparative Example 5 0.870 0.1184 0.4501 0.0279 0.1627 0.7591 0.15182 Comparative Example 6 0.874 0.2871 0.4665 0.2288 0.4328 1.4151 0.28302 Comparative Example 7 0.870 0.1615 0.1637 0.0474 0.1627 0.5353 0.10706

The olefin-based polymer according to an embodiment of the present invention contains a large amount of unsaturated groups in the molecule, so that modification is easy.

Claims (14)

It is prepared by polymerization of an olefinic monomer in the presence of a catalyst including at least one transition metal compound and at least one cocatalyst compound represented by the following formula (1), and has a density of 0.85 to 0.95 g/cm 3 and is unsaturated in the molecule. Olefin-based polymer, having a total amount of at least 0.5 mole %:
[Formula 1]

In Formula 1 above, M is titanium (Ti), zirconium (Zr) or hafnium (Hf),
Each X is independently halogen, C _1-20 alkyl, C _2-20 alkenyl, C _2-20 alkynyl, C _6-20 aryl, C _1-20 alkyl C _6-20 aryl, C _6-20 aryl C _1-20 alkyl, C _1-20 alkylamido, C _6-20 arylamido or C _1-20 alkylidene,
Q is carbon (C), silicon (Si), germanium (Ge) or tin (Sn),
R ¹ to R ¹⁴ are each independently hydrogen, substituted or unsubstituted C _1-20 alkyl, substituted or unsubstituted C _2-20 alkenyl, substituted or unsubstituted C _6-20 aryl, substituted or unsubstituted C _1-20 alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl, substituted or unsubstituted C _1-20 heteroalkyl, substituted or unsubstituted C _3-20 heteroaryl , Substituted or unsubstituted C _1-20 alkylamido, substituted or unsubstituted C _6-20 arylamido, substituted or unsubstituted C _1-20 alkylidene, or substituted or unsubstituted C _1-20 silyl Is,
R ¹ to R ¹² may each independently connect adjacent groups to form a substituted or unsubstituted saturated or unsaturated C _4-20 ring. The method of claim 1, wherein in Formula 1 above, M is zirconium or hafnium, X is each independently halogen or substituted or unsubstituted C _1-20 alkyl, Q is carbon or silicon, and R ¹ to R ¹² are each Independently hydrogen or substituted or unsubstituted C _1-20 alkyl, and R ¹³ and R ¹⁴ are each independently hydrogen, substituted or unsubstituted C _1-20 alkyl, or substituted or unsubstituted C _6-20 aryl , Olefin-based polymer. The olefin-based polymer of claim 1, wherein the cocatalyst compound is at least one selected from the group consisting of a compound represented by Formula 2 below, a compound represented by Formula 3, and a compound represented by Formula 4:
[Formula 2]

[Formula 3]

[Formula 4]
^{[LH] + [Z (A} ) 4] - or ^{[L] + [Z (A} ) 4] -
In Formula 2 above, n is an integer of 2 or more, and R _a is a halogen atom, a C _1-20 hydrocarbon group, or a C _1-20 hydrocarbon group substituted with a halogen,
In Formula 3 above, D is aluminum (Al) or boron (B), and R _b , R _c and R _d are each independently a halogen atom, a C _1-20 hydrocarbon group, a C _1-20 hydrocarbon group substituted with a halogen Or a C _1-20 alkoxy group,
In Formula 4 above, L is a neutral or cationic Lewis base, [LH] ⁺ and [L] ⁺ are Bronsted acid, Z is a Group 13 element, and A is each independently substituted or unsubstituted C _{6 It is a -20} aryl group or a substituted or unsubstituted C _1-20 alkyl group. The olefin-based polymer according to claim 3, wherein the supercatalyst compound represented by Formula 4 is a compound represented by Formula 4-1 below:
[Formula 4-1]

In Formula 4-1 above, R _e , R _f and R _g are each independently hydrogen, a substituted or unsubstituted C _1-20 alkyl group, a substituted or unsubstituted C _2-20 alkenyl group, a substituted or unsubstituted C _6-20 aryl group, substituted or unsubstituted C _1-20 alkyl C _6-20 aryl, substituted or unsubstituted C _6-20 aryl C _1-20 alkyl,
Y is boron (B), aluminum (Al), gallium (Ga) or indium (In),
R _h is a halogen-substituted or unsubstituted C _6-20 aryl group or a halogen-substituted or unsubstituted C _1-20 alkyl group. The olefin-based polymer of claim 4, wherein the supercatalyst compound represented by Formula 4 is a compound represented by Formula 4-2 below:
[Formula 4-2]

. The olefin-based polymer according to claim 1, wherein the catalyst further comprises a carrier supporting a transition metal compound and a cocatalyst compound. The olefin-based polymer according to claim 6, wherein the carrier comprises at least one selected from the group consisting of silica, alumina, and magnesia. The olefin-based polymer according to claim 7, wherein the carrier is silica. The olefin-based polymer according to claim 6, wherein the carrier supports both the transition metal compound and the cocatalyst compound. The method of claim 6, wherein the amount of the transition metal compound supported on the carrier is 0.001 to 1 mmole based on 1 g of the carrier, and the amount of the cocatalyst compound supported on the carrier is 2-15 mmole based on 1 g of the carrier Olefin-based polymer. Polymerizing an olefinic monomer in the presence of a catalyst including at least one transition metal compound and at least one cocatalyst compound represented by Formula 1 below, and the density is 0.85 to 0.95 g/cm 3, and the molecule A method for producing an olefin-based polymer, wherein the total amount of unsaturated groups in is 0.5 mole% or more:
[Formula 1]

In Formula 1 above, M, X, Q and R ¹ to R ¹⁴ are as defined in claim 1. The method for producing an olefin-based polymer according to claim 11, wherein the olefin-based polymer is produced by copolymerizing an olefin-based monomer and an olefin-based comonomer. The method of claim 12, wherein the olefinic monomer is ethylene, and the olefinic comonomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1- Decene, 1-undecene, 1-dodecene, 1-tetradecene, and one or more selected from the group consisting of 1-hexadecene, a method for producing an olefin-based polymer. The method for producing an olefin-based polymer according to claim 13, wherein the olefin-based monomer is ethylene and the olefin-based comonomer is 1-octene.