KR101675509B1 - Polyolefin having excellent properties - Google Patents

Abstract

The present invention relates to a polyolefin having a molecular weight distribution of 1.5 to 3.0 and a BGN (Branch Gradient Number) value of -0.01 to -1. According to the present invention, a polyolefin having excellent mechanical properties and impact strength can be provided.

Description

[0001] POLYOLEFIN HAVING EXCELLENT PROPERTIES [

The present invention relates to a polyolefin having excellent physical properties, and more particularly to a polyolefin having a narrow molecular weight distribution and excellent mechanical properties.

Dow has published [Me ₂ Si (Me ₄ C ₅ ) NtBu] TiCl ₂ (CGC) in the early 1990s (US Pat. No. 5,064,802). In the copolymerization of ethylene and alpha olefins, the CGC Compared with the known metallocene catalysts, the excellent aspects of the CGC are summarized as follows: (1) high molecular weight copolymers with high activity at high polymerization temperatures and (2) - It is also excellent for the copolymerization of α-olefins with large steric hindrance such as hexene and 1-octene. In addition, as the various characteristics of CGC are gradually known during the polymerization reaction, efforts to synthesize the derivatives and use them as polymerization catalysts have been actively made in academia and industry.

One approach is to synthesize and incorporate a variety of metal compounds into which various bridges and nitrogen substituents have been introduced instead of silicon bridges. Opening exemplary metal compounds known to date are as follows (Chem. Rev. 2003, 103 , 283).

The compounds shown in the figure have been introduced with phosphorus (1), ethylene or propylene (2), methylidene (3) and methylene (4) bridges in place of the silicon bridge of the CGC structure, but ethylene polymerization or ethylene and alpha olefins The copolymer did not exhibit excellent results in terms of polymerization activity or copolymerization performance as compared with CGC.

As another approach, a large amount of compounds composed of oxydolides were synthesized instead of the amido ligands of CGC, and some polymerization using the compounds was attempted.

Of all these attempts, however, only a few catalysts have actually been applied to commercial plants. The copolymers of ethylene and alpha olefins polymerized using most transition metal compounds exhibit a narrow molecular weight distribution as compared to LDPE obtained through conventional high pressure processes, but in terms of polymer structure, they do not include long chain bases, Lt; RTI ID = 0.0 > branched < / RTI > branches. In recent years, attempts to obtain a polyolefin-based copolymer having a long chain branching polymer structure and various properties have been actively conducted in academia and industry, and development of new catalysts and processes therefor is still required.

The present invention provides a polyolefin having a comonomer distribution with a new composition while having a narrow molecular weight distribution by controlling the distribution of comonomers according to molecular weight using a hybrid metallocene catalyst.

In order to achieve the above object, an aspect of the present invention provides a polyolefin having a molecular weight distribution of 1.5 to 3 and a BGN (Branch Gradient Number) value calculated by the following formula 1: -0.01 to -1:

[Formula 1]

In Equation (1)

When a molecular weight distribution curve is drawn with the logarithm (log Mw) of the molecular weight (Mw) as the x-axis and the molecular weight distribution (dwt / dlog Mw)

The side chain content of the low molecular weight means the side branch content (branch content of 2 or more carbon atoms per 1,000 carbon atoms, unit: 1,000C) at the left boundary of 80% of the total area except 10% at the left and right ends, The side chain content of high molecular weight means the side chain content at the right border.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polyolefin having a narrow molecular weight distribution and exhibiting a specific comonomer distribution and having excellent impact strength and mechanical properties. Accordingly, the polyolefin of the present invention can be used in various fields such as household articles, automobiles, shock absorbers, etc. which require high impact strength and elasticity by being blended alone or with other polymers.

1 is a graph showing the results of GPC-FTIR measurement of the polyolefin of Example 1. Fig.
2 is a graph showing the results of GPC-FTIR measurement of the polyolefin of Example 2. Fig.
3 is a graph showing the results of GPC-FTIR measurement of the polyolefin of Comparative Example 1. Fig.
4 is a graph showing the results of GPC-FTIR measurement of the polyolefin of Comparative Example 2. Fig.

In the present invention, the terms first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

Moreover, the terminology used herein is for the purpose of describing exemplary embodiments only and is not intended to be limiting of the present invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprising," "comprising," or "having ", and the like are intended to specify the presence of stated features, integers, But do not preclude the presence or addition of one or more other features, integers, steps, components, or combinations thereof.

While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the invention is not intended to be limited to the particular forms disclosed, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.

Hereinafter, the polyolefin according to a specific embodiment of the present invention will be described in detail.

According to one embodiment of the present invention, a polyolefin having a molecular weight distribution of 1.5 to 3 and a BGN (Branch Gradient Number) value of -0.01 to -1 is provided.

In the term BGN (Branch Gradient Number) used in the specification of the present invention, BGN is a measure showing how the content of comonomer such as alpha olefin is distributed according to molecular weight. Branches in the BGN are branches derived from the alpha olefins such as propylene, 1-butene, 1-hexene, 1-octene and the like as comonomers in the polyolefin polymerization process. . The side branch includes both a short carbon branch (SCB) having 2 to 6 carbon atoms and an LCB (long carbon branch) having 7 or more carbon atoms.

Using GPC-FTIR equipment, molecular weight, molecular weight distribution and side-chain content can be measured simultaneously and continuously.

The value of the BGN (Branch Gradient Number) is determined by continuously measuring the molecular weight, the molecular weight distribution and the side chain content by using GPC-FTIR equipment and setting the log value (log Mw) of the molecular weight (Mw) (Dwt / dlog Mw) is plotted on the y-axis, the molecular weight distribution curve of the low molecular weight is calculated by subtracting the side branch content of 80% of the left boundary from the total area : Number / 1,000C), and the side chain content of the high molecular weight means the value calculated by the following formula 1 with the side chain content at the right border of the middle 80%. Here, the content of the side branches means the side branch content of 2 or more carbon atoms per 1,000 carbon atoms.

[Formula 1]

When the BGN value is a positive value, it means that the side chain content is low in the low molecular weight region according to the molecular weight distribution curve to the logarithm of the molecular weight and the side chain content is relatively high in the high molecular weight region. On the other hand, The value of negative (-) means that the side chain content is high in the low molecular weight region and the side chain content is relatively low in the high molecular weight region.

The polyolefin of the present invention has a BGN value measured and calculated in the same manner as described above in the range of about -0.01 to about -1, or about -0.01 to about -0.5, or about -0.01 to about -0.2. That is, the polyolefin of the present invention is characterized by having a high side-chain content in a low molecular weight region and a relatively low side-chain content in a high molecular weight region and a slope thereof falling within the above-mentioned range.

When the BGN value is in the above range and the molecular weight distribution in a narrow range is satisfied at the same time, the physical properties of the polyolefin are optimized so that high impact strength and good mechanical properties can be achieved.

Also, the range of the number of side branch content per 1,000 carbons of the polyolefin of the present invention may range from about 20 to about 120, preferably about 50 to about 100.

The polyolefin of the present invention also has a molecular weight distribution (weight average molecular weight / number average molecular weight) of from about 1.5 to about 3.0, or from about 1.5 to about 2.9, or from about 2 to about 2.9, or from about 2.2 to about 2.9. As described above, the polyolefin of the present invention has a very narrow molecular weight distribution and can exhibit high impact strength.

The polyolefin according to the present invention has a melt flow index (MI) of about 0.1 to about 2,000 g / 10 min, preferably about 0.1 to about 1,000 g / 10 min, measured at 190 DEG C under a load of 2.16 kg in accordance with ASTM 1238 But is not limited thereto.

In addition, the melt flow ratio (MFRR) of the polyolefin of the present invention may be from about 5 to about 15, preferably from about 6 to about 10, but is not limited thereto.

In addition, the density of the polyolefin of the present invention may be, but is not limited to, a density of about 0.85 to about 0.90 g / cc, and preferably about 0.86 to about 0.89 g / cc.

However, when the melt flow index, the melt flow rate ratio, the density, and the like are within the above-mentioned ranges, the physical properties are more optimized and high impact strength and good mechanical properties can be achieved.

The polyolefin according to the present invention is preferably a copolymer of ethylene and an alpha olefin comonomer, which is an olefinic monomer.

The alpha olefin comonomer may be an alpha olefin having 3 or more carbon atoms. Examples of the alpha olefin having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, , 1-tetradecene, 1-hexadecene, 1-octadecene or 1-eicosene.

In the copolymer of the ethylene and alpha olefinic comonomers, the alpha olefin comonomer content may be from about 5 to about 50 weight percent, preferably from about 10 to about 40 weight percent, based on the weight of the total copolymer .

The weight average molecular weight of the polyolefin according to the present invention may be from about 10,000 to about 500,000 g / mol, preferably from about 20,000 to about 200,000 g / mol, but is not limited thereto.

The polyolefin according to the present invention has excellent impact strength when mixed with other polymers and can be used in various fields such as household articles, automobiles, and shock absorbers.

The polyolefin according to the present invention having the above-mentioned characteristics can be obtained by copolymerization with ethylene and an alpha olefin using a mixed metallocene compound containing two metallocene compounds having different structures as a catalyst, The molecular weight distribution and the BGN value as described above.

More specifically, the polyolefin of the present invention comprises: a first metallocene compound represented by the following formula (1); And a second metallocene compound represented by the following formula (2): < EMI ID = 2.0 >

[Chemical Formula 1]

In Formula 1,

R1 and R2 may be the same or different from each other, and each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylsilyl having 1 to 20 carbon atoms, arylsilyl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid of a Group 4 metal substituted with hydrocarbyl; The R1 and R2 or the two R2's may be linked to each other to form a ring by alkyl having 1 to 20 carbon atoms or alkylidene having 6 to 20 carbon atoms;

R3, R3 'and R3 "may be the same or different from each other and each independently represents hydrogen, halogen, alkyl of 1 to 20 carbon atoms, alkenyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms, alkyl of 7 to 20 carbon atoms An aryl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, or an amido group, two or more of R3, R3 'and R3' An aromatic ring may be formed;

CY is a substituted or unsubstituted aliphatic or aromatic ring, the substituent on CY is selected from the group consisting of halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or an alkylamido group having 1 to 20 carbon atoms; An arylamido group having 6 to 20 carbon atoms, and when the number of the substituents is plural, two or more substituents among the substituents may be connected to each other to form an aliphatic or aromatic ring;

M1 is a Group 4 transition metal;

Q1 and Q2 may be the same or different from each other and are each independently halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkylamido of 1 to 20 carbon atoms; Arylamido having 6 to 20 carbon atoms; Or an alkylidene of 1 to 20 carbon atoms;

(2)

In Formula 2,

M2 is a Group 4 transition metal;

Cp is any one selected from the group consisting of cyclopentadienyl, indenyl, 4,5,6,7-tetrahydro-1-indenyl and fluorenyl radical, which may be substituted with hydrocarbons having 1 to 20 carbon atoms ;

R4 is alkyl of 1 to 20 carbon atoms; Alkoxy having 1 to 10 carbon atoms; Alkoxyalkyl of 2 to 20 carbon atoms; Cycloalkyl having 3 to 20 carbon atoms; A heterocycle having 3 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Heteroaryl having 3 to 20 carbon atoms; Aryloxy having 6 to 10 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkylaryl having 7 to 40 carbon atoms; Arylalkyl having 7 to 40 carbon atoms; Arylalkenyl having 8 to 40 carbon atoms; Or an alkynyl group having 2 to 10 carbon atoms;

R5 and R6, which may be the same or different from each other, are each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkoxy having 1 to 10 carbon atoms; Alkoxyalkyl of 2 to 20 carbon atoms, aryl of 6 to 20 carbon atoms; Aryloxy having 6 to 10 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkylaryl having 7 to 40 carbon atoms; Arylalkyl having 7 to 40 carbon atoms; Arylalkenyl having 8 to 40 carbon atoms; Or an alkynyl group having 2 to 10 carbon atoms;

Q3 and Q4 may be the same or different from each other and are each independently halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkylamido of 1 to 20 carbon atoms; Arylamido having 6 to 20 carbon atoms; Or an alkylidene of 1 to 20 carbon atoms;

A is at least one of carbon, germanium, silicon, phosphorus, or nitrogen atom containing radicals which cross-link the Cp ring with J, or a combination thereof;

J is any one selected from the group consisting of NR7, O, PR7 and S, and R7 is as defined in R5 and R6 above.

When the ethylene and alpha olefin comonomers are polymerized using the hybrid metallocene catalyst comprising the first metallocene compound of Formula 1 and the second metallocene compound of Formula 2, A polyolefin having a high side-chain content and a relatively low side-chain content in a high molecular weight region can be obtained.

On the other hand, the polymerization reaction of the ethylene and alpha olefin comonomers can be carried out at about 130 to about 250 ° C, preferably about 140 to about 200 ° C. When the second metallocene compound is used in admixture with the first metallocene compound, the activity of the catalyst can be maintained even in the synthesis process at a high temperature of 130 ° C or higher. In the synthesis reaction of the polyolefin, .

The polymerization reaction of the ethylene and the alpha olefin comonomer may be carried out in a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization process, or an emulsion polymerization process, but is preferably carried out in a solution polymerization reaction in a single reactor Can be done. In the method for producing polyolefin, polyolefin can be synthesized in a single reactor even though two different metallocene catalysts are used, so that a simple manufacturing process can be configured to reduce the processing time and cost.

Specific examples of the first metallocene compound represented by the formula (1) include compounds represented by the following formulas (3) and (4), but are not limited thereto.

 (3)

In Formula 3,

R1, R2, Q1, Q2 and M1 are the same as defined in Formula 1,

And R11 may be the same or different from each other, and each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or an amido group; Two or more of the R < 11 > s may be connected to each other to form an aliphatic ring or an aromatic ring.

 [Chemical Formula 4]

In Formula 4,

R1, R2, Q1, Q2, and M1 are the same as defined in Formula 1,

R12 may be the same or different from each other, and each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or an amido group; Two or more of the R < 12 > s may be connected to each other to form an aliphatic ring or an aromatic ring.

Specific examples of the more preferred compounds for controlling the electronic stereoscopic environment around the metal in the compound of Formula 1 are as follows.

In the following formulas, R2 may independently be hydrogen or a methyl group, and Q1 or Q2 may be the same or different from each other, and each independently may be a methyl group, a dimethylamido group or a chloride group.

Specific examples of the second metallocene compound of Formula 2 include, but are not limited to, the following compounds.

According to an embodiment of the present invention, in the method for producing a polyolefin, the hybrid metallocene catalyst may further include a cocatalyst compound in addition to the first and second metallocene compounds described above.

The promoter compound includes a Group 13 metal of the periodic table and may be at least one selected from the group consisting of compounds represented by the following general formulas (5), (6) and (7)

 [Chemical Formula 5]

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

In the general formula (5), R 8 is a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, c is an integer of 2 or more,

[Chemical Formula 6]

D (R 9) ₃

In Formula 6,

D is aluminum or boron, R9 is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,

(7)

[LH] ⁺ [ZE ₄ ] ^- or [L] ⁺ [ZE ₄ ] ^-

In Formula 7,

L is a neutral or cationic Lewis base, H is a hydrogen atom, Z is a Group 13 element, and E may be the same or different and each independently represents a hydrogen atom, a halogen atom, An aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with phenoxy.

Examples of the compound represented by Formula 5 include methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane, butylaluminoxane, and the like.

Examples of the alkyl metal compound represented by Formula 6 include trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, dimethylisobutylaluminum, dimethylethylaluminum, diethyl Tri-n-butylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, tri-n-butylaluminum, Dimethylaluminum ethoxide, trimethylboron, triethylboron, triisobutylboron, tripropylboron, tributylboron, and the like can be used.

Examples of the compound represented by Formula 7 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammonium tetra (p (O, p-dimethylphenyl) boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, trimethylammoniumtetra (P-trifluoromethylphenyl) boron, tetra (p-trifluoromethylphenyl) boron, trimethylammoniumtetra (p -trifluoromethylphenyl) boron, tributylammonium tetrapentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N , N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium tetraphenylboron, trimethylphosphor Tetramethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra (aluminum) (P-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammoniumtetra (ptrifluoromethylphenyl) aluminum, trimethylammoniumtetra (ptrifluoromethylphenyl) Aluminum, tributylammonium tetrapentafluorophenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetraphenyl aluminum, N, N-diethylanilinium tetrapenta Triphenyl aluminum, diethyl ammonium aluminum tetrapentafluorophenyl aluminum, triphenyl phosphonium tetraphenyl aluminum, trimethyl phosphonium tetraphenyl (P-trifluoromethylphenyl) boron, triphenylcarbonium tetrapentafluorophenylboron, and the like can be used in the present invention. have.

Also, the content of the cocatalyst is in the range of about 1 to about 10,000, preferably about 1 to about 1,000, more preferably about 1 To 100. < / RTI > If the molar ratio is less than 1, the effect of addition of the cocatalyst is insufficient. If the molar ratio is more than 10,000, excess alkyl groups or the like which are not involved in the reaction may interfere with the catalytic reaction and act as catalyst poisons. Side reaction may proceed and excess aluminum or boron may remain in the polymer.

In the preparation of the mixed metallocene catalyst, hydrocarbon solvents such as pentane, hexane, heptane and the like, aromatic solvents such as benzene and toluene may be used as a reaction solvent, but not always limited thereto, and all A solvent may be used.

In the process for producing a polyolefin according to the present invention, the hybrid metallocene catalyst may be an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for olefin polymerization, for example, pentane, hexane, heptane, nonane, decane, An aromatic hydrocarbon solvent such as toluene or benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane or chlorobenzene, or the like. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkylaluminum, and it is also possible to use a further cocatalyst.

The polyolefin having the above-mentioned molecular weight distribution and BGN value can be produced using the hybrid metallocene catalyst. Copolymerization with alpha olefins in the case of hybrid metallocene catalysts is induced by a second metallocene compound, which in particular makes up the higher molecular weight moiety, which has a narrow molecular weight distribution and in which the alpha olefin comonomer is more bonded to the lower molecular weight chain side Thereby making it possible to produce a high-performance polyolefin.

The preparation of the polyolefin may be carried out in one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor or a solution reactor, and may be carried out according to a conventional method, in which the alpha olefin is continuously fed at a constant ratio with ethylene and a comonomer .

When the alpha olefin is copolymerized with ethylene as a comonomer using the mixed metallocene catalyst, the alpha olefin comonomer is preferably selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl- Hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene or 1-eicosene. But is not limited to.

The polymerization temperature when copolymerizing ethylene with the alpha olefin as the comonomer using the hybrid metallocene catalyst may be in the range of about 130 to about 250 ° C, preferably about 140 to about 200 ° C. As described above, when the second metallocene compound is used in admixture with the first metallocene compound, the activity of the catalyst can be maintained even at a high temperature of 130 ° C or higher. Therefore, in the synthesis reaction of the polyolefin, Thereby making the active point 2 or more. In particular, since the metallocene catalyst for synthesis of high-density polyolefins is low in activity at a high temperature range, it is generally not used in a solution polymerization step in which a high reaction temperature is applied, but the second metallocene compound of the above formula (2) When mixed with the first metallocene compound, excellent catalytic activity can be exhibited even in a high temperature range of 130 ° C or higher.

Further, the polymerization pressure is preferably performed at about 1 to about 150 bar, more preferably about 1 to about 100 bar, and most preferably about 10 to about 100 bar.

Meanwhile, in the polymerization reaction of the ethylene and alpha-olefin comonomers, the physical properties of the polyolefin prepared by controlling the content of the second metallocene compound can be controlled.

In particular, the hybrid metallocene catalyst contains a relatively low content of the second metallocene compound. More specifically, the second metallocene compound is present in an amount greater than 0 mol% to less than about 50 mol%, preferably about 5 to about 40 mol%, based on the total amount of the first and second metallocene compounds, And more preferably from about 10 to about 30 mol%. When the second metallocene compound is contained in such a content ratio, a polyolefin having a narrow molecular weight distribution and having a negative BGN value in the above-mentioned range can be provided.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

< Example >

Manufacturing example  1: 1st Metallocene  Preparation of compounds

Manufacturing example  1-1

8- (2,3,4,5- Tetramethyl -1,3- Cyclopentadienyl ) -1,2,3,4-tetrahydroquinoline ((8- (2,3,4,5-Tetramethyl-1,3-cyclopentadienyl) -1,2,3,4-tetrahydroquinoline)

1,2,3,4-tetrahydroquinoline (13.08 g, 98.24 mmol) and diethyl ether (150 mL) were placed in a Schlenk flask. The Schlenk flask was immersed in a -78 ° C low-temperature bath made of dry ice and acetone and stirred for 30 minutes. Subsequently, n-BuLi (n-butyllithium, 39.3 mL, 2.5M, 98.24 mmol) was added via syringe under a nitrogen atmosphere to form a pale yellow slurry. Then, after the flask was stirred for 2 hours, the temperature of the flask was raised to room temperature while removing the produced butane gas. The flask was again immersed in a low-temperature bath at -78 ° C, the temperature was lowered, and then CO ₂ gas was introduced. As the carbon dioxide gas was introduced, the slurry disappeared and became a clear solution. The flask was connected to a bubbler to remove the carbon dioxide gas and raise the temperature to room temperature. After that, excess CO ₂ gas and solvent were removed under vacuum. The flask was transferred to a dry box, and pentane was added thereto, followed by vigorous stirring and filtration to obtain a lithium carbamate of a white solid compound. The white solid compound is coordinated with diethyl ether. The yield is 100%.

^{1 H NMR (C6D6, C5D5N)} : δ 1.90 (t, J = 7.2 Hz, 6H, ether), 1.50 (br s, 2H, quin-CH 2), 2.34 (br s, 2H, quin-CH 2), 3.25 (q, J = 7.2 Hz , 4H, ether), 3.87 (br, s, 2H, quin-CH 2), 6.76 (br d, J = 5.6 Hz, 1H, quin-CH) ppm

¹³ C NMR (C6D6): [delta] 24.24, 28.54, 45.37, 65.95, 121.17, 125.34, 125.57, 142.04, 163.09 (C = O) ppm.

The lithium carbamate compound prepared above (8.47 g, 42.60 mmol) was placed in a Schlenk flask. Then, tetrahydrofuran (4.6 g, 63.9 mmol) and 45 mL of diethyl ether were added in sequence. The Schlenk flask was immersed in acetone and a small amount of dry ice at -20 ° C in a low temperature bath and stirred for 30 minutes. Then, tert-BuLi (25.1 mL, 1.7 M, 42.60 mmol) was added. At this time, the color of the reaction mixture turned red. The mixture was stirred for 6 hours while keeping the temperature at -20 ° C. Of CeCl ₃ · 2LiCl solution (129 mL, 0.33 M, 42.60 mmol) and tetra methyl cyclo non-pentynyl (5.89 g, 42.60 mmol) dissolved in tetrahydrofuran was added to the flask under a given mixture in the syringe, and then, in a nitrogen atmosphere. The temperature of the flask was slowly raised to room temperature. After 1 hour, the thermostat was removed and the temperature was maintained at room temperature. Subsequently, water (15 mL) was added to the flask, and ethyl acetate was added thereto, followed by filtration to obtain a filtrate. The filtrate was transferred to a separatory funnel, followed by addition of hydrochloric acid (2N, 80 mL) and shaking for 12 minutes. A saturated aqueous solution of sodium hydrogencarbonate (160 mL) was added to neutralize the solution, and then the organic layer was extracted. Anhydrous magnesium sulfate was added to the organic layer to remove moisture, followed by filtration, and the filtrate was taken to remove the solvent. The obtained filtrate was purified by column chromatography using hexane and ethyl acetate (v / v, 10: 1) to obtain yellow oil. The yield was 40%.

^{1 H NMR (C6D6): δ} 1.00 (br d, 3H, Cp-CH 3), 1.63 - 1.73 (m, 2H, quin-CH 2), 1.80 (s, 3H, Cp-CH 3), 1.81 (s _{, 3H, Cp-CH 3)} , 1.85 (s, 3H, Cp-CH 3), 2.64 (t, J = 6.0 Hz, 2H, quin-CH 2), 2.84 - 2.90 (br, 2H, quin-CH 2 ), 3.06 (br s, IH, Cp-H), 3.76 (br s, IH, NH), 6.77 (t, J = 7.2 Hz, 1H, quin- , quin-CH), 6.94 (d, J = 2.4 Hz, 1H, quin-CH) ppm.

Manufacturing example  1-2

[(1,2,3,4- Tetrahydroquinoline -8-yl) Tetramethylcyclopentadienyl - Eta 5 , kappa -N] titanium dimethyl) ([(1, 2,3,4- Tetrahydroquinoline -8- yl ) tetramethylcyclopentadienyl - eta5 , close -N] titanium dimethyl )

In a dry box, the compound (8.07 g, 32.0 mmol) prepared in Preparation Example 1-1 and 140 mL of diethyl ether were placed in a round flask, the temperature was lowered to -30 ° C, and n-BuLi (17.7 g, 2.5 M , 64.0 mmol) was slowly added with stirring. The reaction was allowed to proceed for 6 hours while the temperature was raised to room temperature. Thereafter, the solid was obtained by filtration while washing with diethyl ether several times. Vacuum was applied to remove the remaining solvent to obtain a yellow solid di-lithium compound (Compound 4a) (9.83 g). The yield was 95%.

^{1 H NMR (C6D6, C5D5N)} : δ 2.38 (br s, 2H, quin-CH 2), 2.53 (br s, 12H, Cp-CH 3), 3.48 (br s, 2H, quin-CH 2), 4.19 (br s, 2H, quin-CH ₂ ), 6.77 (t, J = 6.8 Hz, 2H, quin-CH), 7.28 ppm.

In a dry box, TiCl ₄ · DME (4.41 g, 15.76 mmol) and diethyl ether (150 mL) were placed in a round flask and MeLi (21.7 mL, 31.52 mmol, 1.4 M) was slowly added with stirring at -30 ° C. After stirring for 15 minutes, a solution of [(1,2,3,4-tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-eta 5, [(1,2,3,4-Tetrahydroquinolin-8-yl) tetramethylcyclopentadienyl-eta5, kapa-N] dilithium) (5.30 g, 15.76 mmol) was placed in a flask. The mixture was stirred for 3 hours while the temperature was raised to room temperature. After completion of the reaction, the solvent was removed by vacuum, dissolved in pentane, and filtered to remove the filtrate. Vacuum was applied to remove the pentane to obtain a dark brown compound (3.70 g). The yield was 71.3%.

^{1 H NMR (C6D6): δ} 0.59 (s, 6H, Ti-CH 3), 1.66 (s, 6H, Cp-CH 3), 1.69 (br t, J = 6.4 Hz, 2H, quin-CH 2), 2.05 (s, 6H, Cp- CH 3), 2.47 (t, J = 6.0 Hz, 2H, quin-CH 2), 4.53 (m, 2H, quin-CH 2), 6.84 (t, J = 7.2 Hz, 1H, quin-CH), 6.93 (d, J = 7.6 Hz, quin-CH), 7.01 (d, J = 6.8 Hz, quin-CH) ppm.

¹³ C NMR (C6D6):? 12.12, 23.08, 27.30, 48.84, 51.01, 119.70, 119.96, 120.95, 126.99, 128.73, 131.67, 136.21 ppm.

Manufacturing example  2: 2nd Metallocene  Preparation of compounds

A second metallocene compound having the above structure was synthesized and prepared according to a known method.

&Lt; Example >

Example  One

A 2L autoclave continuous process reactor was charged with a hexane solvent (5.42 kg / h) and 1-butene (0.8 kg / h), and the temperature at the top of the reactor was preheated to 160 ° C. (0.05 mmol / min), the first metallocene compound (0.45 占 퐉 ol / min) of Production Example 1, the second metallocene compound (0.05 占 퐉 ol / min) of Production Example 2, Anilinium tetrakis (pentafluorophenyl) borate promoter (1.5 μmol / min) was simultaneously added to the reactor. Ethylene (0.87 kg / h) was then fed into the autoclave reactor and maintained at 160 캜 for 30 minutes or more at a pressure of 89 bar in a continuous process, followed by copolymerization to obtain a copolymer. Next, the remaining ethylene gas was taken out, and the polymer solution was dried in a vacuum oven for 12 hours or more, and the physical properties were measured.

Example  2

A 2L autoclave continuous process reactor was charged with hexane solvent (5.58 kg / h) and 1-butene (0.7 kg / h), and the temperature at the top of the reactor was preheated to 160 ° C. (0.35 占 퐉 ol / min), the second metallocene compound (0.15 占 퐉 ol / min) of Production Example 2, and the dimethyl Anilinium tetrakis (pentafluorophenyl) borate promoter (1.5 μmol / min) was simultaneously added to the reactor. Ethylene (0.87 kg / h) was then fed into the autoclave reactor and maintained at 160 캜 for 30 minutes or more at a pressure of 89 bar in a continuous process, followed by copolymerization to obtain a copolymer. Next, the remaining ethylene gas was taken out, and the polymer solution was dried in a vacuum oven for 12 hours or more, and the physical properties were measured.

Comparative Example  One

The product SN318 was prepared with LLDPE of LG Chem manufactured by Ziegler-Natta catalyst.

Comparative Example  2

The product LC565 was prepared as the LLDPE of LG Chem manufactured using only the first metallocene catalyst compound.

< Experimental Example >

In the following manner Physical properties of the polyolefins obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were measured and are shown in Table 1 below.

1) Density: ASTM 1505

2) Melt flow index (MI, 2.16 kg / 10 min): Measuring temperature 190 캜, ASTM 1238

3) Molecular weight and molecular weight distribution: The number-average molecular weight, the weight-average molecular weight and the Z-average molecular weight were measured using Gel Permeation Chromatography-FTIR (GPC-FTIR) The molecular weight distribution is represented by the ratio of the weight average molecular weight to the number average molecular weight.

4) BGN (Branch Gradient Number): When the log value (log Mw) of the molecular weight (Mw) in the GPC-FTIR measurement result is represented by x-axis and the molecular weight distribution (dwt / dlog Mw) When the molecular weight distribution curve is plotted on the axis, the side branch content of the low molecular weight is defined as the side branch content (unit: number / 1,000C) at the left boundary of 80% of the total area excluding the left and right ends of 10% The BGN value was obtained by calculating the value of the content as the side-branch content at the right boundary of the middle 80%, as shown in the following formula (1).

 [Formula 1]

density
(Unit: g / cc) Melt Index (MI)
(Unit: g / 10 min) Molecular weight distribution BGN Example 1 0.865 4.2 2.28 - 0.02 Example 2 0.870 0.9 2.82 - 0.14 Comparative Example 1 0.920 One 3.72 - 0.14 Comparative Example 2 0.865 5 2.25 About 0

The GPC-FTIR measurement results of the polyolefins of Examples 1 and 2 and Comparative Examples 1 and 2 are shown in Figs. 1 to 4, respectively.

1 and 2, the side branch content of 2 or more carbon atoms at the left boundary point (point A) in the middle 80% region of the molecular weight distribution curve area and the side branch content of 2 or more carbon atoms at the right boundary point (point B) It can be confirmed that the BGN value calculated according to the above 1 has a negative value.

3, the polyolefin of Comparative Example 1 also showed negative BGN values of -0.14, but the molecular weight distribution exceeded 3 and did not show sufficient impact strength.

Also, referring to FIG. 4, the polyolefin of Comparative Example 2 showed a BGN value close to zero, indicating that it did not show the characteristic comonomer distribution as in the present invention.

Claims (9)

A polyolefin having a molecular weight distribution of 1.5 to 3.0 and a BGN (Branch Gradient Number) value calculated by the following formula 1 is -0.01 to -1:
[Formula 1]

In Equation (1)
When a molecular weight distribution curve is drawn with the logarithm (log Mw) of the molecular weight (Mw) as the x-axis and the molecular weight distribution (dwt / dlog Mw)
The side chain content of the low molecular weight means the side branch content (branch content of 2 or more carbon atoms per 1,000 carbon atoms, unit: 1,000C) at the left boundary of 80% of the total area except 10% at the left and right ends, The side chain content of high molecular weight means the side chain content at the right border.
The polyolefin according to claim 1, wherein the density is 0.85 to 0.90 g / cc.
The polyolefin according to claim 1, wherein the number of branch branches per 1,000 carbon atoms is 20 to 120.
The polyolefin of claim 1, wherein the polyolefin is selected from the group consisting of ethylene and alpha-olefins, in the presence of a hybrid metallocene catalyst comprising a first metallocene compound represented by the following formula (1) and a second metallocene compound represented by the following formula Polyolefins obtained by polymerizing olefin comonomers:
[Chemical Formula 1]

In Formula 1,
R1 and R2 may be the same or different from each other, and each independently hydrogen; Or alkyl of 1 to 20 carbon atoms;
R3, R3 'and R3 "are hydrogen;
CY is an aliphatic ring;
M1 is titanium;
Q1 and Q2 may be the same or different from each other and are each independently alkyl having 1 to 20 carbon atoms;
(2)

In Formula 2,
M2 is titanium;
Cp is indenyl;
R4 is a heterocycle having 3 to 20 carbon atoms; Or heteroaryl having 3 to 20 carbon atoms;
R5 and R6, which may be the same or different from each other, are each independently hydrogen; Or alkyl of 1 to 20 carbon atoms;
Q3 and Q4 may be the same or different from each other and are each independently alkyl having 1 to 20 carbon atoms;
A is a silicon atom containing radical which bridges the Cp ring with J;
J is NR &lt; 7 &gt; and R &lt; 7 &gt; is as defined in R &lt; 5 &gt;
5. The polyolefin according to claim 4, wherein the hybrid metallocene catalyst comprises the second metallocene compound in an amount of more than 0 mol% to less than 50 mol% based on the total amount of the first and second metallocene compounds.
The polyolefin according to claim 4, wherein the polymerization of ethylene and alpha olefin comonomers is carried out by a continuous solution polymerization process.
5. The polyolefin according to claim 4, wherein the hybrid metallocene catalyst further comprises at least one cocatalyst selected from compounds represented by the following general formulas (5) to (7):
[Chemical Formula 5]
- [Al (R &lt; 8 &gt;) -O] c-
In the general formula (5), R 8 is a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, c is an integer of 2 or more,
[Chemical Formula 6]
D (R 9) ₃
In Formula 6,
D is aluminum or boron, R9 is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen,
(7)
[LH] ⁺ [ZE ₄ ] ^- or [L] ⁺ [ZE ₄ ] ^-
In Formula 7,
L is a neutral or cationic Lewis base, H is a hydrogen atom, Z is a Group 13 element, and E may be the same or different and each independently represents a hydrogen atom, a halogen atom, An aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms which is substituted or unsubstituted with phenoxy.
The polyolefin according to claim 4, wherein the polymerization of ethylene and alpha olefin comonomers is carried out at 130 to 250 ° C.
5. The process of claim 4 wherein said alpha olefin comonomer is selected from the group consisting of propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, , 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicosene.

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