WO2016093549A2 - Olefin-based polymer having excellent melt strength, and film comprising same - Google Patents

Abstract

The present invention relates to an olefin-based polymer having excellent melt strength, and a film comprising the same. According to the present invention, the olefin-based polymer has excellent processability, and haze and mechanical properties, and particularly, has high melt strength so as to be advantageous in an extrusion process, and thus can be used as a film and the like.

Description

 [Name of invention]

 Olefin-based polymer having excellent melt strength and film comprising same [Cross Reference with Related Applications]

 This application claims the benefit of priority based on Korean Patent Application No. 1 2014-0174977 dated December 8, 2014 and Korean Patent Application No. 10-2015-0169813 dated December 1, 2015. All content disclosed in these references is included as part of this specification.

 Technical Field

 The present invention relates to an olefinic polymer having excellent melt strength and a film comprising the same.

 [Technique to become background of invention]

 In general, a polymer film refers to a non-fibrous flat plastic molding having a thickness of 0.25 mm (l / 100 inch) or less. Polymer is light, good barrier property, excellent transparency and relatively low price. It is used in almost all fields such as packaging materials, household goods, automobiles, electronic devices, aircraft, etc. It is easy to process and makes into film. Synthetic polymers, such as polyvinyl chloride and polyethylene terephthalate, have been developed and are widely used as polymer films. Currently, many synthetic polymers are used alone or blended as materials for films.

 In particular, polyethylene (PE) is divided into low density polyethylene, high density polyethylene, and linear low density polyethylene according to density, copolymerization, and branching type, and various polyethylene products have been introduced in the metallocene catalyst system which has been commercialized recently.

 Low-density polyethylene is one of general purpose resins that was used as an insulating material for military radars because of its excellent electrical properties after being successfully synthesized by ICI in 1933. The main uses include general packaging, agriculture, shrink film, paper coating, etc., especially with long chain branching, which is suitable for coating applications due to its excellent melt tension.

Linear low density polyethylene (LLPDE), on the other hand, is prepared by copolymerizing ethylene and alpha olefins at low pressure using a polymerization catalyst, resulting in a narrow molecular weight distribution. It is a resin having a short chain branch of a certain length and no long chain branch. Linear low density polyethylene film has the characteristics of general polyethylene, and has high breaking strength and elongation, and excellent tear strength and falling layer stratification strength. Therefore, the use of stretch film and overlap film, which is difficult to apply to existing low density polyethylene or high density polyethylene, has increased. Doing.

 On the other hand, linear low density polyethylenes using 1-butene or 1-nuxene as comonomers are mostly produced in single gas phase reactors or single loop slurry reactors, and are more productive than processes using 1-octene comonomers, but these products are also used. Due to the limitations of catalyst technology and process technology, physical properties are inferior to those of using 1-octene comonomer, and molecular weight distribution is narrow, resulting in poor processability. In order to solve such processing problems, expensive fluorine-based processing aids are also used, but it takes a long time to stabilize, and thus, loss of raw materials is not economical.

 Many efforts are being made to improve such problems, for example, Korean Patent Crab 218,046, Korean Patent 223, 105, US Patent Crab 5,798,424, US Patent # 6,1 14,276, and Japanese Patent Crab 2,999,162 The new catalyst for magnesium-supported nonmetallocene-based levine polymerization in the back has excellent molecular structure control ability such as comonomer distribution and molecular weight distribution in the polymer chain during leulene copolymerization, so that it is possible to synthesize so-called "high strength linear low density polyethylene". Is reported. High-strength linear low density polyethylene has been introduced as having excellent fall stratification strength and more than twice the layered stratification strength, compared with a film made of general-purpose linear low density polyethylene polymerized under Ziegler-Natta catalyst. However, due to the difficulty in controlling the molecular weight distribution of a single semi-ungunggi polymer phase, it has a typical narrow molecular weight distribution, which causes inferior processability. In order to improve this, in some cases, it is inconvenient to use some mixture of low density polyethylene.

 Against this background, there is a constant demand for manufacturing a better product having a balance between physical properties and processability, and further improvement is required.

[Content of invention] Problem to be solved

 In order to solve the problems of the prior art, the present invention is to provide an olefin-based polymer and a film containing the same having a narrow molecular weight distribution and excellent melt strength and haze characteristics and processability, showing a high productivity.

[Solving means of a _problem],

In order to solve the above problems, according to an embodiment of the present invention, the melt flow index (Ml) and melt strength (MS, melt strength) measured at 190 ^° C, 2.16kg load conditions in accordance with ASTM D1238 is the following formula It provides an olefinic polymer that satisfies 1.

 [Equation 1]

 -32.0 * log MI + 75.2 <MS <-40.9 * log MI + 77.9

 In addition, according to another embodiment of the present invention, a film including the olepin-based polymer is provided.

 【Effects of the Invention】

 The olefin polymer according to the present invention is excellent in workability, haze and mechanical properties, and particularly high in melt strength, which is advantageous for extrusion processing, and thus can be usefully used for films and the like.

 [Brief Description of Drawings]

 1 is a graph showing the relationship between the melt strength (MS) according to the melt flow index (Ml) of the Examples and Comparative Examples of the present invention.

 2 is a graph showing the relationship with the molecular weight distribution according to the melt strength (MS) according to the Examples and Comparative Examples of the present invention.

 [Specific contents to carry out invention]

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

Also, the terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting of the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. As used herein, the terms "comprise", "comprise" or "have" are intended to indicate that there is a feature, number, step, component, or combination thereof, and one or more other features It is to be understood that the present invention does not exclude the possibility of adding or presenting numbers, steps, components, or a combination thereof.

 As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated and described in detail below. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

 Hereinafter, an olefin-based polymer and a film including the same according to specific embodiments of the present invention will be described in detail. According to one embodiment of the invention,

According to ASTM D1238, an olefin-based polymer having a melt flow index (Ml) and a melt strength (MS) satisfying the following formula 1 measured at 190 ^° C. and a load condition of 2.16 kg is provided.

 [Equation 1]

 -32.0 * log MI + 75.2 <MS <-40.9 * log MI + 77.9

 The present invention has completed the present invention based on the fact that the olefin polymer satisfies Equation 1, the physical properties of the polymer can be optimized to achieve high melt strength, excellent processability and good mechanical properties.

Polyethylene film is one of the important polymer products. Linear low density polyethylene (mLLPDE) prepared using a metallocene catalyst in the polyethylene film has achieved very good physical properties when compared to other polymerizers having a similar molecular weight. However, mLLPDE has a disadvantage in that the molecular weight distribution is narrow and the branched chain distribution according to the molecular weight is relatively uniform, resulting in poor processability. As a result, the processing load is large due to the pressure applied to the resin during extrusion, and there is a problem in that optical roughness such as haze is deteriorated due to surface roughness during blowing. These problems In order to improve, a mixture of low density polyethylene (LPDE) having a wide molecular weight distribution and long chain branching in mLLPDE may be used, but this also causes a process inconvenience.

 Thus, the present invention provides an olefinic polymer exhibiting higher melt strength at the same molecular weight or melt index as compared to conventional commercially available linear low density polyethylene. Furthermore, since higher melt strength is shown in the same molecular weight distribution, workability improvement, haze characteristics, and high melt strength which are combined with a narrow molecular weight distribution can be simultaneously achieved.

 Melt strength is an important factor affecting the processability and productivity of the film, and the melt strength must be high during extrusion of blown film to improve the bubble processability, thereby improving the processability of the film. Furthermore, it may be advantageous in terms of productivity.

 Compared to the general linear low density polyethylene, the leulevine-based polymer of the present invention satisfying Equation 1 may exhibit improved processability by showing a narrow molecular weight distribution and excellent melt strength while showing an equivalent level of physical strength.

 For an ellefin-based polymer having a similar melt flow index (Ml), if the melt strength is too low or too high out of the range of Equation 1 above, the workability during the extrusion processing or the mechanical properties of the film may not be reduced. have.

In addition, according to one embodiment of the present invention, the olefin-based polymer has a melt flow index (Ml) measured at 190 ^° C., 2.16 kg derating conditions according to ASTM D1238, from about 0.1 to about 2 gA0 mm, or from about 0.1 to about About 1.8 g / 10 min, or about 0.1 to 1.5 g 10 min. If the melt flow index is too high, long chain branches are not produced, so that the melt strength is difficult to rise, and if too low, the workability is poor, so the above range is preferable in this respect.

Further, according to one embodiment of the present invention, ASTM according to D1238 a melt flow rate of the olefin-based polymer measured at 190 ^° C ratio _{(MFRR, MI 2 L6 / MI} 2. 16) is about 10 to about 100, or from about 20 to about 100, or about 20 to 80.

The olefin polymer of the present invention has a melt strength (MS) of about 60 mN or more, For example, about 60 to about 150 mN, or about 60 to about 120 mN, or about 70 to about 150 mN, or about 70 to about 120 mN.

 In addition, the olefinic polymer of the present invention also has a molecular weight distribution (weight average molecular weight / number average molecular weight) of 4 or less, for example, about 1 to about 4, or about 1, when the melt strength (MS) is 70 m / N or more. Generally from about 3.5 to about 3.5, or from about 2 to about 3.5. &Quot; A broader molecular weight distribution results in higher melt strength, while lowering the other physical strength of the polymer and increasing the high molecular weight portion of the surface upon extrusion of the blown film. There is a problem that haze increases. However, the olefinic polymer of the present invention can exhibit a high melt strength without sacrificing physical properties with a narrow molecular weight distribution by properly including the long chain branching.

 In addition, the olefin polymer of the present invention can satisfy a constant relationship between melt strength and molecular weight distribution. For example, when the melt strength of the present invention is 70 mN or more, the molecular weight distribution is 4 or less. More specifically, the leupin-based polymers of the present invention have a molecular weight distribution in the range of about 1 to about 4 when in the range of about 70 to about 150 mN. As described above, high melt strength is required for processability and narrow molecular weight distribution is required for physical strength. However, in general olefin polymers, melt strength and molecular weight distribution are proportional to each other, so that high melt strength and low molecular weight distribution are simultaneously used. Hard to achieve. However, the olefin polymer of the present invention has an advantage that the molecular weight distribution is maintained at 4 or less even at a high melt strength of 70 mN or more, so that these opposing physical properties can be simultaneously implemented.

In addition, according to an embodiment of the present invention, the density of the olefinic polymer may be about 0.910 to about 0.950 g / cc, or about 0.910 to about 0.930 g / cc, but is not limited thereto. If the density is too high, exceeding 0.950 g / cc, it is not preferable because the probability of introducing long chain branching is small. When the olefin polymer of the present invention satisfies Equation 1 above, when the melt flow index, the melt flow rate ratio, the melt strength, the density, the molecular weight distribution, and the like are in the above-described ranges, the physical properties are more optimized to provide good workability, Haze and mechanical properties can be achieved. The olefin polymer according to the present invention is preferably a copolymer of ethylene and alpha olefin comonomers, which are olefinic monomers.

 As the alpha olefin pin comonomer, an alpha olefin having 3 or more carbon atoms may be used. Alpha olefins having 3 or more carbon atoms include propylene, 1-butene, 1-phen¾1 4-methyl-1-pentene, 1-nuxene, 1-heptene, 1-octene, 1-decene, 1-undecene and 1-dodecene ， 1-tetradecene, 1 ᅳ nucleodecene, 1 octadecene or 1-eicosene.

 The olefin polymer according to the present invention exhibits the same level of physical strength as that of the conventional linear low density polyethylene, and has high melt strength during extrusion, so that it has excellent bubble stability and good workability, and has good haze characteristics. It can be usefully used for such purposes.

 The olefin-based polymer according to the present invention having the above-mentioned characteristics uses a common supported metallocene compound including two or more metallocene compounds of different structures as a catalyst, and is copolymerized with yylene and alpha olepin. It can be obtained, such olefinic polymer may have the physical properties as described above. More specifically, the olefin-based polymer of the present invention as described above i) a first catalyst represented by the following formula (1); And ii) at least one selected from the group consisting of a second catalyst represented by the following formula (2) and a third catalyst represented by the following formula (3), in the presence of a common supported catalyst, polymerizing ethylene and alpha olepin comonomers: Can be obtained.

[

 In Chemical Formula 1,

 M is a Group 4 transition metal;

 B is carbon, silicon or germanium;

Qi and Q ₂ are each independently hydrogen, halogen, C o alkyl, C: alkenyl

C _6-20 aryl, C _7-20 alkylaryl, C group ₂₀ arylalkyl, d_ ₂₀ alkoxy, C ₂ .20 alkoxyalkyl, C heterocycloalkyl, or C ₅ ¦ ₂₀ heteroaryl;

Xi and ¾ are each independently halogen, C _1-20 alkyl, C ₂ ᅳ ₂₀ alkenyl, C, Aryl, nitro, amido, alkylsilyl, C alkoxy, or C _1-20 sulfonate; Is the following Chemical Formula 2a,

C ₂ is the following Formula 2a or 2b,

 [

 In Chemical Formulas 2a and 2b,

Ri to R ₁₃ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, CO silylalkyl, _ ₂₀ alkoxysilyl,. ₂ o ether, ₂₀ silyl ether, C _I-20 alkoxy, C _{6 20} aryl, C ₀ alkylaryl, or C group ₂₀ arylalkyl,

R ' _! To R ' ₃ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, or C ₆ _ ₂₀ aryl,

[Formula 2]

 In Chemical Formula 2,

To Rio, and R _'10 to ₁₃ are each independently hydrogen, C ₀ alkyl, C _2-20 alkenyl, C _{6 20} aryl, C _7-20 alkylaryl, C ₂₀ arylalkyl, C _{2 20} alkoxyalkyl or C _{1 -20} or amine, or R ₁₃ and R _I0 to R'u) to two or more connected to each other adjacent R'n of 1 or more aliphatic rings, to form a ring, or heterocyclic, the aliphatic chain, Aromatic rings, or hetero rings, are unsubstituted or substituted with .20 alkyl;

Q is -CH ₂ CH _2- , -C (Z0 (Z ₂ )-or -Si (Z0 (Z ₂ )-;

Z _! And Z ₂ are each independently hydrogen, C o alkyl, C ₃ _ ₂₀ cycloalkyl, d_ ₂₀ alkoxy, C _{2 20} alkoxyalkyl, C _{6 20} aryl, C ₆ _ ₁₀ aryloxy, C ₂ . ₂₀ alkenyl, C alkylaryl, or C ₄₀ arylalkyl;

M ₂ is a Group 4 transition metal;

¾ and ¾ are each independently halogen, ₂₀ alkyl, C ₂ . ₂₀ alkenyl, C _6-20 aryl, nitro, amido, ₂₀ alkylsilyl, C _1-20 alkoxy, or C _1-20 sulfonate;

 [

 In Chemical Formula 3,

M ₃ is a Group 4 transition metal;

¾ and ¾ are each independently halogen, C _1-20 alkyl, C _{2 20} alkenyl, C, Aryl, nitro, amido, C _1-20 alkylsilyl, C _1-20 alkoxy, or C _1-20 sulfonate;

Ri 4 to R ₁₉ are each independently hydrogen, C _1-20 alkyl, C ₂ _ ₂₀ alkenyl, C ^ alkoxy, C _6-20 aryl, C ₇ _ ₂₀ alkylaryl, C ₇ _ ₂₀ arylalkyl, Cwo alkyl Silyl, C « ₀ arylsilyl, or C _1-20 amine; Or two or more adjacent ones of R ₁₄ to R ₁₇ are connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings;

L ₂ is _ ₁₀ straight or branched alkylene;

D ₂ is -0-, -S-, -N (R)-or -Si (R) (R ')-, wherein R and R' are each independently hydrogen, halogen, c _1-20 alkyl, c _2-20 alkenyl, or c _{6 20} aryl;

A ₂ is hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C ₆ _ ₂₀ aryl, C ₂₀ alkylaryl,

C _7-20 arylalkyl, C _1-20 alkoxy, C _2-20 alkoxyalkyl, c _2-20 heterocycloalkyl, or C _5-20 heteroaryl;

B is carbon, silicon, or germanium, and is a bridge that binds a cyclopentadienyl series ligand and JR19 _zy by a covalent bond;

 J is a periodic table group 15 element or group 16 element;

 z is the oxidation number of the element J;

 y is the number of bonds of the J elements.

In particular, the first catalyst represented by Chemical Formula 1 is characterized in that a silyl group is substituted with d (Formula 2a). In addition, the indene derivative of (Formula 2a) has a lower electron density than an indenoindole derivative or fluorenyl derivative, and includes a silyl group having a large steric hindrance, and thus has a similar structure due to steric hindrance and electron density. Compared to the metallocene compound, a relatively low molecular weight olefin polymer can be polymerized with high activity. In addition, fluorenyl derivatives, which may be represented as C ₂ (Formula 2b), form a crosslinked structure by a bridge, and exhibit high polymerization activity by locking a non-covalent electron pair which may act as a Lewis base to the ligand structure. Preferably, in Formula 1, Μ is zirconium, Β is silicon, Qi and Q ₂ are each independently ₂₀ alkyl or C _2-20 alkoxyalkyl, X! And X ₂ are halogen. More preferably, ^ is methyl and (is 6-tert-subspecially-nuclear chamber. Also, preferably, in Formulas 2a and 2b, to R ₁₃ is hydrogen, and 1 ' ₃ is C _1-20 alkyl. More preferably, R ₃ is methyl.

 The manufacturing method of the said 1st catalyst is concretely demonstrated to the Example mentioned later.

 In the common supported catalyst, the first catalyst represented by formula (1) mainly contributes to making a high molecular weight copolymer, and the catalyst represented by formula (2) or formula (3) may contribute to making a relatively high molecular weight copolymer.

Preferably, in the above Formula 2, R ₁₀ to R ₁₃ and R _'10 to' ₁₃ are each independently hydrogen, C o alkyl, C _{2 20,} or alkoxyalkyl, or R ₁₀ to Ri3, and R _'10 to R' Two or more adjacent of ₁₃ are linked to each other to form one or more aliphatic rings or aromatic rings, wherein the aliphatic rings or aromatic rings are unsubstituted or substituted with C _1-20 alkyl; Q is -CH ₂ CH _2- , -C (Z (Z ₂ )-or-^ () (¾)-, and _\ and ¾ are each independently C _1-20 alkyl or C ₂ _ ₂₀ alkoxyalkyl; M ₂ is zirconium; ¾ and are halogen.

More preferably, in Formula 2, R ₁₀ to R ₁₃ and R _'10 to 1' ₁₃ are each independently hydrogen, methyl or 6-tert-buteuk upon-or haeksil, or R ₁₀ to R ₁₃ and R ' two or more adjacent u) to R ′ ₁₃ are linked to each other to form one or more benzene rings or cyclonucleic acid rings, wherein the benzene rings are unsubstituted or substituted with tert-butoxy; Q is -CH ₂ CH _2- , -C (Z,) (Z ₂ )-or -Si (Z0 (Z ₂ )-; ¾ and Z ₂ are each independently methyl or 6-tert-subspecific-nucleus M ₂ is zirconium and X ₃ and ¾ are chloro.

 Representative examples of are as follows:

 The manufacturing method of the said 2nd catalyst is concretely demonstrated to the Example mentioned later.

 The third catalyst represented by Chemical Formula 3 may contribute to making a copolymer having a molecular weight intermediate between the first catalyst and the second catalyst.

Preferably, in Chemical Formula 3, M ₃ is titanium; And X ₆ is halogen; R ₁₄ to R ₁₉ are C _I-20 alkyl; L ₂ is C _M0 straight or branched alkylene; D ₂ is -0-; A ₂ is C ₂₀ alkyl; B is silicon; J is nitrogen; z is the oxidation number of the element J; y is the number of bonds of the J elements.

Representative examples of the compound represented by Formula 3 are as follows:

 The method for preparing the third catalyst will be described in detail in Examples described later.

 In the common supported catalyst according to the present invention, the carrier may be a carrier containing a hydroxy group on the surface, and preferably has a highly reactive hydroxyl group and a siloxane group which are dried to remove moisture on the surface. Carriers may be used.

For example, silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, and these are usually oxides, carbonates, sulfates, such as Na ₂ 0, ₂ C0 ₃ , BaS0 ₄ , and Mg (N0 ₃ ) ₂ . , And nitrate components.

 In the common supported catalyst according to the present invention, the mass ratio of the catalyst to the carrier is preferably 1: 1 to 1: 1000. When including the carrier and the catalyst in the mass ratio, it may be advantageous in terms of maintaining the activity and economical efficiency of the catalyst by showing the appropriate supported catalyst activity.

 In addition, the catalyst represented by Formula 0 above (1) and ii) the above formula

The mass ratio of at least one selected from the group consisting of a second catalyst represented by 2 and a third catalyst represented by Chemical Formula 3 is preferably 1: 100 to 100: 1. It may be advantageous in terms of maintaining the activity and economical efficiency of the catalyst by showing the optimum catalytic activity in the mass ratio.

 In addition to the above catalysts, further promoters may be used to prepare the olefin polymer. The promoter may further include one or more of the promoter compounds represented by the following Formula 4, Formula 5 or Formula 6.

[Formula ⁴ ]

-[A1 (R ₃₀ ) -O] _m -in Chemical Formula 4, R ₃₀ may be the same as or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

 m is an integer of 2 or more;

[Formula ⁵ ]

 J (R3 l) 3

 In Chemical Formula 5,

R ₃₁ is as defined in Formula 4 above;

 J is aluminum or boron;

 [Formula 6]

[EH] ⁺ [ZA ₄ ] ^" or [E] ⁺ [ZA ₄ ]

 In Chemical Formula 6,

 Ε is a neutral or cationic Lewis base;

 Η is a hydrogen atom;

 Ζ is a Group 13 element;

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

 Examples of the compound represented by the formula (4) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and the like, and more preferred compound is methyl aluminoxane.

Examples of the compound represented by Formula 5 include trimethylaluminum triethylaluminum, triisobutylaluminum, tripropylaluminum tributylaluminum, dimethylchloroaluminum, triisopropylaluminum tri-S-butylaluminum, tricyclopentylaluminum, and tripentyl Aluminum triisopentyl aluminum trinuclear silaluminum, trioctyl aluminum, dimethylaluminum, methyldiethylaluminum, triphenylaluminum tri-P-allyl aluminum, dimethylaluminum methoxide, dimethylaluminum trimethylbotriethylboron, triiso Butyl boron, tripropyl boron Tributylboron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.

 Examples of the compound represented by Formula 6 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra (P—lryl) Boron,

Trimethylammonium tetra (ο, ρ-dimethylphenyl) boron ，

Tributylammonium tetra (Ρ-trifluoromethylphenyl) boron ，

Trimethylammonium tetra (Ρ-trifluoromethylphenyl) boron,

Tributylammonium tetrapentafluorophenylboron,

Ν, shall not Ν- diethyl help tetraphenyl boron, ^'

Ν, Ν-diethylanilinium tetrapentafluorophenylborone ，

Diethyl ammonium tetrapentafluorophenyl boron, triphenyl phosphonium tetraphenyl boron, trimethyl phosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tree Propyl ammonium tetraphenyl aluminum,

Trimethylammonium tetra (Ρ-ryll) aluminum,

Tripropylammonium tetra (Ρ-ryl) aluminum,

Triethylammonium tetra (ο, ρ-dimethylphenyl) aluminum ，

Tributylammonium tetra (Ρ-trifluoromethylphenyl) aluminum,

Trimethylammonium tetra (Ρ-trifluoromethylphenyl) aluminum,

Tributylammonium tetrapentafluorophenylaluminum ，

 Ν, Ν-diethylanilinium tetraphenylaluminum,

_Ν , _{Ν -diethylanilinium tetrapentafluorophenylaluminum} ，

Diethylammonium tetrapenta tetraphenyl aluminum,

Triphenylphosphonium tetraphenylaluminum, trimethylphosphonium tetraphenylaluminum, tripropylammonium tetra (Ρ-ryll) boron,

Triethylammonium tetra (ο, ρ-dimethylphenyl) boron ，

Tributylammonium tetra (Ρ-trifluoromethylphenyl) boron,

Triphenylcarbonium tetra (Ρ-trifluoromethylphenyl) boron, Triphenylcarbonium tetrapentafluorophenylboron, and the like.

 The common supported catalyst according to the present invention is prepared by supporting a cocatalyst compound on a carrier, supporting the first catalyst on the carrier, and supporting the second catalyst and / or the third catalyst on the carrier. The order of loading of the catalyst can be changed as necessary.

 In the preparation of the common supported catalyst, a hydrocarbon solvent such as pentane, nucleic acid, heptane, or the like, or an aromatic solvent such as benzene or toluene may be used. In addition, the metallocene compound and the cocatalyst compound may be used in a form supported on silica or alumina.

 The leupin-based polymer of the present invention can be prepared by a production method comprising the step of polymerizing ethylene and an alpha olefin monomer in the presence of the common supported catalyst.

 Specific examples of the alpha-olefin monomers include propylene, 1-butene, 1_pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1 -Dodecene, 1-tetradecene, 1-nuxadecene, 1-eicosene, and the like, and two or more thereof may be mixed and copolymerized.

The content of the alpha olefin which is the comonomer is not particularly limited and may be appropriately selected depending on the use, purpose, and the like of the ethylene-alpha olefin polymer. More specifically, it may be more than 0 and 99 mol% or less. ^■

 The polymerization reaction may be carried out by homopolymerization with one olefinic monomer or copolymerization with two or more monomers using one continuous slurry polymerization reactor, a loop slurry reactor, a gas phase reactor, or a solution reactor.

The common supported catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, nucleic acid, heptane, nonane, decane, and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, chlorine such as dichloromethane and chlorobenzene. The solution may be dissolved or diluted in a hydrocarbon solvent substituted with an atom or the like. The solvent used herein is preferably used by removing a small amount of water, air, or the like acting as a catalyst poison by treating a small amount of alkyl aluminum, and may be carried out by further using a promoter. According to another embodiment of the present invention, there is provided a film comprising the above-described olefinic polymer.

 Film comprising the olefinic polymer of the present invention, as described above in the description of the olefinic polymer, exhibits the same level of physical strength as compared to the conventional linear low density polyethylene, while the melt strength during extrusion processing is high bubble stability It has excellent bubble stability and good workability, and its haze property is good, so it can be usefully used depending on the needs.

 According to one embodiment of the invention, the film comprising the olefin-based polymer has a haze of less than 20%, for example about 1 to about 20%, or about 1 to about 50, measured according to ISO 13468 standards at a thickness of 50. 18%, or about 1 to about 15% of good haze properties.

The film of the present invention, for example, using the olefin polymer, injection molding method, compression molding method, extrusion molding method, injection compression molding method, foam injection molding method, inflation method (inflation), T die method (T die), calender method It can be produced by (Calendar), blow molding method, vacuum molding method, and the like, in addition to the processing method generally used in the technical field to which the present invention belongs can be used without particular limitation. ^■

 Hereinafter, preferred embodiments will be presented to assist in understanding the present invention. However, the following examples are provided only for better understanding of the present invention, and the present invention is not limited thereto.

<Example>

 Synthesis Example of Metallocene Compound

Step 1) Preparation of Ligand Compound 4.05 g (20 mmol) of ((IH-inden-3 -yl) methyl) trimethylsilane ((1 H-inden-3 -yl) methyl) trimethylsilane was added to a dried 250 mL Schlenk flask (first flask). It was dissolved in 40 mL of diethyl ether under gas. After cooling to 0 ^° C, 9.6 mL (24 mmol) of 2.5 M n-BuLi nucleic acid solution was slowly added dropwise. The reaction mixture was slowly warmed to room temperature and then stirred for 24 hours. In another 250 mL Schlenk flask, a solution prepared by dissolving 2.713 g (10 mmol) of (6-tert-butoxynucleosil) dichloro (methyl) silane in 30 mL of nucleic acid was prepared, cooled to -78 ^° C, and then The mixture of 1 flask was slowly added dropwise. After the dropwise addition, the mixture was slowly warmed to room temperature and stirred for 24 hours. 50 mL of water was added thereto, and the organic layer was extracted three times with ether (50 mL × 3). A moderate amount of MgS0 ₄ was added to the combined organic layers, followed by stirring. After filtering and drying the solvent under reduced pressure, 6.1 g (molecular weight: 603.11, 10.05 mmol, 100.5% yield) of a yellow oily ligand compound was obtained. The obtained ligand compound was used for the preparation of the metallocene compound without separate separation process.

NMR (500 MHz, CDC1 ₃ ): 0.02 (18H, m), 0.82 (3H, m), 1.15 (3H, m), 1.17

(9H, m), 1.42 (H, m), l ^' .96 (2H, m), 2.02 (2H, m), 3.21 (2H, m), 3.31 (IH, s), 5.86 (IH, m) , 6.10 (IH, m), 7.14 (3H, m), 7.14 (2H, m) 7.32 (3H, m) Step 2) Preparation of metallocene compound

In a 250 mL Schlenk flask dried in an oven, the ligand compound synthesized in Step 1 was dissolved in 4 equivalents of MTBE and 60 mL of toluene, and then 2 equivalents of n-BuLi nucleic acid solution was added thereto. After one day, all of the solvent inside the flask was removed under vacuum and dissolved in the same amount of toluene. One equivalent of ZrCl ₄ (THF) ₂ was taken in a glove box and placed in a 250 mL Schlenk flask to prepare a suspension in which luluene was added. After the above two flasks were incubated to −78 ^° C., the lithiated ligand compound was slowly added to the toluene suspension of ZrCl ₄ (THF) ₂ . After the injection, the reaction mixture was slowly raised to room temperature, stirred for one day to proceed with the reaction, and then removed by vacuum vacuum to about 1/5 of the volume of toluene in the mixture, and the nucleic acid of about 5 times the volume of the remaining Recrystallization was added. Filter the mixture to avoid contact with outside air 61

 SI

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T80ClO / SlOZaM / X3d 6 ^ SC60 / 910Z OAV Add 2,713 g (10 mmol) of (6-tert-butoxyhexyl) dichloro (methyl) silane) and 30 mL of nucleic acid, and measure to -78 ^° C. To the mixture prepared above was added dropwise. The mixture was slowly warmed to room temperature and stirred for 24 hours. 50 mL of water was added thereto to quench the organic layer, and the organic layer was separated and dried over MgSO _4. As a result, 3.882 g (9.013 mmol, 90%) of the product was obtained.

 NMR criteria purity (wt%) = l 00%, Mw = 430.70

1 H NMR (500 MHz, CDC1 ₃ ): -0.45, -0.22, -0.07, 0.54 (total 3H, s), 0.87 (1H, m), 1.13 (9H, m), 1.16-1.46 (10H, m), 3.25 (2H, m), 3.57 (1H, m), 6.75, 6.85, 6.90, 7.11 _: 7.12, 7.19 (total 4H, m), 7.22-7.45 (4H, m), 7.48-7.51 (4H, m) steps 2) Preparation of Metallocene Compounds

In a 250 mL Schlenk flask dried in Aubonne, the ligand compound synthesized in Step 1 was added, and dissolved in 4 equivalents of MTBE and 60 mL of toluene. 2.1 equivalent n-BuLi nucleic acid solution was added thereto, lithiated for 24 hours, and then all the solvents were removed by vacuum depressurization. This was obtained only Li-salt through the schlenk filter in a nucleic acid solvent (3.092 g, 6.987 mmol). Purification was carried out to obtain a more pure catalyst precursor. 2.1 equivalents of ZrCl ₄ (THF) ₂ was taken in a glove box, placed in a 250 mL Schlenk flask, and suluene was added to prepare a suspension. After both flasks were cooled down to -78 ^° C, the lithiated ligand compound was slowly added to the toluene suspension of ZrCl ₄ (THF) ₂ . The mixture was slowly warmed to room temperature and stirred for one day, after which the toluene in the mixture was removed through vacuum decompression and recrystallized by addition of a volume of nucleic acid of the previous solvent. The prepared nucleic acid slurry was filtered under argon, and the filtered solid and the filtrate were both evaporated under vacuum reduced pressure. The remaining filter cake (filter cake) and filtrate were confirmed through NMR, respectively, and weighed in a glove box to confirm the yield and purity.

 1.321 g (2.806 mmol, 40.2%) of yellow oil was obtained from 3.1 g (6.987 mmol) of the ligand compound and stored as a toluene solution (0.3371 mmol / mg).

NMR criteria purity (wt%) = 100%, Mw: 605.85 NMR (500 MHz, CDC1 ₃ ): 0.88 (3H, m), 1.15 (9H, m), 1.17-1.47 (10H, m), 1.53 (4H, d), 1.63 (3H, m), 1.81 (1H , m), 6.12 (2H, m), 7.15 (2H, m), 7.22-7.59 (8H, m)

 Step 1) Preparation of Ligand Compound

 In a dried 250 mL Schlenk flask

Add 5.25 g (23.6 mmol) of 2- (6-tert-butoxynucleosil) cyclopenta-1,3-diene (2- (6-tert-butoxyhexyl) cydopenta-l, 3- diene) and add 50 mL of methanol and acetone. 4 mL was added and then cooled to 0 ^° C. 2.95 mL (1.5 equivalents) of pyridine was added dropwise thereto, and then slowly warmed to room temperature and stirred for 7 hours. 50 mL of water was added thereto, quenched, and the organic layer was separated and dried over MgS0 ₄ . As a result, 2- (6-tert-butoxynuxyl) -5- (propane-2-ylidene) cyclopenta-1,3-diene (2- (6-tert-butoxy hexyl) -5- (propaan- It was confirmed by NMR that 5.0 g (19.07 mmol, 80.7%) of 2-ylidene) cyclopenta-l, 3-diene) was produced, which was dissolved in ether.

 In another dried 250 mL Schlenk flask

2.784 g (10 mmol) of 2,7-di-tert-butyl-9H-fluorene was added to make argon, and 50 mL of ether was removed under reduced pressure. Put melted. The solution was stirred at 0 ^° C and then 4.8 mL (12 mmol) of 2.5M n-BuLi nucleic acid solution was added dropwise, and the temperature was raised to room temperature, followed by stirring for one day. The solution was added dropwise to an ether solution of 2- (6-tert-subspecification) -5- (propane-2-ylidene) cyclopenta-1,3-diene, prepared before, and stirred for one day. 50 mL of water was added thereto, quenched, the organic layer was separated, dried over MgS0 ₄ , and filtered to obtain a pure solution. The solution was evaporated under vacuum reduced pressure to give 5.0 g (9.36 mmol, 93.6%) of oil. NMR criteria purity (wt%) = l 00%, Mw = 540. ⁸ 6

NMR (500 MHz, CDC1 ₃ ): 0.87 (IH, m), 0.99 (6H, m), 1.19 (9H, s), 1.30 (11H, s), 1.41 (11, s), 1.51-1.67 (5H , m), 3.00, 3.13 (IH, s), 3.35 (2H, m), 3.87, 4.05, 4.09, 4.11 (IH, s), 5.72, 5.97, 6.14, 6.61 (3H, s), 7.28 (IH, m), 7.35 (IH, m), 7.42 (IH, m), 7.58 (2H, m), 7.69 (2H, d) step 2) Preparation of metallocene compound

In a 250 mL Schlenk flask dried in an oven, the ligand compound synthesized in Step 1 was dissolved in 4 equivalents of MTBE and toluene, and 2.1 equivalents of n-BuLi hexane solution was added thereto, followed by lithiation for 24 hours. 2.1 equivalents of ZrCl ₄ (THF) ₂ was taken in a glove box, placed in a 250 mL Schlenk flask, and ether was added to prepare a suspension. After both flasks were cooled down to -78 ^° C, the lithiated ligand compound was slowly added to the suspension of ZrCl ₄ (THF) ₂ . The mixture was slowly warmed to room temperature and stirred for one day, after which the ether in the mixture was removed to about 1/5 volume by vacuum decompression and recrystallized by adding 5 times the volume of nucleic acid of the remaining solvent. The prepared nucleic acid slurry was filtered under argon, and the filtered solid and the filtrate were both evaporated under vacuum reduced pressure. The remaining filter cake (filter cake) and filtrate were confirmed through NMR, respectively, and weighed in a glove box to confirm the yield and purity. 4.4 g (6.3 mmol, 67.4%) of a brown solid were obtained from 5.1 g (9.4 mmol) of ligand compounds.

 NMR standard purity (wt%) = l 00%, Mw: 700.98

1 H NMR (500 MHz, CDC1 ₃ ): 1.17 (9H, s), 1.23-1.26 (6H, m), 1.27 (12H, s), 1.38 (6H, s), 1.40-1.44 (4H, m), 2.33 (3H, s), 2.36 (3H, s), 3.33 (2H, t), 5.31 (IH, m), 5.54 (IH, m), 5.95 (IH, m), 7.39 (IH, m), 7.58 ( 2H, m), 7.62 (IH, m), 7.70 (IH, s), 8.00 (lH, t) Synthesis Example 2-4

 Step 1) Preparation of Ligand Compound

1.162 g (10 mmol) of indene was added to a 250 mL Schlenk flask (first flask) dried under argon, and dissolved in a co-solvent of 5 mL of ether and 40 mL of nucleic acid. The solution was cooled to 0 ^° C. and then 4.8 mL (12 mmol) of 2.5 M n-BuLi nucleic acid solution was added dropwise. The mixture was slowly warmed to room temperature and stirred for one day. In another 250 mL Schlenk flask (a second flask) ^{(6-tert-appendix} when hexyl) dichloro (methyl) silane ((6-tert-butoxyhexyl) dichloro (methyl) silane) 2.713 g (10 mmol) and the nucleic acids 100 mL Put-cooled to ⁷ 8 ^° C, and then a mixture of 1 flask prepared above was added dropwise.

Another dried 250 mL Schlenk flask (third flask) was added 2.063 g (10 mmol) of 2-methyl- ⁴ -phenyl indene and dissolved in 40 mL of ether. After cooling the solution to 0 ^° C. 4.8 mL (12 mmol) of 2.5 M n-BuLi nucleic acid solution was added dropwise. The mixture was slowly warmed to room temperature and stirred for one day. 0.1 mol% of copper cyanide was added dropwise thereto, followed by stirring for 1 hour. The mixture was placed in the previous second flask and stirred for one day. 50 mL of water was added thereto, followed by quenching, work-up with ether, an organic layer separated, and dried over MgS <. As a result, 5.53 g (10.61 mmol, 106.1%) of the product was obtained as a brown oil.

 NMR standard purity (wt%) = 100%, Mw: 520.82

NMR (500 MHz, CDC1 ₃ ): -0.44, -0.36, -0.28, -0.19, 0.09-0.031 (total 3H, m), 0.84 (IH, m), 1.09 (9H, s), 1.23-1.47 ( 10H, m), 2.14 (3H, s), 3.25 (2H, m), 3.45 (2H.m), 6.38, 6.53, 6.88, 6.92 (total 2H, m), 6.93 (IH, m), 7.11-7.24 (2H, m), 7.28-7.32 (3H, m), 7.35 (2H, m), 7.44 (3H, m), 7.53 (2H, m) Step 2) Preparation of Metallocene Compound

In a 250 mL Schlenk flask dried in an oven, the ligand compound synthesized in Step 1 was dissolved in 4 equivalents of MTBE and toluene, and 2.1 equivalents of n-BuLi solution was added thereto, followed by lithiation for 24 hours. 2.1 equivalents of ZrCl ₄ (THF) ₂ was taken in a glove box, placed in a 250 mL Schlenk flask, and ether was added to prepare a suspension. After both flasks were cooled down to -78 ^° C, the lithiated ligand compound was slowly added to the suspension of ZrCl ₄ (THF) ₂ . The mixture was slowly warmed to room temperature, stirred for one day, vacuum reduced and the toluene solution was filtered under argon to remove LiCl, a filtered solid filter cake. The filtrate was vacuum-reduced to remove toluene and recrystallized by adding about the same amount of pentane as the previous solvent. The prepared pentane slurry * was filtered under argon, and the filtered solid and the filtrate were both evaporated under vacuum reduced pressure. The remaining filter cake (filter cake) and filtrate were confirmed through NMR, respectively, and weighed in a glove box to confirm the yield and purity. As a result, 3.15 g (4.63 mmol, 46.3%) of orange solids were obtained.

 NMR criteria purity (wt%) = l 00%, Mw: 680.93

NMR (500 MHz, CDC1 ₃ ): 0.01 (3H, s), 0.89 (3H, m), 1.19 (9H, s), 1.26-1.33 (6H, m), 1.50 (4H, m), 2.06, 2.15 , 2.36 (total 3H, m), 3.35 (2H, m), 3.66 (1H, s), 6.11-6.99 (3H, s), 7.13-7.17 (2H, m), 7.36-7.68 (10H, m) Example 2-5

itert-Bu-0- (: H ₂ V) MeSi (9-C Hg) ₂ ZrCl ₂

 1) Preparation of Ligand Compound

1.0 mole of a Grignard reagent tert-Bu-0- (CH ₂ ) ₆ MgCl solution was obtained from the reaction between the tert-Bu-0- (CH ₂ ) ₆ Cl compound and Mg (0) in THF solvent. The Grignard compound prepared above was added to a polar flask containing MeSiCl ₃ compound (176.1 mL, 1.5 mol) and THF (2.0 mL) at −30 ^° C., stirred at room temperature for 8 hours or more, and filtered. Was dried in vacuo to give a compound of tert-Bu-0- (CH ₂ ) ₆ SiMeCl ₂ (yield 92%). Add fluorene (3.33 g, 20 mmol), nucleic acid (100 mL) and MTBE (methyl tert-butyl ether, 1.2 mL, 10 mmol) at -20 ^° C, and add 8 ml of n-BuLi (2.5 M). in Hexane) was slowly added and stirred at room temperature for 6 hours. After the agitation was terminated, the reactor temperature was changed to -30 ^° C and the solution of tert-Bu-0- (CH ₂ ) ₆ SiMeCl2 (2.7 g, 10 mmol) dissolved in nucleic acid (100 ml) at -30 ^° C. To the above prepared fluorenyl lithium solution was slowly added over 1 hour. After stirring at room temperature for at least 8 hours, water was added for extraction, and evaporated.

(tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-C ₁₃ H ₁₀ ) ₂ compound was obtained (5.3 g, yield 100%). The structure of the ligand was confirmed by 1 H-NMR.

1 H NMR (500 MHz, CDC1 ₃ ): -0.35 (MeSi, 3H, s), 0.26 (Si-CH ₂ , 2H, m), 0.58

(CH ₂ , 2H, m), 0.95 (CH ₂ , 4H, m), 1.17 (tert-BuO, 9H, s), 1.29 (CH ₂ , 2H, m), 3.21 (tert-BuO-CH ₂ , 2H , t), 4.10 (Flu-9H, 2H, s), 7.25 (Flu-H, 4H, m), 7.35 (Flu-H, 4H, m), 7.40 (Flu-H, 4H, m), 7.85 ( Flu-H, 4H, d). 2) Preparation of Metallocene Compounds

4.8 ml of n-BuLi (20 mL) in (tert-Bu-O- (CH ₂ ) ₆ ) MeSi (9-Ci ₃ H ₁₀ ) ₂ (3.18 g, 6 mmol) / MTBE (20 mL) at -20 ^° C 2.5M in Hexane) was added slowly and reacted for at least 8 hours while raising the temperature to room temperature. Then, the prepared dilithium salts slurry solution was prepared at -20 ^° C. ZrCl ₄ (THF) ₂ (2.26 g, 6 mmol) Slowly add to slurry solution of nucleic acid (20 mL) and at room temperature for 8 hours. More reaction. The precipitate was filtered and washed several times with nucleic acid to give (tert-Bu-0- (CH ₂ ) ₆ ) MeSi (9-C ₁₃ H ₉ ) ₂ ZrCl ₂ compound as a red solid (4.3 g, yield 94.5%). ).

 1 H NMR (500 MHz, C6D6): 1.15 (tert-BuO, 9H, s), 1.26 (MeSi, 3H, s), 1.58 (Si-CH2, 2H, m), 1.66 (CH2, 4H, m), 1.91 ( CH2, 4H, m), 3.32 (tert-BuO-CH2, 2H, t), 6.86 (Flu-H, 2H, t), 6.90 (Flu-H, 2H, t), 7.15 (Flu-H, 4H, m), 7.60 (Flu-H, 4H, dd), 7.64 (Flu-H, 2H, d), 7.77 (Flu-H, 2H, d) Synthesis Example 3

 tBu-O-rCH7½ (CH ^ SirC5 (CH 4) (tBu-N) TiCl7

50 g of Mg (s) was added to a 10 L recoil at room temperature, followed by 300 mL of THF. Added. After adding 0.5 g of I ₂ , the reactor temperature was maintained at 50 ^° C. After the reaction temperature was stabilized, 250 g of 6-t-butthoxyhexyl chloride was added to the reaction vessel at a rate of 5 mL / min using a feeding pump. The addition of 6-t-butoxynucleus chloride was observed to increase the reactor silver by 4-5 ^° C. The mixture was stirred for 12 hours while adding 6-t-butoxynuxyl chloride. After 12 hours, a black reaction solution was obtained. 2 mL of the resulting black solution was taken, water was added thereto, an organic layer was obtained, and 6-t-butoxynucleic acid (6-t-buthoxyhexane) was confirmed by 1 H-NMR. remind

It can be seen that the Gringanrd reaction proceeded well from 6-t-butoxynucleic acid. Thus, 6-t-butoxyhexyl magnesium chloride was synthesized.

500 g of MeSiCl ₃ and 1 L of THF were added to the reaction vessel, followed by cooling the reaction temperature to -20 ^° C. 560 g of the synthesized 6-t-butoxynuclear magnesium chloride was added to the reactor at a rate of 5 mL / min using a feeding pump. After the feeding of the Grignard reagent (feeding) was completed, the reactor was stirred for 12 hours while slowly lowering to room temperature. After 12 hours of reaction, white MgCl ₂ salt was produced. 4 L of nucleic acid was added to remove the salt through a labdori to obtain a filter solution. After adding the obtained filter solution to the reaction, the nucleic acid was removed at 70 ^° C to obtain a pale yellow liquid. The obtained liquid was confirmed to be a desired methyl (6-t-butoxy hexyl) dichlorosilane} compound through 1 H-NMR.

1 H-NMR (CDC1 ₃ ): 3.3 (t, 2H), 1,5 (m, 3H), 1.3 (m, 5H), 1.2 (s, 9H), 1.1 (m, 2H), 0.7 (s, 3H )

1.2 mol (150 g) of tetramethylcyclopentadiene and 2.4 L of THF were added to the reaction vessel and the reaction temperature was changed to -20 ^° C. _The reactor was added at a rate of 5 mL / min using _n- BuLi 480 mL feeding pump. After n-BuLi was added, the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature. After 12 hours of reaction, an equivalent of methyl (6-t-butoxy hexyl) dichlorosilane (326 g, 350 mL) was added quickly to the reactor. 12 hours while slowly raising the temperature to room temperature After stirring, the reaction mixture was cooled to 0 ^° C., and 2 equivalents of t—BuNH ₂ was added thereto. The reactor temperature was stirred for 12 hours while slowly warming to room temperature. After 12 hours of reaction, THF was removed and 4 L of nucleic acid was added to obtain a filter solution from which salts were removed through labdori. After adding the filter solution to the reactor again, the nucleic acid was removed at 70 ^° C to obtain a yellow solution. The yellow solution obtained was identified as methyl (6-t-butoxynucleosil) (tetramethyl CpH) t-butylaminosilane (Methyl (6-t-buthoxyhexyl) (tetramethylCpH) t-Butylaminosilane) compound by 1 H-NMR. .

TiCl ₃ (THF) ₃ (10) to the dilithium salt of -78 ^° C ligand synthesized in THF solution from n-BuLi and ligand dimethyl (tetramethyl CpH) t-butylaminesilane (Dimethyl (tetramethylCpH) t-Butylaminosilane) mmol) was added rapidly. The semi-aqueous solution was slowly stirred at -78 ^° C for room temperature for 12 hours. After stirring for 12 hours, an equivalent amount of PK¾ (10 mmol) was added to the semi-aqueous solution at room temperature, followed by stirring for 12 hours. After stirring for 12 hours, a dark black solution was obtained. After removing THF from the resulting semi-aqueous solution, nucleic acid was added to filter the product. After removing the nucleic acid from the resulting filter solution, the desired ([methyl (6-t-buthoxyhexyl) silyl 5-tetramethylCp) (t-But ^^

(tBu-0- (CH ₂ ) ₆ ) (CH ₃ ) Si (C ₅ (CH ₃ ) ₄ ) (tBu-N) TiCl ₂ .

1 H-NMR (CDC1 ₃ ): 3.3 (s, 4H), 2.2 (s, 6H), 2.1 (s, 6H), 1.8 to 0.8 (m), 1.4 (s, 9H), 1.2 (s, 9H), Preparation of 0.7 (s, 3H) common supported catalyst

 Preparation Example 1

2.0 kg of toluene solution was added to a 20 L sus high-pressure reactor, and 1,000 g of silica (SP2412, manufactured by Grace Davison) was added, followed by stirring while raising the reaction temperature to 40 ^° C. 30 wt% methylaluminoxane (MAO) / 2.8 kg of toluene solution (Albemarle) was added, and the temperature was reduced to 70 ^° C., followed by stirring at 200 rpm for 12 hours. After the reactor temperature was lowered to 40 ^° C., the stirring was stopped and settled for 10 minutes, followed by decantation of the reaction solution.

2.0 kg of toluene was added to the reactor, and 30 g of the compound of Synthesis Example 1 and 1,000 mL solution was added to the reactor and heated to 85 ^° C., followed by stirring for 90 minutes. After the reactor temperature was lowered to 40 ^° C., stirring was stopped and Serering for 30 minutes followed by decantation of the reaction solution. 2.0 kg of nucleic acid was added to the reaction vessel, decanted, and dried at 80 ^° C. for 3 hours.

3.0 kg of toluene was added to the reactor, 50 g of the compound of Synthesis Example 2-4 and 1,000 mL of toluene were added to the reactor, and the mixture was stirred at 40 ^° C. for 90 minutes. After the reactor temperature was lowered to room temperature, the stirring was stopped, the serration was performed for 30 minutes, and the reaction solution was decanted. 3.0 kg of nucleic acid was added to the reactor, the nucleic acid slurry solution was transferred to a 20L filter dryer, and the nucleic acid solution was filtered. Dried under reduced pressure at 50 ^° C. for 4 hours to prepare a 1.50 kg-SiO ₂ common supported catalyst. Preparation Example 2

2.0 kg of toluene solution was added to a 20 L sus high-pressure reactor, 1,050 g of silica (SP2412, manufactured by Grace Davison) was added, followed by stirring while raising the reactor temperature to 40 ^° C. 3.3 kg of 30 wt% methylaluminoxane (MAO) / luene solution (Albemarle) was added thereto, and the temperature was reduced to 70 ^° C., followed by stirring at 200 rpm for 6 hours. After the reaction was lowered to 40, the agitation was stopped and the reaction solution was decanted after 10 minutes of sterilization. 2.0 kg of toluene was added to the reactor, the mixture was stirred for 10 minutes, the stirring was stopped, the separator was stirred for 10 minutes, and the reaction solution was decanted.

1,000 mL of toluene, 33 g of the compound of Synthesis Example 2-3 and 25 g of the compound of Synthesis Example 1 were added to a 2,000 mL schlenk flask, and the mixture was stirred at room temperature for 30 minutes. 2.0 kg of toluene was added to the reactor, and the prepared Schlenk flask reaction solution was introduced into the reactor, heated to 85 ^° C., and stirred for 90 minutes. After the reactor temperature was lowered to 40 ^° C., stirring was stopped and serration was carried out for 30 minutes, followed by decantation of the reaction solution.

2.0 kg of nucleic acid was added to the reaction vessel and decanted, followed by drying at 80 ° C. for 3 hours. 3.0 kg of toluene was added to the reactor, 20 g of the compound of Synthesis Example 2-1 and 1,000 mL of toluene solution were added to the reactor, and the mixture was heated at 40 ^° C. for 90 minutes. Stirred.

After the reactor was lowered to room temperature, the stirring was stopped, the serration was performed for 30 minutes, and the reaction solution was decanted. 3.0 kg of nucleic acid was added to the reaction vessel, the nucleic acid slurry solution was transferred to a 20L filter dryer, and the nucleic acid solution was filtered. Drying under reduced pressure at 50 ^° C for 4 hours to prepare a 1.55 kg-Si ⁽ hybrid supported catalyst. Comparative Preparation Example 1

3.0 kg of toluene solution was added to a 20 L sus high-pressure reactor, 1,200 g of silica (SP2412, manufactured by Grace Davison) was added, followed by stirring while raising the reactor temperature to 40 ^° C. After dispersing the silica in 60 minutes, 7.5 kg of 10 wt% methylaluminoxane (MAO) / luene solution was added thereto, the temperature was raised to 80 ^° C., and the mixture was stirred at 200 rpm for 12 hours. After the reaction temperature was lowered to 40 ^° C. again, the stirring was stopped and the reaction solution was decanted after being settled for 60 minutes. 3.0 kg of toluene was added and stirred for 10 minutes, after which the stirring was stopped, serling for 60 minutes and the toluene solution was decanted. 2.0 kg of toluene was added to the reactor, a solution was prepared by putting 33.2 g of the compound of Synthesis Example 2-5 and 1,500 mL of toluene into a flask to prepare a solution, and sonication was performed for 30 minutes. The compound / toluene solution of Synthesis Example 2-5 thus prepared was added to the reactor and stirred at 200 rpm for 90 minutes. Agitation was stopped and serration for 60 minutes followed by decantation of the reaction solution. 2.0 kg of toluene was added to the reactor, a solution was prepared by placing a flask of Compound 5 of Synthesis Example 2-1 and 1,500 mL of toluene in a flask to prepare a solution for 30 minutes. Thus prepared compound / toluene solution of Synthesis Example 2-1 to the reactor and stirred for 90 minutes at 200 rpm. Stirring was steamed and serling for 60 minutes before the reaction solution was decanted.

2.0 kg of toluene was added to the reactor, a solution was prepared by placing 36.7 g of the compound of Synthesis Example 3 and 500 mL of toluene in a flask to prepare a solution, and sonication was performed for 30 minutes. The compound / toluene solution of Synthesis Example 3 prepared as described above was added to the reactor and stirred for 90 minutes at 200 rpm. After lowering the reaction temperature to room temperature Agitation was stopped and serering for 60 minutes followed by decantation of the reaction solution. 2.0 kg of toluene was added to the reactor and the mixture was stirred for 10 minutes. Then, the stirring was stopped, and Serering was performed for 60 minutes, and the toluene solution was decanted.

3.0 kg of nucleic acid was added to the reactor, the nucleic acid slurry was transferred to a filter dryer, and the nucleic acid solution was filtered. Dried under reduced pressure at 50 ^° C. for 4 hours to prepare l, 130g-SiO ₂ common supported catalyst. Comparative Production Example 2

3.0 kg of toluene solution was added to a 20 L sus high-pressure reactor, 1,200 g of silica (SP2412, manufactured by Grace Davison) was added, followed by stirring while raising the reactor temperature to 40 ^° C. After the silica was sufficiently dispersed for 60 minutes, 5 kg of 10 wt% methylaluminoxane (MAO) / luene solution was added thereto, the silver was raised to 80 ^° C., and stirred at 200 rpm for 12 hours. After the reaction temperature was lowered to 40 ^° C. again, the stirring was stopped and the reaction was destationed for 60 minutes, followed by decantation of the reaction solution. 3.0 kg of toluene was added and stirred for 10 minutes, after which the stirring was stopped, serling for 60 minutes, and the toluene solution was decanted. 2.0 kg of toluene was added to the reactor, a solution was prepared by putting 30.5 g of the compound of Synthesis Example 2-3 and 1500 mL of toluene in a flask to prepare a solution, and sonication was performed for 30 minutes. The compound / toluene solution of Synthesis Example 2-3 prepared as described above was added to the reactor and stirred for 90 minutes at 200 rpm. Agitation was stopped and serration for 60 minutes followed by decantation of the reaction solution. 2.0 kg of toluene was added to the reaction machine, a solution was prepared by placing a flask of Compound 1 (). 3 g of Synthesis Example 2-2 and 1,500 mL of toluene into a flask, followed by sonication for 30 minutes. The compound / toluene solution of Synthesis Example 2-2 thus prepared was added to the reactor and stirred for 90 minutes at 200 rpm. Agitation was stopped and serration for 60 minutes followed by decantation of the reaction solution. .

2.0 kg of toluene was added to the reaction machine, a solution was prepared by placing 36.7 g of the compound of Synthesis Example 3 and 500 mL of toluene in a flask to prepare a solution, and sonication was performed for 30 minutes. The compound / toluene solution of Synthesis Example 3 prepared as described above was added to the reaction vessel and stirred at 200 rpm for 90 minutes. After lowering the half-unggi temperature to silver Agitation was stopped and serering for 60 minutes followed by decantation of the reaction solution. 2.0 kg of toluene was added to the reactor and the mixture was stirred for 10 minutes. Then, the stirring was stopped, the serration was performed for 60 minutes, and the toluene solution was decanted.

3.0 kg of nucleic acid was added to the reaction vessel, the nucleic acid slurry was transferred to a filter dryer, and the nucleic acid solution was filtered. The reaction mixture was dried at 50 ^° C. under reduced pressure for 4 hours to prepare a supported catalyst for 850 g-SiO ₂ . Examples of leupine polymerization

 Example 1

Ethylene-1-nuxene copolymerization was carried out using a continuous polymerization reactor (volume 140L) which is an isobutane slurry loop process. The reaction velocity was operated at about 111 Ί / _8, ethylene, 1-hexene haeksen Ο hydrogen gas and comonomers needed for polymerization), it was successively added with a constant rate. The reaction pressure was 40 bar and the polymerization temperature was performed at 84 ^° C.

 Detailed polymerization conditions of Examples 1 to 6 are shown in Table 1 below, Comparative Examples 1 to 6.

Polymerization conditions of 3 are shown in Table 2, respectively. .

 Table 1

Example No. Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Catalyst Preparation Example 1 Preparation Example 1 Preparation Example 1 Preparation Example 1 Preparation Example 2 Preparation Example 2 Ethylene 25 25 25 25 22 22

Input quantity (kg / hr)

 1-N-Hexane 8.7 8.8 8.5 8.5 18.2 15.0 Input (wt%)

Hydrogen 25 28 35 36 20 11

Dosage (ppm)

Slurry density (g / L) 550 548 543 544 554 550 Catalyst activity 6.7 5.5 5.1 5.1 4.4 5.3 (kgPE / kgSi0 ₂ / hr)

Bulk 0.44 0.42 0.41 0.42 0.40 0.40 density (g / mL) Settling 60 49 48 49 53 50 efficiency (%)

Table 2

Comparative Example 4

 LGC's LUCENE SP330, a commercial mLLDPE prepared by slurry loop process polymerization, was prepared. Comparative Example 5

 LGC's LUCENE SP310, a commercial mLLDPE prepared by slurry loop process synthesis, was prepared. Comparative Example 6

 LG Chem's LUCENE SP510, a commercial mLLDPE prepared by slurry loop process polymerization, was prepared.

Experimental Example

The polymers obtained from Examples 1 to 6 and Comparative Examples 1 to 6 were then formed into a film by the following method, and the results of measuring the physical properties thereof were shown in Table 3, respectively. Table 4 shows.

 1) Density: ASTM 1505

2) Melt Flow Index (Ml, 2.16 kg / 10 min): Measurement Silver 190 ^° C, ASTM 1238

3) Melt Flow Index (Ml, 21.6 kg / 10min): Measurement Temperature 190 ^° C, ASTM 1238 4) Melt Strength: Capillary Rheometer (Gottfert)

The sample was connected to Rheotens of Rheo-tester 2000) and measured five times under the following conditions, and then the average value was taken.

Sample specification: Pellets were placed in a capillary die at a temperature of 190 ^° C., and melted for 5 minutes, and then the resin was constantly measured at a piston speed of 5 mm / s using rhetens.

 Capillary die Size: Lo / Do = l 5

 Distance from capillary die to rheothens wheel ： 80mm

Wheel acceleration: 12mm / s ²

5) Molecular weight, and molecular weight distribution: measurement temperature 160 ^° C, HT-GPC (Agilent

PL-GPC 220) was used to measure the number average molecular weight and the weight average molecular weight, and the molecular weight distribution was expressed as the ratio of the weight average molecular weight and the number average molecular weight.

6) Film forming conditions: Film forming was performed by using a film blowing method. Film-forming temperature is 100 to 200 ^° C, and BUR (blow up ratio) was set to 2.0 to 3.0.

 7) Haze (%): Measured according to ISO 13468 standard. At this time, the thickness of the specimen was 50 kPa, measured 10 times per specimen and the average value was taken.

Table 3

 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6

MI (g / 10min) 0.27 0.40 0.67 0.72 0.94 1.05 Density (g / cm ³ ) 0.926 0.927 0.927 0.927 0.921 0.921

MFRR 74 69 59 62 40 37

(MI _2I . ₆ / MI _{2. 16} )

Molecular Weight Distribution 3.04 3.09 3.02 3.18 2.82 2.78

Table 4

In addition, the relationship between the melt strength (MS) according to the melt flow index (Ml) and the molecular weight distribution according to the melt strength (MS) is shown in the graphs of the olefinic polymers of Examples and Comparative Examples.

 1 is a graph showing the relationship between the melt strength (MS) according to the melt flow index (Ml) of the Examples and Comparative Examples of the present invention.

 In FIG. 1, red round dots correspond to Examples 1 to 6, respectively, in turn, and black square dots correspond to Comparative Examples 1 to 6, respectively, in order. In addition, the red line (A) connects each point of the embodiments, the black line (B) connects each point of the comparative examples.

2 is a graph showing the relationship with the molecular weight distribution according to the melt strength (MS) according to the Examples and Comparative Examples of the present invention. In FIG. 2, red equilateral dots correspond to Examples 6, 3, 4, and 2, respectively, and black square dots sequentially correspond to Comparative Example 5, Comparative Example 4, and Comparative Example, respectively. Corresponds to 3 and Comparative Example 1. In addition, the red line (A) connects each point of the embodiments, the black line (B) connects each point of the comparative examples.

 Referring to Tables 3 to 4 and FIG. 1, the leulevine-based polymer according to the present invention satisfies the following Equation 1 in terms of the melt strength (MS) according to the melt flow index (Ml), but the olefinic polymer of the comparative example is I was not satisfied.

[Equation ^1]

 -32.0 * log MI + 75.2 <MS <-40.9 * log MI + 77.9

 In addition, referring to Tables 3 to 4 and Figure 2, the olefin polymer of the embodiment according to the present invention showed a characteristic that the molecular weight distribution (Mw / Mn) is all 4 or less when the melt strength (MS) is 70m N or more, The leupin-based polymer of the comparative example did not satisfy the relationship between this characteristic melt strength and molecular weight distribution.

Claims

[Claim] [Claim 1] An olefin polymer in which the melt flow index (Ml) and the melt strength (MS, melt strength) measured at 190 ° C and 2.16 kg load conditions according to ASTM D1238 satisfy the following formula 1. :

 [Equation 1]

 -32.0 * log MI + 75.2 <MS <-40.9 * log MI + 77.9

[Claim 2]

 The method of claim 1,

An olefinic polymer having a melt flow index (Ml) of 0.1 to 2 g / 10 min, measured at 190 ^° C., 2.16 kg loading conditions in accordance with ASTM D1238.

[Claim 3]

 According to claim 1,

Ellefin-based polymer having a melt flow rate ratio (MFRR, MI _21.6 / MI _2.16 ) measured at 190 ^° C. according to ASTM D1238 of 10 to 100.

[Claim 4]

 The method of claim 1,

 An olefinic polymer having a melt strength (MS) of 60 to 150 mN.

[Claim 5]

 According to claim 11,

 The olefin polymer whose molecular weight distribution (Mw / Mn) is 4 or less.

[Claim 6]

 The method of claim 1,

An olefinic polymer having a density of 0.910 to 0.950 g cc.

[Claim 7]

 The method of claim 1,

 Ethylene; And propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene,

A copolymer with at least one alpha olefin comonomer selected from the group consisting of 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-nuxadecene and 1-eicosene , Olefinic polymer.

[Claim 8]

 A film comprising the olefinic polymer of claim 1.

【Claim ⁹ 】

 The method of claim 8,

 Less than 20% of haze measured according to ISO 13468 standard at thickness 50 卿

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