WO2020091177A1 - Novel transition metal compound and method for preparaing polypropylene using same - Google Patents

Abstract

The present invention provides a novel transition metal compound having excellent catalytic activity and being useful for producing a polypropylene having a high impact strength, and a method for preparing polypropylene using same.

Description

 【Name of invention】

 New transition metal compound and manufacturing method of polypropylene using the same [Technical field]

 Mutual citation with relevant application (s)

 This application is filed on November 2, 2018, Korean Patent Application No. 2018-0133858, and

Claims the benefit of priority based on Korean Patent Application No. 2019-0069233 dated June 12, 2019, and all contents disclosed in the literature of the Korean patent application are included as part of this specification.

 The present invention relates to a novel transition metal compound and a method for producing polypropylene using the same.

 【Background technology】

 The olefin polymerization catalyst system can be classified into a Ziegler-Natta catalyst system and a metallocene catalyst system, and these two highly active catalyst systems have been developed to suit each characteristic. Since the Ziegler Natta catalyst is a multi-activation catalyst with multiple active sites, the molecular weight distribution of polymers produced using this is characterized by a wide molecular weight distribution, and the composition distribution of the comonomer is not uniform. There is a problem that there is a limit to securing desired properties.

 On the other hand, the metallocene catalyst is composed of a cocatalyst combination of a main catalyst mainly composed of a transition metal compound and an organometallic compound mainly composed of aluminum. Metallocene catalysts are homogeneous complex catalysts and are single-site catalysts. Accordingly, the polymer produced using the metallocene catalyst has a narrow molecular weight distribution and a uniform composition distribution of the comonomer. In addition, it is possible to change the stereoregularity, copolymerization properties, molecular weight, crystallinity, etc. of the polymer produced through modification of the ligand structure and the polymerization conditions in the metallocene catalyst.

 Recently, due to changes in environmental awareness, many products are pursuing a reduction in the generation of volatile organic compounds (V0C). However, in the case of the Ziegler-Natta catalyst U / N, which is mainly used for the production of impact polypropylene (impact PP), there is a problem of generating high V0C.

To solve this, manufacturing Impact PP using metallocene catalyst 2020/091177 1 »（： 1 ^ 1 {2019/007152

A method was proposed. In this case, it is possible to reduce the generation amount of the total volatile organic compound 070 compared to 1 / ^, but the impact strength of the produced polymer was low, so it was difficult to apply realistically.

 【Detailed explanation of the invention】

 【Technical tasks】

 Accordingly, it is an object of the present invention to provide a novel transition metal compound that exhibits excellent catalytic activity and is useful for the production of polypropylene having high impact strength, and a method for producing homo polypropylene using the same.

 【Technical Solution】

 Accordingly, according to an embodiment of the present invention, a transition metal compound represented by Chemical Formula 1 is provided:

 [Formula 1]

In Chemical Formula 1,

 Urine is carbon (or silicon ());

 Is a Group 4 transition metal;

01-20 is substituted with alkyl, or 01-20 alkyl or unsubstituted 0 _6-20 2020/091177 1 »（： 1 ^ 1 {2019/007152

Aryl;

Seedlings ² 0 ₆ alkyl substituted with 01-20 -20 aryl;

 ^ And are each independently 01-20 alkyl;

X ¹ and X ² are each independently halogen.

 In addition, according to another embodiment of the present invention, there is provided a catalyst composition comprising the transition metal compound.

 According to another embodiment of the invention, in the presence of the catalyst composition, comprising the step of polymerizing a propylene monomer by introducing hydrogen, provides a method for producing homo polypropylene.

 【Effects of the Invention】

The transition metal compound according to the invention is 361 years 0 02 - get the ^"structure of Symmetr ic, shows excellent catalytic activity when used as a polymerization catalyst for the production of polypropylene, it is possible to also improve the impact strength of the polypropylene is prepared . In addition, the transition metal compound can reduce 170 (:) generated in the production process of polypropylene.

 【The best form for carrying out the invention】

The terminology used herein is only used to describe exemplary embodiments and is not intended to limit the invention. Singular expressions include plural expressions unless the context clearly indicates otherwise. In the present specification, terms such as `` include <sup>1</sup> '', `` have '' or `` have '' are intended to designate the presence of a implemented feature, step, component, or combination thereof, and one or more other features. It should be understood that the existence or addition possibilities of the fields, steps, components, or combinations thereof are not excluded in advance.

 The invention can be applied to various changes and can have various forms, and thus, specific embodiments will be illustrated and described in detail below. However, this is not intended to limit the invention to a specific disclosure form, and it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the invention.

Hereinafter, the transition metal compound according to a specific embodiment of the invention, it 2020/091177 1 »（： 1 ^ 1 {2019/007152

A catalyst composition and a method for producing homo polypropylene using the same will be described.

 Specifically, the transition metal compound according to an embodiment of the present invention is represented by the following Chemical Formula 1:

 [Formula 1]

In Chemical Formula 1,

 Shows are carbon （0 or silicon （）;

 Is a Group 4 transition metal;

^ Is optionally substituted with alkyl, 01-20, or 01-20 alkyl or unsubstituted 0 _6-20 aryl;

^ Is 0 ₆ -20 aryl substituted with 01-20 alkyl;

^ And parent ⁴ are each independently 01-20 alkyl;

X ¹ and X ² are each independently halogen.

 In the present specification, unless otherwise specified, the following terms may be defined as follows.

In halogen,） is fluorine (, chlorine (□), bromine () or iodine (I) 2020/091177 1 »（： 1 ^ 1 {2019/007152

Can be.

The 01-20 alkyl group may be a straight chain, branched or cyclic alkyl group. Specifically, 0 _1-20 alkyl group is 0 _1-15 straight chain alkyl group; 0 _1-10 straight chain alkyl group; 0 _1-5 straight chain alkyl group; ₀₃ -20 branched or cyclic alkyl group; ₀₃ -15 branched or cyclic alkyl group; Or 0 _3-10 branched or cyclic alkyl. More specifically, （： 1_20 alkyl group is methyl group, ethyl group, 11-propyl group,

-Profile group, 11-butyl group, 0-butyl group, 16_butyl group, 11-pentyl group,

1½0-pentyl group or cyclonuclear group.

0 _2-20 alkenyl group may be a straight chain alkenyl, branched or cyclic Al. Specifically, 0 _2-20 0 _2-20 straight-chain alkenyl group an alkenyl group, an 0 _2-10 straight chain alkenyl, straight chain alkenyl groups 02-5, 0 _3-20 branched alkenyl, branched alkenyl groups ₀₃ -15 , 0 _3-10 branched alkenyl group, ¾- ₂₀ cyclic alkenyl group or (： _5-10 cyclic alkenyl group. More specifically, the alkenyl group of C2-20 may be an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, or a cyclonuclear group.

0 _6-30 aryl may mean an aromatic hydrocarbon between mono-, bi- or tri. Specifically, 0 _6-30 aryl may be a phenyl group, a naphthyl group or an anthracenyl group.

0 _{7-30 Alkylaryl} may mean a substituent in which one or more hydrogens of aryl are substituted by alkyl. Specifically, 0 _7-30 alkylaryl is methylphenyl, ethylphenyl, propylphenyl,

-Propylphenyl, 11-butylphenyl,

It may be a butyl phenyl or cyclohexyl phenyl.

0 _7-30 aryl may be the hydrogen of one or more alkyl substituents, by means a substituted aryl group. Specifically, 0 _7-30 arylalkyl may be a benzyl group, phenylpropyl or phenyl nucleus.

The transition metal compound of Formula 1, in the polymerization of polypropylene

While having a structure, it is possible to realize all the characteristics of each ligand of both indene structures.

It has a structure. Accordingly, since it has various characteristics of the two indene structural ligands or can selectively take advantage of it, it can exhibit better catalytic activity. In addition, the transition metal compound of Chemical Formula 1 is a bridge group connecting two indene structural ligands, and includes a divalent functional group A substituted with alkyl groups (R ³ and R ⁴ ) having 1 or more carbon atoms. Accordingly, the atomic size is increased, the available angle is increased, and it is possible to exhibit better catalytic activity due to easy access to monomers during polymer production.

In addition, in the transition metal compound of Chemical Formula 1, one of the two indene structural ligands is substituted with R ¹ at position 3, and the other ligand is replaced with methyl and R ² at positions 2 and 4, respectively. ， Two ligand structures are different and have an asymmetric structure. Accordingly, when manufacturing the polypropylene polymer, it is possible to exhibit an effect of lowering the melting point by controlling the tact ici ty in the molecular structure.

In addition, in the case of a ligand in which only position 3 is substituted, compared with the case where other positions are substituted, the polymer to be prepared may exhibit a narrower molecular weight distribution. Substituent R ¹ at position 3 is specifically, C ^ o or C _{3-1 ()} alkyl; Or Ci- ₂₀ or C ₆ 아릴 aryl substituted or unsubstituted with Ci- ₂ o alkyl. More specifically, the substituent is C _3-i o or C _4-i o straight-chain alkyl such as n-butyl and n-heptyl; Cs-io pulverized alkyl such as isopropyl, t-butyl, etc .; Phenyl; Or t- butylphenyl C _3, such as-may be a phenyl substituted by ₆ branched alkyl, it can exhibit a high catalytic activity than the above-described functional group.

 In the case of ligands in which positions 2 and 4 are substituted, position 2 is methyl,

Position 4 may be substituted with a functional group R ² , specifically C _6-20 aryl substituted with Ci- ₂₀ alkyl. In this way, the carbon at a specific position of the ligand may be substituted with the above-described functional groups, thereby exhibiting better catalytic activity by an inducting effect capable of supplying sufficient electrons. More specifically, R ² in formula (I) may be a phenyl group substituted with a C _3-6 branched alkyl, such as tert- butylphenyl, and the substitution position of C ₃ -6 branched alkyl group on the phenyl group, R ² It may be the 4th position corresponding to the position and the para position.

In addition, the transition metal compound of Chemical Formula 1 may include a Group 4 transition metal such as zirconium (Zr) or hafnium (Hf) as the center metal (M). 2020/091177 1 »（： 1/10 公 019/007152

Among these, when the transition metal compound contains zirconium (計) as the center metal, it has a higher affinity because it has more orbitals capable of accepting electrons, as compared to the case of other group 4 transition metals such as It can be combined with a monomer, and as a result, it can exhibit a better catalytic activity improvement effect.

In addition, in Chemical Formula 1, X ¹ and X ² may be each independently chloro.

In addition, in Chemical Formula 1, the show may be more specifically silicon (), and the substituents ^ and for the show are the same as each other in terms of improving the solubility by increasing solubility, and may be alkyl. Specifically, 0 _1-4 straight-chain alkyl, and more specifically, each may be a methyl group. Thus, by having the same alkyl group as each other as a substituent for the show of the bridge group, it is excellent in solubility in preparing the supported catalyst, and can exhibit improved loading reactivity.

 Representative examples of the transition metal compound of Formula 1 include compounds having the following structure:

2020/091177 1 »（： 1/10 公 019/007152

The transition metal compound of Chemical Formula 1 may be prepared by reacting a ligand compound of Chemical Formula 2 with a group 4 transition metal-containing halide:

 [Formula 2]

2020/091177 1 »(： 1 ^ 1 {2019/007152

In Formula 2 to ^ and shows are as defined above. Reaction Scheme 1 below shows a ligand compound used in the preparation of the transition metal compound according to an embodiment of the present invention, and a process for preparing the transition metal compound using the ligand compound. Scheme 1 below is only an example for illustrating the present invention, and the present invention is not limited thereto.

Referring to Scheme 1 below, in the transition metal compound of Formula 1 according to an embodiment of the present invention, the first indene compound (I) in which position 3 is substituted with a functional group of parent ¹ is butyl lithium (11 in 1 ! Ni), in the presence of an alkyl lithium, such as dimethyldichlorosilane, reacting with a bridge group providing compound (II), to prepare a bridge group bonded indene compound (III); The bridged bond-indene compound (III) is substituted with methyl and urine ² at positions 2 and 4, respectively, in the presence of alkyl lithium such as butylium (11 to 11 teeth) and (: 成) Reacting with the diindene compound (IV) to prepare the ligand compound (2) of Formula 2; and reacting the ligand compound (2) with a halide containing a Group 4 transition metal such as ¾ (： 1 ₄ ) , The step of preparing the transition metal compound (1) of Formula 1; may be prepared by a manufacturing method comprising a.

 [Scheme 1]

In Reaction Scheme 1, 1, ¹ to ¹ , X ¹ and X ² are as defined above, and X is a halogen group such as chloro.

 The reaction in each step may be performed by applying known reactions. For more detailed synthesis methods, reference may be made to the preparation examples described later.

The transition metal compound of Formula 1 is

Due to its structure, it is three-dimensionally regular and has a narrow molecular weight distribution, showing excellent impact strength. 2020/091177 1 »（： 1 ^ 1 {2019/007152

Polypropylene can be produced. In addition, the transition metal compound may reduce the amount of 170: generated in the polymer manufacturing process.

 Accordingly, according to another embodiment of the present invention, a catalyst composition comprising the above-described transition metal compound is provided.

 Specifically, the catalyst composition includes the transition metal compound of Formula 1 as a single catalyst. Accordingly, compared with the case of mixing and using two or more types of catalysts, the molecular weight distribution of the polymer to be produced is significantly narrowed, so that the strength characteristics can be improved.

 Further, in the catalyst composition, the transition metal compound may be used as a single component or may be used in the form of a supported catalyst supported on a carrier. When the transition metal compound is used in the form of a supported catalyst, it is possible to further improve the morphology and physical properties of the produced polypropylene, and can also be suitably used for slurry polymerization, bulk polymerization, and gas phase polymerization processes.

Specifically, as the carrier, a carrier having a hydroxy group, a silanol group, or a siloxane group having high reactivity on the surface may be used, and for this purpose, the surface may be modified by calcination (^ 1 (： 比 3 011)), or dried. It can be used in ^"the moisture is removed. For example, silica produced by calcining silica gel, silica dried at high temperature, silica-alumina, and silica-magnesia can be used, and these are typically ₂ 0, ¾ ¥ ₃ , 能 and ¾ 位 0 炯₃ ） _2, etc. It may contain oxide, carbonate, sulfate, and nitrate components.

When calcining or drying the carrier, the temperature may be 200 to 600, and 250 to 600

Can be. The calcination or drying temperature for the carrier is 200

If it is as low as below, there is a possibility that the moisture remaining on the carrier is too large and the surface moisture and the co-catalyst may react, and the co-catalyst loading rate may be relatively high due to the hydroxyl group present in excess. A positive cocatalyst is required. In addition, when the drying or calcination temperature is too high, in excess of 6001 :, the surface area decreases as the pores on the surface of the carrier are merged, and a lot of hydroxyl groups or silanol groups disappear on the surface. May decrease. 2020/091177 1 »（： 1 ^ 1 {2019/007152

The amount of hydroxy groups on the surface of the carrier can be controlled by the method and conditions of the carrier or drying conditions, such as temperature, time, vacuum or spray drying. If the amount of the hydroxy group is too low, there are fewer reaction sites with the cocatalyst, and if it is too large, it may be due to moisture other than the hydroxy group present on the surface of the carrier particle. In one example, the amount of hydroxy groups on the surface of the carrier may be 0. 1 to 10_01 八 or 0.5 to 5 0111101 / dragon.

 Among the above-mentioned carriers, in the case of silica produced by calcining silica, especially silica gel, since the transition metal compound is chemically bound to the silica carrier, there are almost no catalysts released from the carrier surface in the propylene polymerization process. As a result, when polypropylene is produced by slurry polymerization or gas phase polymerization, fouling between the walls of the reactor or polymer particles can be minimized.

In addition, if the transition metal compound is included in the catalyst composition in the form of a supported catalyst, the transition metal compound is per carrier weight, for example, based on 1 for silica, 10 11 11101 or more, or 30

Or more, and may be supported in a content range of 100 11101 or less, or 80 ^ 1 ^) 1 or less. When supported in the above content range, it shows an appropriate supported catalytic activity, which can be advantageous in terms of maintaining the activity of the catalyst and economical efficiency.

 In addition, the catalyst composition may further include a cocatalyst in terms of improving high activity and process stability, in addition to the transition metal compound and carrier. The cocatalyst may include one or more of the compounds represented by the following Chemical Formula 3, Chemical Formula 4 or Chemical Formula 5.

 [Formula 3]

_ [Show 1 (¾ ₁ ) -0] „ ₁ _

 In Chemical Formula 3,

May be the same or different, each independently halogen; 0 _1-20 hydrocarbon group; Or a hydrocarbon substituted with halogen;

 Is an integer of 2 or more;

[Formula 4] 2020/091177 1 »（： 1 ^ 1 {2019/007152

1 ⁽ ¾ ₂ ⁾ ₃

 In Chemical Formula 4,

2 may be the same or different from each other, and each independently halogen; 0 _1-20 hydrocarbon group; Or a halogen substituted _-20 hydrocarbon;

 Is aluminum or boron;

 [Formula 5]

田 レ] -or sash ⁺ [2¾] _

 In Chemical Formula 5,

 The seedling is a neutral or cationic Lewis base;

 Is a hydrogen atom;

 å is a group 13 element;

May be the same or different from each other, and each independently one or more hydrogen atoms are halogen, _{-2 ()} hydrocarbon, alkoxy or phenoxy substituted or unsubstituted, (： _{6-2 ()} aryl group or _{-2 ( )} .

 Examples of the compound represented by Formula 3 include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, or alkyl aluminoxane-based compounds such as butyl aluminoxane, any one or a mixture of two or more of which Can be used.

Further, examples of the compound represented by Chemical Formula 4 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri _ aluminum, tricyclopentyl aluminum, Tripentyl aluminum, triisopentyl aluminum, trinuclear aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, tri Ethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, and more specifically, may be selected from trimetal aluminum, triethyl aluminum, and triisobutyl aluminum. In addition, examples of the compound represented by the formula (5) is triethyl ammonium tetraphenyl boron, tributyl ammonium tetraphenyl boron, 2020/091177 1 »（： 1 ^ 1 {2019/007152

Trimethylammonium tetraphenylboron, tripropylammoniumtetraphenylboron, trimethylammoniumtetra (!)-Tolyl) boron, trimethylammoniumtetra (0,1) -dimethylphenyl) boron, tributylammoniumtetra (!) -Trifluoromethylphenyl) boron, Trimethylammonium tetra (I)-Trifluoromethylphenyl) boron,

Tributyl ammonium tetrapentafluorophenyl boron,

Diethylanilinium tetraphenylboron,

Diethylanilinium tetrapentafluorophenyl boron,

Diethylammonium tetrapentafluorophenylboron, triphenylphosphoniumtetraphenylboron, trimethylphosphoniumtetraphenylboron, triethylammoniumtetraphenylaluminum, tributylammoniumtetraphenylaluminum, trimethylammoniumtetraphenylaluminum, tri Propyl ammonium tetraphenyl aluminum, trimethyl ammonium tetra (tolyl) aluminum, tripropyl ammonium tetra (I) -tolyl) aluminum, triethyl ammonium tetra (0, 1) -dimethylphenyl) aluminum,

Tributyl ammonium tetra (trifluoromethylphenyl) aluminum,

Trimethylammonium tetra (trifluoromethylphenyl) aluminum. '

Tributylammonium tetrapentafluorophenylaluminum, _ diethylanilinium tetraphenylaluminum, _ diethylanilinium tetrapentafluorophenylaluminum,

Diethyl ammonium tetrapentafluorophenyl aluminum,

Triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammoniumtetra (I) -tolyl) boron, triethylammoniumtetra (0, V-dimethylphenyl) boron, tributylammoniumtetra （! ） -Trifluoromethylphenyl) boron, triphenylcarbonium tetra (I) -trifluoromethylphenyl) boron, or triphenylcarbonium tetrapentafluorophenyl boron, either or both The above mixture can be used.

Among the above cocatalysts, considering that it can exhibit better catalytic activity when used with the transition metal compound, the cocatalyst is a compound represented by Chemical Formula 3, more specifically 0 ₁ such as methylaluminoxane. _-20 may be an alkyl aluminoxane-based compound. The alkyl aluminoxane-based compound acts as a scavenger (61¾ d) of hydroxyl groups present on the surface of the carrier to catalyze 2020/091177 1 »（： 1 ^ 1 {2019/007152

It improves the activity and converts the halogen group of the catalyst precursor to a methyl group to promote chain growth during the polymerization of polypropylene.

 The cocatalyst may be supported in an amount of 8 ^ 01 or more, or 1011 ^ 01 or more, and 25 ^ 01 or less, or 20 ^ 01 or less based on the weight of carrier, for example, for silica 1. When included in the above-mentioned content range, it is possible to sufficiently obtain the effect of reducing the generation of fine powder together with the effect of improving the catalyst activity according to the use of the cocatalyst.

 In addition, the catalyst composition may further include an antistatic agent. As such an antistatic agent, specifically, an ethoxylated alkylamine represented by the following Chemical Formula 6 may be used, and in addition, any component known as an antistatic agent may be used without limitation. When the catalyst composition includes an antistatic agent, the generation of static electricity is suppressed in the polypropylene polymerization process, so that physical properties of the produced polypropylene can be further improved.

 [Formula 6]

!? ¾-（（¾ 抑₂ child） ₂

In the above formula (6), silver (may be _8-30 alkyl, and when ^ contains an alkyl group having a carbon number in the above range, it may exhibit a fine powder reducing effect through an excellent antistatic action without causing unpleasant odor.

More specifically, the ethoxylated alkyl amines or seedlings ⁷ in the formula (6) is a straight chain alkyl of ¾- _22, or (in: _{12 to 18} straight chain alkyl, or (: _13-15 straight-chain alkyl of one One of these compounds alone or a mixture of two or more may be used. Also, commercially available company 111ra 163 (manufactured by 0 炯) may be used.

 In addition, when an antistatic agent is further included, it may be included for 1 to 1¾, more specifically for 1 to 5 based on the carrier 10½.

In addition, when the catalyst composition includes both the above-described carrier, cocatalyst, and antistatic agent, the catalyst composition may include supporting a cocatalyst compound on a carrier, and supporting the transition metal compound on the carrier; And injecting an antistatic agent in a slurry state and heat-treating the carrier on which the cocatalyst and the transition metal compound are supported; and may be prepared by a manufacturing method. The supported catalyst having a structure determined according to the loading order is 2020/091177 1 »（： 1 ^ 1 {2019/007152

In addition to the higher catalytic activity in the production process of polypropylene, it can exhibit excellent process stability.

 Further, the catalyst composition may be used in a slurry (h) state in a solvent or in a diluted state depending on a polymerization method, or may be used in the form of a mud catalyst mixed with a mixture of oil and grease.

 When used in a slurry or in a diluted state in a solvent, the solvent is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for the polymerization process of propylene monomers, such as pentane, nucleic acid, heptane, nonane, decane, and Isomers and aromatic hydrocarbon solvents such as toluene and benzene, or hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene, and any one or a mixture of two or more thereof may be used. In this case, the catalyst composition may further include the above-described solvent, and a small amount of alkyl aluminum may be removed from the solvent before use to remove a small amount of water or air that can act as a catalyst poison.

 In addition, when a polymerization method such as continuous bulk polymerization is used, the catalyst composition may be used in the form of a mud catalyst mixed with a mixture of oil and grease. In this case, the amount of the volatile organic compound contained in the produced homo polypropylene can be further reduced compared to the case where it is dissolved or diluted in a solvent, and as a result, the odor resulting from the volatile organic compound is also reduced. I can do it.

 The catalyst composition having the above configuration can reduce the amount of mc generated during the production of homopolypropylene, and increase the impact strength.

 Accordingly, according to another embodiment of the present invention, a method for producing homo polypropylene using a catalyst composition comprising the transition metal compound of Chemical Formula 1, and a polypropylene prepared accordingly are provided.

 Specifically, the production method of the polypropylene includes the step of polymerizing a propylene monomer by introducing hydrogen in the presence of the catalyst composition comprising the transition metal compound of Formula 1 above.

In the production method of the homo polypropylene, the polymerization process is performed by contacting the catalyst composition and propylene under hydrogen gas. 2020/091177 1 »（： 1 ^ 1 {2019/007152

Can be.

 At this time, the hydrogen gas may be introduced in an amount of 50 to 700 µm based on the total weight of the propylene monomer. When hydrogen gas is used in the above-described content range, catalytic activity can be increased, and physical properties such as narrowing the molecular weight distribution of the produced polypropylene can be appropriately controlled to improve processability and increase strength characteristics. More specifically, the hydrogen gas is 70 抑! n or more, or 10¾)! L or more, and may be added in a content of 50 如 껜 1 or less, or 30¾） 抑 1 or less.

 The polymerization process may be performed by a continuous polymerization process, for example, a variety of polymerization processes known as polymerization reactions of olefin monomers such as a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization process, a slurry polymerization process or an emulsion polymerization process. Can be. In particular, a continuous bulk-slurry polymerization process may be preferable in terms of obtaining a uniform molecular weight distribution and commercial production of the product.

In addition, the polymerization reaction

Above, it can be carried out at a temperature of 1101: or less or 1001: or less, and further controlling pressure conditions,

Or more, or 30 1¾ 八: or more, 100 1¾ "011 ² or less, or

501¾ £ 八: Can be performed under the following pressure.

 In addition, a trialkyl aluminum such as triethyl aluminum may be selectively added during the reaction.

When moisture or impurities are present in the polymerization reactor, a part of the catalyst is decomposed ((16 （: 01111X） 3 ^ 1011). The above-described trialkyl aluminum is used to pre-exist the moisture contained in the reactor or the impurities or monomers. Since it plays the role of catching, it is possible to maximize the activity of the catalyst used in the production, and as a result, a homo polypropylene having excellent physical properties, particularly a narrow molecular weight distribution, can be produced more efficiently. Specifically, in the trialkyl aluminum, alkyl is as defined above, specifically, is alkyl, and more specifically, it may be a straight or branched chain alkyl of _-6 such as detyl, ethyl, isobutyl, and the like.

In addition, the trialkyl aluminum (standard) is the total amount of the propylene monomer With respect to the weight of 300 ppm or more, or 400 ppm or more, it may be added in a content of 600 ppm or less, or 450 ppm or less, and in the presence of trialkyl aluminum in this content range, homo polypropylene having excellent strength characteristics is superior to polymerization. It can be easily manufactured.

Homo polypropylene according to an embodiment of the invention produced by the above-described manufacturing method, may exhibit increased strength characteristics with excellent workability. Specifically, the homo polypropylene can exhibit excellent processability by exhibiting a low melting temperature (Tm) of 145 ° C or less, and accordingly, it is possible to lower the processing temperature during the processing process using the homo polypropylene, thereby reducing the effect of energy slicing ¹ . It can be obtained and blending is easy.

Meanwhile, in the present invention, the melting temperature or melting point can be determined immediately using a differential scanning calorimeter (DSC). Specifically, after increasing the temperature of the homo polypropylene to 200 ^° C,

It was maintained at that temperature for 5 minutes, and then, the temperature was lowered to 30 ^° C, and the temperature was increased again to measure the temperature at the top of the DSC (Di f ferent i al Scanning Calorimeter, TA) curve as the melting point. can do. At this time, the speed of the temperature rise and fall is 10 ^° C / min, respectively, the melting point is the result measured in the second temperature rise section.

 In addition, the homo polypropylene produced by the above production method has a high weight average molecular weight of 340,000 g / mol or more and a melt index of 7 g / 10 min or less (2.16 kg at 23 CTC according to ASTM D1238) under the conditions of inputting 100 ppm of hydrogen gas during polymerization. (Measured by load). Thus, it is possible to produce a wide range of grades by controlling the amount of hydrogen gas input.

In addition, the homo polypropylene produced by the above-described manufacturing method shows a narrow molecular weight distribution of 2.7 or less together with the above-mentioned melting temperature, melting index and weight average molecular weight. As a result, excellent stiffness and impact strength characteristics can be exhibited. Meanwhile, in the present invention, the weight average molecular weight (Mw) and molecular weight distribution (MWD) of the homo polypropylene can be measured using gel permeation chromatography (GPC), and MWD is the weight average molecular weight (Mw) and number. After measuring the average molecular weight (Mn), it can be determined by the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn). Specifically, it can be measured by using a Waters PL-GPC220 instrument using a Polymer Laboratories ies PLgel MIX-B 300mm length column. At this time, the evaluation temperature is 160 ^° C, 1,2,4 -trichlorobenzene is used as a solvent, and the flow rate is lmL / min. In addition, the sample is prepared at a concentration of lOmg / lOmL, and then supplied in an amount of 200 uL. The values of Mw and Mn are derived using an assay curve formed using polystyrene standards. At this time, the molecular weight of the polystyrene standard U / mol) was 2,000 / 10,000 / 30,000 / 70,000 / 200, 000/700, 000 / 2,000,000 / 4,000, 000/10, 000, 00◦.

 As described above, the homo polypropylene according to an embodiment of the present invention exhibits excellent melt processability when molding into various products such as various molded articles, as it has a low melting temperature and a melt index, and a narrow molecular weight distribution and a high weight average molecular weight. It can also exhibit improved mechanical properties such as high impact strength.

 Accordingly, according to another embodiment of the present invention, a molded article comprising the above-mentioned homo polypropylene is provided. The product can be prepared according to conventional methods, except for using the homo polypropylene of one embodiment described above. Hereinafter, preferred embodiments are presented to help understanding of the present invention. However, the following examples are only for illustrating the present invention, and the contents of the present invention are not limited by the following examples.

 <Production of transition metal compounds>

Preparation Example 1-1 2020/091177 1 »（： 1/10 公 019/007152

Step 1: Preparation of dimethylsilanediyl (3 -phenyl-1H-indene-1yl) (2 -methyl- 4- (4-tert-butylphenyl) -1H-indene)

3 -Phenyl-1H-indene (3-phenyl-lH-indene) 1 equivalent (leq) was dissolved in a mixed solution of toluene / THF (10/1 volume ratio, 0.5M), then n-BuLi at -25 ^° C ( 1.05eq) was slowly added dropwise, followed by stirring at room temperature for 3 hours. After dichlorodimethyl silane (Di chloro dimethyl Si lane) (1.05 eq) was added to the resulting reactant at -10 ^° C, the mixture was stirred overnight at room temperature to prepare a mono-Si solution. In another reactor, 2 -methyl- 4- (4-tert-butylphenyl) indene (2-Me_4- (4-tBuPh) Indene) (1 eq) was mixed with toluene / THF (5/1 volume ratio, 0.7M) After dissolving in, n-BuLi (1.05 eq) was slowly added dropwise at -25 ^° C, followed by stirring at room temperature for 3 hours. CuCN (2 mol%) was added to the resulting reaction mixture, and after stirring for 30 minutes, the mono-Si solution was added thereto. Thereafter, the mixture was stirred overnight at room temperature, worked-up with water, and dried to obtain a ligand. Step 2: Preparation of dimethylsilanediyl (3 -phenyl-1H-indene-1yl) (2 -methyl- 4- (4-tert-butylphenyl) -1H-indene-1yl) zirconium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene / diethyl ether (2/1 volume ratio, 0.53M) and n-BuLi (2.05eq) was added at -25 ^° C. 2020/091177 1 »（： 1/10 公 019/007152

Then, the mixture was stirred at room temperature for 5 hours. For the resulting reactant, in a separate flask

(Slurry prepared by mixing 1 root in toluene (0.17 則)-

After adding at 25, the mixture was stirred overnight at room temperature.

 When the reaction is completed, the solvent is vacuum dried, dichloromethane 0X1) is re-injected, the needle (： 1 is removed through a filter), and the filtrate is vacuum dried.

1X1 / nucleic acid was added to recrystallize at room temperature. The resulting solid was then filtered and dried in vacuo to give the titled transition metal compound in the solid phase.

 ? 3 （10-large.: 7.72 （（1 （1, 2¾, 7.56 （6, 2¾, 7.5-6.7 （US, 12, 6.61 （1 \ ｛））, 6.07 （large））, 2.15 （3 ， 1.46 （ £, 3 ， 1.3 （child）, 1.07

In the same manner as in Production Example 1-1, except that 3-11-butyl-in-indene was used instead of 3 -phenyl-in_indene in Step 1 of Preparation Example 1-1, Dimethylsilanediyl (3-11 -butyl-in-indene-1 -yl) (2 -methyl-4

Butylphenyl) -in-inden-1-yl) zirconium dichloride was prepared. 2020/091177 1 »（： 1 ^ 1 {2019/007152

: 7.57 （（1, within）, 7.4-6.8 （1）, 6.61 （inside）, 5.67 （£, large）, 2.86 （1 ;, tae）, 2. 16 （3 ， 1.58 （2 ， 1.42, year ）, 1.33 （£,）, 1.4-1.2 （111, ¾）, 1.03 （， 310, 0.92 （b） ?? 111

In step 1 of Preparation Example 1-1, except that 3- 0 -propyl-vs_indene is used instead of 3 -phenyl-111-indene, the same method as in Preparation Example 1-1 is performed, Dimethylsilanediyl of the above structure (3- 0 -propyl-

1) (2 -methyl- 4- (4 hema 6 -butylphenyl)--inden-1 -yl) zirconium dichloride was prepared.

? ₃₆₁₁ （Urinary University 0: 7.58 （(1, within), 7.3-6.8 （this, 1011）, 6.6 （£, within), 5.69 （inside）, 2.41 （inside）, 1.42 （year）, 1.33 （to ）, 1.01 （Mt. Mountain）, 0.82

Preparation Example 1-4 2020/091177 1 »（： 1/10 公 019/007152

The same as in Production Example 1-1, except that 3- (4-1; -butylphenyl) -in_indene is used instead of 3-phenyl-in_indene in Step 1 of Preparation Example 1-1. Dimethylsilanediyl (3- (4-1; -butylphenyl) -in-inden- 1-day) (2 -methyl- 4- (4 ara butylphenyl) -in_inden-1 in the same way. -Sun) Zirconium dichloride was prepared.

? 3 (10-large.: 7.58 （（1, large）, 7.4-6.7 細, 1）, 6.72 （large）, 6. 12 （, 1.42 （year）, 1.33 （£, ■, 0.83 （£ , 1） ^ Production Example 1-5

2020/091177 1 »（： 1 ^ 1 {2019/007152

In Step 1 of Preparation Example 1-1, except for using 3-11-propyl-in-inden instead of 3 -phenyl-111-indene, in the same manner as in Preparation Example 1-1, Dimethylsilanediyl (3-11 -propyl- 111-inden-1 -yl) (2 -methyl- 4- (4a6 _butylphenyl) -in_indene-1yl) zirconium dichloride was prepared.

3611 （1 〔广 대。: 7.55 （line, within） ， 7.4-6.8 （, 1010 ， 6.60 （£, 111）, 5.65 （£, 1 \ ｛）, 2.21 （tae）, 2.16 ， year）, 1.42 ， Year), 1.33 細, within 1), 1.03 （£, 抑）, 0.92

Comparative Production Example 1-1

2020/091177 1 »（： 1/10 公 019/007152

Step 1: Preparation of dimethylsilanediyl (vs-inden-1-yl) (2-methyl- 4- (4a6-butylphenyl) _in_inden)

3-11-Butyl-in-inden (1 6 (1) was dissolved in a toluene / large mixed solution (10/1 volume ratio, 0.5 約), then 11 cold 11 ni (1.05 6 (1) was slowly added dropwise at -251: Then, the mixture was stirred at room temperature for 3 hours, and dichlorodimethylsilane (1.05 6 (1)) was added to the resulting reaction mixture at-° C, followed by stirring overnight at room temperature to prepare a L-solution. Methyl- 4- (4a6 _ butylphenyl) indene (2-1 (-4- (4-1;-8 ¾) 1 _{11 (} 16116) (1 6 (!) Toluene / 抑 mixed solution (5 / After dissolving in 1 volume ratio, 0.7¾1), 11-61111 (1.05 6 (!)) Was slowly added dropwise to -251: and stirred at room temperature for 3 hours. (： 1 £ (2 11101%)) After the addition and stirring for 30 minutes, the 1110110-solution prepared above was added thereto, followed by stirring overnight at room temperature, drying with 0 to -1 avoidance using water, and drying to obtain a ligand Step 2: Dimethylsil Randiyl (in-inden- 1 -yl) (2 -methyl- Preparation of 4- (4 6 -butylphenyl) -v_indene-1 -yl) zirconium dichloride

The ligand prepared above was dissolved in a mixed solution of toluene / diethyl ether (2/1 volume ratio, 0.53 cc), and then 11-11 teeth (2.05 roots) were added at -251: and stirred at room temperature for 5 hours. For the resultant reactant, a slurry prepared by mixing 社 (： 1 ₄ (1 6 (!) In toluene (0.17 ¾0) in a separate flask was added at -25, and stirred at room temperature overnight. When the reaction was completed, the solvent was vacuum dried, 1X1 was re-injected, and after removing the needle (: 1) through a filter, the filtrate was vacuum dried, and 1X1 / nucleic acid was added to recrystallize at room temperature. Thereafter, the resulting solid was filtered and dried in vacuo to obtain the titled transition metal compound in the solid phase.

 : 7.6-6.8 （1310 ， 6.2 （(1, within), 2.6, 2.5 （this, within）,

1.3 （child） ， 1.4 ， 1.3

Step 1: Preparation of 4- （4-tert-butylphenyl） -1H-indene）

7 -Bromo-: LH-Indene (1 eq), 4-t-Bu-Ph-B (0H) ₂ （1.2 eq）, Pd (PPh ₃ ) ₄ （5 mol%, 7-Bromo-1H- Indene leq standard) and Na ₂ C0 ₃ (2.5 eq) were put in a flask, toluene / Et0H / ¾0 (2 / l / l volume ratio, 0.3 M) was added and stirred at 80 ^° C for 12 hours. After work-up using water, it was dried and recrystallized using MeOH. Step 2: Preparation of dimethylsilanediyl (4- (4-tert-butylphenyl) -1H-indene-1yl) (2-methyl- 4- (4-tert-butylphenyl) -1H-indene) 2020/091177 1 »（： 1 ^ 1 {2019/007152

After dissolving 4- (4-卜 butylphenyl) -to-indene (1 6 (1)) prepared in the above in a mixed solution of toluene / 抑 (10/1 volume ratio, 0.5 ¾!), -251: to 11-811 The needle (1.05 6 <3) was slowly added dropwise and stirred at room temperature for 3 hours. Then, dichlorodimethylsilane (1.05 6 (!) Was added at -101: and stirred overnight at room temperature to prepare a 010110- ^ solution.

In a separate reactor

Mixing solution (5/1 volume ratio, dissolved in 0.7¾0, 11_ 加 니 (1.05 6 (1)) was slowly added dropwise at _25 ^° （：, and stirred at room temperature for 3 hours. To the resultant reactant, (： 1 £ (2 1%)) was added and stirred for 30 minutes, and then the 1 ^ 0110- ^ solution prepared above was added thereto. Then, stir overnight at room temperature and use water

After \ vork_up and drying, a ligand was obtained. Step 3: Dimethylsilanediyl (4- (4a6 _butylphenyl) -in-inden-1-yl) (2 -methyl- 4- (4 6-butylphenyl)-: in-inden-1-yl ） Preparation of zirconium dichloride

The ligand prepared above was dissolved in a toluene / diethyl ether mixed solution (2/1 volume ratio, 0.53¾0, and then _25

(2.05 6 （!） Rules were added and stirred at room temperature for 5 hours. For the resulting reactant, in a separate flask

Slurry prepared by mixing-

After injection, the mixture was stirred overnight at room temperature.

 When the reaction was completed, the solvent was vacuum dried, 1X1 was re-introduced, and after removing the knee through a filter, the filtrate was vacuum dried, and 1X1 / nucleic acid was added to recrystallize at room temperature. Then, the resulting solid was filtered and dried in vacuo to obtain the titled transition metal compound in the solid phase.

此-Large。: 7.6-6.7 細, 16 則, 5.91 （in the mountain）, 2. 11 （£,）, 1.25, 1.20 （example） ， 1.41 ， 1. 11 ， 310? 1 仰. Comparative Production Example 1-3 2020/091177 1 »（： 1/10 公 019/007152

Same as in Comparative Production Examples 1-2 except that 7-bromo-2-methyl-in-indene was used in Step 1 of Comparative Production Example 1-2 instead of 7-bromo-111-indene. It was carried out by the method to obtain dimethylsilanediylbis (2-methyl-4- (4a6 _ butylphenyl) -in-inden-1-yl) zirconium dichloride.

Appearance-large .: 7.64 （（1, 210, 7.57 （Year of Mountain））, 7.45 ， 4 ， 7.38 （山 2¾ ， 7. 11 （¾）, 7.0, 2¾, 2.25 （抑） ， 1.33

Comparative Production Example 1-4

Step 1: Preparation of 7- (4'-tert-butylphenyl) -2 -methyl- 1-indanon

7 -bromo-2 -methyl-1-indanone (1 eq), 4-tBu-Ph_B (0H) _{2 (} 1.2 eq),

Pd (PPh _{3) 4 (} 5 mol%) and Na ₂ C0 _{3 (} 2.5 eq) were added to the flask and mixed solution of toluene / Et0H / ¾0 (2/1/1 volume ratio, 0.3 was added and then 12 at 80 ° C) The mixture was stirred for hours, dried after work-up with water and recrystallized using MeOH Step 2: Preparation of 7- (4'-tert-butylphenyl) -1,2-dimethyl-1H-indene

Mg turnings (5 eq) were added to the flask, Et (5 M) was added, and a small amount of Mel was added. When the reflux was started by gradually raising the temperature of the resulting mixed solution, a solution in which Mel (5 eq) was dissolved in Et ₂ 0 (l M) was slowly added dropwise. After reacting for 1 hour, it was cooled to 0 ^° C.

In a separate flask, a solution in which 7- (4'-tert-butylphenyl) -2 -methyl-1-indanone (1 eq) was dissolved in Et ₂ 0 (0.8 M), the flask was cooled to 0 ^° C. Into the dropwise for 30 minutes. After stirring for 15 minutes, the temperature was gradually increased to room temperature, and 6 N HCK0.5 M) was added dropwise. After stirring for 30 minutes, extraction was performed with water and Et ₂ 0, the organic layer was dried, and recrystallized using MeOH to prepare 7- (4'-tert-butylphenyl) -1,2 -dimethyl-1H-indene. . Step 3: Dimethylsilanediyl (2.3 -dimethyl-1H-inden-1-yl) (2 -methyl-4- (4- 2020/091177 1 »(： 1 ^ 1 {2019/007152! ：-Butylphenyl) -in-inden)

After dissolving 2, 3 -dimethyl-in_indene (1 6 (!) In a toluene / 抑 mixed solution (10/1 volume ratio, 0.5 ¾0), for the resulting solution, -251: to 11 cold 11 ni (1.05 root After slowly adding dropwise, the mixture was stirred at room temperature for 3 hours. Subsequently, dichlorodimethylsilane (1.05 6 (1)) was added at -10 ^° (:), followed by stirring overnight at room temperature to prepare a 110-solution.

 After dissolving 2-1¾-4- (4 children 8; 11¾) ^ (16116 (1 6 (!)) In a toluene / dae mixture solution (5/1 volume ratio, 0 / ¾) in a separate reactor -251: to 11 The inner 11 teeth (1.05 6 (!)) Were slowly added dropwise, followed by stirring at room temperature for 3 hours only. After adding ⑶ (2 1%) to the resulting reactant and stirring for 30 minutes, a 110- ^ solution prepared above was added to the mixture. Thereafter, the mixture was stirred overnight at room temperature, \ vork-up with water, and dried to obtain a ligand. Step 4 ： Dimethylsilane diyl (2, 3-dimethyl-in-inden-1-yl) (2-methyl- 4- (4-la!:-Butylphenyl) -in_inden-1-yl) zirconium di Preparation of chloride

The ligand prepared above was dissolved in a toluene / diethyl ether mixed solution (2/1 volume ratio, 0.53¾0, and then added at -251: gani (about 2.05)) and stirred at room temperature for 5 hours. For the resulting reactant, （： 1 ₄ （1 明） in a separate flask toluene (0. The slurry produced by mixing in 17 ¾0 _

After injection, the mixture was stirred overnight at room temperature.

 When the reaction was completed, the solvent was vacuum dried, 1X1 was re-injected, and after removing the needle (： 1 through the filter, the filtrate was vacuum dried and recrystallized at room temperature by adding £ 01 / nucleic acid. Thereafter, the resulting solid was filtered and dried in vacuo to obtain the titled transition metal compound in the solid phase.

 De 如-large 。: 7.6-6.8 (in 111, 1), 6.36 (£, large), 2. 12, year), 1.94

（£,）, 1.69 （de, 311）, 1.33 （£, 911）, 1.32 （£, 610

Comparative Production Example 1-5 2020/091177 1 »（： 1/10 公 019/007152

 1-611 In Step 3 of Comparative Production Example 1-4, except that 2, 3 -dimethyl-4- (4-butylphenyl) -in_indene was used instead of 2, 3 -dimethyl-in-indene. By performing the same method as in Comparative Production Example 1-4, dimethylsilanediyl (2,3-dimethyl- 4- (4ara 卜 butylphenyl) -111-indene-1 -yl) (2 -methyl- 4- (4A-Butylphenyl) _ Dae-Inden-1-yl) Zirconium dichloride was prepared.

 ? 36 0-Large:: 7.67-6.99 細, 1st), 6.97 （inside）, 2.25 ， 3 ， 1.97 （£, 3 ， 1.67 （year）, 1.34 （to）, 1.33 （£, child）, 1.31 （ £, to)

Step 1 ： Preparation of dimethylsilanediyl bis (3-propyl-1H-indene) (Dimethylsi lanediyl bi s (3-propyl-lH-indene)

After dissolving 3-pr opy 1-1H-1 ndene (1 equiv) in Toluene / THF (10/1, 0.5 M), n-BuLi (1.05 eq) was slowly added dropwise at -25 ^° C, and then 3 at room temperature. Stir for hours. Subsequently, CuCN (2 mol%) was added, stirred for 30 minutes, and then dichlorodimethyl Si lane (0.5 eq) was added at -10 ^° C, followed by stirring overnight at room temperature. Then, after work-up with water and dried, a ligand was obtained. Step 2: Preparation of dimethylsilanediyl bis (3-propyl-inden-1-yl) zirconium dichloride (Dimethylsi lanediyl bi s- (3-propyl-inden-l-yl) zirconium dichlor ide)

The ligand was dissolved in Toluene / Ether (2/1, 0.53M) and n_ BuLi (2.05 eq) was added at -25 ^° C, followed by stirring at room temperature for 5 hours. ZrCU (1 eq) was added to Toluene (0.17 M) into the flask, and the mixture was stirred overnight at room temperature.

 When the reaction is completed, the solvent is vacuum dried and DCM is re-injected to remove LiCl through f i ter, etc., the filtrate is vacuum dried, and DCM / Hexane is added to recrystallize at room temperature. Then, the resulting solid was f i l ter and dried in vacuo to obtain a solid metallocene compound.

 Pseudo-rac: 7.41-7.32 (m, 抑), 7.21 (t, 2H); 6.17 (s, 2H), 2.01 (s, 4H), 1.41-1.33 (m, 4H), 1.09 (t, 6H), 1.03 (s, 6H) ppm

Comparative Production Example 1-7

Step 1: Dimethylsilanediyl (3-butyl-1H-indene-L-yl) (2-methyl-1H-indene) (Dimethyl si lanediyl (3-buty 卜 lH-inden-l-yl) (2-methy卜 lH-indene))

After dissolving 3-buty 1-1H-1 ndene (1 equiv) in Toluene / THF (10/1, 0.5 M), n-BuLi (1.05 eq) was slowly added dropwise at -25 ^° C, and then 3 hours at room temperature. While stirring. Subsequently, Di chloro dimethyl Si lane (1.05 eq) was added at -10 ^° C, followed by stirring overnight at room temperature. After 2-Me-l-H-Indene (1 eq) was dissolved in Toluene / THF (5/1, 0.7M) in another reactor, n-BuLi (1.05 eq) was slowly added dropwise at -25 ^° C, and then at room temperature. It was stirred for 3 hours. after

After adding CuCN (2 mol%) and stirring for 30 minutes, the first reactant, a mono-Si solution, was added. Thereafter, the mixture was stirred overnight at room temperature, worked-up with water, and dried to obtain a ligand. Step 2: Dimethylsilanediyl (3-butyl-1H-indene-1yl) (2-methyl-1H-indene-1yl) zirconium dichloride (Dimethylsi lanediyl (3-buty 1-1H ^to i nden- l ^~ y 1) Preparation of (2-methyl-lH-inde-l-yl) zirconium di chloride)

The ligand was dissolved in Toluene / Ether (2/1, 0.53M) and n_ BuLi (2.05 eq) was added at _25 ^° C, followed by stirring at room temperature for 5 hours. ZrC14 (1 eq) was added to Toluene (0.17 M) in a flask, and then stirred at room temperature overnight.

When the reaction is completed, the solvent is vacuum dried and DCM is re-injected to remove LiCl through fil ter, the filtrate is vacuum dried, and DCM / Hexane is added. 2020/091177 1 »（： 1 ^ 1 {2019/007152

Recrystallize at room temperature. Subsequently, the resulting solid was dried under vacuum to obtain a solid metallocene compound.

如-Large 。: 7.38-7.31 （111, E）, 7.21-7.23 細, Tae), 6.41 （large）, 6. 17 （inside）, 1.93 （1 :, 如）, 1.82 （3 ， 1.48-1.39 細， Printing） ， 1.32 ， 311）, 1.03

Comparative Production Example 1-8

In Step 1 of Preparation Example 1-1, 3-:!-Butyl-in-indene was used instead of 3 -phenyl-111-indene and 2 -methyl-4- (4a6 _butylphenyl) indene was used. Dimethylsilanediyl (3-butyl-111-inden-1-yl) (2) was carried out in the same manner as in Production Example 1-1, except that 2-methyl- 4-phenylindene was used. -Methyl- 4-phenyl-in-inden-1-yl) zirconium dichloride was prepared.

 Esan.-Large.: 7.58 （(1, within), 7.5-6.8 （US, 1] high), 6.61 （£, within), 5.68 （£, large), 2.86 （b）, 2. 18 ， 3 ， 1.59 細 ，）, 1.43 （3¾ ， 1.4-

1.2 （111, ¾）, 1.05 （£, year）, 0.93 （1 ;，

<Production of metallocene supported catalyst>

Preparation Example 2-1 Silica gel (SYL0P0L 952Xä, calcinated under 250 ^° C, lOOg) was placed in a 2L reactor under Ar, and 10% by weight of methylaluminoxane (766 mL of MA⑴ toluene solution (corresponding to 10 mmol per Si li ca lg) was slowly injected at room temperature. The mixture was stirred for 15 hours at 90 ^° C. After completion of the reaction, the mixture was cooled to room temperature and left to stand for 15 minutes to decant the solvent using cannula. 700 y mol of the transition metal compound prepared in Preparation Example 1-1 was dissolved in 400 mL of toluene, and then transferred to a reactor using cannula After stirring at 50 ^° C for 5 hours, cooled to room temperature and 15 The solvent was decanted by using cannula for 1 minute, 400 mL of toluene was added, stirred for 1 minute, and left for 15 minutes to decant the solvent using cannula twice. As a method, 400 mL of nucleic acid was added, stirred for 1 minute, left for 15 minutes to decant the solvent using cannula, and an antistatic agent (Atmer 163ä, 3 g manufactured by CR0DA) was dissolved in nucleic acid 400 and transferred to the reactor using cannula. The mixture was stirred for 20 minutes at room temperature and transferred to a glass filter to remove the solvent, primary drying under vacuum at room temperature for 5 hours, and secondary drying under vacuum for 4 hours at 45 ° C to obtain a supported catalyst. To 2-5, and Comparative Production Examples 2-1 to 2-8

Instead of the transition metal compound prepared in Preparation Example 1-1 ^· Preparation Example 1-

A metallocene supported catalyst was carried out in the same manner as in Production Example 2-1, except that each of the transition metal compounds prepared in 2 to 1-5 or Comparative Production Examples 1-1 to 1-8 was used respectively. Was prepared. <Production of homo polypropylene>

 Example 1

The 2 L stainless reactor was vacuum-dried at 65 ^° C., cooled, and 450 ppm of triethylaluminum (1M solut ion in Hexane) was added at room temperature, and 100 ppm of hydrogen gas was added, followed by 770 g of propylene. After stirring for 10 minutes, the metallocene supported catalyst prepared in Preparation Example 2-1 20 mg and Nucleic acid 20 was used to introduce the slurry into the reactor under nitrogen pressure. Then, the reactor temperature was gradually elevated to 70: 1, and then a polymerization process was performed for 1 hour. After completion of the reaction, unreacted propylene was vented. Examples 2 to 5, and Comparative Examples 1 to 8

 In Example 1, instead of the metallocene-supported catalyst of Production Example 2-1, the metallocene-supported catalysts of Production Examples 2-2 to 2-5 or Comparative Production Examples 2-1 to 2-8 were used. Homopolypropylene was prepared by performing the same method as in Example 1 except for the above. Test Example 1

 In addition to the activity of the metallocene supported catalyst used in Examples and Comparative Examples, physical properties were evaluated in the following manner for the produced homo polypropylene. The results are shown in Table 1 below.

 (1) Activity (Act ivi ty, kg PP / g cat hr): It was calculated as the ratio of the weight of the produced polymer (kg PP) per supported catalyst mass (g) used based on the unit time (h).

(2) Melting point (Tm, ^° C): After increasing the temperature of homo polypropylene to 20CTC, keep it at that temperature for 5 minutes, then lower to 30 ^° C, and increase the temperature again to increase DSC (Di f ferent i al Scanning Calorimeter, manufactured by TA) The top of the curve was used as the melting point. At this time, the rate of temperature rise and fall was 10 ^° C / min, and the melting point was used as the result measured in the second temperature rise section.

(3) Melt Index (MI, g / 10min): Measured under a load of 2.16 kg at 230 ^° C according to ASTM D1238, and expressed as the weight (g) of the polymer melted for 10 minutes.

(4) Weight average molecular weight g / mol and molecular weight distribution (MWD, polydi spers ty ty index): The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured using gel permeation chromatography (GPC), respectively. Then, the molecular weight distribution was calculated by the ratio of Mw / Mn. Specifically, Polymer Laboratories PLgel 2020/091177 1 »（： 1 ^ 1 {2019/007152

Measurements were made using a ᄄ 220 instrument using a 300_ length column in-house. At this time, the evaluation temperature is 160 ^° (:, 1,2, 4 -trichlorobenzene was used as a solvent, the flow rate was 11/11. Samples were prepared at a concentration of 101 Pa / 10, and then supplied in an amount of 200. The values of and were derived using an assay curve formed using polystyrene standards. The molecular weight of the polystyrene standard (yong / 11101) was 9 of 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000, 000.

[Table 11

2020/091177 1 »（： 1/10 公 019/007152

As a result of the experiment, the supported catalysts of Preparation Examples 2-1 to 2-5 containing the transition metal compound according to the present invention exhibited a high catalytic activity of 14 PP / g or more, from which the polymer was prepared using the transition metal compound. 2020/091177 1 »（： 1 ^ 1 {2019/007152

Excellent productivity and morphological improvement effect can be expected.

 In addition, the homo polypropylenes of Examples 1 to 5 prepared by using the supported catalysts of Preparation Examples 2-1 to 2-5, respectively, exhibited a low ¾ of 1451: or less, from which the processability of the homo polypropylene was improved. ， As a result, when manufacturing a molded product using homo polypropylene, it is possible to predict the effect of reducing energy by reducing the processing temperature and improving processability due to easy mixing.

 In addition, the homo polypropylene of Examples 1 to 5 showed a high of 340,000 for / 11101 or higher and a low of 7 for / 101 11 for injection of hydrogen gas during the polymerization reaction. From this, it can be seen that a wide range of ^ 3 (16 production) is possible by controlling the amount of hydrogen gas input during the polymerization reaction.

 In addition, the homo polypropylenes of Examples 1 to 5 can be expected to exhibit excellent stiffness and impact strength characteristics by exhibiting a narrow _ of 2.7 or less in addition to the above-described physical properties.

On the other hand, in the case of Comparative Examples 1 to 8, the activity of the catalyst used for polymer production is very low, and it is also produced by introducing the same amount of hydrogen gas during the polymerization reaction.

Was low.

In particular, the polymer of Comparative Example 1 prepared using the catalyst of Comparative Preparation Examples 2-1 in which the first ligand structure of the transition metal compound is unsubstituted, uses a transition metal compound in which one or more hydrogens in the first ligand are substituted. Compared to the prepared Examples 1 to 5, and Comparative Examples 2 to 5, significantly increased,

Greatly reduced. From these results, it can be seen that the substitution in the first ligand affects the physical properties of the polymer, especially and.

In addition, the polymer of Comparative Example 2 prepared using the transition metal compound in which the 4th position in the first ligand is substituted, compared to Example 4 using the transition metal compound in which the same substituent is bonded to the 3rd position, Polymer

Equal level, but

¾! Increased, increased significantly

Decreased.

In addition, in the first ligand, the polymer of Comparative Example 3 prepared using the transition metal compound in which the 2nd position was further substituted in addition to the 4th position, compared to Comparative Example 2, significantly decreased,

Although it increased, ¾ increased significantly and ¾ ■) also increased. In addition, in the first ligand structure of the transition metal compound, the polymers of Comparative Examples 4 and 5 prepared by using the transition metal compound in which position 2 is further substituted or position 2 and 4 are further substituted in addition to position 3 , Compared with the example, the MI increased, the Mw decreased, the MWD increased significantly, and the MWD increased more particularly when the 4th position was further substituted.

 In addition, the polymer of Comparative Example 6 prepared using a transition metal compound in which the positions 3 of both the first and second ligand structures in the transition metal compound are identically substituted with an isopropyl group has a low Tm due to a decrease in Tact i ci ty. Although shown, Mw was greatly reduced and MWD and MI were greatly increased. From this, it can be expected that the polymer of Comparative Example 6 has a reduced impact strength characteristic.

 In addition, the polymer of Comparative Example 7 prepared using a transition metal compound substituted only at position 2 in the second ligand structure in the transition metal compound, compared to Example 2, the Mw was significantly reduced, and the terminat ion was accelerated. Is expected. In addition, it was confirmed that the polymer of Comparative Example 8 prepared by using a transition metal compound substituted only with phenyl at the 4th position also had reduced activity and decreased Mw compared to Example 2. This difference is because, in the case of Example 2, the catalytic activity was significantly increased due to the sufficient provision of an induct ive ef fect due to the t-butylphenyl group present at position 4 in the second ligand structure in the transition metal compound.

 From the above results, it can be confirmed that the MI, Mw, and _ of the polymer vary depending on the bonding position and type of the substituents in the first and second ligands, and further comprising the first and second ligands of the indene structure. In the transition metal compound, when the first ligand is substituted only at position 3, and the second ligand is replaced by a predetermined substituent at positions 2 and 4, respectively, to have an asymmetric structure, the effect of the present invention, that is, the polymer It can be seen that the properties of low Tm and MI, high Mw and narrow MWD at can be realized simultaneously.

Claims

2020/091177 1 »(： 1 ^ 1 {2019/007152 [Scope of claim] [Claim 11] Transition metal compound represented by the following formula (1):

 [Formula 1]

In Chemical Formula 1,

 The show is carbon or silicon,

 Is a Group 4 transition metal,

 Silver 01-20 alkyl; Or Ce-20 aryl which is unsubstituted or substituted with ^ -20 alkyl,

Seedling ² is 0 _6-20 aryl substituted with 01-20 alkyl,

 ^ And 0 are each independently 01-20 alkyl,

X ¹ and X ² are each independently halogen.

[Claim 2]

 According to claim 1,

The urine is silicon, and is silver zirconium, a transition metal compound. 2020/091177 1 »（： 1 ^ 1 {2019/007152

【Claim 3】

 According to claim 1,

A is 0 _3-10 straight chain alkyl; 0 _3-10 branched alkyl; Phenyl; Or 0 _3-10 branched alkyl group substituted phenyl, transition metal compound.

[Claim 4]

 According to claim 1,

Recall I? ² is a transition metal compound which is a phenyl group substituted with 0 _3-6 branched alkyl.

【Claim 5】

 According to claim 1,

 Wherein ^ and each are methyl groups, transition metal compounds.

[Claim 6]

 According to claim 1,

 The transition metal compound is one selected from the group consisting of compounds of the following structure:

2020/091177 1 »（： 1 ^ 1 {2019/007152

【Claim 7】

 A catalyst composition comprising the transition metal compound according to claim 1.

【Claim 8】

 The method of claim 7,

 The catalyst composition further comprises a carrier, the catalyst composition.

[Claim 9]

 According to claim 7,

 The catalyst composition further comprises at least one co-catalyst selected from the group consisting of compounds of formulas 3 to 5, catalyst composition:

 [Formula 3]

_ [Hour (¾1) -0] „ ₎ -in formula 3 above,

The same as or different from each other, and each independently halogen; _-20 hydrocarbons; Or a hydrocarbon substituted with halogen; 2020/091177 1 »（： 1 ^ 1 {2019/007152

«1 is an integer greater than or equal to 2;

 [Formula 4]

1 ₂ ） ₃

 In Chemical Formula 4,

Yo ₁₂ is the same or different from each other, each independently halogen; _-20 hydrocarbons; Or a halogen substituted _-20 hydrocarbon;

 1 is aluminum or boron;

 [Formula 5]

[ᅡ ᅡ ⁺ or [리 + [2¾

 In the above formula (5) ’

 The seedling is a neutral or cationic Lewis base;

 Is a hydrogen atom;

 1 is a group 13 element;

The yaw is the same or different from each other, and each independently one or more hydrogen atoms are halogen, ( ₂₀ hydrocarbons, alkoxy or phenoxy substituted or unsubstituted, ( _6-20 aryl group or _-20 alkyl group).

【Claim 10】

 The method of claim 9,

 The cocatalyst is a catalyst composition selected from the group consisting of methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and mixtures thereof.

【Claim 11】

 According to claim 7,

 The catalyst composition further comprises an antistatic agent, the catalyst composition.

【Claim 12】

 The method of claim 11,

The antistatic agent, represented by the following formula (6), ethoxylated 2020/091177 1 »（： 1 ^ 1 {2019/007152

Alkylamine, catalyst composition:

 [Formula 6]

1 抑-（抑₂抑₂ child） ₂

In the above formula (6), silver (: _8-30 alkyl.

【Claim 13】

 In the presence of the catalyst composition according to claim 7, comprising the step of polymerizing a propylene monomer by introducing hydrogen, a method for producing homopolypropylene. [Claim 14]

 The method of claim 13,

 The hydrogen is introduced in a content of 50 to 700 based on the total weight of the propylene monomer, a method for producing homopolypropylene. 【Claim 15】

 The method of claim 13,

 The homo polypropylene is to satisfy the following conditions, the production method of the homo polypropylene:

 Melting temperature 1451: or less

 {[） 況 ¾1 1） The melt index measured at 2301: 2.161¾ load according to 1238

7 use / 10111 five II or less

[10 weight average molecular weight 340, 000 seedlings / ½ ₀ 1 or more

 ） Molecular weight distribution 2.7 or less