KR102566283B1 - Supported hybrid metallocene catalyst and method for preparing polyolefine using the same - Google Patents

Abstract

According to the present invention, a supported mixed metallocene catalyst having excellent resin processability and rigidity and simultaneously improving ductility and a method for preparing a polyolefin polymer using the same are provided.

Description

Hybrid supported metallocene catalyst and method for producing polyolefin using the same

The present invention relates to a hybrid supported metallocene catalyst that has high activity and can improve physical properties by improving resin processability and stiffness and ductility, and a method for preparing polyolefin using the same.

Recently, for purposes such as weight reduction of automobiles, polyolefin products having a low specific gravity have been developed for use as substitutes for plastics or metals having a high specific gravity. In this process, the need for high-strength polyolefin products is increasing.

Ziegler-Natta catalyst-applied polyolefins are the mainstream, but recently, conversion to polypropylene products (mPP) with metallocene catalysts, which have low odor and low elution characteristics, is accelerating.

That is, olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed according to their respective characteristics. Ziegler-Natta catalyst has been widely applied to existing commercial processes since its invention in the 1950s, but since it is a multi-site catalyst in which several active sites are mixed, it is characterized by a wide molecular weight distribution of the polymer and comonomer There is a problem that there is a limit to securing desired physical properties because the composition distribution of is not uniform.

On the other hand, the metallocene catalyst is composed of a combination of a main catalyst containing a transition metal compound as a main component and a cocatalyst containing an organometallic compound containing aluminum as a main component. Such a catalyst is a single site catalyst as a homogeneous complex catalyst, and a polymer with a narrow molecular weight distribution and a uniform composition distribution of comonomers is obtained according to the characteristics of a single site, and the ligand structure of the catalyst is modified. And it has properties that can change the tacticity, copolymerization characteristics, molecular weight, crystallinity, etc. of the polymer according to the change of polymerization conditions.

Polypropylene produced using the metallocene catalyst has advantages of high rigidity and exhibiting resin characteristics without off-flavor due to a narrow molecular weight distribution and high stereoregularity. However, this method has limitations in that processability and physical properties of the resin are inferior to conventional Ziegler-Natta catalysts. In particular, the conventional metallocene catalyst has a problem of deterioration in resin processability and physical properties when preparing a propylene-ethylene random copolymer.

In the present invention, when providing a metallocene catalyst, by introducing two specific catalyst precursors, the molecular weight distribution can be improved compared to the existing mPP and processability can be improved, and the hybrid supported metallocene catalyst and the production of a polyolefin polymer using the same is to provide a way

Another object of the present invention is a hybrid supported metallocene catalyst with improved stiffness and improved toughness compared to ZNPP by introducing more comonomers into the polymer region while maintaining high activity catalyst characteristics, and polyolefin using the same It is to provide a method for producing a polymer.

Accordingly, according to the present invention,

A first transition metal compound represented by Formula 1 below;

A second transition metal compound represented by Formula 2 below; and

Provides a hybrid supported metallocene catalyst comprising:

[Formula 1]

In Formula 1,

M ₁ is a Group 4 transition metal;

X ₁ and X ₂ are each independently the same or different halogen,

A ₁ is silicon or germanium;

R ₁ to R ₂ are each independently the same as or different from each other, and are C _1-20 alkyl or C _6-20 aryl;

R ₃ to R ₄ are each independently identical to or different from each other, and C _7-40 alkylaryl;

[Formula 2]

In Formula 2,

M ₂ is zirconium or hafnium;

X ₃ and X ₄ are each independently the same or different halogen;

A ₂ is silicon or germanium;

R ₅ to R ₆ are each independently identical to or different from each other, and are C _1-20 alkyl, C _1-20 alkoxy, or C _2-20 alkoxyalkyl;

R ₇ are each independently identical to or different from each other, and C _7-40 alkylaryl;

R ₈ to R ₁₀ are each independently the same as or different from each other, and are hydrogen, halogen, C _1-20 alkyl, C _1-20 alkoxy or C _6-20 aryl.

In addition, according to another embodiment of the present invention, there is provided a method for producing a polyolefin polymer comprising the step of copolymerizing an alpha-olefin monomer and ethylene while introducing hydrogen in the presence of the hybrid supported metallocene catalyst.

According to the present invention, by using two types of specific transition metal compounds, while maintaining highly active catalytic properties, more comonomers are introduced into the polymer region to exhibit high stiffness compared to ZNPP (Ziegler-Natta polypropylene) , can provide a hybrid supported metallocene catalyst suitable for the production of polyolefin polymers, specifically polyolefin random copolymers, in which toughness can be improved.

Therefore, the present invention can improve the rigidity and ductility of a polyolefin random copolymer, especially a propylene-ethylene random copolymer resin, along with processability by using the supported hybrid metallocene catalyst.

Terms used in this specification are only used to describe exemplary embodiments, and are not intended to limit the invention. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "comprise", "comprise" or "having" are intended to indicate that there is an embodied feature, step, component, or combination thereof, but one or more other features or steps; It should be understood that the presence or addition of components, or combinations thereof, is not previously excluded.

Since the invention can have various changes and various forms, specific embodiments will be exemplified and described in detail below. However, it should be understood that this is not intended to limit the invention to a particular disclosed form, and includes all modifications, equivalents, and substitutes included in the spirit and scope of the invention.

Hereinafter, a hybrid supported metallocene catalyst according to a preferred embodiment of the present invention and a method for preparing a polyolefin polymer using the same will be described in more detail.

According to one embodiment of the present invention, the first transition metal compound represented by Formula 1; A second transition metal compound represented by Formula 2 below; And a carrier; there is provided a hybrid supported metallocene catalyst comprising:

[Formula 1]

In Formula 1,

M ₁ is a Group 4 transition metal;

X ₁ and X ₂ are each independently the same or different halogen,

A ₁ is silicon or germanium;

R ₁ to R ₂ are each independently the same as or different from each other, and are C _1-20 alkyl or C _6-20 aryl;

R ₃ to R ₄ are each independently identical to or different from each other, and C _7-40 alkylaryl;

[Formula 2]

In Formula 2,

M ₂ is zirconium or hafnium;

X ₃ and X ₄ are each independently the same or different halogen;

A ₂ is silicon or germanium;

R ₅ to R ₆ are each independently identical to or different from each other, and are C _1-20 alkyl, C _1-20 alkoxy, or C _2-20 alkoxyalkyl;

R ₇ are each independently identical to or different from each other, and C _7-40 alkylaryl;

R ₈ to R ₁₀ are each independently the same as or different from each other, and are hydrogen, halogen, C _1-20 alkyl, C _1-20 alkoxy or C _6-20 aryl.

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

The halogen may be fluorine (F), chlorine (Cl), bromine (Br) or iodine (I).

The C _1-20 alkyl group may be a straight-chain, branched-chain or cyclic alkyl group, more preferably a straight-chain or branched-chain alkyl group. Specifically, the C _1-20 alkyl group is a C _1-15 straight chain alkyl group; C _1-10 straight chain alkyl group; C _1-5 straight chain alkyl group; C _3-20 branched or cyclic alkyl group; C _3-15 branched or cyclic alkyl group; Or it may be a C _3-10 branched chain or cyclic alkyl group. More specifically, the C1-20 alkyl group is methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo -May be a pentyl group or a cyclohexyl group.

C _1-20 alkoxy can be straight chain, branched chain or cyclic alkoxy. Specifically, examples of C _1-20 alkoxy include methoxy, ethoxy, n-butoxy, tert-butoxy, phenyloxy, cyclohexyloxy, and the like, but are not limited thereto.

C _2-20 alkoxyalkyl may mean a substituent in which one or more hydrogens of alkyl are substituted with alkoxy. Specifically, as C _2-20 alkoxyalkyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, butoxymethyl, butoxyethyl, butoxypropyl, butoxybutyl, butoxyheptyl, butoxy Hexyl, etc. may be mentioned, but is not limited thereto.

C _6-20 aryl can mean a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. Specifically, C _6-20 aryl may be a phenyl group, a naphthyl group, or an anthracenyl group.

C _7-40 alkylaryl may include a substituent in which one or more hydrogens of the aryl are substituted with C _1-20 alkyl. Specifically, the C _7-40 alkylaryl may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl or cyclohexylphenyl.

In Formula 1, A ₁ may be silicon, and substituents R ₁ and R ₂ of A ₁ may be identical to each other in terms of improving loading efficiency by increasing solubility, may be C _1-10 alkyl groups, and may be more Specifically, it may be C _1-6 straight-chain or branched-chain alkyl, C _1-4 straight-chain or branched-chain alkyl group, and more specifically methyl, ethyl, or tert-butyl, respectively.

In addition, the 2-position of both indenyl groups, which are ligands, is specifically substituted with an isopropyl group and a methyl group, so that the two indenyl groups have higher hydrogen reactivity than the same catalyst, so that desired MI products can be prepared even under low hydrogen conditions. show the advantages of

Preferably, the R ₃ and R ₄ may each independently be a phenyl group substituted with a C _3-6 branched chain alkyl group, more specifically, a C _3-6 branched chain alkyl group substituted such as tert-butyl phenyl. It may be a phenyl group. In addition, the substitution position of the alkyl group for the phenyl group may be position 4 corresponding to the position R ₃ or R ₄ bonded to the indenyl group and the para position.

Also, in Formula 1, X ₁ and X ₂ may each independently represent chloro.

A representative example of the compound represented by Formula 1 may be any one of the following structures:

In addition, in the mixed metallocene-supported catalyst according to an embodiment of the present invention, the second transition metal compound represented by Chemical Formula 2 enables isotacticity to be maintained during the polymerization of alpha-olefin and ethylene. Accordingly, since it has an ansa-metallocene structure and has various characteristics or selective advantages in the case of two indenyl groups, it can exhibit more excellent catalytic activity. In addition, since the two indenyl groups are substituted with a bulky group such as a C _7-40 alkylaryl group, preferably a C _6-20 aryl (R ₇ ) substituted with a C _1-20 alkyl, steric hindrance is provided to obtain Inhibits the formation of mesoforms.

Therefore, when the compound of Formula 2 is supported on a carrier together with the first transition metal of Formula 1, a hybrid supported metallocene catalyst specialized for polyolefin random copolymers having desired physical properties can be provided. In particular, the metallocene catalyst using the first and second transition metal compounds has the effect of generating a high molecular weight during random polymerization of ethylene, that is, to generate an ethylene copolymer in the high molecular weight region, so that both stiffness and ductility are obtained. It can show an improvement effect. That is, when the catalyst of the present invention is used, more comonomers are introduced into the polymer region, and compared to ZNPP, stiffness and toughness can be improved.

More specifically, in Formula 2, A ₂ is silicon, M ₂ is zirconium, X ₃ and X ₄ are each independently Cl, and R ₅ and R ₆ are each independently C _1-6 alkyl or C _{2 -20} alkoxyalkyl, wherein R ₇ is each independently C _6-20 aryl substituted with a C _1-6 alkyl group, and R ₈ to R ₁₀ may each independently be hydrogen.

More preferably, R ₇ in Formula 2 may each independently be a phenyl substituted with a C _3-6 branched chain alkyl group.

A representative example of the second transition metal compound represented by Chemical Formula 2 may include a structure represented by Chemical Formula 2-1 below:

[Formula 2-1]

In addition, according to one embodiment of the invention, the mixed supported metallocene catalyst is a 5: 1 to 2: 1 ratio of the first transition metal compound represented by the formula (1) and the second transition metal compound represented by the formula (2). Including by mole When the first and second transition metal compounds are included in the mixing weight ratio, appropriate catalytic activity is exhibited and it may be more advantageous to achieve the physical properties of the random copolymer of alpha-olefin and ethylene. Out of the molar ratio range of the first and second transition metal compounds, the first transition metal compound is included in an excess of 5 moles with respect to 1 mole of the second transition metal compound, or the second transition to 1 mole of the first transition metal compound When the metal compound is included in a molar ratio of less than 2, there is a concern that the effect of improving physical properties due to the difference in the degree of characteristic expression of the polymer prepared from each transition metal compound may be reduced.

In addition, the first and second transition metal compounds can be stably supported on the carrier due to the above-described structural characteristics, and as a result, the polyolefin polymer produced, more specifically, the morphology of the random copolymer of alpha-olefin and ethylene, and It can provide excellent effects optimized for improving physical properties.

Meanwhile, the first and second transition metal compounds represented by Chemical Formulas 1 and 2 may be synthesized by applying known reactions, and reference may be made to Preparation Examples to be described later for a detailed synthesis method.

The first and second transition metal compounds represented by Chemical Formulas 1 and 2 may be sequentially supported on a carrier and used as a supported catalyst.

As the carrier, a carrier containing a hydroxyl group on the surface may be used, and preferably, a carrier having a highly reactive hydroxyl group and a siloxane group, which is dried to remove moisture from the surface, may be used. For example, silica dried at high temperature, silica-alumina, and silica-magnesia may be used, and these are typically oxides, carbonates, such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg(NO ₃ ) ₂ , It may contain sulfate and nitrate components.

The drying temperature of the carrier is preferably 200 to 800 ° C, more preferably 300 to 600 ° C, and most preferably 300 to 400 ° C. When the drying temperature of the support is less than 200 ° C, the moisture on the surface is too high, and the moisture on the surface and the cocatalyst react, and when the drying temperature exceeds 800 ° C, the pores on the surface of the carrier are combined and the surface area is reduced. This is undesirable because only siloxane remains and the reaction site with the cocatalyst decreases.

The amount of hydroxy groups on the surface of the carrier is preferably 0.1 to 10 mmol/g, more preferably 0.5 to 5 mmol/g. The amount of hydroxyl groups on the surface of the carrier can be controlled by the manufacturing 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 less than 0.1 mmol / g, there are few reaction sites with the cocatalyst, and if it exceeds 10 mmol / g, it is not preferable because it may originate from moisture in addition to the hydroxy group present on the surface of the carrier particle. not.

In addition, when supported on a carrier, the mass ratio of the compound of Formula 1 to the carrier is preferably 1:1 to 1:1000. When the carrier and the compound of Formula 1 are included in the above mass ratio, appropriate supported catalytic activity may be exhibited, which may be advantageous in terms of maintaining the activity of the catalyst and economic efficiency.

In addition, in terms of improving high activity and process stability, a cocatalyst may be first supported on the carrier before supporting the transition metal compounds of Chemical Formulas 1 and 2.

Accordingly, the carrier may further include at least one cocatalyst selected from the group consisting of a compound represented by Formula 3, a compound represented by Formula 4, and a compound represented by Formula 5:

[Formula 3]

-[Al(R ₁₁ )-O] _m -

In Formula 3,

R ₁₁ may be the same as or different from each other, and each independently halogen; C _1-20 hydrocarbon; or a C1-20 hydrocarbon substituted with halogen;

m is an integer of 2 or greater;

[Formula 4]

J(R ₁₂ ) ₃

In Formula 4,

R ₁₂ is as defined in Formula 3 above;

J is aluminum or boron;

[Formula 5]

[EH] ⁺ [ZA' ₄ ] ^- or [E]+[ZA' ₄ ] ^-

In Formula 5,

E is a neutral or cationic Lewis base;

H is a hydrogen atom;

Z is a Group 13 element;

A' may be the same as or different from each other, and each independently represents an aryl group having 6 to 20 carbon atoms or a C 1-20 alkyl group in which one or more hydrogen atoms are unsubstituted or substituted with halogen, C1-20 hydrocarbon, alkoxy or phenoxy.

Examples of the compound represented by Formula 3 include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, and butyl aluminoxane, and a more preferred compound is methyl aluminoxane.

Examples of the compound represented by Formula 4 include trimethylaluminum, triethylaluminium, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminium, tri-s-butylaluminum, and tricyclopentylaluminum. , tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Boron, triethylboron, triisobutylboron, tripropylboron, tributylboron, etc. are included, and a more preferable compound is selected from trimethylaluminum, triethylaluminum, and triisobutylaluminum.

Examples of the compound represented by Formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra(p-tolyl). Boron, trimethylammonium tetra (o,p-dimethylphenyl) boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, trimethylammonium tetra (p-trifluoromethylphenyl) boron, tributylammonium tetra Pentafluorophenylboron, N,N-diethylaniliniumtetraphenylboron, N,N-diethylaniliniumtetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenyl boron, trimethylphosphonium tetraphenylboron, triethylammonium tetraphenyl aluminum, tributylammonium tetraphenyl aluminum, trimethylammonium tetraphenyl aluminum, tripropylammonium tetraphenyl aluminum, trimethylammonium tetra(p-tolyl) ) Aluminum, tripropylammonium tetra (p-tolyl) aluminum, triethylammonium tetra (o, p-dimethylphenyl) aluminum, tributylammonium tetra (p-trifluoromethylphenyl) aluminum, trimethylammonium tetra ( p-trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenyl aluminum, N,N-diethylanilinium tetraphenyl aluminum, N,N-diethylanilinium tetrapentafluorophenyl aluminum, di Ethylammonium tetrapentatetraphenyl aluminum, triphenylphosphonium tetraphenyl aluminum, trimethylphosphonium tetraphenyl aluminum, tripropylammonium tetra(p-tolyl) boron, triethylammonium tetra(o,p-dimethylphenyl)boron , tributylammonium tetra(p-trifluoromethylphenyl) boron, triphenylcarbonium tetra(p-trifluoromethylphenyl)boron, triphenylcarbonium tetrapentafluorophenylboron, and the like.

In addition, when the cocatalyst is supported, the content may be 8 to 25 mmol, preferably 10 to 20 mmol, based on the weight of the carrier, for example, 1 g of silica.

The method for preparing the hybrid supported metallocene catalyst of the present invention includes the steps of supporting a cocatalyst compound on a carrier, supporting the compound represented by Formula 1 on the carrier, and supporting the compound represented by Formula 2 on the carrier. It can be prepared by a manufacturing method comprising the step of doing.

In preparing the hybrid supported metallocene catalyst, a hydrocarbon-based solvent such as pentane, hexane, or heptane or an aromatic solvent such as benzene or toluene may be used as a reaction solvent.

In the catalyst composition of the present invention, as an example of the metallocene-supported catalyst including Formula 1, a silica carrier and a cocatalyst are reacted, and after precipitation, the solvent in the upper layer is removed, washed with a solvent, and a catalyst precursor is sequentially added It can be manufactured by proceeding with the process of Therefore, the supported metallocene catalyst of the present invention may be in a form in which an alkylaluminoxane-based cocatalyst and a metallocene compound represented by Formulas 1 and 2 are sequentially supported on a carrier.

In the method for preparing the supported metallocene catalyst of the present invention, the reaction may proceed under an inert atmosphere.

On the other hand, according to another embodiment of the present invention, in the presence of the hybrid supported metallocene catalyst, while introducing hydrogen, an alpha-olefin monomer and ethylene are polymerized. A method for producing a polyolefin polymer may be provided. there is.

Using the hybrid supported metallocene catalyst of the present invention, polyolefin random polymers exhibiting excellent catalytic activity even under high ethylene conditions and having desired physical properties can be prepared.

Specific examples of the alpha olefin monomer include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1- There are dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, and the like, and two or more of them may be mixed and copolymerized, preferably propylene. Thus, the polyolefin polymer may be a random copolymer of propylene and ethylene.

In addition, the content of the alpha-olefin monomer and ethylene can be used as well-known in the art and is not particularly limited. For example, when providing a random polymer using ethylene and propylene monomers, ethylene may be used in an amount of 0.1 to 5% by weight based on the total weight of the monomers.

The hybrid metallocene-supported catalyst may be used in a slurry state in a solvent, in a diluted state, or in the form of a mud catalyst mixed with a mixture of oil and grease, depending on the polymerization method.

When the hybrid metallocene-supported catalyst is used in a slurry state or diluted state in a solvent, the solvent is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for polymerization of propylene monomers, such as pentane, hexane, heptane, nonane, decane, and isomers thereof, 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. can In this case, the catalyst composition may further include the above solvent, and a small amount of water or air that may act as a catalyst poison may be removed by treating the solvent with a small amount of alkylaluminum before use.

In addition, the hydrogen may be added in a predetermined amount based on the total weight of the monomers for preparing the polyolefin polymer, specifically, the total weight of the monomers including propylene and alpha-olefin, but the content may vary depending on the catalyst composition, and the range is not limited As a preferred example, the hydrogen may be added in an amount of 100 to 400 ppm based on the total weight of the monomers.

In addition, the physical properties of the polyolefin polymer prepared by controlling the input amount of the hydrogen gas, in particular, the molecular weight distribution and fluidity can be adjusted within a desired range. Preferably, in the present invention, by introducing hydrogen in the content range as described above, a propylene-ethylene random polymer having a narrow molecular weight distribution of 3 or more or 3.5 to 5 and a melt index of 5 to 40 g / 10 min is provided. can

In addition, the polymerization process may be carried out as a continuous polymerization process, for example, a continuous solution polymerization process, a bulk polymerization process, a suspension polymerization process, a slurry polymerization process or an emulsion polymerization process, etc. Various polymerization processes known as polymerization of olefin monomers this may be employed. In particular, a continuous bulk-slurry polymerization process may be preferred in terms of obtaining a uniform molecular weight distribution and commercial production of the product.

In addition, the polymerization reaction may be carried out at a temperature of 40 ° C or higher, 60 ° C or higher, 110 ° C or lower or 100 ° C or lower, and when the pressure conditions are further controlled, 1 bar or higher, or 5 bar or higher, and 15 bar or lower , or under a pressure of 10 bar or less.

In addition, during the polymerization reaction, trialkyl aluminum such as triethyl aluminum (TIBAL) may be selectively further added.

If moisture or impurities are present in the polymerization reactor, a portion of the catalyst is decomposed. Since the trialkylaluminum serves as a scavenger to preliminarily capture moisture or impurities present in the reactor or moisture contained in the monomers, The activity of the catalyst used in the production can be maximized, and as a result, a polyolefin polymer having excellent physical properties, particularly a narrow molecular weight distribution, can be more efficiently produced. Specifically, in the trialkyl aluminum, alkyl is as defined above, specifically C _1-20 alkyl, more specifically C _1-6 straight-chain or C _3-6 such as methyl, ethyl, isobutyl, etc. may be a branched chain alkyl of

According to this method, the present invention maintains high activity catalyst characteristics by using the above-described mixed metallocene supported catalyst, and introduces more comonomer to the polymer region when providing a polyolefin polymer to achieve high stiffness compared to ZNPP. and improve toughness at the same time.

Preferably, the molecular weight distribution and molecular weight (M) of the polyolefin polymer provided in the present invention can be measured using a GPC-FTIR device. At this time, the polyolefin polymer measured by the apparatus may have a molecular weight distribution of 3.0 or more, and a comonomer incorporation index (CII) value of 0.4 or more defined by Equation 1 below.

[Equation 1]

CII = T1/ T2

(In Equation 1, T1 is the log value (log Mw) of the copolymer molecular weight (M) as the x-axis, and the molecular weight distribution (dwt / dlog Mw) for the log value as the y-axis When the molecular weight distribution curve is drawn , Comonomer content (% by weight) of the polymer region corresponding to the right 20% of the total area,

T2 is the total comonomer content (% by weight).

On the other hand, in the present invention, the molecular weight distribution (MWD) of the polyolefin polymer can be measured using gel permeation chromatography (GPC), and MWD is the weight average molecular weight (Mw) and number average molecular weight (Mn) measured Then, 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 using a Waters PL-GPC220 instrument using a Polymer Laboratories PLgel MIX-B 300 mm long column. At this time, the evaluation temperature is 160°C, 1,2,4-trichlorobenzene is used as a solvent, and the flow rate is 1 mL/min. In addition, the sample is prepared at a concentration of 10mg/10mL and then supplied in an amount of 200μL. A calibration curve formed using polystyrene standards is used to derive the values of Mw and Mn. At this time, nine kinds of molecular weight (g / mol) of the polystyrene standard were used: 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

In addition, the polyolefin polymer according to one embodiment of the present invention may exhibit equivalent or higher catalytic activity compared to conventional mPP. For example, the polyolefin polymer may exhibit a catalytic activity greater than or equal to 13 or from 13 to 20 (kg PP/g Cat.hr).

For example, the polyolefin polymer may have an MFR of 7 g/10min or more and less than 20 g/10min measured under a temperature of 230° C. and a load of 2.16 kg according to ASTM D1238 standard.

In addition, the polyolefin polymer may have a Tm of 130°C or more and 150°C or less.

The xylene soluble content of the polyolefin polymer is 1.0 wt% or less, or 0.9 wt% or less, or 0.8 wt% or less, or 0.7 wt% or less, and 0.1 wt% or more, or 0.2 wt% or more, or 0.3 wt% or more , or 0.4 wt% or more, or 0.5 wt% or more.

For the xylene soluble content of the polyolefin polymer, specifically, xylene was added to the polyolefin polymer sample, heated at 135 ° C. for 1 hour, cooled for 30 minutes, pre-treated, and then, OminiSec (Viscotek Co., Ltd. FIPA) equipment at 1 mL / min. It can be measured by flowing xylene for 4 hours at a flow rate to stabilize the base line of RI, DP, and IP, and then calculating the peak area after measurement by entering the concentration and injection amount of the pretreated sample.

In addition, the polyolefin polymer may have a Tm of 130°C or more and 150°C or less. Specifically, the Tm of the polyolefin polymer was heated to 220 ° C, maintained at that temperature for 5 minutes, lowered to 20 ° C, and then increased again. At this time, the rate of increase and decrease of temperature was It can be measured by controlling each at 10 °C/min.

The polyolefin polymer may have a flexural modulus (FM) of 1300 (kg/cm 2 ) or more and 1500 (kg/cm 2 ) or less. Specifically, FM of the polyolefin polymer may be measured by the ASTM D790 method.

The Izod impact strength of the polyolefin polymer may be 4 (kg.cm/cm) or more (kg.cm/cm). Specifically, the Izod impact strength of the polyolefin polymer may be measured by ASTM D256A and ISO180 methods.

Hereinafter, a preferred embodiment is presented to aid understanding of the present invention. However, the following examples are only provided to more easily understand the present invention, and the content of the present invention is not limited thereby.

Hybrid Supported Metallocene Catalyst Preparation

Preparation Example 1

[Formula 1-1] [Formula 2-1]

After putting 10 g of silica SP2408HT and toluene into a 500 mL reactor, 10 mmol of methylaluminoxane (MAO) was added and reacted at 90° C. for 12 hours. After precipitation of the reactants, the upper layer was removed and washed once with toluene.

Here, after dissolving 15 µmol of the compound of Chemical Formula 1-1 (Cat1) in toluene, the mixture was reacted at 50°C for 2 hours. After completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed once with toluene.

Subsequently, 75 μmol of the compound of Chemical Formula 2-1 (Cat2) was dissolved in toluene and reacted at 50° C. for 4 hours. After completion of the reaction, the precipitation was completed, the upper solution was removed, and the remaining reaction product was washed sequentially with toluene and hexane, and then vacuum dried to obtain a metallocene-supported catalyst in the form of solid particles.

Preparation Example 2

After putting 10 g of silica SP2408HT and toluene into a 500 mL reactor, 10 mmol of methylaluminoxane (MAO) was added and reacted at 90° C. for 12 hours. After precipitation of the reactants, the upper layer was removed and washed once with toluene.

Here, after dissolving 30 µmol of the compound of Chemical Formula 1 (Cat1) in toluene), the mixture was reacted at 50°C for 2 hours. After completion of the reaction, the upper layer solution was removed and the remaining reaction product was washed once with toluene.

Subsequently, 60 μmol of the compound of Formula 2 (Cat2) was dissolved in toluene, and reacted at 60° C. for 4 hours. After completion of the reaction, the precipitation was completed, the upper solution was removed, and the remaining reaction product was washed sequentially with toluene and hexane, and then vacuum dried to obtain a metallocene-supported catalyst in the form of solid particles.

Comparative Preparation Example 1

After putting 10 g of silica SP2408HT and toluene into a 500 mL reactor, 10 mmol of methylaluminoxane (MAO) was added and reacted at 90° C. for 12 hours. After precipitation of the reactants, the upper layer was removed and washed once with toluene.

Here, after dissolving 70 µmol of the compound of Chemical Formula 2-1 (Cat2) in toluene, the mixture was reacted at 50°C for 5 hours. After completion of the reaction, the precipitation was completed, the upper solution was removed, and the remaining reaction product was washed sequentially with toluene and hexane, and then vacuum dried to obtain a metallocene-supported catalyst in the form of solid particles.

Comparative Preparation Example 2

After putting 10 g of silica SP2408HT and toluene into a 500 mL reactor, 10 mmol of methylaluminoxane (MAO) was added and reacted at 90° C. for 12 hours. After precipitation of the reactants, the upper layer was removed and washed once with toluene.

Here, after dissolving 80 μmol of the compound of Formula 1-1 (Cat1) in toluene, the mixture was reacted at 50° C. for 5 hours. After completion of the reaction, the precipitation was completed, the upper solution was removed, and the remaining reaction product was washed sequentially with toluene and hexane, and then vacuum dried to obtain a metallocene-supported catalyst in the form of solid particles.

polyolefin manufacturing

Reference Example 1: Homo polymerization

3mL of triethylaluminum was put in a 2L stainless reactor at room temperature under Ar conditions, 330ppm of hydrogen gas was added, and then 770g of 1.5L of propylene was added. After stirring at 500 rpm for 10 minutes, 30 mg of the hybrid supported catalyst prepared in Preparation Example 1 and 20 mL of hexane were mixed to form a slurry, and then the slurry was introduced into the reactor under Ar conditions.

Subsequently, the temperature of the reactor was gradually raised to 70° C., followed by polymerization for 1 hour. After completion of the reaction, unreacted propylene was vented and dried to obtain homopolypropylene.

(Polymerization conditions: TEAL 3cc, C3 770g, H2 330ppm, 70℃, 1hr)

Reference Example 2: Homo polymerization

3mL of triethylaluminum was put in a 2L stainless reactor at room temperature under Ar conditions, 330ppm of hydrogen gas was added, and then 770g of 1.5L of propylene was added. After stirring at 500 rpm for 10 minutes, 30 mg of the hybrid supported catalyst prepared in Preparation Example 2 and 20 mL of hexane were mixed to form a slurry, and then the slurry was introduced into the reactor under Ar conditions.

Subsequently, the temperature of the reactor was gradually raised to 70° C., followed by polymerization for 1 hour. After completion of the reaction, unreacted propylene was vented and dried to obtain homopolypropylene.

(Polymerization conditions: TEAL 3cc, C3 770g, H2 330ppm, 70℃, 1hr)

Example 1: Ethylene Random Polymerization

3mL of triethylaluminum was put in a 2L stainless reactor at room temperature under Ar conditions, 330ppm of hydrogen gas was added, and then 770g of 1.5L of propylene was added. After stirring for 10 minutes, 30 mg of the hybrid supported catalyst prepared in Preparation Example 1 and 20 mL of hexane were mixed to form a slurry, and then the slurry was introduced into the reactor under Ar conditions.

Then, while ethylene gas was introduced into the reactor at a rate of 200 cc/min through the MFC, the temperature of the reactor was gradually raised to 70° C., followed by polymerization for 1 hour. After completion of the reaction, unreacted propylene and ethylene were vented, dried and removed, and then a propylene-ethylene random copolymer was obtained.

(Polymerization conditions: TEAL 3cc, C3 770g, C2 input: 2wt% based on total monomers, H2 330ppm, 70℃, 1hr)

Example 2: Ethylene Random Polymerization

3mL of triethylaluminum was put in a 2L stainless reactor at room temperature under Ar conditions, 330ppm of hydrogen gas was added, and then 770g of 1.5L of propylene was added. After stirring for 10 minutes, 30 mg of the hybrid supported catalyst prepared in Preparation Example 2 and 20 mL of hexane were mixed to form a slurry, and then the slurry was introduced into the reactor under Ar conditions.

Then, while ethylene gas was introduced into the reactor at a rate of 200 cc/min through the MFC, the temperature of the reactor was gradually raised to 70° C., followed by polymerization for 1 hour. After completion of the reaction, unreacted propylene and ethylene were vented, dried and removed, and then a propylene-ethylene random copolymer was obtained.

Example 3: Ethylene Random Polymerization

3mL of triethylaluminum was put in a 2L stainless reactor at room temperature under Ar conditions, 330ppm of hydrogen gas was added, and then 770g of 1.5L of propylene was added. After stirring for 10 minutes, 30 mg of the hybrid supported catalyst prepared in Preparation Example 1 and 20 mL of hexane were mixed to form a slurry, and then the slurry was introduced into the reactor under Ar conditions.

Subsequently, while introducing ethylene gas into the reactor at a rate of 400 cc/min through the MFC, the temperature of the reactor was gradually raised to 70° C., followed by polymerization for 1 hour. After completion of the reaction, unreacted propylene and ethylene were vented, dried and removed, and then a propylene-ethylene random copolymer was obtained.

(Polymerization conditions: TEAL 3cc, C3 770g, C2 input: 4wt% based on total monomers, H2 330ppm, 70℃, 1hr)

Comparative Examples 1 and 2: Homo polymerization

In Reference Example 1, it was carried out in the same manner as in Example 1, except that the catalysts prepared in Comparative Preparation Examples 1 and 2 were used instead of the hybrid supported catalyst prepared in Preparation Example 1, respectively. was manufactured.

Comparative Example 3: Homo polymerization

In Reference Example 1, the same as in Reference Example 1 except that the catalysts prepared in Comparative Preparation Examples 1 and 2 were used in a 50:50 (mass ratio) ratio instead of the mixed supported catalyst prepared in Preparation Example 1. By carrying out the method, homo polypropylene was prepared.

Comparative Examples 4 and 5: Ethylene random polymerization

In Example 1, propylene- An ethylene random copolymer was prepared.

Comparative Example 6: Ethylene random polymerization

In Example 1, the same as in Example 1 except that the catalysts prepared in Comparative Preparation Examples 1 and 2 were used in a 50:50 (mass ratio) ratio instead of the mixed supported catalyst prepared in Preparation Example 1. By carrying out the method, homo polypropylene was prepared.

[Experimental Example 1]

Evaluation of polyolefin polymer properties

The activity of the catalyst used in the Reference Examples, Examples and Comparative Examples and the physical properties of the obtained polymer were evaluated in the following manner, and the results are shown in Table 1.

(1) Catalytic activity

It was calculated as the ratio of the weight of the produced polymer (kg PP) per the supported catalyst mass (g) used per unit time (h).

(2) Melt index (MFR = MI, 2.16kg)

It was 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.

(3) Melting temperature (Tm): The melting point of the polymer was measured using a differential scanning calorimeter (DSC, device name: DSC 2920, manufacturer: TA instrument). Specifically, after heating the polymer to 220 ° C., the temperature was maintained for 5 minutes, and then lowered to 20 ° C. and then increased again.

(4) weight average molecular weight (Mw), number average molecular weight (Mn) and molecular weight distribution (MWD):

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were measured using gel permeation chromatography (GPC: gel permeation chromatography, manufactured by Waters), and the molecular weight distribution (MWD) was divided by the weight average molecular weight by the number average molecular weight. =Mw/Mn) was calculated.

Specifically, polymer samples were evaluated using a Waters PL-GPC220 instrument using a Polymer Laboratories PLgel MIX-B 300 mm long column. The evaluation temperature was 160 °C, 1,2,4-trichlorobenzene was used as a solvent, and the flow rate was measured at a rate of 1 mL/min. The sample was prepared at a concentration of 10mg/10mL and then supplied in an amount of 200 μL. The values of Mw and Mn were determined using a calibration curve formed using polystyrene standards. The molecular weight (g/mol) of polystyrene standard was 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000.

(5) Comonomer incorporation index (CII): After measuring the molecular weight (M) of the polyolefin polymer using a GPC-FTIR apparatus, the CCI was measured based on the following formula 1.

Specifically, as in (4) above, the polymer sample was dissolved in 1,2,4-trichlorobenzene as a solvent, and then measured at 160 ° C using a PerkinElmer Spectrum 100 FT-IR connected to GPC (PL-GPC220) .

[Equation 1]

CII = T1/ T2

(In Equation 1, T1 is the log value (log Mw) of the copolymer molecular weight (M) as the x-axis, and the molecular weight distribution (dwt / dlog Mw) for the log value as the y-axis When the molecular weight distribution curve is drawn , Comonomer content (% by weight) of the polymer region corresponding to the right 20% of the total area,

T2 is the total comonomer content (% by weight).

(6) Xylene soluble content (XS)

Xylene was added to the polyolefin polymer, heated at 135° C. for 1 hour, and pretreated by cooling for 30 minutes. In OminiSec (Viscotek's FIPA) equipment, xylene was flowed for 4 hours at a flow rate of 1 mL/min, and RI (Refractive Index), DP (Pressure across middle of bridge), IP (Inlet pressure through bridge top) When the base line of the bottom was stabilized, the concentration of the pretreated sample and the amount of injection were measured, and then the peak area was calculated. (2) Log Mw (<4.5) and Log Mw (>6.0): calculated through the above GPC curve graph.

(7) FM (flexural modulus): measured according to ASTM D790.

(8) IZOD impact strength: Izod impact strength was measured according to ASTM D256A

catalyst activation MFR C2 Tm MWD CII X.S FM IZOD (23℃) kg PP/g Cat.hr g/10min wt% ℃ wt% (kg/cm²) (kg.cm/cm) reference example One Preparation Example 1 15.1 11.8 - 154 2.9 - 0.8 17,000 3.0 2 Preparation Example 2 14.0 760. - 153 2.9 - 0.7 17,700 3.0 line
city
yes One Preparation Example 1 18.4 18.5 2.0 146 3.5 0.45 0.6 13,500 4.5 2 Preparation Example 2 16.8 12.4 2.0 146 3.6 0.54 0.7 13,500 4.5 3 Preparation Example 2 17.3 7.8 4.0 139 3.8 0.57 0.7 13,000 5.0 rain
school
yes One comparison
Preparation Example 1 14.4 9.4 - 151 2.9 - 0.8 16,600 3.0 2 comparison
Preparation Example 2 10.2 104.4 - 155 2.2 - 0.5 15,400 3.5 3 Cat* 11.7 64.4 - 154 2.9 - 0.7 16,800 2.5 4 Comparative Manufacturing Example 1 18.2 26.4 2.0 144 2.9 0.29 0.7 12,500 4.0 5 Comparative Manufacturing Example 2 12.4 12.6 2.0 148 2.3 0.35 0.5 12,000 4.0 6 Cat* Fouling** - 2.0 - - 0.7 - - * Polymerization of the catalyst amount of Comparative Preparation Example 1 + Comparative Preparation Example 2 at a ratio of 50:50 (mass ratio)
** reactor fouling

As confirmed in Table 1, Examples 1 to 3 obtained a CII of 0.4 or more compared to Comparative Examples 4 and 5, as the hybrid supported metallocene catalyst including two types of specific transition metal compounds was used. Accordingly, the FM and Izod impact strengths were improved. Therefore, the present invention could provide a propylene-ethylene random copolymer with improved rigidity and ductility as well as excellent resin processability compared to the prior art.

Claims (13)

A first transition metal compound represented by Formula 1 below;
A second transition metal compound represented by Formula 2 below; and
Including; carrier;
Hybrid Supported Metallocene Catalysts Used in the Preparation of Polyolefin Random Copolymers:
[Formula 1]

In Formula 1,
M ₁ is a Group 4 transition metal;
X ₁ and X ₂ are each independently the same or different halogen,
A ₁ is silicon or germanium;
R ₁ and R ₂ are each independently C _1-6 straight or branched chain alkyl;
R ₃ and R ₄ are each independently identical to or different from each other, and C _7-40 alkylaryl;
[Formula 2]

In Formula 2,
M ₂ is zirconium;
X ₃ and X ₄ are each independently the same or different halogen;
A ₂ is silicon or germanium;
R ₅ and R ₆ are each independently the same as or different from each other, and are C _1-20 alkyl, C _1-20 alkoxy, or C _2-20 alkoxyalkyl;
R ₇ are each independently identical to or different from each other, and C _7-40 alkylaryl;
R ₈ to R ₁₀ are each independently the same as or different from each other, and are hydrogen, halogen, C _1-20 alkyl, C _1-20 alkoxy or C _6-20 aryl.
The hybrid supported catalyst according to claim 1, wherein A ₁ in Formula 1 is silicon, M ₁ is zirconium or hafnium, and R ₃ and R ₄ are each independently a phenyl group substituted with a C _3-6 branched chain alkyl group. .
The hybrid supported metallocene catalyst according to claim 1, wherein the first transition metal compound is one of the following chemical formulas.

According to claim 1,
In Formula 2, A ₂ is silicon, M ₂ is zirconium, X ₃ and X ₄ are each independently Cl, and R ₅ and R ₆ are each independently C _1-6 alkyl or C _2-20 alkoxyalkyl. And, wherein R ₇ is each independently a C _6-20 aryl substituted with a C _1-6 alkyl group, and R ₈ to R ₁₀ are each independently hydrogen, a hybrid supported metallocene catalyst.
According to claim 1,
R ₇ in Formula 2 is each independently a phenyl substituted with a C _3-6 branched chain alkyl group, a hybrid supported metallocene catalyst.
The hybrid supported metallocene catalyst of claim 1, wherein the second transition metal compound has a structure represented by Formula 2-1:
[Formula 2-1]

According to claim 1,
The first transition metal compound and the second transition metal compound are included in a molar ratio of 5: 1 to 2: 1, the hybrid supported metallocene catalyst.
According to claim 1,
The carrier further comprises at least one cocatalyst selected from the group consisting of a compound represented by Formula 3, a compound represented by Formula 4, and a compound represented by Formula 5, a hybrid supported metallocene catalyst:
[Formula 3]
-[Al(R ₁₁ )-O] _m -
In Formula 3,
R ₁₁ may be the same as or different from each other, and each independently halogen; C _1-20 hydrocarbon; or C _1-20 hydrocarbon substituted with halogen;
m is an integer of 2 or greater;
[Formula 4]
J(R ₁₂ ) ₃
In Formula 4,
R ₁₂ is a C _1-20 hydrocarbon such as R ₁₁ defined in Formula 3, and is a C _1-20 alkyl group or a C _6-20 aryl group;
J is aluminum or boron;
[Formula 5]
[EH] ⁺ [ZA' ₄ ] ^- or [E]+[ZA' ₄ ] ^-
In Formula 5,
E is a neutral or cationic Lewis base;
H is a hydrogen atom;
Z is a Group 13 element;
A' may be the same as or different from each other, and each independently represents an aryl group having 6 to 20 carbon atoms or a C _1-20 alkyl group in which one or more hydrogen atoms are unsubstituted or substituted with halogen, C _1-20 hydrocarbon, alkoxy or phenoxy. am.
In the presence of the hybrid supported metallocene catalyst according to any one of claims 1 to 8, polymerizing alpha-olefin monomers and ethylene while introducing hydrogen,
The molecular weight distribution is 3.5 to 5, the comonomer incorporation index (CII) value defined by the following formula 1 is 0.4 or more,
Those whose flexural modulus measured according to ASTM D790 is 1300 (kg/cm2) or more and 1500 (kg/cm2) or less
A polyolefin random copolymer having an Izod impact strength of 4 (kg.cm/cm) or more (kg.cm/cm) measured according to ASTM D256A,
A method for producing polyolefin polymers.
[Equation 1]
CII = T1/ T2
(In Equation 1, T1 is the log value (log Mw) of the copolymer molecular weight (M) as the x-axis, and the molecular weight distribution (dwt / dlog Mw) for the log value as the y-axis When the molecular weight distribution curve is drawn , Comonomer content (% by weight) of the polymer region corresponding to the right 20% of the total area,
T2 is the total comonomer content (% by weight).
According to claim 9,
The method for producing a polyolefin polymer wherein the hydrogen is added in an amount of 100 to 400 ppm based on the total weight of the monomers.
According to claim 9,
The alpha-olefin is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-eicosene, and any one or more selected from the group consisting of, a method for producing a polyolefin polymer.
delete According to claim 9,
The method of producing a polyolefin polymer, wherein the polyolefin polymer is a random copolymer of propylene and ethylene.