KR102086767B1 - Propylene-alpha olefin copolymer - Google Patents

Abstract

The propylene-alpha olefin copolymer according to the present invention can produce a propylene-alpha olefin copolymer having a different melting point depending on the type and content of the comonomer alpha olefin, in particular the type and content of the alpha comonomer as the comonomer. Since the melting point satisfies a specific relational expression, there is an advantage that the desired melting point can be easily adjusted as necessary.

Description

Propylene-alpha olefin copolymer

The present invention relates to a propylene-alpha olefin copolymer and a method for manufacturing the same, which can easily adjust a desired melting point according to the type and content of the alpha olefin as a comonomer.

Olefin polymerization catalyst systems can be classified into Ziegler-Natta and metallocene catalyst systems, and these two highly active catalyst systems have been developed to suit each characteristic. The Ziegler Natta catalyst has been widely applied to existing commercial processes since it was invented in the 50s, but because it is a multi-site catalyst with multiple active sites, the molecular weight distribution of the polymer is characterized by a wide range of comonomers. There is a problem that there is a limit to securing desired physical properties because the distribution is not uniform.

The metallocene catalyst is composed of a combination of a main catalyst having a transition metal compound as a main component and a cocatalyst having an organometallic compound having aluminum as a main component. Such a catalyst is a homogeneous complex catalyst and is a single site catalyst. The molecular weight distribution is narrow according to the properties of a single active point, and a polymer having a uniform composition distribution of a comonomer is obtained, and the stereoregularity, copolymerization characteristics, molecular weight, crystallinity, etc. of the polymer are changed according to modification of the ligand structure and polymerization conditions of the catalyst. It has characteristics that can change.

On the other hand, the ansa-metallocene (ansa-metallocene) compound is an organometallic compound comprising two ligands connected to each other by a bridge group, the rotation of the ligand is prevented by the bridge group, and the metal center Activity and structure are determined. Such ansa-metallocene compounds are used as catalysts in the production of olefinic homopolymers or copolymers. In particular, an ansa-metallocene compound containing a cyclopentadienyl-fluorenyl ligand can produce high molecular weight polyethylene, through which it is possible to control the microstructure of polypropylene. Is known. In addition, it is known that an ansa-metallocene compound containing an indenyl ligand has excellent activity and can produce an olefin-based polymer with improved stereoregularity.

On the other hand, since the melting point, which is one of the properties considered important in the propylene-based copolymer, is influenced by the amount of hydrogen addition, the type and content of the comonomer, there is a problem that it is difficult to manufacture a propylene-based copolymer having a desired melting point.

Accordingly, in the present invention, when a propylene-based copolymer was prepared using a metallocene catalyst as described below, it was confirmed that the melting point can be easily adjusted according to the type and content of the comonomer.

The present invention is to provide a propylene-alpha olefin copolymer and a method for producing the same, which can easily control the desired melting point by satisfying a specific relational expression of the type, content and melting point of the alpha olefin as a comonomer.

In order to solve the above problems, the present invention provides the following propylene-alpha olefin copolymer.

The weight average molecular weight is 150,000 to 350,000,

The melting point (Tm) is 120 to 155 ° C,

Satisfying Equation 1 below,

Propylene-alpha olefin copolymer:

[Equation 1]

(-15.6 × x + 150) <y <(-15.6 × x + 155)

In Equation 1,

x is the sum of the values of each alpha olefin content (wt%) of the propylene-alpha olefin copolymer divided by its carbon number,

y is the melting point (° C) of the propylene-alpha olefin copolymer.

The propylene-alpha olefin copolymer according to the present invention is made of a catalyst as will be described later, and a propylene-alpha olefin copolymer having a different melting point according to the type and content of the alpha olefin as a comonomer can be prepared. In particular, since the type and content and the melting point of the alpha olefin, which is a comonomer, satisfy a specific relational expression as in Equation 1, there is an advantage that the desired melting point can be easily adjusted as necessary.

Equation 1 means the relationship between the type and content of the comonomer alpha olefin and the melting point, x means the type and content of the comonomer alpha olefin, and y means the melting point.

More specifically, x denotes the total sum of the values of each alpha olefin content (wt%) of the propylene-alpha olefin copolymer divided by its carbon number. In one example, when the comonomer of the propylene-alpha olefin copolymer is ethylene, the value obtained by dividing the ethylene content (wt%) by 2 carbon atoms of ethylene is x. As another example, when the comonomer of the propylene-alpha olefin copolymer is ethylene and 1-butene, the content of ethylene (wt%) divided by 2 carbon atoms of ethylene and the content of 1-butylene (wt %) Divided by 4 carbons of 1-butylene is the sum of x.

According to one embodiment of the present invention, in the case of the propylene-alpha olefin copolymer according to the present invention satisfies the above equation (1), it was confirmed that the propylene-alpha olefin copolymer of the comparative example does not satisfy this.

More preferably, the propylene-alpha olefin copolymer according to the present invention satisfies the following equation 1-1:

[Equation 1-1]

(-15.6 × x + 152) <y <(-15.6 × x + 153)

In Equation 1, x and y are as defined above.

Preferably, the melting point of the propylene-alpha olefin copolymer is 126 to 141 ° C.

Also preferably, the propylene-alpha olefin copolymer has a melt index (MFR, 2.16 kg, 230 ° C) measured in accordance with ASTM 1238 of 5 to 25 g / 10 min. The melt index may be adjusted according to the amount of hydrogen added during copolymerization of the propylene-alpha olefin copolymer.

In addition, the alpha olefin, which is a comonomer of the propylene-alpha olefin copolymer, is preferably an alpha olefin having 2 to 20 carbon atoms excluding propylene. Specific examples thereof include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, And one or more selected from the group consisting of 1-octadecene, 1-eicocene and mixtures thereof.

Further, preferably, the propylene-alpha olefin copolymer according to the present invention is a propylene / ethylene copolymer or a propylene / ethylene / 1-butene copolymer.

When the propylene-alpha olefin copolymer according to the present invention is a propylene / ethylene copolymer, the melting point (Tm) is preferably 130 to 145 ° C, and the melt index (MFR, 2.16 kg, 230 ° C) measured according to ASTM 1238 ) Is 10 to 25 g / 10 min.

In addition, when the propylene-alpha olefin copolymer according to the present invention is a propylene / ethylene / 1-butene copolymer, the melting point (Tm) is preferably 125 to 130 ° C, and the melt index (MFR) measured according to ASTM 1238 , 2.16 kg, 230 ° C) is 5-10 g / 10 min.

Meanwhile, the propylene-alpha olefin copolymer according to the present invention copolymerizes propylene and one or more alpha olefins in the presence of a hybrid supported catalyst comprising a compound represented by the following formula (1), a compound represented by the following formula (2) and a carrier Can be prepared by:

[Formula 1]

In Chemical Formula 1,

X is the same or different halogen from each other,

R ₁ is C _6-20 aryl substituted with C _1-20 alkyl,

R ₂ , R ₃ and R ₄ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl, C _1-20 ether, C _1-20 silyl ether, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,

A is carbon, silicon, or germanium,

R ₅ is C _1-20 alkyl substituted with C _1-20 alkoxy,

R ₆ is hydrogen, C _1-20 alkyl, or C _2-20 alkenyl,

[Formula 2]

In Chemical Formula 2,

X 'is the same or different halogen from each other,

R ' ₁ is C _6-20 aryl substituted with C _1-20 alkyl,

R ' ₂ , R' ₃ and R ' ₄ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 Alkoxysilyl, C _1-20 ether, C _1-20 silyl ether, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C7-20 arylalkyl,

A 'is carbon, silicon, or germanium,

R ' ₅ is C _1-20 alkyl substituted with C _1-20 alkoxy,

R ' ₆ is hydrogen, C _1-20 alkyl, or C _2-20 alkenyl.

The compounds represented by Chemical Formulas 1 and 2 have an ansa-metallocene structure, and include two indenyl groups as ligands. In particular, a functional group capable of acting as a Lewis base as an oxygen-donor is substituted in a bridge group connecting the ligand, thereby maximizing activity as a catalyst. In addition, since a bulky group such as C _6-20 aryl (R ₁ ) substituted with C _1-20 alkyl is substituted with an indenyl group, steric hindrance is imparted to suppress the formation of mesoforms. Accordingly, when the compounds represented by Chemical Formulas 1 and 2 are used as a catalyst in the production of an olefin polymer, an olefin polymer having desired physical properties can be more easily prepared.

In addition, the compound represented by Chemical Formula 1 has high activity of the catalyst by including zirconium (Zr) as a metal atom, and the compound represented by Chemical Formula 2 contains hafnium (Hf) as a metal atom, thereby providing a high molecular weight olefin polymer. Polymerization is possible. In particular, when the olefin-based polymer is prepared by increasing the content of the comonomer with a conventional catalyst, the olefin-based polymer having a high MI value is produced instead of Tm, but there is a difficulty in the process. The advantage of inclusion is that olefin-based polymers having both low Tm and MI values can be produced.

The molar ratio of the compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 is preferably 2: 1 to 1: 5. It can be advantageous in terms of maintaining the activity and economic efficiency of the catalyst by showing the optimum catalyst activity and physical properties in the molar ratio.

In Chemical Formula 1, preferably, R ₁ is phenyl substituted with tert-butyl. More preferably, R ₁ is 4-tert-butyl-phenyl.

Also preferably, R ₂ , R ₃ and R ₄ are hydrogen.

Also preferably, A is silicone.

Also preferably, R ₅ is 6-tert-butoxy-hexyl and R ₆ is methyl.

Representative examples of the compound represented by Formula 1 are as follows:

In addition, the present invention provides a method for preparing a compound represented by Formula 1, as represented by Reaction Scheme 1 below:

[Scheme 1]

Step 1 is a step of preparing a compound represented by Formula 1-4 by reacting the compound represented by Formula 1-2 with the compound represented by Formula 1-3. It is preferable to use alkyllithium (for example, n-butyllithium) for the reaction, and the reaction temperature is -200 to 0 ° C, more preferably -150 to 0 ° C. Toluene, THF, or the like can be used as the solvent. At this time, after separating the organic layer from the product, the step of vacuum drying the separated organic layer and removing excess reactants may be further performed.

Step 2 is a step of preparing a compound represented by Formula 1 by reacting a compound represented by Formula 1-4 with a compound represented by Formula 1-5. It is preferable to use alkyllithium (for example, n-butyllithium) for the reaction, and the reaction temperature is -200 to 0 ° C, more preferably -150 to 0 ° C. As a solvent, ether, hexane, etc. can be used.

In the above formula (2), preferably, R ' ₁ is phenyl substituted with tert-butyl. More preferably, R ' ₁ is 4-tert-butyl-phenyl.

Also preferably, R ' ₂ , R' ₃ and R ' ₄ are hydrogen.

Also preferably, A 'is silicone.

Also preferably, R ' ₅ is 6-tert-butoxy-hexyl and R' ₆ is methyl.

Representative examples of the compound represented by Formula 2 are as follows:

In addition, the present invention provides a method for preparing a compound represented by Formula 2, as represented by Scheme 2 below:

[Scheme 2]

Step 1 is a step of preparing a compound represented by Formula 2-4 by reacting a compound represented by Formula 2-3 with a compound represented by Formula 2-2. It is preferable to use alkyllithium (for example, n-butyllithium) for the reaction, and the reaction temperature is -200 to 0 ° C, more preferably -150 to 0 ° C. Toluene, THF, or the like can be used as the solvent. At this time, after separating the organic layer from the product, the step of vacuum drying the separated organic layer and removing excess reactants may be further performed.

Step 2 is a step of preparing a compound represented by Formula 2 by reacting the compound represented by Formula 2-4 with the compound represented by Formula 2-5. It is preferable to use alkyllithium (for example, n-butyllithium) for the reaction, and the reaction temperature is -200 to 0 ° C, more preferably -150 to 0 ° C. As a solvent, ether, hexane, etc. can be used.

In addition, preferably X and X ', R ₁ and R' ₁ , R ₂ and R ' ₂ , R ₃ and R' ₃ , R ₄ and R ' ₄ , A and A', R ₅ and R ' ₅ , And R ₆ and R ' ₆ are the same as each other. That is, it is preferable that only the metal atom in the compound represented by Formula 1 and the compound represented by Formula 2 have a different structure.

In the hybrid supported catalyst according to the present invention, a carrier containing a hydroxy group on the surface may be used as the carrier, and preferably a carrier having a highly reactive hydroxy group and a siloxane group that has been dried to remove moisture on the surface. Can be used. For example, silica dried at high temperature, silica-alumina, and silica-magnesia can be used, and these are usually oxides, carbonates, such as Na ₂ O, K ₂ CO ₃ , BaSO ₄ , and Mg (NO ₃ ) ₂ , 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 carrier is less than 200 ° C, there is too much moisture, and the surface water and the co-catalyst react, and when it exceeds 800 ° C, the surface area decreases as the pores on the surface of the carrier are combined, and there are many hydroxyl groups on the surface. It is not preferable because the reaction site with the co-catalyst decreases because only the siloxane group disappears.

The amount of hydroxy groups on the surface of the carrier is preferably 0.1 to 10 mmol / g, and more preferably 0.5 to 5 mmol / g. The amount of hydroxy groups on the surface of the carrier can be controlled by the method and conditions for preparing the carrier or drying conditions, such as temperature, time, vacuum or spray drying.

When the amount of the hydroxy group is less than 0.1 mmol / g, the reaction site with the cocatalyst is small, and if it exceeds 10 mmol / g, it is not preferable because it may be due to moisture other than the hydroxy group present on the surface of the carrier particle. not.

In the hybrid supported catalyst according to the present invention, the mass ratio of the catalyst (the compound represented by Formula 1 and the compound represented by Formula 2) to the carrier is preferably 1: 1 to 1: 1000. When the carrier and the catalyst are included in the above mass ratio, it can be advantageous in terms of maintaining the activity and economical efficiency of the catalyst by exhibiting appropriate supported catalyst activity.

In addition to the catalyst, a cocatalyst can be further used. The cocatalyst may further include one or more of the cocatalyst compounds represented by the following Chemical Formula 3, Chemical Formula 4 or Chemical Formula 5.

[Formula 3]

-[Al (R ₃₀ ) -O] _m-

In Chemical Formula 3,

R ₃₀ may be the same as or different from each other, and each independently halogen; Hydrocarbons having 1 to 20 carbon atoms; Or a hydrocarbon having 1 to 20 carbon atoms substituted with halogen;

m is an integer of 2 or more;

[Formula 4]

J (R ₃₁ ) ₃

In Chemical Formula 4,

R ₃₁ is as defined in Formula 3 above;

J is aluminum or boron;

[Formula 5]

_{^{[EH] + [ZA 4]}} - or _{^{[E] + [ZA 4]}} -

In Chemical 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 or different from each other, and each independently one or more hydrogen atoms are halogen, a hydrocarbon having 1 to 20 carbons, an alkoxy or phenoxy substituted or unsubstituted aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms. .

Examples of the compound represented by Chemical Formula 3 include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane, and more preferred compounds are methyl aluminoxane.

Examples of the compound represented by Chemical Formula 4 are trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-s-butyl aluminum, tricyclopentyl aluminum , Tripentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl Boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron, and the like, and more preferable compounds are selected from trimethyl aluminum, triethyl aluminum, and triisobutyl aluminum.

Examples of the compound represented by Chemical Formula 5 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, trimethylammoniumtetra (p-tolyl) Boron, trimethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p-trifluoromethylphenyl) boron, trimethylammoniumtetra (p-trifluoromethylphenyl) boron, tributylammoniumtetra Pentafluorophenylboron, N, N-diethylanilinium tetraphenylboron, N, N-diethylanilinium tetrapentafluorophenylboron, diethylammonium tetrapentafluorophenylboron, triphenylphosphonium Tetraphenyl boron, trimethylphosphonium tetraphenyl boron, triethyl ammonium tetraphenyl aluminum, tributyl ammonium tetraphenyl aluminum, trimethyl ammonium tetraphenyl aluminum, tri Lipropylammoniumtetraphenylaluminum, trimethylammoniumtetra (p-tolyl) aluminum, tripropylammoniumtetra (p-tolyl) aluminum, triethylammoniumtetra (o, p-dimethylphenyl) aluminum, tributylammonium Tetra (p-trifluoromethylphenyl) aluminum, trimethylammoniumtetra (p-trifluoromethylphenyl) aluminum, tributylammoniumtetrapentafluorophenylaluminum, N, N-diethylaniliniumtetraphenylaluminum, N , N-diethylanilinium tetrapentafluorophenylaluminum, diethylammoniumtetrapentatetraphenylaluminum, triphenylphosphoniumtetraphenylaluminum, trimethylphosphoniumtetraphenylaluminum, tripropylammoniumtetra (p-tolyl) Boron, triethylammoniumtetra (o, p-dimethylphenyl) boron, tributylammoniumtetra (p-trifluoromethylphenyl) boron, triphenylcarboniumtetra (p-triflo Phenyl) boron and the like, triphenylamine car I phenylboronic as Titanium tetra-penta flow.

The hybrid supported catalyst according to the present invention is prepared by supporting a cocatalyst compound on a carrier, supporting a compound represented by Formula 1 on the carrier, and supporting a compound represented by Formula 2 on the carrier. You can, and the order of loading can be changed as needed.

When preparing the hybrid supported catalyst, a hydrocarbon-based solvent such as pentane, hexane, heptane, or the like, or an aromatic-based solvent such as benzene and toluene may be used. In addition, the metallocene compound and the cocatalyst compound can also be used in a form supported on silica or alumina.

Meanwhile, the polymerization reaction of the propylene-alpha olefin copolymer according to the present invention using the supported catalyst may be performed using one continuous slurry polymerization reactor, loop slurry reactor, gas phase reactor, or solution reactor.

The supported catalyst is substituted with an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and their isomers and aromatic hydrocarbon solvents such as toluene and benzene, and chlorine atoms such as dichloromethane and chlorobenzene. It can be dissolved or diluted in a hydrocarbon solvent or the like and injected. The solvent used here is preferably used by removing a small amount of water or air acting as a catalyst poison by treating with a small amount of alkyl aluminum, and it is also possible to further use a cocatalyst.

Here, the polymerization may be performed by reacting for 1 to 24 hours under a temperature of 25 to 500 ° C and a pressure of 1 to 100 kgf / cm 2. At this time, the polymerization reaction temperature is preferably 25 to 200 ° C, more preferably 50 to 100 ° C. Further, the polymerization reaction pressure is preferably 1 to 70 kgf / cm 2, and more preferably 5 to 40 kgf / cm 2. The polymerization reaction time is preferably 1 to 5 hours.

The polymerization process may control the molecular weight range and MFR of the propylene-alpha olefin copolymer finally produced according to hydrogenation or non-addition conditions. In particular, a propylene-alpha olefin copolymer having a high molecular weight can be prepared under conditions in which no hydrogen is added, and a low molecular weight propylene-alpha olefin copolymer can be produced even with a small amount of hydrogen addition when hydrogen is added. At this time, the hydrogen content added to the polymerization process is in the range of 0.07 L to 4 L under 1 atmosphere of the reactor condition, or supplied at a pressure of 1 bar to 40 bar, or 168 ppm to 8,000 ppm in the hydrogen molar content range compared to the olefinic monomer. Can be supplied.

As described above, the propylene-alpha olefin copolymer according to the present invention can produce a propylene-alpha olefin copolymer having a different melting point depending on the type and content of the comonomer alpha olefin, in particular, the comonomer alpha olefin. Since the type and content of and the melting point satisfy a specific relational expression, there is an advantage that the desired melting point can be easily adjusted as necessary.

Hereinafter, preferred embodiments are presented to help understanding of the invention. However, the following examples are only for illustrating the invention, and the invention is not limited thereto.

Manufacturing example  One

Step 1) Preparation of (6-t-butoxyhexyl) (methyl) -bis (2-methyl-4-tert-butyl-phenylindenyl) silane

2-methyl-4-tert-butylphenylindene (20.0 g, 76 mmol) was dissolved in toluene / THF = 10/1 solution (230 mL), followed by n-butyllithium solution (2.5 M, hexane solvent, 22 g) was slowly added dropwise at 0 ° C., and then stirred at room temperature for one day. Then, (6-t-butoxyhexyl) dichloromethylsilane (1.27 g) was slowly added dropwise to the mixed solution at -78 ° C, stirred for about 10 minutes, and then stirred at room temperature for one day. Then, water was added to separate the organic layer, and then the solvent was distilled under reduced pressure to obtain (6-t-butoxyhexyl) (methyl) -bis (2-methyl-4-tert-butyl-phenylindenyl) silane.

¹ H NMR (500 MHz, CDCl ₃ , 7.26 ppm): -0.20-0.03 (3H, m), 1.26 (9H, s), 0.50-1.20 (4H, m), 1.20-1.31 (11H, m), 1.40 -1.62 (20H, m), 2.19-2.23 (6H, m), 3.30-3.34 (2H, m), 3.73-3.83 (2H, m), 6.89-6.91 (2H, m), 7.19-7.61 (14H, m)

Step 2) Preparation of [(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4-tert-butylphenylindenyl)] zirconium dichloride

The (6-t-butoxyhexyl) (methyl) -bis (2-methyl-4-tert-butyl-phenylindenyl) silane prepared in Step 1 was added to a toluene / THF = 5/1 solution (95 mL). After dissolving, n-butyllithium solution (2.5 M, hexane solvent, 22 g) was slowly added dropwise at -78 ° C, followed by stirring at room temperature for one day. Bis (N, N'-diphenyl-1,3-propanediamido) dichlorozirconium bis (tetrahydrofuran) [Zr (C ₅ H ₆ NCH ₂ CH ₂ NC ₅ H ₆ ) Cl ₂ (C ₄ H ₈ O) ₂ ] was dissolved in toluene (229 mL), then slowly added dropwise at -78 ° C and stirred at room temperature for one day. After the reaction solution was cooled to -78 ° C, HCl ether solution (1 M, 183 mL) was slowly added dropwise, followed by stirring at 0 ° C for 1 hour. After filtering and drying under vacuum, hexane was added and stirred to precipitate crystals. The precipitated crystals were filtered and dried under reduced pressure to [(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4-tert-butylphenylindenyl)] zirconium dichloride (20.5 g, total 61 %).

¹ H NMR (500 MHz, CDCl ₃ , 7.26 ppm): 1.20 (9H, s), 1.27 (3H, s), 1.34 (18H, s), 1.20-1.90 (10H, m), 2.25 (3H, s) , 2.26 (3H, s), 3.38 (2H, t), 7.00 (2H, s), 7.09-7.13 (2H, m), 7.38 (2H, d), 7.45 (4H, d), 7.58 (4H, d ), 7.59 (2H, d), 7.65 (2H, d)

Manufacturing example  2

Step 1) Preparation of (6-t-butoxyhexyl) (methyl) -bis (2-methyl-4- (4-t-butylphenyl) indenyl)) silane

150 g of 2-methyl-4- (4-t-butylphenyl) -indene was added to a 3 L Schlenk flask, and a toluene / THF (10: 1, 1.73 L) solution was added and dissolved at room temperature. . After the solution was cooled to -20 ° C, 240 mL of an n-butyllithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise and stirred at room temperature for 3 hours. Thereafter, the reaction solution was cooled to -20 ° C, and then 82 g of (6-t-butoxyhexyl) dichloromethylsilane and 512 mg of CuCN were slowly added dropwise. The reaction solution was heated to room temperature, stirred for 12 hours, and 500 mL of water was added. Thereafter, the organic layer was separated, and dehydrated with MgSO4 and filtered. The filtrate was distilled under reduced pressure to obtain a yellow oil.

¹ H NMR (500 MHz, CDCl ₃ , 7.26 ppm): -0.09--0.05 (3H, m), 0.40-0.60 (2H, m), 0.80-1.51 (26H, m), 2.12-2.36 (6H, m ), 3.20 ~ 3.28 (2H, m), 3.67-3.76 (2H, m), 6.81-6.83 (2H, m), 7.10-7.51 (14H, m)

Step 2) Preparation of rac-[(6-t-butoxyhexylmethylsilanediyl) -bis (2-methyl-4- (4-t-butylphenyl) indenyl)] hafnium dichloride

(6-t-butoxyhexyl) (methyl) bis (2-methyl-4- (4-t-butylphenyl)) indenylsilane prepared before 3 L Schlenk flask was added, and di 1 L of ethyl ether was added and dissolved at room temperature. After the solution was cooled to -20 ° C, 240 mL of an n-butyllithium solution (n-BuLi, 2.5 M in hexane) was slowly added dropwise and stirred at room temperature for 3 hours. Thereafter, the reaction solution was cooled to -78 ° C, and then 92 g of hafnium chloride was added. After heating the reaction solution to room temperature, the mixture was stirred for 12 hours, and the solvent was removed under reduced pressure. After adding 1 L of dichloromethane, inorganic salts and the like that were not dissolved were filtered off. The filtrate was dried under reduced pressure, and 300 mL of dichloromethane was added again to precipitate crystals. The precipitated crystals were filtered and dried to obtain 80 g of rac-[(6-t-butoxyhexylmethylsilanediyl) -bis (2-methyl-4- (4-t-butylphenyl) indenyl)] hafnium dichloride. (Rac: meso = 50: 1).

¹ H NMR (500 MHz, CDCl ₃ , 7.26 ppm): 1.19-1.78 (37H, m), 2.33 (3H, s), 2.34 (3H, s), 3.37 (2H, t), 6.91 (2H, s) , 7.05-7.71 (14H, m)

Manufacturing example  3

3 g of silica L203F was pre-weighed in a shrink flask, and then 10 mmol of methylaluminoxane (MAO) was added and reacted at 95 ° C. for 24 hours. After precipitation, the upper layer was removed and washed once with toluene. 60 μmol of the compound prepared in Preparation Example 2 was dissolved in toluene, and then reacted at 75 ° C. for 5 hours. After the completion of the reaction and the precipitation was over, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Then, 20 μmol of the compound prepared in Preparation Example 1 was dissolved in toluene, and further reacted at 75 ° C. for 2 hours. After the completion of the reaction and the precipitation was over, the upper layer solution was removed and the remaining reaction product was washed once with toluene. Dimethylanilininyltetrakis (pentafluorophenyl) borate 64 μmol was added and reacted at 75 ° C. for 5 hours. After the reaction was completed, the mixture was washed with toluene, washed again with hexane, and dried under vacuum to obtain a silica-supported metallocene catalyst in the form of solid particles.

Example  1 to 5

Bulk-slurry polymerization of the propylene-alpha olefin copolymer was performed using a continuous two-loop reactor. At this time, triethylaluminum (TEAL) and hydrogen gas were respectively added using a pump, and the silica-supported metallocene catalyst prepared in Preparation Example 3 was used for oil-grease (mineral oil) for bulk-slurry polymerization. (KAYDOL, White Mineral Oil) and grease (WHITE PROTOPET, 1S Petrolatum) mixed in a 2: 1 weight ratio mud catalyst was used. The production per hour was operated at about 40 kg, and the detailed operating conditions were as shown in Table 1 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Temperature (℃) 65 65 65 60 60 Pressure (kg / cm ³ ) 35 35 35 35 35 Catalyst input (cc / hr) 5.33 4.12 3.53 5.59 4.18 Propylene input (kg / hr) 40 40 40 40 40 TEAL input (ppm) 50 50 50 50 50 Hydrogen input (ppm) 280 220 220 110 150 C2 Feed (wt%) 1.7 2.2 2.5 2.0 2.0 C4 Feed (wt%) - - - 4.0 4.0

Comparative example  1 and 2

SEETEC R3410 and SEETEC T3410 of LG Chemical Co., Ltd. were used as Comparative Examples 1 and 2, respectively.

Experimental example

Physical properties were measured by the following method using the copolymers prepared in the above Examples and Comparative Examples.

1) Weight average molecular weight: The weight average molecular weight of each copolymer was measured using gel permeation chromatography (GPC). At this time, the analysis temperature was set to 160 ° C, and trichlorobenzene was used as the solvent, and it was measured by standardizing with polystyrene.

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

3) Melt Index (MFR): The melt index was measured according to ASTM 1238 (2.16 kg, 230 ° C).

4) Comonomer content: The comonomer content was calculated by analyzing by IR. In addition, the total sum of the values of the comonomer content (wt%) divided by its carbon number was calculated as x.

The results are shown in Table 2 below.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 MFR (g / 10 min) 20.9 15.6 18.8 8.4 6.8 7.1 7.3 C2 (wt%) / C4 (wt%) 1.58 1.83 2.26 1.33 / 3.43 1.40 / 3.80 2.8 2.5 / 3.5 MW (g / mol) 203k 235k 224k 262k 289k 288k 285k MWD 2.9 2.9 2.7 2.9 2.8 3.5 4.0 x 0.79 0.92 1.13 1.52 1.65 1.4 2.13 -15.6 × x + 150 137.7 135.7 132.4 126.2 124.3 128.2 116.8 y (Tm, ℃) 140.2 137.9 134.5 128.9 126.4 147.8 134.9 -15.6 × x + 155 142.7 140.7 137.4 131.2 129.3 133.2 121.8

As shown in Table 2, it was confirmed that the propylene-alpha olefin copolymer according to the present invention is capable of a melting point of a specific relation according to the type and content of the comonomer. Therefore, it was confirmed that the melting point can be easily adjusted by adjusting the type and content of the alpha-olefin, which is a comonomer.

Claims (9)

The weight average molecular weight is 150,000 to 350,000,
The melting point (Tm) is 125 to 130 ° C,
Satisfying Equation 1 below,
Propylene / ethylene / 1-butene copolymer:
[Equation 1]
(-15.6 × x + 150) <y <(-15.6 × x + 155)
In Equation 1,
x is the propylene / ethylene / 1-butene copolymer, the content of ethylene (wt%) divided by 2 carbon atoms of ethylene, and the content of 1-butylene (wt%) to 4 carbon atoms of 1-butylene Is the sum of the divided values,
y is the melting point (° C) of the propylene / ethylene / 1-butene copolymer.
According to claim 1,
Characterized in that satisfying the following equation 1-1,
Propylene / ethylene / 1-butene copolymer:
[Equation 1-1]
(-15.6 × x + 152) <y <(-15.6 × x + 153)
In Equation 1, x and y are as defined in claim 1.
According to claim 1,
Characterized in that the melting point is 126 to 130 ℃,
Propylene / ethylene / 1-butene copolymer.
delete delete delete delete delete According to claim 1,
The propylene / ethylene / 1-butene copolymer is prepared by copolymerizing propylene, ethylene and 1-butene in the presence of a hybrid supported catalyst comprising a compound represented by the following formula (1), a compound represented by the following formula (2) and a carrier Characterized by being,
Propylene / ethylene / 1-butene copolymer:
[Formula 1]

In Chemical Formula 1,
X is the same or different halogen from each other,
R ₁ is C _6-20 aryl substituted with C _1-20 alkyl,
R ₂ , R ₃ and R ₄ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 alkoxysilyl, C _1-20 ether, C _1-20 silyl ether, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C _7-20 arylalkyl,
A is carbon, silicon, or germanium,
R ₅ is C _1-20 alkyl substituted with C _1-20 alkoxy,
R ₆ is hydrogen, C _1-20 alkyl, or C _2-20 alkenyl,
[Formula 2]

In Chemical Formula 2,
X 'is the same or different halogen from each other,
R ' ₁ is C _6-20 aryl substituted with C _1-20 alkyl,
R ' ₂ , R' ₃ and R ' ₄ are each independently hydrogen, halogen, C _1-20 alkyl, C _2-20 alkenyl, C _1-20 alkylsilyl, C _1-20 silylalkyl, C _1-20 Alkoxysilyl, C _1-20 ether, C _1-20 silyl ether, C _1-20 alkoxy, C _6-20 aryl, C _7-20 alkylaryl, or C7-20 arylalkyl,
A 'is carbon, silicon, or germanium,
R ' ₅ is C _1-20 alkyl substituted with C _1-20 alkoxy,
R ' ₆ is hydrogen, C _1-20 alkyl, or C _2-20 alkenyl.