WO2024101539A1 - Propylene-based polymer and manufacturing method thereof - Google Patents

Propylene-based polymer and manufacturing method thereof Download PDF

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WO2024101539A1
WO2024101539A1 PCT/KR2023/001881 KR2023001881W WO2024101539A1 WO 2024101539 A1 WO2024101539 A1 WO 2024101539A1 KR 2023001881 W KR2023001881 W KR 2023001881W WO 2024101539 A1 WO2024101539 A1 WO 2024101539A1
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propylene
based polymer
less
polymer
minutes
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French (fr)
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Myung Jun Park
Jihae Park
Hyeongmin KIM
Sungjae Na
Sangyoung SHIN
Hyoseung PARK
Jisun Choi
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Sk Innovation Co., Ltd.
Sk Geo Centric Co., Ltd.
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Publication of WO2024101539A1 publication Critical patent/WO2024101539A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/11—Melt tension or melt strength
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/26—Use as polymer for film forming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/14—Copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/02—Ziegler natta catalyst

Definitions

  • the present disclosure relates to a propylene-based polymer and a manufacturing method thereof.
  • a propylene polymer (polypropylene, PP) is composed of only carbon and hydrogen and has a low density, it is easy to reproduce, and may implement excellent chemical resistance and a high tensile modulus at a relatively low cost.
  • the propylene-based polymer has difficulty in implementing a high melt strength, and has limitations in thermoforming and processing. Increasing the melt strength of the propylene-based polymer has been an industrial objective for the last several decades, but its success has been limited.
  • LCB long chain branch
  • An object of the present invention is to provide a method capable of manufacturing a high melt strength propylene-based polymer.
  • Another object of the present invention is to provide a propylene-based polymer manufactured according to the method for manufacturing a propylene-based polymer according to the above embodiment.
  • Still another object of the present invention is to provide a film containing the propylene-based polymer according to the above embodiment.
  • a method for manufacturing a propylene-based polymer comprising: a first polymerization step of manufacturing a polymer composition by polymerizing propylene and diene in liquid phase under a Ziegler-Natta catalyst; and a second polymerization step of performing polymerization by adding propylene and ethylene in gas phase to the manufactured polymer composition.
  • a propylene-based polymer manufactured according to the method for manufacturing a propylene-based polymer as described above.
  • the present disclosure relates to a method for manufacturing a propylene-based polymer having an excellent melt strength, a propylene-based polymer manufactured through the same, and a film containing the same.
  • the method for manufacturing a propylene-based polymer according to an embodiment comprises: polymerizing propylene and diene in liquid phase under a Ziegler-Natta catalyst and performing polymerization by adding propylene and ethylene in gas phase, and the propylene-based polymer manufactured through the same may implement physical properties of a high melt strength. Therefore, the propylene-based polymer according to an embodiment is capable of foam molding at a high temperature and thus has excellent processability and productivity.
  • FIG. 1 is a view illustrating results of small amplitude oscillatory shear (SAOS) analysis to confirm shear thinning properties of a propylene-based polymer according to Examples and Comparative Examples.
  • SAOS small amplitude oscillatory shear
  • FIG. 2 is a view illustrating results of measuring a melt strength of propylene-based polymers according to Examples and Comparative Examples.
  • the propylene-based polymer of Example 1 showed a significantly higher melt strength than the propylene-based polymers of Comparative Examples 1 to 3.
  • the melt strength rapidly improved as a pull-off speed increased, reaching a melt strength of about 100 cN or more, and stretching was possible even at a pull-off speed of 300 mm/s or more.
  • FIG. 3 is a view illustrating results of gel permeation chromatography (GPC) analysis to confirm a molecular weight distribution of propylene-based polymers according to Examples and Comparative Examples.
  • the propylene-based polymer of Example 1 had a wide molecular weight distribution (MWD) compared to the propylene-based polymers of Comparative Examples 1 and 2, and thus had a relatively high distribution.
  • a ratio of polymer groups having a molecular weight of 10 6.8 g/mol or more was higher than that of Comparative Example 3.
  • FIG. 4 is a view illustrating results of measuring an elastic modulus to analyze an elasticity of the propylene-based polymer according to Example 1.
  • FIG. 4 in the propylene-based polymer of Example 1, two points where a storage modulus and a loss modulus intersect were confirmed, and relaxation time, which is the reciprocal of an angular frequency value at a crossover modulus at one of them, was longer than that of the Comparative Example.
  • the second polymerization step may be performed at a temperature of 20 °C to 70 °C for 5 minutes to 60 minutes.
  • the second polymerization step may be performed at a temperature of 20 °C to 60 °C, 30 °C to 60 °C, 30 °C to 50 °C, 35 °C to 45 °C, or about 40 °C for 5 minutes to 50 minutes, 10 minutes to 50 minutes, 10 minutes to 40 minutes, 10 minutes to 30 minutes, 15 minutes to 25 minutes, or about 20 minutes.
  • the first polymerization step may comprise adding 1000 ppm to 3000 ppm, 1500 ppm to 2500 ppm, 1800 ppm to 2200 ppm, or about 2000 ppm of hydrogen.
  • the diene may be added at 1 g to 5 g, 2 g to 4 g, or about 3 g
  • the propylene may be added at 500 g to 2000 g, 500 g to 1500 g, 600 g to 1300 g, 700 g to 1200 g, 800 g to 1200 g, 900 g to 1100 g, or about 1000 g.
  • a weight ratio of the propylene to the diene may be 1:100 to 1:500, 1:200 to 1:400, 1:250 to 1:400, 1:300 to 1:400, 1:300 to 1:350, or about 1:330.
  • a molar ratio of the ethylene to the propylene in gas phase may be 1:9 to 9:1.
  • the molar ratio may be 2:8 to 9:1, 3:7 to 9:1, 4:6 to 9:1, 5:5 to 9:1, 6:4 to 9:1, 5:5 to 8:2, 6:4 to 8:2, or about 7:3.
  • it is not necessarily intended to be limited to the above range.
  • the Ziegler-Natta catalyst may comprise a transition metal compound containing a Group 4, 5, or 6 element of the periodic table; and an organometallic compound containing a Group 13 element of the periodic table.
  • the transition metal compound is a main catalyst of the Ziegler-Natta catalyst, and may be a compound containing any one or more of magnesium, titanium, a halogen element, and an internal electron donor.
  • the organometallic compound is a cocatalyst of the Ziegler-Natta catalyst and may be an organoaluminum compound, and may comprise, for example, at least one of trialkyl aluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride or alkyl aluminum sesquihalide.
  • the organicaluminum compound may comprise Al(C 2 H 5 ) 3 , Al(C 2 H 5 ) 2 H, Al(C 3 H 7 ) 3 , Al(C 3 H 7 ) 2 H, Al(i-C 4 H 9 ) 2 H, Al(C 8 H 17 ) 3 , Al(C 12 H 25 ) 3 , Al(C 2 H 5 )(C 12 H 25 ) 2 , Al(i-C 4 H 9 )(C 12 H 25 ) 2 , Al(i-C 4 H 9 ) 2 H, Al(i-C 4 H 9 ) 3 , (C 2 H 5 ) 2 AlCl, (i-C 3 H 9 ) 2 AlCl, or (C 2 H 5 ) 3 Al 2 Cl 3 .
  • a molar ratio of the organometallic compound to the transition metal compound may be, for example, 1:1 to 1:50 or 1:5 to 1:50.
  • the second polymerization step may further comprise: discharging unreacted gas and cooling the temperature to room temperature to terminate the reaction, and then separately collecting the resulting polymer and drying it in a vacuum oven at 40 °C to 80 °C, or about 60 °C, for about 60 minutes or more to finally obtain the polymer.
  • An embodiment provides a propylene-based polymer manufactured according to the method for manufacturing a propylene-based polymer according to the above embodiment.
  • the propylene-based polymer according to an exemplary embodiment has a melt strength of 100 cN or more as measured at 200 °C, and significantly higher melt strength than conventional propylene-based polymers may be implemented.
  • the melt strength may be, for example, 100 cN or more, 105 cN or more, or 110 cN or more, and the upper limit thereof may be, for example, 200 cN or less, 180 cN or less, 160 cN or less, 150 cN or less, or 140 cN or less, or 130 cN or less.
  • the propylene-based polymer according to an exemplary embodiment is useful because processability and productivity may be greatly improved by implementing a high melt strength, and may have improved transparency and hingeability.
  • the propylene-based polymer having a melt strength of 100 cN or more may refer to a propylene-based polymer capable of implementing a melt strength of 100 cN or more regardless of any pull-off speed.
  • the propylene-based polymer according to an exemplary embodiment may be stretchable even at a pull-off speed of 300 mm/s or more while having the above high melt strength (FIG. 2). Specifically, stretching may be possible even at a pull-off speed of 300 mm/s to 400 mm/s or 300 mm/s to 350 mm/s.
  • the melt strength may be obtained by measuring a maximum force until a specimen is broken by pulling at an acceleration of about 3 mm/s 2 to 10 mm/s 2 , 4 mm/s 2 to 9 mm/s 2 , 4 mm/s 2 to 8 mm/s 2 , 5 mm/s 2 to 7 mm/s 2 , or about 6 mm/s 2 when extruded at about 150 °C to 250 °C, 180 °C to 230 °C, 190 °C to 210 °C, or about 200 °C at an extrusion rate of about 8 g/min to 15 g/min, 8 g/min to 13 g/min, 9 g/min to 13 g/min, 10 g/min to 12 g/min, or about 11 g/min.
  • the propylene-based polymer may have a shear thinning index (STI) of 5 or more, which is defined by Equation 1 below:
  • Shear thinning index ⁇ 0.01 / ⁇ 10
  • ⁇ 0.01 and ⁇ 10 are complex viscosities (Pa ⁇ s) at angular frequencies of 0.01 rad/s and 10 rad/s at 230 °C, respectively.
  • a shear thinning phenomenon refers to a phenomenon in which the viscosity of a polymer decreases as the shear rate increases or as the same force is applied for a certain period of time, and such a shear thinning property has a great influence on a molding method of polymers.
  • the propylene-based polymer according to an exemplary embodiment may have the shear thinning index (STI) of 5 or more, 10 or more, 15 or more, 20 or more, 30 or more, 33 or more, or 34 or more, and the upper limit thereof may be 50 or less, 45 or less, 40 or less, 38 or less, 36 or less, or 35 or less. However, it is not necessarily intended to be limited to the above range.
  • the ⁇ 0.01 may be 1.0 x 10 4 or more, 1.5 x 10 4 or more, 2.0 x 10 4 or more, 2.3 x 10 4 or more, 2.4 x 10 4 or more, 2.5 x 10 4 or more, 2.8 x 10 4 or more, 3.0 x 10 4 or more, or 3.5 x 10 4 or more, and the upper limit thereof may be, for example, 6.0 x 10 4 or less, 5.5 x 10 4 or less, 5.0 x 10 4 or less, 4.8 x 10 4 or less, 4.5 x 10 4 or less, 4.3 x 10 4 or less, 4.1 x 10 4 or less, 4.0 x 10 4 or less, 3.8 x 10 4 or less, 3.7 x 10 4 or less, or 3.5 x 10 4 or less.
  • ⁇ 10 may be 2.0 x 10 3 or less, 1.8 x 10 3 or less, 1.6 x 10 3 or less, 1.5 x 10 3 or less, 1.4 x 10 3 or less, 1.3 x 10 3 or less, 1.2 x 10 3 or less, or 1.1 x 10 3 or less, and the lower limit thereof may be, for example 5.0 x 10 2 or more, 8.0 x 10 2 or more, 9.0 x 10 2 or more, or 1.0 x 10 3 or more. However, it is not necessarily intended to be limited to the above range.
  • the propylene-based polymer according to an exemplary embodiment has the shear thinning index (STI) of about 5 or more, thereby implementing properties equivalent to or better than those of conventional developed products.
  • STI shear thinning index
  • the propylene-based polymer according to an exemplary embodiment is implemented with a strain hardening phenomenon equivalent to or significantly higher than that of conventional developed products, and from this, it can be seen that the propylene-based polymer according to an exemplary embodiment comprises various long-chain branches. Therefore, when the propylene-based polymer according to an exemplary embodiment is used, a stable state during processing may be effectively maintained.
  • the relaxation time value of the propylene-based polymer when a reciprocal of an angular frequency value in a crossover modulus of a storage modulus (G') and a loss modulus (G'') at 230 °C based on a Maxwell model is defined as relaxation time, the relaxation time value of the propylene-based polymer according to an exemplary embodiment may be 3.0 s or more. Alternatively, the relaxation time may be 3.3 s or more, 3.5 s or more, 3.7 s or more, 3.8 s or more, 4.0 s or more, or 4.2 s or more.
  • the upper limit may be, for example, 6.0 s or less, 5.5 s or less, 5.2 s or less, 5.0 s or less, 4.8 s or less, 4.5 s or less, or 4.3 s or less. However, it is not necessarily intended to be limited to the above range.
  • the propylene-based polymer according to an exemplary embodiment may have a phase difference (tan ⁇ ) value of 2.0 or less as defined by Equation 3 below when the angular frequency is 0.01 rad/s at 230 °C based on the Maxwell model.
  • G' is a storage modulus and G'' is a loss modulus.
  • the phase difference may be 1.8 or less, 1.5 or less, 1.0 or less, 0.8 or less, 0.6 or less, or 0.5 or less, and the lower limit may be, for example, 0.05 or more, 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, or 0.5 or more.
  • the propylene-based polymer according to an exemplary embodiment may have excellent elasticity due to a long relaxation time and a low phase difference value.
  • the propylene-based polymer according to an exemplary embodiment may comprise 0.5 wt% or more, 1.0 wt% or more, 2.0 wt% or more, 2.2 wt% or more, 2.3 wt% or more, or 2.5 wt% or more of xylene solubles (XS).
  • the upper limit of the xylene solubles may be, for example, 10.0 wt% or less, 8.0 wt% or less, 6.0 wt% or less, 5.0 wt% or less, 4.0 wt% or less, 3.0 wt% or less, or 2.8 wt% or less.
  • Xylene solubles refer to a soluble part in cold xylene among the components contained in the polymer, and may be measured by dissolving the polymer in the xylene and then allowing an insoluble part (residue) to be determined from a cooling solution. Specifically, xylene solubles may be calculated through the following Equation.
  • m 0 is an initial weight of the polymer (g)
  • m 1 is a weight of the residue (g)
  • v 0 is an initial volume of the sample (mL)
  • v 1 is a volume of the sample after analysis (mL).
  • the xylene solubles contain polymer chains with low stereoregularity and may be an indicator of the amount of non-crystalline regions
  • the propylene-based polymer according to the above embodiment may be effectively applied to various fields such as adhesives, films, and packaging materials due to easy handling such as processability and productivity by implementing the above physical properties.
  • the propylene-based polymer may have a ratio of a polymer group having a molecular weight of 10 6.5 g/mol to 10 8.0 g/mol of 2% or more, or 2.5% or more, 3% or more, 3.2% or more, 3.3% or more, or 3.4% or more, or 10% or less, 8% or less, 6% or less, 5% or less, 4% or less, or 3.5% or less, as measured by gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the polymer group may have a ratio of a polymer group having a molecular weight of 10 6.5 g/mol or more of 2% or more, or 2.5% or more, 3% or more, 3.2% or more, 3.3% or more, or 3.4% or more, or 10% or less, 8% or less, or less, 6% or less, 5% or less, 4% or less, or 3.5% or less.
  • the propylene-based polymer according to an exemplary embodiment has a wider molecular weight distribution than the propylene-based polymer of the Comparative Example, and through this, the propylene-based polymers of an exemplary embodiment are not separated from each other and are homogeneously distributed.
  • the propylene-based polymer of an exemplary embodiment has a higher proportion of polymer groups having a molecular weight of 10 6.5 g/mol or more compared to the Comparative Example, which may mean that the propylene-based polymer of an exemplary embodiment has a high molecular weight proportion and that several types of long chain branches (LCBs) are evenly distributed.
  • the propylene-based polymer according to an exemplary embodiment may have a high proportion of polymer groups and comprise various kinds of long chain branches, thereby excellently implementing physical properties such as high melting strength.
  • the propylene-based polymer according to an exemplary embodiment may have a number average molecular weight (Mn) of 30 kg/mol to 80 kg/mol, 40 kg/mol to 60 kg/mol, 45 kg/mol to 55 kg/mol, or about 55 kg/mol, a weight average molecular weight (Mw) of 350 kg/mol to 500 kg/mol, 400 kg/mol to 480 kg/mol, 400 kg/mol to 450 kg/mol, 410 kg/mol to 440 kg/mol, or about 435 kg/mol, and a molecular weight distribution (MWD) of 5 to 15, 6 to 12, 6 to 11, 6 to 10, 7 to 10, 8 to 10, or 8 to 9.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Adhesives, films, or packaging materials containing a high melt strength propylene-based polymer according to an exemplary embodiment are provided, and a high melt strength propylene-based polymer having according to an exemplary embodiment may be applied to various fields because it is very easy to handle such as productivity and processability due to its excellent physical properties.
  • Daploy TM WB140HMS a high melt strength polypropylene (HMSPP) from Borealis, was purchased and prepared.
  • H220P a linear propylene-based polymer from SK, was purchased and prepared.
  • a propylene-based polymer was manufactured in the same manner as in Example 1, except that 1,9-decadiene was not added in a liquid phase polymerization step of the manufacturing method of the propylene-based polymer according to Example 1.
  • melt indices of the propylene-based polymers according to Example 1 and Comparative Examples 1 to 3 are as follows. The melt indices were measured according to the ASTM D1238 standard (230 °C, 2.16 kg load conditions).
  • Example 1 Comp.
  • Example 1 Comp.
  • Example 2 Comp.
  • Example 3 Melt index (dg/min) 2.0 2.3 2.2 6.0
  • the measurement for SAOS analysis was made using a Strain-Controlled Rheomether (ARES) from TA, and performed in a range of 6.3 x 10 -3 to 628 rad/s for angular frequency sweep under the conditions of strain 5%, 230 °C, and pressure holding time (soak time) of 120 seconds using a Plate-Plate Fixture.
  • RAS Strain-Controlled Rheomether
  • the polymer of Example 1 showed a higher zero-shear viscosity and a stronger shear thinning phenomenon than the polymers of Comparative Examples 1 to 3. Through this, it can be confirmed that the propylene-based polymers of Examples have excellent shear thinning properties and thus high processability compared to the propylene-based polymers of Comparative Examples.
  • ⁇ 0.01 and ⁇ 10 are complex viscosities (Pa ⁇ s) at angular frequencies of 0.01 rad/s and 10 rad/s at 230 °C, respectively.
  • Example 1 Comp.
  • Example 1 Comp.
  • Example 2 Comp.
  • Example 3 Complex viscosity ( ⁇ , Pa ⁇ s) 0.01 rad/s 3.75 x 10 4 1.13 x 10 4 1.13 x 10 4 6.66 x 10 3 10 rad/s 1.08 x 10 3 6.75 x 10 2 2.31 x 10 3 9.29 x 10 2 STI 34.72 16.74 4.89 7.17
  • the measurement for melt strength analysis was used by connecting Goettfert Rheotens to a Brabender single-screw extruder, and an orifice die mounted on the extruder having a diameter of 1 mm and a length of 40 mm was used.
  • the extrusion rate was set to 11 g/min, and a filament extruded through the die at 200 °C was pulled at an acceleration of 6 mm/s 2 , and a maximum force until the filament broke was measured and recorded as melt strength.
  • the polymer of Example 1 showed significantly higher melt strength than the polymers of Comparative Examples 1 to 3 having similar melt indices.
  • the melt strength rapidly improved as a pull-off speed increased, reaching a melt strength of about 100 cN or more, and stretching was possible even at a pull-off speed of 300 mm/s or more.
  • Comparative Examples 1 to 3 were stretched to a maximum melt strength of 45 cN to 50 cN, 23 cN to 26 cN, and 80 cN to 90 cN, respectively.
  • the propylene-based polymer according to an exemplary embodiment was a high melt strength propylene-based polymer having a significantly higher melt strength than the polymer of the Comparative Example.
  • GPC analysis was performed using Polymer Char GPC-IR equipment (standard sample: Easical PS1 Polystyrene, temperature: 160 °C, solvent: 1,2,4-trichlorobenzene, viscosity constant: K, ⁇ of polypropylene). About 1.5 mg of the polymer sample was placed in a 1.25 mL vial of high-temperature GPC, 1 mL of 1,2,4-trichlorobenzene (w/BHT) was added, and the mixture was dissolved at 150 °C while stirring for 3 hours or more, and then used for analysis.
  • w/BHT 1,2,4-trichlorobenzene
  • Example 1 Comp.
  • Example 1 Comp.
  • Example 2 Comp.
  • Example 3 Mn (kg/mol) 51 70 64 50 Mw (kg/mol) 435 399 400 454 MWD 8.6 5.7 6.3 9.1
  • Example 1 As a result, it could be seen that as the molecular weight distribution of Example 1 was relatively broad compared to the previously developed propylene-based polymers (Comparative Examples 1 and 2), the polymers were not separated and were homogeneously distributed, and the distribution of the polymers was relatively high. In addition, the molecular weight distribution of Example 1 showed a shoulder around the molecular weight of about 10 6.5 g/mol to 10 7.4 g/mol, and specifically, the ratio of the polymer groups having a molecular weight of 10 6.5 g/mol or more was about 3.5%, which was relatively higher than that of Comparative Example (Comparative Example 1: about 1%, Comparative Example 2: 0.4%, Comparative Example 3: 2.7%).
  • Elastic modulus was measured using a Strain-Controlled Rheomether (ARES) (Maxwell model) from TA, and G' and G'' values were calculated through a TRIOS software.
  • ARES Strain-Controlled Rheomether
  • the linear rheological data of the storage modulus and the loss modulus were fitted, the elastic modulus at the point where the storage modulus and the loss modulus intersect was defined as the crossover modulus, and the reciprocal of the angular frequency value at the crossover modulus was defined as the relaxation time.
  • the values are shown in Table 4 below.
  • Example 1 Comp.
  • Example 1 Comp.
  • Example 2 Comp.
  • Example 3 Crossover modulus (Pa) 8.2 x 10 2 , 2.1 x 10 4 1.1 x 10 4 2.2 x 10 4 2.5 x 10 4
  • Relaxation time (s) 4.2,1.6 x 10 -2 0.02 0.056 0.0098 tan ⁇ 0.5 4.8 11 1.1
  • Example 1 was confirmed to have two crossover modulus, and the relaxation time at one of the crossover modulus was 4.2 s, which was significantly higher than that of the comparative example, and at the same time, the measured phase difference value was very low.
  • the propylene-based polymer of Example had excellent elasticity compared to the propylene-based polymer according to Comparative Example.

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Abstract

The present disclosure relates to a method for manufacturing a propylene-based polymer having an excellent melt strength, a propylene-based polymer manufactured through the same, and a film containing the same. Specifically, the method for manufacturing a propylene-based polymer according to an embodiment includes: polymerizing propylene and diene in liquid phase under a Ziegler-Natta catalyst and performing polymerization by adding propylene and ethylene in gas phase, and the propylene-based polymer manufactured through the same may implement physical properties of a high melt strength. Therefore, the propylene-based polymer according to an embodiment is capable of foam molding at a high temperature and thus has excellent processability and productivity.

Description

PROPYLENE-BASED POLYMER AND MANUFACTURING METHOD THEREOF
The present disclosure relates to a propylene-based polymer and a manufacturing method thereof.
Since a propylene polymer (polypropylene, PP) is composed of only carbon and hydrogen and has a low density, it is easy to reproduce, and may implement excellent chemical resistance and a high tensile modulus at a relatively low cost. However, the propylene-based polymer has difficulty in implementing a high melt strength, and has limitations in thermoforming and processing. Increasing the melt strength of the propylene-based polymer has been an industrial objective for the last several decades, but its success has been limited.
In order to increase melting properties of the propylene-based polymer, it is preferable to have a long chain branch (LCB) having a long polymer chain in a polypropylene main chain. Methods such as blending, solid phase reaction, reaction extrusion, and electron beam irradiation have been reported as techniques for adding long chain branches to a polypropylene main chain.
An object of the present invention is to provide a method capable of manufacturing a high melt strength propylene-based polymer.
Another object of the present invention is to provide a propylene-based polymer manufactured according to the method for manufacturing a propylene-based polymer according to the above embodiment.
Still another object of the present invention is to provide a film containing the propylene-based polymer according to the above embodiment.
In one general aspect, there is provided a method for manufacturing a propylene-based polymer, the method comprising: a first polymerization step of manufacturing a polymer composition by polymerizing propylene and diene in liquid phase under a Ziegler-Natta catalyst; and a second polymerization step of performing polymerization by adding propylene and ethylene in gas phase to the manufactured polymer composition.
In another general aspect, there is provided a propylene-based polymer manufactured according to the method for manufacturing a propylene-based polymer as described above.
In another general aspect, there is provided a film containing the propylene-based polymer as described above.
The present disclosure relates to a method for manufacturing a propylene-based polymer having an excellent melt strength, a propylene-based polymer manufactured through the same, and a film containing the same. Specifically, the method for manufacturing a propylene-based polymer according to an embodiment comprises: polymerizing propylene and diene in liquid phase under a Ziegler-Natta catalyst and performing polymerization by adding propylene and ethylene in gas phase, and the propylene-based polymer manufactured through the same may implement physical properties of a high melt strength. Therefore, the propylene-based polymer according to an embodiment is capable of foam molding at a high temperature and thus has excellent processability and productivity.
FIG. 1 is a view illustrating results of small amplitude oscillatory shear (SAOS) analysis to confirm shear thinning properties of a propylene-based polymer according to Examples and Comparative Examples. As can be seen in FIG. 1, the propylene-based polymer of Example 1 had a higher zero shear viscosity and stronger shear thinning than the propylene-based polymers of Comparative Examples 1 to 3.
FIG. 2 is a view illustrating results of measuring a melt strength of propylene-based polymers according to Examples and Comparative Examples. As can be seen in FIG. 2, the propylene-based polymer of Example 1 showed a significantly higher melt strength than the propylene-based polymers of Comparative Examples 1 to 3. In particular, the melt strength rapidly improved as a pull-off speed increased, reaching a melt strength of about 100 cN or more, and stretching was possible even at a pull-off speed of 300 mm/s or more.
FIG. 3 is a view illustrating results of gel permeation chromatography (GPC) analysis to confirm a molecular weight distribution of propylene-based polymers according to Examples and Comparative Examples. As can be seen in FIG. 3, the propylene-based polymer of Example 1 had a wide molecular weight distribution (MWD) compared to the propylene-based polymers of Comparative Examples 1 and 2, and thus had a relatively high distribution. In addition, a ratio of polymer groups having a molecular weight of 106.8 g/mol or more was higher than that of Comparative Example 3.
FIG. 4 is a view illustrating results of measuring an elastic modulus to analyze an elasticity of the propylene-based polymer according to Example 1. As can be seen in FIG. 4, in the propylene-based polymer of Example 1, two points where a storage modulus and a loss modulus intersect were confirmed, and relaxation time, which is the reciprocal of an angular frequency value at a crossover modulus at one of them, was longer than that of the Comparative Example.
In an exemplary embodiment, the second polymerization step may be performed at a temperature of 20 ℃ to 70 ℃ for 5 minutes to 60 minutes. The second polymerization step may be performed at a temperature of 20 ℃ to 60 ℃, 30 ℃ to 60 ℃, 30 ℃ to 50 ℃, 35 ℃ to 45 ℃, or about 40 ℃ for 5 minutes to 50 minutes, 10 minutes to 50 minutes, 10 minutes to 40 minutes, 10 minutes to 30 minutes, 15 minutes to 25 minutes, or about 20 minutes.
In an exemplary embodiment, the first polymerization step may comprise adding 1000 ppm to 3000 ppm, 1500 ppm to 2500 ppm, 1800 ppm to 2200 ppm, or about 2000 ppm of hydrogen.
In an exemplary embodiment, the diene may be added at 1 g to 5 g, 2 g to 4 g, or about 3 g, and the propylene may be added at 500 g to 2000 g, 500 g to 1500 g, 600 g to 1300 g, 700 g to 1200 g, 800 g to 1200 g, 900 g to 1100 g, or about 1000 g. In an exemplary embodiment, a weight ratio of the propylene to the diene may be 1:100 to 1:500, 1:200 to 1:400, 1:250 to 1:400, 1:300 to 1:400, 1:300 to 1:350, or about 1:330. However, it is not necessarily intended to be limited to the above range.
In an exemplary embodiment, in the second polymerization step, a molar ratio of the ethylene to the propylene in gas phase may be 1:9 to 9:1. Alternatively, the molar ratio may be 2:8 to 9:1, 3:7 to 9:1, 4:6 to 9:1, 5:5 to 9:1, 6:4 to 9:1, 5:5 to 8:2, 6:4 to 8:2, or about 7:3. However, it is not necessarily intended to be limited to the above range.
In an exemplary embodiment, the Ziegler-Natta catalyst (or Ziegler-Natta-based catalyst) may comprise a transition metal compound containing a Group 4, 5, or 6 element of the periodic table; and an organometallic compound containing a Group 13 element of the periodic table. The transition metal compound is a main catalyst of the Ziegler-Natta catalyst, and may be a compound containing any one or more of magnesium, titanium, a halogen element, and an internal electron donor. The organometallic compound is a cocatalyst of the Ziegler-Natta catalyst and may be an organoaluminum compound, and may comprise, for example, at least one of trialkyl aluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride or alkyl aluminum sesquihalide. Specifically, for example, the organicaluminum compound may comprise Al(C2H5)3, Al(C2H5)2H, Al(C3H7)3, Al(C3H7)2H, Al(i-C4H9)2H, Al(C8H17)3, Al(C12H25)3, Al(C2H5)(C12H25)2, Al(i-C4H9)(C12H25)2, Al(i-C4H9)2H, Al(i-C4H9)3, (C2H5)2AlCl, (i-C3H9)2AlCl, or (C2H5)3Al2Cl3.
A molar ratio of the organometallic compound to the transition metal compound may be, for example, 1:1 to 1:50 or 1:5 to 1:50.
In an exemplary embodiment, the second polymerization step may further comprise: discharging unreacted gas and cooling the temperature to room temperature to terminate the reaction, and then separately collecting the resulting polymer and drying it in a vacuum oven at 40 ℃ to 80 ℃, or about 60 ℃, for about 60 minutes or more to finally obtain the polymer.
Hereinafter, the propylene-based polymer provided in an embodiment will be described in detail.
An embodiment provides a propylene-based polymer manufactured according to the method for manufacturing a propylene-based polymer according to the above embodiment.
The propylene-based polymer according to an exemplary embodiment has a melt strength of 100 cN or more as measured at 200 ℃, and significantly higher melt strength than conventional propylene-based polymers may be implemented. In an exemplary embodiment, the melt strength may be, for example, 100 cN or more, 105 cN or more, or 110 cN or more, and the upper limit thereof may be, for example, 200 cN or less, 180 cN or less, 160 cN or less, 150 cN or less, or 140 cN or less, or 130 cN or less. However, it is not necessarily intended to be limited to the above range. The propylene-based polymer according to an exemplary embodiment is useful because processability and productivity may be greatly improved by implementing a high melt strength, and may have improved transparency and hingeability.
The propylene-based polymer having a melt strength of 100 cN or more according to an exemplary embodiment may refer to a propylene-based polymer capable of implementing a melt strength of 100 cN or more regardless of any pull-off speed.
The propylene-based polymer according to an exemplary embodiment may be stretchable even at a pull-off speed of 300 mm/s or more while having the above high melt strength (FIG. 2). Specifically, stretching may be possible even at a pull-off speed of 300 mm/s to 400 mm/s or 300 mm/s to 350 mm/s.
In addition, in an exemplary embodiment, the melt strength may be obtained by measuring a maximum force until a specimen is broken by pulling at an acceleration of about 3 mm/s2 to 10 mm/s2, 4 mm/s2 to 9 mm/s2, 4 mm/s2 to 8 mm/s2, 5 mm/s2 to 7 mm/s2, or about 6 mm/s2 when extruded at about 150 ℃ to 250 ℃, 180 ℃ to 230 ℃, 190 ℃ to 210 ℃, or about 200 ℃ at an extrusion rate of about 8 g/min to 15 g/min, 8 g/min to 13 g/min, 9 g/min to 13 g/min, 10 g/min to 12 g/min, or about 11 g/min.
In an exemplary embodiment, the propylene-based polymer may have a shear thinning index (STI) of 5 or more, which is defined by Equation 1 below:
[Equation 1]
Shear thinning index = η0.01/η10
wherein η0.01 and η10 are complex viscosities (Pa·s) at angular frequencies of 0.01 rad/s and 10 rad/s at 230 ℃, respectively.
A shear thinning phenomenon refers to a phenomenon in which the viscosity of a polymer decreases as the shear rate increases or as the same force is applied for a certain period of time, and such a shear thinning property has a great influence on a molding method of polymers. The propylene-based polymer according to an exemplary embodiment may have the shear thinning index (STI) of 5 or more, 10 or more, 15 or more, 20 or more, 30 or more, 33 or more, or 34 or more, and the upper limit thereof may be 50 or less, 45 or less, 40 or less, 38 or less, 36 or less, or 35 or less. However, it is not necessarily intended to be limited to the above range.
Specifically, the η0.01 may be 1.0 x 104 or more, 1.5 x 104 or more, 2.0 x 104 or more, 2.3 x 104 or more, 2.4 x 104 or more, 2.5 x 104 or more, 2.8 x 104 or more, 3.0 x 104 or more, or 3.5 x 104 or more, and the upper limit thereof may be, for example, 6.0 x 104 or less, 5.5 x 104 or less, 5.0 x 104 or less, 4.8 x 104 or less, 4.5 x 104 or less, 4.3 x 104 or less, 4.1 x 104 or less, 4.0 x 104 or less, 3.8 x 104 or less, 3.7 x 104 or less, or 3.5 x 104 or less. In addition, η10 may be 2.0 x 103 or less, 1.8 x 103 or less, 1.6 x 103 or less, 1.5 x 103 or less, 1.4 x 103 or less, 1.3 x 103 or less, 1.2 x 103 or less, or 1.1 x 103 or less, and the lower limit thereof may be, for example 5.0 x 102 or more, 8.0 x 102 or more, 9.0 x 102 or more, or 1.0 x 103 or more. However, it is not necessarily intended to be limited to the above range. The propylene-based polymer according to an exemplary embodiment has the shear thinning index (STI) of about 5 or more, thereby implementing properties equivalent to or better than those of conventional developed products.
The propylene-based polymer according to an exemplary embodiment is implemented with a strain hardening phenomenon equivalent to or significantly higher than that of conventional developed products, and from this, it can be seen that the propylene-based polymer according to an exemplary embodiment comprises various long-chain branches. Therefore, when the propylene-based polymer according to an exemplary embodiment is used, a stable state during processing may be effectively maintained.
In an exemplary embodiment, when a reciprocal of an angular frequency value in a crossover modulus of a storage modulus (G') and a loss modulus (G'') at 230 ℃ based on a Maxwell model is defined as relaxation time, the relaxation time value of the propylene-based polymer according to an exemplary embodiment may be 3.0 s or more. Alternatively, the relaxation time may be 3.3 s or more, 3.5 s or more, 3.7 s or more, 3.8 s or more, 4.0 s or more, or 4.2 s or more. The upper limit may be, for example, 6.0 s or less, 5.5 s or less, 5.2 s or less, 5.0 s or less, 4.8 s or less, 4.5 s or less, or 4.3 s or less. However, it is not necessarily intended to be limited to the above range.
The propylene-based polymer according to an exemplary embodiment may have a phase difference (tanδ) value of 2.0 or less as defined by Equation 3 below when the angular frequency is 0.01 rad/s at 230 ℃ based on the Maxwell model.
[Equation 3]
tanδ = G''/G'
wherein G' is a storage modulus and G'' is a loss modulus.
In an exemplary embodiment, the phase difference may be 1.8 or less, 1.5 or less, 1.0 or less, 0.8 or less, 0.6 or less, or 0.5 or less, and the lower limit may be, for example, 0.05 or more, 0.1 or more, 0.2 or more, 0.3 or more, 0.4 or more, or 0.5 or more. However, it is not necessarily intended to be limited to the above range. The propylene-based polymer according to an exemplary embodiment may have excellent elasticity due to a long relaxation time and a low phase difference value.
The propylene-based polymer according to an exemplary embodiment may comprise 0.5 wt% or more, 1.0 wt% or more, 2.0 wt% or more, 2.2 wt% or more, 2.3 wt% or more, or 2.5 wt% or more of xylene solubles (XS). The upper limit of the xylene solubles may be, for example, 10.0 wt% or less, 8.0 wt% or less, 6.0 wt% or less, 5.0 wt% or less, 4.0 wt% or less, 3.0 wt% or less, or 2.8 wt% or less. Xylene solubles refer to a soluble part in cold xylene among the components contained in the polymer, and may be measured by dissolving the polymer in the xylene and then allowing an insoluble part (residue) to be determined from a cooling solution. Specifically, xylene solubles may be calculated through the following Equation.
[Equation 4]
Xylene solubles (XS, %) = (100 x m1 x v0) / (m0 x v1)
wherein m0 is an initial weight of the polymer (g), m1 is a weight of the residue (g), v0 is an initial volume of the sample (mL), and v1 is a volume of the sample after analysis (mL). The xylene solubles contain polymer chains with low stereoregularity and may be an indicator of the amount of non-crystalline regions
The propylene-based polymer according to the above embodiment may be effectively applied to various fields such as adhesives, films, and packaging materials due to easy handling such as processability and productivity by implementing the above physical properties.
In an exemplary embodiment, the propylene-based polymer may have a ratio of a polymer group having a molecular weight of 106.5 g/mol to 108.0 g/mol of 2% or more, or 2.5% or more, 3% or more, 3.2% or more, 3.3% or more, or 3.4% or more, or 10% or less, 8% or less, 6% or less, 5% or less, 4% or less, or 3.5% or less, as measured by gel permeation chromatography (GPC). Alternatively, the polymer group may have a ratio of a polymer group having a molecular weight of 106.5 g/mol or more of 2% or more, or 2.5% or more, 3% or more, 3.2% or more, 3.3% or more, or 3.4% or more, or 10% or less, 8% or less, or less, 6% or less, 5% or less, 4% or less, or 3.5% or less. Specifically, it can be seen from FIG. 3 that the propylene-based polymer according to an exemplary embodiment has a wider molecular weight distribution than the propylene-based polymer of the Comparative Example, and through this, the propylene-based polymers of an exemplary embodiment are not separated from each other and are homogeneously distributed. In addition, the propylene-based polymer of an exemplary embodiment has a higher proportion of polymer groups having a molecular weight of 106.5 g/mol or more compared to the Comparative Example, which may mean that the propylene-based polymer of an exemplary embodiment has a high molecular weight proportion and that several types of long chain branches (LCBs) are evenly distributed. As described above, the propylene-based polymer according to an exemplary embodiment may have a high proportion of polymer groups and comprise various kinds of long chain branches, thereby excellently implementing physical properties such as high melting strength.
The propylene-based polymer according to an exemplary embodiment may have a number average molecular weight (Mn) of 30 kg/mol to 80 kg/mol, 40 kg/mol to 60 kg/mol, 45 kg/mol to 55 kg/mol, or about 55 kg/mol, a weight average molecular weight (Mw) of 350 kg/mol to 500 kg/mol, 400 kg/mol to 480 kg/mol, 400 kg/mol to 450 kg/mol, 410 kg/mol to 440 kg/mol, or about 435 kg/mol, and a molecular weight distribution (MWD) of 5 to 15, 6 to 12, 6 to 11, 6 to 10, 7 to 10, 8 to 10, or 8 to 9.
Adhesives, films, or packaging materials containing a high melt strength propylene-based polymer according to an exemplary embodiment are provided, and a high melt strength propylene-based polymer having according to an exemplary embodiment may be applied to various fields because it is very easy to handle such as productivity and processability due to its excellent physical properties.
Hereinafter, Examples and Experimental Examples will be specifically illustrated and described. However, since the following Examples and Experimental Examples are merely illustrative of a part of an implementation, the technology described herein should not be construed as being limited thereto.
<Example 1> Manufacture of propylene-based polymer
Step 1: Liquid phase polymerization
After a 5 L reactor was purged with nitrogen at a high temperature, the temperature of the reactor was lowered to 5 ℃ in a nitrogen atmosphere. 20 mg of Ti-based Ziegler-Natta catalyst (TOHO Titanium), 20 mL of methylcyclohexane, 0.754 g (6.6 mmol) of triisobutylaluminum (Al/Ti=10), 0.1554 g (0.66 mmol) of diethylaminotriethoxysilane (Si / Ti = 1), and 3 g of 1,9-decadiene were added thereto. Subsequently, 1000 g of propylene in liquid phase was added threreto, and then 2000 ppm of hydrogen was added to polymerize the mixture at 70 ℃ for 50 minutes. After the polymerization reaction was completed, the unreacted gas was discharged, the temperature was cooled to room temperature, and then the reaction was terminated.
Step 2: Gas phase polymerization
Propylene and ethylene (molar ratio = 7:3) in gas phase were added to the reactor where the reaction was completed, and then the temperature was raised to 40 ℃ and polymerization was performed for 20 minutes. After the polymerization reaction was completed, the unreacted gas was discharged, the temperature was cooled to room temperature, and then the reaction was terminated. The resulting polymer was collected separately and dried in a vacuum oven at 60 ℃ for 1 hour or more to obtain a white propylene-based polymer.
<Comparative Example 1>
DaployTM WB140HMS, a high melt strength polypropylene (HMSPP) from Borealis, was purchased and prepared.
<Comparative Example 2>
H220P, a linear propylene-based polymer from SK, was purchased and prepared.
<Comparative Example 3>
A propylene-based polymer was manufactured in the same manner as in Example 1, except that 1,9-decadiene was not added in a liquid phase polymerization step of the manufacturing method of the propylene-based polymer according to Example 1.
Melt indices of the propylene-based polymers according to Example 1 and Comparative Examples 1 to 3 are as follows. The melt indices were measured according to the ASTM D1238 standard (230 ℃, 2.16 kg load conditions).
Example 1 Comp. Example 1 Comp. Example 2 Comp. Example 3
Melt index (dg/min) 2.0 2.3 2.2 6.0
<Experimental Example 1>1-1. Small amplitude oscillatory shear (SAOS) analysis
SAOS analysis was performed to confirm the shear thinning properties of the propylene-based polymers of Example 1 and Comparative Examples 1 to 3, and the results are shown in FIG. 1.
The measurement for SAOS analysis was made using a Strain-Controlled Rheomether (ARES) from TA, and performed in a range of 6.3 x 10-3 to 628 rad/s for angular frequency sweep under the conditions of strain 5%, 230 ℃, and pressure holding time (soak time) of 120 seconds using a Plate-Plate Fixture.
As a result of a SAOS analysis, the polymer of Example 1 showed a higher zero-shear viscosity and a stronger shear thinning phenomenon than the polymers of Comparative Examples 1 to 3. Through this, it can be confirmed that the propylene-based polymers of Examples have excellent shear thinning properties and thus high processability compared to the propylene-based polymers of Comparative Examples.
In order to numerically confirm the shear thinning properties of the propylene-based polymers according to Examples and Comparative Examples, after specifying the complex viscosity when the angular frequencies are 0.01 rad/s and 10 rad/s, and calculating the shear thinning index (STI) defined by Equation 1 through this, the results are shown in Table 2 below.
[Equation 1]
Shear thinning index (STI) = η0.01/η10
wherein η0.01 and η10 are complex viscosities (Pa·s) at angular frequencies of 0.01 rad/s and 10 rad/s at 230 ℃, respectively.
Example 1 Comp. Example 1 Comp. Example 2 Comp. Example 3
Complex viscosity
(η, Pa·s)		 0.01 rad/s 3.75 x 104 1.13 x 104 1.13 x 104 6.66 x 103
10 rad/s 1.08 x 103 6.75 x 102 2.31 x 103 9.29 x 102
STI 34.72 16.74 4.89 7.17
It can be confirmed from the above results that the shear thinning index of the propylene-based polymer of Example 1 was significantly higher than that of the propylene-based polymers of Comparative Examples 1 to 3.1-2. Melt strength analysis
The melt strength of the propylene-based polymers of Example 1 and Comparative Examples 1 to 3 were measured, and the results are shown in FIG. 2.
The measurement for melt strength analysis was used by connecting Goettfert Rheotens to a Brabender single-screw extruder, and an orifice die mounted on the extruder having a diameter of 1 mm and a length of 40 mm was used. The extrusion rate was set to 11 g/min, and a filament extruded through the die at 200 ℃ was pulled at an acceleration of 6 mm/s2, and a maximum force until the filament broke was measured and recorded as melt strength.
As a result, the polymer of Example 1 showed significantly higher melt strength than the polymers of Comparative Examples 1 to 3 having similar melt indices. In particular, the melt strength rapidly improved as a pull-off speed increased, reaching a melt strength of about 100 cN or more, and stretching was possible even at a pull-off speed of 300 mm/s or more. Meanwhile, Comparative Examples 1 to 3 were stretched to a maximum melt strength of 45 cN to 50 cN, 23 cN to 26 cN, and 80 cN to 90 cN, respectively. Through this, it can be confirmed that the propylene-based polymer according to an exemplary embodiment was a high melt strength propylene-based polymer having a significantly higher melt strength than the polymer of the Comparative Example.
<Experimental Example 2> Gel permeation chromatography (GPC) analysis
In order to confirm the molecular weight distribution of the propylene-based polymers of Example 1 and Comparative Examples 1 to 3, GPC analysis was performed, and the results are shown in FIG. 3 and Table 3 below.
GPC analysis was performed using Polymer Char GPC-IR equipment (standard sample: Easical PS1 Polystyrene, temperature: 160 ℃, solvent: 1,2,4-trichlorobenzene, viscosity constant: K, α of polypropylene). About 1.5 mg of the polymer sample was placed in a 1.25 mL vial of high-temperature GPC, 1 mL of 1,2,4-trichlorobenzene (w/BHT) was added, and the mixture was dissolved at 150 ℃ while stirring for 3 hours or more, and then used for analysis.
Example 1 Comp. Example 1 Comp. Example 2 Comp. Example 3
Mn (kg/mol) 51 70 64 50
Mw (kg/mol) 435 399 400 454
MWD 8.6 5.7 6.3 9.1
As a result, it could be seen that as the molecular weight distribution of Example 1 was relatively broad compared to the previously developed propylene-based polymers (Comparative Examples 1 and 2), the polymers were not separated and were homogeneously distributed, and the distribution of the polymers was relatively high. In addition, the molecular weight distribution of Example 1 showed a shoulder around the molecular weight of about 106.5 g/mol to 107.4 g/mol, and specifically, the ratio of the polymer groups having a molecular weight of 106.5 g/mol or more was about 3.5%, which was relatively higher than that of Comparative Example (Comparative Example 1: about 1%, Comparative Example 2: 0.4%, Comparative Example 3: 2.7%). Through this, it can be seen that the propylene-based polymer of Example 1 had a high molecular weight and several types of long chain branches (LCB) were evenly distributed, and thus, physical properties such as high melt strength were excellently implemented.<Experimental Example 3> Modulus measurement
In order to analyze the elasticity of the propylene-based polymers of Example 1 and Comparative Examples 1 to 3, the storage modulus (G') and loss modulus (G'') were measured in the following manner, and the results for Example 1 are shown in FIG. 4.
Elastic modulus (modulus) was measured using a Strain-Controlled Rheomether (ARES) (Maxwell model) from TA, and G' and G'' values were calculated through a TRIOS software.
The linear rheological data of the storage modulus and the loss modulus were fitted, the elastic modulus at the point where the storage modulus and the loss modulus intersect was defined as the crossover modulus, and the reciprocal of the angular frequency value at the crossover modulus was defined as the relaxation time. The values are shown in Table 4 below. In addition, the phase difference tanδ (=G''/G') values at an angular frequency of 0.01 rad/s are shown in Table 4 below.
Example 1 Comp. Example 1 Comp. Example 2 Comp. Example 3
Crossover modulus (Pa) 8.2 x 102, 2.1 x 104 1.1 x 104 2.2 x 104 2.5 x 104
Relaxation time (s) 4.2,1.6 x 10-2 0.02 0.056 0.0098
tanδ 0.5 4.8 11 1.1
As a result of the measurement, Example 1 was confirmed to have two crossover modulus, and the relaxation time at one of the crossover modulus was 4.2 s, which was significantly higher than that of the comparative example, and at the same time, the measured phase difference value was very low. Through this, it can be confirmed that the propylene-based polymer of Example had excellent elasticity compared to the propylene-based polymer according to Comparative Example.As described above, although an embodiment has been described in detail with reference to Examples and Experimental Examples, the scope of an embodiment is not limited to specific Examples and should be interpreted according to the accompanying claims.

Claims (17)

  1. A method for manufacturing a propylene-based polymer, the method comprising:
    a first polymerization step of manufacturing a polymer composition by polymerizing propylene and diene in liquid phase under a Ziegler-Natta catalyst; and
    a second polymerization step of performing polymerization by adding propylene and ethylene in gas phase to the manufactured polymer composition.
  2. The method of claim 1, wherein the first polymerization step is performed at 40 ℃ to 150 ℃ for 30 minutes to 100 minutes.
  3. The method of claim 1, wherein the second polymerization step is performed at a temperature of 20 ℃ to 70 ℃ for 5 minutes to 60 minutes.
  4. The method of claim 1, wherein a molar ratio of the ethylene to the propylene in gas phase is 1:9 to 9:1.
  5. The method of claim 1, wherein the diene is at least one selected from 1,3-butadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, and 1,13-tetradecadiene.
  6. The method of claim 1, wherein the Ziegler-Natta catalyst comprises a transition metal compound containing a Group 4, 5, or 6 element of the periodic table; and an organometallic compound containing a Group 13 element of the periodic table.
  7. The method of claim 6, wherein a molar ratio of the organometallic compound to the transition metal compound is 1:1 to 1:50.
  8. The method of claim 6, wherein the organometallic compound contains an organoaluminium compound.
  9. The method of claim 6, wherein a weight ratio of the propylene to the diene in the first polymerization step is 1:100 to 1:500.
  10. A propylene-based polymer manufactured according to the method for manufacturing a propylene-based polymer according to any one of claims 1 to 9.
  11. The propylene-based polymer of claim 10, wherein the propylene-based polymer has a melt strength of 100 cN or more as measured at 200 ℃.
  12. The propylene-based polymer of claim 10, wherein the propylene-based polymer has a shear thinning index (STI) of 5 or more, which is defined by Equation 1 below:
    [Equation 1]
    Shear thinning index = η0.01/η10
    wherein η0.01 and η10 are complex viscosities (Paㆍs) at angular frequencies of 0.01 rad/s and 10 rad/s at 230 ℃, respectively.
  13. The propylene-based polymer of claim 10, wherein η0.01 is 1.0 x 104 or more and η10 is 2.0 x 103 or less.
  14. The propylene-based polymer of claim 10, wherein when a reciprocal of an angular frequency value in any one of crossover moduli of a storage modulus (G') and a loss modulus (G'') at 230 ℃ based on a Maxwell model is defined as relaxation time, the relaxation time is 3.0s or more.
  15. The propylene-based polymer of claim 10, wherein the propylene-based polymer has a phase difference (tanδ) value of 2.0 or less as defined by Equation 3 below when an angular frequency is 0.01 rad/s at 230 ℃ based on the Maxwell model:
    [Equation 3]
    tanδ = G''/G'
    wherein G' is a storage modulus and G'' is a loss modulus.
  16. The propylene-based polymer of claim 10, wherein the propylene-based polymer has a ratio of a polymer group having a molecular weight of 106.5 g/mol to 108.0 g/mol of 2% or more as measured by gel permeation chromatography (GPC).
  17. A film comprising the propylene-based polymer according to claim 10.
PCT/KR2023/001881 2022-11-09 2023-02-09 Propylene-based polymer and manufacturing method thereof WO2024101539A1 (en)

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US5326639A (en) * 1989-08-23 1994-07-05 Himont Incorporated Thermoplastic olefin polymer and method of preparing same
JP2004156019A (en) * 2002-09-09 2004-06-03 Sumitomo Chem Co Ltd Polypropylene composition and film consisting of the same
WO2007102652A1 (en) * 2006-03-06 2007-09-13 Lg Chem, Ltd. Method of polymerizing propylene comprising olefin pre-polymerization step
KR20140120575A (en) * 2013-04-03 2014-10-14 삼성토탈 주식회사 A manufacturing method of a diluted catalyst for a polymerization of olefin and a process for preparation of polyolefin using the diluted catalyst
KR20200071077A (en) * 2017-11-09 2020-06-18 롯데케미칼 주식회사 Manufacturing method of high melt strength polypropylene resin
KR20220049731A (en) * 2020-10-15 2022-04-22 에스케이이노베이션 주식회사 Method for producing polypropylene

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5326639A (en) * 1989-08-23 1994-07-05 Himont Incorporated Thermoplastic olefin polymer and method of preparing same
JP2004156019A (en) * 2002-09-09 2004-06-03 Sumitomo Chem Co Ltd Polypropylene composition and film consisting of the same
WO2007102652A1 (en) * 2006-03-06 2007-09-13 Lg Chem, Ltd. Method of polymerizing propylene comprising olefin pre-polymerization step
KR20140120575A (en) * 2013-04-03 2014-10-14 삼성토탈 주식회사 A manufacturing method of a diluted catalyst for a polymerization of olefin and a process for preparation of polyolefin using the diluted catalyst
KR20200071077A (en) * 2017-11-09 2020-06-18 롯데케미칼 주식회사 Manufacturing method of high melt strength polypropylene resin
KR20220049731A (en) * 2020-10-15 2022-04-22 에스케이이노베이션 주식회사 Method for producing polypropylene

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