WO2015072658A1 - Polymère à base d'oléfine présentant une excellente aptitude à la mise en œuvre - Google Patents

Polymère à base d'oléfine présentant une excellente aptitude à la mise en œuvre Download PDF

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WO2015072658A1
WO2015072658A1 PCT/KR2014/008481 KR2014008481W WO2015072658A1 WO 2015072658 A1 WO2015072658 A1 WO 2015072658A1 KR 2014008481 W KR2014008481 W KR 2014008481W WO 2015072658 A1 WO2015072658 A1 WO 2015072658A1
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group
formula
olefin
based polymer
molecular weight
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PCT/KR2014/008481
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English (en)
Korean (ko)
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승유택
권헌용
이기수
홍대식
정동훈
신은영
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주식회사 엘지화학
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Priority claimed from KR1020140114385A external-priority patent/KR101549209B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to EP14861556.0A priority Critical patent/EP3042918B1/fr
Priority to JP2016531010A priority patent/JP6328239B2/ja
Priority to US15/032,014 priority patent/US9732171B2/en
Publication of WO2015072658A1 publication Critical patent/WO2015072658A1/fr

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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
    • 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

Definitions

  • the present invention relates to an olefin polymer having excellent processability.
  • the metallocene catalyst is composed of a combination of a main catalyst composed mainly of a transition metal compound and a cocatalyst composed of an organometallic compound composed mainly of aluminum, and such a catalyst is a single site catalyst as a homogeneous complex catalyst.
  • the polymer has a narrow molecular weight distribution according to the characteristics of a single active site and a homogeneous composition of the comonomer, and the stereoregularity, copolymerization characteristics, molecular weight, It has the property to change the crystallinity.
  • U.S. Patent No. 5,914,289 describes a method for controlling the molecular weight and molecular weight distribution of a polymer using a metallocene catalyst supported on each carrier, but the amount of solvent used and the time required for preparing the supported catalyst are high. The hassle of having to support the metallocene catalyst to be used on the carrier, respectively.
  • Korean Patent Application No. 2003-12308 discloses a binuclear metallocene in a carrier A method of controlling molecular weight distribution by supporting a catalyst and a mononuclear metallocene catalyst together with an activator to change and polymerize a combination of catalysts in a reactor is disclosed.
  • linear low density polyethylene is prepared by copolymerizing ethylene and alpha olefins at low pressure using a polymerization catalyst, and has a narrow molecular weight distribution, a short chain branch of a constant length, and a long chain branch.
  • Linear low density polyethylene film has the characteristics of general polyethylene, and has high breaking strength and elongation, and excellent tear strength and falling layer stratification strength. Therefore, the use of stretch film and overlap film, which is difficult to apply to existing low density polyethylene or high density polyethylene, has increased. Doing.
  • linear low density polyethylene used as 1-butene or 1-nucenol comonomer is mostly produced in a single vapor phase reactor or a single loop slurry semi-unger, and the productivity is high compared to a process using 1-octene comonomer, but such a product
  • physical properties are inferior to those of using 1-octene comonomer, and there is a problem in that workability is poor due to a narrow molecular weight distribution. Many efforts are being made to improve these problems.
  • US Pat. No. 4,935,474 reports on the preparation of polyethylene having a wide molecular weight distribution using two or more metallocene compounds.
  • U. S. Patent No. 6,828, 394 reports a method for producing polyethylene that has a good comonomer binding property and a good combination thereof, which has good processability and is particularly suitable for films.
  • US Pat. No. 6,841,631 and US Pat. No. 6,894,128 produce polyethylene having bimodal or polycrystalline molecular weight distribution with a metallocene catalyst using at least two kinds of metal compounds, for use in films, blow molding, pipes, and the like. It is reported to be applicable.
  • these products have improved processability, but the molecular weight in the unit particles Since the dispersion state is not uniform, there is a problem that the extrusion tube is rough and the physical properties are not stable even under relatively good extrusion conditions.
  • the present invention is to provide an olefinic polymer having excellent workability and improved transparency and mechanical properties.
  • the present invention has a molecular weight distribution (Mw / Mn) of 3 to 20;
  • melt flow rate ratio (MFR10 / MFR2) value measured by ASTM1238 at 19 CTC is from 9 to 15;
  • a film comprising the olefinic polymer.
  • the olefin polymer according to the present invention is excellent in processability, mechanical properties and transparency, and can be usefully used for applications such as films.
  • FIG. 1 is a graph showing the relationship between the frequency (complex) viscosity of the olefinic polymer in accordance with the Examples and Comparative Examples of the present invention (complex visicosity).
  • Figure 2 is a graph showing the measurement of the molecular weight distribution of the olefin polymer according to an embodiment of the present invention by GPC-FI R.
  • Olefin-based polymer according to the present invention has a molecular weight distribution (Mw / Mn) of 3 to 20, melt flow rate ratio (MFR10 / MFR2) measured by ASTM1238 at 190 ° C. The value is 9 to I 5 , and the slope is -0.55 to -0.35 in the complex viscosity (i [Pa.s]) graph according to the frequency (frequency, co [rad / s]).
  • the olefinic polymer of the present invention exhibits a broad molecular weight distribution (Mw / Mn, PDI) of about 3 to about 20, preferably about 4 to about 15, and may exhibit excellent processability.
  • the weight average molecular weight (Mw) of the olefinic polymer may be about 50,000 to about 200,000 g / mol, preferably about 60,000 to about 150,000 g / mol, but is not limited thereto. no.
  • the leulevine-based polymer of the present invention has a high molecular weight and a wide molecular weight distribution and has excellent physical properties and processability.
  • the olefin copolymer of the present invention has a wider molecular weight distribution and a melt flow rate ratio (MFRR) than the conventionally known olefin copolymer, and thus the fluidity is remarkably improved, and thus, it is possible to exhibit more excellent workability.
  • MFRR melt flow rate ratio
  • the olefin copolymer of the present invention has a melt flow rate ratio (MFRR,
  • MFR10 / MFR2 is in the range of about 9 to about 15, preferably about 9.5 to about 13.
  • the melt flow index measured at 190 ° C., 2.16 kg load according to MFR 2 may be about 0.1 to about 10 g / 10 min, preferably about 0.2 And from about 5 g / 10 min.
  • MFR 10 (melt flow index measured at 19 CTC, 10 kg load according to ASTM D-1238) is from about 0.9 to about 150 g / lOmin, preferably in the range from about 1.9 to about 65 g / lOmin
  • MFR 2 and MFR 10 ranges can be appropriately adjusted in view of the use or application of the olefinic polymer. .
  • the olefin polymer of the present invention has a slope of about ⁇ 0.55 to about ⁇ 0.35, or about ⁇ in a complex viscosity (i [Pa.s]) graph according to frequency (co, [rad / s]). 0.45 to about -0.35.
  • Complex Viscosity Graphs with Frequency are related to fluidity and have high complex viscosity at low frequencies. At higher frequencies, the lower the complex viscosity, the higher the fluidity. That is, it may have a negative slope value, and as the absolute value of the slope value is larger, the fluidity may be higher.
  • the olefinic polymers of the present invention exhibit a significantly higher flowability compared to conventional olefinic polymers having similar densities and weight average molecular weights in the range of slopes from about -0.55 to about -0.35 in complex viscosity plots with frequency. This is related to the wide molecular weight distribution of the olefin polymer of the present invention, and thus, despite the high melt index, the shear thinning effect is much superior, and thus may exhibit excellent fluidity and processability.
  • the density of the olefinic polymer may be 0.910 to 0.940 g / cm 3 , but is not limited thereto.
  • the olefin-based polymer has a maximum SCB content value within the range of 0.2 to 0.8 molecular weight distribution when the weight average molecular weight (M) measured by GPC-FTIR is 0.5 Can be.
  • SCB Short Chain Branching
  • branch having 2 to 6 carbon atoms usually refers to defects that are made when using alpha olefin having 4 or more carbon atoms such as 1-butene, 1-nuxene, 1-octene as a comonomer.
  • GPC-FTIR equipment can be used to continuously measure molecular weight, molecular weight distribution and SCB content simultaneously.
  • the olefin polymer of the present invention is characterized by having a maximum SCB content value within the range of 0.2 to 0.8 molecular weight distribution when the weight average molecular weight (M) measured by GPC-FTIR is 0.5.
  • Figure 2 is a graph measuring the molecular weight distribution of the ellefin-based polymer according to an embodiment of the present invention by GPC-FTIR.
  • the maximum SCB content value appears in the middle region of the molecular weight distribution around the point of the weight average molecular weight (M). That is, when the point where the weight average molecular weight (M) is located is called 5, the point where the minimum molecular weight value appears is 0, and the point where the maximum molecular weight value appears is 1, within the interval of 0.2 to 0.8 on the log graph.
  • Maximum SCB content values can be seen.
  • the maximum SCB content value may appear in the form of an inflection point rather than a divergent value.
  • the characteristic of such molecular weight distribution is that the olefin polymer of the present invention has the highest inflow of comonomers in the middle molecular weight range, that is, the molecular weight distribution region of 30% of the left and right, based on the weight average molecular weight. In the lower 20% low molecular weight region and the upper 20% high molecular weight region, this means that the incorporation of comonomers is less than in the middle molecular weight region.
  • the olefin polymer of the present invention may have an SCB content of 5 to 30, preferably 7 to 20, per 1,000 carbons of the olefin polymer.
  • the olepin-based polymer has a disadvantage in that the workability is improved as the molecular weight distribution is widened, but the haze property is deteriorated and transparency is lowered.
  • the leulevine-based polymer of the present invention may exhibit high transparency despite the wide molecular weight distribution by improving the haze property due to the distribution of comonomers as described above.
  • the olefin polymer according to the present invention has excellent fluidity, processability, transparency, and the like, and can be variously applied according to a use, and in particular, it is possible to provide a film having improved physical properties.
  • the olefinic polymer according to the present invention may be a homopolymer of ethylene, which is an olefinic monomer, or preferably a copolymer of ethylene and an alpha olefinic comonomer.
  • Alpha olefins having 4 or more carbon atoms may be used as the alpha olefin-based comonomer.
  • Alpha-olefins having 4 or more carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-nuxadecene, 1-octadecene, 1-eicosene, and the like, but is not limited thereto.
  • alpha olefins having 4 to 10 carbon atoms are preferable, and one or several kinds of alpha olefins may be used together as comonomers.
  • the content of the alpha olepin-based comonomer may be about 5 to about 20% by weight, preferably about 7 to about 15% by weight, but is not limited thereto. .
  • the olefin polymer as described above may be prepared by using a common metallocene catalyst. It can manufacture.
  • the common metallocene catalyst may include a first metallocene compound represented by Formula 1 below; A second metallocene compound comprising at least one compound selected from the following compounds represented by Formula 2 or Formula 3; Cocatalyst compounds; And a common supported metallocene catalyst comprising a carrier.
  • R1 to R4, R9 and R1 'to R4' are the same as or different from each other, and each independently hydrogen, halogen: C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 Alkylaryl group or C7-C20 arylalkyl group;
  • R5 to R8 are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, or C7 to C20 arylalkyl group
  • Adjacent two of R5 to R8 may be linked to each other to form one or more aliphatic rings, aromatic rings, or hetero rings;
  • L 1 is a C1 to C10 straight or branched alkylene group
  • D1 is -O-, -S-, -N (R)-or -Si (R) (R ')-, wherein R and R' are the same as or different from each other, and are each independently hydrogen, halogen, C1 to C20 alkyl group, An alkenyl group of C2 to C20 or an aryl group of C6 to C20;
  • A1 is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, ci to C20 alkoxy group, C2 to C20 A C20 alkoxyalkyl group, C2 to C20 heterocycloalkyl group, or C5 to C20 heteroaryl group;
  • ⁇ is a Group 4 transition metal
  • XI and X2 are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group ,.
  • R10 to R13 and R10 'to R13' are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 An arylalkyl group of C20 to C20 or an amine group of C1 to C20, and two adjacent R10 to R13 and R10 'to R13' may be connected to each other to form one or more aliphatic rings, aromatic rings, or hetero rings; ;
  • Z1 and Z2 are the same as or different from each other, and each independently hydrogen, an alkyl group of C1 to C20, a cycloalkyl group of C3 to C20, an alkoxy group of C1 to C20, an aryl group of C6 to C20, an aryloxy group of C6 to C10, C2 to C20 alkenyl group, C7 to C40 alkylaryl group, or C7 to C40 arylalkyl group;
  • Q is an alkylene group of CI to C20, a cycloalkylene group of C3 to C20, an arylene group of C6 to C, an alkylarylene group of C7 to C40, or an arylalkylene group of C7 to C40;
  • M 2 is a Group 4 transition metal
  • X3 and X4 are the same as or different from each other, and each independently halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group, A C1 to C20 alkoxy group or a C1 to C20 sulfonate group;
  • M 3 is a Group 4 transition metal
  • X5 and X6 are the same as or different from each other, and each independently halogen, C1 to C20 and an alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, nitro group, amido group, C1 to C20 alkylsilyl group, C1 To C20 alkoxy group, or C1 to C20 sulfonate group;
  • R14 to R19 are the same as or different from each other, and each independently hydrogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C1 to C20 alkoxy group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkylsilyl, C6 to C20 arylsilyl group, or C1 to C20 amine group, two or more adjacent R14 to R17 are connected to each other at least one aliphatic ring , Aromatic rings, or hetero rings;
  • L 2 is a straight or branched chain alkylene group of CI to CIO
  • D2 is -0-, -S-, -N (R)-or -Si (R) (R ')-, wherein R and R' are the same as or different from each other, and are each independently hydrogen, halogen, C1 to C20 alkyl group An alkenyl group of C2 to C20 or an aryl group of C6 to C20;
  • A2 is hydrogen, halogen, C1 to C20 alkyl group, C2 to C20 alkenyl group, C6 to C20 aryl group, C7 to C20 alkylaryl group, C7 to C20 arylalkyl group, C1 to C20 alkoxy group, C2 to C20 A C20 alkoxyalkyl group, a C2 to C20 heterocycloalkyl group, or a C5 to C20 heteroaryl group;
  • B is carbon, silicon, or germanium and is a bridge which binds a cyclopentadienyl series ligand and JR19z-y by a covalent bond;
  • J is a periodic table group 15 element or group 16 element
  • z is the oxidation number of the element J
  • y is the number of bonds of the J elements.
  • the C1 to C20 alkyl group includes a linear or branched alkyl group, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, pentyl group, nuclear chamber group, heptyl group, An octyl group etc. are mentioned, but it is not limited to this.
  • the alkenyl group of C2 to C20 includes a linear or branched alkenyl group, and specifically, may include an allyl group, ethenyl group, propenyl group, butenyl group, pentenyl group, and the like, but is not limited thereto.
  • the C6 to C20 aryl groups include monocyclic or condensed aryl groups, and specifically include phenyl groups, biphenyl groups, naphthyl groups, phenanthrenyl groups, and fluorenyl groups, but are not limited thereto.
  • the C5 to C20 heteroaryl group includes a monocyclic or condensed heteroaryl group, and includes a carbazolyl group, a pyridyl group, a quinoline group, an isoquinoline group, a thiophenyl group, a furanyl group, an imidazole group, an oxazolyl group, a thiazolyl group , Triazine group, tetrahydropyranyl group, tetrahydrofuranyl group and the like, but are not limited thereto.
  • alkoxy group for C 1 to C 20 examples include a hydroxy group, an hydroxy group, a phenyloxy group, a cyclonuxyloxy group, and the like, but are not limited thereto.
  • Examples of the Group 4 transition metal include titanium, zirconium, and hafnium. However, the present invention is not limited thereto.
  • R1 to R9 and R1 'to R8' of Formula 1 are each independently hydrogen, methyl group, ethyl group, propyl group, isopropyl group, ⁇ -butyl group, tert- A butyl group, a pentyl group, a nuclear group, a heptyl group, an octyl group : or a phenyl group is more preferable, but it is not limited to this.
  • L1 of Chemical Formula 1 is more preferably a C4 to C8 linear or branched alkylene group, but is not limited thereto.
  • the alkylene group may be unsubstituted or substituted with an alkyl group of C1 to C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20.
  • A1 of Formula 1 is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, mesoxymethyl group, tert-subspecial
  • the methyl group, 1-hydroxyethyl group, 1-methyl-1-methoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group is more preferable, but is not limited thereto.
  • specific examples of the first metallocene compound represented by Chemical Formula 1 may include a compound represented by the following structural formulas, but is not limited thereto.
  • Q is an alkylene group of CI to C20
  • Z1 and Z2 are each independently hydrogen, an alkyl group of C1 to C20 or an alkoxy group of C1 to C20
  • X3 and X4 may be a halogen, but is not limited thereto.
  • specific examples of the second metallocene compound represented by Chemical Formula 2 may include a compound represented by the following structural formulas.
  • L 2 of Chemical Formula 3 is more preferably a C4 to C8 linear or branched alkylene group, but is not limited thereto.
  • the alkylene group may be unsubstituted or substituted with an alkyl group of C1 to C20, an alkenyl group of C2 to C20, or an aryl group of C6 to C20.
  • A2 of Formula 3 is hydrogen, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, tert-butyl group, methoxymethyl group, tert-buroxy Methyl group, 1-ethoxyethyl group, 1-methyl-1-methoxyethyl group, tetrahydropyranyl group, or tetrahydrofuranyl group is more preferable, but not limited thereto.
  • B in the general formula (3) is silicon
  • J is preferably nitrogen, but is not limited thereto.
  • R14 to R19 of Formula 3 are each independently hydrogen, an alkyl group of C1 to C20, C2 . It may be an alkenyl group of C to C20, or an alkoxy group of C1 to C20, but is not limited thereto.
  • Specific examples of the second metallocene compound represented by Chemical Formula 3 may include a compound represented by the following structural formula, but is not limited thereto. It is not.
  • the first metallocene compound of Chemical Formula 1 forms a structure in which a fluorene derivative is crosslinked by a bridge and has a Lewis acid characteristic of the carrier by having a non-covalent electron pair capable of acting as a Lewis base in the ligand structure. It is supported on and shows high polymerization activity even when it is supported.
  • the fluorene group which is electronically rich, has high activity, the high molecular weight olepin-based polymer can be added.
  • Common supported metallocene catalyst is a second metal selected from one or more of the first metallocene compound represented by Formula 1 and the compound represented by Formula 2 or Formula 3
  • One or more of the sen compounds may be commonly supported on the carrier together with the cocatalyst compound.
  • the first metallocene compound represented by Formula 1 of the common supported metallocene catalyst mainly contributes to making a high molecular weight copolymer
  • the second metallocene compound represented by Formula 2 is a relatively low molecular weight copolymer. It can contribute to making
  • the second metallocene compound represented by Formula 3 may contribute to making a copolymer of moderate molecular weight.
  • the miscibility of high molecular weight and low molecular weight copolymers is compensated for, resulting in a wide molecular weight distribution resulting in high processability and high transparency.
  • the olefinic polymer of this invention can be manufactured.
  • the common supported metallocene catalyst may include at least one first metallocene compound of Formula 1 and at least one second metallocene compound of Formula 2. According to another embodiment of the present invention, the common supported metallocene catalyst may include at least one first metallocene compound of Formula 1 and at least one second metallocene compound of Formula 2, One or more second metallocene compounds may be included.
  • the first metallocene compound represented by Formula 1 and the second metallocene compound selected from the compound represented by Formula 2 or Formula 3 are different from each other. At least two or more metallocene compounds, preferably three different metallocene compounds. Accordingly, the high molecular weight and low molecular weight copolymers are complemented to improve the high molecular weight olefin copolymer, and at the same time, the molecular weight distribution is wide, thereby producing an excellent olefin polymer with excellent physical properties and processability.
  • a co-catalyst supported on a carrier for activating the metallocene compound is an organometallic compound containing a Group 13 metal, and when the olefin is polymerized under a general metallocene catalyst There is no particular limitation as long as it can be used.
  • the cocatalyst compound may include one or more of the cocatalyst compounds represented by the following Chemical Formulas 4 to 6.
  • R20 may be the same 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;
  • n is an integer of 2 or more
  • R20 is as defined in Formula 4 above;
  • L is a neutral or cationic Lewis acid
  • H is a hydrogen atom
  • Z is a group element
  • A may be the same as or different from each other, and each independently is a C6 to C20 aryl group or a C1 to C20 alkyl group, wherein at least one hydrogen atom is unsubstituted or substituted with halogen, C1 to C20 hydrocarbon, alkoxy or phenoxy.
  • Examples of the compound represented by the formula (4) include methyl aluminoxane, ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane and the like, and more preferred compound is methyl aluminoxane.
  • Examples of the compound represented by Formula 5 include trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum, tributyl aluminum, dimethylchloro aluminum, triisopropyl aluminum, tri-S-butyl aluminum, tricyclopentyl aluminum , Tripentylaluminum, triisopentylaluminum, trinuclear silaluminum, trioctylaluminum, ethyldimethylaluminum, methyldiethylaluminum, triphenylaluminum, tri-P-rylylaluminum, dimethylaluminum mesoxide, dimethylaluminum, trimethyl Boron, triethyl boron, triisobutyl boron, tripropyl boron, tributyl boron and the like, and more preferred compounds are selected from trimethylaluminum, triethylaluminum and triisobutylaluminum.
  • Examples of the compound represented by Formula 6 include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra (P-lryl) Boron, trimethylammonium tetra ( ⁇ , ⁇ - dimethylphenyl) boron, tributyl ammonium tetra ( ⁇ -trifluoromethylphenyl) boron, trimethyl ammonium tetra ( ⁇ -trifluoromethylphenyl) boron,
  • Triphenylcarbonium tetrapentafluorophenylboron Triphenylcarbonium tetrapentafluorophenylboron, and the like.
  • the mass ratio of the transition metal to the carrier of the first and second metallocene compounds is preferably 1: 1 to 1: 1,000.
  • the carrier and the metallocene compound in the mass ratio it may be advantageous in terms of maintaining the activity and economical efficiency of the catalyst by showing the appropriate supported catalytic activity.
  • the mass ratio of the cocatalyst compound of formula 4 or 5 to the carrier is preferably 1:20 to 20: 1
  • the mass ratio of the cocatalyst compound of the formula 6 to the carrier is preferably 1:10 to 100: 1.
  • the mass ratio of the said 1st metallocene compound to the said 2nd metallocene compound is 1: 100-100: 1.
  • an appropriate catalytic activity may be exhibited, which may be advantageous in terms of maintaining the activity and economical efficiency of the catalyst.
  • a carrier containing a hydroxyl group on the surface can be used, and preferably, The carrier which has the semi-permanent hydroxyl group and siloxane group from which the water was removed to the surface can be used.
  • silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, which are typically oxides, carbonates, such as Na 2 O, K 2 C0 3 , BaS0 4 , and Mg (0 3 ) 2 , Sulfate, and nitrate components.
  • the drying temperature of the carrier is preferably 100 to 800. If the drying temperature of the carrier is less than 100 ° C, the moisture is too much and the surface of the carrier reacts with the promoter, and if it exceeds 800 ° C, the surface area decreases as the pores on the surface of the carrier are combined, and the surface is hydroxy. It is not preferable because there is a lot of groups and only siloxane groups are left to decrease the reaction space with the promoter.
  • the amount of hydroxyl groups on the surface of the carrier is preferably 0.1 to 10 mmol / g, more preferably 0.2 to 5 mmol / g.
  • the amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions for preparing the carrier or by drying conditions such as temperature, time, vacuum or spray drying.
  • the amount of the hydroxy group is less than 0.1 mmol / g, there is little reaction space with the cocatalyst. If the amount of the hydroxy group is more than 10 mmol / g, it may be due to moisture other than the hydroxy group present on the surface of the carrier particle. not.
  • the common supported metallocene catalyst is prepared by supporting a cocatalyst compound on a carrier, supporting the first metallocene compound on the carrier, and supporting the second metallocene compound on the carrier. can do.
  • the order of the steps of supporting the first and second metallocene compounds may be changed as necessary. That is, the first metallocene compound is first supported on the carrier, and then the second metallocene compound is further supported to prepare a common supported metallocene catalyst, or the second metallocene compound is first supported on the carrier. After that, the first metallocene compound may be supported. Alternatively, the first and second metallocene compounds may be added and supported at the same time.
  • Pentane, nucleic acid, as a reaction solvent in the preparation of the common supported metallocene catalyst Hydrocarbon solvents such as heptanes, or aromatic solvents such as benzene, toluene and the like can be used.
  • the metallocene compound and the cocatalyst compound can also be used in the form of silica or alumina.
  • the olefin polymer according to the present invention can be produced by polymerizing an olefin monomer in the presence of the above-described common supported metallocene catalyst.
  • specific examples of the olefin polymer may include ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nuxene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-ikocene, and the like, and two or more thereof may be mixed and copolymerized.
  • the olefin polymer is more preferably an ethylene / alpha olefin copolymer, but is not limited thereto.
  • the content of alpha olepin, which is the comonomer is not particularly limited, and may be appropriately selected according to the use, purpose, and the like of the olepin-based polymer. More specifically, it may be up to more than 0 to 99 mole 0/0.
  • the polymerization reaction can be carried out by homopolymerization with one olefinic monomer or copolymerization with two or more monomers using one continuous slurry polymerization reaction, loop slurry reaction, gas phase reaction or solution reaction.
  • the common supported metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decan, and isomers thereof and aromatic hydrocarbon solvents such as toluene and benzene, dichloromethane and chlorobenzene. It may be dissolved or liquefied and injected into a hydrocarbon solvent substituted with a chlorine atom such as.
  • the solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkyl aluminum, and may be carried out by further using a promoter.
  • the common supported metallocene catalyst By using the common supported metallocene catalyst, it is possible to produce an urepin-based copolymer having a molecular weight distribution curve of two or more.
  • a relatively high molecular weight olepin-based polymer can be prepared by the first metallocene compound, and the second metallocene Relatively low molecular weight olepin-based polymers can be prepared by the compounds.
  • the common supported metallocene catalyst may include at least one first metallocene compound of Formula 1, at least one second metallocene compound of Formula 2, and
  • high molecular weight, low molecular weight, and medium molecular weight olepin-based polymers are produced to have broad molecular weight distribution and improve the compatibility between high molecular weight and low molecular weight polymers.
  • Olefin-based polymers showing transparency can be produced.
  • the polymerization temperature may be about 25 to about 500 ° C., preferably about 25 to about 200 ° C., more preferably about 50 to about 150 ° C.
  • the polymerization pressure is about 1 to about 100 Kgf / cm 2 , preferably about 1 to about 70 Kgf / cm 2 , more preferably about 5 to about 50
  • Kgf / cm 2 can be.
  • the leulevine-based polymer according to the present invention is a polymer having a high molecular weight and a wide molecular weight distribution as described above by homopolymerization of ethylene or copolymerization of ethylene and alpha olepin using the above common supported metallocene compound as a catalyst. Can be prepared.
  • the olefin polymer of the present invention is excellent in mechanical properties such as tensile strength and tear strength, processability, haze, and the like, and can be variously applied according to a use, and particularly, a film having improved physical properties Can provide.
  • the yellow solution obtained was identified to be methyl (6-t-butoxynucleosil) (tetramethyl CpH) t-butylaminosilane (Methyl (6-t-buthoxyhexyl) (tetramethylCpH) t-Butylaminosilane) compound through 1H-NMRol. .
  • nucleic acid was added to filter the product. After removing the nucleic acid from the filter solution obtained, the desired ([methyl (6-t-buthoxyhexyl) silyl (n5-tetramethylCp) (t-Butylamido)] TiC3 ⁇ 4 (tBu-O- (CH 2 ) 6 ) (CH 3 ) Si (C 5 (CH 3 ) 4 ) (tBu-N) TiCl 2 .
  • the common supported metallocene catalyst obtained in Preparation Example 1 was introduced into an isobutane slurry loop process continuous polymerization reactor (reactor volume 140 L, reaction volume flow rate 7 m / s) to prepare an olefin polymer.
  • 1-hexene was used as comonomer, the reaction pressure was maintained at 40 bar, the polymerization temperature was 88 ° C.
  • Example 2
  • Example 3 An olefin polymer was prepared in the same manner as in Example 1 except that the amount of 1-nuxene used in Example 1 was changed.
  • Example 3 An olefin polymer was prepared in the same manner as in Example 1 except that the amount of 1-nuxene used in Example 1 was changed.
  • Example 4 An olefin polymer was prepared in the same manner as in Example 1, except that the amount of 1-hexene used in Example 1 was changed.
  • Example 4 An olefin polymer was prepared in the same manner as in Example 1, except that the amount of 1-hexene used in Example 1 was changed.
  • the common supported metallocene catalyst obtained in Preparation Example 2 was introduced into an isobutane slurry loop process continuous polymerization reactor (reactor volume 140 L, reaction volume flow rate 7 m / s) to prepare an olefin polymer.
  • a comonomer 1-nucleenol was used, the reactor pressure was maintained at 40 bar, and the polymerization temperature was maintained at 88 ° C.
  • Example 5
  • LG Chem's LUCENE TM SP310 a commercial mLLDPE prepared using slurry loop process, was prepared.
  • the olefin polymers of Examples 1 to 5 and Comparative Example 1 were analyzed after granulation with a biaxial extruder after prescribed an antioxidant (Iganox 1010 + Igafos 168, CIBA).
  • Polymer and film and physical property evaluation
  • MFRio / MFR 2 MFR 10 melt index (MI, 10kg load) divided by MFR 2 (MI, 2.16kg load).
  • Haze The film was molded to a thickness of 0.05 mm and measured based on ASTM D 1003. At this time, 10 measurements were taken per specimen and the average was taken.
  • the ellefin-based polymer according to the present invention exhibits a wider molecular weight distribution than a conventional olefin-based polymer having a similar density and weight average molecular weight, and thus has a high melt index. It can be seen that the shear thinning effect is much better and shows excellent flowability and processability.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

La présente invention porte sur un polymère à base d'oléfine présentant une excellente aptitude à la mise en œuvre. Le polymère à base d'oléfine selon la présente invention a une excellente aptitude à la mise en œuvre dans la mesure où il a une masse moléculaire élevée et une large distribution de masse moléculaire et il présente une transparence améliorée telle que le polymère à base d'oléfine peut être utile pour des utilisations exigées.
PCT/KR2014/008481 2013-11-18 2014-09-11 Polymère à base d'oléfine présentant une excellente aptitude à la mise en œuvre WO2015072658A1 (fr)

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EP14861556.0A EP3042918B1 (fr) 2013-11-18 2014-09-11 Polymère à base d'oléfine présentant une excellente aptitude à la mise en oeuvre
JP2016531010A JP6328239B2 (ja) 2013-11-18 2014-09-11 加工性に優れたオレフィン系重合体
US15/032,014 US9732171B2 (en) 2013-11-18 2014-09-11 Olefin-based polymer with excellent processability

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KR20030012308A (ko) 2001-07-31 2003-02-12 주식회사 예스아이비 배팅형 복권 시스템 및 배팅 방법
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