WO2013066109A1 - Composition de catalyseur hétérogène non supporté pour la polymérisation de polyoléfine et son procédé de préparation - Google Patents

Composition de catalyseur hétérogène non supporté pour la polymérisation de polyoléfine et son procédé de préparation Download PDF

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WO2013066109A1
WO2013066109A1 PCT/KR2012/009190 KR2012009190W WO2013066109A1 WO 2013066109 A1 WO2013066109 A1 WO 2013066109A1 KR 2012009190 W KR2012009190 W KR 2012009190W WO 2013066109 A1 WO2013066109 A1 WO 2013066109A1
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catalyst composition
polyolefin
catalyst
polymerization
group
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PCT/KR2012/009190
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English (en)
Korean (ko)
Inventor
이진우
박철영
최영아
이난영
이동길
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주식회사 엘지화학
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Priority claimed from KR1020120084070A external-priority patent/KR101499819B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to US14/353,666 priority Critical patent/US9631034B2/en
Priority to JP2014539878A priority patent/JP5956595B2/ja
Priority to CN201280054157.1A priority patent/CN103987737B/zh
Publication of WO2013066109A1 publication Critical patent/WO2013066109A1/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
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
    • 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
    • C08L2314/06—Metallocene or single site catalysts

Definitions

  • the present invention relates to a non-uniform single site catalyst composition which does not use a separate carrier and a method for producing a polyolefin polymer using the same.
  • Ansa-metallocene compound is a catalyst compound comprising two ligands connected to each other by a bridge group, the ligand group is prevented from rotating by the bridge group, and the activity and structure of the metal center Is determined.
  • the metallocene compound Ansari metal such as is used as a catalyst, in the production of eulre pingye homopolymer or copolymer.
  • the ansa metallocene compound containing a cyclopentadienyl-fluorenyl ligand can produce a high molecular weight polyethylene, and it is known that the microstructure of the polypropylene can be controlled.
  • ansa metallocene compound containing an indenyl ligand is known to be capable of producing polyolefins with excellent activity and improved stereoregularity.
  • Such a metallocene catalyst may be said to be one of homogeneous catalysts as a complex compound dissolved in a solvent in itself.
  • the Ziegler-Vanatta catalyst system used in the existing commercialization plant is a heterogeneous catalyst in which a metal component as an active point is dispersed in solid carrier particles, and the production process is designed according to the characteristics of the heterogeneous catalyst.
  • it is necessary to convert it into a monolithic catalyst which is fixed to a solid surface using a suitable carrier.
  • the catalyst may be supported on at least one carrier selected from the group consisting of silica, silica-alumina, and silica-magnesia.
  • Supported catalysts are also an important patent item in commercialization technology. But, In order to support the metallocene catalyst, a number of cumbersome steps have to be carried out, and the active point of the catalyst is lost depending on the limit of the amount of catalyst supported on the solid carrier and the state of the carrier, thereby lowering the activity of the supported catalyst.
  • the present invention is to provide a catalyst composition for unsupported non-uniform polyolefin polymerization, which is excellent in activity as a catalyst without using a separate carrier, and which can easily control the microstructure of the olefinic polymer during polyolefin polymerization.
  • the present invention also provides a method for preparing the catalyst composition for unsupported non-uniform polyolefin polymerization.
  • the present invention also provides a method for producing polyolefin using the catalyst composition for unsupported non-uniform polyolefin polymerization.
  • the present invention provides a catalyst composition for unsupported non-uniform polyolefin polymerization comprising an ansa metallocene compound represented by Formula 1 below and a cocatalyst compound represented by Formula 2 below.
  • M 1 is a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide transition metal or an actanide transition metal;
  • X is the same or different halogen from each other
  • A is an element of group 14 and is a bridge group connecting indenyl groups
  • R 1 is alkyl, alkenyl, alkylaryl, arylalkyl or aryl having 1 to 20 carbon atoms;
  • R 2 is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl, alkylaryl, arylalkyl or aryl;
  • R 3 , R 3 ' , R 4 , R 4' , R 5 , R 5 ' , R 6 , R 6' , R 7 , R 7 ' , R 8 , and R 8' are the same as or different from each other, respectively Hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl, alkylaryl, arylalkyl or aryl;
  • n is an integer from 1 to 20;
  • M 2 is a Group 13 metal element
  • R 9 are the same as or different from each other, and are each alkyl, alkenyl, alkylaryl, arylalkyl or aryl having 1 to 20 carbon atoms;
  • n is an integer of 2 or more.
  • the present invention also provides a method for producing the catalyst composition for polymerization of the above unsupported non-uniform polyolefin.
  • the present invention also provides a method for producing a polyolefin, including the step of polymerizing at least one of the urepin monomers in the presence of the catalyst composition.
  • the present invention provides a unsupported heterogeneous metallocene catalyst having a high activity without changing the existing process by using a specific ansa metallocene compound and a promoter compound together to form a homogeneous catalyst without using a solid carrier. It is to provide a composition.
  • Such a catalyst composition of the present invention while excellent in activity as a catalyst, can easily control the microstructure of the olefin-based polymer, it is possible to easily produce a polyolefin polymer having the desired physical properties.
  • single-site catalysts having various ligand forms have a cation form through alkylation with an organometallic compound, which is a promoter, thereby polymerizing olefins.
  • the present inventors in the course of studying the metallocene compound, by reacting the ansa metallocene compound substituted with a specific ligand and a functional group with a specific promoter compound without using a separate solid carrier It is possible to prepare a catalyst composition for unsupported non-uniform pleurepin polymerization having a non-uniform single activity point by the catalyst itself, and to prepare a polyolefin using the catalyst composition thus prepared, it is easy to prepare a polyolefin having excellent desired physical properties. It was confirmed that it can be prepared to complete the present invention.
  • a catalyst composition for unsupported non-uniform polyolefin polymerization that does not use a separate carrier.
  • the "unsupported catalyst” means that the ansa metallocene compound and / or the cocatalyst compound exhibiting catalytic activity are used in the polymerization of polyolefin because they are present in an unsupported state such as silica or alumina. do.
  • heterogeous catalyst or “heterogeneous catalyst” means a catalyst that catalyzes a phase different from the reaction material. By reference, it is distinguished from a “homogeous catalyst” which has the same phase as the reaction material and catalyzes.
  • a catalyst in a form in which the catalyst does not melt during polymerization of eleupine and is present in a separate form together with the monomer and the produced polymer, and only such a heterogeneous catalyst is fouling of the polymer and fouling in the reactor. Can be prevented.
  • the catalyst composition for unsupported non-uniform polyolefin polymerization of the present invention is an ansa metallocene compound represented by the following formula (1) and the following.
  • the promoter compound represented by the formula (2) may be bound.
  • M 1 is a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide transition metal or an actanide transition metal;
  • X is the same or different halogen
  • A is an element of group 14 and is a bridge group connecting indenyl groups
  • R 1 is alkyl having 1 to 20 carbon atoms, alkenyl, alkylaryl, arylalkyl or Aryl;
  • R 2 is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl, alkylaryl, arylalkyl or aryl;
  • R 3 , R 3 ' , R 4 , R 4' , R 5 , R 5 ' , R 6 , R 6' , R 7 , R 7 ' , R 8 , and R 8' are the same as or different from each other, and each hydrogen, C 1 -C 20 alkyl, alkenyl, alkylaryl, arylalkyl or aryl ';
  • n ⁇ r is an integer from 1 to 20;
  • M 2 is a Group 13 metal element
  • R 9 are the same as or different from each other, and are each alkyl, alkenyl, alkylaryl, arylalkyl or aryl having 1 to 20 carbon atoms;
  • n may be an integer of 2 or more.
  • R 1 and R 2 are each alkyl having 1 to 4 carbon atoms;
  • R 3 and R 3 ' are each hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl, or arylalkyl;
  • R 5 and R 5 ' are each hydrogen, aryl having 1 to 20 carbon atoms, or alkylaryl;
  • N is an integer from 1 to 6;
  • R 4, R 4 ', 6 (6', R 7, R 7 ', R 8 eu and R 8' are each hydrogen and A may be a silicon (Si) .
  • the ansa metallocene compound may be an indenyl group as a ligand, and may act as a Lewis base as an oxygen-donor to a bridge group connecting the ligand. It is characterized in that the functional group is substituted.
  • the ansamer thiotavante compound of Formula 1 includes two indenyl groups as ligands, and a Lewis base as an oxygen-donor to a bridge group connecting the ligands.
  • the ansa metallocene compound of Formula 1 may preferably include an indenyl group substituted with an alkyl group at position 2 and an aromatic compound at position 4 as a ligand.
  • the ansa metallocene compound may be effectively used for polypropylene polymerization requiring high stereoregularity by employing an indenyl group ligand instead of a cyclopentyl group or anthracene ligand which can be used for polyethylene polymerization.
  • the cocatalyst compound is characterized by forming a Lewis acid-base bond with the bridge group functional group of the ansa metallocene compound as described above.
  • R 9 is respectively methyl, ethyl, propyl, isopropyl, isopropenyl, n_butyl (n-butyl), sec-butyl (secH ityl), tert-butyl (fer -butyl), pentyl, pentyl, hexyl, octyl, decyl, dodecyl, tree Decyl, tetratradecyl, pentadecyl, pentadecyl, nucledecyl, octadecyl, octodecyl, eikosyl, dokosyl, tetrakosyl, cyclonusil (cyclohexyl), cyclooctyl, phenyl, tolyl, or ethylphenyl; M 2 may be aluminum.
  • m in Formula 2 may be an integer of 2 or more or 2 to 500, preferably an integer of 6 or more or 6 to 300, more preferably 10 or more or an integer of 10 to 100. "As described above, the co-catalyst compound of Formula 2 is Formula
  • the ansa metallocene compound of 1 is characterized in that it comprises a metal element capable of acting as a Lewis acid capable of forming a bond through the Lewis acid-base interaction with the functional group introduced to the bridge group (bridge group) .
  • the cocatalyst compound of Formula 2 may be present in a linear, circular or reticular form, examples of such cocatalyst compounds include methylaluminoxane, ethylaluminoxane, Propyl Aluminoxane, Butyl Aluminoxane, Tetraisobutyl Dialuminoacid
  • tetraethyldialuminoxane may be one or more.
  • the structure of such cocatalyst compounds may be present in a linear, circular, or network form.
  • the cocatalyst compound activates a single active site catalyst to cause polymerization in the future, and at the same time reacts with a functional group such as an alkoxy group substituted in the bridge group of the metallocene compound to form a final metallocene catalyst composition. It allows to form a solid particle form without a separate carrier. That is, while activating the catalyst and at the same time acts as a crosslinking agent for some time, the catalyst composition in the form of particles precipitates and has an excellent effect of obtaining the final catalyst composition in an unsupported heterogeneous state by a simple method.
  • the final catalyst composition according to the present invention is a solid particle, for example, after dissolving the catalyst precursor ansametallocene compound in toluene, dropping or one-shot dropping of a promoter compound such as methylaluminoxane. If the particles are precipitated, and then a solvent such as leuene is removed, a solid catalyst can be obtained without using a separate carrier.
  • the catalyst composition for unsupported non-uniform polyolefin polymerization of the present invention controls the size of the catalyst particles even when the carrier is not used, does not use the carrier, and performs several decantation and washing steps. It has an excellent effect that fouling does not occur during polymerization by a simple method without going through.
  • At least a part of the ansa metallocene compound and the cocatalyst compound in the catalyst composition for unsupported non-uniform polyolefin resin of the present invention may be included in a Lewis acid-base bond state as described above. have.
  • the cocatalyst compound may be additionally included in a state in which the Lewis acid-base bond is not provided, thereby further enhancing the catalytic activity and thus exhibiting excellent catalytic activity without using a carrier.
  • the molar ratio (MVM 1 ) of the transition metal element (M 1 ) of the ansa metallocene compound and the metal element (M 2 ) of the cocatalyst compound may be 70 to 500, preferably 250 to 480, More preferably 300 to 450 Can be.
  • the molar ratio (MVM 1 ) is less than 70, the activation role of the catalyst may be insufficient, and when the molar ratio (MM 1 ) exceeds 500, the particle size is not controlled due to excessive crosslinking reaction. Problems can arise with morphology.
  • the catalyst composition for unsupported non-uniform polyolefin polymerization of the present invention is a Lewis acid of a functional group introduced into a bridge group of the metallocene compound of Formula 1 and a metal element included in the cocatalyst compound of Formula 2. Bonds are formed through base interactions.
  • the catalyst composition of the present invention by the Lewis acid-base bond between the ansa metallocene catalyst compound and the methyl aluminoxane (MA0) promoter compound without a separate carrier, specifically ionic bond Internal crosslinks can be formed by coordinating with each other to form a final unsupported heterogeneous catalyst composition.
  • the present invention can provide a catalyst composition for unsupported non-uniform polyolefin polymerization comprising a coordination bond such as a bond form, that is, a Lewis acid-base bond, as shown by the following Chemical Formula 3.
  • the catalyst composition for unsupported non-uniform polyolefin polymerization of the present invention is not only catalytically activated by a specific cocatalyst compound as described above, but also with the metallocene compound of Formula 3 as described above.
  • the catalyst composition for unsupported non-uniform polyolefin polymerization of the present invention may be said that the metallocene compound and the promoter compound are formed by being linked to each other by a Lewis acid-base bond.
  • the catalyst composition for unsupported non-uniform polyolefin polymerization of the present invention is a heterogeneous catalyst itself as a catalyst composition through the reaction of a specific metallocene compound and a promoter compound without using a separate carrier. It is characterized in that it is produced in a composition.
  • the catalyst composition of the present invention may be one in which the -OR 1 functional group in Chemical Formula 1 of the ansa metallocene compound and the metal ' element of the cocatalyst compound are bonded by Lewis acid-base reaction.
  • the catalyst composition for unsupported non-uniform polyolefin polymerization may be in a solid particle state
  • the average particle diameter of the catalyst may be 20 to 200, preferably 30 to 170 im, more preferably 40 im to 150 ⁇ . If the average particle diameter of the catalyst is less than 20, there is a possibility that the fine powder, particle components in the polymer are increased, 200 In the case of an excess of an annealing, it is difficult to control the temperature during polymerization, thereby increasing the possibility of fouling, and the morphology is also poor.
  • an alkoxy tether group may be attached to the silane bridge, and methylaluminoxane may be used as a promoter.
  • the reaction rate may be controlled by slowly dropping methylaluminoxanoic acid into a single active site catalyst having an alkoxy tether group dissolved in toluene.
  • the carrier it is possible to simplify the manufacturing process, to reduce the cost of using the carrier, it is possible to prevent the reduction of the catalyst activity generated during the supporting process.
  • the method for preparing a catalyst composition for unsupported non-uniform polyolefin polymerization may include reacting an ansa metallocene compound represented by Formula 1 and a promoter compound represented by Formula 2 below.
  • M 1 is a Group 3 transition metal, a Group 4 transition metal, a Group 5 transition metal, a lanthanide transition metal or an actanide transition metal;
  • X is the same or different halogen from each other
  • A is an element of group 14 and is a bridge group connecting indenyl groups
  • R 1 is alkyl ⁇ alkenyl, alkylaryl, arylalkyl or aryl having 1 to 20 carbon atoms;
  • R 2 is hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl, alkylaryl, arylal 3 ⁇ 4 or aryl;
  • R 3 , R 3 ' , R 4 , R 4' , R 5 , R 5 ' , R 6 , R 6' , .R 7 , R 7 ' ⁇ R 8 , and R 8' are the same as or different from each other, Hydrogen, alkyl having 1 to 20 carbon atoms, alkenyl, alkylaryl, arylalkyl or aryl, respectively; ' n is an integer from 1 to 20;
  • M 2 is a Group 13 metal element
  • R 9 are the same as or different from each other, and are each alkyl, alkenyl, alkylaryl, arylalkyl or aryl having 1 to 20 carbon atoms;
  • n is an integer of 2 or more.
  • the metallocene compound or cocatalyst, and Chemical Formula 1 or Chemical Formula 2, Chemical Formula 3, and corresponding substituents are as described above.
  • the molar ratio (MM 1 ) between the transition metal element (M 1 ) of the ansa metallocene compound and the metal element (M 2 ) of the cocatalyst compound may be 70 to 500, preferably 250 to 480, more preferably. May be 300 to 450
  • the molar ratio (MVM 1 ) is less than 70, the activation role of the catalyst may be insufficient, and when the molar ratio (MVM 1 ) exceeds 500, the particle size is not controlled due to excessive crosslinking reaction. Problems can arise with morphology.
  • At least a part of the ansa metallocene compound and the cocatalyst compound may be included in a Lewis acid-base bond state as described above.
  • the cocatalyst compound may be additionally included in a state in which the Lewis acid-base bond is not provided, thereby further enhancing the catalytic activity and thus exhibiting excellent catalytic activity without using a carrier.
  • the ansa metallocene compound or cocatalyst compound may be dissolved in at least one organic solvent selected from the group consisting of toluene, xylene, methylene chloride, ethyl acetate, ethyl ether, nucleic acid, and the like. Rouen, xylene, etc. can be used. At this time, the amount of the organic solvent can be used to adjust the degree to dissolve the metallocene compound or cocatalyst compound, it is possible to control the degree of dilution in terms of the preferred morphology of the catalyst.
  • the concentration of the organic solvent may be 0.1 g / cm 3 or less or 0.1 mg / cm 3 to 0.1 g / cm 3 , preferably 0.05 g / cm 3 or less, and more preferably 0.01 mg / cm 3 or less. have.
  • the dropping speed may be 10 cc / min or less or 0.2 to 10 cc / min, preferably 5 cc / min or less, and more preferably 1 cc / min or less.
  • the dropping speed can be adjusted in terms of effectively maintaining the overall process efficiency. However, if the dropping speed is too fast, for example, if it exceeds 10 cc / min, the reaction proceeds abruptly and the size of the catalyst particles produced is too large. In this case, problems may occur in catalyst injection during polymerization, and the polymer size distribution may be widened.
  • the present invention in addition, in addition to the above-described steps, before or after each of the above steps, the present invention generally performs. Steps to further As it may include, the above-described steps do not limit the manufacturing method of the present invention.
  • a method for producing a polyolefin comprising the step of polymerizing at least one or more olefin monomers in the presence of the unsupported non-uniform catalyst composition.
  • the present invention by reacting a specific ansa metallocene compound with a specific cocatalyst compound to form a heterogeneous metallocene catalyst having a solid particle form to perform olefin polymerization, in particular propylene polymerization.
  • the activity of the catalyst generally has the advantage of obtaining a polymer without fouling while having a very good activity compared to the supported catalyst made by supporting the carrier.
  • the urepin monomers are ethylene, propylene, 1-butene, 1-pentene, 1-nuxene, 4-methyl-1-pente, 1-octene, 1-decene, 1-dodecene, 1 pentadedecene, 1-nucleus It may be at least one selected from the group consisting of decene, 1-octadecene, 1-eicosene, and combinations thereof.
  • the polymerization of the polyolefin can be carried out by reacting for 1 to 24 hours at a temperature and a pressure of 10 to 100 kgf / cm 2 from 25 to 500 ° C i.
  • the polymerization reaction temperature is preferably 25 to 200 ° C (Celsius, Celsius), more preferably 50 to 100 ° C.
  • the polymerization reaction pressure is preferably 1 to 70 kgf / cm 2 , more preferably 5 to 40 kgf / cm 2 .
  • the polymerization reaction time is preferably 1 to 5 hours, more preferably 1 to 2 hours.
  • the polymerization process can control the polymer product and the molecular weight range finally produced according to the hydrogenation or non-addition conditions.
  • a high molecular weight polyolefin can be produced under the condition that hydrogen is not added, and low molecular weight polyolefin can be produced even by adding a small amount of hydrogen when hydrogen is added.
  • the hydrogen content added to the polymerization process is in the range of 0.07 L to 4 L under 1 atmosphere of semi-aqueous conditions, or is supplied at a pressure of 1 bar to 40 bar or 168 ppm to 8 in the molar content of hydrogen relative to the olepin monomer. It can be supplied at 000 ppm.
  • the polyolefin prepared using the unsupported non-uniform polyolefin resin catalyst composition of the present invention may have a higher molecular weight than when using a conventional metallocene catalyst.
  • the resulting polyolefin has a weight average molecular weight (Mw) of 200,000 or more or 200,000 to 200,000. 600,000, preferably 250,000 or more, more preferably 300,000 or more.
  • the catalyst composition for unsupported non-uniform polyolefin reinforcement of the present invention when the polymerization process is carried out under the conditions of adding hydrogen, for example, the conditions of adding 0.37 L of hydrogen under 1 atmosphere of semi-aqueous conditions
  • the resulting polyolefin may have an increased average molecular weight (Mw) of 90,000 or less or 55,000 to 90,000, preferably 85,000 or less, and more preferably 80,000 or less.
  • the polyolefin prepared by this method may have a molecular weight distribution (Mw / Mn) of 1 to 4, preferably 1.2 to 3.5, more preferably 1.5 to 3.
  • the catalyst composition for unsupported non-uniform polyolefin polymerization of the present invention is 6.0 kg, calculated as the ratio of the weight (kg) of the polymer produced per unit weight content (g) of the catalyst used based on the unit time (h). / gCat-hr or more, or 6.0 to 50 kg / gCat-hr, preferably 7.0 kg / gCat-hr or more, more preferably 8.0 kg / gCat-hr or more.
  • the polyolefins thus produced may have a stereoregularity (XI) of at least 90%, preferably at least 92% and more preferably at least 953 ⁇ 4.
  • the stereoregularity diagram (XI) of the polyolefin is a value calculated according to the following formula (1).
  • VbO volume of initial xylene (mL)
  • Vbl volume (mL) of polymer taken from xylene
  • Vb2 volume of collected xylene used in the blank test (mL),
  • W2 sum of the weight of the polymer remaining in the aluminum pan after the evaporation of the aluminum pan and ⁇ xylene (g),
  • W1 weight of aluminum pan (g)
  • B average value (g) of residues remaining in the aluminum pan during the ball test.
  • the catalyst composition for unsupported non-uniform polyolefin resin polymerization of the present invention includes a specific ansa metallocene compound and a specific co-catalyst compound, so that the polyolefin having excellent physical properties can be prepared by using the catalyst itself without a separate carrier. there '.
  • the catalyst composition of the present invention exhibits excellent catalytic activity and can easily control the microstructure of the polymer, thereby easily preparing a polyolefin having desired physical properties.
  • the catalyst composition of the present invention can obtain a very high catalytic activity compared to the ' supported catalyst ' which is supported on the solid support by reacting the existing metallocene compound with the cocatalyst compound.
  • a catalyst composition for non-uniform non-uniform polyolefin polymerization was prepared by using the following method. Synthesis of Metallocene Compounds
  • Step 2 Synthesis of (6-t-butoxynucleosil) (methyl) -bis (2-methyl-4-phenylindenyl) silane
  • Step 3 Synthesis of [(6-t-butoxyhexylmethylsilane-diyl) -bis (2-methyl-4-phenylindenyl)] zirconium dichloride
  • the obtained metallocene compound was equivalent to the homogeneous catalyst melt
  • the molar ratio (Al / Zr) of the metal element of the metallocene compound and methylaluminoxane was set to 375.
  • the upper solution was removed.
  • the unsupported non-uniform metallocene catalyst composition thus obtained is a separate It was prepared as a heterogeneous catalyst composition by only the cocatalyst and the activation reaction itself without using a carrier.
  • Example 2 Carrier in the same manner as in Example 1, except that methylaluminoxane (MA0) was added to the shrink flask in which the metallocene compound was dissolved in one batch instead of dropwise. 0.27 g of an unsupported non-uniform metallocene catalyst having a powder particle form having an average particle diameter of 150 / dl was obtained without using.
  • MA0 methylaluminoxane
  • Triethylaluminum is used instead of methylaluminoxane (MA0) as a promoter, except that the molar ratio (Al / Zr) of the metal element of the metallocene compound and triethylaluminum (TEA) is 50.
  • TMA Triethylaluminum
  • Triisobutylaluminum (TIBA) is used instead of methylaluminoxane (MA0) as a cocatalyst and reacted so that the molar ratio (Al / Zr) of the metal element of the metallocene compound and triisobutylaluminum (TIBA) is 25. Except for the preparation of the unsupported heterogeneous catalyst in the same manner as in Example 2, a catalyst in the form of particles was not obtained. Comparative Example 3
  • methyl aluminoxane (MA0) 52 mirol was added in one batch (One-Shot) and reacted at 90 ° C. for 24 hours. After precipitation, the upper layer was removed and washed twice with toluene to obtain 3 g of a silica carrier carrying methylaluminoxane (MA0).
  • the metal element molar ratio (Al / Zr) of the metallocene compound and methylaluminoxane supported on silica was 215. Thereafter, the resultant was dried in vacuo to obtain 5 g of a silica-supported metallocene catalyst composition having a powder particle form having an average particle diameter of 30 / cc.
  • Triethylaluminum (TEA) was used as a cocatalyst according to Comparative Example 1, and the reaction was carried out such that the molar ratio (Al / Zr) of the metal element of the metallocene compound to the triethylaluminum was 50.
  • a catalyst composition for polyolefin polymerization was prepared in the same manner as in Comparative Example 3, except that the ansa metallocene compound of Formula 5 was prepared and used.
  • Step 2 Preparation of ⁇ dimethylsilanediylbis (2-methyl-4-phenylindenyl)] zirconium dichloride
  • a catalyst composition for polyolefin polymerization was prepared in the same manner as in Comparative Example 3, except that the ansa metallocene compound of Formula 7 was prepared and used.
  • the polypropylene polymer was prepared in the following manner, respectively. Prepared. Propylene polymerization
  • the propylene polymerization process was carried out in a bulk polymerization process using the metallocene catalyst composition under the conditions as shown in Table 1 below.
  • the 2 L stainless steel was dried under vacuum at 65 ° C., and then quenched, triethylaluminum 3 ⁇ was added at room temperature, and 1.5 L of propylene was sequentially added.
  • the metallocene catalyst composition prepared according to Examples 1 and 2 and Comparative Examples 3 to 8, respectively, to 0.02 g or 0.006 g, respectively.
  • the reaction was performed by additionally adding hydrogen gas together with the metallocene catalyst composition (see Table 1). Thereafter, the temperature of the reactor was slowly raised to 70 ° C. and then polymerized for 1 hour. After the reaction was completed, unreacted propylene was vented. At this time, the content and activity of the catalyst composition used and the physical properties of the resulting polymer are measured and shown in Table 1 below.
  • Catalyst activity calculated as the ratio of the weight of polymer produced (kg PP) per catalyst amount (g Cat) used, based on unit time (h).
  • the melting point of the polymer was measured using a Calorimeter, DSC, a device name: DSC 2920, and a TA instrument. ⁇ Specifically, the polymer was heated to 220 ° C and maintained at that temperature for 5 minutes, and then lowered to 20 ° C and increased again. At this time, the rate of rise and fall of temperature was 10 ° C / min, respectively. Adjusted to.
  • Crystallization temperature (Tc) of the polymer The crystallization temperature was determined from a curve appearing while decreasing the temperature under the same conditions as the melting point using DSC.
  • 0-xylene was first prepared in a flask and then 200 mm No. Filtered with 4 extraction paper.
  • the aluminum pan was dried in an oven at 150 ° C. for 30 minutes, then angled in a desiccator and weighed.
  • 100 mL of filtered xylene was collected by a pipette, transferred to an aluminum pan, and heated to 145 to 150 ° C. to evaporate all the xylenes.
  • the aluminum pan was then vacuum dried for 1 hour under a temperature of 100 ⁇ 5 ° C and a pressure of 1 hr, 13.3 kPa. After the aluminum pan is chopped off the desiccator, By repeating the procedure twice, the 0-xylene only blank test was completed with a weight error of 0.0002 g.
  • the polypropylene polymer prepared using a metallocene catalyst was r dried (70 ° C., 13.3 kPa, 60 minutes, vacuum dried), followed by 500 mL of 2 g ⁇ 0.0001 g of the polymer sample, which was detected by a desiccator.
  • Into a flask of 200 mL o-xylene was added thereto. The flask was connected to nitrogen and cooling water and the flask was heated to reflux 0-xylene for 1 hour. Thereafter, the flask was placed in air for 5 minutes, angled to 100 ° C. or less, and the flask was shaken and placed in a thermostat (25 ⁇ 0.5 ° C.) for 30 minutes to precipitate insoluble matters.
  • the resultant solution formed precipitate was 200 ⁇ No. Filtration was repeated with 4 extraction paper until clear. After drying at 150 ° C for 30 minutes, add 100 mL of the filtered solution to a pre-weighed aluminum pan after cooling in a desiccator and evaporate 0-xylene by heating the aluminum pan to 145 to 150 ° C. I was. The evaporated aluminum pan was vacuum dried for 1 hour at a temperature of 70 ⁇ 5 ° C. and a pressure of 13.3 kPa, and weighed in an error of 0.0002 g by repeating the process in a desiccator twice.
  • VbO volume of initial ⁇ xylene (mL)
  • Vbl volume (mL) of polymer taken from xylene
  • Vb2 volume of £ ⁇ xylene taken in the ball test (mL)
  • PDI Molecular weight distribution
  • Mw weight average molecular weight
  • GPC gel permeation chromatography
  • the catalyst size was adjusted to 50 m level by dropwise addition of 10 wt% methylaluminoxane at a rate of 0.5 cc / min, so that the morphology of the polymer was better, and the molecular weight distribution was also reduced to 1.90. It is early and can be seen that the improvement in a significantly narrow range.
  • the size of the final unsupported heterogeneous catalyst composition could be adjusted to 50. It is possible to prepare a catalyst composition with a better morphology of polypropylene obtained after polymerization with a narrower molecular weight distribution.
  • a catalyst having a larger particle size can be obtained.
  • the present invention has the advantage that it is easy to control the microstructure of the olefin polymer during polyolefin polymerization.
  • Comparative Preparation Examples 1 to 7 in which the olefin polymerization process was carried out using the silica supported metallocene catalysts of Comparative Examples 3 to 8 prepared by using the carrier according to the existing process were subjected to a complicated supporting process.
  • the catalyst activity was found to drop significantly below 5.2 kg / gCat-hr.
  • Comparative Examples 3 and 6 the polymerization process itself did not occur, and in Comparative Example 4, the catalytic activity was very low, 0.12 kg / gCat ⁇ hr.
  • the catalysts of Examples 1 to 2 without using a carrier according to the present invention have a very high catalytic activity compared to the catalysts of Comparative Examples 3 to 8 supported on silica, and are controlled by the dropping rate of methylaluminoxane.
  • Example 1 had a catalyst size of 50 to facilitate injection of the catalyst during polymerization, uniform size of the resulting pulley propylene, and better morphology.
  • Examples 1 and 2 are composed of shorter time, lower temperature, and simpler steps than Comparative Examples 3 to 8 using the carrier.

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  • Chemical & Material Sciences (AREA)
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  • 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 concerne une composition de catalyseur de polymérisation de polyoléfine à base de métallocène et, plus particulièrement, une composition de catalyseur hétérogène non supporté pour la polymérisation de polyoléfine, contenant un composé d'ansa-métallocène spécifique et un composé de cocatalyseur liés l'un à l'autre sans support séparé. L'invention concerne également un procédé de préparation de la composition et un procédé de préparation de polyoléfine au moyen de la composition. Selon la présente invention, un composé d'ansa-métallocène spécifique et un composé de cocatalyseur présentant une activité catalytique supérieure et pouvant facilement contrôler la structure fine des polymères à base d'oléfines donnent une composition de catalyseur hétérogène sans qu'un support solide soit utilisé. Ainsi, une composition de catalyseur hétérogène non supporté à base de métallocène possédant une activité élevée est obtenue sans changement des procédés existants.
PCT/KR2012/009190 2011-11-03 2012-11-02 Composition de catalyseur hétérogène non supporté pour la polymérisation de polyoléfine et son procédé de préparation WO2013066109A1 (fr)

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US14/353,666 US9631034B2 (en) 2011-11-03 2012-11-02 Non-supported heterogeneous polyolefin polymerization catalyst composition and method for preparing same
JP2014539878A JP5956595B2 (ja) 2011-11-03 2012-11-02 非担持不均一系ポリオレフィン重合用触媒組成物およびその製造方法
CN201280054157.1A CN103987737B (zh) 2011-11-03 2012-11-02 非负载型非均相聚烯烃聚合反应催化剂组合物及其制备方法

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CN110099934A (zh) * 2017-11-27 2019-08-06 Lg化学株式会社 聚丙烯及其制备方法
US11384180B2 (en) 2017-11-27 2022-07-12 Lg Chem, Ltd. Polypropylene and method for preparing the same

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