KR20020002471A - Polyolefin production - Google Patents

Abstract

Use of a metallocene catalyst component for the preparation of a polyolefin which comprises an isotactic or polyolefin syndiotactic/isotactic block polyolefin having a monomer length of up to C10, which component has the general formula: R"(CpR1R2R3)(Cp'R1'R2')MQ2 wherein Cp is a cyclopentadienyl ring substituted with at least one substituent; Cp' is a substituted fluorenyl ring; R" is a structural bridge imparting stereorigidity to the component; R1 is optionally a substituent on the cyclopentadienyl ring which is distal to the bridge, which distal substituent comprises a bulky group of the formula XR*3 in which X is chosen from Group IVA, and each R* is the same or different and chosen from hydrogen or hydrocarbyl of from 1 to 20 carbon atoms, R2 is optionally a substituent on the cyclopentadienyl ring which is proximal to the bridge and positioned non-vicinal to the distal substituent and is of the formula YR#3 in which Y is chosen from group IVA, and each R# is the same or different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, R3 is optionally a substituent on the cyclopentadienyl ring which is proximal to the bridge and is a hydrogen atom or is of the formula ZR$3, in which Z is chosen from group IVA, and each R$ is the same of different and chosen from hydrogen or hydrocarbyl of 1 to 7 carbon atoms, R1' and R2' are each independently substituent groups on the fluorenyl ring, one of which is a group of the formula AR'''3, in which A is chosen from Group IVA, and each R''' is independently hydrogen or a hydrocarbyl having 1 to 20 carbon atoms and the other is hydrogen or a second group of the formula AR'''3; M is a Group IVB transition metal or vanadium; and each Q is hydrocarbyl having 1 to 20 carbon atoms or is a halogen.

Description

METHOD FOR PRODUCING POLYOLEFIN

Olefins having three or more carbon atoms can be polymerized to produce polymers having stereochemical configurations of the same isotactic. For example, in the polymerization of propylene to form a polypropylene, such an aligned configuration generally includes a methyl group attached to the tertiary carbon atom of a continuous monomer unit on the same plane of an imaginary plane passing through the main chain of the polymer Respectively. This is expressed using the Fischer projection formula:

Another way of representing this structure is to use NMR spectroscopy. According to the Bovey NMR nomenclature for the pentad of the same arrangement, the pentad is ... mmmm, where each "m" is either a "meso" diad or a continuous Lt; / RTI >

In contrast to the same arrangement structure, a syndiotactic polymer is a polymer in which a methyl group is attached to a tertiary carbon atom of a continuous monomer unit of a chain present on the other plane of the plane of the polymer. The structure of such an ordered polymer appears as follows using the Fischer projection formula.

In the NMR nomenclature, the ordered array pentad is denoted as ... rrrr ... where "r" is a "racemic" diad that retains the methyl groups that are consecutively present on the other plane of the plane.

In contrast to homologous and ordered sequences polymers, atactic polymers do not represent repeating units in a regular order. Unlike ordered arrays or identical aligned polymers, the hybrid aligned polymers are not crystalline and form a substantially waxy product.

Although catalysts can form all three types of polymers, catalysts that produce homogeneous or ordered copolymers predominantly and small amounts of hybrid ordered polymers are preferred. The C2 symmetric metallocene catalyst is a catalyst known in the production of the polyolefin. An example of this is a C2 symmetrical bisindenyl type zirconocene capable of producing the same ordered polypropylene having a high molecular weight and a high melting point. However, such a method of producing a metallocene catalyst is expensive and takes a considerable amount of time. Most importantly, the final catalyst is often composed of a mixture of undesired proportions of racemic isomers and meso isomers. Therefore, it is necessary to prevent the meso stereoisomers from being separated during the polymerization reaction to form a hybrid aligned polypropylene.

EP-A-0426644 relates to an ordered copolymer of olefins such as propylene, obtainable using isopropyl (fluorenyl) (cyclopentadienyl) zirconium dichloride as the catalyst component. As a result of measuring the amount of rrrr, the regular array type pentad, the order arrangement was found to be 73 to 80%.

EP 747406 relates to the polymerization of olefin monomers which form a regular arrangement / identical arrangement block polyolefins, especially block polypropylene. The component of the polymerization catalyst is 3-trimethylsilylcyclopentadienyl-9-fluorenyl zirconium or hafnium dichloride with isopropylidene or diphenylmethylidene crosslinking.

EP-A-0537130 discloses the use of a C1 symmetric metallocene catalyst for the preparation of the same ordered polypropylene. A preferred catalyst is isopropylidene (3-t- butyl-fluorenyl-cyclopentadienyl) ZrCl _2. The catalyst has a bulky tert-butyl group located on the cyclopentadienyl ring in-situ from an isopropylidene bridge. This catalyst is composed of only one stereoisomer, which is advantageous in that it is not necessary to isolate the metallocene isomer in the final stage of its synthesis. While the process for making polypropylene using this catalyst produces the same ordered polypropylene, the polymer product is devoid of mechanical properties due to the presence of regiodefects and relatively low molecular weight.

Positional defects do not result in completely identical aligned polyolefins in which the respective monomer units are positioned side-by-side in the polymer chain and are arranged in a head-to-tail state, and the monomers are improperly inserted to form a head- - Occurs when a tail miss occurs. This so-called (2-1) positional defect is partially transferred by a so-called (1-3) insertion through an isomerization process in which the units of four -CH ₂ groups are left in the skeleton of the polypropylene chain. This results in the same ordered polypropylene of low molecular weight with low melting point resulting in adverse effects on the physical and mechanical properties of the polymer. EP-A-0881236 discusses the problem with providing isopropylidene (5-methyl-3t-butylcyclopentadienylfluorene) zirconium dichloride as part of the polymerization catalyst. However, the polypropylene obtained by using the catalyst has a molecular weight (Mw) in the range of 213900 to 458500, and a microtacticity characteristic of mmmm pentad is in the range of 82.8 to 86.8%. The melting points of the polymers are in the range of 139.3 to 143.8.

EP-A-577581 discloses a process for the preparation of ordered polypropylenes using metallocene catalysts with substituted fluorenyl groups at positions 2 and 7 and unsubstituted cyclopentadienyl rings. However, the above metallocene catalysts are not used to describe the same arrangement or a method of producing a regular array / uniformly arranged block polyolefin.

EP-A-0748824 discloses the use of chirality transition metal compounds and aluminoxanes to produce stereoregularly ordered polypropylene with the same reported pentad content of 0.972 or less reported. However, there is no data on the amount of false-insertion of monomers in polypropylene.

The present invention relates to metallocene catalyst components for use in the production of polyolefins, especially polypropylene. The present invention also relates to a catalyst system containing a metallocene catalyst component and to a process for preparing such a polyolefin.

1 to 12 show structures of preferred catalyst components of the present invention.

Fig. 13 shows the results of differential scanning calorimetry analysis on the same aligned polypropylene prepared at 40 占 폚 using the catalyst shown in Fig.

Summary of the Invention

The present invention is intended to overcome the disadvantages of the prior art.

In a first aspect, the present invention relates to the use of a metallocene catalyst component represented by the following formula in the preparation of a polyolefin comprising the same arrangement or a polyolefin regular arrangement / identical arrangement block polyolefin with a monomer length of C10 or less.

R " (C _p R ₁ R ₂ R ₃ ) (C _p 'R ₁ ' R ₂ ') MQ ₂

Wherein C _p is a cyclopentadienyl ring substituted with one or more substituents; C _p 'is a substituted fluorenyl ring; R " is a structural bridge that confers stereorigidity on said component; R < ₁ > is optionally a substituent on the cyclopentadienyl ring in-situ from said bridge, said in situ substituent having the formula XR ^* ₃ wherein X is selected from group IVA and each R ^* is the same or different from each other and is selected from hydrogen or hydrocarbyl having from 1 to 20 carbon atoms; R < ₂ > is a substituent on the cyclopentadienyl ring which are adjacent to the cross-linked and located away from the home position substituent, the formula YR # ₃ (wherein, Y is selected from the ⅳA group, and each R # is the same or different and hydrogen or is selected) from hydrocarbyl holding 1 to 7 carbon atoms; R ₃ is optionally it is cyclopentyl adjacent to the cross-linking Diethoxy selected from a hydrogen atom, or or the formula ZR $ ₃ (wherein, Z is ⅣA group as a substituent on the ring carbonyl and each R $ is the same or different from each other and from hydrocarbyl of 1 to 7 carbon atoms or a hydrogen Wherein R ₁ 'and R ₂ ' are each independently a substituent on the fluorenyl ring, one of which is selected from the group of the formula AR "' ₃ wherein A is selected from the group IVA, each R" Hydrogen or hydrocarbyl having from 1 to 20 carbon atoms and the other is hydrogen or a second group having the formula AR "'₃; M is a Group IVB transition metal or vanadium; Each Q is a hydrocarbyl having 1 to 20 carbon atoms or is a halogen.

The polyolefins prepared using the metallocene catalyst component of the present invention surprisingly were found to have very good microarray properties, especially when measured at pentad distribution levels at ¹³ C nmr. Polyolefins have also been found to be substantially free of site defects. Thus, the prepared polyolefins typically have high weight average molecular weights in excess of 500,000 and improved mechanical properties including melting points greater than 10 DEG C compared to prior art values.

Applicants have surprisingly found that when the fluorenyl ring in the metallocene catalyst is substituted at any particular position, preferably position 3 and / or position 6, the alignment of the polymer produced is significantly improved and the position of the polymer It was found that defect generation was also significantly reduced.

According to the present invention, the fluorenyl ring may be substituted with a radical of the formula AR ''' ₃ (wherein A is preferably carbon or silicon and more preferably carbon). When A is carbon, AR ''' ₃ can be, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, Alkyl, aryl, alkenyl, alkylaryl or arylalkyl. When A is silicon, AR ''' ₃ may be Si (CH ₃ ) ₃ . It is preferable that at least _{one of} R ' ₁ and R' ₂ is t-butyl. It is more preferable that both R ' ₁ and R' ₂ are the same.

Moreover, Applicants have also found that when the catalyst of the present invention is used in the production of polypropylene, its melting point is generally higher than 150 ° C, which can be significantly improved over the prior art to 165 ° C.

It is preferred that the structural bridging R " is alkylidene having 1 to 20 aliphatic or aromatic carbon atoms, dialkyl germanium or silicon or siloxane, alkylphosphene or amine bridging two Cp rings. R " It is preferable that the Cp rings are isopropylidene cross-linked at the 2-position of isopropylidene. Or R " is diphenylmethylidene.

M is preferably zirconium or titanium, and most preferably zirconium. Q is selected from alkyl, aryl, alkenyl, alkylaryl or arylalkyl, preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, Lt; / RTI > Q is preferably halogen.

The choice of the substitution pattern on the cyclopentadienyl ring depends on the desired stereochemistry of the polyolefin product. The metallocene catalyst component of the present invention can be used to prepare the same aligned polyolefin or ordered arrangement / identical aligned block polyolefin. The polyolefin may be a homopolymer or a copolymer. Rule arrangement / homologous arrangement Where a polyolefin is desired, it is preferred that the cyclopentadienyl ring be substituted at the site of said cross-linking. Therefore, R < ₁ > is not hydrogen but a substituent on the cyclopentadienyl ring. Preferably, R < _{1 >} is a bulky substituent at the in position.

For R ₁ , which is a bulky in situ substituent, it is preferred that X is C or Si; R ^* is alkyl, aryl, alkenyl, alkylaryl or arylalkyl, preferably methyl, ethyl, , Isobutyl, amyl, isoamyl, hexyl, heptyl, octyl, nonyl, decyl, cetyl or phenyl. R ₁ may be hydrocarbyl attached to a single carbon atom in the cyclopentadienyl ring or may comprise a hydrocarbyl bonded to two carbon atoms in the ring. R ₁ is preferably C (CH ₃ ) ₃ , C (CH ₃ ) ₂ Ph, CPh ₃ or Si (CH ₃ ) ₃ , and most preferably C (CH ₃ ) ₃ .

When the same aligned polyolefin is desired, it is preferred that R ₁ and R ₂ are both not hydrogen. R ₂ preferably includes a CH ₃ group as a substituent on the cyclopentadienyl ring adjacent to the crosslinking.

The cyclopentadienyl ring may also be substituted by R < ₃ > in the formation of the same aligned polyolefin. R ₃ is preferably CH ₃ .

In a further aspect, the metallocene catalyst component for use in preparing the polyolefin comprises (i) a catalyst component as defined above; And (ii) a positional isomer thereof wherein R < ₂ > is adjacent to the cross-linking and adjacent to the in-situ substituent.

These regioisomers are relatively easy to prepare because they are often formed as " by-products " in the synthetic route in which the catalyst component (i) can be prepared.

Surprisingly, it has been found that catalyst components comprising both regioisomers can be used in the preparation of polyolefins having a molecular weight distribution in a polycondensation mode, especially in a binary mode.

In a further aspect, a catalyst system is used in the production of a polyolefin, said system comprising: (a) a catalyst component as defined above; And (b) an aluminum- or boron-containing co-catalyst for activating the catalyst component. Suitable aluminum-containing co-catalysts include alumoxane, alkyl aluminum and / or Lewis acids.

Alumoxanes which can be used in the process of the present invention are well known and are preferred to include oligomeric linear and / or cyclic alkyl alumoxanes, examples of which are the following formulas I and II. In the formula, I represents oligomeric linear alumoxane and II represents oligomeric cyclic alumoxane.

Wherein n is 1 to 40, preferably 10 to 20; m is from 3 to 40, preferably from 3 to 20; R is a C ₁ to C ₈ alkyl group and is preferably methyl. In general, for example, in the production of alumoxane from aluminum trimethyl and water, mixtures of linear and cyclic compounds can be obtained.

Suitable boron-containing co-catalysts include triphenylcarbenium boronates such as tetrakis-pentafluorophenyl-borato-triphenylcarbenium as described in EP-A-0427696, or EP-A-0277004 [L'-H] + [B Ar1 Ar2 X3 X4] - as described in US Pat.

The catalyst system can be used in a melt polymerization reaction process, which is either a homogeneous process or a non-uniform slurry process. In the dissolution method, typical solvents include hydrocarbons having 4 to 7 carbon atoms such as heptene, toluene or cyclohexane. In the slurry process, the catalyst system needs to be immobilized on an inert support, especially on a porous solid support such as talc, inorganic oxide and a resinous support material such as polyolefin. Preferably, the support material is an inorganic oxide that is in the final divided form.

Suitable inorganic oxide materials that are preferably used in accordance with the present invention include Group 2a, Group 3a, Group 4a or Group 4b metal oxides such as, for example, silica, alumina, and mixtures thereof. Other inorganic oxides which can be used alone or can be used with silica or alumina include magnesia, titania, zirconia and the like. However, other suitable support materials include, for example, finely divided functionalized polyolefins such as finely divided polyethylene.

The support is preferably silica having a surface area of 200 to 700 m < 2 > / g and a pore volume of 0.5 to 3 ml / g.

The amounts of alumoxane and metallocene usefully employed in the preparation of solid support catalysts can vary widely. The molar ratio of aluminum: transition metal is preferably 1: 1 to 100: 1, more preferably 5: 1 to 50: 1.

The order of adding metallocene and alumoxane to the support material may vary. According to a preferred embodiment of the present invention, a mixture of metallocene catalyst components is added to the slurry after alumoxane dissolved in a suitable inert hydrocarbon solvent is added to the slurry support material in the same or other suitable hydrocarbon liquid .

Preferred solvents include mineral oils and various hydrocarbons that are liquid at the reaction temperature and that do not react with the respective components. Illustrative examples of useful solvents include alkanes such as pentane, iso-pentane, hexane, heptane, octane and nonane; Cycloalkanes such as cyclopentane and cyclohexane; And aromatic solvents such as benzene, toluene, ethylbenzene and diethylbenzene.

Preferably, the support material is slurried in toluene and the metallocene and alumoxane are slurried in toluene and then added to the support material.

In a further aspect, the invention provides the use of a catalyst component as defined above in the production of a polyolefin, preferably a polypropylene, and an auxiliary catalyst to activate said catalyst component. Although the present invention provides the use of a metallocene catalyst that is preferably substituted at position 3 and / or 6 of the fluorenyl ring, it is preferred that R < ₂ >, which includes (i) a catalytic component and (ii) In particular polypropylene, having a molecular weight distribution of the multifunctional mode, preferably a molecular weight distribution of the dual mode, is prepared using a metallocene catalyst component located adjacent to the crosslinker and located adjacent to the remote substituent Should be.

In a further aspect, the present invention provides a process for the production of polyolefins, in particular polypropylene, comprising contacting the catalyst system as defined above with at least one olefin, preferably propylene, in the reaction zone under polymerization conditions.

The catalyst component may be prepared by any suitable method known in the art. Generally, the process for preparing the catalyst component comprises forming and separating a crosslinked dicyclopentadiene, followed by subsequent reaction with a halogenated metal to produce a crosslinked metallocene catalyst.

In one embodiment, the process for preparing the crosslinked metallocene catalyst component comprises contacting the cyclopentadiene with the substituted fluorene under reaction conditions sufficient to produce the crosslinked dicyclopentadiene . The process comprises reacting a crosslinked substituted dicyclopentadiene with a compound of the formula MQk as defined above wherein M and Q are each as defined above and k is 0? K ≪ / RTI > < = 4) to produce a crosslinked metallocene. The step of contacting the crosslinked substituted dicyclopentadiene with the metal compound may be carried out in a chlorinated solvent.

In a further embodiment, the process comprises contacting the cyclopentadiene with an alkyl silyl chloride of formula R 2 Si Hal2 wherein R is hydrocarbyl having 1 to 20 carbon atoms and Hal is halogen . A second equivalent of substituted fluorene is added to produce a silicone crosslinked cyclopentadienyl substituted fluorenyl ligand. Subsequent steps are analogous to those methods for preparing cross-linked substituted cyclopentadienyl-fluorenyl ligands coordinated with metals such as Zr, Hf and Ti.

In a further embodiment, the method comprises contacting the substituted cyclopentadiene with a fulvene producing agent such as acetone to produce substituted fulvene. Thereafter, in the second step, the fulvene reacts with substituted fluorenes at positions 3 and / or 6, preferably positions 3 and 6, to form MCl ₄ , where M is Zr, Hf or Ti To form a carbon-bridged substituted cyclopentadiene-fluorenyl ligand that produces the desired metallocene catalyst.

In a further aspect, the present invention provides a Pentad distribution that provides the same ordered polyolefin having a monomer length of C10 or less as measured by ¹³ C nmr and comprising at least 80% and preferably at least 87% mmmm. The pentad distribution preferably comprises at least 90%, more preferably at least 95% mmmm, as measured by ¹³ C nmr. Preferably, the amount of 2-1 and 1-3 monomer inserting in the polyolefin is less than 0.5%, more preferably less than 0.2, and most preferably is undetectable as measured by ¹³ C nmr.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention will now be described more fully hereinafter with reference to the accompanying drawings, which are merely illustrative of the invention.

Example 1

Preparation of isopropylidene [(3-t-butyl-5-methyl-cyclopentadienyl) - (3,6-di-t- butyl-fluorenyl)] zirconium dihydrochloride

A. Preparation of 3,6,6-trimethylpulvene

reaction

Methanol

Me-Cp + acetone -------------> 3,6,6-Me3-Ful

Pyrrolidene

Way

A round bottomed flask equipped with magnetic stir bar and N ₂ inlet was charged with 350 ml of methanol containing methylcyclopentadiene newly prepared under N ₂ (at -78 ° C). To this solution was added a solution of 28.6 g (0.493 mol) of acetone in 50 ml of methanol dropwise. Then, 52.5 g (0.738 mol) of pyrrolidene was added. The reaction mixture was stirred at ambient temperature for 24 hours. After neutralization with acetic acid and separation of the organic phase, the solvent was evaporated and the remaining yellow oil was distilled. 3,6,6-Me3-Ful and 2,6,6-Me3-Ful were obtained in a yield of 65%.

B. Preparation of 1-methyl-3-t-butylcyclopentadiene

reaction

ether

3,6,6-Me3-Ful + Me-Li -----------> 1-Me-3-t-Bu-Cp

0 ℃

Way

50 g (0.417 mol) of 3,6,6-Me3-t-Bu-Ful was added to a one liter flask, dissolved in 500 ml of diethyl ether and cooled to 0 deg. To the solution, 260.4 mL (0.417 mol) of methyl lithium in ether (1.6 mol) was added dropwise. The reaction was complete after a few hours. After adding 75 ml of a saturated solution of NH ₄ Cl in water, the organic phase was separated and dried over MgSO ₄ . Evaporation of the solvent resulted in separation of the yellow oil. After distillation, 33.65 g (59.28%) of 1-Me-3-t-Bu-Cp was obtained.

C. Preparation of 1,6,6-trimethyl-3-t-butylphenol

reaction

Methanol

1-Me-3-t-Bu-Cp + acetone -----------> 1,6,6-Me3-3-t-Bu-Ful

Pyrrolidene

Way

30 g (0.220 mol) of 1-Me-3-t-Bu-Cp dissolved in 60 ml of methanol was placed in a 1 liter flask. The mixture was cooled to -78 < 0 > C. 5.11 g (0.88 mol) of acetone in 20 ml methanol was slowly added. In the next step, 9.4 g (0.132 mol) of pyrrolidene in 20 ml methanol was added. After one week, the reaction was terminated by the addition of 20 ml of acetic acid. The organic phase was separated, dried and evaporated to give 16.95 g of an orange oil (yield, 43.66%).

D. Preparation of 2,2 - [(3-t-butyl-5-methyl-cyclopentadienyl) - (3,6-di-t- butyl-fluorenyl)

reaction

THF

3,6-dt-Bu-Flu + Me-Li ----------- → (3,6-dt-Bu-Ful) -Li +

0 ℃

THF

(3,6-di-Bu-Flu) -Li ⁺ + 1,6,6-Me3-3-t-Bu-Ful- -Me-Cp) (3,6-dT-Bu-Flu)

Way

1.5 g (5.387 mmol) of 3,6-dt-Bu-Flu in 100 ml anhydrous tetrahydrofuran was placed in a 250 ml flask under N ₂ and the solution was pre-cooled to 0 ° C. 3,6-dt-Bu-Flu was prepared according to Shoji Kajigaeshi et al. Bull. Chem. Soc. Jpn. 59, 97-103 (1986), or Liebigs Ann, M. Bruch et al. Chem. 1976, 74-88. Then, 3.4 ml (5.387 mmol) of methyl lithium solution was added dropwise to the solution. This solution was red and was maintained at room temperature for 4 more hours. Thereafter, a solution of 0.9497 g (5.382 mmol) in 10 ml anhydrous tetrahydrofuran was added to the solution. The reaction was continued for 24 hours. After adding 40 mL of saturated NH ₄ Cl solution in water, the yellow organic phase was separated and dried over anhydrous MgSO ₄ . Evaporation of the solvent yielded 2.36 g (yield, 96.32%) of orange solid product.

Preparation of E.Ipropylidene [(3-t-butyl-5-methylcyclopentadienyl) - (3,6-di-t- butyl-fluorenyl)] zirconium dichloride (1)

reaction

THF

Me2C (3-t-Bu-5-Me-Cp) (3,6-dt-

0 ℃

Me2C (3-t-Bu-5-Me-Cp) -Li + (3,6-dt-

ZrCl ₄

Me2C (3-t-Bu-5-Me-Cp) -Li + (3,6-dt-Bu-

n-C5

Me2C (3-t-Bu- 5-Me-Cp) (3,6-dt-Bu-Flu) ZrCl 2 + 2LiCl

Way

₂ g (4.398 mmol) of ligand were dissolved in 100 ml of anhydrous tetrahydrofuran under N ₂ , and the solution was pre-cooled to 0 ° C. A solution of 5.5 ml (8.796 mmol) of methyllithium (1.6 mol / diethyl ether) was added to the solution with a drop. After 3 hours, the solvent was removed in vacuo and the red powder was washed with 2 x 100 mL of pentane. Red lice were added to pentane of anionic ligand and 100㎖ under N ₂ to flask 250㎖. 1.02 g (4.398 mmol) of zirconium tetrachloride was added to this suspension. The reaction mixture turned reddish brown and stirred overnight in a glove box. After filtration, the orange solution was removed in vacuo at 40 캜 to obtain 2.3 g (85.18%) of orange powder. Generally, the metallocene is soluble in pentane. According to ¹ H NMR of the product, the product of isopropylidene (2 (or 4) -methyl-3-t-butylcyclopentadienyl-3,6-di-t-butylfluorenyl) ZrCl ₂ (2) The two isomers appear to be formed as a less stereogenic second product.

Example 2

Preparation of isopropylidene [(3-methylcyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] zirconium dichloride

The procedure of Example 1 was repeated except that the ligand of Step D was replaced by 2,2 - [(3-methyl-cyclopentadienyl) - (3,6-di-t-butyl- Synthetic methods were used.

A. Preparation of 2,2 - [(3-methyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] -

Way

This ligand was carried out in the same manner as in Step D, except that 1,6,6, -trimethyl-3-t-butylphenol contained 0.6475 g (5.387 mmol) of 3,6,6-trimethylpullene (Described in Example 1, Step A).

Example 3

Preparation of isopropylidene [(3-t-butyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] zirconium dichloride

The ligand of Step D was replaced with 2,2 - [(3-t-butyl-cyclopentadienyl) - (3,6-di-t-butyl- fluorenyl)] - The synthesis method of Example 1 was used except that

A. Preparation of 2,2 - [(3-t-butyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] -

Way

This ligand was prepared in the same manner as in Step D, but 1,6,6-trimethyl-3-t-butylphenol was replaced with 0.8742 g (5.387 mmol) of 6,6-dimethyl-3-t-butylphenol.

B. Preparation of 6,6-dimethyl-3-t-butylphenol

Way

Was carried out using the synthetic method according to Step A of Example 1, replacing methylcyclopentadiene with t-butylcyclopendadiene.

C. Preparation of t-butylcyclopentadiene

Way

The method of synthesis of step B of Example 1 was carried out by replacing 3,6,6-trimethylpulven with 6,6-dimethylpulven.

Example 4a

Preparation of isopropylidene [(3-trimethylsilyl-cyclopendadienyl) - (3,6-di-t-butyl-fluorenyl)] zirconium dichloride

The synthesis procedure of Example 1 was repeated except that the ligand of Step D was replaced by diphenyl [(3-trimethylsilyl-cyclopentadienyl) - (3,6-di-t-butyl- Were used.

A. Preparation of 2,2 - [(3-trimethylsilyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] propane

Way

A ligand was prepared in the same manner as in the step D of Example 1 except that 1,6,6-trimethyl-3-t-butylphenol was replaced by 1,2407 g (5.387 mmol) of 6,6-dimethylpulvene .

B. Preparation of 2,2 - [(3-trimethylsilyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] propane

reaction

THF

Me 2 C (Cp) (3,6-dt-Bu-Flu) + Me-Li ------------- →

Me2C (Li + Cp-) (3,6-d-t-Bu-Flu)

Me 2 C (Li + Cp -) (3,6-dt-Bu-Flu) + Me 3 Si-

Me2C (3-Me3Si-Cp) (3,6-d-t-Bu-Flu) + LiCl

Way

First, 10 g (0.026 mol) of 2,2- (cyclopentadienyl) (3,6-di-t-butyl-fluorenyl) propane was dissolved in 300 ml of tetrahydrofuran under N ₂ , Lt; / RTI > Then 16.25 ml (0.026 mol) of methyllithium was added dropwise to this solution at room temperature (the flask was precooled with a water bath). After stirring for 1 hour, 3.3 ml (0.026 mol) of chlorotrimethylsilane was added to this solution. The reaction mixture was further stirred for 3 h. The solvent was then removed in vacuo. One liter of pentane was added to the solid orange residue, and the reaction mixture was heated at 40 占 폚 for 10 minutes. The orange solution was filtered (to remove 1.40 g of the residue LiCl), concentrated to 100 ml and then cooled to give the product 2,2- (3-trimethylsilyl-cyclopentadienyl) fluorenyl) propane And crystallized. The raw product was beige color. The crystallized product had a white color, which was provided in a yield of 65% -70%. The product was stored under N _2.

Example 4b

Preparation of diphenylmethylidene [(3-trimethylsilyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] zirconium dichloride

The ligand of Step D is reacted with diphenyl [(3-trimethylsilyl-cyclopentadienyl) - (3,6-di

-t-butyl-fluorenyl) methylene was used in place of the compound of Example 1,

A. Preparation of 1,1,1,1-diphenyl [(3-trimethylsilyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] methane

Way

The preparation of this ligand was carried out in the same manner as in Step D of Example 1, but replacing 1,6,6-trimethyl-3-t-butylphenol with 1.2407 g (5.387 mmol) of 6,6- Respectively.

B. Preparation of diphenyl [(3-trimethylsilyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] methane

reaction

THF

Me 2 C (Cp) (3,6-dt-Bu-Flu) + Me-Li ------------- →

Me2C (Li + Cp-) (3,6-d-t-Bu-Flu)

Me 2 C (Li + Cp -) (3,6-dt-Bu-Flu) + Me 3 Si-

Me2C (3-Me3Si-Cp) (3,6-d-t-Bu-Flu) + LiCl

Way

First, 10 g (0.026 mol) of 2,2- (cyclopentadienyl) (3,6-di-t-butyl-fluorenyl) propane was dissolved in 300 ml of tetrahydrofuran under N ₂ , Lt; / RTI > Then 16.25 ml (0.026 mol) of methyllithium was added dropwise to this solution at room temperature (the flask was precooled with a water bath). After stirring for 1 hour, 3.3 ml (0.026 mol) of chlorotrimethylsilane was added to this solution. The reaction mixture was further stirred for 3 hours. The solvent was then removed in vacuo. One liter of pentane was added to the solid orange residue. The reaction mixture was heated at 40 < 0 > C for 10 min. The orange solution was filtered (to remove 1.40 g of residual LiCl), concentrated to 100 ml and then cooled to give the product 2,2- (3-trimethylsilyl-cyclopentadienyl) (3,6-di -t-butyl-fluorenyl) propane. The raw product was beige in color. The crystallized product had a white color, which was provided in a yield of 65% -70%. The product was stored under N _2.

Example 5

Preparation of isopropylidene [(3,5-dimethyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] zirconium dichloride

The procedure of Example D was repeated except that the ligand of Step D was replaced by 2,2 - [(3,5-dimethyl-cyclopentadienyl) - (3,6-di-t-butyl- 1 was used.

A. Preparation of 2,2 - [(3,5-dimethyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] -

Way

Using the same procedure as Step D of Example 1 but replacing 1,6,6-trimethyl-3-t-butylphenol with 0.8742 g (5.387 mmol) of 1,3,6,6- Ligand.

B. Preparation of 1,3,6,6-tetramethyl fulvene

The synthesis procedure was used according to Step A of Example 1, replacing methylcyclopentadiene with 1,3-dimethylcyclopentadiene.

C. Preparation of 1,3-dimethylcyclopentadiene

reaction

ether

3-Me-Cp = O + CH 3 -Mg-Br ----------- → 1,3-Me2-Cp-O-Mg-Be

0 ℃

1,3-Me2-Cp-O- Mg-Br + H 2 O ----------- → 1,3-Me2-Cp + Mg-Br-OH

Way

195 ml (0.585 mol) of methylmagnesium bromide (3.0 moles of solution / diethyl ether) in 200 ml anhydrous diethyl ether under nitrogen was placed in a 2 liter flask and the solution was pre-cooled to 0 占 폚. A solution of 47.15 g (0.4905 mol) of 3-methyl-2-cyclopentenone in 100 ml diethyl ether was then added to the solution at 0 째 C for 3 hours and then at 10 째 C for 1 hour. The product was transferred to a 5 liter flask, precooled at 0 C, containing 1 liter of water. This solution was yellow. The yellow organic phase was separated and the solvent was removed under vacuum (500 mbar) at room temperature. Evaporation of the solvent gave a clear orange solution. After distillation, 31.83 g (yield, 65.95%) of 1,3-dimethylcyclopentadiene was obtained. The product was a colorless, unstable liquid, which was used directly in the preparation of 1,3,6,6-trimethylpulvene.

Example 6

Preparation of diphenylmethylidene [(3-methyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] zirconium dichloride

(3-methyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] thiophene instead of the ligand of step D, using the synthetic procedure according to example 1, Propane. ≪ / RTI >

A. Preparation of 1,1,1,1-diphenyl [(3-methyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)

Way

The preparation of the ligand was carried out in the same manner as in step 1 of Example 1 except for replacing 1,6, 6-trimethyl-3-t-butylphenol with 1.2407 g (5.387 mmol) 3-methyl-6,6- D.

B. Preparation of 3-methyl-6,6-diphenyl fulvene

Way

The fulvene was prepared in the same manner as described in Step A of Example 1 except that acetone was used instead of 1.3162 g (5.387 mmol) of 6,6-diphenylfulvene.

Example 7

Preparation of dipetylmenylidene [(3-t-butyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] zirconium dichloride

The synthesis of Example 1 was repeated except that the ligand of Step D was replaced by diphenyl [(3-t-butyl-cyclopentadienyl) - (3,6-di-t- butyl-fluorenyl) Procedure was performed.

A. Preparation of 1,1,1,1-diphenyl [(3-t-butyl-cyclopentadienyl) - (3,6-t-butyl-fluorenyl)] methane

Way

The ligand was prepared in the same manner as in the step A of Example 4 except that 6,6-dimethyl-3-t-butylphenol was replaced with 3-t-butyl-6,6-diphenylphenol.

B. Preparation of 3-t-butyl-6,6-diphetyl fulvene

Way

The title compound was prepared in the same manner as in the step A of Example 1 except that acetone was replaced with benzophenone and methylcyclopentadiene was replaced with t-butylcyclopentadiene (the synthesis procedure is described in Step C of Example 4) .

Example 8

Preparation of diphenylmethylidene [(3-trimethylsilyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] zirconium dichloride

Way

The ligand of Step D was replaced with 2,2-diphenyl [(3-trimethylsilyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl) Lt; / RTI >

A. Preparation of 1,1,1,1-diphenyl [(3-trimethylsilyl-cyclopentadienyl) - (3,6-di-t-butyl-fluorenyl)] methane

Way

The procedure of Example 4 was repeated except for replacing 2,2 - [(cyclopentadiene) (fluorenyl) propane] with 2,2-diphenyl [(cyclopentadienyl) (fluorenyl)] propane The above procedure was used to prepare the ligand.

B. Preparation of 2,2-diphenyl [(cyclopentadienyl) - (3,6-di-t-butyl-pullulanenyl)] propane

Way

The ligand was prepared in the same manner as described in Example 1, D, except that 1,6,6-trimethyl-3-t-butylphenol was replaced by 6,6-diphenylfulvene.

Example 9

Polymerization reaction method

Each polymerization reaction was carried out in a 4 liter bench type reactor containing pure propylene. Three minutes before entering the reactor, the metallocene (0.5-5 mg) previously contacted with 1 mL of MAO (methylaluminoxane) (30% solution in toluene from WITCO) was introduced to initiate the polymerization reaction.

Table 1 below shows the fine alignment of the polymer obtained using the catalyst according to Example 1 under the polymerization reaction conditions described above. The results were obtained using a ¹³ C NMR spectrometer. The polypropylene contained more than 95% of pentads with the same pure arrangement (mmmm). The polypropylene had a molecular weight (Mw) of 530,000 and a melting point of 153 占 폚. Melting point was measured by DSC analysis as shown in Fig. The sample was held at 25 占 폚 for 1 minute, heated at 25 占 폚 to 220 占 폚 at a rate of 20 占 폚 / min, and maintained at 220 占 폚 for 5 minutes. Thereafter, the sample was cooled at 220 캜 to 25 캜 at a rate of 20 캜 / minute, maintained at 25 캜 for 3 minutes, and then heated at 25 캜 to 220 캜 at a rate of 20 캜 / minute.

Pentad stereo-order distribution (%) mmmm 95.7 mmmr 1.70 rmmr 0.00 mmrr 1.70 mrmm + rmmr 0.00 mrmr 0.00 rrrr 0.00 mrrr 0.00 mrrm 0.80

Test Number T Pol ° C Hydrogen M12 Activity T (melting point) T (recrystallization temperature) Mn Mw Mz D mmmm% One 60 ° C 0 NI 11,299 160.5 110.9 140,620 450,834 971,692 3.2 96.23 2 60 ° C 0 NI 4,889 156.8 115.6 152,183 576,644 1,238,131 3.8 95.15 3 60 ° C 0 NI 0.5 15,772 161.4 114.0 151,062 515,399 1,092,618 3.4 96.07 4 80 ℃ 0 NI 21,859 155.7 102.7 90,958 215,031 417,006 2.4 94.18 5 60 ° C 0 NI 24,115 159.5 112.9 177,211 637,977 1,344,283 3.6 96.16 6 80 ℃ 0 NI 1.9 41,546 154.9 106.9 119,201 286,072 568,665 2.4 95.17 7 40 ℃ 0 NI 1,177 157.2 112.2 186,032 1,363,315 3,506,808 7.3 97.30 8 60 ° C 1 NI 14.7 36,530 161.7 116.1 64,952 199,020 727,048 3.1 97.10 9 60 ° C 2 NI 158.0 25,659 160.5 116.5 35,877 94,120 174,790 2.6 97.50 After xylene extraction: Test Number T Pol ° C Hydrogen Soluble xylene content (%) Mn Mw Mz D mmmm% One 60 ° C 0 NI 0.58 119,675 425, 468 1,004,487 3.6 95.3 3 60 ° C 0 NI 0.60 143,213 464,465 1,032,093 3.2 94.6 8 60 ° C 1 NI 0.14 69,301 204,803 447,736 3.0 97.0

Table 2 above illustrates the production of the same ordered polypropylene using the catalyst of Example 1 under the polymerization conditions described above. The resulting homologous aligned propylene contained in some cases more than 97% pentads of exactly the same configuration (mmmm). High weight average molecular weights were obtained at 40 캜 and 60 캜, especially when there was no added hydrogen. Polymerization temperatures of about 60 DEG C have been found to be particularly useful because they are obtained as a result of the combination with microarrays having relatively high molecular weight and high catalytic activity.

Claims (31)

Use of a metallocene catalyst component represented by the following formula (I) in the production of a polyolefin comprising the same configuration polyolefin or a regular arrangement / the same configuration block polyolefin having a monomer length of C10 or less. [Chemical Formula 1] R " (C _p R ₁ R ₂ R ₃ ) (C _p 'R ₁ ' R ₂ ') MQ ₂ Wherein C _p is a cyclopentadienyl ring substituted with one or more substituents; C _p 'is a substituted fluorenyl ring; R " is a structural bridge that confers stereorigidity on said component; R < ₁ > is optionally a substituent on the cyclopentadienyl ring in-situ from said bridge, said in situ substituent having the formula XR ^* ₃ comprises a bulky group of (wherein, X is selected from the group ⅳA, each R ^* is the same or different and each is selected from hydrocarbyl of 1 to 20 carbon or a hydrogen atom) and; R ₂ is optionally a is a substituent on the cyclopentadienyl ring which are adjacent to the cross-linked and located away from the home position substituent, the formula YR # ₃ (wherein, Y is selected from the ⅳA group, and each R # is the same or different, and hydrogen or selected from hydrocarbyl holding 1-7 carbon atoms), and; R ₃ is a cycloalkyl optionally are adjacent to the cross-linking Diethoxy other a hydrogen atom or or formula ZR $ ₃ (wherein, Z as a substituent on the ring carbonyl is selected from the group ⅣA, each R $ is the same or different and each is hydrocarbyl for a hydrogen or a 1 to 7 carbon atom , Wherein R ₁ 'and R ₂ ' are each independently a substituent on the fluorenyl ring, one of which is selected from the group of the formula AR "' ₃ wherein A is selected from the group IVA, each R" Independently are hydrogen or hydrocarbyl having from 1 to 20 carbon atoms and the other is hydrogen or a second group having the formula AR "'₃; M is a Group IVB transition metal or vanadium; Each Q is a hydrocarbyl having 1 to 20 carbon atoms or is a halogen. The use according to claim 1, wherein R ₁ 'and R ₂ ' are present at positions 3 and 6 on the fluorenyl ring. 3. Use according to claim 1 or 2, characterized in that A is carbon or silicon. The use according to claim 3, wherein AR ''' ₃ is a hydrocarbyl having 1 to 20 carbon atoms. The use according to claim 4, wherein AR ''' ₃ is C (CH ₃ ) ₃ . The use according to claim 2, wherein AR ''' ₃ is Si (CH ₃ ) ₃ . The use according to any one of claims 1 to 6, wherein R ₁ 'and R ₂ ' are the same. 8. Use according to any one of claims 1 to 7, characterized in that R " is dialkyl germanium having from 1 to 20 carbon atoms or silicon or siloxane, alkylphosphine or amine. 9. Use according to claim 8, characterized in that R " is isopropylidene, dimethylsilanediyl or diphenylmethylidene. 10. Use according to any one of claims 1 to 9, characterized in that M is zirconium or titanium. 11. Use according to any one of the claims 1 to 10, characterized in that Q is halogen. 12. Use according to any one of claims 1 to 11, characterized in that R ₁ is C (CH ₃ ) ₃ , C (CH ₃ ) ₂ Ph, CPh ₃ or Si (CH ₃ ) ₃ . 13. The method of claim 12 wherein, R ₁ is a purpose characterized in that the C (CH _{3) 3.} 14. Use according to any one of the claims 1 to 13, characterized in that Y is carbon. 15. Use according to any one of the claims 1 to 14, characterized in that Z is carbon. Of claim 1 to claim 15 wherein any one of Compounds, R ₂ is the purpose, characterized in that CH _3. The process according to any one of the preceding claim to any of the preceding Compounds 16, R ₃ is the purpose, characterized in that CH _3. 18. A process as claimed in any one of claims 1 to 17 wherein the metallocene catalyst component is isopropylidene-3-t-butyl-5-methyl-cyclopentadienyl 3,6 di-t-butylfluorenyl ZrCl _{2. &} Lt; / RTI > 19. A process as claimed in any one of claims 1 to 18, wherein the metallocene catalyst component comprises (i) a catalyst component according to any one of claims 1 to 18; And (ii) positional isomers located adjacent to and adjacent to the bridge, wherein R < ₂ > is in close proximity to the in situ substituent. 18. A process as claimed in any one of claims 1 to 17 wherein the metallocene catalyst component is isopropylidene- (3-t-butyl-5-methylcyclopentadienyl-3,6-di- ZrCl ₂ and isopropylidene- (3-t-butyl-2-methylcyclopentadienyl-3,6-di-t-butylfluorenyl) ZrCl ₂ . 20. Use according to any of the claims 1 to 20, characterized in that the catalyst component is part of a catalyst system which further comprises an aluminum- or boron-containing co-catalyst capable of activating the catalyst component. 18. Use according to claim 17, characterized in that the catalyst system further comprises an inert support. Any one of claims 1 to 13 Compounds according to any of the preceding, R ₁ is a substituent on the cyclopentadienyl ring, polyolefins purpose characterized in that the polyolefin similar arrangement / isotactic block. 18. Use according to any one of the claims 1 to 17, characterized in that R < ₁ > and R < ₂ > are two substituents on the cyclopentadienyl ring and the polyolefin is the same arrangement polyolefin. 21. Use according to claim 19 or 20, characterized in that the polyolefin comprises the same ordered polyolefin with a multimodal molecular weight distribution. A monomer having a length of C10 or less, comprising contacting the catalyst as defined in claim 21 or 22 with one or more olefins under polymerization conditions to produce the same aligned polyolefin or similar arrangement / identical aligned block polyolefin, Containing polyolefin. 27. The process according to claim 26, wherein the olefin is propylene. 27. The process of claim 26, wherein the at least two olefins are present in the reaction zone to produce a polyolefin copolymer. The amounts of 2-1 and 1-3 monomers inserted in the polyolefin are not detected, and the same arrangement of polyolefins having a pentad distribution and a monomer of C10 or less in length, including 87 mm% or more mmmm as measured by ¹³ C nmr. 30. The polyolefin of claim 29, wherein the pentad distribution comprises at least 95% mmmm as measured at ¹³ C nmr. A polyolefin according to any one of claims 29 to 30, characterized in that it comprises polypropylene.