JP2002030108A - Catalyst composition for preparation of polyolefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyolefin having a high glass transition temperature in a high yield. SOLUTION: A catalyst composition comprising a metallocene compound (I) and a specific activation promoter is used as an olefin polymerization catalyst. R1 and R2 are each H, a halogen, alkyl, alkenyl, aryl, 7-20C alkylaryl or 7-20C arylalkyl, or two R1's and two R2's each form a 4-20C ring; X is C, Si, Ge or Sn; n is 2-12; R3 and R4 are each H, a halogen, alkyl, alkenyl, aryl, 7-20C alkylaryl or 7-20C arylalkyl; M is a group IVb metal; and Y is an anionic ligand.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst composition for producing a polyolefin, a method for producing a polyolefin, and a metallocene catalyst, and more particularly, to a cycloolefin copolymer having a high cycloolefin conversion and a high glass transition temperature. The present invention relates to a catalyst composition useful for the production, a method for producing a polyolefin, and a metallocene catalyst. The catalyst composition of the present invention can maintain high activity under high-temperature reaction conditions.

[0002]

2. Description of the Related Art Hitherto, olefin-based polymers have been widely used. Among them, olefin-based polymers generally used are polyolefins, that is, a monopolymer of one olefin or a copolymer of at least two olefins. . Typically, these polyolefins are used in applications such as blow molding, injection molding, extrusion coating, films, sheets, pipes, wires, and cables.

As an example of polyolefin, ethylene propylene elastomer (ethylene propylene rubber [EP
R]), which are universally used in end applications due to their weatherability, excellent heat aging properties and their ability to be mixed with large amounts of fillers and plasticizers. Typical automotive applications are radiators, heated hoses, vacuum tubes, weather strips, sponge door seals, and the like.
Typical industrial applications are sponge parts, gaskets, and seals.

[0004] Another commonly used polyolefin is
It is a cycloolefin copolymer (COC). Among them, copolymers of cycloolefin and ethylene have high transparency, heat resistance, heat aging, chemical resistance, solvent resistance,
Good balance of dielectric properties and rigidity. For this reason, ethylene / cycloolefin copolymers are suitable for use in the field of optical materials such as optical memory disks and optical fibers.

As described in US Pat. Nos. 5,559,119 (Abe et al.) And 5,602,219 (Aulbach et al.), Ethylene / cycloolefin copolymers are It is usually produced in the presence of a metallocene / aluminoxane catalyst system. U.S. Pat. No. 5,559,199 discloses isopropylidene (cyclopentadienylmethylcyclopentadienyl) zirconium dichloride.
Metallocenes such as thylcyclopentadienyl) zirconium dichloride) have been disclosed. US Patent No. 5,60
No. 2,219, dimethylsilyl- (1-indenyl) -cyclopentadienyl zirconium dichloride (di
methylsilyl- (1-indenyl) -cyclopentadienylzirconiu
metallocenes, such as m. dichloride).

[0006] However, there are some problems with the conventional methods for producing ethylene-cycloolefin copolymers. First, the cycloolefin conversion (cycloolefin uptake) is too low. Second, due to the high uptake of ethylene, the glass transition temperature (T
g) is too low.

[0007] To increase the conversion of cycloolefins, a commonly used technique is to increase the reaction temperature and pressure. This technique increases both the conversion of cycloolefin and ethylene and lowers the glass transition temperature of the resulting copolymer.

[0008]

SUMMARY OF THE INVENTION The present invention provides a catalyst composition for producing polyolefins, especially ethylene / cycloolefin copolymers having a high cycloolefin uptake and a high glass transition temperature. Aim.

[0009]

The catalyst composition for producing the polyolefin of the present invention comprises (a) a metallocene compound represented by the chemical formula (I), (b) (1) aluminoxane, and (2) AlR ¹¹ The object is achieved by including a mixture of R ¹² R ¹³ and a borate and (3) an activating co-catalyst selected from the group consisting of a mixture of AlR ¹¹ R ¹² R ¹³ and an aluminoxane.

[0010]

Embedded image

R ¹ is the same or different and is hydrogen, halogen, alkyl, alkenyl, aryl, 7-20
Alkylaryl groups having 7 carbon atoms and 7 to 2
A saturated ring system having from 4 to 20 carbon atoms selected from the group consisting of arylalkyl groups having 0 carbon atoms or two adjacent R ^{1 s} linked by an associated carbon atom. ) Or form an unsaturated ring system. R ² is the same or different and is selected from the group consisting of hydrogen, halogen, an alkyl group, an alkenyl group, an aryl group, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms. Selected or
Form a saturated or unsaturated ring bonded through two adjacent carbon atoms to which R ² is accompanied having from 4 to 20 carbon atoms.

X is a selected group IVA element consisting of carbon, silicon, germanium and tin. n is 2 to 1
2. R ³ and R ⁴ are the same or different and are hydrogen,
Halogen, alkyl group, alkenyl group, aryl group, 7
It is selected from the group consisting of alkylaryl groups having from 20 to 20 carbon atoms and arylalkyl groups having from 7 to 20 carbon atoms. M is an IV having an oxidation state of +4
It is a Group B transition metal. Y is the same or different and each is an anion ligand having a valence of -1. R ¹¹ , R
¹² and R ¹³ are an aliphatic group having 1 to 20 carbon atoms or an aromatic group having 6 to 10 carbon atoms.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The catalyst composition of the present invention contains a metallocene compound (complex) represented by the chemical formula (I) and an activating cocatalyst. The catalyst composition of the present invention is useful for producing a polyolefin. In the catalyst composition of the present invention, X (group IVA element such as C, Si, Ge, Sn, etc.) in the chemical formula (I) is bridged with-(CR ³ R ⁴ ) _n- to form a cyclic structure. One of the features is that the metallocene compound described above is included.

Conventional metallocenes for preparing cycloolefin copolymers in the aforementioned US Pat. Nos. 5,559,199 and 5,602,219, for example,
Isopropylidene (cyclopentadienylmethylcyclopentadienyl) zirconium dichloride and dimethylsilyl- (1-indenyl) -cyclopentadienylzirconium dichloride have two methyl groups at the carbon or silicon atom of the metallocene. Are combined. The chemical structure of the metallocene is shown in the table below for clarity.
Cp represents unsubstituted or substituted cyclopentadienyl, and θ1, θ2, and θ3 represent angles formed by one Cp, a group IVA element, and the other Cp (Cp-IVA-Cp). ) And is referred to as a biteangle.

[0015]

[Outside 1]

Unlike the metallocenes of US Pat. Nos. 5,559,199 and 5,602,219, in the present invention, group IVA elements such as carbon are bridged to-(CR ³ R ⁴ ) _n-. Form an annular structure. As a result of this bridge, Cp
The angle formed by -IVA-Cp increases. That is, the angle theta ₃ is larger than theta ₁ and theta _2.

Equation PM3 (semi-empirica
l)), US Pat. No. 5,559,199
The isopropylidene (cyclopentadienylmethylcyclopentadienyl) zirconium dichloride has a bite angle (θ ₁ ) of 101.9 °, which is used in US Pat. No. 5,602,219. 1-
The bite angle (θ ₂ ) of (indenyl) -cyclopentadienyl zirconium dichloride is 98.7 °.

The cyclobutylidene (1-η) used in the present invention is
⁵ - cyclopentadienyl) (1-eta ⁵ - indenyl) -
Bis (dimethylamino) zirconium (cyclobutyliden)
^{e (1-η 5 -cyclopentadienyl)} (1-η 5 -indenyl)
The bite angle (θ ₃ ) of -bis (dimethylamino) zirconium is 104.13 °, which is much larger than θ ₁ and θ ₂ . Thus, in theory, the metallocene compounds used in the present invention are reactive with large monomers (such as cycloolefins). The experimental data of the present invention shown below are consistent with this theoretical result.

When a conventional metallocene compound is used as a catalyst to produce a copolymer of a cycloolefin and an acyclic olefin (such as ethylene), the bite angle is small, so that a cycloolefin larger than ethylene is used as a metallocene active site. It is difficult to contact. For this reason,
Incorporation of cycloolefin into copolymer (incorpor
ation amount) decreases. However, when the metallocene compound of the present invention is used as a catalyst, since the bite angle is large, the chance that the cycloolefin comes into contact with the metallocene compound is increased, whereby the cycloolefin uptake can be increased.

Hereinafter, the scientific basis will be described. In a bridged metallocene, when the bite angle between the two Cp rings opens, the active center of the metal moves outward. Thereby, the coordination rate ratio of the cycloolefin to the acyclic olefin relative to the active center of the catalyst is increased as compared with the other catalysts, and accordingly, the ratio of the acyclic olefin to the acyclic olefin contained in the obtained copolymer is increased. The proportion of cycloolefin increases. Therefore, the glass transition temperature of the copolymer increases, and the polymerization activity (polymerization activit
y) also increases.

In the bridged metallocene catalyst, the bite angle caused by the carbon bridge is clearly greater than that caused by the silicon bridge. One of the reasons is that the elemental radius of carbon (0.77
Å) is smaller than the elemental radius of silicon (1.11Å). Another reason is that the electronegativity of carbon (2.5) is greater than the electronegativity of silicon (1.8). Therefore, the binding energy of carbon-carbon is carbon-
Because Cp bridges with Group IVA elements because it is much larger than silicon, silicon bridges are more deformed than carbon, resulting in smaller bite angles.

In the chemical formula (I), R ¹ and R ² are
Alkyl group, alkenyl group, aryl group, alkylaryl group having 7 to 20 (preferably 1 to 15) carbon atoms and 7 to 20 (preferably 7 to 15)
When selected from the group consisting of arylalkyl groups having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, 6 to
An aryl group having 10 carbon atoms, an alkylaryl group having 7 to 10 carbon atoms, and an arylalkyl group having 7 to 10 carbon atoms are preferable.

Representative examples of R ¹ and R ² include hydrogen, methyl, ethyl, propyl, butyl, isobutyl,
Examples include a pentyl group, an isopentyl group, a hexyl group, a 2-ethylhexyl group, a heptyl group, an octyl group, a vinyl group, an allyl group, an isopropenyl group, a phenyl group and a tolyl group.

When two adjacent R ¹ or two R ² are linked by an associated carbon atom to form a ring having 4 to 20 (preferably 4 to 6) carbon atoms, R ¹
Or R ² forms a saturated or unsaturated polycyclic cyclopentadienyl ring such as an indenyl group, a tetrahydroindenyl group, a fluorenyl group and an octahydrofluorenyl group together with an accompanying cyclopentadienyl ring. Can be.

Representative examples of such rings include η ⁵ -cyclopentadienyl group, η ⁵ -methylcyclopentadienyl group, η ⁵ -ethylcyclopentadienyl group, η ⁵ -propylcyclopentadienyl group, eta ⁵ - tetramethylcyclopentadienyl group, eta ⁵ - pentamethylcyclopentadienyl group, eta ^{5-n-butylcyclopentadienyl} group,
Examples include an indenyl group, a tetrahydroindenyl group, a fluorenyl group, an octahydrofluorenyl group, and the like.

Y is hydrogen, having 1 to 20 carbon atoms
Hydrocarbon groups, halogens, having 6 to 20 carbon atoms
Aryl group, alkyl having 7 to 20 carbon atoms
Aryl groups, aryl groups having 7 to 20 carbon atoms
Alkyl group, alkoxy having 1 to 20 carbon atoms
Groups, aryloxy groups having 6 to 20 carbon atoms
(Aryloxy), NH_Two, NHR⁷, NR⁷R⁸,-(C =
O) NH_Two,-(C = O) NHR⁹,-(C = O) NR⁹
R^TenCan be R⁷, R⁸, R⁹, And R^Ten
Is an alkyl group having from 1 to 20 carbon atoms each
is there. Preferred Y groups are methyl, ethyl, phenyl
Group, chlorine, bromine, methoxy group, ethoxy group, -NH _Two,
-NH (CH_Three), -N (CH_Three)_Two, -N (C_TwoH_Five)_Two,
−N (C_ThreeH₇)_TwoAnd so on.

The metallocene compound represented by the chemical formula (I) can form a catalyst composition that can be used for producing a polyolefin by being combined with an activating cocatalyst.

The cocatalysts used in the present invention are (1) aluminoxane, (2) a mixture of AlR ¹¹ R ¹² R ¹³ and borate, and (3) a mixture of AlR ¹¹ R ¹² R ¹³ and aluminoxane. be able to. R ¹¹ , R ¹² , and R ¹³
Is an aliphatic group having 1 to 20 carbon atoms or 6-1
An aromatic group having 0 carbon atoms. The preferred aluminoxane is methylaluminoxane. AlR ¹¹
Representative examples of R ¹² R ¹³ include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tributylaluminum,
Triisobutylaluminum (TIBA) and the like.

Representative examples of the borate include N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate (N, N-dimethylanilinium tetrakis (pentafluo).
rophenyl) borate), triphenylcarbenium tetrakis (pentafluorophenyl) borate (triphenyl)
carbenium tetrakis (pentafluorophenyl) borate),
Trimethyl ammonium tetrakis (pentafluorophenyl) borate
tafluorophenyl) borate), ferrocenium tetrakis (pentafluorophenyl) borate (ferrocenium te
trakis (pentafluorophenyl) borate), dimethyl ferrocenium tetrakis (pentafluorophenyl) borate
enyl) borate), silver tetrakis (pentafluorophenyl) borate (silver tetrakis (pentafluorophenyl)
borate).

By using the catalyst composition of the present invention,
Polyolefins can be synthesized. In the presence of an amount of the catalyst composition of the present invention that exhibits a catalytic effect under polymerization conditions, one olefin is polymerized (homopolymerized) or at least two olefins are polymerized (copolymerized). Polymerization).

According to the invention, the preferred olefin is a cycloolefin. The polymerization of the present invention is preferably a homopolymerization of a cycloolefin or a copolymerization of a cycloolefin and an acyclic olefin.

Cycloolefins suitable for use in the present invention include bicycloheptene, tricyclodecene, tricycloundecene, tetracyclododecene, pentacyclopentadecene, pentacyclopentadecadiene, pentacyclohexadecene, hexacyclo Heptadecene,
Heptacycloeicosene, heptacyclopheneicosene, octacyclodokosen, nonacyclopentacosene,
Nonacyclohexacocene and the like are included. Representative examples include:
Norbornene, tetracyclododecene, dicyclopentadiene, ethylidene norbornene and the like are included.

Preferred acyclic olefins are ethylene or α-olefins. Representative examples of α-olefins include olefins having 3 to 12 carbon atoms, such as propylene, 1-butene, 1-pentene, 1-hexene, 1-octene.

In particular, the catalyst composition of the present invention comprises an acyclic olefin such as an ethylene / cycloolefin copolymer.
Useful for producing cycloolefin copolymers. By using this special catalyst composition, the obtained ethylene / cycloolefin copolymer has a high conversion of cycloolefin and a high glass transition temperature.

By using the special catalyst composition of the present invention, the polyolefin formed is 60 to 300 ° C., preferably 120 to 300 ° C., particularly preferably 250 to 3 ° C.
It will have a glass transition temperature in the range of 00 ° C.

The novel catalyst composition disclosed in the present invention comprises:
It can be used in slurry reactions, gas phase reactions, and solution polymerization reactions. The experimental results of the present invention demonstrate that the specific catalyst composition of the present invention has excellent activity at higher reaction temperatures.
This excellent activity increases the uptake of cycloolefin and also increases the glass transition temperature of the resulting cycloolefin copolymer. This cannot be achieved with similar conventional catalysts.

Further, the present invention provides a novel metallocene catalyst having a structure selected from the following three chemical formulas.

[0038]

Embedded image

[0039]

Embedded image

[0040]

Embedded image

R is a hydrocarbyl group having 1 to 20 carbon atoms.

In order to further clarify the above-mentioned objects, features and advantages of the present invention, preferred embodiments of the present invention will be described below in more detail, but this does not limit the present invention. In addition, any person who is familiar with the technology can add various variations and colors without departing from the spirit and scope of the present invention.

[0043]

EXAMPLES Synthesis of metallocenes Example 1: Synthesis of 1-cyclopentadienyl-1-indenylcyclobutane (bridged cyclopentadiene) Indene (5.8 g, 50 mmol) was charged with 50 ml of THF (tetrahydrofuran). Placed in a 250 ml round bottom flask. Then, place the flask in an ice bath (ic
e bath), n-butyllithium (n-BuLi)
40 ml (1.6 M, 64 mmol) were added. The mixture turned red-orange. The flask was removed from the ice bath and the mixture was stirred for 3 hours. Subsequently, the reaction mixture is stripped under vacuum to remove the solvent and pentane 5
Washing with 0 ml removed excess n-BuLi and filtration yielded a precipitate.

The precipitate was then dissolved in 50 ml of THF and 6,6-trimethylenefulvene (5.9 g, 50 mmol) was slowly added to the solution in an ice bath. After stirring for 24 hours, 1 ml of water was added to the mixture to terminate the reaction. Then, the reaction mixture was stripped under vacuum to remove the solvent, dissolved in 100 ml of hexane, and filtered to obtain a filtrate. The crude product (filtrate, etc.) was subjected to column chromatography (20 g of silica gel as packing material, 100 g of hexane as eluent).
% Used). Then, the solution was concentrated under reduced pressure to obtain a faded yellow liquid (8.2 g, yield 70%).

Example 2 Synthesis of 1-methylcyclopentadienyl-1-indenyl-cyclobutane Indene (2.9 g, 25 mmol) was added to 30 ml of THF.
Was placed in a 250 ml round bottom flask. Then, the flask was placed in an ice bath, and 20 ml of n-butyllithium (n-BuLi) (1.6 M, 32 mmol) was used.
Was added. The mixture turned red-orange. The flask was removed from the ice bath and the mixture was stirred for 3 hours.
Subsequently, the reaction mixture is stripped under vacuum to remove the solvent and washed with 50 ml of pentane to remove excess n-BuLi.
Was removed and filtered to obtain a precipitate.

Then, the precipitate was dissolved in 30 ml of THF, placed in an ice bath, and washed with 3-methyl-6,6-trimethylenefulve.
ne) (3.3 g, 25 mmol) was slowly added to the solution. After stirring for 24 hours, 1 ml of water was added to the mixture to terminate the reaction. Then, the reaction mixture was stripped under vacuum to remove the solvent, dissolved with 50 ml of hexane,
Filtration gave a filtrate. The crude product (filtrate, etc.) was subjected to column chromatography (20 g of silica gel as packing material).
(100% hexane was used as eluent). The solution was concentrated under reduced pressure to obtain a faded yellow liquid (4.7 g, yield 75.8%).

Example 3 Preparation of Metallocene Catalyst Cyclobutylidene (1-η ⁵ -cyclopentadienyl)
(1-eta ⁵ - indenyl) bis (dimethylamino) obtained in Synthesis Example 1 Zirconium 1-cyclopentadienyl-1-indenyl cyclobutane (0.94 g, 4 mmol) and Zr
(N (CH ₃ ) ₂ ) ₄ (1 g, 3.7 mmol) was placed in a 100 ml round bottom flask, 20 ml of toluene was added, and the mixture was reacted at room temperature for 15 hours. The reaction mixture was then stripped under vacuum to remove the solvent and 50 ml of pentane was added to dissolve the residue. The solution was filtered and the filtrate was concentrated to give a yellow solid (1.45 g, yield 95%).

[0048] Example 4: Production cyclobutylidene metallocene catalyst (1-eta ⁵ - methylcyclopentadienyl) - was obtained in (1-eta ^5-indenyl) bis Synthesis Example 2 (dimethylamino) zirconium 1- Methylcyclopentadienyl-1-
Indenylcyclobutane (0.99 g, 4 mmol) was placed in a 100 ml round bottom flask, and toluene 20 m
was added and the mixture was reacted at room temperature for 15 hours.
The reaction mixture was then stripped under vacuum to remove the solvent and 50 ml of pentane was added to dissolve the residue.
The solution was filtered and the filtrate was concentrated to give a yellow solid (1.54 g, yield 98%).

Synthesis of Polymer Example A: Synthesis of Ethylene / Norbornene Copolymer Sodium was added and toluene was refluxed to give a water content of 10
Moisture was removed until it became less than ppm. Norbornene 5
00g and 88 g of dry toluene were mixed under nitrogen to obtain 85 g.
A weight percent norbornene solution was obtained.

After heating the reactor having a capacity of 500 ml to 105 ° C. and evacuating for 1 hour, the reactor was purged with nitrogen three to four times to completely remove water and oxygen, and the temperature of the reactor was adjusted to 100 ° C. . After the temperature has stabilized, 100 g of a 85% by weight norbornene solution are introduced into the reactor under nitrogen and the speed is increased to 250 rpm.
After stirring at pm, 4 ml of 1.49 M MAO (methylaluminoxane) was injected into the reactor with a syringe.

Subsequently, ethylene was introduced into the reactor to replace and release nitrogen, and the above procedure was repeated again. Finally, ethylene at a pressure of 15 kg / cm ² was introduced into the reactor until the solution was saturated. 1 mg of the metallocene complex obtained in Example 3 was placed in 1 ml of toluene and dissolved in a glove box. Then, 3 ml of MAO was added to the metallocene solution for activation for 5 minutes, and then the metallocene solution was injected into the reactor to carry out polymerization.
Stirred at rpm. The reaction time was 30 minutes.

After the completion of the polymerization reaction, the reaction solution was poured into an acetone solution containing dilute hydrochloric acid to precipitate a product. The product is washed 2-3 times with acetone, filtered,
Dry in vacuum oven at 12 ° C. for 12 hours. The obtained copolymer was 43.2 g. Table 1 shows the results of this example.
Shown in

Examples BF A variety of cycloolefin copolymers were prepared by repeating the procedure described in Example A, except that the reaction temperature, metallocene dose, and MAO dose were varied. The metallocenes used in Examples AF are the same. Table 1 shows the obtained results.
Shown in

[0054]

[Table 1]

Example G (compared with Example A) Sodium was added and toluene was refluxed to give a water content of 10
Moisture was removed until it became less than ppm. Norbornene 5
00g and 88 g of dry toluene were mixed under nitrogen to obtain 85 g.
A weight percent norbornene solution was obtained.

After heating the reactor having a volume of 500 ml to 105 ° C. and evacuating for 1 hour, the reactor was purged with nitrogen three to four times to completely remove water and oxygen, and the temperature of the reactor was adjusted to 100 ° C. . After the temperature has stabilized, 100 g of a 85% by weight norbornene solution are introduced into the reactor under nitrogen and the speed is increased to 250 rpm.
After stirring at pm, 4 ml of 1.49 M MAO was injected into the reactor with a syringe.

Subsequently, ethylene was introduced into the reactor to replace and release nitrogen, and the above procedure was repeated again. Finally, ethylene at a pressure of 15 kg / cm ² was introduced into the reactor until the solution was saturated. Diphenylmethylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride (9
1 mg of -fluorenyl) zirconium dichloride) was placed in 1 ml of toluene and dissolved in a glove box. Then, 3 ml of MAO was added to the metallocene solution for activation for 5 minutes, after which the metallocene solution was injected into the reactor to carry out polymerization, and the mixture was stirred at a speed of 500 rpm.
The reaction time was 30 minutes.

After the completion of the polymerization reaction, the reaction solution was poured into an acetone solution containing dilute hydrochloric acid to precipitate a product. The product is washed 2-3 times with acetone, filtered,
Dry in vacuum oven at 12 ° C. for 12 hours. The obtained copolymer was 26.9 g. Table 2 shows the obtained results.

Example H (Compared with Example E) A cycloolefin copolymer was prepared by repeating the procedure described in Example G except that the reaction temperature was changed. The metallocene used in Example G and Example H is the same.
Table 2 shows the obtained results.

[0060]

[Table 2]

EXAMPLES I-K The procedure described in Example A was repeated except that the reaction temperature was set at 120 ° C., the reaction time was increased by 1 hour, and the ethylene pressure, metallocene dose, and MAO dose were changed. Various cycloolefin copolymers with high glass transition temperature were prepared. The metallocene used in Examples I-K is the same as that used in Example A. Table 3 shows the obtained results.

[0062]

[Table 3]

Example L (compared with Example J) Sodium was added and toluene was refluxed to give a water content of 10
Moisture was removed until it became less than ppm. Norbornene 5
00g and 88 g of dry toluene were mixed under nitrogen to obtain 85 g.
A weight percent norbornene solution was obtained.

After heating the reactor having a capacity of 500 ml to 105 ° C. and evacuating for 1 hour, the reactor was purged with nitrogen three to four times to completely remove water and oxygen. The reactor temperature was adjusted to 100 ° C. After the temperature has stabilized, 100 g of a 85% by weight norbornene solution are introduced into the reactor under nitrogen and a speed of 250
After stirring at rpm, 4 ml of 1.49 M MAO was injected into the reactor with a syringe.

Subsequently, ethylene was introduced into the reactor to displace and release nitrogen, and the above procedure was repeated again. Finally, ethylene at a pressure of 5 kg / cm ² was introduced into the reactor until the solution was saturated. Diphenylmethylidene (cyclopentadienyl) (9-fluorenyl) zirconium dichloride (9-f
luorenyl) zirconium dichloride) 1 mg in toluene 1
and dissolved in a glove box. Then add 3 ml of MAO to the metallocene solution to activate 5 min.
After that, the metallocene solution was injected into the reactor to perform polymerization, and the mixture was stirred at a speed of 500 rpm. The reaction time was 60 minutes.

After the completion of the polymerization reaction, the reaction solution was poured into an acetone solution containing dilute hydrochloric acid to precipitate a product. The product is washed 2-3 times with acetone, filtered,
Dry in vacuum oven at 12 ° C. for 12 hours. The amount of the obtained copolymer was 15.3 g. Table 4 shows the obtained results.

[0067]

[Table 4]

Examples M to O A variety of cycloolefin copolymers were prepared by repeating the procedure described in Example A, except that the reaction temperature was set at 120 ° C. and the ethylene pressure, metallocene dosage, and MAO dosage were varied. Manufactured. The metallocene used in Examples M to O is the same as that used in Example A. Table 5 shows the obtained results.

[0069]

[Table 5]

Examples PS Reaction temperature, ethylene pressure, metallocene dose, and MA
A variety of cycloolefin copolymers were prepared by repeating the procedure described in Example A except that the O dosage was varied. The metallocenes used in Examples PS are the same as those used in Example A. In these examples, different concentrations of norbornene were used. Table 6 shows the obtained results.

[0071]

[Table 6]

Example T Sodium was added and toluene was refluxed to give a water content of 10
Moisture was removed until it became less than ppm. Norbornene 5
00g and 88 g of dry toluene were mixed under nitrogen to obtain 85 g.
A weight percent norbornene solution was obtained.

After heating the reactor having a volume of 500 ml to 105 ° C. and evacuating for 1 hour, the reactor was purged with nitrogen three to four times to completely remove water and oxygen. The reactor temperature was adjusted to 100 ° C. After the temperature has stabilized, 100 g of a 85% by weight norbornene solution are introduced into the reactor under nitrogen and a speed of 250
After stirring at rpm, 4 ml of 1.49 M MAO was injected into the reactor with a syringe.

Subsequently, ethylene was introduced into the reactor to replace and release nitrogen, and the above procedure was repeated again. Finally, ethylene at a pressure of 15 kg / cm ² was introduced into the reactor until the solution was saturated. 1 mg of the metallocene complex obtained in Example 4 was placed in 1 ml of toluene and dissolved in a glove box. Then, 3 ml of MAO was added to the metallocene solution for activation for 5 minutes, and then the metallocene solution was injected into the reactor to carry out polymerization.
Stirred at 0 rpm. The reaction time was 30 minutes.

After the completion of the polymerization reaction, the reaction solution was poured into an acetone solution containing dilute hydrochloric acid to precipitate a product. The product is washed 2-3 times with acetone, filtered,
Dry in vacuum oven at 12 ° C. for 12 hours. The amount of the obtained copolymer was 27.9 g. Table 7 shows the obtained results.

[0076]

[Table 7]

Although the preferred embodiments of the present invention have been disclosed above, they are not intended to limit the invention in any way, and anyone skilled in the art will not depart from the spirit and scope of the invention. Can add various fluctuations and colors, and the protection scope of the present invention is based on the contents specified in the claims.

[0078]

The catalyst composition of the present invention (metallocene catalyst)
According to this method, a polyolefin having a high glass transition temperature at a high olefin conversion can be produced. The catalyst composition of the present invention can maintain high activity under high-temperature reaction conditions.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Wei Yu-hime, No. 24, Shuangxi Village, Baoshan Township, Hsinchu County, Taiwan No. 24 F-Term (Reference) 4J028 AA01A AB00A AB01A AC01A AC10A AC28A BA00A BA01B BA02B BB00A BB01B BB02B BC12B BC15B BC25B EA01 EA02 EB02 EB03 EB04 EB05 EB07 EB08 EB09 EB17 EB18 EB26 EC01 EC02 ED01 ED06 EF01 FA02 GA19 GB01 GB05 4J100 AA02P AA03P AA04P AA07P AA16P AA19P AR09Q AR11Q AR10Q CA03 FA04

Claims (25)

[Claims] (A) Chemical formula (I) (R ¹ is the same or different and is a group consisting of hydrogen, halogen, alkyl group, alkenyl group, aryl group, alkylaryl group having 7 to 20 carbon atoms and arylalkyl group having 7 to 20 carbon atoms. Two or more adjacent R ¹ are linked by an associated carbon atom to form a saturated or unsaturated ring having 4 to 20 carbon atoms; R ² is the same or different,
Selected from the group consisting of hydrogen, halogen, an alkyl group, an alkenyl group, an aryl group, an alkylaryl group having 7 to 20 carbon atoms, and an arylalkyl group having 7 to 20 carbon atoms, or adjacent to form a saturated or unsaturated ring with two binding to 4 to 20 carbon atoms by the carbon atom to which R ² is accompanied; X
Is selected from the group consisting of carbon, silicon, germanium and tin; n is 2-12; R ³ and R ⁴ are the same or different and are hydrogen, halogen, alkyl, alkenyl, aryl, 7-7 Y is selected from the group consisting of alkylaryl groups having 20 carbon atoms and arylalkyl groups having 7-20 carbon atoms; M is a transition metal of Group IVB having an oxidation state of +4; The same or different anion ligands each having a valence of -1);
(B) (1) aluminoxane, (2) AlR ¹¹ R ¹² R ¹³
And a borate and (3) an activating co-catalyst selected from the group consisting of a mixture of AlR ¹¹ R ¹² R ¹³ and an aluminoxane (R ¹¹ , R ¹² and R ^{13 each} have 1 to 20 carbon atoms). An aliphatic group having an atom or an aromatic group having 6 to 10 carbon atoms). 2. R ¹ and R ² are each hydrogen, 1 to
Alkyl groups having 10 carbon atoms, alkenyl groups having 10 to 10 carbon atoms, aryl groups having 6 to 10 carbon atoms, alkylaryl groups having 7 to 10 carbon atoms and 7 to 10 The catalyst composition according to claim 1, wherein the catalyst composition is selected from the group consisting of arylalkyl groups having two carbon atoms. 3. R ¹ and R ² are each hydrogen, methyl, ethyl, propyl, butyl, isobutyl, pentyl, isopentyl, hexyl, 2-ethylhexyl, heptyl, octyl. , Vinyl group,
3. The catalyst composition according to claim 2, wherein the catalyst composition is selected from the group consisting of an allyl group, an isopropenyl group, a phenyl group and a tolyl group. 4. The catalyst composition according to claim 1, wherein two adjacent R ¹ are linked by an associated carbon atom to form a ring having 4 to 20 carbon atoms. 5. The two adjacent R ^{1 s} combine to form a saturated or unsaturated polycyclic cyclopentadienyl ligand with an associated cyclopentadienyl ring.
A catalyst composition as described. 6. The catalyst according to claim 5, wherein two adjacent R ¹ combine to form an indenyl group, a tetrahydroindenyl group, a fluorenyl group or an octahydrofluorenyl group together with an associated cyclopentadienyl ring. Composition. 7. The catalyst composition according to claim 1, wherein two adjacent R ² are linked by an associated carbon atom to form a ring having 4 to 20 carbon atoms. 8. bonded two adjacent R ^2, together with the accompanying cyclopentadienyl ring to form a polycyclic cyclopentadienyl ligand saturated or unsaturated claim 7
A catalyst composition as described. 9. The catalyst according to claim 8, wherein two adjacent R ² combine to form an indenyl group, a tetrahydroindenyl group, a fluorenyl group or an octahydrofluorenyl group together with an associated cyclopentadienyl ring. Composition. 10. The catalyst composition according to claim 1, wherein X is carbon. 11. Y is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogen, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, 7-20 or arylalkyl group having a carbon atom, an alkoxy group having 1 to 20 carbon atoms, 1-20 aryloxy group having carbon ^{_{atoms, -NH 2, -NHR 7, -NR}} 7 R ⁸ ,-(C = O) N
_{H 2, - (C = O} ) NHR 9 and ^{- (C = O) NR 9} R
¹⁰ selected from the group consisting of R ⁷ , R ⁸ , R ⁹ , and R ¹⁰
Is an alkyl group having from 1 to 20 carbon atoms. 12. The catalyst composition according to claim 1, wherein Y is —N (CH ₃ ) ₂ . 13. The catalyst composition according to claim 1, which is present in an amount effective to act as a catalyst under polymerization conditions.
A method for producing a polyolefin, comprising a step of polymerizing one olefin or a step (b) of polymerizing at least two olefins. 14. The method of claim 13, comprising (a) polymerizing one olefin, wherein said olefin is a cycloolefin. 15. A method comprising the step of: (b) polymerizing at least two olefins, wherein the olefins are at least one.
14. The method according to claim 13, which is at least one cycloolefin and at least one acyclic olefin. 16. The method according to claim 16, wherein the cycloolefin is bicycloheptane, tricyclodecene, tricycloundecene, tetracyclododecene, pentacyclopentadecene, pentacyclopentadecadien, pentacyclohexadecene, hexacycloheptadecene, heptacycloeico. 16. The method of claim 15, wherein the method is selected from the group consisting of sen, heptacyclopheneicosene, octacyclodokosene, nonacyclopentacosene, and nonacyclohexacocene. 17. The method of claim 15, wherein said acyclic olefin is ethylene or an α-olefin having 3 to 12 carbon atoms. 18. The method according to claim 18, wherein the α-olefin is propylene,
18. The method of claim 17, wherein the method is selected from the group consisting of 1-butene, 1-pentene, 1-hexene, and 1-octene. 19. The method of claim 15, wherein said cycloolefin is norbornene and said acyclic olefin is ethylene. 20. The method according to claim 15, wherein the glass transition temperature of the obtained polyolefin is in the range of 60 to 300 ° C. 21. The polyolefin obtained has a glass transition temperature in the range of 120 to 300 ° C.
The described method. 22. The obtained polyolefin has a glass transition temperature in the range of 250 to 300 ° C.
The described method. 23. Chemical formula (II) (R is a hydrocarbyl group having 1 to 20 carbon atoms). A metallocene catalyst having a structure represented by the following formula: 24. Chemical formula (III) (R is a hydrocarbyl group having 1 to 20 carbon atoms). A metallocene catalyst having a structure represented by the following formula: 25. Chemical formula (IV) (R is a hydrocarbyl group having 1 to 20 carbon atoms). A metallocene catalyst having a structure represented by the following formula: