JPH09194552A - Iso-syndio-block polypropylene - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer having iso linkages and syndio-linkages in a polymer chain and usable for various kinds of uses singly or in combination with another polymer. SOLUTION: This polymer has a meso pentad fraction of the methyl spectrum determined by<13> C-NMR of 20-80%, a recemic pentad fraction of the methyl spectrum of 20-80% and the sum of the fractions of 40-100%, all based on the strength of the total methyl spectrum. This polymer can be obtained by carrying out propylene polymerization using a specific metallocene compound as a catalyst-constituting component. Further, the catalyst system contains a compound which can produce a cationic metallocene compound by reacting a metallocene compound of the formula [M<1> is a transition metal of the group 4, 5 or 6 in the periodic table; R<1> is independently a 1-12C hydrocarbon; R<2> and R<3> are each independently a 1-20C hydrocarbon, etc.; R<4> and R<5> are each independently a 1-20C hydrocarbon; X<1> and X<2> are each independently H, a 1-20C hydrocarbon, etc.; (n) and (m) are each an integer of 0-4] with the metallocene compound, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polypropylene polymer. More specifically, it relates to an iso-syndio-block polypropylene having an iso chain and a syndio chain in the polymer chain.

[0002]

2. Description of the Related Art Polypropylene can be roughly classified into three types of polymers according to the steric arrangement of methyl groups in its side chain. Atactic polypropylene in which tertiary carbon atoms are randomly arranged in a molecular chain, isotactic polypropylene in which tertiary carbon atoms are arranged in the same molecular chain, and adjacent tertiary carbon atoms in a molecular chain Are syndiotactic polypropylenes having opposite arrangements.

Hemiisotactic polypropylene is known as a polypropylene having both an isotactic chain and a syndiotactic chain in the polymer chain. JP-A-3-193796 discloses that hemiisotactic polypropylene can be obtained in the polymerization of propylene using a metallocene catalyst composed of isopropylidene (3-methylcyclopentadienyl) (fluorenyl) zirconium dichloride and methylaluminoxane. Is disclosed. The fine structure of this hemiisotactic polypropylene has a mesopentad fraction of 14% based on the isotactic structure and a racemic pentad fraction of 19% based on the syndiotactic structure, and has a short isotactic and syndiotactic chain. It is suggested that it is distributed.

That is, hitherto, there has been no case where an iso-syndio-block polypropylene having a long isotactic and syndiotactic chain in the molecule has been synthesized.

[0005]

SUMMARY OF THE INVENTION The present invention is to provide a novel iso-syndio-block polypropylene having long chain isochain and syndio chain in the polymer chain.

[0006]

Means for Solving the Problems The present inventors have solved the above problems and found that an iso-syndio-block polypropylene having a long chain isochain and a syndio chain can be obtained, and completed the present invention. It was

That is, according to the present invention, the mesopentad fraction of the methyl group spectrum measured by ¹³ C-NMR is in the range of 20 to 80% of the intensity of all methyl groups, and the racemic pentad fraction of the methyl group spectrum is It is an iso-syndio-block polypropylene characterized in that it is in the range of 20 to 80% of the strength of all methyl groups and the sum of the mesopentad fraction and the racemic pentad fraction is in the range of 40 to 100%.

The iso-syndio-block polypropylene of the present invention can be obtained by carrying out propylene polymerization using a specific metallocene compound as a catalyst constituent component.

The catalyst system comprises (a) a metallocene compound, (b) a compound which reacts with the metallocene compound to form a cationic metallocene compound, and (c) an organometallic compound, if necessary. Is.

The specific metallocene compound (a) used in the present invention is represented by the following general formula (1)

[0011]

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[Wherein M ¹ is a periodic table group 4, group 5 or group 6]
Group ¹ transition metal compound, R ¹ is independently a hydrocarbon group having 1 to 12 carbon atoms, R ² and R ³ are benzocyclic substituents of a fluorenyl group, and each independently has a carbon number of 1
To a hydrocarbon group having 20 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a silicon-containing hydrocarbon group having 3 to 20 carbon atoms, or a halogen atom. Y is a group bridging the silicon compound-substituted cyclopentadienyl group and the fluorenyl group, which is a carbon atom or a silicon atom, and R ⁴ and R ⁵ are substituents of the bridging atom Y, each independently having 1 carbon atom. To 20 hydrocarbon groups.
X ¹ and X ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen atom. Also, n and m
Is an integer of 0 to 4. ].

As a catalyst useful for obtaining the polymer of the present invention, M ¹ is preferably titanium, zirconium or hafnium, more preferably zirconium.

R ^1's each independently represent a hydrocarbon group having 1 to 20 carbon atoms, specifically, methyl, ethyl, propyl,
Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, isopropyl, isobutyl,
Alkyl groups such as s-butyl, t-butyl and cyclohexyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, aryl groups such as phenyl, methylphenyl, ethylphenyl, biphenyl and naphthyl, and arylalkyl groups such as benzyl and phenylethyl. Etc.

R ² and R ³ are substituents on the benzo ring of the fluorenyl group, each independently being a hydrocarbon group having 1 to 20 carbon atoms or an oxygen-containing hydrocarbon group, or a silicon-containing carbon group having 3 to 20 carbon atoms. Indicates a hydrogen group or a halogen atom. Specifically, methyl, ethyl, propyl, pentyl, hexyl,
Hydrocarbon groups having 1 to 20 carbon atoms such as alkyl groups such as heptyl, decyl, isopropyl, isobutyl, s-butyl, t-butyl, aryl groups such as phenyl and tolyl, arylalkyl groups such as benzyl; methoxy, ethoxy. , Alkoxy groups such as propoxy, butoxy, isopropoxy, aryloxy groups such as phenoxy and methylphenoxy, oxygen-containing hydrocarbon groups having 1 to 20 carbon atoms such as arylalkoxy groups such as phenylmethoxy and phenylethoxy; trimethylsilyl, triethylsilyl, etc. Alkylsilyl groups, arylsilyl groups such as phenyldimethylsilyl and diphenylmethylsilyl, alkenylsilyl groups such as allyldimethylsilyl, and the like, and silicon-containing hydrocarbon groups having 3 to 20 carbon atoms; halogens such as fluorine, chlorine, bromine, and iodine. atom And the like.

Y is a group which bridges a silicon compound-substituted cyclopentadienyl group and a fluorenyl group, and is a carbon atom or a silicon atom.

R ⁴ and R ⁵ are substituents of the bridging atom Y, each independently a hydrocarbon group having 1 to 20 carbon atoms, and specifically, the same hydrocarbons as those exemplified above for R ^1. It is a base. In order to improve the rigidity of the metallocene compound and the molecular weight of the obtained polymer, at least one of R ⁴ and R ⁵ is preferably a bulky alkyl group or aryl group.

X ¹ and X ² are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen atom. Specifically, except for a hydrogen atom, it has ¹ to 20 carbon atoms similar to R ¹ described above.
And a halogen atom such as fluorine, chlorine, bromine or iodine.

M, which represents the number of substituents on the benzo ring of the fluorenyl group, is an integer of 0 to 4, and n is also an integer of 0 to 4.

Specific metallocene compounds include diphenylmethylene (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) zirconium dimethyl, diphenyl. Methylene (3- (triethylsilyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3- (triethylsilyl) cyclopentadienyl) (fluorenyl)
Zirconium dimethyl, diphenylmethylene (3- (phenyldimethylsilyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (3- (phenyldimethylsilyl) cyclopentadienyl) (fluorenyl) zirconium dimethyl, diphenylsilanediyl (3 -(Trimethylsilyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilanediyl (3- (trimethylsilyl) cyclopentadienyl) (fluorenyl) zirconium dimethyl, diphenylsilanediyl (3- (triethylsilyl) cyclopentadienyl) (Fluorenyl) zirconium dichloride, diphenylsilanediyl (3- (triethylsilyl) cyclopentadienyl)
(Fluorenyl) zirconium dimethyl, diphenylsilanediyl (3- (phenyldimethylsilyl) cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylsilanediyl (3- (phenyldimethylsilyl) cyclopentadienyl) (fluorenyl) zirconium dimethyl, Diphenylmethylene (3- (trimethylsilyl) cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, diphenylmethylene (3- (trimethylsilyl) cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium Dimethyl, diphenylmethylene (3- (trimethylsilyl) cyclopentadienyl) (2,7-di-t-butylfluorenyl) zirconium dichloride, diphenylmethylene (3 (Trimethylsilyl) cyclopentadienyl) (2,7-t-butylfluorenyl) zirconium dimethyl, diphenylmethylene (3- (trimethylsilyl) cyclopentadienyl) (2,7-diphenylfluorenyl) zirconium dichloride, diphenyl Examples thereof include methylene (3- (trimethylsilyl) cyclopentadienyl) (2,7-diphenylfluorenyl) zirconium dimethyl, or those in which a zirconium atom is replaced with a titanium atom or a hafnium atom, but the present invention is not limited thereto. Not a thing.

The compound (b) which reacts with the metallocene compound (a) to produce a cationic metallocene compound is a compound which provides a counter anion to the produced cationic metallocene compound. The compound (b) is not particularly limited as long as it has the above-mentioned properties, but preferably a protic acid (2), a Lewis acid (3), an ionizable ionic compound (4) and a Lewis acidic compound (5) are exemplified. To be done.

The above protonic acid is represented by the following general formula (2) [HL ¹ _l ] [M ² R ⁶ ₄ ] (2) [wherein, H is a proton and L ¹ is independently a Lewis base. , 1 is 0 <l ≦ 2, M ² is a boron atom, an aluminum atom or a gallium atom, and R ⁶
Are each independently a halogen-substituted aryl group having 6 to 20 carbon atoms. ] It is a compound represented by these. Specific examples of the protonic acid represented by the general formula (2) include diethyloxonium tetrakis (pentafluorophenyl) borate,
Examples thereof include tetramethyleneoxonium tetrakis (pentafluorophenyl) borate and N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, but are not limited thereto.

The Lewis acid is represented by the following general formula (3) [C] [M ² R ⁶ ₄ ] (3) [wherein C is a carbonium cation or tropylium cation, and M ² is a boron atom or an aluminum atom. Alternatively, it is a gallium atom, and each R ⁶ is independently a halogen-substituted aryl group having 6 to 20 carbon atoms. ] It is a compound represented by these. Specific examples of the Lewis acid represented by the general formula (3) include trityl tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) aluminate, tropylium tetrakis (pentafluorophenyl) borate, tropylium tetrakis. Examples thereof include (pentafluorophenyl) aluminate, but are not limited thereto.

The ionized ionic compound is represented by the following general formula (4) [M ³ L ² _r ] [M ² R ⁶ ₄ ] (4) [wherein M ³ is a group 1, 2 or 8 group in the periodic table, 9 races, 10
Is a cation of a metal selected from Group 11, Group 11 or Group 12, L ² is a Lewis base or a cyclopentadienyl group, r is 0 ≦ r ≦ 2, M ² is a boron atom, an aluminum atom or It is a gallium atom, and each R ⁶ is independently a halogen-substituted aryl group having 6 to 20 carbon atoms. ] It is a compound represented by these. Specific examples of the ionizable ionic compound represented by the general formula (4) include lithium salts such as lithium tetrakis (pentafluorophenyl) borate and lithium tetrakis (pentafluorophenyl) aluminate, ether complexes thereof, and ferrose. Examples thereof include, but are not limited to, ferrocenium salts such as aluminum tetrakis (pentafluorophenyl) borate and ferrocenium tetrakis (pentafluorophenyl) aluminate.

The Lewis acidic compound has the following general formula (5) [M ² R ⁶ ₃ ] (5) [wherein, M ² is a boron atom, an aluminum atom or a gallium atom, and R ⁶ is independently a carbon atom. Number 6 to 20
Is a halogen-substituted aryl group. ] It is a compound represented by these. Specific examples of the Lewis acidic compound represented by the general formula (5) include tris (pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl) borane and tris (2,3,4). , 5-tetraphenylphenyl) borane, tris (3,4,5-trifluorophenyl) borane, phenylbis (pentafluorophenyl) borane, tris (3,4,5-trifluorophenyl) aluminum and the like. However, the present invention is not limited to these.

When a metallocene compound is used as a catalyst, a solvent is provided which forms a cationic metallocene compound including alkylation and hydrolyzation of the metallocene compound, protects the produced cationic metallocene compound from a catalyst poison, or provides a reaction field. As an essential role, an organometallic compound represented by the following general formula (6) having at least one alkyl group can be used.

[M ⁴ R ⁷ _s ] (6) [In the formula, M ⁴ is an element of Group 1, Group 2 or Group 13 of the periodic table, Sn or Zn. R ⁷ is independently a hydrogen atom, an alkyl group or an alkoxy group having 1 to 24 carbon atoms, or an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an alkylaryl group or an alkylaryl having 6 to 24 carbon atoms. It is an oxy group, and at least one R ⁷ is a hydrogen atom, an alkyl group having 1 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group or an alkylaryl group. s is equal to the oxidation number of M ⁴ . ] Is an organometallic compound represented by the formula:

Examples of the compound represented by the general formula (6) include trimethylaluminum, triethylaluminum, triisopropylaluminum and tri-n-.
Propyl aluminum, triisobutyl aluminum,
Tri-n-butylaluminum, triamylaluminum, dimethylaluminum ethoxide, diethylaluminum ethoxide, diisopropylaluminum ethoxide, di-n-propylaluminum ethoxide, diisobutylaluminum ethoxide, di-n-
Butyl aluminum ethoxide, dimethyl aluminum hydride, diethyl aluminum hydride,
Organic aluminum compounds such as diisopropyl aluminum hydride, di-n-propyl aluminum hydride, diisobutyl aluminum hydride, di-n-butyl aluminum hydride, organic lithium compounds such as methyl lithium and butyl lithium, methyl magnesium bromide, ethyl magnesium bromide, etc. The organic magnesium compound and the like can be exemplified, but the invention is not limited thereto. Of these organometallic compounds, preferred are organoaluminum compounds.

The method for preparing a catalyst from the above-mentioned catalyst constituents is not particularly limited, and as a preparation method, a method of mixing in a solvent inert with respect to each component or using a propylene monomer for polymerization as a solvent is used. Can be mentioned. Further, the reaction of these components is not particularly limited in the order of contact of each component as long as it is a condition that a cationic metallocene compound is produced, and the temperature and the treatment time for this treatment are also not particularly limited.

In the catalyst system, the amount of the protonic acid, Lewis acid, ionized ionic compound and / or Lewis acidic compound with respect to the metallocene compound (a) is 0.1.
˜100 times mol, particularly 0.5 to 30
It is preferable that the molar amount is twice.

Further, the amount of the third component, organometallic compound (c), which is used separately from the above, is not particularly limited, but is preferably 100,000 times or less the molar amount of the transition metal compound, and if the amount is more than this amount, the amount of the transition metal compound is reduced. It is necessary to consider the ash process. Considering the viewpoints of stabilizing the cationic metallocene compound and eliminating the catalyst poison, it is preferable to use the organometallic compound in a range of 1 to 10000 times by mole.

Polymerization of propylene using the metallocene catalyst in the present invention can be carried out by any of ordinary polymerization methods such as slurry polymerization, gas phase polymerization and bulk polymerization using propylene as a polymerization medium.

When the solvent is used during the polymerization, any of the commonly used organic solvents may be used. Specifically, benzene, toluene, xylene, butane, pentane,
Hexane, heptane, cyclohexane, methylene chloride and the like can be mentioned.

In producing polypropylene using the method of the present invention, there are no particular restrictions on the polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure and monomer concentration, but the polymerization temperature is -100 to 300 ° C, the polymerization time. Is preferably 10 seconds to 20 hours, and the polymerization pressure is preferably in the range of atmospheric pressure to 100 kg / cm ² G. It is also possible to adjust the molecular weight using hydrogen or the like during polymerization. The polymerization is batch type,
Both semi-continuous and continuous methods can be used. Further, the polypropylene obtained after the completion of the polymerization,
Polypropylene can be obtained by separating and recovering from the polymerization solvent by a conventionally known method and drying.

By polymerizing under the above conditions, an iso-syndio-block polypropylene containing a long iso chain and a syndio chain can be produced.

[0036]

EXAMPLES Examples of the present invention will be shown below.

Example 1 Toluene 500 ml and propylene 500 as solvents
ml was added to a 21 reactor and the reactor temperature was set to 40 ° C.

On the other hand, in another container, diphenylmethylene (3-trimethylsilylcyclopentadienyl) (fluorenyl) zirconium dichloride 4.6 μmo
1 was dissolved in toluene, and a toluene solution of triisobutylaluminum (triisobutylaluminum 20
1% by adding 1.2 mmol in terms of aluminum)
Stirred for 0 minutes. Next, this mixture was added to a solution in which 5.5 μmol of N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate was dissolved in 10 ml of toluene, and the mixture was stirred for 10 minutes, and the obtained mixture was subjected to the above reaction under nitrogen pressure. Was supplied to the vessel.

After the mixture was supplied to the reactor, the reactor was stirred at 600 rpm at 60 rpm for 60 minutes to carry out a polymerization reaction. The obtained polymer was dried under vacuum at 100 ° C. for 6 hours. As a result, 39.5 g of a polymer was obtained. The number average molecular weight measured by gel permeation chromatography and calculated in terms of polypropylene was 141920, the weight average molecular weight was 298700, and Mw / Mn was 2.1. ^{By 13} C-NMR, o-dichlorobenzene / d ₆
The fine structure of polypropylene measured with tetramethylsilane at 0 ppm in a solution of benzene has a racemic pentad fraction of 46.5% and a mesopentad fraction of 33.8%.
It was calculated. ¹³ C of polypropylene obtained according to the present invention
-The 19-23 ppm part of the NMR spectrum is shown in FIG. In addition, solvent extraction of propylene, hexane as a solvent,
When carried out with heptane and octane, the presence of iso and syndio chains was confirmed in all the fractions, and the polypropylene according to the present invention was an iso-syndio-block polymer.

[0040]

INDUSTRIAL APPLICABILITY The iso-syndio-block polypropylene of the present invention can be used alone or in combination with other polymers for various purposes.

[Brief description of the drawings]

FIG. 1 ¹³ C-NM of polypropylene obtained by the present invention
It is an R spectrum (19-23 ppm part).

Claims (1)

[Claims] 1. The mesopentad fraction of the spectrum of methyl groups measured by ¹³ C-NMR is 20 that of the intensity of all methyl groups.
To 80%, the racemic pentad fraction of the methyl group spectrum is in the range of 20 to 80% of the intensity of all methyl groups, and the sum of the mesopentad fraction and the racemic pentad fraction is in the range of 40 to 100%. An iso-syndio-block polypropylene characterized in that