JPH11349634A - Propylene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a propylene polymer having isotactic regularity enough to retain rigidity and heat resistance, wherein the rate of meso-racemic- racemic-meso bonded parts of a sequence composed of five head-to-tail bonded propylene units, the weight-average molecular weight, and the total of 2,1- and 3,1-different bonds are specified. SOLUTION: Propylene is polymerized in the presence of a polymerization catalyst comprising (A) a transition metal compound of formula I, (B) an aluminumoxy compound, at least one substance selected among an ionic compound which reacts with component A to form a cation, or the like and optionally, a microparticulate support and an organoaluminum compound to obtain a polymer in which the rate of meso-racemic-racemic-meso bonds of a sequence of five head-to-tail bonded propylene units is 9 mol.% or below as measured by C-NMR, either terminal of the propylene polymer contains a 1-propenyl group of formula II, the weight-average molecular weight is 1,000-1,000,000, and the total of 2,1- and 3,1-different bonds is 0.1 mol.% or below.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel propylene polymer having a high isotactic triad fraction and a specific amount of terminal structure. More specifically, the present invention relates to an isotactic propylene polymer having a vinyl group at a terminal. The polymer of the present invention can be used as a macromer having stereoregularity that can be polymerized with a Ziegler-Natta catalyst, and also has a special function that is excellent in compatibilizing agent, adhesiveness, paintability, etc. by modifying the terminal. It can be used as a polypropylene having

[0002]

2. Description of the Related Art Propylene polymers have attracted attention for their excellent rigidity, heat resistance, moldability, transparency and chemical resistance, and have been used in various industrial materials, various containers, daily necessities, films and fibers. Widely used in applications. Conventional propylene polymers often use hydrogen to adjust the molecular weight, and the terminal is a saturated hydrocarbon group. On the other hand, with the advent of metallocene catalysts, low-molecular-weight stereoregular propylene polymers have been obtained, but their terminals have an isobutenyl structure due to β-hydrogen abstraction, which makes them difficult for olefin polymerization catalysts such as Ziegler-Natta and metallocene catalysts. Not suitable for use as a macromer.

On the other hand, it has been reported that when bis (pentamethylcyclopentadienyl) zirconium dichloride is used, a low polymer having a terminal vinyl group is produced. However, the polymer obtained with this catalyst system is a liquid low polymer having a low molecular weight, and is a propylene polymer having an atactic structure without stereoregularity, and therefore has high rigidity and heat resistance. There is a demand for the development of a propylene polymer having an isotactic stereoregularity, which can be obtained only in a low polymer, has a widely used isotactic stereoregularity, and has a terminal vinyl group.

[0004]

DISCLOSURE OF THE INVENTION The present invention relates to a propylene polymer having a vinyl structure at its end so that it can be polymerized with an ordinary olefin polymerization catalyst, and which has an isotacticity sufficient to maintain rigidity and heat resistance. It has been found as a result of investigation for the purpose of creating a propylene polymer having regularity.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of such circumstances, and provides a novel propylene polymer having a high isotactic triad fraction and a specific terminal structure. A propylene polymer having the characteristics of the following conditions (A), (B), (C) and (D) is excellent in rigidity, heat resistance, moldability, gloss and olefin. It is based on the finding that polymerizability to the catalyst is expected.

Accordingly, the propylene polymer according to the present invention has the following conditions (A), (B), (C) and (D)
Is satisfied. (A) ¹³ C-
As measured by NMR, the ratio of meso-racemic-racemic-meso-chains in the five-chain propylene unit consisting of head-to-tail bonds is 9
Mol% or less, -Containing a propenyl group, (C) having a weight average molecular weight Mw measured by gel permeation chromatography (GPC) in the range of 1,000 to 1,000,000, (D) 2,1- and The total of 1,3-hetero bonds is not more than 0.1 mol%.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS <propylene polymer> propylene polymer according to the present invention was measured by ¹³ C-NMR, head -
The ratio of the meso-racemic-racemic-meso chain in the five propylene units consisting of the tail bond is 9 mol% or less, preferably 7.5 mol% or less. In addition, meso-racemic
The racemic-meso linkage is hereinafter referred to as mrrm.

Here, the method of measuring the ¹³ C-NMR spectrum is as follows. ^{The 13} C-NMR spectrum is 10
50-500m in the sample tube for mmΦ NMR measurement
g sample was completely dissolved in a solvent obtained by adding about 0.5 ml of deuterated benzene as a lock solvent to about 2.0 ml of o-dichlorobenzene, and measured at 130 ° C. by a proton complete decoupling method. Waltz 1 for decoupling
I used 6. As the measurement conditions, a flip angle of 65 ° and a pulse interval of 5T ₁ or more (T ₁ is the longest value among the spin lattice relaxation times of the methyl group) were selected. Since T ₁ of the methylene group and the methine group is shorter than the methyl group in the propylene polymer, the recovery of the magnetization of all carbons is 99% or more under these measurement conditions. The observation frequency was 124 MHz or more, and the digital resolution was 0.008 ppm or less (that is, the acquisition time was 1 second or more at the observation frequency of 125 MH).

The chemical shift is set at 21.8 ppm for the third unit of the five units of the propylene unit, which has head-to-tail bonds and the same direction of branching of the methyl group, and the chemical shift of the other carbon signals is the same. Was used as a reference. In this standard, PPPPP (mmmm) and PPPP
(Mmmr)
The signal based on the methyl group in the unit is 21.44 to 2
In the range of 2.10 ppm, the signal based on the methyl group of the second unit in the five propylene units represented by PPPPP (mmrr) is in the range of 20.94 to 21.14 ppm, and the signal of propylene represented by PPPPP (mrrm) is in the range of 20.94 to 21.14 ppm. The signal based on the methyl group of the second unit in the five units appears in the range of 19.70 to 20.04 ppm. Here, the PPPP (mrrm) of the 5-chain part of the propylene unit
The upper limit of [mrrm] indicating the ratio of is represented by the following equation. The condition (A) of the invention is that the polymer of the present invention has [mrm] of 9% or less, preferably 7.5% or less.

[0010]

[Mrrm] = I (mrrm) / {I (mmmm) + I (mmmr) + I (mmrr) + I (mrrm) -I (2,1)} (Formula 1) I (2,1) = ( 1/4) {A + A + A + A} (Equation 2)

In this (Equation 1), I (mmmm),
I (mmmr), I (mmrr), and I (mrrm) are integral values of the signal based on the methyl group of the second unit in each of the five chains of propylene units. A in equation (2),
A, A, and A represent 42.3 ppm, 38.6 ppm, 36.0 pp, and 32.3 ppm, respectively, derived from the partial structure (I).
This is the integrated value of the signal at 5.9 ppm. The structure and partial structure of m or r are represented by the following formula.

[0012]

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[0013]

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The propylene polymer may have a structure in which the insertion of propylene is reversed as shown in the structures (I) and (II) in addition to the bond of mm and mr. It is considered that such a partial structure is caused by positional irregularities generated during the polymerization of the propylene polymer. The propylene monomer is usually a 1,2-insertion in which the methylene side is bonded to the catalyst center metal side, but rarely a 2,1-insertion or a 1,1-insertion.
3- May be inserted. The monomer polymerized by the 2,1-insertion forms a position irregular unit represented by the partial structure (I) of the chemical formula (4) in the polymer chain. Also,
The monomer polymerized by the 1,3-insertion forms a position irregular unit represented by the partial structure (II) of the chemical formula (5) in the polymer chain.

The mm fraction in the total polymer chain of the propylene polymer according to the present invention is represented by the following formula. by the way,
In partial structure (II), as a result of 1,3-insertion,
It has disappeared by an amount corresponding to the number. In the propylene polymer of the present invention, the partial structures (I) and (II) containing regiorandom units based on propylene 2,1-insertion and 1,3-insertion are 0.1 mol% or less. Is the condition (D). The numerical values of various definitions shall be quantified as follows.

[0016]

(Equation 2)

In this formula, ΔICH ₃ indicates the area of all methyl groups (19 to 22 ppm). A, A
, A, A, A, A, A, A and A
Are 42.3 ppm, 35.9 ppm and 38.
6 ppm, 30.6 ppm, 36.0 ppm, 31.5
ppm, 31.0 ppm, 37.2 ppm, 27.4 p
pm, and indicates the abundance ratio of carbon shown in the partial structures (I) and (II). The ratio of 2,1-inserted propylene and the ratio of 1,3-inserted propylene with respect to the total propylene insertion are calculated by the following formulas.

[0018]

(Equation 3)

The propylene polymer according to the present invention is substantially a homopolymer of propylene, but as long as the conditions (A) and (B) relating to the propylene insertion form are satisfied, a small amount of α-olefin other than propylene (ethylene For example, 6.0 mol% based on propylene.
Up to an amount of α-olefin.

The terminal structure is represented by ¹³ C-NMR and ¹ H-N
Determined by MR. The homopolymer of propylene may include the structures of (Chemical Formula 1) to (Chemical Formula ¹³ ), but the 1-propenyl terminal (Chemical Formula 11) has a characteristic ¹³ C-NMR signal, δ11
5.5 (1st place), δ137.5 (2nd place), δ41.5
The presence or absence can be determined by (3rd place). The structure of each terminal is defined as follows.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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At this time, the assignment of signals at various terminals in the ¹³ C-NMR spectrum is as follows: signals characteristic of the 1-propenyl terminal (formula 11) are δ115.5 (1st position) and δ137.5.
(Position 2), δ41.5 (position 3), δ30.9 (position 4), and signals characteristic of the isobutenyl terminal (formula 10) are as follows:
δ111.5 (1st place), δ144.7 (2nd place), δ2
2.5 (methyl at the 2nd position), and characteristic signals at the propyl terminal (Formula 8) are δ14.4 (1st), δ20.2 (2
), Δ 39.8 (position 3), δ 30.7 (position 4), and a signal characteristic of a dimethyl terminal (Formula 6) is δ22.
6 (1st place), δ23.7 (1st place), δ25.9 (2nd place)
It is. The assignment of the characteristic signal at the isobutenyl terminal (Chemical Formula 10) is from Reference 5, the assignment of the signal characteristic at the propyl terminal (Chemical Formula 8) is from Document 5, and the assignment of the characteristic signal at the dimethyl terminal (Chemical Formula 6) is as follows. Reference 6 was used. The assignment of the characteristic signal to the 1-propenyl terminal (Chemical formula 11) is based on the terminal signal δ115.4 (1 position) and δ137.8 (2) of the analogous compound 4-methyl-1-hexene assigned in Reference 1. Rank), δ
It was performed by comparison with 41.3 (third place). The distinction between (Chem. 11) and the 1-butenyl terminal (Chem. 12) and the long-chain vinyl terminal (Chem.
This was performed by estimating the chemical shift of the signal characteristic in 4) from the chemical shift of a compound having a similar structure assigned in Reference 1. The signal characteristic of (Formula 12) is δ114.1.
(1st place), δ139.3 (2nd place), δ31.9 (3rd place)
Δ114.2 (1st position), δ139.1 (2nd position), δ
It was estimated to be 34.0 (third place).

On the other hand, in the ¹ H-NMR spectrum, a double bond hydrogen signal (δ5.8 at the 1-propenyl terminal (Formula 11)) was obtained.
4-5.74, δ 5.02 to 4.96) and the double bond hydrogen signal at the isobutenyl terminus (Chem. 10) (δ 4.78 to
4.66) is the other saturated hydrogen signal (δ 2.60 to
0.40). The assignment of the double bond hydrogen signal was performed from the spectra of the analogous compounds 1-decene and 2-methyl-1- assigned in Reference 7.

Mole% of propylene unit of 1-propenyl terminal (formula 11) and isobutenyl terminal (formula 10),
[1-Pr-Δ] and [i-Bu-Δ] are ¹ H-NM
It was determined from the following equation based on the R integral value.

[0033]

[1−Pr−Δ] = B / {(1/6) (B + B + B + B)} (Equation 6)

[0034]

[I-Bu- [Delta]] = (1/2) B / {(1/6) (B + B + B + B)} (Equation 7)

In this equation, B is an integral value of a signal of 2.60 to 0.40 ppm derived from saturated hydrogen.
Is the integral value of the signal of 5.84 to 5.74 ppm,
B is the integrated value of the signal of 5.02 to 4.96 ppm, and B is the integrated value of the signal of 4.78 to 4.66 ppm. Mol% of 1-propenyl terminal (formula 11) and isobutenyl terminal (formula 10) in the olefin structural unit,
[1-Pr-Δ] _db and [i-Bu-Δ] _db are ¹ H-
It was determined from the following equation based on the NMR integrated value.

[0036]

[1-Pr-Δ] _db = B / {B + (1/2) (B + B)} (Equation 8)

[0037]

[I-Bu-Δ] _db = (１ ／) B / {B + (１ ／) (B + B)} (Equation 9)

In the present invention, it is preferable that the polymer having one terminal having a 1-propenyl terminal (allyl terminal) (formula 11) is present in an amount of at least 35 mol% with respect to the isobutenyl terminal. References relating to NMR assignments are listed below. 1) Lindeman, L .; P. Adams, J .; Q. Anal. Chem. 43 (1971) 1245 2) Cooperus, P .; A. Clague, A .; D. H. Van Dongen, J .; P. C. M. Org. Magn. Reson. 8 (1976) 426 3) Zambelli, A .; Locatgelli, P .; Et al. Macromol. 13 (1980) 267-270 (2, 1) 4) Grassi, A .; Zambelli, A .; Macromol. 21 (1988) 617-622 (1,3) 5) Zambelli, A .; Macromol. 12 (1979) 154 n-propyl, 2-methylene-propenyl (vinylidene) 6) Zambelli, A .; et al. Macromol. 15 (1982) 211-212 dimethyl (i-propyl) 7) Aldrich NMR data collection

The molecular weight of the propylene polymer of the present invention is GP
C has a weight average of 1,000 to 1,000,000. It is preferably 1,000 to 400,000, more preferably 1,000 to 100,000, and particularly preferably 1,000 to 50,000. The preferred molecular weight varies depending on the application, but when used as a macromer,
It is desirable that the molecular weight is less than 0000 both in handling and in the role of branching.

<Production of Propylene Polymer> The process for producing a propylene polymer according to the present invention is carried out by using a propylene homopolymer satisfying the above-mentioned properties or a 6 mol% or less ethylene or α-olefin polymer other than propylene. There is no particular limitation as long as it gives a copolymer.
Among them, a catalyst system suitable for producing the polymer of the present invention is a metallocene catalyst, for example, a catalyst component (A) as shown below: at least one metallocene selected from transition metal compounds described below. Compound and catalyst component (B): [(B) -1] aluminum oxy compound,
[(B) -2] an ionic compound or a Lewis acid capable of converting the catalyst component (A) into a cation by reacting with the catalyst component (A), [(B) -3]: an ion excluding silicate Exchangeable layered compound or inorganic silicate, and optional component (C): fine-particle carrier, and / or optional component (D):
It is a catalyst system composed of an organic aluminum compound.

The polymer according to the present invention is obtained by polymerizing propylene or copolymerizing propylene with ethylene or an α-olefin other than propylene, preferably in the presence of the catalyst.

<Catalyst Component (A)> First, examples of the transition metal compound of the catalyst component (A) capable of providing the polymer of the present invention will be described. Incidentally, as long as the polymer of the present invention is obtained, it goes without saying that the catalyst component (A) is not limited to this example and may be optional. The catalyst component (A) has the following general formula [I]
Is a typical example.

[0043]

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(Where R¹, R^Two, R^Four, R^FiveEach
Independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms
Or a silicon-containing hydrocarbon group having 1 to 18 carbon atoms,
R^Three, R⁶Are each independently a five-membered ring
On the other hand, a divalent saturated group having 3 to 10 carbon atoms to form a condensed ring
Or an unsaturated hydrocarbon group. Preferably R^ThreeAnd R
⁶At least one has 5 to 10 carbon atoms. This
Chi, R¹, R^FourIs preferably a branched hydrocarbon
And more preferably an isopropyl group. R⁷, R
⁸Is independently a hydrocarbon group having 1 to 20 carbon atoms or
C1-20 halogenated hydrocarbon group, oxygen-containing carbon
And hydrogen, nitrogen-containing hydrocarbons, and phosphorus-containing hydrocarbons.
m and n each independently represent an integer of 0 to 20. Q is two
At least one carbon atom having 1 or 2 carbon atoms,
0 hydrocarbon group, halogenated hydrocarbon having 1 to 20 carbon atoms
Nitrogen group, oxygen-containing hydrocarbon group, nitrogen-containing hydrocarbon group, phosphorus-containing
Alkylene group having a hydrocarbon group, or at least
One C1-C20 hydrocarbon group, C1-C20
Halogenated hydrocarbon groups, oxygen-containing hydrocarbon groups, nitrogen-containing
Silylene groups having a hydrocarbon group or a phosphorus-containing hydrocarbon group
Or at least one hydrocarbon group having 1 to 20 carbon atoms,
A halogenated hydrocarbon group having a prime number of 1 to 20, an oxygen-containing carbon
Has hydrogen group, nitrogen-containing hydrocarbon group, and phosphorus-containing hydrocarbon group
Germylene group. X and Y are each independently water
An element atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A halogenated hydrocarbon group having 1 to 20 carbon atoms, 1 to 2 carbon atoms
0 oxygen-containing hydrocarbon group, amino group, 1-20 carbon atoms
Represents a nitrogen-containing hydrocarbon group, and M represents a transition in group 3 to 6 of the periodic table
Indicates metal. )

The transition represented by the general formula [I] according to the present invention
The transfer metal compound has a substituent R¹, R^Two, And R^ThreeHave
And a substituent R^Four, R^Five, And R⁶With
The five-membered ring ligand is in the sense of relative position via the group Q
Asymmetric with respect to the plane containing M, X, and Y
And compounds that are symmetric. However, high activity,
Production of high molecular weight and high melting point α-olefin polymer
To do so, the substituent R¹, R^Two, And R^ThreeHaving
A five-membered ring ligand and a substituent R^Four, R^Five, And R ⁶Have
A five-membered ring ligand in terms of relative position via group Q
Asymmetric with respect to the plane containing M, X, and Y,
In other words, two opposing faces across a plane including M, X and Y
Five-membered ligand is not mirror image of entity with respect to the plane
Use compounds.

R ¹ , R ² , R ⁴ and R ⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms or a silicon-containing hydrocarbon group having 1 to 18 carbon atoms, as described above. . More specifically, R ¹ , R ² , R ⁴ , R
⁵ is each independently (a) a hydrogen atom, (b) a hydrocarbon group having 1 to 10 carbon atoms, for example, methyl, ethyl, n-
Propyl, i-propyl, n-butyl, i-butyl, s
-Butyl, t-butyl, n-pentyl, n-hexyl,
Cyclopropyl, cyclopentyl, cyclohexyl, alkyl groups such as methylcyclohexyl, vinyl, propenyl, alkenyl groups such as cyclohexenyl, benzyl, phenylethyl, arylalkyl such as phenylpropyl, and trans-styryl such as arylalkenyl groups;
Aryl groups such as phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, α-naphthyl and β-naphthyl; (c) silicon-containing hydrocarbon groups having 1 to 18 carbon atoms, for example, trimethylsilyl, triethylsilyl, t-butyl A trialkylsilyl group such as dimethylsilyl; a triarylsilyl group such as triphenylsilyl; an (alkyl) (aryl) silyl group such as dimethylphenylsilyl; and an alkylsilylalkyl group such as bis (trimethylsilyl) methyl. Among them, R ¹ and R ⁴ are preferably a hydrocarbon group having 1 to 10 carbon atoms such as isopropyl, tertbutyl, cyclopropyl, phenyl, cyclopentyl, etc., and R ² and R ⁵ are hydrogen atoms. Is preferred.

R ³ and R ⁶ each independently represent a divalent C ³ -C 3 forming a condensed ring with the five-membered ring to which they are bonded.
Shows 10 saturated or unsaturated hydrocarbon groups. Therefore, the condensed ring is a 5- to 12-membered ring. Preferably, at least one of R ³ and R ⁶ forms a condensed ring composed of a 7 to 12-membered ring. At this time, at least one of the condensed rings is 7
It is preferably a 10-membered ring, and more preferably both of the condensed rings are a 7-membered ring.

Specific examples of such R ³ and R ⁶ are as follows. Divalent saturated hydrocarbon groups such as trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, etc., propenylene, 2-butenylene, 1,3-butadienylene, 1-pentenylene,
2-pentenylene, 1,3-pentadienylene, 1,4
-Pentadienylene, 1-hexanylene, 2-hexanylene, 3-hexanylene, 1,3-hexadienylene,
Examples thereof include divalent unsaturated hydrocarbon groups such as 1,4-hexadienylene, 1,5-hexadienylene, 2,4-hexadienylene, 2,5-hexadienylene, and 1,3,5-hexatrylene. Of these, pentamethylene, 1,3-pentadienylene, 1,4-pentadienylene, and 1,3,5-hexatrienylene are preferred,
3-Pentadienylene and 1,4-pentadienylene are particularly preferred.

R ⁷ and R ⁸ each independently have 1 to 2 carbon atoms.
A hydrocarbon group of 0 or a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, and a phosphorus-containing hydrocarbon group. More specifically, (a) a hydrocarbon group having 1 to 20 carbon atoms, for example, methyl, ethyl,
alkyl groups such as n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, n-hexyl, cyclopropyl, cyclopentyl, cyclohexyl, methylcyclohexyl, vinyl, propenyl, Alkenyl groups such as cyclohexenyl; arylalkyl groups such as benzyl, phenylethyl and phenylpropyl; arylalkenyl groups such as trans-styryl; phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, α-naphthyl, β-naphthyl and acenaphthenyl And phenanthrenyl, anthracenyl and the like. Of these, methyl, ethyl, n-propyl, i-propyl,
C1-C4 alkyl groups such as n-butyl, i-butyl, s-butyl, t-butyl, cyclopropyl, phenyl, tolyl, dimethylphenyl, ethylphenyl, trimethylphenyl, α-naphthyl, β-naphthyl, etc. And an aryl group having 6 to 20 carbon atoms is preferable.

Examples of the other groups represented by R ⁷ and R ⁸ include (ii) a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, and a phosphorus-containing hydrocarbon group. Can be Examples of the halogen atom constituting the halogenated hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The halogenated hydrocarbon group having 1 to 20 carbon atoms is, for example, a compound in which a fluorine atom is substituted at an arbitrary position of the hydrocarbon group having 1 to 20 carbon atoms when a halogen atom is exemplified by a fluorine atom. Specifically, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, iodomethyl, 2,2,2-trifluoroethyl,
2,2,1,1-tetrafluoroethyl, pentafluoroethyl, pentachloroethyl, pentafluoropropyl, nonafluorobutyl, trifluorovinyl, 1,1
-Difluorobenzyl, 1,1,2,2-tetrafluorophenylethyl, o- or m- or p-fluorophenyl, o- or m- or p-chlorophenyl, o- or m- or p-bromo Phenyl, 2,
4- or 3,5- or 2,6- or 2,5-
Difluorophenyl, 2,4- or 3,5- or 2,6- or 2,5-dichlorophenyl, 2,
4,6-trifluorophenyl, 2,4,6-trichlorophenyl, pentafluorophenyl, pentachlorophenyl, 4-fluoronaphthyl, 4-chloronaphthyl,
2,4-difluoronaphthyl, heptafluoro-α-naphthyl, heptachloro-α-naphthyl, o- or m
-Or p-trifluoromethylphenyl, o- or m- or p-trichloromethylphenyl, 2,4
-Or 3,5- or 2,6- or 2,5-di-trifluoromethylphenyl, 2,4- or 3,
5- or 2,6- or 2,5-di-trichloromethylphenyl, 2,4,6-tri-trifluoromethylphenyl, 4-trifluoromethylnaphthyl, 4-trichloromethylnaphthyl, 2,4-di -Trifluoromethylnaphthyl group and the like. Of these, a fluorinated hydrocarbon group or a chlorinated hydrocarbon group is preferable, and an o- or m- or p-fluorophenyl group, or o
-Or m- or p-chlorophenyl, or o- or m- or p-trifluoromethylphenyl are particularly preferred. Examples of the oxygen-containing hydrocarbon group include methoxy, ethoxy, propoxy, phenoxy, ethoxyethyl, furyl, methoxyphenyl, and methyl cellosolve. Further, as the nitrogen-containing hydrocarbon group,
Examples thereof include dimethylamino, diethylamino, pyridyl, indolyl, carbazolyl, dimethylaminophenyl, and quinolyl groups. Examples of the phosphorus-containing hydrocarbon group include dimethylphosphino, diphenylphosphino, and dimethylphosphinoethyl groups.

M and n each independently represent an integer of 0 to 20. Preferably, m and n are 0-5. Here, when m or n, or both m and n are integers of 2 to 20, a plurality of groups R ⁷ (R ⁸ ) may be the same or different. When m, n, is 2 or more, these groups may be linked to form a new ring structure. Q is a bond of two 5-membered rings, at least one of 1 to 1 carbon atoms
20 hydrocarbon groups, halogenated hydrocarbon groups having 1 to 20 carbon atoms, oxygen-containing hydrocarbon groups, nitrogen-containing hydrocarbon groups, alkylene groups having a phosphorus-containing hydrocarbon group, or at least one of 1 to 20 carbon atoms A hydrocarbon group having 1 to 20 carbon atoms
A halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a silylene group having a phosphorus-containing hydrocarbon group or at least one hydrocarbon group having 1 to 20 carbon atoms,
A germylene group having a halogenated hydrocarbon group, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, and a phosphorus-containing hydrocarbon group having 1 to 20 carbon atoms is shown. Specific examples of Q as the crosslinking group containing a hydrocarbon group include methylene, methylmethylene, dimethylmethylene, 1,2-ethylene, 1,3-
Alkylene groups such as trimethylene, 1,4-tetramethylene, 1,2-cyclohexylene, and 1,4-cyclohexylene; arylalkylene groups such as (methyl) (phenyl) methylene and diphenylmethylene; silylene groups; methylsilylene Alkylsilylene groups such as dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methyl (phenyl) silylene, methyl (tolyl)
(Alkyl) (aryl) silylene groups such as silylene; arylsilylene groups such as diphenylsilylene; alkyl oligosilylene groups such as tetramethyldisilylene; germylene groups; having the above divalent hydrocarbon group having 1 to 20 carbon atoms. Examples thereof include an alkylgermylene group in which silicon of a silylene group is substituted with germanium; an (alkyl) (aryl) germylene group; and an arylgermylene group.
Among them, a silylene group having a hydrocarbon group having 1 to 20 carbon atoms, or a germylene group having a hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkylsilylene group,
(Alkyl) (aryl) silylene groups or arylsilylene groups are particularly preferred. Examples of the halogen atom constituting the halogenated hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Specifically, (fluoromethyl) methylmethylene, (difluoromethyl) methylmethylene, (trifluoromethyl) methylmethylene, (4-fluorophenyl) methylmethylene, ditrifluoromethylmethylene, 1,2-ditrifluoromethylethylene, (Fluoromethyl) methylsilylene, (chloromethyl) methylsilylene, di (chloromethyl) silylene, di (trifluoromethyl) silylene, (1,1,
1-trifluoropropyl) methylsilylene, (2-fluorophenyl) methylsilylene, (3-fluorophenyl) methylsilylene, (4-fluorophenyl) methylsilylene, (2-chlorophenyl) methylsilylene,
(3-chlorophenyl) methylsilylene, (4-chlorophenyl) methylsilylene, (2-trifluoromethylphenyl) methylsilylene, (3-trifluoromethylphenyl) methylsilylene, (3-trifluoromethylphenyl) methylsilylene, ( 4-trifluoromethylphenyl) methylsilylene, (3,5-difluorophenyl) methylsilylene, (2,4,6-trifluorophenyl) methylsilylene, (4-fluorophenyl) ethylsilylene, (4-chlorophenyl) ethyl Examples thereof include silylene, (4-fluorophenyl) (chloromethyl) silylene, di (4-fluorophenyl) silylene, di (4-chlorophenyl) silylene, and a germylene group in which silicon of the silylene group is replaced with germanium. .

Examples of the crosslinking group having an oxygen-containing hydrocarbon group include phenoxymethylsilylene, methoxyphenylmethylsilylene, ethoxyethylmethylsilylene, dimethoxyphenylsilylene, diethoxyethylsilylene, and the like.
Various substituted germylene groups are exemplified. Examples of the nitrogen-containing hydrocarbon group-containing crosslinking group include diethylaminoethylmethylsilylene, dimethylaminophenylmethylsilylene, dipyridylsilylene, and the like. Examples of the phosphorus-containing hydrocarbon group-containing cross-linking group include diphenylphosphinoethylmethylsilylene and bis (dimethylphosphinomethyl) silylene.

X and Y each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
A halogenated hydrocarbon group of 20; an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms; an amino group; a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, specifically, a hydrogen atom; a fluorine atom, a chlorine atom, A halogen atom such as a bromine atom or an iodine atom; a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group similar to those described above for R ⁷ and R ⁸ ; an alkoxy group such as methoxy, ethoxy, propoxy, cyclopropoxy and butoxy;
Phenoxy, methylphenoxy, dimethylphenoxy,
1 carbon atom such as an aryloxy group such as naphthoxy and an arylalkoxy group such as phenylmethoxy and naphthylmethoxy
To 20 oxygen-containing hydrocarbon groups; amino groups; alkylamino groups such as methylamino, dimethylamino, ethylamino, and diethylamino; arylamino groups such as phenylamino and diphenylamino; and (alkyl) such as (methyl) (phenyl) amino ) (Aryl) amino groups and other nitrogen-containing hydrocarbon groups having 1 to 20 carbon atoms.
Among them, a hydrogen atom, a halogen atom, a carbon number of 1 to
0 hydrocarbon groups and nitrogen-containing hydrocarbon groups having 1 to 20 carbon atoms are preferable, and further halogen atoms, hydrocarbon groups having 1 to 20 carbon atoms and nitrogen-containing hydrocarbon groups having 1 to 20 carbon atoms are preferable, and in particular, A chlorine atom, a methyl group, an i-butyl group, a phenyl group, a dimethylamino group, and a diethylamino group are preferred.

M represents a transition metal of Groups 3 to 6 of the periodic table, preferably a transition metal of Group 4 of titanium, zirconium and hafnium, more preferably zirconium and hafnium. The transition metal compound represented by the general formula [I] according to the present invention can be synthesized by any method suitable for forming a substituent or a bond. A typical synthetic route is as follows. Note that H ₂ Ra and H ₂ Rb each have the following structure.

[0055]

Embedded image (R ^{1 to} R ⁸ , n and m are the same as described above)

H_TwoRa + n-C_FourH₉Li → HRaLi + C_FourH_Ten H_TwoRb + n-C_FourH₉Li → HRbLi + C_FourH_Ten HRaLi + HRbLi + QCl_Two→ HRa-Q-HR
b + 2LiCl HRa-Q-HRb + 2n-C_FourH₉Li → LiRa-
Q-LiRb + 2C_FourH _Ten LiRa-Q-LiRb + ZrCl_Four→ (Ra-QR
b) ZrCl_Two+ 2LiCl_Two

The production of metal salts of cyclopentadienyl compounds such as the above-mentioned HRaLi and HRbLi may involve, for example, an addition reaction of an alkyl group or an aryl group as described in European Patent No. 679418. It may be synthesized by a method. Specifically, an alkyllithium compound, an aryllithium compound and an azulene compound are reacted in an inert solvent to generate a lithium salt of a dihydroazulenyl compound. Examples of the alkyl lithium compound include methyl lithium, i-propyl lithium, n
-Butyl lithium, t-butyl lithium and the like are used,
Phenyllithium, p-
Chlorophenyllithium, p-fluorophenyllithium, p-trifluoromethylphenyllithium, naphthyllithium and the like are used. As the inert solvent, hexane, benzene, toluene, diethyl ether, tetrahydrofuran, a mixed solvent thereof or the like is used.

The following are non-limiting examples of the transition metal compound represented by the general formula [I] according to the present invention. Although these compounds are simply referred to by their chemical names only, their steric structures mean both the compounds having asymmetry and the compounds having symmetry according to the present invention. (1) Dichlorodimethylsilylenebis (2-isopropyl-4-phenyl4Hazulenyl) zirconium (2) Dichlorophenylmethylsilylenebis (2-isopropyl-4-phenyl4Hazulenyl) zirconium (3) Dichloro (4-chlorophenyl) methylsilylenebis (2-Isopropyl-4-phenyl 4H azulenyl) zirconium (4) Dichlorodi (chloromethyl) silylenebis (2-
Isopropyl-4-phenyl 4H azulenyl) zirconium dichloride (5) Dichlorodimethylsilylene bis (2-cyclopentyl-4-phenyl 4H azulenyl) zirconium (6) (4-Fluorophenyl) methylsilylene bis (2-cyclopentyl-4-phenyl 4H Azulenyl)
Zirconium (7) Dichlorodimethylsilylene bis (2-isopropyl-4-naphthyl 4H azulenyl) zirconium (8) Dichloro (chloromethyl) methylsilylene bis (2-isopropyl-4-naphthyl 4H azulenyl) zirconium (9) Dichloro (4- Fluorophenyl) methylsilylenebis (2-isopropyl-4-naphthyl4Hazulenyl) zirconium (10) dichloro (4-chlorophenyl) methylsilylenebis (2, isopropyl, 8-methyl-4-phenyl4Hazulenyl) zirconium (11) dichloro Dimethylsilylene bis (2-cyclopropyl, 4-phenyl 4H azulenyl) zirconium (12) Dichlorodimethyl silylene bis (2-cyclobutyl, 4-phenyl 4H azulenyl) zirconium (13) Di Chlorodimethylsilylene bis (2-isopropyl, 4-naphthyl, 4H azulenyl) zirconium (14) Dichlorodimethylsilylene bis (2-isopropyl, 4-anthracenyl 4H azulenyl) zirconium (15) Dichlorodiethylsilylene bis (2-isopropyl, 4- Phenyl 4H azulenyl) zirconium (16) dichlorophenylmethylsilylene bis (2-isopropyl, 4-phenyl 4H azulenyl) zirconium (17) dichloro, 1,2-ethylenebis (2-isopropyl, 4-phenyl 4H azulenyl) zirconium (18) Dichloro, 2,3-butylenebis (2-isopropyl, 4-phenyl 4H azulenyl) zirconium (19) Dichloro, isopropylidene bis (2-isopropyl, 4-phenyl 4H azulene) ) Zirconium (20) dimethyl, dimethylsilylene bis (2-cyclopropyl-4-phenyl-4H-azulenyl) zirconium (21) dibenzyl, dimethylsilylenebis (2-cyclopropyl-4-phenyl-4H-azulenyl) zirconium

In the above compound, one or both of the dichlorides forming the X and Y parts in the general formula [I] are a hydrogen atom, a bromine atom, an iodine atom, a methyl group, a phenyl group, a fluorophenyl group, Compounds replacing benzyl, methoxy, dimethylamino and diethylamino groups can also be exemplified. In addition, instead of zirconium as the central metal of the compound exemplified above, yttrium, lanthanum, scandium, titanium, hafnium,
Compounds changed to tantalum, niobium, vanadium, tungsten, and molybdenum can also be exemplified.

Catalyst component (B) The catalyst component (B) reacts with [(B) -1] aluminum oxy compound and [(B) -2] catalyst component (A) to convert the catalyst component (A) into a cation. It is an ionic compound or Lewis acid that can be converted, an ion-exchangeable layered compound other than [(B) -3] silicate, or an inorganic silicate. Certain Lewis acids can also be regarded as "ionic compounds capable of converting the catalyst component (A) into cations by reacting with the catalyst component (A)". Therefore, "Lewis acid"
Compounds that belong to both the ionic compound and the ionic compound capable of converting the catalyst component (A) into a cation by reacting with the catalyst component (A) are to be understood as belonging to either one. As the component [(B) -1] aluminum oxy compound, specifically, the following general formulas [II] and [III]
] Or [IV].

[0061]

Embedded image

In each of the above formulas, R ¹¹ and R ¹² represent a hydrogen atom, a hydrocarbon residue or a halogenated hydrocarbon group, preferably a C 1-10, particularly preferably a C 1-6 hydrocarbon residue. Represents a group. The plurality of R ¹¹ may be the same or different. p represents an integer of 0 to 40, preferably 2 to 30. The compounds of the general formulas [II] and [III]
A compound also called alumoxane, which is obtained by reacting one kind of trialkylaluminum or two or more kinds of trialkylaluminums with water. Specifically, (a) methylalumoxane, ethylalumoxane obtained from one kind of trialkylaluminum and water,
Examples thereof include propylalumoxane, butylalumoxane, isobutylalumoxane, and (b) methylethylalumoxane, methylbutylalumoxane, and methylisobutylalumoxane obtained from two kinds of trialkylaluminums and water. Of these, methylalumoxane and methylisobutylalumoxane are preferred.

The above-mentioned alumoxanes can be used in combination of two or more in each group and between each group. The above alumoxane can be prepared under various known conditions. Specifically, the following method can be exemplified. (A) A method of directly reacting trialkylaluminum with water using a suitable organic solvent such as toluene, benzene or ether. (B) Salt hydrate having trialkylaluminum and water of crystallization, for example, water of copper sulfate or aluminum sulfate (C) Method of reacting trialkylaluminum with water impregnated in silica gel, etc. (d) Mixing trimethylaluminum and triisobutylaluminum and adding an appropriate organic solvent such as toluene, benzene, ether, etc. (E) A method in which trimethylaluminum and triisobutylaluminum are mixed and heated and reacted with a salt hydrate having water of crystallization, for example, copper sulfate, aluminum sulfate and a hydrate (f) Silica gel, etc. Impregnated with water and treated with triisobutylaluminum Then, a method of additional treatment with trimethylaluminum (g) A method of synthesizing methylalumoxane and isobutylalumoxane by a known method, mixing these two components in a predetermined amount, and causing a heat reaction (h) Aromatic substances such as benzene and toluene A salt having water of crystallization such as copper sulfate pentahydrate is added to a hydrocarbon solvent,
Method of reacting with trimethylaluminum at a temperature of about 40 ° C.

The amount of water used in the reaction is usually 0.5 to 1.5 in molar ratio to trimethylaluminum. The methylalumoxane obtained by the above method is a linear or cyclic organoaluminum polymer. The compound represented by the general formula [IV] is composed of one type of trialkylaluminum, or two or more types of trialkylaluminums, and 10: 1 to 1: (alkyl) boronic acid represented by the following general formula [V]. It can be obtained by a reaction of 1 (molar ratio). In the general formula [V], R ¹² represents a hydrogen atom having 1 to 10 carbon atoms, preferably a hydrocarbon residue having 1 to 6 carbon atoms or a halogenated hydrocarbon group.

[0065]

Embedded image R ¹² B- (OH) ₂ [V]

Specifically, the following reaction products can be exemplified. (A) Trimethylaluminum and methylboronic acid 2:
(B) 2: 1 reaction product of triisobutylaluminum and methylboronic acid (c) 1: 1: 1 reaction product of trimethylaluminum, triisobutylaluminum and methylboronic acid (d) 2: 2 reaction of trimethylaluminum and methylboronic acid
1 Reactant (e) Triethylaluminum and butylboronic acid 2:
1 Reactant The ionic compound capable of converting the component (A) into a cation by reacting with the component (A) of the component [(B) -2] is a compound represented by the general formula [VI]. Is mentioned.

[0067]

[K] ^{e +} [Z] ^e- [VI]

In the general formula [VI], K is an ionic cation component, and examples thereof include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation. In addition, cations of metals which are easily reduced by themselves, cations of organic metals, and the like can also be mentioned. Specific examples of the above cation include triphenylcarbonium, diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium, tripropylammonium, tributylammonium, N, N
-Dimethylanilinium, dipropylammonium, dicyclohexylammonium, triphenylphosphonium, trimethylphosphonium, tri (dimethylphenyl) phosphonium, tri (methylphenyl) phosphonium, triphenylsulfonium, triphenyloxonium, triethyloxonium, pyrylium and silver Ion, gold ion, platinum ion, copper ion, palladium ion, mercury ion, ferrocenium ion and the like.

Z in the above general formula [VI] is an ionic anion component, which is a component (generally a non-coordinating component) which becomes a counter anion to the converted cation species in component (A). . Examples of Z include an organic boron compound anion, an organic aluminum compound anion, an organic gallium compound anion, an organic phosphorus compound anion, an organic arsenic compound anion, an organic antimony compound anion, and the like, and specific examples include the following compounds. .

(A) Tetraphenylboron, tetrakis (3,4,5-trifluorophenyl) boron, tetrakis (3,5-di (trifluoromethyl) phenyl) boron, tetrakis (3,5-di (t- Butyl) phenyl) boron, tetrakis (pentafluorophenyl) boron, etc. (b) tetraphenylaluminum, tetrakis (3,3)
4,5-trifluorophenyl) aluminum, tetrakis (3,5-di (trifluoromethyl) phenyl) aluminum, tetrakis (3,5-di (t-butyl) phenyl) aluminum, tetrakis (pentafluorophenyl) aluminum, etc. (C) tetraphenylgallium, tetrakis (3,4,
5-trifluorophenyl) gallium, tetrakis (3,5-di (trifluoromethyl) phenyl) gallium, tetrakis (3,5-di (t-butyl) phenyl)
Gallium, tetrakis (pentafluorophenyl) gallium, etc. (d) tetraphenyl phosphorus, tetrakis (pentafluorophenyl) phosphorous, etc. (e) tetraphenyl arsenic, tetrakis (pentafluorophenyl) arsenic, etc. (f) tetraphenyl antimony, tetrakis (penta) (G) decaborate, undecaborate, carbado decaborate, decachloro decaborate, etc.

The Lewis acid, particularly the catalyst component (A), is
Lewis acids that can be converted to thiones include various organic
Iodine compounds, metal halides, solid acids, or
On-exchangeable layered silicates are exemplified.
Include the following compounds. (A) triphenylboron, tris (3,5-difluoro
Lophenyl) boron, tris (pentafluorophenyl)
B) Organic boron compounds such as boron (b) aluminum chloride, aluminum bromide, aluminum iodide
Luminium, magnesium chloride, magnesium bromide, yo
Magnesium iodide, magnesium chlorobromide, chloroiodide
Magnesium, magnesium bromide iodide, magnesium chloride
Hydride, magnesium chloride hydroxy
, Magnesium bromide hydroxide, magnesium chloride
Alkoxide, magnesium bromide alkoxide, etc.
Metal halide compounds (c) Solid acids such as silica-alumina, alumina, etc., Component [(B) -3]
Hexagonal close packing type, antimony type, CdCl_TwoType,
CdI_TwoIon crystallization with layered crystal structure such as mold
And specific examples thereof include α-Zr (HA
sO_Four)_Two・ H _TwoO, α-Zr (HPO_Four)_Two, Α-Z
r (KPO_Four)_Two・ 3H_TwoO, α-Ti (HP
O_Four)_Two, Α-Ti (HAsO_Four)_Two・ H_TwoO, α-S
n (HPO_Four)_Two・ H_TwoO, γ-Zr (HPO_Four)_Two,
γ-Ti (HPO_Four)_Two, Γ-Ti (NH _FourPO_Four)_Two
・ H_TwoCrystalline acidic salts of polyvalent metals such as O are mentioned.

The above ionic exchangeable layered compound may be used after being subjected to a salt treatment and / or an acid treatment, if necessary. In a state where neither salt treatment nor acid treatment has been applied,
An ion-exchangeable layered compound other than silicate is a compound having a crystal structure in which planes formed by ionic bonds and the like are stacked in parallel with a weak bonding force, and contained ions can be exchanged.

Examples of the inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. These may use synthetic products, or may use naturally occurring minerals. Specific examples of clay and clay minerals include allophane group such as allophane, dickite, nacrite, kaolinite, kaolin group such as anoxite, metahaloisite, halloysite group such as halloysite, chrysotile,
Razardite, serpentine family such as antigorite, montmorillonite, sauconites, beidellite, nontronite, saponite, smectites such as hectorite, vermiculite minerals such as vermiculite, mica minerals such as illite, sericite, chlorite, attapulgite, Sepiolite, paigorskite, bentonite, kibushi clay, gairome clay, hisingelite, pyrophyllite,
Ryokudei stone group and the like. These may form a mixed layer. Examples of the artificially synthesized product include synthetic mica, synthetic hectorite, synthetic saponite, and synthetic teniolite.

Among the above inorganic silicates, kaolins such as deckite, nacrite, kaolinite, and anoxite; halosites such as metahalosite and halosite; serpentine stones such as chrysotile, lizardite, and antigolite Tribe, montmorillonite, zaukonite, beidellite, nontronite, smectites such as saponite, hectorite, vermiculite minerals such as vermiculite, illite, sericite, mica minerals such as chlorite, synthetic mica, synthetic hectorite, synthetic saponite, synthetic Teniolite is preferred, smectites such as montmorillonite, sauconites, beidellite, nontronite, saponite, hectorite, vermiculite minerals such as vermiculite, synthetic mica, synthetic hectorite, synthetic saponite, and synthetic tenilite. Light is more preferable. These may be used as they are without any special treatment,
It may be used after processing such as ball milling and sieving. Further, they may be used alone or as a mixture of two or more.

The above-mentioned ion-exchangeable layered compound and inorganic silicate can change the acid strength of the solid by salt treatment and / or acid treatment. In the salt treatment, the surface area and the interlayer distance can be changed by forming an ion complex, a molecular complex, an organic derivative, and the like. That is, by using the ion exchange property and replacing the exchangeable ions between the layers with another large bulky ion, a layered material in which the layers are expanded can be obtained.

The cation of the exchangeable metal contained in the compound which has not been subjected to the above pretreatment is not less than 40%, preferably not less than 60%, with the cation dissociated from the following salts and / or acids. Is preferred. The salt used for the ion exchange is a compound containing a cation containing at least one atom selected from the group consisting of atoms of groups 1 to 14, and preferably 1 to 14
A compound comprising at least one cation containing at least one atom selected from the group consisting of group atoms and at least one anion selected from the group consisting of halogen atoms, inorganic acids, and organic acids; a cation comprising at least one atom selected from the group consisting to 14 group atoms, Cl, Br, I, F , PO 4, SO 4, NO 3,
CO ₃ , C ₂ O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ C
OCHCOCH ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (C
lO ₄ ) ₂ , O (SO ₄ ), OH, O ₂ Cl ₂ , OCl
₃ , a compound comprising at least one anion selected from the group consisting of OOCH, OOCCH ₂ CH ₃ , C ₂ H ₄ O ₄ and C ₆ H ₅ O ₇ . Further, two or more of these salts may be used simultaneously.

The acid used for the above ion exchange is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid.
Two or more kinds may be used simultaneously. As a method of combining the salt treatment and the acid treatment, there are a method of performing the salt treatment and then the acid treatment, a method of performing the acid treatment and then performing the salt treatment, and a method of simultaneously performing the salt treatment and the acid treatment. In addition,
The acid treatment removes impurities on the surface, and has a crystal structure of Al,
This has the effect of eluting some cations such as Fe, Mg, and Li.

The conditions for the treatment with salts and acids are not particularly limited, but usually the concentration of salts and acids is 0.1 to 30.
It is preferable that the treatment is carried out under the conditions that the weight%, the treatment temperature is from room temperature to the boiling point of the solvent used, the treatment time is from 5 minutes to 24 hours, and at least a part of the compound to be treated is eluted. Also,
Salts and acids are generally used in aqueous solution. When performing the above-mentioned salt treatment and / or acid treatment, shape control may be performed by pulverization, granulation, or the like before, during, or after the treatment. Further, another chemical treatment such as an alkali treatment or an organic substance treatment may be used in combination. The component thus obtained has a pore volume of not less than 0.1 cc / g, particularly not less than 0.3 to 5 cc / g, having a pore volume with a radius of 20 ° or more measured by a mercury intrusion method.
Are preferred. Such component [(B) -3] usually contains adsorbed water and interlayer water. Here, the adsorbed water refers to water adsorbed on the surface of an ion-exchangeable layered compound other than silicate or an inorganic silicate or a crystal fracture surface, and the interlayer water is water existing between crystal layers.

In the present invention, the component [(B) -3]
It is preferable to use after removing the above-mentioned adsorbed water and interlayer water. The dehydration method is not particularly limited, and methods such as thermal dehydration, thermal dehydration under a gas flow, thermal dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. The heating temperature is set to a temperature range in which interlayer water does not remain.
The temperature is set to 0 ° C. or higher, preferably 150 ° C. or higher, but high temperature conditions that cause structural destruction are not preferable. The heating time is at least 0.5 hour, preferably at least 1 hour. At this time, the moisture content of the component [(B) -3] after dehydration and drying is 3% when the moisture content when dehydrated for 2 hours at a temperature of 200 ° C. and a pressure of 1 mmHg is 3% by weight. It is preferable that the content be not more than weight%. In the present invention, when the component [(B) -3] which has been dehydrated and adjusted to have a water content of 3% by weight or less is used, when the component (B) -3 comes into contact with the essential component (A) and the optional component (D) described later. Also, it is important to be treated so as to maintain the same moisture content.

[0080]Optional component (C) The fine particle carrier as the optional component (C) may be inorganic or organic.
5 μm to 5 mm, preferably 1 μm
Granular or fine particles having a particle size of 0 to 2 mm
It is a carrier. Examples of the inorganic carrier include, for example, SiO 2
_Two, Al_TwoO_Three, MgO, ZrO, TiO_Two, B
_TwoO_Three, ZnO, and other oxides, SiO_Two-MgO, Si
O_Two-Al _TwoO_Three, SiO_Two-TiO_Two, SiO_Two-C
r_TwoO_Three, SiO_Two-Al_TwoO_Three-Complex oxidation of MgO, etc.
Objects and the like.

Examples of the organic carrier include (co) polymers of α-olefins having 2 to 14 carbon atoms such as ethylene, propylene 1-butene and 4-methyl-1-pentene, styrene, divinylbenzene and the like. And a porous polymer fine particle carrier comprising a (co) polymer of an aromatic unsaturated hydrocarbon. Their specific surface areas are between 20 and 1000
m ² / g, preferably 50~700m ² / g, a pore volume of 0.1 cm ² / g or more, preferably 0.3cm
² / g, more preferably 0.8 cm ² / g or more.

Component (D) An example of the organoaluminum compound as the optional component (D) is represented by the following general formula [VII].

[0083]

[Of 18] ^{_{AlR 13 a P 3-a [}} VII]

In the general formula [VII], R ¹³ has 1 to 2 carbon atoms.
0 represents a hydrocarbon group, P represents hydrogen, a halogen, or an alkoxy group, and a represents an integer greater than 0 and 3 or less. Specific examples of the organoaluminum compound represented by the general formula [VII] include trialkylaluminums such as trimethylaluminum, triethylaluminum, tripropylaluminum, and triisobutylaluminum; halogens such as diethylaluminummonochloride and diethylaluminummonomethoxide. Or an alkoxy-containing alkyl aluminum. Of these, trialkylaluminum is preferred. In the catalyst of the present invention, aluminoxanes such as methylaluminoxane can be used as the component (D).

The catalyst for olefin polymerization in the present invention comprises:
Optional components other than the fine particle carrier include, for example, active hydrogen-containing compounds such as H ₂ O, methanol, ethanol, and butanol; electron-donating compounds such as ethers, esters, and amines; phenyl borate; dimethylmethoxyaluminum;
It can contain an alkoxy-containing compound such as phenyl phosphite, tetraethoxysilane, diphenyldimethoxysilane, and the like.

The olefin polymerization catalyst of the present invention excludes an aluminum oxy compound, an ionic compound capable of reacting with the catalyst component (A) to convert the catalyst component (A) into a cation, or a Lewis acid or silicate. The ion-exchange layered compound or the inorganic silicate can be used alone as the catalyst component (B), or can be used in an appropriate combination of these three components. One or more of the lower alkylaluminum, halogen-containing alkylaluminum, alkylaluminum hydride, alkoxy-containing alkylaluminum, and aryloxy-containing alkylaluminum are optional components, but may be an aluminum oxy compound, an ionic compound or It is preferable to include it in the olefin polymerization catalyst in combination with the Lewis acid.

The olefin polymerization catalyst according to the present invention may be used in the presence or absence of the monomer to be polymerized inside or outside the polymerization tank, in the presence of the above components (A) and (B).
Can be prepared by contact. That is, the components (A) and (B) and, if necessary, the component (D) and the like may be separately introduced into the polymerization tank, or the components (A) and (B) may be contacted in advance and then polymerized. It may be introduced into the tank. Alternatively, the mixture of the component (A) and the component (B) may be impregnated with the component (C) and then introduced into the polymerization tank. Further, the components (A), (B) and (D) may be used after being brought into contact simultaneously, or the respective components may be sequentially reacted.

The above components may be brought into contact with each other in an inert gas such as nitrogen or an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene or xylene. The contact temperature is between -20 ° C and the boiling point of the solvent, preferably between 0 ° C and the boiling point of the solvent. The catalyst thus prepared may be used without washing after preparation,
It may be used after washing. Further, new components may be used in combination as needed after preparation.

When the components (A), (B) and (C) or (D) are brought into contact with each other in advance, a monomer to be polymerized is present to polymerize a part of the α-olefin. Polymerization can also be performed. That is, before polymerization, olefins such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane and styrene are preliminarily prepared. A prepolymerized product that has been polymerized and optionally washed can be used as a catalyst.

The preliminary polymerization is preferably carried out in an inert solvent under mild conditions, and the amount of the prepolymerization is 0.1 g / g of the solid catalyst.
It is desirable to carry out the reaction so as to produce from 01 to 1000 g, preferably from 0.1 to 100 g, of the polymer. The amounts of component (A) and component (B) used are arbitrary. For example, in the case of solvent polymerization, the amount of component (A) used is 10 as transition metal atoms.
The range is preferably ^{-7 to} 102 mmol / L, more preferably 10 ^-4 to 1 mmol / L. In the case of an aluminum oxy compound, the molar ratio of Al / transition metal is usually 10
~ 100,000, preferably 100-20,000,
More preferably, it is in the range of 100 to 10,000.
On the other hand, when an ionic compound or Lewis acid is used as the component (B), the molar ratio thereof to the transition metal is usually 0.1 to 1,000, preferably 0.5 to 100,
More preferably, it is in the range of 1 to 50.

When an ion-exchangeable layered compound other than silicate or an inorganic silicate and an organic aluminum compound as an optional component (D) are used, it can be handled in the same manner as the other components (B). The contact method is not particularly limited,
The following method can be exemplified. a) Contacting the component (A) with the component [(B) -3]. b) The component (D) is added after the component (A) is brought into contact with the component [(B) -3]. c) After contacting the component (A) with the component (D), the component [(B) -3] is added. d) The component (A) is added after the component [(B) -3] is brought into contact with the component (D). In addition, the three components may be contacted simultaneously.

At the time of contacting each of the above components, a fine particle carrier which is an optional component (C) may coexist, or after contacting with each of the above components, it may be brought into contact with the fine particle carrier. The use amount of each of the above components is such that the component (A) is usually 0.0001 to 10 mmol, preferably 0.001 to 5 mmol per 1 g of the component [(B) -3], and the component (D) is 0.1%.
01 to 10,000 mmol, preferably 0.1 to 10
0 mmol. The atomic ratio of the transition metal in the component (A) to the aluminum in the component (D) is usually 1: 0.0
1 to 1,000,000, preferably 1: 0.1 to 10
It is 0000. The catalyst thus prepared is
It may be used without washing after preparation, or may be used after washing. Further, if necessary, the component (D) may be newly used in combination. The amount of the component (D) used at this time is 1: 0 to 10,000 by the atomic ratio of the aluminum in the component (D) to the transition metal in the component (A).
It is chosen to be zero.

Before the polymerization, ethylene, propylene, 1-
Butene, 1-hexene, 1-octene, 4-methyl-1
An olefin such as -pentene, 3-methyl-1-butene, vinylcycloalkane, styrene or the like is preliminarily polymerized and, if necessary, washed, can be used as a catalyst. This preliminary polymerization is preferably carried out in an inert solvent under mild conditions, and is preferably 0.01 to 1 g per solid catalyst.
It is desirable to carry out the reaction so as to produce 1,000 g, preferably 0.1 to 100 g, of the polymer.

Next, a method for producing a propylene polymer according to the present invention will be described. In the present invention, polymerization or copolymerization is carried out by bringing the aforementioned catalyst into contact with an α-olefin. The catalyst in the present invention is applied not only to solvent polymerization using a solvent but also to liquid phase solventless polymerization, gas phase polymerization, and melt polymerization substantially using no solvent. Further, the polymerization system may be either continuous polymerization or batch polymerization.

Solvents for the solvent polymerization include hexane, heptane, pentane, cyclohexane, benzene,
Inert saturated fatty acids or aromatic hydrocarbons, such as toluene, alone or in mixtures are used. The polymerization temperature is usually -78 to 250C, preferably -20 to 100C. There is no limitation on the polymerization method as long as a polymer having the characteristics of the present invention can be obtained. The olefin pressure of the reaction system is not particularly limited, but is preferably from normal pressure to 2000 kg.
f / cm ² , more preferably from normal pressure to 50 kg / cm ²
・ It is in the range of G. Further, for example, the molecular weight can be adjusted by known means such as selection of temperature and pressure or introduction of hydrogen.

[0096]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist. In the following examples, the catalyst synthesis step and the polymerization step were all performed under a purified nitrogen atmosphere, and the solvent was dehydrated with MS-4A, and then deaerated by bubbling with purified nitrogen before use. (1) MFR measurement: heat stabilizer (BH
6 g of an acetone solution (0.6% by weight) of T) were added.
Next, after drying the above-mentioned polymer, it was charged into a melt indexer (230 ° C.) and dried under a load of 2.16 kg.
Let stand for minutes. Thereafter, the amount of the polymer extruded was measured, converted into the amount per 10 minutes, and used as the MFR value. (2) Measurement of molecular weight distribution: Determined by the ratio (Q value) between the weight average molecular weight (Mw) obtained by GPC and the number average molecular weight (Mn) (both in terms of polypropylene). GP
As the C apparatus, “150CV type” manufactured by Waters was used. Ortho-dichlorobenzene was used as the solvent, and the measurement temperature was 135 ° C.

(3) Measurement of melting point: DSC (“TA2000” manufactured by DuPont) was used at 20 ° C./min at 10 ° C./min.
The temperature was determined by measuring the temperature at the second time after the temperature was raised and lowered to 00 ° C. once. (4) Measurement of ¹³ C-NMR and ¹ H-NMR of polymer The ¹³ C-NMR spectrum of the polymer (MK-3-93) was 100 m in a 10 mmΦ NMR measurement sample tube.
g sample was completely dissolved in a solvent obtained by adding about 0.5 ml of deuterated benzene as a lock solvent to about 2.0 ml of o-dichlorobenzene, and measured at 130 ° C. by a proton complete decoupling method. As the measurement conditions, a flip angle of 65 ° and a pulse interval of 5T ₁ or more (T ₁ is the longest value among the spin lattice relaxation times of the methyl group) were selected. Since T ₁ of the methylene group and the methine group is shorter than the methyl group in the propylene polymer, the recovery of the magnetization of all carbons is 99% or more under these measurement conditions. ¹ H-NMR was also measured using a sample prepared in the same manner.

The ¹³ C-NMR chemical shift was set as 21.8 ppm for the third group of methyl group of 5 propylene units in which head-to-tail bond and methyl group branching direction were the same, and 21.8 ppm for other carbon peaks. The chemical shift was based on this.
The chemical shift based on this standard almost coincides with the value based on the standard based on the signal of tetramethylsilane being 0.0 ppm and the standard based on the standard based on 2.0 ppm for hexamethyldisiloxane. ^{The 1} H-NMR chemical shift was set such that the signal on the high magnetic field side of o-dichlorobenzene was 6.94 ppm, and the chemical shifts of the other hydrogen peaks were based on this.

Example-1 Polymerization Data of Hf / Clay (1) Chemical Treatment of Clay Minerals 10 g of montmorillonite ("Kunipia F" manufactured by Kunimine Kogyo KK) in dilute sulfuric acid consisting of 10 g of sulfuric acid and 90 ml of demineralized water.
Was dispersed, heated to the boiling point, and then stirred for 6 hours. Thereafter, the collected montmorillonite was sufficiently washed with demineralized water, preliminarily dried, and then dried at 200 ° C. for 2 hours to obtain a chemically treated clay mineral. To 200 mg of the chemically treated montmorillonite, a concentration of 0.4 mol /
0.8m3 of triethylaluminum in toluene
was added and stirred at room temperature for 1 hour. Thereafter, the slurry was washed with toluene to obtain a slurry of 33 mg clay mineral / ml toluene.

(2) Polymerization of propylene 0.25 mmol of triisobutylaluminum (manufactured by Tosoh Akzo Co., Ltd.) in a 1 L stirred autoclave.
(In terms of Al atoms) was introduced. On the other hand, 1.4 mg of dichlorodimethylsilanediylbis (2-isopropyl, 4-phenyl 4H azulenyl) hafnium diluted with toluene was introduced into a catalyst feeder with a rupture plate, and the triethylaluminum obtained in Example 1 (1) was further introduced. 50 mg of the treated montmorillonite and 0.015 mmol of triisobutylaluminum (in terms of Al atom) were introduced. Thereafter, 700 ml of propylene was introduced into the autoclave, the rupture plate was cut at room temperature, and the temperature was raised to 80 ° C., followed by polymerization for 1 hour. As a result, 16.5 g of a polymer was obtained. The complex activity was 1.4 × 10 ⁴ g-polymer / g-complex, the catalytic activity was 0.3 × 10 ³ g-polymer / g-catalyst, and the MFR of the polymer was 312 (g / 10
Min), melting point is 156.6 ° C., Mw is 0.93 × 10 ⁵ ,
Q was 2.6. [Mrm] of the polymer is 6.5
No mol%, 2,1-bond was detected, and 1,3-bond was 0.05 mol%. [1-Pr-Δ] = 0.014 mol% [i-Bu-Δ] = 0.024 mol% [1-Pr-Δ] _db = 17.7 mol% [i-Bu-Δ] _db = 31.0 mol% [1-Pr-Δ] / [i-Bu-Δ] = 36.4 / 6
3.6

Example-2 Polymerization Data of Hf / MAO at Low Pressure Toluene 20 was placed in a stirred autoclave having an internal volume of 1 L.
0 ml was introduced, the temperature was raised to 40 ° C., and methyl alumoxane (MMAO, manufactured by Tosoh Akzo Co., Ltd.) 38 mmol (Al
Subsequently, after introducing propylene, the temperature was raised to 50 ° C., and the propylene pressure was maintained at 1 kg / cm ² . On the other hand, 6 mg of dichlorodimethylsilanediylbis (2-isopropyl, 4-phenyl 4H azulenyl) hafnium diluted with toluene was introduced into a catalyst feeder with a rupturable plate.
The rupture disk was cut, and a polymerization operation was performed for 4 hours while maintaining the pressure. As a result, 9.2 g of a polymer was obtained. The complex activity was 1.0 × 10 ² g-polymer / g-complex, the melting point was 114.2 ° C., and the Mw was <5.6 × 10 ³ .
[Mrrm] = 7.0 mol%. 2,1-bond and 1,
3- No binding was detected. [1-Pr-Δ] = 0.52 mol% [i-Bu-Δ] = 0.89 mol% [1-Pr-Δ] _db = 24.5 mol% [i-Bu-Δ] _db = 42 0.2 mol% [1-Pr-Δ] / [i-Bu-Δ] = 36.7 / 6
3.3

[0102]

According to the present invention described above, the present invention provides a polymer having a high isotactic triad fraction and having a terminal vinyl having a specific structure. A propylene polymer having such characteristics is expected to be polymerizable with respect to an olefin catalyst, despite being excellent in rigidity, heat resistance, moldability, and gloss.

[Brief description of the drawings]

FIG. 1 is a flowchart for helping the understanding of the invention.

Claims (3)

[Claims] 1. A propylene polymer, which satisfies the following conditions (A), (B), (C) and (D). (A) the proportion of a meso-racemic-racemic-meso chain of 5 propylene units consisting of head-to-tail bonds measured by ¹³ C-NMR is 9 mol% or less; -Containing a propenyl group, (C) having a weight average molecular weight Mw measured by gel permeation chromatography (GPC) in the range of 1,000 to 1,000,000, (D) 2,1- and The total of 1,3-hetero bonds is not more than 0.1 mol%. 2. A propylene polymer having a terminal propenyl group which satisfies the following conditions (A), (B), (C) and (D), contains 35% or more of a propylene polymer having a terminal isobutenyl group. A propylene polymer characterized by being obtained. (A) the proportion of a meso-racemic-racemic-meso chain of 5 propylene units consisting of head-to-tail bonds measured by ¹³ C-NMR is 9 mol% or less; -Containing a propenyl group, (C) having a weight average molecular weight Mw measured by gel permeation chromatography (GPC) in the range of 1,000 to 1,000,000, (D) 2,1- and The total of 1,3-hetero bonds is not more than 0.1 mol%. 3. The following essential catalyst components (A) and (B)
And the propylene polymer according to claim 1, which is an α-olefin polymerization catalyst containing an optional component (C) and / or an optional component (D), if necessary. Catalyst component (B) Aluminum oxy compound, component (A)
At least one substance selected from the group consisting of an ionic compound capable of converting the component (A) into a cation by reacting with a cation, a Lewis acid, an ion-exchangeable layered compound other than silicate, and an inorganic silicate; Component (C) fine particle carrier Optional component (D) organoaluminum compound (In the general formula [I], R ¹ , R ² , R ⁴ , and R ⁵ are each independently a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a silicon-containing hydrocarbon group having 1 to 18 carbon atoms. , R
³ and R ⁶ each independently represent a divalent saturated or unsaturated hydrocarbon group having 3 to 10 carbon atoms which forms a condensed ring with the five-membered ring to which it is bonded. R ⁷ and R ⁸ each independently represent a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon, a nitrogen-containing hydrocarbon, or a phosphorus-containing hydrocarbon. m and n each independently represent an integer of 0 to 20. Q is a bond of two 5-membered rings, at least one of a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, and phosphorus An alkylene group having a containing hydrocarbon group, or at least one of 1 to 2 carbon atoms
0 hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, a silylene group having a phosphorus-containing hydrocarbon group, or at least one of 1 to 20 carbon atoms. And a germylene group having a hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, and a phosphorus-containing hydrocarbon group. X and Y each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing hydrocarbon group having 1 to 20 carbon atoms, an amino group, It represents a nitrogen-containing hydrocarbon group having 1 to 20 carbon atoms, and M represents a transition metal belonging to Groups 3 to 6 of the periodic table. )