JPH08283343A - Propylene elastomer - Google Patents

Abstract

PURPOSE: To obtain a propylene elastomer excellent in rigidity, heat resistance, scratch resistance, transparency, etc., by selecting an elastomer comprising a specified amount of propylene units and a specified amount of 1-butene units and having specified properties. CONSTITUTION: An elastomer comprising 50-95mol% propylene units (A) and 5-50mol% 1-butene units (B) and having such properties that, when the<13> C-NMR spectrum of the side chain CH3 groups of the second unit A of a chain composed of three head-to-tail-bonded As or of a propylene/butene chain composed of three head-to-tail-bonded As and Bs and containing A as the second unit is measured and the total area of the peaks appearing in the range of 19.5-21.9ppm is taken as 100%, the area of the peak appearing in the range of 21.0-21.9ppm is 90% or above, that the intrinsic viscosity is 0.1-12dl/g as measured is decalin at 135 deg., that the molecular weight distribution (Mw/Mn) as determined by GPC is 3 or below, and that the parameter B value representing the randomness of the comonomer chain distribution is 1.0-1.5.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel propylene elastomer having excellent rigidity, heat resistance, scratch resistance, transparency, heat sealability and blocking ability.

[0002]

TECHNICAL BACKGROUND OF THE INVENTION Propylene-based elastomers are used in films, sheets and the like because they are excellent in scratch resistance, transparency, heat resistance and heat sealability.

Among such propylene-based elastomers, the propylene-based elastomer, which is a copolymer of propylene and 1-butene, is conventionally composed of a solid titanium catalyst or a metallocene compound such as zirconium or hafnium and an alkylaluminoxane. It is manufactured using a metallocene catalyst.

However, the conventional propylene-based elastomer produced as described above is not always sufficient in heat sealability, blocking resistance and heat resistance. Therefore, it has been desired to develop a propylene-based elastomer which is excellent not only in shock absorption, heat resistance, transparency and rigidity but also in heat sealability and blocking resistance.

In view of the above-mentioned conventional techniques, the present inventors have investigated propylene-based elastomers, which are copolymers of propylene and 1-butene, and found that the triad tacticity of the propylene chain portion composed of head-to-tail bonds. (Head-
It has been found that a propylene-based elastomer having a high degree of stereoregularity, which is tail-bonded and has the same branching direction of all methyl groups) and has high stereoregularity. And such a propylene-based elastomer,
By using a specific metallocene compound catalyst component,
The inventors have completed the present invention by finding that they can be manufactured efficiently.

The applicant of the present invention has previously filed Japanese Patent Application Laid-Open No. 62-119.
Japanese Patent No. 212 discloses a propylene-based elastomer in which propylene and other α-olefins are regularly head-to-tail bonded. This propylene-based elastomer is produced using a metallocene compound such as ethylene bis (4,5,6,7-tetrahydro-1-indenyl) zirconium dichloride, and has a composition ( The same comonomer ratio) has a higher melting point.

[0007]

OBJECTS OF THE INVENTION It is an object of the present invention to provide a novel propylene elastomer having excellent rigidity, heat resistance, scratch resistance, transparency, heat sealability and blocking ability.

[0008]

SUMMARY OF THE INVENTION The propylene elastomer according to the present invention comprises (1) a unit derived from propylene in an amount of 50 to 95 mol% and a unit derived from 1-butene in an amount of 5 to 50 mol%. , (2) (i) head-to-tail linked propylene unit 3 chains, or
(ii) Side chain methyl group of the propylene unit of the second unit in the propylene / butene 3 chain which is composed of head-to-tail bonded propylene units and butene units and contains propylene units in the second unit ¹³ C- When the NMR spectrum (hexachlorobutadiene solution, tetramethylsilane standard) was measured and the total area of the peaks appearing at 19.5 to 21.9 ppm was taken as 100%, the area of peaks appearing at 21.0 to 21.9 ppm Is 90% or more, and (3) the intrinsic viscosity measured in decalin at 135 ° C. is 0.1.
1 to 12 dl / g, (4) gel permeation chromatography (GP
The molecular weight distribution (Mw / Mn) determined by C) is 3 or less, and (5) the parameter B value showing the randomness of the copolymerized monomer chain distribution is 1.0 to 1.5. .

The propylene elastomer according to the present invention has the above-mentioned (5) parameter B value of 1.0 to 1.3.
And (6) the melting point Tm measured by a differential scanning calorimeter is 6
The melting point Tm is 0 to 140 ° C., and the relationship between the 1-butene constitutional unit content M (mol%) is −2.6 M + 125.
≤ Tm ≤ -2.6M + 145, and (7) the relationship between the crystallinity C measured by the X-ray diffraction method and the 1-butene constitutional unit content M (mol%) is C ≥ -1.5M + 65. Is desirable.

The propylene elastomer according to the present invention as described above comprises [A] a metallocene compound represented by the following general formula (A), [B] [B-1] an organoaluminum oxy compound, and / or
Alternatively, in the presence of an olefin polymerization catalyst containing [B-2] a compound which reacts with the metallocene compound [A] to form an ion pair, and optionally [C] an organoaluminum compound,
The propylene-based elastomer according to claim 1 or 2, which is obtained by copolymerizing propylene and 1-butene;

[0011]

Embedded image

[Wherein M is a transition metal atom of Groups IV to VIB of the Periodic Table, and R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, a halogen atom, or a C 1-20 carbon atom] Hydrocarbon radical,
It is a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and some of the groups adjacent to each other are bonded to each other to form these groups. A ring may be formed together with the carbon atom to be bonded, X ¹ and X ² may be the same or different from each other, and a hydrogen atom, a halogen atom, and a carbon number of 1 to 20.
Is a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, and Y is a divalent hydrocarbon group having 1 to 20 carbon atoms or 2 having 1 to 20 carbon atoms. Valent halogenated hydrocarbon group, divalent silicon-containing group, divalent germanium-containing group, -O-, -CO-, -S-, -S
_{O -, - SO 2 -,} - NR 7 -, - P (R 7) -, - P
^{(O) (R 7) -} , - BR 7 - or -AlR ⁷ - (provided that R ⁷ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group of 1 to 20 carbon atoms )
Is. ].

In the present invention, among the metallocene compounds [A] represented by the formula (A), those represented by the following general formula [I] or [II] are preferable.

[0014]

[Chemical 6]

[Wherein M is IVB, VB, VIB of the periodic table]
R ¹¹ and R ¹² may be the same or different from each other, are the same as R ¹ in the formula (A), and R ¹³ and R ¹⁴ may be the same or different from each other. Often, it is an alkyl group or an aryl group having 1 to 20 carbon atoms, and X ¹ , X ² , and Y are the same as those in the above formula (A). ]

[0016]

[Chemical 7]

[Wherein M is a transition metal of Group IVB of the periodic table, R ²¹ may be the same or different from each other,
A hydrogen atom, a halogen atom, optionally halogenated alkyl group having 1 to 10 carbon atoms, an aryl group, or -NR ₂ of 6 to 10 carbon atoms, -SR, -OSiR _3, -SiR ₃
Or -PR ₂ group (provided that R is a halogen atom, carbon number 1)
Alkyl group of 10 to 10 or aryl group of 6 to 10 carbon atoms), R ^{22 to} R ²⁸ are the same as those of R ²¹ described above, or adjacent R ^{22 to} R ²⁸ together with the atom to which they are bonded. , An aromatic ring or an aliphatic ring may be formed, and X ³ and X ⁴ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. Alkoxy group, C6-C10 aryl group, C6-C10 aryloxy group, C2-1
0 alkenyl group, C7-40 arylalkyl group, C7-40 alkylaryl group, C8-
40 arylalkenyl groups, OH groups or halogen atoms,

[0018]

Embedded image

-Sn-, -O-, -S-, = SO, = S
O ₂ , = NR ²⁹ , = CO, = PR ²⁹ or = P (O) R
²⁹ . (However, R ²⁹ and R ³⁰ may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Group, carbon number 6-10
Fluoroaryl group, alkoxy group having 1 to 10 carbon atoms, alkenyl group having 2 to 10 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, arylalkenyl group having 8 to 40 carbon atoms or alkyl having 7 to 40 carbon atoms It may be an aryl group or R ²⁹ and R ³⁰ may each form a ring with the atoms to which they are attached, and M ² is silicon, germanium or tin. )].

[0020]

DETAILED DESCRIPTION OF THE INVENTION The propylene-based elastomer according to the present invention will be specifically described below. (1) The propylene-based elastomer according to the present invention is a random copolymer of propylene and 1-butene, and has 50 to 95 mol% of units derived from propylene, preferably 6 units.
0-93 mol%, more preferably 70-90 mol%, containing 1-butene derived units in an amount of 5-50 mol%, preferably 7-40 mol%, more preferably 10-30 mol%. ing.

The propylene-based elastomer may contain a small amount of units derived from olefins other than propylene and 1-butene, for example, 10 mol% or less, preferably 5 mol% or less.

(2) Stereoregularity of Propylene Elastomer (Triad Tacticity: mm Fraction) The stereoregularity of the propylene elastomer according to the present invention can be evaluated by triad tacticity (mm fraction). it can.

The mm fraction is defined as the proportion of methyl groups having the same branching direction when the three head-to-tail bonded propylene unit chains present in the polymer chain are represented by a surface zigzag structure. It is determined from the ¹³ C-NMR spectrum as described below.

When the mm fraction is determined from a ¹³ C-NMR spectrum, specifically, as the three chains containing propylene units present in the polymer chain, (i) three chains of head-to-tail bonded propylene units, and (ii) The mm fraction is measured for a propylene unit / butene unit 3 chain consisting of head-to-tail bonded propylene units and butene units and the second unit being a propylene unit.

The mm fraction can be determined from the peak intensity of the side chain methyl group of the second unit (propylene unit) in these three chains (i) and (ii). The details will be described below. The ¹³ C-NMR spectrum of the propylene-based elastomer is measured by the complete proton decoupling method at 120 ° C. after completely dissolving the propylene-based elastomer in hexachlorobutadiene containing a small amount of deuterated benzene as a lock solvent in a sample tube. To be done. The measurement conditions are a flip angle of 45 ° and a pulse interval of 3.4T _1.
Above (T ₁ is the longest value of the spin lattice relaxation time of the methyl group). Since T ₁ of methylene group and methine group is shorter than that of methyl group, the recovery of magnetization of all carbons in the sample is 99% or more under this condition. Regarding the chemical shift, the methyl group carbon peak of the third unit of the 5-chain (mmmm) propylene unit head-to-tail bonded based on tetramethylsilane was set to 21.593 ppm, and the other carbon peaks were set to this reference.

In the ¹³ C-NMR spectrum of the propylene-based elastomer thus measured, the side chain methyl group of the propylene unit was observed in the methyl carbon region (about 1
9.5 to 21.9 ppm) is the first peak area (about 21.0 to 21.0 ppm)
21.9ppm), 2nd peak area (about 20.2-21.0pp)
m) and the third peak region (about 19.5 to 20.2 ppm).

Within each of these regions, the second molecule in the head-to-tail linked three-molecular chain (i) and (ii) as shown in Table 1 is shown.
A side chain methyl group peak of the unit unit (propylene unit) is observed.

[0028]

[Table 1]

In the table, P is a unit derived from propylene,
B represents a unit derived from 1-butene. Among the three chains (i) and (ii) shown in Table 1 (i) and (ii), the (i) 3 chain is composed entirely of propylene units, PPP (mm), PPP.
The direction of the methyl group for (mr) and PPP (rr) is illustrated below by a surface zigzag structure. (Ii) mm, mr and rr bonds of 3 chains (PPB, BPB) containing butene units are attached to this PPP. According to

[0030]

[Chemical 9]

In the first region, mm-coupled PPP, PP
The methyl group at the second unit (propylene unit) in the B and BPB3 chains resonates. In the second region, mr-bonded PP
P, PPB, BPB3 PPB, BPB3 bonded to the second unit (propylene unit) methyl group in the chain and rr-bonded
The methyl group at the second unit (propylene unit) in the chain resonates. In the third region, the methyl group at the second unit (propylene unit) of the rr-bonded PPP3 chain resonates.

Therefore, the triad tacticity (mm fraction) of a propylene-based elastomer is (i) three chains of propylene units head-to-tail bonded, or (ii) propylene units head-to-tail bonded and a butene unit, A propylene / butene 3-chain containing a propylene unit in the second unit was analyzed by a ¹³ C-NMR spectrum (hexachlorobutadiene solution, tetramethylsilane as a standard) with respect to the side chain methyl group of the propylene unit in the second unit in the three chains. ), 21.0 to 21.9 ppm when the total area of the peaks appearing in 19.5 to 21.9 ppm (methyl carbon region) is 100%
The ratio (percentage) of the peak area appearing in the (first region) is obtained from the following formula.

[0033]

[Equation 1]

The propylene elastomer according to the present invention has a mm fraction thus obtained of 90% or more, preferably 92% or more, more preferably 94% or more.
The propylene-based elastomer has the following structure (ii) in addition to the three chains (i) and (ii) head-to-tail bonded as described above.
i), (iv) and (v) have a small amount of a partial structure containing a positional disorder unit, and the peak derived from the side chain methyl group of the propylene unit due to such another bond is also as described above. Observed in the methyl carbon region (19.5 to 21.9 ppm) of.

[0035]

[Chemical 10]

Of the methyl groups derived from the above structures (iii), (iv) and (v), the methyl group carbon A and the methyl group carbon B resonate at 17.3 ppm and 17.0 ppm, respectively. The peaks based on A and carbon B are the first
It does not appear in the ~ 3 region (19.5 to 21.9 ppm). Further, since both carbon A and carbon B do not participate in the propylene 3 chain based on the head-to-tail bond, they do not need to be considered in the above calculation of triad tacticity (mm fraction).

Further, a peak based on the methyl group carbon C, a peak based on the methyl group carbon D and a peak based on the methyl group carbon D'appear in the second region, and a peak based on the methyl group carbon E and a methyl group carbon E '. Based on the third peak
Appears in the area.

Therefore, in the 1st to 3rd methyl carbon regions,
PPE-methyl group (side chain methyl group in propylene-propylene-ethylene chain) (around 20.7 ppm), EPE
-Methyl group (side chain methyl group in ethylene-propylene-ethylene chain) (around 19.8 ppm), methyl group C, methyl group D, methyl group D ', methyl group E and methyl group E'.
A peak based on appears.

Thus, in the methyl carbon region, peaks of methyl groups not based on the head-to-tail bond 3 chains (i) and (ii) are also observed. Is corrected as follows.

The peak area based on the PPE-methyl group is
It can be determined from the peak area of the PPE-methine group (resonant at around 30.6 ppm), and the peak area based on the EPE-methyl group can be determined from the peak area of the EPE-methine group (resonant at around 32.9 ppm). it can.

The peak area based on the methyl group C can be obtained from the peak areas of the adjacent methine groups (resonance near 31.3 ppm). The peak area based on the methyl group D can be obtained from 1/2 of the sum of the peak areas of the peaks based on the αβ methylene carbon of the above structure (iv) (resonance at resonance at around 34.3 ppm and around 34.5 ppm). ,
The peak area based on the methyl group D ′ can be obtained from the area of the peak (resonance near 33.3 ppm) based on the methine group adjacent to the methyl group of the methyl group E ′ in the above structure (v).

The peak area based on the methyl group E can be determined from the peak area of the adjacent methine carbon (resonance at around 33.7 ppm), and the peak area based on the methyl group E'is adjacent to the methine carbon (33. Resonance around 3ppm)
It can be determined from the peak area of.

Therefore, by subtracting these peak areas from the total peak areas of the second region and the third region, head-to-tail linked propylene unit 3 chains (i) and (i
The peak area of the methyl group based on i) can be calculated.

As described above, the peak area of the methyl group based on the head-to-tail-bonded propylene unit 3 chains (i) and (ii) can be evaluated, and thus the mm fraction can be determined according to the above formula. Each carbon peak in the spectrum can be assigned by referring to the literature (Polymer, 30 , 1350 (1989)).

(3) Intrinsic Viscosity [η] The propylene elastomer according to the present invention has a viscosity of 135 ° C.
Intrinsic viscosity [η] measured in decalin is 0.1-12d
l / g preferably 0.5 to 12 dl / g, more preferably 1 to
It is 12 dl / g.

(4) Molecular Weight Distribution The propylene elastomer according to the present invention has a molecular weight distribution (Mw / Mn) determined by gel permeation chromatography GPC of 3 or less, preferably 2.0 to 3.0. Is 2.0 to 2.5.

(5) Randomness In the propylene-based elastomer according to the present invention, the parameter B value indicating the randomness of the copolymerized monomer chain distribution is
It is 1.0 to 1.5, preferably 1.0 to 1.3, and more preferably 1.0 to 1.2.

This parameter B value is Coleman et al. (BD
Cole-man and TGFox, J. Polym.Sci., Al , 3183 (1963)
) And is defined as follows. B = P ₁₂ / (2P ₁ · P ₂ ), where P ₁ and P ₂ are the first monomer and second monomer content fractions, respectively, and P ₁₂ is the (first monomer) -in the entire bimolecular chain. (Second monomer) The ratio of the chain. When the B value is 1, the Bernoulli statistics are followed, when B <1, the copolymer is block-like, and when B> 1, it is alternating.

In addition to the above characteristics, the propylene-based elastomer according to the present invention has (6) a melting point Tm of 6 as measured by a differential scanning calorimeter.
0 to 140 ° C., preferably 80 to 130 ° C., and the melting point Tm and 1-butene constitutional unit content M
The relationship with (mol%) is -2.6 M + 125 ≤ Tm
It is desirable that ≦ −2.6M + 145.

(7) The relationship between the crystallinity C measured by the X-ray diffraction method and the 1-butene constitutional unit content M (mol%) is C.
It is desirable that ≧ −1.5M + 65.

The propylene-based elastomer according to the present invention as described above is (8) a hetero-bonding unit (positional irregular unit) based on 2,1-insertion or 1,3-insertion of propylene present in the propylene chain. It may have a small amount of structure containing.

During polymerization, propylene is usually 1,2-inserted (the methylene side is bonded to the catalyst) to form a head-to-tail propylene chain as described above, but rarely is 2,1-inserted or 1-inserted. , 3-May be inserted. The 2,1-inserted and 1,3-inserted propylene have the same structure (iii), (i
Form a positional disorder unit as shown by v) and (v). 2,1-insertion of propylene in the polymer building units and
The ratio of 1,3-insertion is ¹³ C--N, which is the same as the above-mentioned stereoregularity.
Using the MR spectrum, it can be obtained from the following formula with reference to Polymer, 30 , 1350 (1989).

The proportion of regio-irregular units based on the 2,1-insertion of propylene can be calculated from the following formula.

[0054]

[Equation 2]

Note that due to overlapping peaks, Iα
If the area such as β is difficult to obtain directly from the spectrum, it can be corrected with a carbon peak having the corresponding area.

The propylene-based elastomer according to the present invention has a hetero-bonding unit based on the 2,1-insertion of propylene present in the propylene chain obtained as described above.
0.01% or more of all propylene constitutional units, specifically 0.01
It may be contained at a ratio of about 1.0%.

The proportion of regio-irregular units based on the 1,3-insertion of propylene in the propylene-based elastomer can be determined from the βγ peak (resonance near 27.4 ppm).

In the propylene-based elastomer according to the present invention, the proportion of different bonds based on 1,3-insertion of propylene may be 0.50% or less. The propylene elastomer according to the present invention as described above includes [A] a specific metallocene compound, [B] [B-1] an organoaluminum oxy compound, and / or
Alternatively, propylene and 1-butene are co-existed in the presence of an olefin polymerization catalyst composed of a compound [B-2] which reacts with a metallocene compound [A] to form an ion pair, and optionally [C] an organoaluminum compound. Obtained by polymerizing.

The olefin polymerization catalyst used in the present invention will be described below. [A] Metallocene Compound The propylene elastomer according to the present invention is produced using the metallocene compound [A] represented by the following general formula (A).

[0060]

[Chemical 11]

In the formula, M is a transition metal of Groups IV to VIB of the Periodic Table, specifically titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, or tungsten, preferably titanium. , Zirconium and hafnium, particularly preferably zirconium.

Substituents R ^{1 to} R ⁴ R ¹ , R ² , R ³ and R ⁴ may be the same as or different from each other, and are each a hydrogen atom, a halogen atom or a carbon number 1 to which a halogen may be substituted. 20 hydrocarbon groups, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, nitrogen-containing groups or phosphorus-containing groups, and a ring together with carbon atoms to which some of the groups adjacent to each other are bonded to each other. May be formed. It should be noted that each two R ¹ displayed
To R ⁴ indicate that when they are bonded to each other to form a ring, they are preferably bonded by a combination of the same symbols, for example, R ¹ and R ¹ are bonded to each other to form a ring. Indicates that is preferable.

Specific examples of the halogen atom include fluorine, chlorine, bromine and iodine. 1 to 20 carbon atoms
The hydrocarbon group of, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, cyclohexyl, octyl, nonyl, dodecyl, Alkyl groups such as eicosyl, norbornyl and adamantyl, alkenyl groups such as vinyl, propenyl and cyclohexenyl, arylalkyl groups such as benzyl, phenylethyl and phenylpropyl, phenyl, tolyl, dimethylphenyl, trimethylphenyl, ethylphenyl and propylphenyl, Biphenyl, α- or β
-Aryl groups such as naphthyl, methylnaphthyl, anthracenyl, phenanthryl, benzylphenyl, pyrenyl, acenaphthyl, phenalenyl, aceanthrylenyl, tetrahydronaphthyl, indanyl and biphenylyl.

The ring formed by combining these hydrocarbon groups includes a benzene ring, a naphthalene ring, an acenaphthene ring,
Condensed ring groups such as indene ring, benzene ring, naphthalene ring,
Examples thereof include groups in which a hydrogen atom on a condensed ring group such as an acenaphthene ring and an indene ring is substituted with an alkyl group such as methyl, ethyl, propyl and butyl.

Further, these hydrocarbon groups may be substituted with halogen. As the silicon-containing group, a monohydrocarbon-substituted silyl group such as methylsilyl or phenylsilyl,
Dihydrocarbon-substituted silyl such as dimethylsilyl and diphenylsilyl, trimethylsilyl, triethylsilyl, tripropylsilyl, tricyclohexylsilyl, triphenylsilyl, dimethylphenylsilyl, methyldiphenylsilyl, tritolylsilyl, trinaphthylsilyl and other trihydrocarbons Examples thereof include silyl ethers of hydrocarbon-substituted silyl such as substituted silyl and trimethylsilyl ether, silicon-substituted alkyl groups such as trimethylsilylmethyl, and silicon-substituted aryl groups such as trimethylphenyl.

Examples of the oxygen-containing group include a hydroxy group, an alkoxy group such as methoxy, ethoxy, propoxy and butoxy, an allyloxy group such as phenoxy, methylphenoxy, dimethylphenoxy and naphthoxy, and an arylalkoxy group such as phenylmethoxy and phenylethoxy. Can be mentioned.

As the sulfur-containing group, a substituent in which oxygen of the oxygen-containing compound is substituted with sulfur, and methyl sulfonate, trifluoromethane sulfonate, phenyl sulfonate, benzyl sulfonate, p-toluene sulfonate, Trimethylbenzene sulfonate,
Sulfonate groups such as triisobutylbenzene sulfonate, p-chlorobenzene sulfonate, pentafluorobenzene sulfonate, methylsulfinate, phenylsulfinate, benzenesulfinate, p-toluenesulfinate, trimethylbenzene Examples thereof include sulfinate groups such as sulfinate and pentafluorobenzene sulfinate.

As the nitrogen-containing group, an amino group, an alkylamino group such as methylamino, dimethylamino, diethylamino, dipropylamino, dibutylamino, dicyclohexylamino, phenylamino, diphenylamino, ditolylamino, dinaphthylamino, methylphenylamino. And an arylamino group or an alkylarylamino group.

Examples of the phosphorus-containing group include dimethylphosphino and diphenylphosphino. X ¹ and X ² X ¹ and X ² represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with halogen,
It is an oxygen-containing group or a sulfur-containing group. Specific examples of these atoms or groups include those similar to the atoms or groups shown for R ^{1 to} R ⁴ .

Y Y has 1 to 20 carbon atoms which may be substituted with halogen.
Divalent hydrocarbon group, divalent silicon-containing group, divalent germanium-containing group, —O—, —CO—, —S—, —SO
_{-, - SO 2 -, -} NR 7 -, - P (R 7) -, - P
^{(O) (R 7) -} , - BR 7 - or -AlR ⁷ - a. (However, R ⁷ is a hydrogen atom, the same halogen atom as described above, or a carbon atom which may be substituted with halogen.
Is a hydrocarbon group. ) Specifically, as the divalent hydrocarbon group having 1 to 20 carbon atoms, methylene, dimethylmethylene, 1,2-ethylene, dimethyl-1,2-ethylene, 1,3-trimethylene, 1,4- Alkylene groups such as tetramethylene, 1,2-cyclohexylene, 1,4-cyclohexylene, diphenylmethylene, diphenyl
Examples include aryl alkylene groups such as -1,2-ethylene. In addition, the carbon number of 1 to 20 such as chloromethylene
And a halogenated hydrocarbon group obtained by halogenating the divalent hydrocarbon group.

Examples of the divalent silicon-containing group include methylsilylene, dimethylsilylene, diethylsilylene, di (n-propyl) silylene, di (i-propyl) silylene, di (cyclohexyl) silylene, methylphenylsilylene, diphenylsilylene, Alkylsilylene such as di (p-tolyl) silylene and di (p-chlorophenyl) silylene, alkylarylsilylene, arylsilylene group, alkyldisilyl such as tetramethyl-1,2-disilyl, tetraphenyl-1,2-disilyl , Alkylaryldisilyl, aryldisilyl groups and the like.

Examples of the divalent germanium-containing group include compounds obtained by substituting germanium for silicon in the divalent silicon-containing group. In the present invention, among the metallocene compounds represented by the above formula (A), the metallocene compound represented by the following formula [I] is preferably used.

[0073]

[Chemical 12]

Substituents R ¹¹ and R ¹² R ¹¹ and R ¹² may be the same or different and are the same as R ^{1 to} R ⁴ in the formula (A).

Substituents R ¹³ and R ¹⁴ R ¹³ and R ^{14, which} may be the same or different, are alkyl or aryl groups having 1 to 20 carbon atoms. Examples of the alkyl group or aryl group include the same groups as those represented by R ¹¹ and R ¹² .

These alkyl groups or aryl groups are
It may be substituted with a halogen or an organic silyl group (silicon-containing group). Among these, a secondary or tertiary alkyl group and an aryl group having 6 to 15 carbon atoms are preferable.

X ¹ and X ² Examples of X ¹ and X ² include those similar to the above formula (A). Of these, a halogen atom and a hydrocarbon group having 1 to 20 carbon atoms are preferable.

Examples of Y Y include those similar to the above formula (A). Of these, a divalent silicon-containing group and a divalent germanium-containing group are preferable, a divalent silicon-containing group is more preferable, and alkylsilylene, alkylarylsilylene, and arylsilylene are more preferable.

Specific examples of the metallocene compound represented by the above general formula [I] are shown below. rac-Dimethylsilylene-bis (2,4,6-trimethyl-1-indenyl) zirconium dichloride, rac-Dimethylsilylene-bis (2-methyl-4,6-)
Diphenyl-1-indenyl) zirconium dichloride, r
ac-dimethylsilylene-bis (2-methyl-4-phenyl-6-isopropyl-1-indenyl) zirconium dichloride, r
ac-dimethylsilylene-bis (2-methyl-4-α-naphthyl-6
-Isopropyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-i-propyl-6-methyl-1-indenyl) zirconium dichloride,
rac-Dimethylsilylene-bis (2-methyl-4-methyl-6-methyl-1-indenyl) zirconium dichloride, rac-Dimethylsilylene-bis (2-methyl-4-methyl-6-i-propyl-1-indenyl) ) Zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4,6-di (i-propyl) -1
-Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4,6-di (sec-butyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-ethyl-4,6-) Di (i-propyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2-n-propyl-4,6-di (i-propyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene
-Bis (2-methyl-4,6-di (i-propyl) -1-indenyl) titanium dichloride, rac-dimethylsilylene-bis (2-methyl-4,6-di (i-propyl) -1-indenyl ) Hafnium dichloride etc.

The indene derivative ligand of the metallocene compound represented by the above formula [I] can be synthesized by a conventional organic synthesis method, for example, by the following reaction steps.

[0081]

[Chemical 13]

The metallocene compound used in the present invention is
From the indene derivative obtained as described above, for example, Journal of Organometallic Chem. 288 (1985), Nos. 63-
It can be synthesized according to a known method described on page 67, JP-A-4-268307 and the like.

In the present invention, the metallocene compound [A]
As EP-549900 and Canada-2084
The compound represented by the following formula [II] described in No. 017 can also be used.

[0084]

Embedded image

In the formula, M is a transition metal atom of Group IVB of the periodic table, specifically titanium, zirconium or hafnium, particularly preferably zirconium.
R ^{21 s} may be the same or different from each other, and are a hydrogen atom, a halogen atom, preferably a fluorine atom or a chlorine atom, an optionally halogenated alkyl group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, and 6 carbon atoms. 10 preferably C6-8 aryl _{group, -NR 2, -SR, -OSiR 3} ,
-SiR ₃ or -PR ₂ groups (where R is preferably a halogen atom chlorine atom, an alkyl group or an aryl group having 6 to 10 carbon atoms, preferably 6-8 1-10 preferably 1-3 carbon atoms) is.

R ^{22 to} R ^{28, which} may be the same or different, are the same atoms or groups as those of R ²¹ , and these R ^{22 to} R ²⁸ are the same.
^At least two groups adjacent to each other among ²⁸ may form an aromatic ring or an aliphatic ring together with the atoms to which they are bonded.

X ³ and X ⁴ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an OH group, an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and 1 to 1 carbon atoms.
10 preferably 1 to 3 alkoxy groups, 6 to 10 carbon atoms
Preferably 6-8 aryl group, 6-10 carbon atoms, preferably 6-8 aryloxy group, 2-10 carbon atoms, preferably 2-4 alkenyl group, 7-40 carbon atoms, preferably 7-10 aryl. An alkyl group, an alkylaryl group having 7 to 40 carbon atoms, preferably 7 to 12 carbon atoms, and an arylalkenyl group having 8 to 40 carbon atoms, preferably 8 to 12 carbon atoms.

[0088]

[Chemical 15]

-Sn-, -O-, -S-, = SO, = S
O ₂ , = NR ²⁹ , = CO, = PR ²⁹ or = P (O) R
²⁹ . However, R ²⁹ and R ^{30, which} may be the same or different, are each a hydrogen atom, a halogen atom, or a carbon number of 1.
-10, preferably 1-4 alkyl group, especially methyl group, C1-C10 fluoroalkyl group, preferably CF
₃ groups, an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms,
Aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms, fluoroaryl group having 6 to 10 carbon atoms, preferably pentafluorophenyl group, alkoxy group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms, especially methoxy group, 2 carbon atoms -10, preferably 2
To 4 alkenyl groups, 7 to 40 carbon atoms, preferably 7 to 1 carbon atoms
0 arylalkyl group having 8 to 40 carbon atoms, preferably 8
To 12 arylalkenyl groups, and 7 to 40 carbon atoms, preferably 7 to 12 arylalkyl groups.

R ²⁹ and R ³⁰ may form a ring together with the atom to which they are bonded. M ² is silicon, germanium or tin.

The above-mentioned alkyl group is a linear or branched alkyl group, and halogen (halogenated) is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, particularly a fluorine atom or a chlorine atom.

Among the compounds represented by the formula [II], M is zirconium or hafnium,
R ²¹ is the same as each other and is an alkyl group having 1 to 4 carbon atoms, R ^{22 to} R ²⁸ may be the same or different from each other, and is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, X ³ and X ^{4, which} may be the same or different, are alkyl groups having 1 to 3 carbon atoms or halogen atoms,

[0093]

Embedded image

(M ² is silicon, R ²⁹ and R
³⁰ may be the same as or different from each other, and have 1 to 1 carbon atoms.
It is an alkyl group having 4 or an aryl group having 6 to 10 carbon atoms. ) Are preferred, and the substituents R ²² and R ^{28 are}
Is more preferably a hydrogen atom, and R ^{23 to} R ²⁷ are more preferably compounds having an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.

Further, M is zirconium and R
²¹ is an alkyl group having 1 to 4 carbon atoms which are the same as each other,
R ²² and R ²⁸ are hydrogen atoms, R ^{23 to} R ²⁷ may be the same or different, are an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and X ³ and X ⁴ are both Is a chlorine atom,

[0096]

[Chemical 17]

(M ² is silicon, R ²⁹ and R ³⁰
May be the same or different from each other and have 1 to 4 carbon atoms.
Is an alkyl group or an aryl group having 6 to 10 carbon atoms. In particular, M is zirconium, R ²¹ is a methyl group, and R ^{22 to} R ²⁸ are
A hydrogen atom, X ³ and X ⁴ are chlorine atoms,

[0098]

Embedded image

Compounds that are are preferred. Specific examples of the metallocene compound represented by the formula [II] are shown below. rac-Dimethylsilylene-bis (4,5-benzo-1-indenyl) zirconium dichloride, rac-Dimethylsilylene
-Bis (2-methyl-4,5-benzo-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-α-acenaphtho-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2 , 3,6-Trimethyl-
4,5-benzo-1-indenyl) zirconium dichloride, r
ac-methylphenylsilylene-bis (2-methyl-4,5-benzo-1-indenyl) zirconium dichloride, rac-diphenylsilylene-bis (2-methyl-4,5-benzo-1-indenyl) zirconium dichloride, rac -Diphenylsilylene-bis (2-methyl-α-acenaphtho-1-indenyl) zirconium dichloride, rac-methylphenylsilylene-bis (2-methyl-α-acenaphtho-1-indenyl) zirconium dichloride, rac-1,2- Ethanediyl-bis (2-methyl-4,5-benzo-1-indenyl) zirconium dichloride, rac-1,2-ethanediyl-bis (2-methyl-α-acenaphtho-1-indenyl) zirconium dichloride, rac-1, 2
-Butanediyl-bis (2-methyl-4,5-benzo-1-indenyl) zirconium dichloride, rac-1,2-butanediyl-
Bis (2-methyl-α-acenaphtho-1-indenyl) zirconium dichloride, etc.

In addition, compounds in which zirconium in the above compounds is replaced with titanium or hafnium can also be mentioned. In the present invention, the general formula [I] or [II]
The racemic metallocene compound represented by is used as the catalyst component, but R type or S type can also be used.

The metallocene compounds as described above can be used in combination of two or more kinds. In the present invention, as the metallocene compound [A], among these, rac-dimethylsilylene-bis (2-methyl-4,6-diisopropyl-1-)
Indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-α-acenaphtho-1-indenyl)
Zirconium dichloride, rac-dimethylsilylene-bis {1- (2-methyl-4,5-benzo-1-indenyl) zirconium dichloride and the like are particularly preferably used.

[B-1] Organoaluminum Oxy Compound Forming the Olefin Polymerization Catalyst Used in the Present Invention [B
-1] Organoaluminum oxy compound (hereinafter referred to as "component [B-1]
May be described. ) May be a conventionally known aluminoxane, or may be a benzene-insoluble organic aluminum oxy compound as exemplified in JP-A-2-78687.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, ceric chloride hydrate, etc. A method in which an organoaluminum compound such as trialkylaluminum is added to the hydrocarbon medium suspension and reacted. (2) A method in which water, ice, or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether, or tetrahydrofuran. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organometallic component. Further, the solvent or the unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent or suspended in the poor solvent of the aluminoxane.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include trimethylaluminum, triethylaluminum, tripropylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, trisec-butyl. Aluminum, tritert-butylaluminum, tripentylaluminum, trihexylaluminum, trioctylaluminum, trialkylaluminum such as tridecylaluminum, tricycloalkylaluminum such as tricyclohexylaluminum, tricyclooctylaluminum, dimethylaluminum chloride, diethylaluminum. Chloride, diethyl aluminum bromide, diisobutyl aluminum chloride, etc. Alkylaluminum halides, diethylaluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride, dimethyl aluminum methoxide, dialkylaluminum alkoxides such as diethylaluminum ethoxide and dialkylaluminum Ally Loki Sid such as diethyl aluminum phenoxide and the like.

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable. Further, as the organoaluminum compound used when preparing the aluminoxane, isoprenylaluminum represented by the following general formula can also be used.

[0107] _{(i-C 4 H 9)} x Al y (C 5 H 10) z ... [II] ( wherein, x, y, z are each a positive number, and z ≧ 2x.) Above Such organoaluminum compounds may be used in combination of two or more.

Solvents used for the aluminoxane solution or suspension include benzene, toluene, xylene,
Aromatic hydrocarbons such as cumene and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane and octadecane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane , Petroleum fractions such as gasoline, kerosene, and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons, and alicyclic hydrocarbons, and particularly hydrocarbon solvents such as chlorinated compounds and brominated compounds. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

[B-2] Compound Forming Ion Pair [B-2] Forming Catalyst for Olefin Polymerization Used in the Present Invention [B
-2] As the compound which reacts with the metallocene compound [A] to form an ion pair (hereinafter, sometimes referred to as "component [B-2]"), JP-A-1-501950 and JP-A-1501950 are available. 1-502036, JP-A-3-179005
Japanese Patent Laid-Open No. 3-179006, Japanese Patent Laid-Open No. 3-2900
No. 07703, JP-A-3-207704, U
Examples thereof include Lewis acids, ionic compounds and carborane compounds described in S-547718.

As the Lewis acid, triphenylboron,
Tris (4-fluorophenyl) boron, Tris (p-tolyl) boron, Tris (o-tolyl) boron, Tris (3,5-
Dimethylphenyl) boron, Tris (pentafluorophenyl) boron, MgCl ₂ , Al ₂ O ₃ , SiO ₂ -Al ₂
Examples include O _{3 and the} like.

Examples of the ionic compound include triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, and ferroferrite. Examples include cerium tetra (pentafluorophenyl) borate.

Examples of the carborane compound include dodecaborane, 1-carbaundecaborane, bis-n-butylammonium (1-carbedodeca) borate, tri-n-butylammonium (7,8-dicarbaundeca) borate and tri-n-butylammonium. (Trideca hydride-7-carbaundeca) borate etc. can be illustrated.

Two or more kinds of the compounds [B-2] which react with the metallocene compound to form an ion pair as described above can be used in combination. [C] Organoaluminum Compound In the present invention, a [C] organoaluminum compound (hereinafter sometimes referred to as “component [C]”) may be used when forming a catalyst for olefin polymerization. Examples of the organoaluminum compound [C] include organoaluminum compounds represented by the following general formula [III].

R ⁹ _n AlX _3-n [III] (In the formula, R ⁹ is a hydrocarbon group having 1 to 12 carbon atoms, and X is
Is a halogen atom or a hydrogen atom, and n is 1 to 3. ) The hydrocarbon group having 1 to 12 carbon atoms is, for example, an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an isobutyl group, a pentyl group. Group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group and the like.

Such an organoaluminum compound [C]
Specifically, the following compounds may be mentioned. Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, trioctyl aluminum, tri (2-ethylhexyl) aluminum, trialkyl aluminum such as tridecyl aluminum, alkenyl aluminum such as isoprenyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride. , Diisopropyl aluminum chloride, diisobutyl aluminum chloride, dimethyl aluminum bromide, etc., dialkyl aluminum halides, methyl aluminum sesquichloride, ethyl aluminum sesquichloride, isopropyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, etc. Alkyl aluminum dihalides such as umsesquihalide, methyl aluminum dichloride, ethyl aluminum dichloride, isopropyl aluminum dichloride and ethyl aluminum dibromide, and alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

As the organoaluminum compound [C], a compound represented by the following general formula [IV] can also be used. R ⁹ _n AlL _3-n ... [IV] (In the formula, R ⁹ is the same as above, L is an —OR ¹⁰ group,
OSiR ¹¹ ₃ group, -OAlR ¹² ₂ group, -NR ¹³ ₂ group, -Si
R ¹⁴ ₃ group or —N (R ¹⁵ ) AlR ¹⁶ ₂ group, and n is 1 to
2, R ¹⁰ , R ¹¹ , R ¹² and R ¹⁶ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group and the like, and R ¹³ is a hydrogen atom, a methyl group, an ethyl group, isopropyl group. Group, phenyl group, trimethylsilylene group and the like, and R ¹⁴ and R ¹⁵ are methyl group, ethyl group and the like. ) Among such organoaluminum compounds, R ⁷ _n A
a compound represented by l (OAlR ¹⁰ ₂ ) _3-n , such as Et ₂
AlOAlEt ₂ , (iso-Bu) ₂ AlOAl (iso-Bu) ₂
Are preferred.

[0117] Among the above general formula [III] and an organoaluminum compound represented by the [IV], formula R ⁷ compound represented by ₃ Al are preferred, especially those wherein R ⁷ is an isoalkyl group.

The olefin polymerization catalyst used in the present invention comprises the component [A], the component [B-1] (or the component [B-2]) and, if desired, the component [C] in an inert hydrocarbon solvent or an olefin. It can be prepared by mixing in a solvent.

Specific examples of the inert hydrocarbon solvent used for preparing the olefin polymerization catalyst include propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene and other aliphatic hydrocarbons, cyclopentane, Examples thereof include alicyclic hydrocarbons such as cyclohexane and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and mixtures thereof.

The order of mixing the respective components when preparing the olefin polymerization catalyst is arbitrary, but the component [B-1] or the component [B
-2]) and component [A], or component [B-1] and component [C], and then component [A], or component [A] and component [B- 1] (or component [B-2]) and then component [C], or alternatively component [A] and component [C], then component component [B-1]
(Or component [B-2]) is preferably mixed.

When mixing the above components, the components [B-
The atomic ratio (Al / transition metal) of aluminum in 1] to the transition metal in component [A] is usually 10 to 10,000,
It is preferably 20 to 5000, and the concentration of the component (A) is about 10 ^-8 to 10 ^-1 mol / liter, preferably 10
It is in the range of ^{-7 to} 5 x 10 ^-2 mol / liter.

When the component [B-2] is used, the molar ratio of the component [A] to the component [B-2] (component [A] / component [B-2]) is usually 0.01 to 10, It is preferably in the range of 0.1 to 5,
The concentration of the component [A] is in the range of about 10 ⁻⁸ to 10 ⁻¹ mol / liter, preferably 10 ^{−7 to} 5 × 10 ⁻² mol / liter.

[0123] Component When using the [C], the atomic ratio of component [C] aluminum atom (Al _C) and the aluminum atom in the component [B-1] in _{(Al B-1) (Al} C / Al _B-1 )
Is usually in the range of 0.02 to 20, preferably 0.2 to 10.

The above catalyst components may be mixed in the polymerization vessel, or may be mixed in advance and added to the polymerization vessel.
The mixing temperature when mixing in advance is usually -50 to 150 ° C,
It is preferably -20 to 120 ° C, and the contact time is 1 to 1
000 minutes, preferably 5 to 600 minutes. Also,
The mixing temperature may be changed during the mixing contact.

The olefin polymerization catalyst used in the present invention is prepared by adding the above-mentioned components [A] and [B] to an inorganic or organic particulate carrier which is a granular or particulate solid.
And a solid olefin polymerization catalyst carrying at least one component of the component [C].

The inorganic carrier is preferably a porous oxide, and examples thereof include SiO ₂ and Al ₂ O ₃ . Examples of the granular or fine particle solid of the organic compound include polymers or copolymers produced mainly from α-olefin such as ethylene, propylene, 1-butene, or styrene.

The olefin polymerization catalyst used in the present invention comprises the above-mentioned particulate carrier, component [A], component [B],
It may be an olefin polymer produced by prepolymerization and, if desired, an olefin polymerization catalyst formed from the component [C].

As the olefin used in the prepolymerization, olefins such as propylene, ethylene and 1-butene are used, but a mixture of these and other olefins may be used.

The olefin polymerization catalyst used in the present invention may contain, in addition to the above components, other components useful for olefin polymerization, for example, water as a catalyst component.

The propylene-based elastomer according to the present invention can be produced by copolymerizing propylene and 1-butene in the presence of the above-mentioned olefin polymerization catalyst so that the final composition ratio will be obtained. it can.

Polymerization can be carried out by either liquid phase polymerization such as suspension polymerization or solution polymerization, or gas phase polymerization. In the liquid phase polymerization method, it is possible to use the same inert hydrocarbon solvent used in the above-mentioned catalyst preparation, and propylene can also be used as a solvent.

The polymerization temperature is usually in the range of -50 to 100 ° C., preferably 0 to 90 ° C. when carrying out the suspension polymerization method, and usually when carrying out the solution polymerization method. It is desirable that the temperature is in the range of 0 to 250 ° C, preferably 20 to 200 ° C. When carrying out the gas phase polymerization method, the polymerization temperature is usually 0 to 120 ° C., preferably 20 to 120 ° C.
It is preferably in the range of 100 ° C.

The polymerization pressure is usually from atmospheric pressure to 100 kg / c.
m ² , preferably under conditions of atmospheric pressure to 50 kg / cm ² ,
The polymerization reaction can be carried out by any of batch method, semi-continuous method and continuous method.

It is also possible to carry out the polymerization in two or more stages under different reaction conditions. The molecular weight of the resulting propylene-based elastomer depends on whether hydrogen is present in the polymerization system,
Alternatively, it can be adjusted by changing the polymerization temperature and the polymerization pressure.

[0135]

The propylene-based elastomer according to the present invention has high triad tacticity and is excellent in rigidity, heat resistance, scratch resistance, transparency, heat sealability and blocking resistance, and is suitable for sheets, films and the like. It can be preferably used and can also be preferably used as a sealant.

In particular, the film containing the propylene-based elastomer according to the present invention does not change its heat-sealing temperature with time even when it is stored for a long period of time, and stable heat-sealing work can be secured.

Further, the propylene-based elastomer according to the present invention has a lower melting point when the composition ratio of propylene and 1-butene is the same as that of the conventional elastomer, so that the heat-sealing temperature is Can be cooled to a lower temperature. Furthermore, the propylene-based elastomer molded product according to the present invention has high surface hardness, and thus is not easily scratched.

[0138]

EXAMPLES The present invention will now be specifically described with reference to examples, but the present invention is not limited to these examples.

[0139]

[Physical property measurement method]

[1-Butene content] It was determined using ¹³ C-NMR.

[Intrinsic viscosity [η]] Measured in decalin at 135 ° C. and shown in dl / g. [Molecular weight distribution (Mw / Mn)] Molecular weight distribution (Mw / M
n) was measured as follows using GPC-150C manufactured by Millipore.

The separation column was TSK GNH HT, the column size was 27 mm in diameter and 600 mm in length, the column temperature was 140 ° C., the mobile phase was o-dichlorobenzene (Wako Pure Chemical Industries) and an antioxidant. As BH
Using T (Takeda Yakuhin) 0.025% by weight, the sample was moved at 1.0 ml / min, the sample concentration was 0.1% by weight, the sample injection amount was 500 microliters, and a differential refractometer was used as a detector. . Standard polystyrene has a molecular weight of Mw <100
0 and Mw> 4 × 10 ⁶ were manufactured by Tosoh Corporation, and 1000 <Mw <4 × 10 ⁶ were manufactured by Pressure Chemicals.

[B value] The composition distribution B value is 10 mm.
¹³ C-NM of a sample obtained by uniformly dissolving about 200 mg of copolymer in 1 ml of hexachlorobutadiene in a φ sample tube.
The R spectrum is usually measured at a measurement temperature of 120 ° C., a measurement frequency of 25.05 MHz, a spectrum width of 1500 Hz, a filter width of 1500 Hz, and a pulse repetition time of 4.2 se.
c, the number of times of integration is 2000 to 5000 times, and P _E , P _o , and P _OE are calculated from the spectra.

[Triad tacticity] ¹³ C-with hexachlorobutadiene solution (based on tetramethylsilane)
The NMR spectrum was measured to be 21.0-2 with respect to the total area (100%) of the peaks appearing at 19.5-21.9 ppm.
The ratio (%) of the peak area appearing at 1.9 ppm was determined.

[Ratio of heterogeneous bonds based on 2,1-insertion] Poly
mer, 30 , 1350 (1989)) with reference to ¹³ C-NMR spectrum.

[Melting point (Tm)] About 5 mg of a sample was packed in an aluminum pan, heated to 200 ° C. at 10 ° C./minute, kept at 200 ° C. for 5 minutes, then cooled to room temperature at 20 ° C./minute, and then 10 ° C. It was determined from the endothermic curve when the temperature was raised in 1 / min. For the measurement, a Perkin Elmer DSC-7 type device was used.

[Crystallinity] The crystallinity was determined by X-ray diffraction measurement of a 1.0 mm thick pressed sheet that had been at least 24 hours after molding.

[Heat-seal start temperature] Preparation of film A 0.1 mm-thick aluminum sheet and PE were formed on a press plate.
A sheet made of T and an aluminum sheet having a thickness of 100 μm, the center of which was cut into a 15 cm × 15 cm square, were laid in this order, and 3.3 g of a sample was placed in the center (cutout portion). Then, a PET sheet, an aluminum plate, and a press plate are further stacked in this order.

A sample sandwiched between the above-mentioned press plates is put at 200 ° C.
After preheating for about 7 minutes, pressurize (50kg / cm ² to remove air bubbles in the sample).
G) Repeat the depressurizing operation several times. Then finally 100kg /
The pressure is raised to cm ² G, and pressure heating is performed for 2 minutes. After depressurization, the press plate is taken out of the press machine, transferred to another press machine in which the pressure-bonded portion is kept at 0 ° C., pressure-cooled at 100 kg / cm ² G for 4 minutes, then depressurized, and the sample is taken out. A film having a uniform thickness of about 150 to 170 μm of the obtained film is used for measuring the heat seal strength.

Measurement of Heat Sealing Strength A film is cut into 15 mm-width strips, the two sheets are overlapped, and this is further sandwiched between two Teflon films having a thickness of 0.1 mm, and heat sealing is performed thereon. The heat sealing is performed by keeping the lower temperature of the heat sealing constant at 70 ° C. and changing only the temperature of the upper portion of the hot plate in steps of 5 ° C. The pressure during heat sealing is 2 kg / cm ² , the heat sealing time is 1 second, and the seal width is 5 mm (so the sealing area is 15 mm ×
5 mm).

The heat-sealing strength is the peel strength of the film heat-sealed at each of the above heat-sealing temperatures of 30c.
It is determined by conducting a tensile test at a tensile speed of m / min.

The peel strength at each heat-sealing temperature in increments of 5 ° C. was obtained by the above-described method, and a plot of heat-sealing temperature vs. peel strength was connected by a curve. 300g / based on this curve
The heat seal temperature at which the peel strength is 15 cm is set as the heat seal start temperature.

Measurement of Heat Seal Strength of Aging Treatment The aging treatment of the film is carried out by placing it in a constant temperature bath at 50 ° C. for 7 days. When aging, attach papers to both sides of the film so that the two do not touch each other. The heat-sealing start temperature of the film subjected to this aging treatment is measured by the method described above.

[Martens Hardness] The Martens hardness is measured by using a Martens scratch tester manufactured by Tokyo Koki Co., Ltd., by applying a constant load (5 g) to a diamond weight and scratching a 1 mm press sheet surface. To do. The width of the scratch mark of the tested test piece is measured by a microscope, and the reciprocal (mm ^-1 ) of the read value is obtained, which is taken as the Martens hardness.

[Blocking Stress] ASTM D189
Evaluation was made according to 3. Cut out two films with a width of 10 cm and a length of 15 cm and stack them. This is sandwiched between two glass plates with a load of 10 kg and placed in an air oven at 50 ° C. The sample was taken out after 7 days, the peel strength was measured, and the peel strength per 1 cm was taken as the blocking value.

[Haze] The film prepared for measuring the above heat-sealing start temperature was tested according to ASTM D1003-
It measured based on 61.

[0156]

[Production Example 1] [Dimethylsilylene-bis (2-methyl-α-acenaphtho-1
-Production of indenyl) zirconium dichloride (metallocene compound represented by the formula [II]) 120 g (0.900 mol) of AlCl _{3 in} a three-neck flask under an Ar atmosphere, CS
₂ 600 ml of the mixture was cooled to 5 ° C. in an ice bath and stirred.

In this, 110 g of acenaphthene (0.71
4 mol) and stirred for 5 minutes, using a dropping funnel,
A mixture of 90 ml of methacryloyl chloride (0.921 mol) and 100 ml of CS ₂ was added over 1 hour. After completion of the dropping, the mixture was further stirred at 5 ° C. for 1 hour. The reaction solution was poured into ice water and the product was extracted with ether. The ethereal phase was washed with saturated aqueous NaHCO ₃ followed by saturated aqueous NaCl,
It was dried over Na ₂ SO ₄ and then concentrated. The resulting viscous oil was purified by a silica gel column using CH ₂ Cl ₂ and hexane as a developing solvent to obtain 61 g (0.275 mol, yield 31%) of a ketone (a) represented by the following formula as a semi-solid. It was

[0158]

[Chemical 19]

The physical properties of the obtained product are shown below. M ⁺ 222 IR (KBr) 1690 cm ^-1 NMR (CDCl ₃ ) 1.36 (3H, d, J = 7H
z), 3.43 (4H, s), 7.24 (1H, s) 7.38 (1H, d, J = 8Hz) 7.62 (1H, t, J = 8Hz) 8.58 (1H, d, J = 8 Hz) 25 g of the above-mentioned ketone (a) in a three-neck flask under Ar atmosphere.
(0.113 mol), anhydrous tetrahydrofuran 500 ml
, And cooled to 5 ° C. in an ice bath. In which LiAl
3.2 g (0.084 mol) of H ₄ was added portionwise over 20 minutes. After the addition was completed, the mixture was stirred at 5 ° C for 2 hours. After adding Celite to the reaction solution, saturated NH ₄ Cl aqueous solution was carefully added to decompose excess LiAlH ₄ .

After adding Na ₂ SO ₄ and stirring for 10 minutes,
The reaction mixture was filtered using a celite-filled funnel. The residue was washed with CH ₂ Cl ₂ and the filtrate was concentrated to obtain 26 g of a pale yellow solid. This solid was dissolved in CH ₂ Cl ₂ and passed through a short silica gel column, followed by concentration to obtain 24 g (0.107 mmol, yield 95%) of a stereoisomer mixture of alcohol (b) represented by the following formula. .

[0161]

Embedded image

This alcohol (b) was dehydrated without further purification to obtain an olefin (c). That is, alcohol (b) 8.80 g (39.29 mmol),
100 ml of benzene, 100 mg of p-toluenesulfonic acid
(0.53 mmol) mixture at 40 ° C. under Ar atmosphere.
The mixture was heated and stirred for 20 minutes. K ₂ CO ₃ and Na ₂ SO ₄ were added to the reaction mixture and filtered through a Celite funnel.

The residue was washed with CH ₂ Cl ₂ and the filtrate was concentrated to obtain 7.92 g of crude olefin 3. The crude product was purified by a silica gel column using hexane and CH ₂ Cl ₂ as a developing solvent, and 7.10 g (34.5 mmol, yield 88%) of an olefin (c) represented by the following formula as a semi-solid.
Obtained.

[0164]

[Chemical 21]

The physical properties of the obtained product are shown below. M ⁺ 206 NMR (CDCl ₃ ) 2.24 (3H, bs), 3.41 (6H, bs), 6.
98 (1H, bs), 7.22 (1H, d, J = 8H
z), 7.36 (1H, s), 7.42 (1H, t, J =
8 Hz), 7.70 (1 H, d, J = 8 Hz) 6.01 g (29.17) of olefin (c) under Ar atmosphere.
Mmol), 84 ml of anhydrous ether, 72 m of CuCN
The mixture of g (0.80 mmol) was cooled in an ice bath into which 20.54 of a 1.56 M n-BuLi hexane solution was added.
ml (32.04 mmol) using a dropping funnel, 30
Added over a minute. After completion of dropping, the ice bath was removed and the mixture was stirred at room temperature for 1.5 hours. A solution of 1.97 ml (16.03 mmol) of dimethyldichlorosilane in 5 ml of anhydrous ether was added thereto over 25 minutes, and then the mixture was stirred for 16 hours at room temperature. After cooling the reaction mixture with an ice bath, water was added,
The ether phase was separated and the aqueous phase was extracted with CH ₂ Cl ₂ .
The ether and CH ₂ Cl ₂ phases were combined, dried over Na ₂ SO ₄ , and then concentrated to obtain a crude silylated product. The crude silylated product was rinsed and purified with CH ₂ Cl ₂ -hexane (1: 8 v / v) to obtain 5.19 g (11.09 mmol, yield 79) of the silylated product (d) represented by the following formula as a white solid. %)Obtained.

[0166]

[Chemical formula 22]

The physical properties of the obtained product are shown below. ^{M + 468 mp 191~194 ℃ NMR (} CDCl 3) -0.39, -0.35, -0.27 ( together 6H, s each), 2.33,2.39 (together 6H, each s ) 3.39 (8H, bs), 3.97 (2H, bs) 7.03 to 7.93 (10H, m) Under Ar atmosphere, silylated product (d) 2.00 g (4.27 mmol), anhydrous A mixture of 120 ml of tetrahydrofuran was cooled to -50 ° C using a dry ice-acetone bath, and 5.47 ml of a hexane solution of 1.56M n-BuLi was added.
(8.53 mmol) was added over 20 minutes using a dropping funnel. After completion of dropping, the bath was removed and the mixture was stirred at room temperature for 1.5 hours. Tetrahydrofuran was distilled off under reduced pressure, 40 ml of anhydrous hexane was added, and the mixture was stirred and depressurized again to distill off hexane. The reaction vessel was cooled to −50 ° C. using a dry ice-acetone bath, 120 ml of CH ₂ Cl ₂ at −30 ° C. was added, and subsequently 0.99 g (4.2 g of ZrCl ₄₎ was added.
7 mmol) was added, stirring was continued, and the mixture was left for 16 hours. The reaction mixture was filtered, the residue washed with CH ₂ Cl ₂ and the filtrate concentrated to give 2.30 g of crude product.

The crude product was purified using tetrahydrofuran and CH ₂ Cl _{2. As a result} , a racemic dimethylsilylene-bis (2-methyl-α represented by the following formula as a CH ₂ Cl ₂ -soluble and tetrahydrofuran-insoluble substance was obtained. -Acenaphtho-1-indenyl) zirconium dichloride 40
0 mg (0.64 mmol, yield 15%) was obtained.

[0169]

[Chemical formula 23]

The physical properties of the obtained product are shown below. M ⁺ 626 NMR (CDCl ₃ ) 1.36 (6H, s), 2.37 (6H, s), 3.20
~ 3.50 (8H, m) 7.10-7.75 (10H, m)

[0171]

EXAMPLE 1 900 ml of hexane and 70 g of 1-butene were charged into a 2 liter autoclave that had been sufficiently replaced with nitrogen, and 1 mmol of triisobutylaluminum was added to the autoclave.
After raising the temperature to 0 ° C, propylene was supplied to the total pressure 14kg /
cm ² G, methylaluminoxane 0.40 mmol, rac-dimethylsilylene-bis (2-methyl-α-acenaphtho-1-indenyl) zirconium dichloride obtained in Preparation Example 1 was converted to Zr atom and 0.002 Then, propylene was continuously fed to carry out polymerization for 60 minutes while keeping the total pressure at 14 kg / cm ² G.

After the polymerization, the polymer was degassed and recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours. The obtained polymer (propylene elastomer) is 89.
2 g, polymerization activity is 45 kg polymer / mmol Z
It was r · hr. This polymer contained 8.2 mol% of units derived from 1-butene. Intrinsic viscosity [η]
Was 1.82 dl / g and the melting point was 115.8 ° C. The percentage of heterologous bonds based on the 2,1-insertion was about 0.38%.

Table 2 shows the measured physical properties of the obtained polymer.

[0174]

EXAMPLE 2 900 ml of hexane and 100 g of 1-butene were charged into a 2 liter autoclave which had been sufficiently replaced with nitrogen, and 1 mmol of triisobutylaluminum was added.
After raising the temperature to 70 ℃, propylene is fed and the total pressure is 14kg.
/ Cm ² G, methylaluminoxane 0.30 mmol,
Rac-Dimethylsilylene-bis (2-methyl-α-acenaphtho-1-indenyl) zirconium dichloride obtained in Preparation Example 1 was added in an amount of 0.002 mmol in terms of Zr atom,
Polymerization was carried out for 60 minutes while continuously supplying propylene and keeping the total pressure at 14 kg / cm ² G.

After the polymerization, the polymer was degassed and recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours. The obtained polymer (propylene elastomer) is 65.
3 g, polymerization activity is 33 kg polymer / mmol Z
It was r · hr. This polymer contained 13.0 mol% of units derived from 1-butene. The intrinsic viscosity [η] was 1.81 dl / g and the melting point was 102.3 ° C. The ratio of heterologous bonds based on 2,1-insertion is about 0.36%
Met. Table 2 shows the measured physical properties of the obtained polymer.

[0176]

Example 3 A 2 liter autoclave, which had been sufficiently replaced with nitrogen, was charged with 950 ml of hexane and 130 g of 1-butene, and 1 mmol of triisobutylaluminum was added.
After raising the temperature to 70 ℃, propylene is fed and the total pressure is 14kg.
/ Cm ² G, methylaluminoxane 0.30 mmol,
Rac-Dimethylsilylene-bis (2-methyl-α-acenaphtho-1-indenyl) zirconium dichloride obtained in Preparation Example 1 was added in an amount of 0.002 mmol in terms of Zr atom,
Polymerization was carried out for 60 minutes while continuously supplying propylene and keeping the total pressure at 14 kg / cm ² G.

After the polymerization, the polymer was degassed and recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours. The obtained polymer (propylene elastomer) is 44.
0 g, polymerization activity is 22 kg polymer / mmol Z
It was r · hr. This polymer contained 17.7 mol% of units derived from 1-butene. The intrinsic viscosity [η] was 1.79 dl / g and the melting point was 89.1 ° C. The ratio of heterologous bonds based on 2,1-insertion is about 0.35.
%Met.

Table 2 shows the measured physical properties of the obtained polymer.

[0179]

[Comparative Example 1] 830 ml of hexane and 100 g of 1-butene were charged into a 2-liter autoclave which had been sufficiently replaced with nitrogen, and 1 mmol of triisobutylaluminum was added.
After raising the temperature to 70 ° C, propylene is supplied to bring the total pressure to 7 kg /
cm ² G, 1 mmol of triethylaluminum, and 0.005 mmol of titanium catalyst supported on magnesium chloride in terms of Ti atoms were added, and propylene was continuously supplied to maintain the total pressure at 7 kg / cm ² G. While performing the polymerization for 30 minutes. After the polymerization, the mixture was degassed, the polymer was recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours.

The amount of the polymer obtained was 33.7 g, and the polymerization activity was 14 kg.polymer / mmol Zr.hr. This polymer contains 2 units derived from 1-butene.
The content was 5.3 mol%. Intrinsic viscosity [η] is 1.89
dl / g, melting point was 110.0 ° C. The rate of heterologous binding based on the 2,1-insertion was below the detection limit.

Table 2 shows the measured physical properties of the obtained polymer.

[0182]

[Table 2]

[0183]

[Production Example 2] [Synthesis of rac-dimethylsilylene-bis (2-methyl-4,6-diisopropyl-1-indenyl) zirconium dichloride (metallocene compound represented by the formula [I])] (2-methyl-4, 6-diisopropyl) indene (compound
) Synthesis: 123 g (0.92 mol) of aluminum chloride and 200 ml of carbon disulfide in a 1 liter reactor which has been sufficiently replaced with nitrogen.
Charge 1,3 diisopropylbenzene 78m into this
l (0.41 mole) and methacryloyl chloride 45m
A solution of 1 (0.41 mol) and 40 ml of carbon disulfide was added dropwise at 20 to 25 ° C. After reacting for 12 hours at room temperature, the mixture was added to 1 kg of ice and extracted with ether. The resulting ether solution was washed with saturated aqueous sodium hydrogen carbonate, the ether layer was further washed with water, and the ether layer was concentrated.
g of oil were obtained. This oil was purified by silica gel column chromatography (developing solvent: n-hexane) to give 2-methyl-4,6-diisopropyl-1-indanone and 2-methyl-4,6-diisopropyl-1-indanone.
Mixture of methyl-5,7-diisopropyl-1-indanone 43
g was obtained (yield: 47%).

A 1 liter reactor which had been sufficiently replaced with nitrogen was charged with 3.3 g (86 mmol) of sodium borohydride and 40 ml of ethyl alcohol, and the mixture 2
1.1 g (78.6 mmol) and ethyl alcohol 30 m
The mixed solution of 1 was added dropwise at 50 ° C. 1 at 60 ℃ after dropping
After reacting for 2 hours at 70 ° C., 30 ml of acetone was added while cooling the reaction solution with water. Concentrate the reaction solution,
After drying to dryness, 300 ml of ether and 100 ml of water were added for extraction. The ether layer was washed with water and dried over anhydrous sodium sulfate. The ether layer was concentrated and then dried to obtain 21.1 g of pale yellow viscous alcohol (yield: 99%).

21.0 g (79 mmol) of the above alcohol and 500 ml of benzene were charged into a 1 liter reactor which had been sufficiently purged with nitrogen, and 50 mg (0.55 mmol) of paratoluenesulfonic acid monohydrate was added thereto. And refluxed for 1 hour. After completion of the reaction, the mixture was poured into 300 ml of saturated aqueous sodium hydrogen carbonate, the ether layer was washed with water, and dried over anhydrous sodium sulfate. The ether layer was concentrated and dried under reduced pressure to give the desired indene derivative as a pale yellow-green oil.
9 g were obtained. When this oil was purified by silica gel column chromatography (developing solvent: n-hexane), the target indene derivative was converted to colorless amorphous 17.
6 g was obtained (yield: 95%).

NMR (CDCl ₃ , ppm): δ = 1.32 (3H, d, J = 7.2 Hz), 2.16
(3H, s), 2.74 to 3.20 (2H, m), 3.2
8 (2H, m), 6.60 (1H, s), 6.98 (1
H, s), 7.12 (1H, s) 1,1'-dimethylsilylene-bis (2-methyl-4,6-diisop)
Synthesis of lopyruindene (compound)
7.0 g (31 mmol), copper cyanide 76 mg (0.9
Millimol), 60 ml of diethyl ether were charged,
Cooled to 10 ° C. A hexane solution of n-butyllithium (31 mmol) was added to this solution. After the temperature was raised to room temperature, it was cooled to -10 ° C again, and 1.9 ml (15.5 mmol) of dimethyldichlorosilane was added dropwise over 30 minutes.
The reaction was carried out for 1 hour. After completion of the reaction, the mixture was added to 40 ml of saturated aqueous ammonium chloride solution, extracted with n-hexane, washed with water, and dried over magnesium sulfate. The salt was removed, and the yellow oil obtained by concentrating the organic layer under reduced pressure was purified by silica gel column chromatography (developing solvent: n-hexane) to give the compound as a colorless amorphous product (6.1 g).
Obtained (yield: 73%).

NMR (CDCl ₃ , ppm): δ = 1.25 to 1.40 (30 H, m), 2.18 (3
H, s), 2.24 (3H, s), 2.92 (2H, q,
J = 6.8Hz), 3.23 (2H, q, J = 6.8Hz),
3.65 (2H, br.s), 6.73 (2H, br.s),
6.97 (2H, br.s), 7.10 to 7.23 (2H, b
r.s) rac-dimethylsilylene-bis (2-methyl-4,6-diisopro)
Synthesis of Pyrindenyl) zirconium dichloride 5.9 g (12.2 mmol) of the compound obtained above and 100 ml of tetrahydrofuran were charged in a 300 ml reactor which was sufficiently replaced with nitrogen, and the mixture was cooled to -78 ° C and stirred. To this, 15.4 ml of n-butyllithium (n-hexane solution, 1.58N, 24.4 mmol) was added dropwise over 20 minutes, and the mixture was stirred for 1 hour while maintaining the temperature to prepare an anion solution. Then, the temperature was slowly raised to room temperature.

At the same time, 100 ml of tetrahydrofuran was charged into a 300 ml reactor which had been sufficiently replaced with nitrogen, and -7
It was cooled to 8 ° C. and stirred. After slowly adding 2.85 g (12.2 mmol) of zirconium tetrachloride, the temperature was raised to room temperature. The above-mentioned anion solution is added to this 30
The mixture was added dropwise over minutes and stirred at room temperature for 12 hours. After completion of the reaction, the mixture was concentrated under reduced pressure and the precipitated solid was washed 3 times with 300 ml of hexane to remove insoluble matter. The obtained hexane solution was concentrated to about 50 ml and cooled at 6 ° C for 12 hours. The precipitated solid was removed, and the resulting solution was mixed with ¹ H-N
When analyzed by MR, it was a mixture of racemate and meso body (9: 1). 150 ml of hexane to this mixture
Was added and recrystallized again to obtain 0.15 g of yellow columnar crystals of the above target compound (yield: 2%).

The FD mass spectrometry result of the obtained compound was 644 (M ⁺ ). NMR (CDCl ₃ , ppm): δ = 1.28 (6H, s) 1.20-1.36 (24H, m), 2.85 (2H,
q, J = 6.8Hz), 3.04 (2H, q, J = 6.8H)
z), 6.80 (2H, s), 7.05 (2H, s), 7.
26 (2H, s)

[0190]

[Example 4] 900 ml of hexane and 70 g of 1-butene were charged into a 2 liter autoclave which had been sufficiently replaced with nitrogen, and 1 mmol of triisobutylaluminum was added to the autoclave.
After raising the temperature to 0 ° C, propylene was supplied to the total pressure 14kg /
cm ² G, 0.40 mmol of methylaluminoxane, rac-dimethylsilylene-bis (2-methyl-4,6-diisopropyl-1-indenyl) zirconium dichloride prepared in Preparation Example 2 was converted to Zr atom and converted to 0. 0.002 mmol was added, and propylene was continuously supplied to bring the total pressure to 14 kg / cm ² G.
Polymerization was carried out for 60 minutes while maintaining

After the polymerization, the polymer was degassed and recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours. The obtained polymer (propylene elastomer) is 31.
7 g, polymerization activity is 16 kg polymer / mmol Z
It was r · hr. This polymer contained 6.2 mol% of units derived from 1-butene. Intrinsic viscosity [η]
Was 1.83 dl / g and the melting point was 118.2 ° C. The percentage of heterologous bonds based on the 2,1-insertion was about 0.88%.

Table 3 shows the measured physical properties of the obtained polymer.

[0193]

Example 5 900 ml of hexane and 100 g of 1-butene were charged into a 2-liter autoclave which had been sufficiently replaced with nitrogen, and 1 mmol of triisobutylaluminum was added.
After raising the temperature to 70 ℃, propylene is fed and the total pressure is 14kg.
/ Cm ² G, methylaluminoxane 0.30 mmol,
Rac-Dimethylsilylene-bis (2-
Methyl-4,6-diisopropyl-1-indenyl) zirconium dichloride was added in an amount of 0.002 mmol in terms of Zr atom, and propylene was continuously supplied so that the total pressure was 14 kg / cm.
Polymerization was carried out for 60 minutes while maintaining ² G.

After the polymerization, the polymer was degassed and recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours. The obtained polymer (propylene elastomer) is 19.
0 g, polymerization activity is 10 kg polymer / mmol Z
It was r · hr. This polymer contained 11.0 mol% of units derived from 1-butene. The intrinsic viscosity [η] was 1.74 dl / g and the melting point was 105.1 ° C. The ratio of heterologous bonds based on 2,1-insertion is about 0.86%
Met. Table 3 shows the measured physical properties of the obtained polymer.

[0195]

Example 6 Into a 2 liter autoclave which had been sufficiently replaced with nitrogen, 950 ml of hexane and 130 g of 1-butene were charged, and 1 mmol of triisobutylaluminum was added.
After raising the temperature to 70 ℃, propylene is fed and the total pressure is 14kg.
/ Cm ² G, methylaluminoxane 0.30 mmol,
Rac-Dimethylsilylene-bis (2-
Methyl-4,6-diisopropyl-1-indenyl) zirconium dichloride was added in an amount of 0.002 mmol in terms of Zr atom, and propylene was continuously supplied so that the total pressure was 14 kg / cm.
Polymerization was carried out for 60 minutes while maintaining ² G.

After the polymerization, the polymer was degassed and recovered in a large amount of methanol, and dried under reduced pressure at 110 ° C. for 12 hours. The obtained polymer (propylene elastomer) was 10.
1 g, polymerization activity is 5 kg polymer / mmol Zr
・ It was hr. This polymer contained 15 mol% of units derived from 1-butene. The intrinsic viscosity [η] is
The melting point was 1.52 dl / g and the melting point was 91.0 ° C. 2,1-
The percentage of heterologous bonds based on insertion was about 0.88%.

Table 3 shows the measured physical properties of the obtained polymer.

[0198]

[Table 3]

Claims (4)

[Claims] (1) 50 to 50 units derived from propylene
95 mol% in an amount of 5 to 50 mol% of units derived from 1-butene, (2) (i) head-to-tail linked propylene units 3 chains, or
(ii) Side chain methyl group of the propylene unit of the second unit in the propylene / butene 3 chain which is composed of head-to-tail bonded propylene units and butene units and contains propylene units in the second unit ¹³ C- The NMR spectrum (hexachlorobutadiene solution, tetramethylsilane standard) was measured, and the total area of the peaks appearing at 19.5 to 21.9 ppm was 100.
%, The peak area appearing at 21.0 to 21.9 ppm is 90% or more, and (3) the intrinsic viscosity measured in decalin at 135 ° C is 0.0.
1 to 12 dl / g, (4) gel permeation chromatography (GP
The molecular weight distribution (Mw / Mn) determined by C) is 3 or less, and (5) the parameter B value indicating the randomness of the copolymerized monomer chain distribution is 1.0 to 1.5. Propylene elastomer. 2. The characteristics (1) to (4) are satisfied, the parameter B value (5) is 1.0 to 1.3, and (6) measured by a differential scanning calorimeter. Melting point Tm is 6
0 to 140 ° C., the melting point Tm, and 1-butene structural unit content M (mol%)
The relationship with is −2.6M + 125 ≦ Tm ≦ −2.6M + 145
And (7) the relationship between the crystallinity C measured by the X-ray diffraction method and the 1-butene constitutional unit content M (mol%) is C ≥ -1.5M + 65. Item 1. The propylene-based elastomer according to Item 1. 3. [A] a metallocene compound represented by the following general formula (A), [B] [B-1] an organoaluminum oxy compound, and / or
Alternatively, propylene and 1-butene are added in the presence of an olefin polymerization catalyst containing [B-2] a compound which reacts with a metallocene compound [A] to form an ion pair, and optionally [C] an organoaluminum compound. The propylene-based elastomer according to claim 1 or 2, which is obtained by copolymerization; [In the formula, M is a transition metal atom of groups IV to VIB of the periodic table, and R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms. A halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and those groups in which some of the groups adjacent to each other are bound to each other. May form a ring with the carbon atom to which is bonded, X ¹ and X ² may be the same or different from each other, and are a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a carbon number 1 To 20 halogenated hydrocarbon groups, oxygen-containing groups or sulfur-containing groups, Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 to carbon atoms
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, -O-, -CO-,-
S -, - SO -, - SO 2 -, - NR 7 -, - P
^{(R 7) -, - P} (O) (R 7) -, - BR 7 - or -AlR ⁷ - (provided that R ⁷ is a hydrogen atom, a halogen atom,
A hydrocarbon group having 1 to 20 carbon atoms and a halogenated hydrocarbon group having 1 to 20 carbon atoms). ]. 4. The propylene-based elastomer according to claim 3, wherein the metallocene compound [A] is represented by the following formula [I] or [II]; [In the formula, M is a transition metal of Group IVB, VB or VIB of the Periodic Table, R ¹¹ and R ¹² may be the same or different from each other, and a hydrogen atom, a halogen atom, a C 1 to C 20 A hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and R ¹³ and R ¹⁴ are the same or different from each other. May be an alkyl group or an aryl group having 1 to 20 carbon atoms, X ¹ and X ² may be the same or different from each other, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, It is a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group or a sulfur-containing group, Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, 1 to carbon atoms
20 divalent halogenated hydrocarbon groups, divalent silicon-containing groups, divalent germanium-containing groups, -O-, -CO-,-
S -, - SO -, - SO 2 -, - NR 7 -, - P
^{(R 7) -, - P} (O) (R 7) -, - BR 7 - or -AlR ⁷ - (provided that R ⁷ is a hydrogen atom, a halogen atom,
A hydrocarbon group having 1 to 20 carbon atoms and a halogenated hydrocarbon group having 1 to 20 carbon atoms). ], [Chemical 3] [In the formula, M is a transition metal of Group IVB of the Periodic Table, R ²¹ may be the same or different from each other, and are a hydrogen atom, a halogen atom, or an optionally halogenated C 1-10 alkyl group, an aryl group, or -NR ₂ of 6 to 10 carbon atoms, -SR, -OSiR _3, -SiR ₃ or -PR ₂ radicals (wherein R is a halogen atom, C1-10
Or an aryl group having 6 to 10 carbon atoms), R ^{22 to} R ²⁸ are the same as R ²¹ described above, or adjacent R ^{22 to} R ²⁸ together with the atom to which they are bonded are aromatic. May form a group- or an aliphatic ring, X ³ and X ⁴ may be the same or different from each other, and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 carbon atom.
An alkoxy group having 10 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms,
An aryloxy group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an arylalkyl group having 7 to 40 carbon atoms,
Alkylaryl group having 7 to 40 carbon atoms, 8 to 40 carbon atoms
An arylalkenyl group, an OH group or a halogen atom of -Sn -, - O -, - S -, = SO, = SO 2, = NR
²⁹ , = CO, = PR ²⁹ or = P (O) R ²⁹ .
(However, R ²⁹ and R ³⁰ may be the same or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms. Group, fluoroaryl group having 6 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, 2 carbon atoms
A C-10 alkenyl group, a C7-40 arylalkyl group, a C8-40 arylalkenyl group or a C7-40 alkylaryl group, or R ²⁹ and R ³⁰ are each a group thereof. It may also form a ring with the atom to which it is attached, M ² is silicon, germanium or tin. )].