JP2002128832A - Propylene/ethylene copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene/ethylene copolymer having highly controlled stereoregularity and exhibitting high heat-resistance and rigidity though having enough low temperature heat sealability and transparency. SOLUTION: The propylene/ethylene copolymer is constituted to satisfy the following characteristics (1)-(3): (1) The content of an ethylene unit is 0.1-3.3 wt.% in terms of a weight reference of the propylene/ethylene copolymer. (2) Isotactic triad fraction (I3) is >=0.50 but <0.95. (3) The ratio of molar number of a propylene unit derived from 2,1-insertion reaction of a propylene monomer with respect to the total molar number of the propylene unit constituting the propylene/ethylene copolymer is >=0.05% but <0.5%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel propylene / ethylene copolymer produced using an olefin polymerization catalyst. More specifically, the present invention relates to a propylene / ethylene copolymer in which stereoregularity is highly controlled.

[0002]

2. Description of the Related Art As a prior example of a propylene polymer controlling stereoregularity, for example, Japanese Unexamined Patent Publication No. 10-27350
No. 7 discloses that (A) an isotactic triad fraction of 97% or more measured by ¹³ C-NMR of a propylene unit chain portion comprising a head-tail bond is (B) ¹³ C-
The ratio of the position irregular units based on the 2,1-insertion of the propylene monomer in the total propylene insertion measured by NMR is 0.5 to 2.0%, and the position based on the 1,3-insertion of the propylene monomer. 0.06 irregular units
To 0.4%, and (C) the weight average molecular weight Mw measured by gel permeation chromatography (GPC) is in the range of 10,000 to 1,000,000. Highly stereoregular propylene polymers have been reported that feature.

Further, Japanese Patent Application Laid-Open No. 11-171925 discloses that (A) the isotactic triad fraction of a propylene unit chain portion comprising a head-to-tail bond measured by ¹³ C-NMR is 98% or more, B) Measured by ¹³ C-NMR,
The proportion of regio-irregular units based on 2,1-insertion of propylene monomer in all propylene insertions is 0.03% or less, and the proportion of regio-irregular units based on 1,3-insertion of propylene monomer is 0.06% As described above, (C) the weight average molecular weight is 10,000 to 1,000,000, and (D) the melting point is 160 ° C.
High stereoregularity propylene polymers characterized by the above are reported.

Japanese Patent Application Laid-Open No. Hei 7-145212 discloses that (a) triad tacticity of a propylene unit chain composed of a head-to-tail bond measured by ¹³ C-NMR is 90.0% or more; (B) The proportion of regio-irregular units based on the 2,1-insertion of the propylene monomer in the total propylene insertion measured by ¹³ C-NMR is 0.7% or more, and the ratio of the 1,3-insertion of the propylene monomer is (C) 135 ° C.
Intrinsic viscosity measured in decalin of 0.1 to 12 dl / g
, A propylene-based polymer having high rigidity and high heat resistance has been reported.

Japanese Patent Application Laid-Open No. 7-149832 discloses that (a) 95 to 99.5 mol% of a propylene unit and 0.5 to 5 mol% of an ethylene unit;
¹³ C-NMR of a propylene unit chain consisting of a tail bond
The triad tacticity measured in step (c) is 90.0% or more, and (c) the proportion of the position irregular units based on the 2,1-insertion of the propylene monomer in the total propylene insertion is 0, as measured by ¹³ C-NMR. 0.5% or more and the ratio of the position irregular units based on the 1,3-insertion of the propylene monomer is 0.0
5% or less, and (d) a propylene copolymer having high rigidity and high heat resistance, characterized in that the intrinsic viscosity measured in decalin at 135 ° C. is in the range of 0.1 to 12 dl / g. It has been reported.

Japanese Patent Application Laid-Open No. 11-302470 discloses the following article.
Propylene homopolymer satisfying the requirements (1) to (6), or
Or propylene-α-ole
Fin-random copolymers have been reported. (1) Melt flow rate is 0.5 to 50.0 g / 10
Minutes, (2) Memory effect is 0.9 ~
1.4, and (3) the main value determined with a differential scanning calorimeter.
When the temperature of the melting peak [TP] is 100 to 160 ° C.
(4) Melting end temperature determined by differential scanning calorimeter
Degree [TE] (° C) is [TP]-[TE] ≤ 8
And (5) a propylene unit chain comprising a head-to-tail bond
of,¹³Isotactic triatometry measured by C-NMR
The de-fraction is 97% or more; (6) ¹³By C-NMR
Measured, of the propylene monomer in the total propylene insertion
The ratio of the position irregular units based on 2,1-insertion is 0.5 to
2.0% and 1,3-insertion of propylene monomer
0.06-0.4% of position irregular units based on
Range.

Japanese Patent Application Laid-Open No. 8-73532 discloses that
(A) 95 to 99.5 mol% of a propylene unit and 0.5 to 5 mol% of an ethylene unit, and (b) ¹³ C—N
The triad tacticity of the propylene unit chain composed of head-to-tail bonds determined by MR is 95.0% or more, and (c) 2,3 of the propylene monomer in the total propylene insertion determined by ¹³ C-NMR. The proportion of regiorandom units based on 1-insertion is 0.05% to 0.5%, and (d) the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 12 dl / g. Propylene-based copolymers, which are characterized in that:

Further, JP-A-7-149833 discloses that (a) 50 to 95 mol% of a propylene unit and 5 to 50 mol% of an ethylene unit, and (b) ¹³ C-
The triad tacticity of a propylene unit chain composed of head-to-tail bonds determined by NMR is 90.0%
(C) the proportion of regio-irregular units based on the 2,1-insertion of the propylene monomer in the total propylene insertion determined by ¹³ C-NMR is 0.05 to 0.5%, and (d) ) A propylene-based elastomer characterized in that the intrinsic viscosity [η] measured in decalin at 135 ° C is in the range of 0.1 to 12 dl / g is disclosed.

[0009] JP-A-7-138326 discloses that
(A) 50 to 95 mol% of a propylene unit and 5 to 50 mol% of an ethylene unit, and (b) triad tacticity of a propylene unit chain composed of head-to-tail bonds, as determined by ¹³ C-NMR. Is not less than 90.0%, and (c) the proportion of regio-irregular units based on the 2,1-insertion of the propylene monomer in the total propylene insertion is not less than 0.5%, as determined by ¹³ C-NMR, and The proportion of regio-irregular units based on the 1,3-insertion of the propylene monomer is 0.
It is reported that the propylene-based elastomer is not more than 0.05%, and (d) has an intrinsic viscosity in a range of 0.1 to 12 dl / g measured at 135 ° C. in decalin.

Japanese Patent Application Laid-Open No. 8-283343 discloses (1)
(2) (i) three chains of head-to-tail bonded propylene units containing 50 to 95 mol% of units derived from propylene and 5 to 50 mol% of units derived from 1-butene; Or (ii) a side chain methyl group of a propylene unit of the second unit in a propylene / butene three-chain chain comprising a propylene unit and a butene unit in a head-to-tail bond and containing the propylene unit as the second unit; NMR spectrum (based on hexachlorobutadiene solution and tetramethylsilane) was measured, and assuming that the total area of peaks appearing from 19.5 to 21.9 ppm was 100%, 21.0 to 21.9 pp
m is 90% or more, and (3) 13
Intrinsic viscosity measured in decalin at 5 ° C. is 0.1 to 12 d
(4) molecular weight distribution (Mw / g) determined by gel permeation chromatography (GPC).
Mn) is 3 or less, and (5) a propylene-based elastomer characterized in that the parameter B value indicating the randomness of the copolymer monomer chain distribution is from 1.0 to 1.5. As described in the detailed description in the specification, the propylene-based elastomer includes (8) 2,1-insertion or 1,1-insertion of propylene present in a propylene chain.
It may have a small amount of a structure containing a heterogeneous bond unit (positional irregular unit) based on 3-insertion. In particular, in Examples, the amount of heterogeneous bond based on 2,1-insertion is 0.35 to 0.35.
An example of a 0.88% propylene-based elastomer is described.

However, these polymers still have sufficiently low-temperature heat sealability and transparency, and yet their stereoregularity is still sufficiently controlled to be used in applications requiring high heat resistance and rigidity. It was not what was done.

[0012]

SUMMARY OF THE INVENTION The present invention provides a propylene / ethylene copolymer obtained by using an olefin polymerization catalyst, wherein the propylene / ethylene copolymer has a highly controlled stereoregularity. The purpose is to do. When the propylene / ethylene copolymer of the present invention is used, various molded products excellent in rigidity, heat resistance and transparency can be obtained. Further, since the extraction ratio to the solvent is low, it can be suitably used in the fields of food packaging films and food storage containers.

[0013]

The present invention is produced using an olefin polymerization catalyst and has the following properties (1) to (3).
Is a propylene / ethylene copolymer characterized by satisfying the following conditions: Characteristic (1) The content of the ethylene unit is 0.1 to 3.3% by mass. Property (2) Isotactic triad fraction (I ₃ )
Is 0.50 or more and less than 0.95. Characteristic (3) The propylene monomer is 2,1-1-based on the total number of moles of the propylene units constituting the propylene polymer.
The proportion occupied by the number of moles of propylene units caused by the insertion reaction is 0.05% or more and less than 0.5%.

[0014] The characteristic requirement (1) of the propylene / ethylene copolymer of the present invention is that the content of ethylene unit is 0.1 to 3.3% by weight, preferably 0.1 to 3.3% by weight, based on the weight of the propylene / ethylene copolymer. , 0.5 to 3.3% by weight, more preferably 1.0 to 3.3% by weight, particularly preferably 2.
0 to 3.0% by weight. When the content of ethylene units is
If it is less than 0.1% by weight, the low-temperature heat sealability and transparency are insufficient. If it is more than 3.3% by weight, rigidity and impact resistance may be insufficient.

The characteristic requirement (2) of the propylene / ethylene copolymer of the present invention is that the copolymer has an isotactic triad fraction (I ₃ ) of 0.50 or more and less than 0.95;
Preferably, it is 0.70 or more and less than 0.95, and more preferably 0.80 or more and less than 0.95.

The characteristic requirement (3) of the propylene / ethylene copolymer of the present invention is that the propylene monomer has a 2,1-insertion reaction with respect to the total number of moles of propylene units constituting the propylene / ethylene copolymer. The proportion of the moles of the resulting propylene units occupies 0.05% or more and less than 0.5%, preferably 0.05% or more and less than 0.45%, more preferably 0.1% or more and 0.4%. Is less than. Propylene monomer 2,2
1- If the proportion of the number of moles of propylene units due to the insertion reaction occupies less than 0.05%, the low-temperature heat-sealing property and transparency are insufficient, and if it is 0.5% or more, the rigidity is low. , Heat resistance may be insufficient.

Further, based on the total number of moles of propylene units constituting the propylene / ethylene copolymer of the present invention,
The proportion of the moles of propylene units caused by the 1,3-insertion reaction of the propylene monomer is preferably 0.5% or less, more preferably 0.3% or less, and still more preferably 0.2% or less. , Most preferably less than 0.05%.

The propylene unit resulting from the 2,1-insertion reaction of the propylene monomer with respect to the isotactic triad fraction (I ₃ ) and the total number of moles of the propylene unit constituting the propylene / ethylene copolymer. And the proportion occupied by each of the number of moles of propylene units resulting from the 1,3-insertion reaction of the propylene monomer can be determined based on the measurement results of ¹³ C nuclear magnetic resonance spectrum measured according to the following method. .

That is, a test sample (propylene / ethylene copolymer) was added to a mixed solution of o-dichlorobenzene / brominated benzene = 8/2 by weight so that the concentration in the mixed solution was 20% by weight. Dissolve in For this test solution, the measurement wavelength is 67.20 MHz, and the measurement temperature is 130 ° C.
A ¹³ C nuclear magnetic resonance spectrum is measured under the following conditions. As a measuring device, for example, “JEOL-” manufactured by JEOL Ltd.
GX270 NMR (trade name) "can be used.

The "isotactic triad fraction (I ₃ )" was proposed in JP-A-7-149833 and JP-A-8-283343 based on the measurement result of the ¹³ C nuclear magnetic resonance spectrum. It is calculated by the method.

Isotactic triad fraction (I ₃ )
Represents the ratio of three consecutive meso-bonded propylene units to the total number of propylene units in the propylene / ethylene copolymer molecular chain. Therefore, the higher the isotactic triad fraction (I ₃ ), the higher the isotacticity.

On the other hand, with respect to the total number of moles of propylene units constituting the propylene / ethylene copolymer, the number of moles of propylene units due to the 2,1-insertion reaction of propylene monomer and 1,3-insertion of propylene monomers The proportion occupied by the number of moles of propylene units due to the reaction is determined by T. Tsutsui et al. Based on the results of the above-mentioned ¹³ C nuclear magnetic resonance spectrum measurement as “Polymer (Polymer), 30, 1350 (19)
89)), which is an index indicating the stereoregularity of a polymer mainly composed of propylene, which is determined by the method disclosed in "89)".

The propylene / ethylene copolymer of the present invention has the above-mentioned various properties, and is preferably 100 to 150 ° C., more preferably 110 to 14 ° C.
It has a melting point of 0 ° C, particularly preferably 115-135 ° C.

The melting point (Tm) can be measured using a “DSC7 differential scanning calorimeter” manufactured by Perkin Elmer. First, a propylene / ethylene copolymer as a test sample was heated from room temperature to 230 ° C. at a rate of 30 ° C./min, held at the same temperature for 10 minutes, and then cooled at a rate of −20 ° C./min to −20. The temperature is lowered to ° C. and kept at the same temperature for 10 minutes. Thereafter, when the temperature was raised again at a rate of 20 ° C./min, the temperature at which the melting peak was reached was taken as the melting point.

Further, the propylene / ethylene copolymer of the present invention is obtained by gel permeation chromatography (G
PC) has a weight average molecular weight (Mw) of preferably 10,000 to 1,000,000 g / mol, more preferably 80,000 to 500,000 g.
/ Mol, most preferably 100,000-400,0
It is in the range of 00 g / mol.

In the propylene / ethylene copolymer of the present invention, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight is preferably 1.5 to 3.8, more preferably 1. 5-3.5, most preferably 1.8
It has a value of ~ 2.5.

The propylene / ethylene copolymer of the present invention has a melt flow rate (measured in accordance with JIS K7210 under conditions 14 in Table 1) of preferably 0.3 to 0.3.
300 g / 10 min, more preferably 0.5 to 100
g / 10 min. If the melt flow rate is less than 0.3 g / 10 min,
If it is more than g / 10 min, it is not preferable because processing by a conventionally known molding method becomes difficult.

The production method of the propylene / ethylene copolymer of the present invention is not particularly limited as long as the obtained copolymer satisfies the characteristic requirements of the present invention, but preferably the following (1) Alternatively, it can be produced using any of the olefin polymerization catalysts roughly classified into (2).

(1) Metallocene compound (hereinafter referred to as “(A)
Component ". ), Activating compounds (hereinafter,
It may be referred to as “(B) component”. ), A fine particle carrier (hereinafter sometimes referred to as “component (C)”), and an organic aluminum compound (hereinafter, referred to as “component (C)”) used if desired.
It may be referred to as “(D) component”. ) And an organoaluminum compound (hereinafter sometimes referred to as a component (D ′)), wherein the catalyst is a metallocene-supported catalyst (hereinafter sometimes referred to as “metallocene-supported catalyst I”). An olefin polymerization catalyst comprising:

(2) Component (A), a specific ion-exchange layered compound or inorganic silicate (hereinafter sometimes referred to as component (E)), and component (D) used as required. A metallocene-supported catalyst (hereinafter sometimes referred to as “metallocene-supported catalyst II”), and an olefin polymerization catalyst comprising the component (D ′).

As the metallocene compound of the component (A),
Preferably, a metallocene compound represented by the following general formula (1) is used. _{Q (C 5 H 4-m} R 1 m) (C 5 H 4-n R 2 n) MXY (1) Incidentally, in the formula _{(1), (C 5 H} 4-m R 1 m) and (C ₅ H _4-n R
² _n ) represents a cyclopentadienyl group, and C ₅ H _4-m and C _5
5 H _4-n represents a cyclopentadienyl ring. m is 1-3
And an integer of 3 is preferred. n is
Independently of m, an integer of 2 or 3 is shown, and an integer of 3 is preferred.

R ¹ and R ² are bonding groups bonded to C ₅ H _4-m and C ₅ H _4-n , respectively, and independently of each other,
A hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group,
Alternatively, it represents a heteroaromatic group. Each of R ¹ _m and each of R ² _n may be the same or different from each other.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-butyl group, an isobutyl group and a t-
Examples thereof include a butyl group, an n-hexyl group, an n-octyl group, a cyclohexyl group, and a phenyl group, and preferred are a methyl group, a t-butyl group, and a phenyl group.

A preferred example of the silicon-containing hydrocarbon group having 1 to 20 carbon atoms is a trimethylsilyl group.

The heteroaromatic group has a heteroaromatic ring and, if desired, at least one bonding group bonded to the ring.

As the heteroaromatic ring, those having a monocyclic or polycyclic structure can be used, preferably a monocyclic or bicyclic heteroaromatic ring, and particularly preferably a monocyclic heteroaromatic ring. is there.

The hetero atom of the heteroaromatic ring is not particularly limited. Preferred is a heteroaromatic ring containing an oxygen atom or a sulfur atom as a heteroatom, and particularly preferred is a heteroaromatic ring containing an oxygen atom. Specifically, preferred examples of the aromatic ring include a furyl ring, a thienyl ring, a benzofuryl ring and a benzothienyl ring. More preferred specific heteroaromatic ring is a 2-furyl ring, 2-thienyl ring, 2-benzofuryl ring or 2-benzothienyl ring, and particularly preferred is a 2-furyl ring.

If desired, the bonding group which may be bonded to the heteroaromatic ring is a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group. The hydrocarbon group and silicon-containing hydrocarbon group having 1 to 20 carbon atoms, C ₅ H _4-m and C ₅ H _4-n those described above as the binding group which binds to the same hydrocarbon groups and silicon-containing hydrocarbon Hydrogen groups can be mentioned.

The heteroaromatic group preferably has a heteroaromatic ring and at least one bonding group bonded to the ring. Specifically, the heteroaromatic ring is a furyl ring, a thienyl ring, a benzofuryl ring or a benzothienyl ring, and at least one bonding group bonded to the ring is a methyl group, an ethyl group, an n-butyl group, an isobutyl group. And a heteroaromatic group such as a t-butyl group, a phenyl group or a trimethylsilyl group. Further preferably, the heteroaromatic ring is a 2-furyl ring, a 2-thienyl ring, a 2-benzofuryl ring or a 2-benzothienyl ring, and at least one bonding group bonded to the ring is a methyl group, t
-A heteroaromatic group which is a butyl group, a phenyl group or a trimethylsilyl group. Specifically, a 2- (5-methyl) -furyl group, a 2- (5-t-butyl) -furyl group, a 2- (5-trimethylsilyl) -furyl group,
(5-methyl) -thienyl group, 2- (5-t-butyl)
-Thienyl group, 2- (5-trimethylsilyl) -thienyl group, 2- (4,5-dimethyl) -furyl group, 2-
Examples thereof include a (4,5-dimethyl) -thienyl group, a 2-benzofuryl group, and a 2-benzothienyl group.

A pair of R ² out of R ² _n are bonded to each other to form a monocyclic or polycyclic ring. The number of rings is not particularly limited, but is preferably 1 to 5, and particularly preferably 1 or 2. The ring structure in which at least one ring (ie, a monocyclic or polycyclic ring) formed by the pair of R ² bonded to each other together with the cyclopentadienyl ring C ₅ H _4-n is preferably an indenyl ring, It is a tetrahydroindenyl ring, a benzoindenyl ring, a fluorenyl ring, a dihydroazulenyl ring or a cyclopentaphenanthrene ring, and more preferably an indenyl ring, a benzoindenyl ring or a dihydroazulenyl ring.

[0041] when m is 2 or 3, R ¹ a pair of the R ¹ _m is bonded to each other, independently of the ring where the pair of R ² to form, at least one ring (i.e. mono- Or polycyclic). The ring structure formed by combining at least one ring formed by the pair of R ¹ with a cyclopentadienyl ring C ₅ H _{4- m} is preferably an indenyl ring, a tetrahydroindenyl ring, a benzoindenyl ring. Ring, a fluorenyl ring, a dihydroazulenyl ring or a cyclopentaphenanthrene ring, more preferably an indenyl ring, a benzoindenyl ring,
It is a dihydroazulenyl ring.

At least one ring formed by the pair of R ¹ and at least one ring formed by the pair of R ² may be the same or different. A ring structure composed of at least one ring formed by a pair of R ¹ and C ₅ H _{4- m} is an indenyl ring, a benzoindenyl ring, or a dihydroazulenyl ring, and a pair of R ² forms ring structure composed of at least one ring and C ₅ H _4-n are indenyl ring, benzindenyl ring, or for a dihydro Azure cycloalkenyl ring. Further preferred are cyclic structure composed of at least one ring and C ₅ H _4-m a pair of R ¹ to form, and, at least one pair of R ² to form ring C ₅ H _{4- The} ring structure composed of _n and
It is a metallocene compound that is an indenyl ring, a benzoindenyl ring, or a dihydroazulenyl ring.

At least one ring formed by the pair of R ¹ and at least one ring formed by the pair of R ² independently have at least one bonding group bonded to each ring. Is also good. At least one bonding group bonded to each ring is a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group or a heteroaromatic group.

Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-butyl group, an isobutyl group and a t-
Examples thereof include a butyl group, an n-hexyl group, an n-octyl group, a cyclohexyl group, and a phenyl group, and preferred are a methyl group, a t-butyl group, and a phenyl group.

A preferred example of the silicon-containing hydrocarbon group having 1 to 20 carbon atoms is a trimethylsilyl group.

The heteroaromatic group has a heteroaromatic ring and, if desired, at least one bonding group bonded to the ring.

As the heteroaromatic ring, those having a monocyclic or polycyclic structure can be used, but a monocyclic or bicyclic heteroaromatic ring is preferred, and a monocyclic heteroaromatic ring is particularly preferred. .

The hetero atom of the heteroaromatic ring is not particularly limited. Preferred is a heteroaromatic ring containing an oxygen atom or a sulfur atom as a hetero atom. Particularly preferred are heteroaromatic rings containing an oxygen atom as a heteroatom. More specifically, preferred examples of the heteroaromatic ring include a furyl ring, a thienyl ring, a benzofuryl ring and a benzothienyl ring, and more preferred are a 2-furyl ring, a 2-thienyl ring, a 2-benzofuryl ring and a 2-benzofuryl ring. A benzothienyl ring, and particularly preferred is a 2-furyl ring.

If desired, the bonding group which may be bonded to the heteroaromatic ring is a hydrocarbon group having 1 to 20 carbon atoms or a silicon-containing hydrocarbon group. The hydrocarbon group and silicon-containing hydrocarbon group having 1 to 20 carbon atoms may include the same as those exemplified above as binding group attached to the C ₅ H _4-m and C ₅ H _4-n .

The heteroaromatic group preferably has a heteroaromatic ring and at least one bonding group bonded to the ring. Specifically, the heteroaromatic ring is a furyl ring, a thienyl ring, a benzofuryl ring or a benzothienyl ring, and at least one bonding group bonded to the ring is a methyl group, an ethyl group, an n-butyl group, an isobutyl group. And a heteroaromatic group such as a t-butyl group, a phenyl group or a trimethylsilyl group. Further preferably, the heteroaromatic ring is a 2-furyl ring, a 2-thienyl ring, a 2-benzofuryl ring or a 2-benzothienyl ring, and at least one bonding group bonded to the ring is a methyl group, t
A heteroaromatic group which is a -butyl group, a phenyl group or a trimethylsilyl group, and specifically, a 2- (5-methyl) -furyl group, a 2- (5-t-butyl) -furyl group, a 2- ( 5-trimethylsilyl) -furyl group, 2-
(5-methyl) -thienyl group, 2- (5-t-butyl)
-Thienyl group, 2- (5-trimethylsilyl) -thienyl group, 2- (4,5-dimethyl) -furyl group, 2-
Examples thereof include a (4,5-dimethyl) -thienyl group, a 2-benzofuryl group, and a 2-benzothienyl group.

In the production of the propylene polymer of the present invention, a group of bonding groups represented by R ¹ _m and R ² _n , at least one ring formed by the pair of R ¹ and the pair of R ² Wherein at least one of the bonding groups or bonding groups bonded to at least one ring formed by
A metallocene compound which is the above-described heteroaromatic group having a heteroaromatic ring and at least one bonding group bonded to the ring can be preferably used.

Q is (C ₅ H _4-m R ¹ _m ) and (C ₅ H _4-m R ¹ _m )
_4-n R ² _n ) are any divalent hydrocarbon groups, unsubstituted silylene groups, hydrocarbon-substituted silylene groups, or
A boron compound having R ³ ₂ NB structure. Where R
³ represents a hydrocarbon group, a silicon-containing hydrocarbon group or a heteroaromatic group. Specific examples of Q include a methylene group, an ethylene group, a dimethylsilylene group, a diphenylsilylene group, a dimethylamidoborane group, a diisopropylamidoborane group, and a bis (trimethylsilyl) amidoborane group, and preferably a dimethylsilylene group. .

M represents a titanium atom, a zirconium atom or a hafnium atom, and a zirconium atom is particularly preferred.

X and Y each independently represent a hydrogen atom, a halogen atom or a hydrocarbon group.

The propylene / ethylene copolymer of the present invention
For manufacture, n is an integer of 3; _FiveH_4-nR^Two _nsmell
And a pair of R^TwoIs bonded to at least one ring
(Monocyclic or polycyclic), and the pair of R^TwoLess than
Outside R^TwoIs at least a heteroaromatic ring and a bond to the ring
Is also a heteroaromatic group as described above having one linking group
Metallocene compounds can be suitably used. A pair of R^TwoIs shaped
At least one ring and C_FiveH_{Four- n}Ring composed of
The preferred structure is an indenyl ring, tetrahydro
Indenyl ring, benzoindenyl ring, fluorenyl ring,
Dihydroazulenyl ring or cyclopentaphenance
Rene ring, more preferably indenyl ring, benzene
A zoindenyl ring and a dihydroazulenyl ring.

The propylene / ethylene copolymer of the present invention
For the production of coalescence, n is an integer of 3;_FiveH_4-nR^Two _nTo
Where a pair of R^TwoAre connected to each other by at least one
Forming a ring, the pair of R^TwoR other than^TwoBut cyclope
Antadienyl ring C_FiveH_4-nIs bonded to the 2-position of
Metallocene compounds can be suitably used. The pair of R ^Two
At least one ring formed by_FiveH_{Four- n}Consists of
The preferred ring structure is an indenyl ring,
Droindenyl ring, benzoindenyl ring, fluorenyl
Ring, dihydroazulenyl ring or cyclopentaphena
A nitrogen ring, more preferably an indenyl ring,
A benzoindenyl ring and a dihydroazulenyl ring.

[0057] Further, R ² other than the R ² of the pair is preferably a preceding heteroaromatic group having at least one bond group bonded to the heteroaromatic ring and ring.

In the production of the propylene / ethylene copolymer of the present invention, further, at least one of the difference in R ¹ and R ^{2 and} the difference in the position of their bond to the cyclopentadienyl ring. A metallocene compound having a structure containing no transition plane containing a transition metal M can be preferably used.

The propylene / ethylene copolymer of the present invention
For the production of the union,¹ _mAnd R ^Two _nA bonding group represented by
Group and a pair of R¹And a pair of R^Two
Of the bonding group or bonding groups bonded to the ring formed by
At least one linking group has a heteroaromatic ring and the heteroaromatic ring
A hydrocarbon group having 1 to 20 carbon atoms bonded to an aromatic ring or
A heteroaromatic group having a silicon-containing hydrocarbon group;
The heteroaromatic ring is 2-furyl ring, 2-thienyl
Ring, 2-benzofuryl ring or 2-benzothienyl
Metallocene compounds that are rings can be suitably used.

The propylene / ethylene copolymer of the present invention
For the production of the union,¹ _mAnd R ^Two _nA bonding group represented by
Group, and said pair of R¹A ring formed by
A pair of R^TwoA bonding group or bonding group bonded to the ring formed by
At least one linking group in the group is 2- (5-methyl)
Ru) -furyl group, 2- (5-t-butyl) -furyl group,
2- (5-trimethylsilyl) -furyl group, 2- (5-
Methyl) -thienyl group, 2- (5-t-butyl) -thiene
A nyl group, a 2- (5-trimethylsilyl) -thienyl group,
2- (4,5-dimethyl) -furyl group, 2- (4,5-dimethyl
Dimethyl) -thienyl group, 2-benzofuryl group,
Is preferably a metallocene compound which is a 2-benzothienyl group.
Can be used appropriately.

Non-limiting examples of metallocene compounds that can be suitably used for producing the propylene / ethylene copolymer of the present invention include dimethylsilylenebis (2- (2- (5-
Methyl) -furyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -furyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl)) -Furyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -indenyl) zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -thienyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -thienyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t
-Butyl) -thienyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-
Trimethylsilyl) -thienyl) -indenyl) zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -furyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-phenyl) -furyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -furyl)-
4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -4,5-benzoindenyl) zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -thienyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-phenyl) -thienyl) -4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -thienyl)
-4,5-benzoindenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -thienyl) -4,5-benzoindenyl)
Zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -furyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-phenyl) -furyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -furyl) -4
-Phenyl-indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -4-phenyl-indenyl) zirconium dichloride;

Dimethylsilylenebis (2- (2- (5-
Methyl) -thienyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-phenyl) -thienyl) -4-phenyl-
Indenyl) zirconium dichloride, dimethylsilylene bis (2- (2- (5-t-butyl) -thienyl)
-4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -thienyl) -4-phenyl-indenyl)
Zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride,
Dimethylsilylene bis (2- (2- (5-t-butyl)
-Furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-trimethylsilyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -thienyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-phenyl) -thienyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis ( 2- (2- (5-t-butyl) -thienyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -thienyl)-
4-phenyl-dihydroazulenyl) zirconium dichloride and the like.

Of these, a more preferred metallocene compound is dimethylsilylenebis (2- (2- (5-methyl)
-Furyl) -indenyl) zirconium dichloride,
Dimethylsilylene bis (2- (2- (5-t-butyl)
-Furyl) -indenyl) zirconium dichloride,
Dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -thienyl) -indenyl) zirconium dichloride, dimethylsilylenebis ( 2- (2- (5-t-butyl) -thienyl) -indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -thienyl) -indenyl) zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -furyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2-
(2- (5-t-butyl) -furyl) -4-phenyl-
Indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -furyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -thienyl)- 4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2
-(5-t-butyl) -thienyl) -4-phenyl-indenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-trimethylsilyl) -thienyl) -4-phenyl-indenyl) zirconium dichloride,

Dimethylsilylenebis (2- (2- (5-
Methyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylene Bis (2- (2- (5-trimethylsilyl) -furyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-methyl) -thienyl) -4-phenyl-dihydro Azulenyl) zirconium dichloride, dimethylsilylenebis (2- (2- (5-t-butyl) -thienyl) -4-phenyl-dihydroazulenyl) zirconium dichloride, or dimethylsilylenebis (2- (2- (5 -Trimethylsilyl) -thienyl) -4-phenyl- Hydroazulenyl) zirconium dichloride.

As the component (B), an organic aluminum oxy compound or a compound which forms an ion pair by reacting with the component (A) is used.

As the organic aluminum oxy compound, an aluminoxane represented by the following general formula (2) or (3) is used.

[0074]

[0075]

In the formulas (2) and (3), R ³ has 1 carbon atom.
To 6 hydrocarbon groups. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, isobutyl group, pentyl group and hexyl group, allyl group, 2-methylallyl group, propenyl group, isopropenyl group and 2-methyl-1 Alkenyl groups such as -propenyl group and butenyl group,
Examples include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, and an aryl group. Among these, the carbon number is 1 to
4 hydrocarbon groups are preferred. Particularly preferred is a case where the hydrocarbon group is an alkyl group. Each R ³ may be the same or different. q is an integer of 4 to 30, preferably 6 to 30, and particularly preferably 8 to 30.

The above-mentioned aluminoxane can be prepared under various known conditions. Specifically, the following method can be exemplified. That is, a method in which a trialkylaluminum is directly reacted with water in an organic solvent such as toluene and ether, and a reaction between a trialkylaluminum and salts having water of crystallization such as copper sulfate hydrate and aluminum sulfate hydrate. A method of reacting trialkylaluminum with water impregnated in silica gel or the like. A method in which a mixture of trimethylaluminum and triisobutylaluminum is directly reacted with water in an organic solvent such as toluene and ether, and a mixture of trimethylaluminum and triisobutylaluminum is mixed with copper sulfate hydrate and aluminum sulfate hydrate. And a method of reacting triisobutylaluminum with water impregnated with silica gel or the like and then further reacting trimethylaluminum.

Compounds which form an ion pair by reacting with the component (A) are described in JP-A-1-501950, JP-A-1-502036, JP-A-3-179905, and JP-A-3-17905. 179006, JP-A-3-20
7704, Lewis acids, ionic compounds and borane compounds described in US Pat.
Carborane compounds can be mentioned.

As the Lewis acid, a Lewis acid containing a boron atom is preferable, and specific examples thereof include, but are not limited to, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, and tris (3,5). -Fluorophenyl) boron, tris (4-fluoromethylphenyl)
Examples include boron, tris (p-tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, and tris (pentafluorophenyl) boron. Of these, tris (pentafluorophenyl) boron is particularly preferred.

The ionic compound is a salt comprising a cationic compound and an anionic compound. The anionic compound serves to stabilize the transition metal cation species by reacting with the metallocene compound to cationize the metallocene compound and form an ion pair. Examples of such an anionic compound include an organic boron compound anion, an organic arsenic compound anion, and an organic aluminum compound anion. A compound which is relatively bulky and stabilizes a transition metal cation is preferable. Examples of the cationic compound include a metal cation, an organic metal cation, a carbonium cation, a tripium cation, an oxonium cation, a sulfonium cation, a phosphonium cation, and an ammonium cation. Specific examples include a triphenylcarbenium cation, a tributylammonium cation, an N, N-dimethylammonium cation, and a ferrocenium cation.

The ionic compound is preferably an ionic compound containing a boron compound as an anionic compound. Examples of such ionic compounds include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, trialkylphosphonium salts, and triarylphosphonium salts each containing a boron compound. can do.

Examples of the trialkyl-substituted ammonium salt containing a boron compound include triethylammonium tetra (phenyl) boron, tripropylammonium tetra (phenyl) boron, tri (n-butyl) ammonium tetra (phenyl) boron, trimethylammonium (p -Tolyl) boron, trimethylammonium (o-
Tolyl) boron, tributylammonium tetra (pentafluorophenyl) boron, tripropylammonium tetra (o, p-dimethylphenyl) boron, tributylammonium tetra (m, m-dimethylphenyl)
Examples include boron, tributylammonium tetra (p-trifluoromethylphenyl) boron, tri (n-butyl) ammonium tetra (o-tolyl) boron, and tri (n-butyl) ammonium tetra (4-fluorophenyl) boron.

The N, N-dialkylanilinium salts containing boron compounds include N, N-dimethylanilinium tetra (phenyl) boron, N, N-diethylanilinium tetra (phenyl) boron, N, N , N
-2,4,6-pentamethylanilinium (phenyl)
Boron and the like.

Examples of the dialkylammonium salt containing a boron compound include di (n-propyl) ammonium tetra (pentafluorophenyl) boron and dicyclohexylammonium tetra (pentafluorophenyl) boron.

Examples of the trialkylphosphonium salt or triarylphosphonium salt containing a boron compound include, for example, trimethylphosphonium tetra (phenyl) boron and tri (methylphenyl) phosphonium tetra (phenyl) Boron and tri (dimethylphenyl) phosphonium tetra (phenyl) boron.

Further, as ionic compounds containing a boron atom, triphenylcarbenium tetrakis (pentafluorophenyl) borate, N, N-dimethylaniliniumtetrakis (pentafluorophenyl) borate, ferrocenium tetra (pentafluorophenyl) )
Borates can also be mentioned.

Among the above components (B), aluminoxanes are particularly preferably used.

The component (D) is represented by the general formula
AlR ⁴ _s R ⁵ compound represented by _t X _{3- (s + t)} can be preferably used. In the formula, R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, a hydrocarbon group such as an aryl group, an alkoxy group, a fluorine atom, a methyl group, a trifluorophenyl group, or the like. X represents a phenyl group which may have a substituent; X represents a halogen atom;
And t indicate any integer satisfying 0 <s + t ≦ 3.

The component (D) represented by the above general formula includes, for example, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-butylaluminum,
Trialkylaluminums such as tri-n-hexylaluminum and tri-n-octylaluminum; dialkylaluminum halides such as dimethylaluminum chloride, dimethylaluminum bromide, diethylaluminum chloride and diisopropylaluminum chloride; methylaluminum sesquichloride and ethylaluminum sesquichloride Aluminum sesquihalides such as ethyl aluminum sesquibromide, isopropyl aluminum sesquichloride and the like;
Mixtures of more than one species. Preferred is trialkylaluminum.

The component (C) used for producing the metallocene-supported catalyst I is an inorganic carrier or an organic carrier, and has a particle diameter of 1 to 500 μm, preferably 5 to 300 μm, more preferably 10 to 300 μm. ~ 150 μm
Granular or spherical fine particles of a solid inorganic or organic fine particle carrier are used.

These inorganic fine particle carriers have a specific surface area of 5
0 to 1,000 m ² / g, preferably 100 to 700 m ²
/ G, and the pore volume is preferably in the range of 0.3 to 2.5 m ³ / g.

Examples of the inorganic fine particle carrier include metal oxides,
For example, SiO ₂ , Al ₂ O ₃ , MgO, TiO ₂ , Zn
O, a mixture thereof or a composite oxide thereof is preferable, and a carrier containing SiO ₂ or Al ₂ O ₃ as a main component is particularly preferable. As more specific inorganic compounds,
_{SiO 2, Al 2 O 3,} MgO, SiO 2 -Al 2 O 3, Si
_{O 2 -MgO, SiO 2 -TiO 2} , SiO 2 -Al 2 O 3 -
MgO and the like are mentioned, and SiO ₂ is particularly preferable.

Prior to use, the inorganic fine particle carrier is
Usually, 100 to 1,000 ° C, preferably 300 to 90
The material fired at 0 ° C, particularly preferably 400 to 900 ° C, is used. The amount of water adsorbed on the surface of the inorganic fine particle carrier after firing is 0.1% by weight or less, preferably 0.01% by weight or less, and the surface hydroxyl group content is 1.0% by weight or more, preferably 1.5 to 4.0%. % By weight, more preferably 2.0 to 3.5
% By weight. Further, these inorganic fine particle carriers may be subjected to a contact treatment with an organic aluminum compound and / or a halogen-containing silicon compound before use.

Examples of the fine particle organic carrier include fine particle organic polymers, for example, fine particle polymers of polyolefins such as polyethylene, polypropylene, poly-1-butene and poly-4-methyl-1-pentene, and fine particle polymers such as polystyrene. Can be exemplified.

The component (E) used in the production of the metallocene-supported catalyst II may be an ion-exchange layered compound or an inorganic silicate. The “ion-exchangeable layered compound” referred to in the present invention does not include a silicate.

The above-mentioned ion-exchangeable layered compound includes
Hexagonal close packing type, antimony type, CdCl_TwoType,
CdI_TwoIon crystallinity with layered crystal structure such as mold
And specific examples thereof include α-Zr (H
AsO_Four)_Two・ H_TwoO, α-Zr (HPO_Four)_Two, Α-Zr
(KPO_Four)_Two・ 3H_TwoO, α-Ti (HPO_Four)_Two, Α-
Ti (HAsO_Four)_Two・ H_TwoO, α-Sn (HPO_Four)_Two・
H_TwoO, γ-Zr (HPO _Four)_Two, Γ-Ti (HP
O_Four)_Two, Γ-Ti (NH_FourPO_Four)_Two・ H_TwoPolyvalent metals such as O
And crystalline acid salts thereof.

The above-mentioned ion-exchange layered compound may be used after being subjected to salt treatment and / or acid treatment, if necessary. An ion-exchange layered compound in a state where neither salt treatment nor acid treatment has been applied 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 to each other, Exchange is possible.

Examples of the above inorganic silicate include clay, clay mineral, zeolite, and diatomaceous earth. They are,
Synthetic products may be used, or naturally occurring minerals may be used. Specific examples of clays and clay minerals include allophanes such as allophane, kaolins such as dickite, nacrite, kaolinite, and anoxite, halloysites such as metahaloisite and halloysite, and serpentines such as chrysotile, lizardite, and antigolite. Stone tribe, montmorillonite, sauconite, beidellite,
Non-tronite, saponite, smectites such as hectorite, vermiculite minerals such as vermiculite,
Examples include mica minerals such as illite, sericite, chlorite, attapulgite, sepiolite, palygorskite, bentonite, Kibushi clay, gairome clay, hissingelite, pyrophyllite, and ryokudeite group. 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, kaolin family,
Halosite family, serpentine family, smectite, vermiculite mineral, mica mineral, synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite are preferred, and smectite, vermiculite mineral, synthetic mica, synthetic hectorite, synthetic saponite, synthetic teniolite are further preferred. preferable. These may be used as they are without any particular treatment, or may be used after having been subjected to treatments such as ball milling and sieving. Also, even if these are used alone,
Two or more kinds may be used as a mixture.

The acid strength of the above-mentioned inorganic silicate can be changed, if necessary, 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 component (E) may be used without any treatment, but it is preferable that the exchangeable metal cation contained is ion-exchanged with a cation dissociated from the following salts and / or acids. .

The salts used for the above ion exchange are 1 to
At least one element selected from the group consisting of Group 14 atoms
Is a compound containing a cation containing a proton, preferably
Is at least selected from the group consisting of atoms of groups 1 to 14
A cation containing one type of atom, a halogen atom, an inorganic acid,
At least one element selected from the group consisting of
Consisting of an anion derived from an atom or an atomic group
And more preferably a compound consisting of atoms of groups 2 to 14.
Cation containing at least one atom selected from the group consisting of
And Cl, Br, I, F, PO_Four, SO_Four, NO_Three, C
O_Three, C_TwoO_Four, ClO _Three, ClO_Four, OOCCH_Three, CH_Three
COCHCOCH_Three, OCI_Two, O (NO_Three)_Two, O (Cl
O_Four)_Two, O (SO_Four), OH, O_TwoCl_Two, OCI_Three, OO
CH, OOCCH_TwoCH_Three, C_TwoH_FourO_Four, C₆H_FiveO₇Consisting of
At least one anion selected from the group consisting of
Compound. These salts may be used in combination of two or more.
May be used.

The acid used for the above-mentioned ion exchange is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid and oxalic acid, and two or more of them may be used simultaneously. As a method of combining the salt treatment and the acid treatment, a method of performing an acid treatment after performing the salt treatment, a method of performing the salt treatment after performing the acid treatment, a method of simultaneously performing the salt treatment and the acid treatment,
There is a method of performing salt treatment and acid treatment at the same time after performing salt treatment. In addition, the acid treatment has an effect of removing ions on the surface and ion exchange, and has a crystal structure of Al, Fe, M
It has the effect of eluting some cations such as g and Li.

The treatment conditions with salts and acids are not particularly limited. However, usually the salt and acid concentrations are at 0.
It is preferable that the treatment is performed under the conditions of 1 to 30% by weight, the treatment temperature in the temperature range from room temperature to the boiling point of the solvent used, the treatment time in 5 minutes to 24 hours, and the elution of at least a part of the compound to be treated. In addition, salts and acids are generally used in an aqueous solution.

In the case of performing the salt treatment and / or the acid treatment, the shape may be controlled by pulverization or granulation before, during, or after the treatment. Further, other chemical treatments such as an alkali treatment, an organic compound treatment, and an organic metal treatment may be used in combination. The component (E) thus obtained has a pore volume of at least 20 ° in a radius of at least 0.1 ° C. measured by a mercury intrusion method.
It is preferably c / g or more, particularly preferably 0.3 to 5 cc / g. Such a component (E), when treated in an aqueous solution, contains adsorbed water and interlayer water. Here, the adsorbed water is
The water adsorbed on the surface of the ion-exchange layered compound or the inorganic silicate or the crystal fracture surface, and the interlayer water is water existing between the layers of the crystal.

The component (E) is preferably used after removing the adsorbed water and interlayer water as described above. The dehydration method is not particularly limited, and methods such as heat dehydration, heat dehydration under a gas flow, heat dehydration under reduced pressure, and azeotropic dehydration with an organic solvent are used. The heating temperature is in a temperature range in which adsorbed water and interlayer water do not remain, and is usually 100 ° C. or higher, preferably 150 ° C. or higher. However, high temperature conditions that cause structural destruction are not preferable. Heating time is 0.5
The time is at least one hour, preferably at least one hour. At that time, the weight loss of the component (E) after dehydration and drying was 200 ° C.
The value is preferably 3% by weight or less as a value when sucked for 2 hours under the condition of a pressure of 1 mmHg. In the present invention, when the component (E) whose weight loss is adjusted to 3% by weight or less is used, the same weight loss state is maintained even when the component (A) and the component (D) come into contact with each other. It is preferable to handle it.

Next, a method for producing the metallocene-supported catalysts I and II will be described.

The metallocene-supported catalyst I is obtained by reacting the component (A) with the component (B) and optionally the component (D) in the presence of the component (C). The order in which the components (A) and (B) are added to the component (C) can be arbitrarily changed. For example, component (A) dissolved in a suitable hydrocarbon solvent can be added first to component (C), and then component (B). Also,
The component (B) and the component (A) previously reacted can be added simultaneously to the component (C). The component (B) can be added first to the component (C), and then the component (A) can be added. The temperature during the reaction is usually -20 to 100 ° C, preferably 0 to 100 ° C, and the time required for the reaction is usually 0.1 minutes or more, preferably 1 minute to 200 minutes. The metallocene-supported catalyst obtained as described above can be used after preliminarily polymerizing with a small amount of olefin if necessary.

As the olefin used for the prepolymerization, ethylene, propylene, 1-butene, 1-hexene, 3-olefin
Examples thereof include methyl-1-butene and 4-methyl-1-pentene, and a mixture of two or more olefins may be used.

The metallocene-supported catalyst I suitably used for producing the propylene / ethylene copolymer of the present invention is a metallocene-supported catalyst prepared by sequentially carrying out the following steps (a) to (c). Or the following (a) step
(D) Pre-activated metallocene-supported catalysts obtained by sequentially performing the steps.

(A) a step of reacting a metallocene compound as the component (A) with an aluminoxane as one of the components (B) in an inert solvent to obtain a metallocene catalyst;
(a) the metallocene catalyst obtained in the step and the inorganic fine particle carrier,
A step of allowing the metallocene catalyst to be supported on the inorganic fine particle carrier by contacting at a temperature of 85 to 150 ° C. in the presence of an inert solvent to obtain a crude metallocene-supported catalyst; (c) supporting the crude metallocene obtained in the step (b) The slurry containing the type catalyst is -50
At least 2 with aliphatic hydrocarbons at a temperature of
Step of obtaining a purified metallocene-supported catalyst by washing twice,
(D) The olefin is prepolymerized by contacting the metallocene-supported catalyst obtained in the above step (c) with the olefin, and 0.01 to 100 kg of an olefin prepolymer per 1 kg of the metallocene-supported catalyst is further added to the metallocene-supported catalyst. Obtaining a preactivated metallocene-carrying catalyst by supporting the catalyst on a catalyst.

In the step (a), an aluminum atom of 10 to 10 mol of the metallocene compound (A) is used.
1,000 moles, preferably 20-500 moles, of aluminoxane in an inert solvent at -50 to 100C,
The metallocene compound (A) is reacted with aluminoxane, preferably at a temperature of 0 to 50 ° C. for 1 minute to 10 hours, preferably 3 minutes to 5 hours, to produce a metallocene catalyst.

The use of an inert solvent is preferable in order to promote the reaction uniformly and efficiently. The amount of the inert solvent used is not particularly limited, but is usually 10 to 10,000 liters, preferably 1 to 1 mol per 1 mol of the metallocene compound (A).
It is about 0 to 1,000 liters.

As the inert solvent used in the above reaction,
For example, benzene, toluene, xylene, aromatic hydrocarbons such as cumene, butane, tetramethylbutane, pentane, ethylpentane, trimethylpentane, hexane,
Methylhexane, ethylhexane, dimethylhexane,
Aliphatic hydrocarbons such as heptane, methylheptane, octane, nonane, decane, hexadecane, octadecane,
Alicyclic hydrocarbons such as cyclopentane, methylcyclopentane, cyclohexane and cyclooctane, the above-mentioned aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons obtained by substituting alicyclic hydrocarbons with halogens, and mixed solvents thereof; No.

Also, ethers such as ethyl ether and tetrahydrofuran can be used. A preferred inert solvent is an aromatic hydrocarbon. Alternatively, a commercially available solvent of an aluminoxane solution may be used as it is, or may be used in addition to other aromatic hydrocarbons.

In the step (b) following the step (a),
By contacting the metallocene catalyst obtained in the step (a) with the inorganic fine particle carrier at a temperature of 85 to 150 ° C. in the presence of the inert solvent used as the reaction solvent in the step (a), the metallocene catalyst is A crude metallocene-supported catalyst as a solid product supported on an inorganic fine particle carrier is obtained. In this contact reaction, an inert solvent can be additionally used as necessary.

The ratio of the metallocene catalyst to the inorganic fine particle carrier in the crude metallocene-supported catalyst depends on the transition derived from the metallocene compound (A) contained in the reaction product of the metallocene compound (A) and the aluminoxane as the metallocene catalyst. The inorganic fine particle carrier is 1 to 1,
000 kg, preferably 5 to 500 kg.
The amount of the inert solvent used in the step (b) is based on 1 mol of the transition metal atom derived from the metallocene compound (A) contained in the reaction product of the metallocene compound (A) as the metallocene catalyst and the aluminoxane. 10 to 10,000
Liters, preferably 10 to 1,000 liters.

The contact between the metallocene catalyst and the inorganic fine particle carrier is 85 to 150 ° C., preferably 90 to 130 ° C.
Particularly preferably, the reaction is carried out at a temperature of 95 to 120 ° C. for 5 minutes to 100 hours, preferably for 10 minutes to 50 hours. In particular, the temperature condition is an important factor, and by contacting within the above temperature range, the obtained metallocene-supported catalyst has a high polymerization activity, and when this catalyst is used for olefin polymerization, the obtained olefin polymer is high. It becomes a polymer having a bulk specific gravity and good particle properties.

In the following step (c), the crude metallocene-supported catalyst containing the inert solvent obtained in step (b) is
By washing at least twice with an aliphatic hydrocarbon at a temperature of 50 to 50 ° C., the purified metallocene-supported catalyst is obtained.

As the aliphatic hydrocarbon used for washing, the aliphatic hydrocarbons exemplified as the inert solvent and a mixture thereof can be used. Preferably, it is n-hexane, isopentane or a mixture thereof.

As a cleaning method in the step (c), for example,
(b) After completion of the step, after the inert solvent is separated from the slurry comprising the inert solvent and the crude metallocene-supported catalyst by filtration, centrifugation, decantation, or the like, the crude metallocene is separated using an aliphatic hydrocarbon. A method of washing the supported catalyst can be adopted. Further, after completion of the step (b), an aliphatic hydrocarbon is added without separating the inert solvent from the slurry comprising the inert solvent and the crude metallocene catalyst, and a mixed solvent of the inert solvent and the aliphatic hydrocarbon is added. After separation by the same means as described above, a method of washing the crude metallocene-supported catalyst using an aliphatic hydrocarbon may be employed. As the cleaning method performed in the step (c), the latter method is more preferable.

In the washing, 1 to 500 liters, preferably 10 to 100 liters, of an aliphatic hydrocarbon is used for 1 kg of the inorganic fine particle carrier used in the step (b), and the washing is performed in a range of -50 to 50 ° C, preferably -30 to 40
C., particularly preferably at a temperature of -30 to 30.degree. C., until the metallocene catalyst is not eluted into the washed aliphatic hydrocarbon. It is sufficient to wash at least two times, usually four times or more, but it is not limited to this.

The washing temperature condition is an important factor. The metallocene-supported catalyst obtained by washing within the above temperature range has a high polymerization activity, and is obtained when olefin polymerization is carried out using this catalyst. Olefin polymers have particularly high bulk specific gravity and good particle properties.

As described above, the preactivated metallocene-supported catalyst which can be suitably used for the production of the propylene / ethylene copolymer of the present invention is, as described in step (d), the metallocene-supported catalyst obtained in step (c). The olefin is prepolymerized by contacting the olefin catalyst with the olefin catalyst, and 0.01 to 100 kg of an olefin prepolymer per kg of the metallocene-supported catalyst is further supported on the metallocene-supported catalyst.

Preactivated metallocene supported catalyst I
As the olefin prepolymer supported on
-20 olefins, such as ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 2-methyl-1-pentene, 1-hexene, 1-
Examples include homopolymers such as octene, 1-decene, and 1-dodecene, and copolymers composed of a combination of two or more thereof. In particular, ethylene homopolymer, propylene homopolymer, ethylene mainly composed of ethylene and ethylene An ethylene / olefin copolymer with an olefin other than propylene, or a propylene / olefin copolymer of propylene mainly containing propylene and an olefin other than propylene is preferred. These olefin prepolymers are 13
Intrinsic viscosity [η] measured in decalin at 5 ° C. is 0.1 to 0.1
It is preferably in the range of 10 dl / g, preferably 0.2 to 7 dl / g.

A preferred olefin prepolymerization method is as follows:
This is a method in which an olefin is introduced into a slurry in which the metallocene-supported catalyst obtained in the step (c) is dispersed in an aliphatic hydrocarbon to bring the olefin into contact with the metallocene-supported catalyst to prepolymerize the olefin. As a slurry in which the metallocene-supported catalyst is dispersed in an aliphatic hydrocarbon, the catalyst obtained in the final stage of the step (c) may be used without separating the catalyst from the aliphatic hydrocarbon,
After separation, it may be used again after being redispersed in a similar aliphatic hydrocarbon.

The prepolymerization of the olefin can be carried out in a liquid phase using the olefin itself to be polymerized as a solvent or in a gas phase without using a solvent. It is preferable to carry out the prepolymerization in the presence of an aliphatic hydrocarbon in order to proceed uniformly.

[0128] Preliminary polymerization of olefins carried out in aliphatic hydrocarbons, to the supported metallocene catalyst 1 kg, aliphatic hydrocarbons 0.005～5M ^3, preferably 0.01～1M ³
Olefin in a slurry consisting of 0.01 to 1,000.
0 kg, preferably 0.1-500 kg, and -5
Under a temperature condition of 0 to 100 ° C, preferably 0 to 50 ° C,
It is carried out by contacting the olefin for 1 minute to 50 hours, preferably for 3 minutes to 20 hours.

In the above-mentioned olefin prepolymerization, the metallocene-supported catalyst contains a metallocene compound (A),
Since the reaction product of aluminoxane is preferably supported as the activating compound (B), it is not particularly necessary to newly add an organic aluminum compound such as a trialkylaluminum or a cocatalyst represented by aluminoxane. Can also be added. The amount of these cocatalysts to be added is preferably within a range of 1,000 mol or less, preferably 500 mol or less as aluminum atoms per 1 mol of transition metal atoms derived from the metallocene compound in the metallocene-supported catalyst.

In the production of the propylene / ethylene copolymer of the present invention, the above olefin prepolymerization is carried out in the presence of hydrogen, and the weight average molecular weight (Mw) of the resulting olefin prepolymer is from 100,000 to 500,000 g. / M
It is desirable to control so as to be within the range of ol.

The metallocene-supported catalyst II which can be suitably used for producing the propylene polymer of the present invention is prepared by bringing the components (A) and (E) into contact with the component (D). The contact method is not particularly limited, but the following method can be exemplified. (1) The component (A) is brought into contact with the component (E). (2) After contacting the components (A) and (E), (D)
Add ingredients. (3) After contacting the component (A) and the component (D), the component (E)
Add ingredients. (4) After contacting the component (E) and the component (D), the component (A)
Add ingredients. (5) The components (A), (E) and (D) are simultaneously contacted.

This contact may be carried out not only at the time of catalyst preparation but also at the time of prepolymerization of an olefin or at the time of production of a propylene / ethylene copolymer. Further, at the time of or after the contact of the above components, polyethylene, a polymer such as polypropylene, silica, a solid of an inorganic oxide such as alumina, coexist with each component, or by contacting each component Is also good.

The above components may be contacted in an inert gas such as nitrogen or an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene and xylene. The contact is performed in a temperature range having a lower limit of −20 ° C. and the upper limit of the boiling point of the solvent, and particularly preferably a temperature range of lower temperature of the room temperature and upper limit of the boiling point of the solvent.

The amounts of the components used are as follows.
That is, the amount of the component (A) is usually 10 ^{−4 to} 10 mmol, preferably 10 ^{−3 to 5} mmol per 1 g of the component (E).
l, and the component (D) is usually 0.01 to 10 ⁴ mmol
1, preferably 0.1 to 100 mmol. Also,
The atomic ratio of the transition metal in the component (A) to the aluminum in the component (D) is usually 1: 0.01 to 10 ⁶ , preferably 1: 0.1 to 10 ⁵ . The catalyst thus prepared may be used without washing after preparation, or may be used after washing.

Further, if necessary, the component (D) may be additionally used. That is, when the catalyst is prepared using the component (A) and / or the component (E) and the component (D),
Apart from this catalyst preparation, the component (D) may be additionally added to the reaction system. At this time, the amount of the component (D) used is usually 1: 0 to 10 ⁴ , preferably the atomic ratio of the aluminum atom in the component (D) to the transition metal atom derived from the metallocene compound of the component (A). 1: 1 to 10 ³ .

Also, in the case of the metallocene-supported catalyst II prepared as described above, similarly to the case of the metallocene-supported catalyst I, the olefin is prepolymerized, and the olefin prepolymer is added to the supported catalyst. After further loading, it can be used for the production of the propylene / ethylene copolymer of the present invention.

The metallocene-supported catalyst I or II obtained above is further used in combination with an organoaluminum compound (component (D ′)) as a catalyst for olefin polymerization, which is suitably used for the production of the propylene polymer of the present invention. Is done.

In the production of the propylene polymer, the component (D ′) used in combination with the metallocene-supported catalyst I or II contains the metallocene-supported catalyst I or II.
The organoaluminum compound used in the production of II is selected from those described above, but may be the same as the organoaluminum compound used in the production of the metallocene-supported catalyst I or II, or may be another organoaluminum compound. It may be.

The amount of the component (D ′) used in the production of the propylene polymer depends on the metallocene-supported catalyst I or the catalyst I.
II or preactivated metallocene supported catalyst I or II
1 to 5,000 as Al atoms in the component (D ') per mole of the transition metal atom derived from the metallocene compound (A).
The proportion is 0 mol, preferably 5 to 3,000 mol, particularly preferably 10 to 1,000 mol.

The amount of the metallocene-supported catalyst I or II or the preactivated metallocene-supported catalyst I or II is used per 1 liter of the polymerization volume in terms of transition metal atoms derived from the metallocene compound (A) in the catalyst. , 1 × 10
^-10 to 1 × 10 ^-3 mol, preferably 1 × 10 ^-9 to 1 × 1
^0-4 moles. By setting the amount of the catalyst in the above range, an efficient and controlled polymerization reaction rate of propylene can be maintained.

The term “polymerization volume” refers to the volume of the liquid phase portion in the polymerization vessel in the case of liquid phase polymerization and the volume of the gas phase portion in the polymerization vessel in the case of gas phase polymerization. means.

As the process for producing the propylene / ethylene copolymer of the present invention, a known propylene polymerization process can be used, butane, pentane, hexane,
Aliphatic hydrocarbons such as heptane and isooctane, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, aromatic hydrocarbons such as toluene, xylene and ethylbenzene, gasoline fractions and hydrogenated diesel oil fractions A slurry polymerization method in which propylene is polymerized in an active solvent can be employed. Further, a bulk polymerization method using propylene itself as a solvent or a gas phase polymerization method in which propylene is polymerized in a gas phase can also be adopted.
A polymerization process combining two or more of these processes can also be employed. As a combination of the polymerization processes, a combination in which the first stage is performed by a bulk polymerization method and the subsequent second stage is performed by a gas phase polymerization method is most preferable. Also, a solution polymerization process can be used. Among these, a gas phase polymerization method is most preferably used, and among them, a gas phase polymerization method having a horizontal reactor having a stirrer rotatable about a horizontal axis is most preferably used.

In the production of the propylene / ethylene polymer of the present invention, the polymerization temperature is -50 to 150 ° C., preferably 20 to 150 ° C.
120 ° C., more preferably 40 to 100 ° C., and the polymerization pressure is from atmospheric pressure to 9.9 MPa (gage pressure), preferably 0.4.
It is carried out under conditions of up to 5.0 MPa (gage pressure). If necessary, the molecular weight of the propylene / ethylene copolymer obtained by introducing a chain transfer agent such as hydrogen may be adjusted.

After the completion of the polymerization reaction, unreacted monomers and hydrogen are separated from the polymerization system, and a catalyst deactivation treatment or the like is performed to obtain a propylene polymer.

The propylene / ethylene copolymer of the present invention may contain, if necessary, an antioxidant, an ultraviolet absorber, an antistatic agent, a nucleating agent, a lubricant, a flame retardant, an antiblocking agent, a coloring agent, an inorganic or organic material. After blending various additives such as fillers and various synthetic resins, the mixture is usually heated and melt-kneaded at a temperature of 190 to 350 ° C. for about 20 seconds to 30 minutes using a melt kneading machine, and if necessary, a strand is mixed. After being extruded into a shape, the product is further cut into granules, that is, pellets, and used for the production of various molded products.

[0146]

EXAMPLES The present invention will be described below in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Definitions of terms used in Examples and Comparative Examples and measurement methods are as follows. (1) Melt flow rate (MFR) (unit: g / 10)
Min): Condition 14 in Table 1 based on JIS K7210
(Under a load of 21.18 N and a temperature of 230 ° C.). (2) Isotactic triad fraction (I ₃ ): As a measuring device, “JEOL-GX27” manufactured by JEOL Ltd. was used.
"0" (trade name) was measured by the method described above. (3) With respect to the total number of moles of propylene units constituting the propylene / ethylene copolymer, the number of moles of propylene units resulting from the 2,1-insertion reaction of propylene monomers and the 1,3-insertion reaction of propylene monomers Of the number of moles of propylene units due to
%): "JEOL" manufactured by JEOL Ltd.
-GX270 "(trade name) was measured by the method described above. The lower detection limit was 0.02 mol%. (4) Melting point (° C.): “DSC7” manufactured by Perkin-Elmer
Using a "type differential scanning calorimeter". (5) Content of ethylene unit in propylene / ethylene copolymer (unit: wt%): determined by ¹³ C NMR measurement.

[0147]

Example 1 [rac-dimethylsilylenebis (2-
(Synthesis of (2- (5-methyl) -furyl) -indenyl) zirconium dichloride] (1) Synthesis of 2- (2- (5-methyl) -furyl) -indene 2-Methyl was placed in a 500 ml glass reaction vessel. Franc 2
0 g (0.24 mol) and 250 ml of THF were added, and the mixture was cooled to -50 ° C in a dry ice-methanol bath. 160 ml (0.24 mol) of a 1.50 mol / L n-butyllithium-hexane solution was added dropwise thereto. After dropping, the mixture was returned to room temperature and stirred for 3 hours. It was cooled again to −30 ° C. in a dry ice-methanol bath, and
100 ml of a THF solution containing g (0.24 mol) was added dropwise. After the dropwise addition, the mixture was returned to room temperature and stirred for 16 hours. The reaction solution was cooled to −20 ° C. in a dry ice-methanol bath,
100 ml of 2N hydrochloric acid was added dropwise. The reaction solution was transferred to a separating funnel and washed with a saline solution until neutral, anhydrous sodium sulfate was added, and the mixture was allowed to stand overnight to dry. The anhydrous sodium sulfate was filtered, and the solvent was distilled off under reduced pressure. Thereto, 600 ml of toluene and 0.5 g of p-toluenesulfonic acid (2.6 g) were added.
mmol) and heated under reflux for 1 hour. The reaction solution was transferred to a separating funnel and washed with a saline solution until neutral,
Anhydrous sodium sulfate was added and left overnight to dry. The anhydrous sodium sulfate was filtered, the solvent was distilled off under reduced pressure, and the residue was purified by a silica gel column to obtain 22 g of 2- (2- (5-methyl) -furyl) -indene as pale yellow crystals (46% yield). . The structure was confirmed by NMR.

(2) Synthesis of dimethylbis (2- (2- (5-methyl) -furyl) -indenyl) silane In a 200 ml glass reaction vessel, 2- (2- (5-methyl) -furyl)- 30 g of inden (0.15 mo
l), copper isocyanate 0.9 g (7.4 mmol), T
HF (300 ml) was added, and the mixture was cooled to -70 ° C in a dry ice-methanol bath. Here, 1.50 mol / L of n
-Butyl lithium-hexane solution 102 ml (0.15
mol) was added dropwise. After the dropwise addition, the mixture was stirred for 16 hours while gradually returning to room temperature. It was cooled again to -50 ° C in a dry ice-methanol bath, and dimethyldichlorosilane 9.9 was obtained.
70 ml of a THF solution containing g (0.077 mol) was added dropwise. After the dropwise addition, the mixture was stirred for 16 hours while gradually returning to room temperature. Distilled water was added to the reaction solution, transferred to a separating funnel, and washed with saline until neutral. Anhydrous sodium sulfate was added thereto, and the mixture was allowed to stand overnight to dry the reaction solution. Anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure, the residue was purified on a silica gel column, and recrystallized from hexane to give dimethylbis (2-
27 g (78% yield) of colorless crystals of (2- (5-methyl) -furyl) -indenyl) silane were obtained.

(3) Dimethylsilylenebis (2- (2-
Synthesis of (5-methyl) -furyl) -indenyl) zirconium dichloride In a 100 ml glass reaction vessel, dimethylbis (2-
(2- (5-methyl) -furyl) -indenyl) silane 5.0 g (0.011 mol), diethyl ether 10
Add 0 ml and dry ice-methanol bath at -70 ° C
Cooled down. Here, 15 ml (0.023 mol) of a 1.50 mol / L n-butyllithium-hexane solution
Was added dropwise. After the dropwise addition, the mixture was returned to room temperature and stirred for 16 hours. The solvent of the reaction solution was concentrated under reduced pressure to about 20 ml, and toluene 1
70 ml in a dry ice-methanol bath.
Cooled to ° C. There, 2.6 g of zirconium tetrachloride
(0.012 mol) was added. Thereafter, the mixture was stirred for 2 days while gradually returning to room temperature. The solvent was distilled off under reduced pressure, and recrystallization was performed with toluene / hexane. As a metallocene compound, rac-dimethylsilylenebis (2- (2- (5-
2.8 g (yield 42%) of methyl) -furyl) -indenyl) zirconium dichloride (purity 99% or more) was obtained. ¹ H-NMR measured for the metallocene compound
The values (CDCl ₃ ) were as follows: ¹ H-NMR value (CDCl ₃ ): δ 1.12 (s, 6
H), δ 2.42 (s, 6H), δ 6.07 (d, 2
H), δ 6.27 (d, 2H), δ 6.71 (t, 2
H), δ 6.92 (s, 2H), δ 6.92 (d, 2
H), δ 7.31 (t, 2H), δ 7.54 (d, 2
H).

[Production of preactivated metallocene-supported catalyst] (1) Production of metallocene-supported catalyst A toluene solution of methylaluminoxane (concentration: 3 89 mol (267 mmo in terms of Al atom) of mol / liter, trade name: PMAO, manufactured by Tosoh Akzo Co., Ltd.
l) and 0.929 mmol of the chiral dimethylsilylenebis (2- (2- (5-methyl) -furyl) -indenyl) zirconium dichloride synthesized above as a metallocene compound were added, and the mixture was stirred at a temperature of 25 ° C. for 15 minutes. The reaction was carried out while holding the mixture to obtain a reaction product of the metallocene compound and the aluminoxane, that is, a metallocene catalyst. Subsequently, silica having an average particle diameter of 51 μm (SYLOPOL® 948, which was previously calcined under reduced pressure at a temperature of 750 ° C. for 8 hours) was added to the reactor.
6.7 g of Grace Devison) was added, the temperature of the reactor was raised to 110 ° C., and the reaction product obtained above was brought into contact with silica by stirring and maintained for 60 minutes.
A slurry containing the crude metallocene supported catalyst carrying the metallocene catalyst was obtained. Next, the temperature of the reactor was reduced by -1.
After cooling to 0 ° C, while keeping the temperature of the reactor at -10 ° C, 250 ml of n-hexane was added and stirred for 10 minutes, then the stirrer was stopped, and the solvent was separated by decantation. Subsequently, while maintaining the temperature of the reactor at −10 ° C., 250 ml of n-hexane was charged into the reactor and stirred and washed for 5 minutes. Then, the agitator was stopped and the washing solvent was separated by decantation. Was repeated four times to obtain a purified metallocene-supported catalyst. further,
250 ml of n-hexane was charged into the reactor, and the metallocene-supported catalyst was dispersed to form a slurry.

(2) Production of Preactivated Metallocene-Supported Catalyst A metallocene-supported catalyst obtained in the above (1) and n
-Transfer the slurry with hexane and bring the reactor temperature to 0 ° C
Was adjusted to Then, while maintaining the temperature of the reaction vessel at 0 ° C. while stirring, a propylene / hydrogen mixed gas having a molar ratio of 10: 1 was supplied at a supply rate of 300 ml / min for 40 minutes to perform prepolymerization. A reaction mixture containing the crude preactivated metallocene supported catalyst supported on the catalyst was obtained. After the used n-hexane solvent was separated from the reaction mixture by decantation,
Hexane (250 ml) was charged and stirred for 5 minutes to wash the preactivated metallocene-supported catalyst, and the washing operation of separating the washing solvent by decantation was repeated 5 times. Next, 250 ml of n-hexane was charged into the reactor, and the obtained preactivated metallocene-supported catalyst was dispersed in n-hexane to form a slurry. The solvent of the slurry of the obtained preactivated metallocene-supported catalyst and n-hexane was separated by filtration, and then dried under reduced pressure at a temperature of 25 ° C. to obtain a preactivated metallocene-supported catalyst composed of solid particles. The obtained preactivated metallocene-supported catalyst was analyzed to determine how many g of the propylene polymer was supported per 1 g of the metallocene-supported catalyst. As a result, the supported catalyst 1 before pre-activation
1 g of the propylene polymer was supported per g.

[Production of propylene / ethylene copolymer]
A horizontal gas-phase reactor having an inner volume of 3 liters sufficiently purged with nitrogen is heated to 70 ° C., and 150 g of coarse propylene polymer particles are heated.
And 0.5 mmol of triethylaluminum, and 5
Stirred at 85 rpm for minutes. Next, the pre-activated metallocene-supported catalyst prepared above was added with 87 mg per metallocene-supported catalyst before pre-activation, and further,
Stir for 5 minutes. Next, a propylene / ethylene mixed monomer is supplied into the reactor, and while maintaining the ethylene monomer concentration in the reactor at 2.8 mol%, the reaction pressure is increased to 2.3.
Pressurized to MPa (gauge pressure), 70 ° C and 2.3M
Polymerization was performed under constant polymerization conditions of Pa (gauge pressure), and when the amount of the produced propylene / ethylene copolymer reached 300 g, the monomer supply was stopped, and the pressure was reduced to atmospheric pressure.
Under a nitrogen stream, 300 g of a powdery polymer was withdrawn from the reactor. Then, 150 g of the above propylene polymer coarse particles
Instead of using 150 g of the powdery polymer remaining in the reactor after the withdrawing operation, the same polymerization was performed twice as described above, and the polymerization was performed using the third polymerization result. The activity was calculated and the obtained propylene / ethylene copolymer was analyzed. The polymerization time was about 1.5 hours each.

The polymerization activity was measured for the supported catalyst 1 before pre-activation.
It was 2300 g · polymer / g · catalyst per g.
When the obtained propylene / ethylene copolymer was analyzed, the weight average molecular weight (Mw) was 2.01 × 10 ⁵ g / m 2.
ol, the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) (Mw / Mn) is 2.5, and the MFR is 6.6.
g / 10 minutes, the content of ethylene units is 2.0% by weight, the melting point is 122 ° C., the isotactic triad fraction (I ₃ ) is 0.913, and the propylene / ethylene copolymer is constituted. The ratio of the number of moles of the propylene unit due to the 2,1-insertion reaction of the propylene monomer to the total number of moles of the propylene unit is 0.41 mol.
%, And the ratio of the number of moles of propylene units caused by the 1,3-insertion reaction of the propylene monomer to the total number of moles of propylene units constituting the propylene / ethylene copolymer is less than a detection limit value, That is, 0.02mo
less than 1%.

[0154]

By using the propylene / ethylene copolymer of the present invention, various molded products having excellent rigidity, heat resistance, transparency and low-temperature heat sealability can be obtained. Also,
Since the extraction ratio to the solvent is low, it can be suitably used in the fields of food packaging films and food storage containers.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Masato Nakano 5-1, Goi Kaigan, Ichihara-shi, Chiba Chisso Petrochemical Co., Ltd. Polymer Research Laboratory (72) Inventor Yoshiyuki Oki 5-1-1, Goi Kaigan, Ichihara-shi, Chiba Chisso Petrochemical Co., Ltd. Polymer Research Laboratory (72) Inventor Joh Yamamoto 1 at 5 Goi Kaigan, Ichihara City, Chiba Prefecture Chisso Petrochemical Co., Ltd. Polymer Research Laboratory F term (reference) BA01B BB00A BB00B BB01B BC12B BC25B CA30A DA02 EB02 EB04 EC02 ED02 ED09 GA15 4J100 AA02Q AA03P CA04 CA11 DA41 FA10 4J128 AA01 AB00 AB01 AC01 AC08 AC09 AC26 AC27 AD00 AE00 BA00B02B01B02B02B01B02B01B02B02B02B02B02B02B02B02B02B02B02B02B02B01

Claims (3)

[Claims] 1. A propylene / ethylene copolymer produced using an olefin polymerization catalyst and satisfying the following properties (1) to (3). (1) The content of ethylene units is 0.1 to 3.3% by weight based on the weight of the propylene / ethylene copolymer. (2) The isotactic triad fraction (I ₃ )
It is 0.50 or more and less than 0.95. (3) The ratio of the number of moles of propylene units caused by the 2,1-insertion reaction of the propylene monomer to the total number of moles of propylene units constituting the propylene / ethylene copolymer is 0.05% or more. Less than 0.5%. 2. An olefin polymerization catalyst comprising: a metallocene compound represented by the following general formula (1); an activating compound;
2. The propylene / ethylene copolymer according to claim 1, wherein the propylene / ethylene copolymer is a metallocene-supported catalyst produced by using a fine particle carrier, an organic aluminum compound if desired, and an olefin polymerization catalyst containing the organic aluminum compound. . _{Q (C 5 H 4-m} R 1 m) (C 5 H 4-n R 2 n) MXY (1) ( _{wherein, (C 5 H 4-m} R 1 m) and (C ₅ H _4-n R ² _n ) represents a cyclopentadienyl group, and C ₅ H _4-m and C ₅ H _4-n
Represents a cyclopentadienyl ring. m represents an integer of 1 to 3, and n represents an integer of 2 or 3 independently of m. R ¹ and R ² are C ₅ H _4-m and C ₅ H, respectively.
A bonding group bonded to _4-n , which independently represents a hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group or a heteroaromatic group. Each of R ¹ _m and each of R ² _n may be the same or different from each other. A pair of R ² out of R ² _n are bonded to each other to form at least one ring. When m is an integer of 2 or 3, R ¹ _m
And one pair of R ¹ may bond to each other to form at least one ring independently of the ring formed by the pair of R ² . The ring formed by the pair of R ¹ and the ring formed by the pair of R ² may have, independently of each other, at least one bonding group bonded to the ring. A hydrocarbon group of the formulas 1 to 20, a silicon-containing hydrocarbon group or a heteroaromatic group. Where R ¹ _m and R ² _n
And at least one of the bonding groups or bonding groups bonded to the ring formed by the pair of R ¹ and the ring formed by the pair of R ² is a heteroaromatic A heteroaromatic group having a heteroaromatic ring and at least one bonding group bonded to the heteroaromatic ring, wherein the bonding group has 1 to 2 carbon atoms.
0 hydrocarbon group or silicon-containing hydrocarbon group.
Q represents a divalent hydrocarbon group, an unsubstituted silylene group, each of which crosslinks (C ₅ H _4-m R ¹ _m ) and (C ₅ H _4-n R ² _n );
Hydrocarbon-substituted silylene group, or a boron compound having R ³ ₂ NB structure. Here, R ³ is a hydrocarbon group,
It represents a silicon-containing hydrocarbon group or a heteroaromatic group.
M represents a titanium atom, a zirconium atom or a hafnium atom. X and Y may be the same or different and represent a hydrogen atom, a halogen atom or a hydrocarbon group. ) 3. A metallocene-supported catalyst is produced using a metallocene compound represented by the general formula (1) of claim 2, an ion-exchange layered compound or an inorganic silicate, and if desired, an organoaluminum compound. The propylene / ethylene copolymer according to claim 2, which is a metallocene-supported catalyst.