JP2002284817A - Propylenepolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a propylene polymer which is excellent in stiffness and heat resistance, contains a high-mol.-wt. component in a high content, and is excellent in moldability. SOLUTION: This propylene polymer has following characteristics: (1) the melt flow rate(MFR) measured at 230 deg.C under a load of 2.16 kg is 0.1-1,000 g/10 min; (2) the isotactic triad fraction (mm) measured by<13> C-NMR is 99.0% or higher; (3) the Q value measured by GPC is 2.0-6.0; (4) the relation between melt flow rate (MFR: g/10 min) measured at 230 deg.C under a load of 2.16 kg and the memory effect(ME) measured at 190 deg.C under an orifice diameter of 1.0 mm satisfies equation (I): (ME)>=-0.26×log(MFR)+1.40 (I); (5) the amount of xylene solubles (CXS) at 23 deg.C satisfies equation (II): CXS<=0.5×[C 2]+0.2×log(MFR)+0.5 (II) (wherein [C2] is the ethylene monomer content (wt.%) in the polymer); and (6) the melting point (Tm) measured by DSC is 120 deg.C or higher.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a propylene polymer which is excellent in rigidity and heat resistance, has a high molecular weight component, and is excellent in moldability and appearance.

[0002]

2. Description of the Related Art Propylene polymers are rigid, heat-resistant,
It is noted for its excellent moldability, transparency and chemical resistance, and is widely used in various applications such as various industrial materials, various containers, daily necessities, films and fibers.

In general, metallocene catalysts using a metallocene transition metal compound are widely used because they have high activity and the resulting propylene-based polymer has excellent physical properties due to its excellent steric structure. However, on the other hand, the propylene-based polymer produced using a metallocene catalyst has a narrow molecular weight distribution, and as a result, the memory effect (ME)
Has a disadvantage that the molding processability is reduced and molding workability is inferior. ME is a value that is a measure of the non-Newtonian property of a resin. The larger the value, the wider the molecular weight distribution,
Particularly, due to the influence of the high molecular weight component, a favorable tendency is exhibited for the moldability.

As a method for obtaining a propylene polymer having a large ME, a method of carrying out polymerization using a specific magnesium-supported Ziegler-Natta catalyst is known.
Because of a large amount of cold xylene solubles (CXS), there is a disadvantage that stickiness or rigidity and heat resistance deteriorate.

[0005]

SUMMARY OF THE INVENTION In view of the above problems, the present invention provides a propylene-based polymer which is not only excellent in rigidity and heat resistance, but also has a high molecular weight component and excellent moldability. It is.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a propylene polymer having specific physical properties, a propylene polymer having excellent stereoregularity and high ME despite having a small amount of CXS. By providing
It has been found that the above problem is solved.

That is, the propylene-based polymer of the present invention is characterized by having the following physical properties. (1) The melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg is 0.1 to 1000 g / 10 minutes,
(2) Isotactic triad fraction (mm) measured by ¹³ C-NMR is 99.0% or more, and (3) Q value measured by gel permeation column chromatography (GPC) (weight average molecular weight (Mw) ) And number average molecular weight (M
n) is 2.0 to 6.0, (4) 230 ° C, 2.1
MFR measured at 6 kg load and memory effect (ME) measured at 190 ° C. and orifice diameter 1.0 mm
Satisfies the following formula (I): (ME) ≧ −0.26 × log (MFR) +1.40 (I) (5) Amount dissolved in xylene at 23 ° C. (CXS)
(Unit: wt%) satisfying the following formula (II): CXS ≦ 0.5 × [C2] + 0.2 × log (MFR) +0.5 (II) (where [C2] is ethylene in the polymer (6) The melting point (Tm) measured by DSC is 120 ° C. or higher, and in the present invention, a propylene-based polymer is polymerized using a metallocene catalyst. It is characterized by the following.

[0008]

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel propylene-based polymer which maintains the following physical conditions (1) to (6). Condition (1) MFR The propylene-based polymer of the present invention has a temperature of 230 ° C. and 2.16 k
The melt flow rate (MFR) measured under a g load is 0.
It is in the range of 1 to 1000 g / 10 minutes. MFR is 0.1
If it is less than, the fluidity of the polymer becomes extremely poor, which is not preferable for molding. On the other hand, if the MFR exceeds 1,000, the impact resistance of the polymer is extremely lowered, which is not preferable. Preferably it is in the range of 0.5 to 500. MF
Preferable applications are limited by the size of R, but when used for injection molding, MFR is 10 to 300, and when used for film and sheet molding, MFR is 0.5 to 1
0, more preferably in the range of 1.0 to 10.

Condition (2) Stereoregularity The propylene-based polymer of the present invention is a polymer having a head-to-tail bond.
Of the pyrene unit chain, ¹³Isota measured by C-NMR
Octyl triad fraction, i.e., any fraction in the polymer chain
In the three chains of propylene units, each propylene unit is head-to-tail
Bond and the direction of the methyl branch in the propylene unit is the same.
The ratio of three propylene units in one unit is 99% or more,
More preferably, it is 99.5% or more. In addition, Isota
In the following, the fraction of the tactic triad is referred to as the mm fraction.
There is.

The isotactic triad fraction (m
m fraction) is a value indicating that the steric structure of the methyl group in the polypropylene molecular chain is controlled isotactically, and a higher value means a higher degree of control. If this value is less than the above range, there is a disadvantage that heat resistance is poor. Here, the measurement of the ¹³ C-NMR spectrum can be performed by the following method. ¹³ CN
In the MR spectrum, a sample of 350 to 500 mg was completely dissolved in a solvent in which about 0.5 ml of deuterated benzene as a lock solvent was added to about 2.0 ml of o-dichlorobenzene in a 10 mmφ NMR sample tube. Later, 13
It is measured at 0 ° C. by the complete proton decoupling method. As the measurement conditions, a flip angle of 65 ° and a pulse interval of 5T ₁ or more (T ₁ is the longest value among the spin lattice relaxation times of the methyl group) are selected. In the propylene polymer, T ₁ of the methylene group and the methine group is shorter than the methyl group,
Under these measurement conditions, the recovery of magnetization of all carbons is 99% or more.

The method for identifying the NMR peak of the propylene polymer according to the present invention is in accordance with a known method described in JP-A-10-273507. That is, the chemical shift is head-to-tail bond, and the propylene unit 5 has the same direction of methyl branch.
The methyl unit of the third unit in the chain is set at 21.8 ppm, and the chemical shift of other carbon peaks is based on this. According to this criterion, a peak based on a methyl group of the second unit in three chains of propylene units represented by PPP [mm] is used.
In the range of 21.3 to 22.2 ppm, PPP [m
The peak based on the methyl group of the second unit in the three chains of propylene units represented by [r] is within the range of 20.5 to 21.3 ppm, and the peak of the second unit in the three chains of propylene units represented by PPP [rr] is in the range of 20.5 to 21.3 ppm. The peak based on the methyl group in the unit is 19.7.
Appears in the range of ２20.5 ppm.

Condition (3) Molecular weight distribution (Q value) The molecular weight distribution of the propylene-based polymer of the present invention is determined by the Q value (weight average molecular weight (Mw) and number average molecular weight) measured by gel permeation column chromatography (GPC). (Ratio of (Mn)) is in the range of 2.0 to 6.0. When the Q value is lower than 2.0, the resin pressure increases during polymer molding, which is not preferable for operation. On the other hand, when the Q value exceeds 6.0, the molecular weight distribution also spreads to the low molecular weight side, and as a result, the low molecular weight component also increases. In the polymer of the present invention, since the low molecular weight component and the CXS component are essentially small, emphasis is placed on molding characteristics, and the preferable Q value is in the range of 4.0 to 6.0, more preferably 4.0 to 5.0. 0.0.

Condition (4) Correlation between ME and MFR In the propylene-based polymer of the present invention, a memory effect (ME), which is an index indicating the abundance ratio of a high molecular weight component in the polymer, and an index indicating an average molecular weight of the polymer. The correlation with a certain MFR is in a specific relationship (formula (I) below). (ME) ≧ −0.26 × log (MFR) +1.40 (I) It is empirically known that ME has a first-order correlation with MFR. Generally, the higher the molecular weight (ie, the smaller the value of MFR), the stronger the effect of the high molecular weight component appears, and thus the larger the value of ME. The polymer of the present invention is characterized in that the ME in terms of MFR is larger than that of a conventionally known polymer. It is known that when the amount of the high molecular weight component is large, the molding characteristics are excellent, and the propylene-based polymer of the present invention is excellent in the molding characteristics. More preferably, the following formula (I-1) is satisfied. (ME) ≧ −0.26 × log (MFR) +1.55 (I-1)

Condition (5) CXS In the present invention, the propylene-based polymer may be a copolymer. The (co) polymer of the present invention has an amount of dissolution in xylene (CXS) at 23 ° C., which is an index of the amount of low crystalline components in the polymer, and an MFR, which is an index of the molecular weight of the polymer.
And the ethylene unit content [C2] (unit:% by weight) in the polymer, which is an index of the crystallinity of the polymer, is characterized by satisfying a specific relational expression (the following expression (II)). In the case of a propylene homopolymer, [C2] may be set to zero in the following formula. It is empirically known that CXS has a first order correlation with MFR and ethylene content. In general, the smaller the molecular weight (that is, the larger the value of MFR), the easier it is to dissolve in the solvent, and thus the larger the value of CXS. In addition, the higher the ethylene content, the lower the crystallinity of the polymer becomes and the more easily the polymer becomes soluble in a solvent, so that the value of CXS increases. The content of the ethylene comonomer in the present invention is in the range of 0 to 5% by weight, but is preferably a homopolymer. CXS ≦ 0.5 × [C2] + 0.2 × log (MFR) +0.5 (II) (where [C2] represents the ethylene unit content (% by weight) in the polymer)

The present invention is characterized by low CXS, and low in low crystal components and low molecular weight components which cause stickiness, rigidity and heat resistance of molded products. More preferably, the following formula (II-1): CXS ≦ 0.5 × [C2] + 0.2 × log (MFR) +0.5 (II-1) It is a polymer in a relationship. CXS ≦ 0.5 × [C2] + 0.2 × log (MFR) +0.3 (II-2)

Condition (6) Melting Point (Tm) The propylene-based polymer of the present invention is characterized in that the melting point Tm (° C.) measured by DSC is 130 ° C. or higher. For applications where emphasis is placed on rigidity and heat resistance, the melting point can be improved by reducing the amount of comonomer used during polymerization and decreasing the ethylene content in the polymer. Generally, when the ethylene content is about 5.0% by weight, the melting point of the propylene-ethylene random copolymer is about 120 ° C. The melting point of the polymer in the present invention is preferably 149 ° C. or higher, more preferably 155 ° C.
° C or higher, more preferably 158 ° C or higher.

<Production of Propylene Polymer> The method for producing a propylene polymer according to the present invention is not particularly limited as long as it provides a propylene polymer satisfying the above-mentioned physical properties. A suitable catalyst system for producing the polymer is a metallocene catalyst, and it is preferable to use a specific metallocene catalyst. For example, it can be produced using a catalyst as shown below.

Component A: at least one metallocene compound selected from transition metal compounds described below; Component B: at least one compound selected from the group consisting of ion-exchanged layered silicates; C: Organoaluminum Compound (Component A) The component A transition metal compound that forms a polymerization catalyst preferable for producing a propylene polymer in the present invention is a transition metal compound represented by the following general formula (1).

[0019]

Embedded image

[Wherein Q represents a binding group bridging two conjugated five-membered ligands, M represents titanium, zirconium,
X represents a metal atom selected from hafnium, and X and Y represent a hydrogen atom bonded to M, a halogen atom, a hydrocarbon group, an alkoxy group, an amino group, a nitrogen-containing hydrocarbon group,
A phosphorus-containing hydrocarbon group or a silicon-containing hydrocarbon group, and R ¹ and R ³ are each hydrogen,
A hydrocarbon group, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a boron-containing hydrocarbon group, or a phosphorus-containing hydrocarbon group. And R ² is hydrogen,
A hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a boron-containing hydrocarbon group, or phosphorus A hydrocarbon group is contained, and among them, an aryl group having 6 to 16 carbon atoms is preferable. ]
Q represents a divalent bonding group bridging two conjugated five-membered ring ligands, for example, (a) a divalent hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms; B) a silylene group or an oligosilylene group, (c) a silylene or oligosilylene group having a hydrocarbon group having 1 to 20, preferably 1 to 12 carbon atoms as a substituent, (d) a germylene group, or (e) a carbon number. Examples thereof include a germylene group having 1 to 20 hydrocarbon groups as a substituent. Of these, a silylene group having an alkylene group or a hydrocarbon group as a substituent is preferred.

X and Y are each independently, that is, they may be the same or different, and represent the following. (A) hydrogen, (b) halogen, (c) 1-20 carbon atoms,
Preferably a hydrocarbon group of 1 to 12 or (d) an oxygen, nitrogen or silicon-containing carbon number of 1 to 2
0, preferably 1 to 12 hydrocarbon groups, of which preferred are hydrogen, chlorine, methyl, isobutyl,
Examples include a phenyl, dimethylamide, diethylamide group and the like.

R ¹ and R ³ are hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, an oxygen-containing hydrocarbon group. Represents a hydrogen group, a boron-containing hydrocarbon group, a phosphorus-containing hydrocarbon group, specifically, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, phenyl group,
Examples thereof include a naphthyl group, a butenyl group and a butadienyl group. Further, in addition to hydrocarbon groups, halogen, silicon, nitrogen, oxygen, boron, containing phosphorus, methoxy group, ethoxy group, phenoxy group, trimethylsilyl group, diethylamino group, diphenylamino group, pyrazolyl group, indolyl group, dimethyl Phosphino group, diphenylphosphino group, diphenylboron group, dimethoxyboron group,
Etc. can be illustrated as a typical example. Among these, a hydrocarbon group is preferable, and in particular, methyl, ethyl,
Particularly preferred are propyl and butyl.

R ² is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms,
It shows a silicon-containing hydrocarbon group, a nitrogen-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a boron-containing hydrocarbon group, and a phosphorus-containing hydrocarbon group, and among them, preferably has 6 to 16 carbon atoms.
Aryl group, specifically, phenyl, α-naphthyl, β-naphthyl, anthracenyl, phenanthryl,
Pyrenyl, acenaphthyl, phenalenyl, aceanthrenyl and the like.

Further, these aryl groups include halogen,
Substituted with a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a nitrogen-containing hydrocarbon group, an oxygen-containing hydrocarbon group, a boron-containing hydrocarbon group, a phosphorus-containing hydrocarbon group It may be something. Of these, phenyl and naphthyl are preferred.

M is a metal selected from titanium, zirconium and hafnium, and is preferably zirconium.

The following are non-limiting examples of the above transition metal compounds. 1. Ethylenebis (2-methyl-4-phenyl-4H-
1. (azulenyl) hafnium dichloride Ethylenebis (2-ethyl-4-phenyl-4H-
Azulenyl) hafnium dichloride Ethylenebis (2-methyl-4-naphthyl-4H-
3. (azulenyl) hafnium dichloride Ethylenebis (2-ethyl-4-naphthyl-4H-
4. (azulenyl) hafnium dichloride Ethylenebis (2-ethyl-4- (4-chloro-2
-Naphthyl-4H-azulenyl)) hafnium dichloride Ethylenebis (2-ethyl-4-biphenyl-4H
-Azulenyl) hafnium dichloride7. Ethylenebis (2-ethyl-4- (2-fluoro-
7. 4-biphenyl) -4H-azulenyl) hafnium dichloride 8. isopropylidenebis (2-methyl-4-phenyl-4H-azulenyl) hafnium dichloride 9. isopropylidenebis (2-ethyl-4-phenyl-4H-azulenyl) hafnium dichloride Isopropylidenebis (2-methyl-4-naphthyl-4H-azulenyl) hafnium dichloride

11. 11. isopropylidenebis (2-ethyl-4-naphthyl-4H-azulenyl) hafnium dichloride Isopropylidenebis (2-ethyl-4- (4-
12. chloro-2-naphthyl-4H-azulenyl)) hafnium dichloride 13. isopropylidenebis (2-ethyl-4-biphenyl-4H-azulenyl) hafnium dichloride Isopropylidenebis (2-ethyl-4- (2-
14. fluoro-4-biphenyl) -4H-azulenyl) hafnium dichloride 15. Dimethylsilylenebis (2-methyl-4-phenyl-4H-azulenyl) hafnium dichloride 16. Dimethylsilylenebis (2-ethyl-4-phenyl-4H-azulenyl) hafnium dichloride 17. Dimethylsilylenebis (2-methyl-4-naphthyl-4H-azulenyl) hafnium dichloride 18. Dimethylsilylenebis (2-ethyl-4-naphthyl-4H-azulenyl) hafnium dichloride Dimethylsilylenebis (2-ethyl-4- (4-
Chloro-2-naphthyl-4H-azulenyl)) hafnium dichloride Dimethylsilylenebis (2-ethyl-4-biphenyl-4H-azulenyl) hafnium dichloride

21. 21. Dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azulenyl) hafnium dichloride 23. diphenylsilylenebis (2-methyl-4-phenyl-4H-azulenyl) hafnium dichloride 23. diphenylsilylenebis (2-ethyl-4-phenyl-4H-azulenyl) hafnium dichloride 25. Diphenylsilylenebis (2-methyl-4-naphthyl-4H-azulenyl) hafnium dichloride 26. diphenylsilylenebis (2-ethyl-4-naphthyl-4H-azulenyl) hafnium dichloride Diphenylsilylene bis (2-ethyl-4- (4
-Chloro-2-naphthyl-4H-azulenyl)) hafnium dichloride27. 28. diphenylsilylenebis (2-ethyl-4-biphenyl-4H-azulenyl) hafnium dichloride Diphenylsilylene bis (2-ethyl-4- (2
-Fluoro-4-biphenyl) -4H-azulenyl) hafnium dichloride 29. 30. Dimethylgermylene bis (2-methyl-4-phenyl-4H-azulenyl) hafnium dichloride Dimethylgermylene bis (2-ethyl-4-phenyl-4H-azulenyl) hafnium dichloride

31. Dimethylgermylene bis (2-methyl-4-naphthyl-4H-azulenyl) hafnium dichloride 32. 33. Dimethylgermylene bis (2-ethyl-4-naphthyl-4H-azulenyl) hafnium dichloride Dimethylgermylene bis (2-ethyl-4- (4
-Chloro-2-naphthyl-4H-azulenyl)) hafnium dichloride 34. Dimethylgermylene bis (2-ethyl-4-biphenyl-4H-azulenyl) hafnium dichloride 35. Dimethylgermylene bis (2-ethyl-4- (2
36. -fluoro-4-biphenyl) -4H-azulenyl) hafnium dichloride Dimethylsilylenebis (2-ethyl-4- (3-
Chloro-4-tbutyl-4H-azulenyl)) hafnium dichloride and the like.

Among these, dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azulenyl) hafnium dichloride and dimethylsilylenebis (2-ethyl-4- (4-chloro) -2
-Naphthyl-4H-azulenyl)) hafnium dichloride and dimethylsilylenebis (2-ethyl-4- (3-chloro-4-tbutyl-4H-azulenyl)) hafnium dichloride are preferred.

The nomenclature is based on the structure of the compound before complexation of the transition metal compound having a 2,4-substituted azulene skeleton substituted at the 2-position and 4-position shown in the general formula (1). Organic Chemistry Biochemical Nomenclature (1) Kenzo Hirayama, Kazuo Hirayama (Nankodo).

The transition metal compounds having a hydroazulene skeleton shown above include 1,4-dihydroazulene,
Transition metal compounds obtained from uncomplexed compounds having 2,4-dihydroazulene, 3,4-dihydroazulene, 3a, 4-dihydroazulene, 4,8a-dihydroazulene skeleton, or complexations having these skeletons A transition metal compound obtained from a mixture of the preceding compounds, or 1,
6-dihydroazulene, 2,6-dihydroazulene,
3,6-dihydroazulene, 3a, 6-dihydroazulene, a transition metal compound obtained from an uncomplexed compound having a 6,8a-dihydroazulene skeleton, or a mixture of uncomplexed compounds having these skeletons. The resulting transition metal compound or 1,8-dihydroazulene, 2,8
-Dihydroazulene, 3,8-dihydroazulene, 3
a, 8-dihydroazulene, a transition metal compound obtained from an uncomplexed compound having an 8,8a-dihydroazulene skeleton, or a transition metal compound obtained from a mixture of uncomplexed compounds having these skeletons Means

Further, compounds in which one or both of the chlorides of these compounds are replaced with bromine, iodine, hydrogen, methylphenyl, benzyl, alkoxy, dimethylamide, diethylamide, etc. further,
In place of the above-mentioned zirconium, compounds replacing titanium, hafnium and the like can also be exemplified.

(Component B) In the present invention, at least one compound selected from the group consisting of the ion-exchanged layered silicates used as the component B has a surface formed by ionic bonding or the like with a weak bonding force to each other. A silicate compound having a crystal structure stacked in parallel and containing exchangeable ions. Most ion-exchanged phyllosilicates occur naturally mainly as a main component of clay minerals, but these ion-exchanged phyllosilicates are not limited to those of natural origin but are artificially synthesized. You may.

Specific examples of ion-exchangeable layered silicates include, for example, “Clay Mineralogy” written by Haruo Shimizu, Asakura Shoten (19)
95)), a known layered silicate described in
Smectites such as montmorillonite, zauconite, beidellite, nontronite, saponite, hectorite, stevensite, bentonite and teniolite, vermiculite and mica are preferred.

Although the component B can be used without any particular treatment, it is also preferable to subject the component B to a chemical treatment. Here, the chemical treatment may be any of a surface treatment for removing impurities adhering to the surface and a treatment that affects the crystal structure of the clay. Specifically, acid treatment, alkali treatment, salt treatment, organic matter treatment and the like can be mentioned.

In the present invention, at least 40%, preferably at least 60%, of the exchangeable Group 1 metal cations contained in the ion-exchangeable phyllosilicate before being treated with the salts are represented by the following salts: It is preferable to perform ion exchange with a more dissociated cation. Salts used in the salt treatment for the purpose of ion exchange include a cation containing at least one atom selected from the group consisting of atoms of groups 1 to 14 and a group consisting of a halogen atom, an inorganic acid and an organic acid. A compound comprising at least one anion selected from the group consisting of a cation containing at least one atom selected from the group consisting of atoms of groups 2 to 14;
l, Br, I, F, PO 4, SO 4, NO 3, CO 3, C 2
O ₄ , ClO ₄ , OOCCH ₃ , CH ₃ COCHCOC
H ₃ , OCl ₂ , O (NO ₃ ) ₂ , O (ClO ₄ ) ₂ , O (S
O ₄ ), OH, O ₂ Cl ₂ , OCl ₃ , OOCH, OOCC
It is H ₂ CH _3, consists of a C ₂ H ₄ O ₄ and C ₅ of at least one anion selected from the group consisting of H ₅ O ₇ compound.

Specifically, LiF, LiCl, LiB
r, LiI, Li_TwoSO_Four, Li (CH _ThreeCOO), Li
CO_Three, Li (C₆H_FiveO₇), LiCHO_Two, LiC
_TwoO_Four, LiClO_Four, Li_ThreePO_FourCaCl_Two, CaS
O_Four, CaC_TwoO_Four, Ca (NO_Three)_Two, Ca_Three(C₆H
_FiveO₇)_Two, MgCl_Two, MgBr_Two, MgSO_Four, Mg (P
O_Four)_Two, Mg (ClO_Four)_Two, MgC_TwoO_Four, Mg (N
O_Three)_Two, Mg (OOCCH_Three)_Two, MgC_FourH_FourO_Four, Ti
(OOCCH_Three)_Four, Ti (CO_Three)_Two, Ti (NO_Three)_Four,
Ti (SO_Four) _Two, TiF_Four, TiCl_Four, Zr (OOCC
H_Three)_Four, Zr (CO_Three)_Two, Zr (NO_Three)_Four, Zr (SO
_Four)_Two, ZrF_Four, ZrCl_Four, ZrOCl_Two, ZrO (N
O_Three)_Two, ZrO (ClO_Four)_Two, ZrO (SO_Four), HF
(OOCCH_Three)_Four, HF (CO_Three) _Two, HF (NO_Three)_Four,
HF (SO_Four)_Two, HFOCl_Two, HFF_Four, HFCl_Four,
V (CH_ThreeCOCHCOCH_Three)_Three, VOSO_Four, VOCl
_Three, VCl_Three, VCl_Four, VBr_Three, Cr (CH_ThreeCOCH
COCH_Three)_Three, Cr (OOCCH_Three)_TwoOH, Cr (NO
_Three)_Three, Cr (ClO_Four)_Three, CrPO_Four, Cr_Two(S
O_Four)_Three, CrO_TwoCl_Two, CrF_Three, CrCl_Three, CrBr
_Three, CrI_Three, Mn (OOCCH_Three)_Two, Mn (CH_ThreeCO
CHCOCH_Three)_Two, MnCO_Three, Mn (NO_Three)_Two, Mn
O, Mn (ClO_Four)_Two, MnF_Two, MnCl_Two, Fe (O
OCCH_Three)_Two, Fe (CH_ThreeCOCHCOCH_Three)_Three, F
eCO_Three, Fe (NO_Three)_Three, Fe (ClO_Four)_Three, FeP
O_Four, FeSO_Four, Fe_Two(SO_Four)_Three, FeF_Three, FeCl
_Three, FeC₆H_FiveO₇, Co (OOCCH_Three)_Two, Co (CH
_ThreeCOCHCOCH_Three)_Three, CoCO_Three, Co (NO_Three)_Two,
CoC_TwoO_Four, Co (ClO_Four)_Two, Co_Three(PO_Four)_Two, C
oSO_Four, CoF_Two, CoCl_Two, NiCO_Three, Ni (NO
_Three)_Two, NiC_TwoO_Four, Ni (ClO_Four)_Two, NiSO_Four, N
iCl _Two, NiBr_Two, Zn (OOCCH_Three)_Two, Zn (C
H_ThreeCOCHCOCH_Three)_Two, ZnCO_Three, Zn (N
O_Three)_Two, Zn (ClO_Four)_Two, Zn_Three(PO_Four)_Two, ZnS
O_Four, ZnF_Two, ZnCl_Two, AlF_Three, AlCl_Three, Al
Br_Three, AlI_Three, Al_Two(SO_Four)_Three, Al_Two(C
_TwoO_Four)_Three, Al (CH_ThreeCOCHCOCH_Three)_Three, Al (N
O_Three)_Three, AlPO_Four, GeCl_Four, GeBr_Four, GeI_Four,
And the like.

The acid treatment can remove impurities on the surface and can also elute a part or all of cations such as Al, Fe, Mg, etc. having a crystal structure.

The acid used in the acid treatment is preferably selected from hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid and oxalic acid. The salt and the acid used for the treatment may be two or more. The treatment conditions with salts and acids are not particularly limited, but usually, the conditions of salt and acid concentrations of 0.1 to 50% by weight, treatment temperature of room temperature to boiling point, and treatment time of 5 minutes to 24 hours are selected. Then, it is preferable to carry out the reaction under conditions that elute at least a part of a substance constituting at least one compound selected from the group consisting of ion-exchange layered silicates. Further, salts and acids are generally used in an aqueous solution.

These ion-exchange layered silicates usually contain adsorbed water and interlayer water. In the present invention, it is preferable to remove these adsorbed water and interlayer water to use as component B.

The method of heat-treating the ion-exchanged layered silicate for adsorbed water and interlayer water is not particularly limited, but it is necessary to select conditions so that interlayer water does not remain and structural destruction does not occur. The heating time is at least 0.5 hour, preferably at least 1 hour. At this time, component B after removal
Is preferably 3% by weight or less, more preferably 1% by weight or less, when the moisture content when dehydrated for 2 hours under the condition of a temperature of 200 ° C. and a pressure of 1 mmHg is 0% by weight. .

As described above, in the present invention, a particularly preferable component B is an ion-exchangeable layered silicate having a water content of 3% by weight or less, obtained by performing a salt treatment and / or an acid treatment. It is.

As the component B, it is preferable to use spherical particles having an average particle diameter of 5 μm or more. If the shape of the particles is spherical, natural products or commercially available products may be used as they are,
Particles in which the shape and particle size of the particles are controlled by granulation, sizing, sorting, or the like may be used.

The granulation method used here includes, for example, a stirring granulation method and a spray granulation method, but commercially available products can also be used. In addition, at the time of granulation, organic substances, inorganic solvents, inorganic salts,
Various binders may be used.

The spherical particles obtained as described above have a particle size of 0.2 to suppress crushing and generation of fine powder in the polymerization step.
It is desirable to have a compressive breaking strength of not less than MPa, particularly preferably not less than 0.5 MPa. In the case of such a particle strength, the effect of improving the particle properties is effectively exhibited, particularly when prepolymerization is performed.

(Component C) In the preferred polymerization catalyst of the present invention, examples of the organoaluminum compound optionally used as the component C include a compound represented by the following general formula: AlR _a P _3-a (wherein, R represents a group having 1 to 3 carbon atoms) 20 hydrocarbon groups, P is hydrogen, halogen, alkoxy group, a is a trialkylaluminum such as trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum or diethylaluminum monochrome represented by 0 <a ≦ 3 Ride, alkyl aluminum containing halogen or alkoxy such as diethyl aluminum monomethoxide. In addition, aluminoxanes such as methylaluminoxane can also be used. Of these, trialkyl aluminum is particularly preferred.

<Preparation / Use of Catalyst> Component A, component B and, if necessary, component C are brought into contact to form a catalyst. The contact method is not particularly limited, but the contact can be performed in the following order. This contact may be performed not only at the time of preparing the catalyst but also at the time of prepolymerization with olefin or at the time of polymerization of olefin.

1) Contact component A with component B 2) Add component C after contacting component A with component B 3) Add component B after contacting component A with component C 4) Component After contacting B and component C, component A is added. In addition, three components may be contacted simultaneously.

Upon or after the contact of each component of the catalyst, a solid such as a polymer such as polyethylene and polypropylene, or an inorganic oxide such as silica and alumina may coexist or be brought into contact. The contact may be performed in an inert gas such as nitrogen or an inert hydrocarbon solvent such as pentane, hexane, heptane, toluene, or xylene. The contact temperature is-
It is carried out between 20 ° C. and the boiling point of the solvent, particularly preferably between room temperature and the boiling point of the solvent.

The catalyst thus obtained may be used after preparation without washing with an inert solvent, especially a hydrocarbon such as hexane, heptane or the like, or may be used after washing with the solvent. Is also good.

If necessary, the component C may be newly used in combination. The amount of component C used at this time is selected so that the atomic ratio of aluminum in component C to transition metal in component A is 1: 0 to 10,000.

Before the polymerization, ethylene, propylene, 1-
Butene, 1-hexene, 1-octene, 4-methyl-1
Pentene, 3-methyl-1-butene, vinylcycloalkane, olefins such as styrene are preliminarily polymerized,
If necessary, the washed product can be used as a catalyst.

This preliminary polymerization is preferably carried out in an inert solvent under mild conditions.
0.01 to 1000 g, preferably 0.1 to 100 g,
Is desirably performed so as to produce a polymer of The polymerization reaction is carried out in the presence or absence of a solvent such as an inert hydrocarbon such as butane, pentane, hexane, heptane, toluene or cyclohexane or a liquefied α-olefin.
The temperature is −50 ° C. to 250 ° C., and the pressure is not particularly limited, but is preferably normal pressure to about 2000 kg · f / cm ^2.
Range. The polymerization can be carried out by any of batch, continuous and semi-batch methods.

In addition, the presence of hydrogen as a molecular weight regulator in the polymerization system can control the molecular weight and molecular weight distribution to obtain a desired polymer. Among the catalyst systems described in the present invention, a specific metallocene complex,
When montmorillonite is combined with component B,
Active sites having lower hydrogen responsiveness than normal metallocene active sites are also generated, and a high molecular weight component is generated. Even if hydrogen as a molecular weight modifier is present, the weight average molecular weight can be adjusted while almost maintaining the abundance of the high molecular weight component, so that the molecular weight distribution is within the range of Q value suitable for resin processing moldability. Can be.

Further, since the Q value also depends on the polymerization temperature and the polymerization pressure, the Q value can be controlled to a desired value by optimizing these conditions.

The change with time of the hydrogen concentration in the polymerization system has a great effect not only on the molecular weight of the produced polymer but also on its distribution. For example, in the case of a hydrogen batch feed, in order to obtain a desired MFR, it is necessary to determine the initial condition of the hydrogen feed amount by incorporating a deviation in the molecular weight of the produced polymer with the lapse of time of hydrogen consumption. Although the MFR can be adjusted, it is not preferable because a large amount of a low molecular weight polymer is produced and adversely affects the physical properties of the product. Therefore, in the present invention, it is preferable to introduce hydrogen continuously so that the hydrogen concentration becomes constant during the polymerization.

At this time, regarding the hydrogen, both in the case where the bulk polymerization is carried out by the batch method and in the case where the gas phase polymerization is carried out, the hydrogen concentration in the gas phase in the autoclave is continuously adjusted so as to be constant during the polymerization. Preferably, it is introduced. The control range can be set to any value from 1 ppm to 10,000 ppm in concentration.

When a continuous polymerization method is used, the same method is preferably used. The range of the concentration setting can be arbitrarily set in the range of the hydrogen concentration of 1 ppm to 10,000 ppm. By these techniques, a desired polymer having the physical properties of the present invention can be obtained.

As long as the physical properties of the polymer disclosed in the present invention are not impaired, α-olefins other than ethylene (C ₄ to
Copolymerization may be carried out by adding a small amount of C ₆ ). The amount of the α-olefin used at this time may be added up to 6.0 mol% based on propylene.

[0061]

The following examples are provided to further illustrate the present invention. The present invention is not limited by these embodiments without departing from the gist thereof.

The following catalyst synthesis step and polymerization step were all performed in a purified nitrogen atmosphere. The solvent used was dehydrated with Molecular Sieve MS-4A.

Hereinafter, a method and an apparatus for measuring each physical property value in the present invention will be described. Sample propylene resin and IR
GANOX1010 (manufactured by Ciba Specialty Chemicals) 0.10% by weight, IRGAFOS168 Ciba
(Specialty Chemicals) 0.10% by weight and calcium stearate at a compounding ratio of 0.05% by weight (% by weight), and kneaded and granulated with a single screw extruder to obtain a pellet-shaped resin composition. Obtained. The following measurements were performed on the obtained sample pellets.

(1) MFR (Melt Flow Rate): Measuring method of melt indexer manufactured by Takara MFR (unit: g / 10 min) is JIS-K7
210 (230 ° C., 2.16 kg load).

(2) GPC: The weight average molecular weight Mw and the number average molecular weight Mn were determined by using a GPC150C type apparatus manufactured by Waters and three AD80M / S columns manufactured by Showa Denko.
Ortho-dichlorobenzene was used as the solvent, and the measurement temperature was 140
C.

(3) ME (Memory Effect): Apparatus Melt indexer manufactured by Takara Co., Ltd. Measuring method At 190 ° C., an orifice diameter of 1.0 mm and a length of 8.0 mm were extruded under a load, and the extrusion speed was 0.1 g / min. At this time, the polymer extruded from the orifice was rapidly cooled in methanol, and the value of the strand diameter at that time was calculated.

(4) CXS: For CXS, about 1 g of a polypropylene powder sample was precisely weighed in an eggplant-shaped flask, and
Then, 00 ml of xylene was added, and the mixture was boiled under heating and completely dissolved. Thereafter, this was quenched in a water bath at 23 ° C., the precipitated solid portion was filtered, 50 ml of the filtrate was evaporated to dryness in a platinum dish, and further dried under reduced pressure and weighed. CXS
Was calculated as the amount of xylene solubles (% by weight) in the polypropylene powder sample.

(5) Ethylene unit content: Ethylene unit content in the polymer derived from ethylene comonomer (unit:
(% By weight) was obtained by pressing the obtained polymer to form a sheet, and measuring the sheet by an IR method. Specifically, 730c
It was calculated from the height of the methylene chain-derived peak observed near m ^-1 .

(6) Melting point (Tm): DSC manufactured by Seiko
Using a measuring device, take a sample (about 5 mg), melt at 200 ° C for 5 minutes, cool down to 40 ° C at a rate of 10 ° C / min, crystallize, then heat up to 200 ° C at 10 ° C / min. Evaluation was made based on the melting peak temperature and the melting end temperature when melting was performed.

Example 1 (1) Dichloro {1,1′-dimethylsilylenebis [2
-Ethyl-4- (4-chloro-2-naphthyl) -4H-
Azulenyl] Synthesis of racemic hafnium: 2-bromo-4-chloronaphthalene (2.50 g, 10.30 m
mol) was dissolved in a mixed solvent of diethyl ether (50 mL) and hexane (7.5 mL), and a hexane solution of n-butyllithium (6.8 mL, 10.4 mmol,
1.53N) was added dropwise at 19 ° C. The mixture was stirred at 20 ° C. for 1 hour, and 2-ethylazulene (1.47 g, 9.
41 mmol) at 5 ° C. and stirred at room temperature for 1 hour.
On the way, diethyl ether (5.0 mL) was added. After standing, the supernatant solution was removed, and the precipitate was washed with hexane (20 m
L). Hexane (25 mL) was added there,
After cooling to 0 ° C., tetrahydrofuran (25 mL) was added. N-Methylimidazole (30 μL) and dimethyldichlorosilane (0.51 mL, 4.20 mmol) were added, and the mixture was stirred at 0 ° C. for 1.5 hours. Thereafter, a saturated aqueous solution of ammonium chloride (50 mL) was added, and the mixture was separated. The organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure.
As a crude product, dimethylsilylenebis [2-ethyl-
4- (4-Chloro-2-naphthyl) -1,4-dihydroazulene] (3.11 g) was obtained.

Next, the reaction product (3.0) obtained above was obtained.
9 g, 4.21 mmol) in diethyl ether (44 m
L) and dissolved at -70 ° C in a hexane solution of n-butyllithium (5.5 mL, 8.41 mmol, 1.53 mol).
1 / L) was added dropwise, the temperature was gradually raised, and the mixture was stirred at room temperature for 2 hours. The solvent was distilled off, and toluene (11 mL) and diethyl ether (99 mL) were added. After cooling to -70 ° C, hafnium tetrachloride (1.375 g, 4.29 mmol) was added, the temperature was gradually raised, and the mixture was stirred at room temperature overnight. After concentrating the obtained slurry solution to one third, it was filtered using Celite, washed with toluene (15 mL), and the filtrate was concentrated.
The crude product was washed five times with diethyl ether (10 mL) to give dichloro {1,1'-dimethylsilylenebis [2-ethyl-4- (4-chloro-2-naphthyl) -4].
H-azulenyl] racemic hafnium (1.20
g, 27% yield).

¹ H-NMR (300 MHz, CDCl ₃ )
δ 1.00 (s, 6H, SiMe ₂ ), 1.00 (t,
J = 7.8Hz, 6H, 2- CH 3 CH 2), 2.40-
2.59 (m, 2H, 2- CH 3 CHH), 2.59-
2.75 (m, 2H, 2- CH 3 CHH), 5.22
(D, J = 4.2 Hz, 2H, 4-H), 5.83-
5.93 (m, 6H), 6.04-6.08 (m, 2
H), 6.80 (d, J = 12 Hz, 2H), 7.50
−7.60 (m, 4H, arom), 7.59 (d, J
= 1.5 Hz, 2H, arom), 7.73 (d, J =
0.6 Hz, 2H, arom), 7.81-7.84
(M, 2H, arom), 8.22-8.25 (m, 2
H, arom).

[Chemical Treatment of Ion-Exchangeable Layered Silicate]
A vacuum stirrer was set in a 00 ml round bottom flask, 196.5 g of ion-exchanged water was charged, and then sulfuric acid 5
1.25 g (525 mmol) was charged and stirred. Further, 12.45 g (520 mmol) of lithium hydroxide was added and dissolved.

Further, 51.65 g of commercially available granulated montmorillonite (Benclay SL, manufactured by Mizusawa Chemical Co., Ltd., average particle size: 16.2 μm) was added, followed by stirring. Thereafter, the temperature is raised to 100 ° C. over 10 minutes and maintained for 280 minutes. Then 1
Cooled to 50 ° C. over time. This slurry is collected with a diameter of 1
Vacuum filtration was performed using a device in which an aspirator was connected to a 1.5 cm nutche and a suction bottle. The cake was recovered, re-slurried by adding 1.6 l of pure water, and filtered. This operation was repeated three more times. Filtration was completed within a few minutes. The pH of the final washing solution (filtrate) was 5. The recovered cake is placed in a nitrogen atmosphere 1
Dry overnight at 10 ° C. As a result, 41.6 g of a chemically treated product was obtained.

When the composition was analyzed by X-ray fluorescence,
The molar ratio of the constituent element to silicon as the main component is Al
/Si=0.223, Mg / Si = 0.048, Fe /
Si was 0.028.

[Preparation of Catalyst / Preliminary Polymerization] The following operation
It carried out using the solvent and monomer which were deoxidized and dehydrated under inert gas. The chemically treated ion-exchanged layered silicate granules produced above were dried under reduced pressure at 200 ° C. for 4 hours.

10 g of the chemically treated montmorillonite obtained above was introduced into a 1000 ml eggplant-shaped flask, and 58 ml of heptane and 42 ml of a heptane solution of triethylaluminum (0.6 mmol / ml) (2.5 mm / 2.5 mm) were added.
ol / g carrier) and stirred at room temperature. One hour later, it was washed three times with heptane, and finally the supernatant was removed.

Next, 120 ml of a contact solution of dimethylsilylenebis (2-ethyl-4- (4-chloro-2-naphthyldihydroazulenyl) hafnium dichloride and triisobutylaluminum in a heptane solution (M = 280.
2 μmol, Al / Hf = 10) were prepared, added at room temperature, and stirred for 60 minutes. Subsequently, the solution was introduced into the previously prepared montmorillonite slurry and stirred for 60 minutes.

Subsequently, the montmorillonite slurry prepared above and dimethylsilylenebis (2) were placed in a 1.0-liter stirred autoclave sufficiently purged with nitrogen.
-A mixed solution of -ethyl-4- (4-chloro-2-naphthyldihydroazulenyl) hafnium dichloride was introduced,
Further heptane was introduced until the total volume reached 500 ml and kept at 30 ° C.

Then, propylene was added at a constant speed of 5 g / hr.
Introduced at 40 ° C. for 4 hours and subsequently maintained at 50 ° C. for 2 hours. The prepolymerized catalyst slurry was recovered by siphon and
It dried under reduced pressure at ° C. By this operation, a prepolymerized catalyst containing 4.6 g of polypropylene per 1 g of the catalyst was obtained.

[Polymerization] After sufficiently replacing the inside of an autoclave having an internal volume of 200 liters with propylene, 45000 g of sufficiently dehydrated liquefied propylene was introduced and kept at 30 ° C. To this was added 470 ml of a triisobutylaluminum / normal heptane solution (50 g / l). Thereafter, 2.5 NL of hydrogen and 0.5 g of the above-mentioned solid catalyst component were injected with argon to initiate polymerization, and 40 mi to 75 ° C.
The reaction was heated at 75 ° C. for 3 hours. During this time, hydrogen was introduced at a constant rate of 0.15 g / hr. Thereafter, 100 ml of ethanol was injected to stop the reaction, and the remaining gas was purged to obtain 18.4 kg of a polymer.

The analysis of this polymer showed that the isotactic triad fraction was 99.5% and the MFR was 11.30 g.
/ 10 min. Having a weight average molecular weight of 224 according to GPC.
Mw / Mn was 3.27. Melting point 15
At 8.5 ° C., CXS was 0.40% by weight, and ME was 1.36.

<Example 2> [Polymerization] After sufficiently replacing the inside of an autoclave having an internal volume of 200 liters with propylene, 4500 g of sufficiently dehydrated liquefied propylene was introduced and kept at 30 ° C. to this,
470 ml of a triisobutylaluminum / normal heptane solution (50 g / l) was added. 2.0N hydrogen
L, 0.5 g of the solid catalyst component synthesized in Example 1 was pressurized with argon to initiate polymerization, and the temperature was raised to 75 ° C. over 40 minutes and reacted at 75 ° C. for 3 hours. During this time, hydrogen was introduced at a constant rate of 0.10 g / hr. Thereafter, 100 ml of ethanol was injected to stop the reaction, and the residual gas was purged.
As a result, 15.4 kg of a polymer was obtained.

Analysis of this polymer showed that the isotactic triad fraction was 99.3% and the MFR was 4.64 g /
10 min. Weight average molecular weight by GPC is 3033
00, Mw / Mn 3.69, melting point Tm 157.5
C, CXS was 0.45% by weight, and ME was 1.49.

<Example 3> [Polymerization] After sufficiently replacing the inside of an autoclave having an internal volume of 200 liters with propylene, 4500 g of sufficiently dehydrated liquefied propylene was introduced and kept at 30 ° C. to this,
470 ml of a triisobutylaluminum / normal heptane solution (50 g / l) was added. 2.0N hydrogen
L, 0.675 kg of ethylene and 0.5 g of the solid catalyst component synthesized in Example 1 were pressurized with argon to initiate polymerization, and the temperature was raised to 75 ° C. over 40 minutes and reacted at 75 ° C. for 3 hours. During this time, hydrogen was introduced at a constant rate of 0.10 g / hr. Thereafter, 100 ml of ethanol was injected to stop the reaction, and the remaining gas was purged to obtain 14.3 kg of a polymer.

Analysis of this polymer showed that the isotactic triad fraction was 99.4% and the MFR was 6.07 g /
10 min. , Weight average molecular weight by GPC is 2555
00, Mw / Mn 3.17, melting point Tm 149.2
° C, ethylene content 1.22% by weight, CXS 0.5
0% by weight and ME was 1.44.

Comparative Example 1 The same polymer analysis and physical property measurement were performed on PP HOMO polymer (product name: MA3UQ) manufactured by Nippon Polychem Co., Ltd. manufactured using a Ziegler-Natta catalyst.

Analysis of this polymer showed that the isotactic triad fraction was 97.8% and the MFR was 7.80 g /
10 min. Weight average molecular weight by GPC is 3100
00, Q value is 4.5, melting point Tm is 164.0 ° C, CXS
Was 1.8% by weight and ME was 1.33.

Comparative Example 2 (1) Synthesis of [(r) -dimethylsilylenebis (2-methylbenzoindenyl) zirconium dichloride] Organometallics, 1994, 13, 9
Synthesized according to the method described in 64 documents.

(2) Synthesis of catalyst A glass reactor having an inner volume of 0.5 l and equipped with a stirring blade was charged with W.
2.4 g of MAOON SiO ₂ manufactured by ITCO (20.
7 mmol-Al), 50 ml of n-heptane was introduced, and 20.0 ml (0.0637 m) of a (r) -dimethylsilylenebis (2-methylphenylindenyl) zirconium dichloride solution diluted in toluene in advance.
mol), followed by 4.14 ml of triisobutylaluminum (TIBA) · n-heptane solution (3.0 ml).
3 mmol) was added. After reacting at room temperature for 2 hours, propylene was allowed to flow to carry out preliminary polymerization.

(3) Polymerization After thoroughly replacing the inside of a 200 L stirred autoclave with propylene, 3 g of triethylaluminum diluted with n-heptane and 45 kg of liquefied propylene were added, and the internal temperature was maintained at 30 ° C. . Then, 1.1 g of the previously synthesized solid catalyst (by weight excluding the prepolymerized polymer)
Was added and 5.0 NL of hydrogen was added.

Thereafter, the temperature was raised to 65 ° C. to start polymerization, and the temperature was maintained for 3 hours. Here 100m ethanol
The reaction was stopped by adding 1. The residual gas was purged and the polymer was dried. As a result, 7.0 kg of a polymer was obtained.

Further, regarding the polymer, MFR =
5.00 g / 10 min, isotactic triad fraction 95.0%, Q value 2.8, melting point Tm 150.9
° C, CXS was 0.5% by weight, and ME was 1.1.

Example 4 [Synthesis of Complex] (1) Dimethylsilylenebis (2-ethyl-4- (2-fluoro-
Synthesis of racemic 4-biphenyl) -4H-azulenyl) hafnium dichloride: (a) synthesis of racemic-meso mixture; 2-fluoro-4-
Bromobiphenyl (4.63 g, 18.5 mmol) in diethyl ether (40 mL) and hexane (40 mL)
And a pentane solution of t-butyllithium (22.8 mL, 36.9 mmol, 1.62 N) was added dropwise at −78 ° C., and the mixture was stirred at −5 ° C. for 2 hours.

To this solution was added 2-methylazulene (2.36
g, 16.6 mmol) and stirred at room temperature for 1.5 hours. After cooling to 0 ° C., tetrahydrofuran (40 mL) was added. N-Methylimidazole (40 μL) and dimethyldichlorosilane (1.0 mL, 8.30 mmol) were added, the temperature was raised to room temperature, and the mixture was stirred at room temperature for 1 hour. After this,
The organic phase was dried over magnesium sulfate, and the solvent was distilled off under reduced pressure to give dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenylyl) -1,4-dihydrogen. Azulene) (6.3)
g) was obtained.

Next, the crude product obtained above was dissolved in diethyl ether (23 mL), and a hexane solution of n-butyllithium (10.3 mL, 16.6 mm) was added at −78 ° C.
ol, 1.56 mol / L), and the mixture was gradually heated and stirred at room temperature for 2 hours. Further, toluene (185 m
L), the mixture was cooled to -78 ° C, hafnium tetrachloride (2.65 g, 8.3 mmol) was added, and the mixture was gradually heated and stirred at room temperature overnight. Most of the solvent was distilled off from the obtained slurry solution under reduced pressure, filtered, and then toluene (4 m
L), hexane (9 mL), ethanol (20 mL),
After washing with hexane (10 mL), dichloro ｛1,
1'-dimethylsilylenebis [2-ethyl-4- (2-
Fluoro-4-biphenylyl) -4H-azulenyl]}
A racemic-meso mixture of hafnium (1.22 mg, 16% yield) was obtained.

(B) Purification of the racemic form: The racemic-meso mixture (1.1 g) obtained above was purified by adding dichloromethane (30 g)
ml), and suspended with a high-pressure mercury lamp (100 W).
Spectral irradiation was performed. The solvent was distilled off from this solution under reduced pressure. Dichloromethane (40 mL) was added to the obtained solid to suspend it, and the solid was filtered. After washing with hexane (3 mL) and drying under reduced pressure, a racemate (577 mg, 52%) was obtained.

[0098]¹H NMR (300MHz, CDCl_Three) δ1.02 (s, 6 H,
 SiMe_Two), 1.08 (t, J = 8 Hz, 6 H, CH _ThreeCH_Two), 2.54 (sept, J = 8 Hz, 2 H, CH_ThreeCH_Two), 2.70 (sept, J = 8 Hz,
2 H, CH_ThreeCH_Two), 5.07 (br s, 2 H, 4-H), 5.85-6.10
(m, 8 H), 6.83 (d, J = 12 Hz, 2 H), 7.30-7.6 (m, 1
6 H, arom).

[Chemical treatment of ion-exchange layered silicate] A 5 L separable flask equipped with a stirring blade and a reflux device was placed
500 g of ion-exchanged water was charged, and 249 g (5.93 mol) of lithium hydroxide monohydrate was further charged and stirred. Separately, 581 g of sulfuric acid
(5.93 mol) was diluted with 500 g of ion-exchanged water, and added dropwise to the aqueous lithium hydroxide solution using a dropping funnel. At this time, a part of the sulfuric acid was consumed in the neutralization reaction, lithium sulfate was generated in the system, and the sulfuric acid became excessive, resulting in an acidic solution.

Further, commercially available granulated montmorillonite (Benclay SL, manufactured by Mizusawa Chemical Co., Ltd., average particle size: 28.0 μm)
After 350 g of m) was added, the mixture was stirred. Thereafter, the temperature was raised to 108 ° C. over 30 minutes and maintained for 150 minutes. Then, it cooled to 50 degreeC over 1 hour. This slurry was subjected to reduced pressure filtration using a device in which an aspirator was connected to a nutsche and a suction bottle. The cake was collected, 5.0 L of pure water was added thereto to reslurry, and filtration was performed. This operation was repeated four more times. Filtration was completed within a few minutes. Final wash (filtrate)
Had a pH of 5.

The recovered cake was dried at 110 ° C. overnight under a nitrogen atmosphere. As a result, 275 g of a chemically treated product was obtained. When the composition was analyzed by X-ray fluorescence, the molar ratio of the constituent elements to silicon, which was the main component, was Al / Si = 0.21, Mg / Si = 0.
046, Fe / Si = 0.022.

[Preparation of Catalyst / Preliminary Polymerization]
It carried out using the solvent and monomer which were deoxidized and dehydrated under inert gas. The chemically treated ion-exchanged layered silicate granules produced above were dried under reduced pressure at 200 ° C. for 4 hours.

Into an autoclave having an inner volume of 10 L, 200 g of the chemically treated montmorillonite obtained above was introduced, and 1160 heptane was added.
ml of triethylaluminum in heptane (0.
6 mmol / ml) 840 ml (0.5 mol) is added over 30 minutes, and at 25 ° C.
Stir for 1 hour. Thereafter, the slurry was allowed to settle statically, 1300 ml of the supernatant was extracted, washed twice with 2600 ml of heptane, and adjusted by adding heptane so that the total amount of heptane finally became 1200 ml.

Next, 5.93 g (6 mol) of dimethylsilylenebis (2-ethyl-4- (2-fluoro-4-biphenyl) -4H-azulenyl) hafnium dichloride and heptane 51 were placed in a 2 L flask.
After adding 6 ml and stirring well, 84 ml (11.8 g) of a heptane solution of triisobutylaluminum (140 mg / ml) was added at room temperature, and the mixture was stirred for 60 minutes. Subsequently, the above solution was introduced into the montmorillonite slurry previously prepared in the autoclave, and stirred for 60 minutes. Subsequently, heptane was further introduced until the total volume became 5 L, and kept at 30 ° C. Propylene was introduced therein at a constant rate of 100 g / hr at 40 ° C. for 4 hours, and subsequently maintained at 50 ° C. for 2 hours. The pre-polymerized catalyst slurry was recovered by a siphon, the supernatant was removed, and then dried at 40 ° C. under reduced pressure. By this operation, 2.
A prepolymerized catalyst containing 0 g was obtained.

[Polymerization] Liquefied propylene, hydrogen and TIBA were continuously fed into a liquid-phase polymerization tank having a stirrer having an internal volume of 400 liters. The feed amounts of liquefied propylene and TIBA were 90 kg / hr and 21.2 g / hr, respectively, and hydrogen was fed such that the molar concentration [H2] became 30 ppm.
Further, the solid catalyst component (A) obtained above was fed as a solid component contained in (A) at a rate of 1.36 g / hr. Further, the polymerization tank was cooled such that the polymerization temperature became 65 ° C. The slurry polymerized in this polymerization tank was extracted using a slurry pump.

The rate of withdrawing the slurry was about 10.8 kg / hr as the polypropylene particles contained in the slurry. The average residence time of the polypropylene particles in the liquid phase polymerization tank was 2 hours. The average particle diameter Dp50 of the polypropylene particles is 436 (the average CE is 7900 g / g,
MFR is 2.3 g / 10min, CXS is 0.26% by weight, Q value is 4.5, ME is
It was 1.54. The catalyst efficiency CE is defined as the yield (g) of polypropylene per 1 g of the solid component contained in the solid catalyst component (A).

Example 5 The same operation as in Example 4 was carried out except that the hydrogen concentration [H2] was kept at 200 ppm, the amount of the feed catalyst was set at 1.63 g, and the average residence time was set at 1.5 hours. The average particle size Dp50 of the polymer obtained at that time was 457, the average CE was 10300 g / g, the polymer MFR was 63/10 min, the CXS was 0.20% by weight, the Q value was 4.0, and the ME was 1.23.

[0108]

[Table 1]

[0109]

According to the present invention, it is possible to provide a propylene polymer which is not only excellent in rigidity and heat resistance but also has a high molecular weight component and is excellent in moldability.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J100 AA02Q AA03P CA01 CA04 CA11 DA04 DA24 DA39 DA43 FA10

Claims (2)

[Claims] 1. A propylene-based polymer having the following physical properties. (1) The melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg is 0.1 to 1000 g / 10 minutes,
(2) Isotactic triad fraction (mm) measured by ¹³ C-NMR is 99.0% or more; (3) Q value measured by gel permeation column chromatography (GPC) (weight average molecular weight (Mw) ) And number average molecular weight (M
n) is 2.0 to 6.0, (4) 230 ° C, 2.1
MFR measured at 6 kg load and Memory Effect (ME) measured at 190 ° C. and orifice diameter 1.0 mm
Satisfies the following formula (I): (ME) ≧ −0.26 × log (MFR) +1.40 (I) (5) Amount dissolved in xylene at 23 ° C. (CXS)
(Unit: wt%) satisfying the following formula (II): CXS ≦ 0.5 × [C2] + 0.2 × log (MFR) +0.5 (II) (where [C2] is ethylene in the polymer (6) The melting point (Tm) measured by DSC is 120 ° C. or higher. 2. The propylene polymer according to claim 1, wherein the propylene polymer is polymerized using a metallocene catalyst.