JPH11130807A - Transition metallic compound, catalyst for polymerizing propylene, production of propylene polymer using the same catalyst and propylene polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound which is a catalyst component for polymerizing propylene capable of efficiently producing a propylene polymer having vinyl groups at molecular terminals. SOLUTION: This compound is represented by the formula [R<1> to R<4> , X<1> and X<2> are each H, a halogen, a 1-20C hydrocarbon or the like; R<5> and R<6> are each a halogen, a 1-20C hydrocarbon, a 1-20C halogen-containing hydrocarbon or the like; Y is a 1-20C hydrocarbon, a 1-20C halogen-containing hydrocarbon or the like; M<1> is a group IV, VA or VIA transition metal of the periodic table), e.g. 1,2-ethanediyl[1-(4,7-diisopropylindenyl)] [2-(4,7- diisopropylindenyl)]hafnium(IV)dichloride. The compound represented by the formula is obtained by carrying out the Friedel-Crafts reaction of a raw material compound, providing an indanone derivative, reducing the carbonyl group, then dehydrating the resultant compound, converting the dehydrated compound into a monoformic acid ester of a diol, subsequently hydrolyzing and dehydrating the obtained compound and then conducting the Witting reaction of the prepared compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a transition metal compound useful as a catalyst component for propylene polymerization, a highly active propylene polymerization catalyst containing the same, and a vinyl group at the molecular terminal obtained by using the polymerization catalyst. The present invention relates to a propylene polymer having the same and a method for efficiently producing the propylene polymer.

[0002]

2. Description of the Related Art Heretofore, as a highly active soluble olefin polymerization catalyst, a catalyst comprising a combination of a transition metal compound and an aluminoxane has been known (Japanese Patent Laid-Open No. 58-19 / 1983).
309, JP-A-60-217209). In addition, it has been reported that cationic species are useful as active species of soluble olefin polymerization catalysts ("J. Am.C.
hem. Soc., 81 , 81 (1959); 82 , 1953 (1960); 107, 7219
(1985) "). An example of isolating this active species and applying it to olefin polymerization is described in" J. Am. Chem. Soc., 108, 74.
10 (1986) ", Japanese Patent Publication No. Hei.
JP-A-139504, EP-A-468651 and the like, and JP-A-3-207704, International Patent Publication No. 92-1723 and the like as examples in which an organic aluminum compound is used in combination with this active species. ₃ R
EP-A-519746 can be mentioned as an example of an olefin polymerization catalyst comprising a transition metal compound having a ligand containing a group and an organoaluminum oxy compound.

[0003] In addition, long-chain branched polyolefins have high melt viscosity and excellent mechanical properties. For producing long-chain branched polyolefins, it is effective to use polyolefins having a vinyl group at the end as macromonomers. It is described in JP-A-1-502636, and examples of polyethylene are also reported. However,
There is no report on long-chain branched polypropylene.

[0004] 1,2-ethanediylbis (1- (4,7-dimethylindenyl)) zirconium dichloride is used as a catalyst component of a transition metal compound for producing a polypropylene having a terminal vinyl group used in the synthesis of this long-chain branched polyolefin. And isopropylidenebis (1- (3-t
-Butylindenyl)) zirconium dichloride and the like have been reported ("Polym. Prepr., 38 , 776 (1997)").

[0005] However, this polymerization catalyst has a small amount of terminal vinyl groups, and thus is not sufficient as a catalyst for producing a macromonomer for synthesizing a branched polyolefin. There was a problem and improvement was desired. Further, Japanese Unexamined Patent Publication No.
No. 109214 discloses a method for producing a propylene-based low polymer having a vinyl group at a terminal by reacting propylene with an olefin other than propylene. The purpose was to produce an olefin codimer, and it was not possible to produce a branched macroolefin for synthesizing polyolefin.

[0006]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a propylene polymer having a vinyl group at a molecular terminal and a transition metal compound which is a catalyst component for propylene polymerization capable of efficiently producing the polymer. It is an object of the present invention to provide a catalyst for propyne polymerization and a method for producing a propylene polymer.

[0007]

Means for Solving the Problems The inventors of the present invention have made intensive studies to achieve the above object, and as a result, have achieved the object by producing a propylene polymer using a specific catalyst system. I found out what could be done. The present invention has been completed based on such findings. That is, the present invention provides the following transition metal compound, propylene polymerization catalyst,
An object of the present invention is to provide a method for producing a propylene polymer using the catalyst and a propylene polymer. (1) General formula (I)

[0008]

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(Where R¹~ R^FourAre each independently water
An element atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
C1-C20 halogen-containing hydrocarbon group, silicon-containing
Group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus
Represents a containing group;¹And R^TwoBond with each other to form a ring
May be. R^Five, R⁶Are independently halogen sources
, A hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms.
Hydrogen-containing hydrocarbon groups, silicon-containing groups, oxygen-containing groups,
Shows an ow containing group, a nitrogen containing group or a phosphorus containing group. X¹
And X^TwoAre independently a hydrogen atom and a halogen atom
, A hydrocarbon group having 1 to 20 carbon atoms and a hydrocarbon group having 1 to 20 carbon atoms.
Hydrogen-containing hydrocarbon groups, silicon-containing groups, oxygen-containing groups,
Represents an ow-containing group, a nitrogen-containing group or a phosphorus-containing group, and Y is
A divalent group that binds two ligands and has 1 to 1 carbon atoms
20 hydrocarbon groups, halogen-containing carbon atoms having 1 to 20 carbon atoms
Hydrogen group, silicon-containing group, germanium-containing group, -O-,
-CO-, -S-, -SO_Two-, -NR⁷-, -PR⁷
-, -P (O) R⁷-, -BR ⁷-Or -AlR⁷−
And R⁷Is a hydrogen atom, a halogen atom, and a carbon number of 1 to 2.
0 hydrocarbon group, halogen-containing hydrocarbon having 1 to 20 carbon atoms
Represents an elementary group. M¹Is the group IVA, VA, VIA of the periodic table
Indicates a transition metal. The transition metal compound represented by). (2) (A) the transition metal compound according to claim 1,
(B) (a) an organoaluminum oxy compound and
(B) reacting with the above transition metal compound to convert to a cation
And at least one selected from ionic compounds
For propylene polymerization, characterized by containing
Medium. (3) (A) the transition metal compound according to claim 1,
(B) (a) an organoaluminum oxy compound and
(B) reacting with the above transition metal compound to convert to a cation
At least one selected from ionic compounds,
And (C) an organoaluminum compound
A catalyst for propylene polymerization, comprising: (4) The catalyst for propylene polymerization according to (2) or (3).
Characterized in that propylene is polymerized in the presence of
A method for producing a pyrene polymer. (5) General formula (II)

[0010]

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(Wherein, R ^{8 to} R ¹³ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
It represents a halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group having 1 to 20 carbon atoms. X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, It represents a nitrogen-containing group or a phosphorus-containing group, and M ¹ represents a transition metal of Groups IVA, VA, and VIA of the periodic table. A) a transition metal compound represented by
(B) propylene comprising (a) an organoaluminum oxy compound and (b) at least one selected from ionic compounds capable of reacting with the transition metal compound to be converted to cations. A method for producing a propylene polymer, comprising polymerizing propylene in the presence of a polymerization catalyst. (6) (A) the transition metal compound described in (5), and (B)
(A) An organic aluminum oxy compound and (b) at least one selected from ionic compounds capable of reacting with the transition metal compound to be converted into a cation, and (C) an organic aluminum compound. A method for producing a propylene polymer, comprising polymerizing propylene in the presence of a propylene polymerization catalyst. (7) The number of terminal vinyl groups per molecule produced by the method for producing an olefin polymer according to any one of (4) to (6) is> 0.6, and the weight average molecular weight is 20.
A propylene polymer which is 0 to 100,000. (8) The propylene polymer according to (7), wherein the isotactic pentad fraction ([mmmm]) based on the measurement of nuclear magnetic resonance spectrum is 60% or more.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The transition metal compound of the present invention is a novel compound having a structure represented by the aforementioned general formula (I). That is,

[0013]

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In the general formula (I), R¹~ R
^FourAre independently a hydrogen atom, a halogen atom, a carbon number
Contains 1 to 20 hydrocarbon groups and 1 to 20 carbon atoms
Hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing
Group, nitrogen-containing group or phosphorus-containing group, as a specific example
Is a hydrogen atom, and halogen atoms are chlorine and odor.
And fluorine, iodine atoms. 1-20 carbon atoms
Examples of the hydrocarbon group include methyl group, ethyl group, n
-Propyl group, isopropyl group, n-butyl group, isobutyl
Tyl group, t-butyl group, n-hexyl group, n-decyl group
Alkyl groups such as phenyl group, 1-naphthyl group, 2-
Aryl groups such as naphthyl group and arals such as benzyl group
And a halogen having 1 to 20 carbon atoms.
The contained hydrocarbon groups include trifluoromethyl
At least one hydrogen atom of the hydrocarbon group is a suitable halogen atom
And a group substituted with a child. In addition, trimethyl
Silicon such as a ruyl group and dimethyl (t-butyl) silyl group
Containing group, methoxy group, ethoxy group, dimethylamino group
Which oxygen- or nitrogen-containing groups can be mentioned
You. Also, R¹And R^TwoFluorene
Any ring may be formed. R^Five, R⁶Are independent
Represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
1-20 halogen-containing hydrocarbon groups, silicon-containing groups, acids
Group containing sulfur, group containing sulfur, group containing nitrogen or group containing phosphorus
Is shown. Specific examples of the above R except for a hydrogen atom ¹~ R
^FourAnd the groups mentioned above. R¹, R^Twoas,
Hydrogen and an alkyl group having 6 or less carbon atoms are preferable.
Element, methyl group, ethyl group, isopropyl group, cyclohexyl
A sil group is more preferred, and hydrogen is even more preferred. Also,
R^Three~ R⁶Is preferably an alkyl group having 6 or less carbon atoms.
Methyl, ethyl, isopropyl, cyclohexyl
Xyl groups are more preferred, and isopropyl groups are even more preferred.
New

X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group,
It represents an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and specific examples include the groups described above for R ^{1 to} R ⁴ . Y is a divalent group bonding two ligands, and is a hydrocarbon group having 1 to 20 carbon atoms,
20 halogen-containing hydrocarbon groups, silicon-containing groups, germanium-containing groups, -O-, -CO-, -S-, -SO
^{_{2 -, - NR 7 -,}} - PR 7 -, - P (O) R 7 -, -
BR ⁷ — or —AlR ⁷ —, wherein R ⁷ is a hydrogen atom,
Halogen atom, hydrocarbon group having 1 to 20 carbon atoms, 1 carbon atom
And -20 to 20 halogen-containing hydrocarbon groups. Specific examples include methylene, ethylene, ethylidene, isopropylidene, cyclohexylidene, 1,2-cyclohexylene,
Dimethylsilylene, tetramethyldisilylene, dimethylgermylene, methylborylidene (CH3 -B =), methylaluminidene (CH3 -Al =), phenylphosphylidene (Ph-P =), phenylphosphoridene (PhP
O =), 1,2-phenylene, vinylene (-CH = CH
-), Vinylidene (CH2 = C =), methylimide, oxygen (-O-), sulfur (-S-) and the like. Of these, methylene, ethylene, ethylidene and isopropylidene are easily synthesized and obtained. Preferred in terms of rate.

M ¹ represents a transition metal belonging to the group IVA, VA or VIA of the periodic table, and specific examples thereof include titanium, zirconium, hafnium, vanadium and chromium. Titanium,
Zirconium and hafnium are preferred, with hafnium being particularly preferred. Specific examples of the transition metal compound represented by the general formula (I) include 1,2-ethanediyl (1
-(4,7-diisopropylindenyl)) (2-
(4,7-diisopropylindenyl) hafnium dichloride, 1,2-ethanediyl (9-fluorenyl)
(2- (4,7-diisopropylindenyl) hafnium dichloride, isopropylidene (1- (4,7-diisopropylindenyl)) (2- (4,7-diisopropylindenyl) hafnium dichloride, 1,2-ethanediyl (1- (4,7-dimethylindenyl)) (2
-(4,7-diisopropylindenyl) hafnium dichloride, 1,2-ethanediyl (9-fluorenyl)
(2- (4,7-dimethylindenyl)) hafnium dichloride, isopropylidene (1- (4,7-dimethylindenyl)) (2- (4,7-diisopropylindenyl) hafnium dichloride and the like, and Examples of the compound include those obtained by substituting hafnium with zirconium or titanium in the compound of the formula (1), but are not limited thereto, and may be a similar compound of a metal element of another group.

The transition metal compound of the present invention can be synthesized by any method. A typical synthetic route is as follows.

[0018]

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In this synthetic route, the starting compound [1]
Is commercially available or can be obtained by known alkylation, halogenation and the like. For example, the compound [1] is subjected to a Friedel-Crafts reaction in the same manner as described in "Synthesis, 222 (1980)" to obtain an indanone derivative [2], and the carbonyl group is reduced and then dehydrated. Thus, compound [3] is obtained. This compound [3] was prepared using, for example, "Organic Syntheses Collective Volume V" pp.6
The compound [4] can be obtained by converting the diol into a monoformate in the same manner as described in 47, followed by hydrolysis and dehydration. The compound [1] is introduced with a precursor of the bonding group Y by a Wittig reaction in the same manner as described in, for example, "Can. J. Chem. 55 , 562 (1977)". Further, for example, a leaving group E was introduced by a method similar to the method described in “Handbook of Organic Chemistry Experiment 3-Synthesis Reaction [I]-”, page 132 (Chemical Doujin), and the obtained compound [5] And a compound [6] which can be produced by the same production method as the compound [3] to obtain a compound [7] which is a ligand of the transition metal compound represented by the general formula (I). be able to. This compound [7] is
For example, "J. Organomet. Chem. 369, 359 (1989)" similar to the method described method, i.e., by reaction of the corresponding substituted cycloalkenyl anion with halide of the M ^1,
The transition metal compound represented by the general formula (I) can be obtained.

Specific examples include the following synthetic routes.

[0021]

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The propylene polymerization catalyst of the present invention comprises (A)
A transition metal compound represented by the general formula (I);
(A) an organoaluminum oxy compound and (b) at least one selected from ionic compounds capable of reacting with the transition metal compound of the component (A) to be converted into a cation, and optionally (C) an organoaluminum compound And a catalyst containing In the polymerization catalyst, the transition metal compound represented by the general formula (I) used as the component (A) may be used alone or in combination of two or more.

The aluminoxane of the component (a) is represented by the following general formula (III)

[0024]

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(Wherein R ¹⁴ represents an alkyl group, alkenyl group, aryl group having 1 to 20, preferably 1 to 12 carbon atoms,
It represents a hydrocarbon group such as an arylalkyl group or a halogen atom, and n represents the degree of polymerization, and is usually an integer of 2 to 50, preferably 2 to 40. In addition, each R ¹⁴ may be the same or different. Aluminoxane represented by the following general formula (IV):

[0026]

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(Wherein, R ¹⁴ and n are the same as described above). Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The means is not particularly limited, and the reaction may be performed according to a known method. For example,
Dissolve the organic aluminum compound in the organic solvent,
A method in which this is brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization, and water is added later,
A method of reacting water of crystallization contained in metal salts or the like, water adsorbed on inorganic or organic substances with an organoaluminum compound,
There is a method in which a tetraalkyldialuminoxane is reacted with a trialkylaluminum and then with water. The aluminoxane may be toluene-insoluble. These aluminoxanes may be used alone or in a combination of two or more.

On the other hand, as the component (b), the component (A)
Which can react with the transition metal compound
Any compounds can be used as long as they are on compounds.
Is represented by the following general formulas (V) and (VI) ([L¹-R^Fifteen]^{k +})_a([Z]^-)_b ... (V) ([L^Two]^{k +})_a([Z]^-)_b ... (VI) (However, L^TwoIs M^Two, R¹⁶R¹⁷M^Three, R¹⁸ _ThreeC or
R¹⁹M^ThreeIt is. ) (In the formulas (V) and (VI), L¹Is a Lewis base, [Z]^-
Is a non-coordinating anion [Z¹]^-Or [Z^Two]^-This
Here [Z¹]^-Is an anion in which multiple groups are bonded to an element
That is, [M^FourG¹G^Two... G^f]^-(Where M^FourIs
Group 5 to 15 element of the periodic table, preferably 13 of the periodic table
Group 15 elements are shown. G¹~ G^fAre hydrogen atoms,
Halogen atom, alkyl group having 1 to 20 carbon atoms, 2 carbon atoms
Dialkylamino group having 1 to 40 carbon atoms and alcohol having 1 to 20 carbon atoms
Xy group, aryl group having 6 to 20 carbon atoms, 6 to 20 carbon atoms
Aryloxy group, alkyl aryl having 7 to 40 carbon atoms
Group, an arylalkyl group having 7 to 40 carbon atoms, 1 carbon atom
To 20 halogen-substituted hydrocarbon groups and 1 to 20 carbon atoms
Siloxy group, organic metalloid group or C2-20
Represents a hetero atom-containing hydrocarbon group. G¹~ G^fOut of
Two or more may form a ring. f is [(center metal M^Four
+1)]. ), [Z^Two] ^-Is acid digestion
The log of the reciprocal of the separation constant (pKa) is -10 or less.
Ted acid alone or Brønsted acid and Lewis acid
Combined conjugate bases, or generally defined as superacids
2 shows a conjugate base of an acid. In addition, Lewis base is coordinated.
You may. Also, R^FifteenIs a hydrogen atom, an alkyl group having 1 to 20 carbon atoms.
Alkyl group, aryl group having 6 to 20 carbon atoms, alkyl ant
A aryl group or an arylalkyl group;¹⁶And R
¹⁷Is cyclopentadienyl group, substituted cyclopen
Tadienyl group, indenyl group or fluorenyl group, R¹⁸
Is an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkyl
It represents an aryl group or an aralkyl group. R¹⁹Is Tetrafu
Macrocyclic ligands such as phenylporphyrins and phthalocyanines
Is shown. k is [L¹-R^Fifteen], [L^Two] With the ionic valence of
An integer of 1 to 3, a is an integer of 1 or more, b = (k × a)
You. M^TwoAre elements of the periodic table Nos. 1-3, 11-13, and 17
And M^ThreeIs the 7th to 12th element of the periodic table
Shows prime. ) Is preferably used.
it can.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, and triethylphosphine Phosphines such as triphenylphosphine and diphenylphosphine; thioethers such as tetrahydrothiophene; esters such as ethyl benzoate; and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹⁵ include hydrogen, a methyl group,
Examples of R ¹⁶ and R ¹⁷ include an ethyl group, a benzyl group, and a trityl group. Specific examples of R ¹⁶ and R ¹⁷ include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, and a pentamethylcyclopentane. And a dienyl group. Specific examples of R ¹⁸ include:
Examples thereof include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ¹⁹ include tetraphenylporphyrin, phthalocyanine, allyl group, and methallyl group. Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I.
_{3 and the} like. Specific examples of M ³ include M
n, Fe, Co, Ni, Zn and the like.

[Z ¹ ] ⁻ , that is, [M ⁴ G ¹ G]
² ... G ^f ] ^- , as a specific example of M ⁴ ,
B, Al, Si, P, As, Sb, etc., preferably B and Al can be mentioned. In addition, G ^1, G ² ~G
Specific examples of ^f include a dimethylamino group, a diethylamino group or the like as a dialkylamino group, a methoxy group, an ethoxy group, or an alkoxy group or an aryloxy group.
As hydrocarbon groups such as n-butoxy group and phenoxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-octyl group,
Fluorine, chlorine, bromine, iodine, and hydrocarbons containing hetero atoms as halogen atoms such as n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butylphenyl group, and 3,5-dimethylphenyl group Groups such as p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group, Examples of organic metalloid groups such as bis (trimethylsilyl) methyl group include a pentamethylantimony group, a trimethylsilyl group, a trimethylgermyl group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group.

Further, a non-coordinating anion, ie, pK
a alone or Brensted acid having a of -10 or less
The conjugate base of the combination of Ted and Lewis acids [Z^Two]
^-As a specific example of trifluoromethanesulfonic acid
Neon (CF_ThreeSO_Three)^-, Bis (trifluoromethane
Sulfonyl) methyl anion, bis (trifluorometa)
Bisulfonyl) benzyl anion, bis (trifluoro
Methanesulfonyl) amide, perchlorate anion (ClO
_Four)^-, Trifluoroacetate anion (CF_ThreeCO
O)^-, Hexafluoroantimony anion (Sb
F₆)^-, Fluorosulfonic acid anion (FS
O_Three)^-, Chlorosulfonic acid anion (ClS
O_Three)^-, Fluorosulfonate anion / 5-fluoride
Nchimon (FSO_Three/ SbF_Five)^-, Fluorosulfone
Acid anion / 5-arsenic fluoride (FSO_Three/ As
F_Five)^-, Trifluoromethanesulfonic acid / 5-fluorinated
Antimony (CF_ThreeSO_Three/ SbF_Five) ^-Etc.
be able to.

Specific examples of the component (b) include triethylammonium tetraphenylborate,
Tri-n-butylammonium tetraphenylborate,
Trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate,
Benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, tetraphenyl Benzylpyridinium borate, methyl tetraphenylborate (2-cyanopyridinium),
Triethylammonium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, tri-n-butylammonium tetrakis (pentafluorophenyl) borate, tri-tetrakis (pentafluorophenyl) borate Phenylammonium, tetra-n-butylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, benzyl (tri-n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentane) Methyldiphenylammonium fluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, tetrakis ( Methylanilinium borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, methylpyridinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) ) Benzylpyridinium borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium),
Benzyl (2-cyanopyridinium) tetrakis (pentafluorophenyl) borate, Methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), Triphenylphosphonium tetrakis (pentafluorophenyl) borate, Tetrakis [bis (3 5-
Ditrifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate,
Manganese tetraphenylporphyrin tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl)
(1,1′-dimethylferrocenium borate), decamethylferrocenium tetrakis (pentafluorophenyl) borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis ( Lithium pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetraphenylporphyrin manganese tetrakis (pentafluorophenyl) borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, Silver chlorate, silver trifluoroacetate,
Silver trifluoromethanesulfonate and the like can be mentioned.

The component (b) may be used alone or in combination of two or more. The ratio of the components (A) and (B) used in the polymerization catalyst of the present invention is as follows:
When the component (a) is used as the component (B), the molar ratio is preferably from 1: 1 to 1: 1,000,000, more preferably from 1:10 to 1: 10,000, and (b). When the components are used, the molar ratio is preferably 10: 1 to 1:
100, more preferably 2: 1 to 1:10. Further, as the component (B), (a) and (b) can be used alone or in combination of two or more.

The polymerization catalyst of the present invention may contain the above components (A) and (B) as main components, or may contain the components (A), (B) and (C). )
It may contain an organic aluminum compound as a main component. Here, as the organoaluminum compound of the component (C), a general formula (VII) R ²⁰ _v AlQ _3-v (VII) (wherein, R ²⁰ is an alkyl group having 1 to 10 carbon atoms, and Q is hydrogen Atom, alkoxy group having 1 to 20 carbon atoms, 6 to 20 carbon atoms
Represents an aryl group or a halogen atom, and v is an integer of 1 to 3. ) Is used.

Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride and dimethylaluminum. Examples thereof include aluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride. These organoaluminum compounds may be used alone or in combination of two or more. The use ratio of the component (A) to the component (C) is preferably a molar ratio, preferably 1 :.
1-1: 10,000, more preferably 1: 5-1: 1:
2,000, more preferably 1:10 to 1: 1,000
0. By using the component (C), the polymerization activity per transition metal can be improved. However, if it is too much, the organoaluminum compound is wasted and a large amount remains in the polymer, which is not preferable.

In the present invention, at least the catalyst component
One can be used by supporting it on a suitable carrier. this
There is no particular limitation on the type of carrier, and
Body, other inorganic and organic carriers
Can be used, but there is nothing especially in terms of morphology control.
Organic oxide carriers or other inorganic carriers are preferred. Nothing
As the organic oxide carrier, specifically, SiO 2_Two, Al_Two
O_Three, MgO, ZrO_Two, TiO_Two, Fe_TwoO_Three, B_Two
O_Three, CaO, ZnO, BaO, ThO_TwoOr a mixture of these
Compounds such as silica alumina, zeolite, ferrai
And glass fiber. this
Among them, especially SiO_Two, Al_TwoO_ThreeIs preferred. What
In addition, the above inorganic oxide carrier contains a small amount of carbonate, nitrate,
It may contain an acid salt or the like. On the other hand, other carriers
And MgCl_Two, Mg (OC_TwoH _Five)_TwoMagnesi
General formula MgR represented by a compound such as^{twenty one} _XX^Three _yso
The magnesium compound represented and its complex salts are listed.
be able to. Where R ^{twenty one}Is an alk having 1 to 20 carbon atoms
Group, an alkoxy group having 1 to 20 carbon atoms or 6 to 2 carbon atoms
An aryl group of 0, X^ThreeIs a halogen atom or carbon number 1
20 represents an alkyl group, x is 0 to 2, y is 0 to 2
And x + y = 2. Each R^{twenty one}And X ^ThreeEach
They may be the same or different.

As the organic carrier, polystyrene,
Styrene-divinylbenzene copolymer, polyethylene,
Polypropylene, substituted polystyrene, polyarylate
Which polymer, starch, carbon, etc.
Wear. The carrier used in the present invention is MgC
l_Two, MgCl (OC_TwoH_Five), Mg (OC
_TwoH_Five) _Two, SiO_Two, Al_TwoO_ThreeAre preferred. Ma
The properties of the carrier differ depending on the type and manufacturing method,
The average particle size is usually 1 to 300 μm, preferably 10 to 20
0 μm, more preferably 20 to 100 μm. Particle size
When the particle size is small, fine powder in the polymer increases, and when the particle size is large,
Coarse particles in the coalescence increase, lowering the bulk density and clogging the hopper
It causes a ball. The specific surface area of the carrier is usually 1 to
1,000m^Two/ G, preferably 50 to 500 m^Two/
g, pore volume is usually 0.1-5cm^Three/ G, preferably
0.3-3cm^Three/ G. Specific surface area or pore volume
If any of the above deviates from the above range, the catalytic activity decreases.
Sometimes. The specific surface area and pore volume are, for example,
Calculated from the volume of nitrogen gas adsorbed according to the BET method
("J. Am. Chem. Soc.,60, 309 (1983) "
reference). Further, the carrier is usually 150 to 1,000.
C, preferably fired at 200-800C
Is desirable.

When at least one of the catalyst components is carried on the carrier, it is desirable to carry at least one of the components (A) and (B), preferably both the components (A) and (B). The method for supporting at least one of the component (A) and the component (B) on the carrier is not particularly limited. For example, a method of mixing the carrier with at least one of the component (A) and the component (B). A method in which a carrier is treated with an organoaluminum compound or a halogen-containing silicon compound, and then mixed with at least one of the component (A) and the component (B) in an inert solvent, the carrier and the component (A) and / or (B) A method in which the component is reacted with an organoaluminum compound or a halogen-containing silicon compound, a method in which the component (A) or the component (B) is supported on a carrier, and then mixed with the component (B) or the component (A); A method of mixing the contact reactant of the component and the component (B) with the carrier, and a method of coexisting the carrier during the contact reaction between the component (A) and the component (B) may be used. Can. In the above reaction,
An organoaluminum compound as the component (C) can be added.

The catalyst thus obtained may be subjected to solvent distillation once, taken out as a solid, and then used for polymerization, or may be used for polymerization as it is. Further, in the present invention, a catalyst can be produced by performing an operation of loading at least one of the component (A) and the component (B) on a carrier in a polymerization system. For example, at least one of the component (A) and the component (B), a carrier and, if necessary, the organoaluminum compound of the component (C) are added,
A method in which an olefin such as ethylene is added at normal pressure to 20 kg / cm ^{2 and} prepolymerization is performed at −20 to 200 ° C. for about 1 minute to 2 hours to generate catalyst particles can be used.

In the present invention, the use ratio of the component (a) to the carrier is preferably from 1: 0.5 to 0.5 by weight.
The ratio is preferably 1: 1,000, more preferably 1: 1 to 1:50, and the ratio of the component (b) to the carrier is preferably 1: 5 to 10,000 by weight, more preferably 1: 5 to 10,000. Is preferably 1:10 to 1: 500. When two or more catalyst components (B) are used as a mixture, it is desirable that the weight ratio of each component (B) to the carrier be within the above range. The ratio of the component (A) to the carrier is preferably in a weight ratio of 1: 5 to 1: 10,000.
0, more preferably 1:10 to 1: 500. If the ratio of the component (B) (component (a) or (b)) to the carrier or the ratio of the component (A) to the carrier deviates from the above range, the activity may be reduced. The average particle size of the polymerization catalyst of the present invention thus prepared is usually 2 to 200 μm, preferably 10 to 200 μm.
150 μm, particularly preferably 20 to 100 μm,
The specific surface area is usually 20~1,000m ² / g, preferably from 50 to 500 m ² / g. If the average particle size is less than 2 μm, fine powder in the polymer may increase,
If it exceeds μm, coarse particles in the polymer may increase. If the specific surface area is less than 20 m ² / g, the activity may decrease, and if it exceeds 1,000 m ² / g, the bulk density of the polymer may decrease. In the catalyst of the present invention, the amount of transition metal in 100 g of the support is usually 0.05 to
It is preferably 10 g, particularly preferably 0.1 to 2 g. If the amount of the transition metal is out of the above range, the activity may be low. By supporting on a carrier in this manner, an industrially advantageous production method can be obtained. According to the method for producing a propylene polymer of the present invention, (A) the transition metal compound represented by the general formula (I), (B) (a) an organoaluminum oxy compound, and (b) the (A) component A polymerization catalyst containing at least one selected from ionic compounds that can be converted to cations by reacting with a transition metal compound of the formula (I) and optionally (C) an organoaluminum compound;

[0042]

Embedded image

A transition metal compound represented by the formula (B):
Polymerization containing at least one selected from (a) an organoaluminum oxy compound and (b) an ionic compound capable of reacting with the transition metal compound to be converted to a cation, and optionally (C) an organoaluminum compound Propylene can be suitably polymerized using a catalyst. The transition metal compound represented by the general formula (II) is a double-bridged complex. In the general formula (II), R
^{8 to} R ¹³ each independently represent a hydrogen atom, a halogen atom,
A hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, or a phosphorus-containing group. In addition, as a halogen atom, chlorine,
Bromine, fluorine and iodine atoms. Carbon number 1-2
Examples of the hydrocarbon group of 0 include a methyl group, an ethyl group,
alkyl groups such as n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group, n-decyl group, phenyl group, 1-naphthyl group, 2
-An aryl group such as a naphthyl group, an aralkyl group such as a benzyl group, and the like, and the halogen-containing hydrocarbon group having 1 to 20 carbon atoms includes at least one hydrogen atom of the above hydrocarbon group such as trifluoromethyl. Is a group substituted with a suitable halogen atom. Further, there may be mentioned silicon-containing groups such as trimethylsilyl group and dimethyl (t-butyl) silyl group, and oxygen-containing groups and nitrogen-containing groups such as methoxy group, ethoxy group and dimethylamino group. R ^{8 to} R ¹³ are preferably hydrogen and an alkyl group having 6 or less carbon atoms, more preferably hydrogen, methyl group, ethyl group, isopropyl group and cyclohexyl group, and further preferably hydrogen. X ¹ , X ² and M ¹ are the same as described above. The components (B) and (C) are the same as the above-mentioned polymerization catalyst.

Examples of the transition metal compound having an indenyl skeleton represented by the general formula (II) include (1,2 ′)
-Ethylene) (2,1'-ethylene) -bis (indenyl) hafnium dichloride, (1,2'-ethylene)
(2,1′-ethylene) -bis (3-methylindenyl) hafnium dichloride, (1,2′-ethylene)
(2,1′-ethylene) -bis (4,5-benzoindenyl) hafnium dichloride, (1,2′-ethylene)
(2,1′-ethylene) -bis (4-isopropylindenyl) hafnium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (5,6-dimethylindenyl) hafnium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4,7-diisopropylindenyl) hafnium dichloride,
2'-ethylene) (2,1'-ethylene) -bis (4-
Phenylindenyl) hafnium dichloride, (1,
2'-ethylene) (2,1'-ethylene) -bis (3-
Methyl-4-isopropylindenyl) hafnium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (5,6-benzoindenyl) hafnium dichloride and the like, and hafnium in these compounds is zirconium or There can be mentioned those substituted with titanium.

In the present invention, the transition metal compound of the component (a) may be used alone or in combination of two or more. In the present invention, propylene is used as a raw material monomer, but it is also possible to copolymerize 50 mol% or less of an α-olefin having 2 to 20 carbon atoms. Examples of the α-olefin include ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-
Pentene, 1-hexene, 4-methyl-1-pentene,
Examples thereof include 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, styrene, p-methylstyrene, isopropylstyrene, and t-butylstyrene.

In the present invention, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. Particularly preferred are the synthetic method and the gas phase polymerization method. Regarding the polymerization conditions, the polymerization temperature is usually −100 to 250 ° C.,
Preferably -50 to 200 ° C, more preferably 0 to 13
0 ° C. The proportion of the catalyst to the reaction raw material, the raw material monomer / component (A) (molar ratio) is preferably 1 to 10 ^8, it is preferable that the particular 100 to 10 ^5. Further, the polymerization time is usually 5 minutes to 10 hours, and the reaction pressure is preferably normal pressure to 200 kg / cm ² G, particularly preferably normal pressure to 100 kg / cm ² G. Methods for controlling the molecular weight of the polymer include the type of each catalyst component, the amount used,
The method includes selection of a polymerization temperature, and polymerization in the presence of hydrogen. When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene;
Alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, aliphatic hydrocarbons such as pentane, hexane, heptane and octane, and halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in a combination of two or more. Further, a monomer such as propylene may be used as the solvent. In addition, depending on the polymerization method, it can be carried out without a solvent.

In the present invention, prepolymerization can be carried out using the polymerization catalyst. The prepolymerization can be carried out by bringing a small amount of olefin into contact with the solid catalyst component, but the method is not particularly limited,
A known method can be used. There is no particular limitation on the olefin used for the prepolymerization, for example, ethylene,
Examples thereof include α-olefins having 3 to 20 carbon atoms or mixtures thereof, and it is advantageous to use the same olefin as the monomer used in the polymerization. The pre-polymerization temperature is usually -20 to 200C, preferably -10 to 130C, more preferably 0 to 80C.
It is. In the prepolymerization, an inert hydrocarbon, an aliphatic hydrocarbon, an aromatic hydrocarbon, a monomer, or the like can be used as a solvent. Particularly preferred among these are aliphatic hydrocarbons. Further, the prepolymerization may be performed without a solvent. In the prepolymerization, the intrinsic viscosity [η] (measured in decalin at 135 ° C.) of the prepolymerized product is 0.1 deciliter / g or more, and the amount of the prepolymerized product per 1 mmol of the transition metal component in the catalyst is 1%. Up to 10,000
g, particularly preferably 10 to 1,000 g. Thus, the propylene polymer of the present invention can be efficiently obtained.

The propylene polymer of the present invention is produced by the above-mentioned method for producing a propylene polymer and has a terminal vinyl group number per molecule> 0.6 and a weight average molecular weight of 20.
0 to 100,000; and the above-mentioned olefin polymer having an isotactic pentad fraction ([mmmm]) of 60% or more as measured by a nuclear magnetic resonance spectrum.

Among the characteristics of the propylene polymer according to the present invention, the number of terminal vinyl groups per molecule is calculated based on the measurement results of an infrared absorption spectrum according to the following method. That is, a propylene polymer was formed into a film having a thickness of about 100 μm, and the transmittance of a peak at 907 cm ⁻¹ was measured with an IR-810 infrared spectrophotometer manufactured by JASCO Corporation.
The number of terminal vinyl groups per 000 carbon atoms is calculated, and the number of terminal vinyl groups per molecule is calculated. The calculation is performed according to the following formula (see “Polymer Analysis Handbook”, edited by the Japan Society for Analytical Chemistry, page 240).

N _1000C = 1.14 × log (I ₀ / I)
× (1 / (D × T)) n _chain = n _1000C × Mn / 14000 In the formula, each symbol indicates the following content. n _1000C : number of terminal vinyl groups per 1000 carbon atoms n _chain : number of terminal vinyl groups per molecule I ₀ : transmittance at baseline I: transmittance at 907 cm ^-1 D: density of polymer (g / cm ³ ) T : Film thickness (mm) Mn: number average molecular weight The number of terminal vinyl groups per molecule according to the present invention is greater than 0.6, preferably greater than 0.7. More preferably, it is larger than 0.8.

The olefin polymer of the present invention that satisfies the above characteristics indicates that the molecular terminal selectively contains a vinyl group. The weight average molecular weight (Mw) and the above number average molecular weight (Mn) are determined by gel permeation chromatography (GPC) according to the following method.
Calculated based on the measurement results of That is, using 240 μl of a 1,2,4-trichlorobenzene (containing 300 ppm of BHT) solution having a polymer concentration of 0.1% by weight / volume,
The column is determined using a mixed polystyrene gel column (for example, GMH6HT manufactured by Tosoh Corporation) at 145 ° C. at a flow rate of 1.0 ml / min.
An infrared detector is used for detection, and a wavelength of 3.41 μm is used.

The weight average molecular weight (Mw) according to the present invention is 2
00 to 100,000, preferably 5,000 to
30,000. Among the properties of the olefin polymer according to the present invention, the isotactic pentad fraction ([mm
mm]) is calculated based on the measurement result of the ¹³ C nuclear magnetic resonance spectrum according to the following method. That is, a sample obtained by dissolving 200 mg of a polymer at 135 ° C. in 3 ml of a mixed solvent of 1,2,4-trichlorobenzene / deuterated benzene (C ₆ D ₆ ) = 9/1 by weight was used.
It is determined by measuring at 130 ° C. and 10,000 times. As the measuring device, for example, a Lambda-500 NMR measuring device manufactured by JEOL Ltd. is used.

The term "isotactic pentad fraction ([mmmm])" used in the present invention refers to "Macromolecules, 6 , 925 (197)" by A. Zambelli et al.
3) In pentad units in the polypropylene molecular chain measured by the ¹³ C nuclear magnetic resonance spectrum proposed in
It means isotactic fraction. The method for determining the assignment of peaks in the measurement of the ¹³ C nuclear magnetic resonance spectrum is described in "Macromolecules," by A. Zambelli et al.
8 , 687 (1975) ".

As described above, the isotactic pentad fraction ([mmmm]), which is a characteristic of the olefin polymer according to the present invention, is such that five consecutive meso bonds present in all propylene monomer units in the polypropylene molecule are formed. Of the propylene monomer unit used. Therefore, isotactic pentad fraction ([mmmm])
The higher the value, the higher the isotacticity. A characteristic of the polypropylene of the present invention is that the isotactic pentad fraction ([mmmm]) is 60.0% or more, preferably 70.0% or more, more preferably 80.0% or more. .

The propylene polymer of the present invention that satisfies the above-mentioned properties exhibits high isotacticity, which comprises a highly controlled meso-bonded chain.

[0056]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In addition, each physical property of the propylene polymer was measured according to the method described in the specification text except for the melting point. Melting point: DSC7 manufactured by Perkin-Elmer
Using a type differential scanning calorimeter, the propylene polymer was heated from room temperature to 220 ° C. under a temperature rising condition of 10 ° C./min, kept at the same temperature for 3 minutes, and then kept at -10 ° C./min at 0 ° C. And kept at the same temperature for 3 minutes.
The measurement was performed under the condition that the temperature was raised to 0 ° C. Example 1 Production of 1,2-ethanediyl (1- (4,7-diisopropylindenyl)) (2- (4,7-diisopropylindenyl)) hafnium (IV) dichloride (1) 4,7- Production of diisopropyl-1-indanone 48.7 g (0.3 m) of p-cymene was placed in a 1-liter three-necked flask connected to an aqueous sodium hydroxide trap.
ol), 38.0 g of 2-chloropropionyl chloride
(0.3 mol) and 500 ml of methylene chloride were introduced. While stirring with a magnetic stirrer, aluminum chloride was gradually added under a nitrogen stream and an ice bath until hydrogen chloride was no longer generated. After completion of the reaction, the reaction solution was charged into a beaker containing ice while stirring. After the organic phase was washed twice with water, it was further washed once with an aqueous sodium hydrogen carbonate solution and dried over anhydrous sodium sulfate. After filtering off the drying agent, methylene chloride was distilled off to obtain an oily compound. 300 ml of concentrated sulfuric acid was put into a 1-liter round bottom flask connected to a dropping funnel, and the oily compound was gradually dropped at room temperature under a nitrogen atmosphere while stirring using a magnetic stirrer. After the dropwise addition, the mixture was stirred at 80 ° C. for 1 hour, and the obtained reaction solution was put into a beaker containing ice. After extraction with diethyl ether three times, the extract was dried over anhydrous magnesium sulfate. After filtering off the drying agent, diethyl ether was distilled off, and the residue was separated using a silica gel column with methylene chloride as a developing solution.
50 g (0.232 mol) of a crude product of 4,7-diisopropyl-1-indanone was obtained in a yield of 77%. (2) Production of 4,7-diisopropylindene 200 ml of dry diethyl ether and 4.4 g of lithium aluminum hydride were placed in a 500 ml round bottom flask to which a dropping funnel and a Dimroth were connected.
(0.116 mol) and 50 g of the above-mentioned 4,7-diisopropyl-1-indanone crude product (0.23 mol) at room temperature under a nitrogen atmosphere while stirring using a magnetic stirrer.
2 mol) of a dry diethyl ether solution (200 ml) was slowly added dropwise. After the addition, 200 ml of water was added to the reaction solution under ice cooling. 3 with diethyl ether
After the first extraction, the extract was dried over anhydrous magnesium sulfate. After filtering off the drying agent, diethyl ether was distilled off to obtain an oily compound. The oily compound, 250 ml of toluene and 3.0 g of pyridinium p-toluenesulfonate were placed in a 1 liter round bottom flask connected to a Dean-Stark water separator, and heated under reflux for 1 hour. After heating, 300 ml of water was added to the reaction solution. The organic phase was separated with a separating funnel and washed twice with water, and the obtained organic phase was dried over anhydrous magnesium sulfate. After filtering off the desiccant, toluene was distilled off, and 38.5 g (0.19 g) of a crude product of 4,7-diisopropylindene was obtained.
mol), with a yield of 83%. (3) Production of 4,7-diisopropyl-2-indanone 81 ml of formic acid and 30% hydrogen peroxide solution 23 were placed in a 300 ml eggplant flask connected to a dropping funnel.
28.5 g of the above crude product of 4,7-diisopropylindene while maintaining the temperature at 30 to 45 ° C.
(0.143 mol) was gradually added dropwise. After stirring overnight at room temperature, formic acid was distilled off under reduced pressure. The residue was transferred to a 1-liter eggplant flask, and diluted sulfuric acid (25 g of concentrated sulfuric acid in water 6
(00 ml solution) and steam distillation was carried out.
After extracting the distillate three times with diethyl ether, the extract was dried over anhydrous magnesium sulfate. After the desiccant was filtered off, diethyl ether was distilled off and 4,7-diisopropyl-2 was removed.
10.2 g of crude indanone (0.047 mol
1), yield 33%. (4) Production of ethyl 2- (4,7-diisopropylindenyl) acetate A 300-ml three-necked flask connected to a stirrer and two dropping funnels was purged with nitrogen, and then subjected to a nitrogen stream.
1.4g sodium hydride (purity 60%) into flask
(0.047 mol) and tetrahydrofuran (TH
F) Put 7 ml, put 7.4 g (0.033 mol) of ethyl diethylphosphonoacetate and 50 ml of THF into one dropping funnel and 4,7-diisopropyl-2-indanone 6.0 into the other dropping funnel.
g (0.028 mol) and 50 ml of THF. While stirring, a THF solution of ethyl diethylphosphonoacetate was added dropwise under ice cooling, and the mixture was further stirred at room temperature for 30 minutes. Then, under ice cooling, 4,7-diisopropyl-
A THF solution of 2-indanone was added dropwise, and the mixture was further stirred at room temperature for 1 hour. After completion of the stirring, 50 ml of water was added, the reaction solution was extracted three times with diethyl ether, and the extract was dried over anhydrous magnesium sulfate. After the desiccant was filtered off, diethyl ether was distilled off, and a crude product of ethyl 2- (4,7-diisopropylindenyl) acetate was obtained at 7.69.
g (0.027 mol) in a yield of 97%. (5) Production of 1-bromo-2- (2- (4,7-diisopropylindenyl)) ethane 30 connected with a stirrer, a dropping funnel and a Dimroth.
After replacing the 0 ml three-necked flask with nitrogen, 1.05 g of lithium aluminum hydride was placed in a nitrogen stream.
(0.028 mol) and 50 ml of THF, and the above-mentioned 2- (4,
7.69 g of ethyl 7-diisopropylindenyl) acetate
(0.027 mol) of a THF solution (50 ml) was slowly added dropwise at a rate of spontaneous reflux. After the dropwise addition, the mixture was further stirred at room temperature for 30 minutes, and 100 ml of diluted hydrochloric acid was added. After extracting the reaction solution with 200 ml of diethyl ether, the extract was dried over anhydrous magnesium sulfate. After filtering off the desiccant, diethyl ether was distilled off,
6.13 g (0.0%) of a crude product of 1-hydroxy-2- (2- (4,7-diisopropylindenyl)) ethane
25 mol) and a yield of 93%. The above-mentioned 1-hydroxy-2- (2- (4,7-diisopropylindenyl)) ethane was transferred to a 300 ml eggplant flask connected to a dropping funnel, and triphenylphosphine 6.60.
g (0.025 mol) and 100 ml of methylene chloride were added. While stirring, 4.47 g (0.025 mol) of N-bromosuccinimide was gradually added, and the mixture was further stirred at room temperature for 1 hour. From the obtained reaction solution, methylene chloride was distilled off under reduced pressure, and the residue was separated with a silica gel column using a 4/1 (v / v) solution of hexane / methylene chloride as a developing solution. Bromo-2
5.2 g (0.017 mol) of-(2- (4,7-diisopropylindenyl)) ethane was obtained in a yield of 63%. (6) Production of 1- (1- (4,7-diisopropylindenyl))-2- (2- (4,7-diisopropylindenyl)) ethane A 300-mL Schlenk tube purged with nitrogen under a nitrogen stream. 3.3 g of 4,7-diisopropylindene
(0.017 mol) and 30 ml of dry THF were added, and 5.5 ml of a 3.04 Mn-butyllithium hexane solution was gradually added dropwise at −78 ° C. under cooling. After further stirring at room temperature for 1 hour, 5.2 g (0.017 mo) of 1-bromo-2- (2- (4,7-diisopropylindenyl)) ethane was cooled at −78 ° C.
A solution of l) in 10 ml of THF was slowly added dropwise.
The solvent was distilled off from the obtained reaction solution under reduced pressure, and the residue was separated with a silica gel column using a 5/1 (v / v) solution of hexane / methylene chloride as a developing solution.
(1- (4,7-diisopropylindenyl))-2-
3.2 g (0.075 mol) of (2- (4,7-diisopropylindenyl)) ethane was obtained in a yield of 28%. (7) Production of 1,2-ethanediyl (1- (4,7-diisopropylindenyl)) (2- (4,7-diisopropylindenyl)) hafnium (IV) dichloride A 300 ml Schlenk tube purged with nitrogen. Under a nitrogen stream, 1.38 g (3.24 mmol) of 1- (1- (4,7-diisopropylindenyl) -2- (2- (4,7-diisopropylindenyl)) ethane and 30 ml of dry diethyl ether At -78 ° C
Under cooling, 2.1 ml of a 3.04 Mn-butyllithium hexane solution was gradually added dropwise. After further stirring overnight at room temperature, the solvent was distilled off, the remaining lithium salt was washed with 100 ml of dry hexane, and then the hexane was filtered off. 25 ml of dehydrated toluene was added to a Schlenk tube containing a lithium salt, and 1.0 g (3.1 mmol) of hafnium tetrachloride was added thereto while cooling at -78 ° C.
1) A suspension of 50 ml of dry toluene was gradually added dropwise. After further stirring at room temperature for 4 hours, the solution was filtered, and the solvent was distilled off from the filtrate under reduced pressure. 20 ml of dry hexane was added to the residue, and the mixture was recrystallized at -78 ° C to give 1,2-ethanediyl (1- (4,7
-Diisopropylindenyl)) (2- (4,7-diisopropylindenyl)) hafnium (IV) dichloride was obtained in an amount of 0.6 g (0.9 mmol) in a yield of 28%.

The ¹ H-NMR of the transition metal compound was measured by CDC
The l ₃ as a solvent, the results of measurement using a JEOL Co. EX-90, shown in FIG. Example 2 Production of Propylene Polymer A 1.4-liter stainless steel pressure-resistant autoclave equipped with a stirrer was heated to 50 ° C., sufficiently dried under reduced pressure, returned to atmospheric pressure with dry nitrogen, and cooled to room temperature. Under dry nitrogen flow, 400 ml of dry deoxygenated toluene and 2 mmol of methylaluminoxane (toluene solution manufactured by Albemarle) in terms of aluminum atoms were introduced. 500 rp
After stirring at m, the temperature was raised to 60 ° C. in 5 minutes, and then the mixture was further stirred for 5 minutes. In addition, 1,
0.1 ml of a toluene solution of 1 micromol of 2-ethanediyl (1- (4,7-diisopropylindenyl)) (2- (4,7-diisopropylindenyl)) hafnium (IV) dichloride was charged. Propylene was continuously supplied at a pressure of 7.0 kg / cm ² G and reacted for 1 hour. After the completion of the reaction, unreacted propylene was quickly depressurized, and propylene was purged with dry nitrogen. Then, the reaction mixture was poured into a large amount of methanol to stop the reaction.
By filtering and drying the precipitated white polymer,
14.9 g of a propylene polymer were obtained. Table 1 shows the evaluation results of the obtained propylene polymers. Example 3 Using (1,2′-ethylene) (2,1′-ethylene) bisindene produced by the method described in International Patent Publication No. 96-853, (1) was prepared in the same manner as in Example 1 (7). , 2'-Ethylene) (2,1'-ethylene) bisindenylhafnium (IV) dichloride was prepared.

In Example 2, 1,2-ethanediyl (1- (4,7-diisopropylindenyl)) (2-
(4,7-diisopropylindenyl)) hafnium (IV) dichloride 1 micromolar instead of (1,
2′-ethylene) (2,1′-ethylene) bisindenylhafnium (IV) dichloride 2 μmol,
A propylene polymer was produced in the same manner as in Example 2 except that the polymerization temperature was changed to 80 ° C. Propylene polymer 28.
8 g were obtained. Table 1 shows the evaluation results of the obtained propylene polymers. Example 4 In Example 2, 1,2-ethanediyl (1- (4,7-diisopropylindenyl)) (2-
1,4-ethanediyl (1- (4,7-diisopropylindenyl)) (2- (4,7-diisopropylindenyl)) hafnium (IV) dichloride
(4,7-Diisopropylindenyl)) A propylene polymer was produced in the same manner as in Example 2 except that zirconium (IV) dichloride was used. 8. Propylene polymer
5 g were obtained. Table 1 shows the evaluation results of the obtained propylene polymers. Comparative Example 1 In Example 2, 1,2-ethanediyl (1- (4,7-diisopropylindenyl)) (2-
(4,7-diisopropylindenyl)) hafnium (IV) dichloride 1 micromol instead of 1,2-
Ethanediylbis (1-indenyl) zirconium (I
V) 5 micromoles of dichloride, polymerization temperature of 80 ° C.
A propylene polymer was produced in the same manner as in Example 2, except that 57.4 g of a propylene polymer were obtained.
Table 1 shows the evaluation results of the obtained propylene polymers. Comparative Example 2 In Example 2, 1,2-ethanediyl (1- (4,7-diisopropylindenyl)) (2-
(4,7-diisopropylindenyl)) hafnium (IV) dichloride 1 micromol instead of 1,2-
Ethanediylbis ((4,7-dimethylindenyl))
5 micromoles of zirconium (IV) dichloride,
A propylene polymer was produced in the same manner as in Example 2, except that the propylene pressure was set to 1.0 kg / cm ² G and the polymerization time was set to 30 minutes. 5.3 g of a propylene polymer were obtained. Table 1 shows the evaluation results of the obtained propylene polymers.

[0059]

[Table 1]

[0060]

According to the present invention, a propylene polymer having a vinyl group at a molecular terminal, a transition metal compound which is a catalyst component for propylene polymerization, a catalyst for propyne polymerization, and a propylene polymer capable of efficiently producing the polymer Can be provided.

[Brief description of the drawings]

¹ H-N in FIG. 1 the transition metal compound obtained in Example 1
It is an MR chart (CDCl ₃ solvent).

Claims (8)

[Claims] 1. A compound of the general formula (I)(Where R¹~ R^FourIs independently a hydrogen atom, a halo
Gen atom, C 1-20 hydrocarbon group, C 1-2
0 halogen-containing hydrocarbon group, silicon-containing group, oxygen-containing
Group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group.
Then R¹And R^TwoMay combine with each other to form a ring
No. R^Five, R⁶Are each independently a halogen atom, carbon
Containing hydrocarbon groups having 1 to 20 carbon atoms and halogens having 1 to 20 carbon atoms
Hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing
Group, nitrogen-containing group or phosphorus-containing group. X¹And X
^TwoAre independently a hydrogen atom, a halogen atom and a carbon number
Contains 1 to 20 hydrocarbon groups and 1 to 20 carbon atoms
Hydrocarbon group, silicon-containing group, oxygen-containing group, sulfur-containing
Group, a nitrogen-containing group or a phosphorus-containing group;
A divalent group that binds a ligand and has 1 to 20 carbon atoms
A hydride group, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms,
Silicon-containing group, germanium-containing group, -O-, -CO
-, -S-, -SO_Two-, -NR⁷-, -PR⁷−, −
P (O) R⁷-, -BR ⁷-Or -AlR⁷Indicates-
Then R⁷Is a hydrogen atom, a halogen atom, a C1-20
Hydrocarbon group, halogen-containing hydrocarbon group having 1 to 20 carbon atoms
Is shown. M¹Is the transition of the IVA, VA, VIA group of the periodic table
Indicates metal. The transition metal compound represented by). 2. An ionic compound which can be converted into a cation by reacting (A) the transition metal compound according to claim 1 with (B) (a) an organoaluminum oxy compound and (b) the transition metal compound. A propylene polymerization catalyst comprising at least one selected from the group consisting of: 3. An ionic compound which can be converted into a cation by reacting (A) the transition metal compound according to claim 1 with (B) (a) an organoaluminum oxy compound and (b) the transition metal compound. At least one selected from the
And (C) an organoaluminum compound. 4. A method for producing a propylene polymer, comprising polymerizing propylene in the presence of the catalyst for propylene polymerization according to claim 2 or 3. 5. A compound of the general formula (II) (Wherein, R ^{8 to} R ¹³ each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
0 represents a halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. X ¹ and X ² each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms,
0 represents a halogen-containing hydrocarbon group, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group, and M ¹ represents a transition metal belonging to Groups IVA, VA, and VIA of the periodic table. A) a transition metal compound represented by the formula (B):
A propylene polymerization catalyst comprising: (a) an organoaluminum oxy compound and (b) at least one selected from ionic compounds capable of reacting with the transition metal compound to be converted to a cation. In the presence of
A method for producing a propylene polymer, comprising polymerizing propylene. 6. An ionic compound which can be converted into a cation by reacting (A) the transition metal compound of claim 5 with (B) (a) an organoaluminum oxy compound and (b) the transition metal compound. At least one selected from the
And (C) a method for producing a propylene polymer, characterized in that propylene is polymerized in the presence of a propylene polymerization catalyst, which is characterized by containing an organoaluminum compound. 7. The method for producing a propylene polymer according to claim 4, wherein the number of terminal vinyl groups per molecule is> 0.6 and the weight average molecular weight is 200 to 100,000. A propylene polymer. 8. An isotactic pentad fraction ([mmmm]) of 60 based on measurement of a nuclear magnetic resonance spectrum.
% Of the propylene polymer according to claim 7.