JP3398426B2 - Method for producing polyolefin - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] The present invention relates to the production of polyolefins.
About the method. Specifically, a molecular weight having a desired molecular weight
The present invention relates to a method for producing a polyolefin having a wide distribution. [0002] 2. Description of the Related Art A conjugated π
Groups having a substituent, especially cyclopentadiene and derivatives thereof
Metals, such as metallocene compounds having a ligand as a ligand
Compound, obtained by reaction of trialkylaluminum with water
Is known in combination with alkylaluminoxane
ing. For example, Japanese Patent Application Laid-Open No.
Dienyl zirconium dichloride and methylaluminum
A method for polymerizing olefins using sun as a catalyst has been disclosed.
And JP-A-61-130314, JP-A-61-264010,
1-301704 and JP-A-2-41303 describe isotactic ports.
Α-olefin or syndiotactic poly α-
Process for producing olefins and their stereoregular poly-α-
A polymerization catalyst for producing olefins is disclosed.
You. On the other hand, cyclopentadiene and its derivatives
Metallocene compounds having a ligand as a ligand
Can convert olefins without using methylaluminoxane
It has been reported to polymerize. For example, R.F.JORDAN
Is described in J. Am. Chem. Soc., 1986, 108, 7410.
Biscyclopentadiamine having nilborane as an anion
Zirconium having enyl and methyl groups as ligands
Report that cationic complex has polymerization activity of ethylene
ing. Turner et al., J. Am. Chem. Soc., 1989, 111.
Volume 2728, ion-pair zirconium complex
It reports that it has ethylene polymerization activity. Further Za
mbelli et al. in Macromolecules, 1989, Vol. 22, pp. 2186-2189.
Zyl having a derivative of cyclopentadiene as a ligand
Conium compounds, trimethyl aluminum and fluoro
Combination of dimethylaluminum and propylene
By combining, isotactic polypropylene
It reports that it can be obtained. [0004] SUMMARY OF THE INVENTION The above method is intended for transition metals.
Per activity is good, and the obtained polymer
Transition metal compounds used by tacticity and tacticity
This is an excellent method that allows selection according to the type of object.
Use these catalysts to produce polymers of the desired molecular weight.
When hydrogen is used as a chain transfer agent,
The molecular weight is adjusted by controlling the addition amount. Toko
However, depending on the type of transition metal compound, hydrogen is added.
May not show polymerization activity due to
Cannot be obtained. Also,
Regardless of the catalyst used, the molecular weight
The cloth is very narrow, around 2 and there is a problem with the moldability of the polymer
was there. At least two species to broaden the molecular weight distribution
Molecular weight by polymerization with a class of transition metal compounds
It is described in JP-A-3-212408 that a polymer having a wide distribution can be obtained.
It is listed. Polymerizes using two transition metal compounds
The polymer obtained by the gel permeation chromatography
The molecular weight distribution certainly spreads when measured with a matograph.
But the distribution has two or more peaks
When a polymer is formed into a film under the influence of
And the physical properties of other molded products deteriorate.
No, you can only get something with low commercial value. [0005] Means for Solving the Problems The present inventors have solved the above problems.
Polyol of desired molecular weight with wide molecular weight distribution
After intensive study on the method of obtaining fins
Compounds were found to be effective in controlling the molecular weight
completed. That is, the present invention relates to a transition metallization having a ligand.
Compound and aluminoxane or transition metal with ligand
Reacting a reactant of a compound with an organometallic compound with the reactant
From compounds that form ionic compounds
To produce polyolefin using a catalyst component consisting of
The presence of a compound having a hydrosilyl group
Method for producing polyolefin, which is carried out in the presence
It is. Transition gold having a ligand used in the present invention
Examples of the genus compounds include the compounds described in the above-mentioned documents.
It can be, but in addition, the following general formula (Formula 4) or
Wherein A and B are monovalent or divalent unsaturated
A hydrocarbon residue, or a nitrogen atom or oxygen bonded to M
Atom, silicon atom, phosphorus atom or sulfur atom
A 'and B' are bridged by R
The same or different monovalent or divalent unsaturated hydrocarbons
A nitrogen atom, an oxygen atom bonded to an elemental residue or M,
R represents a ligand containing a phosphorus atom or a sulfur atom;
Atom, oxygen atom, silicon atom, phosphorus atom or sulfur atom
Straight-chain saturated hydrocarbon residue which may have a residue or side chain
A group or its straight-chain carbon atoms are partially or entirely composed of silicon
Substituted with a germanium atom or a tin atom
The residue is selected from group 4 or group 5 of the periodic table
X is a halogen atom bonded to M;
Element atom, nitrogen atom, oxygen atom, silicon atom, boron atom, phosphorus
A ligand containing an atom or a sulfur atom is shown. )
A transition metal compound having a ligand is exemplified. [0008] Embedded image [0009] Embedded image Here, unsaturated hydrocarbons represented by A and B
The residue may be a monocyclic ring having 5 to 50 carbon atoms, or a multiple ring.
A group having a conjugated π electron in the ring can be exemplified.
Lopetadienyl or some or all of its hydrogen
Substituted with a hydrocarbon residue having 1 to 10 carbon atoms (this
Here, the hydrocarbon residue has its terminal again
It may have a structure bonded to an ene ring. ) Or a
Polycyclic aromatic hydrocarbon residues such as ndenyl and fluorenyl
Or some or all of its hydrogens do not have 1 carbon atom
And those substituted with 10 hydrocarbon residues.
Further, a nitrogen atom, an oxygen atom, and a silicon atom bonded to M
Ligands containing a ligand, a phosphorus atom or a sulfur atom include COR ′,
NR '_Two, OR ', OSiR'_Three, SiR '_Three , GeR '_Three , PR '_Two, POR '_Two ,
SR ', SOR', SO_TwoR '(R' is hydrogen or C1-C20)
Hydrocarbons or some of them are heteroatoms
(Replaced residue). these
May be the same or different. The ligand represented by A 'or B'
Monocyclic or polycyclic conjugated π-electrons having 5 to 50 carbon atoms
Group having a child, COR ', NR'_Two, OR ', OSiR'_Three, SiR '_Three ,
GeR ' _Three , PR '_Two, POR '_Two , SR ', SOR', SO_TwoR '(R' is hydrogen
Or hydrocarbons having 1 to 20 carbon atoms or any of them
(Replacement of some of which are replaced with hetero atoms)
The ligand bonded to the metal atom M is exemplified. these
May be the same or different. Here A 'and
And B ′ have a structure cross-linked by R.
You. The divalent groups represented by R include -O-, -S-
 , -S-S-, -SO-, -SO_Two-, -CO-, -NR "-, -PR"-, -PO
R "-, -OSiR"_TwoO- or represented by the following general formula (Formula 6)
Methylene group or some of the carbon atoms in the methylene group
Or all of them are silicon, germanium, or tin
Silylene group, germylene group, stannylene
Examples of the base are exemplified. [0013] ## STR6 ##-(R "_TwoC) n-(R "_TwoSi) m- (R "_TwoGe) p- (R "_TwoSn) q− (Wherein R "is a hydrogen atom or a carbon atom having 1 to 20 carbon atoms)
Represents a hydrogen residue and two R "may be the same or different
Where n, m, p, and q are integers of 0 to 4 and
represents an integer satisfying n + m + p + q ≦ 4. ) X is fluorine, chlorine, bromine, iodine, etc.
Rogen atom or CR '_Three, CH_TwoSiR '_Two, COR ', NR'_Two, OR ',
OSiR '_Three, SiR '_Three , GeR '_Three , PR '_Two, POR '_Two , SR ', SOR',
SO_TwoR '(R' is hydrogen or a hydrocarbon having 1 to 20 carbon atoms or
Is the residue in which some of them are replaced with heteroatoms
Group) and the like. In the present invention, transition metallation having a ligand
Using a catalyst consisting of a combination of
If the aluminoxane is
The following general formula (Chemical Formula) obtained by hydrolyzing minium with water
Compounds represented by 7) or (8) can be exemplified.
Among them, methyl aluminoki, in which R is a methyl group
Those having n of 5 or more are preferably used. Transition
As the ratio of aluminoxane to metal transfer compound
Is from 1 to 10,000 mol times, usually from 10 to 5000 mol times. [0016] Embedded image [0017] Embedded image A transition metal compound having a ligand and an organic compound
Reacts with reactants with metal compounds to form ionic compounds
From the compound (ion pair compound)
When using a catalyst component consisting of
Is a compound represented by the following general formula (Formula 9).
You. [0019] Embedded image [Q]⁺[Y]^- Here, Q is a cation component of the ionic compound.
Min, carbonium cation, tropylium
Cations, ammonium cations, oxonium cations,
Ruphonium cation, phosphonium cation, etc.
I can do it. Specific examples of these cations include
Phenylcarbonium, diphenylcarbonium, cyclo
Heptatrienium, tributylammonium, N, N
-Dimethylanilinium, dipropylammonium, di
Cyclohexylammonium, triphenylphosphonium
, Trimethylphosphonium, triphenylsulfonium
, Triphenyloxonium, triethyloxonium
And pyrylium. Y is an anionic component of an ionic compound.
And a boron compound anion and an aluminum compound
Nion, gallium compound anion, phosphorus compound anion
, Arsenic compound anion, organic antimony compound anion
Such as tetraphenylboron,
Tetrakis (pentafluorophenyl) boron, tetra
Phenylaluminum, tetrakis (pentafluorop
Enyl) aluminum, tetraphenylgallium, tet
Lakis (pentafluorophenyl) gallium, hexaf
Luorolin, hexafluoroarsenic, hexafluoroan
Chimon and the like. The organic compound to be reacted with the transition metal compound in the present invention
The metal compounds are of Group 1, 2, 12, and 13 of the Periodic Table.
Metal atoms, preferably aluminum, zinc or
Halogen or oxygen atoms for magnesium
Is a hydrogen atom or alkyl, alkoxy, aryl, etc.
Are coordinated and if there are multiple ligands,
May be the same or different, but
At least one is an alkyl group. example
For example, one alkyl residue having 1 to 12 carbon atoms or
An alkyl metal compound coordinated by two or more,
Alkali metal halide with a group coordinated with another atom or residue
And alkyl metal alkoxides. Inside
Also has at least one alkyl residue having 2 or more carbon atoms
Coordinated alkyl aluminum compounds are preferably used.
You. In the case where the metal atom is aluminum,
An example of a preferred organometallic compound is trimethyl alcohol.
Luminium, triethyl aluminum, tri-n-propyl
Aluminum, triisopropylaluminum, trialuminum
Butyl aluminum, triisobutyl aluminum,
Lipentyl aluminum, trihexyl aluminum,
Triheptyl aluminum, trioctyl aluminum
Aluminum, tridecyl aluminum, isoprenyl aluminum
Aluminum, diethyl aluminum hydride, diisopropyl
Aluminum hydride, diisobutylaluminum
Hydride, diethylaluminum chloride,
-N-propyl aluminum chloride, diisopropyl
Aluminum chloride, diisobutylaluminum chloride
Chloride, diethylaluminum ethoxide, diisoprop
Ropyl aluminum isopropoxide, ethyl aluminum
Umsesquichloride, isopropyl aluminum sesame
Cychloride, isobutylaluminum sesquichlori
, Ethyl aluminum dichloride, isopropyl alcohol
Luminium dichloride, isobutylaluminum dichloride
Chloride, ethyl aluminum diisopropoxide, etc.
No. Treating the transition metal compound with an organometallic compound
There is no particular limitation on the method of mixing, just mixing the two
Just fine. Usually, transition metal compounds are solid,
Compounds are often liquid or solid and should be treated in hydrocarbon solvents.
Preferably. Organic gold for transition metal compounds
The use ratio of the genus compound is 1 to 100,000 times, usually 1
It is up to 5000 mole times. The processing temperature is not particularly limited,
Usually, it is preferably carried out at a temperature of -20 to 100 ° C. Also
The temperature at which these mixtures are stored is not particularly limited.
However, it is also preferable to store at a temperature of −20 to 100 ° C.
New The processing time does not need to be particularly limited.
In the case of
If any are present, after they have been dissolved in the solvent
Then you can use it anytime. Of course, as mentioned above,
Keep as it is until use and use it as needed
Things are also possible. Also, the concentration of the reactants in the hydrocarbon solvent
Is stable even at very high concentrations
Although it is not necessary to specify the
As concentration, 10^-7~ 1 mol / l, preferably 10^-Five
0.10.1 mol / liter. The compounds forming the above ionic compounds
The amount used is based on the transition metal compound used in the catalyst.
It is 0.1 to 100,000 mole times, usually 0.5 to 10,000 mole times. It has a hydrosilyl group used in the present invention.
Is a compound represented by the following general formula (Chemical Formula 10), wherein R is a hydrocarbon
The residue, n, represents an integer of 1 to 3. ) Silanization
It is a compound. [0027] [Image Omitted] R_nSiH_4-n Compounds having a hydrosilyl group include:
Methyl silane, ethyl silane, propyl silane, butyl
Silane, pentylsilane, hexylsilane, heptylsi
Orchid, octylsilane, dimethylsilane, diethylsila
, Dipropylsilane, dibutylsilane, dipentylsilyl
Orchid, dihexylsilane, diheptylsilane, dioctyl
Silane, trimethylsilane, triethylsilane, trisilane
Propylsilane, tributylsilane, tripentylsila
, Trihexylsilane, triheptylsilane, trio
Butylsilane and branched alkyl groups
And the like. Hydrosilyl for the above transition metal compound
The ratio of the compound having a group
-1/100000 of propylene
~ 1/10, below which is not effective in controlling molecular weight
And using more than this will not improve the effect.
In addition, the activity is greatly reduced and is not practical. The preparation of a catalyst using the catalyst component in the present invention.
Examples of solvents used for production, polymerization or processing
For example, propane, butane, isobutane, pentane, hex
Sun, heptane, octane, nonane, decane, cyclope
, Cyclohexane, cycloheptane, methylcycl
Saturated hydrocarbons such as hexane, benzene,
Aromatic hydrocarbon compounds such as ene and xylene, and further salts
Halogenated hydrocarbons such as methylene chloride and chlorobenzene
Compounds are also available. In the present invention, olefins include
Len, propylene, butene-1, pentene-1, hexene
1, heptene-1, octene-1, nonene-1, decene-1, c
Ndecene-1, dodecene-1, tridecene-1, tetradecene
-1, pentadecene-1, hexadecene-1, octadecene-1
Other than linear α-olefins such as 3-methylbutene-1, 4-
Branched α such as methylpentene-1,4,4-dimethylpentene-1
-Olefins, cyclopentene, cyclooctene, nor
Cyclic olefins such as bornene are exemplified.
Not only olefins alone but also mixtures of olefins or small amounts
And mixtures with ethylene and diene. And even ste
Len and α-methylstyrene can also be used. The polymerization conditions are not particularly limited and are not limited.
Solvent polymerization using an active medium or a substantially inert medium
A bulk polymerization method or a gas phase polymerization method in which a body does not exist can be used.
The polymerization temperature and polymerization pressure are used in a known manner.
General conditions are used, and the polymerization temperature is from -100 to
200 ° C, polymerization pressure from normal pressure to 100 kg / cm^Two-G
It is common. [0033] The present invention will be further described with reference to the following examples.
You. Embodiment 1 Methylaluminoxane (manufactured by Tosoh Akzo, polymerization degree 1
6.2) Dissolve 0.22 g in 1 liter of toluene and 2 litres
Into an autoclave and add 0.1 g of diethylsilane
Was charged. 5 kg / cm with propylene^Two-G
Diphenylmethylene (cyclopentadienyl-2,6-di-t
(ert-butylfluorenyl) zirconium dichloride 1mg
Was added to 50 ml of toluene and added at 20 ° C for 2 hours
Polymerized. Next, unreacted propylene is purged and
The limer was filtered out, dried and weighed 82
g of polymer were obtained. This polymer is¹³According to C-NMR
The syndiotactic pentad fraction is 0.95, 135
Intrinsic viscosity (hereinafter referred to as η) measured with tetralin solution at ℃
Is 1.49, 1,2,4-trichlorobenzene as solvent
Ratio of weight average molecular weight and number average molecular weight measured by PC
(Hereinafter referred to as MW / MN) was 5.3. Comparative Example 1 Except for using 2Nl of hydrogen instead of diethylsilane
When propylene was polymerized in the same manner as in Example 1, 75 g was obtained.
Was obtained. Syndiotactic of this polymer
The pentad fraction is 0.95, η is 1.57, MW / MN is 2.3
Met. Embodiment 2 Diphenylmethylene (cyclopentadienyl-2,6-di-t
(ert-butylfluorenyl) zirconium dichloride
Instead, isopropenyl (cyclopentadienyl-1-fur
(Orenyl) zirconium dichloride as catalyst component
Example 1 was the same as Example 1 except that the amount of diethylsilane was 0.02 g.
The polymerization of propylene was performed in the same manner.
Got a remar. Syndiotactic pen of this polymer
The tod fraction is 0.92, η is 1.23, and MW / MN is 4.8.
Was. Comparative Example 2 Except that 2Nl of hydrogen was used instead of diethylsilane
When propylene was polymerized in the same manner as in Example 2.
12.7 g of polymer were obtained. Syndiotactic of this polymer
Tic pentad fraction is 0.92, η is 1.25, MW / MN
Was 2.2. [0038] According to the present invention, the catalyst can be obtained by performing the method of the present invention.
Highly active, controlled molecular weight, wide molecular weight distribution
It is possible to produce polyolefin with good productivity,
It is extremely valuable industrially.

[Brief description of the drawings] FIG. 1 is a flowchart for helping an understanding of the present invention.

Claims (1)

(57) [Claims] [Claim 1] In the following general formula (Chemical Formula 1) or (Chemical Formula 2)
A transition metal compound represented by Embedded image (Wherein A and B are the same or different coordination including a monovalent or divalent unsaturated hydrocarbon residue, or a nitrogen atom, oxygen atom, silicon atom, phosphorus atom or sulfur atom bonded to M) A ′ and B ′ are the same or different monovalent or divalent unsaturated hydrocarbon residues bridged by R,
Or a ligand containing a nitrogen atom, an oxygen atom, a phosphorus atom or a sulfur atom bonded to M, and R represents a residue or a side containing a divalent nitrogen atom, an oxygen atom, a silicon atom, a phosphorus atom or a sulfur atom. A linear saturated hydrocarbon residue which may have a chain or a residue in which part or all of the straight-chain carbon atoms are substituted with a silicon atom, a germanium atom or a tin atom,
M is a zirconium atom, and X is a halogen atom, a carbon atom, a nitrogen atom, an oxygen atom, a silicon atom,
A ligand containing a boron atom, a phosphorus atom or a sulfur atom is shown. A) A method for producing a polyolefin using a catalyst component comprising a combination of aluminoxane or a reactant of a transition metal compound having a ligand and an organometallic compound and a compound which reacts with the reactant to form an ionic compound. In the above, the polymerization reaction is carried out by the following general formula (Chemical Formula 3)
A hydride residue, n represents an integer of 1 to 3. ),
Compound having a hydrosilyl group (Formula 3) (wherein R is a carbon
A process for producing a polyolefin, which is carried out in the presence of a hydride group, and n represents an integer of 1 to 3) . Embedded image