JPH09241315A - Production of polyolefin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polyolefin at good efficiency by using a specified compound having a perfluoroalkanesulfonylimide group as the catalyst. SOLUTION: An olefin represented by formula II (wherein R is a lower alkyl or phenyl) is polymerized in the presence of the following compound A and methylaluminoxane to obtain a polyolefin represented by formula III (wherein R is as defined in formula II). Compound A is represented by formula I [wherein X is H, a lower alkyl or -N-(T<1> f )T<2> f (wherein T<1> f is -SO2 R<1> f ; T<2> f is -SO2 R<2> f (wherein R<1> f and R<2> f are each fluorine or the like)); R<1> is cyclopentadienyl, -N(T<3> f )R<6> , -N(T<4> f )T<5> f or the like; R<2> is cyclopentadienyl group, -N(T<6> f )R<8> , -N(T<7> f )T<8> f (T<3> f is -SO2 R<3> f , T<4> f is -SO2 R<4> f , T<5> f is -SO2 R<5> f , T<6> f is SO2 R<6> f , T<7> f is -SO2 R<7> f , T<8> f is -SO2 R<8> f (wherein R<3> f to R<8> f are each fluorine or the like)) or the like; M is a transition metal or the like; (m) is 0 or 1; (p) is 0 or 1; and (n) is a number determined by (p) and (m)].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to general formula [III]

[0002]

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[In the formula, R represents a lower alkyl group or a substituted or unsubstituted phenyl group. ] It is related with the manufacturing method of the polyolefins shown by these.

[0004]

Conventionally, as a method for producing polyolefins, Kaminsky-Sinn type titanocene, zirconocene, hafnocene complex and the like have been used as a catalyst to polymerize propylene and styrene to produce polypropylene and polystyrene. The method etc. are known.

[0005]

Means for Solving the Problems As a result of intensive investigations, the present inventors have found that in the polymerization reaction of olefins,
The inventors have found that polyolefins can be produced by using a compound having various perfluoroalkanesulfonylimide groups as a catalyst, and have arrived at the present invention.

That is, the present invention is based on the general formula [I]

[0007]

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[Wherein X is hydrogen, a lower alkyl group or
-N (T_f ¹) T_f ^Two[T_f ¹Is -SO_TwoR_f ¹Represents T_f ^TwoIs
-SO_TwoR_f ^Two(R_f ¹And R_f ^TwoAre each independently fluorine
Represents an atom or a lower perfluoroalkyl group. )
You. ], And R¹Is a substituted or unsubstituted cyclopen
Tadienyl group, -OR^Five, -N (T_f ^Three) R⁶Or -N
(T _f ^Four) T_f ^FiveRepresents R^TwoIs a substituted or non-replaced sequence
Lopentadienyl group, -OR⁷, -N (T_f ⁶) R⁸Or
-N (T_f ⁷) T_f ⁸[T_f ^ThreeIs -SO_TwoR_f ^ThreeRepresents T_f ^FourIs
-SO_TwoR_f ^FourRepresents T_f ^FiveIs -SO_TwoR_f ^FiveRepresents T_f ⁶Is
-SO_TwoR_f ⁶Represents T_f ⁷Is -SO_TwoR_f ⁷Represents T_f ⁸Is
-SO_TwoR_f ⁸(R_f ^Three, R_f ^Four, R_f ^Five, R_f ⁶, R_f ⁷And R_f
⁸Are each independently a fluorine atom or lower perfluoro
Represents an alkyl group. ) And R^Five, R⁶, R⁷And R⁸
Each independently represent a lower alkyl group, or R
^FiveAnd R⁷, R^FiveAnd R⁸, R⁶And R⁷, Or
R⁶And R⁸Together form a divalent group
You. ], M is an alkali metal, an alkaline earth metal,
Rare earth elements, transition metals, boron, aluminum, galiu
Aluminum, indium, thallium, silicon, germanium, stainless steel
, Lead, arsenic, antimony, bismuth, selenium or te
Represents an element selected from Lulu, m is 0 or 1,
p is 0 or 1, and when m = 1 and p = 1,
n represents an integer corresponding to the valence of M−2, m = 1 and
For p = 0 and for m = 0 and p = 1, n is
Represents an integer with a valence of -1 of the corresponding M, m = 0 and p =
In the case of 0, n represents the integer of the valency of the corresponding M,
-N (T_f ¹) T_f ^Two, -N (T_f ^Three) R⁶, -N (T_f ^Four) T_f
^Five, -N (T_f ⁶) R⁸Or -N (T_f ⁷) T_f ⁸Little of
Have at least one. ] And the compound represented by
In the presence of lualumoxane, the compound of the general formula [II]

[0009]

[Chemical 6]

[In the formula, R represents a lower alkyl group or a substituted or unsubstituted phenyl group. ] The general formula [III] characterized by polymerizing olefins represented by

[0011]

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[In the formula, R represents a lower alkyl group or a substituted or unsubstituted phenyl group. ] It is a manufacturing method of the polyolefins shown by these.

The method for producing the polyolefins of the present invention will be described in detail below. In the method for producing a polyolefin of the present invention, the compound represented by the general formula [I]

[0014]

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[Wherein X is hydrogen, a lower alkyl group or
-N (T_f ¹) T_f ^Two[T_f ¹Is -SO_TwoR_f ¹Represents T_f ^TwoIs
-SO_TwoR_f ^Two(R_f ¹And R_f ^TwoAre each independently fluorine
Represents an atom or a lower perfluoroalkyl group. )
You. ], And R¹Is a substituted or unsubstituted cyclopen
Tadienyl group, -OR^Five, -N (T_f ^Three) R⁶Or -N
(T _f ^Four) T_f ^FiveRepresents R^TwoIs a substituted or non-replaced sequence
Lopentadienyl group, -OR⁷, -N (T_f ⁶) R⁸Or
-N (T_f ⁷) T_f ⁸[T_f ^ThreeIs -SO_TwoR_f ^ThreeRepresents T_f ^FourIs
-SO_TwoR_f ^FourRepresents T_f ^FiveIs -SO_TwoR_f ^FiveRepresents T_f ⁶Is
-SO_TwoR_f ⁶Represents T_f ⁷Is -SO_TwoR_f ⁷Represents T_f ⁸Is
-SO_TwoR_f ⁸(R_f ^Three, R_f ^Four, R_f ^Five, R_f ⁶, R_f ⁷And R_f
⁸Are each independently a fluorine atom or lower perfluoro
Represents an alkyl group. ) And R^Five, R⁶, R⁷And R⁸
Each independently represent a lower alkyl group, or R
^FiveAnd R⁷, R^FiveAnd R⁸, R⁶And R⁷, Or
R⁶And R⁸Together form a divalent group
You. ], M is an alkali metal, an alkaline earth metal,
Rare earth elements, transition metals, boron, aluminum, galiu
Aluminum, indium, thallium, silicon, germanium, stainless steel
, Lead, arsenic, antimony, bismuth, selenium or te
Represents an element selected from Lulu, m is 0 or 1,
p is 0 or 1, and when m = 1 and p = 1,
n represents an integer corresponding to the valence of M−2, m = 1 and
For p = 0 and for m = 0 and p = 1, n is
Represents an integer with a valence of -1 of the corresponding M, m = 0 and p =
In the case of 0, n represents the integer of the valency of the corresponding M,
-N (T_f ¹) T_f ^Two, -N (T_f ^Three) R⁶, -N (T_f ^Four) T_f
^Five, -N (T_f ⁶) R⁸Or -N (T_f ⁷) T_f ⁸Little of
Have at least one. ] The compound represented by
Used.

Many elements can be used as M, which is the central element of the compound represented by the general formula [I],
Specifically, alkali metals, alkaline earth metals, rare earth elements, transition metals, boron, aluminum, gallium, indium, thallium, silicon, germanium, tin,
An element selected from lead, arsenic, antimony, bismuth, selenium, or tellurium can be used.

The alkali metal in the present invention means
Indicates lithium, sodium, potassium, rubidium, cesium or francium. The alkaline earth metal in the present invention means beryllium, magnesium, calcium, strontium, barium or radium. The rare earth element in the present invention means scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium. Further, the transition metal in the present invention, titanium, zirconium, hafnium, vanadium,
Indicates niobium, tantalum, chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium or mercury.

Further, as the ligand of M, which is the central element of the compound represented by the general formula [I] used in the method for producing polyolefins of the present invention, X is hydrogen,
Lower alkyl or ^{_{-N (T f 1) T f}} 2 [T _f ¹ is -SO
It represents ₂ R _f ^1, T _f ² represents -SO ^₂ R _{f 2} (represents. The R _f ¹ and R _f ² each independently represents a fluorine atom or a lower perfluoroalkyl group). ] And R ¹ is a substituted or unsubstituted cyclopentadienyl group, —O
^{_{R 5, -N (T f 3}} ) R 6 or ^{_{-N (T f 4) T f}} 5 is used, as R ² is a substituted or unsubstituted cyclopentadienyl group, -OR ^7, -N (T _f ⁶⁾ R ⁸ or -N
(T _f ⁷⁾ T _f ⁸ [T _f ³ represents ^{_{-SO 2 R f 3, T f}} 4 is -S
Represents O ₂ R _f ⁴ , T _f ⁵ represents -SO ₂ R _f ⁵ , and T _f ⁶ represents -S.
Represents ^{_{O 2 R f 6, T f}} 7 represents ^{_{-SO 2 R f 7, T f}} 8 is -S
O ₅ R _f ⁸ (R _f ³ , R _f ⁴ , R _f ⁵ , R _f ⁶ , R _f ⁷ and R _f ⁸ each independently represents a fluorine atom or a lower perfluoroalkyl group), and R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a lower alkyl group, or R ⁵ and R ⁷ , R ⁵ and R ⁸ , R ⁶ and R ⁷ , or R ⁶
And R ⁸ together form a divalent group. ]
Is used.

Further, m is 0 or 1, p is 0 or
Is 1 and m = 1 and p = 1, that is,
The compound represented by the formula [I] is R¹And R^TwoHave both sides
In this case, n represents the integer of valence-2 of the corresponding M.
, M = 1 and p = 0 and m = 0 and p = 1
In other words, when the compound represented by the general formula [I] is R¹
Or R^TwoN has only one of
Represents an integer of valence-1 of M, and is a field of m = 0 and p = 0.
That is, the compound represented by the general formula [I] is R ¹You
And R^TwoN does not have any of the above,
Represents the integer of the valence of.

The above ligands X and R¹And R^TwoWhich is
Although such a combination may be used, a compound represented by the general formula [I]
In order for a compound to exhibit sufficient catalytic activity, a strong electron
Perfluoroalkanesulfonylimide group that attracts
-N (T_f ¹) T_f ^Two, -N (T _f ^Three) R⁶, -N (T_f ^Four) T_f
^Five, -N (T_f ⁶) R⁸Or -N (T_f ⁷) T_f ⁸Little of
It is necessary to have at least one, stronger Louis
In order to show the acid activity of these
Having more sulfonylsulfonyl groups is preferred
Yes.

The lower alkyl group in the present invention refers to an alkyl group having a straight or branched chain having 1 to 10 carbon atoms, specifically, for example, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-
Examples thereof include a butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, and an n-octyl group. Further, the lower perfluoroalkyl group in the present invention,
It represents a perfluoroalkyl group having a straight or branched chain having 1 to 10 carbon atoms, and specifically, for example, trifluoromethyl group, pentafluoroethyl group, n-heptafluoropropyl group, iso-heptafluoropropyl group. , N-nonafluorobutyl group, iso-nonafluorobutyl group, sec-nonafluorobutyl group, tert-
Examples thereof include a nonafluorobutyl group, an n-undecafluoropentyl group, an n-tridecafluorohexyl group, an n-pentadecafluoroheptyl group and an n-heptadecafluorooctyl group.

Further, the above R in the present invention is^Five, R⁶, R
⁷, R⁸Are each independently a lower alkyl group
And m = 1 and p = 1, that is, the general formula
The compound represented by [I] is R¹And R^TwoHave both
In that case, R¹R included in^FiveOr R⁶And R^Twoinclude
R⁷Or R⁸Two of them in a set, that is,
R ^FiveAnd R⁷, R^FiveAnd R⁸, R⁶And R⁷Ai
Is R⁶And R⁸Together form a divalent group
You may.

In the method for producing a polyolefin of the present invention, the compound represented by the general formula [II] is present in the presence of the compound represented by the general formula [I] and methylalumoxane.

[0024]

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[In the formula, R represents a lower alkyl group or a substituted or unsubstituted phenyl group. ] The general formula [III] by polymerizing the olefins represented by

[0026]

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[In the formula, R represents a lower alkyl group or a substituted or unsubstituted phenyl group. ] The polyolefins shown by these can be manufactured.

Further, the compound represented by the general formula [I] used as a catalyst in the method for producing a polyolefin of the present invention is usually 0.01 to 1 mol of the olefins represented by the general formula [II]. Mol to 50 mol, preferably 0.1 mol to 30 mol, more preferably 1 mol to 2
It is recommended to use 0 mol. If the amount used is less than this range, the reaction does not proceed sufficiently and causes a decrease in the degree of polymerization, or the reaction rate decreases and it takes a long time to complete the reaction, and the desired product is efficiently produced. In some cases, problems such as the inability to manufacture may occur, which is not preferable. Use of more than this range hardly changes the reaction rate and the like, and is only disadvantageous economically, which is not preferable.

In the method for producing polyolefins of the present invention, a solvent is usually used, but the solvent used is not particularly limited, and commonly used solvents can be widely used. Water, methanol, ethanol, n-propanol, iso-propanol,
Alcohols such as n-butanol, iso-butanol, sec-butanol, tert-butanol, n-
Aliphatic hydrocarbons such as pentane, n-hexane, n-heptane, and n-octane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, benzene, toluene, o-xylene, m- Aromatic hydrocarbons such as xylene and p-xylene, halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane (EDC) and chlorobenzene, diethyl ether, dioxane, tetrahydrofuran (THF), ethylene glycol dimethyl ether and the like. Ketones such as ethers, acetone, methyl ethyl ketone and methyl isobutyl ketone, esters such as ethyl acetate, butyl acetate and γ-butyrolactone, nitriles such as acetonitrile and benzonitrile, and tertiary amines such as pyridine. S, N, N-dimethylformamide (DMF), N, N- dimethylacetamide (DMA
c), acid amides such as N-methylpyrrolidone, sulfur-containing compounds such as dimethylsulfoxide (DMSO) and sulfolane, nitro compounds such as nitromethane and nitroethane, organic acids such as acetic acid, propionic acid, butyric acid and isobutyric acid; Organic acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride and isobutyric anhydride can be exemplified.

The reaction temperature in the method for producing a polyolefin of the present invention may be usually around room temperature,
The reaction proceeds at a sufficient reaction rate. As a matter of course,
The reaction proceeds efficiently even under heating, but under cooling,
For example, the reaction proceeds at a sufficient reaction rate even at around 0 ° C. However, even if heating or cooling, there is almost no change in the reaction speed, etc., the number of steps for heating and cooling increases, and the operation becomes complicated.Moreover, it takes time to perform heating and cooling, resulting in poor efficiency. This is not preferred. Further, when the temperature is too low, the reaction does not proceed sufficiently, which may cause a decrease in the degree of polymerization, or a problem that the reaction rate decreases and it takes a long time to complete the reaction. On the other hand, when the temperature is too high, decomposition may occur during the reaction, which is not preferable.

In the present invention, the polyolefins represented by the general formula [III] can be produced as described above.

[0032]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[0033]

Example 1 Polymerization Reaction of Propylene (Production of Polypropylene) Methylalumoxane [M] was added to a 100 mL autoclave.
AO, 1M MAO in toluene: 2.5 mL (2.
5 mmol)] and polypropylene (9 L) were charged, and the mixture was cooled at −196 ° C. for 30 minutes or more. Cp ₂ Ti (M
e) (NTf ₂ ) [Cp: cyclopentadienyl group, T
f: trifluoromethanesulfonyl group (-SO ₂ C
F ₃ ), 2 mM Cp ₂ Ti (Me) (NTf ₂ ) in toluene: 25 mL (0.05 mmol)]-196
Injected at ° C. The temperature was raised to 0 ° C. and the mixture was stirred for 1 hour. The reaction was terminated by injecting methanol and HCl. The product was washed with a large excess of methanol and then under reduced pressure at 60 ° C for 6
It was dried for an hour to obtain polypropylene. The obtained polypropylene had a molecular weight of 1.4 × 10 ⁴ .

[0034] Alternatively Cp ₂ Zr polymerization reaction of Example 2 Propylene (Production of _{polypropylene) Cp 2 Ti (Me) (} NTf 2)
Reaction was carried out in the same manner as in Example 1 except that (Me) (NTf ₂ ) was used. The molecular weight of the obtained polypropylene is
It was 2.3 × 10 ⁴ .

[0035]Example 3 Polymerization reaction of styrene (polystyrene production) Add styrene (10 mL) to a 100 mL Schlenk tube,
Ruen (5 mL) and MAO [1M MAO Torue
Solution: 3 mL (3 mmol)] and stir for a few minutes
did. Cp_TwoTi (Me) (NTf_Two) [50 mM Cp
_TwoTi (Me) (NTf_Two) Toluene solution: 2 mL
(0.1 mmol)] at room temperature. Raise to 50 ℃
Allow to warm and stir for 5 hours. Inject methanol and HCl
Then, the reaction was terminated. The product with a large excess of methanol
Wash and dry under reduced pressure at 60 ° C for 6 hours.
I got it. The molecular weight of the obtained polystyrene is 8.6 ×.
10 ^ThreeMet.

[0036]

According to the production method of the present invention, polyolefins can be produced efficiently.

Claims (4)

[Claims] 1. A compound represented by the general formula [I]:[In the formula, X is hydrogen, a lower alkyl group or -N (T_f ¹)
T_f ^Two[T_f ¹Is -SO_TwoR_f ¹Represents T_f ^TwoIs -SO_TwoR
_f ^Two(R_f ¹And R_f ^TwoAre each independently a fluorine atom or
Represents a lower perfluoroalkyl group. ). ] To the table
Then R¹Is a substituted or unsubstituted cyclopentadienyl
Group, -OR^Five, -N (T_f ^Three) R⁶Or -N (T _f ^Four) T_f ^Five
Represents R^TwoIs a substituted or unsubstituted cyclopentadiene
Nyl group, -OR⁷, -N (T_f ⁶) R⁸Or -N (T_f ⁷)
T_f ⁸[T_f ^ThreeIs -SO_TwoR_f ^ThreeRepresents T_f ^FourIs -SO_TwoR_f ^FourTo
Represent, T_f ^FiveIs -SO_TwoR_f ^FiveRepresents T_f ⁶Is -SO_TwoR_f ⁶To
Represent, T_f ⁷Is -SO_TwoR_f ⁷Represents T_f ⁸Is -SO_TwoR
_f ⁸(R_f ^Three, R_f ^Four, R_f ^Five, R_f ⁶, R_f ⁷And R_f ⁸Each
Independently fluorine atom or lower perfluoroalkyl group
Represents ) And R^Five, R⁶, R⁷And R⁸Are each
Independently represents a lower alkyl group, or R^Fiveand
R⁷, R^FiveAnd R⁸, R⁶And R⁷Or R⁶And
And R⁸Together form a divalent group. ] To the table
, M is an alkali metal, alkaline earth metal, rare earth element
Element, transition metal, boron, aluminum, gallium, in
Dium, thallium, silicon, germanium, tin, lead,
From arsenic, antimony, bismuth, selenium or tellurium
Represents the selected element, m is 0 or 1 and p is 0 or
Or 1 and if m = 1 and p = 1, then n is
Represents the integer of valence-2 of M, where m = 1 and p = 0
And if m = 0 and p = 1 then n is applicable
When the valence of M is -1 and m = 0 and p = 0
, N represents the integer of the valence of the corresponding M, and -N (T
_f ¹) T_f ^Two, -N (T_f ^Three) R⁶, -N (T_f ^Four) T_f ^Five, -N
(T_f ⁶) R⁸Or -N (T_f ⁷) T_f ⁸At least of
Also has one. ] And the compound represented by
In the presence of moxane, the compound of the general formula [II][Wherein R is a lower alkyl group or a substituted or unsubstituted
Represents a phenyl group. ] Polymerization of olefins
The general formula [III] is characterized by[Wherein R is a lower alkyl group or a substituted or unsubstituted
Represents a phenyl group. ] Of polyolefins
Production method. 2. T _f ¹ , T _f ² , T _f ³ , T _f ⁴ , T _f ⁵ , T _f ⁶ , T
_The method for producing a polyolefin according to claim 1, wherein _f ⁷ and T _f ⁸ are —SO ₂ CF ₃ . 3. The method for producing a polyolefin according to claim 1 or 2, wherein M is titanium or zirconium. 4. The method for producing a polyolefin according to any one of claims 1 to 3, wherein R is a methyl group or a phenyl group.