JPH05222120A - Cationic polymerization catalyst and method of cationically polymerizing olefin - Google Patents

Abstract

PURPOSE:To attain a high catalytic activity in the production of a low-molecular olefin polymer. CONSTITUTION:The title catalyst comprises: a halogenated hydrocarbon and an organoaluminumoxy compound; or a halogenated hydrocarbon, an organotin oxide, and an organoaluminum compound; or a halogenated hydrocarbon, an organoaluminum compound, and water. An olefin is cationically polymerized in the presence of this catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst used for producing a low polymer of an olefin and a method for cationically polymerizing an olefin using the catalyst.

[0002]

BACKGROUND OF THE INVENTION Low polymers of olefins are detergents,
It is used as a sizing agent for papermaking, a lubricating oil raw material intermediate and an additive. Regarding the catalyst for producing such a low polymer of olefin, for example, JP-A-63-5134 is used.
JP-A No. 0-202 describes that an α-olefin can be dimerized with high selectivity by a catalyst system composed of a metallocene and an organoaluminumoxy compound. JP 63
No. 308007 discloses a supported titanium composition in which a titanium compound is supported on a chloride of a metal as a transition metal catalyst component, and a catalyst having 6 carbon atoms in the presence of a catalyst composed of an organoaluminum compound and / or an aluminoxane as an organometallic compound component. Disclosed is a method for producing a liquid α-olefin polymer, which comprises polymerizing 12 to 12 α-olefins. Japanese Unexamined Patent Publication (Kokai) No. 1-207248 discloses a method for producing a propylene low polymer which produces a low polymer having a vinyl group at a terminal by a catalyst system composed of a metallocene and an organoaluminumoxy compound. All of these conventionally known catalysts for low polymerization of olefins use transition metal compounds.

Under these circumstances, the present inventors have conducted extensive studies to obtain a new cation catalyst for low polymerization of olefins. As a result, an organoaluminum oxy compound or a component capable of forming an organoaluminum oxy compound, It has been found that a low polymerization catalyst of olefin can be obtained by combining with a halogenated hydrocarbon. As a result of further studies, by combining an organoaluminum oxy compound or a component capable of forming an organoaluminum oxy compound with a specific halogenated hydrocarbon, it has a polymerization activity equivalent to that of a catalyst containing a conventional transition metal compound. The present invention has been completed by finding that a catalyst for low polymerization of olefins can be obtained.

[0004]

An object of the present invention is to provide a cationic polymerization catalyst capable of producing a highly active low-polymer olefin, and a method for cationic olefin polymerization using this catalyst. The purpose is to do.

[0005]

SUMMARY OF THE INVENTION The first cationic polymerization catalyst according to the present invention is characterized by comprising a halogenated hydrocarbon [A] and an organoaluminum oxy compound [B].

The second cationic polymerization catalyst according to the present invention is
[A] a halogenated hydrocarbon, [C] an organotin oxide, and [D] an organoaluminum compound.

The third cationic polymerization catalyst according to the present invention is
It is characterized by comprising [A] halogenated hydrocarbon, [D] organoaluminum compound, and [E] water.

The olefin polymerization method according to the present invention is characterized by cationically polymerizing an olefin in the presence of the above-mentioned catalyst. According to the present invention, a low polymer of olefin can be produced with high activity.

[0009]

DETAILED DESCRIPTION OF THE INVENTION The olefin polymerization catalyst according to the present invention and the olefin polymerization method using the catalyst will be specifically described below. The first catalyst according to the present invention is
It is composed of a halogenated hydrocarbon [A] and an organoaluminum oxy compound [B].

The [A] halogenated hydrocarbon (hereinafter sometimes referred to as the component [A]) used in the first catalyst according to the present invention is a compound represented by the following general formula [I]. .. ^{R 1 R 2 R 3 C-} X ... [I] ( wherein, R ¹ to R ³ are hydrogen or carbon number 1 each independently
It is a hydrocarbon group of 20 and R ¹ and R ² may combine with each other to form a ring. X is halogen. In the formula [I], R ^{1 to} R ³ are each independently hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, specifically, alkyl groups such as a methyl group, an ethyl group, a propyl group and a butyl group. Group; cycloalkyl group such as cyclohexyl group; aryl group such as phenyl group, naphthyl group, anthryl group; aralkyl group such as benzyl group. Also, R ¹ and R ²
And may combine with each other to form a ring such as a 6-membered ring or a 7-membered ring.

X is chlorine, bromine or iodine. Specific examples of the compound represented by the above general formula [I] include the following compounds.

[0012]

[Chemical 1]

[0013]

[Chemical 2]

Of these, tert-BuCl is preferred.
The [B] organoaluminum oxy compound (hereinafter sometimes referred to as the component [B]) used in the first cationic polymerization catalyst according to the present invention may be a conventionally known aluminoxane. JP-A-2-78687
It may be a benzene-insoluble organoaluminum oxy compound as exemplified in Japanese Patent Laid-open Publication.

The conventionally known aluminoxane can be produced, for example, by the following method. (1) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, and ceric chloride hydrate A method of recovering a hydrocarbon solution by adding an organoaluminum compound such as trialkylaluminum to the hydrocarbon medium suspension and reacting the same.

(2) A method in which water, ice or steam is directly applied to an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran to recover it as a hydrocarbon solution. (3) A method of reacting an organoaluminum compound such as trialkylaluminum with an organotin oxide such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of organic metal component. Alternatively, the solvent or unreacted organoaluminum compound may be removed by distillation from the recovered solution of the aluminoxane, and then redissolved in the solvent. Specifically as the organoaluminum compound used in the production of the aluminoxane as described above,
Trimethyl aluminum, triethyl aluminum, tripropyl aluminum, triisopropyl aluminum, tri n-butyl aluminum, triisobutyl aluminum, tri sec-butyl aluminum, tri tert-butyl aluminum, tripentyl aluminum, trihexyl aluminum, trioctyl aluminum, tridecyl Aluminum, tricyclohexylaluminum,
Trialkyl aluminum such as tricyclooctyl aluminum; dimethyl aluminum chloride, diethyl aluminum chloride, diethyl aluminum bromide,
Dialkyl aluminum halides such as diisobutyl aluminum chloride; Dialkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride; Dialkyl aluminum alkoxides such as dimethyl aluminum methoxide and diethyl aluminum ethoxide; Dialkyl aluminum aryloxides such as diethyl aluminum phenoxide. To be

Of these, trialkylaluminum is particularly preferable. Further, as the organoaluminum compound, isoprenylaluminum represented by the following general formula [II] can also be used. _{(i-C 4 H 9)} x Al y C 5 H 10) z ... [II] ( wherein, x, y, z are each a positive number, and z ≧ 2x.) the organic aluminum compound , Alone or in combination.

As the solvent used in the production of aluminoxane, aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, pentane, hexane,
Aliphatic hydrocarbons such as heptane, octane, decane, dodecane, hexadecane, octadecane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane, methylcyclopentane, petroleum fractions such as gasoline, kerosene, and light oil, or the above aromas. Examples thereof include halides of group hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, and particularly hydrocarbon solvents such as chlorinated compounds and brominated compounds. Other,
Ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are particularly preferable.

The second cationic polymerization catalyst according to the present invention is
It consists of [A] halogenated hydrocarbon, [C] organotin oxide and [D] organoaluminum compound. As the [A] halogenated hydrocarbon used in the second cationic polymerization catalyst according to the present invention, the same halogenated hydrocarbon used in the above-mentioned first cationic polymerization catalyst can be used.

Used in the second catalyst according to the present invention
[C] Organotin oxide (hereinafter referred to as component [C]
There is. ) Is Sn-O-Sn or Sn-OH
The compound which has a structure can be mentioned. Sn-O-
Examples of the compound having an Sn structure include (CH₃)₂Sn
O, (C₂H_Five)₂SnO, (n-C₃H₇)₂SnO, (i-C₃H₇)₂
SnO, (i-C _FourH₉)₂SnO, (n-C_FourH₉)₂SnO, (n-C₆
H₁₃)₂SnO, (n-C₈H₁₇)₂SnO, (2-ethylhexyl)
₂SnO, Ph₂SnO, (C₆H_FiveCH₂)₂SnO, (CH₃) (C
₂H_Five) SnO, (CH₃) (C_FourH₉) SnO etc. general formula RR'Sn
Compound represented by O (note that the compound represented by RR'SnO
The object usually has a polymer structure. ), [(CH₃)₃S
n]₂O, [(C₂H_Five)₃Sn]₂O, [(n-C₃H₇)₃Sn]₂O, [(n
-C_FourH₉)₃Sn]₂O, [(i-C₃H₇)₃Sn]₂O, [(C₂H_Five)
₂(C_FourH₉) Sn]₂O, [(i-C_FourH₉)₃Sn]₂O, [(s-C
_FourH₉)₃Sn]₂O, [(C_FiveH₁₁)₃Sn]₂O, [(neo-C_FiveH₁₁)₃
Sn]₂O, [(n-C₈H₁₇)₃Sn]₂O, [(C₆H₁₃)₃Sn]
₂O,

[0022]

[Chemical 3]

A compound represented by the general formula (R ₂ Sn) ₂ O

[0024]

[Chemical 4]

Cyclic compounds such as CH ₃ SnO _1.5 , C ₂ H ₅
SnO _1.5 , n-C ₃ H ₇ SnO _1.5 , i-C ₃ H ₇ SnO _1.5 , n-C
₄ H ₉ SnO _1.5 , i-C ₄ H ₉ SnO _1.5 , n-C ₅ H ₁₁ Sn
O _1.5 , neo-C ₅ H ₁₁ SnO _1.5 , C ₈ H ₁₇ CnO _1.5 , Ph
Can be exemplified compounds represented by the general formula RSnO _1.5 such as SnO _1.5.

Examples of compounds having a Sn--OH structure
For example, (CH₃)₃SnOH, (i-C₃H₇)₃SnOH, (C
₂H_Five)₃SnOH, (n-C₃H₇)₃SnOH, (n-C_FourH₉)₃Sn
OH, (i-C_FourH₉)₃SnOH, (n-C_FiveH₁₁)₃SnOH, (n-
C ₈H₁₇)₃SnOH, (2-ethylhexyl)₃SnOH, Ph₃
SnOH, (C₆H_FiveCH₂)₃SnOH, (C_FourH₉) (C₆H_Five)
(C₆H_FiveCH₂) SnOH, Me₂(C₆H_Five) SnOH, (CH₂
= CH)₃General formula R such as SnOH₃Compound represented by SnOH
Thing, CH₃Sn (O) OH, Cl₂CHSn (O) OH, C₂H_Five
Sn (O) OH, (CH₂= CH) Sn (O) OH, BrCH₂C
H₂Sn (O) OH, i-C₃H₇Sn (O) OH, CH₂= CHC
H₂Sn (O) OH, CH₃COCH₂Sn (O) OH, n-C_FourH
₉Sn (O) OH, i-C_FourH₉Sn (O) OH, C₆H_FiveCH₂Sn
(O) OH, C₈H₁₇Sn (O) OH, C₁₂H_{twenty five}Sn (O) O
H, C₆H_Five-CH = CC₆H_FiveSn (O) OH, C₆H_FiveSn
(O) OH,

[0027]

[Chemical 5]

RSn (O) OH such as 1-C ₁₀ H ₇ Sn (O) OH
And the like. Of _{these, (CH 3) 2 SnO,} (C 2 H 5) 2 SnO, (n-C 3 H 7) 2 Sn
_{O, (i-C 4 H} 9) 2 SnO, (n-C 4 H 9) 2 SnO, (CH 3) (C
₂ H ₅ ) SnO, (CH ₃ ) (C ₄ H ₉ ) SnO, [(CH ₃ ) ₃ Sn]
₂ O, [(C ₂ H ₅ ) ₃ Sn] ₂ O, [(n-C ₃ H ₇ ) ₃ Sn] ₂ O, [(n-
_{C 4 H 9) 3 Sn]} 2 O, [(i-C 3 H 7) 3 Sn] 2 O, [(C 2 H 5)
_{2 (C 4 H 9) Sn} ] 2 O, [(i-C 4 H 9) 3 Sn] 2 O, [(s-C 4 H 9)
It is preferable to use ₃ Sn] ₂ O or the like.

Examples of the [D] organoaluminum compound (hereinafter sometimes referred to as the component [D]) used in the second cationic polymerization catalyst according to the present invention are represented by the following general formula [III]. Examples of the organic aluminum compound include R ⁴ _n AlH _3-n ... [III] (In the formula, R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms, and n
Is 1 to 3. In the above formula [III], R ⁴ is a hydrocarbon group having 1 to 12 carbon atoms such as an alkyl group, a cycloalkyl group or an aryl group, and specifically, a methyl group, an ethyl group, n-
Examples thereof include propyl group, isopropyl group, isobutyl group, pentyl group, hexyl group, octyl group, cyclopentyl group, cyclohexyl group, phenyl group and tolyl group.

Specific examples of such an organoaluminum compound include the following compounds. Trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum,
Trialkyl aluminums such as trioctyl aluminum and tri-2-ethylhexyl aluminum; alkenyl aluminums such as isoprenyl aluminum; alkyl aluminum hydrides such as diethyl aluminum hydride and diisobutyl aluminum hydride.

Further, as the organic aluminum compound [D], a compound represented by the following general formula [IV] can also be used. R ⁴ _n AlX _3-n ... [IV] (In the formula, R ⁴ is the same as above, X is a —OR ⁵ group,
OSiR ⁶ ₃ group, -OAlR ⁷ ₂ group, -NR ⁸ ₂ group, -SiR
⁹ ₃ groups or —N (R ¹⁰ ) AlR ¹¹ ₂ groups, and n is 1 to 2
And R ⁵ , R ⁶ , R ⁷ and R ¹¹ are a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexyl group, a phenyl group, etc., and R ⁷ is a hydrogen atom, a methyl group, an ethyl group, an isopropyl group, It is a phenyl group, a trimethylsilyl group or the like, and R ⁹ and R ¹⁰ are a methyl group, an ethyl group or the like. ) Specifically, as such an organoaluminum compound,
The following compounds may be mentioned.

(I) Compounds represented by the general formula R ⁴ _n Al (OR ⁵ ) _3-n , such as dimethyl aluminum methoxide, diethyl aluminum ethoxide, diisobutyl aluminum methoxide and the like. (Ii) a compound represented by the general formula R ⁴ _n Al (OSiR ⁶ ₃ ) _3-n , such as Me ₂ Al (OSiMe ₃ ), Et ₂ Al (OSiMe ₃ ),
_{(iso-Bu) 2 Al (} OSiMe 3), (iso-Bu) 2 Al (OSiEt 3)
etc.

(Iii) A compound represented by the general formula R ⁴ _n Al (OAlR ⁷ ₂ ) _3-n , for example, Et ₂ AlOAlEt ₂ , (iso-Bu) ₂
AlOAl (iso-Bu) _{2 and the} like. (Iv) a compound represented by the general formula R ⁴ _n Al (NR ⁸ ₂ ) _3-n ,
For example, Me ₂ AlNEt ₂ , Et ₂ AlNHMe, Me ₂ AlNHE
t, Et ₂ AlN (SiMe ₃ ) ₂ , (iso-Bu) ₂ AlN (SiMe ₃ ) ₂
etc.

(V) A compound represented by the general formula R ⁴ _n Al (SiR ⁹ ₃ ) _3-n , for example, Me ₂ AlSiMe ₃ , (iso-Bu) ₂ AlSi.
Me ₃ etc.

[0035]

[Chemical 6]

(In the above chemical formula, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.) Of the organoaluminum compounds represented by the above general formulas [III] and [IV], Among them, R ⁴ ₃ Al, R ⁴ _n Al (OR ⁵ ) _3-n , R ⁴
_An organoaluminum compound represented by _n Al (OA1R ⁷ ₂ ) _3-n can be mentioned as a preferable example, and one in which R ⁴ is a methyl group is particularly preferable. These organoaluminum compounds may be used as a mixture of two or more kinds.

The third cationic polymerization catalyst according to the present invention is
It consists of [A] halogenated hydrocarbon, [D] organoaluminum compound, and [E] water. As the [A] halogenated hydrocarbon used in the third cationic polymerization catalyst according to the present invention, the same halogenated hydrocarbons used in the above-mentioned first and second cationic polymerization catalysts are used. As the organoaluminum compound D], the same organoaluminum compound used in the above-mentioned second cationic polymerization catalyst is used.

[E] Water (hereinafter sometimes referred to as component [E]) used in the third cationic polymerization catalyst according to the present invention includes hydrocarbon solvents such as benzene, toluene, hexane, and tetrahydrofuran. Water dissolved in or dispersed in an ether solvent such as, or steam or ice. In addition, as [E] water, water of crystallization of salts such as magnesium chloride, magnesium sulfate, aluminum sulfate, copper sulfate, nickel sulfate, iron sulfate and ceric chloride, or inorganic compounds or polymers such as silica, alumina and aluminum hydroxide. It is also possible to use adsorbed water or the like that has been adsorbed on the like.

The first cationic polymerization catalyst according to the present invention is
It can be prepared by mixing and contacting the above-mentioned [A] halogenated hydrocarbon and [B] organoaluminum oxy compound in an inert hydrocarbon solvent or in an olefin medium. The mixing order at this time is arbitrarily selected. In this case, the component [A] can also be used as a solvent.

When the components [A] and [B] are mixed, the molar ratio of the components [A] and the components [B] ([B] /
[A]) is 0.001-1000, preferably 0.1-1
It is preferably 0, more preferably 0.5 to 2.
The temperature at the time of mixing the component [A] and the component [B] is usually in the range of -50 to 150 ° C, preferably 0 to 100 ° C, and the contact time is usually 1 minute to 12 hours, preferably 5 minutes. ~ 6 hours range. It is desirable to carry out the mixing contact with stirring.

The second cationic polymerization catalyst according to the present invention is
It can be prepared by mixing and contacting the above-mentioned [A] halogenated hydrocarbon, [C] organotin oxide and [D] organoaluminum compound in an inert hydrocarbon solvent or in an olefin medium. In this case, the component [C]
And component [D] are mixed and contacted to form an organoaluminum oxy compound, and then component [A] is mixed and contacted, or component [C] is contacted with component [D] in a plurality of times to form an organic compound. It is selected to form an aluminum oxy compound and then to bring the component [A] into mixed contact.

When the component [A], the component [C] and the component [D] are mixed, the aluminum atom (A
l) and the oxygen atom (O) in the component [C] (Al /
O) is usually 0.5 or more, preferably 0.8 to 10, and more preferably 1 to 5. Further, the ratio (Al / Hal) of the aluminum atom (Al) in the component [D] to the halogen atom (Hal) in the component [A] is usually 0.
It is desirable that it is 01 to 100, preferably 0.1 to 10, and more preferably 0.5 to 2.

The temperature for mixing the components [A], [C] and [D] is usually in the range of -50 to 150 ° C, preferably 0 to 100 ° C, and the contact time is usually 5 minutes to. 1
It is 2 hours, preferably 5 minutes to 6 hours. Particularly, the temperature at the time of mixing the component [C] and the component [D] is -100 to
The temperature is in the range of 200 ° C., preferably 0 to 100 ° C., and the contact time is 5 minutes to 12 hours, preferably 5 minutes to 6 hours. It is desirable to carry out the mixing contact with stirring.

The third cationic polymerization catalyst according to the present invention is
It can be prepared by mixing and contacting the above-mentioned [A] halogenated hydrocarbon, [D] organoaluminum compound and [E] water in an inert hydrocarbon solvent or in an olefin medium. In this case, it is selected that the component [D] and the component [E] are mixed and brought into contact with each other to form an organoaluminum oxy compound, and then the component [A] is mixed and brought into contact therewith.

When the components [A], [D] and [E] are mixed, the ratio of the oxygen atom (O) in the component [E] to the Al atom (Al) in the component [D] ( Al / O) is usually 0.1 to 10, preferably 0.1 to 2. In addition, the aluminum atom (Al) in the component [D]
To the halogen atom (Hal) in the component [A] (Al
/ Hal) is usually 0.01 to 100, preferably 0.1 to
It is desirable that it is 10, more preferably 0.5-2.

The temperature for mixing the components [A], [D] and [E] is usually in the range of -50 to 150 ° C, preferably 0 to 100 ° C, and the contact time is usually 5 minutes to. Four
It is 8 hours, preferably 5 minutes to 6 hours. In particular, the temperature for mixing the component [D] and the component [E] is -50 to 1
The temperature is in the range of 50 ° C., preferably 0 to 100 ° C., and the contact time is 5 minutes to 72 hours, preferably 24 hours to 48 hours. It is desirable to carry out the mixing contact with stirring.

Specific examples of the inert hydrocarbon medium used in the preparation of the catalyst of the present invention include aromatic hydrocarbons such as benzene, toluene, xylene, cumene and cymene, pentane, hexane, heptane, octane and decane. Aliphatic hydrocarbons such as dodecane, hexadecane and octadecane, alicyclic hydrocarbons such as cyclopentane, cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil or the above aromatic hydrocarbons and aliphatics Hydrocarbons, halides of alicyclic hydrocarbons, especially hydrocarbon solvents such as chlorinated compounds and brominated compounds are mentioned. In addition, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons are preferable, and toluene is particularly preferable.

In carrying out the cationic polymerization of olefins using the above catalyst, the [B] organoaluminumoxy compound and the [D] organoaluminum compound are converted into Al atoms as the concentration in the polymerization system to be 0.001. ~ 5
0 mg atom / liter, preferably 0.01-1
It is preferably used in an amount of 0 milligram atom / liter. Further, the [A] halogenated hydrocarbon used at this time has a ratio (Al) of the halogen atom (Hal) in the component [A] to the aluminum atom (Al) used for the polymerization (Al
/ Hal) is usually 0.01 to 100, preferably 0.1 to
10, more preferably 0.5 to 2 is used. When using the [C] organotin oxide, the ratio (Al / O) of the aluminum atom (Al) in the polymerization system to the oxygen atom (O) in the component [C] is usually 0.5 or more, It is preferably 0.8 to 10, and more preferably 1 to 5. When [E] water is used, the ratio (Al / O) of the aluminum atom (Al) in the polymerization system to the oxygen atom (O) in the component [E] is usually 0.1 to 10, preferably 0.
It is preferably 1 to 2.

The olefin polymerization temperature is usually -76 to 1.
The temperature is in the range of 50 ° C, preferably 0 to 80 ° C, and the higher the temperature, the higher the molecular weight of the polymer can be obtained. The polymerization pressure is usually 1 to 50 kg / cm ² , preferably 1 to 30 k.
The polymerization reaction can be carried out by any of a batch system, a semi-continuous system and a continuous system under the condition of g / cm ² . It is also possible to carry out the polymerization in two or more stages under different reaction conditions.

The olefins which can be polymerized by such a cationic polymerization catalyst include ethylene and α-olefins having 3 to 20 carbon atoms such as propylene, 1-butene, 1-pentene, 1-hexene and 4-. Methyl-1-
Pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; cyclic olefins having 3 to 20 carbon atoms, such as cyclopentene, cyclohexene, cycloheptene, norbornene, 5 -Methyl-2-norbornene, tetracyclododecene, 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-
Octahydronaphthalene and the like can be mentioned. In addition, styrene, vinyl ether, vinyl cyclohexane,
Cyclopentadiene, indene, diene and the like can also be used.

The molecular weight of the olefin polymer obtained by the present invention is usually 1500 or less, and generally 500 to 1
It is about 000.

[0052]

EFFECT OF THE INVENTION According to the cationic polymerization catalyst and the olefin cationic polymerization method of the present invention, a highly active and low olefin polymer can be produced.

[0053]

EXAMPLES The cationic polymerization catalyst and the olefin cationic polymerization method of the present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples. The dimethyltin oxide used in this example is dimethyltin chloride (Wako Pure Chemical Industries, Ltd.) from Albert K. Sawyer, “Organotin Compounds volume”.
It was synthesized according to 1 ”.

The oligomer obtained by the polymerization was confirmed by the following method. The molecular weight is field desorption mass spectrometry using JASCO JMS-DX300 (hereinafter "FD
-MS ". ), And gas chromatograph-mass spectrometry (hereinafter “GC-MS”) for lower molecular weight substances.
Is abbreviated. ). For gas chromatography (hereinafter abbreviated as "GLC"), Shimadzu GC-15A was used, and a column of silicon OV-17 (3 m) was used.
Injection at 50 ° C, detection at 240 ° C, column temperature 13
After holding at 0 ° C. for 10 minutes, the temperature was raised at 10 ° C. per minute, and held at 200 ° C. for 10 minutes. The molecular weights of some high molecular weight compounds are determined from a calibration curve using polystyrene as a standard substance by gel filtration chromatography (hereinafter abbreviated as “GPC”), or the intrinsic viscosity measured in decalin at 135 ° C. Was analyzed by asking.

The catalytic activity is g oligomer / mmolAl ·
Expressed in hr.

[0056]

[Manufacturing Example] [Manufacture of methylaluminoxane] Fully nitrogen-substituted 4
Flask 00ml, Al ₂ (SO ₄₎ of 37 g ₃ · 1
After charging 4H ₂ O and 125 ml of toluene and cooling to 0 ° C., 500 mmol of trimethylaluminum diluted with 125 ml of toluene was added dropwise. Then, the temperature was raised to 40 ° C., and the reaction was continued at that temperature for 48 hours. After the reaction,
Solid-liquid separation was performed by filtration, and toluene was further removed from the filtrate to obtain a white solid (9.1 g). The yield was 31.4%.

[0057]

Example 1 400 ml of purified toluene was charged into a glass-made polymerization vessel having an internal volume of 500 ml which had been sufficiently replaced with nitrogen, and propylene gas (100 liters / hr) was passed therethrough to
Saturated propylene at 5 ° C. After that, 0.09 ml
(The concentration in the polymerization solution is 2 mmol / liter) tert-butyl chloride (hereinafter sometimes abbreviated as “tBuCl”) (Wako Pure Chemical Industries) and the methylaluminoxane obtained above (hereinafter sometimes referred to as “MAO”) Was added so that the concentration in the polymerization solution would be 2 mg atom / liter in terms of aluminum atom, and the polymerization was started.
After 30 seconds from the start, all the propylene gas in circulation was absorbed, and the polymerization temperature reached a maximum of 30 ° C. even in a dry ice / isopropyl alcohol cooling bath. After that, the polymerization changed around 20 ° C., so that after 20 minutes, the propylene gas was switched to nitrogen gas and the polymerization was completely stopped by isobutyl alcohol.

Reserve 25 ml of the polymer solution for analysis (10
Min., 20 minutes) and then washed with hydrochloric acid water and the solvent was distilled off (100 mmHg, 80 ° C.) to obtain 166 g (284 g oligomer / mmolAl · hr) of an oily oligomer which is a typical cationic polymerization product. .. The cationic polymer was able to detect oligomers up to a tetramer by GC-MS. Further, it was found that toluene was incorporated in the oligomer chain. FD-
When it was analyzed by MS, it showed the highest peak at m / z; 556, which has a molecular weight corresponding to a decamer of propylene when calculated with one molecule of toluene incorporated in the oligomer chain. This oligomer was transferred to an evaporation dish and dried at 130 ° C. for 10 hours to obtain a high molecular weight product. Therefore, the intrinsic viscosity was measured and found to be 0.02 dl / g.

[0059]

COMPARATIVE EXAMPLE 1 In Example 1, polymerization was carried out only with methylaluminoxane without using tert-butyl chloride, but no oligomer was obtained. There was no temperature change during 30 minutes of operation.

[0060]

COMPARATIVE EXAMPLE 2 In Example 2, polymerization was carried out only with tert-butyl chloride without using methylaluminoxane, but no oligomer was obtained. There was no temperature change during 30 minutes of operation.

[0061]

Example 2 A gas with an internal volume of 500 ml that had been sufficiently replaced with nitrogen.
Charge 400 ml of purified toluene into a Lath polymerization vessel and
Pyrene gas (100 liters / hr) is circulated, and 0
Propylene was fully saturated at 5 ° C. Then trime
Chill aluminum (hereinafter sometimes abbreviated as “TMA”)
It ) Toluene solution (concentration in the polymerization solution is aluminum
3 mg atom / liter in terms of atoms), Dimethy
Rustin oxide (Me ₂SnO) (Wako Pure Chemical Industries) 132m
g (concentration in the polymerization solution 2 mmol) was added, and tert-
Butyl chloride 0.09 ml (concentration in polymerization solution 2 mmo
1 / l) was added to initiate the polymerization. The polymerization temperature is
Keep the temperature around 10 ° C and stop the polymerization in 10 minutes.
It was The polymerization solution was washed with hydrochloric acid and the solvent was distilled off (100 mH
g, 80 ° C), 12.6g (189g oligo)
An oligomer of mer / mmolAl · hr) was obtained.

[0062]

[Comparative Example 3] Polymerization was carried out in the same manner as in Example 2 except that trimethylaluminum was used and dimethyltin oxide and tert-butyl chloride were not used. The polymerization proceeded at 3 ° C., and after 30 minutes, the polymerization was stopped, and then the polymerization liquid was washed with hydrochloric acid water and the solvent was distilled off (100 mHg, 80 ° C.), but only 10 mg or less of an oligomer was obtained. This was dissolved in a small amount of toluene and analyzed by GLC to confirm an oligomer.

[0063]

Comparative Example 4 Polymerization was carried out in the same manner as in Example 2 except that trimethylaluminum and tert-butyl chloride were used and dimethyltin oxide was not used. The polymerization proceeded at 3 ° C., and after 30 minutes, the polymerization was stopped, the polymerization solution was washed with hydrochloric acid water, and the solvent was distilled off (100 mHg, 80 ° C.).
20 mg of oligomer was obtained.

[0064]

Comparative Example 5 Polymerization was carried out in the same manner as in Example 2 except that dimethyltin oxide and tert-butyl chloride were used and trimethylaluminum was not used. The polymerization proceeded to 3 ° C., and after 30 minutes, the polymerization was stopped, and then the polymerization solution was washed with hydrochloric acid water and the solvent was distilled off (100 mmHg, 80 ° C.), but no oligomer was obtained.

[0065]

Comparative Example 6 Polymerization was carried out in the same manner as in Example 2 except that dimethyltin oxide was used and tert-butyl chloride and trimethylaluminum were not used. The polymerization proceeded at 3 ° C., and after 30 minutes, the polymerization was stopped, and then the polymerization solution was washed with hydrochloric acid water and the solvent was distilled off (100 mmHg, 80 ° C.), but no oligomer was obtained.

[0066]

Example 3 350 ml of purified toluene and 50 ml of styrene (Wako Pure Chemical Industries, untreated) were charged into a glass polymerization vessel having an internal volume of 500 ml which had been sufficiently replaced with nitrogen, and bubbled with nitrogen gas for 5 minutes under ice cooling. After bubbling, while maintaining the system under nitrogen atmosphere, tert-butyl chloride 0.09m
l (concentration in the polymerization solution 2 mmol / liter) and a toluene solution of aluminoxane synthesized from triisobutylaluminum (hereinafter sometimes abbreviated as "IBA-O") (concentration in the polymerization solution 2 mmol / liter) were charged. Then, the polymerization was started. After initiation the temperature rose to 20 ° C. The polymerization was terminated after 10 minutes, and the polymerization was completely stopped with isobutyl alcohol. The polymerization solution was washed with hydrochloric acid water and the solvent was distilled off (100 mmHg, 80 ° C.) to give a typical cationic polymerization product, an oily oligomer 2.
4.4 g (73 g oligomer / mmol Al · hr) was obtained.

[0067]

Comparative Example 7 Polymerization was carried out in the same manner as in Example 3, except that methylaluminoxane was used and tert-butyl chloride was not used. Polymerization proceeded at 3 ° C. After 30 minutes, the polymerization was stopped. After washing the polymerization solution with hydrochloric acid, the solvent is distilled off (1
(00 mmHg, 80 ° C.), but no oligomer was obtained.

[0068]

Example 4 A glass polymerization vessel having an internal volume of 500 ml, which had been sufficiently replaced with nitrogen, was charged with 250 ml of purified toluene and 150 ml of 4-methylpentene-1 (hereinafter sometimes abbreviated as "4MP-1"). The mixture was bubbled with nitrogen gas for 5 minutes under ice cooling. After bubbling, while maintaining the system under a nitrogen atmosphere, 0.09 ml of tert-butyl chloride (concentration in the polymerization solution: 2 mmol / liter) and a toluene solution of aluminoxane synthesized from triisobutylaluminum (concentration in the polymerization solution: 2 mmol / liter) were added. Charge and start the polymerization. Immediately after the start, the temperature rose to 70 ° C.
After 2 minutes, the polymerization was terminated, and the polymerization was completely stopped with isobutyl alcohol. The polymerization solution was washed with hydrochloric acid water and the solvent was distilled off (100 mmHg, 80 ° C.) to give 80.4 g of an oily oligomer which is a typical cationic polymerization product.
(1206 g oligomer / mmolAl · hr) was obtained.

[0069]

Example 5 400 ml of purified toluene was charged into a glass polymerization vessel having an inner volume of 500 ml which had been sufficiently replaced with nitrogen, and propylene gas (100 liters / hr) was passed therethrough to
Propylene was fully saturated at 5 ° C. After that, 0.09 ml of tert-butyl chloride (concentration of 2 mmo in the polymerization solution)
(l / l) and a toluene solution of aluminoxane synthesized from triisobutylaluminum (concentration of 2 mmol / l in the polymerization solution) were charged to initiate polymerization. After the start, ice cooling was stopped and the bath was changed to a dry ice / isopropyl alcohol cooling bath in order to keep the temperature at 5 to 10 ° C. After the completion of the polymerization, propylene was stopped and the polymerization was completely stopped by isobutyl alcohol. The polymerization solution was washed with hydrochloric acid water and the solvent was distilled off (100 mmHg,
80.degree. C.) and 39.04 g (58.6 g oligomer / m) of an oily oligomer which is a typical product of cationic polymerization.
molAl.hr) was obtained.

[0070]

Example 6 400 ml of purified toluene was charged into a glass polymerization vessel having an internal volume of 500 ml which had been sufficiently replaced with nitrogen, and water 6
3 mg (3.5 mmol) was suspended. After that, trimethylaluminum (1 mmol / toluene ml) 2m
1 (concentration in polymerization solution: 5 mmol / liter) was added, and 0.22 ml of tert-butyl chloride (concentration in polymerization solution: 5 mmol / liter) was added to initiate polymerization. 1
After stirring at 40 ° C. at night, propylene was conducted to keep the temperature at about 10 ° C. and the polymerization was stopped in 30 minutes. The polymerization solution was washed with hydrochloric acid water, and the solvent was distilled off (100 mHg, 80
℃), 8.6g (8.6g oligomer / mmo
An oligomer of 1Al.hr) was obtained.

The above results are shown in Table 1.

[0072]

[Table 1]

Claims (6)

[Claims] 1. A cationic polymerization catalyst comprising a halogenated hydrocarbon [A] and an organoaluminum oxy compound [B]. 2. A cationic polymerization catalyst comprising [A] a halogenated hydrocarbon, [C] an organotin oxide, and [D] an organoaluminum compound. 3. A cationic polymerization catalyst comprising [A] a halogenated hydrocarbon, [D] an organoaluminum compound, and [E] water. 4. A method for cationically polymerizing an olefin, which comprises cationically polymerizing an olefin in the presence of the catalyst according to claim 1. 5. A method for cationically polymerizing an olefin, which comprises cationically polymerizing an olefin in the presence of the catalyst according to claim 2. 6. A method for cationically polymerizing an olefin, which comprises cationically polymerizing an olefin in the presence of the catalyst according to claim 3.