JP2001247609A - Method for producing addition polymerization catalyst and addition polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently producing an addition polymerization catalyst high in polymerization activity and an addition polymer. SOLUTION: The addition polymerization catalyst is produced by bringing (A), (B), and (C) into contact with each other, and the addition polymer is produced by using the said polymerization catalyst. In this method, (A) is an organic aluminum compound; (B) is one or more boron compounds selected from the group consisting of (B1) a boron compound described by the general formula: BQ1Q2Q3, (B2) a boron compound described by the general formula: G+(BQ1Q2Q3Q4)-, and (B3) a boron compound described by the general formula: (L-H)+(BQ1Q2Q3Q4)-, (wherein B is a boron atom; Q1 to Q4 are halogen atoms, hydrocarbon groups, hydrocarbon group halides, heterocyclic ring groups, substituent silyl groups, alkoxy groups, or 2-substituted amino groups, which may be the same as or different from each other; G+ is an inorganic, organic, or organometallic cation; L is a neutral Lewis base, and (L-H)+ is a Broensted acid), and (C) is a solid inorganic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an addition polymerization catalyst and a method for producing an addition polymer.

[0002]

2. Description of the Related Art An addition polymerizable monomer by a catalyst obtained by contacting a metallocene-based or non-metallocene-based transition metal complex as a catalyst component with an activator (promoter component) such as an organoaluminum compound. Polymerization methods are well known. However, transition metal complexes, which are the catalyst components of these catalysts, are difficult and expensive to synthesize, and it is desired to develop a catalyst that is inexpensive and can be easily synthesized.

On the other hand, it has long been known that polyethylene can be obtained by bringing alkylaluminum itself used as a cocatalyst into contact with ethylene. For example, Angew. Chem., Vol. 64, p. 323 (195)
2), Makromol. Chem., 193, 1283 (1992). Recently, the polymerization of ethylene and propylene with a catalyst combining alkylaluminum and a specific boron compound has been promoted by ACS Polymer Prep.
rints, Vol. 39, No. 2, 510 pages (1998)
Has been reported to.

A report on ethylene addition polymerization using a catalyst obtained by combining an aluminum complex having an amidinate ligand or a pyridinodiimine ligand with a specific boron compound is disclosed in, for example, J. Am. Chem. Soc., No. 119.
Volume, 8125 (1997), J. Am. Chem. So
c., Volume 120, 8277 (1998), Che.
m. Commun., p. 2523 (1998), International Patent Application WO 98/40421, U.S. Pat.
No. 777120 and U.S. Pat. No. 5,973,088 are known.

[0005] It is also known to polymerize addition polymerizable monomers with a catalyst having an organic aluminum compound supported on a carrier. For example, as an example of supporting on metal acetate, see JP-A-52-2.
No. 890, as an example supported on metal chloride, Polymer
Preprints, Japan, Vol. 46, p. 216 (1997)
), Polymer Preprints, Japan, Vol. 46, p. 1215 (1997).

[0006]

However, these addition polymerization catalysts have not always been satisfactory from the viewpoint of polymerization activity. In view of the above situation, an object of the present invention, that is, an object of the present invention, is to provide a catalyst for addition polymerization having high polymerization activity and a method for efficiently producing an addition polymer.

[0007]

The present invention provides the following (A):
A catalyst for addition polymerization obtained by contacting (B) and (C),
And a method for producing an addition polymer using the addition polymerization catalyst. (A) an organic aluminum compound (B) below (B1) ~ one or more boron compounds selected from (B3) (B1) general formula BQ ¹ Q ² Q ³ boron compound represented by (B2) formula G ⁺ ( ^{BQ 1 Q 2 Q 3 Q 4} ) - in the boron compound represented by (B3) formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4)
^- the boron compound represented (where, B is a boron atom, Q ¹ to Q ⁴ are a halogen atom, a hydrocarbon group, halogenated hydrocarbon group, a heterocyclic group,
A substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. G ⁺
Is an inorganic, organic or organometallic cation. L is a neutral Lewis base and (LH) ⁺ is a Bronsted acid. (C) Solid Inorganic Compound Hereinafter, the present invention will be described in detail.

[0008]

DETAILED DESCRIPTION OF THE INVENTION (A) Organoaluminum Compound The organoaluminum compound used in the present invention is Al-
Although it is an aluminum compound having a C bond and various compounds can be used, one or more aluminum compounds selected from the following (A1) to (A4) are preferable. (A1) the general formula _{R r Al (OR) o H} p X 1 organoaluminum compound represented by _q (A2) an organoaluminum compound represented by the general formula M ¹ AlR ₄ (A3) formula {-Al (R A) a cyclic aluminoxane having a structure represented by -O-｝ _j (A4) a general formula R ｛-Al (R) -O-｝ _k AlR ₂
Linear aluminoxane having a structure represented by the following formula (where R represents each independently a hydrocarbon group having 1 to 20 carbon atoms, X ¹ each independently represents a halogen atom, and M ¹ represents an alkali metal atom. R represents a number satisfying 0 <r ≦ 3, o represents a number satisfying 0 ≦ o <3, p represents a number satisfying 0 ≦ p <3, and q represents 0 ≦ q <.
Represents a number satisfying 3, and r + o + p + q = 3. j represents an integer of 2 or more, and k represents an integer of 1 or more. )

As the organoaluminum compound (A1), the following compounds can be exemplified. Formula _{R r Al (OR) 3-} r organic aluminum compound represented by (wherein, the carbon atoms R are each independently 1
-20, preferably 1-15, more preferably 1-8 hydrocarbon groups. r is 0 <r ≦ 3, preferably 1 ≦ r
Represents a number satisfying ≦ 3. ) General formula R _r AlX ¹ organoaluminum compound represented by the _3-r (wherein, R carbon atoms are each independently 1-2
It represents 0, preferably 1 to 15, more preferably 1 to 8 hydrocarbon groups, and X ¹ each independently represents a halogen atom. r represents a number satisfying 0 <r ≦ 3, preferably 0 <r <3. ) An organoaluminum compound represented by the general formula R _r AlH _3-r (wherein, R independently represents 1 to 2 carbon atoms)
0, preferably 1 to 15, more preferably 1 to 8 hydrocarbon groups. r is 0 <r ≦ 3, preferably 2 ≦ r <3
Represents a number that satisfies ) General formula _{R r Al (OR) o X} 1 organoaluminum compound represented by _q (where, 1 to 20 carbon atoms each R is independently, preferably 1 to 15, more preferably 1 to 8
And X ¹ each independently represents a halogen atom. r is a number satisfying 0 <r ≦ 3, and o is 0
Represents a number satisfying ≦ o <3, q represents a number satisfying 0 ≦ q <3, and r + o + q = 3. In the general formulas representing the above organoaluminum compounds, R is preferably each independently an alkyl group or an aryl group, and X ¹ is preferably each independently a chlorine atom or a bromine atom.

Specific examples of the above-mentioned organoaluminum compounds include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, trioctylaluminum and the like.
n-alkylaluminum; triisopropylaluminum, triisobutylaluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-
Methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2
Tri-branched alkyl aluminum such as -methylhexyl aluminum, tri-3-methylhexyl aluminum and tri-2-ethylhexyl aluminum; tricycloalkyl aluminum such as tricyclohexyl aluminum; triphenyl aluminum and tolyl aluminum Trialkenyl aluminum such as triisoprenyl aluminum; alkyl aluminum dialkoxide such as isobutyl aluminum dimethoxide, isobutyl aluminum diethoxide and isobutyl aluminum diisopropoxide; dialkyl such as diethyl aluminum ethoxide and dibutyl aluminum butoxide Aluminum alkoxide; ethyl aluminum sesquibutoxide, butyl aluminum sesquibutoxide Alkyl sesquichloride alkoxides such Kibutokishido; methyl aluminum bis (2,6-di -tert- butyl 4-methyl phenoxide), ethylaluminum bis (2,6-di -tert
-Butyl-4-methylphenoxide) or the like; a partially aryloxylated alkylaluminum such as the above-mentioned organoaluminum compound;
A partially alkoxylated alkylaluminum having an average composition of 5.

Specific examples of the organoaluminum compound include alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide; dimethyl aluminum chloride, diethyl aluminum chloride, dipropyl aluminum chloride, diisobutyl aluminum Dialkylaluminum halides such as chloride, dihexylaluminum chloride and butylaluminum bromide; methylaluminum dichloride, ethylaluminum dichloride,
Examples thereof include alkyl aluminum dihalides such as propyl aluminum dichloride, isobutyl aluminum dichloride, hexyl aluminum dichloride, octyl aluminum dichloride, and butyl aluminum dibromide.

Specific examples of the organoaluminum compound include dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride and diisobutylaluminum hydride; and other parts such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride. Alkylaluminium which has been hydrogenated.

Specific examples of the above-mentioned organoaluminum compound include partially aluminum-alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxycyclolide, butylaluminum butoxycyclolide and ethylaluminum ethoxypromide.

The organoaluminum compound (A2) is an organoaluminum compound represented by the general formula M ¹ AlR ₄ . Here, M ¹ represents an alkali metal atom. Such an alkali metal atom is preferably a lithium atom, a sodium atom or a potassium atom, and particularly preferably a lithium atom. Organoaluminum compound (A
Particularly preferred as 2) is LiAl (C ₂ H ₅ ) ₄ or LiAl (C ₇ H ₁₅ ) ₄ .

[0015] formula {-Al (R) -O-} cyclic aluminoxane having a structure represented by _j (A3), represented by the general formula R {-Al (R) -O-} k AlR 2 Specific examples of R in the linear aluminoxane having a structure (A4) include alkyl groups such as methyl group, ethyl group, normal propyl group, isopropyl group, normal butyl group, isobutyl group, normal pentyl group, and neopentyl group. can do. j is an integer of 2 or more;
k is an integer of 1 or more. Preferably, R is a methyl group or an isobutyl group, j is 2 to 40, and k is 1 to 40.

The above aluminoxane is made by various methods. The method is not particularly limited, and may be made according to a known method. For example, a solution prepared by dissolving a trialkylaluminum (for example, trimethylaluminum or the like) in a suitable organic solvent (such as a hydrocarbon such as benzene or an aliphatic hydrocarbon such as hexane) is prepared by contacting with water. Further, a method in which a trialkylaluminum (for example, trimethylaluminum or the like) is brought into contact with a metal salt (for example, copper sulfate hydrate or the like) containing water of crystallization can be exemplified. It is believed that the aluminoxane thus obtained is usually a mixture of (A3) and (A4).

As the organoaluminum compound used in the present invention, the above-mentioned organoaluminum compound (A
1), more preferably the above-mentioned organoaluminum compound, and among them, trialkylaluminum is particularly preferred, and most preferably trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, or tri-aluminum
n-octyl aluminum.

(B) Boron Compound In the present invention, the boron compound (B) includes (B1)
General formula BQ¹ Q^Two Q ^Three A boron compound represented by the formula (B
2) General formula G⁺ (BQ¹ Q^Two Q^Three Q^Four )^ー Represented by
Boron compound, (B3) General formula (LH)⁺ (BQ¹ 
Q^Two Q^Three Q^Four ) ^ー Selected from boron compounds represented by
One or more boron compounds are used.

In the boron compound (B1) represented by the general formula BQ ¹ Q ² Q ³ , B is a trivalent boron atom, and Q ^{1 to} Q ³ are a halogen atom, a hydrocarbon group or a halogen atom. Hydrocarbon group, heterocyclic group, substituted silyl group,
An alkoxy group or a disubstituted amino group, which may be the same or different. Q ^{1 to} Q ³ are preferably each independently a halogen atom, having 1 to 2 carbon atoms.
0 hydrocarbon group, halogenated hydrocarbon group having 1 to 20 carbon atoms, heterocyclic group having 1 to 20 carbon atoms, 1 carbon atom
To 20 substituted silyl groups, alkoxy groups having 1 to 20 carbon atoms or disubstituted amino groups having 2 to 20 carbon atoms, and more preferably Q ^{1 to} Q ³ are each independently a halogen atom or a carbon atom having 1 to 20 carbon atoms. 20 hydrocarbon groups, 1 carbon atom
To 20 halogenated hydrocarbon groups, or 1 to 1 carbon atoms
20 heterocyclic groups. More preferably, Q ^{1 to} Q ³
Is each independently a fluorinated hydrocarbon group having 1 to 20 carbon atoms containing at least one fluorine atom, and particularly preferably Q ^{1 to} Q ³ are each independently at least 1
It is a fluorinated aryl group having 6 to 20 carbon atoms including two fluorine atoms.

Specific examples of the compound (B1) include tris (pentafluorophenyl) borane, tris (2,3,
5,6-tetrafluorophenyl) borane, tris (2,3,4,5-tetrafluorophenyl) borane,
Tris (3,4,5-trifluorophenyl) borane,
Tris (2,3,4-trifluorophenyl) borane,
Phenylbis (pentafluorophenyl) borane and the like can be mentioned, and most preferred is tris (pentafluorophenyl) borane.

In the boron compound (B2) represented by the general formula G ⁺ (BQ ¹ Q ² Q ³ Q ⁴ ) ^- , G ⁺ is an inorganic compound;
An organic or organometallic cation, B is a boron atom in a trivalent valence state, and Q ^{1 to} Q ⁴ are (B)
Is the same as Q ¹ to Q ³ in 1).

General formula G⁺ (BQ¹ Q^Two Q^Three Q^Four )^- so
G in the compound represented⁺ Specific examples of the inorganic
Lithium cation, sodium cation,
Potassium cation, silver cation, etc.
On: ferrocenium cation, alkyl-substituted ferro
Cerium cations and the like
Rukyphosphonium cation, tetraarylphosphoni
Cation, tetraalkylammonium, trial
Killsulfonium cation, diaryliodonium cation
Thion, trialkylcarbenium cation, triary
Alkenyl cation. G⁺ age
And preferably a carbenium cation, particularly preferred
Is a triphenylcarbenium cation. (BQ
¹ Q^Two Q ^Three Q^Four )^- As the tetrakis (pentaflu
Orophenyl) borate, tetrakis (2,3,5,6)
-Tetrafluorophenyl) borate, tetrakis
(2,3,4,5-tetrafluorophenyl) volley
G, tetrakis (3,4,5-trifluorophenyl)
Borate, tetrakis (2,3,4-trifluorophen)
Nyl) borate, phenyl tris (pentafluorophene)
Nyl) borate, tetrakis (3,5-bistrifluoro)
Romethylphenyl) borate and the like.

Specific examples of these combinations include lithium tetrakis (3,5-bistrifluoromethylphenyl) borate, sodium tetrakis (3,5-bistrifluoromethylphenyl) borate and potassium tetrakis (3,5-bistrifluoromethylphenyl). Phenyl)
Borate, silver tetrakis (pentafluorophenyl) borate, ferrocenium tetrakis (pentafluorophenyl) borate, 1,1′-dimethylferrocenium tetrakis (pentafluorophenyl) borate, tetrabutylphosphonium tetrakis (pentafluorophenyl) borate, Tetraphenylphosphonium tetrakis (pentafluorophenyl) borate, tetramethylammonium tetrakis (pentafluorophenyl) borate, trimethylsulfonium tetrakis (pentafluorophenyl) borate, diphenyliodonium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluoro) Phenyl) borate, triphenylcarbeniumtetrakis (3,5-bistrif) (Fluoromethylphenyl) borate and the like, and most preferably, triphenylcarbeniumtetrakis (pentafluorophenyl) borate.

The formula (LH) ⁺ (BQ ¹ Q ² Q
³ Q ^{4) -} In the boron compound (B3) represented by, L is a neutral Lewis base, (L-H) ⁺ is a Bronsted acid, B is a trivalent valence state boron atom And Q ^{1 to} Q ⁴ represent Q in the compound (B1) described above.
Is the same as that of the ¹ ~Q ^3.

The general formula (LH) ⁺ (BQ ¹ Q ² Q ³ Q
^{4) -} Examples of Bronsted acid (L-H) ⁺ of the compound represented by trialkyl, N, N-dialkyl anilinium, dialkyl ammonium, triarylphosphonium and the like, Examples of (BQ ¹ Q ² Q ³ Q ⁴ ) ⁻ include the same as described above.

Specific examples of these combinations include triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, and tri ( n-butyl) ammonium tetrakis (3,5-bistrifluoromethylphenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, N, N
-Dimethylanilinium tetrakis (3,5-bistrifluoromethylphenyl) borate, diisopropylammonium tetrakis (pentafluorophenyl) borate, dicyclohexylammonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakis (pentafluorophenyl) borate,
Tri (methylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, tri (dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate and the like can be mentioned. Most preferably, tri (n-butyl) ammonium tetrakis (pentafluoro) is used. Phenyl) borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

The boron compound used in the present invention is preferably (B2) or (B3), particularly preferably triphenylcarbenium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) ) Borate or N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

(C) Solid Inorganic Compound The solid inorganic compound used in the present invention is an inorganic compound which is solid at normal temperature and normal pressure, and is at least one solid selected from the following (C1) to (C3). Inorganic compounds are preferred. (C1) Bronsted acid salt of a metal selected from Groups 1 to 16 of the Periodic Table of the Elements (C2) oxide of a metal or silicon selected from Groups 1 to 16 of the Periodic Table of the Elements (C3) layered Silicate compounds

The Bronsted acid salt of such a metal (C1)
Specific examples of the metal used for lithium, beryllium,
Sodium, magnesium, aluminum, potassium,
Calcium, scandium, titanium, vanadium,
Chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, cadmium, indium, bell, antimony, cesium, barium, Lanthanum, hafnium, tantalum, tungsten, rhenium, osnium, iridium, platinum, gold,
Mercury, thallium, lead, bismuth, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbinium, dysprosium, holmium,
Erbium, thulium, ytterbium, lutetium,
Thorium and the like, preferably a metal selected from Groups 1 to 3 and 6 to 16 of the periodic table of the element,
More preferably sodium, magnesium, manganese,
Iron, cobalt or nickel.

Examples of the Brönsted acid include hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid and the like.

The Bronsted acid salt of the metal (C1)
And more preferably a metal halide compound,
More preferably, halogenation represented by the following general formula (1)
It is a metal compound. M^Two _mX^Two _n (1) (where M^Two Is selected from Groups 1 to 16 of the Periodic Table of the Elements
X represents a metal atom represented by ^Two Represents a halogen atom. m is
Represents a number of 1 or more, and n is a product of valence number of metal atom and m.
Represents )

M ² in the general formula (1) represents a metal atom selected from Groups 1 to 16 of the Periodic Table of the Elements, preferably a metal atom selected from Groups 1 to 3 and 6 to 16 It is. Specific examples include lithium, beryllium, sodium, magnesium, aluminum, potassium, calcium, scandium, chromium, manganese, iron, cobalt, nickel, copper, zinc, Gallium, germanium, rubidium, strontium, yttrium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, bell, antimony, cesium, barium , Lanthanum, tungsten, rhenium, osnium, iridium, platinum, gold, mercury, thallium, lead, bismuth, polonium, francium, radium Atom, actium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbinium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, thorium, Examples include a protactium atom, a uranium atom, a neptunium and the like, and more preferably a sodium atom, a magnesium atom, a manganese atom, an iron atom, a cobalt atom or a nickel atom.

X ² in the above formula (1) represents a halogen atom, and specific examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a chlorine atom, a bromine atom or an iodine atom. .

Specific examples of the metal halide represented by the general formula (1) include zinc (II) fluoride, aluminum fluoride, antimony (III) fluoride, antimony (V) fluoride, and yttrium fluoride. , Iridium (I) fluoride, iridium (II) fluoride, iridium (III) fluoride, iridium (IV), iridium (V), iridium (VI), indium (III), Osmium (IV) fluoride, osmium (V) fluoride, osmium (VI) fluoride, cadmium fluoride,
Gadolinium (III) fluoride, potassium fluoride, gallium (III) fluoride, calcium fluoride, gold (II)
I), silver (I) fluoride, silver (II) fluoride, chromium (II) fluoride, chromium (III) fluoride, chromium (IV) fluoride,
Chromium (V), Chromium (VI), Cobalt (II), Cobalt (III), Samarium (II), Samarium (III), Mercury (I), Fluoride Mercury (II) fluoride, scandium fluoride, tin (II) fluoride, tin (IV), strontium fluoride, cesium fluoride, cerium (III), cerium (IV), thallium ( I), thallium (III) fluoride, tungsten (IV), tungsten (V), tungsten (VI), tantalum (III), tantalum (IV), tantalum (V) ), Thulium (III) fluoride, iron (II) fluoride, iron (III) fluoride, diiron pentafluoride, copper (I) fluoride, copper (II) fluoride, thorium (IV) fluoride, Sodium fluoride, lead (II) fluoride, lead (IV) fluoride, niofluoride (IV), niobium fluoride (V), nickel fluoride (II),
Neptunium fluoride (III), Neptunium fluoride (I
V), platinum fluoride (IV), platinum fluoride (V), platinum fluoride (VI), palladium fluoride (II), palladium fluoride (IV), barium fluoride, bismuth fluoride (III), fluorine fluoride Plutonium (III) fluoride, beryllium fluoride, holmium (III) fluoride, magnesium fluoride, manganese (II) fluoride, manganese (III) fluoride, manganese (IV) fluoride, molybdenum (II) fluoride, fluorine Molybdenum (III) fluoride, molybdenum (IV) fluoride, europium (II) fluoride, europium (III) fluoride, lanthanum fluoride, lithium fluoride, ruthenium (II) fluoride, ruthenium (III), fluorine Rubidium fluoride, rhenium fluoride (IV), rhenium fluoride (V), rhenium fluoride (V
I), rhenium fluoride (VII), rhodium fluoride (II
I), rhodium (IV) fluoride, rhodium (V) fluoride,
Metal fluorides such as rhodium (VI) fluoride;

Zinc chloride (I), zinc chloride (II), aluminum chloride, antimony chloride (III), antimony chloride (IV), yttrium chloride (III), iridium chloride (I), iridium chloride (II), iridium chloride (II
I), iridium (IV) chloride, indium (I) chloride,
Indium (II) chloride, indium (III) chloride, osmium (III) chloride, osmium (IV) chloride, osmium (V) chloride, cadmium (II) chloride, potassium chloride,
Gallium chloride (I), gallium chloride (II), gallium chloride (III), calcium chloride, gold chloride (I), gold chloride (I
II), gold dichloride, silver chloride, chromium (II) chloride, chromium (III) chloride, chromium (IV) chloride, cobalt (II) chloride,
Mercury (I) chloride, mercury (II) chloride, scandium chloride,
Tin (II) chloride, tin (IV) chloride, strontium chloride, cerium (III) chloride, cerium (IV) chloride, thallium (I), thallium (III) chloride, thallium dichloride, thallium trichloride, tungsten chloride ( II), tungsten (III) chloride, tungsten (IV) chloride, tungsten (V) chloride, tungsten (VI), tantalum (III) chloride, tantalum (IV) chloride, tantalum (V) chloride, iron (II) chloride , Iron (III) chloride, copper (I) chloride, copper (II) chloride, thorium (IV) chloride, sodium chloride, lead (II) chloride, lead (IV) chloride, niobium (II) chloride
I), niobium (IV) chloride, niobium (V) chloride, nickel (II) chloride, neodymium (II) chloride, neodymium (II) chloride
I), platinum (II) chloride, platinum (IV) chloride, platinum trichloride,
Palladium (II) chloride, bismuth (III) chloride, praseodymium (III) chloride, plutonium (III) chloride, plutonium (IV) chloride, beryllium chloride, magnesium chloride, manganese (II) chloride, molybdenum (II) chloride, molybdenum chloride (III), molybdenum (IV) chloride, molybdenum (V) chloride, europium (II) chloride, europium (III) chloride, lanthanum chloride, lithium chloride, ruthenium (III) chloride, rubidium chloride, rhenium chloride (II)
Metal chlorides such as I), rhenium (IV) chloride, rhenium (V), rhenium (VI), rhodium (I) chloride, rhodium (II) chloride and rhodium (III) chloride;

Zinc (II) bromide, aluminum bromide, antimony bromide, yttrium bromide, iridium (I) bromide, iridium (II) bromide, iridium (II) bromide
I), iridium (IV) bromide, indium (I) bromide,
Indium dibromide, indium (III) bromide, osmium (III) bromide, osmium (IV) bromide, cadmium bromide, potassium bromide, gallium bromide (I), gallium dibromide, gallium bromide ( III), calcium bromide, gold (I) bromide, gold (III) bromide, silver bromide, chromium (II) bromide,
Chromium (III) bromide, cobalt (II) bromide, mercury (I) bromide, mercury (II) bromide, scandium bromide, tin (II) bromide, tin (IV) bromide, strontium bromide, Cesium bromide, cerium (III) bromide, thallium (I) bromide,
Thallium (III) bromide, tungsten (II) bromide, tungsten (III) bromide, tungsten (IV) bromide (IV), tungsten (V) bromide, tungsten (VI) bromide, tantalum (III) bromide, odor Tantalum (IV) bromide, tantalum bromide (V), iron (II) bromide, iron (III) bromide, ferrous bromobromide,
Copper (I) bromide, copper (II) bromide, thorium (IV) bromide, sodium bromide, lead (II) bromide, niobium (III) bromide, niobium (IV) bromide, niobium bromide ( V), nickel bromide (I
I), platinum (II) bromide, platinum (IV) bromide, platinum tribromide,
Palladium (II) bromide, barium bromide, bismuth bromide,
Plutonium (III) bromide, beryllium bromide, magnesium bromide, manganese (II) bromide, molybdenum bromide (I
I), molybdenum (III) bromide, molybdenum (IV) bromide,
Europium (II) bromide, Europium (III) bromide,
Lanthanum bromide, lithium bromide, ruthenium (II) bromide,
Metal bromides such as ruthenium (III) bromide, rubidium bromide, rhenium (III) bromide, rhenium (IV) bromide, rhenium (V), rhodium (II) bromide and rhodium (III) bromide ;

Zinc (II) iodide, aluminum iodide,
Antimony tetraiodide, antimony iodide (III), yttrium iodide, iridium iodide (I), iridium iodide (II), iridium iodide (III), iridium iodide (IV), indium iodide (I ), Indium (III) iodide, uranium (III) iodide, uranium (IV) iodide, osmium (I) iodide, osmium (II) iodide, osmium (III) iodide, cadmium iodide, iodide Potassium, gallium (I) iodide, gallium (III) iodide, calcium iodide, gold (I) iodide,
Gold (III) iodide, silver iodide, chromium (II) iodide, chromium (III) iodide, cobalt (I) iodide, cobalt (III) iodide, mercury iodide (I), mercury iodide ( I
I), scandium iodide, tin (II) iodide, tin (IV) iodide, strontium iodide, cesium iodide,
Cerium (II) iodide, cerium (III) iodide, thallium (I) iodide, thallium (III) iodide, tungsten (II) iodide, tungsten (III) iodide, tungsten (IV) iodide, iodine Tungsten (V), tungsten (VI), tantalum (IV), tantalum (V), iron (II), iron (II)
I), ferric octiodide, copper (I) iodide, copper iodide (I
I), thorium (IV) iodide, sodium iodide, lead (II) iodide, niobium (III) iodide, niobium (IV) iodide, nickel (II) iodide, neptunium (III) iodide, iodine Neptunium (IV), platinum iodide (I
I), platinum (IV) iodide, platinum triiodide, palladium (II) iodide, barium iodide, bismuth iodide (II
I), plutonium (III) iodide, beryllium iodide,
Magnesium iodide, manganese iodide (II), molybdenum iodide (II), molybdenum iodide (III), molybdenum iodide (IV), europium iodide (II), europium iodide (III), lanthanum iodide, Lithium iodide, ruthenium (II) iodide, ruthenium iodide (II
Examples of metal iodides include I), rubidium iodide, rhenium (III) iodide, rhenium (IV) iodide, rhenium iodide (V), rhodium (II) iodide, and rhodium (III) iodide. Can be. Particularly preferred as the Bronsted acid salt of the metal (C1) is sodium chloride, sodium iodide, magnesium chloride, manganese chloride (I
I), iron (II) chloride, or nickel (II) bromide.

The metals selected from Groups 1 to 16 of the periodic table of the elements in the metal or silicon oxide (C2) are the same as those described in the above (C1). Specific examples of the metal oxide in the metal or silicon oxide (C2) include zinc oxide, aluminum oxide, antimony (III) oxide, diantimony tetroxide, antimony (V) oxide, and ytterbium oxide (I
I), ytterbium (III) oxide, yttrium oxide,
Yttrium aluminum oxide, yttrium iron oxide,
Iridium (III) oxide, Iridium (IV) oxide, Indium (I) oxide, Indium (II) oxide, Indium (III) oxide, Erbium (III) oxide, Osmium (IV) oxide, Osmium (VIII), Cadmium oxide (II), gadolinium (III) oxide, potassium oxide,
Gallium (I) oxide, gallium (III) oxide, calcium oxide, gold oxide, gold (III) oxide, silver (I) oxide, silver monoxide, silver (III) oxide, trisilver monoxide, chromium oxide (I
I), chromium (III) oxide, chromium (IV) oxide, chromium (V) oxide, chromium (VI) oxide, cobalt (II) oxide, cobalt (III) oxide, cobalt (IV) oxide, tricobalt tetroxide, Cobalt (III) oxide Cobalt (II), samarium (III) oxide, zirconium (II) oxide, zirconium (IV) oxide, mercury (I), mercury (II) oxide, scandium oxide, tin (II) oxide, oxidation Tin (IV), strontium oxide, cesium oxide, cerium oxide (II
I), cerium oxide (IV), thallium oxide (I), thallium oxide (III), tetrathallium trioxide, tungsten oxide (IV), tungsten oxide (VI), tantalum oxide (I
I), tantalum oxide (IV), tantalum oxide (V), titanium oxide (II), titanium oxide (III), titanium oxide (I
V), iron (II) oxide, iron (III) oxide, triiron tetroxide, iron (IV) oxide, terbinium (III) oxide, terbinium (IV) oxide, copper (I) oxide, copper (II) oxide, Thorium (IV) oxide, sodium oxide, lead (II) oxide, lead oxide (I
V), trilead tetroxide, dilead trioxide, niobium oxide (II), niobium oxide (IV), niobium oxide (V), nickel oxide (I
I), dimanganese (III) manganese (II), neodymium (III), platinum (II) oxide, platinum (IV) oxide, triplatinum tetroxide, vanadium (II) oxide, vanadium (III) oxide, oxidation Vanadium (IV), vanadium (V) oxide, hafnium (IV) oxide, palladium oxide (I
I), palladium (IV) oxide, dipalladium trioxide, barium oxide, bismuth (III) oxide, bismuth oxide (I
V), bismuth oxide (V), arsenic oxide, beryllium oxide, boron oxide, magnesium oxide, manganese oxide (I
I), manganese oxide (III), manganese oxide (IV), manganese oxide (VII), trimanganese tetroxide, pentamanganese pentoxide, manganese (IV) oxide barium, molybdenum oxide (I
I), molybdenum (III) oxide, molybdenum (IV) oxide,
Molybdenum (V) oxide, molybdenum (VI) oxide, europium (II) oxide, europium (III) oxide, trieuropium tetroxide, lanthanum oxide, lithium oxide, lutetium (III) oxide, ruthenium oxide (IV), ruthenium oxide ( VIII), rubidium oxide, rhenium oxide (II
I), rhenium (IV) oxide, rhenium (VI), rhenium (VII), rhodium (III), rhodium (IV), calcium aluminum dioxide, potassium iron (III) dioxide, silica, germanium dioxide, dioxide Selenium, potassium thallium (III) dioxide, lithium thallium (III) dioxide, tellurium dioxide, sodium aluminum dioxide, sodium indium (III) dioxide,
Sodium iron (III) dioxide, dipotassium lead (I
I), disodium lead (II), lithium aluminum dioxide, lithium indium (III), lithium gallium (III), lithium iron dioxide (II)
I), indium (III) gallium (III), potassium niobium trioxide (V), silver antimony trioxide (V),
Indium trilithium trioxide, calcium tritin (IV) oxide, dipotassium tin (IV) oxide, calcium aluminum tetroxide, calcium aluminum (II) tetroxide, trisodium bismuth tetroxide (V), tin tetroxide (IV) dicalcium, strontium diammoxide, strontium diindium (III) tetroxide, tetrasodium titanium tetroxide (IV), diiron (II) titanium tetroxide (IV), dibarium titanium tetroxide (IV) , Dialuminum iron tetroxide, copper (II) tetroxide, bismuth (III), lead tetroxide (IV) dicalcium, lead tetroxide (II) diiron (II)
I), dibarium lead (IV) oxide, digallium tetroxide (I
II) calcium, barium dioxide (III) barium,
Barium diiron (III) tetroxide, barium tetroxide, beryllium tetroxide, magnesium tetroxide, magnesium tetroxide (III), magnesium tetroxide (III), titanium pentoxide (IV ) Diiron (III), diselenium pentoxide, dititanium pentoxide (dipotassium), ditellurium pentoxide, diarsenic pentoxide, tricalcium dialuminum pentaoxide, octalithium pentoxide (IV), octahedral Oxides such as potassium acid and sodium octaborate can be exemplified.

The oxide (C2) is preferably magnesium oxide, aluminum oxide, silica, triiron tetroxide, titanium (IV) oxide, zirconium (IV) oxide or manganese oxide, particularly preferably silica or quaternary oxide. It is ferric oxide.

The oxide (C2) may be used alone or as a composite or a mixture containing the oxide. Moreover, a hydroxyl group may be attached to the surface. Such composites or mixtures include natural or synthetic zeolites, silica-manganese oxide, silica-aluminum oxide, silica-titanium oxide, silica-vanadium oxide, silica-titanium oxide-magnesium oxide, and the like.

In general, the layered silicate compound (C3) is composed of SiO ₄ tetrahedrons connected at three vertices to form a two-dimensional sheet, which is combined with other ions (ions of aluminum, magnesium, iron, etc.). It overlaps and becomes a crystal having a layered structure, and is generally called a clay mineral belonging to phyllosilicate.

Specific examples of the layered silicate compound include kaolin minerals such as kaolinite, naclite, dickite, metahaloisite, halloysite, etc .; antigolite, chrysotile, amesite, clonsteadite,
Serpentine minerals such as chamosite; smectites such as montmorillonite, beidellite, nontronite, saponite, hectorite; muscovite, paragonite, sericite, dorsaldonite, sea chlorite, phlogopite, fluorphlogopite,
Mica clay minerals such as biotite and scale mica; pyrophyllite, talc; vermiculite; chlorite such as pennin, cocoaite, and sudolite; colensite; tosdite; It may be done. Among these, smectites, mica clay minerals and talc are more preferred.

The layered silicate compound may be subjected to a chemical treatment. As the chemical treatment, a surface treatment for removing impurities adhering to the surface, or a treatment for introducing a bulky guest compound between the layers and expanding the layers may be performed. For example, the lipophilic treatment may be performed so as to be easily dispersed and / or swelled in an organic solvent such as an aliphatic hydrocarbon solvent such as hexane or heptane or an aromatic hydrocarbon solvent such as toluene or xylene. The lipophilic treatment is generally a treatment of exchanging exchangeable cations existing between layers of the layered silicate compound with organic cations or the like. Examples of the organic cation include an organic ammonium ion and an organic complex cation. Among them, a quaternary ammonium ion is particularly often used.

Particularly preferred as solid inorganic compounds used in the present invention are sodium chloride, sodium iodide, magnesium chloride, manganese (II) chloride, iron (II) chloride, nickel (II) bromide, silica, tetroxide. Three iron, montmorillonite or synthetic saponite.

The solid inorganic compound used in the present invention may be used as it is, or may be subjected to a treatment such as pulverization (grinding) using a ball mill or agate mortar, or sieving.
Further, they may be used alone or in combination of two or more.

In using the catalyst for addition polymerization of the present invention, the amount of the organoaluminum compound (A) used is usually from 10 ^-6 to 10 in terms of the concentration of the organoaluminum compound (A) in the polymerization system.
It can be selected over a wide range such as mol / l. Preferably it is in the range of 10 ^{-5 to} 1 mol / l.

The amount of the boron compound (B) used is such that the molar ratio [(A) / (B)] to the organoaluminum compound (A) is usually in the range of 0.1 to 10,000, preferably 0.5 to 5
000 is used.

The amount of the solid inorganic compound (C) used is such that the concentration of the solid inorganic compound (C) in the polymerization system is usually 0.001.
It can be selected over a wide range such as from mg / l to 1000 g / l. Preferably it is in the range of 0.01 mg / l to 100 g / l.

As a method of supplying each component to the polymerization tank,
For example, it is supplied in an inert gas such as nitrogen or argon without moisture. The catalyst components (A), (B) and (C) may be supplied individually or may be supplied in contact with each other in advance.

The polymerization temperature is usually from -80 to 300 ° C, preferably from -40 to 280 ° C.
More preferably, it is 20 to 250 ° C. The polymerization pressure is not particularly limited, but is preferably about normal pressure to about 150 atm from the viewpoint of industrial and economical use. The polymerization time is generally appropriately determined depending on the kind of the target polymer and the reaction apparatus, but can usually range from 1 minute to 40 hours.

The polymerization process may be either a continuous type or a batch type. Slurry polymerization or solvent polymerization using a hydrocarbon solvent such as propane, pentane, hexane, heptane, octane, toluene, xylene or a halogenated aromatic hydrocarbon solvent such as chlorobenzene or o-dichlorobenzene, or liquid phase polymerization without solvent Alternatively, gas phase polymerization is also possible.

Furthermore, in the present invention, the usual Ziggler
An electron donor, which is the third component used in the Natta catalyst system, can also be used.

The method for producing an addition polymer of the present invention is a method for producing an addition polymer using the above-mentioned catalyst for addition polymerization.
Preferably, using the above-described addition polymerization catalyst, an addition polymerizable monomer is homopolymerized or an addition polymer production method in which an addition polymerizable monomer is copolymerized with another addition polymerizable monomer. is there.

The addition polymerizable monomer used in the production method of the addition polymer of the present invention is selected from olefins, vinyl esters, ethylenically unsaturated carboxylic acids or their esters, and alkenyl aromatic hydrocarbons. And olefins are particularly preferred.

The olefins may have 2 carbon atoms.
Up to 20 olefins, particularly ethylene, α-olefins having 3 to 20 carbon atoms, diolefins having 4 to 20 carbon atoms, and the like, and two or more monomers can be used at the same time. . Specific examples of olefins include ethylene, propylene, 1-butene, 1
-Linear olefins such as pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,
3-methyl-1-butene, 3-methyl-1-pentene,
Examples include branched olefins such as 4-methyl-1-pentene and vinylcyclohexane, but the present invention is not limited to the above compounds.

The vinyl esters include vinyl acetate, vinyl propionate, vinyl benzoate and the like.

The ethylenically unsaturated carboxylic acids or esters thereof are preferably acrylate or methacrylate compounds. Specific examples of the acrylate compound include methyl acrylate, and compounds in which the methyl is changed to ethyl, normal propyl, isopropyl, normal butyl, isobutyl, tert-butyl, and the like, and a methacrylic acid ester compound As a specific example of methyl methacrylate or methyl methacrylate, ethyl, normal propyl, isopropyl, normal butyl, isobutyl, tert-
Compounds changed to butyl can be exemplified.

The alkenyl aromatic hydrocarbon includes
Alkenyl compounds having an aromatic hydrocarbon group having 6 to 25 carbon atoms are preferred. Specific examples of the aromatic hydrocarbon group having 6 to 25 carbon atoms include phenyl, tolyl, xylyl, tertiary butylphenyl, vinylphenyl, naphthyl, phenanthryl, and anthracenyl groups. Can be. Preferred are a phenyl group, a tolyl group, a xylyl group, a tertiary butylphenyl group, a vinylphenyl group, and a naphthyl group. Specific examples of such alkenyl aromatic hydrocarbons include alkenylbenzenes such as styrene, 2-phenylpropylene, and 2-phenylbutene; p-methylstyrene, m-methylstyrene, o-methylstyrene, p-ethylstyrene, and m-methylstyrene. Ethyl styrene, o-ethyl styrene, 2,4-dimethyl styrene,
Alkylstyrenes such as 2,5-dimethylstyrene, 3,4-dimethylstyrene, 3,5-dimethylstyrene, 3-methyl-5-ethylstyrene, p-tertiary butylstyrene, and p-secondary butylstyrene; Examples thereof include vinyl naphthalene such as 1-vinyl naphthalene; divinyl benzene such as p-shaped vinyl benzene;

More preferably, the addition polymerizable monomer is ethylene or an α-olefin having 3 to 20 carbon atoms, or a mixture of two or more selected from α-olefins having 3 to 20 carbon atoms and ethylene. It is.

The addition polymerization catalyst of the present invention is preferably used as an olefin polymerization catalyst, and the method for producing an addition polymer of the present invention is suitable for producing an olefin polymer. The copolymer produced by the production method of the addition polymer of the present invention is preferably a copolymer of ethylene and an α-olefin (in particular, a linear low-density polyethylene (LLDPE) is preferable), and constitutes the copolymer. Specific examples of the combination of the monomers include ethylene and propylene, ethylene and 1-butene, ethylene and 1-hexene, ethylene and 1-octene, and the like. However, the present invention should not be limited to these combinations. is not.

Further, in order to adjust the molecular weight of the addition polymer of the present invention, a chain transfer agent such as hydrogen or a silane compound may be added.

[0062]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Examples, but the scope of the present invention is not limited to Examples. In addition, the measurement value of each item in an Example was measured by the following method.

(1) Intrinsic viscosity ([η]: dl / g) Measured at 135 ° C. in tetralin using an Ubbelohde viscometer.

(2) Weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw / Mn) Measured by gel permeation chromatography (GPC) under the following conditions. The calibration curve was prepared using standard polystyrene. The molecular weight distribution is expressed by the ratio (Mw / M) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
n). Model Millipore Waters 150CV type Column Shodex M / S 80 Measurement temperature 145 ° C, solvent orthodichlorobenzene, sample concentration 5mg / 8ml

(3) Melting point (Tm: ° C.) It was measured under the following conditions using SSC-5200 manufactured by Hattori Seiko. Heating: 40 ° C to 150 ° C (10 ° C / min), hold for 5 minutes Cooling: 150 ° C to 40 ° C (5 ° C / min), hold for 10 minutes Measurement: 40 ° C to 160 ° C (5 ° C / min. )

(4) Composition of Comonomer Unit in Copolymer Using AM400 or AC250 manufactured by Bruker,
¹³ C-NMR was measured under the following conditions, and JC Randall,
J. Macro. Sci.-Rev. Macromol. Chem. Phys., C29
(2 & 3), page 201 (1989). Solvent: o-dichlorobenzene / heavy benzene = 4/1 (volume ratio) Concentration: 200 mg / 3 ml Temperature: 135 ° C.

In the following examples, each reagent used at the time of polymerization is as follows.・ Triisobutyl aluminum: Tosoh Akzo Co., Ltd.
A commercially available product, triisobutylaluminum, was diluted with toluene and used as a 1M solution. -Triphenylcarbenium tetrakis (pentafluorophenyl) borate: A commercially available product manufactured by Tosoh Akzo Co., Ltd., which is obtained by diluting triphenylcarbenium tetrakis (pentafluorophenyl) borate with toluene to 0.005.
M used as a solution.・ Manganese (II) chloride (commercially available from Aldrich, purity 9)
9.999%), iron (II) chloride (commercially available from Kanto Chemical Co., Ltd., deer special grade), magnesium chloride (commercially available from Junsei Chemical Co., Ltd., purity 99.99%), nickel (II) bromide (Stre
m Chemicals commercial product, purity 99%), sodium chloride (Kanto Chemical Co., Ltd. commercial, deer special grade), and sodium iodide (Aldrich commercial product, purity 99.999)
%) Used what was ground using an agate mortar under a nitrogen atmosphere. Silica (commercially available from Devison, SMR
49-2903, average particle size 50 μm), montmorillonite (commercially available from Kunimine Industries, Kunipia-F), synthetic saponite (commercially available from Kunimine Industries, Smecton-S)
A) used what was ground using the agate mortar under nitrogen atmosphere. Commercially available iron oxide (II, III) (commercially available from Aldrich, purity 98%) was used as it was.

Example 1 400 ml of a stirring stainless steel autoclave was replaced with argon, 200 ml of purified toluene was charged, and the inside of the autoclave was heated to 35 ° C.
Was adjusted to Triisobutylaluminum 1ml (1m
mol) and 14 mg of manganese (II) chloride. 35
After stirring at 3 ° C. for 3 minutes, 1 ml of triphenylcarbenium tetrakis (pentafluorophenyl) borate (5 μm
ol) and stirred. At this time, the molar ratio [Al] / [B] between the aluminum atom and the boron atom was 200. Feed ethylene gas of 1.0MPa, 40 ℃
For 60 minutes. During this time, ethylene gas was continuously fed so that the pressure in the system became constant. Thereafter, 10 ml of ethanol was injected under pressure to terminate the polymerization. Unreacted ethylene gas is purged and the contents of the autoclave are reduced to 3N.
The solution was poured into 400 ml of ethanol to which 20 ml of hydrochloric acid had been added, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 4 hours. As a result, 7.0 g of polyethylene was obtained. The intrinsic viscosity ([η]) of the obtained polyethylene was 1.
39 dl / g and a weight average molecular weight (Mw) of 756
00, molecular weight distribution (Mw / Mn) 2.0, melting point (T
m) was 136 ° C.

Example 2 Example 1 was repeated, except that the amount of manganese (II) chloride was changed to 9.5 mg of iron (II) chloride. As a result, 2.07 g of polyethylene was obtained. The weight average molecular weight (Mw) of the obtained polyethylene was 7,540.
0, molecular weight distribution (Mw / Mn) is 1.6, melting point (Tm)
Was 136 ° C.

Example 3 Example 1 was repeated, except that manganese (II) chloride was changed to 11.7 mg of magnesium chloride. As a result, 5.24 g of polyethylene was obtained.
The weight average molecular weight (Mw) of the obtained polyethylene is 75.
800, molecular weight distribution (Mw / Mn) 1.7, melting point (T
m) was 136 ° C.

[Example 4] The procedure was carried out in the same manner as in Example 1, except that manganese (II) chloride was changed to 16.1 mg of nickel (II) bromide. As a result, 1.75 g of polyethylene was obtained.
The weight average molecular weight (Mw) of the obtained polyethylene was 78.
500, molecular weight distribution (Mw / Mn) 1.6, melting point (T
m) was 136 ° C.

Example 5 The procedure was performed in the same manner as in Example 1, except that manganese (II) chloride was changed to 11.8 mg of sodium chloride.
As a result, 0.48 g of polyethylene was obtained. The weight average molecular weight (Mw) of the obtained polyethylene was 1340.
00, molecular weight distribution (Mw / Mn) 2.6, melting point (T
m) was 136 ° C.

Example 6 Example 1 was repeated except that manganese (II) chloride was changed to 13.5 mg of sodium iodide. As a result, 0.63 g of polyethylene was obtained.
The weight average molecular weight (Mw) of the obtained polyethylene was 74.
300, molecular weight distribution (Mw / Mn) 1.6, melting point (T
m) was 136 ° C.

Example 7 400 ml of a stirring stainless steel autoclave was replaced with argon, 200 ml of purified toluene was charged, and the inside of the autoclave was heated to 25 ° C.
Was adjusted to Triisobutylaluminum 1ml (1m
mol) and 12 mg of silica. After stirring at 35 ° C. for 3 minutes, 1 ml (5 μmol) of triphenylcarbenium tetrakis (pentafluorophenyl) borate was added and stirred. At this time, the molar ratio [Al] / [B] between the aluminum atom and the boron atom was 200. After 30 minutes, ethylene gas of 1.0 MPa was fed, and 40 ° C.
For 60 minutes. During this time, ethylene gas was continuously fed so that the pressure in the system became constant. Thereafter, 10 ml of ethanol was injected under pressure to terminate the polymerization. Unreacted ethylene gas is purged and the contents of the autoclave are reduced to 3N.
The solution was poured into 400 ml of ethanol to which 20 ml of hydrochloric acid had been added, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 4 hours. As a result, 8.39 g of polyethylene was obtained. The intrinsic viscosity ([η]) of the obtained polyethylene is 1.32 dl / g, and the weight average molecular weight (Mw) is 7
4900, molecular weight distribution (Mw / Mn) was 1.9, and melting point (Tm) was 136 ° C.

Example 8 The same procedure as in Example 1 was carried out, except that the silica was changed to 13 mg of iron oxide in Example 7, and the procedure was carried out. As a result, 1.87 g of polyethylene was obtained. The weight average molecular weight (Mw) of the obtained polyethylene was 82250, and the molecular weight distribution (Mw / M
n) was 2.1 and the melting point (Tm) was 136 ° C.

Example 9 Example 1 was repeated except that the silica was changed to 15 mg of montmorillonite.
The same apparatus and the same procedure were used. As a result, 7.
75 g of polyethylene were obtained. The intrinsic viscosity ([η]) of the obtained polyethylene is 1.39 dl / g, the weight average molecular weight (Mw) is 74220, and the molecular weight distribution (Mw)
/ Mn) was 1.8 and the melting point (Tm) was 136 ° C.

[Example 10] The procedure was performed in the same manner as in Example 1, except that the silica was changed to 13.6 mg of synthetic saponite. As a result, 2.69 g of polyethylene was obtained. The weight average molecular weight (Mw) of the obtained polyethylene was 72750, the molecular weight distribution (Mw / Mn) was 1.8, and the melting point (Tm) was 13
6 ° C.

Example 11 A 400 ml stirred autoclave made of stainless steel was replaced with argon, and 100 ml of purified toluene, 100 ml of 1-hexene, and 1.0 MPa of ethylene gas were charged.
Adjusted to ° C. Triisobutylaluminum 1 ml (1
mmol) and 27.5 mg of manganese (II) chloride. After stirring at 40 ° C. for 3 minutes, triphenylcarbenium tetrakis (pentafluorophenyl) borate 3 ml
(15 μmol) and stirred. At this time, the molar ratio [Al] / [B] between the aluminum atom and the boron atom is 6
It was 7. A 1.0 MPa ethylene gas was fed, and polymerization was performed at 40 ° C. for 60 minutes. During this time, ethylene gas was continuously fed so that the pressure in the system became constant. Thereafter, 10 ml of ethanol was added to terminate the polymerization. Unreacted ethylene gas is purged and the contents of the autoclave are reduced to 3N.
The solution was poured into 400 ml of ethanol to which 20 ml of hydrochloric acid had been added, and the precipitated polymer was separated by filtration and dried at 80 ° C. for about 4 hours. As a result, 1.36 g of a copolymer was obtained. The intrinsic viscosity ([η]) of the obtained copolymer is 1.1.
5 dl / g and a weight average molecular weight (Mw) of 5740
0, molecular weight distribution (Mw / Mn) was 1.7. The 1-hexene unit composition in the copolymer was 0.11, and the melting point (Tm) was 69 ° C.

Example 12 Example 12 was repeated, except that manganese (II) chloride was changed to 33 mg of silica. As a result, 4.10 g of a copolymer was obtained. The intrinsic viscosity ([η]) of the obtained copolymer was 1.05 dl / g, the weight average molecular weight (Mw) was 61580, and the molecular weight distribution (Mw / Mn) was 1.7. 1- in the copolymer
Hexene unit composition: 0.11, melting point (Tm): 82
° C.

[Comparative Example 1] 400 ml of a stirring stainless steel autoclave was replaced with argon, 200 ml of purified toluene was charged, and the inside of the autoclave was heated to 35 ° C.
Was adjusted to Triisobutylaluminum 1ml (1m
mol) and 13 mg of manganese (II) chloride. 1.
An ethylene gas of 0 MPa was fed, and maintained at 40 ° C. for 60 minutes. Thereafter, 10 ml of ethanol was injected.
Unreacted ethylene gas was purged, and the contents of the autoclave were replaced with 400 ml of ethanol containing 20 ml of 3N hydrochloric acid.
l. As a result, polyethylene was not obtained.

[Comparative Example 2] A 400 ml stirring type stainless steel autoclave was replaced with argon, 200 ml of purified toluene was charged, and the inside of the autoclave was heated to 35 ° C.
Was adjusted to Manganese (II) chloride 10mg and triphenylcarbenium tetrakis (pentafluorophenyl)
1 ml (5 μmol) of borate was added. 1.0MPa
Was fed and kept at 40 ° C. for 60 minutes. Thereafter, 10 ml of ethanol was injected. Unreacted ethylene gas is purged and the contents of the autoclave are reduced to 3N.
The solution was added to 400 ml of ethanol to which 20 ml of hydrochloric acid had been added. As a result, polyethylene was not obtained.

[0082]

As described in detail above, according to the present invention,
A catalyst for addition polymerization showing high polymerization activity and a method for efficiently producing an addition polymer are provided. According to the present invention, a conventional solid catalyst component (titanium atom,
A high polymerization activity can be exhibited without using a transition metal compound such as a metallocene complex or a solid catalyst component having a halogen atom and an electron donor as essential components, and a higher molecular weight olefin polymer can be produced. Therefore, the value of the present invention is very large.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J015 DA04 DA05 4J028 AA00A AA01A AB00A AB01A AC00A AC01A AC31A AC41A AC45A AC49A AC50A BA00A BA02B BB00A BB02B BC12B BC13B BC15B BC16B BC17B BC18 EB25 EB02 EB02 BC19 EB02 BC19 EB02 EB25 EB26 EC01 EC02 GA01 GA04 GA06 GA19

Claims (9)

[Claims] 1. An addition polymerization catalyst comprising the following components (A), (B) and (C): (A) an organic aluminum compound (B) below (B1) ~ one or more boron compounds selected from (B3) (B1) general formula BQ ¹ Q ² Q ³ boron compound represented by (B2) formula G ⁺ ( ^{BQ 1 Q 2 Q 3 Q 4} ) - in the boron compound represented by (B3) formula ^{(L-H) + (BQ} 1 Q 2 Q 3 Q 4)
^- the boron compound represented (where, B is a boron atom, Q ¹ to Q ⁴ are a halogen atom, a hydrocarbon group, halogenated hydrocarbon group, a heterocyclic group,
A substituted silyl group, an alkoxy group or a disubstituted amino group, which may be the same or different. G ⁺
Is an inorganic, organic or organometallic cation. L is a neutral Lewis base and (LH) ⁺ is a Bronsted acid. (C) Solid inorganic compound 2. The method according to claim 1, wherein the organoaluminum compound has the following (A1)
The catalyst for addition polymerization according to claim 1, which is one or more aluminum compounds selected from the group consisting of (A4) to (A4). (A1) the general formula _{R r Al (OR) o H} p X 1 organoaluminum compound represented by _q (A2) an organoaluminum compound represented by the general formula M ¹ AlR ₄ (A3) formula {-Al (R A) a cyclic aluminoxane having a structure represented by -O-｝ _j (A4) a general formula R ｛-Al (R) -O-｝ _k AlR ₂
Linear aluminoxane having a structure represented by the following formula (where R represents each independently a hydrocarbon group having 1 to 20 carbon atoms, X ¹ each independently represents a halogen atom, and M ¹ represents an alkali metal atom. R represents a number satisfying 0 <r ≦ 3, o represents a number satisfying 0 ≦ o <3, p represents a number satisfying 0 ≦ p <3, and q represents 0 ≦ q <.
Represents a number satisfying 3, and r + o + p + q = 3. j represents an integer of 2 or more, and k represents an integer of 1 or more. ) 3. The solid inorganic compound according to any one of the following (C1) to (C)
3. The catalyst for addition polymerization according to claim 1, which is at least one solid selected from 3). (C1) Bronsted acid salt of a metal selected from Groups 1 to 16 of the Periodic Table of the Elements (C2) oxide of a metal or silicon selected from Groups 1 to 16 of the Periodic Table of the Elements (C3) layered Silicate compounds 4. A solid inorganic compound represented by the following general formula (1):
The metal halide according to claim 1 or 2,
Catalyst for addition polymerization. M^Two _mX^Two _n (1) (where M^Two Is selected from Groups 1 to 16 of the Periodic Table of the Elements
X represents a metal atom represented by ^Two Represents a halogen atom. m is
Represents a number of 1 or more, and n is a product of valence number of metal atom and m.
Represents ) 5. The catalyst for addition polymerization according to claim 1, wherein the solid inorganic compound is an oxide of a metal or silicon selected from Groups 1 to 16 of the periodic table of the elements. 6. The catalyst for addition polymerization according to claim 1, wherein the solid inorganic compound is a clay mineral. 7. A method for producing an addition polymer, wherein an addition polymerizable monomer is polymerized using the catalyst for addition polymerization according to claim 1. 8. The method for producing an addition polymer according to claim 7, wherein the addition polymerizable monomer is ethylene or an α-olefin having 3 to 20 carbon atoms. 9. An addition polymerizable monomer having 3 to 20 carbon atoms.
The method for producing an addition polymer according to claim 7, wherein the mixture is a mixture of two or more kinds selected from α-olefins and ethylene.