WO2004046205A1

WO2004046205A1 - Process for the production of propylene copolymers

Info

Publication number: WO2004046205A1
Application number: PCT/JP2003/014412
Authority: WO
Inventors: Ryouji Mori; Yasushi Tohi; Kourei Kuroiwa; Naomi Urakawa
Original assignee: Mitsui Chemicals, Inc.
Priority date: 2002-11-15
Filing date: 2003-11-13
Publication date: 2004-06-03
Also published as: JP4205402B2; JP2004161957A

Abstract

The invention provides a process for the production of propylene copolymers which attains an excellent polymerization activity, permits high-temperature polymerization, and can give a propylene copolymer having a high molecular weight. The process comprises copolymerizing propylene with a comonomer in the presence of a catalyst consisting of both (a) a transition metal complex represented by the general formula (1) or (2) and a compound selected from among (b) compounds capable of reacting with the complex (a) to form inonic complexes, (c) organoaluminum compounds, and (d) organoaluminum oxy compounds: (1) (2) wherein R1 to R8 are each hydrogen, hydrocarbyl (except t-butyl), or the like (with the proviso that all of R1 to R8 are not hydrogen), and adjacent two of R1 to R8 may be united to form a ring; Y is a hydrocarbon group, silylene, or the like; A is a divalent hydrocarbon group having 2 to 20 carbon atoms; Z is carbon or silicon; M is Ti, Zr, Hf, or the like; X is halogeno, a hydrocarbon group, or the like; and j is an integer of 1 to 4.

Description

Production method of propylene copolymer

The present invention relates to a method for producing a propylene-based copolymer, and more particularly, to a propylene-based copolymer by copolymerizing propylene or the like in the presence of a catalyst containing a specific transition metal complex.

The present invention relates to a method for producing a propylene-based copolymer for producing a coalescence. , Food background technology

Propylene copolymers are used in various applications as thermoplastic resins or as modifiers for thermoplastic resins. As a polymerization catalyst used for producing a propylene-based copolymer, a titanium-based catalyst and a meta-opened catalyst are known. However, when propylene is copolymerized using a titanium-based catalyst, there are problems in that the composition of propylene that can be produced is limited and the compatibility is not uniform due to the wide molecular weight distribution. . On the other hand, when propylene is copolymerized using a meta-aqueous catalyst, it has excellent copolymerizability with polyolefin and can be polymerized in a wide range of compositions, but its molecular weight does not increase when polymerized at high temperatures. However, there was a problem that cost reduction could not be realized due to low polymerization activity.

By the way, J. Am. Chem. Soc., 1988, 110, 6255-6256 states that isopropylidene (cyclopentagenenyl) (9) obtained by bridging cyclopentene and fluorene with isopropylidene by J. A. Ewen et al. -It has been discovered that in the presence of a transition metal catalyst having a ligand of fluorene) and an aluminoxane, polypropylene having a high tacticity and a syndiotactic pentad fraction exceeding 0.7 can be obtained. Have been.

Also, Japanese Patent Application Laid-Open No. 2-274740 discloses that a copolymer of propylene and ethylene having a high molecular weight can be obtained using a catalyst similar to the above-described transition metal catalyst exhibiting syndiotactic polypropylene activity. It has been reported. These forces while Transition metal catalysts have poor polymerization performance at high temperatures, and there is room for further improvement, especially in molecular weight.

The present inventors have conducted intensive studies in view of such a situation, and as a result, by using a specific transition metal catalyst, propylene which has excellent polymerization activity, can be produced at high temperature, and has a high power and a high molecular weight. The inventors have found that a system copolymer can be obtained, and have completed the present invention. '' Disclosure of the Invention

An object of the present invention is to provide a method for producing a propylene-based copolymer having excellent polymerization activity, capable of producing a polymer at a high temperature, and having a high molecular weight in the obtained propylene-based copolymer.

The method for producing a propylene copolymer according to the present invention,

(i) a transition metal complex (a) represented by the following general formula (1) or (2);

(b) Compound that reacts with transition metal complex (a) to form an ionic complex

(c) an organoaluminum compound, and

(d) Organoaluminoxy compounds

One or more compounds selected from

Characterized by copolymerizing propylene with at least one kind of olefins other than propylene and polyolefins in the presence of a catalyst system.

(In the formulas (1) and (2), I ¹ , R ² , R ³ , R ⁴ , R \ R ⁶ , R ⁷ and R ⁸ may be the same or different from each other; represents hydrogen (except t- butyl) group or Kei-containing group (Rere although all up R ¹ forces et R ⁸ are such be hydrogen atom.), and adjacent R ¹ to R ⁸ substituent The groups may be joined together to form a ring, Y being an oxygen atom, a zeo atom,

^{^{(Wherein, R 9, R 1D, R}} u, R 12 may be the same or different from each other, a hydrogen atom, a halogen atom, a hydrocarbon group, Q is indicates Kei atom, a germanium atom or a tin atom , G represents a boron atom, a phosphorus atom or a nitrogen atom, n represents an integer of 1 to 4.), and A may partially contain an unsaturated bond and Z or an aromatic ring. Represents a divalent hydrocarbon group having 2 to 20 carbon atoms, and A may have two or more ring structures including a ring formed with Z;

Z represents a carbon atom or a silicon atom,

M represents Ti, Zr, Hf, Rn, Nd, Sm or Ru;

X represents a halogen atom, a hydrocarbon group, an a-one ligand or a neutral ligand capable of coordinating with a lone electron pair.When j is 2 or more, Xs may be the same or different. Represents an integer of 1 to 4. ).

In a preferred embodiment of the present invention, in the above formulas (1) and (2), M is preferably Ti, Zr or Hf.

Further, in the above formula (1) or (2), it is preferable that at least one pair of adjacent substituents from R ¹ to R ⁸ be bonded to each other to form a ring.

Further, Y in the above formula (1) is

And n is preferably 1 or 2. In the preferred response of the present invention, produce a propylene alkylene copolymer comprising propylene units 95-60 mole ^_0/0, the α- Orefin units Contact Yopi Poryen units in a proportion of 5 to 40 mole ^_0/0 Is preferred. BRIEF DESCRIPTION OF THE FIGURES

ai shows an explanatory diagram illustrating an example of a method for preparing the catalyst system used in the present invention. In the present invention, a catalyst system containing the above transition metal complex (a) is used. In some cases, a conventionally known solid titanium catalyst component and an organic aluminum compound other than the above catalyst may be used. It is also possible to use a titanium-based catalyst consisting of: (2) a vanadium-based catalyst consisting of a soluble vanadium compound and an organic aluminum compound. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the method for producing a propylene-based copolymer according to the present invention will be specifically described.

In the method for producing a propylene-based copolymer according to the present invention,

(c) an organoaluminum compound, and

(d) Organoaluminoxy compounds

One or more compounds selected from

Propylene is copolymerized in the presence of a powerful catalyst system.

First, each component constituting the catalyst used in the present invention will be specifically described. ((a) Transition metal complex)

The transition metal complex (a) used in the present invention is a compound represented by the following general formula (1) or (2).

In the formulas (1) and (2), R ¹ R ² , R ³ , RR ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different from each other, and may be a hydrogen atom, a hydrocarbon group (t- (Excluding butyl group) or silicon-containing group (however, all of R ¹ to R ⁸ are not hydrogen atoms). The hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms (excluding t-butyl group), an arylalkyl group having 7 to 20 carbon atoms, and a C 6 to 20 carbon atom. And arylalkyl groups having 7 to 20 carbon atoms. Some of the hydrogen atoms directly bonded to these carbon atoms are halogen atoms, oxygen-containing groups, nitrogen-containing groups, and silicon-containing groups. It also includes those substituted and those in which any two adjacent hydrogen atoms are simultaneously substituted to form an alicyclic or aromatic ring.

The term “silicon-containing group” refers to a group in which a silicon atom is directly and covalently bonded to a ring carbon of a fluorenyl group, and is specifically an alkylsilyl group or a arylsilyl group. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-dimethylpropyl, and 1-ethyl-1 —Methylpropyl, 1,1,2,2-Tetramethylpropyl, _sec —Butyl, 1,1-dimethylbutyl, 1,1,3-Trimethinolebutyl, Neopentinole, Cyclohexylmethinole, Cyclohexinole, 1-Methinole_1-cyclo Hexyl, 1-adamantyl, 2-adamantyl, 2-methyl-1-adamantinole, mentinole, nonoleponore-benle, benzinole, 2-phenenolechinole 1 -Tetrahydronaphthinole, 1-methyl-1-tetrahydronaphthyl, phenyl, naphthyl, tolyl and the like.

The silicon-containing group preferably includes an alkyl or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, and trifluorene. Elsilyl and the like. Adjacent substituents from R ^{1 to} R ⁸ may combine with each other to form a ring, and the adjacent substituents from to R ⁸ may combine with each other to form a substituted fluorenyl group that forms a ring. Are benzofluorenyl, dibenzofluorenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like, and octahydrodibenzofluorenyl is preferable.

Further, the cyclopentene group described in (1) or (2) may be completely substituted with a hydrocarbon group. In this case, the hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, An arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkylaryl group having 7 to 20 carbon atoms, and some of the hydrogen atoms directly bonded to these carbon atoms are Those substituted with a halogen atom, an oxygen-containing group, a nitrogen-containing group, or a silicon-containing group, or those in which any two adjacent hydrogen atoms are simultaneously substituted to form an alicyclic or aromatic ring Including. The above-mentioned silicon-containing group refers to, for example, a cyclopentagenenyl group or a group in which the ring carbon of a fluorenyl group is directly and covalently bonded to a silicon atom, and specifically, an alkylsilyl group It is a arylsilyl group. Specific examples include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-ethylpropyl, 1-ethyl-1-methyl Propyl, 1,1,2,2-tetramethylpropyl, sec-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methynole-1- Cyclohexyl, 1-adamantinole, 2-T-damantyl, 2-methyl-2-adamantyl, menthyl, norvol, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methinole-1-tetrahydronaphthyl, phenyl, naphthyl, tolyl And the like. In the present invention, it is particularly preferable that the adjacent substituents from to R ⁸ are bonded to each other to form a ring. It is also preferred that the adjacent substituents from R ¹ to R ⁴ and the adjacent substituents from R ⁵ to R ⁸ each form a ring. Furthermore, the ring formed by bonding adjacent substituents from R ¹ to R ⁸ to each other may have a substituent such as the above-mentioned hydrocarbon group.

Y is oxygen atom, sulfur atom

Is shown.

Here, R ^g , R ^w , R ^u , and R ¹² may be the same or different and represent a hydrogen atom, a halogen atom, or a hydrocarbon group. Examples of the hydrocarbon group are the same as those described above, and the halogen atom is fluorine, chlorine, bromine or iodine.

Q represents a silicon atom, a germanium atom or a tin atom. G represents a boron, phosphorus or nitrogen atom.

n represents an integer of 1 to 4, preferably 1 to 2.

As Y,

And n is preferably 1 or 2.

Preferred specific examples of Y include, for example, methylene, ethylene, dimethylmethylene,

Methyl tert-butylmethylene, dicyclohexynolemethylene, methylcyclohexylmethylene, methylphenylmethylene, diphenylmethylene, di (p-methynolepheninole) methylene, methinolenafhtinolemethylene, dinaphthylmethylene, tetramethylethylene Divalent hydrocarbon groups such as dimethylsilylene, diisopropylsilylene, methyl tert-butylsilylene, dicyclohexylsilylene, methinolecyclohexyl / resilylene, methinorefhene / 2 / resilylene, diphenylsilylene, methylnaphthylsilylene, dinaphthylsilylene, tetra Methyldish And hydrogenated hydrogen group-substituted silylene groups such as rylene. Particularly, ethylene, diphenylenolethylene, and di (alkylphenyl) methylene are preferred.

A represents a divalent hydrocarbon group having 2 to 20 carbon atoms, including a partially unsaturated bond and / or an aromatic ring, and A represents a ring formed with Z And may contain two or more ring structures.

Z is a carbon atom or a silicon atom.

A and Z combine to form a cycloalkylidene group, a cyclomethylenesilylene group, and the like. Examples of the divalent linking group formed by the bonding of A and Z include cyclopropylidene, cyclobutylidene, cyclopentylidene, cyclohexylidene, cyclohexheptylidene, bicyclo [3.3.1] nolidene, Examples include norpolnylidene, adamantylidene, tetrahydronaphthylidene, dihydroindanilidene, cyclodimethylenesilylene, cyclotrimethylenesilylene, cyclotetramethylenesilylene, cyclopentamethylenesilylene, cyclohexamethylenesilylene, and cyclohexamethylenesilylene.

M represents Ti, Zr, Hf, Rn, Nd, 3111 or 101, and is preferably Ti, Zr or Hf.

X is selected from a halogen atom, a hydrogen atom having 1 to 20 carbon atoms, an anion ligand, or a neutral ligand capable of coordinating with a lone electron pair.

Specific examples of the hydrocarbon group include the same as those described above.

Specific examples of the aeon ligand include an alkoxy group such as methoxy, tert-butoxy, and phenoxy; a carboxylate group such as acetate and benzoate; and a sulfonate group such as mesylate and tosylate.

Specific examples of the neutral ligand capable of coordinating with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethynolephosphine, trifeninolephosphine, dipheninolemethi / lephosphine, or tetrahydrofuran, getyl ether, Ethers such as dioxan and 1,2-dimethoxetane are exemplified.

Of these, X may be the same or different, but at least one is preferably a halogen or an alkyl group.

j is an integer of 1 to 4, and is a number satisfying the valence of the transition metal M. Specific examples of _{MXj, Z r C l 2,} Z r B r 2, Z rMe 2, Z r (OT s) 2, Z r (OMs) 2, Z r (OT f) 2ゝT i C 1 ₂ヽ T i B r ₂ヽ T iMe ₂ヽ T i (OT s) ₂ , T i (OMs) ₂ , T i (OT f) ₂ヽ H f C 1 ₂ , H f B r ₂ヽ H f Me ₂ヽ H f (OTs) ₂ , Hf (OMs) ₂ , H f (OT f) _{2 and the} like. Here, T s represents a p-toluenesulfonyl group, M s represents a methanesulfonyl group, and T f represents a trifluoromethanesulfonyl group.

Next, a method for producing the transition metal complex represented by the general formula (1) or (2) used in the present invention will be described below with specific examples. The transition metal complex represented by the general formula (1) or (2) can be produced, for example, by the following steps. The transition metal complex precursor (3) represented by the general formula (1) can be produced by a method represented by the following formula [A] or [B].

OOZ OAV

(Where R ^ R " ¹ is the same as in the general formula (1), T is an atom belonging to Group 14 of the periodic table such as carbon or silicon, L is an alkali metal. TZ ² is halogen or Anionic ligands, which may be the same or different combinations.

In (7), it is possible to consider the existence of isomers that differ only in the position of the double bond in the cyclopentene ring, and only one of them is exemplified, but only the position of the double bond in the cyclopentagel ring is It may be a different other isomer or a mixture thereof. ) The precursor metal compound (13) of the transition metal complex represented by the general formula (2) can be produced by a method represented by the following formula [C] or [D].

[C] ^

[

(In the formula,! ^ To ⁸ , Υ, and Α are the same as those in the general formula (2), and L is an alkali metal. ZZ ² is a halogen or anion ligand. In addition, (13) and (16) can be considered as isomers that differ only in the position of the double bond in the cyclopentagenenyl ring, and only one of them is exemplified. There is a double bond in the pentajeel ring May be other isomers that differ only in the position, or may be a mixture thereof. )

Examples of the alkali metal used in the reactions [A] to [D] include lithium, sodium and potassium, and examples of the alkaline earth metal include magnesium and calcium. Examples of the halogen include fluorine, chlorine, bromine, and iodine. Specific examples of the anion ligand include an alkoxy group such as methoxy, tert-butoxy, and phenoxy; a carboxylate group such as acetate and benzoate; and a sulfonate group such as mesylate and tosylate.

Next, an example of producing a complex of the group of the present invention from the precursor compound of the general formula (3) or (13) will be shown below, but this does not limit the scope of the invention.

The precursor compound of the general formula (3) or (13) obtained by the reaction of the above [A] to [D] can be used as an alkali metal hydride, an alkali metal hydride or an organic alkali metal in an organic solvent. The metal is brought into contact with the metal at a reaction temperature in the range of 180 ° C to 200 ° C to form a dialkali metal salt.

Examples of the organic solvent used in the above reaction include aliphatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, and decalin; aromatic hydrocarbons such as benzene, toluene, and xylene; THF (tetrahydrofuran), Ethers such as tyl ether, dioxane and 1,2-dimethoxetane; halogenated hydrocarbons such as dichloromethane and chlorophonolem;

Examples of the alkali metal used in the above reaction include lithium, sodium and potassium hydride, and examples of the alkali metal hydride include sodium hydride and hydrogen hydride, and examples of the organic alkali metal include: Examples include methyllithium, butyllithium, phenyllithium and the like.

Next, the above-mentioned diallyl metal salt is represented by the general formula (21)

MZ _k (2 1)

(Where M is gold selected from Group 4 of the periodic table, and Z may be selected from halogen, anion ligands, or neutral ligands capable of coordinating with lone pairs in the same or different combinations. , K is an integer of 3 to 6.) By reacting the compound represented by the formula (1) with an organic solvent, a transition metal complex represented by the formula (1) or (2) can be synthesized.

Preferred specific examples of the compound represented by the general formula (21) include trivalent or tetravalent titanium fluoride, chloride, bromide and iodide, tetravalent zirconium fluoride, chloride, and bromide. And tetravalent hafnium fluorides, chlorides, bromides and iodides, and complexes thereof with ethers such as THF, getyl ether, dioxane or 1,2-dimethoxyethane. As the organic solvent used, the same organic solvents as described above can be used. The reaction between the dialkali metal salt and the compound represented by the general formula (21) is preferably carried out by an equimolar reaction, and the reaction temperature is −80 ° C. to 200 ° C. in the organic solvent. It can be performed within the range.

The meta-mouth compound obtained by the reaction can be isolated and purified by a method such as extraction, recrystallization, or sublimation.

The transition metal complex obtained by such a method is identified by using an analytical technique such as proton nuclear magnetic resonance spectrum, ¹³ C nuclear magnetic resonance spectrum, mass spectrometry and elemental analysis.

Hereinafter, specific examples of the transition metal complex used in the present invention are shown, but the scope of the present invention is not particularly limited by these. First, the ligand structure of the transition metal complex excluding MQj (metal part) is divided into two parts, Bridge (bridge part) and F1u (fluoreel ring part), and specific examples of each partial structure are shown. It is shown below. In the specific examples of Bridge and F1u, points indicated by black circles (•) indicate connection points between Bridge and Cp and F1u, respectively.

9T

o / eoozdf / e :) d contract oo OAV oi-q

6q

8q zq

9q

gq

sq ^^ c ^^ i-q

Ll

zi o / eoozdf / iDd contract 00Z OAV idge Flu No. Bridge Flu No. Bridge Flu No. Bridge Flu a1 b1 51 a6 b1 101 a1 1 b1 151 a16 b1 a1 b2 52 a6 b2 102 a1 1 b2 152 a16 b2 a1 b3 53 a6 b3 103 a1 1 b3 153 a16 b3 a1 b4 54 a6 b4 104 a1 1 b4 154 a16 b4 a1 b5 55 a6 b5 105 a1 1 b5 155 a16 b5 a1 b6 56 a6 b6 106 a1 1 b6 156 a16 b6 a1 b7 57 a6 b7 107 a1 1 b7 157 a16 b7 a1 b8 58 a6 b8 108 a1 1 b8 158 a16 b8 a1 b9 59 a6 b9 109 a1 1 b9 159 a16 b9 a1 b10 60 a6 b10 1 10 a1 1 b10 160 a16 b10 a2 b1 61 a7 b1 1 1 1 a12 b1 161 a17 b1 a2 b2 62 a7 b2 1 12 a12 b2 162 a17 b2 a2 b3 63 a7 b3 1 13 a12 b3 163 a17 b3 a2 b4 64 a7 b4 1 14 a12 b4 164 a17 b4 a2 b5 65 a7 b5 1 15 a12 b5 165 a! 7 b5 a2 b6 66 a7 b6 1 16 a12 b6 166 a! 7 b6 a2 b7 67 a7 b7 1 17 a12 b7 167 a17 b7 a2 b8 68 a7 b8 1 18 a12 b8 168 a17 b8 a2 b9 69 a7 b9 1 19 a12 b9 169 a17 b9 a2 b10 70 a7 b10 120 a12 b10 170 a17 b10 a3 b1 71 a8 b1 121 a13 b1 171 a18 b1 a3 b2 72 a8 b2 122 a13 b2 172 a18 b2 a3 b3 73 a8 b3 123 a13 b3 173 a18 b3 a3 b4 74 a8 b4 124 a13 b4 174 a18 b4 a3 b5 75 a8 b5 125 a13 b5 1 75 a18 b5 a3 b6 76 a8 b6 126 a13 b6 176 a18 b6 a3 b7 77 a8 b7 127 a13 b7 177 a18 b7 a3 b8 78 a8 b8 128 a13 b8 178 a18 b8 a3 b9 79 a8 b9 129 a13 b9 179 a18 b9 a3 b10 80 , a8 b10 130 a13 b10 180 a18 b10 a4 bl 81 a9 b1 131 a14 b1 181 a19 b1 a4 b2 82 a9 b2 132 a14 b2 182 a19 b2 a4 b3 83 a9 b3 133 a1 b3 183 a19 b3 a4 b4 84 a9 b4 134 a14 b4 184 a19 b4 a4 b5 85 a9 b5 135 a14 b5 185 a19 b5 a4 b6 86 a9 b6 136 a14 b6 186 a19 b6 a4 b7 87 a9 b7 137 a! 4 b7 187 a19 b7 a4 b8 88 a9 b8 138 a14 b8 188 a19 b8 a4 b9 89 a9 b9 139 a14 b9 189 a19 b9 a4 b10 90 a9 b10 140 a14 b10 190 a19 b10 a5 b1 91 a10 b1 141 a15 b1 191 a20 b1 a5 b2 92 a10 b2 142 a15 b2 192 a20 b2 a5 b3 93 al O b3 143 a15 b3 193 a20 b3 a5 b4 94 a10 b4 144 a15 b4 194 a20 b4 a5 b5 95 a10 b5 145 a15 b5 195 a20 b5 a5 b6 96 a10 b6 146 a15 b6 196 a20 b6 a5 b7 97 a10 b7 147 a15 b7 197 a20 b7 a5 b8 98 a10 b8 148 a15 b8 198 a20 b8 a5 b9 99 a10 b9 149 a15 b9 199 a20 b9 a5 b10 100 a10 b10 150 a15 b10 200 a20 b10 According to the above table, the ligand structure of No. 15 means a combination of a bridging moiety (a 2) and Furuoreni Le ring moiety (b 6), if ΜΧ metal portion "is Z r C 1 ₂ is The following transition metal complexes are exemplified.

The transition metal complexes (a) as described above can be used alone or in combination of two or more.

Further, the transition metal complex (a) as described above can be used by being supported on a particulate carrier.

The carrier used as required in the present invention is an inorganic or organic compound, and is a granular or fine solid.

Among them, the inorganic compound is preferably a porous oxide, an inorganic halide, a clay, a clay mineral or an ion-exchange layered compound.

Next, the catalyst system used in the present invention is formed.

(b) a compound that reacts with the transition metal catalyst component (a) to form an ionic complex (hereinafter also referred to as an “ionized ionic compound”)

(c) an organoaluminum compound, and

(d) The organic aluminum oxide conjugate (also called aluminoxane or alumoxane) will be described.

((b) ionized ionic compound)

(b) Examples of the ionized ionic compound include JP-A-11-501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, and JP-A-3-207703. Gazette, JP-A-3-207704, Examples thereof include Lewis acids, ionic compounds, borane compounds, carborane compounds and the like described in US Pat. No. 5,321,106. Further, a heteropoly compound and a disopoly compound can also be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as a fluorine, a methyl group, a trifluoromethyl group or a fluorine) is mentioned. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentaf / Examples include feninole boron, tris (ρ-trinole) boron, tris (o-tri / re) porone, and tris (3,5-dimethylphenyl) boron.

Examples of the ionic compound include, for example, a compound represented by the following general formula (3).

R ⁹

_{+ f} I- _h

r¾ R ^f — B— R ^h

I,

R · · (3) In the formula, R ^e is H +, carbemium cation, oxonium cation, ammonium cation, phosphonium cation, Fe-semium cation having a transition metal.

R ^{f to} Ri may be the same or different and are an organic group, preferably an aryl group or a substituted aryl group.

Specific examples of the carbedium cation include tri-substituted carbedium cations such as triphenylcarbene cation, tris (methylphenyl) carbamate cation, and tris (dimethinolephenyl) carbedium cation. .

Specific examples of the above-mentioned ammonium cation include trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, and tri (n-butyl) ammonium cation. Trialkyl ammonium such as triisobutyl ammonium cation N, N-dialkylanilinium cations, such as cations, N, N-dimethylanilumium cations, N, N-ethylethylaninium cations, N, N—2,4,6-pentamethylanilinium cations, disopropyl ammonium And dialkylammonium cations such as dimethyl cation and dicyclohexylammonium cation.

Specific examples of the phosphonium cation include triarylphosphonium cations, tris (methylphenyl) phosphonium cations, and triarylphenol phosphocation cations such as tris (dimethylphenyl) phosphonium cation. I can do it.

Of the above, the R ^e, carbenium Yuumukachion, preferably such as ammonium Niu beam cation, especially triphenyl Cal base - Umukachion, N, N- Jimechinorea two linear Umukachion, N, is N- Jefferies chill § two Liu arm cation preferable.

Specific examples of carbenium salts include triphenylcarbamate tetraphenyl porate, triphenylenolate tetrabenzoate (pentaf / leophenol), borate, and triphenylcarbamatetetrakis (3, 5). —Ditrifluoromethylphenylinoleate) Borate, Tris (4-methinolepheninole) Potassium tetrakis (pentafluoropheninole) Borate, Tris (3,5-dimethylphenyl) carbamine tetrakis (pentafluorophenyl) Porate and the like can be mentioned. Examples of the ammonium salt include a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, and a dialkylammonium salt.

Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium tetratetra-norreborate, tripropyl ammonium tetraphenyl-borate, tri (n-butyl) ammonium tetraphenyl-porate, trimethylammonium tetrakis (p-torinole) porate, trimethylammonium tetrakis (o_tolyl) borate, tri (n-butynole) ammonium tetrakis (pentafluorophenol) borate, triethylammonium tetrakis (pentafluorophenol) ) Porate, tripropylammoniumtetrakis (pentaphnoolenophenyl) borate, tripropylammoniumtetrakis (2,4-dimethylphenylphenyl) borate, tri (n-butyl) ammo-dimethyltetrakis (3,5— Dimethylphenyl) borate, tri (n-butylinole) ammonium tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) ammoniumtetrakis (3,5-ditrifluoromethylphenyl) borate And tri (n-butyl) ammoniumtetrakis (o-tolyl) borate.

Specific examples of N, N-dialkylaniluium salts include, for example, N, N-dimethylaniliniumtetraphenylporate, N, N-dimethylaniliniumtetrakis (pentanenorololophenyl) porate, N-dimethylanilinetetrakis (3,5-ditrinoroleolomethylphenyl) borate, N, N-Jetylanilintetramethylene triporate, N, N-Jetylaniliniumtetrakis (pentafluoro liphenyl) ) Borate, N, N-Jetylaniluiumtetrakis (3,5-ditrifluoromethylphenyl) porate, N, N-2,4,6,1-Pentamethylaniluiumtetraphenylborate, N, N— 2,4,6-pentamethylaniliniumtetrakis (pentafluorophenyl) borate.

Specific examples of dialkylammonium salts include, for example, di (propyl) ammoniumtetrakis (pentaphnoleolopheninole) borate, dicyclohexylolemoniummoniumtetraphenylporate, and the like.

Further, ferrosenium tetrakis (pentaphnolerophenyl) porate, triphenylcarbenyl pentaphenylcyclopent pentagenenyl complex, N, N-ethyl-linium pentaphenylcyclopentagenenyl complex, or the following formula: A borate compound represented by (4) or (5), a borate compound containing active hydrogen represented by (6), a porate compound containing a silyl group represented by (7) can also be mentioned.

(In the formula, Et represents an ethyl group.)

Specifically, as a borane compound, for example,

Decaporane (14), bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaporate, bis [tri (n-butyl) ammonium] pendecaborate, bis [tri] (n-Ptinole) ammonium) Dodecaborate, bis (tri (n-butyl) ammonium) decachlorodecaporate, bis (tri (n-butyl) ammonium) dodecaconide , Tri (n-butyl) ammonium bis (dode hydride dodecaborate) cobaltate (III), bis (tri (n-butylinole) ammonium) bis (dode hydride dodecaporate) nickelate (III) Metal borane anion salts and the like.

Specific examples of the carborane compound include, for example, 4-hydroxylbanonaborane (14), 1,3-dicarpanonaporan (13), .6,9-dicarbadecaborane (14), dodecahydrido 1—Fune Lou 1,3-Dicarpanonaporan, Dodecahydraid 1-methyl-1,3-dicarpanonaran, Pende Hydride 1,3-Dimethyl-1,3-dicarpanonaporan, 7,8-Dicarpandeaborane (1 3), 2, 7-dicarpound power borane (13), ndde power hydride 1, 8 dimethinolate 7, 8-dicarbane decaborane, dodeca hydride 11-methyl 1-2, 7-dicarpound power poran, tri (n _Butyl) Ammonium 1 carbadecaborate, tri (n-butyl) ammonium 1 carbounddecarborate, tri (n-butyl) ammonium 1 lvadeboride Porate, tri (n-butyl) ammonium 1-trimethinoresilyl-one-lude lubadecaborate, tri (n-butyl) ammonium bromide 1-l-lupadecaparate, tri (η-butyl) ammonium 6- Lubadecaborate (14), tri (η-butyl) ammonium 6 1 Lubadecaborate (12), tri (η-butyl) ammonium 7-carboundecaborate (13), tri (η-butyl) ammonium 7,8-zicanolane Decaborate (1 2), tri (n-butyl) ammonium 2,9-dicalpoundatePolate (1 2), tri (n-petit / re) ammonium hydride 1-methyl-1,7-, 9-dicarbanedecaborate Tri (n-butyl) ammonium pentadecahydrate 8-ethyl-7,9-dicarbanedecaporate, tri (n-butyl) ammonium pentadecahydrate-8-butyl-7,9 dicaloundecaprate, tri (N-butyl) ammonium munddecahydride 1-8-aryl-1 7,9-dicarbone decaborate, tri (n-butyl) ammonium mundecahydride 1-9-trimethylsilyl 7,8-dicarbanedecahydrate Borate, tri (n-butyl) ammonium hydroxide, 4, 6-jib mouth, mo 7-calpaun Salt of the Anion such as Kaboreto;

Tri (n-butyl) ammonium bis (nonahydride 1,3-dicarbano naborate) cobaltate (III), tri (n-butyl) ammonium bis (ndecahydride 7,8-dical pounding borate) Ferrate (III), tri (n-butyl) ammonium bis (indica hydride 7,8-dicarbonate power) Cobaltate (III), tri (n-butyl) ammonium bis (indene hydride 1-7,8-) Dicarpound decaborate) nickelate (III), tri (n-butynole) ammonium bis (indene hydride 7,8-dicarbanedecaporate) cuprate (III), tri (n-petinole) ammo-emubis 7,8-dicarpoundecaprate) aurate (III), tri (n-butyl) ammonium Mbis (nonahydride-1.7,8-dimethyl-7,8-dicarboundecaborate) ferrate (III), tri (n-ptinole) ammonium monbis (nonahydride 7,8-dimethinolate 7,8-dicarbazanedeca) (Borate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydride-17,8-dicarbanedecaporate) cobaltate (III), tris [tri (n-butyl) (Ammonium) Bis (dedecahydride-7-calounde borate) chromate (III), bis (tri (n-butynole) ammonium) bis (dedecahydride-1 7-calpooundecaprate) manganate (IV), bis [tri (n-butyl) ammonium] bis (indene hydride-17-carbadecaborate) cobaltate (III), bis (tri-n-butynole) ammonium Metal] bis (ndecahydra, id-1 7-carpoundecaprate) salts of metal carborane anions such as nickelate (IV).

Examples of the porate compound containing active hydrogen include a compound represented by the following general formula (6). .

[BQ _n (G _q (TH) _r ) J-one A +… (6)

Here, B represents boron.

G represents a multi-bonded hydrocarbon radical. Preferred multi-bonded hydrocarbons are alkylene, arylene, ethylene, and alkenyl containing 1 to 20 carbon atoms. Preferred examples of G include phenylene. Examples include len, bisphenylene, naphthalene, methylene, ethylene, 1,3-propylene, 1,4-butadiene, and p-phenylenemethylene. The multi-bonded hydrocarbon radical G has an r + 1 bond, ie one bond bonds to the porate anion, and the other bond r of G bonds to the (TH) group. A ⁺ is a cation.

In the above general formula, T represents 〇, S, NRj, or PRj, and Rj represents a hydrocarbanyl radical, a trihydrocarbanylsilyl radical, a trihydrocarbanylgermanium radical, or a hydride.

q is an integer of 1 or more, preferably 1. T-H groups include 1 OH, —SH, 1 NRH, or 1 PRjH, where Rj is a hydrocarbyl radical or hydrogen having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. is there. Preferred Rj groups are alkyl, cycloalkyl, aryl, arylalkyl or alkylaryl having 1 to 18 carbon atoms. One OH, — SH, -NR .. H or one PRjH can be, for example, one C (O) one OH, -C (S) _SH—C (O) one NRjH, and one C (O) one PRjH. Absent. The most preferred group having active hydrogen is a mono-OH group.

Q is hydride, dihydrocarbylamide, preferably dialkylamide, halide, hydrocarbyloxide, alkoxide, aryloxy, hydrcarbyl, substituted hydrocarbyl radical and the like. Where n + z is 4. Examples of the borate compound containing active hydrogen represented by the above general formula (7) include trifeninole (hydroxyphenyl) borate, dipheninolage (hydroxylone). Enisle) Borate, Trifle-nore (2,4-dihydroxyphenyl) borate, tri (p-tolyl) (hydroxyphenyl) porate, Tris-one (pentafluoro-mouth feninole) (Hydroxyphenole) Polate, Tris 1 (2,4 dimethinolepheny / re) (hydroxypheninole) Porate, tris (3,5-dimethinorefenyl) (hydroxyphenyl) borate, tris (3,5-ditrifluorometylphenyl) (hydroxy) Phenyl) borate, tris- (pentafluorophenol) (2-hydroxyethynole) borate, tris- (pentaphnolerofer) (4-hydroxyp-inole) borate, tris- (pentafrenole) (Ninore) (4-Hydroxy-cyclohexynole) borate, Tris-one (penta Norolefonium 2) (4-(4-hydroxypheninole) phene) porate, tris-1 (pentafflurophenol) (6-hydroxy-12-naphthyl) borate, and most preferably tris (pentaf Norelophenyl) (4-hydroxyphenyl) borate. Further, a compound in which one OH group of the above borate compound is substituted with one NHRj (where R is methyl, ethyl, t-butyl) is also preferable.

Examples of A ⁺ which is a counter cation of the borate compound include a carbomium cation, a tropinolium cation, an ammonium cation, an oxomium cation, a sulfonium cation, and a phosphonium cation. There are also metal cations and organic metal cations whose self-confidence is easily reduced. Specific examples of these cations include triphenylcanolebonium ion, diphenylcarboxamion, cycloheptatrinium, indenium, triethylammonium, tripropylammonium, tripropylammonium, dimethylammonium. Gum, zip mouth pinoreammonium, jisik mouth hexinoleammonium, avian-aged chinoleammonium, N, N-dimethylammonium, getylammonium, 2, 4, 6-pentamethino Reammonium, N, N-Dimethinorefheninoleammonium, G (i-propyl) ammonium, Dicyclohexylammonium, Trifeninolephosphonium, Triphosphonium, Tridimethinolephenolephosphonium, Tri (methylphenyl) phosphonium, triphenyl ^ / phospho-pium ion, Triphene / reoxonium ion, triethyloxonium ion, pyridinium, silver ion, gold ion, platinum Ions, copper ions, palladium ions, mercury ions, and ferrosenium ions. Of these, ammonium ions are particularly preferred.

Examples of the porate compound containing a silyl group include a compound represented by the following general formula (7).

[B-Q _n (G _q (S i R _k R _: Rj _r ) J — A ⁺ … (7)

Here, B represents boron.

G represents a multi-bonded hydrocarbon radical. Preferred multi-bonded hydrocarbons are alkylene, arylene, ethylene and alkali rene radicals having 1 to 20 carbon atoms. Preferred examples of G include phenylene and bisphene. Examples include diene, naphthalene, methylene, ethylene, 1,3-propylene, 1,4-butadiene, and p-phenylenemethylene. The multi-bonded hydrocarbon radical G is an r + 1 bond, ie one bond is bonded to a porate anion, and the other bond r of G is bonded to a (S i R _k RiR _m ) group. A ⁺ is a cation.

R _k , R or R _ra in the above general formula represent a hydrocarber radical, a trihydrocarbanylsilyl radical, a trihydrocarbanylgermanium radical, a hydrogen radical, an alkoxy radical, a hydroxy radical or a hapogen compound radical. . R _k and R _ra may be the same or independent. '

Q is hydride, dihydrocarbyl amide, preferably dialkyl amide, halide, hydrocarbyl oxide, alkoxide, aryloxy, hydrated carbyl, substituted hydrocarbyl radical, etc., and more preferably pentafluorobenzyl It is a radical. Where n + z is 4.

Examples of the silyl group-containing porate compound represented by the above general formula (7) include, for example, triffe-nore (4-dimethinolechlorosilinolephene), borate, dipheninolage (4-dimethylclosilate / rephenyl) porate, triffee -/ Le (4-dimethinole methoxysilylphenyl) borate, tri (p-tolyl) (4-triethoxysilylphenyl) porate, tris (pentafluorophenyl) (4-dimethylchlorosilylphenyl) Porate, Tris- (pentafluorophenyl) (4-1 Dimethinoleme ethoxysilinolephenyl) Borate, Tris-1 (Pentaph / leo-phenyl) (4-trimethoxysilylphenyl) Borate, Tris- (pentafluoro) Phenyl) (6-dimethylchlorosilyl-12-naphthyl) porate. '

A ^{+ as} a counter cation of the borate compound is the same as A ⁺ in the above general formula (6).

The heteropoly compound consists of atoms selected from silicon, phosphorus, titanium, germanium, arsenic and tin, and one or more atoms selected from vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanopanadic acid, arsenic vanadic acid, linniobic acid, germanoniobic acid, siliconomolybdate, phosphomolybdate, titanium molybdate, germanomolybdate, arsenic molybdate, tin molybdate, phosphotungsten Acids, germanotan dastenic acid, tin tungstic acid, phosphomolybdovanadic acid, phosphorustandustpanadic acid, genolemanotantangostvanadic acid, phosphomolybdotangstvanadic acid, germanomolybdotandust vanadic acid, phosphomolybdungstic acid , Linmolybdniobate, and salts of these acids, such as metals of Group 1 or 2 of the Periodic Table, specifically lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium Strontium salts with barium, bird whistle - organic salts with Ruechiru salts and the like can be used.

The (b) ionizable compound as described above is used alone or in combination of two or more.

Further, the ionized ionic compound (b) as described above can also be used by being supported on the above-mentioned particulate carrier.

((c) Organoaluminum compound)

Specific examples of the organoaluminum compound (c) include the following organometallic compounds of Groups 1, 2 and 12 and 13 of the periodic table.

(c- la) — general formula R ^a _ra Al (OR ^b ) _n H _p X _q

(Wherein, R ^a and R ^b may be the same or different from each other, represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, X represents a halogen atom, and ra represents 0 <m≤3, n is 0≤n <3, p is 0≤p <3, q is 0≤q <3, and m + n + p + a = 3.) An organic aluminum compound represented by the formula: '

(c -lb) General formula M ² A 1 R ^a ₄ … (9)

(Wherein, M ² is i, indicates N a or K, R ^a is the number of carbon atoms 1 to 15, preferred properly represents 1-4 hydrocarbon group.)

A complex alkylated product of Group 1 metal and aluminum represented by

Examples of the organic aluminum compound belonging to (c-la) include the following compounds. '

General formula R ^a _ffl Al (OR ^b ) ₃ - _m … (10)

(Wherein, R ^a and R ^b may be the same or different from each other, and represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, and m is preferably 1.5 ≤ m ≤ This is the number 3.)

An organic aluminum compound represented by

Formula ^{_{_{R a m A 1 X 3 _}}} m ... (1 1)

(Wherein, ^Ra represents a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m is preferably 0 to 3).

An organic aluminum compound represented by

General formula RA 1 H ₃ _ _m … (12)

(Wherein,: ^a is from 1 to 15 carbon atoms, preferably an 1-4 hydrocarbon group, m is preferably 2≤m <3.)

An organoaluminum compound represented by

General formula R ^a _ra Al (OR) _n X _q (13)

(In the formula, R ^a and R ^b may be the same or different from each other, represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0 <m≤3, n is 0≤n <3, q is the number 0 q <3, and the force is m + n + q = 3.)

An organic aluminum compound represented by the formula:

More specifically, as the aluminum compound belonging to (c-la),

Trimethylaluminum, Triethylaluminum, Trin_butylaluminum, Tripropylaluminum, Tripentylaluminum, Trihexyla Tri-n-alkyl aluminums such as lumidium, trioctylaluminum and tridecylaluminum;

Triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri2-methylbutylaluminum, tri3-methylbutylaluminum, tri2-methylpentylaluminum, tri3- Tri-branched alkyl aluminum such as methylpentyl aluminum, tri-4-methinolepentyl aluminum, tri-2-methylhexyl aluminum, tri-3-methylhexyl aluminum, tri-21-ethylhexyl aluminum;

Tricycloalkyl aluminum such as tricyclohexyl aluminum and tricyclooctyl aluminum;

Triaryl aluminum such as triphenylenolea / remium, tritrialuminum;

Dialkylaluminum hydrides such as diisopropylaluminum hydride and diisobutylaluminum hydride;

_{_{_{(I- C 4 H 9) x}}} A l y (C 5 H 10) z ... (1 4)

(Where x, y, and z are positive numbers and z≥2 x.)

Alkenyl aluminum such as isoprenylaluminum; alkyl aluminum alkoxide such as isobutylaluminum methoxide, isobutylaluminum ethoxide, and isobutylaluminumisopropoxide;

Dialkyl alcohol alkoxides such as dimethyl aluminum methoxide, getyl aluminum ethoxide and dibutyl aluminum methoxide; alkyl aluminum sesqui alkoxides such as ethyl aluminum sesquiethoxide and butyl aluminum dimethyl sesquibutoxide;

R ₅ A 1 (OR ^b ). Partially alkoxylated alkylaluminum having an average composition represented by, _5, etc .;

Getyl aluminum phenoxide, getyl aluminum (2,6-di-t-butyl_4_methylphenoxide), ethyl aluminum bis (2,6-di-t-t Butyl-4-methylphenoxide), disobutylaluminum (2,6-di-t-butyl-4-methyl-phenoxide), isobutylaluminum bis (2,6-di-t-butyl-4-1) Alkyl aluminum oxides such as methylphenoxide).

Dialkylaluminum halides such as dimethylaluminum chloride, getylaluminum chloride, dibutylaluminum chloride, getylaluminum bromide and diisobutylaluminum chloride;

Alkyl aluminum sesquihalides such as ethyl aluminum sesquichloride, butyl aluminum sesquichloride, and ethyl aluminum sesquibromide; alkyls such as ethyl aluminum dimethyl dichloride, propyl aluminum dichloride, and butyl aluminum disulfide Partially halogenated alkylaluminums such as aluminum dihalide;

Dialkyl aluminum hydrides such as getyl aluminum hydride and dibutyl aluminum hydride;

Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride;

Partially alkoxyl and halogenated alkyl aluminums such as ethylaluminum ethoxychloride, butynoleuminium butoxycyclolide, and ethylaluminum ethoxybutamide can be mentioned.

Further, a compound similar to (c-la) can also be used, and examples thereof include an organic aluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. Specifically, as such a compound,

(C ₂ H ₅ ) ₂ A 1 N (C ₂ H ₅ ) A l (C ₂ H ₅ ) ₂

And the like.

As the compound belonging to the above (c-lb),

L i A 1 (C ₂ H ₅ ) ₄

Li A 1 (C ₇ H ₁₅ ) _{4 and the} like. As the organoaluminum compound, a compound having at least one A 1 -carbon bond in the molecule is preferable.

The above-mentioned (c) organoaluminum compound is used alone or in combination of two or more.

The above (c) organoaluminum compound does not include the following (d) organoaluminum compound.

((d) Organoaluminumoxy compound)

(d) The organic aluminum oxy compound may be a conventionally known aluminoxane, or a benzene-insoluble organic aluminum dimethyl compound as exemplified in JP-A-2-77867. You may.

A conventionally known aluminoxane (alumoxane) is specifically represented by the following general formula. '

In the formula, R is a hydrocarbon group such as a methyl group, an ethyl group, a propyl group, and a butyl group, preferably a methyl group, an ethyl group, and particularly preferably a methyl group. m is an integer of 2 or more, preferably an integer of 5 to 40.

Here, the aluminoxane is represented alkyl O carboxymethyl al Miniumu units Contact Yopi formula expressed alkyl O alkoxy aluminum units (where they are in (OA 1 (R)) is the formula ^{(OA 1 (R a))} , R a And are the same hydrogen groups as R, and R ^a and R ^b are different groups.) They may be formed from a mixed alkyloxyaluminum unit. A conventionally known aluminoxane can be produced, for example, by the following method, and is usually obtained as a solution of a hydrocarbon solvent.

(1) Compounds containing water of adsorption or salts containing water of crystallization, such as salt hydrate magnesium hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, chloride A method in which an organic aluminum compound such as a trialkylaluminum is added to a suspension of a hydrocarbon medium such as cerous hydrate to react the adsorbed water or water of crystallization with the organic aluminum compound. '

(2) A method in which water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.

(3) A method in which an organic aluminum compound such as trialkylaluminum is reacted with an organic stannic acid such as dimethyltin oxide or dibutyltin oxide in a medium such as decane, benzene or toluene.

The aluminoxane may contain a small amount of an organometallic component. Alternatively, the solvent or unreacted organic aluminum compound may be removed from the recovered solution of aluminoxane by distillation, and then redissolved in a solvent or suspended in a poor solvent for aluminoxane.

Specific examples of the organoaluminum compound used for preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (c-la).

Of these, trialkyl aluminum and tricycloalkyl aluminum are preferred, and trimethyl aluminum is particularly preferred.

The above-mentioned organoaluminum compounds are used alone or in combination of two or more.

The aluminoxane prepared from trimethylaluminum is called methylaluminoxane or MAO, and is a particularly frequently used compound.

Solvents used in the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, tamene, and cymene; and aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane. Alicyclic hydrocarbons such as nitrogen, cyclopentene, cyclohexane, cyclooctane, methinolecyclopentane, petroleum fractions such as gasoline, kerosene, and gas oil; or the above aromatic hydrocarbons, aliphatic hydrocarbons, and fats Examples include hydrocarbon solvents such as halides of cyclic hydrocarbons, especially chlorides and bromides. Further, ethers such as ethyl ether and tetrahydrofuran can also be used. Among these solvents, aromatic hydrocarbon and aliphatic hydrocarbon are particularly preferable.

In addition, the benzene-insoluble organoaluminoxy compound has an A1 component soluble in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of A1 atom. Yes, insoluble or poorly soluble in benzene. Examples of the organoaluminum oxy conjugate (d) include a boron-containing organoaluminum oxy conjugate represented by the following general formula (17).

(In the formula, R ° represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same or different, and may be a hydrogen atom, a halogen atom or a carbon atom having 1 to 10 carbon atoms. Represents a hydrocarbon group.)

The organoaluminoxy compound containing boron represented by the general formula (17) is obtained by converting an alkylboronic acid represented by the following general formula (18) and an organic aluminum compound into an inert gas atmosphere. It can be produced by reacting in an inert solvent at a temperature of 180 ° C. to room temperature for 1 minute to 24 hours.

R ^C B. (OH) 2 (18)

(In the formula, R represents the same group as described above.)

Specific examples of the alkylboronic acid represented by the general formula (18) include methylboronic acid, ethylboronic acid, isopropylporonic acid, n-propylboronic acid, n-butylboronic acid, isobutylporonic acid, and n- Xy / Repolonic acid, Cyclohexylboronic acid, Phenylporonic acid, 3,5-Difluorophenylboronic acid, Pentafluorophenylporonic acid, 3,5-Monobis (trifluoromethyl) phenolpolone Acids and the like. Of these, methylpolonic acid, n-butylboronic acid, isopti / repolonic acid, 3,5-diphnoleolopheenolepolonic acid, and pentaphlenolorofenylporic acid are preferred. These may be used alone or in combination of two or more.

Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (c).

Of these, trianolequinolenoleminium and tricycloanolequinolenoleminium are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

The above-mentioned (d) organoaluminoxy compound is used alone or in combination of two or more.

In addition, (d) the organoaluminum oxide conjugate may contain a small amount of an organic compound component of a metal other than aluminum.

Further, the above-mentioned (a) organoaluminum oxide compound can also be used by being supported on the above-mentioned particulate carrier. '' One or more compounds (ii) selected from the components (b), (c) and (d) used together with the transition metal complex (a) in the present invention are not particularly limited as described above. It is preferable to use two or more components in combination. Specifically, it is preferable to use the component (b) and the component (c), the component (b) and the component (d), and the component (b) with the components (c) and (d).

(Production of copolymer)

In the present invention, propylene and at least one other olefin selected from 0; -olefin and polyolefin other than propylene are usually copolymerized in the liquid phase in the presence of the catalyst system. In this case, a hydrogen solvent is generally used, but monoolefin may be used as the solvent. The copolymerization can be carried out by either a patch method or a continuous method. When the copolymerization is carried out by a batch method using the above catalyst system, the concentration of the transition metal complex ( _a ) in the polymerization system is usually 0.0005 to 1 millimol, preferably 1 mol, per liter of polymerization volume. It is used in an amount of 0.001 to 0.5 mmol.

The ionized ionic compound (b) has a molar ratio ((b) / (a)) of the ionized ionic compound (b) to the transition metal complex (a) of 0.5 to 20, preferably 1 to 10. Used in such amounts.

The organoaluminoxy conjugate (d) has a molar ratio (A 1 / M) of the aluminum atom (A 1) to the transition metal atom (M) in the transition metal complex (a) of 1 to 10 000 It is preferably used in an amount such that it becomes 10 to 500.

When the organoaluminum conjugate (c) is used, it is used in an amount of usually about 0 to 5 mmol, preferably about 0 to 2 mmol, per liter of polymerization volume.

The copolymerization reaction is usually carried out at a temperature of 40 to 200 ° C, preferably 40. C to 180 ° C, more preferably in the range of 50 ° C to 150 ° C, and the pressure is higher than 0 to 10 MPa, preferably in the range of more than 0 to 7 MPa. Is

The reaction time (average residence time when the copolymerization is carried out by a continuous method) varies depending on conditions such as the catalyst concentration and the polymerization temperature, but is usually 5 minutes to 3 hours, preferably 10 minutes to 1.5. Time.

The propylene and at least one type of olefin selected from α-olefins and polyolefins other than propylene are supplied to the polymerization system in such amounts that a desired propylene-based copolymer is obtained. At the time of copolymerization, a molecular weight regulator such as hydrogen can be used.

The 0: -olefins other than propylene used in the present invention include ethylene, 1

—Butene, 1-pentene, 1-hexene, 4-—Methylenol 1-pentene, 3-methyl-1-11-pentene, 1-heptene, 1-otaten, 1-nonene, 1-decene, 1-decene, 1-dodecene , 1-tetradecene, 11-hexadecene, and 11-otadecene, and the like. Ethylene, 1-butene, 4-methylen-111-pentene, 11-hexene, and 11-otatenene are preferred. Polyene used in the present invention includes gen or triene. Specific examples of the gen include 1,4-pentane, 1,5-hexadiene, 1,4-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1, Non-conjugated gens such as 7-year-old octadiene, ethylidene norvonolenene, biernorbornene, dicyclopentadiene, 7-methyl_1,6-octadiene, 4-ethylidene-18-methyl-1-1,7-nonadiene; butadiene; A synergistic gen such as isoprene is mentioned. ,

Specific examples of triene include 6,10-dimethinolene 1,5,9-ndenetriene, 4,8-dimethyl-1,4,8-decatriene and 5,9-dimethyl-1,4,8 -Decatriene, 6,9-dimethyl-1,5,8-decatriene, 6,8,9-trimethyl-1,5,8-decatriene, 6-ethylo 10-methyl-1,5,9-one-dekatrien, 4-ethylidene 1,6 , O-octadiene, 7-methyl-1,4-ethylidene-1,6-o-octadiene, 4-ethylidene-1,8-methyl-1,7-nonadien, 7-methyl-4, ethylidene 1,6-nonadiene, 7-etinolide 4-ethylidene — 1,6-nonadiene , 6,7-Dimethyl-4-ethylidene-1,6-octadiene 6,7-Dimethyl-4-ethylidene-1,6-nonadiene, 4-ethylidene-1,

6-decadiene, 7-methyl-4-ethylidene-1,6-decadiene, 7-methyl-1-6-propyl-1-4-ethylidene 1,6-octadiene, 4-ethylidene-1,

Non-conjugated trienes such as 7-nonagen, 8-methyl-4-ethylidene_1,7-nonagen, 4-ethylidene-1,7-dedecanegen;

Conjugated trienes such as 1,3,5-hexatriene are exemplified. Among them, 4,8-dimethyl-1,4,8-decatriene and 4-ethylidene-8-methinole 1,7-nonadien (EMND) are preferred.

The above-mentioned Jen and Trien can be used alone or in combination of two or more. Also, a combination of Trien and Jen can be used. Among these polyenes, those having a norpolenene skeleton are particularly preferred.

When propylene is copolymerized with at least one type of olefin selected from α-olefins other than propylene as described above, propylene is obtained. The system copolymer is usually obtained as a polymerization solution containing this. This polymerization solution is processed by a conventional method to obtain a propylene-based copolymer.

Propylene copolymer

Using the above catalyst system, propylene and at least one kind of olefins selected from olefins other than propylene are copolymerized under the conditions described above. Is obtained.

The propylene-based copolymer obtained from the production method of the present invention has a constitutional unit derived from propylene of 95 mol / ⁰ . To 40 mol ^_0/0, preferably 90-65 mol%, preferably to more desirable to include within the scope of 90 to 70 mol%.

Further, other than propylene α- Orefin is ethylene, 1-butene, 4-methylcarbamoyl Lou 1 one-pentene, 1 one hexene, 1 is preferably selected from Okuten, 5-40 mol structural units derived from these ⁰ / _0, preferably 10 to 35 mole ^_0/0, more preferably 10-30 mol. It is desirable to include within the / ₀ range.

Further, in the propylene-based copolymer obtained by the production method of the present invention, the polyene is preferably selected from the group consisting of gen and triene, and particularly preferably has a norbornene skeleton. It is desirable to include the structural unit derived from this in the range of 0 to 20 mol%.

The iodine value of the propylene copolymer using the above-mentioned polyene is usually 1 to 80, preferably 5 to 60.

The propylene copolymer obtained from the production method of the present invention has a density of 0.855 to 0.904 g / cm ³ , preferably 0.8855 to 900 g / cm ³ , more preferably 0.855 to 900 g / cm ³ . It is preferably in the range of 0.890 gZ cm ³ . It is desirable that the propylene-based copolymer obtained from the production method of the present invention has a melting point (Tm) of 60 ° C. or lower, preferably 40 ° C. or lower, more preferably has no melting point. The propylene copolymer obtained from the production method of the present invention has a melt flow rate (MFR; ASTM D 1238, 190 ° C, load 2.16 kg) of 0.01 to 200 g / 10 minutes, preferably 0.1 to 200 g / 10 minutes. It is desirably in the range of 05 to 100 _§ 10 minutes, more preferably 0.05 to 80 gZlO. The propylene copolymer obtained from the production method of the present invention has a molecular weight distribution (Mw / Mn, in terms of polystyrene, Mw: weight average molecular weight, Mn: number average molecular weight) of 4 or less, preferably measured by GPC. It is desirable to be 3.0 or less. The thermoplastic resin composition containing the propylene copolymer having the above characteristics obtained by the method for producing a propylene copolymer according to the present invention has transparency, flexibility, heat sealing, and impact resistance. Excellent balance with.

(Example)

• Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited to these Examples.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples.

The physical test conditions are described below.

1. Melting point (Tm) and glass transition temperature (Tg): Determine the endothermic curve of DSC, and let the temperature at the maximum peak position be Tm.

For the measurement, the sample was packed in an aluminum pan, heated to 200 ° C at 100 ° C / min, held at 200 ° C for 5 minutes, cooled to 10 ° C / min to 150 ° C, and then cooled to 10 ° C. ° C

It was determined from an endothermic curve when the temperature was increased by Z minutes.

The degree of crystallinity (%) can be determined by calculating the heat of fusion per unit weight from the endothermic peak during DSC measurement and dividing by the heat of fusion of polyethylene crystal 7 Ocal / g. .

2. Intrinsic viscosity []

Measured in decalin at 135 ° C.

3. Molecular weight distribution (Mw / Mn)

The measurement was performed at 140 ° C. by using GPC (genole permeation chromatography) in an orthodichlorobenzene solvent.

4. Composition of copolymer

The composition of the copolymer was as follows: a sample in which about 200 mg of a polymer was uniformly dissolved in 1 m1 hexaclobutadiene in a 10 mm φ sample tube was measured at a measurement temperature of 120 ° C. Frequency 25. 02 MH z, spectral width 1500 H z, pulse repetition time 4. 2 sec., Is determined by ¹³ C-NMR spectra measured under the conditions of the pulse width 6 mu sec..

[Synthesis example 1]

(Synthesis of dipheninolemethylene (cyclopentageninole) (Ottamethinolesig Droben zylfluorenyl) zirconium dichloride)

(i) Synthesis of cyclopent pentagenenyl (Ottamethinole octahydride dibenzofluorenyl) dipheninolemethane

After thoroughly replacing the 200 ml nitrous flask equipped with a magnetic stir bar, a three-way cock and a 50 ml dropping funnel with nitrogen, 4.00 g (10.4 mm o 1) of otatamethyloctahydrodibenzofluorene was added. And 50 ml of tetrahydrofuran. While cooling in an ice-water bath, 6.6 ml (l lmmol) of a 1.63 ml / l n-butyllithium Z hexane solution was slowly added, followed by stirring at room temperature under a nitrogen atmosphere for 1 day to form a red-orange solution. Obtained. While cooling in a methanol / dry ice bath, 3.11 g (13.5 mmo 1) of 6,6-diphenylfulvene, previously dissolved in 3 Om 1 of tetrahydrofuran, were gradually added over 30 minutes using a dropping funnel. Was. Thereafter, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 23 hours under a nitrogen atmosphere to obtain a dark red solution. 2 Oml of 1 N hydrochloric acid was gradually added thereto, followed by stirring for 10 minutes, followed by addition of 100 ml of getyl ether. The resulting two-layer solution was transferred to a 300 ml separatory funnel and shaken several times, after which the colorless and transparent aqueous layer was removed. Subsequently, the obtained organic layer was washed twice with 3 Oml of water, twice with 30 ml of saturated saline, and dried over anhydrous magnesium sulfate for 1 hour. The solid was separated by filtration, and the solid obtained by evaporating the solvent with a rotary evaporator was washed with methanol to obtain 4.64 g of a yellow-white solid. Then, separation by silica gel chromatography (silica gel ^: 200 g, solvent: hexane / dichloromethane mixed solution (hexane: dichloromethane = 9: 1)) was performed, and cyclopentagenenyl (octamethyl) was obtained as a pale yellow solid. Octahydrodibenzofluorenyl) diphenylmethane was obtained. The yield was 3.38 g (5.48 mmo 1), and the yield was 52.9%. Cyclopenta geninole (Otata methyl octahedro dozenbenzofluoreninole) Dipheninolemethane Was identified using ¹ H-NMR spectrum and FD-MS spectrum. The measurement results are shown below.

¾-Hidden spectrum (270MHz, CDCI3): δ / ppm 1.0-1.3 (m, Me (OMOHDBFlu), 24H), 1.5-1.7 (br, CH ₂ (OMOHDBFlu), 8H), 2.8—3.1 (br, CH ₂ (Cp), 1H), 5.3-5.5 (m, CH (9- OMOHDBFlu), 1H), 6.0-6.6 (br, Cp, 4H), 6.9-7.5 (br, Ar (OMOHDBFlu) & Ph. 12H) , 7.29 (s, Ar (OMOHOBFlu), 2H) FD—MS spectrum: M / z 616

(ii) Synthesis of diphenylmethylene (cyclopentagenenyl) (octamethinole octahydride, rhodibenzofluorenyl) zirconium dichloride 100 ml girdal flask equipped with a magnetic stirrer was sufficiently purged with nitrogen. After that, 1.51 g (2.44 mmo 1) of pentagenenyl (otatamethyloctahydrodibenzobenzofluorenyl) diphenylmethane was added thereto, and 35 ml of getyl ether was added to obtain a pale yellow solution. While cooling in an ice-water bath, 3. lml (5: 1 mm 01) of 1.64mo 1/1 n-butyllithium / hexane solution was gradually added, and the mixture was stirred at room temperature under a nitrogen atmosphere for 25 hours. A slurry consisting of a red solid and a red-orange solution was obtained. While cooling in a methanol Z dry ice bath, add 0.884 g (2.34 mmo 1) of the zirconium tetrahydrofuran complex (1: 2) and gradually raise the temperature to room temperature. For 3 days to obtain a slurry composed of a red-pink solid and a red solution. The red solid obtained by evaporating the solvent under reduced pressure was extracted with hexane to obtain a pale red solution. The solvent of this solution was distilled off under reduced pressure to obtain diphenylmethylene (cyclopentagel) (otatamethyloctahydrodibenzofluorenyl) zirconium dichloride as a red-pink solid. The yield was 1.14 g (1.47 mmo 1), and the yield was 62.7%. The identification of diphenylmethylene (cyclopentagenyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride was carried out by means of] H-NMR spectrum and FD-MS spectrum. The measurement results are shown below.

¾Thigh spectrum (270MHz, CDCI3): δ / ppm 0.82 (s, Me (OMOHDBFlu), 6H), 0.94 (s, Me (OMOHDBFlu), 6H), 1.40 (s, Me (OMOHDBFlu), 6H) , 1.46 (s, Me (OMOHDBFlu ), 6H), 1.5 - 1.7 (m, CH 2 (OMOHDBFlu), 8H), 5. 55 (t, J = 2.6Hz, Cp, 2H), 6.8 (s, Ar ( OMOHDBFlu), 2H), 6.27 (t, J = 2.6Hz, Cp, 2H), 7.2-7.5 (m, Ph, 6H), 7.8-8.0 (m, Ph, 4H), 8.05 (s, Ar (Flu), 2H) FD—MS spectrum: M / z 776)

(Example 1) ''

(Synthesis of syndiotactic propylene-ethylene copolymer (1-①)) Vacuum drying was performed. At room temperature, 616.6 ml of heptane was added to a 1.5-liter autoclave, which had been replaced with nitrogen. A 1.0 millimol of isobutyl aluminum is added to a solution of Zm1 in toluene in terms of aluminum atoms so that the amount becomes 0.3 millimol / liter, and propylene is added with stirring to 50.7 liters (25 ° C, 1 atm. ) Charged, heating started and reached 40 ° C. Then, the system was pressurized with ethylene to 0.78 MPa (gauge pressure), and diphenylmethylene (cyclopentagenenyl) synthesized in Synthesis Example 1 (Ottameti / Legich Drovenzoinolenophenol) was synthesized. ) A solution of zirconium dichloride in heptane (0.0003 mM / m 1) and a solution of triphenylcarbenetetra (pentaf / leo-furyl) borate in toluene (0.000003 mM / m 1) were added to each. 0003 mmol / liter, 0.0012 mmol Z liter, and the copolymerization of propylene and ethylene was started.

During the polymerization, the internal pressure was maintained at 0.78 MPa (gage pressure) by continuously supplying ethylene. 1.2 minutes after the start of the polymerization, the polymerization reaction was stopped by adding methyl alcohol. After depressurizing, the polymer solution is taken out, and the polymer solution is washed with 1: 1 water solution containing 5 ml of concentrated hydrochloric acid per 1 liter of the polymer solution, and the catalyst residue is removed. Was transferred to the aqueous phase. After allowing this catalyst mixed solution to stand, the aqueous phase was separated and removed, and further washed twice with distilled water, and the polymerization liquid phase was separated into oil and water. Next, the polymer liquid phase separated from the oil and water was brought into contact with 3 times the volume of acetone under vigorous stirring to precipitate the polymer. After that, the polymer was sufficiently washed with acetone and the solid part (copolymer) was collected by filtration. . It was dried at 130 ° C and 35 OmmHg for 12 hours under flowing nitrogen.

The yield of the syndiotactic propylene-ethylene copolymer obtained as above was 30.7 g, and the intrinsic viscosity [η] measured in dephosphorus at 135 was 4.77 d 1 / g and the polymerization activity is 681.6 kg / mM-cathr. there were. The glass transition temperature Tg is an 28 ° C, the ethylene content is 27.0 molar ^_0/0, the molecular weight was measured by GPC distribution (Mw / M n) is 2 was 3.

[Synthesis example 2]

(Synthesis of di (p-torinole) methylene (cyclopentageninole) (octamethyldihydrobenzoylfluorenyl) zirconium dichloride)

(i) Synthesis of cyclopentagenenyl (otatamethyloctahydrodibenzofluorenyl) di-p-tolylmethane

After sufficiently replacing the 300 ml difluoro flask equipped with a magnetic stirrer, a three-way cock and a 50 m 1 dropping funnel with nitrogen, add 2 98 g (7.7 lmmo 1) of otatamethyl otahydrodibenzofluorene and add tetrahydrofuran. 60 ml was added to obtain a colorless and transparent solution. While cooling in an ice-water bath, 5.2 ml (8.lmmo 1) of a 1.56 mo 1/1 n-butyllithium / hexane solution was gradually added, followed by stirring at room temperature under a nitrogen atmosphere for 7 hours. An orange solution was obtained. While cooling in a methanol Z dry ice bath, 2.40 g (9.27 mmo 1) of 6,6-di_p-tolylfulvene preliminarily dissolved in tetrahydrofuran 3 Om 1 is gradually added using a dropping funnel over 20 minutes. Added. Thereafter, the temperature was gradually raised to room temperature, and the mixture was stirred at room temperature for 21 hours under a nitrogen atmosphere to obtain a dark red solution. 100 ml of a saturated aqueous solution of ammonium chloride was gradually added, followed by 100 ml of getyl ether. The resulting two-layer solution was transferred to a 30 Oml separatory funnel and shaken several times, after which the colorless and transparent aqueous layer was removed. Subsequently, the obtained organic layer was flowed twice with 100 ml of water and once with 100 ml of saturated saline, and dried over anhydrous magnesium sulfate for 30 minutes. The solid was separated by filtration, and the solid obtained by distilling the solvent off with a rotary evaporator was washed with hexane to obtain cyclopentapentaenyl (octamethyl otatahydrodibenzobenzofluorenyl) g-p-tolylmethane as a white solid. . The yield was 3.55 g (5.5 Ommo 1), and the yield was 71.3%. The identification of cyclopentagel (otatamethyloctahydrodibenzofluorene) di-p-tolylmethane was carried out with ¹ H-NMR spectrum and FD-MS spectrum. The measurement results are shown below.

¾-NMR spectrum _{(270MHz, CDC1 3):.} Δ / ppm 0.8-1.7 (m, Me (OMOHDBFlu), 24H), 2.1-2 (br, CH 2 (OMOHDBFlu), 8H), 2.7-3.1 (br, CH ₂ (Cp), 1H), 5.2-5. (M, CH (9- OMOHDBFlu), 1H), 5.8-6.5 (br, Cp, 4H), 6.7-7.5 (br, Ar (OMOHDBFlu) & Ar (p-tol), 10H), 7.29 (s, Ar (OMOHDBFlu), 2H) FD-MS spectrum: M / z 644 (¾f)

(ii) Synthesis of di (p-torinole) methylene (cyclopentagenenyl) (octamethyloctahydroxybenzozofluorenyl) zirconium dichloride

After sufficiently purging the 10 Oml Gildal flask equipped with a magnetic stirrer with nitrogen, the octapentadeninole (Ottamethinole octahydridine benzobenzofluorenyl) g-p-tolylmethane 1.O lg (1.56 mm o 1 ) Was added, and 30 ml of getyl ether was added to obtain a colorless and transparent solution. While cooling in an ice-water bath, gradually add 1.5 ml / l of n-butyllithium hexane solution 2.lml (3.3 mmo 1) and stir at room temperature under a nitrogen atmosphere for 20 hours to obtain a red A slurry consisting of a solid and a red solution was obtained. After adding 0.552 g (1.46 mmo 1) of zirconium tetrachloride / tetrahydrofuran complex (1: 2) while cooling in a methanol / dry ice bath, the temperature is gradually raised to room temperature, and the temperature is increased to room temperature for 24 hours in a nitrogen atmosphere. By stirring, a slurry composed of a red-pink solid and a red solution was obtained. The red solid obtained by evaporating the solvent under reduced pressure was washed with hexane and then extracted with dichloromethane to obtain a red solution. The solvent of this solution was distilled off under reduced pressure to obtain di (p-tolyl) methylene (cyclopentagenenyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride as a red-pink solid. . The yield is 0.825 g (1.02 mmo 1). The yield was 70.2%. The identification of di (p-trinore) methylene (cyclopentadienyl) (otatamethyloctahydrodibenzofluorenyl) zircoium dichloride was performed by using —NMR spectrum FD—MS spectrum. The measurement results are shown below.

¾ -賺Supe spectrum (270 thigh _{z, CDC1 3): δ /} ppm 0.82 (s, Me (OMOHDBFlu), 6H), 0.93 (s, Me (OMOHDBFlu), 6H), 1.40 (s, Me (OMOHDBFlu) , 6H), 1.46 (s, Me (OMOHDBFlu), 6H), 1.5-1.7 (m, CH ₂ (OMOHDBFlu), 8H), 2.32 (s, Me, 6H), 5.53 (t, J = 2.6 Hz , Cp, 2H), 6.17 (s, Ar (OMOHDBFlu), 2H), 6.25 (t, J = 2.6 Hz, Cp, 2H), 7.1-7.3 (m, Ar (p-tol), 4H), 7.6- 7.8 (m, Ar (p-tol), 4H), 8.03 (s, Ar (Flu), 2H) FD-MS spectrum: M / z 804 (It)

(Example 2)

(Synthesis of propylene-ethylene copolymer (1-②))

In Example 1, diphenylmethylene (cyclopentagel) (octamethyldihydrobenzoylfluorenyl) zirconium dichloride was prepared using the di (p-tolyl) methylene (cyclopentane) synthesized in Synthesis Example 2. The same operation as in Synthesis Example 1 was carried out except that the polymerization time was changed to 15 minutes, instead of genyl) (otatamethyl dihydrobenzoylfluorenyl) zirconium dichloride.

The yield of the obtained propylene-ethylene polymer was 29.5 g, the intrinsic viscosity [η] measured in 135 ° C decalin was 4.63 dlZg, and the polymerization activity was 523.7 kg. / mM-cat · hr. The glass transition temperature The T g is one 30. 6 ° C, the ethylene content is 3 1.0 mole ^_0/0, the molecular weight distribution measured by GPC (Mw / Mn) is 2. was 2.

(Example 3)

(Synthesis of propylene-ethylene copolymer (1-3))

In Synthesis Example 1, dipheninolemethylene (cyclopentapentaenyl) (otatamyldihydrobenzoylfluorenyl) zirconium dichloride was synthesized in Synthesis Example 2 to obtain di (p-trinole) methylene (cyclopentagenenyl). (Otamethinoresihydrobenzoylfluorenyl) Changed to zirconium dichloride, and pressurized the system with ethylene to 0.74 MPa (good pressure), and changed the polymerization time to 20 minutes. Other than the above, the same operation as in Synthesis Example 1 was performed.

The yield of the obtained propylene-ethylene copolymer was 58.9 g, 135. The intrinsic viscosity [η] measured in C-decalin was 4.6,1 d 1 / g, and the polymerization activity was 785.2 kg / mM-cat · hr. The glass transition temperature The T g is a one 26.6, Echiren content is 26.1 mole ^_0/0, the molecular weight distribution measured by GPC (Mw / Mn) is 2. 1.

(Example 4)

(Syndiotactic propylene-ethylene copolymer (1 -④)) To a 1.5-liter autoclave dried under reduced pressure and purged with nitrogen, 675.9 ml of heptane was added at room temperature, and then 1.0 ml of triisobutylaluminum Zm1 Propylene was charged at 28.2 liters (25 ° C, 1 atm) with stirring, and the temperature was raised to 70 ° C. Then, the system was pressurized with ethylene to a pressure of 0.76 MPa (gauge pressure), and diphenylmethylene (cyclopentagenenyl) (otatamethyldihydroxybenzoylfluorenyl) synthesized in Synthesis Example 1 was used. Heptane solution of lido (0.0003 mM / m 1) and toluene solution of triphenylcarbenium tetra (pentafluorophenyl) porate (0.0003 mM / m 1) were 0.0003 mmol Z liter, respectively. [0012] In addition, the copolymerization of propylene and ethylene was started so that the volume became liters in milliliters.

During the polymerization, the internal pressure was maintained at 7.8 kg / cm ² G by continuously supplying ethylene. Twenty minutes after the start of the polymerization, the polymerization reaction was stopped by adding methyl alcohol. After depressurizing, the polymer solution is taken out, and the polymer solution is washed with an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water in a ratio of 1: 1. The catalyst residue was transferred to the aqueous phase. After the catalyst mixed solution was allowed to stand, the aqueous phase was separated and removed, and further washed twice with distilled water. The polymerization liquid phase was separated into oil and water. Next, the polymer liquid phase separated from the oil-water mixture was brought into contact with 3 times the volume of acetone under vigorous stirring to precipitate the polymer. After that, the polymer was sufficiently washed with acetone and the solid part (copolymer) was collected by filtration. . It was dried for 12 hours at 130 ° C and 350: 0111111 _§ under flowing nitrogen.

The yield of the syndiotactic propylene-ethylene copolymer obtained as described above was 31.6 g, and the intrinsic viscosity [7] measured in 1'35 'dephosphorus was 2.98 d 1 Zg and the polymerization activity was 420.7 kg ZmM—cat · hr. The glass transition temperature The T g is an 39. 2 ° C, the ethylene content is 38.1 mole ^_0/0, the molecular weight was determined by G PC distribution (Mw / Mn) of 2. two der.

(Example 5) (Synthesis of syndiotactic propylene-ethylene copolymer (1-⑤)) To a 1.5 liter autoclave, which had been replaced with nitrogen, was added 700.5 m1 of heptane at room temperature, followed by drying under reduced pressure. Then, a 1.0 millimol / m1 toluene solution of triisobutylaluminum was added so that the amount of aluminum was converted to 0.3 millimol in terms of aluminum atoms, and 8.8 l of propylene was added with stirring. (25 ° C, 1 atm) was charged, the temperature was raised and reached 90 ° C. Then, the system was pressurized with ethylene to 0.65MPa (gauge pressure), and diphenylmethylene synthesized in Synthesis Example 1 (cyclopentapentageninole) (Otamethinoresihydrobenzobenzoinolef / leorenyl) A heptane solution of zirconium dichloride (0.0003 mM / ml) and a toluene solution of trifenylcarbenyltetra (pentaphnoleolophenolate) porate (0.0003 mM / m 1) were prepared in 0.0003 each. The addition was performed so that the amount became 0.002 mmol / liter, and the copolymerization of propylene and ethylene was started.

During the polymerization, the internal pressure was maintained at 0.65 MPa (gauge pressure) by continuously supplying ethylene. Twenty minutes after the start of the polymerization, the polymerization reaction was stopped by adding methyl alcohol. After depressurization, the polymer solution is taken out, and the polymer solution is washed with 1: 1 water solution containing 5 ml of concentrated hydrochloric acid in a ratio of 1: 1. The residue was transferred to the aqueous phase. After allowing this catalyst mixed solution to stand, the aqueous phase was separated and removed, and further washed twice with distilled water, and the polymerization liquid phase was separated into oil and water. Then, the polymerization liquid phase separated from the oil and water was brought into contact with 3 times the volume of acetone under vigorous stirring to precipitate the polymer. After that, the polymer was sufficiently washed with acetone and a solid part (copolymer) was collected by filtration. It was dried at 130 ° C. and 35 OmmHg for 12 hours under flowing nitrogen.

The yield of the syndiotactic propylene-ethylene copolymer obtained in the manner described above was 5.2 g, and the intrinsic viscosity [η] measured in decalin at 135 was 2.25 d 1 Z g. The polymerization activity was 69.2 kg / mM-cat · hr. The glass transition temperature Tg is _ 29. 2 ° C, the ethylene content is 29.0 molar ^_0/0, the molecular weight distribution measured by GPC (Mw / Mn) is 2. was 3.

(Example 6) (Syndiotactic propylene-ethylene-based copolymer (1-⑥)) '' To a 1.5-liter autoclave dried under reduced pressure and purged with nitrogen, add 70.5 ml of heptane at room temperature, and then add A solution of triisobutylaluminum (hereinafter abbreviated as TIBA) in 1.0 mmol Zm1 toluene solution was converted to aluminum atoms so that the amount became 0.3 mmol / L, and propylene was added under stirring with 18. Eight liters (25 ° C, 1 atm) were inserted, and the temperature was raised to reach 90 ° C. Thereafter, the system is pressurized with ethylene to a pressure of 6.6 kgZcm2G, and diphenylmethylene (cyclopentagel) (otatamethyldihydrobenzoylfluorenyl) zirconium dichloride synthesized by a known method. Heptanes solution (0.0003 mM / m 1) and methylaluminoxane toluene solution (0.3 mM / m 1) were added to give 0.001 mmol / L and 0.3 mmol / L, respectively, and propylene was added. And the copolymerization of ethylene was started.

During the polymerization, the internal pressure was maintained at 6.6 kg / cm2 G by continuously supplying ethylene. Twenty minutes after the start of the polymerization, the polymerization reaction was stopped by adding methyl alcohol. After depressurizing, the polymer solution is taken out, and the polymer solution is washed with an aqueous solution obtained by adding 5 ml of concentrated hydrochloric acid to 1 liter of water in a ratio of 1: 1. The catalyst residue was transferred to the aqueous phase. After the catalyst mixed solution was allowed to stand, the aqueous phase was separated and removed, and further washed twice with distilled water. The polymerization liquid phase was separated into oil and water. Next, the polymer liquid phase separated from the oil-water mixture was brought into contact with 3 times the volume of acetone under vigorous stirring to precipitate the polymer. After that, the polymer was sufficiently washed with acetone and the solid part (copolymer) was collected by filtration. . It was dried at 130 ° C and 35 OmmHg for 12 hours under flowing nitrogen. The yield of the syndiotactic propylene-ethylene copolymer obtained as described above was 31.3 g, and the intrinsic viscosity [] measured in 135 ° C dephosphorus was 3.55 d 1 / g, and the polymerization activity was 250.4 kg / mM-cat.hr. The glass transition temperature Tg is one 28. 2 ° C, the ethylene content is 26.0 mole ^_0/0, the molecular weight was determined by G PC distribution (Mw / Mn) of 2.3 der ivy ₀

(Comparative Example 1)

(Syndiotactic Synthesis of Propylene-Ethylene Copolymer (2-①)) In a 1.5 liter autoclave, dried under reduced pressure and purged with nitrogen, 616.6 ml of heptane was added at room temperature, followed by a 1.0 mmol Zml toluene solution of triisobutylaluminum (hereinafter abbreviated as TIBA). Was converted to aluminum atoms so that the amount became 0.3 mmol / l, and propylene was charged under stirring with 50.7 liters (25 ° C, 1 atm), and the temperature was increased. 40 ° C was reached. Then, the system is pressurized with ethylene to a pressure of 0.68 MPa (gauge pressure), and heptane of diphenylmethylene (cyclopentageninole) (fluorenyl) zirconium dichloride synthesized by a known method is used. A solution (0.000003 mM / m 1) and a toluene solution (0.0003 mM / m 1) of triphenylene pentabenzoate (0.003 mM / m 1) were dissolved in 0.0003 mmol Z-litre, respectively. , 0.0012 mmol Z liter, and the copolymerization of propylene and ethylene was started. ~

During the polymerization, the internal pressure was maintained at 0.68 MPa (gage pressure) by continuously supplying ethylene. 45 minutes after the start of the polymerization, the polymerization reaction was stopped by adding methyl alcohol. After depressurization, the polymer solution was taken out, and the polymer solution was washed with 1: 1 water solution containing 5 ml of concentrated hydrochloric acid per 1 liter of water. The residue was transferred to the aqueous phase. After allowing this catalyst mixed solution to stand, the aqueous phase was separated and removed, and further washed twice with distilled water, and the polymerization liquid phase was separated into oil and water. Then, the polymerization liquid phase separated from the oil and water was brought into contact with 3 times the volume of acetone under vigorous stirring to precipitate the polymer. After that, the polymer was sufficiently washed with acetone and a solid part (copolymer) was collected by filtration. It was dried at 130 ° C. and 35 OmmHg for 12 hours under flowing nitrogen.

The yield of the syndiotactic propylene-ethylene copolymer obtained as described above was 66.3 g, 135. C The intrinsic viscosity [η] measured in phosphoric acid was 2.04 dlZg, and the polymerization activity was 392.7 kg / inM-cat · hr. The glass transition temperature T g is -12.6. Is C, the ethylene content is 21.0 molar ^_0/0, the molecular weight was measured by GPC distribution (Mw / M n) is 2. Atsuta 3.

(Comparative Example 2)

(Syndiotactic propylene-ethylene copolymer (2-②)) To a 1.5 l autoclave dried under reduced pressure and purged with nitrogen, 616.6 ml of heptane is added at room temperature, followed by 1.0 mmol / m'l toluene of triisobutylaluminum (hereinafter abbreviated as TIBA). The solution was converted to aluminum atoms so that the amount was 0.3 mmol / liter, and propylene was charged under stirring with 50.7 liters (25 ° C, 1 atm), and the temperature was raised. And reached 40 ° C. The system is then pressurized with ethylene to a pressure of 0.68 MPa (gauge pressure), and diphenylmethylene (cyclopentagenenyl) (fluorene) zirconium dichloride synthesized by a known method is used. A heptane solution (0.0003 mM / m 1) and a toluene solution of methylaluminoxane (aluminum concentration: 3.00 mM / m 1) were added to give 0.0003 mmol Z liter and 0.12 mmol / L, respectively. Copolymerization of propylene and ethylene was started.

During the polymerization, the internal pressure was maintained at 0.68 MPa (gage pressure) by continuously supplying ethylene. Sixty minutes after the start of the polymerization, the polymerization reaction was stopped by adding methyl alcohol. After depressurization, the polymer solution was taken out, and the polymer solution was washed with 1: 1 water solution containing 5 ml of concentrated hydrochloric acid per 1 liter of water. The residue was transferred to the aqueous phase. After allowing this catalyst mixed solution to stand, the aqueous phase was separated and removed, and further washed twice with distilled water, and the polymerization liquid phase was separated into oil and water. Then, the polymerization liquid phase separated from the oil and water was brought into contact with 3 times the volume of acetone under vigorous stirring to precipitate the polymer. After that, the polymer was sufficiently washed with acetone and a solid part (copolymer) was collected by filtration. It was dried at 130 ° C and 35 OmmHg for 12 hours under flowing nitrogen.

The yield of the syndiotactic propylene-ethylene copolymer obtained in the manner described above was 30.7 g, and the intrinsic viscosity [η] measured in 135 kg and phosphoric acid was 2.01 d 1 / g and the polymerization activity was 136.4 kg / mM_cat · hr. The glass transition temperature Tg is one 26. 2 ° C, the ethylene content is 22.0 mole ^_0/0, the molecular weight distribution measured by G PC (Mw / Mn) is 2.1 der ivy.

(Comparative Example 3)

(Synthesis of syndiotactic propylene-ethylene copolymer (2-③)) In Comparative Example 1, the place where propylene was charged at 50.7 liters (25 ° C, 1 atm) was changed to 28.2 liters, and the place where the temperature was raised to 40 ° C was changed to 70 ° C. The same operation as in Comparative Example 1 was performed, except that the place where polymerization was started and stopped 45 minutes later was changed 20 minutes later.

The yield of the obtained propylene-ethylene copolymer was 35.2 g, the intrinsic viscosity [η] measured in decalin at 135 ° C was 1.38 dlZ _g , and the polymerization activity was 469.1 kg /. mM-cat · hr. The glass transition temperature The T g is one 26. 6 ° C, the ethylene content is 23.1 mole ^_0/0, the molecular weight distribution measured by G PC (Mw / Mn) is 2. 1.

(Comparative Example 4)

Synthesis of Pyrene-Ethylene Copolymer (3- において)) In Comparative Example 1, diphenylmethylene (cycopent pentageninole) (fluorene dinore) dinorecone dichloride was replaced with diphen-noremethylene (cyclopentadiene). 2) Change to (3,6-di-t-butylfluorenyl) zirconium dichloride, and change the loading of propylene to 50.-7 liters (25 ° C, 1 atm) to 28.2 liters The temperature was raised to 40 ° C and the temperature was changed to 70 ° C, and the system was pressurized with ethylene to 6.8 kgZcm ² G, and the pressure was changed to 7.2 kg / cm ² G. The same operation as in Comparative Example 1 was performed, except that the place where polymerization was started and stopped 45 minutes later was changed 20 minutes later.

The yield of the obtained propylene-ethylene copolymer was 38.7 g, the intrinsic viscosity [η] measured in 135 ° C decalin was 1.95 d 1 Zg, and the polymerization activity was 5.16.4 k. g / mM-cat · hr. The glass transition temperature The T g is _ 25. 1 ° C, Echiren content is 21.1 mole ^_0/0, the molecular weight distribution measured by GPC (Mw / Mn) is 2. 1. Industrial applicability

The method for producing a propylene copolymer according to the present invention has excellent polymerization activity, enables high-temperature polymerization production, and provides a propylene copolymer having a high molecular weight.

Claims

Claims (i) Forming an ionic complex by reacting a transition metal complex (a) represented by the following general formula (1) or (2) with (ϋ) (b) a transition metal complex (a) (C) an organoaluminum compound and (d) an organoaluminum conjugate in the presence of a catalyst system comprising at least one compound selected from the group consisting of propylene, an α-olefin other than propylene, A process for producing a propylene-based copolymer, characterized by copolymerizing at least one olefin selected from polyolefins and polyolefins;

(In the formulas (1) and (2), R ¹ R ² , R ³ , RR ⁵ , R ⁶ , R ⁷ and R ⁸ may be the same or different from each other, and represent a hydrogen atom, a hydrocarbon group ( represents a t-butyl group or a silicon-containing group (but not all of R ¹ to R ⁸ are hydrogen atoms), and adjacent substituents of R ¹ to R ⁸ are bonded to each other May form a ring

Y is an oxygen atom, a zeo atom,

^{^{^{(Wherein, R 9, R l R u}}} , R 12 may be the same or different from each other, a hydrogen atom, a halogen atom, a hydrocarbon group, Q is indicates Kei atom, a germanium atom or a tin atom, G represents a boron atom, a phosphorus atom or a nitrogen atom, and n represents an integer of 1 to 4.)

A represents a divalent hydrocarbon group having 2 to 20 carbon atoms which may partially include an unsaturated bond and / or an aromatic ring, and A represents two divalent hydrocarbon groups including a ring formed together with Z. It may contain the above ring structure,

Z represents a carbon atom or a silicon atom,

M represents Ti, Zr, Hf, Rn, Nd, 3111 or 111,

X represents a halogen atom, a hydrocarbon group, an anion ligand or a neutral ligand capable of coordinating with a lone electron pair.When j is 2 or more, Xs may be the same or different and j is 1 Indicates an integer from 4 to 4. ).

2. The method for producing a propylene-based copolymer according to claim 1, wherein in the formulas (1) and (2), M is Ti, Zr or Hf.

3. In the formula (1) or (2), at least one pair of adjacent substituents from R ¹ to R ⁸ is bonded to each other to form a ring. 3. The method for producing a propylene-based copolymer described in 1. above.

4. If Y in the above equation (1) is

4. The method for producing a propylene-based copolymer according to claim 1, wherein n is 1 or 2.