JP3096506B2 - Method for producing cyclic diene polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for efficiently producing a homopolymer or copolymer of a cyclic diene.

[0002]

2. Description of the Related Art Various methods for polymerizing cyclic dienes have been proposed.
For example, "Synthetic Organic Chemistry, 22 (1), 71-74 (1964)" describes an example of polymerization of norbornadiene using a Ziegler-Natta catalyst. However, in this example, sufficient catalytic activity was not obtained. As an example of polymerization of a cyclic unsaturated compound, "Organometallics, 1982 (1), 415-417"
Describes cationic polymerization using a palladium complex, but the yield of polymer per 1 mmol of the catalyst is 8 g.
However, it is hard to say that the catalytic activity is sufficient. Further, JP-A-2-167334 proposes polymerization of a cyclic diene using a catalyst comprising a transition metal compound and an aluminoxane. However, in this method, it is necessary to use aluminoxane at a high ratio to the transition metal compound as the main catalyst, and thus there is a problem that the product must be sufficiently demineralized after polymerization. Recently, a coordination complex compound comprising a special cation and an anion in which a plurality of groups are bonded to a metal has been reported (Japanese publication No. 1-502036), and when this coordination complex compound is used as a co-catalyst, It is known that olefins can be polymerized without using a large amount of a cocatalyst as compared with conventional ones.

On the other hand, the polymerization form of norbornadiene is represented by the general formula

Embedded image Ring-opening polymerization represented by the general formula

Embedded image Vinylene-type polymerization represented by the general formula

Embedded image Are known.

[0004] The ring-opening polymer of the above (1) can be obtained by using WCl ₆ / Me ₄ Sn as a catalyst, but has a drawback of being poor in moldability due to crosslinking. The vinylene polymer of the above formula (2) is obtained using a palladium (Pd) catalyst, but the polymerization temperature is 140 ° C.
Has a problem that the molecular weight is as low as about 5000 and decomposition occurs at about 200 ° C. (J. Appl. Chem. Biotechnol.,
23,601 (1973)). Further, the transannular polymer of the above formula (3) can be obtained by using an AlCl ₃ catalyst, but the polymerization temperature is as low as −123 ° C., and the polymerization conditions are severe.
There is a problem that the polymerization operation is difficult (J. Appl.
ym. Sci., 17, 2223 (1973)).

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a production method capable of efficiently producing a cyclic diene polymer without using a large amount of an organometallic compound as a promoter. Aim.

[0006]

According to one aspect of the present invention, there is provided a catalyst comprising the following compounds (A) and (B) as main components, or the following compounds (A) and (B): ) And a method for producing a cyclic diene-based polymer by performing homopolymerization of a cyclic diene (excluding compounds having only one double bond in the ring) using a catalyst containing (C) as a main component, respectively. I will provide a. (A) a transition metal compound having a cyclopentadienyl-based ligand containing a transition metal selected from Group IVB of the Periodic Table, and (B) a compound which reacts with the transition metal compound to form an ionic complex. And a compound comprising a cation and a boron compound-based anion in which a plurality of groups are bonded to a boron atom. (C) Organoaluminum Compound Another aspect of the present invention is a compound (A) or (B)
And copolymerization of a cyclic diene (excluding compounds having only one double bond in the ring) with an α-olefin using a catalyst containing (C) as a main component. Provided is a method for producing a cyclic diene polymer. (A) a transition metal compound having a cyclopentadienyl-based ligand containing a transition metal selected from Group IVB of the Periodic Table, and (B) a compound which reacts with the transition metal compound to form an ionic complex. Comprising a cation and a boron compound-based anion in which a plurality of groups are bonded to a boron atom (C) an organoaluminum compound

Hereinafter, the present invention will be described in more detail.
FIG. 1 shows the manufacturing method of the present invention. In the present invention,
As the compound (A), a transition metal compound containing a transition metal belonging to Group IVB of the periodic table and having a cyclopentadienyl-based ligand is used.

Here, as the transition metal compound having such a cyclopentadienyl-based ligand, various compounds can be cited, and a transition metal selected from Group IVB of the periodic table, ie, titanium (Ti) , Zirconium (Z
Compounds containing r) or hafnium (Hf) can be suitably used. In particular, the following general formulas (I) and (II)
Or a cyclopentadienyl compound represented by (III) or a derivative thereof is preferable. ^{_{CpM 1 R 1 a R 2 b}} R 3 c ... (I) Cp 2 M 1 R 1 d R 2 e ... (II) (Cp-A f -Cp) M 1 R 1 d R 2 e ... (III)

[In the general formulas (I) to (III), M ¹ is Ti,
Zp represents a Zr or Hf atom; It represents a saturated hydrocarbon group or a chain unsaturated hydrocarbon group. R ¹ , R ² and R ³ each represent a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms;
Σ-binding ligands such as aryl groups, alkylaryl groups or arylalkyl groups, acyloxy groups having 1 to 20 carbon atoms, allyl groups, substituted allyl groups, substituents containing silicon atoms, acetylacetonate groups, A chelating ligand such as a substituted acetylacetonate group or a ligand such as a Lewis base is shown, and A represents a crosslink by a covalent bond.
a, b and c each represent an integer of 0-3, d and e each represent an integer of 0-2, and f represents an integer of 0-6. R ¹ , R ²
And two or more of R ³ may be bonded to each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. (I
In the formulas I) and (III), two Cp's may be the same or different from each other. ]

The substituted cyclopentadienyl group in the above formulas (I) to (III) includes, for example, methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethyl Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,2
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like. Specific examples of R ^{1 to} R ⁴ include, for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom as a halogen atom; a methyl group, an ethyl group, an n-propyl group and an iso group as an alkyl group having 1 to 20 carbon atoms.
-Propyl group, n-butyl group, octyl group, 2-ethylhexyl group; a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a phenoxy group as an alkoxy group having 1 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; A phenyl group as an alkylaryl group or an arylalkyl group,
Tolyl group, xylyl group, benzyl group; heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; trimethylsilyl group, (trimethylsilyl) methyl group as a substituent containing a silicon atom: dimethyl ether, diethyl ether, tetrahydrofuran as a Lewis base And the like, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, N,
Amines such as N-dimethylaniline, pyridine, 2,2'-bipyridine and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; and linear unsaturated hydrocarbons such as ethylene, butadiene, 1-pentene, isoprene and pentadiene; 1-hexene and derivatives thereof; cyclic unsaturated hydrocarbons include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof. Examples of the crosslink by the covalent bond of A include a methylene crosslink, a dimethylmethylene crosslink, an ethylene crosslink, a 1,1′-cyclohexylene crosslink, a dimethylsilylene crosslink, a dimethylgermylene crosslink, and a dimethylstannylene crosslink. (I)
Among the compounds of the formulas (III) to (III), at least two of R ^{1 to} R ^{3 in} the formula (I) and R ¹ and R ^{2 in the} formulas (II) and (III)
Is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.

Examples of such compounds include the following compounds and compounds obtained by substituting zirconium of these compounds with titanium or hafnium. Compounds of formula (I) (pentamethylcyclopentadienyl) trimethylzirconium, (pentamethylcyclopentadienyl) triphenylzirconium, (pentamethylcyclopentadienyl) tribenzylzirconium, (pentamethylcyclopentadienyl) trichloro Zirconium, (pentamethylcyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) trimethylzirconium, (cyclopentadienyl) triphenylzirconium, (cyclopentadienyl) tribenzylzirconium, (cyclopentadienyl) trichloro Zirconium, (cyclopentadienyl) trimethoxyzirconium, (cyclopentadienyl) dimethyl (methoxy) zirconium, (methylcyclopentadienyl) trimethyldi Ruconium, (methylcyclopentadienyl) triphenylzirconium, (methylcyclopentadienyl) tribenzylzirconium, (methylcyclopentadienyl) trichlorozirconium, (methylcyclopentadienyl) dimethyl (methoxy) zirconium,
(Dimethylcyclopentadienyl) trichlorozirconium, (trimethylcyclopentadienyl) trichlorozirconium, (trimethylsilylcyclopentadienyl) trimethylzirconium, (tetramethylcyclopentadienyl) trichlorozirconium,

A compound of formula (II) bis (cyclopentadienyl) dimethylzirconium,
Bis (cyclopentadienyl) diphenyl zirconium, bis (cyclopentadienyl) diethyl zirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium , Bis (cyclopentadienyl) dihydridozirconium, bis (cyclopentadienyl) monochloromonohydridozirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclo Pentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) dimethyl zirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, Scan (pentamethylcyclopentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium,
Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium,

The compound of the formula (III) : ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclo) Pentadienyl) dimethyl zirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropyl (cyclopentadienyl) (9-fluorenyl) dichlorozirconium, [ Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Diphenylmethylene (cyclopentadienyl) (9-fluorenyl) dimethyl zirconium, ethylidene (9-
Fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclohexyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclopentyl (9-fluorenyl) (cyclopentadienyl) dimethyl zirconium, cyclobutyl (9-fluorenyl) (cyclopentane Dienyl) dimethyl zirconium,
Dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3
5-trimethylcyclopentadienyl) dimethyl zirconium, dimethylsilylenebis (indenyl) dichlorozirconium

[0014]

[0015]

[0016]

[0017]

[0018]

Next, as the compound (B), a compound which reacts with a transition metal compound (A) comprising a cation and an anion having a plurality of groups bonded to a specific element to form an ionic complex, especially a cation And a coordination complex compound comprising a boron compound-based anion in which a plurality of groups are bonded to a boron atom. As a compound comprising such a cation and an anion in which a plurality of groups are bonded to an element, a compound represented by the following formula (V) or (VI) can be suitably used. ^{([L 1 -R 7] k} +) p ([M 3 Z 1 Z 2 ... Z n] (nm) -) q ... (V) ([L 2] k +) p ([M 4 Z 1 Z 2 ... ^{Z n] (nm) -)} q ... (VI) ( where, L ² is ^{M 5, R 8 R 9 M} 6, R 10 3 C or R ¹¹
Is an M ⁶⁾

In the formulas (V) and (VI), L ¹ is a Lewis base, M ³ and M ⁴ are VB group, VIB group, V
IIB, VIII, IB, IIB, IIIA, IVA and
Element selected from Group VA, IIIB group of M ⁵ and M ^6, respectively Periodic Table, IVB group, VB group, VIB group, VIIB group, VIII
Family, IA Group, IB, Group IIA, element selected from Group IIB and VIIA group, Z ¹ to Z ⁿ are each a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, 6 carbon atoms
Aryloxy group having 20 to 20 carbon atoms, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, alkylaryl group, arylalkyl group, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 carbon atoms an acyloxy group, an organic metalloid group or a halogen atom, Z ¹ to Z ⁿ may form a ring of two or more thereof with each other. R ⁷
Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
20 aryl group, an alkyl group, or an arylalkyl group, each R ⁸ and R ⁹ are a cyclopentadienyl group, substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹⁰ is 1 to 20 carbon atoms It represents an alkyl group, an aryl group, an alkylaryl group or an arylalkyl group. R ¹¹ is tetraphenylporphyrin,
It shows a macrocyclic ligand such as phthalocyanine. m is M ³ , M
A valence of ⁴ and an integer of 1 to 7; n is an integer of 2 to 8; k is an integer of 1 to 7 as an ionic valence of [L ¹ -R ⁷ ] and [L ² ];
p is an integer of 1 or more, and q = (p × k) / (nm). ]

Specific examples of the above Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amines such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline; Phosphines such as fin, triphenylphosphine and diphenylphosphine;
Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; thioethers such as diethylthioether and tetrahydrothiophene; and esters such as ethylbenzoate. Specific examples of M ³ and M ⁴ include B, Al, Si, P, As, S
b, etc. Specific examples of M ⁵ are Li, Na, Ag, Cu,
Br, I, I _3, etc., Mn Specific examples of M ^6, Fe,
Co, Ni, Zn and the like can be mentioned. Z ¹ Specific examples of the to Z ^n, for example, dimethylamino group as a dialkylamino group, a diethylamino group; methoxy group as alkoxy group having 1 to 20 carbon atoms, an ethoxy group, n- butoxy group; C6-20 Phenoxy group, 2,6-dimethylphenoxy group, naphthyloxy group as aryloxy group; methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, n as alkyl group having 1 to 20 carbon atoms -Octyl group, 2-ethylhexyl group; a phenyl group, p-tolyl group, benzyl group, 4-tert-butylphenyl group, 2,6 as an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group;
-Dimethylphenyl group, 3,5-dimethylphenyl group,
2,4-dimethylphenyl group, 2,3-dimethylphenyl group; p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group, 3,4, 5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoromethyl) phenyl group; F, Cl, Br, I as a halogen atom; pentamethylantimony group, trimethylsilyl group, trimethyl gel as an organic metalloid group Examples include a mill group, a diphenylarsine group, a dicyclohexylantimony group, and a diphenylboron group. R ⁷ , R
Specific examples of the ^ten include the same ones as those described above. Specific examples of the substituted cyclopentadienyl group for R ⁸ and R ⁹ include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Can be Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected as an integer of 1 to 5. Among the compounds of the formulas (V) and (VI),
Preferably, M ³ and M ⁴ are boron.

Among the compounds of the formulas (V) and (VI), the following compounds can be particularly preferably used. Compound of formula (V) Triethylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyltri (n-butyl) ammonium tetraphenylborate, benzyltriphenyltetraborate (N-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, methyltriphenylammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, methyltetraphenylborate (2-cyanopyridinium ), Trimethylsulfonium tetraphenylborate, benzyldimethylsulfonium tetraphenylborate ,

Triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-tetrakis (pentafluorophenyl) borate)
Butyl) ammonium, triphenylammonium tetrakis (pentafluorophenyl) borate, tetrabutylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate, tetraethylammonium tetrakis (pentafluorophenyl) borate (methyltri (n- Butyl) ammonium), tetrakis (pentafluorophenyl) borate (benzyltri (n-butyl) ammonium), methyldiphenylammonium tetrakis (pentafluorophenyl) borate, methyltriphenylammonium tetrakis (pentafluorophenyl) borate tetrakis (pentafluorophenyl) Dimethylammonium borate, Anilinium tetrakis (pentafluorophenyl) borate, Teto Methylanilinium lakis (pentafluorophenyl) borate, dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyl (m-nitroanilinium) tetrakis (pentafluorophenyl) borate, tetrakis Dimethyl (pentafluorophenyl) borate (p-bromoanilinium), pyridinium tetrakis (pentafluorophenyl) borate, p-cyanopyridinium tetrakis (pentafluorophenyl) borate, N-methylpyridinium tetrakis (pentafluorophenyl) borate ), Tetrakis (pentafluorophenyl) borate (N-benzylpyridinium), tetrakis (pentafluorophenyl) borate (o-cyano-N-methylpirate) Dikis), tetrakis (pentafluorophenyl) borate (p-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p-cyano-N-benzylpyridinium), trimethylsulfonium tetrakis (pentafluorophenyl) borate, tetrakis Benzyldimethylsulfonium (pentafluorophenyl) borate, dimethylanilinium tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, tetraphenylphosphonium tetrakis (pentafluorophenyl) borate, triphenylphosphonium tetrakisphenylborate tetrakis (pentafluoro Phenyl) borate triphenylphosphonium tetrakisphenyldiphenylphosphonate tetrakis (pentafluorophenyl) borate dife Ruhosuhoniumu tetrakisphenyl borate diphenylmethyl phosphonium tetrakis (pentafluorophenyl) borate diphenylmethyl phosphonium tetrakis phenyl borate dimethylphenyl phosphonium tetrakis (pentafluorophenyl) borate dimethylphenyl phosphonium hexafluoro arsenic acid triethylammonium,

Compound of formula (VI) Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (manganese tetraphenylporphyrin), ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1 '
-Dimethylferrocenium, decamethylferrocenium tetrakis (pentafluorophenyl) borate, acetylferrocenium tetrakis (pentafluorophenyl) borate, formylferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate Cyanoferrocenium, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, lithium tetrakis (pentafluorophenyl) borate, sodium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (tetra) Phenylporphyrin manganese), tetrakis (pentafluorophenyl) borate (tetraphenylporphyrin iron chloride), tetrakis (pen Fluorophenyl) borate (tetraphenylporphyrin zinc), silver tetrafluoroborate, hexafluoroarsenate, silver hexafluoroantimonate, silver

Compounds other than those of the formulas (V) and (VI), for example, tris (pentafluorophenyl) boron, tris (3,5-bis (trifluoromethyl) phenyl) boron and triphenylboron can also be used. is there.

Examples of the organoaluminum compound as the component (C) include compounds represented by the following general formulas (VII), (VIII) or (IX). R ¹² _r AlQ _3-r (VII) (R ¹² is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to ¹² carbon atoms such as an alkyl group, an alkenyl group, an aryl group and an arylalkyl group; Q is a hydrogen atom; Represents an alkoxy group or a halogen atom having 1 to 20 carbon atoms, and r is in the range of 1 ≦ r ≦ 3.) As the compound of the formula (VII), specifically, trimethylaluminum, triethylaluminum, triisobutyl Examples include aluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, and ethylaluminum sesquichloride.

[0027]

Embedded image (R ¹² is the same as in formula (VII). S represents the degree of polymerization and is usually from 3 to 50.)

[0028]

Embedded image (R ¹² is the same as in formula (VII). S represents the degree of polymerization, and the preferred number of repeating units is 3 to 50.) A cyclic alkylaluminoxane having a repeating unit represented by the formula: Among the compounds of the formulas (VII) to (IX),
Preferred are compounds of the formula (VII), particularly preferred are compounds of the formula (VII) with r = 3, among which trialkylaluminums such as trimethylaluminum, triethylaluminum and triisobutylaluminum.

As a method for producing the aluminoxane, there is a method in which an alkylaluminum is brought into contact with a condensing agent such as water. The method is not particularly limited, and the reaction may be carried out according to a known method. For example, a method in which an organoaluminum compound is dissolved in an organic solvent and then brought into contact with water, a method in which an organoaluminum compound is initially added during polymerization and then water is added, and a crystal water contained in a metal salt or the like is used. A method of reacting water adsorbed on an inorganic or organic substance with an organoaluminum compound, a method of reacting a trialkylaluminoxane with a trialkylaluminum, and further reacting water.

The catalyst used in the present invention comprises the above component (A) and component (B) or the above component (A), component (B) and component (C) as main components. in this case,
The use conditions of the component (A) and the component (B) are not limited, but the ratio (molar ratio) of the component (A) to the component (B) is 1: 0.
01 to 1: 100, particularly 1: 0.5 to 1:10, preferably 1: 1 to 1: 5. The working temperature is preferably in the range of -100 to 250 ° C, and the pressure and time can be set arbitrarily.

The amount of the component (C) used is generally 0 to 2,000 mol, preferably 5 to 5 mol per mol of the component (A).
It is 1,000 mol, particularly preferably 10 to 500 mol. When the component (C) is used, the polymerization activity can be improved. However, when the content is too large, a large amount of the organic aluminum compound remains in the polymer, which is not preferable. The use form of the catalyst is not limited. For example, the components (A) and (B) may be brought into contact with each other in advance, or the contact product may be separated and washed before use. May be used.
Further, the component (C) may be used in contact with the component (A), the component (B) or a contact product of the component (A) and the component (B) in advance. The contact may be made in advance, or may be brought into contact in the polymerization system. Further, the catalyst component can be added in advance to the monomer and the polymerization solvent, or can be added to the polymerization system.

The production method of the present invention provides a catalyst comprising the above-mentioned compounds (A) and (B) as main components or a catalyst comprising the above-mentioned compounds (A), (B) and (C) as main components, respectively. And homopolymerization of a cyclic diene (excluding compounds having only one double bond in the ring). In another embodiment of the production method of the present invention, a cyclic diene (provided that one double bond is present in the ring) is prepared by using a catalyst containing the above-mentioned compounds (A), (B) and (C) as main components. ) And an α-olefin. When homopolymerization or copolymerization of a cyclic diene is performed, the kind of the cyclic diene is not particularly limited, but a norbornadiene represented by the following general formula (X) and other cyclic dienes described below can be suitably used. .

Embedded image (Wherein, R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , and R ¹⁸ each represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a halogen atom. R ^{13 to} R ¹⁸ are the same as each other. Or different ones.)

Examples of the norbornadiene of the above formula (X) include the following. Norbornadiene, 2-methyl-2,5-norbornadiene,
2-ethyl-2,5-norbornadiene, 2-propyl-2,5-norbornadiene, 2-butyl-2,5-norbornadiene, 2-pentyl-2,5-norbornadiene, 2-hexyl-2,5-norbornadiene, 2-
Chloro-2,5-norbornadiene, 2-bromo-2,
5-norbornadiene, 2-fluoro-2,5-norbornadiene, 7,7-dimethyl-2,5-norbornadiene, 7,7-methylethyl-2,5-norbornadiene, 7,7-dichloro-2,5-norbornadiene , 1
-Methyl-2,5-norbornadiene, 1-ethyl-
2,5-norbornadiene, 1-propyl-2,5-norbornadiene, 1-butyl-2,5-norbornadiene, 1-chloro-2,5-norbornadiene, 1-bromo-2,5-norbornadiene, 7-methyl- 2,5-
Norbornadiene, 7-ethyl-2,5-norbornadiene, 7-propyl-2,5-norbornadiene, 7-
Chloro-2,5-norbornadiene, 2,3-dimethyl-2,5-norbornadiene, 1,4-dimethyl-2,
5-norbornadiene, 1,2,3,4-tetramethyl-2,5-norbornadiene

Other cyclic dienes which can be suitably used in the present invention include, for example, 1,3-cyclobutadiene,
1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1,3-cycloheptadiene, 1,4-cycloheptadiene, 1,3-cyclooctadiene, 1,3,5 -Cyclooctatriene, 1,4-cyclooctadiene, dicyclopentadiene,

Embedded image And the like. The cyclic diene may have at least two double bonds, and includes, for example, a cyclic triene.

As the α-olefin to be copolymerized with the cyclic olefin, for example, ethylene, propylene, 1-
Butene, 1-hexene, 4-methyl-1-pentene, 1
Those having 2 to 25 carbon atoms such as -octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene can be suitably used. Particularly preferred among these is ethylene. In the case where a cyclic diene / α-olefin copolymer is produced by the production method of the present invention, the proportion of α-olefin units in the copolymer is preferably from 0.1 to 80 mol% in view of heat resistance. preferable.

In the production method of the present invention, a copolymerizable unsaturated monomer component other than the above may be used, if necessary. Specific examples of such unsaturated monomers which may be optionally copolymerized include those not previously used among α-olefins, cyclic monoolefins, butadiene, isoprene, 1,5-hexadiene and the like. And the like chain diene.

The polymerization methods include bulk polymerization, solution polymerization,
Any method such as suspension polymerization may be used. Further, a batch method or a continuous method may be used. Regarding the polymerization conditions, the polymerization temperature is preferably -100 to 250C, particularly preferably -50 to 200C. The ratio of the catalyst to the reaction raw material is such that the raw material monomer / component (A) (molar ratio) or the raw monomer / component (B) (molar ratio) is 1 to 1
0 ^9, it is preferable that the particular 100 to 10 ^7. Further, the polymerization time is usually from 1 minute to 10 hours, and the reaction pressure is from normal pressure to
100 kg / cm ² G, preferably normal pressure to 50 kg / c
m ² G. As a method for adjusting the molecular weight of the polymer, the amount of each catalyst component used, the selection of the polymerization temperature, and the polymerization reaction in the presence of hydrogen can be performed.

When a polymerization solvent is used, for example, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclohexane, and fats such as pentane, hexane, heptane and octane Group hydrocarbons, halogenated hydrocarbons such as chloroform, dichloromethane and the like can be used. These solvents may be used alone or in combination of two or more. Also, α-
A monomer such as an olefin may be used as a solvent. Further, the cyclic diene-based polymer obtained in the present invention can be hydrogenated if necessary.

[0039]

EXAMPLES Next, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the following examples. In the following Examples and Comparative Examples, physical properties were measured as follows. As Mw measurement device, manufactured by Waters ALC / GPC-1
5C, using trichlorobenzene as a solvent, 135 ° C
Was determined in terms of polystyrene using two TSK-DMH6 columns manufactured by Tosoh Corporation. Intrinsic viscosity [η] Measured in decalin at 135 ° C. 1456c belonging to norbornadiene in norbornadiene content IR
m ^-1 absorption and 1472 cm ^-1 attributed to ethylene component
The ratio of the absorbance to the absorbance was determined and determined from the prepared calibration curve.

Example 1 (1) Preparation of triethylammonium tetrakis (pentafluorophenyl) borate Pentafluorophenyllithium prepared from bromopentafluorobenzene (152 mmol) and butyllithium (152 mmol) was mixed with 45 mmol of boron trichloride. The reaction was performed in hexane. Tris (pentafluorophenyl) boron was obtained as a white solid. By reacting the obtained tris (pentafluorophenyl) boron (41 mmol) with pentafluorophenyllithium (41 mmol), lithium tetrakis (pentafluorophenyl) borate was isolated as a white solid. Next, lithium tetrakis (pentafluorophenyl) borate (1
6 mmol) and triethylamine hydrochloride (16 mmol) were reacted in water to give 12.8 mmol of triethylammonium tetrakis (pentafluorophenyl) borate as a white solid.

The fact that the product is the desired product means that ¹ H-
Confirmed by NMR and ¹³ C-NMR. _{^{1 H-NMR (THFd 8)}} : -CH 3 1.31ppm -CH 2 - 3.27ppm 13 C-NMR: -C 6 F 5 150.7,147.5,140.7, 138.7,137. 4,133.5ppm -CH ₂ - 48.2ppm -CH ₃ 9.1ppm

(2) Preparation of Catalyst 1 mmol of (cyclopentadienyl) trimethyltitanium and 1 mmol of triethylammonium tetrakis (pentafluorophenyl) borate were reacted in 50 ml of toluene at room temperature for 4 hours. After evaporation of the solvent, the solid was washed with 20 ml of petroleum ether. After drying toluene 50
The resulting solution was dissolved in the resulting solution to give a catalyst solution.

(3) Polymerization In a 100 ml flask, 25 mmol of norbornadiene, 0.05 mmol of a catalyst as a transition metal component and 25 ml of toluene were added and reacted at 20 ° C. for 4 hours. The reaction mixture was poured into methanol, and the precipitated white solid was collected by filtration, washed with methanol, and dried. The yield was 0.41 g. Polymerization activity is 170 g / gTi, Mw is 40,9
00. The obtained copolymer was soluble in common solvents such as toluene, chloroform and tetrahydrofuran. According to the infrared absorption spectrum analysis of the obtained polymer, strong absorption based on the structural unit represented by the following (A) was observed at a position of 800 cm ^-1 . From ¹ H-NMR analysis, an absorption based on a carbon-carbon double bond was observed at 6.2 ppm, and an absorption based on a carbon-carbon double bond of the polymer main chain was not observed at 5.3 ppm. Was. Accordingly, this polymer was confirmed to have the structural units represented by the following (A) and (B), and the molar ratio between (A) and (B) was 46:
53.

Embedded image

Example 2 In a 100 ml flask, norbornadiene 2
5 mmol, 0.005 mmol of (cyclopentadienyl) tribenzyltitanium, 0.005 mmol of triethylammonium tetrakis (pentafluorophenyl) borate
Mmol was reacted in 50 ml of toluene. After reacting at 20 ° C. for 4 hours, the reaction mixture was
l. The white precipitate was collected by filtration, washed with 50 ml of methanol, and then dried under reduced pressure to obtain 0.27 g of a white powder. Polymerization activity is 1.1 kg / gTi, Mw is 42.0
00.

Example 3 In a 100 ml flask, norbornadiene 2
5 mmol, 0.005 mmol of (cyclopentadienyl) trimethyltitanium, 0.005 mmol of triethylammonium tetrakis (pentafluorophenyl) borate, and 0.1 mmol of triisobutylaluminum were reacted in 50 ml of toluene. After stirring at 20 ° C. for 4 hours, the reaction mixture was poured into 100 ml of methanol to precipitate a white solid. This was filtered and dried to give 0.9
2 g of solid was obtained. The polymerization activity is 3.8Kg / gT
i and Mw were 61,000.

Example 4 In a 100 ml flask, norbornadiene 2
5 mmol, 0.005 mmol of (pentamethylcyclopentadienyl) trimethyltitanium, 0.005 mmol of triethylammonium tetrakis (pentafluorophenyl) borate, and 0.1 mmol of triisobutylaluminum were reacted in 50 ml of toluene. 2
After stirring at 0 ° C. for 4 hours, the reaction mixture was
At 0 ml a white solid precipitated. This was filtered and dried to obtain 0.45 g of a solid. The polymerization activity was 1.9 kg / gTi.

Example 5 A 500 ml flask was charged with 150 ml of dry toluene, 5 mmol of triisobutylaluminum and 0.025 mmol of bis (cyclopentadienyl) dichlorozirconium. Next, 0.025 mmol of dimethylanilinium tetrakis (pentafluorophenyl) borate and 50 mmol of norbornadiene were added.
The mixture was circulated at 0 liter / hr and polymerization was performed at 25 ° C. for 3 hours. Next, the toluene solution was added to basic acidic methanol to precipitate a polymer, followed by washing with methanol and drying under reduced pressure. 0.35 g of the copolymer was obtained. The polymerization activity was 0.15 Kg / gZr. Also,
The resulting copolymer had a norbornadiene content of 45 mol% and an intrinsic viscosity [η] of 0.21 dl / g.

Comparative Example 1 In a 100 ml flask, norbornadiene 2
5 mmol, (cyclopentadienyl) trimethyltitanium 0.005 mmol, aluminoxane 0.005
The mmol was reacted in 50 ml of toluene at 20 ° C. for 4 hours, but no polymer was obtained.

[0049]

As described above, the catalyst used in the present invention is a homopolymerization of a cyclic diene or a cyclic diene (however,
Compounds having only one double bond in the ring are excluded. ) And α
-Exhibits excellent polymerization activity in copolymerization with olefins. In particular, the catalyst using the organoaluminum compound (C) shows a very high polymerization activity by using a small amount of the organoaluminum compound. Therefore, according to the production method of the present invention, it is possible to efficiently produce a cyclic diene homopolymer or a cyclic diene / α-olefin copolymer without using a large amount of an organometallic compound and omitting the deashing step. Can be.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a manufacturing method of the present invention.

──────────────────────────────────────────────────続 き Continued from the front page (72) Inventor Yasunori Kadori 1280 Kamiizumi, Sodegaura-shi, Chiba Idemitsu Kosan Co., Ltd. (56) References JP-A-58-19309 (JP, A) JP-A-2-167334 ( JP, A) JP-A-61-221206 (JP, A) JP-A-3-207704 (JP, A) JP-A-3-234709 (JP, A) JP-A-5-503546 (JP, A) JP-A Hei 5-505838 (JP, A) Special Table Hei 1-502036 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 32/00-32/08 C08F 4/60-4 / 70

Claims (6)

(57) [Claims] 1. Homopolymerization of a cyclic diene (excluding compounds having only one double bond in the ring) using a catalyst containing the following compounds (A) and (B) as main components. A method for producing a cyclic diene polymer. (A) a transition metal compound having a cyclopentadienyl-based ligand containing a transition metal selected from Group IVB of the Periodic Table, and (B) a compound which reacts with the transition metal compound to form an ionic complex. A compound comprising a cation and a boron compound-based anion in which a plurality of groups are bonded to a boron atom 2. Use of a catalyst having the following compounds (A), (B) and (C) as main components to independently produce a cyclic diene (excluding compounds having only one double bond in the ring). A method for producing a cyclic diene-based polymer, comprising performing polymerization. (A) a transition metal compound having a cyclopentadienyl-based ligand containing a transition metal selected from Group IVB of the Periodic Table, and (B) a compound which reacts with the transition metal compound to form an ionic complex. Comprising a cation and a boron compound-based anion in which a plurality of groups are bonded to a boron atom (C) an organoaluminum compound 3. A cyclic diene (excluding compounds having only one double bond in the ring) using a catalyst containing the following compounds (A), (B) and (C) as main components. A process for producing a cyclic diene polymer, which comprises copolymerizing with an α-olefin. (A) a transition metal compound having a cyclopentadienyl-based ligand containing a transition metal selected from Group IVB of the Periodic Table, and (B) a compound which reacts with the transition metal compound to form an ionic complex. Comprising a cation and a boron compound-based anion in which a plurality of groups are bonded to a boron atom (C) an organoaluminum compound 4. The compound (A) is a transition metal compound having a cyclopentadienyl-based ligand represented by the following general formula (I), (II) or (III). Item 4. The method for producing a cyclic diene polymer according to any one of Items 1 to 3. ^{_{CpM 1 R 1 a R 2 b}} R 3 c ... (I) Cp 2 M 1 R 1 d R 2 e ... (II) (Cp-A f -Cp) M 1 R 1 d R 2 e ... (III) [ In the general formulas (I) to (III), M ¹ is Ti, Zr or Hf
Represents an atomic, Cp represents a cyclopentadienyl group, substituted cyclopentadienyl group, indenyl group, substituted indenyl group, tetrahydroindenyl group, substituted tetrahydroindenyl group, a fluorenyl group or substituted fluorenyl group, R ^1, R ² and R ³ each represent a hydrogen atom, an oxygen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms,
20 alkoxy groups, aryl groups having 6 to 20 carbon atoms, alkylaryl groups, or arylalkyl groups, acyloxy groups having 1 to 20 carbon atoms, allyl groups, substituted allyl groups, substituents containing silicon atoms, acetylacetonate Represents a group, a substituted acetylacetonate group or a Lewis base, A represents a crosslink by a covalent bond, a, b and c are each an integer of 0 to 3, d and e are
An integer of 0 to 2 and f represent an integer of 0 to 6, respectively. ] 5. The cation in the compound (B) is:
IIIB, IVB, VB, VIB, VI of the periodic table
The cyclic diene-based polymer according to any one of claims 1 to 4, comprising an element selected from the group consisting of IB, VIII, IA, IB, IIA, IIB and VIIA. Production method. 6. The method for producing a cyclic diene-based polymer according to claim 2, wherein the compound (C) is triisobutylaluminum.