JPH05320247A - Production of ethylenic polymer composition - Google Patents

Abstract

PURPOSE:To efficiently and stably produce an ethylenic polymer compsn. having an excellent melt flowability and a good processibility. CONSTITUTION:The compsn. is produced by a two-step polymn. process comprising the following steps [I] and [II] in the presence of a catalyst comprising a transition metal compd., a compd. which reacts with the transition metal compd. to form an ionic complex, and an organoaluminum compd. The step [I] comprises (co)polymerizing ethylene into an ethylenic polymer having a density of 0.88g/cm<3> and an intrinsic viscosity [eta] of 0.1-4dl/g and the step [II] comprises (co)polymerizing ethylene into an ethylenic polymer having a density lower than that of the polymer formed in the step [I] and an intrinsic viscosity [eta] at least 1.3 times that of the polymer formed in the step [I], i.e., 1-10dl/d. The order of the two steps may be reversed provided that the second step is conducted in the presence of the ethylenic polymer formed in the first step.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an ethylene-based polymer composition used as a molding material for films, molded articles and the like. The present invention relates to a method for producing an ethylene polymer composition having excellent stability.

[0002]

2. Description of the Related Art Conventionally, the problems to be solved by the invention
A method for polymerizing an olefin using a transition metal compound and an ionic complex as a catalyst has been proposed. However, this polymerization method has an advantage that a polymer having a very narrow molecular weight distribution can be obtained, but has a drawback that the obtained polymer has poor melt moldability.

Further, by using a catalyst composed of a transition metal compound having a ligand having a cycloalkadienyl skeleton and an organoaluminum oxy compound, multi-stage polymerization enables excellent melting characteristics and excellent melt processability. A method for producing a combined composition is known (Japanese Patent Laid-Open No. 23471/1993).
No. 7). However, this method uses a relatively large amount of an organoaluminum oxy compound, which is inferior in stability and is expensive, and is not satisfactory for industrial use.

The present invention has been made in view of the above circumstances and provides a method capable of efficiently and stably producing an ethylene polymer composition having a low density, excellent melt fluidity and good processability. The purpose is to provide.

[0005]

In order to achieve the above object, the present invention provides a transition metal compound [A], a compound [B] which reacts with the transition metal compound to form an ionic complex, and an organic compound. Using a catalyst made of an aluminum compound [C], ethylene or ethylene and another α-olefin are polymerized or copolymerized to have a density of 0.88 g / cm ³ or more and an intrinsic viscosity [η] of 0.1 to 4 dl. / G and an ethylene-based polymer forming step [I] and a catalyst comprising the above-mentioned compounds [A], [B] and [C] are used to copolymerize ethylene with another α-olefin, A step [II] of forming an ethylene-based polymer having a density lower than that of the polymer of step [I] and an intrinsic viscosity [η] of 1.3 times or more that of the polymer of step [I] and 1 to 10 dl / g. ] And (However, before and after steps [I] and [II] ), The density by performing subsequent polymerization in the presence of polymers in the preceding stage is 0.86
To 0.94 g / cm ³ , and the intrinsic viscosity [η] is 0.2 to 7 d
Provided is a method for producing an ethylene-based polymer composition, which comprises obtaining 1 / g of the ethylene-based polymer composition.

The present invention will be described in more detail below.
In the present invention, as the transition metal compound [A], a transition metal compound containing a transition metal belonging to IVB group, VB group, VIB group, VIIB group, and VIII group of the periodic table can be used. As the above transition metal, specifically, titanium, zirconium, hafnium, chromium, manganese, nickel, palladium, platinum and the like are preferable, and among them, zirconium, hafnium, titanium, nickel and palladium are preferable.

Examples of such a transition metal compound include various compounds. Particularly, a compound containing a transition metal of IVB group or VIII group, especially a transition metal selected from IVB group of the periodic table, that is, titanium (Ti). ), Zirconium (Zr) or hafnium (Hf) is preferably used, and in particular, a cyclopentadienyl compound represented by the following general formula (I), (II) or (III) or a compound thereof A derivative, a compound represented by the following general formula (IV) or a derivative thereof is preferable.

CpM ¹ R ¹ _a R ² _b R ³ _c (I) Cp ₂ M ¹ R ¹ _a R ² _b (II) (Cp-A _e -Cp) M ¹ R ¹ _a R ² _b (( III) M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d (IV)

[In the formulas (I) to (IV), M ¹ is Ti, Zr.
Or Hf atom, Cp is a cyclopentadienyl group,
A cyclic unsaturated hydrocarbon group or a chain unsaturated hydrocarbon group such as a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, a tetrahydroindenyl group, a substituted tetrahydroindenyl group, a fluorenyl group or a substituted fluorenyl group is shown. R ¹ , R ² , R ³ and R ⁴ are each σ
A binding ligand, a chelating ligand, a Lewis base, or another ligand is shown. Specific examples of the σ binding ligand include a hydrogen atom, an oxygen atom, a halogen atom, and a carbon number of 1 to 1. 20 alkyl groups, 1-20 carbon alkoxy groups, 6 carbon atoms
Examples include 20 aryl groups, alkylaryl groups or arylalkyl groups, acyloxy groups having 1 to 20 carbon atoms, allyl groups, substituted allyl groups, and substituents containing a silicon atom, and examples of chelating ligands include Examples thereof include an acetylacetonate group and a substituted acetylacetonate group. A indicates crosslinking by covalent bond. a, b, c and d
Are integers of 0 to 4, respectively, and e is an integer of 0 to 6. R
Two or more of ¹ , R ² , R ³ and R ⁴ may combine with each other to form a ring. When Cp has a substituent, the substituent is preferably an alkyl group having 1 to 20 carbon atoms. In the formulas (II) and (III), the two Cp's may be the same or different from each other. ]

Examples of the substituted cyclopentadienyl group in the above formulas (I) to (III) include methylcyclopentadienyl group, ethylcyclopentadienyl group, isopropylcyclopentadienyl group, 1,2-dimethyl. Cyclopentadienyl group, tetramethylcyclopentadienyl group, 1,3-dimethylcyclopentadienyl group, 1,
2,3-trimethylcyclopentadienyl group, 1,2,
4-trimethylcyclopentadienyl group, pentamethylcyclopentadienyl group, trimethylsilylcyclopentadienyl group and the like can be mentioned. In addition, (I) ~ (I
Specific examples of R ^{1 to} R ^{4 in} the formula V) 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 and n-propyl as an alkyl group having 1 to 20 carbon atoms. Group, iso-propyl group,
n-butyl group, octyl group, 2-ethylhexyl group; methoxy group, ethoxy group, propoxy group, butoxy group, phenoxy group as alkoxy group having 1 to 20 carbon atoms; aryl group having 6 to 20 carbon atoms, alkylaryl group or Phenyl group, tolyl group, xylyl group, benzyl group as an arylalkyl group; heptadecylcarbonyloxy group as an acyloxy group having 1 to 20 carbon atoms; trimethylsilyl group as a substituent containing a silicon atom, (trimethylsilyl) methyl group: Lewis base As dimethyl ether,
Ethers such as diethyl ether and tetrahydrofuran, thioethers such as tetrahydrothiophene, esters such as ethylbenzoate, nitriles such as acetonitrile and benzonitrile, trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 2, Amines such as 2'-bipyridine and phenanthroline; phosphines such as triethylphosphine and triphenylphosphine; ethylene, butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and their derivatives as chain unsaturated hydrocarbons;
Examples of the cyclic unsaturated hydrocarbon include benzene, toluene, xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene, cyclooctatetraene and derivatives thereof. Examples of the cross-linking by the covalent bond of A in the formula (III) include methylene cross-link, dimethyl methylene cross-link, ethylene cross-link, 1,1′-
Examples thereof include cyclohexylene crosslinks, dimethylsilylene crosslinks, dimethylgermylene crosslinks, and dimethylstannylene crosslinks.

Examples of such compounds include the following compounds and compounds in which zirconium of these compounds is replaced with titanium or hafnium. Compound 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) dimethyl zirconium,
Bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) diethylzirconium, bis (cyclopentadienyl) dibenzylzirconium, bis (cyclopentadienyl) dimethoxyzirconium, bis (cyclopentadienyl) dichlorozirconium , Bis (cyclopentadienyl) dihydride zirconium, bis (cyclopentadienyl) monochloromonohydride zirconium, bis (methylcyclopentadienyl) dimethylzirconium, bis (methylcyclopentadienyl) dichlorozirconium, bis (methylcyclo Pentadienyl) dibenzylzirconium, bis (pentamethylcyclopentadienyl) dimethylzirconium, bis (pentamethylcyclopentadienyl) dichlorozirconium, Scan (pentamethylcyclopentadienyl) dibenzyl zirconium, bis (pentamethylcyclopentadienyl) chloromethyl zirconium,
Bis (pentamethylcyclopentadienyl) hydridomethylzirconium, (cyclopentadienyl) (pentamethylcyclopentadienyl) dichlorozirconium,

Compound of formula (III) ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) dichlorozirconium, ethylenebis (tetrahydroindenyl) dimethylzirconium, ethylenebis (tetrahydroindenyl) dichlorozirconium, dimethylsilylenebis (cyclo) Pentadienyl) dimethylzirconium, dimethylsilylenebis (cyclopentadienyl) dichlorozirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dimethylzirconium, isopropylidene (cyclopentadienyl) (9-fluorenyl) dichlorozirconium , [Phenyl (methyl) methylene] (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, diphenylmethylene (cyclopen Tadienyl)
(9-fluorenyl) dimethylzirconium, ethylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclohexylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Cyclopentylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, cyclobutylidene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium, dimethylsilylene (9-fluorenyl) (cyclopentadienyl) dimethylzirconium,
Dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dichlorozirconium, dimethylsilylenebis (2,3,5-trimethylcyclopentadienyl) dimethylzirconium, dimethylsilylenebis (indenyl) dichlorozirconium

As examples of compounds other than the cyclopentadienyl compounds represented by the above general formulas (I), (II) and (III), compounds of the above formula (IV), that is, the following general formula M ¹ R ¹ _a R ² _b R ³ _c R ⁴ _d (IV) [wherein, M ¹ is a Ti, Zr or Hf atom, R ¹ _a , R
² _b , R ³ _c and R ⁴ _d each represent an α-bonding ligand, a chelating ligand or a Lewis base, which may be the same or different. Often, a, b, c and d each represent an integer of 0-4. ], A zirconium compound, a titanium compound and a hafnium compound having at least one of halogen, an alkyl group and an alkoxy group such as the following compounds. Tetramethylzirconium, tetrabenzylzirconium, tetramethoxyzirconium, tetraethoxyzirconium, tetrabutoxyzirconium, tetrachlorozirconium, tetrabromozirconium, butoxytrichlorozirconium, dibutoxydichlorozirconium, bis (2,5
-Di-t-butylphenoxy) dimethyl zirconium,
Bis (2,5-di-t-butylphenoxy) dichlorozirconium, zirconium bis (acetylacetonate). Thus, if the compound of formula (IV) is used as the compound [A], no special compound is used. The ethylene-based polymer can be industrially advantageously produced.

The transition metal compound containing a VB to VIII group transition metal is not particularly limited, and specific examples of the chromium compound include, for example, tetramethylchromium and tetra (t).
-Butoxy) chromium, bis (cyclopentadienyl) chromium, hydridotricarbonyl (cyclopentadienyl) chromium, hexacarbonyl (cyclopentadienyl) chromium, bis (benzene) chromium, tricarbonyl tris (triphenylphosphonate) Examples thereof include chromium, tris (allyl) chromium, triphenyltris (tetrahydrofuran) chromium, chromium tris (acetylacetonate) and the like.

Specific examples of the manganese compound include tricarbonyl (cyclopentadienyl) manganese, pentacarbonylmethylmanganese, bis (cyclopentadienyl) manganese, manganese bis (acetylacetonate) and the like.

Specific examples of the nickel compound include, for example, dicarbonylbis (triphenylphosphine) nickel, dibromobis (triphenylphosphine) nickel, dinitrogen bis (bis (tricyclohexylphosphine) nickel), and chlorohydridobis (tricyclohexyl). Phosphine) nickel, chloro (phenyl) bis (triphenylphosphine) nickel, dimethylbis (trimethylphosphine) nickel, diethyl (2,
2'-bipyridyl) nickel, bis (allyl) nickel, bis (cyclopentadienyl) nickel, bis (methylcyclopentadienyl) nickel, bis (pentamethylcyclopentadienyl) nickel, allyl (cyclopentadienyl) Nickel, (cyclopentadienyl)
(Cyclooctadiene) nickel tetrafluoroborate, bis (cyclooctadiene) nickel, nickel bisacetylacetonate, allyl nickel chloride,
Tetrakis (triphenylphosphine) nickel, nickel chloride, (C ₆ H ₅ ) Ni {OC (C ₆ H ₅ ) CH = P (C ₆ H ₅ ) ₂ } {P (C
₆ H ₅ ) ₃ }, (C ₆ H ₅ ) Ni {OC (C ₆ H ₅ ) C (SO ₃ Na) = P (C ₆ H ₅ ) ₂ } {P (C
₆ H ₅ ) ₃ } and the like.

Specific examples of the palladium compound include dichlorobis (benzonitrile) palladium, carbonyltris (triphenylphosphine) palladium,
Dichlorobis (triethylphosphine) palladium, bis (t-butyl isocyanide) palladium, palladium bis (acetylacetonate), dichloro (tetraphenylcyclobutadiene) palladium, dichloro (1,5
-Cyclooctadiene) palladium, allyl (cyclopentadienyl) palladium, bis (allyl) palladium, allyl (1,5-cyclooctadiene) palladium tetrafluoroborate, (acetylacetonate)
Examples include (1,5-cyclooctadiene) palladium tetrafluoroborate, tetrakis (acetonitrile) palladium ditetrafluoroborate, and the like.

Any compound that reacts with the transition metal compound [A] to form an ionic complex can be used as the compound [B]. A compound consisting of a bound anion, that is, compound (B) is a group IIIB, IVB or VB of the periodic table.
Tribe, VIB, VIIB, VIII, IA, IB, IIA, IIB
A cation containing an element selected from Group IVA, Group VIIA, and multiple groups are group VB, VIB, VIIB, VIII of the periodic table.
A compound consisting of an anion bound to an element selected from the group IB, IB, IIB, IIIA, IVA and VA, especially a coordination complex compound consisting of a cation and an anion in which a plurality of groups are bound to an element is preferable. Can be used for As the compound composed of such a cation and an anion in which a plurality of groups are bound to an element, a compound represented by the following formula (VI) or (VII) can be preferably used. ([L ¹ −
R ⁷ ] ^{k +} ) _p ([M ³ Z ¹ Z ² … Z ⁿ ] ^(nm)- ) _q … (V
^{I) ([L 2] k} +) p ([M 4 Z 1 Z 2 ... Z n] (nm) -) q ... (VII) ( where, L ² is ^{M 5, R 8 R 9 M} 6, R 10 ₃ C or R ¹¹ M ⁶ )

[In the formulas (VI) and (VII), L ¹ is a Lewis base, M ³ and M ⁴ are VB group, VIB group and V group of the periodic table, respectively.
IIB, VIII, IB, IIB, IIIA, IVA and
Elements selected from Group VA, preferably elements selected from Group IIIA, Group IVA and Group VA, M ⁵ and M ⁶ are Group IIIB, Group IVB, Group VB, Group VIB, Group VIB of the periodic table, respectively.
Elements selected from Group III, Group IA, Group IB, Group IIA, Group IIB and Group VIIA, Z ^{1 to} Z ⁿ are a hydrogen atom, a dialkylamino group, an alkoxy group having 1 to 20 carbon atoms, and a carbon number of 6 respectively.
To C20 aryloxy group, C1 to C20 alkyl group, C6 to C20 aryl group, alkylaryl group, arylalkyl group, C1 to C20 halogen-substituted hydrocarbon group, C1 to C20 2 represents an acyloxy group, an organic metalloid group or a halogen atom, and two or more of Z ^{1 to} Z ⁿ may be bonded to each other to form a ring. R ⁷
Is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and 6 to 6 carbon atoms
20 represents an aryl group, an alkylaryl group or an arylalkyl group, R ⁸ and R ⁹ are each a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ¹⁰ is a C 1-20 group. An alkyl group, an aryl group, an alkylaryl group or an arylalkyl group is shown. R ¹¹ is tetraphenylporphyrin,
A macrocyclic ligand such as phthalocyanine is shown. m is M ³ , M
^{4 has} an valence of 1 to 7, n is an integer of 2 to 8, k is an ionic number of [L ¹ -R ⁷ ] and [L ² ] and is an integer of 1 to 7,
p is an integer of 1 or more, and q = (p × k) / (nm). ]

Specific examples of the Lewis base include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine,
Amine such as trimethylamine, triethylamine, tri-n-butylamine, N, N-dimethylaniline, methyldiphenylamine, pyridine, p-promo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, triethylphosphine Phosphines such as fin, triphenylphosphine and diphenylphosphine,
Examples thereof include ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, thioethers such as diethyl thioether and tetrahydrothiophene, and esters such as ethyl benzoate. Specific examples of M ³ and M ⁴ include B, Al, Si, P, As and Sb.
Etc., preferably B or P, and specific examples of M ⁵ are Li,
Specific examples of Na, Ag, Cu, Br, I, I _3, etc. and M ⁶ include Mn, Fe, Co, Ni, Zn and the like.

Specific examples of Z ^{1 to} Z ⁿ include, for example, a dimethylamino group and a diethylamino group as a dialkylamino group; a methoxy group, an ethoxy group, an n-butoxy group as an alkoxy group having 1 to 20 carbon atoms; and a carbon number of 6 A phenoxy group, a 2,6-dimethylphenoxy group, a naphthyloxy group as an aryloxy group having 20 to 20 carbon atoms, a methyl group, an ethyl group, an n-propyl group having an alkyl group having 1 to 20 carbon atoms,
iso-propyl group, n-butyl group, n-octyl group,
2-ethylhexyl group; aryl group having 6 to 20 carbon atoms,
As an alkylaryl group or an arylalkyl group, a phenyl group, a p-tolyl group, a benzyl group, a 4-tert-butylphenyl group, a 2,6-dimethylphenyl group,
3,5-dimethylphenyl group, 2,4-dimethylphenyl group, 2,3-dimethylphenyl group; p-fluorophenyl group, 3,5-difluorophenyl group as a halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, Pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-di (trifluoromethyl) phenyl group; F, Cl, Br as halogen atoms
I: Examples of the organic metalloid group include pentamethylantimony group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexylantimony group and diphenylboron group. Specific examples of R ⁷ and R ¹⁰ include:
Examples are the same as those listed above. R ⁸ and R ⁹
Specific examples of the substituted cyclopentadienyl group include those substituted with an alkyl group such as a methylcyclopentadienyl group, a butylcyclopentadienyl group, and a pentamethylcyclopentadienyl group. Here, the alkyl group usually has 1 to 6 carbon atoms, and the number of substituted alkyl groups can be selected by an integer of 1 to 5. (VI), (VI
Among the compounds of formula I), those in which M ³ and M ⁴ are boron are more preferable.

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

Triethylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triphenylammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl)
Tetrabutylammonium borate, 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, dimethyldiphenylammonium tetrakis (pentafluorophenyl) borate, anilinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluoro) (Phenyl) methylanilinium borate,
Dimethylanilinium tetrakis (pentafluorophenyl) borate, trimethylanilinium tetrakis (pentafluorophenyl) borate, dimethyl (m-nitroanilinium) tetrakis (pentafluorophenyl) borate, dimethyl tetrakis (pentafluorophenyl) borate (p-bromo) Anilinium),

Pyridinium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (p-cyanopyridinium), tetrakis (pentafluorophenyl) borate (N-methylpyridinium), tetrakis (pentafluorophenyl) borate (N
-Benzylpyridinium), tetrakis (pentafluorophenyl) borate (O-cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p
-Cyano-N-methylpyridinium), tetrakis (pentafluorophenyl) borate (p-cyano-N-benzylpyridinium), tetrakis (pentafluorophenyl) borate trimethylsulfonium, tetrakis (pentafluorophenyl) borate benzyldimethylsulfonium, tetrakis ( Pentafluorophenyl) tetraphenylphosphonium borate, tetrakis (pentafluorophenyl) triphenylphosphonium borate, tetrakis (3,5-ditrifluoromethylphenyl) dimethylanilinium borate, triethylammonium hexafluoroarsenate,

Compound of formula (VII) : ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylborate (tetraphenylporphyrin-manganese), ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) borate (1,1'-
Dimethylferrocenium), tetrakis (pentafluorophenyl) borate decamethylferrocenium, tetrakis (pentafluorophenyl) borate acetylferrocenium, tetrakis (pentafluorophenyl) borate formylferrocenium, 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) boric acid (tetraphenylporphyrin iron chloride), tetrakis (pentafluoro) Phenyl) borate (tetraphenylporphyrin zinc), silver tetrafluoroborate, hexafluoroarsenate, silver hexafluoroantimonate, silver

Among the compounds of the formulas (VI) and (VII), preferred are the compounds of the formula (VI) in which [L ¹ -R ⁷ ] does not have a proton, that is, quaternary ammonium salts, 3 -Grade oxonium salts, tertiary thionium salts, etc., and these are excellent in long-term storage stability. Also, (VI),
Compounds other than formula (VII), such as tri (pentafluorophenyl) boron, tri (3,5-di (trifluoromethyl) phenyl) boron, triphenylboron, etc., can also be used.

Examples of the organoaluminum compound as the component [C] include those represented by the following general formula (VIII), (IX) or (X). R ¹² _r AlQ _3-r (VIII) (R ¹² is a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 12 alkyl groups, alkenyl groups, aryl groups, arylalkyl groups, etc., Q is a hydrogen atom, It represents an alkoxy group having 1 to 20 carbon atoms or a halogen atom, and r is in the range of 1 ≦ r ≦ 3.) Specific examples of the compound of formula (VIII) include trimethylaluminum, triethylaluminum, and triisopropyl. Aluminum, triisobutyl aluminum, dimethyl aluminum chloride, diethyl aluminum chloride, methyl aluminum dichloride, ethyl aluminum dichloride, dimethyl aluminum fluoride, diisobutyl aluminum hydride, diethyl aluminum hydride, ethyl aluminum sesquichloride and the like can be mentioned.

[0029]

[Chemical 2] (R < ¹² > shows the same thing as a formula (VIII). S shows a polymerization degree and is 3-50 normally, Preferably it is 7-40.) The chain | strand-shaped aluminoxane shown by these.

[0030]

[Chemical 3] (R ¹² is the same as in formula (VIII), s is the degree of polymerization, and the number of repeating units is preferably 3 to 50, preferably 7 to 40.) Cyclic alkyl having a repeating unit Aluminoxane. Among the compounds of the formulas (VIII) to (X), the alkyl group-containing aluminum compound or aluminoxane having at least one alkyl group having 3 or more carbon atoms, and particularly having at least one branched alkyl group is preferable. Particularly preferred is triisobutylaluminum or aluminoxane having a degree of polymerization of 7 or more. When this triisobutylaluminum, aluminoxane having a degree of polymerization of 7 or more, or a mixture thereof is used, high activity can be obtained. Further, a modified aluminoxane which is insoluble in a general solvent obtained by modifying the aluminoxane represented by the formulas (IX) to (X) with a compound having active hydrogen such as water is also preferably used.

As a method for producing the aluminoxane, there may be mentioned a method in which an alkylaluminum and a condensing agent such as water are brought into contact with each other, but the means therefor 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 brought into contact with water, a method in which an organoaluminum compound is initially added at the time of polymerization, and water is added later, water of crystallization contained in a metal salt, etc. There are a method of reacting water adsorbed on an inorganic substance or an organic substance with an organoaluminum compound, a method of reacting a tetraalkyldialuminoxane with a trialkylaluminum, and further reacting water to obtain a solvent-insoluble aluminoxane.

The catalyst used in the present invention is the above-mentioned [A],
It is composed of the components [B] and [C]. in this case,
The use conditions of the [A] component and the [B] component are not particularly limited, but the ratio (molar ratio) of the [A] component: [B] component is 1 :.
It is preferably 0.01 to 1: 100, particularly 1: 0.5 to 1:10, and particularly preferably 1: 1 to 1: 5. The operating 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 usually 1 to 2,000 moles, preferably 5 to 1 mole of the component [A].
The amount is 1,000 mol, particularly preferably 10 to 500 mol. When the component [C] is used, the polymerization activity can be improved, but if it is too much, a large amount of the organoaluminum compound remains in the polymer, which is not preferable.

The mode of use of the catalyst component is not limited, and for example, the components [A] and [B] may be contacted in advance, or the contact product may be separated and washed before use. You may use it by making a contact. Further, the component [C] may be used by being brought into contact with the contact product of the component [A], the component [B] or the component [A] and the component [B] in advance.
The contact may be made in advance or in the polymerization system. Further, the catalyst component can be added to the monomer or the polymerization solvent in advance, or can be added to the polymerization system. The catalyst component can be used by supporting it on an inorganic or organic carrier, if necessary.

The ratio of the catalyst to the reaction raw material is 1 to 10 ^{9 of} raw material monomer / the above-mentioned [A] component (molar ratio) or raw material monomer / the above-mentioned [B] component (molar ratio), particularly 1
It is preferably from 00 to 10 ⁷ .

Polymerization methods include bulk polymerization, solution polymerization,
Any method such as suspension polymerization or gas phase polymerization may be used.
Further, a batch method or a continuous method may be used. 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,
Aliphatic hydrocarbons such as pentane, hexane, heptane and octane, halogenated hydrocarbons such as chloroform and dichloromethane can be used. These solvents may be used alone or in combination of two or more. Further, a monomer such as α-olefin may be used as a solvent.

Regarding the polymerization conditions, the polymerization temperature is -100 to 2
The temperature is preferably 50 ° C, particularly preferably -50 to 200 ° C.
The polymerization time is usually 1 minute to 10 hours, and the reaction pressure is atmospheric pressure to 10
0 Kg / cm ² G, preferably normal pressure to 50 Kg / cm ² G
Is. The method for controlling the molecular weight of the copolymer can be selected by the amount of each catalyst component used, the polymerization temperature, and the polymerization reaction in the presence of hydrogen.

In the present invention, the above-mentioned olefin polymerization catalyst is used to carry out a multistage polymerization comprising the following steps [I] and [II]. Here, the manufacturing method of the present invention is shown in FIG. Step [I] Using a catalyst composed of the compounds [A], [B] and [C], ethylene or ethylene and another α-olefin are polymerized or copolymerized to have a density of 0.88 g / cm ³ or more, It is preferably 0.89 to 0.95 g / cm ³ , and the intrinsic viscosity [η] is 0.1 to 4 dl / g, preferably 0.2 to 3
An ethylene polymer having a dl / g is formed. Step [II] Copolymerizing ethylene and another α-olefin using a catalyst composed of the compounds [A], [B] and [C], and having a density lower than that of the polymer of Step [I], preferably 0.003 g / cm ³ lower, intrinsic viscosity [η] in the process [I]
To form an ethylene-based polymer which is 1.3 times or more, preferably 2 to 10 times, and 1 to 10 dl / g, preferably 1.5 to 7 dl / g, the above polymer. Then, by performing the above two steps [I] and [II], the density becomes 0.
86-0.94 g / cm ³ , preferably 0.88-0.
92 g / cm ³ and an intrinsic viscosity [η] of 0.2 to 7 dl /
An ethylene polymer composition of g, preferably 1 to 5 dl / g is obtained.

In the present invention, as shown in FIGS. 1A and 1B, steps [I] and [II] can be performed in any order. Whatever order is adopted, the second-stage polymerization is carried out in the presence of the polymer in the first-stage, and for that purpose, it is preferable to carry out both steps continuously. In the present invention, another polymerization step may be further provided after the latter step, or a part of the polymer composition obtained in the latter step may be returned to the former step. In this case, it is desirable to use the catalyst used in the former polymerization step as it is without adding a new catalyst in the latter polymerization step, whereby a polymer composition with less fish eyes can be obtained. Further, in the present invention, the weight ratio of the polymer of step [I] to the polymer of step [II] is 1: 0.05 to 1: 1.
It is preferable to perform both steps so that the ratio is preferably 5 to 1: 1 to 1:10.

The α-olefin other than ethylene which can be used for the copolymerization in the present invention is not particularly limited, but the α-olefin having 3 to 20 carbon atoms, specifically propylene, 1 -Butene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene Etc. can be mentioned. In the present invention, when ethylene is copolymerized with another α-olefin, it is particularly preferable to copolymerize ethylene with an α-olefin having 3 to 10 carbon atoms. Ethylene and α with 3 to 10 carbon atoms
-Copolymerization ratio with olefin is 99.9:
0.1-80: 20, preferably 99.5: 0.5-8
It is 5:15. Further, in the present invention, in addition to the above α-olefin, other unsaturated compounds, for example, vinyl aromatic compounds such as styrene, p-methylstyrene, isopropylstyrene and t-butylstyrene, butadiene, isoprene and 1,5-hexadiene. It is possible to copolymerize with a small amount of chain diolefins such as. Usually, the amount of the other unsaturated compound is 20 mol% or less based on the other α-olefin.

[0041]

EXAMPLES Next, the present invention will be illustrated concretely by examples, but the present invention is not limited to the following examples. Example (1) Synthesis of dimethylanilinium tetra (pentafluorophenyl) borate Pentafluorophenyllithium prepared from 152 mmol bromopentafluorobenzene and 152 mmol butyllithium was reacted with 45 mmol boron trichloride in hexane, Tri (pentafluorophenyl) boron was obtained as a white solid. The obtained tri (pentafluorophenyl) boron 41 mmol was reacted with pentafluorophenyllithium 41 mmol to isolate lithium tetra (pentafluorophenyl) boron as a white solid. Next, 16 mmol of lithium tetra (pentafluorophenyl) boron and 16 mmol of dimethylaniline hydrochloride were reacted in water to obtain 11.4 mmol of dimethylanilinium tetra (pentafluorophenyl) borate as a white solid. It was confirmed by ¹ H-NMR and ¹³ C-NMR that the product was the target product.

(2) Manufacture of ethylene-based polymer composition 1 liter of a stainless steel autoclave was purged with nitrogen, and then 300 ml of 4-methyl-1-pentene was charged,
The temperature was raised to 60 ° C. Next, 0.2 mmol of triisobutylaluminum, 0.01 mmol of dimethylanilinium tetra (pentafluorophenyl) borate obtained in (1) above, and 0.01 mmol of biscyclopentadienylzirconium monochloride monohydride were added,
15 at 7 kg / cm ² · G while feeding ethylene
Polymerization was carried out for a minute [Step II]. Then add 2.0
pressurized with kg / cm ² · G, a total pressure of 9kg / cm ² · G, was carried out for 30 minutes polymerization at 65 ° C. [Step I]. After the polymerization, the polymerization was stopped with methanol, and the polymer composition was recovered. The obtained polymer composition had an intrinsic viscosity [η] of 1.57 dl / g, a density of 0.905 g / cm ³ , a melting point of 99 ° C., Mw of 112,000, and Mn of 54,000.
Met. However, the intrinsic viscosity [η] is a value measured in decalin at 135 ° C., the density is a density gradient tube value, the melting point is a DSC value, and Mw and Mn are GPC values.
It is a value measured under the following conditions. GPC: Waters ALC / GPC 150C Column: Tosoh TSK HM + GMH6 × 2 Solvent: 1,2,4-trichlorobenzene Temperature: 135 ° C. Flow rate: 1.0 ml / min In addition, only the above step [II] was obtained. The obtained polymer had an intrinsic viscosity [η] of 2.20 dl / g and a density of 0.891 g / cm ³ .

[0043]

As described above, according to the method for producing an ethylene polymer composition of the present invention, it is possible to efficiently and stably produce an ethylene polymer composition having good melting characteristics and molding stability. You can

[Brief description of drawings]

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

[Chemical 1]

Claims (1)

[Claims] 1. A catalyst comprising a transition metal compound [A], a compound [B] which reacts with the transition metal compound to form an ionic complex, and an organoaluminum compound [C],
By polymerizing or copolymerizing ethylene or ethylene and another α-olefin, an ethylene polymer having a density of 0.88 g / cm ³ or more and an intrinsic viscosity [η] of 0.1 to 4 dl / g is formed. Using the catalyst composed of the step [I] and the above-mentioned compounds [A], [B] and [C], ethylene is copolymerized with other α-olefin so that the density is lower than that of the polymer of the step [I]. And a step [II] for forming an ethylene polymer having an intrinsic viscosity [η] of 1.3 times or more that of the polymer of step [I] and 1 to 10 dl / g (provided that step [I], [I
I] before or after), and the density is 0.86 to 0.94 g by carrying out the latter-stage polymerization in the presence of the polymer obtained in the first-stage.
/ Cm < ³ >, intrinsic viscosity [[eta]] of 0.2 to 7 dl / g is obtained, and an ethylene polymer composition is produced.