JP6031994B2 - Ethylene polymer and process for producing the same - Google Patents

Description

  The present invention relates to an ethylene polymer having a long chain branch.

  Low density polyethylene (LDPE) produced by the high pressure radical method is a branched polyolefin, and its side chain has a non-linear dendritic structure. Such a structure is excellent in molding processability such as melt fluidity and melt tension, and is advantageous when the polymer is melt-processed. On the other hand, it has a drawback of reducing the mechanical strength of the solid polymer.

  For this reason, linear high density polyethylene (HDPE) and linear low density polyethylene (LLDPE) obtained with Ziegler catalysts or metallocene catalysts are generally used in applications that require the mechanical strength of solid polymers. . However, these HDPE and LLDPE do not have good moldability, which is an advantage of LDPE.

  As a technique for improving the molding processability of HDPE and LLDPE by the method for producing an ethylene polymer, for example, (a) a method of widening the molecular weight distribution by a multistage polymerization method using a conventional Ziegler catalyst (for example, Patent Documents 1 to 3) (B) A method for producing an ethylene polymer having a long chain branch using a traditional Cr catalyst, and (c) an ethylene system having a long chain branch obtained by polymerizing ethylene in the presence of a non-conjugated diene. A method for producing a polymer (for example, see Patent Document 4), (d) a method for producing an ethylene-based polymer having a long chain branch by copolymerization of a macromonomer and ethylene (for example, see Patent Document 5), (E) A method for producing an ethylene polymer having a long chain branch and having a narrow molecular weight distribution by polymerizing ethylene with a specific catalyst (for example, see Patent Document 6) is proposed. To have. However, the moldability of the ethylene polymer obtained by these methods is still not sufficient. Further, the ethylene polymers obtained by the methods (a), (b) and (d) have a problem that the mechanical strength is lowered due to the broadening of the molecular weight distribution. Further, the ethylene polymer obtained by the method (c) has a problem in that it contains a complex crosslinked product that is insoluble in a solvent and infusible with heating, and the mechanical strength is lowered. Furthermore, with regard to the ethylene polymer obtained by the method (c), the low density ethylene polymer has long chain branching, which is excellent in workability but poor in mechanical strength. When the density is increased, the mechanical strength is improved. However, there is a problem that the number of long-chain branches is reduced and the molding processability is poor.

  In addition, as an ethylene polymer having long chain branching and excellent moldability, simultaneously with the synthesis of a specific macromonomer, a copolymer of ethylene and, if necessary, an α-olefin having 3 or more carbon atoms (for example, Patent Document 7) or a specific macromonomer, and then copolymerized ethylene and, if necessary, an α-olefin having 3 or more carbon atoms (for example, see Patent Document 8). However, the molecular weight distribution of these polymers is not controlled, and the ratio of long chain branching to a molecular weight of 100,000 or more is high, resulting in high viscosity, and molding processability due to a synergistic effect with high viscosity by long chain branching. There was a problem that was significantly worse.

JP-A-2-53811 JP-A-2-132109 JP-A-10-182742 JP-A-9-227626 JP 2004-346304 A JP 2011-105934 A JP 2004-346304 A JP 2006-321991 A

  The present invention has been made to solve the above-described problems of the prior art, and provides an ethylene-based polymer having both good moldability of LDPE and mechanical strength of HDPE and LLDPE, and a method for producing the same. To do.

  The present invention has been found as a result of intensive studies on the above-described object.

That is, the present invention relates to an ethylene polymer having the following characteristics (i) to (iv) and a method for producing the same.
(I) an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 or more carbon atoms,
(Ii) The density (kg / m ³ ) is 935 or more and 960 or less,
(Iii) Among two peaks in molecular weight measurement by GPC, the weight ratio of the low molecular weight polyethylene component [A] and the high molecular weight polyethylene component [B] when molecular weight fractionation is in the range of 95/5 to 80/20. Yes,
(Iv) The number average molecular weight (Mn) of the low molecular weight polyethylene component [A] is 1,000 or more and less than 150,000, the number of terminal vinyls is 0.10 or more and less than 3.0 per 1000 carbons of the main chain, long chain The number of branches is 0 or more and 0.05 or less per 1000 carbon atoms of the main chain,
(V) Mn of the high molecular weight polyethylene component [B] is 150,000 to 10,000,000, the number of terminal vinyls is 0 to 0.05 per 1000 carbons of the main chain, and the number of long chain branches is the main chain It is 0.20 or more and less than 3.0 per 1000 carbon atoms.

The density (kg / m ³ ) of the ethylene polymer of the present invention is a value measured by a density gradient tube method in accordance with JIS K6760 (1995), and is 935 or more and 960 or less, preferably 940 or more and 960 or less. Especially preferably, it is 945 or more and 960 or less. When the density of the ethylene polymer is less than 935, the rigidity of the ethylene polymer is lowered, and when it exceeds 960, the low temperature workability is lowered.

  The ethylene polymer of the present invention shows two peaks in the molecular weight measurement by GPC. The peak top molecular weight (Mp) is obtained by dividing the molecular weight distribution curve obtained by GPC measurement into two peaks by the method described later, and evaluating the top molecular weight of the high molecular weight side peak and the low molecular weight side peak. The case of 100,000 or more was assumed to have two Mp. When it was less than 100,000, the top molecular weight of the actually measured molecular weight distribution curve was defined as one Mp.

  The molecular weight distribution curve was divided as follows. The standard deviation is 0.30 with respect to LogM of the molecular weight distribution curve in which the weight ratio is plotted against LogM which is the logarithm of molecular weight obtained by GPC measurement, and an arbitrary average value (molecular weight at the peak top position) A composite curve is created by adding together two logarithmic distribution curves having) at an arbitrary ratio. Further, the average value and the ratio are obtained so that the deviation sum of squares of the weight ratio with respect to the same molecular weight (M) value of the actually measured molecular weight distribution curve and the composite curve becomes a minimum value. The minimum value of the deviation sum of squares was set to 0.5% or less with respect to the deviation sum of squares when the ratios of the respective peaks were all zero. When the average value and the ratio giving the minimum value of the deviation sum of squares were obtained, the molecular weight at the peak top of each logarithmic distribution curve obtained by dividing into two lognormal distribution curves was defined as Mp. The lower molecular weight of these two logarithmic distribution curves is the low molecular weight polyethylene component [A], and the higher molecular weight is the high molecular weight polyethylene component [B].

  The weight ratio of the low molecular weight polyethylene component [A] and the high molecular weight polyethylene component [B] when the molecular weight of the ethylene polymer of the present invention is fractionated is 95/5 to 80/20, preferably 95/5 to 85. / 15, particularly preferably 95/5 to 90/10. When the high molecular weight polyethylene component [B] when the molecular weight of the ethylene polymer is fractionated is less than 5%, the impact resistance is lowered, and when it exceeds 20%, the fluidity is lowered.

The number of long chain branches in the low molecular weight polyethylene component [A] when the molecular weight of the ethylene polymer of the present invention is fractionated is the number of branches of hexyl groups or more detected by ¹³ C-NMR measurement, and 1,000 It is 0 or more and 0.05 or less, preferably 0 or more and 0.03 or less per carbon atom. When the number of long chain branches of the low molecular weight polyethylene component [A] of the ethylene polymer exceeds 0.05, the melt fluidity of the ethylene polymer is lowered.

The number of long chain branches in the high molecular weight polyethylene component [B] when molecular weight fractionation of the ethylene-based polymer of the present invention is the number of branches of hexyl groups or more detected by ¹³ C-NMR measurement, 1,000 It is 0.10 or more and less than 3.0 per carbon atom, preferably 0.25 or more and less than 3.0, and more preferably 0.30 or more and less than 3.0. When the number of long chain branches of the high molecular weight polyethylene component [B] of the ethylene polymer is 0.10 or less, the moldability of the ethylene polymer is lowered. If it is 3.0 or more, the viscosity becomes high and the molding processability of the ethylene polymer is lowered.

  The Mw / Mn of the ethylene polymer in the present invention is preferably in the range of 3.0 to 6.0, particularly preferably 3.0 to 5.0, and more preferably 3.0 to 4 0.0 or less.

  The Mn of the ethylene polymer in the present invention is preferably 15,000 or more and 10,000,000 or less, and if the Mn of the ethylene polymer is 15,000 or more, the impact resistance of the ethylene polymer is good. .

  The melt flow rate (MFR) (g / 10 min) of the ethylene polymer of the present invention is preferably 0.1 or more and 100 or less, particularly preferably 1.0 or more and 100 or less, and further preferably 10 or more. 100 or less.

  Examples of the α-olefin having 3 or more carbon atoms used in the present invention include propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene. 1-eicosene, 4-methyl-1-pentene, 3-methyl-1-butene, vinylcycloalkane and the like. Two or more of these olefins can be mixed and used.

  The ethylene polymer of the present invention is an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 or more carbon atoms, and copolymerizes ethylene and, if necessary, an α-olefin having 3 or more carbon atoms. Can be manufactured. After synthesizing a specific macromonomer, ethylene, if necessary, a method of copolymerizing an α-olefin having 3 or more carbon atoms, simultaneously with the synthesis of a specific macromonomer, ethylene, and if necessary, α having 3 or more carbon atoms -A method of copolymerizing olefins can be used.

  The ethylene-based polymer of the present invention has the general formula (1)

(In the formula, M ¹ is a titanium atom, a zirconium atom or a hafnium atom, and X is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, Carbon-carbon bond of C1-C20 alkoxy group, C1-C20 hydrocarbon group-substituted amino group, C1-C20 hydrocarbon group-substituted silyl group, C1-C20 hydrocarbon group Oxygen introduced between them, nitrogen introduced between carbon-carbon bonds of a hydrocarbon group having 1 to 20 carbon atoms, or silicon between carbon-carbon bonds of a hydrocarbon group having 1 to 20 carbon atoms R ¹ is a hydrocarbon group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or a hydrocarbon group-substituted silyl having 1 to 20 carbon atoms. Group, carbon having 1 to 20 carbon atoms One in which oxygen is introduced between the carbon-carbon bonds of the hydrogen group, one in which nitrogen is introduced between the carbon-carbon bonds of the hydrocarbon group having 1 to 20 carbon atoms, or the carbon of the hydrocarbon group having 1 to 20 carbon atoms R ² is independently a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, or a carbon number. An alkoxy group having 1 to 20 carbon atoms, a substituted silyl group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, in which oxygen is introduced between carbon-carbon bonds, and a carbon atom having 1 to 20 carbon atoms is introduced in the silicon bond between carbon and carbon of the hydrocarbon group or those having 1 to 20 carbon atoms was introduced nitrogen bond between carbon and carbon hydrogen group .R ³ is hydrogen independently Atom, hydrocarbon group having 1 to 20 carbon atoms, 2 carbon atoms Oxygen introduced between carbon and carbon bonds of 20 dialkylamino groups, C1-20 alkoxy groups, C1-20 hydrocarbon group-substituted silyl groups, C1-20 hydrocarbon groups And those in which nitrogen is introduced between the carbon-carbon bonds of the hydrocarbon group having 1 to 20 carbon atoms, or silicon is introduced between the carbon-carbon bonds in the hydrocarbon group having 1 to 20 carbon atoms.)
It can manufacture using the catalyst for olefin polymerization containing the transition metal compound (A) represented by these, the modified clay compound (B) processed with the organic compound, and the organoaluminum compound (C).

In general formula (1), M ¹ is a titanium atom, a zirconium atom or a hafnium atom. Specific examples of X, R ¹ , R ² and R ³ are given below. Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group and their isomer substituents, phenyl group, indenyl group, naphthyl group, fluorenyl group, biphenylenyl. Examples include groups. Examples of the dialkylamino group having 1 to 20 carbon atoms include a dimethylamino group and a diethylamino group. As a C1-C20 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, a phenoxy group etc. can be illustrated. Examples of the hydrocarbon group-substituted amino group having 1 to 20 carbon atoms include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, diisopropylamino group, diphenylamino group, methylphenylamino group and the like. . Examples of the hydrocarbon group-substituted silyl group having 1 to 20 carbon atoms include trimethylsilyl group, tritert-butylsilyl group, ditert-butylmethylsilyl group, tert-butyldimethylsilyl group, triphenylsilyl group, diphenylmethylsilyl group, phenyl A dimethylsilyl group etc. can be illustrated. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which oxygen is introduced between the carbon bonds include a methoxymethylene group and an ethoxymethylene group. Examples of the hydrocarbon group having 1 to 20 carbon atoms in which nitrogen is introduced between carbon bonds include a dimethylaminomethylene group and a diethylaminomethylene group. As what introduce | transduced the silicon | silicone between the carbon-carbon bonds of a C1-C20 hydrocarbon group, a trimethyl silyl methylene group, a tert- butyl dimethyl silyl methylene group, etc. can be illustrated. Specific examples of the transition metal compound represented by the general formula (1) used in the present invention include the following compounds. Specific examples of the transition metal compound (A) include dimethylsilanediyl (cyclopentadienyl) (7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (7-ethylindenyl) zirconium dichloride, dimethyl Silanediyl (cyclopentadienyl) (7-phenylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,7-dimethylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2 -Methoxy-7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2-dimethylamino-7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadiyl) Nyl) (2-trimethylsilyl-7-methylindenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (7-methylindenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (2 , 7-dimethylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (7-methylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride, Dimethylsilanediyl (cyclopentadienyl) (4-isopropyl-7-dimethylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-phenyl-7-dimethyl Ndenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-methoxy-7-dimethylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (4-dimethylamino-7-dimethylindenyl) zirconium Dichloride, dimethylsilanediyl (cyclopentadienyl) (4-trimethylsilyl-7-dimethylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilane Diyl (cyclopentadienyl) (3,4,7-trimethylindenyl) zirconium dichloride, dimethylsilanediyl (cyclopentadienyl) (2,3,4,7-tetramethylindenyl) Zirconium dichloride, dimethylsilanediyl (3,4-dimethylcyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilanediyl (3,4-bis (trimethylsilyl) cyclopentadienyl) (2 , 4,7-trimethylindenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (4-phenyl) -7-methylindenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride, dimethylsilanediyl (tetramethylcyclope) Tadienyl) (2,4,7-trimethylindenyl) zirconium dichloride and other zirconium compounds, compounds in which the zirconium atom is changed to a titanium atom, hafnium atom, and the dichloro form of the above transition metal compounds are dimethyl, diethyl, dihydro, Although the compound etc. which were changed into the diphenyl body and the dibenzyl body can be illustrated, it is not limited to these. The organically modified clay compound (B) has the following general formula (2)

(In the formula, R ^{4 to} R ⁶ are each independently a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an alkylamino group having 1 to 18 carbon atoms, and an alkyl having 1 to 18 carbon atoms. A silyl group, a hydrocarbon group having 1 to 18 carbon atoms in which oxygen is introduced between the carbon bonds, and a part of the hydrocarbon group having 1 to 18 carbon atoms is an alkylamino group having 1 to 30 carbon atoms. When a part of carbon of the hydrocarbon group having 1 to 18 carbon atoms is substituted with silicon, and one of R ^{4 to} R ⁶ is a substituent having 18 carbon atoms, The remaining substituents have 10 or less carbon atoms, M ² is an atom of Group 15 of the periodic table, and [A ⁻ ] is an anion.)
As a specific example of the organic compound, the following can be exemplified.

In the general formula (2), examples of the hydrocarbon group having 1 to 18 carbon atoms of R ⁴ , R ⁵ and R ⁶ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an allyl group, an n-butyl group, Isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, neopentyl, tert-pentyl, cyclopentyl, n- Hexyl group, isohexyl group, 3-methylpentyl group, 4-methylpentyl group, neohexyl group, 2,3-dimethylbutyl group, 2,2-dimethylbutyl group, 4-methyl-2-pentyl, 3,3-dimethyl 2-butyl group, 1,1-dimethylbutyl group, 2,3-dimethyl-2-butyl group, cyclohexyl group, n-heptyl group, cycloheptyl group Group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, n-octyl group, isooctyl group, 1,5-dimethylhexyl group, 1-methylheptyl group, 2-ethylhexyl group, tert- Octyl group, 2,3-dimethylcyclohexyl group, 2- (1-cyclohexenyl) ethyl group, n-nonyl group, n-decyl group, isodecyl group, geranyl group, n-undecyl group, n-dodecyl group, cyclododecyl group Examples thereof include a group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, and phenyl group.

  Examples of the alkoxy group having 1 to 18 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group, and a phenoxy group.

  A C1-C18 alkylamino group is an amino group which has the said C1-C18 hydrocarbon group as a substituent, and is a dimethylamino group, a diethylamino group, a dipropylamino group, a dibutylamino group, a diisopropylamino group. , Diphenylamino group, methylphenylamino group and the like.

  The alkylsilyl group having 1 to 18 carbon atoms is a silyl group having the above hydrocarbon group having 1 to 18 carbon atoms as a substituent, and includes a trimethylsilyl group, a tritert-butylsilyl group, a ditert-butylmethylsilyl group, a tert- Examples thereof include a butyldimethylsilyl group, a triphenylsilyl group, a diphenylmethylsilyl group, and a phenyldimethylsilyl group.

  Examples of the hydrocarbon group having 1 to 18 carbon atoms in which oxygen is introduced between the carbon bonds include a methoxymethylene group and an ethoxymethylene group.

  As what substituted a part of said C1-C18 hydrocarbon group by the C1-C18 alkylamino group, a dimethylaminomethylene group, a diethylaminomethylene group, etc. can be illustrated.

  As what substituted a part of carbon of the said C1-C18 hydrocarbon group with silicon, a trimethylsilylmethylene group, a tert- butyldimethylsilylmethylene group, etc. can be illustrated.

When one of R ^{4 to} R ⁶ is a substituent having 18 carbon atoms, the remaining substituent has 10 or less carbon atoms. For example, when R ⁴ is an n-octadecyl group, R ⁵ , R ⁶ can be exemplified by the relationship such that both must be substituents having fewer carbon atoms than the n-decyl group, but is not limited thereto.

M ² is an atom of Group 15 of the Periodic Table, and can be exemplified by a nitrogen atom or a phosphorus atom. Specific examples of the organic compound represented by the general formula (2) when M ² is a nitrogen atom include methylamine hydrochloride, ethylamine hydrochloride, n-propylamine hydrochloride, isopropylamine hydrochloride, n-butylamine. Hydrochloride, isobutylamine hydrochloride, tert-butylamine hydrochloride, n-pentylamine hydrochloride, isopentylamine hydrochloride, 2-methylbutylamine hydrochloride, neopentylamine hydrochloride, tert-pentylamine hydrochloride, n-hexyl Amine hydrochloride, isohexylamine hydrochloride, n-heptylamine hydrochloride, n-octylamine hydrochloride, n-nonylamine hydrochloride, n-decylamine hydrochloride, n-undecylamine hydrochloride, n-dodecylamine hydrochloride , N-tetradecylamine hydrochloride, n-hexadecylamine hydrochloride, n-octadecy Ruamine hydrochloride, allylamine hydrochloride, cyclopentylamine hydrochloride, dimethylamine hydrochloride, diethylamine hydrochloride, diallylamine hydrochloride, trimethylamine hydrochloride, tri-n-butylamine hydrochloride, triallylamine hydrochloride, hexylamine hydrochloride, 2- Aminoheptane hydrochloride, 3-aminoheptane hydrochloride, n-heptylamine hydrochloride, 1,5-dimethylhexylamine hydrochloride, 1-methylheptylamine hydrochloride, n-octylamine hydrochloride, tert-octylamine hydrochloride , Nonylamine hydrochloride, decylamine hydrochloride, undecylamine hydrochloride, dodecylamine hydrochloride, tridecylamine hydrochloride, tetradecylamine hydrochloride, pentadecylamine hydrochloride, hexadecylamine hydrochloride, heptadecylamine hydrochloride, Octadecylami Hydrochloride, cyclohexylamine hydrochloride, cycloheptylamine hydrochloride, 2-methylcyclohexylamine hydrochloride, 3-methylcyclohexylamine hydrochloride, 4-methylcyclohexylamine hydrochloride, 2,3-dimethylcyclohexylamine hydrochloride, cyclododecyl Amine hydrochloride, 2- (1-cyclohexenyl) ethylamine hydrochloride, geranylamine hydrochloride, N-methylhexylamine hydrochloride, dihexylamine hydrochloride, bis (2-ethylhexyl) amine hydrochloride, dioctylamine hydrochloride, didecylamine Hydrochloride, N-methylcyclohexylamine hydrochloride, N-ethylcyclohexylamine hydrochloride, N-isopropylcyclohexylamine hydrochloride, N-tert-butylcyclohexylamine hydrochloride, N-allylcyclohexylamine hydrochloride N, N-dimethyloctylamine hydrochloride, N, N-dimethylundecylamine hydrochloride, N, N-dimethyldodecylamine hydrochloride, N, N-dimethyl-n-tetradecylamine hydrochloride, N, N- Dimethyl-n-hexadecylamine hydrochloride, N, N-dimethyl-n-octadecylamine hydrochloride, trihexylamine hydrochloride, triisooctylamine hydrochloride, trioctylamine hydrochloride, triisodecylamine hydrochloride, tri Dodecylamine hydrochloride, N-methyl-N-octadecyl-1-octadecylamine hydrochloride, N, N-dimethylcyclohexylamine hydrochloride, N, N-dimethylcyclohexylmethylamine hydrochloride, N, N-diethylcyclohexylamine hydrochloride Pyrrolidine hydrochloride, piperidine hydrochloride, 2,5-dimethylpyrrolidine hydrochloride, 2-methylpiperidine hydrochloride, 3-methylpiperidine hydrochloride, 4-methylpiperidine hydrochloride, 2,6-dimethylpiperidine hydrochloride, 3,3-dimethylpiperidine hydrochloride, 3,5-dimethylpiperidine hydrochloride, 2- Ethylpiperidine hydrochloride, 2,2,6,6-tetramethylpiperidine hydrochloride, 1-methylpyrrolidine hydrochloride, 1-methylpiperidine hydrochloride, 1-ethylpiperidine hydrochloride, 1-butylpyrrolidine hydrochloride, 1,2 , 2,6,6-pentamethylpiperidine hydrochloride and the like, hydrochlorides of aliphatic amines, aniline hydrochloride, N-methylaniline hydrochloride, N-ethylaniline hydrochloride, N-allylaniline hydrochloride, o-toluidine hydrochloride Salt, m-toluidine hydrochloride, p-toluidine hydrochloride, N, N-dimethylaniline hydrochloride, N-methyl-o-toluidine salt Hydrochloric acid salts, hydrochlorides of aromatic amines such as N-methyl-m-toluidine hydrochloride, N-methyl-p-toluidine hydrochloride and hydrochlorides of the above compounds Examples of the compound replaced with a hydrogen salt or a sulfate can be exemplified, but the present invention is not limited thereto.

Examples of the compound in which M ² is a phosphorus atom include compounds such as P, P-dimethyl-octadecylphosphine hydrochloride, P, P-diethyl-octadecylphosphine hydrochloride, P, P-dipropyl-octadecylphosphine hydrochloride, Examples thereof include, but are not limited to, compounds in which hydrochloride is replaced with hydrofluoride, hydrobromide, hydroiodide, or sulfate.

[A ⁻ ] is an anion such as fluorine ion, chlorine ion, bromine ion, iodine ion, sulfate ion, nitrate ion, phosphate ion, perchlorate ion, oxalate ion, citrate ion, succinate ion, tetra Although fluoroborate ion or hexafluorophosphate ion can be used, it is not limited to these.

  The clay compound used for the organically modified clay (B) belongs to the smectite group hectorite.

  The modified clay compound treated with the organic compound introduces organic ions between the clay compound layers to form an ionic complex.

  In the organic compound treatment of the clay compound, it is preferable to perform the treatment by selecting the conditions of the clay compound concentration of 0.1 to 30% by weight and the treatment temperature of 0 to 150 ° C. Further, the organic compound may be prepared as a solid and dissolved in a solvent for use, or a solution of the organic compound may be prepared by a chemical reaction in the solvent and used as it is. Regarding the reaction amount ratio between the clay compound and the organic compound, it is preferable to use an organic compound having an equivalent amount or more with respect to exchangeable cations of the clay compound. As the treatment solvent, aliphatic hydrocarbons such as pentane, hexane or heptane, aromatic hydrocarbons such as benzene or toluene, alcohols such as ethyl alcohol or methyl alcohol, ethers such as ethyl ether or n-butyl ether, Halogenated hydrocarbons such as methylene chloride or chloroform, acetone, 1,4-dioxane, tetrahydrofuran, water or the like can be used, but preferably alcohols or water is used alone or as a component of a solvent. .

  Further, the particle size of the organically modified clay compound (B) used in the present invention is not particularly limited, but if it is too small, it will be difficult to settle the catalyst, and if it is too large, the catalyst will not be efficiently prepared. It is preferable that the thickness is 1 to 100 μm. The method for adjusting the particle size is not particularly limited, and large particles may be pulverized to an appropriate particle size, small particles may be granulated to an appropriate particle size, or pulverization and granulation may be combined. Also good. The particle size may be adjusted for unmodified clay or for modified organically modified clay.

The method of pulverization and granulation is not particularly limited. For pulverization, impact mill, rotary mill, cascade mill, cutter mill, cage mill, impact pulverizer, conical mill, colloid mill, compound mill, jet mill, vibration mill, stamp mill Tube mill, disk mill, tower mill, medium agitator mill, hammer mill, pin mill, fret mill, pebble mill, ball mill, attritor, planetary mill,
Ring ball mill, ring roll mill, rod mill, roller mill, roll crusher, etc., as granulation rolling granulation, fluidized bed granulation, stirring granulation, compression granulation, extrusion granulation, crush granulation, melt granulation, Any method such as spray granulation may be used.

  The organoaluminum compound (C) is a constituent component of the catalyst for producing an ethylene polymer of the present invention, and is used together with the transition metal compound (A) and the organically modified clay (B).

  The organoaluminum compound (C) is represented by the following general formula (3)

(Wherein R ⁷ is a hydrocarbon group having 1 to 20 carbon atoms, and R ⁸ is each independently a hydrocarbon group having 1 to 20 carbon atoms, a hydrogen atom, or a chlorine atom.)
It is represented by Examples of the hydrocarbon group having 1 to 20 carbon atoms of R ⁷ and R ⁸ include the same groups as those exemplified for X, R ¹ , R ² and R ³ . As the organoaluminum compound (C), a compound capable of alkylating a transition metal compound is preferable, and specific examples include alkylaluminum such as trimethylaluminum, triethylaluminum, and triisobutylaluminum.

  The longest interatomic distance of the transition metal compound (A) in the present invention may be larger than the interlayer distance of the organically modified clay compound (B) that reacts with the transition metal compound (A) to form a cationic transition metal compound. preferable. The longest interatomic distance of the transition metal compound (A) is the longest interatomic distance in the structure optimized by CAChe / MM3 calculation, and the interlayer distance of the organically modified clay compound (B) is in a low angle range by XRD. The value obtained by subtracting the thickness of the clay plate from the 2θ value of the 001 diffraction line is used.

  Organically modified clay compound (B) (component (B)) that reacts with transition metal compound (A) (component (A)) and transition metal compound (A) in the present invention to form a cationic transition metal compound, and organic Although there is no restriction | limiting in the ratio of aluminum compound (C) ((C) component), The ratio shown next is desirable.

  The molar ratio of the component (A) to the component (C) per metal atom is in the range of (component A) :( component C) = 100: 1 to 1: 100000, particularly in the range of 1: 1 to 1: 10000. It is preferable that the weight ratio of the component (A) to the component (B) is (component A) :( component B) = 10: 1 to 1: 10000, particularly 3: 1 to 1: 1000. It is preferable.

  The olefin polymerization catalyst of the present invention may be polymerized by using it as a solid catalyst supported on a carrier. Although there is no restriction | limiting in particular in a support | carrier, It is preferable that it is an inorganic oxide. Specific examples of inorganic oxides include oxides of alkaline earth metals such as magnesia and calcia, oxides of typical elements such as alumina and silica, oxides of lanthanide rare earth elements such as cerium oxide and samarium oxide Examples include oxides of actinide rare earths such as actinium oxide and thorium oxide, oxides of transition metal elements such as titania, zirconia, copper oxide and silver oxide, and composite oxides such as silica-alumina and silica-magnesia. However, it is not limited to these.

  There is no restriction on the method for preparing the olefin polymerization catalyst comprising the component (A), the component (B), and the component (C), and the preparation method is as follows. The method of using and mixing can be mentioned. Moreover, there is no restriction | limiting also about the order which makes these components react, and the temperature and processing time which perform this process also have no restriction | limiting. It is also possible to prepare an olefin polymerization catalyst using two or more of each component.

  The catalyst in the present invention can be used in any of usual polymerization processes, that is, slurry polymerization, gas phase polymerization, high pressure polymerization, solution polymerization, and bulk polymerization.

  In the present invention, polymerization means not only homopolymerization but also copolymerization, and the ethylene-based polymer obtained by these polymerizations is used in the meaning including not only a homopolymer but also a copolymer.

  The polymerization of the ethylene-based polymer in the present invention can be carried out either in the gas phase or in the liquid phase. Particularly when the polymerization is carried out in the gas phase, it is possible to efficiently and stably produce a polyolefin having a uniform particle shape. . Further, when the polymerization is performed in a liquid phase, the solvent used may be any organic solvent that is generally used, and specific examples include benzene, toluene, xylene, pentane, hexane, heptane, and the like. Olefin itself such as 1-butene, 1-octene, 1-hexene can be used as a solvent.

  The olefin used in the present invention is an α-olefin such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, styrene and styrene derivatives, butadiene, 1,4-hexadiene, 5 -Ethylidene-2-norbornene, dicyclopentadiene, 4-methyl-1,4-hexadiene, conjugated and non-conjugated dienes such as 7-methyl-1,6-octadiene, and cyclic olefins such as cyclobutene. Further, three or more kinds of components can be mixed and polymerized, such as ethylene, propylene and styrene, ethylene, 1-hexene and styrene, ethylene, propylene, and ethylidene norbornene.

There are no particular restrictions on the polymerization conditions such as polymerization temperature, polymerization time, polymerization pressure, and monomer concentration in producing the ethylene-based polymer using the method of the present invention, but the polymerization temperature is −100 to 300 ° C., the polymerization time. Is preferably 10 seconds to 20 hours, and the polymerization pressure is preferably from normal pressure to 3000 kg / cm ² G. It is also possible to adjust the molecular weight using hydrogen during polymerization. The polymerization can be carried out by any of batch, semi-continuous and continuous methods, and can be carried out in two or more stages by changing the polymerization conditions. The ethylene polymer obtained after the completion of the polymerization can be obtained by separating and recovering from the polymerization solvent by a conventionally known method and drying.

  The ethylene polymer produced in the present invention includes, for example, heat stabilizer, weather stabilizer, antistatic agent, antifogging agent, antiblocking agent, slip agent, lubricant, nucleating agent, pigment, carbon black, talc, glass powder. In addition, known additives such as inorganic fillers or reinforcing agents such as glass fibers, organic fillers or reinforcing agents, flame retardants, and neutron shielding agents can be blended.

  The ethylene polymer produced in the present invention can also be used by mixing with other thermoplastic resins, such as HDPE, LLDPE, LDPE, polypropylene, poly-1-butene, poly-4-methyl-1-pentene. , Ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, polystyrene, and these maleic anhydride graft products.

  ADVANTAGE OF THE INVENTION According to this invention, the ethylene-type polymer which is excellent in the process suitability with respect to slurry polymerization, has a favorable morphology, and has the good moldability of LDPE and the mechanical strength of HDPE and LLDPE can be produced economically.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise noted, the reagents used were commercially available products or those synthesized according to known methods.

  A jet mill (trade name: CO-JET SYSTEM α MARK III, manufactured by Seishin Enterprise Co., Ltd.) was used for pulverization of the organically modified clay. MT3000) was used to measure ethanol as a dispersant.

  Preparation of the ethylene polymer production catalyst, production of the ethylene polymer and solvent purification were all carried out under an inert gas atmosphere. A hexane solution (20 wt%) of triisobutylaluminum manufactured by Tosoh Finechem Co., Ltd. was used.

Furthermore, various physical properties of the ethylene-based polymer in the examples were measured by the following methods.
Weight average molecular weight (Mw), number average molecular weight (Mn), ratio of weight average molecular weight to number average molecular weight (Mw / Mn) and peak top molecular weight (Mp) were measured by GPC. The column temperature was set to 140 ° C. using a GPC device (trade name: HLC-8121 GPC / HT, manufactured by Tosoh Corporation) and a column (trade name: TSKgel GMHhr-H (20) HT, manufactured by Tosoh Corporation). The measurement was performed using 1,2,4-trichlorobenzene as an eluent. A measurement sample was prepared at a concentration of 1.0 mg / ml, and 0.3 ml was injected and measured. The calibration curve of molecular weight was calibrated using a polystyrene sample having a known molecular weight. In addition, Mw and Mn were calculated | required as a value of linear polyethylene conversion.

The density was measured by a density gradient tube method in accordance with JIS K6760 (1995).
MFR (melt flow rate) was measured by a method according to ASTM D1238 Condition E.
For molecular weight fractionation, a glass bead packed column (diameter: 21 mm, length: 60 cm) is used as the column, the column temperature is set to 130 ° C., and 1 g of sample dissolved in 30 mL of xylene is injected. Next, distillate is removed by using a xylene / 2-ethoxyethanol ratio of 5/5 as a developing solvent. Thereafter, using xylene as a developing solvent, the components remaining in the column are distilled off to obtain a polymer solution. A component having Mn of 100,000 or more was recovered by adding 5-fold amount of methanol to the obtained polymer solution to precipitate the polymer, filtering and drying.

  The number of long-chain branches was determined by 13C-NMR using a JNM-GSX400 nuclear magnetic resonance apparatus manufactured by JEOL Ltd., and the number of branches equal to or greater than the hexyl group. The solvent is benzene-d6 / orthodichlorobenzene (volume ratio 30/70). The number per 1,000 main chain methylene carbons (chemical shift: 30 ppm) was determined from the average value of the peaks of α-carbon (34.6 ppm) and β-carbon (27.3 ppm).

  The sample for melt tension measurement was prepared by adding a heat-resistant stabilizer (Ciba Specialty Chemicals, Irganox 1010TM; 1,500 ppm, Irgafos 168TM; 1,500 ppm) to an internal mixer (Toyo Seiki Seisakusho, The product kneaded for 30 minutes at 190 ° C. and 30 rpm in a nitrogen stream was used.

  To measure the melt tension, a capillary viscometer (Toyo Seiki Seisakusho, trade name Capillograph) with a barrel diameter of 9.55 mm is attached with a die with a length of 8 mm and a diameter of 2.095 mm so that the inflow angle is 90 °. It was measured. The temperature was set to 160 ° C., the piston lowering speed was set to 10 mm / min, the stretch ratio was set to 47, and the load (mN) required for take-up was the melt tension. When the maximum draw ratio was less than 47, the load (mN) required for taking-up at the highest draw ratio that did not break was taken as the melt tension.

Example 1
(1) Denaturation of clay 300 mL of industrial alcohol (trade name Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 300 mL of distilled water are placed in a 1 L flask, and 15.0 g of concentrated hydrochloric acid and N, N-dimethylmyristylamine ( After adding 29.0 g (120 mmol) of Lion Corporation (trade name) Armin DM14D) and heating to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), 60 The mixture was heated to 0 ° C. and stirred for 1 hour while maintaining the temperature. The slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 122 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm. The interlayer distance calculated from the XRD measurement was 5.2 mm.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then calculated by computational chemistry. 0.5116 g of dimethylsilylene (cyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride having a maximum distance between the two atoms of 9.6 mm and 142 mL of 20% triisobutylaluminum were added. And stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 mL of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 15.72 wt%).
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum was added to a 2 L autoclave, and 75.10 mg (corresponding to a solid content of 14.30 mg) of the catalyst suspension obtained in (2) was added. After raising the temperature to ° C., 3.6 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.90 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 500 ppm). . After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 44.4 g of polymer (activity: 3,110 g / g catalyst). The polymer had an MFR of 13.6 g / 10 min and a density of 946 kg / m3. The number average molecular weight was 15,800, and the ratio of weight average molecular weight to number average molecular weight (Mw / Mn) was 4.0. The weight ratio of the polyethylene components [A] and [B] when molecular weight fractionation was 88.6 / 11.4. The Mn of the polyethylene component [A] was 12,400, the number of terminal vinyls was 0.37 per 1,000 carbons, and the number of long chain branches was 0.02 per 1,000 carbons. Moreover, Mn of the polyethylene component [B] at the time of molecular weight fractionation was 181,000, the number of terminal vinyls was not detected, and the number of long chain branches was 0.39 per 1,000 carbons. The melt tension was 67 mN.

Example 2
(1) Denaturation of clay 300 mL of industrial alcohol (product name: Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 300 mL of distilled water are placed in a 1 L flask, and 18.8 g of concentrated hydrochloric acid and N, N-dimethylpalmitylamine are added. After adding 40.4 g (150 mmol) (Lion Corporation (trade name) Armin DM16D) and heating to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS), The mixture was heated to 60 ° C. and stirred for 1 hour while maintaining the temperature. This slurry was separated by filtration, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 135 g of an organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm. The interlayer distance calculated from the XRD measurement was 6.9 mm.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then calculated by computational chemistry. 0.5123 g of dimethylsilylene (cyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride having a maximum distance between the two atoms of 9.6 mm and 142 mL of 20% triisobutylaluminum were added. And stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 mL of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 15.90 wt%).
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum in a 2 L autoclave, and 65.83 mg (corresponding to a solid content of 12.31 mg) of the catalyst suspension obtained in (2) were added. After raising the temperature to ° C., 3.6 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.90 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 500 ppm). . After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 72.7 g of polymer (activity: 5,900 g / g catalyst). The polymer had an MFR of 19.4 g / 10 min and a density of 947 kg / m 3. The number average molecular weight was 15,300, and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) was 3.7. The weight ratio of the polyethylene components [A] and [B] when molecular weight fractionation was 90.2 / 9.8. The Mn of the polyethylene component [A] was 11,900, the number of terminal vinyls was 0.32 per 1,000 carbons, and the number of long chain branches was 0.03 per 1,000 carbons. The Mn of the polyethylene component [B] when molecular weight fractionation was 167,000, the number of terminal vinyls was not detected, and the number of long chain branches was 0.35 per 1,000 carbons. The melt tension was 63 mN.

Example 3
(1) Denaturation of clay 300 mL of industrial alcohol (trade name: Echinen F-3, manufactured by Nippon Alcohol Sales Co., Ltd.) and 300 mL of distilled water are placed in a 1 L flask, and 12.5 g of concentrated hydrochloric acid and N, N-dimethylstearylamine ( 29.8 g (100 mmol) of Lion Corporation (trade name) Armin DM18D) was added and heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS). The mixture was heated to 0 ° C. and stirred for 1 hour while maintaining the temperature. The slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 118 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm. The interlayer distance calculated from the XRD measurement was 8.6 mm.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then calculated by computational chemistry. 0.5123 g of dimethylsilylene (cyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride having a maximum distance between the two atoms of 9.6 mm and 142 mL of 20% triisobutylaluminum were added. And stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 mL of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 15.90 wt%).
(3) Polymerization 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added to a 2 L autoclave, and 51.87 mg (corresponding to a solid content of 8.91 mg) of the catalyst suspension obtained in (2) was added. After raising the temperature to ° C., 3.6 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.90 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 500 ppm). . After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 57.0 g of polymer (activity: 6,400 g / g catalyst). The polymer had an MFR of 15.8 g / 10 min and a density of 946 kg / m3. The number average molecular weight was 15,500, and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) was 4.0. The weight ratio of the polyethylene components [A] and [B] when molecular weight fractionation was 89.5 / 10.5. Mn of the polyethylene component [A] was 12,700, the number of terminal vinyls was 0.35 per 1,000 carbons, and the number of long chain branches was 0.01 per 1,000 carbons. The Mn of the polyethylene component [B] when molecular weight fractionation was 173,000, the number of terminal vinyls was not detected, and the number of long chain branches was 0.34 per 1,000 carbons. The melt tension was 57 mN.

Reference example 1
(1) Modification of clay The same procedure as in (1) of Example 1 was performed.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then calculated by computational chemistry. 0.5123 g of dimethylsilylene (cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride having a maximum distance of 9.8 mm between the two atoms formed and 142 mL of 20% triisobutylaluminum The mixture was added and stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 mL of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 15.90 wt%).
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum in a 2 L autoclave, and 65.83 mg (corresponding to a solid content of 12.31 mg) of the catalyst suspension obtained in (2) were added. After raising the temperature to ° C., 3.6 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.90 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 500 ppm). . After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 72.7 g of polymer (activity: 5,900 g / g catalyst). The polymer had an MFR of 10.7 g / 10 min and a density of 947 kg / m3. The number average molecular weight was 18,400, and the ratio of weight average molecular weight to number average molecular weight (Mw / Mn) was 4.2. The weight ratio of the polyethylene components [A] and [B] when molecular weight fractionation was 84.2 / 15.8. Mn of the polyethylene component [A] was 13,800, the number of terminal vinyls was 0.14 per 1,000 carbons, and the number of long chain branches was 0.01 per 1,000 carbons. The Mn of the polyethylene component [B] when molecular weight fractionation was 194,000, the number of terminal vinyls was not detected, and the number of long chain branches was 0.21 per 1,000 carbons. The melt tension was 44 mN.

Comparative Example 1
(1) Denaturation of clay 300 mL of industrial alcohol (trade name Echinen F-3 manufactured by Nippon Alcohol Sales Co., Ltd.) and 300 mL of distilled water are placed in a 1 L flask, and 12.5 g of concentrated hydrochloric acid and N-methyldioleilamine (Lion Corporation) 64.3 g (120 mmol) made by company (trade name) Armin M2O) was added and heated to 45 ° C. to disperse 100 g of synthetic hectorite (Rockwood Additives (trade name) Laponite RDS) and then to 60 ° C. The mixture was heated up and stirred for 1 hour while maintaining the temperature. The slurry was filtered, washed twice with 600 mL of water at 60 ° C., and dried in an oven at 85 ° C. for 12 hours to obtain 118 g of organically modified clay. This organically modified clay was crushed by a jet mill to have a median diameter of 15 μm. The interlayer distance calculated from the XRD measurement was 20.4 mm.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then calculated by computational chemistry. 0.5201 g of dimethylsilylene (cyclopentadienyl) (4,7-ditrimethyl-1-indenyl) zirconium dichloride having a maximum distance between the two atoms of 9.6 mm and 142 mL of 20% triisobutylaluminum were added. And stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 mL of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 15.90 wt%).
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum in a 2 L autoclave, 38.83 mg (corresponding to a solid content of 6.67 mg) of the catalyst suspension obtained in (2) were added, and 85 After raising the temperature to 0 ° C., ethylene was continuously supplied so that the partial pressure was 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 108 g of polymer (activity: 16,200 g / g catalyst). The polymer had an MFR of 22.3 g / 10 min and a density of 950 kg / m 3. The number average molecular weight was 12,100, and the ratio of weight average molecular weight to number average molecular weight (Mw / Mn) was 3.2. The weight ratio of the polyethylene components [A] and [B] when molecular weight fractionation was 100/0. Mn of the polyethylene component [A] was 12,100, the number of terminal vinyls was 0.31 per 1,000 carbons, and the number of long chain branches was 0.01 per 1,000 carbons. The melt tension was 12 mN.

Comparative Example 2
(1) Modification of clay The same procedure as (1) of Comparative Example 1 was performed.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then calculated by computational chemistry 0.4406 g of dimethylsilylene (cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride having a maximum distance of 9.8 cm between the two atoms was added, and 142 mL of 20% triisobutylaluminum was added. And stirred at 60 ° C. for 3 hours. After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 mL of hexane, and then 200 mL of hexane was added to obtain a catalyst suspension (solid weight: 12.4 wt%).
(3) Polymerization 1.2 L of hexane and 1.0 mL of 20% triisobutylaluminum were added to a 2 L autoclave, and 52 mg of the catalyst suspension obtained in (2) (corresponding to a solid content of 6.4 mg) was added to 80 ° C. After the temperature increase, 6.0 g of 1-butene was added, and an ethylene / hydrogen mixed gas was continuously supplied so that the partial pressure became 0.85 MPa (concentration of hydrogen in the ethylene / hydrogen mixed gas: 590 ppm). After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 61.8 g of polymer (activity: 9,700 g / g catalyst). The polymer had an MFR of 15.4 g / 10 min and a density of 948 kg / m3. Moreover, the number average molecular weight was 12,700, and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) was 3.0. The weight ratio of the polyethylene components [A] and [B] when molecular weight fractionation was 100/0. Mn of the polyethylene component [A] was 12,700, the number of terminal vinyls was 0.11 per 1,000 carbons, and the number of long chain branches was 0.01 per 1,000 carbons. The melt tension was 14 mN.

Comparative Example 3
(1) Modification of clay The same procedure as in (1) of Example 1 was performed.
(2) Preparation of catalyst suspension After substituting a 300 mL flask equipped with a thermometer and a reflux tube with nitrogen, 25.0 g of the organically modified clay obtained in (1) and 108 mL of hexane were added, and then calculated by computational chemistry. 0.5201 g of dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride having a maximum distance between the two atoms of 9.2 mm and 142 mL of 20% triisobutylaluminum were added and stirred at 60 ° C. for 3 hours. . After cooling to 45 ° C., the supernatant was taken out, washed 5 times with 200 mL of hexane, and then 200 ml of hexane was added to obtain a catalyst suspension (solid weight: 15.90 wt%).
(3) Polymerization 1.2 L of hexane, 1.0 mL of 20% triisobutylaluminum in a 2 L autoclave, 38.83 mg (corresponding to a solid content of 6.67 mg) of the catalyst suspension obtained in (2) were added, and 85 After raising the temperature to 0 ° C., ethylene was continuously supplied so that the partial pressure was 0.90 MPa. After 90 minutes, the pressure was released, and the slurry was filtered and dried to obtain 108 g of polymer (activity: 16,200 g / g catalyst). This polymer had an MFR of 20.1 g / 10 min and a density of 945 kg / m 3. The number average molecular weight was 11,400, and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) was 3.8. The weight ratio of the polyethylene components [A] and [B] upon molecular weight fractionation was 97.3 / 2.7. The Mn of the polyethylene component [A] was 8,500, the number of terminal vinyls was 0.21 per 1,000 carbons, and the number of long chain branches was not detected. The Mn of the polyethylene component [B] was 14,800, the number of terminal vinyls was not detected, and the number of long chain branches was 0.04 per 1,000 carbons. The melt tension was 13 mN.

Comparative Example 4
The number average molecular weight of the low density polyethylene (trade name Petrocene 205, MFR 3 g / 10 min, density 924 kg / m 3, manufactured by Tosoh Corporation) obtained by the high pressure radical polymerization method is 18,200, and the ratio of the weight average molecular weight to the number average molecular weight (Mw / Mn) was 7.1. The weight ratio of the polyethylene components [A] and [B] when molecular weight fractionation was 93.3 / 6.7. The number of terminal vinyls in the polyethylene component [B] was not detected, and the number of long-chain branches was 7.5 per 1,000 carbons. The melt tension was 90 mN.

(1): Dimethylsilylene (cyclopentadienyl) (4,7-dimethyl-1-indenyl) zirconium dichloride (2): Dimethylsilylene (cyclopentadienyl) (2,4,7-trimethylindenyl) zirconium dichloride (3): Dimethylsilylene (cyclopentadienyl) (indenyl) zirconium dichloride (4): Dimethylsilylene (cyclopentadienyl) (2,4,7-trimethyl-1-indenyl) zirconium dichloride (B-1): N, N-dimethylmyristylamine hydrochloride-modified hectorite (B-2): N, N-dimethylpalmitylamine hydrochloride-modified hectorite (B-3): N, N-dimethylstearylamine hydrochloride-modified hectorite ( B-4): N-methyldioleilamine hydrochloride-modified hectorite

Claims (3)

Dimethylsilanediyl (cyclopentadienyl) (4,7-dimethylindenyl) zirconium dichloride (A), clay compound belonging to smectite group hectorite is N, N-dimethylmyristylamine hydrochloride, N, N-dimethylpalmityl The following characteristics (i) to (v) obtained by an olefin polymerization catalyst comprising a modified clay compound (B) and an organoaluminum compound (C) treated with amine hydrochloride or N, N-dimethylstearylamine hydrochloride: A method for producing an ethylene polymer.
(I) an ethylene homopolymer or a copolymer of ethylene and an α-olefin having 3 or more carbon atoms,
(Ii) The density (kg / m ³ ) is 935 or more and 960 or less,
(Iii) Among two peaks in molecular weight measurement by GPC, the weight ratio of the low molecular weight polyethylene component [A] and the high molecular weight polyethylene component [B] when molecular weight fractionation is in the range of 95/5 to 80/20. Yes,
(Iv) The number average molecular weight (Mn) of the low molecular weight polyethylene component [A] is 1,000 or more and less than 150,000, the number of terminal vinyls is 0.10 or more and less than 3.0 per 1000 carbons of the main chain, long chain The number of branches is 0 or more and 0.05 or less per 1000 carbon atoms of the main chain,
(V) Mn of the high molecular weight polyethylene component [B] is 150,000 to 10,000,000, the number of terminal vinyls is 0 to 0.05 per 1000 carbons of the main chain, and the number of long chain branches is the main chain It is 0.20 or more and less than 3.0 per 1000 carbon atoms. 2. The production of an ethylene polymer according to claim 1, wherein Mw / Mn, which is a ratio of the weight average molecular weight (Mw) of the ethylene polymer to Mn, is in the range of 3.0 to 6.0. Method. 3. The method for producing an ethylene polymer according to claim 2, wherein Mn of the ethylene polymer is 15,000 or more and 10,000,000 or less.