JP2005200445A - Fuel oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fuel oil composition which does not cause crystal growth of a wax and a rise in viscosity, remarkably reduces the cold filter plugging point (CFPP) and the pour point, and has excellent cold flowability. <P>SOLUTION: The fuel oil composition comprises (A) a medium fraction fuel oil having a boiling point of 150-400°C and (B) a fuel oil flowability improving agent composed of an α-olefin (co)polymer which is obtained by polymerization with the use of a metallocene catalyst as the main catalyst and has (i) (a) 20-100 mol% constituting unit derived from at least one monomer selected from 8-20C α-olefins and (b) 0-80 mol% constituting unit derived from ethylene and (ii) an intrinsic viscosity [η] measured in decalin at 135°C in the range of 0.1-1.0 dl/g. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a fuel oil composition, and more specifically, a fuel oil composition having excellent low-temperature fluidity, comprising a middle distillate fuel oil and a fuel oil fluidity improver comprising a specific α-olefin (co) polymer. It is about things.

When middle distillate fuel oil such as light oil and heavy oil is used or stored at low temperature, wax crystals contained in the oil grow, and when such wax-grown oil is used, piping is blocked or oil There is a problem that the overall viscosity is extremely increased and the fluidity is lost. In order to solve such a problem, a fluidity improver such as ethylene / α-olefin copolymer is added to the middle distillate fuel. It is known.

  It is also known to add a hydroxyl-terminated polybutadiene having 1,2-bonds of 70% or more or a hydrogenated product thereof to the middle distillate fuel oil in order to reduce the low temperature filter clogging point (CFPP). .

  However, even if these additives are used, the low temperature fluidity and CFPP of the fuel oil cannot be improved sufficiently, and further improvements are desired.

  The problem to be solved by the present invention is to provide a fuel oil composition in which the low temperature filter clogging point (CFPP) and the pour point are greatly reduced by the addition of a low concentration flowability improver.

  As a result of intensive studies to solve the above problems, an α-olefin (co) polymer obtained by (co) polymerizing an α-olefin having a specific number of carbon atoms is excellent as a fluidity improver for fuel oil. The present inventors have found that they have CFPP lowering ability and pour point lowering ability and have completed the present invention.

That is, the present invention provides (A) a middle distillate fuel oil having a boiling point of 150 ° C to 400 ° C,
(B) 20-100 mol% of structural units derived from at least one monomer selected from (i) (a) an α-olefin having 8-20 carbon atoms, polymerized using a metallocene catalyst as the main catalyst (B) containing structural units derived from ethylene in an amount ranging from 0 to 80 mol%,
(Ii) Fuel oil fluidity improvement comprising an α-olefin (co) polymer, wherein the intrinsic viscosity [η] measured in decalin at 135 ° C. is in the range of 0.1 to 1.0 dl / g. It is a fuel oil composition characterized by including an agent.

The fuel oil composition of the present invention does not have wax crystal growth or viscosity increase, has a low temperature filter clogging point and a pour point, and is excellent in low temperature fluidity.

  Hereinafter, the present invention will be described in detail.

The middle distillate fuel oil used in the present invention has a boiling point of 150 ° C. to 400 ° C., and typical ones thereof are light oil, A heavy oil, etc. It is particularly preferable that the temperature is not less than 200 ° C., for example, 200 ° C. or less, preferably 115 ° C. to 190 ° C., and the clogging point of the low temperature filter is in the range of −10 ° C. to + 10 ° C.

  These middle distillate fuel oils may be one or a mixture of two or more.

  The (a) α-olefin having 8 to 20 carbon atoms constituting the (B) α-olefin (co) polymer used in the present invention includes 1-octene, 1-nonene, 1-decene, 1-undecene. 1-dodecene, 1-tricene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene linear α-olefin and 8- Examples include α-olefins having a branch such as methyl-1-nonene, 7-methyl-1-decene, 6-methyl-1-undecene, and 6,8-dimethyl-1-decene. 10 to 20 linear α-olefins.

  The (B) α-olefin (co) polymer used in the present invention is a homopolymer of a monomer comprising at least one or more of the above (a) α-olefin having 8 to 20 carbon atoms, or (b ) Copolymer with ethylene. Furthermore, a C3-C6 alpha olefin can also be included as a copolymerization component as needed. Examples of the α-olefin having 3 to 6 carbon atoms include linear α-olefins such as propylene, 1-butene, 1-pentene, and 1-hexene, and branched α-olefins such as 4-methyl-1-pentene. Mention may be made of olefins. These α-olefins can be used alone or in combination of two or more.

  The content of the structural unit derived from (a) the α-olefin having 8 to 20 carbon atoms constituting the (B) α-olefin (co) polymer used in the present invention is in the range of 20 to 100 mol%. , Preferably 30 to 100 mol%, more preferably 50 to 100 mol%.

  The content of the structural unit derived from (b) ethylene constituting the (B) α-olefin (co) polymer used in the present invention is in the range of 0 to 80 mol%, preferably 0 to 70 mol. %, More preferably 0 to 50 mol%.

  Furthermore, it is preferable that the content rate of the structural unit guide | induced from the C3-C6 alpha-olefin added as needed is the range of 0-30 mol%.

  The intrinsic viscosity [η] measured in decalin at 135 ° C. of the (B) α-olefin (co) polymer used in the present invention is in the range of 0.1 to 1.0 dl / g, preferably 0.8. It exists in the range of 15-0.8 dl / g, More preferably, it exists in the range of 0.2-0.5 dl / g.

  The number average molecular weight (Mn) of the (B) α-olefin (co) polymer used in the present invention is in the range of 5,000 to 100,000, preferably 7,000 to 80,000, more preferably 10 , 50,000 to 50,000.

  The number average molecular weight can be measured by gel permeation chromatography (GPC) calibrated using a standard substance (monodisperse polystyrene) having a known molecular weight.

  The molecular weight distribution (Mw / Mn) of the (B) α-olefin (co) polymer used in the present invention measured by gel permeation chromatography is 3 or less, preferably 2.8 or less, more preferably. 2 or less.

Further, the α-olefin (co) polymer of the present invention preferably has a high stereoregularity in the α-olefin chain portion. In particular, when the content of the structural unit derived from the (a) α-olefin having 8 to 20 carbon atoms constituting the (B) α-olefin (co) polymer is 50 to 100 mol%, α The olefin chain moiety has a syndiotactic structure.

  The syndiotactic structure has a three-dimensional structure in which the side chains are alternately positioned in opposite directions with respect to the main chain formed from carbon-carbon bonds among the structures in which the three-dimensional structure of the side chains is regularly controlled. Is. Tacticity is used as an index representing the degree of regularity, and syndiotacticity is used as an index representing the degree of syndiotactic structure.

Syndiotacticity is determined by a method described in known literature [Macromolecules 24, 2334 (1991); Polymer, 30, 1350 (1989)] using ¹³ C-NMR (isotope carbon nuclear magnetic resonance spectrum). Can be sought.

^The tacticity determined by ¹³ C-NMR is the abundance ratio of a plurality of consecutive constitutional units (ie, the abundance ratio of the relative conformation of consecutive constitutional units). Can be indicated by a triad. The tacticity in the present invention is a triad having a syndiotacticity of 50% or more, and preferably 70% or more.

  Here, syndiotacticity (hereinafter also referred to as triad syndiotacticity, rr fraction) as seen in the triad chain will be described.

The rr fraction of the α-olefin (co) polymer is determined by the ¹³ C-NMR spectrum of the α-olefin (co) polymer and the following formula (7), and the α-olefin unit 3 chain portion bonded head-to-tail. It is calculated | required as intensity | strength (area) ratio of the side chain 1st methylene group ([C3] in Chemical formula (8)) of the 2nd unit.

rr fraction (%) = PPP (rr) / {PPP (mm) + PPP (mr) + PPP (rr)} (7)
(Wherein, PPP (mm), PPP (mr), and PPP (rr) represent the first side chain of the second unit of the 3-chain unit of α-olefin units bonded head-to-tail, respectively, as observed in the 13 C-NMR spectrum. This is the area of the methylene group [C3].)

(Wherein R1, R2, R3 = C _n H _{2n + 1} , 0 ≦ n ≦ 17, which may be the same or different)

  Such PPP (mm), PPP (mr), and PPP (rr) each represent a three-unit chain of α-olefin having a head-to-tail bond having the following structure.

(Wherein R1, R2, R3 = C _n H _{2n + 1} , 0 ≦ n ≦ 17, which may be the same or different)

Production of α-olefin (co) polymer As the metallocene catalyst used in the production of the above α-olefin (co) polymer, JP-A-2-41303, JP-A-41305, JP-A-2 -274703, JP-A-2-274704, JP-A-3-179005, JP-A-3-179006, JP-A-4-69394, JP-A-5-17589, JP-A-8 Catalyst system as described in JP-A No. 1202015 or J. A. Ewen et al., “J. Am. Chem. Soc., 1988, 110, 6255-6256” can be used. Examples thereof include a catalyst system comprising a bridged transition metal compound having an asymmetric ligand and a promoter such as organoaluminum.

Examples of the metallocene catalyst component for producing the α-olefin (co) polymer in the present invention include group 4 transition metal compounds represented by the following general formulas (12), (13), and (14) as transition metal compounds. be able to.
First, the Group 4 transition metal compound represented by the general formula (12) will be described.

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are selected from a hydrogen atom, a hydrocarbon group and a silicon-containing hydrocarbon group. May be the same or different from each other, and among the groups represented by R ¹ to R ⁸ and R ⁹ to R ¹⁰ , adjacent groups may be bonded to each other to form a ring, and Y represents a carbon atom or a silicon atom N represents an integer of 2 to 4, M represents a metal selected from Group 4 of the periodic table, j represents an integer of 1 to 4, Q represents a halogen atom, a hydrocarbon group, an anionic ligand, and (Selected from neutral ligands that can be coordinated by a lone pair, and when j is 2 or more, Qs may be the same or different from each other.)
In the general formula (12), the hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 7 to 20 carbon atoms. And may contain one or more ring structures.

  In addition to alkyl, alkenyl, alkynyl, and aryl groups composed only of carbon and hydrogen, some of the hydrogen atoms directly connected to these carbon atoms are halogen atoms, oxygen-containing groups, nitrogen-containing groups, and any two adjacent hydrogen atoms. Are substituted at the same time to form an alicyclic or aromatic ring.

  Specific examples thereof include methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n- Linear hydrocarbon groups such as nonyl and n-decanyl; isopropyl, isobutyl, s-butyl, t-butyl, t-amyl, neopentyl, 3-methylpentyl, 1,1- Diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl- Branched hydrocarbon groups such as 2-methylpropyl group and cyclopropylmethyl group; cyclic saturated hydrocarbons such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group and adamantyl group Group: phenyl group, naphth Cyclic unsaturated hydrocarbon groups such as benzene, biphenyl, phenanthryl, and anthracenyl groups; saturated hydrocarbon groups substituted with aryl groups such as benzyl and cumyl, oxygen atoms such as methoxy, ethoxy, and phenoxy Hydrocarbon groups, N-methylamino groups, N, N-dimethylamino groups, nitrogen-containing hydrocarbon groups such as N-phenylamino groups, trifluoromethyl groups, tribromomethyl groups, pentafluoroethyl groups, pentafluorophenyl And a halogen atom-containing hydrocarbon group such as a group.

  In the general formula (12), the silicon-containing hydrocarbon group is preferably an alkyl or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms, such as a cyclopentadienyl group, an indenyl group, or a fluorenyl group. This indicates a group in which the ring carbon of the group is directly covalently bonded to the silicon atom, and specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, triphenylsilyl and the like.

In the present invention, R ¹ to R ^{10 in} the general formula (12) are selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different. Specific examples of preferred hydrocarbon groups and silicon-containing hydrocarbon groups include the same as those described above.

The adjacent substituents from R ¹ to R ⁸ on the cyclopentadienyl ring of the general formula (12) may be bonded to each other to form a ring.

  M in the general formula (12) is a group 4 element of the periodic table, that is, zirconium, titanium or hafnium, preferably zirconium.

  Y is a Group 14 atom, preferably a carbon atom or a silicon atom. n is an integer of 2 to 4, preferably 2 or 3, particularly preferably 2.

  Q is the same or different combination from the group consisting of halogen, hydrocarbon group, neutral having 10 or less carbon atoms, conjugated or non-conjugated diene, anionic ligand and neutral ligand capable of coordinating with a lone electron pair. To be elected. When Q is a hydrocarbon group, it is more preferably a hydrocarbon group having 1 to 10 carbon atoms.

Specific examples of the halogen are fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group are methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2, 2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1, Examples include 1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like. Neutral having 10 or less carbon atoms, and specific examples of the conjugated or non-conjugated dienes, s- cis - or s- trans eta ^{4-1,3-butadiene,} s- cis - or s- trans eta ⁴ - 1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4- Dibenzyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s -Trans-η ⁴ -1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene and the like. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of the neutral ligand that can coordinate with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. When j is an integer greater than or equal to 2, several Q may be the same or different.

In Formula (12), there are a plurality of Ys of 2 to 4, but the Ys may be the same or different from each other. The plurality of R ⁹ and the plurality of R ¹⁰ bonded to Y may be the same as or different from each other. For example, a plurality of R ⁹ bonded to the same Y may be different from each other, or a plurality of R ⁹ bonded to different Y may be the same. R ⁹ or R ¹⁰ may form a ring.

Specific examples of the Group 4 transition metal compound represented by the general formula (12) are shown below, but the scope of the present invention is not particularly limited by this.
Ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (3,6-ditert -Butyl fluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, propylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, propylene (cyclopentadienyl) ( 2,7-ditert-butylfluorenyl) zirconium dichloride, propylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, propylene (cyclopentadienyl) (octamethyloctahydro Dibenzofluorenyl) zirconium dichlor Tetramethylethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, tetramethylethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, tetramethylethylene (cyclopentadienyl) ) (3,6-ditert-butylfluorenyl) zirconium dichloride, tetramethylethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, tetramethyldisylylene (cyclopentadienyl) ( Fluorenyl) zirconium dichloride, tetramethyldisilene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, tetramethyldisilene (cyclopentadienyl) (3,6-ditert-butyl Fluorenyl) zirconium dichloride, tetra Methyldisilene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dimethylethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylethylene (cyclopentadienyl) (2,7-di tert-butylfluorenyl) zirconium dichloride, dimethylethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, dimethylethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorene) Nyl) zirconium dichloride, ethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, ethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, ethylene (cyclopentadienyl) (3 , 6-Ditert-butyl Oleenyl) hafnium dichloride, ethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dichloride, propylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, propylene (cyclopentadienyl) (2,7- Di-tert-butylfluorenyl) hafnium dichloride, propylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dichloride, propylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) ) Hafnium dichloride, ethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, ethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, ethylene (cyclopentadienyl) (3, 6-ditert-butylfluorenyl) Titanium dichloride, ethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) titanium dichloride, propylene (cyclopentadienyl) (fluorenyl) titanium dichloride, propylene (cyclopentadienyl) (2,7-di tert-butylfluorenyl) titanium dichloride, propylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) titanium dichloride, propylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Titanium dichloride, ethylene (cyclopentadienyl) (fluorenyl) zirconium dimethyl, ethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dimethyl, ethylene (cyclopentadienyl) (3,6 -Di-tert-butylfluorenyl) zirconium Dimethyl, ethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, propylene (cyclopentadienyl) (fluorenyl) zirconium dimethyl, propylene (cyclopentadienyl) (2,7-ditert- Butylfluorenyl) zirconium dimethyl, propylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dimethyl, propylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dimethyl , Ethylene (cyclopentadienyl) (fluorenyl) hafnium dimethyl, ethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dimethyl, ethylene (cyclopentadienyl) (3,6-di tert-butylfluorenyl) hafnium dimethyl, ethyl (Cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dimethyl, propylene (cyclopentadienyl) (fluorenyl) hafnium dimethyl, propylene (cyclopentadienyl) (2,7-ditert-butylfluorene Nyl) hafnium dimethyl, propylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) hafnium dimethyl, propylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) hafnium dimethyl, etc. can do.
Next, the Group 4 transition metal compound represented by the general formulas (13) and (14) will be described.

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹¹ and R ¹² are selected from a hydrogen atom, a hydrocarbon group and a silicon-containing hydrocarbon group. May be the same or different from each other, and adjacent groups among the groups represented by R ¹ to R ⁸ may be bonded to each other to form a ring. In the case of the general formula (13), R ¹ and R ⁸ R ¹¹ or R ¹² may be bonded to each other to form a ring, and A is a divalent divalent having 2 to 20 carbon atoms and may contain an unsaturated bond and / or an aromatic ring. Represents a hydrocarbon group, A may include two or more ring structures including a ring formed with Y, Y is a carbon atom or a silicon atom, and M is selected from Group 4 of the periodic table. Represents a metal, j is an integer of 1 to 4, Q is a halogen atom, a hydrocarbon group, an anionic ligand, and a lone electron In it is selected from coordinating neutral ligands capable, when j is 2 or more Q may be the same or different.).

  In the general formulas (13) and (14), the hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or carbon. These are alkylaryl groups of several 7 to 20, and may contain one or more ring structures.

  In addition to alkyl, alkenyl, alkynyl, and aryl groups composed only of carbon and hydrogen, some of the hydrogen atoms directly connected to these carbon atoms are halogen atoms, oxygen-containing groups, nitrogen-containing groups, and any two adjacent hydrogen atoms. Are substituted at the same time to form an alicyclic or aromatic ring.

  Specific examples thereof include methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n- Linear hydrocarbon groups such as nonyl and n-decanyl; isopropyl, isobutyl, s-butyl, t-butyl, t-amyl, neopentyl, 3-methylpentyl, 1,1- Diethylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl- Branched hydrocarbon groups such as 2-methylpropyl group and cyclopropylmethyl group; cyclic saturated hydrocarbons such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group and adamantyl group Group: phenyl group, naphth Cyclic unsaturated hydrocarbon groups such as benzene, biphenyl, phenanthryl, and anthracenyl groups; saturated hydrocarbon groups substituted with aryl groups such as benzyl and cumyl, oxygen atoms such as methoxy, ethoxy, and phenoxy Hydrocarbon groups, N-methylamino groups, N, N-dimethylamino groups, nitrogen-containing hydrocarbon groups such as N-phenylamino groups, trifluoromethyl groups, tribromomethyl groups, pentafluoroethyl groups, pentafluorophenyl And a halogen atom-containing hydrocarbon group such as a group.

  In the general formulas (13) and (14), the silicon-containing hydrocarbon group is preferably an alkyl or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms, such as a cyclopentadienyl group, Indenyl group and fluorenyl group represent a group in which the ring carbon is directly covalently bonded to a silicon atom, and specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, triphenylsilyl and the like.

In the present invention, R ¹ to R ¹⁰ in the general formulas (13) and (14) are selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different. Specific examples of preferred hydrocarbon groups and silicon-containing hydrocarbon groups include the same as those described above.

The adjacent substituents from R ¹ to R ⁸ on the cyclopentadienyl ring of the general formulas (13) and (14) may be bonded to each other to form a ring.

  M in the general formulas (13) and (14) is a group 4 element of the periodic table, that is, zirconium, titanium, or hafnium, preferably zirconium.

  Y is a Group 14 atom, preferably a carbon atom or a silicon atom. Q is the same or different combination from the group consisting of halogen, hydrocarbon group, neutral having 10 or less carbon atoms, conjugated or non-conjugated diene, anionic ligand and neutral ligand capable of coordinating with a lone electron pair. To be elected. When Q is a hydrocarbon group, it is more preferably a hydrocarbon group having 1 to 10 carbon atoms.

Specific examples of the halogen are fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group are methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2, 2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1, Examples include 1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like. Neutral having 10 or less carbon atoms, and specific examples of the conjugated or non-conjugated dienes, s- cis - or s- trans eta ^{4-1,3-butadiene,} s- cis - or s- trans eta ⁴ - 1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4- Dibenzyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s -Trans-η ⁴ -1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene and the like. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of the neutral ligand that can coordinate with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. When j is an integer greater than or equal to 2, several Q may be the same or different.

R ¹¹ and R ¹² are selected from a hydrocarbon group and a silicon-containing group, and may be the same or different. Examples of the hydrocarbon group and the silicon-containing group include the same groups as described above.

R ¹¹ and R ¹² may be bonded to each other to form a ring.
When R ¹¹ and R ¹² are an aryl group such as a phenyl group or an alkylaryl group, it is preferable that R ¹ to R ⁸ are not simultaneously hydrogen. Specifically, any two or more substituents of R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , and R ⁷ are not hydrogen or adjacent groups of R ² to R ⁷ are bonded to each other. To form a ring.

  Specific examples of the Group 4 transition metal compounds represented by the above general formulas (13) and (14) are shown below, but the scope of the present invention is not particularly limited thereby.

Cyclopentylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, monophenyl monomethylmethylene ( Cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadi) (Enyl) (fluorenyl) zirconium dichloride, diethylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (phenyl) Olenyl) hafnium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) hafnium dichloride, adamantylidene (cyclopentadienyl) (fluorenyl) hafnium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride Dimethylmethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (fluorenyl) hafnium dichloride, diethylmethylene (Cyclopentadienyl) (fluorenyl) hafnium dichloride, cyclopentylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, cyclohexylidene Lopentadienyl) (fluorenyl) titanium dichloride, adamantylidene (cyclopentadienyl) (fluorenyl) titanium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, dimethylmethylene (cyclopentadienyl) (fluorenyl) Titanium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (fluorenyl) titanium dichloride, diethylmethylene (cyclopentadienyl) (fluorenyl) titanium dichloride, Di (p-tolyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (fluorenyl) di Conium dichloride, di (p-n-butylphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, (p-tolyl) (Phenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadiene) (Enyl) (fluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dimethyl, (p-tert-butylphenyl) (phenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride , (Pn-ethylphenyl) (phenyl) methylene (Si Lopentadienyl) (fluorenyl) zirconium dichloride, (4-biphenyl) (phenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, dimethylsilylene (Cyclopentadienyl) (fluorenyl) zirconium dichloride diphenylsilylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, Cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, Monopheny Monomethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (Cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride Diethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Cyclohexylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, adamantyl Den (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, dimethyl Methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p -Tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diethylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, Cyclopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, cyclohexylide (Cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, monophenylmonomethyl Methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, dimethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, diphenylmethylene ( Cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, Diethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) hafnium dichloride, cyclopentylidene (cyclopent Tadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, cyclohexylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, adamantylidene (cyclopentadiene) Enyl) (2,7-ditert-butylfluorenyl) titanium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, dimethylmethylene (cyclopentadiyl) Enyl) (2,7-ditert-butylfluorenyl) titanium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, di (p-tolyl) methylene ( Cyclopentadienyl) (2,7-ditert-butylfluorenyl) titanium dichloride, diethylmethylene (cyclopentadienyl) (2, 7-ditert-butylfluorenyl) titanium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene ( Cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p -tert-butylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (2,7- Dimethylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-n-butylphenyl) Tylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-n-butylphenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium Dichloride, di (p-n-butylphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2, 7-ditert-butylfluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadi) Enyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium di Chloride, (p-tolyl) (phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-isopropylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzo Fluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) ( Octamethyloctahydrodibenzofluorenyl) zirconium dimethyl, (p-tolyl) (phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-isopropylphenyl) Methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconi Um dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2 , 7-Ditert-butylfluorenyl) zirconium dimethyl, (p-tolyl) (phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-isopropyl) Phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (3,6-ditert-butyl Fluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dimethyl, (p-tert-butylphenyl) (phenyl) methylene (cyclo Pentadienyl) (2,7- tert-butylfluorenyl) zirconium dichloride, (p-tert-butylphenyl) (phenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, (p-tert-butylphenyl) ( Phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (pn-ethylphenyl) (phenyl) methylene (cyclopentadienyl) (2,7-ditert-butyl Fluorenyl) zirconium dichloride, (pn-ethylphenyl) (phenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, (pn-ethylphenyl) (phenyl) methylene (cyclopentadiene) Enyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (4-biphenyl) (phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zyl Conium dichloride, (4-biphenyl) (phenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, (4-biphenyl) (phenyl) methylene (cyclopentadienyl) (3, 6-ditert-butylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene ( Cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, bis (3 , 4-Dimethylphenyl) methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, bis (3,4-dimethylphenyl) methylene (cyclopentadiene) ) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride, bis (3,5-dimethylphenyl) methylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, bis ( 3,5-dimethylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, bis (4-cyclohexylphenyl) methylene (cyclopentadienyl) (2,7-di-tert- Butylfluorenyl) zirconium dichloride, bis (4-cyclohexylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, bis {3- (trifluoromethyl) phenyl} methylene (cyclopenta Dienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, bis {3- (trif Oromethyl) phenyl} methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, bis {3,5-bis (trifluoromethyl) phenyl} methylene (cyclopentadienyl) (2,7- Di-tert-butylfluorenyl) zirconium dichloride, bis {3,5-bis (trifluoromethyl) phenyl} methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dimethylsilylene Pentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) (2,7-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilylene Pentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, diphenylsilylene ( Cyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, dimethylsilylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, diphenylsilylene (cyclopentadienyl) ) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride and the like.

  In addition, as the promoter component, at least one compound selected from the following [1] to [4] can be used.

[1] Organometallic compound As the organometallic compound used for producing the α-olefin (co) polymer of the present invention, the following organometallic compounds are specifically used.

(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. A dialkyl compound of a Group 2 or Group 12 metal represented by the following periodic table.

[2] Organoaluminum compound Forming the catalyst for olefin polymerization [2] As the organoaluminum compound, for example, an organoaluminum compound represented by the following general formula (16), a group I metal represented by the following general formula (17) And a complex alkylated product of aluminum and aluminum.

(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, and m represents 0. <M ≦ 3, n is 0 ≦ n <3, p is a number of 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3). Specific examples of such compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, and diisobutylaluminum hydride.

(Wherein M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms). Alkylate complex of aluminum and aluminum. Examples of such compounds include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

[3] Organoaluminum oxy compound [3] The organoaluminum oxy compound used in the present invention may be a conventionally known aluminoxane, or a benzene-insoluble organic compound as exemplified in JP-A-2-78687. An aluminum oxy compound may be used.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

  Specifically, as the organoaluminum compound used in preparing the aluminoxane, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.

  The above organoaluminum compounds are used singly or in combination of two or more.

[4] Compound that forms an ion pair by reacting with a transition metal compound [4] (hereinafter referred to as “ionized ionic compound”) that forms an ion pair by reacting with a transition metal compound No. 501950, JP-A-1-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106. And Lewis acids, ionic compounds, borane compounds and carborane compounds described in the above.

  Such ionized ionic compounds [4] are used singly or in combination of two or more.

  Component [1] has a molar ratio [[1] / M] of component [1] to all transition metal atoms (M) in the transition metal compound used as a catalyst of usually 0.01 to 5000, preferably 0. It is used in such an amount that it becomes 0.05 to 2000. Component [2] has a molar ratio [[2] / M] of component [2] to all transition metal atoms (M) in the transition metal compound used as a catalyst of usually 100 to 25000, preferably 500 to 10,000. Is used in such an amount that Component [3] has a molar ratio [[3] / M] of the aluminum atoms in component [3] and the total transition metals (M) in the transition metal compound used as a catalyst, usually 10 to 5000, preferably Is used in such an amount as to be 20-2000. Component [4] has a molar ratio [[4] / M] of component [4] and the transition metal atom (M) in the transition metal compound used as a catalyst, usually 1 to 50, preferably 1 to 20 Is used in such an amount that

  Examples of the method for producing an α-olefin (co) polymer used in the present invention include (a) an α-olefin having 8 to 20 carbon atoms and (b) ethylene in the presence of the catalyst as described above. If necessary, an α-olefin having 3 to 6 carbon atoms is usually copolymerized in a liquid phase. At this time, a hydrocarbon solvent such as hexane or toluene is generally used as a polymerization solvent, but an α-olefin may be used as a solvent.

The polymerization reaction may be carried out by either a batch method or a continuous method, and the normal temperature is −20 ° C. to + 150 ° C., preferably 0 to 120 ° C., more preferably 0 to 100 ° C., and the pressure exceeds 0. And 7.8 MPa (80 kgf / cm ² , gauge pressure) or less, preferably more than 0 and 4.9 MPa (50 kgf / cm ² , gauge pressure) or less.

  In the polymerization, (a) an α-olefin having 8 to 20 carbon atoms, (b) ethylene and an α-olefin having 3 to 6 carbon atoms introduced as needed are α-olefins (co) having a specific composition. It is fed into the polymerization system in such an amount ratio that a polymer is obtained. In the polymerization, a molecular weight regulator such as hydrogen can be added.

  The (B) α-olefin (co) polymer used as a fluidity improver in the present invention is contained in the fuel oil composition in an amount of 50 ppm to 5,000 ppm, preferably 100 ppm to 2,000 ppm.

[Example]
EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these.

Average molecular weight / number distribution of molecular weight Average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were measured as follows using GPC (Chromatopack C-R4A) manufactured by Shimadzu Corporation. TSK as a separation column
G6000H XL, G4000H XL, G3000H XL, G2000H XL are used, the column temperature is 40 ° C., the mobile phase is tetrahydrofuran (Wako Pure Chemical Industries), the development rate is 0.8 ml / min, and the sample concentration is 0.2. The amount of sample injection was 200 microliters, and a differential refractometer was used as a detector. As the standard polystyrene, those manufactured by Tosoh Corporation were used.

Performance Evaluation of Fuel Oil Compositions Polymers of the following examples were added to commercially available No. 2 diesel oil (sulfur content: 0.1% by weight) at a ratio of 100 ppm or 1,000 ppm, and these fuel oil compositions were low in temperature. Filter clogging point (CFPP) and pour point were evaluated.
The clogging point of the low temperature filter was measured according to the method described in JIS K 2288, and the pour point was measured according to the method described in JIS K 2269.

  A glass autoclave with an internal volume of 1000 ml was equipped with a thermometer, a gas blowing tube, and a glass stirring blade, and sufficiently substituted with nitrogen. Thereafter, 450 ml of n-decane and 50 ml of 1-decene were charged, and the temperature was adjusted to 130 ° C. while nitrogen was circulated at 50 liters / hour. On the other hand, a magnetic stirrer chip was placed in a 30 ml branch flask with a sufficient internal volume substituted with nitrogen, and 0.002 mmol of a toluene solution of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride as a transition metal compound, and methyl 2 mmol of aluminoxane in toluene (Al = 1.53M) was added and stirred for 30 minutes. The nitrogen in the glass autoclave was stopped, then ethylene was passed in an amount of 20 liter / hour and hydrogen in an amount of 30 liter / hour, and then the above solution was added to initiate the polymerization. During the polymerization, ethylene was continuously supplied at a rate of 20 liters / hour and hydrogen at a rate of 30 liters / hour, and polymerization was carried out at 130 ° C. for 20 minutes under normal pressure, and then a small amount of isopropanol was added to terminate the polymerization. The polymer solution was added to 300 ml of 1N hydrochloric acid and stirred. This solution was transferred to a separatory funnel, and the organic layer was separated. The organic layer was washed with water, and the solvent and unreacted 1-decene were distilled off at 175 ° C. under reduced pressure (1 mmHg). The obtained transparent liquid polymer was 46.52 g, and the polymerization activity was 69.8 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, the ethylene content was 73 mol%, [η] = 0.46 dl / g, Mw = 101,910, Mn = 65,330, and Mw / Mn = 1.56.

  The performance evaluation results of the fuel oil composition using the obtained polymer are shown in Table 1.

  A glass autoclave with an internal volume of 1000 ml was equipped with a thermometer, a gas blowing tube, and a glass stirring blade, and sufficiently substituted with nitrogen. Thereafter, 250 ml of n-decane and 250 ml of 1-decene were charged, and the temperature was set to 110 ° C. while nitrogen was circulated at 50 liters / hour. On the other hand, a magnetic stirrer chip was placed in a 30 ml branch flask with a sufficient internal volume substituted with nitrogen, and 0.002 mmol of a toluene solution of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride as a transition metal compound, and methyl 2 mmol of aluminoxane in toluene (Al = 1.53M) was added and stirred for 30 minutes. Nitrogen in the glass autoclave was stopped, then ethylene was passed in an amount of 5 liter / hour and hydrogen in an amount of 40 liter / hour, and then the above solution was added to initiate the polymerization. During the polymerization, ethylene was continuously supplied at a rate of 5 liters / hour and hydrogen at a rate of 40 liters / hour. Polymerization was carried out at 110 ° C. for 20 minutes under normal pressure, and then a small amount of isopropanol was added to terminate the polymerization. The polymer solution was added to 300 ml of 1N hydrochloric acid and stirred. This solution was transferred to a separatory funnel, and the organic layer was separated. The organic layer was washed with water, and the solvent and unreacted 1-decene were distilled off at 175 ° C. under reduced pressure (1 mmHg). The obtained transparent liquid polymer was 34.73 g, and the polymerization activity was 52.10 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, the ethylene content was 15 mol%, [η] = 0.18 dl / g, Mw = 31,890, Mn = 19,130, and Mw / Mn = 1.67. Moreover, the syndiotacticity seen from the triad chain of the polymer was 65%.

  The performance evaluation results of the fuel oil composition using the obtained polymer are shown in Table 1.

A glass autoclave with an internal volume of 1000 ml was equipped with a thermometer, a gas blowing tube, and a glass stirring blade, and sufficiently substituted with nitrogen. Thereafter, 250 ml of toluene and 250 ml of 1-decene were charged, and the temperature was set to 50 ° C. while flowing nitrogen at 50 liters / hour. On the other hand, a magnetic stirrer chip was placed in a 30 ml branch flask with a sufficient internal volume substituted with nitrogen, and 0.002 mmol of a toluene solution of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride as a transition metal compound, and methyl 2 mmol of aluminoxane in toluene (Al = 1.53M) was added and stirred for 30 minutes. Nitrogen in the glass autoclave was stopped, then ethylene was passed in an amount of 5 liters / hour and hydrogen in an amount of 10 liters / hour, and then the above solution was added to initiate polymerization. During the polymerization, ethylene was continuously supplied at a rate of 5 liters / hour and hydrogen at a rate of 10 liters / hour, polymerization was carried out at 50 ° C. for 60 minutes under normal pressure, and then a small amount of isopropanol was added to terminate the polymerization. The polymer solution was added to 300 ml of 1N hydrochloric acid and stirred. This solution was transferred to a separatory funnel, and the organic layer was separated. The organic layer was washed with water, and the solvent and unreacted 1-decene were distilled off at 175 ° C. under reduced pressure (1 mmHg). The obtained transparent liquid polymer was 51.90 g, and the polymerization activity was 25.95 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, the ethylene content was 21 mol%, [η] = 0.48 dl / g, Mw = 117,550, Mn = 71,020, and Mw / Mn = 1.66. Further, the syndiotacticity as seen by the triad chain of the polymer was 54%.

  The performance evaluation results of the fuel oil composition using the obtained polymer are shown in Table 1.

A glass autoclave with an internal volume of 1000 ml was equipped with a thermometer, a gas blowing tube, and a glass stirring blade, and sufficiently substituted with nitrogen. Thereafter, 250 ml of n-heptane and 250 ml of 1-decene were charged, and the temperature was raised to 80 ° C. while flowing nitrogen at 50 liters / hour. On the other hand, a magnetic stirrer chip was placed in a 30 ml branch flask with a sufficient internal volume substituted with nitrogen, and 0.002 mmol of a toluene solution of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride as a transition metal compound, and methyl 2 mmol of aluminoxane in toluene (Al = 1.53M) was added and stirred for 30 minutes. Nitrogen in the glass autoclave was stopped, and then hydrogen was passed in an amount of 35 liters / hour, and then the above solution was added to initiate polymerization. During the polymerization, hydrogen was continuously supplied in an amount of 35 liters / hour, polymerization was performed at 80 ° C. for 60 minutes under normal pressure, and then a small amount of isopropanol was added to terminate the polymerization. The polymer solution was added to 300 ml of 1N hydrochloric acid and stirred. This solution was transferred to a separatory funnel, and the organic layer was separated. The organic layer was washed with water, and the solvent and unreacted 1-decene were distilled off at 175 ° C. under reduced pressure (1 mmHg). The obtained transparent liquid polymer was 29.43 g, and the polymerization activity was 14.72 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, [η] = 0.18 dl / g, Mw = 34,140, Mn = 23,120, and Mw / Mn = 1.48. Moreover, the syndiotacticity seen from the triad chain of the polymer was 81%.

  The performance evaluation results of the fuel oil composition using the obtained polymer are shown in Table 1.

[Comparative Example 1]
A glass autoclave with an internal volume of 1000 ml was equipped with a thermometer, a gas blowing tube, and a glass stirring blade, and sufficiently substituted with nitrogen. Thereafter, 250 ml of n-decane and 250 ml of 1-decene were charged, and the temperature was adjusted to 150 ° C. while nitrogen was circulated at 50 liters / hour. On the other hand, a magnetic stirrer chip was placed in a 30 ml branch flask with a sufficient internal volume substituted with nitrogen, and 0.002 mmol of a toluene solution of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride as a transition metal compound, and methyl 2 mmol of aluminoxane in toluene (Al = 1.53M) was added and stirred for 30 minutes. Nitrogen in the glass autoclave was stopped, then ethylene was passed in an amount of 20 liter / hour and hydrogen in an amount of 20 liter / hour, and then the above solution was added to initiate polymerization. During the polymerization, ethylene was continuously supplied at a rate of 20 liters / hour and hydrogen at a rate of 20 liters / hour, and polymerization was carried out at 150 ° C. for 60 minutes under normal pressure, and then a small amount of isopropanol was added to terminate the polymerization. The polymer solution was added to 300 ml of 1N hydrochloric acid and stirred. This solution was transferred to a separatory funnel, and the organic layer was separated. The organic layer was washed with water, and the solvent and unreacted 1-decene were distilled off at 175 ° C. under reduced pressure (1 mmHg). The obtained transparent liquid polymer was 16.82 g, and the polymerization activity was 8.41 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, the ethylene content was 35 mol%, [η] = 0.09 dl / g, Mw = 15,790, Mn = 10,520, and Mw / Mn = 1.50. Further, the syndiotacticity as seen by the triad chain of the polymer was 46%.

  The performance evaluation results of the fuel oil composition using the obtained polymer are shown in Table 1.

[Comparative Example 2]
A glass autoclave with an internal volume of 1000 ml was equipped with a thermometer, a gas blowing tube, and a glass stirring blade, and sufficiently substituted with nitrogen. Thereafter, 500 ml of toluene was charged, and the temperature was adjusted to 60 ° C. while flowing nitrogen at 50 liters / hour. On the other hand, a magnetic stirrer chip was placed in a 30 ml branch flask having a sufficient internal volume substituted with nitrogen, and 0.04 mmol of a toluene solution of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride as a transition metal compound, and 10 mmol of a toluene solution of methylaluminoxane (Al = 1.53M) was added and stirred for 30 minutes. Nitrogen in the glass autoclave was stopped, then ethylene was passed in an amount of 25 liter / hour and propylene in an amount of 25 liter / hour, and then the above solution was added to initiate the polymerization. During the polymerization, ethylene was continuously supplied at a rate of 25 liters / hour and propylene at a rate of 25 liters / hour, and polymerization was performed at 60 ° C. for 30 minutes under normal pressure, and then a small amount of isopropanol was added to terminate the polymerization. The polymer solution was added to 300 ml of 1N hydrochloric acid and stirred. This solution was transferred to a separatory funnel, and the organic layer was separated. The organic layer was washed with water, and the solvent was distilled off at 160 ° C. under reduced pressure (1 mmHg). The obtained transparent liquid polymer was 18.85 g, and the polymerization activity was 0.94 kg-polymer / mmol-Zr · hr. As a result of polymer analysis, the ethylene content was 71 mol%, [η] = 0.20 dl / g, Mw = 13,340, Mn = 6,770, and Mw / Mn = 1.57.

  The performance evaluation results of the fuel oil composition using the obtained polymer are shown in Table 1.

[Comparative Example 3]
Results of performance evaluation of fuel oil composition using commercially available polydecene (Mw = 27,450, Mn = 10,850, Mw / Mn = 2.53, atactic polymer (syndiotacticity <40%)) are shown. It was shown in 1.

The fuel oil composition of the present invention has no wax crystal growth or viscosity increase, has a low temperature filter clogging point and a low pour point, and is excellent in low temperature fluidity. The conventional problem that the viscosity is extremely increased and the fluidity is lost can be solved.

Claims (8)

(A) a middle distillate fuel oil having a boiling point of 150 ° C to 400 ° C;
(B) 20-100 mol% of structural units derived from at least one monomer selected from (i) (a) an α-olefin having 8-20 carbon atoms, polymerized using a metallocene catalyst as the main catalyst (B) containing structural units derived from ethylene in an amount ranging from 0 to 80 mol%,
(Ii) a fuel oil fluidity improver comprising an α-olefin (co) polymer having an intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 0.1 to 1.0 dl / g. A fuel oil composition characterized by the above. The fuel oil composition according to claim 1, wherein the metallocene catalyst is a metallocene catalyst represented by the following general formula (1).

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are selected from a hydrogen atom, a hydrocarbon group and a silicon-containing hydrocarbon group. May be the same or different from each other, and among the groups represented by R ¹ to R ⁸ and R ⁹ to R ¹⁰ , adjacent groups may be bonded to each other to form a ring, and Y represents a carbon atom or a silicon atom N represents an integer of 2 to 4, M represents a metal selected from Group 4 of the periodic table, j represents an integer of 1 to 4, Q represents a halogen atom, a hydrocarbon group, an anionic ligand, and And selected from neutral ligands capable of coordinating with a lone pair, and when j is 2 or more, Qs may be the same or different from each other). The fuel oil composition according to claim 1, wherein the metallocene catalyst is a metallocene catalyst represented by the following general formula (2) or (3).

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹¹ and R ¹² are selected from a hydrogen atom, a hydrocarbon group and a silicon-containing hydrocarbon group. May be the same or different from each other, and adjacent groups among the groups represented by R ¹ to R ⁸ may be bonded to each other to form a ring. In the case of the general formula (2), R ¹ and R ⁸ R ¹¹ or R ¹² may be bonded to each other to form a ring, and A is a divalent divalent having 2 to 20 carbon atoms and may contain an unsaturated bond and / or an aromatic ring. Represents a hydrocarbon group, A may include two or more ring structures including a ring formed with Y, Y is a carbon atom or a silicon atom, and M is selected from Group 4 of the periodic table. Represents a metal, j is an integer of 1 to 4, Q is a halogen atom, a hydrocarbon group, an anionic ligand and a lone pair Selected from coordinating neutral ligands capable, Q is may be the same or different when j is 2 or more). The fuel oil composition according to claim 1, wherein the metallocene catalyst is a metallocene catalyst represented by the following general formula (4).

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are selected from a hydrogen atom, a hydrocarbon group and a silicon-containing hydrocarbon group. R ¹ to R ⁸ may not be hydrogen at the same time, and adjacent groups among the groups represented by R ¹ to R ⁸ and R ⁹ to R ¹⁰ are bonded to each other to form a ring. Y is a carbon atom or a silicon atom, n is an integer of 2 to 4, M is a metal selected from Group 4 of the periodic table, j is an integer of 1 to 4, and Q is a halogen atom. It is selected from an atom, a hydrocarbon group, an anionic ligand, and a neutral ligand capable of coordinating with a lone electron pair, and when j is 2 or more, Q may be the same or different. The fuel oil composition according to claim 1, wherein the metallocene catalyst is a metallocene catalyst represented by the following general formula (5) or (6).

Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ¹¹ and R ¹² are selected from a hydrogen atom, a hydrocarbon group and a silicon-containing hydrocarbon group. R ¹ to R ⁸ may not be hydrogen at the same time, and adjacent groups among the groups represented by R ¹ to R ⁸ may be bonded to each other to form a ring. In the case of (5), R ¹ to R ⁸ are not simultaneously hydrogen, but a group selected from R ¹ and R ⁸ and R ¹¹ or R ¹² may be bonded to each other to form a ring, and A is an unsaturated bond And / or a divalent hydrocarbon group having 2 to 20 carbon atoms which may contain an aromatic ring, and A may contain two or more ring structures including a ring formed with Y , Y is a carbon atom or a silicon atom, M represents a metal selected from Group 4 of the periodic table, and j is an integer of 1 to 4 Q is selected from a halogen atom, a hydrocarbon group, an anionic ligand and a neutral ligand capable of coordinating with a lone pair, and when j is 2 or more, Q may be the same or different from each other ). In the above (B) α-olefin (co) polymer, the structural unit derived from at least one monomer selected from (a) an α-olefin having 8 to 20 carbon atoms is in the range of 50 to 100 mol%. (B) a structural unit derived from ethylene in an amount of 0 to 50 mol%, and a syndiotacticity by triad display of the α-olefin unit chain portion determined by ¹³ C-NMR method It is 50% or more, The fuel oil composition of Claims 1-5 characterized by the above-mentioned. The number average molecular weight (Mn) of the (B) α-olefin (co) polymer is in the range of 5,000 to 100,000, and the molecular weight distribution (Mw / Mn) is 3 or less. Item 7. The fuel oil composition according to Item 1-6. The fuel oil composition according to claim 1, which contains the (B) α-olefin (co) polymer at a concentration of 50 to 5,000 ppm.