CN102858929B

CN102858929B - Lubricating oil composition

Info

Publication number: CN102858929B
Application number: CN201180020141.4A
Authority: CN
Inventors: 阿部昌太; 金重良辅; 饭村百合子; 土肥靖; 乌海道生; 吉园纯一
Original assignee: Mitsui Chemical Industry Co Ltd
Current assignee: Mitsui Chemical Industry Co Ltd
Priority date: 2010-05-11
Filing date: 2011-05-10
Publication date: 2015-11-25
Anticipated expiration: 2031-05-10
Also published as: JPWO2011142345A1; JP5606526B2; EP2570472A1; US20120135903A1; BR112012028520A2; EP2570472A4; CN102858929A; WO2011142345A1; EP2570472B1

Abstract

Lubricating oil composition of the present invention comprise following (i) ~ (iii), the kinematic viscosity in 40 DEG C is 30mm ²/ more than s, 750mm ²/ below s, and the boron atom containing more than 5ppm, below 75ppm.(i) (being total to) polymkeric substance that 90 ~ 10 quality % are following, the kinematic viscosity of being somebody's turn to do in 100 DEG C of (being total to) polymkeric substance is 45mm ²/ below s, more than the 60mol% of structural unit is made up of 1-decene, and acid value is less than 0.1mgKOH/g; (ii) (being total to) polymkeric substance that 5 ~ 85 quality % are following, the kinematic viscosity of being somebody's turn to do in 100 DEG C of (being total to) polymkeric substance is 35mm ²/ more than s, 1,500mm ²/ below s, and more than the 90mol% of structural unit is made up of 1-octene, and molecular weight distribution is less than 1.8; (iii) (i) ~ total (iii) (wherein, is set to 100 quality % by the fatty acid ester of 5 ~ 15 quality %.）。

Description

Lubricating oil composition

Technical field

The present invention relates to lubricating oil composition and the wind-driven generator gear being filled with this lubricating oil composition.

Background technology

Lubricating grease lubricating oil, gear oil, hydraulic pressure wet goods require multiple performance, and, in recent years, with harshization etc. of the high performance of oil engine and industrial machinery, superpower, operational conditions, the performance of the resistance to abrasion in each portion of continuous claimed apparatus, thermotolerance, resistance to mud, lubrication oil consumption characteristic, fuel saving equal altitudes.In addition, environment for use harshization of lubricating oil, and on the other hand from the consideration to environmental problem, there is the trend of seeking long lifetime, therefore, need the lowering viscousity caused by the shear-stress of gear when reducing plant running, namely need the shear stability improving lubricating oil.In addition, on the other hand, in order to ensure the raising of the energy conversion efficiency of device or the good oilness of pole low temperature environment lower device, lubricating oil at high temperature keeps oil film, more keeps the such temperature-viscosity characteristic of mobility to be paid attention at low temperatures.

Therefore, lubricating grease lubricating oil, gear oil, hydraulic pressure wet goods need for the long lifetime, i.e. low vapo(u)rability, and have good temperature-viscosity characteristic.

Particularly in recent years enjoying as renewable energy source in the aerogenerator gazed at, for being the wheel casing of electric power by wind power transformation, being arranged on eminence to obtain more stable wind-force.And, from the view point of the stable supplying of wind-force, wind direction, be not only arranged on inland, and have and be much arranged on sea.Therefore, the maintenance of gear, namely the replacing of lubricating oil is very difficult, result, has higher shear stability for lubricating oil requirements.In addition, from the view point of by the energy conversion efficiency of wind-force to electric power, require such as good under-40 DEG C of such pole low temperatures oilness, namely require lubricating oil high workability at low ambient temperatures.

In addition, in wind-driven generator gear oil, need high anti-micro-pitting corrosion.Micro-spot corrosion is the fatigue process that rolling bearing elastohydrodynamic behaviour (EHL) region under high loads caused before closing on gear destruction due to the circulation of excessive stress.Peeled off by the small pieces from gear teeth face caused by stress under compression repeatedly under this higher load condition and be called micro-spot corrosion, the lubricating oil that wind-driven generator gear oil uses needs high resistance to micro-pitting corrosion.

For above-mentioned background, carry out the exploitation (patent documentation 1,2 etc.) of various ucon oil.

Prior art document

Patent documentation

Patent documentation 1: Japanese Unexamined Patent Application Publication 2008-542524 publication

Patent documentation 2: Japanese Unexamined Patent Application Publication 2009-500489 publication

Summary of the invention

Invent problem to be solved

But patent documentation 1, lubricating oil composition described in patent documentation 2 particularly require at wind-driven generator gear oil the leeway that the field of high shear stability is improved like that.

Problem to be solved by this invention relates to and has high oxidation stability, thermotolerance and the lubricating oil composition of high temperature-viscosity excellent and lubricating oil, has both high shear stability and excellent low-temperature viscosity profiles and the lubricating oil composition with excellent resistance to micro-pitting corrosion particularly in providing.

For solving the method for problem

Conduct in-depth research to solve above-mentioned problem, found that, by by specific lubricant base, by the alpha-olefin homopolymerization of specific carbonatoms or coordinate with specific ratio with other alpha-olefin copolymer and the low-molecular weight polymer with specific molecular weight distribution that obtains and specific ester, it is made to contain boron atom specifically to measure, very excellent shear stability, temperature-viscosity characteristic, low-temperature viscosity profiles, resistance to micro-pitting corrosion will be shown, thus complete the present invention.

That is, the lubricating oil composition that the present invention relates to be comprise following (i) ~ (iii), the kinematic viscosity in 40 DEG C is 30mm ²/ more than s, 750mm ²/ below s, and the lubricating oil composition of boron atom containing more than 5ppm, below 75ppm.

(i) (being total to) polymkeric substance that 90 ~ 10 quality % are following, the kinematic viscosity of being somebody's turn to do in 100 DEG C of (being total to) polymkeric substance is 45mm ²/ below s, and more than the 60mol% of structural unit is made up of 1-decene, acid value is less than 0.1mgKOH/g;

(ii) (being total to) polymkeric substance that 5 ~ 85 quality % are following, the kinematic viscosity of being somebody's turn to do in 100 DEG C of (being total to) polymkeric substance is 35mm ²/ more than s, 1,500mm ²/ below s, and more than the 90mol% of structural unit is made up of 1-octene, and the molecular weight distribution recorded by gel permeation chromatography is less than 1.8;

(iii) the kinematic viscosity in 100 DEG C of 5 ~ 15 quality % is 20mm ²the fatty acid ester of/below s,

(wherein, (i) ~ total is (iii) set to 100 quality %.）

The effect of invention

According to the present invention, can obtain compared with existing lubricating oil, there is excellent shear stability, also with the lubricating oil composition of high temperature-viscosity characteristic, excellent low-temperature viscosity profiles and resistance to micro-pitting corrosion.Even if the lubricating oil composition that also can maintain above-mentioned characteristic under the high-load condition being called extreme boundary lubrication condition especially can be obtained.

Accompanying drawing explanation

Fig. 1 is the figure of the example for illustration of wind power generation plant of the present invention, represents the wind power generation plant sectional view that obtains of partial cutoff along its length, and represents the stereographic map from observing wind power generation plant near local, the direction of paper.

Fig. 2 is the stereographic map of the magnifying state in the X portion observing the wind power generation plant shown in Fig. 1.

Fig. 3 is the stereographic map of the magnifying state in the Y portion observing the wind power generation plant shown in Fig. 1.

Fig. 4 is the stereographic map of the driving string module used during the driving of diagram wind power generation plant is used.

Embodiment

" lubricating oil composition "

Kinematic viscosity in 40 DEG C of lubricating oil composition of the present invention is 30mm ²/ more than s, 750mm ²/ below s, the kinematic viscosity more preferably in 40 DEG C is 190mm ²/ more than s, 750mm ²/ below s.If 750mm ²/ below s, then fuel saving performance and energy conversion efficiency excellence.In addition, if the kinematic viscosity in 40 DEG C is 30mm ²/ more than s, then at high temperature show good lubricating property, if 190mm ²/ more than s, then as the oilness of the gear GSO in higher load condition.If the kinematic viscosity in 40 DEG C is in above-mentioned scope, even if then at high temperature also can keep sufficient oil film, therefore shear stability is also more excellent.

In addition, in lubricating oil composition, the kinematic viscosity in 40 DEG C can by the kinematic viscosity in 100 DEG C of appropriate change (i) decene (being total to) polymkeric substance described later and (ii) octene (being total to) polymkeric substance or (i) decene (being total to) polymkeric substance and (ii) octene (being total to) polymkeric substance use level and regulate.Such as, proportioning can be calculated according to method described in JISK-2283 annex 1, adjust accordingly.

Lubricating oil composition of the present invention comprises following kinematic viscosity (i) in 100 DEG C is in addition 45mm ²(being total to) polymkeric substance comprising 1-decene of/below s and the kinematic viscosity (ii) in 100 DEG C are 35mm ²/ more than s, 1,500mm ²(being total to) polymkeric substance comprising 1-octene of/below s.Wherein, in this manual, " (being total to) polymkeric substance " comprises both of homopolymer and multipolymer.

Comprise (being total to) polymkeric substance of 1-decene and comprise (being total to) polymkeric substance of 1-octene, preferably adding up to more than the 80 quality % in lubricating oil composition of the present invention.If be in this scope, then there is high oxidative stability, thermotolerance.

In the present invention, be 45mm as the kinematic viscosity (i) in 100 DEG C ²(being total to) polymkeric substance comprising 1-decene of/below s, industrially known with the common name of poly-alpha-olefin (PAO), the base oil generally as lubricating oil uses.(being total to) polymkeric substance comprising 1-decene is like this with NEXBASE(NESTEOIL Inc.), SPECTRASYN(EXXONMOBILCHEMICAL Inc.), DURASYN(INEOS Inc.) etc. trade mark sell, can easily buy.Should (being total to) polymkeric substance be the homopolymer of 1-decene, or be the multipolymer of 1-decene and 1-octene and/or 1-laurylene, but at least more than the 60mol% of its structural unit be made up of 1-decene.If with the multipolymer of 1-octene, then low-temperature viscosity profiles can reduce sometimes, if with the multipolymer of 1-laurylene, then shear stability reduces sometimes, therefore preferably uses the homopolymer of 1-decene.

In addition, the acid value that above-mentioned (being total to) polymkeric substance (i) comprising 1-decene preferably records according to JISK2501 is less than 0.1mgKOH/g.Be more preferably less than 0.05mgKOH/g.If be in this scope, then the oxidative stability of obtained lubricating oil composition, excellent heat resistance.

(i) the kinematic viscosity comprised in 100 DEG C of (being total to) polymkeric substance of 1-decene is 45mm ²/ below s, is preferably 11mm ²/ below s.If at 11mm ²/ below s, then the low-temperature viscosity profiles of lubricating oil composition is more excellent.

(i) (being total to) polymkeric substance comprising 1-decene can be used alone, and also can mix two or more use.

In addition, 1-decene (being total to) polymkeric substance can by existing known method manufacture.Such as use as BF ₃or AlCl ₃such catalyzer, obtains (being total to) polymkeric substance with desired molecular weight by the adjustment of polymerization temperature, polymerization time etc.The kinematic viscosity in 100 DEG C can be adjusted by this molecular weight adjustment (if namely high molecular then becomes high viscosity, if lower molecular weight then becomes low viscosity).In addition, be less than 0.1mgKOH/g to acid value be adjusted to, usual method to obtain (being total to) polymkeric substance and carry out hydrogenation process by known method.The manufacture method of these 1-decene (being total to) polymkeric substance, in US patent 3,149, No. 178,3,382, No. 291,3,742, No. 082,3,780, No. 128,4,172, No. 855 and 4, has open in the patents such as 956, No. 122.

Be 35mm as the kinematic viscosity (ii) in 100 DEG C ²/ more than s, 1,500mm ²(being total to) polymkeric substance that/below s is formed, is 8 using carbonatoms, obtains (being total to) polymkeric substance by 1-octene as monomer polymerization, and the containing ratio of this structural unit is 90 ~ 100mol%, is preferably 95 ~ 100mol%.In other words, should (being total to) polymkeric substance be the homopolymer of 1-octene, or with the multipolymer of other monomer.If be in this scope, then the character of lubricating oil composition of the present invention is identical with the lubricating oil composition of the polymkeric substance obtained containing homopolymerization 1-octene in fact.In lubricating oil composition, by combining so (ii) octene (being total to) polymkeric substance in (i) decene (being total to) polymkeric substance, can improve shear stability and low-temperature viscosity profiles, and oxidative stability, thermotolerance, temperature-viscosity characteristic also can improve.In order to make the shear stability of lubricating oil composition and low-temperature viscosity profiles improve further, preferably together use the homopolymer of 1-octene with (i) decene (being total to) polymkeric substance.

The monomer of main composition (being total to) polymkeric substance is (ii) 1-octene.If carbonatoms is 6, when being 1-hexene, then have temperature-viscosity characteristic and the significantly reduced situation of low-temperature viscosity profiles.In addition, if carbonatoms is 10, when being 1-decene, then have the significantly reduced situation of shear stability of lubricating oil composition.

In addition, shear stability is evaluated by the KRL shear stability test according to the method recorded in Deutsche Industry Norm DIN52350-6.By lubricating oil composition 60 DEG C, be placed in shearing condition during 20hr under (1450rpm), evaluate the kinematic viscosity in 40 DEG C before relative to test, the kinematic viscosity reduced rate in 40 DEG C after test, this value is less, then shear stability is more excellent.

In addition, as the 1-octene of raw material compared with 1-decene, can obtain at an easy rate.Therefore, the ucon oil composition as recorded in patent documentation 1 or patent documentation 2 that lubricating oil composition of the present invention obtains with respect to prior art, relatively reduce the usage quantity of 1-decene, therefore there is the advantage that industrially also can manufacture at low cost.

Structural unit beyond the 1-octene of formation (being total to) polymkeric substance is (ii) preferably the alpha-olefin of carbonatoms 2 ~ 14 (except 1-octene.), the containing ratio of these structural units is the scope of 0 ~ 10mol%, is preferably the scope of 0 ~ 5mol%.If alpha-olefin is selected among said structure unit and/or alpha-olefin is above-mentioned content, then oxidative stability, thermotolerance, the low-temperature viscosity profiles excellence of lubricating oil composition.

Kinematic viscosity in 100 DEG C of (being total to) polymkeric substance of the 1-of comprising octene of the present invention is 35mm ²/ more than s, 1,500mm ²/ below s.Be preferably 150mm ²/ more than s, 1,200mm ²/ below s, if at 150mm ²/ more than s, then in gear oil, Industrial Oil or wind-driven generator gear oil, bearing oil, relative to (being total to) polymkeric substance comprising 1-decene as lubricant base, the content with (being total to) polymkeric substance of the full-bodied 1-of comprising octene relatively reduces, and therefore low-temperature viscosity profiles is excellent.If 1,200mm ²/ below s, then shear stability is more excellent.

In addition, number-average molecular weight can be measured by the gel permeation chromatography (GPC) using the known reference material (monodisperse polystyrene (PSt)) of molecular weight to correct, the number-average molecular weight (Mn) of (being total to) polymkeric substance using 1-octene as monomer of the present invention is preferably 500 ~ 15, the scope of 000, be more preferably 3, the scope of 000 ~ 12,000.If number-average molecular weight is within the scope of this, then the low-temperature viscosity profiles of obtained lubricating oil composition and the balancing good of shear stability.

In addition, the molecular weight distribution (Mw/Mn) of (being total to) polymkeric substance of the 1-of comprising octene of the present invention is the scope of 1.8, is preferably the scope of 1.1 ~ 1.8, is more preferably the scope of 1.2 ~ 1.7.If be in this scope, then the shear stability of obtained lubricating oil composition is excellent.

(ii) (being total to) polymkeric substance comprising octene both may be used singly or in combination of two or more use.

(manufacture (ii) comprising (being total to) polymkeric substance of octene of the present invention)

When the manufacture of (being total to) polymkeric substance comprising 1-octene as above, can by reference to such as at Japanese Unexamined Patent Publication 2-41303 publication, Japanese Unexamined Patent Publication 2-41305 publication, Japanese Unexamined Patent Publication 2-274703 publication, Japanese Unexamined Patent Publication 2-274704 publication, Japanese Unexamined Patent Publication 3-179005 publication, Japanese Unexamined Patent Publication 3-179006 publication, Japanese Unexamined Patent Publication 3-193796 publication, Japanese Unexamined Patent Publication 4-69394 publication, Japanese Unexamined Patent Publication 5-17589 publication, Japanese Unexamined Patent Publication 6-122718 publication, Japanese Unexamined Patent Publication 8-120127 publication, Japanese Unexamined Patent Publication 8-239414 publication, Japanese Unexamined Patent Publication 10-087716 publication, Japanese Unexamined Patent Publication 2000-212194 publication or WO01/27124, WO02/074855, WO04/029062, EP0881236, that records in EP1416000 is such, the catalyzer used when manufacturing alpha-olefin (being total to) polymkeric substance manufactures.

Specifically, when the manufacture of (being total to) polymkeric substance using 1-octene as monomer, such as, by comprise transistion metal compound (transistion metal compound etc. of periodictable IVB race) (A) with

(B) be selected from (B-1) organometallic compound,

(B-2) organo-aluminium compound,

(B-3) organoalurrunoxy compound and

(B-4) to react and under forming the existence of the catalyst for olefines polymerizing of the compound of more than at least a kind in the compound of ion pair with above-mentioned IVB group transition metal compound (A), by the homopolymerization of 1-octene, or by 1-octene and other monomer copolymerization above-mentioned, homopolymer or multipolymer can be obtained thus.

Further describe, transistion metal compound (A) and compound (B) as described below.

((A) transistion metal compound)

The transistion metal compound (A) used in the present invention, as long as have the transistion metal compound of the period of element Table IV ~ VI race of known olefinic polymerization ability, can use without particular limitation, but such as can illustrate the transition metal halide of period of element Table IV ~ VI race, transition-metal-alkyl compound, magnesium/transition metal alkoxide compound, non-crosslinked or bridging property metallocene compound etc.Be preferably period of element Table IV race, the halogenide being more preferably the transition metal of IVB race, the alkylide of transition metal, magnesium/transition metal alkoxide compound, non-crosslinked or bridging property metallocene compound etc.Below, the optimal way for these transistion metal compounds (A) is described.

As transition metal halide, transition-metal-alkyl compound, magnesium/transition metal alkoxide compound, specifically, titanium tetrachloride, dimethyl titanium dichloride, tetrabenzyl titanium, tetrabenzyl zirconium, four titanium butoxide etc. can be illustrated.

As non-crosslinked or bridging property metallocene compound, can exemplified as have cyclopentadienyi skeleton periodic table of elements IVB race transistion metal compound, the compound shown in following general formula (1).

ML _x…（1）

In formula, M represents the a kind of transition metal atoms being selected from periodic table of elements IV race, is preferably the zirconium of the transition metal of IVB race, titanium or hafnium.X is the valence of transition metal, represents the number of L.L represents and the dentate of transition-metal coordination or group, at least 1 L is the dentate with cyclopentadienyi skeleton, the L beyond the dentate with this cyclopentadienyi skeleton be selected from halogen with identical or different combination, neutrality, conjugation or non-conjugated diene that alkyl that hydrogen atom, carbonatoms are 1 ~ 10, carbonatoms are less than 10, anion binding base or can with kind of the group of 1 in the neutral dentate of lone-pair electron coordination or atom.

As the dentate with cyclopentadienyi skeleton, such as, can illustrate cyclopentadienyl, alkyl substituted cyclopentadienyl, indenyl, alkyl substituted indenyl, 4,5,6,7-tetrahydro indenyls, fluorenyl, alkyl replacement fluorenyl etc.These groups can by the replacement such as halogen atom, trialkylsilkl.

The compound shown in above-mentioned general formula (1) comprise more than 2 there is the dentate of cyclopentadienyi skeleton time, wherein 2 dentates with cyclopentadienyi skeleton each other can via combinations such as alkylidene group, substituted alkylene, silylene, replacement silylenes.(in the following description, sometimes such compound is called " bridging property metallocene compound ".In addition, sometimes by being called " non-crosslinked metallocene compound " beyond such compound.）

As wherein preferred compound, the compound shown in following general formula (2) can be illustrated.

ML _aX _b…（2）

(in formula, M represents the a kind of transition metal atoms be selected from periodic table of elements IV race, be preferably the zirconium of the transition metal of IVB race, titanium or hafnium, L is the dentate with transition-metal coordination, a is the integer of more than 1, represent the number of L, X is combined with transition metal, halogen is selected from identical or different combination, hydrogen atom, carbonatoms is the alkyl of 1 ~ 10, carbonatoms is the neutrality of less than 10, conjugation or non-conjugated diene, anion binding base or can with kind of the group of 1 in the neutral dentate of lone-pair electron coordination or atom, b is the integer of more than 1, represent the number of X.）

In above-mentioned general formula (2), L is the dentate with transition-metal coordination, and wherein at least 1 for having the dentate of cyclopentadienyi skeleton.As the dentate with cyclopentadienyi skeleton, such as, cyclopentadienyl can be illustrated; The alkyl substituted cyclopentadienyls such as methyl cyclopentadienyl, dimethylcyclo-pentadienyl, trimethylammonium cyclopentadienyl, tetramethyl-ring pentadienyl, pentamethylcyclopentadiene base, ethyicydopentadi etanyf group, methylethyl cyclopentadienyl, propyl-cyclopentadienyl, methyl-propyl cyclopentadienyl, butyl cyclopentadienyl, methyl butyl cyclopentadienyl, hexyl cyclopentadienyl; Indenyl; 4,5,6,7-tetrahydro indenyl; Fluorenyl etc.These groups can by the replacement such as halogen atom, trialkylsilkl.

In above-mentioned general formula (2), a is the integer of more than 1, represents the number of L.

In above-mentioned general formula (2), M is zirconium, titanium or hafnium.

X is combined with transition metal, halogen is selected from identical or different combination, hydrogen atom, carbonatoms is the alkyl of 1 ~ 10, carbonatoms is the neutrality of less than 10, conjugation or non-conjugated diene, anion binding base or can with kind of the group of 1 in the neutral dentate of lone-pair electron coordination or atom, as the concrete example of halogen, for fluorine, chlorine, bromine, iodine, as the concrete example of alkyl, methyl can be enumerated, ethyl, n-propyl, sec.-propyl, 2-methyl-propyl, 1, 1-dimethyl propyl, 2, 2-dimethyl propyl, 1, 1-diethylpropyl, 1-ethyl-1-methyl-propyl, 1, 1, 2, 2-tetramethyl-propyl group, sec-butyl, the tertiary butyl, 1, 1-dimethylbutyl, 1, 1, 3-trimethyl butyl, neo-pentyl, cyclohexyl methyl, cyclohexyl, 1-methyl isophthalic acid-cyclohexyl etc.Be the neutrality of less than 10, the concrete example of conjugation or non-conjugated diene as carbonatoms, the cis-or trans-η of s-of s-can be enumerated ⁴cis-or the trans-η of s-of-1,3-butadiene, s- ⁴cis-or the trans-η of s-of-Isosorbide-5-Nitrae-phenylbenzene-1,3-butadiene, s- ⁴-3-methyl isophthalic acid, the cis-or trans-η of s-of 3-pentadiene, s- ⁴cis-or the trans-η of s-of-Isosorbide-5-Nitrae-dibenzyl-1,3-butadiene, s- ⁴cis-or the trans-η of s-of-2,4-hexadienes, s- ⁴cis-or the trans-η of s-of-1,3-pentadiene, s- ⁴cis-or the trans-η of s-of-Isosorbide-5-Nitrae-xylyl-1,3-butadiene, s- ⁴-Isosorbide-5-Nitrae-bis-(trimethyl silyl)-1,3-butadiene etc.As the concrete example of anion binding base, the alkoxyl groups such as methoxyl group, tert.-butoxy, phenoxy group can be enumerated, the carboxylic acid ester groups such as acetic ester, benzoic ether, the sulfonate group such as methanesulfonates, tosylate etc.As can with the concrete example of the neutral dentate of lone-pair electron coordination, the ethers such as the organo phosphorous compoundss such as trimethyl-phosphine, triethyl phosphine, triphenylphosphine, diphenyl methyl phosphine or tetrahydrofuran (THF), Anaesthetie Ether, diox, 1,2-glycol dimethyl ether can be enumerated.Among them, X can identically also can be different combinations.

In above-mentioned general formula (2), b is the integer of more than 1, represents the number of X.

The compound shown in above-mentioned general formula (2) comprise more than 2 there is the dentate of cyclopentadienyi skeleton time, wherein 2 dentates with cyclopentadienyi skeleton can via the alkylidene group such as ethylidene, propylidene; The substituted alkylenes such as diphenylmethylene; The alkylidene groups such as isopropylidene; Silylene; Dimethylsilylene, diphenylsilylene, aminomethyl phenyl silylene etc. replace the combinations such as silylene.In addition, more than 2 dentates with cyclopentadienyi skeleton can be the same or different.

When the compound shown in above-mentioned general formula (2) is the dentate with 2 cyclopentadienyi skeleton, more specifically, as shown in following general formula (3) or (4).

(in formula, M represents the a kind of transition metal atoms be selected from periodic table of elements IV race, is preferably the zirconium of the transition metal of IVB race, titanium or hafnium, R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰be selected from hydrogen, alkyl, hydrocarbyl silyl, can be the same or different respectively, from R ¹to R ¹⁰adjacent substituting group also can be combined with each other formation ring, X be selected from halogen with identical or different combination, neutrality, conjugation or non-conjugated diene that alkyl that hydrogen atom, carbonatoms are 1 ~ 10, carbonatoms are less than 10, anion binding base or can with kind of the group of 1 in the neutral dentate of lone-pair electron coordination or atom, n is 1 or 2, represents the number of X.）

(in formula, M represents the a kind of transition metal atoms be selected from periodic table of elements IV race, is preferably the zirconium of the transition metal of IVB race, titanium or hafnium, R ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸be selected from hydrogen, alkyl, hydrocarbyl silyl, can be the same or different respectively, from R ¹to R ⁸adjacent substituting group also can be combined with each other formation ring, X be selected from halogen with identical or different combination, neutrality, conjugation or non-conjugated diene that alkyl that hydrogen atom, carbonatoms are 1 ~ 10, carbonatoms are less than 10, anion binding base or can with kind of the group of 1 in the neutral dentate of lone-pair electron coordination or atom, n is 1 or 2, represent the number of X, Q is selected from carbon, silicon or germanium, Y ¹and Y ²be selected from hydrogen, alkyl, hydrocarbyl silyl, can be the same or different respectively, can be combined with each other formation ring.）

In above-mentioned general formula (3) or (4), as alkyl, be preferably the alkaryl of the alkyl of carbonatoms 1 ~ 20, the aralkyl of carbonatoms 7 ~ 20, the aryl of carbonatoms 6 ~ 20 or carbonatoms 7 ~ 20, the ring structure of more than 1 can be comprised.As its concrete example, methyl, ethyl, n-propyl, sec.-propyl, 2-methyl-propyl, 1 can be enumerated, 1-dimethyl propyl, 2,2-dimethyl propyls, 1,1-diethylpropyl, 1-ethyl-1-methyl-propyl, 1,1,2,2-tetramethyl-propyl group, sec-butyl, the tertiary butyl, 1,1-dimethylbutyl, 1,1,3-trimethyl butyl, neo-pentyl, cyclohexyl methyl, cyclohexyl, 1-methyl isophthalic acid-cyclohexyl, 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, base, norcamphyl, benzyl, 2-phenylethyl, 1-tetrahydro naphthyl, 1-methyl isophthalic acid-tetrahydro naphthyl, phenyl, naphthyl, tolyl etc.

In above-mentioned general formula (3) or (4), as hydrocarbyl silyl, be preferably the alkyl or aryl silyl of Siliciumatom number 1 ~ 4, carbonatoms 3 ~ 20, as its concrete example, trimethyl silyl, t-butyldimethylsilyl, triphenyl-silyl etc. can be enumerated.

In the present invention, the R of above-mentioned general formula (3) ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸, R ⁹, R ¹⁰be selected from hydrogen, alkyl, hydrocarbyl silyl, can be the same or different respectively.As the concrete example of preferred alkyl, hydrocarbyl silyl, group same as described above can be enumerated.In addition, the R of above-mentioned general formula (4) ¹, R ², R ³, R ⁴, R ⁵, R ⁶, R ⁷, R ⁸be selected from hydrogen, alkyl, hydrocarbyl silyl, can be the same or different respectively.As the concrete example of preferred alkyl, hydrocarbyl silyl, group same as described above can be enumerated.

In the cyclopentadienyl rings of above-mentioned general formula (3) from R ¹to R ¹⁰adjacent substituting group can be combined with each other formation ring.As such substituted cyclopentadienyl, indenyl, 2-methylindenyl, tetrahydro indenyl, 2-methyl tetrahydro indenyl, 2 can be enumerated, 4,4-trimethylammonium tetrahydro indenyl, fluorenyl, benzo fluorenyl, dibenzo fluorenyl, octahydro dibenzo fluorenyl, prestox octahydro dibenzo fluorenyl etc.In addition, in the cyclopentadienyl rings of above-mentioned general formula (4) from R ¹to R ⁸adjacent substituting group also can be combined with each other formation ring.As such substituted cyclopentadienyl, indenyl, 2-methylindenyl, tetrahydro indenyl, 2-methyl tetrahydro indenyl, 2 can be enumerated, 4,4-trimethylammonium tetrahydro indenyl, fluorenyl, benzo fluorenyl, dibenzo fluorenyl, octahydro dibenzo fluorenyl, prestox octahydro dibenzo fluorenyl etc.

In the present invention, the M of general formula (3) or (4) represents the a kind of transition metal atoms being selected from periodic table of elements IV race, is preferably the zirconium of the transition metal of IVB race, titanium or hafnium.

X is selected from halogen with identical or different combination, hydrogen atom, carbonatoms is the alkyl of 1 ~ 10, carbonatoms is the neutrality of less than 10, conjugation or non-conjugated diene, anion binding base or can with kind of the group of 1 in the neutral dentate of lone-pair electron coordination or atom, as the concrete example of halogen, for fluorine, chlorine, bromine, iodine, as the concrete example of alkyl, methyl can be enumerated, ethyl, n-propyl, sec.-propyl, 2-methyl-propyl, 1, 1-dimethyl propyl, 2, 2-dimethyl propyl, 1, 1-diethylpropyl, 1-ethyl-1-methyl-propyl, 1, 1, 2, 2-tetramethyl-propyl group, sec-butyl, the tertiary butyl, 1, 1-dimethylbutyl, 1, 1, 3-trimethyl butyl, neo-pentyl, cyclohexyl methyl, cyclohexyl, 1-methyl isophthalic acid-cyclohexyl etc.Be the neutrality of less than 10, the concrete example of conjugation or non-conjugated diene as carbonatoms, the cis-or trans-η of s-of s-can be enumerated ⁴cis-or the trans-η of s-of-1,3-butadiene, s- ⁴cis-or the trans-η of s-of-Isosorbide-5-Nitrae-phenylbenzene-1,3-butadiene, s- ⁴-3-methyl isophthalic acid, the cis-or trans-η of s-of 3-pentadiene, s- ⁴cis-or the trans-η of s-of-Isosorbide-5-Nitrae-dibenzyl-1,3-butadiene, s- ⁴cis-or the trans-η of s-of-2,4-hexadienes, s- ⁴cis-or the trans-η of s-of-1,3-pentadiene, s- ⁴cis-or the trans-η of s-of-Isosorbide-5-Nitrae-xylyl-1,3-butadiene, s- ⁴-Isosorbide-5-Nitrae-bis-(trimethyl silyl)-1,3-butadiene etc.As the concrete example of anion binding base, the carboxylic acid ester groups such as the alkoxyl groups such as methoxyl group, tert.-butoxy, phenoxy group, acetic ester, benzoic ether can be enumerated, the sulfonate group such as methanesulfonates, tosylate etc.As can with the concrete example of the neutral dentate of lone-pair electron coordination, the ethers such as the organo phosphorous compoundss such as trimethyl-phosphine, triethyl phosphine, triphenylphosphine, diphenyl methyl phosphine or tetrahydrofuran (THF), Anaesthetie Ether, diox, 1,2-glycol dimethyl ether can be enumerated.Among them, X can identically also can be different combinations.

N is 1 or 2, represents the number of X.

As above-mentioned general formula (3), specifically, cyclopentadienyl trichloride can be enumerated, cyclopentadienyl tri-chlorination zirconium, two (cyclopentadienyl) titanium dichloride, two (cyclopentadienyl) zirconium dichloride, two (pentamethylcyclopentadiene base) zirconium dichloride, (cyclopentadienyl) (pentamethylcyclopentadiene base) zirconium dichloride, two (methyl cyclopentadienyl) zirconium dichloride, two (ethyicydopentadi etanyf group) zirconium dichloride, two (propyl-cyclopentadienyl) zirconium dichloride, comprise two (butyl cyclopentadienyl) zirconium dichlorides of two (n-butyl cyclopentadienyl) zirconium dichlorides etc., comprise two (dimethylcyclo-pentadienyl) zirconium dichlorides of two (1,3-dimethylcyclo-pentadienyl) zirconium dichlorides etc., comprise two (diethyl cyclopentadienyl) zirconium dichlorides of two (1,3-diethyl cyclopentadienyl) zirconium dichlorides etc., two (methylethyl cyclopentadienyl) zirconium dichloride, comprise two (methyl-propyl cyclopentadienyl) zirconium dichlorides of two (1-methyl-3-n-propyl cyclopentadienyl) zirconium dichlorides etc., comprise two (methyl butyl cyclopentadienyl) zirconium dichlorides etc. of two (1-methyl-3-n-butyl cyclopentadienyl) zirconium dichlorides etc., as above-mentioned general formula (4), specifically, ethylenebis (indenyl) zirconium dichloride can be illustrated, ethylenebis (1-indenyl) titanium dichloride, ethylenebis (4,5,6,7-tetrahydro indenyl) zirconium dichloride, two (methyl cyclopentadienyl) zirconium dichloride of dimethylsilylene, two (dimethylcyclo-pentadienyl) zirconium dichloride of dimethylsilylene, two (di-t-butyl cyclopentadienyl) zirconium dichloride of dimethylsilylene, two (indenyl) zirconium dichloride of dimethylsilylene, two (2-methylindenyl) zirconium dichloride of dimethylsilylene, two (2-methyl-4, the 5-benzo indenyl) zirconium dichloride of dimethylsilylene, two (the 2-methyl 4-phenyl indenyl) zirconium dichloride of dimethylsilylene, two (2-methyl-4-naphthyl indenyl) zirconium dichloride of dimethylsilylene, two (2-methylindenyl) zirconium dichloride of dimethylethylene, two (2-methyl-4, the 5-benzo indenyl) zirconium dichloride of dimethylethylene, two (the 2-methyl 4-phenyl indenyl) zirconium dichloride of dimethylethylene, two (2-methyl-4-naphthyl indenyl) zirconium dichloride of dimethylethylene, isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, isopropylidene (methyl cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (t-butyl cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (methyl-t-butyl cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (methyl-t-butyl cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, isopropylidene (methyl-t-butyl cyclopentadienyl) (prestox octahydro compound dibenzo fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, diphenylmethylene (methyl cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (t-butyl cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (methyl-t-butyl cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (methyl-t-butyl cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, diphenylmethylene (methyl-t-butyl cyclopentadienyl) (prestox octahydro compound dibenzo fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-di-t-butyl fluorenyl) zirconium dichloride, cyclohexylidene (methyl cyclopentadienyl) (fluorenyl) zirconium dichloride,

Cyclohexylidene (t-butyl cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (methyl-t-butyl cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylidene (methyl-t-butyl cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, cyclohexylidene (methyl-t-butyl cyclopentadienyl) (prestox octahydro compound dibenzo fluorenyl) zirconium dichloride, two (p-methylphenyl) methylene radical (cyclopentadienyl) (fluorenyl) zirconium dichloride, two (p-methylphenyl) methylene radical (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, two (p-methylphenyl) methylene radical (cyclopentadienyl) (2, 7-dimethyl fluorenyl) zirconium dichloride, two (p-methylphenyl) methylene radical (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (to tert-butyl-phenyl) methylene radical (cyclopentadienyl) (fluorenyl) zirconium dichloride, two (to tert-butyl-phenyl) methylene radical (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, two (to tert-butyl-phenyl) methylene radical (cyclopentadienyl) (2, 7-dimethyl fluorenyl) zirconium dichloride, two (to tert-butyl-phenyl) methylene radical (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (to n-butylphenyl) methylene radical (cyclopentadienyl) (fluorenyl) zirconium dichloride, two (to n-butylphenyl) methylene radical (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, two (to n-butylphenyl) methylene radical (cyclopentadienyl) (2, 7-dimethyl fluorenyl) zirconium dichloride, two (to n-butylphenyl) methylene radical (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (tolyl) methylene radical (cyclopentadienyl) (fluorenyl) zirconium dichloride, two (tolyl) methylene radical (cyclopentadienyls) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, two (tolyl) methylene radical (cyclopentadienyls) (2, 7-dimethyl fluorenyl) zirconium dichloride, two (tolyl) methylene radical (cyclopentadienyls) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (p-methylphenyl) methylene radical (cyclopentadienyl) (fluorenyl) zirconium dimethyl, two (p-methylphenyl) methylene radical (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (to tert-butyl-phenyl) methylene radical (cyclopentadienyl) (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (p-methylphenyl) methylene radical (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dimethyl, two (to tert-butyl-phenyl) methylene radical (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, two (p-methylphenyl) methylene radical (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dimethyl, two (p-isopropyl phenyl) methylene radical (cyclopentadienyls) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (to tert-butyl-phenyl) methylene radical (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (4-xenyl) methylene radical (cyclopentadienyl) (fluorenyl) zirconium dichloride, two (4-xenyl) methylene radical (cyclopentadienyls) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, two (4-xenyl) methylene radical (cyclopentadienyls) (2, 7-dimethyl fluorenyl) zirconium dichloride, two (4-xenyl) methylene radical (cyclopentadienyls) (3, 6-di-t-butyl fluorenyl) zirconium dichloride cyclopentylidene (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, sub-adamantyl (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, single phenyl monomethyl methylene radical (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, dimethylated methylene base (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, two (p-methylphenyl) methylene radical (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, diethyl methylene radical (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, sub-adamantyl (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, single phenyl monomethyl methylene radical (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, dimethylated methylene base (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, two (p-methylphenyl) methylene radical (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, diethyl methylene radical (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, sub-adamantyl (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, single phenyl monomethyl methylene radical (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, dimethylated methylene base (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, two (p-methylphenyl) methylene radical (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, diethyl methylene radical (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (prestox tetrahydrochysene two ring five fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (prestox tetrahydrochysene two ring five fluorenyl) zirconium dichloride,

Sub-adamantyl (cyclopentadienyl) (prestox tetrahydrochysene two ring five fluorenyl) zirconium dichloride, single phenyl monomethyl methylene radical (cyclopentadienyl) (prestox tetrahydrochysene two ring five fluorenyl) zirconium dichloride, dimethylated methylene base (cyclopentadienyl) (prestox tetrahydrochysene two ring five fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (prestox tetrahydrochysene two ring five fluorenyl) zirconium dichloride, two (p-methylphenyl) methylene radical (cyclopentadienyl) (prestox tetrahydrochysene two ring five fluorenyl) zirconium dichloride, diethyl methylene radical (cyclopentadienyl) (prestox tetrahydrochysene two ring five fluorenyl) zirconium dichloride, cyclopentylidene (cyclopentadienyl) (dibenzo fluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (dibenzo fluorenyl) zirconium dichloride, sub-adamantyl (cyclopentadienyl) (dibenzo fluorenyl) zirconium dichloride, single phenyl monomethyl methylene radical (cyclopentadienyl) (dibenzo fluorenyl) zirconium dichloride, dimethylated methylene base (cyclopentadienyl) (dibenzo fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (dibenzo fluorenyl) zirconium dichloride, two (p-methylphenyl) methylene radical (cyclopentadienyl) (dibenzo fluorenyl) zirconium dichloride, diethyl methylene radical (cyclopentadienyl) (dibenzo fluorenyl) zirconium dichloride, ethylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, ethylidene (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, ethylidene (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, ethylidene (cyclopentadienyl) (prestox tetrahydrochysene two ring five fluorenyl) zirconium dichloride, ethylidene (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, propylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, propylidene (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, propylidene (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, propylidene (cyclopentadienyl) (prestox tetrahydrochysene two ring five fluorenyl) zirconium dichloride, propylidene (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, (methyl) (p-methylphenyl) methylene radical (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, (methyl) (phenyl) methylene radical (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, (methyl) (p-methylphenyl) methylene radical (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, (methyl) (phenyl) methylene radical (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, (methyl) (p-methylphenyl) methylene radical (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, (methyl) (phenyl) methylene radical (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, (methyl) (benzyl) methylene radical (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, (methyl) (benzyl) methylene radical (cyclopentadienyl) (3, 6-di-t-butyl fluorenyl) zirconium dichloride, (methyl) (benzyl) methylene radical (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, (methyl) (benzyl) methylene radical (cyclopentadienyl) (2, 7-di-t-butyl fluorenyl) zirconium dichloride, (methyl) (benzyl) methylene radical (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride, (methyl) (benzyl) methylene radical (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride etc.

In addition, except there are the titanium compound of same three-dimensional arrangement or hafnium compound and bromide, iodide etc., the transistion metal compound recorded in such as Japanese Unexamined Patent Publication 3-9913 publication, Japanese Unexamined Patent Publication 2-131488 publication, Japanese Unexamined Patent Publication 3-21607 publication, Japanese Unexamined Patent Publication 3-106907 publication, Japanese Unexamined Patent Publication 3-188092 publication, Japanese Unexamined Patent Publication 4-69394 publication, Japanese Unexamined Patent Publication 4-300887 publication, WO01/27124A1 etc. can also be enumerated.

In polymerization example of the present invention with compare the transistion metal compound (A) that uses in polymerization example and specifically, be following formula (6), but not by any restriction of this compound in the present invention.In addition, following formula (5), the transistion metal compound (A) shown in (7), (8) ~ (9) can also be used.

In addition, in polymerization example of the present invention, compound (6) is recited as (methyl) (p-methylphenyl) methylene radical (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride.

The structure of the transistion metal compound obtained is by 270MHz1H-NMR(NEC GSH-270), FD-mass analysis (NEC SX-102A) determines.

These transistion metal compounds (A) can be used alone a kind, also can combine two or more and use.

((B-1) organometallic compound)

As (B-1) organometallic compound, specifically, the organometallic compound shown in following formula (10) can be used.

General formula R ^ar ^bm ³(10)

(in formula, R ^aand R ^bmutually can be the same or different, represent that carbonatoms is 1 ~ 15, is preferably the alkyl of 1 ~ 4, M ³for Mg, Zn or Cd.) shown in periodic table of elements IIA race or the dialkyl compound of IIB race metal.

In addition, these organometallic compounds (B-1) can be used alone a kind, also can combine two or more and use.

((B-2) organo-aluminium compound)

As (B-2) organo-aluminium compound forming catalyst for olefines polymerizing, the complexing alkylide etc. of the such as organo-aluminium compound shown in following general formula (11), the IA race metal shown in following general formula (12) and aluminium can be enumerated.

R ^a _mAl(OR ^b) _nH _pX ² _q…（11）

(in formula, R ^aand R ^bmutually can be the same or different, represent that carbonatoms is 1 ~ 15, is preferably the alkyl of 1 ~ 4, X ²represent halogen atom, m is the number of 0 < m≤3, and n is the number of 0≤n < 3, and p is the number of 0≤p < 3, and q is the number of 0≤q < 3, and m+n+p+q=3.) shown in organo-aluminium compound.As the concrete example of such compound, trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, diisobutyl aluminium hydride can be illustrated.

M ²AlR ^a ₄…（12）

(in formula, M ²represent Li, Na or K, R ^arepresent that carbonatoms is 1 ~ 15, is preferably the alkyl of 1 ~ 4.) shown in periodic table of elements IA race's metal and the complexing alkylide of aluminium.As such compound, LiAl (C can be illustrated ₂h ₅) ₄, LiAl (C ₇h ₁₅) ₄deng.

As the organo-aluminium compound shown in above-mentioned general formula (11), such as, can illustrate following general formula (13), (14), (15) or the compound etc. shown in (16).

R ^a _mAl(OR ^b) _3-m…（13）

(in formula, R ^aand R ^bmutually can be the same or different, represent that carbonatoms is 1 ~ 15, is preferably the alkyl of 1 ~ 4, m is preferably the number of 1.5≤m≤3.）

R ^a _mAlX ² _3-m…（14）

(in formula, R ^arepresent that carbonatoms is 1 ~ 15, is preferably the alkyl of 1 ~ 4, X ²represent halogen atom, m is preferably 0 < m < 3.）

R ^a _mAlH _3-m…（15）

(in formula, R ^arepresent that carbonatoms is 1 ~ 15, is preferably the alkyl of 1 ~ 4, m is preferably 2≤m < 3.）

R ^a _mAl(OR ^b) _nX ² _q…（16）

(in formula, R ^aand R ^bmutually can be the same or different, represent that carbonatoms is 1 ~ 15, is preferably the alkyl of 1 ~ 4, X ²represent halogen atom, m is the number of 0 < m≤3, and n is the number of 0≤n < 3, and q is the number of 0≤q < 3, and m+n+q=3.）

As the aluminum compound shown in above-mentioned general formula (13), (14), (15) or (16), more specifically, the three alkyl aluminium such as trimethyl aluminium, triethyl aluminum, three n-butylaluminum, tri-propyl aluminum, three amyl group aluminium, three hexyl aluminium, trioctylaluminum, three decyl aluminium can be enumerated; The three branched-chain alkyl aluminium such as triisopropylaluminiuand, triisobutyl aluminium, three sec-butyl aluminium, tri-tert aluminium, three 2-methyl butyl aluminium, three 3-methyl butyl aluminium, three 2-methyl amyl aluminium, three 3-methyl amyl aluminium, three 4-methyl amyl aluminium, three 2-methylhexyl aluminium, three 3-methylhexyl aluminium, three 2-ethylhexyl aluminium; The tricyclic alkyl aluminium such as thricyclohexyl aluminium, three ring octyl group aluminium; The triaryl aluminums such as triphenyl aluminum, trimethylphenyl aluminium; The dialkyl group aluminum hydride such as di-isopropyl aluminum hydride, diisobutyl aluminium hydride; General formula (i-C ₄h ₉) _xal _y(C ₅h ₁₀) _z(in formula, x, y, z is positive number, z≤2x.) etc. shown in the thiazolinyl aluminium such as prenyl aluminium; The alkyl aluminum alkoxide such as isobutyl-first aluminum oxide, isobutyl-ethoxyquin aluminium, isobutyl-AIP; The dialkyl group aluminum alkoxide such as dimethyl methyl aluminum oxide, diethyl ethoxy aluminium, dibutyl fourth aluminum oxide; The alkyl sesquialter aluminum alkoxide such as ethyl sesquialter ethoxyquin aluminium, butyl sesquialter fourth aluminum oxide; There is general formula R ^a _2.5al (OR ^b) _0.5deng shown in the oxyalkylated aluminum alkyls of part of average composition; Diethylbenzene aluminum oxide, diethyl (2,6-di-t-butyl-4-methylbenzene is oxidized) aluminium, ethyl two (2,6-di-t-butyl-4-methylbenzene be oxidized) aluminium, diisobutyl (2,6-di-t-butyl-4-methylbenzene is oxidized) the alkyl virtue aluminum oxide such as aluminium, two (oxidation of 2, the 6-di-t-butyl-4-methylbenzene) aluminium of isobutyl-; The dialkylaluminum halides such as dimethylaluminum chloride, diethyl aluminum chloride, dibutyl aluminum chloride, diethyl aluminum bromide, diisobutyl aluminum chloride; The alkyl sesquihalide aluminium such as ethyl aluminium sesquichloride, butyl sesquichloride, ethyl sesquialter aluminum bromide; The partially halogenated aluminum alkylss such as alkyl dihalides aluminium such as ethylaluminum dichloride, propyl group al dichloride, butyl aluminum dibromide; The dialkyl group such as ADEH, dibutyl aluminum hydride aluminum hydride; Other the partially hydrogenated aluminum alkyls such as the alkyl aluminum dihydride such as ethyl dihydroaluminium, propyl group aluminum dihydride; The aluminum alkyls etc. of the part alkoxide such as ethyl oxyethyl group aluminum chloride, butyl butoxy aluminum chloride, ethyl oxyethyl group aluminum bromide and halogenation.

In addition, also can use and compound like the compounds shown in above-mentioned general formula (11), the organo-aluminium compound that the aluminum compound such as can enumerating more than 2 obtains via nitrogen-atoms combination.As such compound, specifically, (C can be enumerated ₂h ₅) ₂alN (C ₂h ₅) Al (C ₂h ₅) ₂deng.

As the compound shown in above-mentioned general formula (12), such as, LiAl (C can be enumerated ₂h ₅) ₄, LiAl (C ₇h ₁₅) ₄deng.

Also the compound that can form above-mentioned organo-aluminium compound in polymerization system can be used in addition, the combination of such as aluminum halide and lithium alkylide, or the combination etc. of aluminum halide and alkyl magnesium.

Among them, preferably have machine aluminium compound.

The complexing alkylide of the organo-aluminium compound shown in above-mentioned general formula (11) or the IA race metal shown in above-mentioned general formula (12) and aluminium, can be used alone a kind or combine two or more use.

((B-3) organoalurrunoxy compound)

(B-3) organoalurrunoxy compound can be existing known aikyiaiurnirsoxan beta, or also can be such benzene-insoluble organoalurrunoxy compound illustrated in Japanese Unexamined Patent Publication 2-78687 publication.

Existing known aikyiaiurnirsoxan beta, such as can by method manufacture as described below, and the solution usually used as hydrocarbon solvent obtains.

(I) at the compound containing planar water or containing in the hydrocarbon medium suspension liquid such as salt, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerous compounds hydrate of crystal water, add the organo-aluminium compounds such as trialkylaluminium, make the method that planar water or crystal water and organo-aluminium compound are reacted.

(II) in the media such as benzene, toluene, ether, tetrahydrofuran (THF), water, ice or water vapour is made to directly act on the method for the organo-aluminium compounds such as trialkylaluminium.

(III) method making the organo-aluminium compounds such as the organotin oxides such as dimethyl tin oxide, Dibutyltin oxide and trialkylaluminium react in the media such as decane, benzene, toluene.

In addition, this aikyiaiurnirsoxan beta also can containing a small amount of organometallic components.Also can, by after solvent or unreacted organo-aluminium compound distillation removing from the solution of reclaimed above-mentioned aikyiaiurnirsoxan beta, it be made to dissolve in a solvent again or be suspended in the lean solvent of aikyiaiurnirsoxan beta in addition.

As the organo-aluminium compound used when preparing aikyiaiurnirsoxan beta, specifically, the organo-aluminium compound identical with the material illustrated in the organo-aluminium compound belonging to above-mentioned (B-2) can be enumerated.

Among them, preferred trialkylaluminium, tricyclic alkyl aluminium, particularly preferably trimethyl aluminium.

Organo-aluminium compound as above can be used alone a kind, or also can combine two or more use.

In addition, benzene-insoluble organoalurrunoxy compound, converts in Al atom, the Al composition dissolved in the benzene of 60 DEG C is generally less than 10%, is preferably less than 5%, is particularly preferably less than 2%, that is, be preferably organoalurrunoxy compound that is insoluble or insoluble relative to benzene.

In addition, the aikyiaiurnirsoxan beta prepared from trimethyl aluminium is called as methylaluminoxane or MAO, is the compound especially often used.

As the solvent of the preparation for aikyiaiurnirsoxan beta, the aromatic hydrocarbonss such as benzene,toluene,xylene, isopropyl benzene, cymene can be enumerated, the aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, n-Hexadecane, octadecane, the clicyclic hydrocarbons such as pentamethylene, hexanaphthene, cyclooctane, methylcyclopentane, the petroleum fractionss such as gasoline, kerosene, light oil or above-mentioned aromatic hydrocarbons, aliphatic hydrocarbon, the halogenide of clicyclic hydrocarbon, the particularly hydrocarbon solvent such as muriate, bromide.The ethers such as ether, tetrahydrofuran (THF) can also be used in addition.Particularly preferably aromatic hydrocarbons or aliphatic hydrocarbon among these solvents.

As organoalurrunoxy compound, the organoalurrunoxy compound containing boron shown in following general formula (17) can be enumerated.

(in formula, R ^crepresent that carbonatoms is the alkyl of 1 ~ 10.R ^dmutually can be the same or different, represent that hydrogen atom, halogen atom or carbonatoms are the alkyl of 1 ~ 10.）

The organoalurrunoxy compound containing boron shown in above-mentioned general formula (17), can by by the alkylboronic acids shown in following general formula (18) and organo-aluminium compound under inactive gas atmosphere gas and in torpescence solvent, manufacture with the thermotonus 1 minute ~ 24 hours of-80 DEG C ~ room temperature.

R ^cB(OH) ₂（18）

(in formula, R ^crepresent group same as described above.）

As the concrete example of the alkylboronic acids shown in above-mentioned general formula (18), methyl-boron-dihydroxide, ethyl-boron dihydroxide, sec.-propyl boric acid, n-propyl boric acid, n-Butaneboronic acid, isobutaneboronic acid, n-hexyl boric acid, cyclohexyl boric acid, phenyl-boron dihydroxide, 3 can be enumerated, 5-difluorophenyl boronic acid, pentafluorophenylboronic acid, 3,5-two (trifluoromethyl) phenyl-boron dihydroxides etc.Among them, preferable methyl boric acid, n-Butaneboronic acid, isobutaneboronic acid, 3,5-difluorophenyl boronic acid, pentafluorophenylboronic acid.They can be used alone a kind or combine two or more use.

As the organo-aluminium compound reacted with such alkylboronic acids, specifically, the organo-aluminium compound identical with the illustrative material as the organo-aluminium compound shown in above-mentioned general formula (11) or (12) can be enumerated.

Among them, preferred trialkylaluminium, tricyclic alkyl aluminium, particularly preferably trimethyl aluminium, triethyl aluminum, triisobutyl aluminium.They can be used alone a kind or combine two or more use.

These organoalurrunoxy compound (B-3) can be used alone a kind, or combine two or more use.

(compound that (B-4) is right with above-mentioned IV group transition metal compound (A) reacting forming ion)

As the compound (B-4) right with above-mentioned IV group transition metal compound (A) reacting forming ion, Japanese Unexamined Patent Publication 1-501950 publication, Japanese Unexamined Patent Publication 1-502036 publication, Japanese Unexamined Patent Publication 3-179005 publication, Japanese Unexamined Patent Publication 3-179006 publication, Japanese Unexamined Patent Publication 3-207703 publication, Japanese Unexamined Patent Publication 3-207704 publication, Lewis acid, ionic compound, borane compound and caborane compounds etc. described in No. USP-5321106 etc. can be enumerated.

Specifically, as Lewis acid, BR can be enumerated ₃(R is for can have substituent phenyl or the fluorine such as fluorine, methyl, trifluoromethyl.) shown in compound, such as can enumerate boron trifluoride, triphenyl-boron, three (4-fluorophenyl) boron, three (3,5-difluorophenyl) boron, three (4-trifluoromethylphenyl) boron, three (pentafluorophenyl group) boron, three (p-methylphenyl) boron, three (o-tolyl) boron, three (3,5-3,5-dimethylphenyl) boron, trimethyl-boron, tri-isobutyl-boron etc.

As ionic compound, such as, can enumerate the compound shown in following general formula (19).

In formula, as R ^e+, can H be enumerated ⁺, carbocation, oxygen positively charged ion, ammonium cation, phosphonium cation, cycloheptatriene base positively charged ion, there is the ferrocene cation etc. of transition metal.R ^f~ R ⁱmutually can be the same or different, is organic radical, is preferably aryl or substituted aryl.

As above-mentioned carbocation, specifically, triphenylcarbenium cation, three (aminomethyl phenyl) carbocation, three (3,5-dimethylphenyl) carbocation etc. three can be enumerated and replace carbocation etc.

As above-mentioned ammonium cation, specifically, trialkylammonium cation, the N such as trimethyl ammonium cation, triethyl ammonium positively charged ion, three (n-propyl) ammonium cation, triisopropyl ammonium cation, three (normal-butyl) ammonium cation, triisobutyl ammonium cation can be enumerated, N-dimethylanilinium cation, N, N-diethylbenzene ammonium cation, N, N-2,4, the dialkyl ammonium cations etc. such as N, N-dialkyl benzene ammonium cation, di-isopropyl ammonium cation, dicyclohexyl ammonium cation such as 6-pentamethylbenzene ammonium cation.

As Shang Shu phosphonium cation, specifically, triphenyl phosphonium positively charged ion, three (aminomethyl phenyl) phosphonium cation, three (the San Fang Ji phosphonium cations etc. such as 3,5-dimethylphenyl) phosphonium cation can be enumerated.

Among above-mentioned, as R ^e, preferred carbocation, ammonium cation etc., particularly preferably triphenylcarbenium cation, N, N-dimethylanilinium cation, N, N-diethylbenzene ammonium cation.

As carbon salt, specifically, triphenylcarbenium tetraphenyl borate salts, triphenylcarbenium four (pentafluorophenyl group) borate, triphenylcarbenium four (3 can be enumerated, 5-di-trifluoromethyl phenyl) borate, three (4-aminomethyl phenyl) carbon four (pentafluorophenyl group) borate, three (3,5-3,5-dimethylphenyl) carbon four (pentafluorophenyl group) borate etc.

As ammonium salt, trialkyl-substituted ammonium, N, N-dialkyl benzene ammonium salt, dialkyl ammonium salt etc. can be enumerated.

As trialkyl-substituted ammonium, specifically, such as triethyl ammonium tetraphenyl borate salts can be enumerated, tripropyl ammonium tetraphenyl borate salts, three (normal-butyl) ammonium tetraphenyl borate salts, trimethyl ammonium four (p-methylphenyl) borate, trimethyl ammonium four (o-tolyl) borate, three (normal-butyl) ammonium four (pentafluorophenyl group) borate, triethyl ammonium four (pentafluorophenyl group) borate, tripropyl ammonium four (pentafluorophenyl group) borate, tripropyl ammonium four (2,4-3,5-dimethylphenyl) borate, three (normal-butyl) ammonium four (3,5-3,5-dimethylphenyl) borate, three (normal-butyl) ammonium four (4-trifluoromethyl) borate, three (normal-butyl) ammonium four (3,5-di-trifluoromethyl phenyl) borate, three (normal-butyl) ammonium four (o-tolyl) borate, two-octadecyl methyl ammonium tetraphenyl borate salts, two-octadecyl methyl ammonium four (p-methylphenyl) borate, two-octadecyl methyl ammonium four (o-tolyl) borate, two-octadecyl methyl ammonium four (pentafluorophenyl group) borate, two-octadecyl methyl ammonium four (2,4-3,5-dimethylphenyl) borate, two-octadecyl methyl ammonium four (3,5-3,5-dimethylphenyl) borate, two-octadecyl methyl ammonium four (4-trifluoromethyl) borate, two-octadecyl methyl ammonium four (3,5-di-trifluoromethyl phenyl) borate, two-octadecyl methyl ammonium etc.

As N, N-dialkyl benzene ammonium salt, specifically, such as N can be enumerated, N-dimethyl puratized agricultural spray tetraphenyl borate salts, N, N-dimethyl puratized agricultural spray four (pentafluorophenyl group) borate, N, N-dimethyl puratized agricultural spray four (3, 5-di-trifluoromethyl phenyl) borate, N, N-diethyl puratized agricultural spray tetraphenyl borate salts, N, N-diethyl puratized agricultural spray four (pentafluorophenyl group) borate, N, N-diethyl puratized agricultural spray four (3, 5-di-trifluoromethyl phenyl) borate, N, N-2, 4, 6-pentamethyl-puratized agricultural spray tetraphenyl borate salts, N, N-2, 4, 6-pentamethyl-puratized agricultural spray four (pentafluorophenyl group) borate etc.

As dialkyl ammonium salt, specifically, such as, two (1-propyl group) ammonium four (pentafluorophenyl group) borate, dicyclohexyl ammonium tetraphenyl borate salts etc. can be enumerated.

In addition, the borate compound etc. containing silyl shown in the borate compound containing active hydrogen shown in ferrocene four (pentafluorophenyl group) borate, triphenylcarbenium Pentaphenylcyclopentadiene polymerization of olefin using catalyst compound, N, N-diethyl puratized agricultural spray Pentaphenylcyclopentadiene polymerization of olefin using catalyst compound or following formula (20) or the borate compound shown in (21) or following formula (22) or following formula (23) can be enumerated.

(in formula, Et represents ethyl.）

[B-Qn(Gq(T-H)r)z] ^-A ⁺（22）

In formula (22), B represents boron.G represents many associativities hydrocarbon free radical, as alkylidene group, propine, ethylidene, alkarylene free radical that preferred many associativities hydrocarbon is containing 1 ~ 20 carbon atom, as the preference of G, can enumerate phenylene, biphenylene, naphthylidene, methylene radical, ethylidene, propylidene, Isosorbide-5-Nitrae-divinyl, to phenylene methylene radical.Many associativities free radical G has r+1 key, and namely a key is combined with borate anion, and other key r of G is combined with (T-H) base.A ⁺for positively charged ion.

T in above-mentioned formula (22) represents O, S, NR ^jor PR ^j, R ^jrepresent hydrogenized carbonyl free radical, three hydrogenized carbonyl silyl free radicals, three hydrogenized carbonyl germanium free radical or hydride.Q is the integer of more than 1, is preferably 1.As T-H group ,-OH ,-SH ,-NRH or-PR can be enumerated ^jh, wherein R ^jfor carbonatoms 1 ~ 18, the hydrogenate hydrocarbon methyl free radicals being preferably carbonatoms 1 ~ 10 or hydrogen.Preferred R ^jgroup is alkyl, cycloalkyl, allyl group, allyl alkyl or the polyoxyethylene base with 1 ~ 18 carbon atom.-OH ,-SH ,-NR ^jh or-PR ^jh such as, also can be-C (O)-OH ,-C (S)-SH-C (O)-NR ^jh and C (O)-PR ^jh.The most preferred group with active hydrogen is-OH base.Q is hydride, dialkyl acid amides, preferably dialkyl amide, halogenide, hydrocarbyl oxide, alkoxide, allyl oxidation thing, alkyl, substituted hydrocarbyl radical etc.Wherein, n+z is 4.

As [B-Qn (Gq (T-H) r) z] of above-mentioned formula (22), such as, triphenyl (hydroxy phenyl) borate can be enumerated, phenylbenzene-two (hydroxy phenyl) borate, triphenyl (2,4-dihydroxy phenyl) borate, three (p-methylphenyl) (hydroxy phenyl) borate, three (pentafluorophenyl group) (hydroxy phenyl) borate, three (2,4-3,5-dimethylphenyl) (hydroxy phenyl) borate, three (3,5-3,5-dimethylphenyl) (hydroxy phenyl) borate, three [3,5-bis-(trifluoromethyl) phenyl] (hydroxy phenyl) borate, three (pentafluorophenyl groups) (2-hydroxyethyl) borate, three (pentafluorophenyl groups) (4-hydroxybutyl) borate, three (pentafluorophenyl groups) (4-hydroxy-cyclohexyl) borate, three (pentafluorophenyl groups) [4-(4-hydroxy phenyl) phenyl] borate, three (pentafluorophenyl groups) (6-hydroxyl-2-naphthyl) borates etc., most preferably are three (pentafluorophenyl groups) (4-hydroxy phenyl) borate.-OH the base of preferred above-mentioned borate compound is by-NHR in addition ^j(wherein, R ^jfor methyl, ethyl, the tertiary butyl) compound that replaces.As the A of the balance cation of borate compound ⁺, can enumerate carbocation, positively charged ion, ammonium cation, oxygen positively charged ion, sulfonium cation, phosphonium cation etc.Positively charged ion, the organometallic positively charged ion of the metal that itself easily reduces can also be enumerated.As these cationic concrete examples, triphenylcarbonium ion can be enumerated, phenylbenzene carbon ion, cycloheptatriene ion, indenes ion, three second ammoniums, 3 third ammoniums, three fourth ammoniums, dimethylammonium, dipropyl ammonium, two hexamethylene ammoniums, three pungent ammoniums, N, N-dimethylammonium, diethyl ammonium, 2, 4, 6-pentamethyl-ammonium, N, N-3,5-dimethylphenyl ammonium, two (sec.-propyl) ammonium, dicyclohexyl ammonium, triphenyl phosphonium, San Phosphonium, three-Er Jia base Ben Ji Phosphonium, three (aminomethyl phenyl) Phosphonium, triphenyl phosphonium ion, triphenyl oxonium ion, triethyl oxonium ion, pyrinium, silver ions, gold ion, platinum ion, cupric ion, palladium ion, mercury ion, ferricinium ion etc.Wherein particularly preferably ammonium ion.

[B-Qn(Gq(SiR ^kR ^lR ^m)r)z] ^-A ⁺…（23）

In formula (23), B represents boron.G represents many associativities hydrocarbon free radical, as alkylidene group, propine, ethylidene, alkarylene free radical that preferred many associativities hydrocarbon is containing 1 ~ 20 carbon atom, as the preferred example of G, can enumerate phenylene, biphenylene, naphthylidene, methylene radical, ethylidene, propylidene, Isosorbide-5-Nitrae-divinyl, to phenylene methylene radical.Many associativities free radical G has r+1 key, and namely a key is combined with borate anions, other key r and the (SiR of G ^kr ^lr ^m) base combination.A ⁺for positively charged ion.Q is the integer of more than 1, is preferably 1.

R in above-mentioned formula (24) ^k, R ^l, R ^mrepresent hydrogenized carbonyl free radical, three hydrogenized carbonyl silyl free radicals, three hydrogenized carbonyl germanium free radicals, hydroperoxyl radical, alkoxy radical, hydroxyl radical free radical or halogen compound free radical.R ^k, R ^l, R ^mcan identical also can be independent.Q is hydride, dialkyl acid amides, is preferably dialkyl amide, halogenide, hydrocarbyl oxide, alkoxide, allyl oxidation thing, alkyl, substituted hydrocarbyl radical etc., is more preferably PFBBR free radical.Wherein, n+z is 4.

As [B-Qn (Gq (the SiR in above-mentioned formula (23) ^kr ^lr ^m) r) z] ^-, such as can enumerate triphenyl (4-dimethylchlorosilane base phenyl) borate, phenylbenzene-two (4-dimethylchlorosilane base phenyl) borate, triphenyl (4-dimethylmethoxysilylgroups groups phenyl) borate, three (p-methylphenyls) (4-triethoxysilyl phenyl) borate, three (pentafluorophenyl groups) (4-dimethylchlorosilane base phenyl) borate, three (pentafluorophenyl groups) (4-dimethylmethoxysilylgroups groups phenyl) borate, three (pentafluorophenyl groups) (4-trimethoxysilylphenyl) borate, three (pentafluorophenyl groups) (6-dimethylchlorosilane base-2 naphthyl) borate etc.

As the A of the balance cation of borate compound ⁺, can enumerate and the A in above-mentioned formula (22) ⁺identical ion.

As borane compound, specifically, such as, Decaboron tetradecahydride can be enumerated, two [three (normal-butyl) ammonium] borate in the ninth of the ten Heavenly Stems, two [three (normal-butyl) ammonium] borate in the last of the ten Heavenly stems, two [three (normal-butyl) ammonium] 11-borate salt, two [three (normal-butyl) ammonium] Dodecaborate salt, two [three (normal-butyl) ammonium] ten chlorine borates in the last of the ten Heavenly stems, the salt of the negatively charged ion such as two [three (normal-butyl) ammonium] ten dichloro Dodecaborate salts, two (the ten dihydro Dodecaborate salts) cobaltates (III) of three (normal-butyl) ammonium, the salt etc. of the metallo-borane negatively charged ion such as two [three (normal-butyl) ammonium] two (ten dihydro Dodecaborate salts) nickelate (III).

As caborane compounds, specifically, such as 4-carbon borine in the ninth of the ten Heavenly Stems can be enumerated, 1,3-bis-carbon borine in the ninth of the ten Heavenly Stems, 6,9-dicarbadecaborane, ten dihydro-1-phenyl-1,3-bis-carbon borines in the ninth of the ten Heavenly Stems, ten dihydro-1-methyl isophthalic acids, 3-bis-carbon borine in the ninth of the ten Heavenly Stems, 11 hydrogenation-1,3-dimethyl-1,3-bis-carbon borines in the ninth of the ten Heavenly Stems, 7,8-bis-carbon 11 borine, 2,7-bis-carbon 11 borine, 11 hydrogenation-7,8-dimethyl-7,8-bis-carbon 11 borines, ten dihydro-11-methyl-2,7-bis-carbon 11 borines, 1-carbon boric acid in the last of the ten Heavenly stems three (normal-butyl) ammonium, 1-carbon 11-borate three (normal-butyl) ammonium, 1-carbon ten hypoboric acid three (normal-butyl) ammonium, 1-trimethyl silyl-1-carbon boric acid in the last of the ten Heavenly stems three (normal-butyl) ammonium, bromo-1-carbon ten hypoboric acid three (normal-butyl) ammonium, 6-carbon boric acid in the last of the ten Heavenly stems three (normal-butyl) ammonium, 6-carbon boric acid in the last of the ten Heavenly stems three (normal-butyl) ammonium, 7-carbon 11-borate three (normal-butyl) ammonium, 7,8-bis-carbon 11-borate three (normal-butyl) ammonium, 2,9-bis-carbon 11-borate three (normal-butyl) ammonium, ten dihydro-8-methyl-7,9-bis-carbon 11-borate three (normal-butyl) ammoniums, 11 hydrogenation-8-ethyl-7,9-bis-carbon 11-borate three (normal-butyl) ammoniums, 11 hydrogenation-8-butyl-7,9-bis-carbon 11-borate three (normal-butyl) ammoniums, 11 hydrogenation-8-allyl group-7,9-bis-carbon 11-borate three (normal-butyl) ammoniums, 11 hydrogenation-9-trimethyl silyl-7,8-bis-carbon 11-borate three (normal-butyl) ammoniums, the salt of the negatively charged ion such as 11 hydrogenation-4,6-bis-bromo-7-carbon 11-borate three (normal-butyl) ammonium, two (nine hydrogenations-1 of three (normal-butyl) ammonium, 3-bis-carbon boric acid in the ninth of the ten Heavenly Stems) cobaltates (III), two (11 hydrogenations-7 of three (normal-butyl) ammonium, 8-bis-carbon 11-borate) wustite (III), two (11 hydrogenations-7 of three (normal-butyl) ammonium, 8-bis-carbon 11-borate) cobaltates (III), two (11 hydrogenations-7 of three (normal-butyl) ammonium, 8-bis-carbon 11-borate) nickelate (III), two (11 hydrogenations-7 of three (normal-butyl) ammonium, 8-bis-carbon 11-borate) cuprate (III), two (11 hydrogenations-7 of three (normal-butyl) ammonium, 8-bis-carbon 11-borate) aurate (III), two (nine hydrogenations-7 of three (normal-butyl) ammonium, 8-dimethyl-7, 8-bis-carbon 11-borate) wustite (III), two (nine hydrogenations-7 of three (normal-butyl) ammonium, 8-dimethyl-7, 8-bis-carbon 11-borate) chromic salt (III), two (the tribromo octahydro-7 of three (normal-butyl) ammonium, 8-bis-carbon 11-borate) cobaltates (III), three [three (normal-butyl) ammoniums] two (11 hydrogenation-7-carbon 11-borate) chromic salt (III), two [three (normal-butyl) ammonium] two (11 hydrogenation-7-carbon 11-borate) manganate (IV), two [three (normal-butyl) ammonium] two (11 hydrogenation-7-carbon 11-borate) cobaltates (III), the salt etc. of the metallocarborane negatively charged ion such as two [three (normal-butyl) ammonium] two (11 hydrogenation-7-carbon 11-borate) nickelate (IV).

In addition, to react with IVB group transition metal compound (A) as above and the compound (B-4) forming ion pair also can mix two or more uses.

As (B) composition used in the present invention, specifically, the MAO/ toluene solution etc. of that have employed above-mentioned shown (B-3) organoalurrunoxy compound, commercially available NipponAluminumAlkyls Co., Ltd. can suitably be used.

In addition, in the adjustment of catalyst for olefines polymerizing used in the present invention, carrier can be used as required.Carrier is generally inorganic or organic compound, is particulate state or particulate solid.Wherein, as mineral compound, Porous oxide compound, butter, clay, clay mineral or ion exchangeable lamellar compound etc. can be enumerated.

As Porous oxide compound, specifically, SiO can be used ₂, Al ₂o ₃, MgO, ZrO, TiO ₂, B ₂o ₃, CaO, ZnO, BaO, ThO ₂deng or comprise these mixture or mixture, such as can use natural or synthetic zeolite, SiO ₂-MgO, SiO ₂-Al ₂o ₃, SiO ₂-TiO ₂, SiO ₂-V ₂o ₅, SiO ₂-Cr ₂o ₃, SiO ₂-TiO ₂-MgO etc.

Octene (being total to) the polymkeric substance (ii) preferred alpha-olefin (being total to) that makes under the existence of catalyst for olefines polymerizing as above is polymerized and manufactures.

Describe in detail below and manufacture octene (being total to) polymkeric substance concrete mode (ii).

In the present invention, polyreaction can be implemented in hydrocarbon medium.As such hydrocarbon medium, specifically, the aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, kerosene can be enumerated, the clicyclic hydrocarbons such as pentamethylene, hexanaphthene, methylcyclopentane, the aromatic hydrocarbonss such as benzene,toluene,xylene, the petroleum fractionss etc. such as the halons such as ethylene chloride, chlorobenzene, methylene dichloride, gasoline, kerosene, light oil.In addition, the alkene used in polymerization can be also used in.

In the present invention, be polymerized under the existence of catalyst for olefines polymerizing as above, but now, above-mentioned IV group transition metal compound (A), as the concentration of the transition metal atoms in polymerization reaction system, usually with 10 ^-8~ 1 grammeatom/liter, preferably with 10 ^-7~ 10 ^-1grammeatom/liter scope amount use.

(B-1) composition uses with the amount that the mol ratio ((B-1)/M) of the total transition metal atoms (M) in (B-1) composition and (A) composition is generally 0.01 ~ 5000, be preferably 0.05 ~ 2000.(B-2) composition uses with the amount that the mol ratio ((B-2)/M) of the total transition metal atoms (M) in (B-2) composition and (A) composition is generally 100 ~ 25000, be preferably 500 ~ 10000.(B-3) composition uses with the amount that the mol ratio ((B-3)/M) of the total transition metal (M) in the aluminium atom in (B-3) composition and (A) composition is generally 10 ~ 5000, be preferably 20 ~ 2000.(B-4) composition uses with the amount that the mol ratio ((B-4)/M) of the transition metal atoms (M) in (B-4) composition and (A) composition is generally 1 ~ 50, be preferably 1 ~ 20.

In addition, use the polymerization temperature of the alkene of such olefin polymerization catalysis, be generally-50 ~+200 DEG C, be preferably the scope of 0 ~ 180 DEG C.Polymerization pressure is usually in normal pressure ~ 10MPa gauge pressure, and preferably under the condition of normal pressure ~ 5MPa gauge pressure, polyreaction also can be undertaken by any one method in batch type, semi continuous, continous way.Also can be divided into the 2 different stages of reaction conditions more than is in addition polymerized.The molecular weight of the olefin polymer obtained also can be present in polymerization system by making hydrogen, or makes polymerization temperature variations to regulate.

In addition, the kinematic viscosity in 100 DEG C of olefin polymer depends on the molecular weight of polymkeric substance.That is, be more high molecular then more for high viscosity, be more lower molecular weight be more then low viscosity, therefore by kinematic viscosity that the adjustment of above-mentioned molecular weight adjusts in 100 DEG C.In addition, the low molecular weight compositions of the polymkeric substance obtained can be removed by the existing known method utilizing underpressure distillation such, the molecular weight distribution (Mw/Mn) of obtained polymkeric substance is adjusted to less than 1.8.

In addition, in the present invention, be 20mm containing the kinematic viscosity (iii) in 100 DEG C ²the fatty acid ester of/below s.If kinematic viscosity is in this scope, then when adjusting the kinematic viscosity of lubricating oil composition entirety, can add the sufficient addition of the suppression of the swelling of seal oil agent.

(iii) be 20mm as the kinematic viscosity in 100 DEG C ²the fatty acid ester of/below s, is not particularly limited, but can enumerate the fatty acid ester be only made up of carbon, oxygen, hydrogen of the following stated.

The monoesters manufactured by monoprotic acid and alcohol can be enumerated; By the diester manufactured by diprotic acid and alcohol or dibasic alcohol and monoprotic acid or acid mixture; Dibasic alcohol, trivalent alcohol (such as TriMethylolPropane(TMP)), tetravalent alcohol (such as tetramethylolmethane), hexavalent alcohol (such as dipentaerythritol) etc. react with monoprotic acid or acid mixture the polyol ester etc. manufacturing and obtain.As the example of these esters, tridecyl pelargonate, two-2-ethyl hexyl adipate, two-2-ethylhexylazelate, trimethylolpropane tri-heptanoate, pentaerythritol tetraheptanoate etc. can be enumerated as ester.

Specifically, from the view point of the consistency with 1-decene (being total to) polymkeric substance selected in the present invention or 1-octene (being total to) polymkeric substance, forming the alcohol position of ester, to be preferably hydroxyl be that 2 officials can above alcohol, and lipid acid position is preferably the lipid acid that carbonatoms is more than 8.Wherein, about lipid acid in manufacturing cost, the carbonatoms industrially easily obtained be less than 20 lipid acid take advantage.No matter the lipid acid forming ester is a kind or acid mixture of more than two kinds, performance disclosed in the present invention can both be given full play to.More specifically, TriMethylolPropane(TMP) lauric acid stearic acid can be enumerated and mix three esters or diisodecyl adipate etc., these the stable hydrocarbon composition such with 1-decene (being total to) polymkeric substance, 1-octene (being total to) polymkeric substance and described later there is polar group antioxidant, corrosion inhibitor, anti-wear agent, friction regulator, yield point depressant, the stablizer such as rust-preventive agent and defoamer consistency in preferred.

Lubricating oil composition of the present invention, when the total of (i) decene (being total to) polymkeric substance, (ii) octene (being total to) polymkeric substance and (iii) ester is set to 100 quality %, with 90 ~ 10 quality %, preferably contain (i) decene (being total to) polymkeric substance with the amount of 80 ~ 20 quality %, contain (ii) octene (being total to) polymkeric substance with the amount of 5 ~ 85 quality %, contain ester (iii) with the amount of 5 ~ 15 quality %.If contain (i) decene (being total to) polymkeric substance, (ii) octene (being total to) polymkeric substance and (iii) ester with above-mentioned scope, then can obtain the lubricating oil composition of the balancing good of shear stability and low-temperature viscosity profiles.In addition, by containing the ester of more than 5 quality %, the good suitability relative to the resin of various internal combustion device, industrial machinery inside or the such seal oil material of elastomerics can be obtained.Specifically, the swelling of seal oil material can be suppressed.From the view point of oxidative stability or thermotolerance, the amount of preferred ester is below 15 quality %.Wherein, (i) ~ total is (iii) set to 100 quality %.

In addition, as one of the feature of lubricating oil composition of the present invention, the boron atom containing more than 5ppm, below 75ppm can be enumerated.Wherein, 1ppm refers to the meaning containing boron 1mg in composition 1kg.Found by the present invention, by the boron containing certain concentration in lubricating oil composition, particularly resistance to micro-pitting corrosion is improved.In addition, also find, the performance of the aftermentioned extreme pressure agent added arbitrarily in lubricating oil composition can be made to give full play to.In addition, the boron atom in lubricating oil composition is from boron compound described later.In addition, the content of the boron atom in lubricating oil composition, as described in embodiment described later, is measured by ICP Emission Spectrophotometer method.

As the mechanism showing such effect, such as, can consider hypothesis as described below.

Gear part in industrial machinery etc., in high-load condition (also referred to as extreme boundary lubrication condition), the surface protrusion of surface of friction is worn out the oil film of lubricating oil and metallic contact occurs, cause the rising of frictional surface temperature and strong shearing thus, oil film is caused to depart from or removing from surface of friction, friction, abrasion increase, finally reach scorification, and have the possibility that can not lubricate.

(therefore, in lubricating oil composition of the present invention, under this extreme boundary lubrication condition, be preferably added with the extreme pressure agent described later that can form the reaction tunicle higher with the affinity of metal in metallic surface.Infer the tunicle of metallic surface obtained by this extreme pressure agent, for be subject to by gear parts at high load conditions, by Repeated Compression stress cause peel off small from the flank of tooth, raising namely for the endurance quality of micro-spot corrosion is effective.）

But, reaching extreme pressure agent before metallic surface forms the such extreme boundary lubrication condition of epithelium as described later, other organic composition of hydrocarbon or formation lubricating oil composition, owing to heating, shearing and carbonization before extreme boundary lubrication condition, has the possibility forming carbide tunicle in metallic surface.

Can think that boron-containing compound is before above-mentioned carbide tunicle is formed, interference carbide or carbide former, play a role as the dispersion agent preventing carbide from adhering to metallic surface.In addition, because boron has the affinity with metal, the part that carry extreme pressure property or abrasion resistance can therefore be inferred.

Particularly there is micro-spot corrosion of metal-stripping about in the region of microcosmic, can think that boron-containing compound is very large to the intervention of metal, in lubricating oil composition, play resistance to micro-pitting corrosion during the content of the boron atom of more than 5ppm.If consider the long-time running of device, then preferably containing more than 20ppm.But, boron-containing compound due to 1-decene (being total to) polymkeric substance for the main component as lubricating oil composition of the present invention and the such stable hydrocarbon polarity of 1-octene (being total to) polymkeric substance very high, therefore from the view point of consistency, the content of boron atom needs for below 75ppm, is preferably below 50ppm.If can think and exceed this scope, then due to compatible bad and aggegation occurs, suppress the low-temperature viscosity profiles of lubricating oil composition as agglomeration.

Contained boron-containing compound can be organic compound, also can be mineral compound.Mineral compound comprises boric acid, its acid anhydrides, oxide compound, halogenide.Organoboron compound comprises acid amides and the ester of boron.In addition, also can comprise acylations amine that boronation obtains, fatty acid ester that epoxide that dispersion agent that boronation obtains, boronation obtain, glycerine boronation obtain.

As used boron-containing compound, comprise boron oxide; Boron oxide hydrate; Boron trioxide; Boron trifluoride; Boron tribromide; Boron trichloride; Boric acid (i.e. alkyl-B (OH) ₂or aryl-B (OH) ₂), boric acid (i.e. H ₃bO ₃), tetraboric acid (i.e. H ₂b ₄o ₇), metaboric acid (i.e. HBO ₂), the boron acid amides of such boric acid such as boron trioxide and such boric acid and various ester.Also the trihalid of boron and the coordination compound of ether, organic acid, mineral acid or hydrocarbon can be used.In the example of such coordination compound, comprise boron trifluoride-triethyl, boron trifluoride-phosphoric, boron trichloride-Mono Chloro Acetic Acid, boron tribromide-diox and boron trifluoride methyl ethyl ether etc.

From the view point of the consistency of other composition with lubricating oil composition, wish that boron-containing compound is organic compound.

As the concrete example of boric acid, comprise methyl-boron-dihydroxide, phenyl-boronic acid, cyclohexyl boric acid, to heptyl benzene ylboronic acid and dodecyl boric acid etc.In preferred boron-containing compound, such as, comprise the boron oxide that boron oxide, boron oxide hydrate and boron trioxide are such.

In boric acid ester, comprise boric acid and such as methyl alcohol, ethanol, Virahol, butanols, amylalcohol, hexanol, hexalin, cyclopentanol, 1-octanol, sec-n-octyl alcohol, dodecanol, behenyl alcohol, oleyl alcohol, Stearyl alcohol, benzylalcohol, 2-butylcyclohexyl alcohol, ethylene glycol, propylene glycol, trimethylene glycol, 1, 3-butyleneglycol, 2, 4-hexylene glycol, 1, 2-cyclohexanediol, 1, 3-ethohexadiol, glycerine, tetramethylolmethane Diethylene Glycol, Trivalin SF, cellosolve, Triethylene glycol, tripropylene glycol, phenol, naphthols, p-butylphenol, adjacent, p-diheptyl phenol, positive cyclohexylphenol, 2, two (the p-hydroxybenzene)-propane of 2-, polyisobutene (molecular weight 1, 500) phenol replaced, chloroethanol, ortho chloro phenol, m-nitrophenol, single organic ester of such alcohol such as 6-bromine octanol and 7-ketone group-decyl alcohol or phenol, two organic esters and three organic esters.Lower alcohol, 1,2-glycol and 1-3-glycol, namely to have the preparation of alcohol to boric acid ester being about less than 8 carbon atoms be useful.

The preparation method of the ester of boric acid is known, such as, can enumerate the preparation of the three-organic borate undertaken by the reaction of boron trichloride and the alcohol of 3 moles or the reaction of phenol or boron oxide and alcohol or phenol.In addition, as other method, tetraboric acid and the alcohol of 3 moles or the direct esterification of phenol can be enumerated, as other method, such as, the cyclic boronate alkylene ester formed by the direct esterification of boric acid and glycol can be enumerated and formed.

In some modes, boron-containing compound is the compound that oil-soluble ashless dispersant boronation obtains.

Ashless dispersant has basic nitrogen and/or at least one hydroxyl in the molecule.The ashless dispersant that can obtain by boronation is reacted by making the basic nitrogen in ashless dispersant and/or hydroxyl and boron.As preferred dispersion agent, comprise alkenyl succinic acid imide, alkenyl succinate acid esters, alkenyl succinate acid ester-amide, Mannich base, hydrocarbyl polyamine or polymer based polyamines etc.

Alkenyl succinic acid imide can be formed by the existing method such as heating together with polyamines that alkenyl succinic anhydride, acid, sour-ester, acyl halide or lower alkyl esters and at least one are contained primary amino.Alkenyl succinic anhydride can by being heated to such as about 180-220 DEG C and easily manufacturing by the mixture of alkene and maleic anhydride.This alkene is polymkeric substance or the multipolymer of the lower monoolefinic such as ethene, propylene, 1-butylene, iso-butylene etc. and their mixture.To be gel permeation chromatography (GPC) number-average molecular weight be in illustrative thiazolinyl source 10,000 or its above polyisobutene, such as, be the polyisobutene of from about 500 to about 2,500 and then such as from about 800 to about 1,500.In certain mode, the molecular weight of polyisobutene is from about 700 to about 5,000.The ratio of polyisobutylene succinic anhydride and amine is from about 1.4 to about 3 and then is such as from about 1.8 to about 2.2.

Lubricant compositions in the present invention can contain a kind of above-mentioned boron-containing compound, also can use combination of more than two kinds.

Lubricating oil composition of the present invention is preferably also containing the extreme pressure agent of more than a kind.

The extreme pressure agent of the application refers to (i) ~ (iii) beyond composition and there is the general name of the material of anti-scorification effect, be not particularly limited, sulfide-based, the sulphur class extreme pressure agent such as sulfoxide type, sulfone class, thiophosphinic acid ester class, thiocarbonic ester class, sulfuration grease, olefine sulfide can be illustrated; The phosphoric acid classes such as phosphoric acid ester, phosphorous acid ester, phosphate amine salt, phosphorous acid ester amine; The halogen-based compounds etc. such as chlorinated hydrocarbon.In addition, also two or more kinds may be used these compounds.

But before reaching extreme boundary lubrication condition, other organic composition of hydrocarbon or formation lubricating oil composition with regard to carbonization before extreme boundary lubrication condition, may form carbide tunicle in metallic surface due to heating, shearing.Therefore, in the use that extreme pressure agent is independent, extreme pressure agent is hindered because of carbide tunicle with contacting of metallic surface, possibly cannot expect the sufficient effect of extreme pressure agent.

As the method for adding boron-containing compound in lubricating oil composition, although also boron-containing compound can be added separately, but lubricating oil composition of the present invention due to 1-decene (being total to) polymkeric substance and the such stable hydrocarbon of 1-octene (being total to) polymkeric substance for main component, therefore from the view point of the dispersiveness of boron-containing compound, preferably add with the state being dissolved in the lubricant base such as mineral oil or 1-decene (being total to) polymkeric substance.In addition, in where method in office, boron-containing compound with the content of the boron atom in lubricating oil composition be more than 5ppm, the mode of below 75ppm coordinates.

Specifically, be combined with in advance among so-called extreme pressure agent combination (package) of each compositions such as extreme pressure agent composition, the extreme pressure agent that the state more preferably selecting to have dissolved is added with boron-containing compound combines the method be added in lubricating oil composition.

When adding specified amount boron-containing compound as extreme pressure agent combination, in lubricating oil composition of the present invention, be preferably the mode of 2 ~ 5 quality % with extreme pressure agent combination addition relative to (i) ~ (iii) 100 quality %, select the extreme pressure agent containing boron-containing compound to combine.Extreme pressure agent composition, adds in extreme pressure agent combination owing to considering the concentration that can disperse fully in lubricating oil composition, therefore in the restriction of its upper limit of concentration, sometimes when being less than 2 quality %, cannot expect sufficient effect to extreme pressure property.On the contrary, when more than 5 quality %, sometimes owing to there is aggegation with the compatible bad of 1-decene (being total to) polymkeric substance in lubricating oil composition and the such stable hydrocarbon composition of 1-octene (being total to) polymkeric substance, the low-temperature viscosity profiles of lubricating oil composition is suppressed as agglomeration.

As preferred extreme pressure agent (combination), Anglamol98A, AFTONCHEMICAL Inc. of LUBRIZOL Inc. HITEC1532 etc. can be enumerated, from the view point of the balance of boron-containing compound and other composition, can be applicable to especially using AFTONCHEMICAL Inc. HITEC307.

In addition, lubricating oil composition of the present invention also can contain the additives such as viscosity index improver, antioxidant, corrosion inhibitor, anti-wear agent, friction regulator, yield point depressant, rust-preventive agent and defoamer.

As the additive that lubricating oil composition of the present invention uses, can illustrate following material, they can be used alone or in combination of two or more kinds.

Detergent dispersant: can illustrate metal sulfonate, metal phenolates, metal phosphinate hydrochlorate, bromosuccinimide etc., uses with the scope of 0 ~ 15 quality % relative to (i) ~ (iii) 100 quality % usually.

Anti-wear agent: inorganic or organic molybdenum, graphite, antimony sulfide, the tetrafluoroethylene etc. such as molybdenumdisulphide can be illustrated.Anti-wear agent, as required, uses with the scope of 0 ~ 3 quality % relative to (i) ~ (iii) 100 quality %.

Antioxidant: the compound that the phenol such as 2,6 di tert butyl 4 methyl phenol or amine can be enumerated.Antioxidant, as required, uses with the scope of 0 ~ 3 quality % relative to (i) ~ (iii) 100 quality %.

Rust-preventive agent: the compounds such as various amine compound, carboxylic metallic salt, polyol ester, phosphorus compound, sulfonate can be enumerated.Rust-preventive agent, as required, uses with the scope of 0 ~ 3 quality % relative to (i) ~ (iii) 100 quality %.

Defoamer: the compound etc. that can illustrate the organosilicon compound such as dimethyl siloxane, silicone dispersion, alcohols or ester class.Defoamer, as required, uses with the scope of 0 ~ 0.2 quality % relative to (i) ~ (iii) 100 quality %.

Except above-mentioned additive, non-emulsifying agent, tinting material, oiliness improver (oiliness improver) etc. can be used as required.

In addition, lubricating oil composition of the present invention has specific (ii) octene (being total to) polymkeric substance owing to combining in specific (i) decene (being total to) polymkeric substance, and therefore shear stability is excellent.Shear stability is evaluated by the KRL shear stability test based on the method recorded in Deutsche Industry Norm DIN52350-6.Specifically, by lubricating oil composition 60 DEG C, be placed in shearing condition during 20hr under (1450rpm), obtain the reduced rate of the kinematic viscosity in latter 40 DEG C of test relative to the kinematic viscosity in first 40 DEG C of test.This value is less, represents that shear stability is more excellent.In lubricating oil composition of the present invention, when the kinematic viscosity in 40 DEG C is adjusted to 288mm ²/ more than s, 352mm ²during/below s, be that the kinematic viscosity reduced rate after the KRL shear stability test of benchmark mensuration in 40 DEG C is less than 10% usually with DIN52350-6, be preferably less than 5%.In addition, the kinematic viscosity in 40 DEG C is 288mm ²/ more than s, 352mm ²/ below s, represents that this lubricating oil composition is viscosity grade (ISO3448) VG320.In addition, if viscosity grade, be then particularly suitable for wind-driven generator gear.

Like this, lubricating oil composition of the present invention is owing to containing specific (i) decene (being total to) polymkeric substance, (ii) octene (being total to) polymkeric substance, (iii) ester, and specifically to measure containing boron atom, therefore shear stability, low-temperature viscosity profiles and resistance to micro-spot corrosion are excellent, and the balance of oxidative stability, thermotolerance and temperature-viscosity characteristic is also excellent.

" purposes "

Lubricating oil composition of the present invention can use as Industrial Oil (gear oil, hydraulic efficiency oil) and lubricating grease base oil.In addition, as mentioned above, lubricating oil composition of the present invention, due to shear stability, low-temperature viscosity profiles and resistance to micro-pitting corrosion excellence, is therefore particularly suitable as wind-driven generator lubricating oil and uses.In addition, if shear stability and resistance to micro-pitting corrosion excellence, safeguard for then avoiding during wind-driven generator gear.In addition, from the view point of wind-force to the energy conversion efficiency of electric power, low-temperature viscosity profiles excellence is also preferred.

Wind-driven generator gear of the present invention, utilizes above-mentioned lubricating oil composition and is lubricated.

Fig. 1 ~ 4 represent the example with the wind power generation plant of above-mentioned wind-driven generator gear.Above-mentioned wind power generation plant possesses the power transmission of sun and planet gear (gear) formula, specifically, there is rotor head 1, storage opening 2, roller bearing 3, rotor carrier 4, bearing 5, outer race 6, inner race 7, towing pin 8, drive section 9, by driving section 10, generator 11, sun wheel 12, hollow gear 13, hollow gear 14, power electric device shell 15, sun and planet gear carrier 16, vibration damping device 17 and fixed guide 18.Identical with disclosed in Japanese Unexamined Patent Publication 2000-337245 publication of the function in each portion and action.

Lubricating oil composition of the present invention is suitable for the lubrication of said gear portion (gear part).

As mentioned above, the present invention relates to following (1) ~ (7).

(1) lubricating oil composition, its comprise following (i) ~ (iii), the kinematic viscosity in 40 DEG C is 30mm ²/ more than s, 750mm ²/ below s, and the boron atom containing more than 5ppm, below 75ppm.

(i) the kinematic viscosity in 100 DEG C of 90 ~ 10 quality % is 45mm ²/ below s, is derived from the structural unit of 1-decene containing more than 60mol%, and acid value is less than (being total to) polymkeric substance of 0.1mgKOH/g

(ii) the kinematic viscosity in 100 DEG C of 5 ~ 85 quality % is 35mm ²/ more than s, 1,500mm ²/ below s, is derived from the structural unit of 1-octene containing more than 90mol%, and the molecular weight distribution recorded by gel permeation chromatography is (being total to) polymkeric substance of less than 1.8

(iii) the kinematic viscosity in 100 DEG C of 5 ~ 15 quality % is 20mm ²the fatty acid ester of/below s

(wherein, (i) ~ total is (iii) set to 100 quality %.）

Above-mentioned lubricating oil composition, because in specific (i) decene (being total to) polymkeric substance, combination has specific (ii) octene (being total to) polymkeric substance, therefore shear stability, low-temperature viscosity profiles and temperature-viscosity excellent.In addition, because Boron contents is in specific scope, therefore resistance to micro-pitting corrosion and low-temperature viscosity profiles excellence.

(2) lubricating oil composition as recorded in (1), is characterized in that, also containing the extreme pressure agent of more than a kind.

(3) lubricating oil composition as recorded in (1) or (2), wherein, the kinematic viscosity in 40 DEG C of above-mentioned lubricating oil composition is 190mm ²/ more than s, 750mm ²/ below s.

When the kinematic viscosity in 40 DEG C is 750mm ²during/below s, fuel saving performance and energy conversion efficiency excellence.In addition, when being 190mm ²during/more than s, as oilness and the shear stability of the gear GSO under high temperature and/or higher load condition.

(4) lubricating oil composition recorded any one of (1) ~ (3), wherein, the kinematic viscosity in 40 DEG C of above-mentioned lubricating oil composition is 288mm ²/ more than s, 352mm ²/ below s, is less than 10% according to the kinematic viscosity reduced rate in 40 DEG C after the KRL shear stability test that DIN52350-6 records.

Like this when shear stability is excellent, be particularly suitable for wind-driven generator gear.

(5) lubricating oil composition recorded any one of (1) ~ (4), wherein, the kinematic viscosity in 100 DEG C of (ii) octene (being total to) polymkeric substance is 150mm ²/ more than s, 1,200mm ²/ below s.

When the kinematic viscosity in 100 DEG C is 150mm ²during/more than s, play excellent low-temperature viscosity profiles.In addition, if 1,200mm ²/ below s, then shear stability is more excellent.

(6) lubricating oil composition recorded any one of (1) ~ (5), wherein, the kinematic viscosity in 100 DEG C of (i) decene (being total to) polymkeric substance is 11mm ²/ below s.

When the kinematic viscosity in 100 DEG C is 11mm ²during/below s, the low-temperature viscosity profiles of lubricating oil composition is more excellent.

(7) lubricating oil composition recorded any one of (1) ~ (6) is utilized to carry out the wind-driven generator gear lubricated.

Such wind-driven generator gear can avoid safeguarding, also excellent to the energy conversion efficiency of electric power from wind-force.

Embodiment

, further illustrate the present invention based on embodiment below, but the present invention is not limited to these.

< molecular-weight average molecular weight distribution >

Number-average molecular weight (Mn) and molecular weight distribution (Mw/Mn) use the GPC(ChromatoPacC-R4A of Shimadzu Seisakusho Ltd.) measure as follows.As separator column, use TSKG6000HXL, G4000HXL, G3000HXL, G2000HXL, column temperature is set to 40 DEG C, tetrahydrofuran (THF) (with Guang Chun medicine Co., Ltd. system) is used in moving phase, development rate is set to 0.8ml/ minute, sample solution concentration is set to 0.2 quality %, sample injection rate is set to 20 microlitres, use differential refractometer as detector.As polystyrene standard, use the product of TOSOH Co., Ltd..

< viscosity characteristics >

Kinematic viscosity in 100 DEG C and 40 DEG C and viscosity index measure according to the method recorded in JISK2283, calculate.

< shear stability >

The shear stability of lubricating oil composition, according to the method recorded in DIN52350-6, uses KRL shear stability test machine to evaluate.By compounded oil 60 DEG C, be placed in shearing condition during 20hr under (1450rpm), the reduced rate of the kinematic viscosity in 40 DEG C before and after evaluation test.

After giving shear-stress according to aforesaid method, if the reduced rate of kinematic viscosity is less than 10%, then show good weather resistance.If the reduced rate of kinematic viscosity is less than 5%, then show very excellent weather resistance.

<-30 DEG C of viscosity >

-30 DEG C of viscosity, according to ASTMD2983, utilize Brookfield viscometer determining.Consider that-30 DEG C of viscosity classification are 3 following ranks by measuring the error caused.

High: to be greater than 100,000mPas

In: be greater than 80,000 and be 100, below 000mPas

Low: 80, below 000mPas

If-30 DEG C of viscosity are 100, below 000mPas, then can maintain good oilness under the pole low temperature being low to moderate about-40 DEG C, fuel saving, energy conversion efficiency that display is excellent.If particularly 80, below 000mPas, then show very excellent fuel saving, energy conversion efficiency.If be greater than 100,000mPas at-30 DEG C, then the fuel saving under the low temperature environment of pole, energy conversion efficiency are just not enough.

The defective load stage > of the micro-spot corrosion of <

By the micro-pittingtest of FVA-54/7 by actuation techniques research alliance (FVA) defined, measure defective load stage.If defective load stage is more than 10, then show excellent resistance to micro-pitting corrosion.

< (i) comprises (being total to) polymkeric substance > of 1-decene

(i) be 45mm as the kinematic viscosity in 100 DEG C ²/ below s, comprise decene (being total to) polymkeric substance of 1-decene, use the kinematic viscosity in the poly-alpha-olefin (PAO) of NESTEOIL Inc., NEXBASE2006(100 DEG C to be 6mm ²/ s).0.1mgKOH/g is less than according to the acid value that JISK2501 measures.

< is (ii) with (being total to) polymkeric substance > that 1-octene is monomer

(ii) octene (being total to) polymkeric substance being monomer with 1-octene is manufactured by following polymerization example.

Wherein, (methyl) (p-methylphenyl) methylene radical (cyclopentadienyl) (the prestox octahydro dibenzo fluorenyl) zirconium dichloride used in polymerization example is synthesized by following method.

(6, the synthesis of 6 '-methyl (p-methylphenyl) fulvene)

Under nitrogen atmosphere gas, in 3 mouthfuls of flasks of 200ml, add cyclopentadiene lithium 5.9g(81.9mmol), then add dehydration diethyl ether 100ml and stir.This pulp solution is cooled with an ice bath, drips 4 '-methyl acetophenone 10.0g(74.5mmol).Then stirring at room temperature 20 hours, by the solution diluted hydrochloric acid aqueous solution quenching obtained.Add hexane 50ml, after cleaning this organic layer with water, carry out drying with anhydrous magnesium sulfate.The viscous liquid obtained, except desolventizing, is carried out pillar layer separation with hexane, obtains the object (receipts amount 9.8g, yield 72%) of Red viscous liquid by distillation.

(synthesis of (methyl) (p-methylphenyl) cyclopentadienyl (prestox octahydro dibenzo fluorenyl) methane)

Under nitrogen atmosphere gas, tetrahydrofuran (THF) 80ml and prestox octahydro dibenzo fluorenes 5.0g(12.9mmol is mixed in 3 mouthfuls of flasks of 200ml), after this solution is cooled to-20 DEG C, slowly drip n-Butyl Lithium 8.45ml(1.61M hexane solution, 13.5mmol), stirring at room temperature 5 hours.Then after this reaction solution being cooled to-20 DEG C, slowly 6 are dripped, 6 '-methyl (p-methylphenyl) fulvene 2.6g(14.2mmol), slowly go up to room temperature limit and stir 1 hour in limit.By this reaction solution with after diluted hydrochloric acid aqueous solution quenching, use diethyl ether.After the organic layer saturated sodium bicarbonate aqueous solution obtained, saturated aqueous common salt being cleaned, carry out drying with anhydrous magnesium sulfate.Distillation is except after desolventizing, and the solid recrystallize will obtained with methyl alcohol, obtains the object product (receipts amount 7.2g, yield 98%) of white solid.

< is ester > (iii)

(iii) be 20mm as the kinematic viscosity in 100 DEG C ²the ester of/below s, is used as the diisodecyl adipate (DIDA) of large eight chemical companies of fatty acid ester.

< extreme pressure agent combination >

Extreme pressure agent A: the extreme pressure agent combination as Boron contents being 1,260ppm, uses commercially available extreme pressure agent combination (AFTONCHEMICAL Inc. HITEC307).

Extreme pressure agent B: the extreme pressure agent combination being less than 10ppm as Boron contents, uses commercially available extreme pressure agent combination (AFTONCHEMICAL Inc. HITEC343).

Boron contents in extreme pressure agent combination is measured by ICP Emission Spectrophotometer method.In addition, the Boron contents in lubricating oil composition is tried to achieve from the use level conversion of the Boron contents extreme pressure agent combination and each composition.

[polymerization example 1]

In the stainless steel autoclave of internal volume 2L of fully having carried out nitrogen displacement, load 1-octene 1000ml, by after intrasystem temperature to 65 DEG C, make stagnation pressure be 3MPa-G by supply hydrogen.Then with the n-heptane solution 0.0007mmol of nitrogen press-in triisobutyl aluminium 0.4mmol, two (p-methylphenyl) methylene radical (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride and the hexane solution (MMAO-3A:Tosoh-finechem Inc.) of methylaluminoxane counting 0.35mmol with Al concentration, agitation revolution is set to 400rpm, carries out polymerization in 60 minutes at 70 DEG C.Polymerization is stopped by adding a small amount of Virahol in system.After de-pressure, add normal heptane in the solution taken out after, move to separating funnel, add 1N hydrochloric acid 100ml and vibrate, leave standstill after about 10 minutes, carry out oily water separation.After separated and collected organic layer, washing organic layer, adds a small amount of sodium sulfate in organic layer, leaves standstill and dewaters for about 10 minutes.Then, filter, after removing sodium sulfate, at 135 DEG C, (300mmHg) distillation removing normal heptane and unreacted 1-octene under decompression.The transparent liquid polymer (1-octene polymer) obtained is 83.7g.

The molecular weight (Mn) that the 1-octene polymer (polymkeric substance 1) of the transparent liquid obtained is recorded by gel permeation chromatography is 6,450, and dispersion (Mw/Mn) is 1.67.In addition, the kinematic viscosity recorded by the method recorded in JISK2283 is 300mm in 100 DEG C ²/ s is 3,750mm in 40 DEG C ²/ s, the viscosity index calculated from these kinematic viscosity is 227.

[polymerization example 2]

In the stainless steel autoclave of internal volume 2L of fully having carried out nitrogen displacement, load 1-octene 1000ml, by after intrasystem temperature to 45 DEG C, make stagnation pressure be 3MPa-G by supply hydrogen.Then with the n-heptane solution 0.001mmol of nitrogen press-in triisobutyl aluminium 0.4mmol, two (p-methylphenyl) methylene radical (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride and the hexane solution (MMAO-3A:Tosoh-finechem Inc.) of methylaluminoxane counting 0.50mmol with Al concentration, agitation revolution is set to 400rpm, carries out polymerization in 60 minutes at 50 DEG C.Polymerization is stopped by adding a small amount of Virahol in system.After de-pressure, add normal heptane in the solution taken out after, move to separating funnel, the hydrochloric acid 100ml adding 1N vibrates, and leaves standstill after about 10 minutes, carries out oily water separation.After separated and collected organic layer, washing organic layer, adds a small amount of sodium sulfate in organic layer, leaves standstill and dewaters for about 10 minutes.Then, filter, after removing sodium sulfate, at 135 DEG C, (300mmHg) distillation removing normal heptane and unreacted 1-octene under decompression.The transparent liquid polymer (1-octene polymer) obtained is 107.6g.

The molecular weight (Mn) that the 1-octene polymer (polymkeric substance 2) of the transparent liquid obtained is recorded by gel permeation chromatography is 9,940, and dispersion (Mw/Mn) is 1.64.In addition, the kinematic viscosity recorded by the method recorded in JISK2283 is 640mm in 100 DEG C ²/ s is 9,604mm in 40 DEG C ²/ s, the viscosity index calculated from these kinematic viscosity is 253.

[polymerization example 3]

In the stainless steel autoclave of internal volume 2L of fully having carried out nitrogen displacement, load 1-octene 1000ml, by after the temperature to 35 in system DEG C, make stagnation pressure be 3MPa-G by supply hydrogen.Then with the n-heptane solution 0.001mmol of nitrogen press-in triisobutyl aluminium 0.4mmol, two (p-methylphenyl) methylene radical (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride and the hexane solution (MMAO-3A:Tosoh-finechem Inc.) of methylaluminoxane counting 0.50mmol with Al concentration, agitation revolution is set to 400rpm, carries out polymerization in 60 minutes at 40 DEG C.Polymerization is stopped by adding a small amount of Virahol in system.After de-pressure, add normal heptane in the solution taken out after, move to separating funnel, the hydrochloric acid 100ml adding 1N vibrates, and leaves standstill after about 10 minutes, carries out oily water separation.After separated and collected organic layer, washing organic layer, adds a small amount of sodium sulfate in organic layer, leaves standstill and dewaters for about 10 minutes.Then, filter, after removing sodium sulfate, at 135 DEG C, (300mmHg) distillation removing normal heptane and unreacted 1-octene under decompression.The transparent liquid polymer (1-octene polymer) obtained is 108.8g.

The molecular weight (Mn) that the 1-octene polymer (polymkeric substance 3) of the transparent liquid obtained is recorded by gel permeation chromatography is 11,430, and dispersion (Mw/Mn) is 1.66.In addition, the kinematic viscosity recorded by the method recorded in JISK2283 is 920mm in 100 DEG C ²/ s is 14,720mm in 40 DEG C ²/ s, the viscosity index calculated from these kinematic viscosity is 269.

[polymerization example 4]

In the stainless steel autoclave of internal volume 2L of fully having carried out nitrogen displacement, load normal heptane 300ml and 1-hexene 700ml, by after intrasystem temperature to 75 DEG C, make stagnation pressure be 3MPa-G by supply hydrogen.Then with the n-heptane solution 0.0015mmol of nitrogen press-in triisobutyl aluminium 0.4mmol, two (p-methylphenyl) methylene radical (cyclopentadienyl) (prestox octahydro dibenzo fluorenyl) zirconium dichloride and the hexane solution (MMAO-3A:Tosoh-finechem Inc.) of methylaluminoxane counting 0.75mmol with Al concentration, agitation revolution is set to 400rpm, carries out polymerization in 60 minutes at 80 DEG C.Polymerization is stopped by adding a small amount of Virahol in system.After de-pressure, add normal heptane in the solution taken out after, move to separating funnel, the hydrochloric acid 100ml adding 1N vibrates, and leaves standstill after about 10 minutes, carries out oily water separation.After separated and collected organic layer, washing organic layer, adds a small amount of sodium sulfate in organic layer, leaves standstill and dewaters for about 10 minutes.Then, filter, after removing sodium sulfate, at 135 DEG C, (300mmHg) distillation removing normal heptane and unreacted 1-hexene under decompression.The transparent liquid polymer (1-hexene oligomerization thing) obtained is 333.0g.

The molecular weight (Mn) that the 1-hexene oligomerization thing (polymkeric substance 4) of the transparent liquid obtained records according to gel permeation chromatography is 3,900, and dispersion (Mw/Mn) is 1.73.In addition, the kinematic viscosity recorded by the method recorded in JISK2283 is 319mm in 100 DEG C ²/ s is 6,296mm in 40 DEG C ²/ s, the viscosity index calculated from these kinematic viscosity is 190.

[embodiment 1]

Coordinate the ester of polymkeric substance 1,10.3 quality %, the extreme pressure agent A of 2.7 quality % that obtain in (being total to) polymkeric substance comprising 1-decene of 33.2 quality %, polymerization example 1 as the 56.5 quality % of (being total to) polymkeric substance being monomer with 1-octene, carry out cooperation adjustment, make 40 DEG C of kinematic viscosity be 288 ~ 352mm ²/ s.Represent the lubricating property of the lubricating oil composition obtained in Table 1.

[embodiment 2]

Coordinate the ester of polymkeric substance 2,10.3 quality %, the extreme pressure agent A of 2.7 quality % that obtain in (being total to) polymkeric substance comprising 1-decene of 45.5 quality %, polymerization example 2 as the 44.2 quality % of (being total to) polymkeric substance being monomer with 1-octene, carry out cooperation adjustment, make 40 DEG C of kinematic viscosity be 288 ~ 352mm ²/ s.Represent the lubricating property of the lubricating oil composition obtained in Table 1.

[embodiment 3]

Coordinate the ester of polymkeric substance 3,10.3 quality %, the extreme pressure agent A of 2.7 quality % that obtain in (being total to) polymkeric substance comprising 1-decene of 49.7 quality %, polymerization example 3 as the 40.0 quality % of (being total to) polymkeric substance being monomer with 1-octene, carry out cooperation adjustment, make 40 DEG C of kinematic viscosity be 288 ~ 352mm ²/ s.Represent the lubricating property of the lubricating oil composition obtained in Table 1.

[embodiment 4]

Coordinate the ester of polymkeric substance 2,10.4 quality %, the extreme pressure agent A of 3.5 quality % that obtain in (being total to) polymkeric substance comprising 1-decene of 45.4 quality %, polymerization example 2 as the 44.2 quality % of (being total to) polymkeric substance being monomer with 1-octene, carry out cooperation adjustment, make 40 DEG C of kinematic viscosity be 288 ~ 352mm ²/ s.Represent the lubricating property of the lubricating oil composition obtained in Table 1.

[comparative example 1]

Coordinate the ester of polymkeric substance 1,10.6 quality %, the extreme pressure agent A of 6.0 quality % that obtain in (being total to) polymkeric substance comprising 1-decene of 32.3 quality %, polymerization example 1 as the 57.1 quality % of (being total to) polymkeric substance being monomer with 1-octene, carry out cooperation adjustment, make 40 DEG C of kinematic viscosity be 288 ~ 352mm ²/ s.Represent the lubricating property of the lubricating oil composition obtained in table 2.

[comparative example 2]

Coordinate (being total to) polymkeric substance comprising 1-decene of 23.6 quality %, as SpectrasynUltra-150, the ester of 10.3 quality %, the extreme pressure agent A of 2.7 quality % of ExxonMobil Chemical of 66.1 quality % of polymkeric substance taking 1-decene as monomer, carry out cooperation adjustment, make 40 DEG C of kinematic viscosity be 288 ~ 352mm ²/ s.Represent the lubricating property of the lubricating oil composition obtained in table 2.

[comparative example 3]

Coordinate (being total to) polymkeric substance comprising 1-decene of 34.0 quality %, as ExxonMobil Chemical SpectrasynUltra-300, the ester of 10.3 quality %, the extreme pressure agent A of 2.7 quality % of 55.7 quality % of polymkeric substance taking 1-decene as monomer, carry out cooperation adjustment, make 40 DEG C of kinematic viscosity be 288 ~ 352mm ²/ s.Represent the lubricating property of the lubricating oil composition obtained in table 2.

[comparative example 4]

Coordinate (being total to) polymkeric substance comprising 1-decene of 51.2 quality %, as SpectrasynUltra-1000, the ester of 10.3 quality %, the extreme pressure agent A of 2.7 quality % of ExxonMobil Chemical of 38.5 quality % of polymkeric substance taking 1-decene as monomer, carry out cooperation adjustment, make 40 DEG C of kinematic viscosity be 288 ~ 352mm ²/ s.Represent the lubricating property of the lubricating oil composition obtained in table 2.

[comparative example 5]

Except the extreme pressure agent A in embodiment 1 is changed into except extreme pressure agent B, carry out according to embodiment 1.Represent the lubricating property of the lubricating oil composition obtained in table 2.

[table 1]

	Embodiment 1	Embodiment 2	Embodiment 3	Embodiment 4
					PAO (i) content (quality %)	33.2	45.5	49.7	45.4
Polymkeric substance (ii) content (quality %)	56.5	44.2	40.0	44.2
					Ester content (quality %)	10.3	10.3	10.3	10.4
Extreme pressure agent content (quality %)	2.7	2.7	2.7	3.5
					Boron contents (ppm)	33	33	33	44
40 DEG C of kinematic viscosity (mm ²/s）	325	326	329	328
					-30 DEG C of viscosity (mPas)	In	Low	Low	In
Shear stability (kinematic viscosity reduced rate, %)	2.3	5.8	9.8	5.8
					The defective load stage of micro-spot corrosion	>10	>10	>10	>10

[table 2]

	Comparative example 1	Comparative example 2	Comparative example 3	Comparative example 4	Comparative example 5
						PAO (i) content (quality %)	32.3	236	34.0	512	332
Polymkeric substance (ii) content (quality %)	57.1	66.1	55.7	38.5	565
						Ester content (quality %)	10.6	10.3	10.3	10.3	10.3
Extreme pressure agent content (quality %)	60	27	27	27	27
						Boron contents (ppm)	76	33	33	33	<1
40 DEG C of kinematic viscosity (mm ²/s）	326	315	320	319	325
						-30 DEG C of viscosity (mPas)	High	In	Low	Low	In
Shear stability (kinematic viscosity reduced rate, %)	23	10.4	17.9	51	23
						The defective load stage of micro-spot corrosion	>10	>10	>10	>10	8

Polymerization example 1 ~ 3 be polymerized comparing with the monomer of carbonatoms 6, polymer phase that namely 1-hexene is monomer shown in example 4, viscosity index, i.e. temperature-viscosity excellent.Therefore, the low-temperature viscosity profiles of known lubricating oil composition of the present invention, than the lubricating oil composition excellence of the polymkeric substance that cooperation is monomer with 1-hexene.

With the comparative example 1(table 2 of Boron contents more than 75ppm) compared with, embodiment 1 ~ 4(table 1)-30 DEG C of viscosity excellences.

In addition, with in lubricating oil composition containing the comparative example 2 ~ 4(table 2 of polymkeric substance taking 1-decene as monomer) compared with, embodiment 1 ~ 4(table 1) shear stability excellent.

In addition, the comparative example 5(table 2 low with Boron contents) compared with, embodiment 1 ~ 4(table 1) resistance to micro-pitting corrosion excellent.

Nomenclature

1: rotor head

2: storage opening

3: roller bearing

4: rotor carrier

5: bearing

8: towing pin

9: drive section

10: by driving section

11: generator

12: sun wheel

13: hollow gear

14: hollow gear

15: power electric device shell

16: sun and planet gear carrier

17: vibration damping device

18: fixed guide

Claims

1. a lubricating oil composition, is characterized in that:

Comprise following (i) ~ (iii) and the extreme pressure agent containing boron-containing compound, the kinematic viscosity in 40 DEG C is 288mm ²/ more than s, 352mm ²/ below s, and the boron atom containing more than 33ppm, below 44ppm, be less than 10% according to the kinematic viscosity reduced rate in 40 DEG C after the KRL shear stability test that DIN52350-6 records,

I homopolymer that () 49.7 ~ 33.2 quality % are following or multipolymer, the kinematic viscosity in this homopolymer or multipolymer 100 DEG C is 45mm ²/ below s, more than the 60mol% of structural unit is made up of 1-decene, and acid value is less than 0.1mgKOH/g;

(ii) homopolymer that 40.0 ~ 56.5 quality % are following or multipolymer, the kinematic viscosity in this homopolymer or multipolymer 100 DEG C is 150mm ²/ more than s, 1,500mm ²/ below s, more than the 90mol% of structural unit is made up of 1-octene, and the molecular weight distribution recorded by gel permeation chromatography is less than 1.8;

(iii) kinematic viscosity in 100 DEG C of 5 ~ 15 quality % is 20mm ²the fatty acid ester of/below s,

Wherein, the total of (i) ~ (iii) is set to 100 quality %.

2. lubricating oil composition as claimed in claim 1, is characterized in that:

Kinematic viscosity in the homopolymer of described (ii) or 100 DEG C of multipolymer is 150mm ²/ more than s, 1,200mm ²/ below s.

3. lubricating oil composition as claimed in claim 1 or 2, is characterized in that:

Kinematic viscosity in the homopolymer comprising 1-decene of described (i) or 100 DEG C of multipolymer is 11mm ²/ below s.

4. the application of the lubrication for wind-driven generator gear of the lubricating oil composition according to any one of claims 1 to 3.