JP4283120B2 - α−オレフィン(共)重合体とその用途 - Google Patents
α−オレフィン(共)重合体とその用途 Download PDFInfo
- Publication number
- JP4283120B2 JP4283120B2 JP2004005133A JP2004005133A JP4283120B2 JP 4283120 B2 JP4283120 B2 JP 4283120B2 JP 2004005133 A JP2004005133 A JP 2004005133A JP 2004005133 A JP2004005133 A JP 2004005133A JP 4283120 B2 JP4283120 B2 JP 4283120B2
- Authority
- JP
- Japan
- Prior art keywords
- olefin
- polymer
- cyclopentadienyl
- zirconium dichloride
- tert
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004711 α-olefin Substances 0.000 title claims description 67
- 229920000089 Cyclic olefin copolymer Polymers 0.000 title claims description 30
- 229920000642 polymer Polymers 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 239000003921 oil Substances 0.000 claims description 14
- 239000010689 synthetic lubricating oil Substances 0.000 claims description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 13
- 239000005977 Ethylene Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000010687 lubricating oil Substances 0.000 claims description 10
- 239000002199 base oil Substances 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 239000002480 mineral oil Substances 0.000 claims description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 claims description 6
- 238000005227 gel permeation chromatography Methods 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 238000009826 distribution Methods 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 239000010696 ester oil Substances 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 230000000994 depressogenic effect Effects 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 239000002270 dispersing agent Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- -1 3 Chemical class 0.000 description 55
- 150000001875 compounds Chemical class 0.000 description 20
- 239000003054 catalyst Substances 0.000 description 15
- 238000006116 polymerization reaction Methods 0.000 description 11
- 150000003623 transition metal compounds Chemical class 0.000 description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 150000001336 alkenes Chemical class 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 229920013639 polyalphaolefin Polymers 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000037048 polymerization activity Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- QAHYSATYLGMNPK-UHFFFAOYSA-L [Cl-].[Cl-].C(C)(C)(C)C1=C(C=2CC3=CC(=CC=C3C2C=C1)C(C)(C)C)[Zr+2] Chemical compound [Cl-].[Cl-].C(C)(C)(C)C1=C(C=2CC3=CC(=CC=C3C2C=C1)C(C)(C)C)[Zr+2] QAHYSATYLGMNPK-UHFFFAOYSA-L 0.000 description 5
- FCLIIKLPCZLTFC-UHFFFAOYSA-L [Cl-].[Cl-].C(C)(C)(C)C=1C=C(C=2CC3=CC=C(C=C3C2C1)C(C)(C)C)[Zr+2] Chemical compound [Cl-].[Cl-].C(C)(C)(C)C=1C=C(C=2CC3=CC=C(C=C3C2C1)C(C)(C)C)[Zr+2] FCLIIKLPCZLTFC-UHFFFAOYSA-L 0.000 description 5
- RXTJYZGQYBJVSE-UHFFFAOYSA-L [Cl-].[Cl-].C1C2=CC=CC=C2C2=C1C([Zr+2])=CC=C2 Chemical compound [Cl-].[Cl-].C1C2=CC=CC=C2C2=C1C([Zr+2])=CC=C2 RXTJYZGQYBJVSE-UHFFFAOYSA-L 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 150000004996 alkyl benzenes Chemical class 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical group 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000008040 ionic compounds Chemical class 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 229910010199 LiAl Inorganic materials 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000000654 isopropylidene group Chemical group C(C)(C)=* 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- XMGMFRIEKMMMSU-UHFFFAOYSA-N phenylmethylbenzene Chemical group C=1C=CC=CC=1[C]C1=CC=CC=C1 XMGMFRIEKMMMSU-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- UQJDVLPHTXQTRP-UHFFFAOYSA-N 2,2-bis(heptanoyloxymethyl)butyl heptanoate Chemical compound CCCCCCC(=O)OCC(CC)(COC(=O)CCCCCC)COC(=O)CCCCCC UQJDVLPHTXQTRP-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- OPXDZSAOMXUJQQ-UHFFFAOYSA-N 6,8-dimethyldec-1-ene Chemical compound CCC(C)CC(C)CCCC=C OPXDZSAOMXUJQQ-UHFFFAOYSA-N 0.000 description 1
- NRVFNGMXWMOBFU-UHFFFAOYSA-N 6-methylundec-1-ene Chemical compound CCCCCC(C)CCCC=C NRVFNGMXWMOBFU-UHFFFAOYSA-N 0.000 description 1
- HJGMVXXTWSIOFX-UHFFFAOYSA-N 7-methyldec-1-ene Chemical compound CCCC(C)CCCCC=C HJGMVXXTWSIOFX-UHFFFAOYSA-N 0.000 description 1
- DMFDIYIYBVPKNT-UHFFFAOYSA-N 8-methylnon-1-ene Chemical compound CC(C)CCCCCC=C DMFDIYIYBVPKNT-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- VCFVRHAQERGNFA-UHFFFAOYSA-L C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)(=[Si](C)C)C1C2=CC=CC=C2C=C1 Chemical compound C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)(=[Si](C)C)C1C2=CC=CC=C2C=C1 VCFVRHAQERGNFA-UHFFFAOYSA-L 0.000 description 1
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- TUBHXFUALDXXMB-UHFFFAOYSA-L CC(C)(C)C(C=C1C)=C(C)C1[Zr+2](C1(C)C2=C(CC3=C4C=CC=C3)C4=C3C=CCCC3C2(C)C(C)(C)C(C)(C)C1(C)C)=CC1=CC=CC=C1.[Cl-].[Cl-] Chemical compound CC(C)(C)C(C=C1C)=C(C)C1[Zr+2](C1(C)C2=C(CC3=C4C=CC=C3)C4=C3C=CCCC3C2(C)C(C)(C)C(C)(C)C1(C)C)=CC1=CC=CC=C1.[Cl-].[Cl-] TUBHXFUALDXXMB-UHFFFAOYSA-L 0.000 description 1
- UQCXDRMVQVRUKQ-UHFFFAOYSA-L CC(C)(C)C(C=C1C)=C(C)C1[Zr+2](C1=CC=CC2=C1CC1=CC=CC=C21)=C(C1=CC=CC=C1)C1=CC=C(C)C=C1.[Cl-].[Cl-] Chemical compound CC(C)(C)C(C=C1C)=C(C)C1[Zr+2](C1=CC=CC2=C1CC1=CC=CC=C21)=C(C1=CC=CC=C1)C1=CC=C(C)C=C1.[Cl-].[Cl-] UQCXDRMVQVRUKQ-UHFFFAOYSA-L 0.000 description 1
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- VVNCNSJFMMFHPL-VKHMYHEASA-N D-penicillamine Chemical group CC(C)(S)[C@@H](N)C(O)=O VVNCNSJFMMFHPL-VKHMYHEASA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- NCGQPNAQUYGWMI-UHFFFAOYSA-N [3-heptanoyloxy-2,2-bis(heptanoyloxymethyl)propyl] heptanoate Chemical compound CCCCCCC(=O)OCC(COC(=O)CCCCCC)(COC(=O)CCCCCC)COC(=O)CCCCCC NCGQPNAQUYGWMI-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Lubricants (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
即ち、本発明は
(i)(a)炭素原子数8〜20のα−オレフィンから選ばれる少なくとも1種類の単量体から導かれる構成単位を50〜100モル%の範囲で含有し、(b)エチレンから導かれる構成単位を0〜50モル%の範囲の量で含有し、
(ii)数平均分子量(Mn)が500〜15,000の範囲にあり、
(iii)ゲルパーミエーションクロマトグラフィーによって測定した分子量分布(Mw/Mn)が3以下であり、
(iv)100℃での動粘度が8〜500mm2/sの範囲にあり、
(v)13C−NMR法により求められるα−オレフィン単位連鎖部のトリアッド表示によるアイソタクティシティーが50%以上であることを特徴とするα−オレフィン(共)重合体、それからなる合成潤滑油および潤滑油組成物である。
(式中、PPP(mm)、PPP(mr)、PPP(rr)は、それぞれ13C-NMRスペクトルで観察される頭−尾結合したα−オレフィン単位3連鎖部の2単位目の側鎖第一メチレン基[C3]の面積である。)
上記のようなアイソタクティック構造を有するα−オレフィン(共)重合体の製造の際には、特開平3−193796号公報、特開平6−122718号公報、EP公開 0881236号公報、特開2000−212194号公報、特開平10−087716号公報、WO 01/27124号公報に記載されているような、従来、アイソタクティックプロピレン重合体を製造する際に使用される触媒を用いることができる。
)ジルコニウムジクロリド、ジ(p−tert−ブチルフェニル)メチレン(3−tert−ブチル−2,5−ジメチル−シクロペンタジエニル)(オクタメチルオクタヒドロジベンゾフルオレニル)ジルコニウムジクロリド、(p−トリル)(フェニル)メチレン(3−tert−ブチル−2,5−ジメチル−シクロペンタジエニル)(フルオレニル)ジルコニウムジクロリド、(p−トリル)(フェニル)メチレン(3−tert−ブチル−2,5−ジメチル−シクロペンタジエニル)(2,7−ジtert−ブチルフルオレニル)ジルコニウムジクロリド、(p−トリル)(フェニル)メチレン(3−tert−ブチル−2,5−ジメチル−シクロペンタジエニル)(3,6−ジtert−ブチルフルオレニル)ジルコニウムジクロリド、(p−トリル)(フェニル)メチレン(3−tert−ブチル−2,5−ジメチル−シクロペンタジエニル)(オクタメチルオクタヒドロジベンゾフルオレニル)ジルコニウムジクロリド、ジベンジルメチレン(3,5−ジメチル−シクロペンタジエニル)(フルオレニル)ジルコニウムジクロリド、ジベンジルメチレン(3,5−ジメチル−シクロペンタジエニル)(2,7−ジtert−ブチルフルオレニル)ジルコニウムジクロリド、ジベンジルメチレン(3,5−ジメチル−シクロペンタジエニル)(3,6−ジtert−ブチルフルオレニル)ジルコニウムジクロリド、ジベンジルメチレン(3,5−ジメチル−シクロペンタジエニル)(オクタメチルオクタヒドロジベンゾフルオレニル)ジルコニウムジクロリド、ジフェニルメチレン(3,5−ジメチル−シクロペンタジエニル)(フルオレニル)ジルコニウムジメチル、ジフェニルメチレン(3,5−ジメチル−シクロペンタジエニル)(2,7−ジtert−ブチルフルオレニル)ジルコニウムジメチル、ジフェニルメチレン(3,5−ジメチル−シクロペンタジエニル)(3,6−ジtert−ブチルフルオレニル)ジルコニウムジメチル、ジフェニルメチレン(3,5−ジメチル−シクロペンタジエニル)(オクタメチルオクタヒドロジベンゾフルオレニル)ジルコニウムジメチル、ジフェニルメチレン(3,5−ジメチル−シクロペンタジエニル)(フルオレニル)チタニウムジクロリド、ジフェニルメチレン(3,5−ジメチル−シクロペンタジエニル)(2,7−ジtert−ブチルフルオレニル)チタニウムジクロリド、ジフェニルメチレン(3,5−ジメチル−シクロペンタジエニル)(3,6−ジtert−ブチルフルオレニル)チタニウムジクロリド、ジフェニルメチレン(3,5−ジメチル−シクロペンタジエニル)(オクタメチルオクタヒドロジベンゾフルオレニル)チタニウムジクロリド、ジフェニルメチレン(3,5−ジメチル−シクロペンタジエニル)(フルオレニル)ハフニウムジクロリド、ジフェニルメチレン(3,5−ジメチル−シクロペンタジエニル)(2,7−ジtert−ブチルフルオレニル)ハフニウムジクロリド、ジフェニルメチレン(3,5−ジメチル−シクロペンタジエニル)(3,6−ジtert−ブチルフルオレニル)ハフニウムジクロリド、ジフェニルメチレン(3,5−ジメチル−シクロペンタジエニル)(オクタメチルオクタヒドロジベンゾフルオレニル)ハフニウムジクロリドを例示することができる。
[1]有機金属化合物
本発明のα−オレフィン(共)重合体を製造するために用いられる有機金属化合物として、具体的には下記のような有機金属化合物が用いられる。
オレフィン重合用触媒を形成する[2]有機アルミニウム化合物としては、例えば下記一般式(7)で表される有機アルミニウム化合物、下記一般式(8)で表されるI族金属とアルミニウムとの錯アルキル化物などを挙げることができる。
本発明で用いられる[3] 有機アルミニウムオキシ化合物は、従来公知のアルミノキサンであってもよく、また特開平2−78687号公報に例示されているようなベンゼン不溶性の有機アルミニウムオキシ化合物であってもよい。
遷移金属化合物と反応してイオン対を形成する化合物[4] (以下、「イオン化イオン性化合物」という。)としては、特開平1−501950号公報、特開平1−502036号公報、特開平3−179005号公報、特開平3−179006号公報、特開平3−207703号公報、特開平3−207704号公報、USP−5321106号などに記載されたルイス酸、イオン性化合物、ボラン化合物およびカルボラン化合物などを挙げることができる。
(A)上記のα−オレフィン(共)重合体15〜90重量部と、
(B)鉱物油、合成炭化水素油およびエステル油から選ばれる少なくとも1種からなり、100℃での動粘度が2〜10mm2/sの範囲にある低粘度基油10〜85重量部と、
必要に応じて
(C)清浄分散剤、粘度指数向上剤、酸化防止剤、腐食防止剤、耐摩耗剤、摩擦調整剤、流動点降下剤、防錆剤、消泡剤および極圧剤からなる群より選ばれた少なくとも1種類の添加剤からなる。
流動点降下剤:ポリメタクリレート、アルキルナフタレン等を例示することができ、通常0〜3重量%の範囲で用いられる。
極圧剤:スルフィド類、スルホキシド類、スルホン類、チオホスフィネート類、チオカーボネート類、硫化油脂、硫化オレフィン等のイオウ系極圧剤;リン酸エステル、亜リン酸エステル、リン酸エステルアミン塩、亜リン酸エステルアミン類等のリン酸類;塩素化炭化水素等のハロゲン系化合物などを例示することができる。極圧剤は、必要に応じて0〜15重量%の範囲で用いられる。
耐磨耗剤:二硫化モリブデンなどの無機または有機モリブデン化合物、アルキルメルカプチルボレート等の有機ホウ素化合物;グラファイト、硫化アンチモン、ホウ素化合物、ポリテトラフルオロエチレン等を例示することができる。摩耗防止剤は、必要に応じて0〜3重量%の範囲で用いられる。
酸化防止剤:2,6−ジ-tert-ブチル−4−メチルフェノール等のフェノール系やアミン系の化合物が挙げられる。酸化防止剤は、必要に応じて0〜3重量%の範囲で用いられる。
防錆剤:各種アミン化合物、カルボン酸金属塩、多価アルコールエステル、リン化合物、スルホネートなどの化合物が挙げられる。防錆剤は、必要に応じて0〜3重量%の範囲で用いられる。
消泡剤:ジメチルシロキサン、シリカゲル分散体等のシリコーン系化合物、アルコール系またはエステル系の化合物などを例示することができる。消泡剤は、必要に応じて0〜0.2重量%の範囲で用いられる。
以下、実施例に基づいて本発明をさらに具体的に説明するが、本発明はこれらに限定されるものではない。
数平均分子量(Mn)および分子量分布(Mw/Mn)は、島津製作所製のGPC(クロマトパックC−R4A)を用い以下のようにして測定した。分離カラムとして、TSK G6000H XL、G4000H XL、G3000H XL、G2000H XLを用い、カラム温度を40℃とし、移動相にはテトラヒドロフラン(和光純薬)を用い、展開速度を0.8ml/分とし、試料濃度を0.2重量%とし、試料注入量を200マイクロリットルとし、検出器として示差屈折計を用いた。標準ポリスチレンとしては、東ソー社製のものを用いた。
ポリマーの100℃および40℃での動粘度、粘度指数はJIS K2283に記載の方法により測定、算出した。
ポリマーの耐熱酸化安定性はJIS K2514に記載の方法により、銅−鉄触媒の存在下、165.5℃で96時間攪拌した後の、粘度変化率(100℃動粘度)及び全酸価増加を測定することにより評価した。
実施例1において液状ポリマーとして市販の高粘度PAO(アタクティックポリマー、新日鐵化学(株))を用いたこと以外は実施例1と同様に評価を行った。結果を表1及び表2に示した。
実施例1において液状ポリマーとして市販のエチレン・プロピレン共重合体(三井化学(株)ルーカントHC−40)を用いたこと以外は実施例1と同様に評価を行った。結果を表1及び表2に示した。
Claims (6)
- (i)(a)炭素原子数8〜20のα−オレフィンから選ばれる少なくとも1種類の単量体から導かれる構成単位を50〜100モル%の範囲で含有し、(b)エチレンから導かれる構成単位を0〜50モル%の範囲の量で含有し、
(ii)数平均分子量(Mn)が500〜15,000の範囲にあり、
(iii)ゲルパーミエーションクロマトグラフィーによって測定した分子量分布(Mw
/Mn)が3以下であり、
(iv)100℃での動粘度が8〜500mm2/sの範囲にあり、
(v)13C−NMR法により求められるα−オレフィン単位連鎖部のトリアッド表示に
よるアイソタクティシティーが50%以上であるα−オレフィン(共)重合体からなる合成潤滑油。 - 前記α−オレフィン(共)重合体が液状の重合体である請求項1に記載の合成潤滑油。
- 前記α−オレフィン(共)重合体の13C−NMR法により求められるα−オレフィン単位連鎖部のトリアッド表示によるアイソタクティシティーが70%以上である請求項1または2に記載の合成潤滑油。
- α−オレフィンから選ばれる少なくとも1種類の単量体が1−デセンである請求項1〜3のいずれかに記載の合成潤滑油。
- 上記α−オレフィン(共)重合体の数平均分子量(Mn)が1,000〜5,000の範囲であり、100℃での動粘度が20〜100mm2/sの範囲である請求項1〜4のいずれかに記載の合成潤滑油。
- (A)請求項1〜5のいずれかに記載の合成潤滑油15〜90重量部と、
(B)鉱物油、合成炭化水素油およびエステル油から選ばれる少なくとも1種からなり、100℃での動粘度が2〜10mm2/sの範囲にある低粘度基油10〜85重量部と、必要に応じて
(C)清浄分散剤、粘度指数向上剤、酸化防止剤、腐食防止剤、耐摩耗剤、摩擦調整剤、流動点降下剤、防錆剤、消泡剤および極圧剤からなる群より選ばれた少なくとも1種類の添加剤を含むことを特徴とする潤滑油組成物。
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