CN106565618A - 一种由α‑烯烃直接合成润滑油基础油的催化剂配体及其配合物以及制备方法和应用 - Google Patents
一种由α‑烯烃直接合成润滑油基础油的催化剂配体及其配合物以及制备方法和应用 Download PDFInfo
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- CN106565618A CN106565618A CN201610884863.9A CN201610884863A CN106565618A CN 106565618 A CN106565618 A CN 106565618A CN 201610884863 A CN201610884863 A CN 201610884863A CN 106565618 A CN106565618 A CN 106565618A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 239000003446 ligand Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000002199 base oil Substances 0.000 title claims abstract description 16
- 239000004711 α-olefin Substances 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 title claims abstract description 9
- 239000010687 lubricating oil Substances 0.000 title abstract description 6
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- 239000002608 ionic liquid Substances 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 5
- 238000005829 trimerization reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 150000004696 coordination complex Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- -1 pyrrolidones disulfate Chemical class 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229920013639 polyalphaolefin Polymers 0.000 claims description 4
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 3
- 239000011636 chromium(III) chloride Substances 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000011651 chromium Chemical group 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229950004288 tosilate Drugs 0.000 claims description 2
- 229910052720 vanadium Chemical group 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical group [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000003426 co-catalyst Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 150000003233 pyrroles Chemical class 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- 239000002994 raw material Substances 0.000 description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 150000001336 alkenes Chemical group 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 description 4
- 235000011152 sodium sulphate Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical class CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical class [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 150000004040 pyrrolidinones Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 0 *N1CN(*)CN(*)C1 Chemical compound *N1CN(*)CN(*)C1 0.000 description 1
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical class NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229940125890 compound Ia Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
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- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/04—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
- B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
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- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/069—Aluminium compounds without C-aluminium linkages
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/02—Well-defined hydrocarbons
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- B01J2231/20—Olefin oligomerisation or telomerisation
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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Abstract
本发明属于润滑油制备领域，提供了一种由α‑烯烃直接合成润滑油基础油的催化剂配体的制备方法及应用。本发明的配体具有环状对称结构，采用一步合成，容易控制，收率高。与金属络合容易，得到的金属配合物催化α‑烯烃三聚效率高，催化活性好，聚合时使用离子液体作为溶剂可提高催化活性。
Description
技术领域
本发明属于润滑油制备领域，尤其涉及以α-烯烃为原料直接合成润滑油基础油的方法。
背景技术
随着现代工业的快速发展以及环境问题的日益突出，高性能、环境友好型润滑油得到了广泛关注和应用。合成润滑油基础油因其更长的使用周期和优异性能普遍被用户接受。聚α-烯烃(PAO)是一类广泛应用的合成润滑油基础油，是以单体或混合α-烯烃(C8～C12)为原料在催化剂催化作用下聚合生成分子量较低、比较规则的长链烷烃齐聚物(主要为三聚体、四聚体、五聚体)，再进行加氢饱和精制，获得的长链规则烷烃。聚α-烯烃的直链烷烃骨架结构有利于良好的粘温特性，同时多侧链的异构烷烃骨架又有利于保持较好的低温流动。目前国外制造商普遍采用的原料多为α-癸烯等高纯度烯烃，采用该原料所制备的产品具有粘温性好、抗氧化能力强等特点。
发明内容
本发明提供了一种合适的催化剂及聚合溶剂离子液体，可以在非常温和的条件下进行α-烯烃的低聚，并大大提高了反应产率。
本发明提供的催化体系可以使C6～C12的α-烯烃及其混合物聚合为油状聚合物，此油状聚合物经加氢精制得到性能优良的润滑油基础油。
本发明的第一方面，提供了一种由C6～C12的α-烯烃及其混合物合成润滑油基础油的催化剂配体，该催化剂配体为下式Ⅰ所示的对称结构配体，
其中，R为R1、R2、R3是氢原子、碳原子、卤素；R还可以为直链及支链烷烃。
在本发明第二方面，提供了一种制备式Ⅰ配体的方法，步骤如下：
其中，R的定义如上所述。
具体制备工艺步骤如下：向反应瓶中加入化合物A、化合物B、水及甲醇，反应6h，温度为65℃～75℃，反应结束，冷却至室温，加入石油醚，上层有机层分离后用水洗，然后将黄色液体用硫酸钠干燥，然后过滤，旋干，最后用甲醇洗纯化得白色蜡状固体化合物I。
在本发明第三方面，提供了一种金属配合物，所述金属配合物为由本发明所述配体Ⅰ与金属盐反应得到。所述配合物结构如式Ⅱ所示：
其中，R的定义如上所述；其中M为铝、铁、铬或钒。
在本发明第四方面，提供了一种金属配合物Ⅱ的制备方法，步骤如下：
在惰性气体氛围中，使用无水无氧溶剂(乙醇)，将上述配体Ⅰ与金属盐进行反应，得到所需金属配合物。
所述金属盐包括：AlCl3(THF)3、FeCl3(THF)3、CrCl3(THF)3和VCl3(THF)3。进一步优选为CrCl3(THF)3，所述反应在惰性气体中进行，优选为氮气。
在本发明第五方面，提供了一种式Ⅱ金属配合物作为C6～C12的α-烯烃或混合α-烯烃合成润滑油基础油的催化剂的应用方法。
具体的，在一定反应温度下，使用上述式Ⅱ金属配合物催化α-烯烃聚合。
所述反应温度为-20～20℃，进一步优选为-5～3℃。
具体为将提前干燥好的200ml Schlenk瓶在手套箱转换仓抽换氮气三次，移至手套箱内，称取催化剂于Schlenk瓶内，加入溶剂，再加入烷基铝试剂(MAO)。塞上塞子拿出手套箱，将密封好Schlenk瓶放入低温0℃，先把注射器使用氮气抽充三次吸入无水无氧的1-烯烃，在迅速将其注射到Schlenk瓶中，聚合30min，结束反应，过硅胶短柱，用石油醚淋洗，滤液浓缩得到油状聚烯烃(三聚、四聚等)。
作为优选，烷基铝试剂优选为甲基铝氧烷，与催化剂摩尔比为200～2000。
进一步地，所述的溶剂为离子液体。离子液体包括：1，3-吡啶丙烷磺酸硫酸氢盐离子液体、酸性离子液体N-甲基-2吡咯烷酮硫酸氢盐、N-甲基-2吡咯烷酮对甲苯磺酸盐、吗啉阴离子型碱性离子液体1-丁基3-甲基吗啉盐等。
进一步优选离子液体为：1，3-吡啶丙烷磺酸硫酸氢盐离子液体。
进一步地，将所述油状聚烯烃进行加氢反应，采用已有烯烃饱和加氢技术。得到的油状物溴值小于3g/100g，粘度指数150～200，倾点-72～-43℃，100℃下的运动粘度5.24～21.35mm2/s，作为润滑油基础油。
本发明的有益效果：本发明通过选择合适的反应原料以提供合适的官能团，采用一步法合成具有环状结构的催化剂配体，该反应容易控制，收率高。但合成的该类催化剂最大的缺点是在普通的有机溶剂(如甲苯，氯苯，乙醚，正己烷等)中的溶解度非常差，因此在催化聚合反应过程中绝大部分的催化剂是没有参与反应的，这就导致了催化剂的活性较低。本发明针对这一类催化剂极性较大的特点，通过聚合时采用离子液体作为溶剂，大大提高了催化剂的溶解度，这样，在反应过程中，大量的催化剂都可以参与反应，从而使得催化剂的活性得到很大提高。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明，但不以任何方式限制本发明。
本发明提供了式Ⅰ配体化合物
式中，各基团的定义如上所述。
优选的配体结构包括：
本发明提供了式Ⅱ配合物
式中，各基团的定义如上所述。
式Ⅱ配合物结构包括：
实施例1
配体IA的合成
100ml圆底烧瓶加入0.37g十二胺(2mmol)与0.185ml的福尔马林(甲醛水溶液36％)，再加入0.16ml的水和0.6ml的甲醇，在65℃～75℃下搅拌6小时，将反应冷却至室温，再加入0.6ml的石油醚，上层有机层分离后用水洗，然后将黄色液体用硫酸钠干燥，过滤，旋干，最后用甲醇洗纯化得白色蜡状固体化合物IA。收率为92％。
实施例2
配体IB的合成
100ml圆底烧瓶加入0.32g的2，6-二氯苯胺(2mmol)与0.185ml的福尔马林(甲醛水溶液36％)，再加入0.16ml的水和0.6ml的甲醇，在65℃～75℃下搅拌6小时，将反应冷却至室温，再加入0.6ml的石油醚，上层有机层分离后用水洗，然后将黄色液体用硫酸钠干燥，过滤，旋干，最后用甲醇洗纯化得白色蜡状固体化合物IB。收率为81％。
实施例3
配体IC的合成
100ml圆底烧瓶加入0.34g(2mmol)2-溴苯胺和0.185ml的福尔马林(甲醛水溶液36％)，再加入0.16ml的水和0.6ml的甲醇，在65℃～75℃下搅拌6小时，将反应冷却至室温，再加入0.6ml的石油醚，上层有机层分离后用水洗，然后将黄色液体用硫酸钠干燥，过滤，旋干，最后用甲醇洗纯化得白色蜡状固体化合物IC收率为58％。
实施例4
配合物IICrB的合成
手套箱内，称取0.37g CrCl3(THF)3(1mmol)、0.59g(1mmol)的配体IB于20ml反应瓶中，加入8ml无水乙醇，室温反应过夜。手套箱内过滤至Schlenk瓶内，滤饼用无水乙醚洗，得到的滤渣抽干，得到固体产物ID，产率79％。
其他配合物的合成方法同实施例4，区别在于由不同的配体I(IA、IB、IC)与金属盐：AlCl3(THF)3、FeCl3(THF)3、CrCl3(THF)3和VCl3(THF)3进行组合反应得到，产率在75％～95％之间。
实施例5
将提前干燥好的200ml Schlenk瓶在手套箱转换仓抽换氮气三次，移至手套箱内，称取0.075g(0.1mmol)催化剂IICrC于Schlenk瓶内，加入20ml碱性离子液体1-丁基3-甲基吗啉盐，再加入0.58g的MAO。塞上塞子拿出手套箱，将密封好Schlenk瓶置于低温0℃环境中，先把注射器使用氮气抽充三次吸入无水无氧的反应原料1-己烯，再迅速将其注射到Schlenk瓶中，聚合10min，温度为0℃，结束反应，过硅胶短柱，用石油醚淋洗，滤液浓缩得到油状聚1-己烯(三聚)，催化活性3.0×107g/mol×h。
实施例6
制备方法同实施例5，催化剂为IIFeB，离子液体为1，3-吡啶丙烷磺酸硫酸氢盐，反应原料为1-辛烯，反应时间20min，温度为-5℃，得到油状聚合物，催化活性5.0×106g/mol×h。
实施例7
制备方法同实施例5，催化剂为IIAlA，离子液体为N-甲基-2吡咯烷酮硫酸氢盐，反应原料为1-癸烯，反应时间30min，温度为0℃，得到油状聚合物，催化活性7.0×106g/mol×h。
实施例8
制备方法同实施例5，催化剂为IIVA，离子液体为N-甲基-2吡咯烷酮对甲苯磺酸盐，反应原料为α-12烯，反应时间25min，温度为-5℃，得到油状聚合物，催化活性6.5×106g/mol×h。
实施例9
制备方法同实施例5，催化剂为IICrV，离子液体为1，3-吡啶丙烷磺酸硫酸氢盐离子液体，反应原料为1-辛烯与1-癸烯混合物(质量比50：50)，反应时间25min，温度为0℃，得到油状聚合物，催化活性8.5×106g/mol×h。
实施例10
制备方法同实施例5，催化剂为IICrV，离子液体为1，3-吡啶丙烷磺酸硫酸氢盐离子液体，反应原料为混合α烯烃(质量含量93％以上)，反应时间30min，温度为5℃，得到油状聚合物，催化活性4.5×106g/mol×h。
对比实施例1
制备方法同实施例5，催化剂为IIAlA，不使用离子液体，而用甲苯作为溶剂，反应原料为1-癸烯，反应时间30min，温度为0℃，得到油状聚合物，催化活性3.5×105g/mol×h。
对比实施例2
制备方法同实施例5，催化剂为IIFeB，不使用离子液体，而用甲苯作为溶剂，反应原料为1-辛烯，反应时间20min，温度为-5℃，得到油状聚合物，催化活性2.5×105g/mol×h。
将实施例5-10及对比实施例1-2所得油状聚合物进行加氢精制，得到油状产物，产品的理化性能指标见表1。
表1本发明催化制得的润滑油基础油理化性能
注：
润滑油的运动粘度常用毛细管粘度计来测定，参考标准GB/T265-88石油产品运动粘度测定法和动力粘度计算法。通常将油样装入粘度计，置于水浴或油浴中，测定某温度下油样通过毛细管的时间。油样的运动粘度为时间t和粘度计常数c的乘积。
粘度指数的测定根据国家标准GB/T1995-1998石油产品粘度指数计算法，查表根据公式VI＝[(L-U)/(L-H)]×100计算得到，式中：L—低标准油40℃时的运动粘度mm2/s；H—高标准油40℃时的运动粘度mm2/s；U—油品40℃时的运动粘度，mm2/s；
倾点按照国家标准GB/T3535-2006进行测定；
闪点按照GB/T3635-2008《石油产品闪点和燃点的测定克利夫兰开口杯法》进行测定。
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。
Claims (9)
1.一种由α-烯烃直接合成润滑油基础油的催化剂配体，其特征在于：所述催化剂配体为式Ⅰ所示的环状结构配体
其中，R为R1、R2、R3是氢原子、碳原子、卤素；R还可以为直链及支链烷烃。
2.根据权利要求1所述的由α-烯烃直接合成润滑油基础油的催化剂配体的制备方法，其特征在于：所述制备方法步骤如下：
3.根据权利要求1所述的一种由α-烯烃直接合成润滑油基础油的催化剂配体的金属配合物，其特征在于：所述配合物结构式如Ⅱ式所示
其中：M为铝、铁、铬或钒。
4.根据权利要求3所述的金属配合物的制备方法，其特征在于：所述制备方法为：在惰性气体氛围中，使用无水无氧溶剂，将权利要求1所述配体与金属盐进行反应，制备得到所述的金属配合物。
5.根据权利要求4所述的金属配合物的制备方法，其特征在于：所述金属盐包括：AlCl3(THF)3、FeCl3(THF)3、CrCl3(THF)3和VCl3(THF)3。
6.根据权利要求3所述的金属配合物的应用，其特征在于：所述金属配合物用于催化C6～C12的α-烯烃及其混合物直接合成润滑油基础油。
7.根据权利要求6所述的金属配合物的应用，其特征在于：所述应用方法为：在无水无氧、常压、-20℃～20℃反应温度下，以离子液体作为溶剂，甲基铝氧烷为助催化剂，使用所述金属配合物催化а-烯烃聚合，反应结束后，加入乙醇盐酸溶液将其淬灭，制得三聚、四聚、五聚油状聚α-烯烃产物，其中，甲基铝氧烷与催化剂的摩尔比为200～2000。
8.根据权利要求7所述的金属配合物的应用，其特征在于：所述离子液体包括：1，3-吡啶丙烷磺酸硫酸氢盐离子液体、酸性离子液体N-甲基-2吡咯烷酮硫酸氢盐、N-甲基-2吡咯烷酮对甲苯磺酸盐、吗啉阴离子型碱性离子液体1-丁基3-甲基吗啉盐。
9.根据权利要求7所述的金属配合物的应用，其特征在于：将所述的油状聚а-烯经加氢精制后得到润滑油基础油。
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