CN112142799A - 一种吡啶二亚胺铁系配合物及其制备方法与应用 - Google Patents
一种吡啶二亚胺铁系配合物及其制备方法与应用 Download PDFInfo
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- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 38
- -1 Pyridine diimine iron complex Chemical class 0.000 title claims abstract description 35
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000005977 Ethylene Substances 0.000 claims abstract description 45
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 21
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003446 ligand Substances 0.000 claims abstract description 19
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 238000010992 reflux Methods 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229920000098 polyolefin Polymers 0.000 claims abstract description 11
- GWHOGODUVLQCEB-UHFFFAOYSA-N pyridine-2,6-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=N1 GWHOGODUVLQCEB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000019253 formic acid Nutrition 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000010689 synthetic lubricating oil Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000012452 mother liquor Substances 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000012046 mixed solvent Substances 0.000 claims abstract description 4
- 239000011949 solid catalyst Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 18
- 239000004698 Polyethylene Substances 0.000 claims description 9
- WHJXGGISJBFSJJ-UHFFFAOYSA-N iron;pyridine Chemical compound [Fe].C1=CC=NC=C1 WHJXGGISJBFSJJ-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 229910052794 bromium Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 150000001448 anilines Chemical class 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 17
- 238000003780 insertion Methods 0.000 abstract description 5
- 230000037431 insertion Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000006384 oligomerization reaction Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000010687 lubricating oil Substances 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229920013639 polyalphaolefin Polymers 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- IBOFHQZUWNBWNJ-UHFFFAOYSA-N iron;pyridine-2,3-diimine Chemical compound [Fe].N=C1C=CC=NC1=N IBOFHQZUWNBWNJ-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000000314 lubricant Substances 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 229910020257 Cl2F2 Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- YLMFXCIATJJKQL-UHFFFAOYSA-N 2-bromo-4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1Br YLMFXCIATJJKQL-UHFFFAOYSA-N 0.000 description 1
- XRAKCYJTJGTSMM-UHFFFAOYSA-N 2-chloro-4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1Cl XRAKCYJTJGTSMM-UHFFFAOYSA-N 0.000 description 1
- SETOTRGVPANENO-UHFFFAOYSA-N 4-fluoro-2-iodoaniline Chemical compound NC1=CC=C(F)C=C1I SETOTRGVPANENO-UHFFFAOYSA-N 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QILSFLSDHQAZET-UHFFFAOYSA-N diphenylmethanol Chemical compound C=1C=CC=CC=1C(O)C1=CC=CC=C1 QILSFLSDHQAZET-UHFFFAOYSA-N 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
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Abstract
本发明公开了一种吡啶二亚胺铁系配合物及其制备方法与应用,其制备方法包括:以甲醇作溶剂,甲酸作为催化剂,将邻位二苯甲基取代的苯胺与2,6‑吡啶二羰酰氯混合,开启搅拌,于温度条件进行回流反应后,除去溶剂,得粗产品,然后再用C2H5OH/CH2Cl2混合溶剂重结晶析出固体沉淀,过滤干燥得到吡啶二亚胺配体;在氮气保护下,以四氢呋喃为溶剂,将吡啶二亚胺配体与FeCl2·4H2O混合,开启搅拌,在室温下反应,将所得沉淀物过滤,母液在真空中除去溶剂,残余物用***洗涤数次,得到深绿色固体催化剂。本发明提供的吡啶二亚胺铁系配合物,大大提高了乙烯***速率,使得该配合物表现出很好的催化活性,配合物在聚烯烃合成润滑油生产过程中具有很高的应用价值。
Description
技术领域
本发明属于润滑油合成技术领域,涉及聚烯烃合成润滑油技术,具体涉及一种吡啶 二亚胺铁系配合物及其制备方法与应用。
背景技术
随着润滑油规格的日益严格,对高质量润滑油的需求呈增长趋势,对合成油的需求 量明显增长。合成油中的聚α-烯烃(PA0)是市场需求增长最快的品种之一。国外PAO的生产主要采用乙烯齐聚法生产,国内目前主要采用石蜡裂解法生产,其产品质量与国外 相比有较大的差距。
PA0合成油是由α-烯烃在催化剂作用下聚合(主要是三聚体、四聚体和五聚体)而获 得的一类长链烷烃。PAO合成润滑油与同黏度矿物油相比,具有操作温度范围宽、黏温性能好、倾点低、黏度指数高、蒸发损失小、对添加剂感受性好、具有优良的高温热氧 化安定性等特点,此外PA0合成油还有结焦少、无毒和对皮肤有浸润作用等特点,因此 获得广泛的应用,市场需求量逐年增长。
目前,对通过乙烯齐聚法生产PAO合成润滑油的研究重点在于新型催化剂的开发。但是现有的催化剂其活性还是远达不到市场的要求,难以达到乙烯的低聚要求,低聚产 物分布的不是很理想,难以得到低分子量、高支化的油状聚合物,这导致润滑油的性能 提升出现了瓶颈。
所以,急需一种新型催化剂和技术来解决这些问题。
发明内容
发明目的:为了克服现有技术中存在的不足,提供一种吡啶二亚胺铁系配合物及其 制备方法以及将其应用于催化乙烯聚合,用来制备聚烯烃润滑油。
技术方案:为实现上述目的,本发明提供一种吡啶二亚胺铁系配合物,其特征在于, 所述配合物的结构为:
其中,R=Br,Cl,I。
本发明的吡啶二亚胺铁系配合物在亚胺氮原子连接的芳环的一侧邻位上引入大位 阻二苯甲基基团,因其具有较大的位阻效应,能够有效的保护金属中心,增加基态活性中的不稳定性,加快了乙烯***速率,提高了配合物的催化活性。同时,在亚胺氮原子 连接的芳环的另一侧邻位引入卤素原子-Cl、-Br、-I,并且在芳环的对位引入强吸电子基 团-F,吸电子基团的取代基降低了金属中心的电子云密度,亲电性增强,也有利于乙烯 单体的配位***,提高催化活性。此外,该类吡啶二亚胺铁系配合物配体的邻位取代基 的整***阻较低,可以实现乙烯低聚,并具有高活性、高选择性以及理想的低聚产物分 布,得到低分子量、高支化的油状聚合物。
一种吡啶二亚胺铁系配合物的制备方法,包括如下步骤:
S1:吡啶二亚胺配体的制备:
以甲醇作溶剂,甲酸作为催化剂,将邻位二苯甲基取代的苯胺与2,6-吡啶二羰酰氯 混合,开启搅拌,于温度条件进行回流反应后,除去溶剂,得粗产品,然后再用 C2H5OH/CH2Cl2混合溶剂重结晶析出固体沉淀,过滤干燥得到吡啶二亚胺配体;
上述合成反应式如下:
其中,R=Br,Cl,I。
S2:吡啶二亚胺铁系配合物的制备:
在氮气保护下,以四氢呋喃为溶剂,将吡啶二亚胺配体与FeCl2·4H2O混合,开启搅拌,在室温下反应,将所得沉淀物过滤,母液在真空中除去溶剂,残余物用***洗涤 数次,得到深绿色固体催化剂。
上述合成反应式如下:
其中,R=Br,Cl,I。
进一步的,所述步骤S1中苯胺为2-氯-4-氟-6-二苯甲基苯胺、2-溴-4-氟-6-二苯甲基 苯胺和2-碘-4-氟-6-二苯甲基苯胺中的一种或多种。
进一步的,所述步骤S1中苯胺与2,6-吡啶二羰酰氯以2.0:1.0的摩尔比混合,回流反应的温度条件为45℃~55℃,回流反应的时间为12~24小时。
进一步的,所述步骤S2中吡啶二亚胺配体与FeCl2·4H2O以1.0:1.1~1.0:1.5的摩尔比混合,反应时间为12~24小时。
进一步的,所述步骤S1中催化剂甲酸的用量为2,6-吡啶二羰酰氯摩尔量的0.02~0.1 倍。
一种吡啶二亚胺铁系配合物的应用方法,所述配合物用于催化乙烯的聚合,制备聚 烯烃合成润滑油。
本发明涉及的吡啶二亚胺铁系配合物,由于大位阻基团二苯甲基、强吸电子基团-F 以及卤素原子的存在,改变了金属中心周围的电子云密度以及位阻效应,加快了乙烯单体***进程,在助催化剂MMAO的活化下,表现出很高的催化活性。同时,对聚合温 度以及聚合压力进行调控,可以得到高支化度得聚合物。
进一步的,所述配合物催化乙烯聚合的方法为:将配合物与助催化剂(MMAO)组 成复合催化体系,控制催化剂用量、反应温度、乙烯压力、反应时间,催化乙烯聚合, 得到低分子量、高支化度的油状聚乙烯。
进一步的,所述配合物与助催化剂的摩尔比为1:200~1:2000。
进一步的,所述催化剂用量为5~400μmol,反应温度为0~80℃,乙烯压力 0.1~0.8MPa,反应时间为10~120分钟。
有益效果:本发明与现有技术相比,具备如下优点:
1、本发明提供的吡啶二亚胺铁系配合物,在亚胺氮原子连接的芳环的一侧邻位上引入大位阻二苯甲基基团,在亚胺氮原子连接的芳环的另一侧邻位引入卤素原子-Cl、 -Br、-I,并且在芳环的对位引入强吸电子基团-F,大大提高了乙烯***速率,使得该配 合物表现出很好的催化活性;
2、本发明提供的吡啶二亚胺铁系配合物的邻位取代基位阻较低,在一定的聚合条件下,可以实现乙烯低聚,并具有高活性、高选择性以及理想的低聚产物分布,能够得 到低分子量、高支化的油状聚合物;
3、本发明提供的吡啶二亚胺铁系配合物作为催化剂应用到催化乙烯的聚合,制备聚烯烃合成润滑油,该催化剂在助催化剂MMAO的活化下,在催化乙烯聚合过程中表现 出很高的催化活性,可达4.37×106g PE/(mol Fe h)。此外,得到的无定形油状聚乙烯 具有很高的支化度,可达158个支链/1000C。因此,该类配合物在聚烯烃合成润滑油生 产过程中具有很高的应用价值。
具体实施方式
下面结合具体实施例,进一步阐明本发明,应理解这些实施例仅用于说明本发明而 不用于限制本发明的范围,在阅读了本发明之后,本领域技术人员对本发明的各种等价形式的修改均落于本申请所附权利要求所限定的范围。
首先需要说明的是,实施例中所使用的原料和试剂:所有金属有机反应都在N2保护下进行,溶剂均经干燥除氧处理,THF(分析纯),用分子筛预干燥后在N2气氛 下加入Na回流,使用前蒸出。甲苯经分子筛脱水,在N2保护下加入Na回流,使用前 蒸出。***,用分子筛预干燥后在N2气氛下加入Na回流,使用前蒸出。高纯N2和聚合级乙烯单体使用前除氧干燥。无水乙醇,甲醇,二氯甲烷以及甲酸直接使用。2,6- 吡啶二羰酰氯,二苯基甲醇,2-氯-4-氟苯胺,2-溴-4-氟苯胺,2-碘-4-氟苯胺,FeCl2·4H2O 均为市售产品。
实施例1:
(1)吡啶二亚胺配体L1的合成:
将2-氯-4-氟-6-二苯甲基苯胺(1.25g,4.0mmol)与2,6-吡啶二羰酰氯(0.41g,2.0mmol)溶于20ml甲醇中,在搅拌下加入甲酸0.2ml,于55℃下回流反应24小时后, 除去溶剂,得粗产品,然后再用C2H5OH/CH2Cl2(v/v=15:2)混合溶剂重结晶析出固 体沉淀,过滤干燥得到配体1.36g,产率为86%。
1H NMR(400MHz,CDCl3,ppm):δ8.20(d,J=8.4Hz,2H,Py-m-H),8.10(t,1H, Py-p-H),7.68(s,2H,Aryl-H),7.30(m,8H,Ph-H),7.21(m,4H,Ph-H),7.14(m,8H,Ph-H), 6.75(s,2H,Aryl-H),5.48(s,2H,-CHPh2).13C NMR(100MHz,CDCl3,ppm):δ163.3, 152.6,150.5,144.9(C=N),143.4,139.5,136.2,129.9,129.2,128.2,126.2,116.6,114.6, 56.1(-CHPh2).Anal.Calc.for C45H29Cl4F2N3(791.54):C,68.28;H,3.69;N,5.31.Found: C,68.27;H,3.71;N,5.34.
其反应式如下:
(2)吡啶二亚胺铁系配合物C1的合成:
在氮气保护下,向100ml干燥的反应管中加入配体L1(0.79g,1.0mmol)与 FeCl2·4H2O(0.20g,1.0mmol),再加入四氢呋喃30ml作为溶剂,开启搅拌,在室温下 反应24小时,加入正将所得沉淀物过滤,母液在真空中除去溶剂,残余物用***(3×15 ml)洗涤,得到配合物C1(0.86g,产率94%)。
Anal.Calc.for C45H29Cl6F2N3Fe(918.29):C,58.86;H,3.18;N,4.58.Found:C,58.84;H, 3.19;N,4.57.
其反应式如下:
实施例2:
(1)吡啶二亚胺配体L2的合成:
将2-溴-4-氟-6-二苯甲基苯胺(1.42g,4.0mmol)与2,6-吡啶二羰酰氯(0.41g,2.0mmol)溶于20ml甲醇中,在搅拌下加入甲酸0.2ml,于45℃下回流反应12小时后, 除去溶剂,得粗产品,然后再用C2H5OH/CH2Cl2(v/v=15:2)混合溶剂重结晶析出固 体沉淀,过滤干燥得到配体1.44g,产率82%。
1H NMR(400MHz,CDCl3,ppm):δ8.17(d,J=8.1Hz,2H,Py-m-H),8.07(t,1H, Py-p-H),7.57(s,2H,Aryl-H),7.23-7.06(m,20H,Ph-H),6.81(s,2H,Aryl-H),5.53(s,2H, -CHPh2).13C NMR(100MHz,CDCl3,ppm):δ166.1,155.7,153.8,148.2(C=N),146.2, 142.1,139.7,134.2,132.1,130.2,129.2,119.6,117.3,55.6(-CHPh2).Anal.Calc.forC45H29Br2Cl2F2N3(880.45):C,61.39;H,3.32;N,4.77.Found:C,61.37;H,3.33;N,4.78.
其反应式如下:
(2)吡啶二亚胺铁系配合物C2的合成:
在氮气保护下,向100ml干燥的反应管中加入配体L2(0.88g,1.0mmol)与 FeCl2·4H2O(0.20g,1.0mmol),再加入四氢呋喃30ml作为溶剂,开启搅拌,在室温下 反应12小时,加入正将所得沉淀物过滤,母液在真空中除去溶剂,残余物用***(3×15 ml)洗涤,得到配合物C2(0.92g,产率91%)。
Anal.Calc.for C45H29Br2Cl4F2N3Fe(1007.20):C,53.66;H,2.90;N,4.17.Found:C,53.67;H,2.89;N,4.14.
其反应式如下:
实施例3:
(1)吡啶二亚胺配体L3的合成:
将2-碘-4-氟-6-二苯甲基苯胺(1.61g,4.0mmol)与2,6-吡啶二羰酰氯(0.41g,2.0mmol)溶于20ml甲醇中,在搅拌下加入甲酸0.2ml,于50℃下回流反应18小时后, 除去溶剂,得粗产品,然后再用C2H5OH/CH2Cl2(v/v=15:2)混合溶剂重结晶析出固 体沉淀,过滤干燥得到配体1.62g,产率83%。
1H NMR(400MHz,CDCl3,ppm):δ8.22(d,J=8.2Hz,2H,Py-m-H),8.14(t,1H, Py-p-H),7.71(s,2H,Aryl-H),7.35(m,8H,Ph-H),7.26(m,4H,Ph-H),7.17(m,8H,Ph-H), 6.79(s,2H,Aryl-H),5.57(s,2H,-CHPh2).13C NMR(100MHz,CDCl3,ppm):δ164.1, 153.7,151.0,146.2(C=N),144.5,141.3,137.4,131.1,129.2,127.3,124.2,114.6,112.7, 56.1(-CHPh2).Anal.Calc.for C45H29I2Cl2F2N3(974.45):C,55.47;H,3.00;N,4.31.Found: C,55.49;H,2.98;N,4.30.
其反应式如下:
(2)吡啶二亚胺铁系配合物C3的合成:
在氮气保护下,向100ml干燥的反应管中加入配体L3(0.97g,1.0mmol)与 FeCl2·4H2O(0.20g,1.0mmol),再加入四氢呋喃30ml作为溶剂,开启搅拌,在室温下 反应18小时,加入正将所得沉淀物过滤,母液在真空中除去溶剂,残余物用***(3×15 ml)洗涤,得到配合物C3(1.02g,产率93%)。
Anal.Calc.for C47H29I2Cl4F2N3Fe(1101.20):C,49.08;H,2.65;N,3.82.Found:C,49.10; H,2.63;N,3.84.
其反应式如下:
实施例4:
本实施例中将实施例1获取的吡啶二亚胺铁系配合物C1作为催化剂用于乙烯的聚合,制备聚烯烃合成润滑油。具体的制备过程为:
将带有搅拌子的100ml聚合瓶真空-氮气循环置换数次,在氮气氛围下,加入50ml甲苯,再充入乙烯,使乙烯充分吸收至饱和,乙烯压力0.1MPa,然后用带有刻度的注 射器将助催化剂MMAO按照n(Al)/n(Fe)=1000(其中n(Fe)=5μmol)加入反应瓶中,调节 乙烯通入量,使聚合体系的压力维持在1.0atm,设定体系温度为60℃,剧烈搅拌15min 后,用注射器加入配合物C1的甲苯溶液(2ml,5μmol),在60℃下,将乙烯聚合反应 进行10min后,用质量分数为10%的酸化甲醇溶液(100ml)终止反应,震荡沉淀出聚 合产物,过滤沉淀物,用无水甲醇充分洗涤,50℃下真空干燥12小时,得到产品9.28g, 活性3.71×106g PE/(mol Feh)。
实施例5:
本实施例中将实施例2获取的吡啶二亚胺铁系配合物C2作为催化剂用于乙烯的聚合,制备聚烯烃合成润滑油。具体的制备过程为:
将带有搅拌子的100ml聚合瓶真空-氮气循环置换数次,在氮气氛围下,加入50ml甲苯,再充入乙烯,使乙烯充分吸收至饱和,乙烯压力0.8MPa,然后用带有刻度的注 射器将助催化剂MMAO按照n(Al)/n(Fe)=1000(其中n(Fe)=5μmol)加入反应瓶中,调节 乙烯通入量,使聚合体系的压力维持在1.0atm,设定体系温度为80℃,剧烈搅拌15min 后,用注射器加入配合物C2的甲苯溶液(2ml,5μmol),在80℃下,将乙烯聚合反应 进行120min后,用质量分数为10%的酸化甲醇溶液(100ml)终止反应,震荡沉淀出 聚合产物,过滤沉淀物,用无水甲醇充分洗涤,50℃下真空干燥12小时,得到产品9.85 g,活性3.94×106g PE/(mol Feh)。
实施例6:
本实施例中将实施例3获取的吡啶二亚胺铁系配合物C3作为催化剂用于乙烯的聚合,制备聚烯烃合成润滑油。具体的制备过程为:
将带有搅拌子的100ml聚合瓶真空-氮气循环置换数次,在氮气氛围下,加入50ml甲苯,再充入乙烯,使乙烯充分吸收至饱和,乙烯压力0.4MPa,然后用带有刻度的注 射器将助催化剂MMAO按照n(Al)/n(Fe)=1000(其中n(Fe)=5μmol)加入反应瓶中,调 节乙烯通入量,使聚合体系的压力维持在1.0atm,设定体系温度为30℃,剧烈搅拌15min 后,用注射器加入配合物C3的甲苯溶液(2ml,5μmol),在30℃下,将乙烯聚合反应 进行80min后,用质量分数为10%的酸化甲醇溶液(100ml)终止反应,震荡沉淀出聚 合产物,过滤沉淀物,用无水甲醇充分洗涤,50℃下真空干燥12小时,得到产品10.93 g,活性4.37×106g PE/(mol Feh)。
实施例7:
本实施例中对实施例1-3获取的产品性能进行测试,具体如下:
通过高温GPC对上述产品的相对分子量、分子量分布进行了测定,并通过对产品核磁分析确定其支化度。此外,对产品的运动粘度以及倾点进行了测定,详见表1。
表1产品性能测试结果
可见,催化剂C1、C2和C3具备很好的催化活性,另外在实施例4-6以及其他大量 实验证明,在本发明催化剂(吡啶二亚胺铁系配合物)催化乙烯聚合,制备聚烯烃润滑 油的过程中,将新制的吡啶二亚胺铁系配合物与助催化剂MMAO以摩尔比1:200~1:2000 的组成复合催化体系,催化剂用量为5~400μmol(根据催化剂活性而定),控制反应温 度为0~80℃,乙烯压力0.1~0.8MPa,反应时间为10~120分钟,在催化乙烯聚合过程中 表现出较高的催化活性,最高可达4.37×106g PE/(mol Fe h)。此外,得到的无定形油 状聚乙烯具有很高的支化度,最高可达158个支链/1000C。这些性能在现有产品的基础 上都有了明显提升。
Claims (10)
2.根据权利要求1所述的一种吡啶二亚胺铁系配合物的制备方法,其特征在于,包括如下步骤:
S1:吡啶二亚胺配体的制备:
以甲醇作溶剂,甲酸作为催化剂,将邻位二苯甲基取代的苯胺与2,6-吡啶二羰酰氯混合,开启搅拌,于温度条件进行回流反应后,除去溶剂,得粗产品,然后再用C2H5OH/CH2Cl2混合溶剂重结晶析出固体沉淀,过滤干燥得到吡啶二亚胺配体;
S2:吡啶二亚胺铁系配合物的制备:
在氮气保护下,以四氢呋喃为溶剂,将吡啶二亚胺配体与FeCl2·4H2O混合,开启搅拌,在室温下反应,将所得沉淀物过滤,母液在真空中除去溶剂,残余物用***洗涤数次,得到深绿色固体催化剂。
3.根据权利要求2所述的一种吡啶二亚胺铁系配合物的制备方法,其特征在于,所述步骤S1中苯胺为2-氯-4-氟-6-二苯甲基苯胺、2-溴-4-氟-6-二苯甲基苯胺和2-碘-4-氟-6-二苯甲基苯胺中的一种或多种。
4.根据权利要求2所述的一种吡啶二亚胺铁系配合物的制备方法,其特征在于,所述步骤S1中苯胺与2,6-吡啶二羰酰氯以2.0:1.0的摩尔比混合,回流反应的温度条件为45℃~55℃,回流反应的时间为12~24小时。
5.根据权利要求2所述的一种吡啶二亚胺铁系配合物的制备方法,其特征在于,所述步骤S2中吡啶二亚胺配体与FeCl2·4H2O以1.0:1.1~1.0:1.5的摩尔比混合,反应时间为12~24小时。
6.根据权利要求2所述的一种吡啶二亚胺铁系配合物的制备方法,其特征在于,所述步骤S1中催化剂甲酸的用量为2,6-吡啶二羰酰氯摩尔量的0.02~0.1倍。
7.一种吡啶二亚胺铁系配合物的应用方法,其特征在于,所述配合物用于催化乙烯的聚合,制备聚烯烃合成润滑油。
8.根据权利要求7所述的一种吡啶二亚胺铁系配合物的应用方法,其特征在于,所述配合物催化乙烯聚合的方法为:将配合物与助催化剂组成复合催化体系,控制催化剂用量、反应温度、乙烯压力、反应时间,催化乙烯聚合,得到低分子量、高支化度的油状聚乙烯。
9.根据权利要求8所述的一种吡啶二亚胺铁系配合物的应用方法,其特征在于,所述配合物与助催化剂的摩尔比为1:200~1:2000。
10.根据权利要求8所述的一种吡啶二亚胺铁系配合物的应用方法,其特征在于,所述催化剂用量为5~400μmol,反应温度为0~80℃,乙烯压力0.1~0.8MPa,反应时间为10~120分钟。
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CN112876517A (zh) * | 2021-01-22 | 2021-06-01 | 黄志怀 | 一种对位硝基取代的α-二亚胺铁催化剂及其制备方法 |
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CN114656581A (zh) * | 2022-03-28 | 2022-06-24 | 安徽泽升科技有限公司 | 一种电子效应调控的吡啶二亚胺铁催化剂的制备方法 |
CN114656581B (zh) * | 2022-03-28 | 2022-12-06 | 安徽泽升科技有限公司 | 一种电子效应调控的吡啶二亚胺铁催化剂的制备方法 |
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