CN114395056A - 一种nno-配位的铬金属催化剂的制备及其烯烃聚合的应用 - Google Patents
一种nno-配位的铬金属催化剂的制备及其烯烃聚合的应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 42
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 20
- 239000003446 ligand Substances 0.000 claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
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- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 8
- -1 ethylene, propylene, styrene Chemical class 0.000 claims description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
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- 238000001914 filtration Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
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- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
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- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 2
- NPNAXGKROXIVMJ-UHFFFAOYSA-N (2,3,4-trifluorophenyl)boron Chemical compound [B]C1=CC=C(F)C(F)=C1F NPNAXGKROXIVMJ-UHFFFAOYSA-N 0.000 claims description 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical group CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
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- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 claims description 2
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- BPELEZSCHIEMAE-UHFFFAOYSA-N salicylaldehyde imine Chemical compound OC1=CC=CC=C1C=N BPELEZSCHIEMAE-UHFFFAOYSA-N 0.000 description 4
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
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- 229910021562 Chromium(II) fluoride Inorganic materials 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
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- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
本发明涉及一种NNO‑配位的铬金属催化剂的制备及其在烯烃聚合中的应用。本发明引入了NNO‑三齿配体骨架,设计合成了新型NNO‑配位的铬金属催化剂,通过改变配体的取代基,能够方便地调控该结构金属催化剂的空间效应和电子效应,从而实现不同的催化性能。本发明报道的新型NNO‑配位的铬金属催化剂活性高、耐高温性能好,且仅需极少量的MAO助催化剂,降低了成本,具有原始创新性,能够增强我国聚烯烃高分子材料技术市场的竞争能力。
Description
技术领域
本发明涉及配位聚合金属催化剂的制备及其在聚烯烃领域中的应用。
背景技术
随着我国日新月异的科技发展,高分子材料在民用、科研、军用、医疗等多个领域已成为一种不可替代的重要材料。其中聚烯烃材料是高分子材料中应用最广、生产量最大的一种重要的高分子材料。在过去的几十年中,聚烯烃已成为产量最大的合成聚合物。聚烯烃领域是高度技术驱动的,很大程度上依赖于金属络合物催化剂的快速发展,水杨醛亚胺化合物简单、易得且可修饰,因此已被广泛用作前过渡金属配合物和后过渡金属配合物的配体,用于烯烃聚合(Chem.Rev.,2011,111,2363-2449)。例如,Fujita(J.Am.Chem.Soc.,2001,123,6847-6856)和Coates(J.Am.Chem.Soc.,2001,123,5134-5135)报道的前过渡金属钛和锆水杨醛亚胺催化剂在合成新型聚烯烃方面表现出高活性、活性聚合行为和立体规整性控制。而Grubbs(Science,2000,287,460-462)开发的后过渡金属镍水杨醛亚胺催化剂对极性单体具有很强的耐受性,可用于制备功能性聚烯烃。铬金属络合物,无论是非均相的还是均相的,都是最重要的聚烯烃催化剂之一,由于它们在乙烯聚合和齐聚反应中的广泛应用而受到越来越多的关注。然而,含有水杨醛亚胺配体的铬基配合物很少见。2000年,吉布森曾报了这一配体用于合成铬基催化剂,但只获得了低到中等的活性(通常小于105g(PE)·mol-1(Cr)·h-1)(J.Chem.Soc.,Dalton Trans.,2000,1969-1971)。后来,同一研究小组将这种NO双齿配体扩展到NNO-三齿配位体系,并通过高通量筛选(HTS)方法发现了一种活性很高的NNO-Cr催化剂(Chem.Commun.,2002,1038-1039)。NNO-Cr配合物具有庞大的色氨酸基取代基和一个额外的吡啶基-N给体,活性为6.97×106g(PE)·mol-1(Cr)·h-1·bar-1。然而,其需要大量的MAO(相对于Cr的2200当量)来维持高活性,并且在50℃只产生低分子量聚乙烯(MW≈1200g·mol-1)。因此,开发需要少量MAO助催化剂的新型金属催化剂是非常需要的,但具有挑战性。
本发明报道了一种NNO-配位的铬金属催化剂的制备方法及其在烯烃聚合中的应用。本发明引入了NNO-三齿配位水杨醛亚胺骨架,设计合成了新型NNO-三齿配体负载的铬的金属催化剂,通过改变取代基,能够方便地调控该模型金属催化剂的立体效应和电子效应,从而实现不同的催化性能,制备多种结构和多种性能的聚烯烃高分子材料。本发明报道的新型NNO-三齿配位负载的铬的金属化合物的具有原料廉价易得、合成路线简单,产品收率高的特点,在少量MAO的存在下(100-600摩尔当量),铬金属催化剂表现出极高的活性,达1.18×108g(PE)·mol-1(Cr)·h-1,所制备聚乙烯具有高度线性和高分子量。此外,本发明报道了的NNO-配位的铬金属催化剂具有极好耐高温性能。因此,本发明报道的新型NNO-配位的铬金属催化剂活性高、耐高温性能好,且仅需极少量的MAO助催化剂,降低了成本,具有原始创新性,能够增强我国聚烯烃高分子材料技术市场的竞争能力。
发明内容
本发明的目的是提供一种NNO-配位的铬金属催化剂的制备方法及其在烯烃聚合中的应用。
本发明提供一种式(I)所示NNO-配位的铬金属催化剂:
其中,R1选自甲基,乙基,氢,异丙基,氯,氟;R2选自甲基、甲氧基、氢、叔丁基,氯。
优选的,本发明金属化合物选自如下任意一种配合物:
Cr1:L1CrCl2,L1=2,6-(iPr)2-C6H3-NH-C6H4-N=C-3,5-(tBu)2-C6H2-OH
Cr2:L2CrCl2,L2=2,6-(Me)2-C6H3-NH-C6H4-N=C-3,5-(tBu)2-C6H2-OH
Cr3:L3CrCl2,L3=2,6-(H)2-C6H3-NH-C6H4-N=C-3,5-(tBu)2-C6H2-OH
Cr4:L4CrCl2,L4=2,6-(F)2-C6H3-NH-C6H4-N=C-3,5-(tBu)2-C6H2-OH
Cr5:L5CrCl2,L5=2,6-(Me)2-C6H3-NH-C6H4-N=C-3,5-(H)2-C6H2-OH
Cr6:L6CrCl2,L6=2,6-(Me)2-C6H3-NH-C6H4-N=C-3,5-(Cl)2-C6H2-OH
本发明提供了上述NNO-配位的铬金属催化剂的制备方法,包括以下步骤:
将2-N-2,6-R1-C6H4-1-NH2和1摩尔当量的不同取代的水杨醛3,5-R2-C6H2-2-OH-1-CHO在甲醇中混合,加入1mol%当量对甲苯磺酸作为催化剂,室温搅拌得到NNO-三齿配体L1-L6。在氮气氛围下,先1摩尔当量的NNO-三齿配体L1-L6和1.1摩尔当量的NaH在THF中搅拌过夜,再加入1摩尔当量的CrCl3(THF)3在THF中搅拌过夜,除去溶剂后,加入良溶剂溶解并过滤,将良溶剂滤液除去溶剂后加入不良溶剂洗涤得到所述的NNO-配位的铬金属催化剂Cr1-Cr6。
所述良溶剂选自二氯甲烷、甲苯,不良溶剂选自正己烷、乙醚。
本发明还提供了上述NNO-配位的铬金属催化剂(Cr1-Cr6)在催化烯烃聚合反应中的应用。
上述应用中,所述烯烃为乙烯、丙烯、苯乙烯、1-丁烯、1-己烯和1-辛烯中的一种或几种。
上述催化剂还加有助催化剂,助催化剂为三五氟苯基硼、三苯碳鎓四(五氟苯基)硼酸盐、铝氧烷、烷基铝和氯化烷基铝中的一种或几种。所述铝氧烷为甲基铝氧烷、乙基铝氧烷或异丁基铝氧烷;烷基铝为三甲基铝、三乙基铝、三异丁基铝或三正己基铝;氯化烷基铝为一氯二乙基铝、倍半一氯二乙基铝或二氯化乙基铝。
在上述聚合反应中,聚合温度为0-180℃,聚合压力为0.1-5MPa,聚合溶剂为甲苯、己烷、庚烷中的一种或几种。
本发明提供了NNO-配位的铬金属催化剂的制备,以及该化合物催化烯烃聚合的应用。本发明报道的新型NNO-配位的铬金属催化剂活性高、耐高温性能好,且仅需极少量的MAO助催化剂,降低了成本,具有原始创新性,能够增强我国聚烯烃高分子材料技术市场的竞争能力。
附图说明
图1为配合物Cr2的晶体结构图;图2为配合物Cr4的晶体结构图。
具体实施方式
通过实施例进一步说明本发明,但本发明并不限于此。本发明的实施例可以使本专业的技术人员更全面的理解本发明。
下述实施例中所使用的实验方法如无特殊说明,均为常规方法。
本发明中2-N-2,6-iPr-C6H4-1-NH2,2-N-2,6-Me-C6H4-1-NH2,2-N-2,6-H-C6H4-1-NH2,2-N-2,6-Cl-C6H4-1-NH2根据文献J.Mater.Chem.C,2017,5,6202-6209中报道的方法合成。
以下以具体的实施例描述本发明。
实施例1、化合物L1的制备
在氮气中加入1溴-2-硝基苯(12.8g,64mmol)、2,6-二异丙基苯胺(11.34g,64mmol)、CS2CO3(26g,80mmol)、Pd2(dba)3(0.72g,0.8mmol)和BINAP(1.32g,2mmol)。将反应混合物加热至回流过夜,然后冷却至室温。反应混合物用水洗涤。水相用DCM(3×200mL)提取,组合有机相用硫酸镁干燥。脱除溶剂后,用柱层析(SiO2,DCM:PE,2:1)纯化得到黄色固体。得到的黄色固体在SnCl2(91g,0.48mol、189.62g/mol)、盐酸(100mL)和无水乙醇(80mL)加入125mL的氮气氛围中进行还原反应。加热回流过夜,溶液逐渐变为橘黄色。降温至室温后,形成一块黄绿色固体。用2M氢氧化钠将反应混合物碱化至pH=8。水相用乙酸乙酯(3×100mL)提取,组合有机相用硫酸镁干燥。除去溶剂后,柱层析(SiO2,DCM:PE,1:1)纯化,得到薰衣草色固体。得到的薰衣草色固体(6g,约28.2mmol)在甲醇120mL溶液中与3.5-二叔丁基水杨醛(7.03g,30mmol)在对甲苯磺酸催化下反应。混合物在室温下搅拌18h,最后得到棕黄色悬浊液。所得悬浊液经过过滤,得到一部分产品为深黄色固体沉淀物。滤液在真空中抽至干燥,得到配体L1。1H NMR(400MHz,CDCl3):δ13.47(s,1H,OH),8.79(s,1H,N=CH),7.49(d,J=2.3Hz,1H,Ar-H),7.35–7.29(m,2H,Ar-H),7.27(d,J=7.8Hz,2H,Ar-H),7.12(dd,J=7.8,1.1Hz,1H,Ar-H),7.02(t,J=7.7Hz,1H,Ar-H),6.75(t,J=7.7Hz,1H,Ar-H),6.26(d,J=8.1Hz,1H,Ar-H),5.87(s,1H,N-H),3.28–3.14(m,2H,CHMe2),1.48(s,9H,CMe3),1.38(s,9H,CMe3),1.19(dd,J=11.9,6.7Hz,12H,CHMe2).13C NMR(400MHz,CDCl3):δ163.36(N=CH),158.14,147.92,142.21,141.00,137.20,135.44,134.59,128.19,127.95,127.56,126.92,124.00,118.89,118.09,117.66,112.16,35.29,34.39,31.65,29.55,28.51,24.91,23.12.Anal.Calcd for C33H44N2O:C,81.77;H,9.15;N,5.78.Found:C,81.56;H,9.02;N,5.56.
实施例2、化合物L2的制备
实验步骤同实施例1,得到配体L2。1H NMR(400MHz,CDCl3):δ13.41(s,1H,OH),8.75(s,1H,N=CH),7.48(d,J=1.5Hz,1H,Ar-H),7.30(d,J=2.2Hz,1H,Ar-H),7.18–7.10(m,4H,Ar-H),7.03(t,J=7.7Hz,1H,Ar-H),6.77(t,J=7.5Hz,1H,Ar-H),6.25(d,J=8.1Hz,1H,Ar-H),5.84(s,1H,N-H),2.25(s,6H,Ar-Me),1.47(s,9H,CMe3),1.36(s,9H,CMe3).13CNMR(400MHz,CDCl3):δ163.58(N=CH),158.10,141.02,140.48,138.29,137.22,136.78,135.29,128.68,128.21,127.97,127.00,126.34,118.90,118.28,117.99,112.06,35.29,34.38,31.64,29.60,18.51.Anal.Calcd for C29H36N2O:C,81.27;H,8.47;N,6.54.Found:C,81.35;H,8.27;N,6.43.
实施例3、化合物L3的制备
实验步骤同实施例1,得到配体L3。1H NMR(400MHz,CDCl3):δ13.22(s,1H,OH),8.67(s,1H,N=CH),7.48(d,J=2.2Hz,1H,Ar-H),7.36–7.30(m,3H,Ar-H),7.27(d,J=7.7Hz,1H,Ar-H),7.22–7.11(m,4H,Ar-H),7.01(t,J=7.7Hz,1H,Ar-H),6.92(t,J=7.5Hz,1H,Ar-H),6.23(s,1H,N-H),1.47(s,9H,CMe3),1.35(s,9H,CMe3).13C NMR(400MHz,CDCl3):δ164.63(N=CH),158.07,142.27,141.07,137.72,137.65,137.21,129.52,128.42,127.56,127.08,122.17,120.33,119.97,119.09,118.78,115.05,35.27,34.36,31.62,29.56.Anal.Calcd for C27H32N2O:C,80.96;H,8.05;N,6.99.Found:C,80.79;H,8.01;N,6.74.
实施例4、化合物L4的制备
实验步骤同实施例1,得到配体L4。1H NMR(400MHz,CDCl3):δ13.22(s,1H,OH),8.72(s,1H,N=CH),7.49(d,J=2.4Hz,1H,Ar-H),7.29(d,J=2.4Hz,1H,Ar-H),7.18–7.05(m,3H,Ar-H),6.99(t,J=7.9Hz,2H,Ar-H),6.93(td,J=7.7,1.2Hz,1H,Ar-H),6.70(dd,J=8.1,0.9Hz,1H,Ar-H),5.91(s,1H,N-H),1.49(s,9H,CMe3),1.36(s,9H,CMe3).13C NMR(400MHz,CDCl3):δ164.75(N=CH),158.81(d,J=5.5Hz),158.13,156.35(d,J=5.3Hz),141.05,137.78,137.19(d,J=8.0Hz),128.48,127.55,127.17,124.37(t,J=9.6Hz),120.48,119.00(d,J=15.5Hz),118.71(d,J=15.9Hz),113.93,112.16(d,J=5.8Hz),111.99(d,J=5.8Hz),35.28,34.37,31.62,29.58.Anal.Calcd for C27H30F2N2O:C,74.29;H,6.93;N,6.42.Found:C,74.35;H,6.79;N,6.33.
实施例5、化合物L5的制备
实验步骤同实施例1,得到配体L5。1H NMR(400MHz,CDCl3):δ13.11(s,1H,OH),8.75(s,1H,N=CH),7.47(dd,J=7.7,1.6Hz,1H,Ar-H),7.44–7.36(m,1H,Ar-H),7.18–7.08(m,4H,Ar-H),7.08–6.93(m,3H,Ar-H),6.78(td,J=7.6,1.2Hz,1H,Ar-H),6.25(dd,J=8.1,1.1Hz,1H,Ar-H),5.79(s,1H,N-H),2.23(s,6H,Ar-Me).13C NMR(400MHz,CDCl3):δ162.21(N=CH),160.93,140.62,138.04,136.70,134.92,133.30,132.41,128.66,128.38,126.40,119.77,119.49,118.22,118.02,117.29,112.26,18.42.Anal.Calcd for C21H20N2O:C,79.72;H,6.37;N,8.85.Found:C,79.55;H,6.28;N,8.71.
实施例6、化合物L6的制备
实验步骤同实施例1,得到配体L6。1H NMR(400MHz,CDCl3):δ14.05(s,1H,OH),8.68(s,1H,N=CH),7.48(s,1H,Ar-H),7.37(s,1H,Ar-H),7.14(s,5H,Ar-H),6.80(s,1H,Ar-H),6.28(s,1H,Ar-H),5.73(s,1H,N-H),2.23(s,6H,Me).13C NMR(400MHz,CDCl3):δ159.46(N=CH),155.47,140.98,137.55,136.66,133.38,132.63,129.80,129.47,128.71,126.61,123.92,122.80,120.96,118.17,112.84,18.39.Anal.Calcd for C21H18Cl2N2O:C,65.47;H,4.71;N,7.27.Found:C,65.41;H,4.53;N,7.05.
实施例7、催化剂Cr1的制备
取3.05mmol/1.31g配体L1和磁力搅拌子于100mL史莱克瓶A中,抽真空半小时,换三次氮气,转移至手套箱,称取0.08g/1.1摩尔当量NaH加入瓶中。-78℃下加入适量THF,室温搅拌12小时,然后加入CrCl3(THF)3,搅拌过夜后除去溶剂,加入二氯甲烷溶解并过滤,将二氯甲烷滤液除去溶剂后加入乙醚洗涤得到所述的NNO-配位的铬金属催化剂Cr1 1.82g,产率90%。FT-IR(KBr disk,cm-1):3377,2960,1611,1585,1548,1529,1460,1422,1386,1332,1316,1199,1168,1134,1110,1010,965,922,796,786,755,506,452,417.Anal.Calcdfor C37H51Cl2CrN2O2:C,65.48;H,7.57;N,4.13.Found:C,65.46;H,7.52;N,4.02.ESICalcd.for[M-2Cl-THF+OH+Na]+575.27,found 575.29.
实施例8、催化剂Cr2的制备
实验步骤同实施例7,得到绿色粉末Cr2化合物1.7g,产率92%。FT-IR(KBr,cm-1):3484,2953,1608,1584,1529,1460,1391,1316,1251,1197,1169,1111,1010,970,909,807,781,756,510,468,424.Anal.Calcd for C33H43Cl2CrN2O2:C,63.66;H,6.96;N,4.50.Found:C,63.65;H,6.68;N,4.33.ESI Calcd.for[M-2Cl-THF+OH+Na]+519.21,found 519.23.
实施例9、催化剂Cr3的制备
实验步骤同实施例7,得到棕色固体Cr3化合物1.55g,产率87%。FT-IR(KBr,cm-1):3380,2955,1611,1585,1545,1527,1493,1422,1386,1321,1250,1199,1166,1108,1007,965,805,761,750,505,456,419.Anal.Calcd for C31H39Cl2CrN2O2:C,62.62;H,6.61;N,4.71.Found:C,62.49;H,6.38;N,4.65.ESI Calcd.for[M-2Cl-THF+OH+Na]+491.18,found491.20.
实施例10、催化剂Cr4的制备
实验步骤同实施例7,得到绿色粉末Cr4化合物1.66g,产率88%。FT-IR(KBr,cm-1):3170,2954,1602,1585,1549,1528,1492,1424,1388,1314,1253,1198,1166,1109,1002,960,804,762,747,505,413.Anal.Calcd for C31H37Cl2CrF2N2O2:C,59.05;H,5.91;N,4.44.Found:C,59.22;H,5.79;N,4.18.ESI Calcd.for[M-2Cl-THF+OH+Na]+527.16,found527.18.
实施例11、催化剂Cr5的制备
实验步骤同实施例7,得到棕色固体Cr5化合物1.37g,产率90%。FT-IR(KBr disk,cm-1):3406,1610,1584,1536,1440,1392,1326,1212,1179,1149,1108,1012,927,910,796,776,750,505,456,422.Anal.Calcd for C25H27Cl2CrN2O2:C,58.83;H,5.33;N,5.49.Found:C,58.78;H,5.26;N,5.31.ESI Calcd.for[M-2Cl-THF+OH+Na]+407.08,found 407.10.
实施例12、催化剂Cr6的制备
实验步骤同实施例7,得到棕色固体Cr6化合物1.65g,产率95%。FT-IR(KBr,cm-1):3349,1607,1586,1520,1460,1393,1327,1235,1170,1111,1013,966,814,770,758,508,456,423.Anal.Calcd for C25H25Cl4CrN2O2:C,51.84;H,4.35;N,4.84.Found:C,51.82;H,4.32;N,4.63.ESI Calcd.for[M-2Cl-THF+OH+Na]+475.01,found 475.03.
实施例13、Cr1催化乙烯聚合
将高压反应釜连接到高压管线以除去氮气并置换乙烯三次,乙烯氛围下加入甲苯195mL,用注射器注入和助催化剂0.26mL,使Al/Cr=200,乙烯压力40atm,温度80℃。在手套箱中,在装有磁搅拌子的10mL样品瓶中加入1.36mg(2μmol)Cr1配合物,用注射器取5mL无水氯苯,加入样品瓶搅拌5分钟使其溶解,用注射器将催化剂氯苯溶液注入主催加料罐,用45atm的氮气压力将主催化剂压入,(总体积200mL),在80℃下,保持40atm的乙烯压力,,剧烈搅拌反应2min。用10mL盐酸酸化的乙醇溶液中和反应液,得到聚合物沉淀,用乙醇洗涤,聚合物真空干燥过夜,称量。聚合活性:17.3×106g·mol-1(Cr)·h-1。聚合物Mw=144kg·mol-1,Mw/Mn=2.3。
实施例14、Cr2催化乙烯聚合
聚合反应过程与反应条件同实施例13,所用催化剂为Cr2。聚合活性:118×106g·mol-1(Cr)·h-1。聚合物Mw=389kg·mol-1,Mw/Mn=1.6。
实施例15、Cr3催化乙烯聚合
聚合反应过程与反应条件同实施例13,所用催化剂为Cr3。聚合活性:24.0×106g·mol-1(Cr)·h-1。聚合物Mw=223kg·mol-1,Mw/Mn=4.2。
实施例16、Cr4催化乙烯聚合
聚合反应过程与反应条件同实施例13,所用催化剂为Cr4。聚合活性:26.3x106g·mol-1(Cr)·h-1。聚合物Mw=180kg·mol-1,Mw/Mn=10。
实施例17、Cr5催化乙烯聚合
聚合反应过程与反应条件同实施例13,所用催化剂为Cr5。聚合活性:2.85x106g·mol-1(Cr)·h-1。聚合物Mw=456kg·mol-1,Mw/Mn=19。
实施例18、Cr6催化乙烯聚合
聚合反应过程与反应条件同实施例13,所用催化剂为Cr6。聚合活性:2.70x106g·mol-1(Cr)·h-1。聚合物Mw=534kg·mol-1,Mw/Mn=19。
实施例19、Cr2催化乙烯聚合
将高压反应釜连接到高压管线以除去氮气并置换乙烯三次,乙烯氛围下加入甲苯195mL,用注射器注入和助催化剂0.26mL,使Al/Cr=200,乙烯压力5atm,温度80℃。在手套箱中,在装有磁搅拌子的10mL样品瓶中加入1.24mg(2μmol)Cr2配合物,用注射器取5mL无水氯苯,加入样品瓶搅拌5分钟使其溶解,用注射器将催化剂氯苯溶液注入主催加料罐,用6atm的氮气压力将主催化剂压入,(总体积200mL),在80℃下,保持5atm的乙烯压力,,剧烈搅拌反应2min。用10mL盐酸酸化的乙醇溶液中和反应液,得到聚合物沉淀,用乙醇洗涤,聚合物真空干燥过夜,称量。聚合活性:7.05×106g·mol-1(Cr)·h-1。聚合物Mw=149kg·mol-1,Mw/Mn=1.8。
实施例20、Cr2催化乙烯聚合
将高压反应釜连接到高压管线以除去氮气并置换乙烯三次,乙烯氛围下加入甲苯195mL,用注射器注入和助催化剂0.26mL,使Al/Cr=200,乙烯压力20atm,温度80℃。在手套箱中,在装有磁搅拌子的10mL样品瓶中加入1.24mg(2μmol)Cr2配合物,用注射器取5mL无水氯苯,加入样品瓶搅拌5分钟使其溶解,用注射器将催化剂氯苯溶液注入主催加料罐,用23atm的氮气压力将主催化剂压入,(总体积200mL),在80℃下,保持20atm的乙烯压力,,剧烈搅拌反应2min。用10mL盐酸酸化的乙醇溶液中和反应液,得到聚合物沉淀,用乙醇洗涤,聚合物真空干燥过夜,称量。聚合活性:49.5×106g·mol-1(Cr)·h-1。聚合物Mw=200kg·mol-1,Mw/Mn=1.8。
实施例21、Cr2催化乙烯聚合
将高压反应釜连接到高压管线以除去氮气并置换乙烯三次,乙烯氛围下加入甲苯195mL,用注射器注入和助催化剂0.26mL,使Al/Cr=200,乙烯压力40atm,温度20℃。在手套箱中,在装有磁搅拌子的10mL样品瓶中加入1.24mg(2μmol)Cr2配合物,用注射器取5mL无水氯苯,加入样品瓶搅拌5分钟使其溶解,用注射器将催化剂氯苯溶液注入主催加料罐,用45atm的氮气压力将主催化剂压入,(总体积200mL),在20℃下,保持40atm的乙烯压力,,剧烈搅拌反应2min。用10mL盐酸酸化的乙醇溶液中和反应液,得到聚合物沉淀,用乙醇洗涤,聚合物真空干燥过夜,称量。聚合活性:40.5×106g·mol-1(Cr)·h-1。聚合物Mw=15.0kg·mol-1,Mw/Mn=3.1。
实施例22、Cr2催化乙烯聚合
将高压反应釜连接到高压管线以除去氮气并置换乙烯三次,乙烯氛围下加入甲苯195mL,用注射器注入和助催化剂0.26mL,使Al/Cr=200,乙烯压力40atm,温度60℃。在手套箱中,在装有磁搅拌子的10mL样品瓶中加入1.24mg(2μmol)Cr2配合物,用注射器取5mL无水氯苯,加入样品瓶搅拌5分钟使其溶解,用注射器将催化剂氯苯溶液注入主催加料罐,用45atm的氮气压力将主催化剂压入,(总体积200mL),在60℃下,保持40atm的乙烯压力,,剧烈搅拌反应2min。用10mL盐酸酸化的乙醇溶液中和反应液,得到聚合物沉淀,用乙醇洗涤,聚合物真空干燥过夜,称量。聚合活性:66.0×106g·mol-1(Cr)·h-1。聚合物Mw=120kg·mol-1,Mw/Mn=2.6。
实施例23、Cr2催化乙烯聚合
将高压反应釜连接到高压管线以除去氮气并置换乙烯三次,乙烯氛围下加入甲苯195mL,用注射器注入和助催化剂0.26mL,使Al/Cr=200,乙烯压力40atm,温度100℃。在手套箱中,在装有磁搅拌子的10mL样品瓶中加入1.24mg(2μmol)Cr2配合物,用注射器取5mL无水氯苯,加入样品瓶搅拌5分钟使其溶解,用注射器将催化剂氯苯溶液注入主催加料罐,用45atm的氮气压力将主催化剂压入,(总体积200mL),在100℃下,保持40atm的乙烯压力,,剧烈搅拌反应2min。用10mL盐酸酸化的乙醇溶液中和反应液,得到聚合物沉淀,用乙醇洗涤,聚合物真空干燥过夜,称量。聚合活性:101×106g·mol-1(Cr)·h-1。聚合物Mw=246kg·mol-1,Mw/Mn=1.8。
实施例24、Cr2催化乙烯聚合
将高压反应釜连接到高压管线以除去氮气并置换乙烯三次,乙烯氛围下加入甲苯195mL,用注射器注入和助催化剂0.13mL,使Al/Cr=100,乙烯压力40atm,温度80℃。在手套箱中,在装有磁搅拌子的10mL样品瓶中加入1.24mg(2μmol)Cr2配合物,用注射器取5mL无水氯苯,加入样品瓶搅拌5分钟使其溶解,用注射器将催化剂氯苯溶液注入主催加料罐,用45atm的氮气压力将主催化剂压入,(总体积200mL),在80℃下,保持40atm的乙烯压力,,剧烈搅拌反应2min。用10mL盐酸酸化的乙醇溶液中和反应液,得到聚合物沉淀,用乙醇洗涤,聚合物真空干燥过夜,称量。聚合活性:103×106g·mol-1(Cr)·h-1。聚合物Mw=383kg·mol-1,Mw/Mn=1.9。
实施例25、Cr2催化乙烯聚合
将高压反应釜连接到高压管线以除去氮气并置换乙烯三次,乙烯氛围下加入甲苯195mL,用注射器注入和助催化剂0.39mL,使Al/Cr=300,乙烯压力40atm,温度80℃。在手套箱中,在装有磁搅拌子的10mL样品瓶中加入1.24mg(2μmol)Cr2配合物,用注射器取5mL无水氯苯,加入样品瓶搅拌5分钟使其溶解,用注射器将催化剂氯苯溶液注入主催加料罐,用45atm的氮气压力将主催化剂压入,(总体积200mL),在80℃下,保持40atm的乙烯压力,,剧烈搅拌反应2min。用10mL盐酸酸化的乙醇溶液中和反应液,得到聚合物沉淀,用乙醇洗涤,聚合物真空干燥过夜,称量。聚合活性:105×106g·mol-1(Cr)·h-1。聚合物Mw=139kg·mol-1,Mw/Mn=2.2。
实施例26、Cr2催化乙烯聚合
将高压反应釜连接到高压管线以除去氮气并置换乙烯三次,乙烯氛围下加入甲苯195mL,用注射器注入和助催化剂0.78mL,使Al/Cr=600,乙烯压力40atm,温度80℃。在手套箱中,在装有磁搅拌子的10mL样品瓶中加入1.24mg(2μmol)Cr2配合物,用注射器取5mL无水氯苯,加入样品瓶搅拌5分钟使其溶解,用注射器将催化剂氯苯溶液注入主催加料罐,用45atm的氮气压力将主催化剂压入,(总体积200mL),在80℃下,保持40atm的乙烯压力,,剧烈搅拌反应2min。用10mL盐酸酸化的乙醇溶液中和反应液,得到聚合物沉淀,用乙醇洗涤,聚合物真空干燥过夜,称量。聚合活性:72.8×106g·mol-1(Cr)·h-1。聚合物Mw=44.0kg·mol-1,Mw/Mn=2.9。
Claims (8)
2.权利要求1所述NNO-配位的铬金属催化剂的制备方法,包括如下步骤:
在氮气氛围下,将1摩尔当量的NNO-三齿配体和1.1摩尔当量的NaH在THF中搅拌过夜,再加入1摩尔当量的CrCl3(THF)3搅拌过夜,除去溶剂后,加入良溶剂溶解并过滤,将良溶剂滤液除去溶剂后加入不良溶剂洗涤得到所述的NNO-配位的铬金属催化剂。
3.根据权利要求2所述的制备方法,其特征在于:所述良溶剂选自二氯甲烷、甲苯,不良溶剂选自正己烷、乙醚。
4.一种进行烯烃聚合反应的方法,其特征在于:反应的催化剂为权利要求1所述NNO-配位的铬金属催化剂。
5.根据权利要求4所述的方法,其特征在于:所述烯烃为乙烯、丙烯、苯乙烯、1-丁烯、1-己烯和1-辛烯中的一种或几种。
6.根据权利要求4所述的方法,其特征在于:所述催化剂还加有助催化剂,助催化剂为三五氟苯基硼、三苯碳鎓四(五氟苯基)硼酸盐、铝氧烷、烷基铝和氯化烷基铝中的一种或几种。
7.根据权利要求6所述的方法,其特征在于:所述铝氧烷为甲基铝氧烷、乙基铝氧烷或异丁基铝氧烷;烷基铝为三甲基铝、三乙基铝、三异丁基铝或三正己基铝;氯化烷基铝为一氯二乙基铝、倍半一氯二乙基铝或二氯化乙基铝。
8.根据权利要求4所述的方法,其特征在于:聚合温度为0-180℃,聚合压力为0.1-5Mpa,聚合溶剂为甲苯、己烷、庚烷中的一种或几种。
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