CN113087825B - 一种基于蒽骨架双金属催化剂的制备及其烯烃高温溶液聚合的应用 - Google Patents
一种基于蒽骨架双金属催化剂的制备及其烯烃高温溶液聚合的应用 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 125000005577 anthracene group Chemical group 0.000 title claims abstract description 20
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000010528 free radical solution polymerization reaction Methods 0.000 title abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 38
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 15
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 6
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- FJDQFPXHSGXQBY-UHFFFAOYSA-L Cs2CO3 Substances [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 5
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 4
- -1 ethylene, propylene, styrene Chemical class 0.000 claims description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 239000013110 organic ligand Substances 0.000 claims description 4
- YGIUYXOOOGQGIS-UHFFFAOYSA-N 1,8-dichloroanthracene Chemical compound C1=CC(Cl)=C2C=C3C(Cl)=CC=CC3=CC2=C1 YGIUYXOOOGQGIS-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 229910052735 hafnium Chemical group 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 claims description 3
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- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 2
- 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 group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Chemical group 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical group CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 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
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000010992 reflux Methods 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 17
- 239000005977 Ethylene Substances 0.000 abstract description 17
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 abstract description 10
- 238000007334 copolymerization reaction Methods 0.000 abstract description 9
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- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
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- 238000003780 insertion Methods 0.000 abstract description 4
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- SFFFIHNOEGSAIH-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene;ethene Chemical compound C=C.C1C2CCC1C=C2 SFFFIHNOEGSAIH-UHFFFAOYSA-N 0.000 abstract 1
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 abstract 1
- 229920001903 high density polyethylene Polymers 0.000 abstract 1
- 239000004700 high-density polyethylene Substances 0.000 abstract 1
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 12
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- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 2
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- 150000002466 imines Chemical class 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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Abstract
本发明涉及一种基于蒽骨架双金属催化剂的制备及其烯烃高温溶液聚合的应用。本发明引入了蒽骨架，提高了催化剂的耐高温性能，通过改变中心金属和骨架构型，能够方便地调控该模型金属催化剂的立体效应以及电子效应，实现不同的催化性能；可用于乙烯均聚合制备高密度聚乙烯，乙烯/1‑辛烯共聚制备聚烯烃弹性体，乙烯/降冰片烯共聚制备环烯烃共聚物。本发明报道的新型基于蒽骨架胺金属催化剂具有制备简单、活性高、耐高温、共聚性能好的特点，适用于烯烃高温溶液聚合制备聚烯烃弹性体和环烯烃共聚物，并且制备的聚烯烃弹性体具有高的分子量达Mw＝890kg·mol‑1，环烯烃共聚物具有高的共聚单体插入率降达45mol％。因此，本发明报道的基于蒽骨架双金属催化剂具有原始创新性，能够增强我国参与国际高端聚烯烃高分子材料技术市场的竞争能力。
Description
技术领域
本发明涉及一种基于蒽骨架双金属催化剂的制备及其烯烃高温溶液聚合的应用。
背景技术
高分子材料是现代科学技术和社会发展的支柱，在尖端科技、国防建设和国民经济各个领域已成为不可缺少的重要材料。其中聚烯烃是发展最快、产量最大、用途极广的合成树脂。工业化的聚乙烯催化剂有Ziegler-Natta型催化剂(DE Pat889229(1953)；IT Pat545332(1956)和IT Pat 536899(1955))，Phillips型催化剂(Belg.Pat.530617(1955))和茂金属型催化剂(W.Kaminsky,Metalorganic Catalysts for Synthesis andPolymerization,Berlin:Springer,1999)，以及近年来发展的过渡金属配合物型的高效乙烯均聚和共聚催化剂。耐高温催化剂是高温溶液聚合制备聚烯烃弹性体POE的关键。这其中最为重要的是陶氏化学报道的限定几何构型催化剂(EP0416815A2)。2011年Jerzy研究组和2012年Philip P研究组分别报道了胺基亚胺锆、铪配合物催化烯烃聚合(Organometallics2011,30,251–262；Organometallics 2012,31,6244-6251)，催化乙烯与辛烯共聚具有极高的活性，并且催化剂耐高温，适用于高温溶液聚合工艺。双金属催化剂能够通过协同催化效应，提高催化剂的催化性能(Organometallics 2020,39,3268-3274)。
本发明报道了一种基于蒽骨架双金属催化剂的制备方法及其在烯烃聚合中的应用。本发明引入了蒽骨架，提高了催化剂的耐高温性能，通过改变中心金属和骨架构型，能够方便地调控该模型金属催化剂的立体效应以及电子效应，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。本发明报道的新型基于蒽骨架胺金属催化剂具有制备简单、活性高、耐高温、共聚性能好的特点，适用于烯烃高温溶液聚合制备聚烯烃弹性体和环烯烃共聚物，并且制备的聚烯烃弹性体具有更高的分子量，环烯烃共聚物具有更高的共聚单体插入率。因此，本发明报道的基于蒽骨架双金属催化剂具有原始创新性，能够增强我国参与国际高端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基于蒽骨架双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)所示基于蒽骨架双金属催化剂：
其中，M选自钛、锆、铪；X选自甲基、氯、二甲基胺基。
优选的，本发明基于蒽骨架双金属催化剂选自如下任意一种配合物：
syn-Hf2:M＝Hf,X＝NMe2；syn-Zr2:M＝Zr,X＝NMe2；syn-Ti2:M＝Ti,X＝NMe2。
本发明提供了上述基于蒽骨架双金属催化剂的制备方法，包括以下步骤：
在氮气氛围下，Pd(OAc)2(89mg,0.4mmol),dppf(0.456g,0.8mmol),1,8-二氯蒽(1.24g,5mmol),2-甲氧基苯胺(1.85g,15mmol)和Cs2CO3(4.87g,15mmol)加入200mL两口瓶，加入50mL甲苯，回流反应12-24小时。加入水和乙酸乙酯萃取，有机相除水，然后加压出去溶剂；产物通柱层析进行纯化，淋洗剂为石油醚和乙酸乙酯，其体积比为1～20：1，得到有机配体；所得配体溶于无水溶剂，加入2-3摩尔当量M(NMe2)4，反应12-24小时；减压出去溶剂，然后用不良溶剂洗涤得到基于蒽骨架双金属催化剂。
上述制备方法中，所述无水溶剂选自苯、甲苯、二甲苯、正己烷；所述不良溶剂选自正己烷、正戊烷、正庚烷、环己烷。
本发明还提供了上述式(I)所示基于蒽骨架双金属催化剂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、1-辛烯、降冰片烯、环己烯、四环十二碳烯中的一种或几种。
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。
本发明提供了基于蒽骨架双金属催化剂的制备，以及该化合物催化烯烃聚合的应用。本发明报道的新型基于蒽骨架双金属催化剂具有制备简单、活性高、耐高温、共聚性能好的特点，适用于烯烃高温溶液聚合制备聚烯烃弹性体和环烯烃共聚物。
附图说明
图1为配合物syn-Hf2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。
以下以具体的实施例描述本发明。
实施例1、化合物syn-Hf2的制备
在氮气氛围下，Pd(OAc)2(89mg,0.4mmol),dppf(0.456g,0.8mmol),1,8-二氯蒽(1.24g,5mmol),2-甲氧基苯胺(1.85g,15mmol)和Cs2CO3(4.87g,15mmol)加入200mL两口瓶，加入50mL甲苯，回流反应12-24小时。加入水和乙酸乙酯萃取，有机相除水，然后加压出去溶剂；产物通柱层析进行纯化，淋洗剂为石油醚和乙酸乙酯，其体积比为1～20：1，得到有机配体1.42g；取有机配体(0.42g,1mmol)溶于无水溶剂，加入2.2mmol Hf(NMe2)4，反应24小时；减压出去溶剂，然后用正己烷洗涤得到基于蒽骨架双金属催化剂syn-Hf2(0.93g,0.9mmol,90％yield)。1H NMR(400MHz,C6D6)δ9.02(s,1H),8.45(s,1H),7.74(d,J＝8.5Hz,2H),7.50–7.28(m,2H),7.05(d,J＝6.7Hz,2H),6.73(t,J＝7.4Hz,2H),6.63–6.48(m,4H),6.24(d,J＝8.0Hz,2H),3.62(s,6H),3.12–2.03(br,36H).13C NMR(100MHz,C6D6)δ148.04,147.71,147.53,133.69,131.57,128.19,126.13,125.24,124.45,122.84,118.84,115.28,115.23,108.62,56.37,41.61(br).Anal.Calcd for C40H58N8O2Hf2:C,46.21；H,5.62；N,10.78.Found:C,45.98；H,5.45；N,10.66.
实施例2、化合物syn-Zr2的制备
与实施例1方法相同，使用Zr(NMe2)4代替Hf(NMe2)4，得到基于蒽骨架双金属催化剂syn-Zr2(0.73g,0.84mmol,yield 84％)。1H NMR(400MHz,C6D6)δ9.05(s,1H),8.45(s,1H),7.74(d,J＝8.5Hz,2H),7.47–7.30(m,2H),7.08(d,J＝6.8Hz,2H),6.74(t,J＝7.4Hz,2H),6.58(t,J＝12.1Hz,4H),6.26(d,J＝8.0Hz,2H),3.58(s,6H),2.93–2.27(br,36H).13CNMR(C6D6)δ148.08,147.77,147.56,133.80,131.49,127.94,126.21,124.97,124.25,122.27,118.90,114.95,114.57,108.54,56.00,41.91.Anal.Calcd for C40H58N8O2Zr2:C,55.52；H,6.76；N,12.95.Found:C,55.33；H,6.65；N,12.78.
实施例3、化合物syn-Ti2的制备
与实施例1方法相同，使用Ti(NMe2)4代替Hf(NMe2)4，得到基于蒽骨架双金属催化剂syn-Ti2(0.68g,0.87mmol,87％yield)。1H NMR(400MHz,C6D6)δ8.51(s,1H),8.35(s,1H),7.61(d,J＝8.6Hz,2H),7.34–7.30(m,2H),6.75(d,J＝9.1Hz,4H),6.58(t,J＝7.6Hz,2H),6.49(t,J＝7.6Hz,2H),5.76(d,J＝9.3Hz,2H),3.81(s,6H),3.01(s,12H),2.52(s,12H),1.88(s,12H).13C NMR(100MHz,C6D6)δ150.13,148.11,147.15,133.56,130.62,127.61,126.11,124.51,123.63,121.32,120.04,115.44,113.29,108.07,55.51,47.76,44.60,44.18.Anal.Calcd for C40H58N8O2Ti2:C,61.70；H,7.51；N,14.39.Found:C,61.53；H,7.34；N,14.03.
实施例4、syn-Hf2催化乙烯聚合
将装有磁搅拌子的250ml聚合瓶在120℃连续干燥6hrs，趁热抽真空并用N2气置换3次。加入2.08mg(2μmol)syn-Hf2，再加入MAO，使Al/Ti＝2000。然后再抽真空并用乙烯置换3次。用注射器注入50ml的甲苯，在100℃下，保持5atm的乙烯压力，剧烈搅拌反应2min。用5％盐酸酸化的乙醇溶液中和反应液，得到聚合物沉淀，用乙醇，水洗数次，真空烘干至恒重，称量。聚合活性:4.2×106g·mol-1(Ti)·h-1。聚合物Mw＝770kg·mol-1，Mw/Mn＝2.2。
实施例5、syn-Zr2催化乙烯聚合
将装有磁搅拌子的250ml聚合瓶在120℃连续干燥6hrs，趁热抽真空并用N2气置换3次。加入1.73mg(2μmol)syn-Zr2，再加入MAO，使Al/Ti＝2000。然后再抽真空并用乙烯置换3次。用注射器注入50ml的甲苯，在100℃下，保持5atm的乙烯压力，剧烈搅拌反应2min。用5％盐酸酸化的乙醇溶液中和反应液，得到聚合物沉淀，用乙醇，水洗数次，真空烘干至恒重，称量。聚合活性:3.1×106g·mol-1(Ti)·h-1。聚合物Mw＝550kg·mol-1，Mw/Mn＝2.8。
实施例6、syn-Ti2催化乙烯聚合
将装有磁搅拌子的250ml聚合瓶在120℃连续干燥6hrs，趁热抽真空并用N2气置换3次。加入1.56mg(2μmol)syn-Zr2，再加入MAO，使Al/Ti＝2000。然后再抽真空并用乙烯置换3次。用注射器注入50ml的甲苯，在100℃下，保持5atm的乙烯压力，剧烈搅拌反应2min。用5％盐酸酸化的乙醇溶液中和反应液，得到聚合物沉淀，用乙醇，水洗数次，真空烘干至恒重，称量。聚合活性:0.5×106g·mol-1(Ti)·h-1。聚合物Mw＝150kg·mol-1，Mw/Mn＝2.1。
实施例7、syn-Hf2催化乙烯和1-辛烯聚合
将1L高压聚合釜在120℃连续干燥6hrs，趁热抽真空并用N2气置换3次。加入150g甲苯，110g 1-辛烯，MAO 4mmol。升温至140℃，加乙烯压力至4.0MPa。将2.08mg(2μmol)syn-Hf2的甲苯溶液加入加料仓，通过高压氮气加入聚合釜，开始共聚合反应10分钟。然后用5mL乙醇终止反应，待降温后，泄压，将反应液导入乙醇中得到聚合物沉淀，用乙醇，水洗数次，真空烘干至恒重，称量。聚合活性:2.1×107g·mol-1(Ti)·h-1。聚合物Mw＝890kg·mol-1，Mw/Mn＝2.2，1-辛烯插入率12.5mol％。
实施例8、syn-Hf2催化乙烯和降冰片烯共聚合
将装有磁搅拌子的250ml聚合瓶在120℃连续干燥6hrs，趁热抽真空并用N2气置换3次。加入2.08mg(2μmol)syn-Hf2，再加入MAO，使Al/Ti＝2000。然后再抽真空并用乙烯置换3次。用注射器注入50ml的甲苯，在100℃下，加入200mmol降冰片烯，保持5atm的乙烯压力，剧烈搅拌反应2min。用5％盐酸酸化的乙醇溶液中和反应液，得到聚合物沉淀，用乙醇，水洗数次，真空烘干至恒重，称量。聚合活性:6.5×106g·mol-1(Ti)·h-1。聚合物Mw＝40kg·mol-1，Mw/Mn＝3.4，降冰片烯插入率45mol％。
Claims (8)
1.一类基于蒽骨架双金属催化剂，其结构如式(I)所示：
其中，M选自钛、锆、铪；X选自甲基、氯、二甲基胺基。
2.权利要求1所述基于蒽骨架双金属催化剂的制备方法，包括如下步骤：
在氮气氛围下，Pd(OAc)2,dppf,1,8-二氯蒽,2-甲氧基苯胺和Cs2CO3加入200mL两口瓶，加入50mL甲苯，回流反应12-24小时；加入水和乙酸乙酯萃取，有机相除水，然后加压出去溶剂；产物通柱层析进行纯化，淋洗剂为石油醚和乙酸乙酯，其体积比为1～20：1，得到有机配体；所得配体溶于无水溶剂，加入2-3摩尔当量M(NMe2)4，反应12-24小时；减压出去溶剂，然后用不良溶剂洗涤得到基于蒽骨架双金属催化剂。
3.根据权利要求2所述的制备方法，其特征在于：所述无水溶剂选自苯、甲苯、二甲苯、正己烷；所述不良溶剂选自正己烷、正戊烷、正庚烷、环己烷。
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所述基于蒽骨架双金属催化剂。
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、1-辛烯、降冰片烯、环己烯、四环十二碳烯中的一种或几种。
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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