CN1276386A - 一种硅桥连双核茂金属锆化合物 - Google Patents
一种硅桥连双核茂金属锆化合物 Download PDFInfo
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Abstract
本发明涉及茂金属化合物的合成。它是通式(Ⅰ)化合物,其中,R=H、Me4;E=Me2SiOSiMe2、Me2SiSiMe2或Me2SiOSiMe2OSiMe2。将配体的双锂盐滴加到单茂三氯化锆的THF溶液中,室温过夜,分离,用溶剂提纯;本发明与MAO配合使用,用于乙烯和丙烯聚合的催化剂,催化活性高,其活性达到18.0kgPE/mmol.Zrh.以上。
Description
本发明涉及茂金属化合物的合成。
Macromol.Symp.1997,118,129
Polyhedron 1998,17(7)1055
Organometallics,1989,8,2107
曾报道单硅桥连双核茂金属锆化合物的合成在甲苯中长时间回流得到而其它桥较长的配体则得不到双核化合物。
Rn=1~4Me,E=Me2SiOSiMe2;Me2SiOSiMe2OMe2。
水解的硅桥连双核茂金属锆化合物为:Rn=1~4Me。
本发明与MAO配合使用,用于乙烯和丙烯聚合的催化剂,催化活性高,其活性达到18.0kgPE/mmol.Zrh.以上。
实例1化合物1的合成:
在100mL Schlenk瓶中,加入1,2-二(环戊二烯基)四甲基二硅烷1.07g(4.35mmol)和20mL THF。在0℃搅拌下滴加4.35mL n-BuLi(2.0N,8.7mmol)的己烷溶液,加完后室温搅拌2h,得粉红色双锂盐悬浮液。
在100ml Schlenk瓶中,加入3.54g(8.7mmol)CpZrCl3·2THF,20ml THF和20mlDME,搅拌使之完全溶解后,冷却到0℃,将上述制得的双锂盐悬浮液用钢管转移到其中。室温反应过夜。抽滤,用少量冷的THF洗,得1.41g白色固体,该固体在沙氏提取器中用50mL CH2Cl2提取24h。提取液析出白色小晶体。抽滤,用少量CH2Cl2洗,得1.25g(41%)白色微晶1。
实例2化合物2的合成:
100mL Schlenk瓶中,加入3.35g(8.23mmol)CpZrCl3·2THF,40mL THF和20mLDME,0℃滴加4.3mmol[O(Me2SiCpLi)2]++的THF溶液。室温反应过夜,加热至50℃,反应1h,真空除去所有溶剂,残留物中加入20ml CH2Cl2和10mL 6N HCl,分出有机相,用无水MgSO4干燥。过滤,滤液旋转蒸发除去所有溶剂,残留物用少量Et2O洗涤,得1.80g白色固体。该粗产物用CH2Cl2/Et2O重结晶,得1.52g无色片状晶体2。
用同样得方法可合成3,4,5。
实例3化合物6的合成:
100mL圆底瓶中加入1.28g(1.83mmol)1和75ml CH2Cl2,搅拌成悬浮液,加入0.33mL(3.66mmol)苯胺和0.033mL(1.83mmol)H2O,室温反应过夜。过滤,滤液旋转蒸发除去所有溶剂,残留的白色固体用少量石油醚洗两次,然后用CH2Cl2/石油醚重结晶,得0.76g白色针状晶体6。
表1~4为化合物1~6有关的分析及聚合数据。表1 化合物1~6分析数据
表2化合物1~6 1H NMR数据
表3 化合物1~5质谱数据
化合物 | 分子式 | 颜色 | 产率(%) | 元素分析实际(理论) | |
C(%) | H(%) | ||||
1 | C24H30Cl4Si2Zr2 | white solid | 41 | 40.98(41.24) | 4.70(4.33) |
2 | C24H30Cl4OSi2Zr2 | white solid | 51 | 40.35(40.32) | 3.85(4.23) |
3 | C26H36Cl4O2Si3Zr2 | white solid | 30 | 39.24(39.58) | 4.57(4.60) |
4 | C32H46Cl4OSi2Zr2 | white solid | 15 | 46.15(46.41) | 5.50(5.61) |
5 | C34H52Cl4O2Si3Zr2 | white solid | 11 | 44.95(45.31) | 5.64(5.82) |
6 | C24H30Cl2OSi2Zr2 | white solid | 64 | 44.45(44.76) | 4.60(4.70) |
化合物 | δC5H5 | δC5H4 | δSi-CH3 | δC5HMe4 |
1 | 6.40(s,10) | 6.48(t,4),6.41(t,4) | 0.34(s,12) | |
2 | 6.44(s,10) | 6.71(t,4),6.52(t,4) | 0.36(s,12) | |
3 | 6.46(s,10) | 6.74(t,4),6.52(t,4) | 0.36(s,12)0.07(s,6) | |
4 | 6.52(t,4),6.30(t,4) | 0.32(s,12) | 5.90(s,2)1.99(s,12)1.96(s,12) | |
5 | 6.56(t,4),6.30(t,4) | 0.35(s,12)-0.04(s,6) | 5.94(s,2)2.00(s,12)1.96(s,12) | |
6 | 6.31(s)6.28(s),10H | 6.66(m),6.56(m),6.49(m),6.40(m),6.18(m),8H | 0.42(s),.0.40(s),0.35(s),12H |
化合物. | MS(m/e,强度%) |
1 | 644(12,[M-Cl-Me]+),579(65,[M-3Cl]+),559(6),350(16),312(100,[(C5H5)(C5H4SiMe2)ZrCl]+),293(53),220(27) |
2 | 675(4,[M-Cl]+),595(65,[M-3Cl]+),575(8),293(100,[(C5H5)(C5H4SiMe2O)Zr]+), |
3 | 679(5,[M-3Cl]+),459(100,[M-Cp2ZrCl2-Cl]+),407(60,Me3Si2O(C5H4)2ZrCl2)+),349(99,[MeSiO(C5H4)2ZrCl2]+),311(64,[Me2Si(C5H4)2ZrCl]+),293(100,[(C5H5)(C5H4SiMe2O)Zr]+),225(30,[CpZrCl2]+),73(48,Me3Si+) |
4 | 465(53),405(64,[(C5HMe4)(C5H4SiMe2)ZrCl2]+),389(92,[(C5HMe4)(C5H4SiMe2)ZrCl2-CH4]+),369(97,[(C5HMe4)(C5H4SiMe2)ZrCl2-HCl]+),343(34,[(C5HMe4)(C5H4SiMe2)ZrCl2-CH4-HCl]+),297(36),267(27),249(100,[(C5H4SiMe2)ZrCl]+),121(19,[C5HMe4]+) |
5 | 539(28),559(18),465(55),445(32),423(27),367(45),349(26),321(51),295(29),249(100,[(C5H4SiMe2)ZrCl]+),121(43,[C5HMe4]+) |
实例4
乙烯聚合实验在特制的带夹套的250mL三口瓶中进行。该三口瓶装上电动搅拌,用N2气充排三次,真空状态下充入乙烯气体,由电磁阀控制体系压力略高于1atm。加入100mL甲苯,恒温10min使乙烯气体饱和。然后依次加入MAO和催化剂的甲苯溶液,记录配气罐内压力随聚合时间的变化。聚合一定时间后,加入100mL酸化乙醇(含10%HCl)终止反应。抽滤,用100mL乙醇洗涤。得到的聚合物于60℃真空干燥至恒重。称重,计算催化活性。聚合物的分子量用凝胶渗透色谱(GPC)测定。表4 1~6/MAO乙烯聚合数据
聚合条件:[催化剂.]=1.5×10-6mol;Al/Zr=2500;t=30min;1 atm.of monomerpressure;in 100mL甲苯.a).t=25min;b).[Cat.]=0.30×10-6;c).t=10min;d).t=20min.活性:(kgPE/mmolZr·h);Mη:g/mol,determined by GPC in o-C6H4Cl2 at 135℃。
催化剂 | 温度(℃) | 产量(g) | 活性 | Mη(×10-5) | Mw/Mn |
1 | 2030405060 | 3.244.024.243.243.57 | 2.162.682.832.162.38 | 7.897.956.686.774.87 | 2.242.362.672.213.51 |
2 | 203040506070 | 1.402.142.523.295.448.06 | 0.931.431.682.193.635.37 | 5.495.705.694.714.331.74 | 2.762.763.093.512.892.90 |
3 | 20303040506070 | 5.98(a)9.151.81(b)2.13(b)3.58(b)5.49(b)4.57(b) | 4.786.106.037.1011.918.315.2 | 13.438.797.307.796.103.141.69 | 2.012.482.712.402.952.442.83 |
4 | 204060 | 2.541.742.76 | 1.691.161.84 | 11.865.792.48 | 2.543.573.04 |
5 | 20304060 | 4.576.245.494.18 | 3.054.163.668.37 | 7.857.284.742.60 | 2.602.352.553.62 |
6 | 30405060 | 4.365.504.223.06(d) | 2.913.672.813.06 | 5.024.974.183.36 | 2.162.652.442.67 |
Claims (5)
3.权利要求1所说的硅桥连双核茂金属锆化合物的合成方法,其特征在于它的合成步骤是:将配体的双锂盐与单茂三氯化锆反应,摩尔比1∶2,THF为溶剂,室温过夜,分离出产物,用有机溶剂将固体产品提纯,即可。
4.权利要求2所说的硅桥连双核茂金属锆化合物的合成方法,其特征在于它的合成步骤是:在有机溶剂中加入硅桥连双核茂金属锆化合物、苯胺和H2O,其摩尔比为1∶2∶1,室温反应过夜,除去所有溶剂,分离出产物,用有机溶剂将固体产品提纯即可。
5.权利要求1所说的硅桥连双核茂金属锆化合物的应用,其特征在于它可用于乙烯聚合和丙烯聚合。
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100420700C (zh) * | 2007-03-08 | 2008-09-24 | 山东轻工业学院 | 桥联茂金属异双核催化剂及其制备方法与应用 |
CN101190923B (zh) * | 2006-11-29 | 2010-11-03 | 中国石油天然气股份有限公司 | 非对称桥连双核茂化合物及其制备及在烯烃聚合中的应用 |
CN101638447B (zh) * | 2008-07-31 | 2011-10-05 | 中国石油天然气股份有限公司 | 一种负载型双硅桥茂金属催化剂及其制备方法和应用 |
US8609793B2 (en) | 2010-10-07 | 2013-12-17 | Chevron Phillips Chemical Company Lp | Catalyst systems containing a bridged metallocene |
US8629292B2 (en) | 2010-10-07 | 2014-01-14 | Chevron Phillips Chemical Company Lp | Stereoselective synthesis of bridged metallocene complexes |
US8637616B2 (en) | 2010-10-07 | 2014-01-28 | Chevron Philips Chemical Company Lp | Bridged metallocene catalyst systems with switchable hydrogen and comonomer effects |
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Cited By (11)
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CN101190923B (zh) * | 2006-11-29 | 2010-11-03 | 中国石油天然气股份有限公司 | 非对称桥连双核茂化合物及其制备及在烯烃聚合中的应用 |
CN100420700C (zh) * | 2007-03-08 | 2008-09-24 | 山东轻工业学院 | 桥联茂金属异双核催化剂及其制备方法与应用 |
CN101638447B (zh) * | 2008-07-31 | 2011-10-05 | 中国石油天然气股份有限公司 | 一种负载型双硅桥茂金属催化剂及其制备方法和应用 |
US8609793B2 (en) | 2010-10-07 | 2013-12-17 | Chevron Phillips Chemical Company Lp | Catalyst systems containing a bridged metallocene |
US8629292B2 (en) | 2010-10-07 | 2014-01-14 | Chevron Phillips Chemical Company Lp | Stereoselective synthesis of bridged metallocene complexes |
US8637616B2 (en) | 2010-10-07 | 2014-01-28 | Chevron Philips Chemical Company Lp | Bridged metallocene catalyst systems with switchable hydrogen and comonomer effects |
US9018407B2 (en) | 2010-10-07 | 2015-04-28 | Chevron Phillips Chemical Company Lp | Stereoselective synthesis of bridged metallocene complexes |
US9040642B2 (en) | 2010-10-07 | 2015-05-26 | Chevron Phillips Chemical Company Lp | Catalyst systems containing a bridged metallocene |
US9040643B2 (en) | 2010-10-07 | 2015-05-26 | Chevron Phillips Chemical Company Lp | Bridged metallocene catalyst systems with switchable hydrogen and comonomer effects |
CN103772545A (zh) * | 2012-10-23 | 2014-05-07 | 中国石油天然气股份有限公司 | 一种桥连环戊二烯基双金属催化及其应用 |
CN103772545B (zh) * | 2012-10-23 | 2016-08-10 | 中国石油天然气股份有限公司 | 一种桥连环戊二烯基双金属催化剂及其应用 |
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