CN113816980A - 一种锆和铪金属催化剂的合成方法及其在超高分子量聚乙烯制备中的应用 - Google Patents
一种锆和铪金属催化剂的合成方法及其在超高分子量聚乙烯制备中的应用 Download PDFInfo
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- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Abstract
本发明涉及一种锆和铪金属催化剂的制备及其烯烃高温溶液聚合制备超高分子量聚乙烯的应用。本发明报道的新型锆和铪金属催化剂含有刚性、大位阻的camphyl骨架,因而具有耐高温的特点,适用于烯烃高温溶液聚合制备超高分子量聚乙烯,所得聚烯烃重均分子量高于100万。此外,本发明通过原位一步法合成锆和铪金属催化剂,具有制备简单的优点,适于催化剂的大规模制备。因此,本发明报道的锆和铪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
本发明涉及一种锆和铪金属催化剂的制备及其在烯烃聚合中的应用,特别是用于制备超高分子量聚乙烯。
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 Pat 889229(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。超高分子量聚乙烯是一种线型结构的具有优异综合性能的热塑性工程塑料,其发展十分迅速,80年代以前,世界平均年增长率为8.5%,进入80年代以后,增长率高达15%~20%。在中国超高分子量聚乙烯管材在2001年被科学技术部国科计字(2000)056号文件列为国家科技成果重点推广计划,属化工类新材料、新产品。国家计委科技部将超高分子量聚乙烯管材列为当前优先发展的高科技产业重点领域项目。
本发明报道了一类双齿氮配位的锆和铪金属化合物的制备方法及其在烯烃聚合中的应用。本发明在双齿氮配体中引入了莰基骨架,设计合成了新型双齿氮配位的锆和铪金属催化剂。本发明报道的新型双齿氮配位的锆和铪金属催化剂具有制备简单、活性高、耐高温的特点,适用于烯烃高温溶液聚合,所制备聚合物为超高分子量聚乙烯。因此,本发明报道的双齿氮配位的锆和铪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双齿氮配位的锆和铪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(A)-(D)所示双齿氮配位的锆和铪金属催化剂:
本发明提供了上述双齿氮配位的锆和铪金属催化剂的制备方法,包括以下步骤:
氮气氛围下,ZrCl4或HfCl4悬浮于无水溶剂中,在-60至-20℃下,加入4摩尔当量的甲基溴化镁,反应2小时;然后在-60至-20℃下加入1摩尔当量的配体,缓慢升至室温反应4-24小时;减压除去溶剂,加入无水溶剂提取,再次除去溶剂后得到黄色固体产物。
上述制备方法中,所述无水溶剂选自苯、甲苯、二甲苯、正己烷。
本发明提供了一种双齿氮配位的锆和铪金属催化剂的制备方法,具有反应简单,一锅法合成,无需分离中间产物,产率高,原料易得,成本低的特点。
本发明提供了双齿氮配位的锆和铪金属催化剂的制备,以及该催化剂催化烯烃聚合的应用。本发明报道的新型双齿氮配位的锆和铪金属催化剂具有制备简单、活性高、耐高温的特点,适用于烯烃高温溶液聚合制备超高分子量聚乙烯。
附图说明
图1为配合物A的晶体结构图;
图2为配合物C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2,6-Me2-C6H3-N=C(camphyl)-C(camphyl)=N-2,6-Me2-C6H3和2,6-Me2-4-Me-C6H2-N=C(camphyl)-C(camphyl)=N-2,6-Me2-4-Me-C6H2两个化合物是根据文献Macromolecules 2009,42,7789-7796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、催化剂A的制备
称四氯化锆(0.256g,1.1mmol),加5mL干燥的甲苯,在-40℃条件下,缓慢加1.6mL/4.8mmol甲基溴化镁溶液(3M),搅拌2小时。加2,6-Me2-C6H3-N=C(camphyl)-C(camphyl)=N-2,6-Me2-C6H3(0.372g/1mmol),-40℃条件下搅拌两个小时恢复室温,搅拌5小时。避光。除去溶剂,加正己烷提取,过滤,得到产物0.36g,产率64%。1H NMR(400MHZ,C6D6):δ7.19-7.14(m,2H),7.09(t,J=6.6Hz,2H),6.99(t,J=7.4Hz,2H),3.53(br,4H,THF),2.84(s,3H,Me),2.47(s,3H,Me),2.29(s,3H,Me),2.25(s,3H,Me),2.14(d,J=2.6Hz,1H),1.88-180(m,1H),1.67-1.56(m,2H),1.34-1.30(m,1H),1.15(s,3H,Me),1.08(br,4H,THF),0.81(s,3H,Me),0.64(s,3H,Me),0.14(br,3H,Hf-Me),0.04(s,3H,Hf-Me).13C NMR(100MHZ,C6D6):δ150.60,150.37,135.67,133.47,133.36,133.21,128.52,128.49,128.18,127.94,124.50,123.81,119.08,117.44,70.75,57.58,52.13,51.59,34.65,27.88,25.13,21.47,20.35,20.27,20.17,19.96,19.91,12.56.Anal.Calcd for C32H46N2OZr:C,67.91;H,8.19;N,4.95.Found:C,68.03;H,8.01;N,4.78.
实施例2、催化剂B的制备
称四氯化锆(0.256g,1.1mmol),加5mL干燥的甲苯,在-40℃条件下,缓慢加1.6mL/4.8mmol甲基溴化镁溶液(3M),搅拌2小时。加2,6-Me2-4-Me-C6H2-N=C(camphyl)-C(camphyl)=N-2,6-Me2-4-Me-C6H2(0.400g/1mmol),-40℃条件下搅拌两个小时恢复室温,搅拌5小时。避光。除去溶剂,加正己烷提取,过滤,得到产物0.43g,产率72%。1H NMR(400MHZ,C6D6):δ6.98(d,J=5.6Hz,2H),6.90(d,J=6.7Hz,2H),3.58(br,4H,THF),2.83(s,3H),2.46(s,3H),2.30(s,3H),2.26(s,3H),2.25(s,3H),2.23(s,3H),2.19(d,J=3.6Hz,1H),1.87(ddd,J=15.6,8.0,3.7Hz,1H),1.71-1.56(m,2H),1.38-1.30(m,1H),1.19(s,3H),1.10(br,4H,THF),0.85(s,3H),0.66(s,3H),0.16(br,3H),0.05(s,3H).13C NMR(100MHZ,C6D6):δ148.08,147.78,135.30,133.23,133.09,133.02,132.83,132.42,129.33,129.24,129.03,128.96,119.05,117.26,70.60,57.58,52.09,51.61,35.65,34.69,34.38,27.88,25.21,21.40,21.05,20.98,20.41,20.21,20.10,20.01,19.86,12.68.Anal.Calcdfor C34H50N2OZr:C,68.75;H,8.48;N,4.72.Found:C,68.44;H,8.31;N,4.65.
实施例3、催化剂C的制备
称四氯化铪(0.352g,1.1mmol),加5mL干燥的甲苯,在-40℃条件下,缓慢加1.6mL/4.8mmol甲基溴化镁溶液(3M),搅拌2小时。加2,6-Me2-C6H3-N=C(camphyl)-C(camphyl)=N-2,6-Me2-C6H3(0.372g/1mmol),-40℃条件下搅拌两个小时恢复室温,搅拌5小时。避光。除去溶剂,加正己烷提取,过滤,得到产物0.45g,产率69%。1H NMR(400MHZ,C6D6):δ7.16(t,J=7.9Hz,2H),7.10(t,J=7.3Hz,2H),6.97(td,J=7.4,2.5Hz,2H),3.47(br,4H,THF),2.82(s,3H),2.46(s,3H),2.36(s,3H),2.31(s,3H),2.12(d,J=3.4Hz,1H),1.85(ddd,J=11.8,8.0,3.9Hz,1H),1.70-1.58(m,2H),1.39-1.33(m,1H),1.12(s,3H),1.07(s,4H,THF),0.78(s,3H),0.64(s,3H),-0.03(s,3H),-0.05(s,3H).13C NMR(100MHZ,C6D6):δ150.93,150.90,136.02,134.13,133.89,133.77,128.51,128.22,128.16,127.94,124,52,123.75,118.65,117.03,70.71,57.57,52.13,51.27,47.79,45.92,25.10,21.44,20.38,20.28,20.02,19.96,19.88,12.52.Anal.Calcd for C32H46HfN2O:C,58.84;H,7.10;N,4.29.Found:C,58.51;H,6.93;N,4.04.
实施例4、催化剂D的制备
称四氯化铪(0.352g,1.1mmol),加5mL干燥的甲苯,在-40℃条件下,缓慢加1.6mL/4.8mmol甲基溴化镁溶液(3M),搅拌2小时。加2,6-Me2-4-Me-C6H2-N=C(camphyl)-C(camphyl)=N-2,6-Me2-4-Me-C6H2(0.400g/1mmol),-40℃条件下搅拌两个小时恢复室温,搅拌5小时。避光。除去溶剂,加正己烷提取,过滤,得到产物0.57g,产率84%。1H NMR(400MHZ,C6D6):δ6.99(s,1H),6.97(s,1H),6.93(s,2H),3.50(br,4H,THF),2.83(s,3H),2.47(s,3H),2.39(s,3H),2.33(s,3H),2.27(s,3H),2.24(s,3H),2.18(d,J=2.2Hz,1H),1.89(qd,J=8.0,3.4Hz,1H),1.75-1.60(m,2H),1.44-1.34(m,1H),1.17(s,3H),1.07(br,4H,THF),0.84(s,3H),0.66(s,3H),0.00(br,6H).13C NMR(100MHZ,C6D6):δ148.36,148.31,135.68,133.75,133.56,133.42,133.24,132.39,129.33,129.29,128.94,128.89,118.61,116.91,70.78,57.59,52.11,51.33,47.34,45.71,34.75,28.08,25.14,21.36,21.01,20.95,20.42,20.21,19.97,19.95,19.83,12.53.Anal.Calcd for C34H50HfN2O:C,59.94;H,7.40;N,4.11.Found:C,60.12;H,7.52;N,4.01.
实施例5、催化剂A催化乙烯聚合
将1L聚合反应釜在120℃连续真空干燥6小时,通入常压乙烯,220g甲苯,加压至3MPa乙烯,高压氮气加入5.6mg(10μmol)催化剂A和11mg(12μmol)[Ph3C][B(C6F5)4]的甲苯溶液5mL。在120℃下,保持3MPa的乙烯压力,剧烈搅拌反应10min。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:450kg·mol-1(Zr)·h-1。聚合物Mw=2350kg·mol-1,Mw/Mn=2.5。
实施例6、催化剂A催化乙烯和1-辛烯共聚合
将1L聚合反应釜在120℃连续真空干燥6小时,通入常压乙烯,220g的甲苯,120g的1-辛烯,加压至3MPa乙烯,高压氮气加入5.6mg(10μmol)催化剂A和11mg(12μmol)[Ph3C][B(C6F5)4]的甲苯溶液5mL。在120℃下,保持3MPa的乙烯压力,剧烈搅拌反应10min。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:236kg·mol-1(Zr)·h-1。聚合物Mw=1843kg·mol-1,Mw/Mn=1.9,共聚物中1-辛烯含量0.2mol%。
实施例7、催化剂B催化乙烯和1-辛烯共聚合
将1L聚合反应釜在120℃连续真空干燥6小时,通入常压乙烯,220g的甲苯,120g的1-辛烯,加压至3MPa乙烯,高压氮气加入5.9mg(10μmol)催化剂A和11mg(12μmol)[Ph3C][B(C6F5)4]的甲苯溶液5mL。在120℃下,保持3MPa的乙烯压力,剧烈搅拌反应10min。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:388kg·mol-1(Zr)·h-1。聚合物Mw=337kg·mol-1,Mw/Mn=3.3,共聚物中1-辛烯含量1.0mol%。
Claims (8)
2.权利要求1所述锆和铪金属催化剂的制备方法,包括如下步骤:
氮气氛围下,四氯化锆或四氯化铪悬浮于无水溶剂中,在-60至-20℃下,加入4摩尔当量的甲基溴化镁,反应2小时;然后在-60至-20℃下加入1摩尔当量的配体,缓慢升至室温反应4-24小时;减压除去溶剂,加入无水溶剂提取,再次除去溶剂后得到黄色固体产物。
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。
4.一种进行烯烃聚合反应制备超高分子量聚乙烯的方法,其特征在于:反应的催化剂为权利要求1所述锆和铪金属催化剂。
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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