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在开发新的原子转移自由基引发催化体系合成同时具有窄分子量分布和一定立构规整度的絮凝剂聚丙烯酰胺方面进行了探索。以氯乙酸作为引发剂,CuCl/四甲基乙二胺(TMEDA)为催化络合剂,在聚合体系中分别引入Lewis酸Y(OTf)3和AlCl3作为定向聚合控制剂,研究了Lewis酸的加入对最终产物的等规度和ATRP聚合进程的影响。通过探索反应物种配比、溶剂介质和温度对聚合的影响,得到了最优化的聚合结果:最终产物聚丙烯酰胺絮凝剂的立构规整度m~76%,分子量分布指数Mw/Mn~1.03。进一步动力学研究表明,在有Lewis酸参与的情况下,丙烯酰胺的聚合以ATRP机理进行。对所得的高聚物絮凝剂聚丙烯酰胺进行絮凝实验,结果显示,高分子絮凝剂的沉淀效率η值与高聚物的数均分子量Mn、分子量分布指数PDI值以及立构规整度m值有关,其中絮凝剂数均分子量Mn对絮凝效率起决定性作用,而且,絮凝剂具有较低的分子量分布指数PDI值和较大的立构规整度m都有利于絮凝效率的提高。 相似文献
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运用RAFT活性自由基聚合方法探索了具有一定立构规整性的聚丙烯腈的合成。合成得到RAFT聚合的链转移剂MESA,并以1 H NMR进行了表征;以MESA作为链转移剂、碳酸乙烯酯为溶剂,在单体浓度为0.80 M、60℃、原料配比[AN]0/[MESA]0/[AIBN]0为2500∶5∶1的聚合条件下,成功合成出较高分子量(Mn=5.60×104g/mol)、窄分子量分布(PDI=1.15)的聚丙烯腈;进一步在各单体浓度的RAFT聚合中,加入单体摩尔量3%的AlCl3,得到聚丙烯腈数均分子量为6.1×104~6.5×104g/mol,全同立构组成为mm=32.1%~32.6%,聚合产物分子量分布宽度介于1.31~1.38之间,从而实现了在RAFT活性聚合体系中通过Lewis酸的作用合成得到具有一定立构规整性的聚丙烯腈。 相似文献
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茂金属聚合催化剂的研究现状 总被引:2,自引:0,他引:2
198 0年德国汉堡大学的化学家 Sinn等[1] 发现了烯烃聚合用的茂金属催化剂 .茂金属催化剂为两个环戊二烯中间夹有过渡金属如 Zr、Hf、Ti等的具有三明治结构的有机金属化合物 .茂金属催化剂与传统的多相 Ziegler- Natta催化剂相比 ,具有可溶且聚合活性物种单一 ,对乙烯等烯烃的聚合活性高 ,高分子产物的分子量及组成分布窄等特点 .选择不同的茂金属催化剂 ,可获得所需立构规整性的高分子物 ,除能获得全同立构的聚烯烃外 ,还可获得由 Ziegler- Natta催化剂不能合成的间规立构聚烯烃 ,如聚苯乙烯 [2 ]与聚丙烯 [3 ] .由 Ziegler- Natta催化… 相似文献
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采用苯氧铜/正丁基锂(PhOCu/n-BuLi)体系引发MMA聚合, 通过GPC, 1H NMR对聚合物进行了表征. 实验结果表明, 该体系聚合反应速度较快, 温度、引发体系组成是影响聚合物分子量及其分布、单体转化率、引发剂引发效率、聚合物的立构规整性的主要因素; -40 ℃时分子量分布比较窄, 但引发效率也比较低(大约15%). 低引发效率、宽分子量分布与引发剂的聚集状态有关. 分子量与单体浓度、引发剂浓度的关系说明, 该体系具有一定程度的活性聚合特点. 相似文献
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考察了不同磷化合物、催化剂组成、加料方式及反应温度对2-乙基己酸铁(Fe)-三异丁基铝(Al)催化剂上1,3-丁二烯(BD)聚合反应的影响,发现以三苯基磷酸酯(P)为配体的铁系催化剂在己烷中,n(Fe)∶n(P)∶n(Al)=1∶4∶25,加料方式为BD+Fe+P+Al和θ=50 ℃的条件下具有最高的催化活性,聚合产物的分子量分布指数为250,GPC淋出曲线呈单峰分布,表明该催化剂具有单一的活性中心. 经NMR,GPC,DSC和XRD测定,所得聚丁二烯具有较高的1,2-结构含量(95%),较高的间同立构规整度(95%),较高的结晶度(68%),较高的分子量(Mn=74×105)及较高的熔点(189 ℃). 反应条件对聚合产物的立构规整性无明显影响. 相似文献
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为了制备适于制造有机发光场效应管的高分子材料, 通过Suzuki偶联反应, 采用不同Pd催化剂, 合成了一种侧基横挂偶极基团的液晶9-苯亚甲基取代芴-苯共聚物. 考察了不同催化剂对合成的聚合物的分子量、聚合物链中单体单元的结构排列及液晶性质和光学性质的影响. 结果表明, 2种不同的Pd催化剂对合成的聚合物的分子量影响不大, 但对聚合物链的立构规整性以及聚合物的液晶态温度范围有较大的影响. Pd(PPh3)4作催化剂合成的聚合物(PA)中单体单元的结构排列较单一, 立构规整性好, 有较宽的液晶态温度范围. Pd(OAc)2为催化剂合成的聚合物(PB)链中单体单元的结构排列相对复杂, 液晶态温度范围较窄. 聚合物链的立构规整性对其光学性质影响很大. PA具有较高的溶液及固体膜的紫外最大吸收峰值和溶液荧光效率, 其退火膜的激发和发射光谱的半峰宽均比PB的窄, 并且光学性质不随加热条件的变化而变化. 相似文献
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Idota N Nagase K Tanaka K Okano T Annaka M 《Langmuir : the ACS journal of surfaces and colloids》2010,26(23):17781-17784
In this study, stereocontrolled poly(N-isopropylacrylamide) (PIPAAm) brushes were grafted from surfaces by atom transfer radical polymerization (ATRP) in the presence of a Lewis acid, and the effect of PIPAAm brush tacticity on the thermoresponsive wettabiliy was investigated. PIPAAm grafted by ATRP in the presence of Y(OTf)(3) showed high isotacticity, while the control brush polymerized in the absence of Y(OTf)(3) was clearly atactic. The isotacticity and molecular weight of PIPAAm brushes were controlled by polymerization conditions. The wettability of isotactic PIPAAm-grafted surfaces decreased slightly below 10 °C, although the phase transition temperature of atactic surface was 30 °C, and the bulk isotactic polymer was water-insoluble between 5 and 45 °C. 相似文献
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Roya Zahedi Faramarz Afshar Taromi Seyed Heidar Mirjahanmardi Mehdi Nekoomanesh Haghighi Roghayeh Jamjah Khosrow Jadidi 《Polymer Science Series B》2016,58(2):143-151
Two new ethers were synthesized using the Williamson reaction from related alcohols and were used as external donors in propylene polymerization in the presence of the industrial diisobutyl phthalate-based MgCl2-supported Ziegler-Natta catalyst. For comparison the propylene polymerization was carried out in the presence of silane and in the absence of external donors. The produced polymers were characterized by differential scanning calorimetry, xylene extraction, melt flow index, scanning electron microscopy and gel permeation chromatography. The isotacticity, molecular weight and molecular weight distribution, melt flow index, crystallinity degree and thermal properties of polypropylenes were influenced by the type of external donors. 相似文献
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Yury V. Kissin 《Journal of polymer science. Part A, Polymer chemistry》2001,39(10):1681-1695
A previously developed kinetic scheme for ethylene polymerization reactions with heterogeneous Ziegler–Natta catalysts (see Y. V. Kissin, R. I. Mink, & T. E. Nowlin, J Polym Sci Part A: Polym Chem 1999, 37, 4255 and Y. V. Kissin, R. I. Mink, T. E. Nowlin, & A. J. Brandolini, J Polym Sci Part A: Polym Chem 1999, 37, 4273, 4281) states that the catalysts have several types of active centers that have different activities and different stabilities, produce different types of polymer materials, and respond differently to reaction conditions. Each type of center produces a single polymer component (Flory component), a material with a uniform structure (copolymer composition, isotacticity, etc.) and a narrow molecular weight distribution (weight-average molecular weight/number-average molecular weight = 2.0). This article examines several previously known features of ethylene polymerization and copolymerization reactions on the basis of this mechanism. The discussed subjects include temperature and cocatalyst effects on the polymerization kinetics and molecular weight distribution of polymers and reaction parameter effects (temperature, ethylene and hydrogen partial pressures, and α-olefin and cocatalyst concentrations) on the molecular weights of Flory components. The results show that the formulation of the multicenter kinetic scheme and the development of kinetic tools necessary for the application of this scheme significantly expand our understanding of the working of heterogeneous polymerization catalysts and provide additional means for their control. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 1681–1695, 2001 相似文献
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The effects of weight-average molecular(Mw), molecular weight distribution(MWD), and isotacticity on the linear viscoelastic behavior of polybutene-1 melts are studied. It is observed that the linear viscoelastic region becomes slightly narrower with increasing frequency. In frequency sweeps, the transition of the polymer melts flow from Newtonian flow to power-law flow can be observed. The melts with higher Mw and/or broader MWD, as well as higher isotacticity exhibit higher complex viscosity, zero shear viscosity, viscoelasticity moduli, relaxation modulus, broader transition zone, while lower critical shear rate, non-Newtonian index, and the frequency at which elasticity begins to play an important role. The relationship of zero shear viscosity on Mw has been established, which agrees with the classical power law. Furthermore, it is found that the cross-over frequency decreases with increasing Mw and the cross-over modulus increases with narrowing MWD. 相似文献
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Poly(acrylamide) (PAM) with controlled molecular weight and tacticity was prepared by UV-irradiation-initiated controlled/living radical polymerization in the presence of dibenzyl trithiocarbonate (DBTTC) and Y(OTf)3. The rapid and facile photo-initiated controlled/living polymerization at ambient temperature led to controlled molecular weight and narrow polydispersity (Mw/Mn = 1.12-1.24) of PAM. The coordination of Y(OTf)3 with the last two amide groups in the growing chain radical effectively enhanced isotacticity of PAM. The isotactic sequence of dyads (m), triads (mm) and pentads (mmmm) in PAM were 70.32%, 50.95%, and 29.97%, respectively, which were determined by the resonance of methine (CH) groups in PAM under 13C NMR experiment. Factors affecting stereocontrol during the polymerization were studied, including the type of Lewis acids, concentration of Y(OTf)3, and monomer conversion. It is intriguing that the meso tacticity increased gradually with chain propagation and quite higher isotacticity (m = 93.01%, mm = 86.57%) was obtained in the later polymerization stage (conversion 65-85%). 相似文献
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Hou Chen Gaojian Lv Ying Liang Jinming Sun 《Journal of polymer science. Part A, Polymer chemistry》2013,51(16):3328-3332
High performance polyacrylonitrile (PAN) was prepared with Mg powder as both reducing agent (RA) and supplemental activator (SA) by single electron transfer‐living radical polymerization (RASA SET‐LRP). First‐order kinetics of polymerization with respect to monomer concentration, linear increase of molecular weight, and narrow polydispersity with monomer conversion, and the obtained high isotacticity PAN indicate that RASA SET‐LRP in the presence of Mg powder could simultaneously control molecular weight and tacticity of PAN. compared with that obtained with ascorbic acid (VC) as RA, an obvious increase in isotacticity of PAN was observed. the block copolymer pan‐b‐pAN with molecular weight at 112,460, polydispersity at 1.33, and isotacticity at 0.314 was successfully prepared. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3328–3332 相似文献
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烯烃配位聚合催化剂的研究进展 总被引:1,自引:0,他引:1
较全面地综述了配位聚合催化剂和聚合机理的研究进展:高效Ziegler-Natta催化剂催化丙烯、乙烯等烯烃高效聚合,可合成多种高性能聚烯烃,等规聚丙烯的等规度大于98.5%,不同结构和性能的聚乙烯包括线性低密度聚乙烯(LLDPE)、超低密度聚乙烯(VLDPE)、中密度聚乙烯(MDPE)、高密度聚乙烯(HDPE)、双/宽峰分布聚乙烯、超高分子量聚乙烯(UHMWPE)和超低密度双/宽峰分布聚乙烯等;茂金属催化剂催化苯乙烯、乙烯、丙烯、1-丁烯等烯烃的均聚合和共聚合,并概括了其聚合机理;非茂金属催化剂合成多组分、多立体结构嵌段的聚烯烃,极性聚烯烃及超支化聚烯烃等,介绍了链行走和链穿梭机理。展望了配位聚合的发展趋势,认为聚合过程的环境友好、产品使用过程的环境友好、聚烯烃的高性能化和功能化是从事配位聚合工作的全体人员努力的方向。 相似文献