【作者】 张艳中；

【导师】 范志强；

【作者基本信息】 浙江大学 ， 高分子化学与物理， 2003， 博士

【摘要】 首次应用富勒烯氯化物C₆₀Cln/C₇₀Cln(n=18-22，平均值为20，C₆₀/C₇₀=7/3重量比)(以下简称C₆₀Cl₂₀)分别与CuCl/Bpy、Ni（naph）₂/PPh₃组成新型原子转移自由基聚合（ATRP）引发体系引发苯乙烯（St）、甲基丙烯酸甲酯（MMA）及N-乙烯基咔唑（VK）聚合，研究聚合反应规律和聚合反应机理，探讨了所得富勒烯化聚合物的结构和性能；探索在正丁基锂引发苯乙烯和丁二烯阴离子聚合体系中以C₆₀Cl₂₀为偶联剂的偶联反应特征。通过以上方法合成了一系列新型富勒烯化高分子材料(C₆₀-Polymer)。 以C₆₀Cl₂₀/CuCl/Bpy为引发体系在甲苯中于130℃引发苯乙烯聚合，其中各组分摩尔比为C₆₀Cl₂₀/CuCl/Bpy/St=0.05/1/2/100。本体系与普通ATRP（CCl₄作引发剂）体系具有相近的引发聚合反应活性，并且具有CuCl在体系中分散性好的特点。用体积示差折光指数（RI）和紫外（UV）双检测GPC测定不同聚合转化率下所得聚合物的GPC谱图(紫外检测器的波长设定为340nm,含C₆₀的聚苯乙烯在此波长有吸收，普通聚苯乙烯则无吸收)。其中，GPC（RI）谱线为双峰分布（峰a、峰b），GPC（UV）谱线为单峰（带肩峰）并与GPC（RI）谱线中峰b的全部及峰a的小部分重合。深入研究发现，GPC（RI）谱线的峰b（分子量较高）是由C₆₀-PSt贡献的，它随着聚合反应转化率的提高向左移动同时峰面积逐渐增加，表明C₆₀-PSt的分子量随聚合转化率的增加而增加。分子量分布较窄，并且随着聚合反应转化率的增加而变窄，这是ATRP机理的特征之一。在GPC（UV）谱线中存在着的肩峰与GPC（RI）谱线中的峰a有部分重合，这部分可能是C₆₀Cl₂₀引发苯乙烯聚合的产物。另外在GPC（RI）谱线中的峰a不随聚合转化率的变化而移动，推测是由苯乙烯的热聚合所致。因此判断C₆₀Cl₂₀/CuCl/Bpy体系引发苯乙烯聚合为ATRP，但同时存在着C₆₀Cl₂₀引发和热引发苯乙烯聚合。通过顺序加料法成功地制备了苯乙烯和甲基丙烯酸甲酯的嵌段共聚物。 研究C₆₀Cl₂₀/CuCl/Bpy/甲苯体系引发苯乙烯聚合反应特征为：聚合反应速率和所得聚合物的分子量（特性粘度）均随CuCl用量的增加而降低；Bpy/CuCl的最佳摩尔比在1.2左右；聚合反应中ATRP部分随C₆₀Cl₂₀用量的增加而增加；聚合反应活性及聚合物分子量均随C₆₀Cl_n中n值的降低而降低，；所得聚合物分子量随单体浓度的增加而增加。测得聚合反应的表观活化能为93.0KJ/mol。C₆₀Cl₂₀/CuCl/Bpy体系用于引发甲基丙烯酸甲酯聚合，结果与苯乙烯聚合相似。 富勒烯化聚苯乙烯的荧光发射光谱测定结果显示，在650nm附近有强的荧光发射峰，这是由C₆₀Cl₂₀引起的，表明聚合物中含有C₆₀Cl₂₀。根据活性聚合原理估算富勒烯化聚苯乙烯是以C₆₀为核、以4-6条聚合物链为臂的星形大分子；由IR、¹H-NMR和¹³C-NMR的表征结果，推测作为臂的聚苯乙烯大分子为无规结构。富勒烯化聚苯乙烯的光导性测定显示其充电电压（1720v）比普通聚苯乙烯（1340v）高，半率期t_1/2为0.81s比普通PSt（0.92s）低0.11s。可见富勒烯化聚苯乙烯与普通聚苯乙烯相比有较高的电荷接受能力一和光导性。 以C60C12。为单组分引发剂，甲苯为溶剂，在120oC下引发N－乙烯基咋哩（VK）聚合。当VK：C60C12。二100（摩尔卜），WK】0．25g／ml，聚合20h得至转化率为100 ％的棕红色粉末，它能部分溶于甲苯、THF等溶剂。用 FTIR，UVVS，‘b－NMR，DSC和TGA对聚合产物的结构进行表征。经紫外光谱、’3C－NMR谱图研究，认为 PVK链是以两种方式与C0键合，一种为咋哩环与C肋上双键的Diels－Alder反应，另一种为＊olm中C－CI键与乙烯基咋哇的加成反应。初步确定所得C60－PVK的拓朴结构为线形，星形及网状。玻璃化转变温度测定：CeoPVK（Tg＝＝187石℃）高于普通 PVK（Tg ＝＝160．1OC）TGA曲线在150—700C显示三个平台，这可能是由C60PVK的多种拓扑结构所致。 用C6（ 于甲苯溶剂中130OC下引发乙烯基咋哩聚合。所得产物的GPC谱线呈双峰（峰a，峰b）分布，其中分子量较小的峰a约占43％，它可能是由热聚合引起的。峰b的分子量较大为9．97X 10＼其分布为1．33，初步认为是C6。C120／CllCIAspy体系引发VK的ATRp。通过C60IVK的m、UV双检测（设定波长400m）WC谱线以及‘HNMR谱验证了ATRP反应机理的合理性。用）‘匝序加料法成功地制得P（V七－MMA）嵌段共聚物。测得富勒烯化聚乙烯基咋哇的充电电压（斤1300VV纯PVK（V斤1200V）高，表明其电荷接受能力更强。C6小PVK的半衰期h①．715X纯PVKN．895）短。可见富勒烯化聚乙烯基咋哇的光导性得到改善。 以C60C12。为引发剂，以可溶于甲苯的环烷酸镍（Ni（naPh）2）为催化剂，三苯基磷 （Poh）3)为配体组成新型ATRP引发体系引发苯乙烯和甲基丙烯酸甲酯聚合。首先以CCb为引发剂与Ni（naph）z／P（Ph组成引发体系引发苯乙烯聚合来验证Ni（llaph）zMPh）可作为ATRP的催化剂。该引发体系不同转化率下所得聚合物的GPC图表明，聚合反应初期存在热聚合反应，随着聚合反应的进行所得聚合物的分子量与聚合反应转化率呈线性增?更多还原

【Abstract】 Chlorided derivative of Fullerenes(C60/C70=7/3), C60Cln(the value of n is 18-22,the average value is 20) has been used as a novel initiator in atom transfer radical polymerization(ATRP) for the first time. C60 bonded Polystyrene(PSt), poly(N-vinylcarbazole) (PVK) and polymethylmethacrylate(PMMA) were prepared by C60Cl20/CuCl/2,2’-bipyridine(Bpy) and C60Cl20/Ni(naph)2/P(Ph)3 initiator system, respectively. Polymeric processes, polymerization mechanism and the structure of polymers were studied in more detail. C60Cl20 was also used as a novel coupling agent in n-BuLi initiating anionic polymerization of butadiene (Bd) and styrene (St) in the first instance. With the two methods, star-shaped polymer with a chlorided derivative of C60 as core and with predictable average molecular weights and narrow polydispersity indices (PDI) polymer chain arm could be synthesized.C60-bonded polystyrene was prepared by C60Cl20/CuCl/ 2,2’-bipyridine(Bpy) initiator system. The mole ratio of styrene: C60Cl20:CuCl:Bpy was 100:1/20:1:2 and polymerization temperature was 130 C.Compared with ordinary initiator system,CCl4CuCl/Bpy, this initiator system showed better phone state dispersion and similar activity in toluene. There were two peaks(peak a and peak b) in the Gel-permeation chromatography(GPC) of PSt initiated by C60Cl20 detected by refractive index (RI) detector. The peak(b), and a smell part of peak(a), consisted with the GPC curve detected by ultra-violet absorption (UV) detector. The working wavelength for the UV detector was set at 340nm where the polystyrene could not be detected and only C60 and its derivative can be recorded. Which indicted that C60 was chemical bonded into the main chain for the part of polystyrene. The linear increasing of molecular weights (Mn,GPC obtained by UV detector) with conversion indicated that this part of polymerization was ATRP initiated by C60Cl20.The peak(a) of the GPC curve detected by RI detector didn’t move with the conversion increasing, and without C60 in the part of polymer. Therefore the part of polymerization was designed therm polymerization. At the same time,a small quantity of C60-PSt existed in peak(a) ,which was initiated by C60Cl20. After styrene polymerized completely, by adding methymethacrylate the copolymer of polystyrene-block-polymethylmethacrylate can also be compounded.Which also verified a "living" nature of the polymerization. In this initiator system, the polymerization rate and the Mn of PSt were decreased as increasing the content of CuCl. The best mole rate of Bpy/CuCl was about 1.2. The part of ATRP in whole polymerization was decreased as decreasing the content of C60Cl20.As decreasing the value of n in C60Cln, the polymerization activity and the molecular weight of polymer were decreased. As increasing the content of monomer, the molecular weight of polymer increased. The apparent activation energy of this polymerization reaction (Ea) was 93.0KJ.mol-1. This initiator system can be used to initiate MMA too. The fluorescence spectra of C60-PSt which was initiated by C60Cl20 initiator system and PSt in dichloromethane at room temperature and the ex was 248nm were detected. The peak of C60Cl20 in 650nm was found in the fluorescence spectrum of C60-PSt, which also indicted that C60 was chemically bonded to PSt linear. With the "living" nature of this polymerization system, the arm number of this C60-bonded polystyrene was roughly calculate by the formula of Mn,GPC=([M]C%/[I])WM, which was about 4-6. The microstructure of C60-PSt was atactic detected by IR,1H-NMR and 13C-NMR. The photoconducting properties of C60-PSt were studied preliminarily. C60-PSt exhibit a higher charge acceptance (V0=1720) than ordinary PSt(V0=1320) and C60-PSt has a shorter t1/2(0.81s) than PSt2 (0.92s). So C60 bonded polystyrene exhibits better photoconductivity than ordinary PSt.C60 bonded poly(N-vinylcarbazole) has been synthesized in present of C60Cl20 in toluene at 120 C ,VK: C60Cl20 was 100:1 (mole ratio) and the concentration of VK was 0.25g/mL. The fullerenated PVK has a更多还原