两亲性论文:两亲性聚环氧乙烷阴离子开环聚合聚己内酯配位-插入开环聚合胶束

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1、两亲性论文:两亲性 聚环氧乙烷 阴离子开环聚合 聚己内酯 配位-插入开环聚合胶束【中文摘要】由于两亲性共聚物能自组装形成丰富的形态,因而在化学,物理,生物等领域中有着广泛的潜在的用途。在所合成的各种 结构的两亲性共聚物中,聚环氧乙烷(PEO)是其中一个最常见的组成 部分。这是由于聚环氧乙烷既能很好的溶于水,又能溶于大部分的有 机溶剂,更重要的是,当把PEC和其它分子偶合时,它的许多优良性质 也会随之转移到结合物中。在新型生物材料的合成和改性中,PEO作为材料的一部分,将赋予材料新的特性和功能,如亲水性、抗凝血性、 抗巨噬细胞吞噬性、柔性等。由于 PEC的这些特性,使得包含PEO链 段的各种聚合

2、物可能有着很多潜在的应用价值,所以人们在设计各种 结构的两亲性共聚物时都偏向于采用不同的方式引入聚环氧乙烷 (PEO)分子链。本文合成了分子量不同的嵌段共聚物 mPEO-b-PC以及 分子量不同的星型共聚物 PEO3-b-PCL3 PEO4-b-PCL4通过共溶剂的 方法制备了胶束,并观察了胶束的形貌和粒径,主要结果如下:(1)以 自制的一缩二乙二醇单甲醚钾为引发剂,采用阴离子开环聚合的方法 合成了分子量可控的单羟基的聚环氧乙烷 (mPEO)以此mPE前大分 子引发剂,以辛酸亚锡(Sn(Oct)2)为催化剂,通过配位一插入开环聚 合引发 -己内酯开环聚合,制备了两亲性嵌段共聚物 mPEO-b-

3、PCL对 各步产物进行了 1H NMR,GP等表征。用荧光光谱仪测定了嵌段共聚 物在水中的临界胶束浓度(cmc),证明其具有低的临界胶束浓度。通过共溶剂的方法制备了两亲性嵌段共聚物mPEO-b-PC在水溶液中形成的胶束,用透射电镜观察了胶束的形貌,用激光纳米粒度分析仪测定 了胶束的粒径大小、粒径分布以及Zeta电位。 通过阴离子开环聚 合技术合成了三臂星型聚环氧乙烷PEO3四臂星型聚环氧乙烷PEO4以三臂星型聚合物PEO3四臂星型聚合物PEO4为大分子引发 剂,Sn(Oct)2为催化剂,引发 -己内酯(CL)开环聚合,得到了星型共 聚物PEO4-b-PCL4对各步产物进行了 1H NMR, G

4、PC等表征。通过共 溶剂的方法制备了星型嵌段共聚物PEO3-b-PCL3 PEO4-b-PCL4勺胶束,用透射电镜观察了胶束的形貌,用激光纳米粒度分析仪测定了胶 束的粒径大小、粒径分布以及 Zeta电位。【英文摘要】 Amphiphilic and fun cti onal copolymers have attracted more in terests in the last decades for their widely application in self-assembly field. Among the investigated amphiphilic block copoly

5、mers, the most utilized hydrophilic comp onent is poly (ethyle ne oxide) (PEO) due to biocompatibility, lack of im munogen icity and easy cleara nee from the human body, especially the materials modified by PEO can keep someproperties of PEO. Another kind of polymer, such as poly ( -caprolactone) (P

6、CL), has also been widely used asimporta nt drug delivery carriers because of their biocompatibility and biodegradability. In order to meet the in creas ing dema nds for better performa nces and satisfy therequirements of somespecific applications,the biodegradablepolymers PCL modified by PEO have a

7、ttracted more and more attentions.lnthis paper, the block copolymers mPEO-b-PCIwithdiffere nt PCL segme nt molecular weight were successfully syn thesized by the comb in ati on of liv ing anionic polymerizatio n and coord in ati on-i nserti on rin g-ope ning polymerizatio n. By means of PEO-supporte

8、d multifu ncti on al-in itiati ng system, some well-defi ned star-shaped copolymers PEO3-b-PCL3 and PEO4-b-PCL4 were syn thesized and their properties were explored. The main results summarized as follows). A series of amphiphilic block copolymers mPEO-b-PCL with differe nt PCL segme nt molecular we

9、ight were successfully prepared by comb in ati on of anionic ring-opening polymerization with coord in ati on-i nsertion rin g-ope ning polymerizati on. Firstly, the lin ear mPEO was prepared by anionic rin g-ope ning copolymerizati on of EO with 2-(2-methoxyethoxy) ethoxide potassium as the small molecule initiators. Then, the obtaind mPEO was used to initiate the ring-opening polymerization of CL as the macroinitiator, in the absence of Sn(Oct)2 as the catalyst, and amphiphilic block copolymers mPEO-b-PCL were successfully synthesized. By changing the ratios of monomeand

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