基于N-乙烯基内酰胺的环形和线形—树枝状嵌段共聚物研究

发布时间：2018-02-14 22:11

本文关键词：聚(N-乙烯基己内酰胺)(PNVCL) 聚(N-乙烯基吡咯烷酮)(PNVP) 聚[甲基丙烯酸-2-(2-甲氧基乙氧基)乙酯] 环形聚合物苯丙氨酸赖氨酸线形-树枝状嵌段共聚物原子转移自由基聚合(ATRP) 可逆断裂链转移(RAFT)自由基聚合超　出处：《云南师范大学》2017年硕士论文　论文类型：学位论文

【摘要】：聚(N-乙烯基己内酰胺)(PNVCL)和聚(N-乙烯基吡咯烷酮)(PNVP)均为N-乙烯基内酰胺类聚合物,具有水溶性、生物相容性和化学稳定性好等特点。PNVCL和聚[甲基丙烯酸-2-(2-甲氧基乙氧基)乙酯](PMEO_2MA)均具有温度响应性,PNVCL的低临界溶解温度(LCST)在生理温度范围内。环形聚合物和线形-树枝状嵌段共聚物均为拓扑结构高分子,其中环形聚合物由于没有末端基团,与其线形前体相比具有许多特殊的性质;而线形-树枝状聚合物不仅具有线形和树枝化大分子的优点,形成的胶束也更稳定,因此,这些聚合物在生物医药领域具有巨大的应用价值。目前,基于PMEO_2MA的环形聚合物和以PNVP为线形链的线形-树枝状嵌段共聚物尚未见文献报道。本文通过原子转移自由基聚合(ATRP)结合Cu(Ⅰ)催化炔基/叠氮(CuAAC)点击反应,在较高浓度(10 mg/m L)下合成了环形聚[甲基丙烯酸-2-(2-甲氧基乙氧基)乙酯](c-PMEO_2MA)均聚物和环形聚(N-乙烯基己内酰胺)-b-聚[甲基丙烯酸-2-(2-甲氧基乙氧基)乙酯]嵌段共聚物(c-PMEO_2MA-b-PNVCL),用GPCMALLS与~1H NMR、IR对聚合物结构进行了测定。性能研究结果表明:拓扑结构对PMEO_2MA均聚物的LCST影响极小。c-PMEO_2MA的临界胶束浓度(CMC)和粒径均小于其线形前体l-PMEO_2MA。c-PMEO_2MA-b-PNVCL中,PNVCL链段的比例越大,其LCST和CMC越大。链段比例相同的c-PMEO_2MA-b-PNVCL的LCST和CMC均小于其线形前体l-PMEO_2MA-b-PNVCL,而c-PMEO_2MA-b-PNVCL的粒径则大于l-PMEO_2MA-b-PNVCL。这些聚合物均自组装为球形胶束。以黄原酸酯调控的可逆加成-断裂链转移自由基聚合(MADIX/RAFT)结合逐步反应的多肽合成手段,合成了以PNVP为线形链、交替的苯丙氨酸和赖氨酸为树枝化基元的新型两亲性线形-树枝状嵌段共聚物,用GPC-MALLS和~1H NMR对聚合物结构进行了测定,并研究了它们在水溶液中的自组装行为。结果表明,嵌段共聚物的CMC随着疏水性树枝化基元代数的增加而降低,得到的胶束形态为球形,PNVP-b-G2胶束的粒径小于PNVP-b-G3。
[Abstract]:Poly (N-vinylcaprolactam) (PNVCL) and poly (N-vinylpyrrolidone) (PNVP) are N-vinyllactam polymers, which are water-soluble. Good biocompatibility and chemical stability. PNVCL and Poly ([-2-methoxy 2-methoxy ethoxy] ethyl methacrylate] PMEO2MA) all have temperature response and low critical solution temperature (LCSTs) of PNVCL. Ring polymers and linear polymers are in the range of physiological temperature. -dendritic block copolymers are topological polymers, The circular polymer has many special properties compared with its linear precursor because it has no terminal group, and the linear dendritic polymer not only has the advantages of linear and dendritic macromolecules, but also the micelles are more stable. These polymers have great application value in the field of biomedicine. At present, The circular polymer based on PMEO_2MA and the linear dendritic block copolymers with PNVP as linear chain have not been reported in the literature. In this paper, the click-through reaction of alkynyl group / azide CuAAC catalyzed by atom transfer radical polymerization (ATRP) was studied. The block copolymerization of annular poly (-2-methoxy ethoxy) ethyl methacrylate (c-PMEO2MAA) and cyclic poly (N-vinylcaprolactam) -b-[ methacrylate -2-methoxy ethoxy] ethyl ester was synthesized at a higher concentration of 10 mg/m / L ~ (-1). The properties of c-PMEO2MA-b-PNVCLA were determined by GPCMALLS and 1H NMR-IR. The results showed that the effect of topological structure on LCST of PMEO_2MA homopolymer was minimal. The critical micelle concentration of c-PMEO2MA and particle size were smaller than those of l-PMEO2MA.c-PMEO2MA-b-PNVCL. The larger the LCST and CMC, the larger the LCST and CMC. The LCST and CMC of c-PMEO _ 2MA-b-PNVCL with the same segment ratio are smaller than that of l-PMEO _ 2MA-b-PNVCL. the particle size of c-PMEO2MA-b-PNVCLs is larger than that of l-PMEO2MA-b-PNVCL.These polymers are self-assembled into spherical micelles and reversible addition-break chain transfer controlled by xanthate. Free radical polymerization (MADIX / RAFT) combined with stepwise peptide synthesis, A novel amphiphilic linear dendritic block copolymer with PNVP as linear chain and alternate phenylalanine and lysine as dendrimers was synthesized. The structure of the polymer was determined by GPC-MALLS and 1H NMR. The self-assembly behavior of these copolymers in aqueous solution was studied. The results show that the CMC of block copolymers decreases with the increase of hydrophobic dendrimer algebra, and the micelle morphology of PNVP-b-G2 is smaller than that of PNVP-b-G3.
【学位授予单位】：云南师范大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O633.2

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