微米级单分散共聚物微球的制备

用分散聚合法制备了苯乙烯 甲基丙烯酸甲酯微米级单分散共聚物微球 ,粒径为 5 4 μm .将分散聚合体系与乳液聚合体系进行了比较 ,并对共聚物微球的形貌、粒径分布及共聚情况进行了表征研究 .     

细菌聚γ-谷氨酸溶液流变性能的研究

用分散聚合法制备了苯乙烯 甲基丙烯酸甲酯微米级单分散共聚物微球 ,粒径为 5 4 μm .将分散聚合体系与乳液聚合体系进行了比较 ,并对共聚物微球的形貌、粒径分布及共聚情况进行了表征研究     

分散共聚法制备窄分布P(St-co-nBA)微球

用分散共聚法制得窄分布苯乙烯(St)和丙烯酸正丁酯(nBA)的共聚物微球.采用1H-NMR、DSC、FTIR、SEM、LS等对共聚物的结构、形态、性能进行表征,考察了初始单体配比、温度、稳定剂浓度、分散介质极性、引发剂对微球粒径、粒径分布及转化率的影响.实验结果表明,初始单体比nBA/St增大,微球粒径增大,分布变宽,...     

苯胺与吡咯共聚物空心球的自组装制备及性能

以碱性溶液为反应介质,苯胺和吡咯为单体,采用稀释聚合法制备苯胺-吡咯共聚物自组装空心微球.研究了搅拌条件、共聚单体摩尔比、聚合反应介质和聚合时间对共聚物形貌的影响.采用扫描电子显微镜、透射电子显微镜、红外光谱、广角X射线衍射、热重分析仪和四探针技术表征了共聚物的形貌、结构和性能.研究结果表明,聚合反应条件对共聚物的形貌有重大影响,通过调整聚合反应条件,可以实现共聚物形貌的有效调控.共聚单体总摩尔浓度为0.05 mol/L,氨水溶液作为反应介质,在静态条件下反应24 h可以得到尺寸均一、平均外直径为610～863 nm,壳厚144～162 nm的自组装共聚物空心微球.同时,研究了共聚物对银离子的吸附性能,结果表明共聚物对银离子有还原作用,吸附后共聚物表面有纳米银的生成.     

两亲磁性高分子微球的合成与表征

在Fe3O4磁流体存在下 ,通过苯乙烯与聚氧乙烯大分子单体 (MPEO)分散共聚制备两亲磁性高分子微球 .研究了聚氧乙烯大分子单体对微球粒径的影响 .用扫描电子显微镜 (SEM)、原子力显微镜 (AFM)表征了磁性微球的粒径、表面形貌以及表面粗糙度 ,用傅立叶红外光谱 (FTIR)鉴定了共聚物的结构 .随着聚合物中聚氧乙烯大分子单体含量的增加 ,微球表面的粗糙度增加 ,通过改变共聚物中MPEO的含量 ,可以得到含有 0 4～ 3 5mg g羟值的两亲磁性高分子微球     

苯乙烯-甲基丙烯酸羟基乙酯共聚物微球固载金属卟啉催化剂的制备及其催化性能

 将酰氯化的羧基金属卟啉 (MP) 与表面含羟基的苯乙烯-甲基丙烯酸羟基乙酯共聚物微球 (P(St-co-HEMA)) 进行酯化反应, 制备了共聚物微球固载的金属卟啉催化剂 (P(St-co-HEMA)MP). 采用扫描电镜、紫外-可见光谱、红外光谱和热重等手段对微球进行了表征, 并考察了它在“金属卟啉?抗坏血酸?分子氧”体系中催化环己烷羟化反应性能. 结果表明, 共聚物微球固载的金属卟啉比非固载的金属卟啉具有更高的催化活性, 催化剂重复使用 4 次, 仍保持较高催化活性. 各共聚物微球固载的金属卟啉催化活性顺序为 P(St-co-HEMA)FeP > P(St-co-HEMA)MnP > P(St-co-HEMA)CoP.     

不同表面官能团和化学组成共聚物微球的表面生物矿化研究

采用具有不同共聚物组成和端基官能团的聚己内酯-b-聚乙二醇共聚物(PCL-b-PEG),通过双乳液溶剂挥发法制备了一系列具有不同表面性质的生物降解高分子微球.采用生物模拟矿化的方法以磷灰石修饰微球表面.进一步通过扫描电镜、热重分析仪、X-射线衍射仪和光电子能谱仪对微球表面磷灰石的形貌、含量、结构和组成进行了分析.研究了微球表面亲水性、粗糙度、官能团以及矿化时间对于磷灰石形成的影响.最终实验结果表明,随着共聚物中PEG含量增加,微球表面粗糙度和亲水性增加,因此微球表面磷灰石含量增加.同时微球表面官能团以及矿化时间的不同也会对磷灰石的形成和分布产生明显影响.     

温敏梳状嵌段共聚物对PS微球阻抗蛋白吸附作用的研究

采用可逆加成断裂链转移聚合(RAFT)方法和大分子单体技术,制备了温敏性聚N-异丙基丙烯酰胺(PNIPAM)-聚乙烯基吡咯烷酮(PVP)与PNIPAM-聚氧化乙烯(PEO)梳状嵌段共聚物,这些共聚物具有PVP或PEO支链.以溶菌酶为蛋白模型研究了所得共聚物对聚苯乙烯(PS)微球表面蛋白吸附的抑制作用.通过絮凝实验、激光散射法表观粒径测定、电泳迁移率测定及蛋白吸附量的定量数据比较了不同梳状结构的抗蛋白吸附效果.结果表明,预吸附梳状嵌段共聚物可有效阻抗蛋白吸附,亲水支链增加阻抗性能提高,即使环境温度高于PNIPAM的相转变温度也能阻抗蛋白吸附.透射电镜和共聚物胶体粒径测试表明,梳状嵌段共聚物阻抗蛋白吸附的机制是预吸附后PVP或PEO亲水支链在微球表面形成了阻隔层.通过PS微球的变温絮凝实验可评价预吸附聚合物的抗蛋白吸附性能,快速获得定性结果.     

基于3D受限自组装构筑中空介孔氧化硅/碳复合微球

发展简单、高效、可控的方法来制备中空介孔微球是介孔材料领域的研究热点.本工作结合嵌段共聚物的三维受限自组装(3D-CSA)和自模板碳化策略,建立了一种构筑中空介孔微球的新方法 .首先,采用乳液-溶剂挥发法实现嵌段共聚物与全氟辛烷(PFO)在3D受限空间的分级组装,获得了核-壳结构微球,其中壳层由微相分离的嵌段共聚物构成.然后,在壳层的连续相选择性地复合氧化硅,既实现了无机框架的负载,又实现了对连续相聚合物链选择性交联.对复合微球进行煅烧处理后,实现了壳层连续相聚合物的选择性碳化,获得了中空介孔氧化硅/碳复合微球.本研究系统地阐述了核-壳型分级结构微球的形成机理和必备条件,研究了氧化硅前驱体添加量和嵌段共聚物分子量对中空介孔氧化硅/碳复合微球形貌的影响,为制备中空介孔微球材料提供了一种简便、可控的方法.     

新型含苯硼酸基团的两亲性共聚物微球的制备及其糖敏感性能

将3-丙烯酰胺基苯硼酸与马来酸酐改性β-环糊精反应, 合成了一种新型的共聚物, 并采用13C NMR, IR和UV-Vis等技术对共聚物的结构进行了表征. 利用SEM研究了聚合物在甲醇中的自组装形态. 通过在不同溶剂中溶解性能的研究, 探讨了共聚物与甲醇的络合机理以及自组装机理. 以格列奇特为模型药物, 研究了聚合物微球在不同环境下的振荡释放行为. 结果表明, 载药微球在30 min内对葡萄糖刺激迅速响应, 在葡萄糖浓度为3 g/L和无糖环境之间的振荡释放呈“开-关”式自调释放.     

生物可降解磷酸酯-碳酸酯共聚物的合成及性能研究

通过光气，二氯磷酸酯和双酚Ａ反应，合成六种磷酸酯 碳酸酯共聚物，用ＩＲ、１Ｈ ＮＭＲ及元素分析表征了共聚物，测量了Ｍｎ和热学性质．初步研究了在ｐＨ７４磷酸盐缓冲溶液中，核糖核酸酶或碱性磷酸酶存在下的体外降解性能及其对抗肿瘤药物５ Ｆｕ的释放性能．     

Stereocomplexes of Triblock Poly(lactide- PEG2000-lactide) as Carrier of Drugs

Triblock copolymers of poly(lactide)-poly(ethylene-glycol)-poly(lactide) (PLA-PEG₂₀₀₀-PLA) were synthesized by ring-opening polymerization of lactide and PEG₂₀₀₀ diol as co-catalyst. Stereocomplexes with particle sizes ranging from nanometers to microns were obtained by mixing acetonitrile solutions of pairs of enantiomeric homopoly(lactide) and the triblock copolymers. The stereocomplexes exhibited higher crystalline melting temperatures than the optically pure polymers. The ratio of PLA terminals in the copolymers had a significant effect on their stereocomplex degradation and drug release. These stereocomplexes were used for the encapsulation of dexamethasone for controlled release applications. Dexamethasone phosphate loading capacity, in vitro release, degradation and stability of polymers and formulation were investigated for one month. An increase in the dexamethsone phosphate content in the stereocomplex or a decrease in the PLA ratio in the copolymer resulted in a faster release of drug and polymer degradation.     

Synthesis and Properties of Biodegradable Copolymers of 9-Phenyl-2, 4, 8, 10-tetraoxaspiro-[5, 5]undcane-3-one and Ethylene Ethyl Phosphate

Novel biodegradable copolymer poly（CC-co-EEP） was synthesized by ring-opening copolymerization of cyclic carbonate 9-phenyl-2, 4, 8, 10-tetraoxaspiro-[5, 5]undcane-3-one （CC） and ethylene ethyl phosphate （EEP）. The obtained poly （CC-co-EEP）s were characterized by FTIR, ^1H NMR, ^13C NMR and gel permeation chromatography （GPC）. In vitro hydrolytic degradation of the copolymers were investigated in phosphate buffer solution （pH=7.4）. Hydrophilic phosphate units apparently improved the degradability of poly（carbonate-phosphate）.     

侧基带有L-苯丙氨酸的手性两亲嵌段共聚物的合成及其自组装行为

N3-苯丙氨酸与嵌段共聚物聚乙二醇-b-聚炔丙基缩水甘油(MPEO-b-PGPE)发生"click"反应,合成了具有光学活性的两亲嵌段共聚物聚乙二醇-B-聚L-苯丙氨酸三唑基缩水甘油(MPEO-b-PGTP),用1H-NMR和元素分析对其结构和组成进行表征.并对其自组装行为进行研究,滴体积法测定MPEO-b-PGTP溶...     

阻垢剂的性能及其协同效应

阻垢剂的性能及其协同效应路长青，韩应琳，马迎军，赵任辉，刁月民（南京化工大学应用化学系南京２１０００９）关键词有机膦酸，共聚物，阻垢剂，协同效应有机膦酸和某些共聚物是目前使用最广泛的两类冷却水阻垢剂。有机膦酸对许多金属离子，如钙、镁、铁和锌等具有优异...     

生物降解高分子——聚己内酯/聚氧乙烯/聚丙交酯三元共聚物水解行为的研究

以异辛酸亚锡为催化剂 ,通过聚乙二醇醚 (PEG)引发ε 己内酯和L 丙交酯开环聚合 ,制备了PCL/PEO/PLA三元共聚物 .研究了聚合物在 pH7 4磷酸缓冲溶液、37℃条件下的体外降解行为 .采用GPC、1H NMR、DSC和XRD技术研究了聚合物在水解降解过程中分子量、分子量分布、组成、吸水率、结晶性等的变化 .结果表明共聚物的吸水率随聚醚组分含量而增大 ;随水解材料的失重率增大 ,聚醚组分含量下降程度也加大 .此外研究还表明 :聚合物中丙交酯组分含量高时 ,聚合物的结晶结构主要由PLLA形成 .由于聚合物的水解降解首先发生在无定形区和结晶区边缘 ,随着共聚物的降解、结晶性的PLLA低聚物的生成 ,导致了共聚物的分子量呈双峰分布     

乳酸-磷酸酯共聚物为载体的高分子药物的合成及其控释研究

以5-氟尿嘧啶(5-FU)为药物模型,以乳酸-磷酸酯共聚物为高分子药物载体,合成了侧链带药的乳酸-磷酸酯共聚物药物。用¹HNMR、IR、UV谱对其结构进行了表征。测定高分子药物中5-FU的含量,研究了高分子药物的体外释药性能及共聚物组成对释药性能的影响。     

Tuning the release rate of acidic degradation products through macromolecular design of caprolactone-based copolymers

Macromolecular engineering is presented as a tool to control the degradation rate and release rate of acidic degradation products from biomedical polyester ethers. Three different caprolactone/1,5-dioxepan-2-one (CL/DXO) copolymers were synthesized: DXO/CL/DXO triblock, CL/DXO multiblock, and random cross-linked CL/DXO copolymer. The relation of CL and DXO units in all three copolymers was 60/40 mol %. The polymer discs were immersed in phosphate buffer solution at pH 7.4 and 37 degrees C for up to 364 days. After different time periods degradation products were extracted from the buffer solution and analyzed. In addition mass loss, water absorption, molecular weight changes, and changes in thermal properties were determined. The results show that the release rate of acidic degradation products, a possible cause of acidic microclimates and inflammatory responses, is controllable through macromolecular design, i.e., different distribution of the weak linkages in the copolymers.     

Syntheses of amphiphilic biodegradable copolymers of poly(ethyl ethylene phosphate) and poly(3-hydroxybutyrate) for drug delivery

Biodegradable and amphiphilic triblock copolymers poly(ethyl ethylene phosphate)-poly(3-hydroxy-butyrate)-poly(ethyl ethylene phosphate) (PEEP-b-PHB-b-PEEP) have been successfully synthesized through ring-opening polymerization. The structures are confirmed by gel permeation chromatography and NMR analyses. Crystallization investigated by X-ray diffraction reveals that the block copolymer with higher content of poly(ethyl ethylene phosphate) (PEEP) is more amorphous, showing decreased crystallizability. The obtained copolymers self-assemble into biodegradable nanoparticles with a core-shell micellar structure in aqueous solution, verified by the probe-based fluorescence measurements and transmission electronic microscopy (TEM) observation. The hydrophobic poly(3-hydroxybutyrate) (PHB) block serves as the core of the micelles and the micelles are stabilized by the hydrophilic PEEP block. The size and size distribution are related to the compositions of the copolymers. Paclitaxel (PTX) has been encapsulated into the micelles as a model drug and a sustained drug release from the micelles is observed. MTT assay also demonstrates that the block copolymers are biocompatible, rendering these copolymers attractive for drug delivery. Supported by the Specialized Research Fund for the Doctoral Program of Higher Education of China (Grant No.20060358036)     

The Preparation and Biodegradable Properties of Poly(L‐lactic acid)‐Poly(ϵ‐caprolactone) Multiblock Copolymers

Multi‐block copolymers of PLLA and PCL were prepared by a coupling reaction between PLLA and PCL prepolymers with –NCO end groups. FTIR proved that the products were PLLA‐PCL copolymers. The weight‐average molecular weight of the copolymers was up to 180,000 at a composition of 60% PLLA and 40% PCL. The degradation properties of PLLA and PLLA‐PCL copolymers were studied by a soil burial test and a hydrolysis test in a phosphate‐buffer solution. The degradation rate was estimated by the mass loss, molecular weight reduction, pH value changes and swelling index; the degradation rates of the copolymers were a function of the composition of PLLA and PCL. Increasing PCL content in the copolymers resulted in lower degradation rate.