基于ATRP技术的多嵌段共聚物研究进展

原子转移自由基聚合(ATRP)技术是合成结构规整性聚合物的有效途径。综述了近十年来采用ATRP技术合成多嵌段共聚物的研究进展。从引发剂、共聚单体和反应条件等方面讨论了ABA型、ABC型和ABCBA型等类型多嵌段共聚物的合成、性质与潜在应用。对原子转移自由基聚合技术在合成功能性多嵌段共聚物中的应用前景进行了展望。     

含聚氧乙烯链段的两亲嵌段共聚物及接枝共聚物的分子设计,合成及性能

论述了由聚烯链段与聚苯乙烯或聚（甲基）丙烯酸酯链段组成的各种嵌段或接枝共聚物（包括二嵌段、两种三嵌段、星型嵌段、多嵌段、二种规整接枝共聚物等）的分子设计及合成,并总结了其两亲性质、络合碱金属离子性及微观相分离等特性。     

大网均孔苯乙烯共聚物的合成、性质和应用

本文综述了大网均孔苯乙烯共聚物的合成、性质和应用,引用文献60篇。     

Tbβ2AA与甲基丙烯酸甲酯共聚物的荧光性研究

将已合成的铽多元配合物在AIBN引发下与甲基丙烯酸甲酯共聚制得4种含铽共聚物。用元素分析、FT－IR、GPC、UV、DTA－TG表征它们的结构与性质。铽共聚物易溶于普通的有机溶剂，易制得韧性好、热稳定性好的薄膜。荧光性质显示铽共聚物能发射稀土离子的特征荧光，且荧光发射强度在Tb含量4％以下时随着铽含量的增加显线性增加。     

聚(丙烯酰胺-丙烯酸高级酯)的溶液性质研究

采用沉淀聚合法分别合成了丙烯酰胺与丙烯酸十四酯、丙烯酸十六酯、丙烯酸十八酯一系列疏水缔合型共聚物。对共聚物溶液性质及疏水基团浓度、电解质浓度、温度等因素对共聚物溶液性能的影响进行了研究,结果表明这类疏水缔合型聚合物表观出较好的耐温、耐盐等性能。     

H型聚合物的合成及性质

H型聚合物是一种具有轻度支化拓扑结构的高分子,通常具有不同于线型、星型和超支化聚合物的流变性能、本体和溶液组装性能。由于H型聚合物的合成较为复杂,一直以来,科研工作者的工作重点均集中于如何精确合成与构筑,性能研究较为有限。本文根据H型聚合物构筑段的不同从H型均聚物、二元共聚物、三元共聚物、五元共聚物以及其他H型聚合物的合成及性质方面进行了总结和评述,并在此基础上展望了H型聚合物的研究方向和发展趋势。     

星形PLA-PEG嵌段共聚物胶束的制备与表征

以胆酸为引发剂,用辛酸亚锡催化丙交酯开环聚合合成星型CA-PLA。利用DCC为脱水剂,将不同分子量的端羧基化PEG与星型CA-PLA偶联,合成一系列以胆酸为核的星形两亲性嵌段共聚物,用透析法制备共聚物胶束,并用TEM和DLS研究胶束的性质。合成了分子量为6000和12000的两种CA-PLA,其分子量可以通过胆酸羟基与丙交酯的比例进行控制。将分子量2000和5000的PEG分别与两种CA-PLA偶联,合成了四种星型CA-PLA-PEG嵌段共聚物。共聚物胶束形貌为均匀的球形,粒径为20-40nm,且随共聚物中PLA链段分子量的增加而增大,随PEG链段分子量的增加而减小。临界胶束浓度(CMC)低于同等链段长度的线型PLA-PEG嵌段共聚物胶束。     

梯度共聚物接枝纳米粒子的合成及其力学性能

通过RAFT聚合制备了3种不同序列(无规、嵌段及梯度)的丙烯酸正丁酯(BA)/甲基丙烯酸甲酯(MMA)二元共聚物(PBA-r-PMMA、PBA-b-PMMA、PBA-g-PMMA),以及2种含可交联侧链的聚甲基丙烯酸酰氧基丙基三乙氧基硅烷(PTEPM)的三元共聚物PTEPM-b-(PBA-g-PMMA)和PTEPM-b-(PBA-r-PMMA),三元共聚物中PBA/PMMA分别为无规和梯度结构.这5个共聚物中PBA/PMMA段具有相近的分子量和组分比.三元共聚物通过共组装及交联后得到球状的共聚物接枝纳米粒子NP-(PBA-g-PMMA)和NP-g-(PBA-rPMMA). DSC结果表明NP-(PBA-g-PMMA)和PBA-g-PMMA具有较宽的玻璃化转变温度区间(～130℃),证明成功合成了梯度共聚物和接枝梯度共聚物的纳米粒子.通过DMA测试和变温拉伸测试发现,在升温过程中梯度结构二元共聚物及其对应的纳米复合材料力学性能呈现渐进式变化,而无规或嵌段对应物力学性能呈现突变,原因是前者具有较宽的玻璃化转变过程.由于无机内核的作用,NP-(PBA-g-PMMA)和NP-(PBA-r-PM...     

大分子改性剂甲基丙烯酸-丙烯酸丁酯-丙烯腈(MAA-BA-AN)的合成与表征

以甲基丙烯酸(MAA),丙烯酸丁酯(BA)和丙烯腈(AN)为单体,通过自由基溶液聚合法合成了MAABA-AN三元共聚物大分子表面改性剂,其结构和性质经1H NMR,13C NMR,FT-IR,GPC,TGA及DSC等表征.结果表明,MAA-BA-AN的分子量在3000～10000,是无规共聚物,在375℃～475℃内失重.     

功能性两亲嵌段共聚物的研究进展

功能性两亲嵌段共聚物因自身独特的性质而在靶向输送、控制释放、分子识别等领域得到广泛的应用.本文对这类嵌段共聚物的合成方法、其胶束的形成机理、制备形式、表征手段以及一些常见的具有光学活性的两亲嵌段共聚物及其应用进行了综述.     

Model‐Based Design for Preparing Styrene/Methyl Methacrylate Structural Gradient Copolymers

Because of the complexity of monomer sequence formation during polymerization, it is necessary to employ programmed synthesis to prepare copolymers with well‐defined sequences. We introduce a computational tool that can generate recipes to synthesize copolymers with pre‐designed monomer sequences. An efficient design strategy was crafted based on analyzing the impact of varying multiple synthesis factors in forced gradient copolymerization on the targeted properties. Finally, the proposed design tool was applied to generate recipes for several different structural gradient copolymers as case studies. It was shown that a recipe that meets certain targets can be designed in minutes. The recipes that are designed can also be tailored according to different application requirements.

     

Stimuli‐responsive reversible physical networks. II. Design and properties of homogeneous physical networks consisting of periodic copolymers synthesized by living cationic polymerization

The design and precision synthesis of physical networks consisting of copolymers with crystallizable pendant groups are described in this work. Amphiphilic periodic, statistical, and gradient copolymers consisting of octadecyl vinyl ether (ODVE) units were synthesized via living cationic polymerization. The synthesis involved the copolymerization of ODVE and 2‐methoxyethyl vinyl ether (hydrophilic) with an 1‐(isobutoxy)ethyl acetate [CH₃CH(OiBu)OCOCH₃]/Et_1.5AlCl_1.5 initiating system in the presence of a weak Lewis base to yield copolymers with very narrow molecular weight distributions (weight‐average molecular weight/number‐average molecular weight ? 1.2). All aqueous solutions of the copolymers behaved as a viscous liquid above 50 °C. When cooled below 25 °C, the solutions turned into transparent, transient physical gels (exhibiting terminal flow), regardless of the sequence distribution. Viscoelastic studies showed that a periodic copolymer gave a hard gel that was more brittle than the gels obtained from the corresponding statistical and gradient copolymers. This difference and the differences in the relaxation time and relaxation mode distribution of the copolymer gels were consistent with the sequence distributions of ODVE in the respective copolymers. These results indicate that the mechanical properties of a physical network can be controlled by the primary polymer structures. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2712‐2722, 2005     

Tuning the Surface/Bulk Properties by the Control of the Amphiphilic Profile in Gradient Copolymer

Nitroxide Mediated Radical Polymerization (NMP) combined with the Semi-Batch process is used for synthesize poly(N,N-Dimethylacrylamide-grad-Butyl acrylate), called poly(DMA-grad-BuA), in the presence of SG1 as control agent and the alkoxyamine (MAMA) as initiator. The instantaneous composition is used to characterize the gradient copolymers. The variation of the addition rate of DMA influences on the incorporation of DMA in the macromolecular chains. The thermal/rheological properties of gradient copolymers in bulk are also studied and discussed in relation with their local structure.     

Alternating,gradient, block,and block–gradient copolymers of ethylene and norbornene by Pd–Diimine‐Catalyzed “living” copolymerization

We demonstrate, in this article, the facile synthesis of a broad class of low‐polydispersity ethylene–norbornene (E–NB) copolymers having various controllable comonomer composition distributions, including gradient, alternating, diblock, triblock, and block–gradient, through “living”/quasiliving E–NB copolymerization facilitated with a single Pd – diimine catalyst ( 1 ). This synthesis benefits from two remarkable features of catalyst 1 , its high capability in NB incorporation and high versatility in rendering E–NB “living” copolymerization at various NB feed concentrations ([NB]₀) while under an ethylene pressure of 1 atm and at 15 °C. At higher [NB]₀ values between 0.42 and 0.64 M, E–NB copolymerization with 1 renders nearly perfect alternating copolymers. At lower [NB]₀ values (0.11–0.22 M), gradient copolymers yield due to gradual reduction in NB concentration, with the starting chain end containing primarily alternating segments and the finishing end being hyperbranched polyethylene segments. Through two‐stage or three‐stage “living” copolymerization with sequential NB feeding, diblock or triblock copolymers containing gradient block(s) have been designed. This work thus greatly expands the family of E–NB copolymers. All the copolymers have controllable molecular weight and relatively low polydispersity (with polydispersity index below 1.20). Most notably, some of the gradient and block–gradient copolymers have been found to exhibit the characteristic broad glass transitions as a result of their possession of broad composition distribution. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Amphiphilic gradient copolymers of 2‐methyl‐ and 2‐phenyl‐2‐oxazoline: self‐organization in aqueous media and drug encapsulation

Gradient (or pseudo‐diblock) copolymers were synthesized from 2‐methyl‐2‐oxazoline and 2‐phenyl‐2‐oxazoline monomer mixtures via cationic polymerization. The self‐assembling properties of these biocompatible gradient copolymers in aqueous solutions were investigated, in an effort to use the produced nanostructures as nanocarriers for hydrophobic pharmaceutical molecules. Dynamic and static light scattering as well as AFM measurements showed that the copolymers assemble in different supramolecular nanostructures (spherical micelles, vesicles and aggregates) depending on copolymer composition. Fluorescence spectroscopy studies revealed a microenvironment of unusually high polarity inside the nanostructures. This observation is related partly to the gradient structure of the copolymers. The polymeric nanostructures were stable with time. Their structural properties in different aqueous media—PBS buffer, RPMI solution—simulating conditions used in pharmacological/medicinal studies, have been also investigated and a composition dependent behavior was observed. Finally, the hydrophobic drug indomethacin was successfully encapsulated within the gradient copolymer nanostructures and the properties of the mixed aggregates were studied in respect to the initial copolymer assemblies. The produced aggregates encapsulating indomethacin showed a significant increase of their mass and size compared to original purely polymeric ones. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

二氧化碳合成脂肪族聚碳酸酯

介绍了二氧化碳合成脂肪族聚碳酸酯（APC）的合成工艺、催化剂体系、物理化学性能以及改性,并阐述了共聚物性质和应用前景。     

Amino‐Acid‐Based Block Copolymers by RAFT Polymerization

This review summarizes recent advances in the design and synthesis of amino‐acid‐based block copolymers by reversible addition–fragmentation chain transfer (RAFT) polymerization of amino‐acid‐bearing monomers. We will mainly focus on stimuli‐responsive block copolymers, such as pH‐, thermo‐, and dual‐stimuli‐responsive block copolymers, and self‐assembled block copolymers, including amphiphilic and double‐hydrophilic block copolymers having tunable chiroptical properties. We will also highlight recent results in RAFT synthesis of amino‐acid‐based copolymers having various properties, such as catalytic and optoelectronic properties, cross‐linked block copolymer micelles, unimolecular micelles, and organic–inorganic hybrids.     

Imaging of phase segregation in gradient copolymers: Island and hole surface topography

Application of traditional block copolymer microscopy techniques to gradient copolymers yields limited results, due to the low compositional contrast provided from the sinusoidal composition profiles of their phase segregated nanostructures. In contrast, optical microscopy and profilometry allow for the first direct visualization of their phase segregation properties through surface features formed in annealed thin films. Three comonomer systems are studied; one block and one gradient copolymer are compared for each system. Island/hole topography is observed in all block cases. Of the three gradient copolymers, one showed no pattern development and two showed emergence of island/hole patterns, which coarsen over initial annealing and then appear to anneal away. These results are related to the lower driving force for phase segregation from gradient sequencing, which lowers the potential of gradient copolymers to form island/hole patterns and also to pin any patterns formed. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

活性聚合法合成结构精确的含氟嵌段共聚物

结构精确的含氟嵌段共聚物具有优异而独特的化学和物理性能,有广阔的应用前景,因此受到广泛的关注.含氟嵌段共聚物可分为两类,一类是侧基含氟嵌段共聚物,另一类是主链含氟嵌段共聚物.活性聚合为嵌段共聚物的合成提供了最为重要的方法,利用它可以合成结构精确、分子量可控、分子量分布窄的嵌段共聚物.根据单体的反应特性选择不同的聚合方法,可以得到不同的含氟嵌段共聚物.本文主要综述了近几年利用各种活性聚合方法合成结构精确的含氟嵌段共聚物方面的进展.     

Synthesis and thermal properties of diblock copolymers utilizing non-covalent interactions

Diblock copolymers of poly(styrene) and poly(ethylene oxide) were prepared utilizing a bisterpyridine ruthenium complex as non-covalent interaction for the connection of the two blocks. Apart from the synthesis and characterization of four metallo-supramolecular block copolymers, first studies on the thermal properties of the block copolymers have been performed. A complex crystallization behavior was observed and is described in a qualitative fashion. The influence of the metal complex on the thermal stability of the metallo-supramolecular block copolymers remains a question for further investigation.