Sequence distribution of partially hydrolyzed poly(vinyl acetate)

Copolymers of vinyl acetate and vinyl alcohol were studied by differential thermal analysis. The melting points of the copolymers are not a simple function of the composition, but depend on the method of preparation of the copolymers. Partial saponification of poly(vinyl acetate) with sodium hydroxide leads to high melting, ordered copolymers, while reacetylation of poly(vinyl alcohol) leads to low melting, random copolymers. Catalytic alcoholysis of PVAc yields copolymers intermediate in melting point and order. The results are treated by assuming that equal melting points indicate similar sequence length distributions of crystallizable units.     

Hydrogels with Crystalline or Liquid Crystalline Structure

The formation of ordered structure in hydrogels derived from copolymers of hydrophilic and hydrophobic monomers with crystalline or liquid‐crystalline moieties is reviewed. The role of water in the formation of ordered structure and its influence on the thermal and mechanical properties of hydrogels are clarified. For example, by inducing a certain amount of water, an amorphous to crystalline transition occurs in gels of acrylic acid/alkyl acrylate copolymers. On the other hand, water induces a liquid‐crystalline (SmA) to liquid‐crystalline (SmI) transition in copolymers consisting of acrylic acid and 11‐(4′‐cyanobiphenyloxy)undecyl acrylate. These specific features regarding the formation of ordered structures in hydrogels might shed some light on the formation of ordered structure in biological tissues.     

Morphologies and domain sizes of microphase-separated structures of block and graft copolymers of different types

Well-defined block and graft copolymers of different types with different compositions and molecular weights, such as styrene(S)-2-vinylpyridine(P) diblock copolymers, SP star-shaped block copolymers, PSP triblock copolymers, styrene(S)-isoprene(I) multiblock copolymers of the (SI)_n type, ISP triblock copolymers, SPP graft copolymers and their deuterated samples were prepared. Variations of the morphologies with compositions, molecular weight dependences of the lamellar domain sizes and conformations and distributions of block chains in the lamellar domains were studied in the strong segregation limit. Besides typical morphologies such as spherical, cylindrical and lamellar structures, ordered bi- and tri-continuous structures were found between cylindrical and lamellar structures for SP diblock copolymers, PSP and ISP triblock copolymers, respectively. The composition ranges of morphologies are different for the block and graft copolymers of different types. The molecular weight dependences of lamellar domain sizes are about the same, but their magnitudes are not always the same for the block and graft copolymers of different types. These results are well explained by the theories of Helfand-Wasserman and Semenov. Block chains in lamellae are extended along the direction perpendicular to lamellae, but they are contracted along the parallel direction. The former result is well explained by the theories, but the latter is not. Chains adjacent to the junction points between different block chains are localized near the domain interface, but chains at the free-ends of block chains are widely distributed in the domain with the maximum at the center of domain.     

Nanofabrication in Polymer Solutions

Nanostructured materials have drawn a great deal of attention in recent yearsbecause of their promising potentials in future applications.The fabrication of nano-materials has become a highly active research area involving scientists in many differentfields,e.g.,physics,chemistry,biology and materials science and engineering. Theinorganic synthesis including biomineralization by using intermolecular bonds to act in acooperative manner in order to construct organized supramolecular systems by s…     

Well‐defined copolymers based on poly(vinylidene fluoride): From preparation and phase separation to application

Poly(vinylidene fluoride) (PVDF) has reached the second largest production volume of fluoropolymers in recent years, and its popularity can be ascribed to high thermal stability and chemical inertness combined with its ferroelectric behavior. Copolymerization of vinylidene fluoride with other monomers leads to a wide variety of products with modified or improved properties. Besides commercially available fluorinated random copolymers, well‐defined block‐, graft, and alternating copolymers based on PVDF received more attention in recent years. PVDF‐containing block copolymers that may self‐assemble into well‐ordered morphologies are of particular interest, being potential precursors for functional nanostructured materials applicable in membranes and electronics. This Highlight provides an overview of the routes developed towards these materials via conventional and controlled polymerization techniques. In addition, it discusses their nanoscopic phase behavior and current and potential applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2861–2877     

Effects of Sequence Distribution and Physical Aging on Physical Properties of PES/PEES Random, Block, and Alternative Copolymers

IntroductionPhysical aging involves spontaneous changes in thephysical properties of polymer glasses from its nonequi-librium state to the equilibrium state. Aging affectsseveral properties such as specific volume, enthalpy,and mechanical and dielectric r…     

Macroscopic Regulation of Hierarchical Nanostructures in Liquid-crystalline Block Copolymers towards Functional Materials

The great potential of liquid-crystalline block copolymers(LCBCs) containing photoresponsive mesogens toward novel applications in photonics and nanotechnology has been attracting increasing attention, due to the combination of the inherent property of microphase separation of block copolymers and the hierarchically-assembled structures of liquid-crystalline polymers(LCPs). The periodically ordered nanostructures in bulk film of LCBCs can be acquired by supramolecular cooperative motion, derived from the interaction between liquidcrystalline elastic deformation and microphase separation, which are able to improve physical properties of polymer film toward advanced functional applications. Moreover, various micro/nano-patterned structures have been fabricated via light manipulation of photoresponsive LCBCs with good reproducibility and mass production. Thanks to recent developments in synthesis and polymerization techniques, diverse azobenzene-containing LCBCs have been designed, resulting in the creation of a wide variety of novel functions. This review illustrates recent progresses in macroscopic regulation of hierarchical nanostructures in LCBCs towards functional materials. The existing challenges are also discussed, showing perspectives for future studies.     

Controlled Assembly of Block Copolymer Coated Nanoparticles in 2D Arrays

The defined assembly of nanoparticles (NPs) in polymer matrices is an important prerequisite for next‐generation functional materials. A promising approach to control NP positions in polymer matrices at the nanometer scale is the use of block copolymers. It allows the selective deposition of NPs in nanodomains, but the final defined and ordered positioning of the NPs within the domains has not been possible. This can now be achieved by coating NPs with block copolymers. The self‐assembly of block copolymer‐coated NPs directly leads to ordered microdomains containing ordered NP arrays with exactly one NP per unit cell. By variation of the grafting density, the inter‐nanoparticle distance can be controlled from direct NP surface contact to surface separations of several nanometers, determined by the thickness of the polymer shell. The method can be applied to a wide variety of block copolymers and NPs and is thus suitable for a broad range of applications.     

Solute-solvent friction kernels and solution properties of methyl oxazoline-phenyl oxazoline (MeOx-PhOx) copolymers in binary ethanol-water mixtures

Solvent mixtures often alter the solubility of polymeric substances. Statistical copolymers made from 2-methyl-2-oxazoline (MeOx) and 2-phenyl-2-oxazoline (PhOx) are known for their varying solubilities in pure ethanol, pure water and in binary mixtures of ethanol-water. Constrained Molecular Dynamics (MD) simulations have been carried out with an aim to explain the varying solubilities of the statistical MeOx-PhOx copolymers. The solute-solvent dynamic friction kernels calculated through constrained MD simulations corroborate the solubility pattern in these copolymers. The solvation characteristics have been analyzed in terms of the solute-solvent radial distribution functions (RDFs). The ethanol-soluble MeOx-PhOx copolymers exhibit characteristic solute-composition dependence in the dynamic solute-solvent friction kernels, indicating the strength of the solute-solvent correlations. The aggressive solvation by the ethanol molecules in the binary solvent mixtures has been brought out by the O(solute)-H(ethanol) RDFs which exhibit a characteristic dependence on the ethanol content in the solvent composition. The corresponding O(solute)-H(water) RDFs are devoid of any such composition dependence. For all the MeOx-PhOx copolymers, the O-site solvation is strongly dominated by the water molecules and the N-sites are solvated equally by both ethanol and water molecules.     

中孔氧化硅的超分子模板合成及其结构与形貌的调控*

本文综述了近年来利用超分子模板法合成有序中孔氧化硅的研究进展,着重评述了以阳离子型表面活性剂和聚氧乙烯基嵌段共聚物为模板剂时对中孔氧化硅内部结构(包括中孔结构及其结构参数)与外观形貌的调控,并对其今后的发展作了展望.     

Molecularly asymmetric triblock copolymers as a single-molecule route to ordered bidisperse polymer brushes

The conditions signaling the formation of bidisperse brushes in ordered block copolymers are investigated as an A(2) block is progressively grown onto an A(1)B diblock copolymer to form a series of molecularly asymmetric, isomorphic A(1)BA(2) triblock copolymers. Small-angle scattering and self-consistent field theory confirm that the microphase-ordered period decreases when the A(2) block is short relative to the A(1) block, but then increases as A(1)+A(2) bidisperse brushes develop. The mechanical properties systematically follow the spatial distribution of the A(2) block.     

Electrochemically controlled self-assembly of an organometallic block copolymer

A new means of controlling the order-disorder transition of block copolymers is presented. By applying small electrical potentials (2 V/cm) to disordered solutions of an organometallic block copolymer, oriented ordered grains were obtained near the positive electrode. After reversing the electrical bias on the system, the ordered grains disappeared, and new, oriented, ordered regions were formed at the opposite electrode. Our work establishes the concept of electrochemical self-assembly for controlling order formation in block copolymers.     

High frequency acoustic excitations in ordered diblock copolymer studied by inelastic x-ray scattering

The phonon propagation in lamellar nanostructures formed via self-assembling of short styrene-b-isoprene (SI) as well as of its more incompatible styrene-b-(ethylene-alt-propylene) (SEP) counterpart was studied by inelastic x-ray scattering. Irrespective of the physical state of the block copolymers, a single acoustic phonon was observed in SI (ordered and disordered) and SEP (ordered). At GHz frequencies, inelastic light scattering from the same samples revealed very small dispersion in the sound phase velocity but a short phonon lifetime.     

α,ω支化共聚物的自组织形态模拟

建立了适用于α,ω支化共聚物的自洽场理论. 通过数值求解自洽场方程, 模拟了H型、π型α,ω支化共聚物的自组织形态, 模拟结果与实验相一致. 研究了杂臂型α,ω支化共聚物的各种自组织形态及相分离程度与支链体积分率的关系, 讨论了支化点在微相间的密度分布.     

Liquid–crystalline copoly(ester–amide)s prepared from hydroxybenzoic and 4-aminobenzoic acids

Copolycondensations of 3,5-dimethoxy-4-hydroxybenzoic (syringic acid, SGA), 4-hydroxybenzoic(PHB), and 4-aminobenzoic (PAB) acids with diphenyl chlorophosphate(DPCP)/LiCl/pyridine were studied. Random copolycondensations of a wide range of monomer compositions afforded copolymers exhibiting birefringence at room temperature. However, when the sequence of PHB and PAB was fixed by using a newly prepared monomer, 4-(4′-aminobenzoyloxy) benzoic acid (PABBA), the ordered copolymers thus prepared showed birefringence above 200°C, but not at room temperature. Variations in solubility and thermal behavior were also observed in randomly and sequentially prepared copolymers. The monomer sequences in copolymers in random copolycondensations could be changed by controlling the reaction of monomers with DPCP.     

液晶聚芳醚酮的结构与性能研究

以联苯二酚、取代对苯二酚及含氟酮单体为原料 ,通过亲核取代反应 ,合成了系列具有液晶性的新型聚芳醚酮 .研究了聚合物分子结构与性能之间的关系 .由于结晶相是从有序的液晶相转化形成的 ,故侧基含量的增加对液晶聚合物的融熔转变温度无显著影响 .聚合物的液晶稳定性受侧基影响较大 ,含极性侧基的氯取代聚合物的液晶温区比含大空阻侧基的聚合物的液晶温区小得多 ,说明空间几何因素比极性因素对液晶稳定性的影响大 .不同分子量聚合物有不同的液晶有序结构 ,低分子量聚合物具有高有序液晶结构 ,而高分子量聚合物只有低有序的向列相结构 .     

PS-b-PEO-b-PS三嵌段共聚物在选择性溶剂中的胶束化

应用原子转移自由基聚合,制备了一组窄分布的PS-b-PEO-b-PS三嵌段共聚物。用^1HNMR和TEM表征了它们在选择性溶剂中的胶束化行为。^1HNMR结果表明,共聚物苯环上的质子峰出现在良溶剂(CHCl~3)中,而在选择性溶剂水中消失,证明上述三嵌段共聚物在选择性溶剂水中可逆自组装成以PS为核、PEO为壳的胶束。通过TEM考察了胶束的形状及大小,发现体系胶束尺寸呈多分散、粒径大,对形成的原因也提出了可能的解释。     

环境响应性嵌段共聚物的合成、自组装及应用研究进展

近年来具有环境响应性的嵌段共聚物的研发受到了人们的广泛关注。该类型共聚物可以对外界环境刺激产生相应的结构、物理及化学性能的变化。根据外界环境刺激响应机理及类型的不同,可将其分为单一因素、双重因素以及三重因素刺激响应性嵌段共聚物三大类。针对每一类体系,本文重点综述了嵌段共聚物的设计合成、自组装以及应用等研究现状,并概括总结了各种有序聚集体(如胶束、囊泡等)随外界环境刺激(如pH、温度、光、CO_2、氧化还原剂等)所作出的响应性变化。最后,对智能型嵌段共聚物在药物控释、纳米容器制备、生物功能材料等方面潜在的应用价值和今后可能的发展方向进行了展望。     

Surfactant Mediated Microphase Separation in Miscible Block Copolymer of Poly(4-vinyl pyridine-b-hydroxybutylacrylate)

Chinese Journal of Polymer Science - Miscible disordered block copolymers (BCPs) are rarely studied due to the limits in self-assembly into ordered microstructures. Herein, we proposed a facile...