Synthesis and characterization of 6‐ and 12‐arm star polymers by nitroxide‐mediated radical polymerization of St and MA from dendritic TIPNO‐based hexafunctional and dodecafunctional macroinitiators

Dendritic multifunctional macroinitiators having six and 12 TIPNO‐based alkoxyamines, TIPNO‐6 and TIPNO‐12 , were synthesized and used in the living radical polymerization of styrene (St), methyl acrylate (MA), N,N‐dimethylacrylamide (DMAAm), and isoprene (IP). The polymerizations of St initiated with TIPNO‐6 gave 6‐arm star polymers with narrow polydispersities of 1.14–1.18. In the polymerizations of MA initiated with TIPNO‐6 and TIPNO‐12 , the influences of added TIPNO on the polydispersity indexes (PDIs) of the resulting star polymers were first investigated, and this led to the successful formation of poly(MA) star polymers with narrow polydispersities (1.10–1.18). Moreover, the polymerizations of DMAAm and IP from TIPNO‐6 in the presence or absence of TIPNO were briefly investigated. The benzyl ether bonds of the poly(St) and poly(MA) star polymers were cleaved by treating with Me₃SiI or Pd/C, and the resulting arm's parts were analyzed with SEC. The PDIs of the resulting arm parts were low (1.19–1.23), and the M_ns agreed with the M_n,theor, indicating that the poly(St) and poly(MA) star polymers had well‐controlled arms. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4364–4376, 2007     

Weak Attractive Ligand–Polymer and Related Interactions in Catalysis and Reactivity: Impact,Applications, and Modeling

The notion of weak attractive ligand–polymer interactions is introduced, and its potential application, importance, and conceptual links with “cooperative” ligand–substrate interactions are discussed. Synthetic models of weak attractive ligand–polymer interactions are described, in which intramolecular weak C? H???F? C interactions (the existence of which remains contentious) have been detected by NMR spectroscopy and neutron and X‐ray diffraction experiments. These C? H???F? C interactions carry important implications for the design of catalysts for olefin polymerization, because they provide support for the practical feasibility of ortho‐F???H_β ligand–polymer contacts proposed for living Group 4 fluorinated phenoxyimine catalysts. The notion of weak attractive noncovalent interactions between an “active” ligand and the growing polymer chain is a novel concept in polyolefin catalysis.     

A bicontinuous structure in some systems with cubic mesophases

A cubic structure of polymer colloid complexes is studied. The technique of the research includes i) an analysis of well-known literature SAXS data; on this basis, ii) constructing a simple model to estimate geometric structure parameters and to obtain a simulated scattering curve; and iii) comparing the model with the real structure obtained from the SAXS data, using the reconstruction of electron density distribution. A bicontinuous structure in cubic mesophases is formed. Dedicated to the memory of Alexander T. Dembo     

扫描力显微术在高聚物薄膜玻璃化转变研究中的应用

简述了高聚物薄膜玻璃化转变的复杂性，并结合文章作者的的一些研究结果介绍了扫描力显微术(SFM)在研究高聚物玻璃化转变中的一些方法，包括观察高聚物薄膜形貌的变化，测量其摩擦力、粘附力和弹性模量等物理量的变化，最后指出SFM是研究高聚物薄膜玻璃化转变的有力工具。     

Polymorphy in the stereostructure of periodic polymer backbones

We theoretically investigated the polymorphy of the stereostructures of a periodic polymer. Using the polymer's internal conformation parameters of bond lengths, bond angles, and internal rotation angles, we extended the mathematical treatment for designing polymer backbones. We considered those periodic polymers whose unit cell consists of one (m = 1), two (m = 2), or three (m = 3) kinds of atoms. Moreover, for these three types of polymers, we supposed two catenation types for the skeleton atoms; one is a “homorotatory” sequence and the other is a “heterorotatory” one. To specify the backbone's stereostructure, we introduced several conformation parameters such as the helical pitch number n, the translation distance d, and the inclination angle of the skeleton plane Θ. By combining these parameters, we can systematically understand the variety and the possible polymorphy in the stereostructure of a periodic polymer backbone. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2829–2849, 2003     

Using the new in–in method for the synthesis of polyisoprene/polystyrene heteroarm star polymers

The basis of the two‐step in–in method is as follows: star polymers with poly(divinyl benzene) cores, synthesized by the arm‐first method, include many unreacted double bonds in their core, and these double bonds can be attacked by the carbanions of some monomers such as styrene and dienes. In this work, linear polyisoprene chains were used to attack the double bonds existing in the poly(divinyl benzene) cores of polystyrene star polymers, so that a heteroarm star polymer with polystyrene and polyisoprene arms was synthesized. It was later well characterized with size exclusion chromatography, light scattering, viscometry, UV spectroscopy, dynamic mechanical thermal analysis, and ¹H NMR. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 135–142, 2003     

Cellulose-polyamide 66 blends. Part II: Mechanical behavior

Blends of the natural polymer cellulose with a synthetic polymer, polyamide 66, are studied in order to determine if the expected strong interaction between them, due to hydrogen bonds, could improve their mechanical properties such as strength and elongation at break. In a previous work {Part I, J. Polym. Sci. Polym. Phys., 32 , 1437 (1994)}, the preparation technique and the characterization of cellulose-polyamide 66 (PA66) blends were described in detail. Several samples in the composition range between 0 to 70 wt % of PA66 were carefully dried and examined using dynamic mechanical and tensile tests. Based on previous work a new percolation model has been developed. It takes both linear and nonlinear mechanical behaviors into account and allows for the effect of adhesion between material domains. From comparison between experimental and predicted data, it is concluded that a partial miscibility between the amorphous phases of cellulose and PA66 exists and is responsible for a strong adhesion at their interface. Solid-state ¹³C nuclear magnetic resonance has also been used to study these samples and supports the existence of strong interactions between both homopolymers. © 1995 John Wiley & Sons, Inc.     

Statistical approach to light scattering from deformed textured heterogeneous polymer materials

A statistical theory of light scattering from deformed isotropic and textured heterogeneous polymer materials is formulated. Two types of textured structures are analyzed: assemblies of optically isotropic and anisotropic rods and a spatially anisotropic distribution of isotropic spherical inclusion centers. The small-angle H_v light-scattering patterns are calculated. The appearance of scattering from isotropic rods and spheres in deformed materials has been demonstrated. The changes of the H_v scattering patterns as a function of elongation and strucuture parameters are discussed. © 1993 John Wiley & Sons, Inc.     

Electron diffraction investigation of PPTA/nylon 3T blends from shear-oriented anisotropic solutions

Nematic solutions of PPTA and nylon 3T were prepared in H₂SO₄ Optical microscopy was used to ascertain the phase behaviour of the blends. In the studied concentration range, no phase separation was observed. The solutions were shear-oriented and coagulated, and the resulting samples were studied by x-ray and electron diffraction. Nylon 3T crystallised even at a low concentration, which is indicative of a phase separation. Electron diffraction investigations of the oriented samples showed that well-oriented areas, which were predominantly composed of PPTA, adjoined areas where the major component, nylon 3T, showed no orientation. The relative proportion of the unoriented areas increased with increasing nylon concentration. It was concluded that, upon coagulation, the nylon was segregated into separate phases and crystallised unoriented, whereas for PPTA, crystallisation proceeded with very little chain rearrangement therefore preserving the orientation.     

聚合物分散液晶光栅的衍射特性的研究

报道了一种由聚合物分散液晶膜与具有周期性条状电极结构板结合的新型光栅器件，借助于聚合物分散液晶膜的电光特性，这种栅对入射光的散射或衍射取决于对其施加的电压，即它是电场可调的，实验结果显示出当驱动电压超过器件器件阈值电压时，衍射光的强度和衍射斑的可见级次被电场调制，而且它能入射光的线性偏振态变为椭圆偏振态。