Molecular weight effects on phase transitions of side-chain liquid crystalline poly(vinyl ether)s with terminal alkoxybiphenyl groups

Two vinyl ether monomers with alkoxybiphenyl groups, 2-(4′-ethoxy-4-biphenyloxy)ethyl vinyl ether (EtOVE) and 2-(4′-hexyloxy-4-biphenyloxy)ethyl vinyl ether (HexOVE), were polymerized by living cationic polymerization reactions using either the hydrogen iodide/iodine (HI/I₂) or the hydrogen iodide/zinc iodide (HI/ZnI₂) initiator systems, or both. These initiators yield polymers with narrow molecular weight distributions (MWDs) and for comparison broad MWD polymers were also prepared by using the BF₃OEt₂ initiator. The thermal properties and phase transitions of these polymers were determined by differential scanning calorimetry, by visual observations of samples on a hot stage on a polarizing microscope, by polarized light transmission intensity measurements and by wide angle X-ray diffraction analysis. The polymer from EtOVE, P(EtOVE), with a weight average molecular weight, , of less than about 8000 formed both smectic and nematic liquid crystalline, LC, phases after one heating cycle. In contrast, the polymer from this monomer which had an of more than about 8000 exhibited only a nematic LC phase. For the polymer from HexOVE, P(HexOVE), both the narrow and broad MWD samples showed only a nematic LC phase over the range from 2600 to 7300. The phase transitions of both types of polymers are discussed in relation to the molecular weight and MWD of the samples. The effect of the terminal group attached to the biphenyl group in the polymer is considered in relation to its possible steric effects.     

纺丝溶液浓度对UHMWPE冻胶纤维萃取及拉伸性能的影响

通过冻胶纺丝法制备了纺丝溶液质量分数为8％～16％的超高相对分子质量聚乙烯(UHMWPE)冻胶纤维.研究了不同浓度冻胶纤维的相分离、萃取动力学、结晶性能、热性能和拉伸性能.结果表明:冻胶纤维成形之后的相分离过程开始60 min内较为剧烈,在约2000 min达到相分离平衡;冻胶纤维的萃取除油率随浴比的增大或萃取时间的延...     

Phase structure,morphology and phase boundary diagram in an aromatic polyimide (BPDA–PFMB)/m-cresol system

An organo-soluble aromatic polyimide has been synthesized from 3,3′, 4,4′-bis(phenyltetracarboxylic) dianhydride (BPDA) and 2,2′-bis (trifluoromethyl)-4,4′-diaminobiphenyl (PFMB) via a one-step polymerization in m-cresol. The phase boundary diagram for this system has been established by differential scanning calorimetry, polarized light microscopy (PLM) and wide angle X-ray diffraction (WAXD) experiments. A crystallosolvate form I has been found over the entire concentration region at low temperatures. When the temperature is increased, an isotropic phase has been observed below concentrations of about 40%. In the relatively high concentration region between 45 and 95%, a transition from the crystallosolvate from I to a crystallosolvate form II has been observed. Form II exhibits a different WAXD pattern. In a narrow concentration region between the isotropic and the crystallosolvate form II (40–45%), a biphase behavior has been found. The birefringence of this region may be an indication of a liquid crystalline phase. The BPDA–PFMB polymer crystal has been found in the very high concentration region (>95%) for temperatures >250°C. The morphologies of these phases have been investigated via PLM and transmission electron microscopy. Above the gel/sol transition temperature, the form I shows negative birefringent spherulites consisting of thin lamellae. The form II exhibits a tendency of positive birefringent spherulites. Possible mechanisms of the formation of the metastable phase morphology and their associations with the mechanical gel/sol transition are also discussed.     

Molecular dynamics simulation study on the structure and properties of polyimide/silica hybrid materials

A type of polyimide/silica (PI/SiO₂) copolymer model was established through the dehydration of tetraethyl orthosilicate molecules (TEOS) and bonding to a silane coupling agent. The content of SiO₂ was controlled by adjusting the number of molecules which bound to the TEOS. Finally, the silica was formed into a hybrid model (hybrid PI/SiO₂) with a small molecule embedded in the PI. The model was optimized by geometric and molecular dynamics and the changes in the model structure, Young's modulus, shear modulus, and glass-transition temperature (T _g) were analyzed. The results showed that the density and cohesive energy density of the composites could be improved by doping SiO₂ in PI. Young's modulus and shear modulus of PI/SiO₂ hybrid materials were higher than undoped PI. The tensile strength reached 568.15 MPa when the doping content was 9%. Therefore, the structure design and content control of SiO₂ was an effective way to improve the performance of a PI/SiO₂ composite. The variation of T _g and tensile strength of PI/SiO₂ hybrid composites is consistent with that of PI/SiO₂ composite synthesized in real experiment, which will be a convenient method for new material design and performance prediction. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47335.     

Molecular weight effects on the phase morphology of PS/P4VP blend films on homogeneous SAM and heterogeneous SAM/Au substrates

The effects of the molecular weight of polystyrene (PS) component on the phase separation of PS/poly(4-vinylpyridine) (PS/P4VP) blend films on homogeneous alkanethiol self-assembled monolayer (SAM) and heterogeneous SAM/Au substrates have been investigated by means of atomic force microscopy (AFM). For the PS (22.4k)/P4VP (60k) system, owing to the molecular weight of PS component is relatively small, the well-aligned PS and P4VP stripes with good thermal stability are directed by the patterned SAM/Au surfaces. With the increase of the molecular weight of PS component (for the PS (582k)/P4VP (60k) system), the diffusion of P4VP is hindered by the high viscosity of PS during the fast spin-coating process. The phase separation behavior of PS/P4VP on the SAM/Au patterned substrates is similar to that on the homogeneous SAM and cannot be easily directed by the patterned SAM surfaces even though the characteristic length of the lateral domain morphology is commensurate with the stripe width. This indicates that the relative viscosity of the PS is one of the dominant factors in obtaining well-aligned pattern by the phase separation of polymer blends.     

Investigations on matrix network characteristics in NBR/silica nanocomposites: Resolving matrix bulk density and network molecular weight and their alterations due to filler‐curing agent interactions

Presence of filler in an elastomeric composite can affect curing characteristics due to possible interaction with curing agents. Alteration of the curing characteristics can change intrinsic properties of elastomer including its bulk density and swelling behavior. In this study, a series of acrylonitrile butadiene rubber (NBR) with various curing levels was prepared. From the experimental data the bulk density and network molecular weight (M_c,sw) were specified and a relationship was established between these parameters. In order to determine the swelling characteristics of NBR in presence of filler, another series of NBR/silica nanocomposites was prepared with various nanosilica loadings under a constant content of curing agents and curing conditions. With the use of the swelling data and applying the obtained relationship, the M_c,sw and bulk density of the filled NBR matrix were resolved. The M_c,sw values obtained by considering the influence of nanosilica on curing characteristics of NBR were compared with those obtained simply based on bulk density of raw rubber. This comparison confirmed that there are considerable differences between these values. With increasing nanosilica contents, and hence, increasing the negative impact of the filler on reducing curing degree of NBR, the bulk density of filled NBR matrix was decreased. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46170.