Development of new ionomer blend membranes,their characterization,and their application in the perstractive separation of alkenes from alkene–alkane mixtures. I. Polymer modification,ionomer blend membrane preparation,and characterization

In this contribution, the synthesis and characterization of novel ion‐exchange blend membranes which contain the SO₃Ag group for the application in the perstractive separation of alkene–alkane mixtures, where the Ag⁺ ion serves as facilitated transport site for the alkene via formation of a pi complex with the alkene double bond, is presented. In this part of the article, the synthesis and characterization of following blend membrane types are described: (1) acid–base blend membranes of ortho‐sulfone‐sulfonated polysulfone (PSU) with ortho‐sulfone‐diaminated PSU; (2) blend membranes of ortho‐sulfone‐sulfonated PSU with unmodified PSU; (3) blend membranes of ortho‐sulfone‐sulfonated PSU with ortho‐sulfone disilylated PSU. The differently modified PSU types were characterized via ¹H nuclear magnetic resonance (¹H‐NMR). The acid–base blend membranes were characterized via Fourier transfer infrared (FTIR) spectroscopy. It could be indirectly proved that formation of PSU–SO₃ ⁺H₃N–PSU ionic crosslinks takes place. Transmission electron microscopy (TEM) investigations of (1) and (2) yielded the results that these blends are inhomogeneous at the microscopic scale. Mechanical stabilization of these blends is accomplished by physical entanglement of the different macromolecules. The blends (3) were macroscopically inhomogeneous due to the strong difference in hydrophilicity of the blend components. Only the blend 90% PSU–SO₃H 10% PSU[Si(CH₃)₃]₂ formed a blended membrane. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 428–438, 1999     

Preparation,structure, and transport properties of ultrafiltration membranes of poly(vinyl chloride) and poly(vinyl pyrrolidone) blends

Ultrafiltration (UF) membranes based on poly(vinyl chloride) and poly(vinyl pyrrolidone) blends were prepared by the phase inversion method, and the factors governing membrane properties were investigated. The membranes were characterized by scanning electron microscopy and atomic force microscopy. The fouling characteristics of the membranes were determined by UF of aqueous solutions of bovine serum albumin (BSA) over a pH range of 2–9 and varying salt concentrations. The maximum adsorption of the protein on the membrane surface occurred near the isoelectric point (pI 4.8) of BSA, and the presence of the salts increased the fouling of the membrane. The results can be explained in terms of the nature of the membrane polymer and the effect of different ionic environments on the permeability of the deposited protein layer. The net charge on the BSA molecules appears to be a dominant factor in determining the flux of water through the blend membranes. The UF flux is correlated by a model based on the membrane resistance, adsorbed protein resistance, and time dependent resistance of the concentration polarization layer near the membrane surface. The ζ potentials of the membranes were also determined before and after UF to characterize the surface potential of the membrane. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2606–2620, 2000     

Three‐dimensionally braided carbon fiber–epoxy composites,a new type of material for osteosynthesis devices. I. Mechanical properties and moisture absorption behavior

In recent years, three‐dimensionally (3D) braided composites have attracted a great deal of attention because of their high‐impact damage tolerance and fatigue life, superior fracture toughness, and so forth, and have been used in aeronautics, military, and transportation. These advantages make them strong candidates for osteosynthesis devices. In this study, 3D braided carbon fiber–epoxy (C_3D/EP) composites were produced via a simple vacuum impregnation technique. The load‐deflection curve, mechanical properties, and influence of fiber volume fraction, braiding angle, and axial reinforcing fibers were examined to determine their suitability for internal fixation devices. It is found that the C_3D/EP composites have excellent toughness and do not show brittleness when fractured because of their relatively high void content. The flexural, shear, and impact strengths of the C_3D/EP composites are excellent. It was shown that a C_3D/EP composite with a stiffness similar to load‐bearing bones can be made while maintaining enough strength. It is concluded that a relatively higher void content and braiding angle is more suitable for the C_3D/EP composites from the viewpoint of requirements of fracture fixation materials. The moisture absorption behavior and changes in mechanical properties caused by moisture uptake were evaluated. Results show that absorbed moisture slightly decreases mechanical properties of the C_3D/EP composites. Contrary to the unreinforced epoxy, the moisture absorption behavior of the C_3D/EP composites cannot be described with Fick's law of diffusion, probably because of the presence of voids and/or 3D fiber structure. The exact mechanisms should be proposed in further investigations. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1031–1039, 2002     

Studies on thermoplastic polyurethanes based on new diphenylethane‐derivative diols. III. The effect of molecular weight and structure of soft segment on some properties of segmented polyurethanes

Two series of poly(ether urethane)s and one series of poly(ester urethane)s were synthesized, containing, respectively, poly(oxytetramethylene) diol (PTMO) of M _n = 1000 and 2000 and poly(ε‐caprolactone) diol of M _n = 2000 as soft segments. In each series the same hard segment, i.e., 4,4′‐(ethane‐1,2‐diyl)bis(benzenethiohexanol)/hexane‐1,6‐diyl diisocyanate, with different content (～ 14–72 wt %) was used. The polymers were prepared by a one‐step melt polymerization in the presence of dibutyltin dilaurate as a catalyst, at the molar ratio of NCO/OH = 1 (in the case of the polymers from PTMO of M _n = 1000 also at 1.05). For all polymers structures (by FTIR and X‐ray diffraction analysis) and physicochemical, thermal (by differential scanning calorimetry and thermogravimetric analysis), and tensile properties as well as Shore A/D hardness were determined. The resulting polymers were thermoplastic materials with partially crystalline structures (except the polymer with the highest content of PTMO of M _n = 2000). It was found that the poly(ether urethane)s showed lower crystallinity, glass‐transition temperature (T_g), and hardness as well as better thermal stability than the poly(ester urethane)s. Poly(ether urethane)s also exhibited higher tensile strength (up to 23.5 MPa vs. 20.3 MPa) and elongation at break (up to ～ 1950% vs. 1200%) in comparison with the corresponding poly(ester urethane)s. Among the poly(ether urethane)s an increase in soft‐segment length was accompanied by an increase in thermal stability, tensile strength, and elongation at break, as well as a decrease in T_g, crystallinity, and hardness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of copolymeric aliphatic–aromatic esters derived from terephthalic acid, 1,4‐butanediol,and ε‐caprolactone by physical,thermal, and mechanical properties and NMR measurements

In this study, a series of aliphatic–aromatic poly(butylene terephthalate‐co‐ε‐caprolactone) (PBTCL) copolyesters were synthesized from various monomeric compositions of terephthalic acid (TPA), 1,4‐butanediol (BDO), and ε‐caprolactone (CL) in the presence of tetrabutyl titanate (Ti(Obu)₄) and stannous octoate (Sn(Oct)₂) as catalysts through a combination of polycondensation and ring opening polymerization. A significant increase in the melting temperature (T_m) of copolyesters was observed by increasing the TPA/(CL+TPA) molar ratio, starting from the low end (T_m 66.2°C) of pure poly‐ε‐caprolactone PCL upward. We found that PBTCL‐50, which has a TPA/(CL+TPA) 50% molar ratio and polycondensation at 260°C for 1.5 h, resulted in a proper T_m of 139.2°C that facilitates thermal extrusion from biomass or other biodegradable polymers of similar T_m. The number–average molecular weight (M_n) of 7.4 × 10⁴ for PBTCL‐50 was determined from the intrinsic viscosity [η] by using the Berkowitz model of M_n = 1.66 × 10⁵[η]^0.9. Good mechanical properties of PBTCL‐50 have been shown by tensile stretching experiment that indicates tensile strength, elongation, and Young's modulus are 11.9 MPa, 132%, and 257 MPa, respectively. Polymers with aforementioned properties are suitable for manufacturing biodegradable plastic films for downstream agricultural applications or merely for trash bag. This article reveals that the PBTCL‐50 contains all five monomers with different molar ratios and characteristical linkages between each other. The novel structure was furthermore analyzed by ¹H‐ and ¹³C‐NMR spectroscopy. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013