Transport of water and methanol vapors in alkyl substituted poly(norbornene)

This report examines the ability of aliphatic-substituted polynorbornenes to separate methanol vapor from water-wet air streams. Single component transport properties of water and methanol were measured for each candidate polymer at 30 °C. The diffusion coefficient, sorption coefficient, and permeability were determined by measuring the rate of mass gain or loss of a sample due to sorption or desorption. The ratio of the permeabilities of the pure components yielded the ideal selectivity. The materials studied in this were methyl-, nbutyl-, nhexyl-, and ndecyl-polynorbornene. These polymers were glassy, with T_gs of 150-380 °C, and have relatively high fractional free volumes (16-19%). The results of the study showed polynorbornenes were methanol selectivity with ideal selectivities of 1.2-9. This permeation selectivity is due primarily to the solubility selectivity of the materials.     

Ultraviolet irradiation of poly(alkyl acrylates) and poly(alkyl methacrylates)

Acrylic and methacrylic homopolymers containing different side groups were irradiated with ultraviolet light in the presence of air. The changes of molecular weight distributions of the irradiated polymers were analyzed by means of gel permeation chromatography (GPC), and the rates of chain scission and crosslinking were estimated. As the result of this study, it was found that chain scission takes place more easily in polyalkyl methacrylates than in polyalkyl acrylates.     

Antibacterial effect of thiocyanate substituted poly(vinyl chloride)

Poly(vinyl chloride) (PVC) modified in different solvents by nucleophilic substitution with thiocyanate was exposed to Gram-negative bacteria of the strain Staphylococcus capitis. All modified pieces reduced the adhesion of bacteria by between 67 and 79%. More important for the bacteria suppression than the substitution rate was the ratio between thiocyanate and isothiocyanate groups. The best result was obtained with PVC modified in tetrahydrofuran/dimethylsulfoxide, containing only antibacterial active isothiocyanate groups, while inactive thiocyanate groups were absent.     

The effect of co-dopants on the processability of intrinsically conducting polymers

Using a combination of functionalized dopants was found to be a simple method to improve the processability of intrinsically conducting polymers while retaining relatively high levels of conductivity. Two intrinsically conducting polymers, poly(3-octylthiophene) and polyaniline were co-doped with various combinations of dopants. In both systems, solubility was improved and coherent films were formed directly from common organic solvents without the need for a post-processing doping step. Co-doped intrinsically conducting polymer films exhibited conductivities up to 10^?2 S/cm. Additionally, certain polyaniline complexes were capable of being melt processed without loss of conductivity.     

新型光敏聚合物氯代聚肉桂酰胺酮的合成研究

以肉桂酸为原料合成新型含??不饱和酮结构的光敏单体.然后在无水AlCl3、NMP及DCE的存在条件下,将新合成的单体与2,5-二氯对苯二甲酰氯(DCC)进行低温付一克缩聚反应,合成得到一类新型光敏性聚合物材料--氯取代聚肉桂酰胺酮(C-PAMIK).对缩聚反应的工艺条件进行了优化,并初步表征了所得聚合物.     

Chemical stability of some poly(amide imide) type polymers

The stability of some heterocyclic poly(amide imide)s in acidic and alkaline medium was compared to the structurally related polyimide and poly(amide imide)s without other heterocyclic groups. All the polymers have high stability in acidic medium. The introduction of additional heterocycles such as 1,3,4-0xadiazole or phenylquinoxaline into the macromolecular chain of a poly(amide imide) increases substantially the resistance to alkaline medium. Polyamides containing imide rings only in the side chain are more stable to hydrolysis than related polyamide having imide units in the main chain.     

The effect of ion-polymer binding on ionic diffusion in dicarbazole-based conducting polymers

An electrochemical polymerization and characterization is reported on a series of eight dicarbazole-type conducting polymers with different attached functional groups. The influence of the electronic character of the subgroup on the ionic conductivity properties of the polymers was examined. Impedance spectroscopy measurements were used to set the ionic chemical diffusion coefficients, D, in the polymer matrix at a variety of doping levels, for each of the polydicarbazoles. We relate D dependency with potential to morphological and electronic processes in the polymer occurring during oxidation. By combination of cyclic voltammetry and impedance spectroscopy for part of the series we reveal that the diffusion of ions in the matrix is easier in polymers were the functional group is highly electron-attracting.     

Exploring the effect of alkyl end group on poly(L-lactide) oligo-esters. Synthesis and characterization

Poly(L-lactide) (PLLA) oligo-esters with α-hydroxyl-ω-alkyl (alkyl = −CH₂−[CH₂−CH₂]_m−CH₃, where m = 1, 2, 4, 5, 6, 7, 8, 9, and 10) end groups were synthesized by ring-opening polymerization of L-lactide (L-LA) catalyzed by tin(II) 2-ethylhexanoate Sn(Oct)₂ in the presence of aliphatic alcohols as initiators (HO−CH₂−[CH₂−CH₂]_m−CH₃, where m = 1, 2, 4, 5, 6, 7, 8, 9, and 10). High yields (~ 62 to 71%) and M _n(NMR) in the range of 2120–2450 Da (PLLA) were obtained. Effects of alkyl end groups on thermal properties of the oligo-esters were analyzed by DSC, TGA and SAXS. Glass transition temperature (T _g) gradually decreases with increase in the percent of−CH₂−[CH₂−CH₂]_m−CH₃ end group, as results alkyl end group provides most flexibility to PLLA. An important effect of alkyl end group on a double cold crystallization (T _c1 and T _c2) was observed, and is directly related with the segregation phase between alkyl end group and PLLA. TGA analysis revealed that PLLA oligo-esters are more thermally stable with docosyl (−C₂₂H₄₅) respect to the butyl (−C₄H₉) end group, probably is due to steric hindrance of the end group (docosyl respect to butyl) toward intermolecular and intramolecular transesterification. SAXS analysis showed that alkyl end group as docosyl restricted the growth of lamellae thickness (D) due to steric hindrance. Characterization of hydroxyl and alkyl end groups in the PLLA oligo-esters was determined by MALDI-TOF, GPC, FT-IR and ¹ H and ¹³ C NMR.     

Graft copolymers of poly(methyl methacrylate) backbone and poly(propylene oxide-b-ethylene oxide) branches

Summary Two mono-functional macromonomers of poly (propylene oxide-b-ethylene oxide) were synthesized by reaction with methacryloyl chloride. The macromonomers have the same molecular weight and ratio of ethylene oxide and propylene oxide sequences. The reactive methacrylate group can be linked to the ethylene oxide (BuPPOPEO) or to the propylene oxide (BuPEOPPO). These macromonomers showed self-gelling in one week even at low temperature and under a dry atmosphere. Graft copolymers were obtained by reaction of these macromonomers with methyl methacrylate upon free-radical initiation and they were characterized by GPC, VPO, IR and ¹H NMR spectra.     

Effect of branched alkyl groups on physical properties in poly(ethylene-co-branched alkyl methacrylate)s

Summary Poly(ethylene-co-5.4 mol% n-alkyl/branched alkyl methacrylate)s (PEM) were prepared by a dehydrogenchloride reaction of poly(ethylene-co-5.4 mol% alkyl methacrylic chloride) with the corresponding alkyl alcohol to investigate effect of branching structure and length of alkyl ester on a few physical properties of PEM [glass transition temperature (T_g), degree of crystallinity in polyethylene region (X_c) and dielectric molecular motion], where the alkyl groups used here are n-propyl, n-butyl, n-hexyl, n-decyl, 2-ethylhexyl, 3,5,5-trimethylhexyl and 2-(1,3,3-trimethylbutyl)-5,7,7-trimethyloctyl. In the n-alkyl methacrylate copolymers, T_g and X_c were almost unchanged with the presence of alkyl ester, but T_g increased and X_c decreased in the highly branched alkyl methacrylate copolymers even at the low methacrylate content of 5.4 mol%.     

Studies on semiinterpenetrating polymer networks based on poly(vinyl chloride-co-vinyl acetate) and poly(alkyl methacrylates)

A number of semi-interpenetrating polymer networks (IPNs) based on linear poly(vinyl chloride-co-vinyl acetate) and poly(alkyl methacrylates) were synthesized. The semi-IPNs were found to be transparent, high strength materials. The IPNs show only one glass-transition temperature and it is dependent on the composition as studied by differential scanning calorimetry and dynamic mechanical analysis. These IPNs are also characterized by high tan δ values. The tensile strength of the IPNs were found to be higher compared to the starting polymers. In order to compare the properties of these IPNs with the corresponding homopolymers and blends, the latter were synthesized and the properties were studied. © 1994 John Wiley & Sons, Inc.     

The effect of added salt on the flow of highly dilute solutions of poly(ethylene oxide) polymers

Early transition, early turbulence, and drag reduction were detected in flowing solutions of high molecular weight poly(ethylene oxide) condensates. Progressive addition of salt (magnesium sulfate) increased the onset point characterizing deviations from Newtonian flow for 1 ppm Polyox Coagulant solutions and eliminated early transition in the 10 ppm WSR-35 solutions. No further drag reduction was observed when the salt molarity reached the 0.65 level. In the Coagulant solutions the onset wall shear stress characterizing the flow deviation was an inverse function of the intrinsic viscosity of the polymer in the salt solution.     

Comparison of the thermally stable conducting polymers PEDOT, PANi, and PPy using sulfonated poly(imide) templates

We showed that it is possible to use sulfonated poly(amic acid)s (SPAA) to template polymerize 3,4-ethylenedioxythiophene (EDOT) to PEDOT, resulting in an aqueous dispersion of conducting polymer. This study compares PEDOT with poly(aniline) (PANi) and poly(pyrrole) PPy using the same and another, more rigid, poly(amic acid) template. A variety of system parameters, including reaction time, conductivity, and overall thermal stability, were noted to change systematically depending on the systems chosen. PANi-SPAA takes less than one tenth of the reaction time of PEDOT-SPAA (12 h versus 7 days), and results in higher conductivities at room temperature (ca. 10 S/cm). However, it is not as thermally stable as the PEDOT-SPAA system; conductivity is not measureable after annealing at 300 °C. PPy-SPAA was found to be more thermally stable than PANi-SPAA (less mass lost at 300 °C), but it was still more conductive than un-doped PEDOT-SPAA by a factor of 1000 (ca. 1.0 S/cm).     

Contact angle measurements and interpretation: wetting behavior and solid surface tensions for poly(alkyl methacrylate) polymers

Low-rate dynamic contact angles of a large number of liquids were measured on a poly(ethyl methacrylate) (PEMA) polymer using an automated axisymmetric drop shape analysis profile (ADSA-P). The results suggested that not all experimental contact angles can be used for the interpretation in terms of solid surface tensions: eight liquids yielded non-constant contact angles and/or dissolved the polymer on contact. From the experimental contact angles of the remaining four liquids, we found that the liquid-vapor surface tension times the cosine of the contact angle changes smoothly with the liquid-vapor surface tension, i.e. γlv cos ζ depends only on γlv for a given solid surface (or solid surface tension). This contact angle pattern is again in harmony with those from other methacrylate polymer surfaces of different compositions and side-chains. The solid-vapor surface tension of PEMA calculated from the equation-of-state approach for solid-liquid interfacial tensions was found to be 33.6 ± 0.5 mJ/m2 from the experimental contact angles of the four liquids. The experimental results also suggested that surface tension component approaches do not reflect physical reality. In particular, experimental contact angles of polar and nonpolar liquids on polar methacrylate polymers were employed to determine solid surface tension and solid surface tension components. Contrary to the results obtained from the equation-of-state approach, we obtained inconsistent values from the Lifshitz-van der Waals/acid-base (van Oss and Good) approach using the same sets of experimental contact angles.     

Solution behavior of graft copolymers of poly(methyl methacrylate) backbone and poly(propylene oxide-b-ethylene oxide) branches: effect of structure and composition

Summary The effect of structure and composition of poly(methyl methacrylate) (PMMA) main chain and poly(propylene oxide-b-ethylene oxide) (PPO-b-PEO) graft chain on solution behavior was evaluated. Separated samples of homopolymers were also analysed to provide comparisons. The solutions were prepared by dissolving the sample in selective mixtures of tetrahydrofuran (THF) and hexane. The polymer solutions were submitted to viscometric measurements as function of the solvent composition. The ratio of ethylene oxide/propylene oxide (EO/PO) units determines the modification in molecular conformation of the (PPO-b-PEO) block copolymers as function of the solvent composition. The macromolecular structure is the most important factor on the graft copolymers behavior. The structure in which ethylene oxide is linked to the main chain provides higher interaction between graft copolymers and solvent (THF/hexane).     

Synthesis of terpyridine-functionalized poly(phenylenevinylene)s: The role of meta-phenylene linkage on the Cu and Zn chemosensors

A meta-phenylene-containing poly(phenylenevinylene) (PPV) with pendant terdentate terpyridine ligand 2b was synthesized and its fluorescence properties were compared with its isomeric PPV. The meta-phenylene bridge interrupts the resonance connection between the PPV backbone and the metal-chelation sites, while jointing the structurally defined chromophores together. The fluorescence of the polymer, with emission λ_em = 460 nm and ?_fl ≈ 0.45, is found to be selectively quenched by Cu²⁺ ion with interference from Co²⁺ and Ni²⁺ ions. The nature of the quenching process in 2b is probed by using Stern-Volmer analysis, revealing that the quenching results from both dynamic collision and metal chelation. Addition of Zn²⁺ and Cd²⁺ ions only induces partial fluorescence quenching, accompanied with a broad new emission band occurring at ∼560 nm. With the aid of a model compound study, the new emission band at 560 nm is attributed to the complex formation with terpyridine to Zn ratio of 1:1. The study finds that the polymer has the potential for Cu²⁺ and Zn²⁺ sensors.     

Preparation, characterisation and biosensor application of conducting polymers based on ferrocene substituted thiophene and terthiophene

Novel ferrocene-substituted thiophene and terthiophene compounds, trans-1-(3′-thienyl)-2-(ferrocenyl)ethene and trans-1-((2′,2″:5″,2?-terthiophen)-3″-yl)-2-(ferrocenyl)ethene, have been used to produce homopolymer and copolymer materials. The copolymer of trans-1-(3′-thienyl)-2-(ferrocenyl)ethene with pyrrole and the homopolymer of trans-1-((2′,2″:5″,2?-terthiophen)-3″-yl)-2-(ferrocenyl)ethene were characterised using cyclic voltammetry (CV), UV-visible spectroscopy, scanning electron microscopy (SEM) and four point probe conductivity measurements. Results obtained suggest that the ferrocene moiety plays a catalytic role in the electropolymerisation process. Both the copolymer and homopolymer displayed cyclic voltammograms with redox peaks that can be assigned to the ferrocene moiety and the polymer backbone. The UV-visible spectra and morphology of the copolymer of trans-1-(3′-thienyl)-2-(ferrocenyl)ethene with pyrrole were similar to those of polypyrrole, but the spectra and morphology of the homopolymer of trans-1-((2′,2″:5″,2?-terthiophen)-3″-yl)-2-(ferrocenyl)ethene were different from those of polyterthiophene. The conductivity of the copolymer was determined to be 0.13 S cm⁻¹ whereas that of the homopolymer of trans-1-((2′,2″:5″,2?-terthiophen)-3″-yl)-2-(ferrocenyl)ethene was 82.6 μS cm⁻¹. The copolymer or homopolymer modified Pt disk electrodes facilitated access to the redox centre within Cytochrome C during CV, and their potential use as biosensors has been demonstrated.     

Dialkyldithiophosphate substituted on poly(vinylchloride): Synthesis and performance

Preparation of sodium salt of di(2-ethylhexyl)dithiophosphoric acid (DTPANa) by reaction of the corresponding DTPA with sodium hydride has been described. Nucleophilic substitution of chlorine on poly(vinylchloride) (PVC) by a di(2-ethylhexyl)dithiophosphate group resulting in modified polymer (MP) was characterized by the second order rate constant equal to 6.6 × 10^?5 M^?1 s^?1. Formation of homogeneous stable gelled phases composed of MP and DTPA, as well as MP, PVC, and DTPA, was demonstrated. The gelled material is capable of selective separation of metal ions under the conditions of extraction chromatography. © 1993 John Wiley & Sons, Inc.