Genetically Modified Starch as an Industrial Raw Material

Abstract

Starch is an important raw material for industrial applications, both for food and nonfood purposes. Of particular interest is the use of starch as a nonpetroleum chemical stock for the manufacture of biodegradable polymers. Annual EC starch production is nearing 10 million tons, with 80% from cereals and 20% from potatoes, and grows at 4?5% annually. The potential for genetically modified starch is considered very high. Such starch offers significant advantages: 1) chemical modifications, which are expensive and environmentally hazardous, are replaced; 2) novel carbohydrates can be produced.     

Treating the polyelectrolytes as polymers with a draining effect. II. The behavior in the gel permeation chromatography

The behavior of the polyelectrolytes in the gel permeation chromatography (GPC) can be better understood if the modified universal calibration (log([η]M/Φ) vs. elution volume) is used instead of the “classical” universal calibration (log[η]M vs. elution volume). The value of Flory's parameter Φ is obtained from an equation established for nonionic polymers presenting a draining effect, considering that polyelectrolytes also behave as polymers with a draining effect. The modified universal calibration does not apply as successfully to polyelectrolytes as to nonionic polymers, because of their electrostatic exclusion in the pore surface of the GPC columns. Nevertheless, when polyelectrolytes are found in a high salt concentration solution, the modified universal calibration can be used to obtain their molecular mass, using nonionic hydrosoluble polymers as standard polymers. Moreover, considering polyelectrolytes as polymers presenting a draining effect and applying the modified universal calibration provides a better explanation for the electrostatic exclusion of these polymers from the pores of the GPC columns, using the Dubin–Tecklenburg model. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1106–1113, 2006     

“Enabling Technology” Polymers

Abstract

An area of polymer science that is of current and growing industrial importance is where the polymer is the enabling technology that makes a component, system, or process work. Without the special polymer, the technology simply does not operate in a useful manner.

The characteristics of this arena are very different from high volume commodity or engineering polymers. Performance is the overwhelming concern and the material is likely to be highly specialized to achieve optimum performance. Cost is of minor concern because the material is used in small quantities and the value it adds to the end use is exceedingly high. Supply is an issue because even at ultra-high prices the sales dollars generated are too small to be of interest to a large polymer producer. In addition, these polymers are often developed by an end-user company which is not in the business of producing polymers and not eager to share the end-use value with a partner.

One of the industrially important examples of polymers as enabling technology, is photoresists used in semiconductor chip manufacture. Within Raychem examples include: acrylic backbone polymers with crystallizable side chains; conductive, crystalline polymer composites; polymer-dispersed liquid crystal compositions; crosslinked fluorinated aromatic polymides or polyethers which will be discussed in detail.     

Selective Interpolymer Complexation between Acrylic Copolymers and Nonionic Polymers

Abstract

Selective interpolymer complexation has been studied between methacrylic acid-methacrylamide copolymer and some complementary polymers such as poly(methacrylamide), poly(vinyl pyrrolidone), and poly(ethylene oxide). The relative order of complexation ability of the various nonionic polymers has been interpreted on the basis of the nature of interactions between different units of polymers. Configurational environment and neighboring group influences seem to affect interpolymer complex formation.     

Volatile profile of Echinacea purpurea plants after in vitro endophyte infection

Abstract

The differences in volatile profile of Echinacea purpurea plants not-inoculated (EpC) and inoculated with their endophytes from roots (EpR) and stem/leaves (EpS/L) were analysed and compared by GC-FID/GC–MS in an in vitro model. Non-terpenes and sesquiterpene hydrocarbons were the most abundant classes with an opposite behaviour of EpS/L showing a decreased emission of sesquiterpenes and an increase of non-terpene derivatives. The main compounds obtained from EpS/L were (Z)-8-dodecen-1-ol and 1-pentadecene, while germacrene D and β-caryophyllene were the key compounds in EpC and EpR. For the first time, this work indicates that bacterial endophytes modify the aroma profiles of infected and non-infected in vitro plants of the important medicinal plant E. purpurea. Therefore, our model of infection could permit to select endophytic strains to use as biotechnological tool in the production of medicinal plants enriched in volatile bioactive compounds.     

Effect of Aging on the Mechanical Properties of Polymeric Materials

Abstract

Aging can modify polymer structure at the molecular, macromolecular, and/or the morphological level and thus induce changes in the mechanical properties. Stiffness is generally not modified for nonrubbery materials, except for mass transfer (solvent plasticization or plasticizer loss) in amorphous polymers or phase transfer (crystallization or crystal destruction) in semicrystalline polymers. The most significant modulus changes occur in the radiochemical aging of semicrystalline polymers whose amorphous phase is in the rubbery state. Yield properties generally vary in the same way as stiffness. Physical aging at T < T _g can lead to a significant increase in the yield stress. Very general features can be observed for rupture properties, for instance: 1) Only ultimate elongation ε is a pertinent variable in kinetic studies of aging involving tensile testing and related methods, 2) the amplitude of ε variation for a given degradation conversion is considerably higher for initially ductile materials than for brittle ones, and 3) the rupture envelope σ = f(ε), i.e., the ultimate stress, is often very close to the initial tensile curve except for rubbery materials undergoing predominant crosslinking. The mechanisms of ultimate property changes are reviewed. A kinetic approach is proposed for the very important case of heterogeneous, diffusion-controlled aging.     

A comparative study of interaction of ibuprofen with biocompatible polymers

In this paper we are reporting the interaction of a non-steroidal anti-inflammatory drug ibuprofen (IBF) with various biocompatible polymers. Being amphiphilic, the drug interacts with the polymers similar to the interaction of surfactants and polymers. Therefore, we have considered the polymer-amphiphile interaction approach using conductimetry. The polymers of different charges (cationic, anionic, and nonionic) have been taken for the study. It was found that the critical aggregation concentration (cac) decreases on increasing the polymer concentrations of cationic as well as nonionic polymers whereas it increases for anionic polymers. The results imply that anionic IBF interacts with cationic and nonionic polymers more strongly as compared to the anionic polymers. A possible anionic-anionic repulsion is responsible for the weak interaction of IBF with anionic polymers. On the other side, the critical micelle concentration (cmc) increases for all polymers which is a usual indication of the interaction between amphiphiles and polymers. Free energies of aggregation (ΔG_agg) and micellization (ΔG_mic) were also computed with the help of degrees of micelle ionization obtained from the specific conductivity - [IBF] isotherms.     

Polymerization of cyclic imino ethers: From its discovery to the present state of the art

Topics concerning the cationic ring‐opening polymerization of cyclic imino ethers and functional material production based on the resulting polymers are reviewed. Cyclic imino ethers are readily subjected to isomerization polymerization via cationic initiators. Mechanistic studies have provided a new concept, electrophilic polymerization. Double isomerization polymerization and no‐catalyst alternating copolymerization are interesting examples that show characteristics of the ring opening of cyclic imino ethers. The living polymerization of these monomers affords precisely controlled polymeric materials. Through the use of the unique properties of the product polymers, various functional polymeric materials, such as polymeric nonionic surfactants, compatibilizers, hydrogels, stabilizers for dispersion polymerization, biocatalyst modifiers, and supramolecular assemblies, have been developed. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 192–209, 2002     

Basis of Solid-Phase Grafting of Polypropylene

Abstract

The chemical modification of polymers opens new dimensions for the development and design of materials based on plastics. The chemical modification of polymers by reactions is performed by reactions in a melt, in a solution, or in a solid phase. The modification of polymers in solid phases (powder or granular material directly from the polymerization) has great advantages compared with reactions in solution or melt. The advantages are lower costs and, most important, greater creative variability. A special advantage of solid-phase modification of polypropylene (PP) is the fact that the degradation reaction is reduced.     

Phosphate Bonded Refractories and Insulating Materials

Abstract

The fundamental studies in phosphate bonding carried out by Kingery (1) in the USA in early fifties gave rise to worldwide investigations and practical application of a new type of refractories and insulating materials. The use of phosphate binders made it possible to develop a unique class of refractories and insulating materials with principally novel technical properties. Theoretical investigations and power-saving nonwaste technology of their production has been developed in Orgtehstrom from the early seventies. The result of these activities was industrial production of phosphate bonded refractories and insulating materials on a commercial basis; the technology was introduced in all ceramics and glass works of construction material industry of the Latvian SSR.     

Purification of Wastewater Using a Highly Porous Metal-Organic Framework and Graphene-like Materials—A Preliminary Study

ABSTRACT

Water contamination by toxic metals through the discharge of industrial wastewater is a worldwide environmental problem. Heavy metals are currently regarded as important pollutants, becoming a severe public health problem. The adsorption from aqueous solutions of trace metals using metal-organic framework, graphene oxide, or partially reduced graphene oxide was characterized by batch measurements. The choice of these materials was made based on their high surface areas, controlled porosities, and the ability to vary the surface hydrophilicity. These materials were prepared by modified standard protocols to meet project requirements. The adsorption potential of these materials was characterized for several metals.     

Advances in the catalyses of polymerizations

Abstract

Nearly all technical processes for the production of polymers are carried out in the presence of catalysts. In the case of addition polymerization reactions, two mechanisms are possible: Start of the reaction via an initiator (e.g., peroxides) or start via a true catalyst (e.g., Ziegler/ Natta systems). In both areas remarkable progress has been made: Cationic “living” polymerizations of oxacycloalkanes, group transfer polymerization, metal-catalyzed alternating copolymerization of ethylene with carbon monoxide, and metallocene-catalyzed polymerizations of alpha-olefins. The polymerization of alpha-olefins with metallocene catalysts not only leads to the improvement of well-known polymers like polyethylene and polypropylene, but also enables the production of new polymers like syndiotactic polypropylene, syndiotactic polystyrene, and cycloolefin copolymers on an industrial scale.     

Novel nonionic surfactants based on sulfoxides. 2. Homo- and copolymers

The synthesis of new nonionic amphiphilic polymers of the polysoap type is described, as well as their general behaviour in aqueous solution. The polymers were prepared by homopolymerisation of acrylate polymerisable surfactants (or "surfmers"), which bear the nonionic sulfoxide moiety. Alternatively, small hydrophilic acrylate and acrylamide monomers bearing the nonionic sulfoxide moiety were copolymerised with dodecylacrylate and N-dodecyl- N-methylacrylamide. Compared to many other nonionic hydrophilic fragments, a single sulfoxide group behaves as a strongly hydrophilic fragment of small volume. However, its relative hydrophilicity depends sensitively on its precise positioning in the polymers. Properly placed, three sulfoxide groups can balance up to two dodecyl chains to obtain still water-soluble polymers that exhibit typical polysoap properties. Some of the new nonionic polymers show lyotropic liquid-crystalline behaviour at ambient temperature.     

Dispersions of polymer ionomers: I

The principal subject discussed in the current paper is the effect of ionic functional groups in polymers on the formation of nontraditional polymer materials, polymer blends or polymer dispersions. Ionomers are polymers that have a small amount of ionic groups distributed along a nonionic hydrocarbon chain. Specific interactions between components in a polymer blend can induce miscibility of two or more otherwise immiscible polymers. Such interactions include hydrogen bonding, ion-dipole interactions, acid-base interactions or transition metal complexation. Ion-containing polymers provide a means of modifying properties of polymer dispersions by controlling molecular structure through the utilization of ionic interactions. Ionomers having a relatively small number of ionic groups distributed usually along nonionic organic backbone chains can agglomerate into the following structures: (1) multiplets, consisting of a small number of tightly packed ion pairs; and (2) ionic clusters, larger aggregates than multiplets. Ionomers exhibit unique solid-state properties as a result of strong associations among ionic groups attached to the polymer chains. An important potential application of ionomers is in the area of thermoplastic elastomers, where the associations constitute thermally reversible cross-links. The ionic (anionic, cationic or polar) groups are spaced more or less randomly along the polymer chain. Because in this type of ionomer an anionic group falls along the interior of the chain, it trails two hydrocarbon chain segments, and these must be accommodated sterically within any domain structure into which the ionic group enters. The primary effects of ionic functionalization of a polymer are to increase the glass transition temperature, the melt viscosity and the characteristic relaxation times. The polymer microstructure is also affected, and it is generally agreed that in most ionomers, microphase-separated, ion-rich aggregates form as a result of strong ion-dipole attractions. As a consequence of this new phase, additional relaxation processes are often observed in the viscoelastic behavior of ionomers. Light functionalization of polymers can increase the glass transition temperature and gives rise to two new features in viscoelastic behavior: (1) a rubbery plateau above T(g) and (2) a second loss process at elevated temperatures. The rubbery plateau was due to the formation of a physical network. The major effect of the ionic aggregate was to increase the longer time relaxation processes. This in turn increases the melt viscosity and is responsible for the network-like behavior of ionomers above the glass transition temperature. Ionomers rich in polar groups can fulfill the criteria for the self-assembly formation. The reported phenomenon of surface micelle formation has been found to be very general for these materials.     

New Polymers for Optimizing Organic Photovoltaic Cell Performances

The performance of an organic solar cell critically depends on the materials used in the active layer. Desirable characteristics of active layer materials include an intense optical absorption covering broad range of the solar spectrum to maximize photon capture, the ability to effectively separate charges upon photo‐excitation, high charge mobility to allow efficient charge transport to the electrodes, and suitable HOMO and LUMO levels to ensure a high device voltage. In order to optimize these properties simultaneously, we have designed and synthesized conjugated polymers containing alternating electron‐donating and electron‐accepting units. Based on one of the low band gap polymers we designed and synthesized previously, poly[2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene)‐alt‐4,7‐(2,1,3‐benzothiadiazole)], we carried out both side chain and main chain modifications in order to improve performance even further. By incorporating fluorene repeating units into the main chain, it is possible to adjust the absorption characteristics of the polymers while maintaining a desirable HOMO level and good charge carrier mobility. The solubility profile of the polymer can be adjusted by modifying the side chains, and soluble polymer with mobility as high as 7×10^?2 cm²/Vs is realized when a combination of 2‐ethylhexy and hexyl groups are used as side chains. These polymers should be promising candidates for high performance solar cells according to a recently published model (3).     

Dilute solution behaviour of progressively hydrolyzed polyacrylamide in water-N, N dimethylformamide mixtures

The intrinsic viscosities [η’s] of anionic (hydrolyzed; low and high carboxyl content) and nonionic polyacrylamide (unhydrolyzed) were measured in water-N, N dimethylformamide mixtures at various temperatures. Non-polyelectrolyte behavior of low carboxyl content polyacrylamide was observed in mixed solvent system. The plots of [η] vs. solvent composition in a mixed solvent system pass through minima for both high as well as low carboxyl content polymers but through a maximum for nonionic polyacrylamide. Observed minimum for charged polymers may be attributed to the loss of polymer sites available to interact with solvent for H-bonding interaction between neighboring amide and the acid groups. The maximum for nonionic polymer at the particular solvent composition arises for the most powerful cosolvent effect. Existence of two antagonistic effects is apparent in [η] values of nonionic polymer at various temperatures. Huggins constant (K_H) also indicates a significant variation of cosolvency as a function of solvent composition. Activation parameters of viscous flow were calculated using Frenkel-Eyring equation. The volume related parameter and the shape factor were also computed. Shape factor data indicate that polymer molecules are more or less rigid spheres and are not affected by temperature and composition of solvent.     

POLYMERS DERIVED FROM HEXAFLUOROACETONE

Abstract

The continuing demand for polymeric materials with a unique combination of properties has brought forth a sizable research effort concerning the use of trifluoromethyl substituents, particularly the 1,1,1,3,3,3-hexafluoroisopropylidene (HFIP) function derived from the incorporation of hexafluoroacetone (HFA) into the monomer. This work had its beginnings approximately 25 years ago when Rogers briefly reported in a patent the preparation of polyimides (PIs) from an hexafluoroisopropylidenebrideged diamine [1,2]. Since then numerous efforts have been made toward the synthesis, characterization, and evaluation of CF₃-containing polymers. Much of this information is found in patents, indicating the importance of these polymers to industry. At the present time, at least 11 known classes of polymers containing pendant or backbone-incorporated bis-trifluoromethyl groups have been reported. These polymers show promise as film formers, gas separation membranes, seals, soluble polymers, coatings, and in other high-temperature applications. Frequently the polymer properties imparted by the inclusion of the HFIP function encompass: increased solubility, flame resistance, glass transition temperature, thermal stability, oxidation resistance, and environmental stability; decreased color, crystallinity, dielectric constant, and water absorption.     

Recent Progress in the Biological Applications of Reactive Oxygen Species-Responsive Polymers

Abstract

Responsive polymeric materials that are sensitive to biological stimuli including temperature, pH, enzymes, or redox conditions have attracted research interest in recent years. Among these, reactive oxygen species (ROS)-responsive polymers are particularly appealing because of the special role of ROS in living organisms. ROS are the indicator and cause of certain diseases, and they are also important signaling molecules. ROS-responsive polymers could possess the following functions: drug carriers, ROS probes, or medications for certain ROS-related diseases. In this review, we analyze the progress about ROS-responsive polymers made in recent years and predict the future trends of ROS-responsive polymers from the above mentioned perspectives. Due to the limited scope of this review, some older articles are not covered here and are left for more comprehensive reviews.     

Synthesis and characterization of poly(tetrafluoroethyleneperoxides)

Tetrafluoroethylene (TFE) and oxygen react at low temperature in radical conditions to give perfluoropolyether-polyperoxide polymers. This oxypolymerization reaction has been applied on industrial scale for the manufacture of perfluoropolyethers, presently used in many application fields.It is known that highly unstable polymers containing large amounts of peroxidic units -CF₂CF₂OO- can be formed in particular conditions and may represent a potential hazard in the TFE oxypolymerization process. However little has been reported in the literature on the reaction conditions and the characterization of these polymers.In the present paper we describe the synthesis of perfluoropolyether-polyperoxide polymers with high peroxide content up to the nearly pure poly(perfluoroethyleneperoxide). The investigation is particularly focused to elucidate the relationship between reaction conditions, kinetics and polymer structure. The experimental results indicate that the physical chemical properties of these materials are strongly affected by the peroxide content, this latter depending on the reaction conditions, mainly TFE concentration and initiation rate.     

The Development of Polybenzimidazole Composites as Ablative Heat Shields

Abstract

The excellent high-temperature mechanical properties and other desirable characteristics of polybenzimidazole (PBI) polymer systems make these systems attractive candidates for development as ablative heat-shield materials. This paper describes the formulation of several new low-density polybenzimidazole composites. The proposed structure of the basic linear PBI prepolymer and of several highly cross-linked PBI polymers are presented. The cross-linked PBI's were obtained either thermally (by postcuring to a high temperature) or chemically (by the use of either preoxidized polyfunctional amines or triphenyl trimeasate as a comonomer in the polymerization).