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Porous microspheres obtained from 2,3-epoxypropyl methacrylate (GMA) and 1,4-di(methacryloyloxymethyl) naphthalene (DMN) were modified by the reaction of active oxirane group with 1-(2-hydroxyethyl)-2-pyrrolidone (HP). Spherical shape of the copolymers was confirmed by scanning electron microscopy whereas low-temperature nitrogen adsorption–desorption method was applied to determine their porous structure. It was found that the modification process did not change noticeably the internal structure of the materials. The specific surface area for both types of materials ranged from 41 to 106 m2g−1 depending on the molar ratio of the monomers. Changes, however, were observed in reference to thermal properties. They were studied using differential scanning calorimetry and thermogravimetry coupled with FTIR in inert and oxidative conditions. The reaction with HP reinforced thermal stability of the modified microspheres in helium atmosphere. Their initial decomposition temperatures (IDTs) increased to 273–281 °C. In air atmosphere, the values of IDTs were at the same level (248–269 °C). The modified beads decomposed in three (helium) or two (air) stages.

Nowadays, ibuprofen and ketoprofen are widely used over-the-counter medications to treat inflammation, fever, or pain. Their high consumption and improper disposal cause them to get into the environment and often pollute surface water. In this study, the new polymeric porous microspheres based on 4-vinylpyridine (4VP) are presented as effective sorbents for ibuprofen and ketoprofen preconcentration and removal. The porous microspheres were obtained via seed swelling polymerization with the use of two types of methacrylate crosslinkers, i.e., trimethylolpropane trimethacrylate (TRIM) and 1,4-dimethacryloiloxybenzene (14DMB). Additionally, as a reference sorbent, a copolymer of styrene and divinylbenzene was obtained. Porous structure investigations showed that the microspheres possess a specific surface area of about 100 m2/g, but noticeable differences were observed in their internal topography depending on the type of crosslinker used. Moreover, the porous structure of dry and swollen microspheres differs significantly. Swollen copolymers reveal the presence of micropores. The 4VP microspheres are characterized by high thermal stability; their initial decomposition temperature is about 300 °C. The performance of the 4VP copolymers as sorbents in aqueous solutions of drugs was evaluated in static and dynamic modes at three pH values of 3, 7, and 11. The highest sorption efficiency was obtained for ibuprofen and ketoprofen in pH 3. Both 4VP copolymers indicate the high sorption capacity in a static sorption as follows: towards ketoprofen of about 40 mg/g whereas towards ibuprofen of about 90 mg/g and 75 mg/g on copolymer crosslinked with trimethylolpropane trimethacrylate and 1,4-dimethacryloiloxybenzene, respectively. The recovery of ibuprofen and ketoprofen after dynamic sorption experiments was higher than 90%.

Thermal Behavior of Polymeric and Other Advanced Materials is a recently open Special Issue in Materials, which aims to publish original articles, short communications, reviews, and mini-reviews covering the most recent progress in multiple thermal characterizations of diverse materials and provide a platform for scientists from various areas to present their research [...]

The work is a continuation of the research on thermoplastic polyurethane (TPU) elastomers containing sulfur atoms which are incorporated into the polyurethane chain using aliphatic-aromatic chain extenders. These materials show some improved properties in relation to conventional ones, e.g., adhesion to metals, bacterial resistance and refractive index. The present study deals with the detailed characteristics of the process of thermal decomposition of TPU elastomers obtained from 2,2′-[methylenebis(1,4-phenylenemethylenethio)]diethanol, 1,1′-methanediylbis(4-isocyanatobenzene) (MDI) or 1,6-diisocyanatohexane (HDI) and poly(oxytetramethylene) diol of Mn = 2000 g/mol by thermogravimetric analysis coupled on-line with Fourier transform infrared spectroscopy. The analysis was performed under inert and oxidative conditions. All TPU elastomers were found to have a relatively good thermal stability, with those based on aromatic diisocyanate being at an advantage. In helium, they are stable up to 280–282 °C (from HDI) and 299–301 °C (from MDI), whereas in synthetic air up to 252–265 °C (from HDI) and 261–272 °C (from MDI), as measured by the temperature of 1% mass loss. Depending on the content of the hard segments and the tested atmosphere, the TPU elastomers decompose from one to four stages. From the analysis of the volatile decomposition products, it follows that the decomposition of both types of hard segments was accompanied by the evolution of carbonyl sulfide, carbon dioxide, water, sulfide dioxide, alcohols and aromatic compounds. For the hard segment derived from HDI, isocyanates, amines, and unsaturated compounds were also identified, while for the MDI-derived one, aldehydes were discovered. In turn, the polyether soft segment decomposed mainly into aliphatic ethers, aldehydes, and carbon monoxide.

The present study describes the thermal properties of a series of porous microspheres synthesised from the dimethacrylate derivative of m-xylene, i.e. (4,6-dimethyl-1,3-phenylene)dimethylene bis(2-methylprop-2-enoate) and divinylbenzene via an aqueous suspension polymerisation in the presence of toluene and decan-1-ol as porogenic diluents. Various molar ratios of monomers were applied in the syntheses (1:4, 1:1, 4:1). The TG/DSC/FTIR analyses were performed in inert (helium) and oxidative (synthetic air) atmospheres. They revealed that the properties of the copolymeric microspheres were dependent on both their chemical composition and the testing atmosphere. The microspheres were stable up to 229–296 °C (in helium) and 302–308 °C (in synthetic air), as determined on the basis of the temperature of 1% mass loss. However, the most thermally stable were those synthesised at the molar ratio of the dimethacrylate derivative of m-xylene to divinylbenzene equal to 1:4. In helium, the copolymeric beads decomposed in one, two or three stages, whereas in synthetic air in two ones. The basic decomposition volatiles were carbon monoxide, carbon dioxide and organic carbonyl products, including esters, carboxylic acids and aldehydes as well as unsaturated and aromatic compounds.

In this study, new thermoplastic sulfur-containing poly(carbonate-urethane)s (PCURs) were synthesized via a one-step melt polyaddition from diphenylethane-derivative diols with two or ten methylene groups in the aliphatic chain, i.e., 4,4′-(ethane-1,2-diyl)bis(benzenethioethanol) (diol E) and 4,4′-(ethane-1,2-diyl)bis(benzenethiodecanol) (diol D) as nonconventional chain extenders, 1,1′-methanediylbis(4-isocyanatobenzene) and 20–60 mol% poly(hexane-1,6-diyl carbonate) diol of $$\overline{M}_{\rm{n}}$$ = 860 g mol−1 as a soft segment. The PCURs were studied mainly to describe their thermal and mechanical behaviors by means of DSC, TG and TG coupled with FTIR, and Shore hardness and tensile tests. Moreover, their structure and physicochemical and adhesive properties were determined. The results of the study showed that the kind of the chain extender as well as soft-segment content had an impact on the properties of the polymers obtained. They were amorphous or semicrystalline high molar mass materials. The PCURs based on diol D exhibited lower glass transition temperatures in comparison with those based on diol E with shorter aliphatic chain (− 1–24 °C vs. 13–55 °C). Unfortunately, the former polymers revealed somewhat poorer tensile strengths (up to 45.0 MPa vs. 51.8 MPa). Nevertheless, these values were similar to or higher than those obtained for their commercial analogs. The PCURs being diol D derivatives also showed, in general, lower hardness and the modulus of elasticity but higher elongation at break. All the PCURs exhibited a relatively good thermal stability. However, the polymers derived from diol D revealed higher temperatures of 1, 10 and 50% mass losses compared with diol E-based ones (290–298 °C vs. 285–287 °C, 325–336 °C vs. 314–323 °C, 360–381 °C vs. 348–356 °C, respectively). The newly synthesized sulfur-containing PCURs showed better adhesive properties to copper than the analogous polymer based on butane-1,4-diol as a chain extender.

Two series of new sulfur-containing thermoplastic poly(carbonate-urethane)s (PCURs) were prepared by a one-step melt polyaddition from diphenylethane derivative diol, i.e., 4,4′-(ethane-1,2-diyl)bis(benzenethiohexanol) as a nonconventional chain extender, 1,1′-methanediylbis(4-isocyanatobenzene) (MDI) or 1,6-diisocyanatohexane (HDI) and 20–60 mol% poly(hexane-1,6-diyl carbonate) diol of $$\overline{M}_{\text n} = 860$$ g mol−1 as a soft segment. The FTIR and XRD as well as DSC, TG, and TG coupled with FTIR were employed to characterize the PCURs’ structure and thermal properties. Their physicochemical, adhesive, and tensile properties as well as Shore A/D hardness were also studied. The amorphous MDI-based PCURs were transparent materials (transmittance at 800 nm: 83–88%), while the HDI-based ones, showing partially crystalline structures (the degree of crystallinity: of 20–28%), were opaque. The polymers derived from HDI exhibited lower glass-transition temperatures than those obtained from MDI (from – 29 to – 12 °C vs. from 14 to 46 °C) as well as a higher degree of microphase separation. In turn, the PCURs based on MDI revealed higher tensile strength (up to 50.8 MPa vs. up to 33.4 MPa) and better thermal stability (e.g., the temperature of 1% mass loss: 294–305 °C vs. 262–278 °C). These sulfur-containing PCURs exhibited better adhesive properties to copper compared with the conventional PCURs synthesized from butane-1,4-diol as a chain extender.

Suspension–emulsion polymerization was applied to obtain porous microspheres of 2,3-epoxypropyl methacrylate (GMA) cross-linked with 1,4-di(methacryloyloxymethyl)-naphthalene (DMN). In the next step, the porous methacrylate network was modified by subsequent reaction with diethylenetriamine. The newly obtained functionalized material was characterized in detail. After the process of modification, a drop in the value of specific surface area of the functionalized copolymers was observed. Their thermal behavior was monitored by TG/DSC/FTIR methods in inert and oxidative conditions. The reaction with diethylenetriamine resulted in the decrease in thermal resistance of the obtained porous microspheres. Initial decomposition temperatures (IDTs) established in helium atmosphere fell down from 258–269 °C for parent copolymers to 206–220 °C for modified ones. The same situation was observed in synthetic air atmosphere. IDTs decreased from 249–269 to 207–230 °C. Moreover, the thermal decomposition of the functionalized microspheres exhibited multistage decomposition patterns different from parent GMA-DMN copolymers.

This paper presents the thermal properties of highly crosslinked di(methacryloyloxymethyl)naphthalene–divinylbenzene (DMN–DVB) copolymeric microspheres containing polar groups in the structure and their alkyl-bonded derivatives. C8 and C18 alkyl chains were introduced into the aromatic rings of the DMN–DVB porous copolymer by means of the Friedel–Crafts reaction. As a source of C8 and C18 alkyl chains, octyl and octadecyl chlorides were used. It was necessary to check whether the introduction of alkyl chains into the structure of polymeric packing had an impact on its thermal properties. The studies were carried out by thermogravimetry coupled online with FTIR spectroscopy and differential scanning calorimetry in inert atmosphere (helium). It was stated that the modified materials showed 20 and 50% mass losses at higher temperatures than the non-modified one while 1% mass loss was observed at lower temperatures. Moreover, an analysis of volatile decomposition products was performed.

In this study, the synthesis and characterization of permanently porous polymeric microspheres was presented. The microspheres were obtained via suspension polymerization using diverse functional monomers, such as 4,4′-bis(methacryloyloxymethylphenyl)sulphone, 1,4-bis(methacryloyloxymethyl)benzene, 4,4′-bis(methacryloyloxymethylphenyl)methane, N-vinylpyrrolidone, ethylene glycol dimethacrylate, and divinylbenzene as a co-monomer. As porogenic solvents, toluene and chlorobenzene were applied. The main aim of the research was to synthesize polymers having a highly developed internal structure and a good thermal stability. The synthesized materials were characterized by ATR-FTIR, scanning electron microscopy, a size distribution analysis, a low-temperature nitrogen adsorption–desorption method, differential scanning calorimetry, and thermogravimetry coupled with FTIR and inverse gas chromatography. It was found that, depending on the functional monomer, regular microspheres with a specific surface area in the range of 418–746 m2/g can be successfully synthesized. Moreover, all the synthesized copolymers showed a good thermal stability. In helium, they exhibited 5% mass losses at temperatures over 300 °C, whereas in air these values were only slightly lower. In addition, the presence of miscellaneous functional groups promoted diverse kinds of interactions. Therefore, the microspheres can be possibly use in many adsorption techniques including high temperature processes.

Porous copolymers of 1-vinyl-2-pyrrolidone (VP) with 1,4-di(methacryloyloxymethyl) naphthalene (DMN) have been synthesized by suspension polymerization in the presence of inert diluent. They have different specific surface area and contain various amount of strongly polar pyrrolidone groups. Their sorptive properties have been studied using solution of p-chlorophenol. It was found that adsorption strongly depends on the copolymer polarity. Polymeric sorbents were characterized using elemental analysis, ATR-FTIR, thermogravimetry, differential scanning calorimetry, inverse gas chromatography and their porous structure was determined by low-temperature nitrogen adsorption–desorption method.

Thermoplastic polyurethane elastomers (TPUs) containing aliphatic polycarbonate soft segments and hard segments formed by 1,1′-methanediylbis(4-isocyanatocyclohexane) or 1,6-diisocyanatohexane and a combination of two chain extenders, i.e., 2,2′-[sulfanediylbis(benzene-1,4-diyloxy)]diethanol and 3-hydroxy-2-(hydroxymethyl)-2-methylpropanoic acid (DMPA), were synthesized in a one-step catalyzed melt polyaddition process. The obtained colorless, transparent and high-molar-mass materials, which differ in the content of the soft segments (30 or 45 mol%) and DMPA (10 or 20 mol%), were subjected to a series of test. Their structure was examined by FTIR spectroscopy, and the thermal properties were studied using differential scanning calorimetry and thermogravimetry. Moreover, their Shore A/D hardness, tensile, adhesive and optical properties were determined.These modified by an ionic chain extender TPUs were characterized by generally enhanced transmittance (up to 92.7% at 800 nm), tensile strength (up to 49.3 MPa), hardness and adhesive strength, and decreased elongation at break with a slightly worsened thermal stability in comparison with the non-modified ones.

New thermoplastic poly(ether-urethane) elastomers were synthesized by one-step melt poly addition from poly(oxytetramethylene)diol of M¯n = 2000 g mol−1 as soft segment, 1,1′-methanediylbis(4-isocy...

New thermoplastic segmented polyurethanes were obtained by a one-step melt polyaddition using 40, 50 and 60 mol% poly(hexane-1,6-diyl carbonate) diol of \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\bar{M}_{n} = 860$$\end{document}M¯n=860 g mol−1, 1,1′-methanediylbis(4-isocyanatobenzene) and 2,2′-[sulfanediylbis(benzene-1,4-diyloxy)]diethanol, 2,2′-[oxybis(benzene-1,4-diylsulfanediyl)]diethanol or 2,2′-[sulfanediylbis(benzene-1,4-diylsulfanediyl)]diethanol as a chain extender. FTIR, atomic force microscopy, differential scanning calorimetry and thermogravimetry were used to examine the polyurethanes’ structure and thermal properties. Moreover, their Shore A/D hardness, tensile, adhesive and optical attributes were determined. They were transparent high-molar-mass materials showing good tensile strength (up to 51.9 MPa). The polyurethanes exhibited improved adhesion to copper taking into consideration that of conventional ones, and middle or high refractive index values (1.57–1.60), and both these parameters increased with an increase of the content of sulfur atoms in the polyurethane chain. The newly obtained polyurethanes can be considered as materials for numerous medical and optical appliances.

Transport is responsible for around a quarter of EU greenhouse gas emissions making it the second biggest greenhouse gas emitting sector after energy. Biogas is one of the cleanest and most versatile renewable fuels available today, answering on challenges of EU sustainable development strategies. Upgraded biogas–biomethane–has the same advantages as natural gas, but additionally is a sustainable fuel that can be manufactured from local waste streams thereby also solving local waste problems. During the last years, the production and use of biomethane has significantly increased in many European countries. Sweden is world leading both in terms of automotive use of biomethane and its non-grid based transportation.

Faience objects produced from the fourth millennium BC in ancient Egypt are considered as the first high-tech ceramics in human history. Despite extensive studies on manufacturing technology, many aspects of this complex technology remain a mystery and there is no methodology in place to unravel the techniques of Egyptian faience object production. Detailed studies presented herein fill the gaps, verifying standing opinions and allowing certain aspects of faience manufacturing technology to be reconstructed. The object of this innovative investigation is a hemispherical faience bowl discovered by archaeologists excavating a Ptolemaic workshop district at the site of Tell Atrib in the southern Nile Delta. The multiproxy analysis included the application of specialised software and preparation techniques coupled with complementary methods of light and digital microscopy, SEM with EDS, XRD, STA with EGA, as well as image analysis. Sources of raw and accessory materials (mineral and organic binders, fluxes, colourants) used for preparing the silica paste and glaze slurry were determined. The results helped to reconstruct how the raw material was prepared and how faience vessels were made. The bowl was moulded by compression using a two-part mould. The moulded and dried bowl was then covered by glaze slurry using the application method. A synthetic colourant, Egyptian Blue, was probably used to colour the glaze. The item was fired once at a temperature of 1050&ndash, 1150 &deg, C. Oxidised conditions were maintained in the kiln during the firing process and firing at the maximal temperature was relatively short. Application of the multiproxy approach has shed light on the technological aspects of faience bowl manufacturing. The obtained results have confirmed the usefulness of the comprehensive methodology that was applied for the reconstruction of particular manufacturing stages of faience objects.

Three series of new thermoplastic polyurethane elastomers (TPUs) were synthesized by a one-step melt polyaddition from aliphatic–aromatic chain extenders with different content of sulfur atoms, i.e., 2,2′-[sulfanediylbis(benzene-1,4-diyloxy)]diethanol (OSOE), 2,2′-[oxybis(benzene-1,4-diylsulfanediyl)]diethanol (SOSE) or 2,2′-[sulfanediylbis(benzene-1,4-diylsulfanediyl)]diethanol (SSSE), 1,1′-methanediylbis(4-isocyanatobenzene) (MDI) and 40, 50 or 60 mol% poly(oxytetramethylene) diol (PTMO) of $$ \bar{M}_{n} $$ = 1,000 g mol−1 as a soft segment. The structures of all the TPUs were examined by FTIR and atomic force microscopy. Their thermal behavior was investigated by means of differential scanning calorimetry and thermogravimetry (TG). For the selected polymers, the gaseous products evolved during the decomposition process were analyzed by TG-FTIR. Moreover, their physicochemical, tensile and adhesive properties as well as Shore A/D hardness were determined. The resulting TPUs were high-molar-mass materials with structures, which were amorphous or had a low degree of ordering. TPUs based on OSOE and SOSE showed a higher degree of microphase separation and glass-transition temperatures almost independent of soft-segment content (at ~−38 and −31 °C) than those from SSSE (from −28 to 1 °C). All TPUs were stable up to 288–297 °C, as measured by the temperature of 1 % mass loss. Their decomposition occurred in a two-step process and began within the hard segments. The main volatile products were carbon dioxide, carbonyl sulfide, aromatic compounds as well as aliphatic ethers and aldehydes. The polymers with 40 and 50 mol% PTMO content showed good tensile strength (~27–46 MPa), in most cases better than their commercial PTMO/MDI/butane-1,4-diol analogs with similar hardness values.

Two series of new thermoplastic poly(thiourethane-urethane) elastomers (EPTURs), with different hard-segment content (40–60 wt%), were synthesized by a one-step melt polymerization from poly(oxytetramethylene) diol (PTMO) of \( \overline{M}_{\text{n}} \) = 1,000 g mol−1 or poly(hexamethylene carbonate) diol (PHCD) of \( \overline{M}_{\text{n}} \) = 860 g mol−1 as a soft segment, hexane-1,6-diyl diisocyanate and (methylenedi-1,4-phenylene)dimethanethiol as a chain extender at the NCO/(OH + SH) molar ratio of 1. The structures of all the EPTURs were examined by Fourier transform infrared spectroscopy (FTIR), atomic force microscopy and X-ray diffraction analysis. Their thermal behavior was investigated by means of differential scanning calorimetry and thermogravimetric analysis (TG). For the chosen polymers the gaseous products evolved during the decomposition process were analyzed by TG-FTIR. Moreover, physicochemical, adhesive and tensile properties as well as Shore A/D hardness were determined. The resulting high-molecular-mass EPTURs were stable up to 254–262 °C, as measured by the temperature of 1 % mass loss. They decomposed in three or four stages. The main decomposition products were carbonyl sulfide, isocyanate, carbon dioxide, aromatic hydrocarbons as well as aliphatic ethers and aldehydes (in PTMO series) and alcohols (in PHCD series). All the polymers showed partially crystalline structures, associated with crystallization of thiourethane hard segments. Their melting temperatures were in the range of 184–186 °C. The PTMO series EPTURs exhibited better low-temperature properties (glass-transition temperature in the range of −64 to −44 vs. −26 to −22 °C), but poorer tensile strengths (20–28 vs. 37–43 MPa). These EPTURs showed improved adhesive properties in comparison with their polyurethane analogs.

New thermoplastic poly(ether–urethane)s and poly(carbonate–urethane)s were synthesized by a one-step melt polymerization from poly(oxytetramethylene) diol (PTMO) and poly(hexane-1,6-diyl carbonate) diol (PHCD) as soft segments, 4,4′-diphenylmethane diisocyanate, and 2,2′-[methylenebis(1,4-phenylenemethylenethio)]diethanol, 3,3′-[methylenebis(1,4-phenylenemethylenethio)]dipropan-1-ol or 6,6′-[methylenebis(1,4-phenylenemethylenethio)]dihexan-1-ol as unconventional chain extenders. The effects of the kind and amount of the polymer diol and chain extender used on the structure and properties of the polymers were studied. The polymers were examined by Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction analysis, atomic force microscopy, differential scanning calorimetry, thermogravimetric analysis (TGA), TGA coupled with FTIR spectroscopy, and Shore hardness and tensile testing. The obtained high-molecular-weight polymers showed elastomeric or plastic properties. Generally, the PTMO-based polymers exhibited significantly lower glass-transition temperatures (up to −48.1 vs −1.4°C), a higher degree of microphase separation, and ordering in hard-segment domains in comparison with the corresponding PHCD-based ones. Moreover, it was observed that the polymers with the PTMO soft segments showed poorer tensile strengths (up to 36.5 vs 59.6 MPa) but higher elongations at break. All of the polymers exhibited a relatively good thermal stability. Their temperatures of 1% mass loss were in the range 270–320°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Thermoplastic polyurethane elastomers (TPUs) are now widely used because of their excellent properties that include high tensile and tear strength, and good abrasion, impact and chemical resistance. TPUs are multiblock copolymers with alternating sequences of hard segments composed of diisocyanates and simple diols (chain extenders) and soft segments formed by polymer diols. Commonly used hard segments for TPUs are derived from 4,4 � -diphenylmethane diisocyanate (MDI) and aliphatic diols. The aim of our research was to examine the possibility of obtaining TPUs with good tensile properties and thermal stability by using an unconventional aliphatic-aromatic chain extender, containing sulfide linkages. Three series of novel TPUs were synthesized by melt polymerization from poly(oxytetramethylene) diol, poly(e-caprolactone) diol or poly(hexane-1,6-diyl carbonate) diol of number-average molecular weight of 2000 g mol −1 as soft segments, MDI and 3,3 � [methylenebis(1,4-phenylenemethylenethio)]dipropan-1-ol as a chain extender. The structure and basic properties of the polymers were examined using Fourier transfer infrared spectroscopy, X-ray diffraction, atomic force microscopy, differential scanning calorimetry, thermogravimetric analysis, Shore hardness and tensile tests. It is possible to synthesize TPUs from the aliphatic-aromatic chain extender with good tensile properties (strength up to 42.6 MPa and elongation at break up to 750%) and thermal stability. Because the structure of the newly obtained TPUs incorporates sulfur atoms, the TPUs can exhibit improved antibacterial activity and adhesive properties. c � 2011 Society of Chemical Industry

New thermoplastic poly(carbonate-urethane) elastomers Two series of novel thermoplastic poly(carbonate-urethane) elastomers, with different hard-segment content (30 - 60 wt %), were synthesized by melt polymerization from poly(hexane-1,6-diyl carbonate) diol of Mn = 2000 as a soft segment, 4,4'-diphenylmethane diisocyanate (MDI) or hexane-1,6-diyl diisocyanate (HDI) and 6,6'-[methylenebis(1,4-phenylenemethylenethio)]dihexan-1-ol as a chain extender. The structure and basic properties of the polymers were examined by Fourier transform infrared spectroscopy, X-ray diffraction analysis, atomic force microscopy, differential scanning calorimetry, thermogravimetric analysis, Shore hardness and tensile tests. The resulting TPUs were colorless polymers, showing almost amorphous structures. The MDI-based TPUs showed higher tensile strengths (up to 21.3 MPa vs. 15.8 MPa) and elongations at break (up to 550% vs. 425%), but poorer low-temperature properties than the HDI-based analogs.

Sustainable biorefineries have a critical role to play in our common future. The need to provide more goods using renewable resources, combined with advances in science and technology, has provided a receptive environment for biorefi nery systems development. Biorefi neries offer the promise of using fewer non-renewable resources, reducing CO2 emissions, creating new employment, and spurring innovation using clean and effi cient technologies. Lessons are being learned from the establishment of fi rst-generation biofuel operations. The factors that are key to answering the question of biorefi nery sustainability include: the type of feedstock, the conversion technologies and their respective conversion and energy effi ciencies, the types of products (including coproducts) that are manufactured, and what products are substituted by the bioproducts. The BIOPOL review of eight existing biorefi neries indicates that new effi cient biorefi neries can revitalize existing industries and promote regional development, especially in the R&D area. Establishment can be facilitated if existing facilities are used, if there is at least one product which is immediately marketable, and if supportive policies are in place. Economic, environmental, and social dimensions need to be evaluated in an integrated sustainability assessment. Sustainability principles, criteria, and indicators are emerging for bioenergy, biofuels, and bioproducts. Practical assessment methodologies, including data systems, are critical for both sustainable design and to assure consumers, investors, and governments that they are doing the ‘right thing' by purchasing a certain bioproduct. If designed using lifecycle thinking, biorefi neries can be profi table, socially responsible, and produce goods with less environmental impact than conventional products … and potentially even be restorative!

New thermoplastic poly(carbonate-urethane) elastomers (TPCUs) were prepared by a one-step melt polymerization from 20–80 mol% poly(hexane-1,6-diyl carbonate) diol of M ¯ n = 860 as a soft segment, hexane-1,6-diyl diisocyanate and 2,2′-[methylenebis(1,4-phenylenemethylenethio)]diethanol, 3,3′-[methylenebis(1,4-phenylenemethylenethio)]-dipropan-1-ol or 6,6′-[methylenebis(1,4-phenylenemethylenethio)]dihexan-1-ol (H) as new chain extenders at the NCO/OH molar ratio of 1 in the presence of dibutyltin dilaurate as a catalyst. The structures of the TPCUs were examined by FTIR spectroscopy, X-ray diffraction analysis, scanning electron microscopy and atomic force microscopy (AFM). The TPCUs were also characterized by physicochemical, thermal (by differential scanning calorimetry (DSC) and thermogravimetry) and tensile properties as well as Shore A/D hardness. The resulting TPCUs were colorless polymers, showing ordered structures including semicrystalline, with the highest ability to crystallize exhibited by the polymers derived from diol H. The polymers with the soft-segment content of 40–80 mol% (56.4–25.7 wt% of hard segments) exhibited a microphase separation shown by DSC and AFM. The TPCUs showed tensile strength in the range of 8.8–23.3 MPa and elongation at break in the range of 240–670%.

Two series of poly(ether urethane)s and one series of poly(ester urethane)s were synthesized, con- taining, respectively, poly(oxytetramethylene) diol (PTMO) of Mn ¼ 1000 and 2000 and poly(e-caprolactone) diol of Mn ¼ 2000 as soft segments. In each series the same hard segment, i.e., 4,4 0 -(ethane-1,2-diyl)bis(benzenethiohexa- nol)/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 dibutyl- tin dilaurate as a catalyst, at the molar ratio of NCO/ OH ¼ 1 (in the case of the polymers from PTMO of Mn ¼ 1000 also at 1.05). For all polymers structures (by FTIR and X-ray diffraction analysis) and physicochemical, ther- mal (by differential scanning calorimetry and thermogravi- metric 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 Mn ¼ 2000). It was found that the poly(ether urethane)s showed lower crystallinity, glass-transition tem- perature (Tg), and hardness as well as better thermal stabil- ity 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 Tg, crystallinity, and hardness. V C 2008 Wiley Periodicals, Inc. J Appl Polym Sci 110: 1677-1689, 2008

New thermoplastic segmented poly(thiourethane-urethane)s (SPTUUs) were prepared by a one-step melt polymerization from 20 to 80 mol % poly(tetramethylene oxide) of M n = 1000 or poly(hexamethylene carbonate) diol (PHCD) of M n = 860 as soft segments, hexamethylene diisocyanate (HDI) and bis[4-(mercaptomethyl)phenyl]methanone (BMMPM) as a new dithiol chain extender at the NCO/(OH + SH) molar ratio of 1 in the presence of dibutyltin dilaurate as a catalyst. The structures of the SPTUUs were examined by FTIR, X-ray diffraction analysis, and scanning electron microscopy. The SPTUUs were also characterized by physicochemical, thermal, and tensile properties as well as Shore A/D hardness. The SPTUUs with the PHCD soft segments showed better tensile properties than those with the PTMO soft segments. A nonsegmented polythiourethane based on BMMPM and HDI is also described.

Various new thermoplastic segmented polyurethanes were synthesized by a one-step melt polymerization from aliphatic–aromatic α,ω-diols containing sulfur in the aliphatic chain, including 4,4′-(ethane-1,2-diyl)bis(benzenethioethanol), 4,4′-(ethane-1,2-diyl)bis(benzenethiopropanol) and 4,4′-(ethane-1,2-diyl)bis(benzenethiodecanol) as chain extenders, hexane-1,6-diyl diisocyanate (HDI) or 4,4′-diphenylmethane diisocyanate (MDI) and 20–80 mol% poly(oxytetramethylene)diol (PTMO) with molecular weight of 1000 g/mol as a soft segment. The reaction was conducted at the molar ratio of NCO/OH = 1 and 1.05, and in the case of the HDI-based polyurethanes in the presence of dibutyltin dilaurate as a catalyst. The effect of the diisocyanate used on the structure and some physicochemical, thermal and mechanical properties of the segmented polyurethanes were studied. The structures of these polyurethanes were examined by FTIR and X-ray diffraction analysis. The thermal properties were investigated by differential scanning calorimetry and thermogravimetric analysis. Shore hardness and tensile properties were also determined. All the synthesized polymers showed partially crystalline structures. The MDI-based polyurethanes were products with lower crystallinity, higher glass-transition temperature (Tg) and better thermal stability in comparison with the HDI-based ones. The MDI series polymers also exhibited higher tensile strength (up to ∼36 MPa vs. ∼23 MPa) and elongation at break (up to ∼3900% vs. ∼900%), but lower hardness than the analogous HDI series polyurethanes. In both series of the polymers an increase in PTMO soft-segment content was associated with decreased crystallinity, Tg, hardness and tensile strength. An increase in PTMO content also involved an increase in elongation at break.

Five new aliphatic-aromatic thiodiols: 1,2-bis[4-(2′-hydroxyethylthio)phenyl]ethane (C18H22O2S2), 1,2-bis[4-(3′-hydroxypropylthio)phenyl]ethane (C20H26O2S2), 1,2-bis[4-(6′-hydroxyhexylthio)phenyl]ethane (C26H38O2S2), 1,2-bis[4-(10′-hydroxydecylthio)phenyl]ethane (C34H54O2S2), 1,2-bis[4-(11′-hydroxyundecylthio)phenyl]ethane (C36H58O2S2) have been characterized by X-ray powder diffraction. These thiodiols can be used for synthesis of thermoplastic nonsegmented polyurethanes. Experimental 2θ peaks positions, relative peak intensities, values of d and Miller indices as well as unit cell parameters are reported.

New linear polyurethanes derived from 4,4′-bis(6-hydroxyhexylthio)diphenyl ether and methylene bis(4-phenyl isocyanate) were synthesized by either melt or solution polymerization with a strictly equimolar ratio of the monomers. In the solution method, good results were obtained with the aprotic solvent N,N-dimethylformamide at an approximately 20 wt % concentration of the monomers, with dibutyltin dilaurate as a catalyst, the process being conducted at 90–100°C for 4 h. The basic physicochemical properties of the polymers were investigated with thermogravimetric analysis and differential scanning calorimetry. The molecular weight distribution was determined by gel permeation chromatography. Shore hardness and tensile test results were also examined. The structures of the resulting products were confirmed with elemental analysis, Fourier transform infrared, and X-ray diffractometry. The properties of the copolyurethanes, containing various amounts of poly(oxytetramethylene) diol (∼1000) or polycaprolactone diol (∼1250) and synthesized under the conditions for the nonsegmented polyurethanes, were also examined. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 380–388, 2003

A method based on the efficiency energy coefficient (output/input) is proposed for the assessment of renewable energy sources implementation and for evaluation of their potential for CO2 emission reduction. Energy coefficients were evaluated for renewable energy sources (such as solar, wind and biomass) as well as for their conventional substitutes based on coal, oil and gas. Relative coefficients for CO2 emission reduction were calculated in cases where particular conventional energy technology is replaced by appropriate renewable energy technology. Taking into account renewable energy potential in Poland and the calculated relative coefficients, the results of this research indicate a possibility of reducing CO2 emissions in Poland by ad 2030 by about 40 million tonnes per year, i.e. 9·9% of the total emissions in 1989. The biggest share in this substitution comes from the use of biomass (wood and straw) and solar energy (flat-plate collectors).

Two series of high-molar-mass thermoplastic poly(carbonate–urethane)s (PCURs) were synthesized from nonconventional sulfur-containing chain extenders, i.e., 2,2′-[sulfanediylbis(benzene-1,4-diyloxy)]diethanol (diol SE) and 2,2′-[methanediylbis(benzene-1,4-diylmethanediylsulfanediyl)]diethanol (diol ME), 1,1′-methanediylbis(4-isocyanatobenzene) and 30, 45 and 60 mol% aliphatic polycarbonate diol of M n = 2000 g mol−1 (Desmophen® C2200, Bayer) via a one-step melt polyaddition. The PCURs were investigated by FTIR, UV–Vis, atomic force microscopy, X-ray diffraction analysis, differential scanning calorimetry, thermogravimetry (TG) and TG-FTIR. Moreover, their Shore A/D hardness, tensile, adhesive and optical properties were determined. The obtained PCURs were transparent or opaque elastomers, possessing amorphous or partially crystalline structures. The polymers based on diol ME showed lower glass transition temperatures (−9 to (−8) vs. −7 to 20 °C) and better microphase separation. All the PCURs exhibited a relatively good thermal stability. Their temperature of 1 % mass loss was within the range of 284–292 °C with somewhat higher values shown by those obtained from diol ME. The PCURs decomposed in two (from diol ME) or three (from diol SE) stages, and for both types of polymers, the main decomposition occurred at the first stage. All the PCURs based on diol SE exhibited higher tensile strength (33.5–41.9 vs. 27.0–31.5 MPa), but smaller elongation at break (300–400 vs. 450–550 %) than polymers derived from diol ME. Somewhat better adhesive properties and a slightly higher refractive index were found for polymer based on diol ME with two sulfur atoms.

New thermoplastic polyurethane elastomers (TPUs) were obtained by a one-step melt polyaddition from 30, 45 and 60 mol% aliphatic polycarbonate diol of M n = 2000 g mol−1 (Desmophen® C2200, Bayer), 1,1′-methanediylbis(4-isocyanatocyclohexane) (HMDI) or 1,6-diisocyanatohexane (HDI) and 2,2′-[sulfanediylbis(benzene-1,4-diyloxy)]diethanol (acting as a chain extender). The TPUs were examined by FTIR, UV–Vis, atomic force microscopy, X-ray diffraction analysis, differential scanning calorimetry, thermogravimetry (TG) and TG–FTIR. Moreover, their Shore A/D hardness, tensile, adhesive and optical properties were determined. The obtained TPUs were transparent or opaque high molar mass materials, showing amorphous or partially crystalline structures. The HDI-based TPUs exhibited lower glass-transition temperatures than those based on HMDI (from −35 to −31 °C vs. from −20 to 1 °C) as well as a higher degree of microphase separation. The TPUs were stable up to 262–272 °C, taking into account the temperature of 1 % mass loss, with somewhat higher values shown by those from HDI. They decomposed in two stages. The main volatile products of the hard-segment decomposition were carbon dioxide, water and carbonyl sulfide, while aliphatic ethers, aldehydes and unsaturated alcohols, as well as carbon dioxide, originated from the soft-segment decomposition. The synthesized TPUs, with hardness in the range of 80–90°Sh A, possessed a good tensile strength (33.0–38.7 MPa), similar to that of the commercial biodurable medical grade TPU ChronoFlex® AL 80A (37.9 MPa), prepared from aliphatic polycarbonate diol, HMDI and butane-1,4-diol.