Short-chain Diols Research Articles

Closed-Loop Recyclable and Nonpersistent Polyethylene-like Polyesters.

ConspectusAliphatic polyesters based on long-chain monomers were synthesized for the first time almost a century ago. In fact, Carothers' seminal observations that founded the entire field of synthetic polymer fibers were made on such a polyester sample. However, as materials, they have evolved only over the past decade. This is driven by the corresponding monomers becoming practically available from advanced catalytic conversions of plant oils, and future prospects comprise a possible generation from third-generation feedstocks, such as microalgae or waste. Long-chain polyesters such as polyester-18.18 can be considered to be polyethylene chains with a low density of potential breakpoints in the chain. These do not compromise the crystalline structure or the material properties, which resemble linear high-density polyethylene (HDPE), and the materials can also be melt processed by injection molding, film or fiber extrusion, and filament deposition in additive manufacturing. At the same time, they enable closed-loop chemical recycling via solvolysis, which is also possible in mixed waste streams containing polyolefins and even poly(ethylene terephthalate). Recovered monomers possess a quality that enables the generation of recycled polyesters with properties on par with those of the virgin material. The (bio)degradability varies enormously with the constituent monomers. Polyesters based on short-chain diols and long-chain dicarboxylates fully mineralize under industrial composting conditions, despite their HDPE-like crystallinity and hydrophobicity. Fundamental studies of the morphology and thermal behavior of these polymers revealed the location of the in-chain groups and their peculiar role in structure formation during crystallization as well as during melting. All of the concepts outlined were extended to, and elaborated on further, by analogous long-chain aliphatic polymers with other in-chain groups such as carbonates and acetals. The title materials are a potential solution for much needed circular closed-loop recyclable plastics that also as a backstop if lost to the environment will not be persistent for many decades.

Regioselective Olefination and Arylation of Arene-Tethered Diols Using the Easily Foldable Directing Groups.

Arene-tethered diols constitute a valuable class of structural motifs of drug and bioactive natural product molecules. In this study, a regioselective protocol for olefination and arylation of arene-tethered 1,2-diols and 1,3-diols has been developed using easily foldable acetal structures for attaching pyridine and nitrile directing groups. The method overcomes the steric hindrance effect of the short-chain diols and affords products in high yield and regioselectivity. This efficient cascaded catalysis has been successfully utilized in the syntheses of natural products such as peucedanol, decursinol, and marmesin.

The potential of native and engineered Clostridia for biomass biorefining.

Since their first industrial application in the acetone-butanol-ethanol (ABE) fermentation in the early 1900s, Clostridia have found large application in biomass biorefining. Overall, their fermentation products include organic acids (e.g., acetate, butyrate, lactate), short chain alcohols (e.g., ethanol, n-butanol, isobutanol), diols (e.g., 1,2-propanediol, 1,3-propanediol) and H2 which have several applications such as fuels, building block chemicals, solvents, food and cosmetic additives. Advantageously, several clostridial strains are able to use cheap feedstocks such as lignocellulosic biomass, food waste, glycerol or C1-gases (CO2, CO) which confer them additional potential as key players for the development of processes less dependent from fossil fuels and with reduced greenhouse gas emissions. The present review aims to provide a survey of research progress aimed at developing Clostridium-mediated biomass fermentation processes, especially as regards strain improvement by metabolic engineering.

Catalytic activity of nickel and cobalt for amination of ethylene glycol: Which is better?

Metal Ni and Co are widely used in the catalytic amination of alcohols and Ni is more favored due to its better catalytic performance. Here we compared their catalytic performance for the amination of ethylene glycol and unexpectedly found that Co is more active than Ni. DFT calculation results showed that the energy barriers for the dissociation of O-H and C-H bond in an ethylene glycol molecule are smaller on Co (0001) plane, accounting for higher ethylene glycol conversion and primary amine yield on metal Co catalyst. The C-C bond dissociation in a glycolaldehyde (dehydrogenation intermediate of ethylene glycol) molecule has significantly lower energy barrier on Ni (111) plane, being consistent with lower selectivity of primary amine on metal Ni catalyst. We also compared their catalytic performance for the amination of other diols and the results showed that Co is more active when short-chain diols are used as the substrate.

Segmented Polyurethanes and Thermoplastic Elastomers from Elemental Sulfur with Enhanced Thermomechanical Properties and Flame Retardancy

AbstractThe production of elemental sulfur from petroleum refining has created a technological opportunity to increase the valorization of elemental sulfur by the creation of high‐performance sulfur based plastics with improved thermomechanical properties, elasticity and flame retardancy. We report on a synthetic polymerization methodology to prepare the first example of sulfur based segmented multi‐block polyurethanes (SPUs) and thermoplastic elastomers that incorporate an appreciable amount of sulfur into the final target material. This approach applied both the inverse vulcanization of S8 with olefinic alcohols and dynamic covalent polymerizations with dienes to prepare sulfur polyols and terpolyols that were used in polymerizations with aromatic diisocyanates and short chain diols. Using these methods, a new class of high molecular weight, soluble block copolymer polyurethanes were prepared as confirmed by Size Exclusion Chromatography, NMR spectroscopy, thermal analysis, and microscopic imaging. These sulfur‐based polyurethanes were readily solution processed into large area free standing films where both the tensile strength and elasticity of these materials were controlled by variation of the sulfur polyol composition. SPUs with both high tensile strength (13–24 MPa) and ductility (348 % strain at break) were prepared, along with SPU thermoplastic elastomers (578 % strain at break) which are comparable values to classical thermoplastic polyurethanes (TPUs). The incorporation of sulfur into these polyurethanes enhanced flame retardancy in comparison to classical TPUs, which points to the opportunity to impart new properties to polymeric materials as a consequence of using elemental sulfur.

A Viscometric study of mixtures with Hydroxyl-terminated polybutadiene (HTPB) and short chain diols used in the formulations of solid composite propellants.

Hydroxyl-terminated polybutadiene (HTPB) is widely used in the formulations of solid propellants used in rocket motors. Furthermore, in general, chain extenders and short chain diols, such as 1,4-butanediol and 1,2-propanediol, can also be used in propellant formulations to improve mechanical properties, especially tensile strength. However, the incorporation of these diols can result in a considerable increase in the viscosity of the mixture during the processing of propellants. Thus, the present study evaluated the compatibility of these diols with the HTPB prepolymer, through a viscometric study, with the aim to determine the order of addition that results in greater homogeneity for the mixture. It was concluded that 1,4-butanediol, due to its larger chain size, has better compatibility with HTPB resin than 1,2-propanediol. On top of that, it was found that when the resin is added first, it results in mixtures with greater compatibility.

Isolation of RNA and beta-NAD by phenylboronic acid functionalized, monodisperse-porous silica microspheres as sorbent in batch and microfluidic boronate affinity systems.

Monodisperse-porous silica microspheres 5.5 μm in size were obtained by a staged shape templated hydrolysis-condensation method, with a bimodal pore-size distribution. 3-aminophenylboronic acid (APBA) was covalently attached onto the silica microspheres with a capacity of 0.476 mmol APBA/g microspheres. The boronate affinity isolation behaviour of ribonucleic acid (RNA) containing cis-diol at 3'-end was investigated by using APBA attached-silica microspheres as the sorbent in batch fashion. A short-chain diol carrying agent, β-nicotinamide adenine dinucleotide (β-NAD) was used as a target molecule with stronger affinity for phenylboronic acid ligand. The maximum equilibrium adsorptions for RNA and β-NAD were determined as 60 and 159 mg/g sorbent, respectively. By using the synthesized sorbent, phosphate buffer at pH 7.0 containing sorbitol was successfuly used as a mild elution medium for obtaining quantitative desorptions with both RNA and β-NAD. RNA isolations from mammalian and bacterial cells were successfully performed while protecting the structural integrity of RNA via boronate affinity interaction in batch fashion. A microfluidic boronate affinity system including a microcolumn 300 μm in diameter was also constructed using APBA attached-silica microspheres as the stationary phase. The breakthrough curves of microfluidic system were obtained by studying with different feed concentrations of RNA and β-NAD. Quantitative desorptions and satisfactory isolation yields were obtained with RNA and β-NAD in the microfluidic system. The proposed system is useful for boronate affinity applications in genomics or proteomics in which valuable cis-diols at low concentrations are recovered from low-volume samples.

Phosphazene-Catalyzed Alternating Copolymerization of Dihydrocoumarin and Ethylene Oxide: Weaker Is Better

Metal-free alternating copolymerization of 3,4-dihydrocoumarin (DHC) and ethylene oxide (EO) was realized by relatively mild phosphazene bases (t-BuP2 and t-BuP1), which unexpectedly outperformed previously employed t-BuP4 superbase in terms of polymerization rate, monomer conversion, and copolymer molar mass, though macrocycles were still generated when long chains were targeted. Such facts have indicated the occurrence of proton shuttling between phosphazenium cation and alkoxide which reduced chain-end nucleophilicity and thus alleviated side reactions such as backbiting. It was surprising that t-BuP1 whose basicity was too low for the homopolymerization of EO triggered alternating copolymerization, indicating that generation of anionic species (phenoxide) was essential for the epoxide-opening step. Well-defined short-chain diols were subjected to one-pot subsequent chain extension by addition of an aliphatic lactone or a diisocyanate leading to, respectively, block copolymer or polyurethane constitute...

Preparation of CoFe2O4/SiO2Nanocomposites at Low Temperatures Using Short Chain Diols

The preparation of 70% CoFe2O4/30% SiO2(wt%) nanocomposites by sol-gel method using three short chain diols (1,2-ethanediol, 1,3-propanediol, and 1,4-butanediol) as chelators was studied. The Fourier transformed infrared spectra and X-ray diffraction patterns were used to confirm the formation of nanocomposites. The X-ray diffraction analysis showed that the chain length of the carboxylates embedded in the silica matrix influences the formation of crystallized cobalt ferrite as single phase at low temperatures. The influence of the methylene groups number in the precursors and annealing temperature on the nanocrystallite size was revealed. The stability of the obtained compounds was determined by calculation of thermodynamic parameters.

Biocompatibility and hemocompatibility evaluation of polyether urethanes synthesized using DBU organocatalyst

Biomaterials must fulfill some requirements before moving into in vivo application. In vitro test is usually conducted as a preliminary screening evaluation. Although most of the studies are focused in the cytotoxicity, interactions between blood elements and the biomaterials or hemocompatibility must also be considered. Aliphatic polyurethanes have been always considered ideal candidates for in-vivo application due to their versatility. However, the utilization of metal catalyst to promote the polymerization have limited their use. Recently, some organocatalysts have shown to be competitive to tin based catalyst for the preparation of polyurethanes and have relaunched their use in biomedicine. In the present study we carried out the organocatalyzed polymerization of 5 commercially available isocyanates, hexamethylene diisocyanate, isophorone diisocyanate, trans-1,4-cyclohexylene diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate) and l-lysine diisocyanate to analyze the cytotoxicity and hemocompatibility of the resultant polymers as a function of the employed diisocyanate. The diisocyanates were polymerized with hydroxy end-capped oligomeric poly (tetramethylene glycol) (PT2K) as the long chain diol and 1,3-propanediol as the short chain diol. We demonstrated that from selected diisocyanates, lysine diisocyanate based polyurethanes possessed lower cytotoxicity and better hemocompatibility than the other polyurethanes. In comparison with a well known blood compatible polymer such as poly(2-methoxyethyl acrylate), the lysine diisocyanate based polyurethanes showed remarkable values in terms of cytotoxicity and platelet adhesion, but major levels of protein adsorption.

Microbial production of short chain diols.

Short chain diols (propanediols, butanediols, pentanediols) have been widely used in bulk and fine chemical industries as fuels, solvents, polymer monomers and pharmaceutical precursors. The chemical production of short chain diols from fossil resources has been developed and optimized for decades. Consideration of the exhausting fossil resources and the increasing environment issues, the bio-based process to produce short chain diols is attracting interests. Currently, a variety of biotechnologies have been developed for the microbial production of the short chain diols from renewable feed-stocks. In order to efficiently produce bio-diols, the techniques like metabolically engineering the production strains, optimization of the fermentation processes, and integration of a reasonable downstream recovery processes have been thoroughly investigated. In this review, we summarized the recent development in the whole process of bio-diols production including substrate, microorganism, metabolic pathway, fermentation process and downstream process.Electronic supplementary materialThe online version of this article (doi:10.1186/s12934-014-0165-5) contains supplementary material, which is available to authorized users.

Microbial production of short chain diols

Short chain diols (propanediols, butanediols, pentanediols) have been widely used in bulk and fine chemical industries as fuels, solvents, polymer monomers and pharmaceutical precursors. The chemical production of short chain diols from fossil resources has been developed and optimized for decades. Consideration of the exhausting fossil resources and the increasing environment issues, the bio-based process to produce short chain diols is attracting interests. Currently, a variety of biotechnologies have been developed for the microbial production of the short chain diols from renewable feed-stocks. In order to efficiently produce bio-diols, the techniques like metabolically engineering the production strains, optimization of the fermentation processes, and integration of a reasonable downstream recovery processes have been thoroughly investigated. In this review, we summarized the recent development in the whole process of bio-diols production including substrate, microorganism, metabolic pathway, fermentation process and downstream process.

Unexpected efficiency of cyclic amidine catalysts in depolymerizing poly(ethylene terephthalate)

AbstractThis article describes studies on the catalytic activity of several nitrogen‐based organic catalysts for the depolymerization of poly(ethylene terephthalate) (PET), in which a few cyclic amidines work more effectively than a potent, bifunctional guanidine‐based catalyst 1,5,7‐triazabicyclo‐[4,4,0]‐dec‐5‐ene (TBD) in the presence of short chain diols that play a role in activation of carbonyl groups through hydrogen bonding. Further studies prove that the catalytic efficiency at the above specific conditions depends only on the extent of activation of a hydroxyl group rather than simply the pKa of the bases. For glycolysis with excess short‐chain alkanediols, 1,8‐diazabicyclo[5.4.0]undec‐7‐ene is the best catalyst. In contrast, TBD shows outstanding catalytic activity in depolymerizations of PET with mono‐alcohols and longer‐chain diols. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013

Design, polymerization, and properties of high performance thermoplastic polyurethane elastomers from seed-oil derived soft segments

Elevated environmental consciousness among producers and consumers has resulted in significant interest and research in seed oil derived building blocks for polymer synthesis. While slowly making inroads into selected applications, performance deficits have consistently relegated seed oil derived elastomers to roles having low performance requirements, or where biodegradability is paramount. In this article ester alcohol A-B monomers derived from reductively hydroformylated seed oil fatty acids are polymerized to make polyester soft segments. The seed oil components are separated following functionalization and then polymerized to make soft segments of varying molecular weight, functionality, and with varying polymerization initiators. The soft segments are subsequently polymerized with isocyanates and short chain diols to make thermoplastic polyurethane elastomers of varying compositions. High quality elastomers are obtained that meet tensile requirements for demanding applications. The structure, thermodynamic behavior, and mechanical properties of the elastomers are explained semi-quantitatively by combining theory of block copolymer microphase separation and a two-phase composite model. It is proposed that superior properties of the new elastomers could be understood in light of a relatively large Flory-Huggins parameter between the polyester soft segment and the urethane hard segment.

Synthesis of Short-Chain Diols and Unsaturated Alcohols from Secondary Alcohol Substrates by the Rieske Nonheme Mononuclear Iron Oxygenase MdpJ

The Rieske nonheme mononuclear iron oxygenase MdpJ of the fuel oxygenate-degrading bacterial strain Aquincola tertiaricarbonis L108 has been described to attack short-chain tertiary alcohols via hydroxylation and desaturation reactions. Here, we demonstrate that also short-chain secondary alcohols can be transformed by MdpJ. Wild-type cells of strain L108 converted 2-propanol and 2-butanol to 1,2-propanediol and 3-buten-2-ol, respectively, whereas an mdpJ knockout mutant did not show such activity. In addition, wild-type cells converted 3-methyl-2-butanol and 3-pentanol to the corresponding desaturation products 3-methyl-3-buten-2-ol and 1-penten-3-ol, respectively. The enzymatic hydroxylation of 2-propanol resulted in an enantiomeric excess of about 70% for the (R)-enantiomer, indicating that this reaction was favored. Likewise, desaturation of (R)-2-butanol to 3-buten-2-ol was about 2.3-fold faster than conversion of the (S)-enantiomer. The biotechnological potential of MdpJ for the synthesis of enantiopure short-chain alcohols and diols as building block chemicals is discussed.

Cationic Micelles Modulated in the Presence of α,ω‐Alkanediols: A SANS, NMR and Conductometric Study

AbstractThe solution behavior of a typical cationic surfactant, tetradecyltrimethylammonium bromide, in mixed solvent systems composed of water and varying concentrations of α,ω‐alkanediols; 1,2‐ethanediol (ED), 1,4‐butanediol (BD), 1,6‐hexanediol (HD) and 1,8‐octanediol (OD) was examined via electrical conductance measurements, 13C‐NMR spectroscopy and small angle neutron scattering (SANS) measurements. The critical micelle concentration (CMC) values and degree of counterion dissociation (α) indicate that both ED and BD oppose micellization, whereas HD and OD enhance micelle formation. Changes in the 13C‐NMR chemical shifts (∆δ values) reveal that the short chain diols reside almost exclusively in the bulk phase and hence, affect the formation of micelles by altering the solvent properties in the bulk of the solution, whereas HD and OD partition between the pseudomicellar phase and the bulk phase. SANS studies indicated that both the micellar size and aggregation number (Nagg) decrease in the presence of all diols. ED and BD behave like cosolvents and increase the α and CMC values and decrease Nagg. We note that the effect of HD and OD on the properties of the micelles is concentration dependent; at low concentrations, these diols interact with the micelles and behave as cosurfactants (as evidenced by the trends in the micellar properties), while at higher concentrations, they enhance the surfactant solubility and behave as a cosolvent.

Effect of the long chain extender on the properties of linear and castor oil cross-linked PEG-based polyurethane elastomers

Polyurethane (PU) elastomers were elaborated from polyethylene glycol of high molecular weight (MW = 4,000), 1,6-hexamethylene diisocyanate and polyethylene glycol (PEG1500) (MW = 1,500) as a long linear chain extender and/or castor oil as a cross-linker and were obtained in the form of transparent films. These poly(ether urethanes) elastomers are obtained by replacing the short-chain diol monomers with high molecular weight polyethylene glycols (PEG1500). High molecular weight polyethylene glycol (MW = 4,000 and 1,500, respectively) have greater chain length thus producing networks with lower cross-linking densities and higher average molecular weight between two consecutive cross-links. The PU properties were investigated using Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry, mechanical analysis and thermogravimetry. The results showed that the prepared polyurethanes (PUs) had very good tensile properties. The stress–strain data show that the PU elastomers obtained using a 60/40% OHPEG1500/OHcastor oil ratio have the best mechanical properties. The thermal degradation of the castor oil cross-linked PU elastomers starts at 280–300 °C, compared to the thermal degradation of linear PUs which begins at 220 °C. During storage at 25 °C, the morphology and mechanical properties of the elastomer films have been observed to change in time.

Fluoro-silsesquioxane-urethane Hybrid for Thin Film Applications

New fluoropolyurethane hybrids containing fluorinated polyhedral oligomeric silsesquioxane were synthesized for thin film applications using fluoro(13) disilanol isobutyl-POSS (FluoroPOSS) and a short chain fluorodiol and diisocyanate. The kinetics of the urethane reaction was monitored using Fourier transform infrared spectroscopy (FTIR) and the formation of urethane was confirmed using (29)Si Nuclear magnetic resonance spectroscopy (NMR). The effect of addition of FluoroPOSS either in the I step or II step of the two step polymerization reaction is evaluated using various spectroscopic, thermal, microscopic, and diffraction techniques. In general, the major shortcoming of the lack of flexibility of fluoropolyurethane from short chain diol and diisocyanate has been overcome by the use of tethered FluoroPOSS. X-ray photoelectron spectroscopy (XPS), atomic force microscpopy (AFM), and contact angle measurements on the hybrid thin films on silicon wafer demonstrate the migration of FluoroPOSS segment to the air-thin film interface when FluoroPOSS is used in I stage reaction, and it resides at the interface when used as a chain extender. However, in both cases, the formed thin film exhibits ultrahydrophobicity with water contact angle of approximately 107 degrees and low contact angle hysteresis and solvent resistance, which are preferable for protective thin film applications.

A Family of Nanoporous Materials Based on an Amino Acid Backbone

In the pocket: A nanoporous framework with internal surfaces lined with amino acid residues (see structure; Ni cyan, C gray (chiral centers yellow), H white, N blue, O red) is produced by the pillaring of nickel–aspartate layers by 4,4′-bipyridine. The presence of pockets capable of multiple interactions with guest species permits the enantioselective sorption of short-chain diols.

Synthesis and Characterization of New Polyurethane Adhesives

Polyurethane adhesives provide excellent flexibility, impact resistance and durability. Polyurethanes are formed through the reaction of an isocyanate component with polyether or polyester polyols or other active hydrogen compounds. This paper refers to polyurethane adhesives made from polyester polyols with long aliphatic chains (up to 36 carbon atoms) and MDI (diphenylmethane-4,4’-diisocyanate). The polyester polyols have been made from dimer acids obtained from renewable sources and short chain diols. The polyols that were used presented different degrees of unsaturation. The influence of the different raw materials in the adhesives performance is studied. The polyurethanes were produced by reaction between quasi-stoichiometric quantities of polyol and MDI, at several temperatures. The reaction was carried under inert atmosphere and at temperatures below 100°C. Performance of the adhesives was tested by carrying adhesion, hardness and water absorption tests. Characterization of both the polyester polyols and polyurethane adhesives was carried by Fourier Transform Infrared Spectroscopy (FTIR), Differential Scanning Calorimetry (DSC), Magnetic Nuclear Resonance (NMR), X-Ray Diffraction (WAXD), Scanning RMN Imaging of 1H of Stray- Field b (MRI) and Brookfield viscometry.