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Water‐soluble monomers are extensively used in the production of polymeric materials in aqueous media for various applications. Acrylic acid–polyethylene glycol 2‐methyl‐2‐propenyl ether (AA‐HPEG) copolymers belong to the class of comb‐like polycarboxylate ether (PCE) polymers, employed as superplasticizers for cementitious materials. Due to different reactivity ratios of AA and HPEG, semibatch operations with optimized monomer addition profiles are required to enhance the incorporation of HPEG into the copolymer. The kinetics of this system is complex and, like other water‐soluble monomers, depends on monomer concentration, pH, and ionic strength. Despite its high‐volume industrial usage, the kinetics of this system have received little attention in the literature. Furthermore, the presence of the HPEG, with 55 ethylene oxide (EO) units in the side chain, complicates the precise determination of individual monomer conversions. To address this, various characterization methods are evaluated, including proton nuclear magnetic resonance (1H‐NMR) and size‐exclusion chromatography (SEC). Results show that HPEG conversion is determined more accurately using 1H‐NMR signals from the polymer than unreacted monomer signals or SEC traces. Aqueous semibatch AA‐HPEG copolymerization experiments are conducted in acidic media to investigate the effects of comonomer feeding time, initiator and chain‐transfer agent concentrations on the copolymerization kinetics, HPEG incorporation, and molar mass. [ABSTRACT FROM AUTHOR]

In recent years, the design and synthesis of high-performing conjugated materials for the application in organic photovoltaics (OPVs) have achieved lab-scale devices with high power conversion efficiency. However, most of the high-performing materials are still synthesised using complex multistep procedures, resulting in high cost. For the upscaling of OPVs, it is also important to focus on conjugated polymers that can be made via fewer simple synthetic steps. Therefore, an easily synthesised amorphous thiophene−quinoxaline donor polymer, TQ1, has attracted our attention. An analogue, TQ-EH that has the same polymer backbone as TQ1 but with short branched side-chains, was previously reported as a donor polymer with increased crystallinity. We have synthesised copolymers with varied ratios between octyloxy and branched (2-ethylhexyl)oxy-substituted quinoxaline units having the same polymer backbone, with the aim to control the aggregation/crystallisation behaviour of the resulting copolymers. The optical properties, glass transition temperatures and degree of crystallinity of the new copolymers were systematically examined in relation to their copolymer composition, revealing that the composition can be used to fine-tune these properties of conjugated polymers. In addition, multiple sub-Tg transitions were found from some of the polymers, which are not commonly or clearly seen in other conjugated polymers. The new copolymers were tested in photovoltaic devices with a fullerene derivative as the acceptor, achieving slightly higher performances compared to the homopolymers. This work demonstrates that side-chain modification by copolymerisation can fine-tune the properties of conjugated polymers without requiring complex organic synthesis, thereby expanding the number of easily synthesised polymers for future upscaling of OPVs. [ABSTRACT FROM AUTHOR]

[Display omitted] • Multicomponent polymer materials offer superior and adaptable properties. • Single chain nanoparticles represent an intermediate state between polymers and colloids. • Internal cross-linking impacts the structure and dynamics of SCNPs. • QENS studies show different atomic motions based on the SCNP chemical composition. The industrial sector has made significant strides in the development of multicomponent and multiphasic polymer materials, including polymer blends, composites (such as nanocomposites), and various copolymers. Random copolymers, characterized by their statistical arrangement of repeating units, are particularly noteworthy due to their tunability from amorphous to semicrystalline states. In this study, we focus on poly(tetrahydrofuran- ran -epichlorohydrin) (P(THF- ran -ECH)) copolymers, which serve as precursors for single-chain nanoparticles (SCNPs). These SCNP-based materials are of particular interest as they bridge the gap between traditional polymers and colloids. This research comprehensively investigates how the type and degree of internal cross-linking influence the structure and dynamics of P(THF- ran -ECH) copolymers and their SCNPs. Techniques such as quasielastic neutron scattering (QENS), differential scanning calorimetry (DSC), and broadband dielectric spectroscopy (BDS) were employed to study copolymers with varying compositions and levels of cross-linking. By analyzing two samples with different epichlorohydrin (ECH) contents (13 mol% and 27 mol%), we aim to control crystallization and explore its effects on dynamic behavior. Our results show that both the composition and the degree of cross-linking significantly impact the dynamics of the SCNPs, with SCNPs exhibiting slower dynamics compared to their precursor copolymers. Furthermore, semicrystalline samples display faster dynamics in SCNPs than amorphous samples. These findings provide valuable insights for the design and optimization of advanced multicomponent polymer systems. [ABSTRACT FROM AUTHOR]

Dipropargyl ether of bisphenol A (DPEBA) was used to copolymerize with 1, 3-diethynylbenzen (m-DEB) through dimethylsilane linkage in one-pot way to obtain the silicon-containing poly(diethynylbenzene-co-dipropargyl ether of bisphenol A)s (PSAPEs) by Grignard reagents. The reactivity of alkynyl hydrogens in DPEBA and m-DEB were calculated. The reactivity of DPEBA and m-DEB are so similar that they can easily copolymerize with each other to obtain a random copolymer. The content of copolymer segments in the copolymer is larger than that of homopolymer segments in the copolymer when the molar ration of DPEBA in the comonomer composition is less than 50%. With increase of DPEBA content in comonomer composition, the meltability of PSAPEs can be improved, but the curing temperature of PSAPEs increase, and the thermal stability of the cured PSAPEs decrease clearly. The flexural and interlaminar shear strength of the T300 carbon cloth reinforced PSAPEs composites (T300CF/PSAPEs) increase with incorporation of DPEBA in the copolymer matrix. The glass transition temperature of the composites can be over 400 °C. A T300CF/PSAPE-70 composite with 70% of DPEBA as comonomer of the matrix resin displays the flexural strength of 374 MPa at room temperature, and can retain over 88% at 300 °C in 30 min. [ABSTRACT FROM AUTHOR]

Polyhydroxyalkanoate (PHA) synthase is an enzyme that polymerizes the acyl group of hydroxyacyl-coenzyme A (CoA) substrates. Aeromonas caviae PHA synthase (PhaCAc) is an important biocatalyst for the synthesis of a useful PHA copolymer, poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate] [P(3HB-co-3HHx)]. Previously, a PhaCAc mutant with double mutations in asparagine 149 (replaced by serine [N149S]) and aspartate 171 (replaced by glycine [D171G]) was generated to synthesize a 3HHx-rich P(3HB-co-3HHx) and was named PhaCAc NSDG. In this study, to further increase the 3HHx fraction in biosynthesized PHA, PhaCAc was engineered based on the three-dimensional structural information of PHA synthases. First, a homology model of PhaCAc was built to target the residues for site-directed mutagenesis. Three residues, namely tyrosine 318 (Y318), serine 389 (S389), and leucine 436 (L436), were predicted to be involved in substrate recognition by PhaCAc. These PhaCAc NSDG residues were replaced with other amino acids, and the resulting triple mutants were expressed in the engineered strain of Ralstonia eutropha for application in PHA biosynthesis from palm kernel oil. The S389T mutation allowed the synthesis of P(3HB-co-3HHx) with an increased 3HHx fraction without a significant reduction in PHA yield. Thus, a new workhorse enzyme was successfully engineered for the biosynthesis of a higher 3HHx-fraction polymer.

The aim of this study was to synthesize poly(acrylic acid- co -itaconic acid) (PAA- co -PIA) ionomer through a novel precipitation photopolymerization technique. The ionomer was characterized and the effect of its structural parameters, such as molecular weight and copolymer composition were investigated on the mechanical properties of glass-ionomer prepared using the ionomer. Design of experiment (DOE) was used to examine the effect of monomer ratio and the amount of chain transfer agent on the molecular weight and final conversion of the ionomers synthesized through the precipitation photopolymerization. The copolymer compositions were identified using FTIR and 1H-NMR spectroscopy. The molecular weights of the copolymers were evaluated by GPC. A series of PAA- co -PIA copolymers were then synthesized via the photopolymerization technique in three monomer ratios and two molecular weight ranges (high and low) to study the properties of the glass ionomers thereof. Experimental dental glass-ionomer cements were prepared by mixing the synthesized polymers with glass powder and their compressive properties were determined according to ISO 9917-1:2007 after storing for 0, 1, 7 and 28 days in distilled water. The scanning electron microscopy (SEM) was used to study the fracture surface morphology of the cements. The PAA- co -PIA polymers were synthesized by the photopolymerization method in a short time and high purity. The DOE showed that by decreasing the acrylic acid/itaconic acid ratio and increasing the amount of transfer agent, the molecular weight and final conversion decreased significantly. By increasing the itaconic acid content in the copolymer composition and increasing the molecular weight in a constant copolymer composition, the compressive strength and modulus were increased. Microstructures revealed that cements made of the higher molecular weight poly acids showed lower cracks and voids. The precipitation photopolymerization technique provides a promising and facile method in the synthesis of ionomers which are used in dental cements and other application. [ABSTRACT FROM AUTHOR]

This work concerns the preparation and characterization of poly (acrylonitrile-co-methyl methacrylate) Copolymer, P(AN-co-MMA), nano-particles using precipitation polymerization technique. Potassium per-sulfate redox initiation system was used to perform polymerization process in an alcoholic aqueous system. The impact of different polymerization conditions such as comonomer concentration and ratio, polymerization time, polymerization temperatures, initiator concentration and co-solvent composition on the polymerization yield and particle size was studied. Maximum polymerization yield, 70%, was obtained with MMA:AN (90%:10%) comonomer composition. Particle sizes ranging from 16 nm to 1483 nm were obtained and controlled by variation of polymerization conditions. The co-polymerization process was approved by FT-IR and TGA analysis. The copolymer composition was investigated by nitrogen content analysis. Copolymers with a progressive percentage of PAN show thermal stabilities close to PAN Homopolymer. SEM photographs prove spherical structure of the produced copolymers. The investigated system shows promising future in the preparation of nanoparticles from comonomers without using emulsifiers or dispersive agents.

A cross-linked poly acrylic acid tri-polymer is successfully synthesized by batch charging polymerization of poly allyl tris buffer, di-vinyl benzene and acrylic acid and this new method is profitable in terms of reducing the toxicity, faster, purity and cheaper than available methods. The morphological structure of the synthesized polymer is studied by SEM and the characteristic functional groups of the synthesized polymers are identified using FTIR. TGA and DSC techniques were employed to study their thermal characterization. [ABSTRACT FROM AUTHOR]

Highlights • THM-GC was applied to monitor the change in copolymer composition of film samples during soil burial test. • 3 HHx moieties in the polymer chains were preferentially biodegraded owing to their low crystallinity. • Local variation in the degree of biodegradation using only 30 μg of P(3HB-co-3HHx) film sample. Abstract Soil burial biodegradation behavior of poly(3-hydroxybutyrate- co -3-hydroxyhexanoate) [P(3HB- co -3HHx)] was studied based on its copolymer composition determined by thermally assisted hydrolysis and methylation-gas chromatography (THM-GC). The change in copolymer composition of P(3HB- co -3HHx) film samples during soil burial degradation test was monitored in detail by THM-GC. As a result, the copolymer compositions of 3HB units gradually increased, while those of 3HHx units decreased with soil burial time, almost correlating with recovery weight. Based on these results, the biodegradation mechanism of P(3HB- co -3HHx) was elucidated with considering the influence of the crystallinity on the biodegradability. Furthermore, local differences in biodegradability of a given P(3HB- co -3HHx) film after soil burial test were also successfully evaluated from the copolymer compositions obtained by THM-GC. [ABSTRACT FROM AUTHOR]

The error-in-variables-model (EVM) is the most statistically correct non-linear parameter estimation technique for reactivity ratio estimation. However, many polymer researchers are unaware of the advantages of EVM and therefore still choose to use rather erroneous or approximate methods. The procedure is straightforward but it is often avoided because it is seen as mathematically and computationally intensive. Therefore, the goal of this work is to make EVM more accessible to all researchers through a series of focused case studies. All analyses employ a MATLAB-based computational package for copolymerization reactivity ratio estimation. The basis of the package is previous work in our group over many years. This version is an improvement, as it ensures wider compatibility and enhanced flexibility with respect to copolymerization parameter estimation scenarios that can be considered. [ABSTRACT FROM AUTHOR]

The present work investigates the structure properties of copolymers using thermogravimetric analysis, hot stage microscopy, static light scattering, field emission scanning electron microscopy, X-ray diffraction analysis and a Brookfield viscometer. Poly(potassium 1-hydroxyacrylate) (PKHA) is a water-soluble polymer. However, the copolymer of styrene and 2-isopropyl-5-methylene-1,3-dioxolan-4-one is not water soluble at equal molar ratio because the polystyrene reduces the solubility. The effect of styrene on poly(potassium 1-hydroxyacrylate- co-styrene) copolymer, i.e. poly(KHA- co-St), was investigated for the increasing solubility of the copolymer. The solubility was increased at a lower molar ratio of styrene such as 0.4 in the copolymer. It was found that the copolymer was soluble in water when a content ratio of 68/32 mol% of homopolymer was incorporated in poly(KHA68- co-St32) copolymer as determined by NMR analysis. Also the poly(KHA68- co-St32) copolymer was found to be salt tolerant, possessed water absorption capacity and was thermally stable up to 183 °C. Moreover, it is shown that the polystyrene content plays a key role in the thermal stability of the copolymer. © 2017 Society of Chemical Industry [ABSTRACT FROM AUTHOR]

This work concerns the preparation and characterization of poly (acrylonitrile-co-methyl methacrylate) Copolymer, P(AN-co-MMA), nano-particles using precipitation polymerization technique. Potassium per-sulfate redox initiation system was used to perform polymerization process in an alcoholic aqueous system. The impact of different polymerization conditions such as comonomer concentration and ratio, polymerization time, polymerization temperatures, initiator concentration and co-solvent composition on the polymerization yield and particle size was studied. Maximum polymerization yield, 70%, was obtained with MMA:AN (90%:10%) comonomer composition. Particle sizes ranging from 16 nm to 1483 nm were obtained and controlled by variation of polymerization conditions. The co-polymerization process was approved by FT-IR and TGA analysis. The copolymer composition was investigated by nitrogen content analysis. Copolymers with a progressive percentage of PAN show thermal stabilities close to PAN Homopolymer. SEM photographs prove spherical structure of the produced copolymers. The investigated system shows promising future in the preparation of nanoparticles from comonomers without using emulsifiers or dispersive agents. [ABSTRACT FROM AUTHOR]

ABSTRACT Polyimide (PI)-polyurethane-urea (PU) block copolymers (PI-PU75/25, PI-PU50/50, and PI-PU25/75) were prepared by reaction between anhydride-terminated poly(amic acid) prepolymers with various number-average degree of polymerization [ABSTRACT FROM AUTHOR]

Thermally-assisted hydrolysis and methylation-gas chromatography-mass spectrometry (THM-GC-MS) using tetramethylammonium hydroxide (TMAH) is an effective approach for the characterization of condensation polymers with ester linkages such as ultraviolet (UV)-cured acrylate resins. However, for intractably cured acrylic resins, reliable structural characterization is often difficult by conventional THM-GC-MS owing to insufficient THM reactions. In this study, a pretreatment to effectively improve THM efficiency was proposed, in which the resin sample was preliminarily soaked and dissolved in a TMAH-methanol solution in a microtube. An aliquot of the TMAH solution was then introduced into the pyrolyzer at 400 °C to produce THM-GC-MS. The effectiveness of the proposed pretreatment was demonstrated using a UV-cured acrylate copolymer consisting of bulky and high-molecular weight bifunctional acrylate (9,9-Bis[4-(2-acryloyloxy ethoxy) phenyl]fluorene) and monofunctional acylate (2-(9 H-Carbazol-9-yl)ethyl acrylate) monomers, for which THM reactions did not proceed efficiently in conventional THM-GC-MS. Conversely, by the modified THM-GC-MS process with a pretreatment involving immersion at room temperature for 24 h or at 60 °C for 30 min, the characteristic decomposition products for each monomer unit were clearly observed in the chromatograms, and the copolymer composition could be precisely estimated from the relative yields of the observed decomposition products. In addition, a methyl acrylate peak, formed from unreacted acrylate moieties in the photocured copolymer, appeared in the chromatogram. Its relative yields were correlated to the double bond conversion in the cured sample. The observed results were successfully interpreted to clarify the curing process of the photocured acrylate copolymer samples. [Display omitted] • A THM-GC-MS method applicable to intractable UV-cured acrylate was developed. • The cured resin sample was preliminarily immersed and dissolved into a TMAH solution. • The copolymer composition of the intractable acrylate resin was precisely determined. • The double bond conversion was estimated by the modified THM-GC-MS method. • The observed results were interpreted in terms of the photocuring reactions. [ABSTRACT FROM AUTHOR]

Poly(N-isopropylacrylamide-co-N,N'-methylene-bisacrylamide) (P(NIPAAm-co-MBA)) hydrogels were prepared in water using redox initiator. The copolymer composition at high conversion (> 95%) was determined indirectly by HPLC (high performance liquid chromatography) analysis of the leaching water and directly by solid state 13C CP MAS NMR (cross polarization magic angle spinning nuclear magnetic resonance) spectroscopy of the dried gels, and was found to be close to that of the feed. The effect of cross-linker (MBA) content in the copolymer was investigated in the concentration range of 1.1–9.1 mol% (R:90–10; R = mol NIPAAm/mol MBA) on the rheological behaviour and mechanical strength of the hydrogels. Both storage and loss modulus decreased with decreasing cross-linker content as revealed by dynamic rheometry. Gels R70 and R90 with very low cross-linker content (1.2–1.5 mol% MBA) have a very loose network structure, which is significantly different from those with higher cross-linker content manifesting in higher difference in storage modulus. The temperature dependence of the damping factor served the most accurate determination of the volume phase transition temperature, which was not affected by the cross-link density in the investigated range of MBA concentration. Gel R10 with highest cross-linker content (9.1 mol% MBA) behaves anomalously due to heterogeneity and the hindered conformation of the side chains of PNIPAAm.

Thermally assisted hydrolysis and methylation-gas chromatography (THM-GC) in the presence of an organic alkali was validated for the compositional analysis of poly(3-hydroxybutyrate- co -3-hydroxyhexanoate) [P(3HB- co -3HHx)] accumulated in whole bacterial cells. Recombinant Cupriavidus necator Re2058/pCB113 was grown in a batch fermentation with different concentration of palm oil and fructose in order to control the molar fraction of 3HHx in P(3HB- co -3HHx) produced in the cells. Trace amounts (30 μg) of freeze-dried cells were directly subjected to THM-GC in the presence of tetramethylammonium hydroxide (TMAH) at 400 °C. The obtained chromatograms clearly showed nine characteristic peaks, attributed to the THM products from 3HB and 3HHx units in the polymer chains, without any appreciable interference by the bacterial matrix components. Based on these peak intensities, the copolymer compositions were determined rapidly without using any cumbersome and lengthy sample pretreatment as in conventional GC method. Moreover, the compositions thus obtained were strongly correlated with those by NMR and conventional GC involving solvent extraction. [ABSTRACT FROM AUTHOR]