Rigid Aromatic Groups Research Articles

Bio-derived Schiff base vitrimer with outstanding flame retardancy, toughness, antibacterial, dielectric and recycling properties

Thermosetting resins are widely used in high-tech applications for excellent mechanical robustness and chemical resistance. With increasing attention to the environmental and usage safety issues, it is necessary to develop bio-derived, recyclable, tough, and fire-retardant thermosetting resins. Herein, a high-performance, vanillin-based vitrimer (CIP1.0) was prepared. The CIP1.0 with 1.0 wt% phosphorus passes vertical burning (UL-94) V-0 rating with a limiting oxygen index (LOI) of 27.2%. The phosphorus-containing and Schiff base groups act synergistically in gas and condensed phases during combustion, endowing CIP1.0 with outstanding fire retardancy. The CIP1.0 shows excellent toughness with high elongation at break of 45.0% due to the π-π stacking of numerous rigid aromatic groups and appropriate cross-linking density. The highly symmetrical structure and low polarizability of CIP1.0 result in a low dielectric constant. The CIP1.0 exhibits superior antimicrobial properties. The CIP1.0 can be reprocessed by hot-pressing at 140 °C for 10 min. The non-destructive, closed-loop recycling of carbon fibers in the carbon fiber-reinforced CIP1.0 composite can be achieved under mild conditions due to the degradable Schiff base groups of CIP1.0. In this work, a bio-derived, tough, fire-retardant, low dielectric, and antimicrobial vitrimer is prepared to provide a rational strategy for the design of advanced environmentally friendly thermosetting resins.

Bioinspired Nanotubular Structures by Soft-Template Electropolymerization: 3,4-(2,3-naphtylenedioxy)Thiophene Monomers Quenched to Form Dimers

Preparing well-ordered nanotubes on materials surface is a great of interest in many applications. Bio-inspired and theoretical approaches show that porous structures such as nanotubes are key parameters for both surface hydrophobicity and water adhesion. Here, a very easy soft-template electropolymerization approach is used to form nanotubular structures, followed by a bioinspired strategy to control the wetting properties. Fully conjugated monomers based on 3,4-(2,3- naphtylenedioxy)thiophene (NaphDOT) core grafted with many rigid aromatic groups such as phenyl, naphthalene, pyrene, pyrrole, were synthesized. Then, electropolymerization is carried out with these monomers, followed by surface and morphologies characterization of corresponding polymers. We show that even if just dimers are formed by electropolymerization, the resulting polymer can be sufficiently insoluble to form structured films. 3,4-(2,3-naphtylenedioxy)thiophene (NaphDOT) is chosen as a judicious example, due to strong <i>π</i>-stacking interactions, and also their capacity to form nanotubular structures by soft template-electropolymerization in the presence of water (H<sub>2</sub>O). Here, different substituents, polymerizable or not, are grafted on the 2-position of thiophene. Films are formed with all the studied substituents. Nanotubular structures are especially observed with the following substituents: hydroxyl, pyrene and pyrrole, but in the presence of H<sub>2</sub>O. We study also their influence on the surface hydrophobicity.

Synthesis and study of poly (phthalic anhydride-β-cyclodextrin) for the efficient adsorption of cationic dyes from industrial wastewater

In this study, a novel adsorbent capable of efficiently adsorbing cationic dyes, poly (phthalic anhydride-β-cyclodextrin) (PhAEs-β-CD), was synthesized by self-cross-linking of phthalic anhydride (PhA)-modified-β-cyclodextrin. The PhA cross-linker plays a dual role of providing coordination sites for cationic dye binding and contributing to the large specific surface area owing to the existence of rigid aromatic groups. The adsorption properties of PhAEs-β-CD for cationic dyes were investigated, and the results revealed that the adsorbent contains numerous functional groups and has a high specific surface area (332.14 m2/g), which is highly beneficial for cationic dye removal. The maximum adsorption capacities of PhAEs-β-CD were found to be 3288.80 mg·g−1 for basic green 4, 2407.87 mg·g−1 for crystal violet, 2264.40 mg·g−1 for astrazon pink FG, and 1401.33 mg·g−1 for methylene blue. The adsorption mechanism and system were modeled by using the Langmuir isotherm model and the pseudo-second-order kinetic model. The removal efficiency of the adsorbent for basic green 4 reached more than 90 % even after five regeneration cycles, indicating that the adsorbent had good regenerative capacity. These findings demonstrated the potential application of PhAEs-β-CD in dye wastewater treatment.

Aza-phenol Based Macrocyclic Probes Design for "CHEF-on" Multi Analytes Sensor: Crystal Structure Elucidation and Application in Biological Cell Imaging.

Metal bound macrocyclic compounds found in biological systems inspired us to design and synthesize two Robson-type macrocyclic Schiff-base chemosensors, H 2 L1 (H 2 L1=1,11-dimethyl-6,16-dithia-3,9,13,19-tetraaza-1,11(1,3)-dibenzenacycloicosaphane-2,9,12,19-tetraene-1,11-diol) and H 2 L2 (H 2 L2=1,11-dimethyl-6,16-dioxa-3,9,13,19-tetraaza-1,11(1,3)-dibenzenacycloicosaphane-2,9,12,19-tetraene-1,11-diol). Both the chemosensors have been characterized with different spectroscopic techniques. They act as multianalyte sensor and exhibit "turn-on" fluorescence toward different metal ions in 1X PBS (Phosphate Buffered Saline) solution. In presence of Zn2+, Al3+, Cr3+ and Fe3+ ions, H 2 L1 exhibits ∼6-fold enhancement of emission intensity, while H 2 L2 shows ∼6-fold enhancement of emission intensity in the presence of Zn2+, Al3+ and Cr3+ ions. The interaction between the different metal ion and chemosensor have been examined by absorption, emission, and 1H NMR spectroscopy as well as by ESI-MS+ analysis. We have successfully isolated and solved the crystal structure of the complex [Zn(H 2 L1)(NO3)]NO3 (1) by X-ray crystallography. The crystal structure of 1 shows 1:1 metal:ligand stoichiometry and helps to understand the observed PET-Off-CHEF-On sensing mechanism. LOD values of H 2 L1 and H 2 L2 toward metal ions are found to be ∼10-8 and ∼10-7 M, respectively. Large Stokes shifts of the probes against analytes (∼100 nm) make them a suitable candidate for biological cell imaging studies. Robson type phenol based macrocyclic fluorescence sensors are very scarce in the literature. Therefore, the tuning of structural parameters as the number and nature of donor atoms, their relative locations and presence of rigid aromatic groups can lead to the design of new chemosensors, which can accommodate different charged/neutral guest(s) inside its cavity. The study of the spectroscopic properties of this type of macrocyclic ligands and their complexes might open a new avenue of chemosensors.

Additives in Edible Soy Protein Film Incorporation of Polysaccharides, Nano Polysaccharides, Vegetable Oils and Phenolic Additives in Edible Soy Protein Film

Soy protein isolate (SPI) is one such plant derived protein that holds significant potential for fabrication of edible films and packaging materials owing to its smooth, flexible and fair film forming abilities. However, native SPI suffers from several limitations such as poor water resistance, tensile strength, and susceptibility towards microbial attack. Many plants and animal derived compounds have been tried and tested to improve the material properties of these films. Incorporation of polysaccharides, nano polysaccharides, vegetable oils and polyphenolic compounds are explored to attain desirable properties in prepared films. Phenolic compounds are generally targeted to increase the tensile strength and resistance towards microbial attack as they possess rigid planar aromatic ring and hydroxyl groups that make them suitable candidate of choice. Polysaccharides or nanopolysaccharides and vegetable oils are reported to enhance the oxygen, carbon dioxide gas barrier properties of edible films that could delay putrefaction of packaged food items. Moreover, polyphenols and polysaccharide compound also exhibit bacteriostatic and bactericidal effect against S. aureus, L. monocytogenes and E. coli. This review paper summarizes the incorporation of polyphenolics, polysaccharides, nanopolysaccharides and vegetable oils in SPI films followed by their material and antibacterial characterization.

A Lyotropic Liquid Crystal from a Flexible Oligopeptide Amphiphile in Dimethyl Sulfoxide.

Despite the rapid progress in peptide liquid crystals (LCs) due to their prominent properties, our investigation on flexible peptide-based LCs is incomplete, mainly resulted from their unclear formation mechanisms and unexploited applications in organic solvents. Here, we develop a lyotropic LC based on a flexible oligopeptide amphiphile, which aggregates into aligned cylinder-like nanostructures in dimethyl sulfoxide (DMSO). The formation mechanism of lyotropic LC in DMSO was probed by the experimental investigation and molecular dynamics simulation, indicating that the hydrogen bonding and hydrophobic and electrostatic interactions contribute to the formation of ordered nanostructures in the organic solvent. Arising from the orientational order and suitable fluidity, we exploit the application of lyotropic LC as an aligned medium to measure the residual dipolar couplings of bioactive molecules. This study not only offers the understanding of the mechanism to create LC systems without rigid aromatic groups but also expands the applications of ordered bottom-up nanomaterials in organic solvents.

Enhancement of Solid‐State Reversible Photochromism by Incorporation of Rigid Steric Hindrance Groups

AbstractSolid‐state materials with reversible properties are highly attractive, owing to versatile applications in security, sensors, bioimaging, and information storage. Unfortunately, obtaining these materials in the solid state remains a huge challenge. Efficient isomerization usually requires sufficient conformational freedom and cannot be achieved without solvents or matrices. In this study, four structurally simple spiropyran derivatives are prepared that show excellent reversible photochromism under solvent‐free conditions. The large free volumes induced by different rigid aromatic ring groups enable an efficient photoswitching between closed‐ring compounds and their photoisomers. Furthermore, these compounds exhibit mechanochromic properties upon application of a mechanical force. Their color can be maintained for at least 2 days without fading under visible light irradiation at 30 °C, and can be easily erased by heating at 60 °C for 5 min. At least 30 consecutive print–erase cycles can be performed without apparent fatigue. The excellent solid‐state photochromic properties of the present compounds can find application in both UV printing and rewritable paper.

Influence of spacer in the formation of nanorings by templateless electropolymerization

In this original work, we want to control the shape of the resulting porous structures by templateless electropolymerization, by adjusting the spacer (flexible alkyl chains or rigid aromatic groups) between thieno[3,4-b]thiophene and carbazole used as the monomer and the substituent, respectively. A huge change is especially observed from ribbon-like structures to nanorings as the alkyl spacer increases. The presence of a significant amount of water is necessary for the formation of these porous structures because it allows releasing a high amount of gas bubbles. The size and number of nanorings are dependent on both the alkyl spacer and electrochemical parameters such as the number of deposition scans. These surfaces could be used in the future in various potential applications such as in water harvesting, oil/water separation membranes, optical devices, sensors or photocatalysis.

A platinum(II) molecular hinge with motions visualized by phosphorescence changes

With the rapidly growing exploration of artificial molecular machines and their applications, there is a strong demand to develop molecular machines that can have their motional states and configuration/conformation changes detectable by more sensitive and innovative methods. A visual artificial molecular hinge with phosphorescence behavior changes is designed and synthesized using square-planar cyclometalated platinum(II) complex and rigid aromatic alkynyl groups as the building blocks to construct the wings/flaps and axis, respectively. The molecular motions of this single molecular hinge and its reversible processes can be powered by both solvent and temperature changes. The rotary motion can be conveniently observed by the visual phosphorescence changes from deep-red to green emission in real time.

Enantiomeric Amino Acid Schiff Base Copper(II) Complexes as a New Class of RNA-Targeted Metallo-Intercalators: Single X-ray Crystal Structural Details, Comparative in Vitro DNA/RNA Binding Profile, Cleavage, and Cytotoxicity

Chiral enantiomeric amino acid Schiff base copper(II) complexes 1 and 2 (a and b) were synthesized and characterized by various spectroscopic techniques (Fourier transform infrared, UV–vis, electron paramagnetic resonance, electrospray ionization-mass spectrometry, and circular dichroism) and single X-ray crystal diffraction analyses. To understand the selectivity and enantiomeric behavior of the complexes, binding interaction with ct-DNA and tRNA biomolecules was investigated by widely employed optical and hydrodynamic techniques. The binding experiments demonstrated that complexes 1 and 2 (a and b) interact strongly via the intercalative mode with preferential binding toward the tRNA biomolecule compared to ct-DNA. Furthermore, the order of binding propensity was 2a > 2b > 1a > 1b, implicating greater binding affinity of l-enantiomeric complexes, and complex 2a showed the highest binding propensity possessing a rigid aromatic group in the amino acid framework. Scanning electron microscopy analyses of co...

The grafting of phthalic acid onto polyurethane copolymer and its impact on the surface hydrophilicity, tensile stress, and shape recovery properties

Phthalic acid (PA) was grafted onto polyurethane (PU) in the PA series due to its rigid aromatic structure and carboxyl groups, but PA was simply blended with PU in the control CPA series. The cross-link density and solution viscosity of the PA series notably increased with increasing PA content, and the same parameters of the CPA series did not increase. The maximum tensile stress of the PA series sharply increased due to the chemical cross-linking of the grafted PA, and the tensile strain at break slowly decreased with increasing PA content. The shape recovery of the PA series at 10 °C rapidly increased upon the grafting of PA; however, that of the CPA series decreased with increasing PA content. The hydrophilicity of PU was enhanced by the grafting of PA based on the water contact angle and water vapor permeation results. The low temperature flexibility of the PA series improved more than that of the CPA series under freezing conditions with increasing PA content due to the chemical cross-linking and steric and electrostatic repulsion between PU moieties. Overall, the grafted PA definitely increased the maximum tensile stress, shape recovery, and low temperature flexibility of PU.

Ligand effect in the synthesis of hyperbranched polymers via copper‐catalyzed azide‐alkyne cycloaddition polymerization (CuAACP)

ABSTRACTCopper‐catalyzed azide‐alkyne cycloaddition polymerization (CuAACP) of AB2 monomers demonstrated a chain‐growth mechanism without any external ligand because of the complexation of in situ formed triazole groups with Cu catalysts. In this study, we explored the use of various ligands that affected the polymerization kinetics to tune the polymers’ molecular weights and the degree of branching (DB). Eight ligands were studied, including polyethylene glycol monomethyl ether (PEG350, Mn = 350), tris(benzyltriazolylmethyl)amine (TBTA), 2,6‐bis(1‐undecyl‐1H‐benzo[d]imidazol‐2‐yl)pyridine (Py(DBim)2), 2,2′‐bipyridyl (bpy), 4,4′‐di‐n‐nonyl‐2,2′‐bipyridine (dNbpy), N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA), N,N,N′,N″,N″‐penta(n‐butyl)diethylenetriamine (PBuDETA), and N,N,N′,N″,N″‐pentabenzyldiethylenetriamine (PBnDETA). All ligands except PEG350 exhibited stronger coordination with Cu(I) than the polytriazole polymer, which freed the Cu catalyst from polymers and resulted in dominant step‐growth polymerization with simultaneous chain‐growth feature. Meanwhile, the use of PEG350 ligand retained the confined Cu in the polymer, demonstrating a chain‐growth mechanism, but lower polymer molecular weights as compared with the no‐external‐ligand polymerization. Results indicated that aliphatic substituent groups on ligands had little effect on the molecular weights and DB of the polymers, but rigid aromatic substituent groups decreased both values. By varying the ligand species and amounts, hyperbranched polymers with DB value ranging from 0.53 ([TBTA]0/[Cu]0 = 5) to 0.98 ([PMDETA]0/[Cu]0 = 2) have been achieved. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2238–2244

Turn-on fluorescent detection of captopril in urine samples based on hydrophilic hydroxypropyl β-cyclodextrin polymer

Here, one kind of hydrophilic hydroxypropyl β-cyclodextrin cross-linked polymer (HP-CDP) was prepared and used to establish a "turn-on" fluorescent probe for selective determination of captopril in biological samples. The HP-CDP has been synthesized in one step by cross-linking (2-hydroxypropyl)-β-cyclodextrin (HP-β-CD) with a rigid aromatic group linker tetrafluoroterephthalonitrile (TFT), and the synthesis parameters of HP-CDP were optimized with water solubility, yield, and adsorption capacity as indicators. When it was used as a luminescent material, we have found an interesting phenomenon that the fluorescence emission of HP-CDP was quenched after forming a coordination compound with ferric ions, and then recovered after adding a certain concentration of captopril, since captopril can reduce the ferric iron to ferrous ions and cause ligand replacement. Based on this observation, a novel turn-on fluorescent method was developed for the determination of captopril. The method exhibited good linearity in the range of 9.2 × 10-7 to 4.6 × 10-4M (R2 = 0.9982) and a low detection limit of 1.8 × 10-7M at optimum HP-CDP concentration, ferric ion concentration, pH, and incubation time. Moreover, interference experiments demonstrated that this fluorescence sensor had excellent selectivity that can commendably resist the interference from potential foreign substances. The proposed method has been successfully applied to determine captopril in human urine samples and may provide outstanding application potential in the future development of sensors. In addition, it is believed that HP-CDP also has a wide range of applications, for example, as a solubilizer, pollutant adsorbent, or drug carrier. Graphical abstract ᅟ.

Characterization of Polyurethane Grafted with Bis(2-hydroxyethyl) Terephthalate

ABSTRACTBis(2-hydroxyethyl) terephthalate (BHETPA) was grafted onto polyurethane (PU) to investigate the effects of BHETPA, which contains a rigid aromatic group and flexible hydroxyethyl groups, on the physical properties of PU. The cross-link density, viscosity, tensile strength, and shape recovery notably increased with an increase of BHETPA due to chemical cross-linking by BHETPA. A PU sample demonstrated excellent low-temperature flexibility compared with plain PU, showing complete recovery at approximately 0°C. Therefore, grafting BHETPA onto PU modified the thermal behavior and greatly improved the tensile stress, shape recovery, and low-temperature flexibility of PU compared to plain PU.

Determination of quinolones in wastewater by porous β-cyclodextrin polymer based solid-phase extraction coupled with HPLC.

In this research, a novel insoluble sorbent based on cyclodextrin and rigid aromatic groups tetrafluoroacetonitrile was designed for dispersive insoluble solid-phase extraction (DSPE). Due to its high adsorption capacity, this obtained polymer was applied to separation and concentration of trace quinolones in wastewater before HPLC determination. Various parameters influencing the extraction performance were studied and optimized. A DSPE approach coupled with high performance liquid chromatography was developed for the determination of four quinolones in wastewater samples. The limit of quantitation of fleroxacin, ciprofloxacin, gatifloxacin, norfloxacin were 2.67, 3.17, 4.75, 5.50ngmL-1, respectively. The recoveries of four quinolones range from 96.43 to 103.3% with relative standard deviations less than 4.5%. These results demonstrated that the proposed approach based on CDP was efficient, low-cost for extraction of quinolones from wastewater.

Rapid adsorption of Pb, Cu and Cd from aqueous solutions by β-cyclodextrin polymers

Removing heavy metals from aqueous solutions has drawn more and more attentions these years because of their serious global health challenge to human society. To develop an adsorbent with low-cost and high-efficiency for removal of heavy metals (HMs), β-cyclodextrin (β-CD) polymers crosslinked with rigid aromatic groups were prepared and used for lead (Pb), copper (Cu) and cadmium (Cd) removal for the first time. The negatively charged β-CD polymers with large BET surface area were suitable to be used in HMs adsorption. The adsorption process completed in 5min was well fit by Freundlich isotherm model and pseudo-second-order model. The intraparticle diffusion model was also appropriate to describe the adsorption of Pb, Cu and Cd on β-CD polymer. The maximum of adsorption capacities at 25°C for Pb, Cu and Cd were 196.42, 164.43 and 136.43mg/g when the initial concentration was 200mg/L. The HMs adsorption process on the surface of β-CD polymer was an endothermic and spontaneous process. Both of the electrostatic interaction and distribution of Pb, Cu and Cd species influenced the adsorption process at different pH values. The order of removal efficiencies in multi-component adsorption for the three metal ions were Pb > Cu > Cd. The adsorption mechanisms were H+ ions on hydroxyl groups exchanged with heavy metal ions and electrostatic interactions. This study indicated that β-CD polymers could be developed into effective adsorbents for rapid removal of heavy metals.

Transition-metal-based (Co2+, Ni2+ and Cd2+) coordination polymers constructed by a polytopic ligand integrating both flexible aliphatic and rigid aromatic carboxylate groups: Aqueous detection of nitroaromatics

Three transition-metal-based coordination polymers (1: Co2+; 2: Ni2+ and 3: Cd2+) have been solvothermally synthesized from a newly designed polytopic ligand of 4-(carboxymethoxy)-[1,1′-biphenyl]-3,4′-dicarboxylic acid (H3Lws) that integrates both flexible aliphatic and rigid aromatic carboxylate groups. In 1, each H3Lws ligand connects two Co2+ ions in the partially deprotonated form of HLws2−, whereas the H3Lws ligands in 2 and 3 are fully deprotonated (Lws3−), each linking three Ni2+ ions and seven Cd2+ ions, respectively. Compound 1 shows a one-dimensional chain structure, and compound 2 is composed of a two-dimensional waved sheet based on Ni4(μ3-OH)2(μ2-O)4 cluster. Compound 3 has a three-dimensional network structure that is constructed of two-dimensional Cd/O-based layers pillared by Lws3− spacers. Compounds 1–3 exhibit both thermal stability (>340°C) and hydrolytic robustness even under the heating condition. In particular, compound 3 displays the strongest luminescence in aqueous solution, which is almost 2.5-fold greater than that in organic solvents. More importantly, it is proved that compound 3 can serve as a highly sensitive luminescent sensor for aqueous detection of those nitro phenolic aromatics.

Biorenewable Epoxy Resins Derived from Plant-Based Phenolic Acids

Plant-derived phenolic acids are attractive substitutes for petroleum sources for the derivation of polymers, due to their rigid aromatic rings and chemical groups amenable to functionalization. Difunctional phenolic acids were investigated as replacements for the diglycidyl ether of bisphenol A (DGEBA) in anhydride-cured epoxy resins. Functionalization of each phenolic acid was carried out through allylation, followed by epoxidation. Epoxy resins were synthesized through reaction of either epoxidized salicylic acid (ESA) or epoxidized 4-hydroxybenzoic acid (E4HBA) with the curing agent methylhexahydrophthalic anhydride (MHHPA) (catalyzed by 1-methyl-imidazole, 1-MI). The MHHPA anhydride curing agent (catalyzed by 1-MI) was chosen due to the resulting high conversion and advantageous high polymer glass transition temperature. ESA and E4HBA had similar curing behavior to that of DGEBA when cured with MHHPA. A two-step protocol was developed to avoid monomer evaporation and polymer vitrification during curi...

Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer.

The global occurrence in water resources of organic micropollutants, such as pesticides and pharmaceuticals, has raised concerns about potential negative effects on aquatic ecosystems and human health. Activated carbons are the most widespread adsorbent materials used to remove organic pollutants from water but they have several deficiencies, including slow pollutant uptake (of the order of hours) and poor removal of many relatively hydrophilic micropollutants. Furthermore, regenerating spent activated carbon is energy intensive (requiring heating to 500-900 degrees Celsius) and does not fully restore performance. Insoluble polymers of β-cyclodextrin, an inexpensive, sustainably produced macrocycle of glucose, are likewise of interest for removing micropollutants from water by means of adsorption. β-cyclodextrin is known to encapsulate pollutants to form well-defined host-guest complexes, but until now cross-linked β-cyclodextrin polymers have had low surface areas and poor removal performance compared to conventional activated carbons. Here we crosslink β-cyclodextrin with rigid aromatic groups, providing a high-surface-area, mesoporous polymer of β-cyclodextrin. It rapidly sequesters a variety of organic micropollutants with adsorption rate constants 15 to 200 times greater than those of activated carbons and non-porous β-cyclodextrin adsorbent materials. In addition, the polymer can be regenerated several times using a mild washing procedure with no loss in performance. Finally, the polymer outperformed a leading activated carbon for the rapid removal of a complex mixture of organic micropollutants at environmentally relevant concentrations. These findings demonstrate the promise of porous cyclodextrin-based polymers for rapid, flow-through water treatment.

Synthesis and characterization of aqueous (polyurethane/aromatic polyamide sulfone) copolymer dispersions from castor oil

Abstract Aqueous dispersions of castor oil-based polyurethane (PUCO)/aromatic polyamide sulfone (APAS) block copolymers (PUCO-co-APAS) were successfully synthesized via a copolymerization reaction. PUCO was prepared by an emulsion polymerization process in four steps, namely isocyanate-terminated prepolymer preparation step (PUCONCO), neutralization step, chain extension step and dispersion step, using castor oil (CO), toluene diisocyanate (TDI), dimethylol propionic acid (DMPA) and ethylene diamine (EDA) as a chain extender. APAS was prepared by a polycondensation reaction between bis(4-aminophenyl)sulfone (in molar excess) and terephthaloyl chloride to produce amino-terminated APAS. Three PUCO-co-APAS were prepared via a copolymerization reaction between the amino-terminated APAS and isocyanate-terminated PUCONCO prepolymer. APAS, PUCO and PUCO-co-APAS copolymers were characterized using FTIR, 1H NMR, particle size distribution (PSD), zeta potential (ZP), thermal analysis (DSC and TGA) and GPC. The effect of the copolymerization process on the thermal, chemical, physical and mechanical properties of PUCO films was studied. The obtained results revealed that the mean particle size of PUCO decreased from 80 nm to 46–49 nm after the copolymerization process. Additionally, narrower size distribution was obtained by the copolymerization process. However, the molecular weight increased with increasing the amount of APAS in the copolymer chains. The copolymerized samples showed better thermal stability than PUCO as a result of the stronger hydrogen bonds and the rigid aromatic groups introduced by APAS in the copolymeric chains.