Copolymer Chains Research Articles

Favorable Propylene-Incorporated Terpolymerization of Ethylene with CO Mediated by Cationic [P,O]-Pd and Ni Complexes.

Commercial polyketone materials are generally produced by palladium-catalyzed terpolymerization of ethylene and α-olefin with carbon monoxide (CO), and rare examples were reported regarding the incorporation of propylene into an ethylene/CO copolymer chain using a cost-effective nickel catalyst. In this study, we have developed a series of [P,O]-type cationic Pd and Ni complexes supported by a diphosphazane monoxide (PNPO) platform, and the electronic and steric effect on phosphine, amine, and phosphine oxide moieties is systematically investigated for terpolymerization in terms of activity, propylene/CO (C3) incorporation, and molecular weight control. It is observed that the melting temperature (Tm) is proportional to the number of C3 incorporations present in the polymer chain, and the incorporated propylene does not affect the degradation temperature substantially, thus broadening the processing temperature window of the resultant polyketones. Notably, in comparison with dppp-type catalysts, PNPO catalysts exhibited a higher preference for propylene consumption, which is of great importance for making more efficient use of α-olefin resources.

Synthesis of an Immobilized Three-state Switchable Chiral Stationary Phase for HPLC Using a Metal Cation-responsive Optically Active Poly(phenylacetylene) Derivative and Its Chiral Recognition Ability

A metal cation-responsive optically active poly(phenylacetylene)-based copolymer containing a small number of hydroxy groups in the pendant was synthesized and immobilized onto silica gel by crosslinking between the hydroxy groups of the copolymer chains using a dicarboxylic acid as the crosslinker. The obtained immobilized copolymer acted as a three-state switchable chiral stationary phase for high-performance liquid chromatography like the corresponding homopolymer coated on silica gel.

Construction of Fluorescent Conjugated Polytriazole Containing Double-Decker Silsesquioxane: Click Polymerization and Thermal Stability.

This study synthesized two azide-functionalized monomers through p-dichloro xylene and double-decker silsesquioxane (DDSQ) units with NaN3 to form DB-N3 and DDSQ-N3 monomers, respectively. In addition, five different propargyl-functionalized monomers were also prepared from hydroquinone, bisphenol A, bis(4-hydroxyphenyl)methanone, 2,4-dihydroxybenzaldehyde (then reacted with hydrazine hydrate solution) and 1,2-bis(4-hydroxyphenyl)-1,2-diphenylethene with propargyl bromide to form P-B, P-BPA, P-CO, P-NP, and P-TPE monomers, respectively. As a result, various DDSQ-based main chain copolymers could be synthesized using Cu(I)-catalyzed click polymerization through DDSQ-N3 with different propargyl-functionalized monomers, of which the chemical structure and molecular weight could be confirmed by using Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC) analyses. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), scanning electron microscope (SEM), transmission electron microscopy (TEM), and photoluminescence (PL) spectroscopy analyses also could characterize the thermal stability, morphology, and optical behaviors of these DDSQ-based copolymers. All results indicate that the incorporation of an inorganic DDSQ cage could improve the thermal stability such as thermal decomposition temperature and char yield, because of the DDSQ dispersion homogeneously in the copolymer matrix, and this would then affect the optical properties of NP and TPE units in this work.

Unsynchronous conformational transitions induced by the asymmetric adsorption-response of an active diblock copolymer in an inert brush.

To exploit the chemical asymmetry of diblock copolymer chains on the design of high-performance switch sensors, we propose an analytically tractable model system which contains an adsorption-responsive diblock copolymer in an otherwise inert brush, and study its phase transitions by using both analytical theory and self-consistent field calculations. The copolymer chain is chemically asymmetric in the sense that the two blocks assume different adsorption strengths, which is characterized by the defined adsorption ratio. We found that the conformation states, the number of stable phases, and transition types are mainly controlled by the length of each block and the adsorption ratio. In particular, when the length of the ungrafted block is longer than the brush chains, and the adsorption ratio is smaller than a critical value, the copolymer chain shows three thermodynamically stable states, and undergoes two unsynchronous transitions, where the two blocks respond to the adsorption in a different manner, when the adsorption changes from weak to sufficiently strong. For this kind of three-state transition, the transition point, transition barrier, and transition width are evaluated by using the self-consistent field method, and their scaling relationship with respect to the system parameters is extracted, which matches reasonably well with the predictions from the analytical theory. The self-consistent field calculations also indicate that the conformational transitions involved in the three-state transition process are sharp with a low energy barrier, and interestingly, barrier-free transitions are observed. Our finding shows that the three-state transitions not only specify a region where high performance unsynchronous switch sensors can be exploited, but may also provide a useful model understanding the unsynchronous biological processes.

Configuration and dynamics of a self-propelled diblock copolymer chain.

Active polymers are slender or chain-like self-propelled objects. Synthetic chains of self-propelled colloidal particles are one of the examples, which provide a potential way to develop varied active polymers. Here, we study the configuration and dynamics of an active diblock copolymer chain. Our focus is on the competition and the cooperation between the equilibrium self-assembly due to chain heterogeneity and the dynamic self-assembly due to propulsion. Simulations show that an active diblock copolymer chain can form the spiral(+)/tadpole(+) states under forward propulsion and the spiral(-)/tadpole(-)/bean states under backward propulsion. Interestingly, it is easier for the backward-propelled chain to form a spiral. The transitions between the states can be analyzed in terms of work and energy. For forward propulsion, we found a key quantity, i.e. the chirality of the packed self-attractive A block, which determines the configuration of the whole chain and the dynamics. However, no such quantity is found for the backward propulsion. Our results set the foundation for further study of the self-assembly of multiple active copolymer chains and provide a reference for the design and application of polymeric active materials.

Investigating structure and dynamics of unentangled poly(dimethyl-co-diphenyl)siloxane via molecular dynamics simulation.

Polysiloxane is one of the most important polymeric materials in technological use. Polydimethylsiloxane displays glass-like mechanical properties at low temperatures. Incorporation of phenyl siloxane, via copolymerization for example, improves not only the low-temperature elasticity but also enhances its performance over a wide range of temperatures. Copolymerization with the phenyl component can significantly change the microscopic properties of polysiloxanes, such as chain dynamics and relaxation. However, despite much work in the literature, the influence of such changes is still not clearly understood. In this work, we systematically study the structure and dynamics of random poly(dimethyl-co-diphenyl)siloxane via atomistic molecular dynamics simulations. As the molar ratio ϕ of the diphenyl component increases, we find that the size of the linear copolymer chain expands. At the same time, the chain-diffusivity slows down by over an order of magnitudes. The reduced diffusivity appears to be a result of a complex interplay between the structural and dynamic changes induced by phenyl substitution.

Acetate ion addition to and exchange in (1,5-cyclooctadiene)rhodium(I) acetate: relevance for the coagulation of carboxylic acid-functionalized shells of core-crosslinked micelle latexes.

The solution behavior of complex [Rh(COD)(μ-OAc)]2 in the absence and presence of PPN+OAc- in dichloromethane has been investigated in detail by multinuclear NMR spectroscopy. Without additional acetate ions, the compound shows dynamic behavior at room temperature, consistent with an inversion of its C2v structure. Addition of PPN+OAc- reveals an equilibrated generation of [Rh(COD)(OAc)2]-. Rapid exchange is observed at room temperature between the neutral dimer and the anionic mononuclear complex, as well as between the anionic complex and free acetate. Lowering the temperature to 213 K freezes the exchange between the two Rh complexes, but fast exchange between the anionic Rh complex and free acetate maintains coalesced Me (1H and 13C) and COO (13C) NMR resonances. DFT calculations support the experimental data and lean in favour of a dissociative mechanism for the acetate exchange in [Rh(COD)(OAc)2]-. The acetate ligands in complex [Rh(COD)(μ-OAc)]2 are also exchanged in a biphasic (water/organic) system with the methacrylic acid (MAA) functions of hydrosoluble [MMA0.5-co-PEOMA0.5]30 copolymer chains (PEOMA = poly(ethylene oxide) methyl ether methacrylate), resulting in transfer of the Rh complex to the aqueous phase. Exchange with the MAA functions in the same polymer equally takes place for the chloride ligands of [Rh(COD)(μ-Cl)]2. The latter phenomenon rationalizes the coagulation of a core-crosslinked micelle (CCM) latex, where MMA functions are present on the hydrophilic CCM shell, when a dichloromethane solution of [Rh(COD)(μ-Cl)]2 is added.

Dissipative particle dynamics study on the interfacial structure and tension for polymer blends of different copolymer chemical composition distributions

A dissipative particle dynamics (DPD) simulation is used to study the interfacial structure and tension for the polymer blends of different copolymer chemical composition distributions. Four chain lengths of diblock copolymers NAB = 10, 20, 40, and 60 with different microstructures are utilized for simulation. As the copolymer microstructure varied from the nondispersed symmetric diblock copolymer to the bidisperse asymmetric diblock copolymer mixtures, the asymmetry of the copolymer varied from f = 0.5 to 0.9. Our simulations show that (i) increasing the copolymer chain length NAB will significantly enhance the interfacial tension, which indicates that the chain length of the diblock copolymer is the most important factor affecting the compatibilization efficiency. Only when the copolymer chain length NAB = 10 can the asymmetry significantly affect the compatibilization efficiency, and the length of the shorter block is the decisive factor in the compatibilization efficiency of asymmetric diblock copolymers; (ii) with an increase in the asymmetry of the diblock copolymer from f = 0.5 to 0.9, the effective chain length of the diblock copolymer with compatibilization decreases, which results in a reduced number of compatibilized beads of copolymers. Thus, the symmetric block copolymer AB is more effective in reducing the interfacial tension than the asymmetric diblock copolymer mixtures at the same concentration; and (iii) The symmetric diblock copolymers enrich faster at the interfaces when elevating the copolymer concentration, which results in a faster reduction in the interfacial tension than that of the asymmetric bidisperse diblock copolymer mixtures. Our research work expands the understanding of polymer blends containing bidisperse asymmetric diblock copolymer mixtures.

CFD modeling of the ethylene–vinyl acetate copolymerization autoclave reactor: Effects of comonomer ratio on reactor dynamics and copolymer properties

Computational fluid dynamics (CFD) modeling of an industrial ethylene–vinyl acetate autoclave copolymerization reactor was conducted to evaluate the effects of comonomer ratios on reactor dynamics and product properties, including the molecular weight distribution (MWD), and copolymer composition. To accurately predict the MWD of copolymer chains under highly nonideal mixing conditions at a reduced computational cost, the CFD-multicompartment model and probability generating function (PGF) transform were applied. The effectiveness of the developed model was validated by the satisfactorily consistent plant data and simulated results. The model revealed that an increase in the vinyl acetate (VA) content significantly decreased the temperature, promoting combinational termination and chain transfer to polymer reaction for a broad copolymer MWD. The pseudo-kinetic-based analysis showed that VA was consumed more slowly than ethylene, resulting in its lower value in the copolymer composition than that of the comonomer ratios. However, despite nonideal mixing, the copolymer composition was maintained to be uniform for the copolymers produced over the entire reactor volume. In conclusion, the proposed model can be used to understand the governing behaviors of copolymerization under nonideal mixing conditions, design commercial copolymerization reactors, and predict copolymer product qualities.

Amphiphilic random copolymers bearing linear poly(oxyethylene) side chains and lateral dendritic wedges: Synthesis and their emulsifying performances

In this study, we demonstrated nonaqueous macroemulsions stabilized by amphiphilic random copolymers exhibiting linear poly(oxyethylene) side chains and two-generation dendritic wedges along their backbones, which were synthesized by traditional radical random copolymerization of oligo (ethylene glycol) methyl ether methacrylate (POEGMA) with 2-methyl-2-((2-(4-methyl-1H-1,2,3-triazol-1-yl) ethoxy) carbonyl) propane-1,3-diylbis(2,2,5-trimethyl-1,3-dioxane-5-carboxylate)) methacrylate (MPDMA) in THF using AIBN as initiators. PPOEGMA-ran-PMPDMA copolymers containing different molar fractions of MPDMA monomer unit ranging from 0.28 to 0.65 were achieved through the adjustment of the feed ratio of monomer pairs during the copolymerization. Interfacial tension experiments revealed the critical micelle concentrations of PPOEGMA-ran-PMPDMA copolymers decreased with the increase of the contents of MPDMA monomer unit in copolymer chains. [Bmim][PF6]-in-toluene emulsions were subsequently prepared using amphiphilic PPOEGMA-ran-PMPDMA copolymers as macromolecular emulsifiers. The average size of the emulsion droplets showed an increasing tendency with the increase of the contents of MPDMA monomer unit in random copolymer chains. Under the otherwise identical conditions, the emulsifying performances of PPOEGMA-ran-PMPDMA copolymers were better than those of PPOEGMA-b-PMPDMA diblock copolymer counterparts judging from the size of the emulsion droplets and the stability of the emulsions.

Poly(N-vinyl triazole-b-N-vinyl imidazole) Grafted on MWCNTs as Nanofillers to Improve Proton Conducting Membranes

Carbon nanotubes (CNTs) are of particular interest because of their ability to enhance the mechanical strength in the material; however, processing difficulties of CNTs often restrict utilization up to its full potential. To resolve this, in the current study, we have developed a simple and efficient method to functionalize the surface of a multiwalled carbon nanotube (MWCNT) with precise functional polymer chains, which were covalently grafted on the surface of the MWCNT, and delved into an application to demonstrate this material as an efficient nanofiller in developing a proton conducting membrane (PEM) from polybenzimidazole (PBI). At first, the MWCNT surface was converted to a polymerizable surface by attaching a trithiocarbonate based chain transfer agent (CTA). Then, a N-heterocyclic block copolymer, namely poly-N-vinyl-1,2,4-triazole-b-poly-N-vinyl imidazole (pNVT-b-pNVI), was grown from the CTA anchored surface with a one-pot surface initiated reversible addition–fragmentation chain transfer (SI-RAFT) technique. Grafting of block copolymer chain was confirmed by GPC, NMR, TGA, TEM, FESEM, and EDX studies. To the best of our knowledge, this will be the first report of a growing block copolymer structure grafted covalently on the surface of the MWCNT. The novelty of the work was further enhanced by incorporating pNVT-b-pNVI-g-MWCNT as a nanofiller into the oxypolybenzimidazole (OPBI) membrane to obtain homogeneous nanocomposite membranes with excellent thermomechanical and tensile properties, thermal stability, superior proton conduction when doped with phosphoric acid (PA), and PA holding capacity. The nanocomposite membrane with 2.5 wt % nanofiller loading displayed a tensile stress of 1.8 MPa and a strain of 176% at break. The basic N-heterocyclic rings dangling from the block copolymer chains grafted on the MWCNT surface allowed formation of strong H-bonding, acid–base interaction with PA, which is responsible for high acid uptake and superior PA retention, and also exhibited proton conductivity as high as 0.164 S cm–1 at 180 °C, which is a 2.6-fold increment when compared with a pristine OPBI membrane. This significant increase in conductivity is attributed to the proton conducting nanochannel pathway generated along the polymer-g-MWCNT surface.

Fluidized or not fluidized? Biophysical characterization of biohybrid lipid/protein/polymer liposomes and their interaction with tetracaine

BackgroundNanomedicine and the pharmaceutical industry demand the investigation of new biomaterials to improve drug therapies. Combinations of lipids, proteins, and polymers represent innovative platforms for drug delivery. However, little is known about the interactions between such compounds and this knowledge is key to prepare successful drug delivery systems. MethodsBiophysical properties of biohybrid vesicles (BhVs) composed of phospholipids, proteins, and amphiphilic block copolymers, assembled without using organic solvents, were investigated by differential scanning calorimetry and dynamic light scattering. We studied four biohybrid systems; two of them included the effect of incorporating tetracaine. Thermal changes of phospholipids and proteins when interacting with the amphiphilic block copolymers and tetracaine were analyzed. ResultsLysozyme and the copolymers adsorb onto the lipid bilayer modifying the phase transition temperature, enthalpy change, and cooperativity. Dynamic light scattering investigations revealed relevant changes in the size and zeta potential of the BhVs. Interestingly, tetracaine, a membrane-active drug, can fluidize or rigidize BhVs. ConclusionsWe conclude that positively charged regions of lysozyme are necessary to incorporate the block copolymer chains into the lipid membrane, turning the bilayer into a more rigid system. Electrostatic properties and the hydrophilic-lipophilic balance are determinant for the stability of biohybrid membranes. General significanceThis investigation provides fundamental information associated with the performance of biohybrid drug delivery systems and can be of practical significance for designing more efficient drug nanocarriers.

Hunting black color via absorption engineering: EDOT and thiophene-benzothiadiazole based black-to-transmissive copolymer and its electrochromic device application

Neutral state black electrochromics are prominent materials for smart applications such as displays, car rear views, e-papers etc. This work has aimed to obtain a neutral state black electrochromic polymer, by tuning the optical absorbance to whole visible region. Two monomers, 4,7-bis(5-(thiophen-2-yl)thiophen-2-yl)benzo[c] [1,2,5]thiadiazole (TTBTT) and 3,4-ethylenedioxythiophene (EDOT), were selected according to their complementary absorbance behaviors, and they were combined in the same polymer backbone via electrochemical copolymerization technique. Copolymerization was performed using three different monomer feed ratios (2:1, 1:1 and 1:2 (EDOT: TTBTT)). Even though all the copolymers exhibited dark to transmissive colors from neutral to oxidized states, changing the monomer feed resulted in different optical contrast, switching response and color hues for each copolymer. The higher optical contrast (from 17% to 27%) and faster switching response (from 3.6 s to 1.8 s) were recorded as EDOT unit increase in the copolymer chain. A dual type electrochromic device was also constructed using the copolymer and the resulting device was successfully changed its color from black to transmissive.

Copolymerization of Carbonyl Sulfide and Propylene Oxide via a Heterogeneous Prussian Blue Analogue Catalyst with High Productivity and Selectivity.

This study demonstrates the superiority of a stable and well-defined heterogeneous cobalt hexacyanocobaltate (Co3 [Co(CN)6 ]2 ), a typical cobalt Prussian Blue Analogue (CoCo-PBA) that catalyzes the copolymerization of carbonyl sulfide (COS) and propylene oxide (PO) to produce poly(propylene monothiocarbonate)s (PPMTC). The number-average molecular weights of the PPMTC were 66.4 to 139.4 kg/mol, with a polydispersity of 2.0-3.9. The catalyst productivity reached 1040 g polymer/g catalyst (12.0 h). The oxygen-sulfur exchange reaction (O/S ER), which would generate random thiocarbonate and carbonate units, was effectively suppressed, and thus the selectivity of the monothiocarbonate over carbonate linkages was up to >99%. It was shown that no cyclic thiocarbonate byproduct was produced during the heterogeneous catalysis of COS/PO copolymerization using CoCo-PBA as the catalyst. The content of monothiocarbonate and ether units in the copolymer chain could be regulated by tuning the feeding amount of COS.

Acrylamidevinyl acetate copolymer as a new UCST copolymer: Phase transition and aggregation behavior; an experimental and theoretical study

A high sensitive upper critical solution temperature (UCST) copolymer was synthesized through free radical copolymerization with acrylamide (AAm) and vinyl acetate (VA). The UCST behavior is due to a combination of hydrogen bonds and electrostatic potentials between copolymer chains. Turbidimetry, dynamic light scattering, and rheology studies were used to determine the phase transition and aggregation behavior. It is indicated that copolymer with 80% AAm has a phase transition temperature between 38 and 38.2 °C, which is suitable for releasing fever medicine. Also, the temperature gradient for the complete dissolution of the copolymer is 2 °C. The molecular dynamics simulations at a molecular level confirmed the experimental results and indicated that aggregation of copolymer chains below UCST temperature had increased binding energy between polymer chains. The low cytotoxicity and its desirable UCST behavior make the copolymer promising for biomedical applications in the future.

Surface Coassembly of Binary Mixed Polymer Brushes and Linear Block Copolymer Chains.

Binary mixed polymer brushes (BMPBs) are two different homopolymer chains that are covalently anchored to the solid surfaces at high grafting densities. One feature of the BMPBs is the unique ability to make surface phase separation under external stimuli. In this research, we demonstrate that different surface nanostructures can be fabricated by surface coassembly of BMPBs and free block copolymer (BCP) chains. Polystyrene/poly(2-(dimethylamino)ethyl methacrylate) (PS/PDMAEMA) BMPBs on silica particles (PS-PDMAEMA-SiO2) are synthesized by a two-step "grafting to" approach. PDMAEMA-b-PS block copolymer (BCP) chains and PS-PDMAEMA-SiO2 make surface self-assembly and a variety of surface nanostructures are formed in methanol. The grafting densities of PS and PDMAEMA brushes, solvent, and the BCP structures all exert significant influences on the surface morphology. With an increase in PDMAEMA grafting density, the surface structures change from perforated layers, to rods, and to spherical surface micelles (s-micelles). The PS grafting density also exerts an effect on the formation of the surface nanostructures. At low PS grafting density, sparsely distributed s-micelles are produced, and at high density, densely distributed s-micelles are observed. Based on transmission electron microscopy and scanning electron microscopy results, a surface phase diagram is constructed, which provides a guide to the surface morphology control.

Neuronal cell response on aligned fibroporous electrospun mat generated from silver ion complexed ethylene vinyl alcohol copolymer.

Generating electrospun mats with aligned fibers and obtaining neurite extension in the aligned fiber direction could provide hope for fabricating nerve guidance conduits or wraps through an easy method. The growing interest in generating electrospun mats with aligned fibers for tissue engineering is looking for simple methods to generate the same. Here, in this study, ethylene vinyl alcohol copolymer (EVAL) chains were complexed with silver ions (Ag+ ) to generate aligned fibers during the electrospinning process. The fibers thus produced were subjected to physico-chemical characterization and biological studies to ensure their properties and to examine whether suitable for neuronal cell attachment and neurite extension that may be useful in making nerve guidance conduits or wraps. The presence of silver ions and its complex formation with -OH of EVAL has been confirmed with EDX and XPS analysis respectively. The alignment of fibers was visualized from SEM analysis and confirmed using directionality analysis using Fiji-ImageJ software. Mechanical properties done with dumbbells punched out in longitudinal and transverse directions also substantiated the alignment of fibers. The results obtained from direct contact, MTT, and live/dead assay showed the cells are viable on the material. From the actin staining and immunostaining assays, it was evident that the PC12 cells could attach and extend their neurites in an aligned manner on the fibers. The maximum neurite extension was up to 200 μm in length. These properties of electrospun EVAL-Ag mat with aligned fibers indicated that it could be developed as a biocompatible nerve guidance conduit or wrap.

A Novel PolyHIPE‐like Catalyst for Esterification Reactions: on the Synthesis of Sulfonated Poly(styrene‐co‐n‐acylglycerol) and its Use for Efficient Conversion of Oleic Acid to Methyl Oleate

AbstractThe current work describes the synthesis of a new polyHIPE‐like sulfonated poly(styrene‐co‐n‐acylglycerol) and its use as an efficient heterogeneous catalyst to convert oleic acid into methyl oleate in esterification reactions. This new environmentally friendly polymer incorporates n‐acylglycerol macromonomer as a versatile strategy for glycerol valorization. Macroporous micrometric polymer particles are synthesized through suspension polymerization process without using porogenic agents. polyHIPE‐like copolymers formed with different feed compositions of styrene and n‐acylglycerol are chemically modified via sulfonation reactions to form a highly efficient catalyst for esterification of oleic acid to methyl oleate, exhibiting conversions lying in the interval from 52% to 96%, depending mainly on the amount of n‐acylglycerol macromonomer into the copolymer chains. The experimental results indicate the great potential of this new heterogeneous catalyst based on modified poly(styrene‐co‐n‐acylglycerol) to be successfully employed in esterification reactions of vegetable oils intended for the production of long chain alkyl esters of carboxylic acids, widely used as biofuels.

Nano MnOx encapsulated pyrrole-carbazole copolymer and polyvinyl chloride/carbon-coated flexible electrodes for solid-state supercapacitor cell

Pyrrole (Py) and carbazole (Cz) monomers are polymerized simultaneously in the presence of MnOx nanoparticles synthesized chemically on a stainless steel mesh (SSM) electrode by the pulse galvanostatic method in an acetonitrile medium. The resulting p(Py-co-Cz)/MnOx composite is characterized by cyclic voltammetry EIS, GCD XPS, XRD, FESEM, BET, and TEM. Since the current is applied for short periods in the presence of both monomers, p(Py-co-Cz) copolymer chains occur in short lengths, suitable for supercapacitor electrodes. The copolymer has higher Cm and lower Rct values as well as higher porosity that improves ion transport, thus greater stability than the homopolymers. It may be due to tricyclic Cz segments located between Py segments in the chains, which inhibit degradation. During the synthesis, nano-sized MnOx is also encapsulated homogeneously into the p(Py-co-Cz) coating, where 5 % is the weight percentage of manganese. Since the composite combines the advantages of the conductive polymer and metal oxide, it has the lowest Rct and highest Cm values among the coatings here. The p(Py-co-Cz)/MnOx coating with 10 mg cm−2 exhibits a high specific capacitance of 352 F g−1 at 5 A g−1 as well as flexibility, as its specific capacitance remains nearly stable (99 %) up to a bending angle of 90°. The cathode prepared from polyvinyl chloride (PVC)/activated carbon/carbon black on SSM operates within a wide voltage range of 0 to −1.5 V at 98 % cycle stability after 1000 cycles. The asymmetric cell configuration with the flexible anode and cathode electrodes provides 38 kW kg−1 and 5.28 Wh kg−1 at 5 A g−1 at a wide potential range of 2.1 V in PVA/Na2SO4 gel electrolyte, and the cycling stability was 67 % after 1000 cycles.

Fabrication of cellulose-based particles/capsules using gamma radiation-initiated radical precipitation polymerization

Because fossil-based polymer particles are generally not biologically degradable, which has led to their significant accumulations as microplastic is now a serious global problem. Therefore, bio-based polymers synthesized from renewable monomers have received much attention due to their biodegradability and biocompatibility. The biopolymer in particle forms has been recently recognized as a functional material. Dispersed systems mainly synthesized them via radical polymerization. The radicals generated by gamma radiation were applied in this work to reduce chemical consumption, where cellulose acetate butyrate (CAB) was used as the main biopolymer in precipitation polymerization. The generated radical will abstract the hydrogen atom on the CAB chain, giving an active site for radical polymerization. After the comonomers, methacrylic acid and ethylene glycol dimethacrylate, were grafted to the CAB chains, the copolymer chains were self-assembly to form a particle and precipitate out from the continuous phase. Various parameters such as gamma rays dose, water content, and monomer type were studied to obtain high conversion and colloidal stability of the obtained CAB-based particles. It was found that at 10 kGy (cumulative radiation), 0.31 wt% of water and using hydrophilic monomer as hydroxyethyl methacrylate (40 wt%-CAB) was the optimal condition where the CAB-based particles with high conversion (∼≥90%), about 100 nm and high stability were obtained. Moreover, this technique encapsulated Citronella oil, an essential oil model, and found that the capsule size bit increased about 300 nm where %EE and %L E are 60 and 30%, respectively. This result indicated that radiation-initiated radical precipitation polymerization is an easy and potential technique to prepare cellulose-based particles and capsules, which may apply to other biopolymers.