Addition-fragmentation Chain Transfer Polymerization Technique Research Articles

Grafting of nonpolar polyisoprene as midblock and polar polylactide as outer block onto cellulose to produce bio-based thermoplastic elastomers

Sustainable cellulose-graft-diblock copolymers (cellulose-graft-polyisoprene-block-polylactide, MCC-g-PI-b-PLLA, MCC was chemically-modified microcrystalline cellulose) were designed and delicately synthesized for the first time by a mild and facile procedure via combining ring-opening polymerization and reversible addition-fragmentation chain transfer polymerization techniques, which conquered the difficulties in synthesis due to the distinct chemical properties among the MCC backbone, PI and PLLA blocks. Two separate glass transition temperatures were detected for MCC-g-PI-b-PLLA copolymers by differential scanning calorimetry, indicative of microphase separation, consistent with small-angle X-ray scattering and atomic force microscopy measurements. The α-form crystals of PLLA outer blocks were revealed by wide-angle X-ray diffraction measurement. The monotonic and step-cyclic tensile tests revealed that the mechanical property could be tuned by changing the molecular mass of PI midblock. The two ends of the soft PI midblock were anchored by rigid cellulose backbone and hard PLLA outer block, respectively, which served as physical crosslinking points. The rigid cellulose backbones brought the PI rubbery domains and PLLA hard domains together to form a whole hierarchical microstructure, endowing the copolymers with distinguished mechanical property. This work provided a feasible approach to producing environmental-friendly cellulose-based copolymers with fully biomass-derived feedstocks, having a profound impact on the development of sustainable polymer-based materials.

Block and Statistical Copolymers of Methacrylate Monomers with Dimethylamino and Diisopropylamino Groups on the Side Chains: Synthesis, Chemical Modification and Self-Assembly in Aqueous Media.

The synthesis of amphiphilic diblock and statistical (random) copolymers of poly(dimethylamino ethyl methacrylate) and poly((2-(diisopropylamino) ethyl methacrylate) using the reversible addition-fragmentation chain transfer polymerization technique (RAFT polymerization) is reported. The precursor copolymers were chemically modified to create derivative copolymers of polyelectrolyte and polyampholyte nature with novel solution properties. Moreover, their molecular and physicochemical characteristics, as well as their self-assembly in aqueous media as a function of molecular architecture and composition, are investigated by using size exclusion chromatography, spectroscopic characterization techniques and light scattering techniques. Furthermore, the behavior and properties of the obtained micelles and aggregates were studied, depending on the pH, temperature and ionic strength of the aqueous solutions. The response of the systems to changes in these parameters shows interesting behavior and new properties that are useful for their utilization as nanocarriers of pharmaceutical compounds.

Effects of Molecular Structures of Poly(styrene-co-octadecyl maleimide) as a Flow Improver for the Model Crude Oil with a Relatively High Content of Asphaltenes

Poly(styrene-co-maleic anhydride)s (SMAs) with different compositions and molecular weight were synthesized through the reversible addition–fragmentation chain transfer polymerization technique. SMAs were converted to poly(styrene-co-octadecyl maleimide)s (SNODMIs) by amidation with octadecyl amine and subsequent imidization. SNODMIs with octadecyl branches were evaluated as flow improvers in the model crude oil with a high content of asphaltenes. The effects of molecular structures, including molecular weight, branch content, and imidization degree, on the effectiveness of SNODMI in reducing the viscosity and yield stress and improving the morphologies of asphaltene particles were thoroughly investigated using a rotational rheometer with parallel plate geometry and a polarizing microscope with a hot stage, respectively. It has been found that efficacy of SNODMI in reducing the viscosity and yield stress of the model crude oil increases with an increasing branch content of SNODMI. (alt)SNODMI with the highest branch content, approximately 45 mol %, achieved the best performance. Too high or too low molecular weight is not beneficial for SNODMI to improve the flow ability of the model crude oil. The appropriate molecular weight (Mₙ = 3500 Da) is required to achieve the optimal effectiveness. The optimal imidization degree of SNODMI is 100% and is independent of the branch content. The addition of SNODMI in a real crude oil has reduced the viscosity and yield stress by more than 90%.

Graphene oxide grafted poly(acrylic acid) synthesized via surface initiated RAFT as a pH‐responsive additive for mixed matrix membrane

ABSTRACTIncorporation of nanostructured materials into the membrane matrix is a new strategy to improve mechanical and performance properties. Graphene oxide (GO) is one of the advantageous carbon‐based nanomaterials, which recently has been used extensively in this field. However, in the most cases, the surface modification of GO has been considered for the creation of new properties like a response to different stimuli such as temperature, pH, and pressure. In the present study, a well‐defined poly(acrylic acid) was grafted on GO using reversible addition–fragmentation chain transfer polymerization technique. This modified GO was incorporated into the mixed matrix membrane as a pH‐sensitive additive and its effect on the membrane performance was investigated. The membrane with 5 wt % of modified GO provides better hydrophilicity, flux, antifouling, and rejection properties and so the effect of pH change on the aforementioned characteristic properties was studied for this membrane. It is indicated that modified membrane shows different behaviors in acidic and alkaline conditions. In addition, excellent heavy metal separation was observed among rejection tests, especially for Hg ions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47213.

Redox-Responsive Core-Cross-Linked Block Copolymer Micelles for Overcoming Multidrug Resistance in Cancer Cells.

Success of chemotherapy as a treatment for cancer has been often inhibited by multidrug resistance (MDR) of the cancer cells. There is a clear need to generate strategies to overcome this resistance. In this work, we have developed redox-responsive and core-cross-linked micellar nanocarriers using poly(ethylene glycol)-block-poly(2-(methacryloyloxy)ethyl 5-(1,2-dithiolan-3-yl)pentanoate) diblock copolymers (PEG-b-PLAHEMA) with tunable swelling properties for the delivery of drugs toward drug-sensitive MDA-MB-231 and drug-resistant MDA-MB-231 (231R) cancer cells. PEG-b-PLAHEMA containing varying number of 2-(methacryloyloxy)ethyl 5-(1,2-dithiolan-3-yl)pentanoate (LAHEMA) units were synthesized by employing the reversible addition-fragmentation chain transfer polymerization technique. The block copolymer self-assembly, cross-linking induced by reduction, and de-cross-linking triggered time-dependent controlled swelling of micelles were studied using dynamic light scattering, fluorescence spectroscopy, and transmission electron microscopy. In vitro cytotoxicity, cellular uptake efficiency, and glutathione-responsive anticancer activity of doxorubicin (DOX) encapsulated in core-cross-linked block copolymer micelles (CCMs) toward both drug-sensitive and drug-resistant cancer cell lines were evaluated. Significant reduction in IC50 was observed by DOX-loaded CCMs toward drug-resistant 231R cancer cell lines, which was further improved by coencapsulating DOX and verapamil (a P-glycoprotein inhibitor) in CCMs. Thus, these reduction-sensitive biocompatible CCMs with tunable swelling property are very promising in overcoming MDR in cancer cells.

Polysulfobetaine bearing tertiary amide between counterions and its applications

ABSTRACTModified sulfobetaine bearing tertiary amide spacer between the counterions is synthesized and polymerized by reversible addition–fragmentation chain transfer polymerization technique. The tertiary amide spacer influences various characteristics of the zwitterionic polymer. The modified polyzwitterion, PZI, forms coacervates in deionized water. The coacervates are thoroughly characterized by scanning electron microscopy, transmission electron microscopy, and transmittance studies. The ability to form coacervate complexes with functional ingredients has been demonstrated by encapsulating renewable resource actives like ferulic acid. The coacervate complexes have been studied by optical microscopy, transmission electron microscopy, and automated sunscreen sun protection factor analyzer. Synergism is noticed in the coacervate complex. Because of its ability to form self‐coacervates, this novel addition to the zwitterionic family is potentially useful for encapsulating many functional ingredients through coacervate complex formation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46178.

Fucoidan-Mimetic Glycopolymers as Tools for Studying Molecular and Cellular Responses in Human Blood Platelets

The marine sulfated polysaccharide fucoidan displays superior ability to induce platelet aggregation compared to other sulfated polysaccharides. As such, it is an attractive tool for studying molecular and cellular responses in activated platelets. The heterogeneous structure, however, poses a problem in such applications. This study describes the synthesis of sulfated α-l-fucoside-pendant poly(methacryl amides) with homogeneous structures. By using both thiol-mediated chain transfer and reversible addition-fragmentation chain transfer polymerization techniques, glycopolymers with different chain lengths are obtained. These glycopolymers show platelet aggregation response and surface changes similar to those of fucoidan, and cause platelet activation through intracellular signaling as shown by extensive protein tyrosine phosphorylation. As the platelet activating properties of the glycopolymers strongly mimic those of fucoidan, this study concludes these fucoidan-mimetic glycopolymers are unique tools for studying molecular and cellular responses in human blood platelets.

Single-Ion Block Copoly(ionic liquid)s as Electrolytes for All-Solid State Lithium Batteries.

Polymer electrolytes have been proposed as replacement for conventional liquid electrolytes in lithium-ion batteries (LIBs) due to their intrinsic enhanced safety. Nevertheless, the power delivery of these materials is limited by the concentration gradient of the lithium salt. Single-ion conducting polyelectrolytes represent the ideal solution since their nature prevents polarization phenomena. Herein, the preparation of a new family of single-ion conducting block copolymer polyelectrolytes via reversible addition-fragmentation chain transfer polymerization technique is reported. These copolymers comprise poly(lithium 1-[3-(methacryloyloxy)propylsulfonyl]-1-(trifluoromethylsulfonyl)imide) and poly(ethylene glycol) methyl ether methacrylate blocks. The obtained polyelectrolytes show low Tg values in the range of -61 to 0.6 °C, comparatively high ionic conductivity (up to 2.3 × 10(-6) and 1.2 × 10(-5) S cm(-1) at 25 and 55 °C, respectively), wide electrochemical stability (up to 4.5 V versus Li(+)/Li), and a lithium-ion transference number close to unity (0.83). Owing to the combination of all mentioned properties, the prepared polymer materials were used as solid polyelectrolytes and as binders in the elaboration of lithium-metal battery prototypes with high charge/discharge efficiency and excellent specific capacity (up to 130 mAh g(-1)) at C/15 rate.

Enhancement of Localized Surface Plasmon Resonance polymer based biosensor chips using well-defined glycopolymers for lectin detection

Poly(methyl methacrylate) polymer based Localized Surface Plasmon Resonance biosensor chips were successfully fabricated using glycopolymer brushes carrying glucose moieties for the detection of concanavalin A. Poly(pentafluorostyrene), with pre-determined polymer chain lengths, were synthesized via a reversible addition–fragmentation chain transfer polymerization technique. The synthesized poly(pentafluorostyrene), was subsequently converted into glycopolymers via a para-fluoro-thiol “click” reaction and grafted onto the surface of sensor chips. The “glycocluster effect” induced by pendent carbohydrate moieties enabled a stronger affinity for concanavalin A binding, which resulted in a dramatic expansion of the sensors’ response range. It was discovered that the longer polymer brushes did not guarantee additional enhancements for the sensor chips. Instead, they could lead to higher detection limits. In this study, the limit of detection for the sensor chips was discovered to be 1.3nmolL−1 with a saturated response at 1054.2nmolL−1. In addition to the superior performance, the capabilities of the reported sensor chips can be easily manipulated to detect a diverse range of analytes by “clicking” various sensing elements onto the polymer brushes.

Synthesis of a new rhodamine‐containing block copolymer for highly selective and sensitive detection of Cu2+ and CN− ions in aqueous media

AbstractDevelopment of new chemosensors that are selective and sensitive to Cu2+ and CN− ions, especially in aqueous media, is of tremendous importance. We report the synthesis of a new block copolymer that is capable of highly selective and sensitive detection of Cu2+ and CN− ions in aqueous media. Poly(t‐butylacrylate)‐block‐poly(3‐bromopropylacrylate) was prepared using the reversible addition–fragmentation chain transfer polymerization technique. This block copolymer was reacted with 2,4‐dihydroxybenzaldehyde followed by reaction with rhodamine B hydrazide for successful incorporation of the desired rhodamine units into the block copolymer structure. Cu2+‐induced opening of the spirolactam ring of the rhodamine units resulted in rapid and easily noticeable colour change, thus enabling a highly selective detection of Cu2+ ions in aqueous media for concentrations as low as 2 µmol L−1. We further demonstrate that this Cu2+ bound polymer complex can further act as a selective and sensitive sensing platform for CN− in aqueous media with concentrations <1 µmol L−1 (0.06 ppm). Moreover, the polymer can also be used to remove Cu2+ from aqueous media. © 2014 Society of Chemical Industry

Synthesis of novel side‐chain triphenylamine polymers with azobenzene moieties via RAFT polymerization and investigation on their photoelectric properties

AbstractTwo novel and well‐defined polymers, poly[6‐(5‐(diphenylamino)‐2‐((4‐methoxyphenyl)diazenyl)phenoxy)hexyl methacrylate] (PDMMA) and poly[6‐(4‐((3‐ethynylphenyl)diazenyl) phenoxy)hexyl methacrylate] (PDPMMA), which bear triphenylamine (TPA) incorporated to azobenzene either directly (PDMMA) or with an interval (PDPMMA) as pendant groups were successfully prepared via reversible addition‐fragmentation chain transfer polymerization technique. The electrochemical behaviors of PDPMMA and PDMMA were investigated by cyclic voltammograms (CV) measurement. The hole mobilities of the polymer films were determined by fitting the J‐V (current‐voltage) curve into the space‐charge‐limited current method. The influence of photoisomerization of the azobenzene moiety on the behaviors of fluorescence emission, CV and hole mobilities of these two polymers were studied. The fluorescent emission intensities of these two polymers in CH2Cl2 were increased by about 100 times after UV irradiation. The oxidation peak currents (IOX) of the PDMMA and PDPMMA in CH2Cl2 were increased after UV irradiation. The photoisomerization of the azobenzene moiety in PDMMA had significant effect on the electrochemical behavior, compared with that in PDPMMA. The changes of the hole mobility before and after UV irradiation were very small for both polymers. The HOMO energies (EHOMO, HOMO: the highest occupied molecular orbital) of side chain moieties of TPA incorporated with cis‐isomer and trans‐isomer of azobenzene in PDMMA and PDPMMA were obtained by theoretical calculation, which are basically consistent with the experimental results. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Synthesis and characterization of polymethacrylates containing conjugated oligo(phenylene ethynylene)s as side chains

In order to form suitable systems designed for resonance energy transfer, a series of monodisperse methacrylate-based monomers containing rigid π-conjugated oligo(phenylene ethynylenes) with different sizes of the conjugated systems (M1–M3), and therefore different optoelectronic properties, were synthesized and subsequently polymerized using the reversible addition–fragmentation chain transfer polymerization technique (P1–P3). In addition, these oligomers were also copolymerized with methyl methacrylate. The obtained polymers were characterized by 1H NMR spectroscopy, size exclusion chromatography, and analytical ultracentrifugation. The photophysical properties of the polymers were studied by UV–vis absorption and emission spectroscopy in diluted solutions as well as in thin films and compared to the photophysics of the corresponding monomers. Thereby, changes going from monomeric to polymeric systems could be detected in fluorescence quantum yields and lifetimes pointing to energy trapping, e.g., energy transfer. Donor–acceptor copolymers containing different numbers of monomeric units within the side chain exhibit differences in the emission spectra, indicating that energy trapping in polymers is very sensitive to structural properties such as the chain length. UV–vis absorption spectroscopy as well as time-resolved lifetime studies indicate intrapolymer and interpolymer energy transfer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Double imprinting in a single molecularly imprinted polymer format for the determination of ascorbic acid and dopamine

A new molecularly imprinted polymer – carbon composite fiber is constructed using reversible addition-fragmentation chain transfer polymerization technique. The fiber was evaluated as a sensor for the simultaneous determination of ascorbic acid and dopamine at ultratrace level, in aqueous samples, without any cross-reactivity. The binding characteristics of ascorbic acid and dopamine were also evaluated by differential pulse cathodic stripping voltammetry.

Poly[N-(2-hydroxypropyl)methacrylamide]-Based Tissue-Embedding Medium Compatible with MALDI Mass Spectrometry Imaging Experiments

Traditional tissue-sectioning techniques for histological samples utilize various embedding media to stabilize the tissue on a sectioning target and to provide a smooth cutting surface. Due to the ion suppression effect in MALDI ionization and number of background peaks in the low-mass region, these media are not suitable for mass spectrometry imaging (MSI) experiments. To overcome this, droplets of water are often used to mount the tissue on a sectioning target, but the ice block formed around the tissue does not provide a good support for sectioning of fragile samples. In this work, we propose a novel embedding media, compatible with MALDI ionization and MSI experiments, based on poly[N-(2-hydroxypropyl)methacrylamide] (pHPMA). Using a reversible addition-fragmentation chain transfer polymerization technique, well-defined pHPMA polymer with narrow mass distribution was prepared. Benefits of the resulted pHPMA-based embedding media were tested on different tissue samples.

Epoxy-containing ArF resists with narrow molecular weight distribution

Terpolymers consisting of γ-butyrolactone-2-yl methacrylate, 2-methyl-2-adamantyl methacrylate, and 1-methyl-1-(6-methyl-7-oxabicyclo[4,1,0]hept-3-yl)ethyl methacrylate were prepared by the reversible addition-fragmentation chain transfer polymerization technique. The molecular weight distribution of the polymers was 1.29–1.39. Although the polymers have epoxy units and cross-linking of the polymer occurred during prebake treatment, they worked as a highly sensitive positive-tone resist. The cross-linking efficiency of the resist was dependent on the type of amines used as a quencher. The line edge roughness values were dependent on the prebake temperature.

Free‐radical copolymerization of ethyl α‐hydroxymethylacrylate with methyl methacrylate by reversible addition–fragmentation chain transfer

AbstractThe controlled free‐radical homopolymerization of ethyl α‐hydroxymethylacrylate and copolymerization with methyl methacrylate were performed in chlorobenzene at 70 °C by the reversible addition–fragmentation chain transfer polymerization technique with 2,2′‐azobisisobutyronitrile as the initiator. 2‐Phenylprop‐2‐yl dithiobenzoate and 2‐cyanoprop‐2‐yl dithiobenzoate were used as chain‐transfer agents in the homopolymerization, whereas only the former was used in the copolymerization. All reactions presented pseudolinear kinetics. The effect of the monomer feed ratio on the copolymerization kinetics was examined. The conversion level decreased when the proportion of ethyl α‐hydroxymethylacrylate in the monomer feed was larger. Kinetic studies indicated that the radical polymerizations proceeded with apparent living character according to experiments, demonstrating an increase in the molar mass with the monomer conversion and a relatively narrow molar mass distribution. All copolymers were statistical in chain structure, as confirmed by determinations of the monomer reactivity ratios. The monomer reactivity ratios were determined, and the Mayo–Lewis terminal model provided excellent predictions for the variations of the intermolecular structure over the entire conversion range. Additionally, the chemical modification of poly(ethyl α‐hydroxymethylacrylate) was carried out to introduce glucose pendant groups into the structure. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5618–5629, 2006