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Vinyl-addition polynorbornenes are of great interest as versatile templates for the targeted design of polymer materials with desired properties. These polymers possess rigid and saturated backbones, which provide them with high thermal and chemical stability as well as high glass transition temperatures. Vinyl-addition polymers from norbornenes with bromoalkyl groups are widely used as precursors of anion exchange membranes; however, high-molecular-weight homopolymers from such monomers are often difficult to prepare. Herein, we report the systematic study of vinyl-addition polymerization of norbornenes with various bromoalkyl groups on Pd-catalysts bearing N-heterocyclic carbene ligands ((NHC)Pd-systems). Norbornenes with different lengths of hydrocarbon linker (one, two, and four CH2 groups) between the bicyclic norbornene moiety and the bromine atom were used as model monomers, while single- and three-component (NHC)Pd-systems were applied as catalysts. In vinyl-addition polymerization, the reactivity of the investigated monomers varied substantially. The relative reactivity of these monomers was assessed in copolymerization experiments, which showed that the closer the bromine is to the norbornene double-bond, the lower the monomer’s reactivity. The most reactive monomer was the norbornene derivative with the largest substituent (with the longest linker). Tuning the catalyst’s nature and the conditions of polymerization, we succeeded in synthesizing high-molecular-weight homopolymers from norbornenes with bromoalkyl groups (Mn up to 1.4 × 106). The basic physico-chemical properties of the prepared polymers were studied and considered together with the results of vinyl-addition polymerization.

In this work, a novel poly (methylenelactide-g-L-lactide), P(MLA-g-LLA) graft copolymer was synthesized from poly(methylenelactide) (PMLA) and L-lactide (LLA) using 0.03 mol% liquid tin(II) n-butoxide (Sn(OnBu)2) as an initiator by a combination of vinyl addition and ring-opening polymerization (ROP) at 120 °C for 72 h. Proton and carbon-13 nuclear magnetic resonance spectroscopy (1H- and 13C-NMR) and Fourier-transform infrared spectroscopy (FT-IR) confirmed the grafted structure of P(MLA-g-LLA). The P(MLA-g-LLA) melting temperatures (Tm) range of 144–164 °C, which was lower than that of PLA (170–180 °C), while the thermal decomposition temperature (Td) of around 314–335 °C was higher than that of PLA (approx. 300 °C). These results indicated that the grafting reaction could widen the melt processing range of PLA and in doing so increase PLA’s thermal stability during melt processing. The graft copolymers were obtained with weight-average molecular weights (M¯w) = 4200–11,000 g mol−1 and a narrow dispersity (Đ = 1.1–1.4).

Sonodynamic therapy is widely used in clinical studies including cancer therapy. The development of sonosensitizers is important for enhancing the generation of reactive oxygen species (ROS) under sonication. Herein, we have developed poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC)-modified TiO2 nanoparticles as new biocompatible sonosensitizers with high colloidal stability under physiological conditions. To fabricate biocompatible sonosensitizers, a grafting-to approach was adopted with phosphonic-acid-functionalized PMPC, which was prepared by reversible addition–fragmentation chain transfer (RAFT) polymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) using a newly designed water-soluble RAFT agent possessing a phosphonic acid group. The phosphonic acid group can conjugate with the OH groups on the TiO2 nanoparticles. We have clarified that the phosphonic acid end group is more crucial for creating colloidally stable PMPC-modified TiO2 nanoparticles under physiological conditions than carboxylic-acid-functionalized PMPC-modified ones. Furthermore, the enhanced generation of singlet oxygen (1O2), an ROS, in the presence of PMPC-modified TiO2 nanoparticles was confirmed using a 1O2-reactive fluorescent probe. We believe that the PMPC-modified TiO2 nanoparticles prepared herein have potential utility as novel biocompatible sonosensitizers for cancer therapy.

Exploring new polymerization strategies for currently available monomers is a challenge in polymer science. Herein, a bifunctional initiator (BFI) is introduced for the conventional radical polymerization of a vinyl monomer, resulting in linear radical additions-coupling polymerization (LRAsCP). In LRAsCP, the coupling reaction alongside the addition reaction of the radicals contributes to the construction of polymer chains, which leads to stepwise growth of the multiblock structure. Theoretical analysis of LRAsCP predicted variation of some structural parameters of the resulting multiblock polymer (MBP) with the extent of initiation of the BFI and the termination factor of the radicals. Simultaneous and cascade initiations of the BFI were compared. LRAsCP of styrene was conducted, and a kinetics study was carried out. The increment in Mn with polymerization time demonstrated the stepwise mechanism of the formation of the MBP. The variation of the structural parameters of MBP fitted well with the theoretical prediction. Two-step LRAsCP was conducted and multiblock copolymers (MBcP) were obtained either by in situ copolymerization of styrene and MMA or by a second copolymerization of styrene and BMA. The current results demonstrate that the introduction of a BFI to conventional radical polymerization generates a new polymerization strategy, leading to a new chain architecture, which can be extended to other radical polymerizable monomers.

Polyethylene terephthalate (PET) is widely used packaging materials for electrical encapsulation, photovoltaic components, solar junction boxes, food storage, automotive parts, etc. Endowing the PET exterior surfaces with self‐cleaning functionality offers a promising solution to improving durability by resisting dust and dirt accumulation, thereby reducing maintenance costs. A facile and effective strategy is presented for creating robust micro/nano hierarchical structures on PET sheets to achieve superhydrophobicity through surface roughening and reduced surface energy. By integrating a thermal engraving method (utilizing copper micro‐patterned templates fabricated via high‐resolution laser cutting) with polymer modification through reversible addition‐fragmentation chain transfer (RAFT) polymerization to introduce fluorinated functional groups, dual‐scale patterned PET surfaces is successfully generated. Two distinct hierarchical structures, micro‐windowpanes and microgrooves with secondary nanofeatures generated by poly (glycidyl methacrylate)‐block‐poly (pentafluorostyrene) coating, exhibited exceptional water repellent properties, with water contact angles of 155 ± 3° and 151 ± 1°, respectively. The dual‐scale micro‐windowpanes‐structured surfaces exhibited a low sliding (roll‐off) angle of 7.9°, ensuring efficient self‐cleaning performance. The newly developed multifunctional PET surfaces demonstrated outstanding water repellency and effective removal of both water‐soluble (e.g., coffee powder) and water‐insoluble (e.g., sand) contaminants, strong anti‐icing and UV resistance, highlighting their potential for low‐maintenance packaging materials and high‐performance coatings. By integrating a thermal engraving method with polymer modification through reversible addition‐fragmentation chain transfer (RAFT) polymerization to introduce fluorinated functional groups, micro‐nano superhydrophobic PET surfaces are prepared. These newly developed surfaces demonstrate outstanding water repellency and effective removal of both water‐soluble and water‐insoluble contaminants, strong anti‐icing and UV resistance, highlighting their potential for low‐maintenance packaging materials.

Atom transfer radical polyaddition (ATRPA) was utilized herein to synthesize a specific functional polyester. We conducted ATRPA of 4-vinylbenzyl 2-bromo-2-phenylacetate (VBBPA) inimer and successfully obtained a linear type poly(VBBPA) (PVBBPA) polyester with benzylic bromides along the backbone. To obtain a novel amphiphilic polymer bottlebrush, however, the lateral ATRP chain extension of PVBBPA with N-vinyl pyrrolidone (NVP) met the problem of quantitative dimerization. By replacing the bromides to xanthate moieties efficiently, we thus observed a pseudo linear first order reversible addition–fragmentation chain transfer (RAFT) polymerization to obtain novel poly(4-vinylbenzyl-2-phenylacetate)-g-poly(NVP) (PVBPA-g-PNVP) amphiphilic polymer bottlebrushes. The critical micelle concentration (CMC) and particle size of the amphiphilic polymer bottlebrushes were characterized by fluorescence spectroscopy, dynamic light scattering (DLS), and scanning electron microscopy (SEM) (CMCs < 0.5 mg/mL; particle sizes = ca. 100 nm). Toward drug delivery application, we examined release profiles using a model drug of Nile red at different pH environments (3, 5, and 7). Eventually, low cytotoxicity and well cell uptake of the Madin-Darby Canine Kidney Epithelial (MDCK) for the polymer bottlebrush micelles were demonstrated.

Synthesis of poly(epichlorohydrin-g-4-vinylbenzyl-g-methyl methacrylate) [poly(ECH-g-VB-g-MMA)] graft copolymer was carried out by cationic ring-opening polymerization (ROP), reversible addition-fragmentation chain transfer (RAFT) polymerization, and atom transfer radical polymerization (ATRP) methods. In the first stage, poly(epichlorohydrin) [PECH] was synthesized using epichlorohydrin monomer by ROP. In the second stage, macro-RAFT agent was synthesized by a chemical reaction of PECH with potassium ethyl xanthogenate. In the third stage, macro-RAFT agent and 4-vinylbenzyl chloride were used to obtain poly(ECH-g-VBC) graft copolymer by RAFT polymerization. In the last stage, in the ATRP of the methyl methacrylate, chloromethyl groups of the poly4-vinylbenzyl chloride segment of poly(ECH-g-VBC) graft copolymer were used as the starting functional group, poly(ECH-g-VB-g-MMA) graft copolymer with low dispersity was obtained as a result of the polymerization. The product characterization was fulfilled using spectroscopic and thermal analysis techniques such as 1 H-NMR, FT-IR, TGA, SEM and GPC instruments.

In this study, novel triblock copolymers, including poly(N-isopropylacrylamide)-block-poly(ε-caprolactone)-block-poly(N-isopropylacrylamide) (PNIPAM-b-PCL-b-PNIPAM), poly(N-vinyl-pyrrolidone)-block-poly(ε-caprolactone)-block-poly(N-vinyl-pyrrolidone) (PNVP-b-PCL-b-PNVP), poly(N-isopropylacrylamide-co-N,N-dimethylaminoethyl methacrylate)-block-poly(ε-caprolactone)-block-poly(N-isopropylacrylamide-co-N,N-dimethylaminoethyl methacrylate) (P(DMAEMA-co-NIPAM)-b-PCL-b-P(NIPAM-co-DMAEMA)), and poly(N,N-dimethylacrylamide)-block-poly(ε-caprolactone)-block-poly(N,N-dimethylacrylamide) (PDMA-b-PCL-b-PDMA), were synthesized via a combination of ring-opening polymerization (ROP) and reversible addition–fragmentation chain transfer (RAFT) polymerization. The synthesis was performed using novel bifunctional PCL-based RAFT macro chain transfer agents (macroCTAs; MXTPCL-X1 and MXTPCL-X2) with a m-xylene-bis(2-mercaptoethyloxy) core. Initially, m-xylene-bis(1-hydroxy-3-thia-propane) (MXTOH), which has not previously been used in lactone polymerization, was synthesized via the reaction of α,α′-dibromo-m-xylene with 2-mercaptoethanol in the presence of sodium in ethanol. Subsequently, Sn(Oct)2-catalyzed ROP of ε-caprolactone (ε-CL) using MXTOH as an initiator yielded PCL-diol (MXTPCLOH). The resulting PCL-diol underwent further functionalization through esterification and substitution reactions, leading to the formation of PCL-based RAFT macroCTAs. Triblock copolymers were synthesized using these macroCTAs with AIBN as an initiator. The synthesized products, along with their intermediates, were characterized using FTIR and 1H NMR spectroscopy. The number average molecular weight (Mn) and polydispersity index (Ð) of PCL-based macroCTAs were determined by using GPC analysis. The sensor capabilities of the synthesized novel triblock copolymers were investigated on the determination of syringic acid and it was determined that the most sensitive polymer was PNVP-b-PCL-b-PNVP (MXTP2). The working range was between 1.5 µg/mL and 15 µg/mL and the limit of detection (LOD) was found to be 0.44 µg/mL using DPV on MXTP2 polymer sensor.

Thermo-responsive diblock copolymer, poly(N-isopropylacrylamide)-block-poly(N-vinylisobutyramide) was synthesized via switchable reversible addition–fragmentation chain transfer (RAFT) polymerization and its thermal transition behavior was studied. Poly(N-vinylisobutyramide) (PNVIBA), a structural isomer of poly(N-isopropylacrylamide) (PNIPAM) shows a thermo-response character but with a higher lower critical solution temperature (LCST) than PNIPAM. The chain extension of the PNVIBA block from the PNIPAM block proceeded in a controlled manner with a switchable chain transfer reagent, methyl 2-[methyl(4-pyridinyl)carbamothioylthio]propionate. In an aqueous solution, the diblock copolymer shows a thermo-responsive behavior but with a single LCST close to the LCST of PNVIBA, indicating that the interaction between the PNIPAM segment and the PNVIBA segment leads to cooperative aggregation during the self-assembly induced phase separation of the diblock copolymer in solution. Above the LCST of the PNIPAM block, the polymer chains begin to collapse, forming small aggregates, but further aggregation stumbled due to the PNVIBA segment of the diblock copolymer. However, as the temperature approached the LCST of the PNVIBA block, larger aggregates composed of clusters of small aggregates formed, resulting in an opaque solution.

Herein, we report the synthesis via controlled reversible addition-fragmentation chain transfer (RAFT) polymerization of amphiphilic 2-vinylpyridine-b-styrene (2VPy-b-Sty) diblock copolymers of high molar masses (range: 52,100–304,000 g mol−1) and various compositions (range: 2VP content 11.6–59.2 mol%) and their use for the fabrication of nanoporous membranes. The successful synthesis of the amphiphilic diblock copolymers was confirmed through the characterization of their molar masses, molar mass distribution, and composition using GPC and 1H-NMR spectroscopy, respectively. Subsequently, membranes of the diblock copolymers were fabricated following the “phase inversion” technique. The resulting membranes were characterized via scanning electron microscopy which revealed the presence of sphere percolation networks morphology for all diblock copolymers with Mn ranging from 120 to 300 kDa and 2VPy content between 10 and 15 mol% at the optimal conditions. Afterward, the developed membranes were evaluated in terms of their permeability towards water and in terms of their ability to retain two different microorganisms, namely, Enterococcus faecalis and Escherichia coli, that are known to be harmful to human health. The experimental water flux for a membrane with pore size around 60 nm was equal to 31,400 L h−1 m2 and expectedly decreased with the decrease in membrane pore diameter. The retention ability of membranes for Enterococcus faecalis and Escherichia coli was higher than 90%. In particular, the retention ability for Enterococcus faecalis was equal to 98.9% and for Escherichia coli was 91.4%. The toxicity of the produced membrane was also determined, and the measured value was relatively low, at 17%.