Synthesis Of Diblock Copolymers Research Articles

A Versatile Strategy toward Donor-Acceptor Nanofibers with Tunable Length/Composition and Enhanced Photocatalytic Activity.

Living crystallization-driven self-assembly (CDSA) has emerged as an efficient strategy to generate nanofibers of π-conjugated polymers (CPNFs) in a controlled fashion. However, reports of donor-acceptor (D-A) heterojunction CPNFs are extremely rare. The preparation of these materials remains a challenge due to the lack of rational design guidelines for the D-A π-conjugated units. Herein, we report a versatile CDSA strategy based upon carefully designed D-A-co-oligomers in which electron-deficient benzothiadiazole (BT) or dibenzo[b,d]thiophene 5,5-dioxide (FSO) units are attached to the two ends of an oligo(p-phenylene ethynylene) heptamer [BT-OPE7-BT, FSO-OPE7-FSO]. This arrangement with the electron-deficient groups at the two ends of the oligomer enhances the stacking interaction of the A-D-A π-conjugated structure. In contrast, D-A-D structures with a single BT in the middle of a string of OPE units disrupt the packing. We employed oligomers with a terminal alkyne to synthesize diblock copolymers BT-OPE7-BT-b-P2VP and BT-OPE7-BT-b-PNIPAM (P2VP = poly(2-vinylpyridine), PNIPAM = poly(N-isopropylacrylamide)) and FSO-OPE7-FSO-b-P2VP and FSO-OPE7-FSO-b-PNIPAM. CDSA experiments with these copolymers in ethanol were able to generate CPNFs of controlled length by both self-seeding and seeded growth as well as block comicelles with precisely tunable length and composition. Furthermore, the D-A CPNFs with a BT-OPE7-BT-based core demonstrate photocatalytic activity for the photooxidation of sulfide to sulfoxide and benzylamine to N-benzylidenebenzylamine. Given the scope of the oligomer compositions examined and the range of structures formed, we believe that the living CDSA strategy with D-A-based co-oligomers opens future opportunities for the creation of D-A CPNFs with programmable architectures as well as diverse functionalities and applications.

Microphase Separation and Gelation through Polymerization-Induced Self-Assembly Using Star Polyethylene Glycols.

Polymerization-induced self-assembly (PISA) during the synthesis of diblock copolymers has garnered considerable interest; however, architectures beyond diblock copolymers have scarcely been explored. Here, we studied PISA using 4- and 8-arm star polyethylene glycol (PEG), as well as 2-arm (linear) PEG, wherein each terminus of PEG was functionalized with a chain-transfer agent, holding a constant molar mass for each arm. Styrene was polymerized from each PEG terminus through reversible addition-fragmentation chain-transfer (RAFT) polymerization in an ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF6]), with a total solute concentration of 40 wt %. While the styrene monomer is soluble in [BMIM][PF6], polystyrene is not; thus, self-assembly and cross-linking (gelation) occur. Structural analysis by small-angle X-ray scattering revealed that a relatively ordered microphase-separated structure for PISA was observed. Two-arm PEG-PS formed hexagonally packed cylinders, whereas 4- and 8-arm PEG-PS exhibited hexagonal close-packed spheres and disordered spheres. The dynamics, studied by oscillatory rheology, were also influenced by the number of arms; the 4-arm star block copolymers showed the highest plateau modulus. This study demonstrates that the topology is an important factor in controlling the microphase-separated structure and mechanical properties when preparing gels through PISA.

Polyfluorene-poly(ethylene oxide) diblock copolymers: synthesis and electron transport behavior.

Under mild reaction conditions, we synthesized diblock copolymers of poly(9,9-dioctylfluorene)-block-poly(ethylene oxide) (PFO-b-PEO) via end-capping poly(9,9-dioctylfluorene) (PFO) with poly(ethylene oxide) (PEO) on one end. We investigated the thermal, optical, electrochemical and crystalline properties as well as electron transport performance of these polymers. Our results demonstrate that PFO-b-PEO diblock copolymers with short PEO chains (M n = 1000 and 2000 g mol-1) exhibit higher electron mobilities compared to the PFO homopolymer and longer PEO chain (M n = 4000 g mol-1) attached copolymers. This enhanced electron mobility is attributed to the higher crystallinity induced by the shorter PEO chain end-capping.

A visualizable strategy to real-time monitor chiral block copolypeptide assembly by AIE fluorescent probes

Aggregation-induced emission (AIE) luminogens show great potential in many applications. In this study, we have synthesized diblock copolymers poly (ethylene glycol) -b-poly (9-anthrylmethyl-L-lysine) (PEG-b-PLLys-An) and poly (ethylene glycol) -b-poly (9-anthrylmethyl-D-lysine) PEG-b-PDLys-An with opposite handedness by ring-opening polymerization and post-modification. Both diblock copolymers can self-assemble into spherical micelles or planar connected disc-like aggregates at different water fractions. In addition, the copolymers present a typical AIE process concomitant with the self-assembly process. To facilitate the study of chain exchange kinetics, we develope a novel visualizable strategy based on fluorescence variation. This strategy allows us to monitor the real-time chain exchange process by mixing equimolar solutions of PEG44-b-PDLys20-An and PEG44-b-PLLys20-An with varying water volume fractions. We indicate that chain exchange predominantly occurs at low water fractions through a single-molecule extraction and redistribution mechanism rather than micellar fission and fusion. In contrast, the micelles appear to be "kinetically frozen" at high water fractions, suggesting suppressed chain exchange under these conditions. Importantly, our approach offers a visually observable method for probing the dynamics of micellar chain exchange in real time.

Efficient end-group functionalization and diblock copolymer synthesis via Au(III) polymer reagents.

Herein, we describe the synthesis of bench-stable organometallic Au(III) terminated polymer reagents. These reagents mediate the chemoselective S-arylation of thiol-containing small molecules and polymers to yield functionalized mono-telechelic polymers and diblock copolymers, respectively. These transformations proceed rapidly within minutes and produce conjugates in quantitative conversion, making this strategy a robust addition to the polymer functionalization toolbox.

Installing a Single Monomer within Acrylic Polymers Using Photoredox Catalysis.

Incorporating exactly one monomer at a defined position during a chain polymerization is exceptionally challenging due to the statistical nature of monomer addition. Herein, photoinduced electron/energy transfer (PET) enables the incorporation of exactly one vinyl ether into polyacrylates synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Near-quantitative addition (>96%) of a single vinyl ether is achieved while retaining >99% of the thiocarbonylthio chain ends. Kinetic studies reveal that performing the reactions at 2 °C limits unwanted chain breaking events. Finally, the syntheses of diblock copolymers are reported where molecular weights and dispersities are well-controlled on either side of the vinyl ether. Overall, this report introduces an approach to access acrylic copolymers containing exactly one chemical handle at a defined position, enabling novel macromolecular architectures to probe structure-function properties, introduce sites for de/reconstruction, store information, etc.

Structural and optical properties of hybrid materials derived from gold nanoparticles in different polystyrene (PS)-b-poly(4-vinylpyridine) (P4VP) matrices

We introduce the preparation as well as the structural and optical properties of hybrid materials consisting of diblock copolymer matrices with gold nanoparticles. Anionically synthesized diblock copolymers of the PS-b-P4VP sequence, where PS: polystyrene and P4VP: poly(4-vinylpyridine) with well-defined characteristics were utilized as the polymer matrices. The specific pyridine-containing copolymers were selected due to their susceptibility to post-polymerization chemical modification reactions. Basic tertiary amines can be easily modified due to the presence of the nitrogen atom (N) in the 4-position (-para) of the aromatic ring in the monomeric units of poly(4-vinylpyridine). In this manner, the addition of either atoms or whole compounds as ion pairs is enabled. We report that the role of noble metal atoms in polymer matrices is dual. Firstly, microphase separation in the presence of heteroatoms occurs even in cases of extremely low molecular characteristics due to the increased repulsion between the components and secondly the excitation of plasmon resonance at the polymer/nanoparticle interface is induced. We believe that our work sheds light on the driving forces of self-assembly on the studied modified copolymers. The results strongly suggest that the hybrid materials can adopt well-defined morphologies even in very low molecular weights, a fact that renders them promising candidates for photonic applications.

Ultrasound-Responsive Micelle-Encapsulated Mesenchymal Stem Cell-Derived EVs for the Treatment of Lower Limb Microcirculation Disease.

Lower limb microcirculatory ischemic disease is a vascular disorder primarily characterized by limb pain, gangrene, and potential amputation. It can be caused by various factors, such as hyperglycemia, atherosclerosis, and infection. Due to the extremely narrow luminal diameter in lower limb microcirculatory ischemic lesions, both surgical and medical interventions face challenges in achieving satisfactory therapeutic outcomes within the microvessels. Extracellular vesicles derived from mesenchymal stem cells (MSCs-EVs) exhibit promising potential in the treatment of microcirculation ischemic lesions due to their small size and ability to promote angiogenesis. After undergoing substantial losses during the process of EVs transportation, only a minimal fraction of EVs can effectively reach the site of microcirculatory lesions, thereby compromising the therapeutic efficacy for microcirculatory disorders. Herein, an ultrasound-responsive system utilizing 2-(dimethylamino)ethyl methacrylate-b-2-tetrahydropyranyl methacrylate (DMAEMA-b-THPMA) micelles to encapsulate MSCs-EVs has been successfully constructed, with the aim of achieving localized and targeted release of EVs at the site of microcirculatory lesions. The reversible addition-fragmentation chain transfer (RAFT) polymerization method facilitates the successful synthesis of diblock copolymers comprising monomer 2-(dimethylamino)ethyl methacrylate (DMAEMA) and monomer 2-tetrahydropyranyl methacrylate (THPMA). The DMAEMA-b-THPMA micelles exhibit a nanoscale structure, reliable biocompatibility, ultrasound responsiveness, and conspicuous protection of EVs. Furthermore, the implementation of low-energy-density ultrasound can enhance angiogenesis by upregulating the levels of the vascular endothelial growth factor (VEGF). In in vivo experiments, the ultrasound-responsive system of the DMAEMA-b-THPMA micelles and MSCs-EVs synergistically enhances therapeutic efficacy by promoting angiogenesis, improving vascular permeability, and optimizing vascular. In conclusion, this work demonstrates bioapplication of an ultrasound-responsive micellar nanosystem loaded with EVs for the treatment of lower limb microcirculatory ischemic disorders.

Macromol. React. Eng. 2/2023

Macromolecular Reaction EngineeringVolume 17, Issue 2 2370003 Cover PictureFree Access Macromol. React. Eng. 2/2023 First published: 17 April 2023 https://doi.org/10.1002/mren.202370003AboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Graphical Abstract Front Cover: This study deals with the development of a reaction kinetic model describing the inhibition mechanism of RAFT dispersion polymerization by oxygen and its application to investigate the effect of re-initiation on the synthesized polymer quality. The experimental validation of the kinetic model creates a functional digital twin, establishing a valid method for diblock copolymer synthesis from a non-successful polymerization attempt. This is reported by Emil Pashayev, Felix Kandelhard, and Prokopios Georgopanos in article number 2200068. Volume17, Issue2April 20232370003 RelatedInformation

Design and biological evaluation of Repaglinide loaded polymeric nanocarriers for diabetes linked neurodegenerative disorder: QbD-driven optimization, in situ, in vitro and in vivo investigation

Diabetes mellitus is a metabolic disorder characterized by inadequate insulin secretion and signaling dysfunction, leading to a vast spectrum of systemic complications. These complications trigger cascades of events that result in amyloid-beta plaque formation and lead to neurodegenerative disorders such as Alzheimer’s. Repaglinide (REP) an insulinotropic agent, suppresses the down regulatory element antagonist modulator (DREAM) and enhances the ATF6 expression to provide neuroprotection following the DREAM/ATF6/apoptotic pathway. However, oral administration of REP for brain delivery becomes more complicated due to its physicochemical characteristics (high protein binding (>98%), low permeability, short half-life (∼1 h), low bioavailability). Therefore, to circumvent these problems, we develop a polymeric nanocarrier system (PNPs) by in-house synthesized di-block copolymer (PEG-PCL). PNPs were optimized using quality by design approach response surface methodology and characterized by particle size (112.53 ± 5.91 nm), PDI (0.157 ± 0.08), and zeta potential (−6.20 ± 0.82 mV). In vitro release study revealed that PNPs (∼70% in 48 h) followed the Korsmeyer-Peppas model with a Fickian diffusion release pattern, and in intestinal absorption assay PNPs showed increment of ∼1.3 folds compared of REP. Moreover, cellular studies confirmed that REP-loaded PNPs significantly enhance the cellular viability, uptake and reduce the peroxide-induced stress in neuroblastoma SHSY-5Y cells. Further, pharmacokinetic parameters of PNPs showed an increment in tmax (2.46-fold), and Cmax (1.25-fold) associated with REP. In the brain biodistribution study, REP loaded PNPs was sustained for 24 h whereas free REP sustained only for12 h. In DM induced neurodegenerative murine model, a significantly (p < 0.01) enhanced pharmacodynamic was observed in PNP treated group by estimating biochemical and behavioral parameters. Hence, oral administration of REP-loaded PNPs promotes efficient brain uptake and improved efficacy of REP in the diseased model.

A multifunctional polymeric coating with self-adsorbed, antifouling and in situ remineralization properties for caries management.

Dental caries is a biofilm-induced bacterial infectious oral disease, where the early attachment of proteins and pathogenic bacteria to tooth surfaces has been known as the main cause of biofilm formation. Typically, dental caries is commonly accompanied by mineral depletion of enamels, thus causing dental demineralization. Multifunctional materials are highly attractive candidates for treating dental caries. Herein, we successfully synthesized diblock copolymers poly(ethylene glycol)-b-poly(aspartic acid) (PEG-PAsp) and modified them with alendronate sodium (ALN) to serve as bioactive bifunctional coatings (PEG-PAsp-ALN) on teeth. The PEG segments are employed for inhibiting proteins and bacterial adhesion. In addition, due to the presence of both PAsp and ALN, a synergistically strong binding capacity could be achieved with the tooth surface, thus promoting rapid and thorough remineralization in situ, while maintaining excellent safety. The combination treatment can significantly suppress the biofilm formation, which is beneficial for alleviating the demineralization of enamels caused by bacteria, and further, facilitate remineralization in situ. This approach thus demonstrates the potential of the copolymer PEG-PAsp-ALN coating as a multifunctional protecting layer on the tooth surface for high-efficiency prevention and treatment of dental caries.

Targeted poly(L-glutamic acid)-based hybrid peptosomes co-loaded with doxorubicin and USPIONs as a theranostic platform for metastatic breast cancer

Peptosomes, as a vesicular polypeptide-based system and a versatile carrier for co-delivery of hydrophilic and hydrophobic materials, provide great delivery opportunities due to the intrinsic biocompatibility and biodegradability of the polypeptides backbone. In the current study, a novel poly(L-glutamic acid)-block-polylactic acid di-block copolymer (PGA-PLA) was synthesized in two steps. Firstly, γ-benzyl L-glutamate-N-carboxy anhydride (BLG-NCA) and 3,6-dimethyl-1,4-dioxane-2,5-dione were polymerized using N-hexylamine and benzyl alcohol as initiators to produce poly(γ-benzyl L-glutamate (PBLG) and polylactic acid. Then, PBLG was deprotected to produce PGA. Secondly, PGA was conjugated to the benzyl-PLGA to fabricate PGA-PLA diblock copolymer. The synthesized diblock copolymer was used for the encapsulation of doxorubicin, as hydrophilic anticancer and ultra-small superparamagnetic iron oxide nanoparticles (USPIONs) as hydrophobic contrast agent within aqueous core and bilayer of vesicular peptosome, respectively via double emulsion method. The prepared peptosomes (Pep@USPIONs-DOX) controlled the release of DOX (<15 % of the encapsulated DOX release up to 240 h of incubation at the physiological conditions) while increasing the stability and solubility of the hydrophobic USPIONs. Then, AS1411 DNA aptamer was decorated on the surface of the PGA-PLA peptosomes (Apt-Pep@USPIONs-DOX). The prepared targeted and non-targeted platforms showed spherical morphology with hydrodynamic sizes of 265 ± 52 and 229 ± 44 nm respectively. In vitro cellular cytotoxicity and cellular uptake were studied in nucleolin positive (4T1) and nucleolin negative (CHO) cell lines. Cellular uptake of the targeted formulation was greater than that of non-targeted peptosome, while cellular internalization of these peptosomes was identical in CHO cells. Moreover, targeted peptosomes showed greater toxicity than non-targeted peptosome in 4T1 cell line. The prepared theranostic targeted peptosomes demonstrated improved capability in terms of survival rate, biodistribution, tumor suppression efficiency, and MR imaging in the 4T1 tumor-bearing mice.

Phosphorus-containing smart, multifunctional polymers towards materials with dual stimuli responsivity, self-aggregation ability and tunable wettability

A simple, inexpensive and recyclable photo-induced reversible deactivation radical polymerization (RDRP) of a phosphorus-containing monomer, dimethyl(methacryloyloxymethyl) phosphonate (MAPC1) in ionic liquid (without the need for any conventional photoinitiators or dye sensitizers) is developed for the first time to produce low dispersity (Đ ≤ 1.24) phosphorus-containing polymer, PMAPC1 (at least up to 20200 g mol−1) and a series of well-defined multifunctional PMAPC1-b-poly(M) diblock copolymers (where “M” represents polyethylene glycol methacrylate (PEGMA), 2,2,3,3,4,4,5,5-octafluoropentylacrylate (OFPA) and 2-hydroxyethyl methacrylate (HEMA)) thereof. Kinetic monitoring of the photoRDRP of MAPC1 demonstrated good control of the polymerization. Temporal control, catalyst and ionic liquid recyclability of the polymerization was also demonstrated. The synthesized PMAPC1-b-PPEGMA diblock copolymers exhibited a dual (pH and temperature) stimuli-responsive behavior. Cloud point of PMAPC1-b-PPEGMA diblock copolymers can be tuned by changing the PEGMA mol% in the BCP. Amphiphilic PMAPC1-b-PHEMA diblock copolymer undergoes self-aggregation forming spherical nanoobjects. Phosphonate ester moieties of the synthesized diblock copolymers were selectively hydrolyzed to promising PMAPC1(OH)2-b-poly(M) diblock copolymers that could be used for many applications, including dual stimuli-responsive materials, materials with tunable hydrophobicity, and self-aggregation ability.

Single‐Step Expeditious Synthesis of Diblock Copolymers with Different Morphologies by Lewis Pair Polymerization‐Induced Self‐Assembly

AbstractLewis pair polymerization has demonstrated its unique advantages and powerful capability in polymer synthesis. Here we employ strong nucleophilicN‐heterocyclic olefin (NHO) and bulky organoaluminum to construct a frustrated Lewis pair, which can realize the compounded sequence control (CSC) copolymerization and self‐assembly the mixture of dimethylaminoethyl acrylate and fluoride‐functionalized methacrylate into diblock copolymers (di‐BCPs) nano‐assemblies through polymerization‐induced self‐assembly in one‐pot, single‐step manner within minutes. These di‐BCPs were characterized by1H and13C NMR, GPC, DSC, and TEM. By utilizing appropriate solvophilic block and solvophobic block, such Lewis pair polymerization‐induced self‐assembly strategy enables the expeditious, room‐temperature synthesis of di‐BCP nanoparticles with different morphologies, including spheres, worms, vesicles, and even fibers, thus suggesting the great application potential of such method in the future.

Single‐Step Expeditious Synthesis of Diblock Copolymers with Different Morphologies by Lewis Pair Polymerization‐Induced Self‐Assembly

Lewis pair polymerization has demonstrated its unique advantages and powerful capability in polymer synthesis. Here we employ strong nucleophilic N-heterocyclic olefin (NHO) and bulky organoaluminum to construct a frustrated Lewis pair, which can realize the compounded sequence control (CSC) copolymerization and self-assembly the mixture of dimethylaminoethyl acrylate and fluoride-functionalized methacrylate into diblock copolymers (di-BCPs) nano-assemblies through polymerization-induced self-assembly in one-pot, single-step manner within minutes. These di-BCPs were characterized by 1 H and 13 C NMR, GPC, DSC, and TEM. By utilizing appropriate solvophilic block and solvophobic block, such Lewis pair polymerization-induced self-assembly strategy enables the expeditious, room-temperature synthesis of di-BCP nanoparticles with different morphologies, including spheres, worms, vesicles, and even fibers, thus suggesting the great application potential of such method in the future.

Synthesis of styrene-norbornene diblock copolymers via ring-opening metathesis polymerization and nitroxide-mediated radical polymerization

Diblock copolymers containing polynorbornene (PNB) and polystyrene (PS) were synthesized by ring-opening metathesis polymerization (ROMP) and nitroxide-mediated radical polymerization (NMRP) approach. PNB containing nitroxide free radical was prepared by ROMP in presence of Grubbs 2nd generation catalyst and served as a macro-initiator for NMRP of styrene to achieve the targeting diblock copolymers. The effects of the chain transfer agent (CTA) concentration, catalyst amount, reaction time and reaction temperature on the synthesis of macro-initiator as well as the effects of mole ratio of monomer to macro-initiator and reaction time on the synthesis of diblock copolymers were studied. As a result, the diblock copolymers with Mn ranging from 5 kDa to 10 kDa and PDI ranging from 1.5 to 1.8 were obtained successfully. The desired diblock copolymers have broad applications in polymer electrolytes, nanoporous membranes and many other fields.

Organocatalytic, Stereoselective, Cationic Reversible Addition-Fragmentation Chain-Transfer Polymerization of Vinyl Ethers.

Tacticity is a crucial factor affecting the properties of synthetic polymer materials. Here, we introduce a type of chiral organic Brønsted acid catalyst, 1,1'-bi-2-naphthol-derived N,N'-bis(triflyl)phosphoramidimidates (PADIs), for the cationic polymerization of vinyl ethers, which enables the development of the first organocatalytic, highly stereoselective, cationic reversible addition-fragmentation chain-transfer (RAFT) polymerization of vinyl ethers with a trithiocarbonate chain-transfer agent. This metal-free RAFT process could afford isotactic poly(vinyl ethers) with high stereoselectivity, controllable molecular mass, and narrow dispersity at low catalyst loadings (as low as 200 ppm). Moreover, the trithiocarbonate chain-end allows for chain extension to synthesize diblock copolymers comprising an isotactic poly(vinyl ether) block, by a mechanistic switching from stereoselective cationic RAFT polymerization to visible-light-regulated cationic and radical RAFT polymerization.

Molecular and Structure-Properties Comparison of an Anionically Synthesized Diblock Copolymer of the PS-b-PI Sequence and Its Hydrogenated or Sulfonated Derivatives.

An approach to obtaining various nanostructures utilizing a well-studied polystyrene-b-poly(isoprene) or PS-b-PI diblock copolymer system through chemical modification reactions is reported. The complete hydrogenation and partial sulfonation to the susceptible carbon double bonds of the PI segment led to the preparation of [polystyrene-b-poly(ethylene-alt-propylene)] as well as [polystyrene-b-poly(sulfonated isoprene-co-isoprene)], respectively. The hydrogenation of the polyisoprene block results in enhanced segmental immiscibility, whereas the relative sulfonation induces an amphiphilic character in the final modified material. The successful synthesis of the pristine diblock copolymer through anionic polymerization and the relative chemical modification reactions were verified using several molecular and structural characterization techniques. The thin film structure–properties relationship was investigated using atomic force microscopy under various conditions such as different solvents and annealing temperatures. Small-angle X-ray scattering was employed to identify the different observed nanostructures and their evolution upon thermal annealing.

RAFT Polymerization of 2‐(tert‐Butoxycarbonyloxy)Ethyl Methacrylate and Transformation to Functional Polymers via Deprotection and the Subsequent Polymer Reactions

AbstractReversible addition–fragmentation chain transfer (RAFT) polymerization of 2‐(tert‐butoxycarbonyloxy)ethyl methacrylate (BHEMA) is carried out using 4‐cyano‐4‐((dodecylsulfanylthiocarbonyl)sulfanyl)pentanoic acid as the RAFT agent. The polymers with a controlled molecular weight and polydispersity are produced when a large amount of the RAFT agent is used. The RAFT polymerization of isobutyl methacrylate is also carried out using poly(2‐(tert‐butoxycarbonyloxy)ethyl methacrylate) (PBHEMA) as the macro‐RAFT agent in order to synthesize diblock copolymers with a narrow molecular weight distribution. It is revealed that the control of the polymerization of BHEMA is achieved under limited polymerization conditions. Then, the acid‐catalyzed deprotection of tert‐butoxycarbonyloxy groups of PBHEMA is performed in the presence of trifluoroacetic acid at room temperature to obtain polymers with a hydroxy group in the side chain. The hydroxy‐containing polymers are further reacted with 2‐isocyanatoethyl acrylate and methacrylate to synthesize precursor polymers used for a thermally curing system.

Synthesis of Poly(methacrylic acid)-block-Polystyrene Diblock Copolymers at High Solid Contents via RAFT Emulsion Polymerization.

The combination of polymerization–induced self-assembly (PISA) and reversible–addition fragmentation chain transfer (RAFT) emulsion polymerization offers a powerful technique to synthesize diblock copolymers and polymeric nanoparticles in a controlled manner. The RAFT emulsion diblock copolymerization of styrene and methacrylic acid (MAA) by using a trithiocarbonate as surfactant and RAFT agent was investigated. The Z-group of the RAFT agent was modified with a propyl-, butyl- and dodecyl- sidechain, increasing the hydrophobicity of the RAFT agent to offer well-controlled polymerization of poly(methacrylic acid)-block-polystyrene (PMAA-b-PS) diblock copolymers at high solid contents between 30–50 wt% in water. The kinetic data of the PMAA homopolymerization with the three different RAFT agents for various solvents was investigated as well as the RAFT emulsion polymerization of the diblock copolymers in pure water. While the polymerization of PMAA-b-PS with a propyl terminus as a Z-group suffered from slow polymerization rates at solid contents above 30 wt%, the polymerization with a dodecyl sidechain as a Z-group led to full conversion within 2 h, narrow molar mass distributions and all that at a remarkable solid content of up to 50 wt%.