Reversible Chain Transfer Agent Research Articles

Synthesis of Gemini‐Like Methyl Acrylate‐Acrylic Acid‐Methyl Acrylate Triblock Copolymers Surfactants by RAFT Polymerization in Solution and Investigation of their Behavior at the Air–Water Interface

AbstractA series of methyl acrylate‐acrylic acid amphiphilic triblock copolymers (PMA‐PAA‐PMA) were prepared by solution polymerization using S,S′‐bis (α,α‐dimethy1acetic acid) trithiocarbonate (BDAT) as a reversible addition fragmentation chain transfer (RAFT) agent and methyl acrylate (MA) as the first monomer. The triblock copolymers and their common MA homopolymer precursors were characterized in terms of their compositions, molecular weights and behavior at the air–water interface using 1H‐NMR spectroscopy, thermogravimetric analysis, gel permeation chromatography, surface tension, transmission electron microscopy (TEM) and dynamic light scattering respectively. The results indicated that PMA‐PAA‐PMA was successfully synthesized through RAFT polymerization. The polydispersity index (PDI) decreased when the molar ratio [n(MA)/n(AA)] increased, the lowest PDI was obtained at 5.23 wt% RAFT and the molecular weights were consistent with the theoretical value as the RAFT agent percentage varied. The polymer neutralized by sodium hydroxide solution shows a low critical micelle concentration (CMC), which was <10−2 mol L−1 in water. The Amin values increased and showed a maximum with decreased AA chain length. TEM showed that the neutralized polymer formed a special vesicle structure with large pore structure which led to a low CMC and surface tension of water.

Phosphinoyl and thiophosphinoylcarbodithioates: synthesis, molecular structure, and application as new efficient mediators for RAFT polymerization.

New phosphinoyl and thiophosphinoylcarbodithioates were synthesized in a one-pot reaction from the corresponding phosphinochalcogenides. Compounds of this new generation of thiocarbonylthio derivatives have been fully characterized by IR as well as (1)H, (31)P, and (13)C NMR spectroscopy and by mass spectrometry. Their solid-state structures reveal that they are isostructural but crystallize in different space groups. These new compounds are highly efficient reversible chain-transfer agents for the reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene (St) and n-butyl acrylate (nBA), with controlled number-average molecular weights (Mn) and narrow dispersity values (Ð<1.3). The controlled character of the polymerization was further exemplified by MALDI-TOF mass spectrometry and the synthesis of PSt-P(nBA) diblock copolymers.

Low-temperature reversible addition-fragmentation chain transfer (RAFT) polymerization of methyl methacrylate

Controlled/living radical polymerization of methyl methacrylate under the conditions of reversible addition-fragmentation chain transfer was performed. The reaction occurs at high rates, with the control over molecular-weight characteristics of poly(methyl methacrylate) preserved. The polymeric reversible chain-transfer agent exhibits high performance in polymerization of methyl methacrylate and in its block copolymerization with styrene.

Reversible addition-fragmentation chain transfer copolymerization of methyl methacrylate and methyl acrylate

Pseudo-living radical copolymerization of methyl methacrylate and methyl acrylate under reversible addition-fragmentation chain transfer in a mass in the presence of reversible chain transfer agents of different nature was implemented. A comparison of physical and mechanical properties of narrowly dispersed copolymers was performed as well as copolymers obtained by uncontrolled radical polymerization.

Controlling the molecular weight and polydispersity index of polystyrene by varying the initial parameters of addition-fragmentation radical polymerization

Numerical experiments are used to examine how the molecular mass and polydispersity index of polystyrene synthesized by controlled addition-fragmentation radical polymerization depend on various control parameters of the process, such as the temperature and initial concentrations of monomer, initiator, and reversible chain transfer agent.

Effect of macro-RAFT agent on the morphology of polymer dispersed liquid crystals

In this study, macro-(RAFT) reversible additional fragmental chain transfer agent prepared by reversible additional fragmental chain transfer polymerisation has been incorporated into polymer dispersed liquid crystals (PDLCs). The effects of concentration, molecular weight and glass transition temperature of macro-RAFT agent were studied in terms of morphology, polymerisation kinetics, molecular weight of polymer matrix and electro-optical properties of the films. It was found that the key factor influencing morphology was the mobility of macro-RAFT agent chain rather than polymerisation rate and molecular weight of polymer matrix. Furthermore, the decrease in the mobility of macro-RAFT agent chain caused less liquid crystal nematic fraction, smaller liquid crystal domain size and greater driving voltage.

Multi-stimuli responsive supramolecular diblock copolymers

A well-defined cyclobis(paraquat-p-phenylene) (CBPQT4+) end-functionalized poly(n-butyl acrylate) 3 was prepared via RAFT polymerization using a new trithiocarbonate CBPQT4+ derivative 2 as a reversible chain transfer agent. We have shown that the electron-poor CBPQT4+ moiety at the α-chain-end could be specifically modified by complex formation with various functionalized macromolecules featuring complementary electron rich end groups, thereby leading to the corresponding supramolecular diblock copolymers. The latter could be conveniently disassembled upon heating, by applying electrochemical redox processes or by the addition of a competing molecular guest. Furthermore, we can generate new diblock architectures upon the addition of an appropriately functionalized polymer. We also describe preliminarily results regarding the formation of nanostructured architectures both in solution and in thin films.

Synthesis of Telechelic Olefin Polymers via Catalyzed Chain Growth on Multinuclear Alkylene Zinc Compounds

Multinuclear alkylene zinc (MAZ) compounds of the type EtZn-(R″-Zn)n-Et (R″ = ethyl and propyl branched alkylene groups) were synthesized by a simple one-step procedure in nonpolar hydrocarbon solvents from α,ω-dienes (e.g., 1,7-octadiene or 1,9-decadiene) and diethylzinc using a bis(salicylaldiminato)Zr(IV) complex, [(2-methylcyclohexyl)N═CH(2-O-C6H3-3,5-di-tert-butyl)]2ZrMe2, as a catalyst. The MAZ serves as a divalent reversible chain-transfer agent for olefin polymerization, resulting in telechelic Zn-metalated polyolefins whose molecular weights are controllable over a wide range. The Zn-terminated telechelics serve as a polymer precursor for further reactions and can be converted into a variety of telechelic functionalized polyolefins in high yield.

Controlled synthesis of styrene-n-butyl acrylate copolymers with various chain microstructures mediated by dibenzyl trithiocarbonate

Copolymers of styrene and n-butyl acrylate are synthesized via pseudoliving radical copolymerization mediated by dibenzyl trithiocarbonate as a reversible addition fragmentation chain transfer agent. In a wide range of monomer feed compositions, narrowly dispersed compositionally uniform copolymers of desired molecular masses are formed, and their gradient structures are controlled by the compositions of the initial monomer feeds. The effects of the compositions, the chain microstructures, and the compositional homogeneity of the copolymers on their glass-transition temperatures are studied.

Determining the Mark–Houwink parameters of nitrile rubber: a chromatographic investigation of the NBR microstructure

The microstructure of acrylonitrile–butadiene rubber (NBR) was shown to be dependent on the polymerization conditions. The NBR investigated in the current study was obtained via radical copolymerization under azeotropic conditions (AN/BD = 38/62) in organic solution in the presence of either a conventional chain transfer agent or a reversible addition fragmentation chain transfer (RAFT) agent. The variation in the polymer microstructure was proven to originate from different radical environments during the polymerizations with initial radical initiator concentrations in the polymerizations studied ranging from 1.0 mM to 34.1 mM. The variation of the polymer microstructure was evidenced by triple SEC measurements, making use of the simultaneous determination of molecular weights with two independent methods, namely on-line viscometry and on-line light scattering. It is additionally evidenced that the microstructure shows a gradual variation during the course of a polymerization, a behaviour observed when the polymerizations were performed in the presence of an elevated initial radical initiator concentration. Furthermore, experimental evidence for the variation of the NBR microstructure during RAFT polymerizations is provided. At low conversions, a rather uniform polymer is obtained. With increasing conversion, a loss of the controlled character is observed and the microstructures approach those of nitrile rubber obtained by conventionally controlled free radical copolymerizations employing mercaptane transfer agents. Despite the differences in the polymer microstructure, it is possible to report a single set of MHKS parameters for the prepared NBR with azeotropic composition. A linear regression of the Mark–Houwink plots of the samples polymerized under different conditions gives values of K = (49.5 ± 5.5) × 10−5 dL g−1 and α = 0.689 ± 0.010 with a low error margin for SEC separation in THF at 25 °C. Weight average molecular weights of the investigated NBR samples were in the range of 40000 to 155000 g mol−1. The molecular weights of the copolymers determined via universal calibration with the MHKS parameters presented in the current study show a good agreement with molecular weights obtained from light scattering, underpinning the veracity of the obtained parameters.

Preparation of a Self-Crosslinking Resin System at Ambient Temperature

A reversible addition fragmentation chain transfer (RAFT) agent, 2-(dodecylthiocarbonothioylthio)propanoic acid (RAFT-1), was synthesized and characterized. Diacetone acrylamide and poly(ethylene glycol)methyl ether methacrylate were polymerized in the presence of RAFT-1 to give an amphiphilic polymer(RAFT-2). A very stable and narrowly-distributed emulsion was obtained by the micellization of the amphiphilic polymer in water. The self-crosslinking resin system was prepared by adding a crosslinker (adipic dihydrazide) to the prepared emulsion. Upon the evaporation of water of the emulsion, a tough and transparent crosslinked film was prepared, which had good water/solvent resistance and certain adhesiveness.

Classical and pseudoliving radical copolymerization of vinyl acetate and acrylic acid in methanol

The homogeneous free-radical copolymerization of vinyl acetate and acrylic acid is studied at 50 and 70°C in methanol with and without the reversible addition-fragmentation chain-transfer agent benzyl dithiobenzoate. It is shown that, under conditions of reversible addition-fragmentation chain-transfer copolymerization, the limiting conversion is 32% and the number-average molecular mass increases linearly with conversion. At the same time, in the absence of the reversible addition-fragmentation reversible chain-transfer agent, the conversion of the monomers amounts to 63% and the molecular mass of the copolymers decreases with conversion.

Protein Release from Biodegradable PolyHPMA-Lysozyme Conjugates Resulting in Bioactivity Enhancement

A novel biodegradable thiazolidine-2-thione functional chain transfer agent was synthesized and employed as a reversible additional fragmentation chain transfer agent to prepare well-defined semitelechelic poly-N-(2-hydroxypropyl) methacrylamides (polyHPMAs) with predetermined molecular weights and narrow polydispersities. The protein reactive group, thiazolidine-2-thione, was located at the polymer chain ends fixed by biodegradable disulfide bonds. The functional polyHPMA chains were subsequently conjugated to protein (lysozyme) by exploiting reactions between the thiazolidine-2-thione functionality and amine residues on the protein surface to form covalent amide linkages. The in vitro bioactivities of the lysozyme-polyHPMA conjugates were assessed by using Micrococcus lysodeikticus cells as substrates. The lysozyme bioactivity was significantly reduced following the conjugation procedure. However, cleavage of the polymer chains from the bioconjugates (under reducing conditions) yielded free protein and a remarkable recovery of bioactivity. In vivo tests were performed by subcutaneous injection into mice and clearly demonstrated decreased proteolytic degradation for the protein-polymer conjugate when compared with native protein, indicating effective protein protection through a conjugation strategy. This bioreversible approach to conjugation allows for a balance to be made between protein protection and effective bioactivity maintenance.

Growing poly(N‐vinylcarbazole) from the surface of graphene oxide via RAFT polymerization

AbstractA new approach on usage of S‐1‐dodecyl‐S′‐(α,α′‐dimethyl‐α″‐acetic acid)trithiocarbonate (DDAT)‐covalently functionalized graphene oxide (GO) as reversible addition fragmentation chain transfer (RAFT) agent for growing of poly(N‐vinylcarbazole) (PVK) directly from the surface of GO was described. The PVK polymer covalently grafted onto GO has Mn of 8.05 × 103, and a polydispersity of 1.43. The resulting material PVK‐GO shows a good solubility in organic solvents when compared to GO, and a significant energy bandgap of ∼2.49 eV. Bistable electrical switching and nonvolatile rewritable memory effect, with a turn‐on voltage of about −1.7 V and an ON/OFF state current ratio in excess of 103, are demonstrated in the Al/PVK‐GO/ITO structure. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

Chromium and Molybdenum Pentacarbonyl Complexes of Phosphinocarbodithioates: Synthesis, Molecular Structure and Behaviour in RAFT Polymerisation

Molybdenum and chromium pentacarbonyldiphenylphosphinocarbodithioate complexes have been prepared in a one-pot reaction from the corresponding metallocarbonyldiphenylphosphine. The complexes have been characterised by IR, (1)H, (31)P and (13)C NMR spectroscopies and by mass spectrometry. The solid-state structures of [Cr(CO)(5){PPh(2)CS(2)CH(Ph)CH(3)}] (1) and [Mo(CO)(5){PPh(2)CS(2)CH(Ph)CH(3)}] (2) are reported. Compounds 1 and 2 are isostructural and crystallise in the triclinic P1 space group. These new organometallic compounds are highly efficient reversible chain-transfer agents for reversible addition-fragmentation chain-transfer (RAFT) polymerisation of styrene (St) and n-butyl acrylate (nBA), with controlled number-average molar mass values and narrow dispersities (<1.2). The controlled character of the polymerisation was further exemplified by the synthesis of St and nBA diblock copolymers.

Metalloenzymatic radical polymerization using alkyl halides as initiators

A novel initiation strategy for enzyme-induced radical polymerization that makes use of alkyl halides is reported here. The approach is remarkably versatile and can be applied to emulsion polymerization as well as surface-initiated polymerization. The molecular weights of the polymers can be effectively regulated with either irreversible (i.e., L-cysteine) or reversible (i.e., 2-cyano-2-propyl dithiobenzoate) chain transfer agents, the latter resulting in a well-controlled, RAFT-type polymerization process.

Preparation of Self-Crosslinking Core-Shell Latex at Ambient Temperature

A reversible addition fragmentation chain transfer (RAFT) agent, 2- (dodecylthiocarbonothioylthio)propanoic acid (RAFT-1), was synthesized and characterized. Equimolar doses of acrylic acid (AA) and n-butyl acrylate were successively polymerized in the presence of RAFT-1 to give an amphiphilic macro RAFT agent (RAFT-2), which had a calculated average degree of polymerization of ten. Core-shell poly (butyl acrylate-co-diacetoneacrylamide) latex was prepared by using RAFT-2 as a reactive surfactant. The latex was narrowly distributed and very stable, which had a solid concentration as high as 45 wt.% and an average diameter of about 50 nm, Latex films were prepared with the core-shell emulsion and small amount of cross-linking agent, adipic dihydrazide. Results showed that cross-linking reaction occurred with the evaporation of water. The resulting cross-linked latex film was tough and transparent.

Synthesis of core–shell polystyrene nanoparticles by surfactant free emulsion polymerization using macro-RAFT agent

Novel approach for the synthesis of core–shell polystyrene nanoparticles by living hydrophilic polymer consisting of thiocarbonyl thio end group is reported. The surfactant free emulsion polymerization of styrene in the presence of macro-RAFT (reversible addition fragmentation chain transfer) agent is carried out to synthesize stable latex particles with smaller particle size. A macro-RAFT agent is prepared by homopolymerization of sodium styrene sulfonate (NaSS) in aqueous phase by using dithioester as chain transfer agent. This synthesized polystyrene sulfonate–sodium (PSS–Na) based macro-RAFT agent, which is essentially water soluble macromolecular chain transfer agent used for the surfactant-free batch emulsion polymerization of styrene. Transmission electron microscopy (TEM) study of the synthesized colloids shows the narrow particle size distribution with core–shell morphology.

Cleavage of polystyrene-b -poly(ethylene oxide) block copolymers with a trithiocarbonate linkage in solutions

In this work, the polystyrene-b-poly(ethylene oxide) (PS-b-PEO) block copolymers with a trithiocarbonate group between the blocks were prepared by polymerization of styrene in the presence of a trithiocarbonate reversible addition fragmentation chain transfer (RAFT) agent connected with PEO. Decomposition of the trithiocarbonate group by UV irradiation was investigated in three different types of solvent: tetrahydrofuran (THF, common solvent for both blocks), cyclohexane/dioxane mixture (selective solvent for the PS block) and N,N-dimethylformamide (DMF)/ethanol mixture (selective solvent for the PEO block). It is found that cleavage of the block copolymers can take place in all these three solvents and the cleavage ratio ranges from 76 to 86%. The micellar morphologies in selective solvents before and after cleavage were examined. It is observed that the size of the micelles is reduced after cleavage and sometimes aggregation of the micelles occurs due to removal of the corona of micelles. It shows that this work provides a facile and general method for synthesis of cleavable block copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3834–3840, 2010

Controlled radical polymerization of N‐vinylphthalimide using carboxyl‐terminated trithiocarbonate as RAFT agent and preparation of microfibers via electrospinning technique

AbstractReversible addition‐fragmentation chain transfer (RAFT) polymerization of N‐vinylphthalimide in N,N‐dimethylformamide (DMF) solution was carried out using 2‐carboxypropan‐2‐yl dodecyl trithiocarbonate as a reversible chain transfer agent in the presence of 2,2′‐azobisisobutyronitrile. The molecular weights of the polymers increased linearly with the monomer conversion and the molecular weight distributions were relatively narrow (PDI &lt; 1.2). It is confirmed by chain extension reaction that the polymer prepared via RAFT polymerization can be used as a macro‐RAFT agent. The structure of both polymers was characterized and confirmed by size‐exclusion chromatography and 1H‐NMR techniques. Ultrafine microfibers were prepared by electrospinning of poly(N‐vinylphthalimide) in DMF solution. The effects of electrospinning process parameters such as voltage, tip‐to‐collector distance, and solution concentration on the morphology and the average size of the electrospun fibers were studied. To evaluate the fiber diameters, scanning electron microscope micrographs of the microfibers were performed. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010