Reversible Addition-fragmentation Chain Transfer Polymerization Of Styrene Research Articles

RAFT Polymerization of Styrene with Potassium Ethylxanthate as the Chain Transfer Agent

Using potassium ethylxanthate as the chain transfer agent, 2,2’-azobis(isobutyronitrile) (AIBN) as the initiator, reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene was carried out. The influences of reaction temperature, reaction time, and the amounts of the initiator and chain transfer agent on the RAFT polymerization were investigated in terms of monomer conversion, average number molecular weight (Mn) and molecular weight distribution (Ð) of the obtained polymer. Monomer conversion and the Mn of the obtained polystyrene (PS) improved with an increase in the reaction temperature, and the polymerization kinetics exhibited a highly linear relationship, indicating a first-order reaction. When the amounts of the initiator and chain transfer agent were increased, it led to a decreased Mn of the produced PS. Meanwhile, the Ð of the PS was in a relatively narrow range (1.42-1.89). The chain-end functionality was further demonstrated by adding methyl methacrylate to the PS.

Polystyrene-attached graphene oxide with different graft densities via reversible addition-fragmentation chain transfer polymerization and grafting through approach

Graphene oxide (GO) modified with double bond was utilized in grafting polystyrene chains to its surface through reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene. For this purpose, 3-(((2-aminoethyl)amino)dimethylsilyl)propyl methacrylate (OD) including double bond and amine groups was prepared and used for modification of GO in different grafting densities by a ring-opening nucleophilic reaction. Then, polystyrene-grafted GO was obtained by “grafting through” RAFT polymerization of styrene. Successful using of RAFT polymerization, efficiency of the grafting reaction, different characteristics of the graphene-attached and free polystyrene chains were investigated. Proton nuclear magnetic resonance spectroscopy confirmed successful synthesis of OD. Its grafting on GO was also confirmed by using X-ray photoelectron spectroscopy. The neat and modified GO layers were also investigated by Fourier transform infrared and Raman spectroscopies. Size exclusion chromatography was used to study molecular weight and polydispersity index of the attached polystyrene chains. Thermogravimetric analysis provides degradation temperature, char content, and grafting ratio of the modifier and polystyrene chains. Grafting ratio of OD was 10.3 and 4.4% for the modified GO layers with high and low grafting densities, respectively. Layers morphology was visually studied by scanning and transmission electron microscopies. Flat and smooth graphite platelets were changed to wrinkled layers after oxidation, and converted to opaque layers after grafting with polystyrene chains. High length of small molecule modifier in this study resulted in highly efficient grafting reaction.

Partially Biosourced Poly(1,2,3-triazolium)-Based Diblock Copolymers Derived from Levulinic Acid

Partially biobased poly(1,2,3-triazolium)s are synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization of tailor-made 1,2,3-triazole-functionalized (meth)acrylate monomers derived from levulinic acid, followed by N-alkylation of the 1,2,3-triazole moieties by methyl iodide (CH3I) and subsequent anion exchange with lithium bis(trifluoromethylsulfonyl)imide (LiTFSI). Chain extension of a 1,2,3-triazole-functionalized polymethacrylate by RAFT polymerization of styrene followed by N-alkylation with CH3I and anion exchange with LiTFSI affords two poly(1,2,3-triazole)- and two poly(1,2,3-triazolium)-based diblock copolymers (BCPs) with different weight fractions of each block. Discussion of the structure/properties relationships of all obtained materials is based on NMR spectroscopy, size exclusion chromatography, differential scanning calorimetry, thermogravimetric analysis, and broadband dielectric spectroscopy. The morphological and self-assembling properties of neutral and char...

Versatile method via reversible addition-fragmentation transfer polymerization for synthesis of poly styrene/ZnO-nanocomposite

Reversible addition-fragmentation chain transfer (RAFT) polymerization enables the synthesis of controlled architectures for a wide-variety of polymers with defined end and pendant functionalities using mild conditions. A simple synthetic route for the preparation of polystyrene (PS)/ZnO nanocomposite with well-defined structure is demonstrated. ZnO nanoparticles were synthesized by homogeneous precipitation. To reduce the aggregation among ZnO nanoparticles, an effective surface modification method was proposed by grafting polystyrene onto the ZnO particles. The surface of ZnO nanoparticles was firstly treated with a 4-cyano-4-[(4-methoxyphenyl carbon thiol) solfanylvaleric acid] coupling RAFT agent in the presence of THF as a solvent at 65°C. A carboxylic group in raft agent attached to ZnO nanoparticles by the esterification reaction with the hydroxyl groups on the ZnO particle surface. Then, RAFT polymerization of styrene was subsequently conducted to graft PS onto the exterior surface of ZnO nanoparticles by new RAFT agent 4-cyano-4-[(4-methoxyphenyl carbon thiol) solfanylvaleric acid]. The obtained nanocomposite was characterized by Fourier transform infrared spectroscopy (FT-IR), thermo gravimetric (TGA), transmission electron microscopy (TEM), and X-ray powder diffraction (XRD). POLYM. ENG. SCI., 56:187–195, 2016. © 2015 Society of Plastics Engineers

Controlled Radical Polymerization Using a Novel Symmetrical Selenium RAFT Agent

A novel symmetrical selenium-based reversible addition-fragmentation chain transfer (RAFT) agent, Se,Se’-dibenzyl carbonodiselenothioate (Se-RAFT), is synthesized and used in the RAFT polymerization of styrene. The results obtained show that the Se-RAFT agent is involved in the polymerization of styrene, as evidenced by narrow molar-mass distributions (M¯w/M¯n < 1.6) and the incorporation of the Se-RAFT moiety into the resultant polymer. The latter is confirmed by aminolysis, NMR spectroscopy, size-exclusion chromatography (SEC) and UV spectroscopy. This work provides detailed insight into the Se-RAFT polymerization mechanism. The Se-RAFT agent is unique in that the stabilizing and leaving groups are identical.

Photo-Induced Functionalization of Spherical and Planar Surfaces via Caged Thioaldehyde End-Functional Polymers

The synthesis and application of a novel reversible addition-fragmentation chain transfer (RAFT) agent carrying a photocaged thioaldehyde moiety is described (λmax = 355 nm). RAFT polymerization of styrene, dimethylacrylamide and a glycomonomer is evidenced (3600 g mol−1 ≤ Mn ≤ 15 000 g mol−1; 1.07 ≤ Đ ≤ 1.20) with excellent end-group fidelity. The photogenerated thioaldehyde on the chain ends can undergo hetero Diels–Alder reactions with dienes as well as reactions with nucleophiles. The terminal photoreactive polymers are photografted to porous diene-reactive polymeric microspheres. The grafted particles are in-depth characterized via scanning electron microscopy, elemental analysis, X-ray photoelectron spectroscopy, and high resolution FT-IR microscopy, leading to a qualitative as well as quantitative image of the core–shell objects. Grafting densities up to 0.10 molecules nm−2 are reached. The versatility of the thioaldehyde ligation is evidenced by spatially resolved grafting of polystyrene onto nucleophilic groups present in poly (dopamine) (PDA)-coated glass slides and silicon wafers via two-photon direct laser writing (DLW) imaged by ToF-SIMS. The combination of thioaldehyde ligation, RAFT polymerization, and DLW allows for the spatially resolved grafting of a vast range of polymers onto various substrates in any desired pattern with sub-micrometer resolution.

The influence of intermediate radical termination and fragmentation on controlled polymer synthesis via RAFT polymerization

Reversible addition-fragmentation chain transfer (RAFT) polymerization allows the design of tailored polymers by inducing addition and fragmentation reactions via a powerful kinetic mechanism; the process, however, is not well understood. A parametric analysis was conducted in conjunction with experimental data to provide insights into the RAFT mechanism, accounting for the key kinetics events in RAFT polymerization of styrene. The effects of overall, forward and backward fragmentations of intermediate radicals were analysed with experimental data and sensitivity investigations. Our results show that the intermediate radicals undergo relatively fast fragmentation and that the radical cleavage is symmetrical. These factors, critical in design and control, were found to profoundly influence the process kinetics and the final polymer product attributes.

Controlled One‐Pot Synthesis of Polystyrene‐block‐Polycaprolactone Copolymers by Simultaneous RAFT and ROP

A convenient one‐pot method for the controlled synthesis of polystyrene‐block‐polycaprolactone (PS‐b‐PCL) copolymers by simultaneous reversible addition–fragmentation chain transfer (RAFT) and ring‐opening polymerization (ROP) processes is reported. The strategy involves the use of 2‐(benzylsulfanylthiocarbonylsulfanyl)ethanol (1) for the dual roles of chain transfer agent (CTA) in the RAFT polymerization of styrene and co‐initiator in the ROP of ε‐caprolactone. One‐pot poly­merizations using the electrochemically stable ROP catalyst diphenyl phosphate (DPP) yield well‐defined PS‐b‐PCL in a relatively short reaction time (≈4 h; = 9600−43 600 g mol−1; / = 1.21−1.57). Because the hydroxyl group is strategically located on the Z substituent of the CTA, segments of these diblock copolymers are connected through a trithiocarbonate group, thus offering an easy way for subsequent growth of a third segment between PS and PCL. In contrast, an oxidatively unstable Sn(Oct)2 ROP catalyst reacts with (1) leading to multimodal distributions of polymer chains with variable composition. image

Polymethylene‐block‐polystyrene copolymers: A new synthetic approach using a combination of polyhomologation and reversible addition‐fragmentation chain‐transfer polymerization and their microfibers and microspheres fabricated through electrospinning process

ABSTRACTWell‐defined polymethylene‐block‐polystyrene (PM‐b‐PS) diblock copolymers were synthesized via a combination of polyhomologation of ylides and reversible addition‐fragmentation chain‐transfer (RAFT) polymerization of styrene. Trithiocarbonate‐terminated polymethylenes (PM‐TTCB) (Mn = 1400 g mol−1; Mw/Mn = 1.09 and Mn = 2100 g mol−1; Mw/Mn = 1.20) were obtained via an esterification of S−1‐dodecyl‐S′‐(α,α′‐dimethyl‐α″‐acetate) trithiocarbonate with hydroxyl‐terminated polymethylene synthesized via polyhomologation of ylides followed by oxidation. Then, a series of PM‐b‐PS (Mn = 5500–34,000 g mol−1; Mw/Mn = 1.12–1.25) diblock copolymers were obtained by RAFT polymerization of styrene using PM‐TTCB as a macromolecular chain‐transfer agent. The chain structures of all the polymers were characterized by proton nuclear magnetic resonance (1H NMR), gel permeation chromatography, and Fourier transform infrared spectroscopy. The thiocarbonylthio end‐group of PM‐b‐PS was transformed into thiol group by aminolysis and confirmed by UV–vis spectroscopy. In addition, microfibers and microspheres of such diblock copolymers were fabricated by electrospinning process and observed by scanning electron microscopy (SEM). © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2892–2899

Effect of MCM-41 nanoparticles on the kinetics of free radical and RAFT polymerization of styrene

To examine the effect of mobil composition of matter 41 (MCM-41) nanoparticles on the kinetics of free radical and 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (DDMAT)-mediated reversible addition fragmentation chain transfer (RAFT) polymerization, the polymerization reaction using various amounts of as-synthesized MCM-41 were performed. To study the reaction kinetics, conversion, molecular weight and polydispersity index (PDI) were obtained during the polymerization. Also, differential scanning calorimetry (DSC) was used to determine the glass transition temperature (T g) values of samples. According to the results, in free radical polymerization, conversion was increased by adding nanoparticles but the reverse trend was observed in RAFT polymerization. The same results were obtained for molecular weight values. In free radical polymerization, increasing the MCM-41 content led to higher PDI value, while in RAFT polymerization it did not appreciably affect the PDI value. In RAFT polymerization, no induction time was observed which indicates that DDMAT is an appropriate RAFT agent for styrene polymerization. Also in free radical polymerization, the addition of MCM-41 particles reduced T g values in comparison to neat PS. On the other hand, there was an increase in T g value up to 5 wt% of MCM-41 loading and a drastic reduction was observed in 7 wt% MCM-41 loading in the RAFT polymerization. Finally, the T g values of nanocomposites produced by RAFT method were higher than those in the nanocomposites synthesized using the free radical method.

Size-Tunable Nanoparticle Synthesis by RAFT Polymerization in CO2-Induced Miniemulsions

A novel environmentally friendly low-energy emulsification method that relies on pressurization with CO2 to low pressure has been applied to reversible addition–fragmentation chain transfer (RAFT) polymerization of styrene-in-water miniemulsions with the anionic surfactant Dowfax 8390. This method circumvents traditional high-energy homogenization, and over a certain CO2 pressure range, a transparent miniemulsion is formed. RAFT polymerization of styrene using benzyldodecyl trithiocarbonate and the aqueous phase initiator VA-044 was carried out successfully in CO2-induced miniemulsions at 50 °C with good control/livingness. Interestingly, the particle size could be conveniently tuned via the CO2 pressure without altering the recipe, with 6.00, 6.50, and 7.50 MPa generating number-average particle diameters of 98, 89, and 48 nm, respectively, at ∼70% conversion. The smallest particle size corresponded to the pressure range within which the emulsion was transparent.

Reversible addition-fragmentation chain transfer polymerization of a typical hydrophobic monomer of styrene within microreactor of shell-corona hollow microspheres suspending in water

Reversible addition-fragmentation chain transfer (RAFT) polymerization of a typical hydrophobic monomer of styrene within microreactor of shell-corona hollow microspheres of poly(styrene-co-methacrylic acid) suspending in water is studied. The shell-corona hollow microspheres contain a hydrophilic corona of poly(methacrylic acid) (PMAA) and a cross-linked polystyrene shell, which can suspend in water because of the hydrophilic corona of PMAA. The size of the shell-corona hollow microspheres is about 289 nm and the extent of the microcavity of the hollow microsphere is 154 nm. These shell-corona hollow microspheres can act as microreactor, within which the typical hydrophobic monomer of styrene, the RAFT agent of S-benzyl dithiobenzoate and the initiator of 2,2′-azobisisobutyronitrile can be encapsulated and RAFT polymerization of styrene takes place in well controlled manner in water. It is found that the resultant polymer of polystyrene has a competitively low polydispersity index and its number-average molecular weight linearly increases with monomer conversion. The method is believed to be a new strategy of RAFT polymerization of hydrophobic monomer in aqueous solution. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

Synthesis of Poly(vinyl acetate)-b-polystyrene and Poly(vinyl alcohol)-b-polystyrene Copolymers by a Combination of Cobalt-Mediated Radical Polymerization and RAFT Polymerization

Well-defined poly(vinyl acetate)-block-polystyrene (PVAc-b-PSt) block copolymers were successfully synthesized by a combination of cobalt-mediated radical polymerization (CMRP) and reversible addition−fragmentation chain transfer (RAFT) polymerization. PVAc and PVAc-b-PSt (with an average PSt repeating unit of 2 or 6) were first synthesized via CMRP with cobalt(II) acetylacetonate as a regulating agent. The cobalt complexes attached to their ω chain ends were modified into a phenyl dithioester group by reacting with bis(thiobenzoyl) disulfide, producing PVAc and PVAc-b-PSt macro-chain-transfer agents (PVAc-CTA and PVAc-PSt-CTA), respectively. The RAFT polymerization of styrene with PVAc-CTA or PVAc-PSt-CTA was conducted in N,N-dimethylformamide at 80 °C. PVAc-b-PSt block copolymers synthesized with PVAc-PSt6-CTA (with an average PSt repeating unit of 6) exhibited narrowest molecular weight distributions (Mw/Mn = 1.28−1.30) even at high conversions. The PVAc-b-PSt block copolymer (Mn(GPC) = 21 000 g/mol, M...

Effect of stabilizer concentration and controller structure and composition on polymerization rate and molecular weight development in RAFT polymerization of styrene in supercritical carbon dioxide

An experimental study on the reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene in supercritical carbon dioxide is presented. A 38 mL, high-pressure view cell with two frontal and two lateral sapphire windows was used as reactor. Poly(styrene-block-dimethylsiloxane) was used as stabilizer. The performance as RAFT controllers of S-thiobenzoyl thioglycolic acid, methyl naphthalene dithiobenzoate, 4-methyl allyl dithiobenzoate, and benzyl-N,N-dimethyldithiocarbamate was compared. The effect of stabilizer concentration and controller structure and concentration on polymerization rate and molecular weight development was analyzed. Good performance was obtained with the first three controllers, although simultaneous high polymerization rates and low polydispersities were not possible with either of them. The performance of the fourth RAFT controller was poor.

Synthesis of Well‐Defined Polybenzamide‐block‐Polystyrene by Combination of Chain‐Growth Condensation Polymerization and RAFT Polymerization

Well-defined diblock copolymers composed of poly(N-octylbenzamide) and polystyrene were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization of styrene with a polyamide chain transfer agent (CTA) prepared via chain-growth condensation polymerization. Synthesis of a dithioester-type macro-CTA possessing the polyamide segment as an activating group was unsatisfactory due to side reactions and incomplete introduction of the benzyl dithiocarbonyl unit. On the other hand, a dithiobenzoate-CTA containing poly(N-octylbenzamide) as a radical leaving group was easily synthesized, and the RAFT polymerization of styrene with this CTA afforded poly(N-octylbenzamide)-block-polystyrene with controlled molecular weight and narrow polydispersity.

Synthesis and self-assembly behaviors of three-armed amphiphilic block copolymers via RAFT polymerization

The novel trifunctional reversible addition–fragmentation chain transfer (RAFT) agent, tris(1-phenylethyl) 1,3,5-triazine-2,4,6-triyl trithiocarbonate (TTA), was synthesized and used to prepare the three-armed polystyrene (PS3) via RAFT polymerization of styrene (St) in bulk with thermal initiation. The polymerization kinetic plot was first order and the molecular weights of polymers increased with the monomer conversions with narrow molecular weight distributions (Mw/Mn≤1.23). The number of arms of the star PS was analyzed by gel permeation chromatography (GPC), ultraviolet visible (UV–vis) and fluorescence spectra. Furthermore, poly(styrene-b-N-isopropylacrylamide)3 (PS-b-PNIPAAM)3, the three-armed amphiphilic thermosensitive block copolymer, with controlled molecular weight and well-defined structure was also successfully prepared via RAFT chain extension method using the three-armed PS obtained as the macro-RAFT agent and N-isopropylacrylamide as the second monomer. The copolymers obtained were characterized by GPC and 1H nuclear magnetic resonance (NMR) spectra. The self-assembly behaviors of the three-armed amphiphilic block copolymers (PS-b-PNIPAAM)3 in mixed solution (DMF/CH3OH) were also investigated by high performance particle sizer (HPPS) and transmission electron microscopy (TEM). Interestingly, the lower critical solution temperature (LCST) of aqueous solutions of the three-armed amphiphilic block copolymers (PS-b-PNIPAAM)3 decreased with the increase of relative length of PS in the block copolymers.

Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization of Vinyl Monomers Initiated by Poly(methyl methacrylate) Peroxide

AbstractPoly(methyl methacrylate) peroxide (PMMAP) was synthesized and used as the initiator in the reversible addition-fragmentation chain transfer (RAFT) polymerization. Methyl methacrylate (MMA) as the monomer and 2-cyanoprop-2-yl 1-dithionaphthalate (CPDN) as the chain transfer agent was used in the polymerization system. The polymerization was successfully initiated by PMMAP while maintaining features of “living”/controlled radical polymerization such as the number-average molecular weights (Mn) increasing linearly with the monomer conversions and low polydispersity index (PDI) values. The results of 1H NMR and IR spectra confirmed that a small quantity of polymer chains were derived from the PMMAP moieties. The PMMAP can also initiate the RAFT polymerization of styrene (St) and methyl acrylate (MA), and the polymerization proceeded in a “living”/controlled fashion.

Reversible addition‐fragmentation chain transfer (RAFT) polymerization of styrene using novel heterocycle‐containing chain transfer agents

AbstractBACKGROUND: Controlled/‘living’ radical polymerization is a new and robust method to synthesize polymers with predetermined molecular weight, narrow polydispersity and tailored architecture. Several methods have been developed but reversible addition‐fragmentation chain transfer (RAFT) has several advantages over the other methods. It has been reported that the effectiveness of RAFT agents depends strongly on the nature of the Z and R groups.RESULTS: Three new dithiocarbamates, namely (2‐ethoxy carbonyl)‐prop‐2‐yl‐pyrrole‐1‐carbodithioate (CTA‐A), (1‐phenyl ethyl)‐pyrazole‐1‐carbodithioate (CTA‐B) and (2‐ethoxy carbonyl)‐prop‐2‐yl‐pyrazole‐1‐carbodithioate (CTA‐C), were synthesized for studying the effect of the Z and R group of a chain transfer agent on the RAFT polymerization of styrene, initiated by 2,2′‐azobisisobutyronitrile. Well‐controlled molecular weight with narrow polydispersity (1.10–1.46) was achieved. The increase in molecular weight with conversion is linear and follows first‐order kinetics.CONCLUSION: The detailed kinetic results show that the structure of the activating (Z) group of dithiocarbamates has significant effects on the reactivity of dithiocarbamates towards the polymerization of styrene. In the homopolymerization of styrene it was found that, from the polydispersity index of polystyrenes obtained and the kinetic results, the pyrazole‐based dithiocarbamates (CTA‐B and CTA‐C) are very effective compared to the pyrrole‐based dithiocarbamate (CTA‐A). All the polymerizations show controlled living characters. Copyright © 2007 Society of Chemical Industry

Grafting polymer nanoshell onto the exterior surface of mesoporous silica nanoparticles via surface reversible addition-fragmentation chain transfer polymerization

Reversible addition-fragmentation chain transfer (RAFT) functionalities were anchored to the exterior surface of mesoporous silica nanoparticles (MSNs) without changing the mesoporous structure, RAFT polymerization of styrene was subsequently conducted to graft polystyrene (PSt) onto the exterior surface of MSNs, forming a novel core–shell nanostructure with a mesoporous core and a polymer nanoshell. Fourier transform infrared spectroscopy (FT-IR), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA) were used to characterize the produced mesoporous core–shell nanostructure, the results showed that the thickness of the nanoshell increased with the increasing time of polymerization.

An ESR Approach to the Estimation of the Rate Constants of the Addition and Fragmentation Processes Involved in the RAFT Polymerization of Styrene

AbstractThe reversible‐addition‐fragmentation chain transfer (RAFT) controlled radical polymerization of such vinylic monomers as styrene (= ethenylbenzene) has gained increasing popularity in current years. While there is a general agreement on the mechanism of RAFT polymerization, there is an ongoing debate about the values of the rate constants of its key steps, i.e., the addition of the propagating radicals to the mediator and the fragmentation of the resulting spin adducts. By carrying out an ESR spectroscopic investigation of the AIBN‐initiated polymerization of styrene (AIBN = 2,2′‐azobis[2‐methylpropanenitrile]), mediated by benzyl (diethoxyphosphoryl)dithioformate (5) as RAFT agent, we were able to detect and characterize four different radical species involved in the process. By reproducing their concentration–time profiles through a kinetic model, the addition and fragmentation rate constants at 90° of the propagating radicals to and from the mediator were estimated to be ca.107 M−1 s−1 and ca. 103 s−1, respectively. The validity of the kinetic model was supported by hybrid meta DFT calculations with the BB1K functional that predicted addition‐ and fragmentation‐rate‐constant values in good agreement with those estimated from the ESR experiments.