RAFT Polymerization Of Styrene Research Articles

Seeded RAFT Polymerization of Styrene for the Synthesis of Stable Dispersions of Amphiphilic Block Copolymers and Composite Nanoparticles

Seeded RAFT Polymerization of Styrene for the Synthesis of Stable Dispersions of Amphiphilic Block Copolymers and Composite Nanoparticles

Controlling monomer sequence distribution in RAFT polymerization of styrene and acrylic acid

Continuous and semicontinuous RAFT copolymerization was first applied to synthesize well-defined copolymers of styrene and acrylic acid. The obtained copolymers have a different monomer sequence distribution due to different ways of adding acrylic acid to the reaction medium.

Syntheses of benzhydryl 2-propanoyl-functionalized trithiocarbonates and its use as chain transfer agents in the RAFT polymerization of styrene

Abstract The preparation of three new benzhydryl 2-propanoyl-functionalized trithiocarbonate RAFT agents, benzhydryl 2-(ethylsulfanylthiocarbonylsulfanyl)propanoate, benzhydryl 2-(butylsulfanylthiocarbonylsulfanyl)propanoate, benzhydryl 2-(dodecylsulfanylthiocarbonylsulfanyl)propanoate is described. The RAFT polymerization of styrene, mediated by the appropriate benzhydryl 2-(alkylsulfanylthiocarbonylsulfanyl)propanoate as the chain transfer agent, with AIBN as initiator at 70 0C, proceeds via reversible-deactivation radical polymerization processes to produce the corresponding α-benzhydryl 2-propanoyl polystyrene derivative, with the benzhydryl ester group introduced at the α-terminus of the polymer chain. Polymerization kinetics measurements show that each RAFT polymerization reaction follows first order rate kinetics with respect to percentage monomer consumption and the number average molecular weights of the functionalized polymers increase linearly with the percentage monomer conversion to produce functionalized polymers with narrow molecular weight distributions. The percentage monomer conversion with time for each polymerization reaction was monitored by 1H NMR spectroscopy by evaluating the consumption of styrene with respect to polymerization time. Post-RAFT polymerization chain end modification of α-benzhydryl 2-propanoyl-functionalized polystyrene by the acid catalyzed ester hydrolysis reactions with concentrated sulfuric acid afforded the corresponding α-carboxyl functionalized polystyrene derivative, with the retention of the thiocarbonylthio moiety at the ω-terminus of the polymer chain. The benzhydryl 2-propanoyl-functionalized trithiocarbonate chain transfer agents and the different functionalized polystyrene derivatives were characterized by 1H NMR, 13C NMR and FTIR spectroscopy, size exclusion chromatography, thin layer chromatography and mass spectrometry measurements.

RAFT polymerization of styrene mediated by naphthyl-functionalized trithiocarbonate RAFT agents

New oxazolyl benzhydryl and oxazolyl benzyl-functionalized trithiocarbonate RAFT agents, 1-(butylsulfanylthiocarbonylsulfanyl)-1-[4-(4,5-dihydro-4,4-dimethyl-2-oxazolyl)phenyl]-1-phenylmethane and 2-[4-((butylsulfanylthiocarbonylsulfanyl)methyl)phenyl]-4,5-dihydro-4,4-dimethyloxazole, were prepared and employed as chain transfer agents in RAFT polymerization reactions. The RAFT polymerization of styrene, mediated by the appropriate oxazolyl-functionalized trithiocarbonate RAFT agent with AIBN as initiator at 70 °C, proceeded via controlled/living polymerization processes to produce the corresponding α-oxazolyl-functionalized polystyrene derivative, with the oxazolyl group introduced at the α-terminus of the polymer chain and the absence of any unfunctionalized polystyrene. Post-RAFT polymerization chain end modification of α-oxazolyl-functionalized polystyrene by acid-catalyzed hydrolysis reactions with dilute hydrochloric acid afforded the corresponding α-carboxyl-functionalized polystyrene derivative, with the retention of the butylsulfanylthiocarbonylsulfanyl moiety at the ω-terminus of the polymer chain. Polymer kinetic measurements show that each RAFT polymerization reaction follows first-order rate kinetics with respect to the percentage monomer consumption. The oxazolyl-functionalized benzhydryl fragmentation radical provides better control of the re-initiation of the polymerization of styrene than the oxazolyl-functionalized benzyl fragmentation radical. After consumption of the RAFT agent, the number average molecular weights of the functionalized polymers increases linearly with the percentage monomer conversion to produce α-oxazolyl-functionalized polystyrene derivatives with narrow molecular weight distributions. New oxazolyl benzhydryl and oxazolyl benzyl-functionalized trithiocarbonate RAFT agents, 1-(butylsulfanylthiocarbonylsulfanyl)-1-[4-(4,5-dihydro-4,4-dimethyl-2-oxazolyl)phenyl]-1-phenylmethane and 2-[4-((butylsulfanylthiocarbonylsulfanyl)methyl)phenyl]-4,5-dihydro-4,4-dimethyloxazole, were prepared and employed as chain transfer agents in RAFT polymerization reactions. The RAFT polymerization of styrene, mediated by 1-(butylsulfanylthiocarbonylsulfanyl)-1-[4-(4,5-dihydro-4,4-dimethyl-2-oxazolyl)phenyl]-1-phenylmethane or 2-[4-((butylsulfanylthiocarbonylsulfanyl)methyl)phenyl]-4,5-dihydro-4,4-dimethyloxazole as chain transfer agents with AIBN as the initiator at 70 °C, proceeds via a controlled/living polymerization process to produce the corresponding α-oxazolyl-functionalized polystyrene derivative, with the oxazolyl group introduced at the α-terminus of the polymer chain.

Enhanced Control of Phosphinoylcarbodithioate-Mediated RAFT Polymerization: Key Role of Substituents at the Phosphorus Center

New phosphinoylcarbodithioate RAFT agents bearing dicyclohexyl- and di(piperidin-1-yl)phosphinoyl substituents were prepared, and their activity in RAFT polymerization of styrene and n-butyl acrylate was compared to that of previously reported diphenyl and bis(N,N-diisopropylamino) counterparts. Polymerizations were performed in deuterated solvent with quantitative 31P and 1H NMR monitoring. This approach allowed to study the polymer ω chain-end fidelity as well as RAFT agent transformations during the initialization period. It was also successfully applied for the monitoring of the block copolymerization. RAFT agents with cyclohexyl and piperidin-1-yl substituents bonded to the phosphorus center exhibited a marked improvement in the polymerization control with an optimal compromise between overall kinetics and control over molar masses and dispersities along with a significantly enhanced ω chain-end stability during polymerization.

One-Pot Modular Synthesis of Functionalized RAFT Agents Derived from a Single Thiolactone Precursor.

In this paper, the straightforward preparation of a range of functionalized trithiocarbonates as RAFT chain transfer agents (CTAs) is presented. The crucial step in the one-pot, three-step reaction sequence is the aminolysis of a thiolactone precursor as it introduces the desired functional handle (double bond, hydroxyl, furan, protected amine, ...) and generates the corresponding thiol in situ, facilitating further elaboration of the CTA. Furthermore, the newly synthesized trithiocarbonates were positively evaluated as mediators in the RAFT polymerization of styrene, isobornyl acrylate, and N-isopropylacrylamide, while the presence of the end groups in the heterotelechic polymers was confirmed by NMR and UV-vis analysis.

A grafting from approach to graft polystyrene chains at the surface of graphene nanolayers by RAFT polymerization: Various graft densities from hydroxyl groups

(3-Aminopropyl) triethoxysilane was grafted at the surface of GO in low and high different graft densities to yield GOHAL and GOHAH, respectively. Subsequently, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid (RA) was attached at the surface of GOHAL and GOHAH by an amidation reaction to yield GOHRL and GOHRH, respectively. Then, GOHRL and GOHRH were used in grafting from RAFT polymerization of styrene. Grafting of APTES and RA was approved by Fourier transform infrared spectroscopy, X-ray photo electron spectroscopy, and Raman spectroscopy. Expansion of graphene interlayer by oxidation and functionalization processes was evaluated by X-ray diffraction. Conversion values of styrene were calculated using gas chromatography. Molecular weight and PDI values of attached polystyrene (PS) chains were studied by size exclusion chromatography. Thermogravimetric analysis was also used to investigate the degradation temperatures, char contents, and graft contents of modifiers and PS chains. GOHRH and GOHRL reach to char content of 55.3 and 45.2% at 600°C, which shows that weight ratio of modifier (APTES and RA moieties) is 15.3 and 5.2%, respectively. Scanning and transmission electron microscopies show that graphite layers with flat and smooth surface wrinkled after oxidation and turned to opaque layers by grafting PS.

Initiator-chain transfer agent combo in the RAFT polymerization of styrene.

The combo agent with roles of initiator and chain transfer agent was demonstrated in RAFT polymerization of styrene. Polymers with defined structures at both α and ω ends were obtained, which was verified by the successful synthesis of seven-block segments of PS and PMA by sequential addition of monomers in one pot.

Interfacially confined RAFT miniemulsion copolymerization of styrene and butadiene

AbstractIn this study, ammonolyzed poly(styrene‐alt‐maleic anhydride) terminated with dithioester group can be self‐assembled into an amphiphilic macro‐reversible addition‐fragmentation chain transfer (RAFT) agent, and RAFT group will be located in the interface of oil and water. RAFT polymerization of styrene (S) and butadiene (B) will be confined in the interface. The main work is to study the effect of degree of aminolysis, reaction temperature, and ratio of S/B on the polymerization kinetics and living characters. The experimental results revealed that aminolysis of dithioester group would lead to retardation and loss of living characters under higher degree of aminolysis. Interfacially confined RAFT miniemulsion polymerizations were of relatively good controlled/living characters under lower degree of aminolysis before gelation. Increase of reaction temperature and ratio of S/B will accelerate the formation of gelation. Finally, styrene/butadiene copolymer nanoparticles with uniform particle size were formed, and because of microphase segregation “core–shell” morphology with polybutadiene core and polystyrene shell was seen obviously. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Visualization of arborescent architecture of polystyrenes prepared by raft-based initiator-monomer polymerization using atomic force microscopy

This article presents the utilization of “molecular amplification” to visualize the molecular architecture of “arborescent” (tree-like) polystyrenes (arbPSs) using atomic force microscopy (AFM). arbPSs with Mn > 80,000 g/mol were synthesized via initiator-monomer-type (inimer) RAFT polymerization of styrene mediated by 4-vinylbenzyl dithiobenzoate in bulk. These arbPS were then used as macrochain transfer agents for polymerization of vinylbenzyl chloride (VBCl) to give arborescent poly(styrene-block-vinylbenzyl chloride) (arbPS-b-VBCl). Poly(styryl) diphenylethyl lithium (Mn = 11,000 g/mol) was then grafted onto the VBCl units of the arbPS-b-VBCl. The Mn of the amplified arbPSs increased over >10 million g/mol, exceeding the exclusion limit of our size exclusion chromatography equipment. AFM confirmed the proposed branches on branches architecture in the samples, together with lesser branched species. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Separation and quantification of dead species in styrene RAFT polymerization by gradient polymer elution chromatography

In living polymerization, the inevitable dead chain impurities, due to bimolecular termination and side reactions, are not only an obstacle for the synthesis of pure block copolymers but also an impairment in the application performance of the resulting polymer materials. In this paper, a simple separation and quantification method based on gradient polymer elution chromatography (GPEC) was developed to experimentally investigate the dead species in RAFT polymerization of styrene. The RAFT-prepared polystyrene (PSt) was extended with methyl acrylate in a specially-designed chain extension reaction, in which the living PSt chains were extended and transformed into block copolymer, but the remaining dead PSt chains (D-PSt) will remain constant and can be separated and quantified by GPEC. The systematic experimental investigation of the effect of various polymerization parameters on the mass fraction of dead species (fD-PSt) in RAFT-prepared polystyrene (PSt) was implemented. The results clearly demonstrated the initiator concentration and RAFT agent concentration can exhibit a linear and inversely proportional dependence on fD-PSt, respectively. In addition, the dead chains were found to be formed throughout the entire RAFT process. These unambiguous experimental data confirmed the previous theoretical calculation and model prediction, which may be beneficial to understand RAFT processes, optimize polymerization conditions and to minimize dead polymer contaminations. Moreover, the method based on GPEC proposed here was able to fractionate and quantify the dead and living species, which can serve as a powerful tool in the mechanistic study of the living radical polymerizations.

Modeling of Polymerization Kinetics and Molecular Weight Development in the Microwave‐Activated RAFT Polymerization of Styrene

AbstractA kinetic model for polymerization rate and molecular weight development in the RAFT polymerization of styrene activated by microwave irradiation has been developed. The effect of microwave irradiation was modeled assuming that the monomer can decompose into free radicals, even at temperatures where thermal initiation is negligible. The typical reactions of RAFT polymerization were also included in the model. The model was validated using experimental data from the literature for the RAFT polymerization of styrene with and without AIBN as initiator, and using CPDN as RAFT agent. Overall, good agreement between model predictions and experimental data was obtained.magnified image

Substituent Effects on RAFT Polymerization with Benzyl Aryl Trithiocarbonates

AbstractThe RAFT polymerization of styrene in the presence of benzyl aryl trithiocarbonate RAFT agents (Z′SC(=S)SR) has been studied. The values of the apparent transfer constants $\left( {C_{{\rm tr}}^{{\rm app}} } \right)$ of the benzyl aryl trithiocarbonates (0.029 M) in bulk styrene polymerization at 110 °C fall within the range 10–25 depending on substituents on the aryl ring (Z′) and are higher than that of benzyl dodecyl trithiocarbonate 1 for which $C_{{\rm tr}}^{{\rm app}}$ was determined to be 9.4. There is a trend for higher transfer constant, lower dispersity product and better control over polymerization with more electron‐withdrawing substituents with the most active in the series studied being the 3,5‐bis(trifluoromethyl)phenyl derivative.magnified image

Carbazyl RAFT agents synthesized by an improved aqueous phase method and their applications in RAFT polymerization

A series of carbazyl dithiocarbamates as RAFT agents, i.e. benzyl 9H-carbazole-9-carbodithioate ( B), 1-phenylethyl 9H-carbazole-9-carbodithioate ( C), cumyl 9H-carbazole-9-carbodithioate ( D) and tert-butyl 9H-carbazole-9-carbodithioate ( E), were successfully synthesized by an improved aqueous phase method based on a nucleophilic substitution reaction between sodium carbazole-9-carbodithioate ( A) and alkyl halides at room temperature. Furthermore, the optimum reaction conditions and synthetic technology were sought. Compared with the traditional oil-phase method, the expected high-purity RAFT agents were obtained in the form of crystal that was precipitated and separated from the aqueous solution, so that vast organic solvents for purification were avoided. The activities of the carbazyl dithiocarbamates obtained as RAFT agents for the polymerizations of both styrene and methyl methacrylate were determined. The results show that all of the RAFT agents above mentioned are of significant activity in the RAFT polymerization of styrene, but only D has obvious activity in the RAFT polymerization of methyl methacrylate. Therefore, both the novel synthetic method and the carbazyl dithiocarbamates obtained possess potential application in the RAFT polymerization.

RAFT Polymerization of Styrene Using Dithioester with Anthracene Z Group as Chain Transfer Agent

AbstractA novel dithioester, bearing anthracene as Z group, benzyl anthracene-10-carbodithioate (BAC) was successfully synthesized and used as the RAFT agent for the RAFT polymerizations of styrene (St). The results indicated that the polymerization presented the characteristics of “living”/controlled radical polymerization. 1H NMR characterization of obtained polystyrene confirmed that most of the polymer chains were end-capped by the anthracene moiety. The successful chain extension experiment further demonstrated the “living” character of the polymer. The fluorescence investigation of the polymers contained an anthrancene moiety of BAC in the chain end expressed enhanced fluorescence property than that of BAC in CHCl3 solution.

Synthesis and characterization of tris(2,2′‐bipyridine)ruthenium‐cored star‐shaped polymers via RAFT polymerization

AbstractA new bipyridine‐functionalized dithioester was synthesized and further used as a RAFT agent in RAFT polymerization of styrene and N‐isopropylacrylamide. Kinetics analysis indicates that it is an efficient chain transfer agent for RAFT polymerization of the two monomers which produce polystyrene and poly(N‐isopropylacrylamide) polymers with predetermined molecular weights and low polydispersities in addition to the end functionality of bipyridine. The bipyridine end‐functionalized polymers were further used as macroligands for the preparation of star‐shaped metallopolymers. Hydrophobic polystyrene macroligand combined with hydrophiphilic poly(N‐isopropylacrylamide) was complexed with ruthenium ions to produce amphiphilic ruthenium‐cored star‐shaped metallopolymers. The structures of these synthesized metallopolymers were further elucidated by UV–vis, fluorescence, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC) as well as NMR techniques. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4225–4239, 2007

Synthesis and characterization of polystyrene- b-tetraaniline stars from polystyrene stars with surface reactive groups prepared by RAFT polymerization

Functionalized star polymers with tetraaniline on their surface have been successfully prepared by substitution reaction of N-succinimidyl-terminated star polymers with tetraaniline. A novel functional RAFT agent bearing N-succinimidyl group was used in the RAFT polymerization of styrene, and N-succinimidyl groups-terminated polystyrenes with narrow molecular weight distribution were obtained. The star polymers with reactive N-succinimidyl groups on their surface were synthesized via RAFT polymerization of DVB. Polymerization mechanism study by gel permeation chromatography displayed that complete disappearance of linear polymers in the products is difficult. The N-succinimidyl-terminated PSt, polymer stars with surface N-succinimidyl groups and the PSt- b-tetraaniline stars were characterized by 1H NMR spectroscopy, FT-IR and GPC.

RAFT Polymerization of Styrene in the Presence of 2‐Nonyl‐benzoimidazole‐1‐carbodithioic Acid Benzyl Ester

A novel dithiocarbamate, 2‐nonyl‐benzoimidazole‐1‐carbodithioic acid benzyl ester ( 1a ), was synthesized and successfully used in RAFT polymerization of styrene in bulk with thermal initiation. The effect of molar ratio of styrene to RAFT agent on the polymerization was investigated. The linear relationship between ln([M]0/[M]) and polymerization time indicated that the polymerization was first‐order with respect to monomer concentration. The molecular weights increased linearly with monomer conversion and were close to corresponding theoretical values. The molecular weight distributions (M w /M n ) kept very narrow (M w /M n <1.1) at a wide range of conversions of 14.2% to 73.3%. The obtained polymer had a strong ultraviolet absorption at 329 nm, which indicated that the 1a moiety remained at the end of polymer chain.

Synthesis of Well-defined Carbazole Group Labelled Polymer via RAFT Polymerization and Study on the Optical Properties

AbstractBenzyl 9H-carbazole-9-carbodithioate (BCC) was synthesized and characterized. The single-crystal structure of BCC was first reported. The RAFT polymerizations of styrene and acrylates using BCC as the RAFT agent under conventional polymerization conditions were investigated. The results showed that the BCC was an effective RAFT agent for the polymerizations of styrene and acrylates. The well-controlled polymers were labelled with carbazole group, which was confirmed by 1H NMR and the chain extension of the obtained polymer. Azo modified poly(methyl acrylate) (PMA) was synthesized through a postpolymerization azo-coupling scheme. The optical properties of obtained polymer were also characterized. The results showed that the carbazole group labelled polymer exhibited fluorescence and the azo polymer exhibited UV absorption behaviour in N,N-dimethyl formamide (DMF).

Synthesis of 1,3‐benzodioxole end‐functionalized polymers via reversible addition–fragmentation chain transfer polymerization

AbstractReversible addition–fragmentation chain transfer (RAFT) polymerization of styrene was carried out in the presence of a novel RAFT reagent, bearing 1,3‐benzodioxole group, benzo [1,3]dioxole‐5‐carbodithioic acid benzo [1,3]dioxol‐5‐ylmethyl ester (BDCB), to prepare end‐functionalized polystyrene. The polymerization results showed that RAFT polymerization of styrene could be well controlled. Number–average molecular weight (Mn(GPC)) increased linearly with monomer conversion, and molecular weight distributions were narrow (Mw/Mn &lt; 1.4). The successful reaction of chain extension and analysis of 1H NMR spectra confirmed the existence of the functional 1,3‐benzodioxole group at the chain‐end of polystyrene. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3535–3539, 2006