Controlled radical polymerization of styrene initiated by diethyldithiocarbamate‐mediated iniferters

We demonstrated that density functional theory calculations provide a prediction of the trends in C‐S bond dissociation energies and atomic spin densities for radicals using two model compounds as diethyldithiocarbamate (DC)‐mediated iniferters. On the basis of this information, we synthesized 2‐(N,N‐diethyldithiocarbamyl)isobutylic acid (DTCA) and (4‐cyano‐4‐diethyldithiocarbamyl)pentanoic acid (CDPA) as DC‐mediated iniferters. Free‐radical polymerizations of styrene (St) were carried out in benzene initiated by DTCA or CDPA under UV irradiation. The first‐order time‐conversion plots showed the straight line for the UV irradiation system initiated by CDPA indicating the first order in monomer. The number‐average molecular weight (M_n) of the polystyrene (PSt) increased in direct proportion to monomer conversion. The molecular weight distribution (M_w/M_n) of the PSt was in the range of 1.3–1.7. It was concluded this polymerization system proceeded with a controlled radical mechanism. However, photopolymerization of styrene initiated by DTCA showed nonliving polymerization consistent with UV initiation. Theoretical predictions supported these experimental results. Methacrylic acid (MA) could also be polymerized in a living fashion with such a PSt precursor as a macroinitiator because PSt exhibited a DC group at its terminal end. This system could be applied to the architecture of block copolymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 413–418, 2005     

Controlled free radical photopolymerization of styrene initiated by trithiocarbonate

Density functional theory calculations are reported for prediction of the trends in C S bond dissociation energies and atomic spin densities for radicals using S,S′‐bis(α,α′‐dimethyl‐α‐acetic acid) trithiocarbonate (TTCA) and bis(2‐oxo‐2‐phenylethyl) trithiocarbonate (TTCB) as reversible addition fragmentation chain transfer (RAFT) reagents. The calculations predict that the value of the C S bond length (1.865 Å) of TTCA is longer than that (1.826 Å) of TTCB, and TTCA is more effective for the polymerization of styrene (St) compared to TTCB as predicted by density functional theory. In photopolymerizations, pseudo‐first‐order kinetics were confirmed for TTCB‐mediated photopolymerization of St due to the linear increase of ln([M]₀/[M]) up to about 28% conversion, suggesting the living characteristics behavior of the photopolymerization of St in the presence of TTCB. For both TTCA and TTCB the polydispersities change with increasing conversion in the range 1.10–1.45, typical for RAFT‐prepared (co)polymers and well below the theoretical lower limit of 1.50 for a normal free radical polymerization. In addition, the triblock copolymer polystyrene‐block‐poly(butyl acrylate)‐block‐polystyrene (PS PBA PS) was successfully prepared, with very good control over molecular weight and narrow polydispersity (M_w/M_n = 1.45), using PS S C(S) S PS as macro‐photoinitiator under UV irradiation at room temperature. This indicated that this reversible and valid strategy led to a better controlled block copolymer with defined structures. Copyright © 2007 Society of Chemical Industry     

A replicated investigation of nitroxide‐mediated radical polymerization of styrene over a range of reaction conditions

A comprehensive experimental investigation of nitroxide‐mediated radical polymerization (NMRP) of styrene using 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) as controller is presented. Polymerizations with a bimolecular initiator (benzoyl peroxide; BPO) were carried out at 120 and 130°C, with TEMPO/BPO molar ratios ranging from 0.9 to 1.5. Results indicate that increasing temperature increases the rate of polymerization while the decrease in molecular weights is only slight. It was also observed that increasing the ratio of TEMPO/BPO decreased both the rate of polymerization and molecular weights. Probably for the first time in the history of such investigations, the paper contains a comprehensive database, appropriate for parameter estimation in aid of future modelling studies, since it comes from a systematic data collection containing independent replication.     

Benzotriazinyl‐mediated controlled radical polymerization of styrene

The stable free radical polymerization (SFRP) process based on (1,3‐diphenyl‐1,4‐dihydro‐1,2,4‐benzotriazin‐4‐yl), the so‐called ‘Blatter radical’, and several C‐7 substituted derivatives is introduced for the first time for the polymerization of styrene. Polystyrenes characterized by polydispersity indices in the 1.05 ? 1.27 range were obtained in the presence of the Blatter radical and its derivatives containing CF₃, Ph, Fur‐2‐yl and 4‐PhC₆H₄ substituents, while polymerization proceeded either in a non‐controlled manner or in very low polymerization yields in the presence of derivatives containing halogen (Cl, Br, I) substituents. This preliminary investigation, demonstrating the potential use of the Blatter radical and its derivatives in mediated SFRP, creates new opportunities to design and develop radicals to optimize performance in such polymerization processes. © 2013 Society of Chemical Industry     

Photoinitiation of polymerization of styrene by oxotris(dimethyl dithiocarbamato) vanadium(V)

Oxotris(dimethyl dithiocarbamato) vanadium(V) [VO(S₂CN(CH₃)₂)₃] sensitizes the polymerization of styrene when irradiated by light of λ = 365 nm at 25°C. Under the experimental conditions employed, no retardation occurs, and the rate of initiation is independent of monomer concentration. The mean values of the quantum yield of iniiation (?_i) and polymerization (?_o) are 2.85 × 10^?3 and 6.72 respectively. Spectroscopic analysis shows that initiation occurs predominatly through scission of the N,N-dimethyl dithiocarbamate ligand (—SC(S)N(CH₃)₂) with reduction of vanadium(V) to (IV), and VO (S₂CN(CH₃)₂)₂ is the final photolytic product. A reaction mechanism is proposed based on an intramolecular photoredox reaction which leads to the primary formation of SC(S)N(CH₃)₂ radicals and a vanadium(IV) chelate complex. The rellevant kinetic parameters are evaluated. The polystyrene produced shows a photoactivity when irradiated with UV-light.     

Photo‐mediated metal free atom transfer radical polymerization of acrylamide in water

Photo‐mediated metal free atom transfer radical polymerization of acrylamide was conducted at 25 °C in water under visible light irradiation with water soluble 2‐hydroxy‐3‐(4‐benzoylphenoxy)‐N,N,N‐trimethyl‐1‐propaminium chloride (HBTPC) as photoredox catalyst and 2‐hydroxyethyl 2‐bromoisobutyrate as alkyl halide. The polymerization followed first‐order reaction kinetics. The living character of photo‐mediated atom transfer radical polymerization of acrylamide was verified by the linear development of the polymer number average molar mass (M_n,GPC) with monomer conversion and narrow molecular weight distributions (?). The effects of acrylamide concentration, light intensity, amount of HBTPC, and tris(2‐dimethylaminoethyl)amine on polymerization were investigated. Increasing monomer concentration led to a higher M_n,GPC values with narrow ?. The polymerization rate increased with increasing the amount of monomer, light intensity, HBTPC and tris(2‐dimethylaminoethyl)amine. The polymerization was monitored by the periodic light on/off. The structure of polyacrylamide was analyzed by proton nuclear magnetic resonance spectrometer and gel permeation chromatography. Successful chain extension experiments show the controlled nature of the polymerization. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46567.     

Ultrasound‐assisted emulsion polymerization of methyl methacrylate and styrene

In this article, we report on the effect of using ultrasound during emulsion polymerization. This work differs somewhat from that previously reported in that ultrasound is used in conjunction with conventional initiators. The aim is to observe the changes in the nature of polymerization and the synthesized polymer. In this work, reaction conditions and compositions typical of conventional emulsion polymerization are used. Azo‐bisisobutyronitrile and potassium per sulfate are the initiators used. The initial indication is that the rate of polymerization and the final conversion are higher when ultrasound is introduced into the polymerization system. This effect is more pronounced at lower temperatures (50°C) and low initiator concentrations (0.01%). At higher temperatures (70°C) the polymerization rate is seemingly unaffected by the use of ultrasound. The final product in all the experiments is a latex. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 101–104, 2000     

Kinetics of reversible addition–fragmentation transfer (RAFT) miniemulsion polymerization of styrene using dibenzyl trithiocarbonate as RAFT reagent and costabilizer

The roles of dibenzyl trithiocarbonate (DBTTC) as both costabilizer and reversible addition–fragmentation transfer (RAFT) reagent in RAFT miniemulsion polymerizations of styrene were investigated. The effectiveness of DBTTC costabilizer in retarding Ostwald ripening involved in the storage stability of miniemulsion is comparable to that of conventional low‐molecular‐weight costabilizers such as cetyl alcohol, but inferior to that of hexadecane. The major variables chosen for studying kinetics of RAFT miniemulsion polymerizations include the type of initiators and levels of DBTTC and surfactant. At a constant level of DBTTC, the rate of polymerization for benzoyl peroxide (BPO)‐initiated polymerization is slower than that for sodium persulfate (SPS)‐initiated polymerization. Furthermore, the polymerization rate decreases with increasing level of DBTTC for polymerizations initiated by BPO (or SPS). It is the monomer droplet nucleation that governs BPO‐initiated polymerizations. In contrast, for SPS‐initiated polymerizations, the probability for homogeneous nucleation to take place is greatly increased, especially for polymerizations with lower levels of DBTTC and higher levels of surfactant. © 2015 Society of Chemical Industry     

Synthesis of hydroxyl‐terminated copolymer of styrene and 4‐vinylpyridine via nitroxide‐mediated living radical polymerization

The random copolymers of styrene (St) and 4‐vinylpyridine (4‐VP) with hydroxyl end group and low polydispersities were synthesized by nitroxide‐mediated living radical polymerization initiated by azobisisobutyronitrile (AIBN) and 4‐hydroxyl‐2,2,6,6–tetramethylpiperidine‐oxyl (TEMPO‐OH). The experimental results have shown that all synthesized copolymers have narrow molecular weight distribution. The conversion of monomers and the molecular weight of copolymer increased with polymerization time. The copolymerization rate is affected by molar ratios of HTEMPO to AIBN. ¹H‐Nuclear magnetic resonance spectra shows that one end of copolymers was capped by TEMPO‐OH moiety. The use of this method permits the copolymer with hydroxyl chain end and controllable molecular weight and molecular weight distribution. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1842–1847, 2004     

Kinetics of RAFT emulsion polymerization of styrene mediated by oligo(acrylic acid‐b‐styrene) trithiocarbonate

The kinetics of ab initio reversible addition‐fragmentation chain transfer (RAFT) emulsion polymerization of styrene using oligo(acrylic acid‐b‐styrene) trithiocarbonate as both polymerization mediator and surfactant were systematically investigated. The initiator concentration was set much lower than that in the conventional emulsion polymerization to significantly suppress the irreversible termination reaction. It was found that decreased rapidly but the nucleation efficiency of micelles increased with the decrease of the initiator concentrations due to the significant radical exit. The particle number ( ) did not follow the classic Smith–Eward equation but was proportional to [I]^?0.4[S]^0.7. It was suggested that RAFT emulsion polymerization could be fast enough for commercial use even at extremely low initiator concentrations and low macro‐RAFT agent concentrations due to the higher particle nucleation efficiency at lower initiator concentration. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2126–2134, 2016     

Bulk polymerization of styrene catalyzed by bi‐ and trifunctional cyclic initiators

A study of the bulk free‐radical polymerization of styrene in the presence of the cyclic bi‐ and trifunctional initiators cyclohexanone triperoxide, diethylketone triperoxide, acetone triperoxide, cyclohexanone diperoxide, and pinacolone diperoxide is reported. When these multifunctional initiators are used for styrene polymerization at high temperatures, it is possible to produce polymers with high molecular weights and narrow polydispersities at a high reaction rate. Additionally, the former initiators are used in a mixture that shows that the molecular parameters are influenced by the initiator concentration in the initiation system, in addition to the system employed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1–11, 2002     

Mini-emulsion formation and polymerization of styrene

The morphology of an anionic emulsifier/long chain fatty alcohol complex and its change during the formation process were studied. The main factors affecting the morphology, such as various types of anionic emulsifiers and fatty alcohols, their molar ratios and the addition of styrene, were investigated. It was discovered that the rod-like particles of the complex had a length of 0.1 -0-2 μm and diameter of 0.01-0.02 μm. A model of a rod-like particle or molecular aggregate was proposed. Both water-soluble and oil-soluble initiators were used to study the kinetics of styrene mini-emulsion polymerization and polystyrene latex size characteristics.     

Ring‐opening polymerization of styrene oxide with Maghnite‐H+ as ecocatalyst

The polymerization of styrene oxide was carried out at 20°C in chloroform with an acid‐exchanged montmorillonite as acid solid ecocatalyst (Mag‐H⁺). The effect of the amount of catalyst, solvent, and concentration of monomer on yield and molecular weight of polymer was studied. A typical reaction product (PSTO) was analyzed by infrared and nuclear magnetic resonance spectroscopy, as well as by gel‐permeation chromatography and MALDI‐TOFMS. The mechanism of the polymerization appears to be cationic. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1681–1687, 2006     

基于均匀设计的苯乙烯分散聚合反应研究

本文基于均匀设计方法对苯乙烯的分散聚合反应进行了试验设计,并通过回归分析,建立了聚苯乙烯粒子相关性能参数(聚苯乙烯粒子分子量、粒径大小及分布)和各变量(单体浓度、稳定剂用量、引发剂用量和反应介质溶度参数)之间的回归方程。根据回归方程进行了分散聚合反应的配方优化,得到了约束条件下的苯乙烯分散聚合反应配方,实测值与预测值比较结果表明,回归方程的预测值与优化配方制备的PS粒子的各项性能实测值存在一定的偏差(相对偏差在15%以内),但仍对试验配方设计有一定的指导作用。     

2,2,6,6‐Tetramethylpiperidine‐1‐oxyl‐mediated living mini‐emulsion polymerization of styrene under ambient pressure in a semi‐batch process: effect of ascorbic acid

2,2,6,6‐Tetramethylpiperidine‐1‐oxyl (TEMPO)‐mediated living mini‐emulsion polymerization of styrene with feeding of an ascorbic acid aqueous solution throughout the polymerization was performed at 90 °C under ambient pressure. The concentrations of sodium dodecylbenzenesulfonate (SDBS) and ascorbic acid were varied to study the shell polymerization mechanism of latex particles and evolution of growing chains. Interactions between SDBS and ascorbic acid and incompatibility between ascorbic acid and styrene were evident from UV‐visible analyses. High hydrophilicity of ascorbic acid in the aqueous phase was proved using a gravimetric method. Accordingly, the formation of a surface barrier on particles was proposed because of the interactions between SDBS and ascorbic acid. For higher SDBS concentration, the surface barrier on the particles was denser. Therefore, the polymerization rate decreased with increasing SDBS concentration. However, the polymerization rate increased with increasing ascorbic acid concentration. This was due to a higher consumption rate of TEMPO by ascorbic acid. Free TEMPO tended to reside in surface zones of the particles because of the surface activity between the aqueous and oil phases. The surface zones were thus the main loci where TEMPO was consumed by ascorbic acid. The estimated number‐average molecular weight (M_n) of growing chains increased in a linear fashion with conversion. This indicated that the growing chains were produced via living mini‐emulsion polymerization. For these growing chains, the estimated M_n and final polydispersity increased with increasing SDBS concentration. This was caused by a decrease in TEMPO concentration in the surface zones of particles with increasing SDBS concentration. The ‘livingness’ of polystyrene was identified by conducting bulk polymerization of chain extension. Based on the results obtained, a shell polymerization mechanism of latex particles was proposed, and living mini‐emulsion polymerization was limited to the surface zones of particles. Copyright © 2010 Society of Chemical Industry     

A kinetic study on bulk thermal polymerization of styrene

The kinetics of bulk thermal polymerization of styrene over the range of 100–200 °C has been studied based on three stage polymerization model (TSPM) in this paper. TSPM plots showed that the whole polymerization course only exhibits two stages, low conversion stage and gel effect stage, which is consistent with TSPM as the reaction temperature is higher than the glass transition temperature of polystyrene. It was found that the critical conversion, x₁, for the transition from low conversion stage to gel effect stage is independent of the reaction temperature and approximately equal to 0.5. In addition, the apparent reaction rate constants obtained from TSPM plots could be correlated to temperature by Arrhenius equation. Expressions predicting number-average molecular weight were also derived according to TSPM. Using the expressions to treat experimental data available in the literature, it was found that number-average molecular weight is independent of the conversion and relative to the reaction temperature at low conversion stage. However, it varies with the conversions at gel effect stage and the variations are more obvious as the reaction temperature rises.     

溴化苯乙烯/苯乙烯/丙烯腈乳液聚合试验条件探索

以过硫酸钾为引发剂,十二烷基硫酸钠为乳化剂,叔十二烷基硫醇为链转移剂,通过乳液法对溴化苯乙烯、苯乙烯、丙烯腈进行共聚得到溴化苯乙烯-丙烯腈共聚物.考察了引发剂、乳化剂、链转移剂的添加量,反应温度,反应时间,水和单体比例等对聚合反应收率的影响.研究表明：较适宜的反应条件为反应温度80℃,反应时间6h,水与单体质量比4∶1,引发剂质量为单体总质量的0.4％,乳化剂质量为单体总质量的4％,叔十二烷基硫醇为单体总物质的量的2％;上述条件下的产物收率高,相对分子质量4万左右,热分解温度高于350℃.     

Nitroxide‐mediated polymerization of styrene initiated from the surface of montmorillonite clay platelets

Polymer‐grafted montmorillonite (MMT) hybrid composites which possess a hard backbone of MMT and a soft shell of brush‐like polystyrene (PSt) were prepared via “grafting from” strategy based on nitroxide‐mediated radical polymerization (NMRP) using 2,2,6,6‐tetramethylpiperidine‐N‐oxyl (TEMPO) as mediator. Three steps were used to graft PSt chains to the surface of MMT: anchoring of methacrylatoethyl trimethyl ammonium chloride (DMC) onto the surface of MMT by ion exchange reaction first. And then, the surface alkoxyamine initiator was produced in a one‐step process by reacting simultaneously TEMPO, BPO, and DMC in the presence of MMT. Next, PSt chains with controlled molecular weights and polydispersities were grown from the alkoxyamine functionalized MMT surface. The prepared PSt‐g‐MMT hybrid particles have been extensively characterized by FTIR, XPS, XRD, TGA, TEM, respectively. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Controlled radical polymerization of poly(methyl methacrylate‐g‐epichlorohydrin) using N,N‐dithiocarbamate‐mediated iniferters

Poly(epichlorohydrin) (PECH) with pendent N,N‐diethyl dithiocarbamate groups (PECH‐DDC) was prepared by reaction of PECH with sodium N,N‐diethyl dithiocarbamate (DDC) in anhydrous ethanol, before being used as a macrophotoinitiator for the graft polymerization of methyl methacrylate. Photopolymerization was carried out in a photochemical reactor at a wavelength greater than 300 nm. Controlled radical polymerization was confirmed by the linear increase of the molecular weight of polymers with conversion. The polydispersity remained at 1.4–1.6 during polymerization. The formation of PMMA‐g‐PECH copolymer was characterized by GPC, ¹H‐NMR, FTIR spectroscopy, and DSC. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008