The architecture of hydroxy‐functionalized aPS‐b‐random copolymer‐b‐PE via one‐pot strategy combining living free radical polymerization with coordination polymerization

The copolymerization of styrene with ethylene was promoted by CpTiCl₃/BDGE/Zn/MAO catalyst system combining free radical polymerization with coordination polymerization via sequential monomer addition strategy in one‐pot. The effect of polymerization conditions such as temperature, time, ethylene pressure, and Al/Ti molar ratio on the polymerization performance was investigated. The hydroxy‐functionalized aPS‐b‐random copolymer‐b‐PE triblock copolymer was obtained by solvent extraction and determined by GPC, DSC, WAXD, and ¹³C‐NMR. The DSC result indicated that the aPS‐b‐random copolymer‐b‐PE had a T_g at 87°C and a T_m at 119°C which attributed to the T_g of aPS segment and the T_m of PE segment, respectively. The microstructure of the hydroxy‐functionalized aPS‐b‐random copolymer‐b‐PE was further confirmed by WAXD, ¹³C‐NMR, and ¹H‐NMR analysis; and these results demonstrated that the obtained block copolymer consisted of aPS segment, S‐E random copolymer segment, and crystalline PE segment. The connection polymerization of the hydroxy‐functionalized aPS with random copolymer‐b‐PE was revealed by GPC results. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Accelerant‐promoted free radical polymerization of methacrylates by stabilized nitroxide unimolecular initiators: synthesis and characterization

BACKGROUND: This investigation evaluates the effectiveness of initiator adducts for living and controlled polymerization of methacrylates, crosslinking of dimethacrylates and thermal stabilities of the resulting polymers. Adducts of 2,2,6,6‐tetramethyl‐1‐piperidinyloxy with benzoyl peroxide and with azobisisobutyronitrile were prepared and evaluated as stabilized unimolecular initiators for the free radical polymerization of methacrylate monomers using sulfuric acid as catalyst. The monomers used were methyl methacrylate, triethylene glycol dimethacrylate (TEGDMA) and ethoxylated bisphenol A dimethacrylate (EBPADMA). RESULTS: Successful polymerization was achieved at 70 and 130 °C with reaction times ranging from 45 min to 120 h. The dispersity (D) of poly(methyl methacrylate) (PMMA) was 1.09–1.28. The livingness and extent of control over polymerization were confirmed with plots of M_n evolution as a function of monomer conversion and of the first‐order kinetics. The glass transition temperature (T_g) for PMMA was 123–128 °C. The degradation temperature (T_d) for PMMA was 350–410 °C. T_d for poly(TEGMA) was 250–310 °C and for poly(EBPADMA) was 320–390 °C. CONCLUSION: The initiators are suitable for free radical living and controlled polymerization of methacrylates and dimethacrylates under mild thermal and acid‐catalyzed conditions, yielding medium to high molecular weight polymers with low dispersity, high crosslinking and good thermal stability. Copyright © 2008 Society of Chemical Industry     

Poly(methyl methacrylate)-block-polysulfide-block-poly(methyl methacrylate) copolymers obtained by free-radical polymerization combined with oxidative coupling

Summary Poly(methyl methacrylate)-block-polysulfide-block-poly(methyl methacrylate) copolymers were synthesized for the first time through a new method involving the free radical polymerization of MMA in the presence of a thiocol oligomer as a chain transfer agent, followed by chemical oxidation of the remaining SH end-groups. The chain transfer constant of the SH end-groups of the thiocol was estimated from the rate of consumption of the thiol groups versus the rate of consumption of the monomer (C_T=0.67). The triblock copolymers synthesized were characterized by SEC and ¹H NMR measurements.     

Synthesis and characterization of poly[4‐(2‐thiazolylazo)phenyl methacrylate]‐co‐poly(methyl methacrylate)

A new methacrylic monomer, 4‐(2‐thiazolylazo)phenylmethacrylate (TPMA) was synthesized. Copolymerization of the monomer with methyl methacrylate (MMA) was carried out by free radical polymerization in THF solution at 70 ± 0.5°C, using azobisisobutyronitrile (AIBN) as an initiator. The monomer TPMA and the copolymer poly(TPMA‐co‐MMA) were characterized by Fourier transform infrared (FTIR), ¹H nuclear magnetic resonance (NMR), and elemental analysis methods. The polydispersity index of the copolymer was determined using gel permeation chromatography (GPC). Thermogravimetric analysis (TGA) of the copolymer performed in nitrogen revealed that the copolymer was stable to 270°C. The glass transition temperature (T_g) of the copolymer was higher than that of PMMA. The copolymer with a pendent aromatic heterocyclic group can be dissolved in common organic solvents and shows a good film‐forming ability. Both the monomer TPMA and the copolymer poly (TPMA‐co‐MMA) have bright colors: orange and yellow, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2152–2157, 2007     

Transformation of liquid to amorphous solid: The time to vitrify for styrene polymerization

A model is presented for the calculation of the time to vitrify vs. temperature for isothermal polymerization by the chain growth mechanism. The model is based on the glass transition temperature (T_g) rising from its initial value to the reaction temperature. The relationships between T_g and the volume fraction of polymer and monomer, the volume fraction of polymer and the extent of reaction, and the extent of reaction and time are also required. In a plot of temperature vs. time the vitrification curve is generally S-shaped; the time passes through a maximum just above the glass transition temperature. The model applies to linear polymerization in which monomer and high molecular weight polymer are the dominant species, i.e., to chain reactions. In this communication the model is applied to the bulk polymerization of styrene by the free radical mechanism.     

Synthesis of alkyne‐terminated xanthate RAFT agents and their uses for the controlled radical polymerization of N‐vinylpyrrolidone and the synthesis of its block copolymer using click chemistry

Two new alkyne‐terminated xanthate reversible addition‐fragmentation chain‐transfer (RAFT) agents: (S)‐2‐(Propynyl propionate)‐(O‐ethyl xanthate) (X₃) and (S)‐2‐(Propynyl isobutyrate)‐(O‐ethyl xanthate) (X₄) were synthesized and characterized and used for the controlled radical polymerization of N‐vinylpyrrolidone (NVP). X₃ showed better chain transfer ability in the polymerization at 60°C. Molecular weight of the resulted polymer increased linearly with the increase in monomer loading. Kinetics study with X₃ showed the pseudo‐first order kinetics up to 67% monomer conversion. Molecular weight (M_n) of the resulting polymer increased linearly with the increase in the monomer conversion up to around 67%. With the increase in the monomer conversion, polydispersity of the corresponding poly(NVP)s initially decreased from 1.34 to 1.32 and then increased gradually to 1.58. Chain‐end analysis of the resulting polymer by ¹H‐NMR and FTIR showed clearly that polymerization started with radical forming out of xanthate RAFT agent. Living nature of the polymerization was also confirmed from the successful homo‐chain extension experiment and the hetero‐chain extension experiment involving synthesis of poly(NVP)‐b‐polystyrene amphiphilic diblock copolymer. Formed alkyne‐terminated poly(NVP) also allowed easy conjugation to azide‐terminated polystyrene by click chemistry to prepare well‐defined poly(NVP)‐b‐polystyrene block copolymers. Resulting polymers were characterized by GPC, ¹H‐NMR, FTIR, and thermal study. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Free radical polymerization kinetics of monomers functionalized with ?AsO(OH)2 in aqueous media

The free radical polymerization kinetics of the isomer sodium salts of o‐ and p‐methacryloylaminophenylarsonate in aqueous solution have been studied using a dilatometric method. The polymerizations, initiated with potassium persulfate, were carried out at a constant monomer initial concentration of 0.50 mol/L and the initiator initial concentration was fixed at one of the following: 1.00, 2.00, 5.00, 8.00, or 10.00 (× 10^?3 mol/L). Another set of polymerizations were carried out at a constant initiator initial concentration of 2 × 10^?3 mol/L and the monomer initial concentration was fixed at one of the following: 0.20, 0.30, 0.50, 0.70, or 1.00 (mol/L). The polymerization reactions were conducted isothermally at 70°C. The order with respect to initiator was consistent with the classical kinetic rate equation, while the order with respect to monomer was greater that unity. The effects of temperature on the polymerization rate were also investigated and the activation energy gave values of 20.66, 22.68, and 23.22 kcal mol^?1 K^?1 over a temperature range of 50–70°C. For the case of o‐methacryloylaminophenylarsonic acid monomer, its kinetic study was carried out in DMF as solvent and AIBN initiator. p‐Methacryloylaminophenylarsonic acid was too insoluble in DMF to be studied. The polymers obtained were characterized by H‐NMR, IR, and viscosity. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1662–1669, 2004     

Micellar polymerization,characterization, and viscoelasticity of combined thermally insensitive terpolyacrylamides

Polymer chains consisting of water‐soluble polyacrylamides and N‐isopropylacrylamide (NIPAM), hydrophobically modified with low amounts of N,N‐dialkylacrylamides (N,N‐dioctylacrylamide) have been prepared via free radical micellar polymerization, using a hydrophobic initiator derived from 4,4′‐azobis(4‐cyanopentanoic acid) containing a long linear chain of 16 (C16) carbon atoms. This procedure resulted in polyacrylamides containing hydrophobic groups along the chain as well as at the chain ends. These polymers are named “combined associative polymers” and include within their structure a water‐soluble monomer (acrylamide), a thermosensitive monomer (NIPAM) and a hydrophobic monomer. The polymers were characterized by different techniques, also studying the effect of adding a surfactant anion such as sodium dodecylsulfate. The viscoelastic properties as a function of temperature of these associative polymers were investigated using steady‐flow and oscillatory experiments considering the relaxation time (T_R) and the plateau modulus (G₀). The effect of concentration of acrylamide and NIPAM on the viscosity of the associative polymer solutions was investigated. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Synthesis,characterization, and kinetic investigation of acrylic monomers derived from acetaminophen and ρ‐cresol as model drug molecules

In this work, the synthesis, characterization, and kinetic investigation of the free‐radical polymerization of 4‐acetylaminobenzene propenoic ester (ABPE) and 4‐methylbenzene propenoic ester (MBPE) were studied. The kinetic behaviors of ABPE and MBPE in the polymerization initiated by azobisisobutyronitrile in dimethylformamide solutions at temperatures between 50 and 120°C were investigated, and experimental and theoretical conversion–time curves were compared. Both monomers showed a polymerization ceiling temperature (T_c). T_c was calculated with experimental values of k_p/k with a constant concentration of 0.7 mol/L for monomers. T_c was about 141 and 131°C for ABPE and MBPE, respectively. In addition, the solvent effect on the polymerization reaction was investigated via the calculation of the solvent chain‐transfer constant (C_s) for the ABPE monomer. Then, C_s was determined from the average degree of polymerization measured with gel permeation chromatography and the calculation of the overall rate of polymerization at 60°C. The results showed that dimethylformamide as a solvent had no effect on the rate of polymerization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4369–4374, 2006     

Synthesis of amphiphilic heteroarm star‐shaped polymer via free radical polymerization using polyfunctional chain transfer agent and its self‐assembly behavior

Amphiphilic heteroarm star‐shaped polymers have important theoretical and practical significance. In this work, amphiphilic heteroarm star‐shaped polymer was synthesized by the use of polyfunctional chain transfer agent via sequential free radical polymerization in two steps. First, conventional free radical polymerization of methyl methacrylate (MMA) initiated by 2,2′‐azobis (isobutyronitrile) (AIBN) was carried out in the presence of polyfunctional chain transfer agent, pentaerythritol‐tertrakis (3‐mercaptopropinate) (PETMP). At appropriate monomer conversion, about two‐arm s‐PMMA having two residual thiol groups at the chain center was obtained. Second, the s‐PMMA obtained above was used as macro‐chain‐transfer agent for free radical polymerization of acrylic acid (AA). The heteroarm star‐shaped polymer with the hydrophobic PMMA segment and the hydrophilic PAA segment was obtained. The successful synthesis of heteroarm star‐shaped polymers, (PMMA)₂(AA)₂, was confirmed by ¹H‐NMR and its self‐assembly behavior in different solvents. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Control of monodisperse particle size of styrenic–acrylate copolymers in dispersion copolymerization

Syntheses of monodisperse poly[(styrene)‐co‐(n‐butyl acrylate)] and poly[(styrene)‐co‐(2‐ethylhexyl acrylate)] were carried out by dispersion polymerization. The reactions were performed in the mixed solvent of ethanol–water in the presence of azo‐bisisobutyronitrile and poly(N‐vinylpyrrolidone) as the initiator and dispersant, respectively. The effects of reaction parameters, that is the type and concentration of dispersant, ratio of the mixed solvent, reaction temperature, agitation rate, monomer composition between styrene and n‐butyl acrylate or 2‐ethylhexyl acrylate, crosslinking agent and reaction time on the particle size, size distribution and average molecular weights of the resulting copolymer were thoroughly investigated. The resulting copolymer particles were smooth on their spherical surface and the sizes were in the range 0.6–1.8 µm with a narrow size distribution. In most cases, a correlation between small particle sizes with high average molecular weights was observed. The average particle size generally increased with increasing reaction temperature, time and acrylate monomer content. In contrast, the particle size decreased as the molecular weight, concentration of dispersant, polarity of the medium or agitation rate was increased. The glass transition temperature (T_g) of the copolymers can be controlled by the mole ratio of the comonomer. The T_g values decreased when the content of acrylate monomers in the copolymer increased, and T_g values of the synthesized copolymer were in the range 66–102 °C. Instead of using n‐butyl acrylate monomer in the copolymerization, 2‐ethylhexyl acrylate copolymerization with styrene resulted in insignificant changes in the particle sizes but there were significant decreases in T_g values. In this study, the monodisperse particles can be obtained by monitoring the appropriate conditions regarding PVP K‐30 (2–8 wt%), ethanol/water (90/10 wt%), the reaction temperature (70 °C) and the agitation rate (100 rpm). © 2000 Society of Chemical Industry     

Methyl acrylate/1‐octene copolymers: Lewis acid‐mediated polymerization

Copolymerization of methyl acrylate (MA) with 1‐octene (1‐Oct) was conducted in the presence of free radical initiator, 2,2′‐azobis(2‐methylpropionitrile) (AIBN) using heterogeneous Lewis acid, acidic alumina. The polymers obtained were transparent and highly viscous liquids. The copolymer composition calculated from ¹H NMR showed alkene incorporation in the range of 10–61%. The monomodal nature of chromatographic curves corresponding to the molecular weight distribution in gel permeation chromatography (GPC) further confirmed that the polymers obtained are true copolymers. The number–average molecular weights (M_n) of the copolymers were in the range of 1.1 × 10⁴–1.6 × 10⁴ with polydispersity index of 1.75–2.29. The effects of varying the acidic alumina amount, time of polymerization, and monomer infeed on the incorporation of 1‐Oct in the polymer chain were studied. Increased 1‐Oct infeed led to its higher inclusion in the copolymer chain as elucidated by NMR. DEPT‐135 NMR spectral analysis was used to explicate the nature of arrangement of monomer sequences in the copolymer chain. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Controlled radical double ring‐opening polymerization of 2‐methylene‐1,4,6‐trioxaspiro[4,4]nonane

Controlled radical double ring‐opening polymerization of 2‐methylene‐1,4,6‐trioxaspiro[4,4]nonane (MTN) has been achieved with tert‐butyl perbenzoate (TBPB) as initiator in the presence of 2,2,6,6‐tetramethyl‐1‐piperidinyloxy free radical (TEMPO) at 125 °C. The molecular weight polydispersity of the polymers is obviously lower than that of polymers obtained by conventional procedures. As the [TEMPO]/[TBPB] molar ratio increased, the polydispersity decreased and a polydisperty as low as 1.2 was obtained at high TEMPO concentration. With the conversion of the monomer increasing, the molecular weight of the polymers turned higher and a linear relationship between the M_w and the monomer conversion was observed. The monomer conversion, however, did not exceed 30 %. © 2000 Society of Chemical Industry     

Melt rheology of poly(ϵ‐caprolactone)/poly(styrene‐co‐acrylonitrile) blends

Dynamic viscoelastic properties for miscible blends of poly(?‐caprolactone) (PCL) and poly(styrene‐co‐acrylonitrile) (SAN) were measured. It was found that the time–temperature superposition principle is applicable over the entire temperature range studied for the blends. The temperature dependency of the shift factors a_T can be expressed by the Williams–Landel–Ferry equation: log a_T = ?8.86(T ? T_s)/(101.6 + T ? T_s). The compositional dependency of T_s represents the Gordon–Taylor equation. The zero‐shear viscosities are found to increase concavely upward with an increase in weight fraction of SAN at constant temperature, but concavely downward at constant free volume fraction. It is concluded that the relaxation behavior of the PCL/SAN blends is similar to that of a blend consisting of homologous polymers. It is emphasized that the viscoelastic functions of the miscible blends should be compared in the iso‐free volume state. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2037–2041, 2001     

Polymerization of acrylonitrile using potassium peroxydisulfate as an initiator in the presence of a multisite phase‐transfer catalyst: A kinetic study

In this article, the kinetics and mechanism of the free‐radical polymerization of acrylonitrile (AN) using potassium peroxydisulfate (PDS) as a water‐soluble initiator in the presence of synthesized 1,4‐bis(triethyl methyl ammonium) benzene dichloride (DC‐X) as a phase‐transfer catalyst (PTC) were studied. The polymerization reactions were carried out under inert and unstirred conditions at a constant temperature of 60 ± 1°C in cyclohexane/water biphasic media. The rate of polymerization (R_p) increased with an increase in the concentrations of AN, PTC, and PDS. The order with respect to the monomer, initiator, and PTC was found to be 1.0, 0.5, and 0.5, respectively. R_p was independent of the ionic strength and pH of the medium. However, an increase in the polarity of the solvent slightly increased the R_p value. On the basis of the obtained results, a mechanism is proposed for the polymerization reaction. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Investigation of kinetics of 4‐methylpentene‐1 polymerization using Ziegler–Natta‐type catalysts

The kinetics of 4‐methylpentene‐1 (4MP1) polymerization by use of Ziegler–Natta‐type catalyst systems, M(acac)₃‐AlEt₃ (M = Cr, Mn, Fe, and Co), are investigated in benzene medium at 40°C. The effect of various parameters such as Al/M ratio, reaction time, aging time, temperature, catalyst, and monomer concentrations on the rate of polymerization and yield are examined. The rate of polymerization increased linearly with increasing monomer concentration with first‐order dependence, whereas the rate of polymerization with respect to catalyst concentration is found to be 0.5. For all cases, the polymer yield is maximum at an Al/M ratio of 2. The activation energies obtained from linear Arrhenius plots are in the range of 25.27–33.51 kJ mol^?1. It is found that the aging time to give maximum percentage yield of the polymer varies with the catalyst systems. Based on the experimental results, a plausible mechanism is proposed that envisages a free‐radical mechanism. Characterization of the resulting polymer product, for all the cases, through FTIR, ¹H‐NMR, and ¹³C‐NMR studies, showed isomerized polymeric structures with 1,4‐structure as dominant. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2468–2477, 2003     

Polymerization of methyl methacrylate with Nickel(II)α‐benzoinoxime complex

Polymerizations of methyl methacrylate (MMA) monomer initiated by a novel Ni(II)α‐benzoinoxime complex have been achieved under homogeneous conditions in the 25–60°C temperature range. The activity for polymerization increases with reaction temperature and by carrying out the polymerization in solution of low‐polarity solvents without any induction time. The obtained polymers have weight‐average molecular weights about 10⁵ and slight broad polydispersity indexes (2.2 ≤ M_w/M_n ≤ 3.3). Dependence of rate constants polymerization and decomposition of initiator (k_app and k_d, respectively) on temperature was investigated and activation parameters were computed from Arrhenius plot. ¹H‐NMR analysis of PMMA revealed a syndio‐rich atactic microstructure in agreement with conventional radical process. Radical scavenger TEMPO effect together with microstructure and molecular weight distributions data supported that the polymerization proceed via free radical mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis of multi‐arm star polystyrene with hyperbranched polyester initiators by atom transfer radical polymerization

Multi‐arm star polystyrenes with hyperbranched polyester (HP3) core were prepared by atom transfer radical polymerization (ATRP). The structures of the polymers were investigated with FTIR and ¹H NMR. GPC results showed that the resultant polymers had relatively broad polydispersity indices that arouse from the macromolecular initiator (HP3‐Br). The thermal properties were studied using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). DSC analysis indicated that polystyrene star polymers had only the glass transition temperatures (T_g), which changes with the weight ratio of multi‐functional macroinitiator‐to‐monomer. In addition, these star polymers could form the spherical micelles in the selected solvent (THF/n‐hexane). © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 728–733, 2006     

Poly(ethylene oxide)‐block‐polystyrene copolymers obtained by radical polymerization involving chain‐transfer processes

Poly(ethylene oxide)‐block‐polystyrene (PEO–PSt) block copolymers were prepared by radical polymerization of styrene in the presence of iodoacetate—terminated PEO (PEO‐I) as a macromolecular chain‐transfer agent. PEO‐I was synthesized by successively converting the OH end‐group of α‐methoxy ω‐hydroxy PEO to chloroacetate and then to the iodoacetate. The chain‐transfer constant of PEO‐I was estimated from the rate of consumption of the transfer agent versus the rate of consumption of the monomer (C_{tr, PEO‐I} = 0.23). Due to the involvement of degenerative transfer, styrene polymerization in the presence of PEO‐I displayed some of the characteristics of a controlled/‘living’ process, namely an increase in the molecular weight and decrease of polydispersity with monomer conversion. However, because of the slow consumption of PEO‐I due to its low chain‐transfer constant, this process was not a fully controlled one, as indicated by the polydispersity being higher than in a controlled polymerization process (1.65 versus < 1.5). The formation of PEO–PSt block copolymers was confirmed by the use of size‐exclusion chromatography and ¹H NMR spectroscopy. Copyright © 2004 Society of Chemical Industry     

Preparation of heat‐resistant branched poly(styrene‐alt‐NPMI) by ATRP with divinylbenzene as the branching agent

Heat‐resistant branched poly(styrene‐alt‐NPMI) has been prepared via atom transfer radical polymerization (ATRP) of styrene (St) and N‐phenyl maleimide (NPMI) with divinylbenzene (DVB) as the branching agent in anisole at 80°C. Gas chromatography (GC) was used to determine the conversion of the reactants. Triple detection gel permeation chromatography (TD‐GPC) was used to analyze the copolymers. The results show that the polymerization yields primary chains predominately in the early stages and the formation of branched molecules occurs mainly when conversion is higher than 50%. As expected, higher dosage of DVB in our investigation range favors the formation of polymers with higher degree of branching. All the resulting branched poly(styrene‐alt‐NPMI)s have glass transition temperature (T_g) above 175°C, extrapolated initial weight loss temperature (T_i) above 410°C and statistic heat‐resistant index above 200°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011