Semicontinuous emulsion polymerization of vinyl acetate: Effect of ethoxylation degree of nonionic emulsifiers

Poly(vinyl acetate) latices were prepared in the presence of an ammonium persulfate initiator, 10–50 mol of an ethoxylated nonylphenol nonionic emulsifier, and a poly(vinyl alcohol) colloid stabilizer by applying semicontinuous emulsion polymerization (delayed monomer and initiator addition process) in a laboratory scale similar to industrial practice. Two approaches were applied: the molar concentration of the nonionic emulsifier was kept constant and the weight ratios in the polymerization recipe varied or the weight ratios were kept constant. The effects of the change in the ethoxylation degree of the emulsifier to the final latex viscosity, average polymer molecular weight, polymer grafting degree, surface tension of the latex, and the surface free energy of the dried films were investigated. It was determined that the resultant latex viscosity decreases and the viscosity‐average polymer molecular weight increases with increase of the nonionic emulsifier ethoxylation degree. The increase of the ethoxylation degree does not seriously affect the surface tension of the resultant latex or the surface free energy of the dried poly(vinyl acetate) films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 844–851, 2002     

Preparation of emulsifier‐free polystyrene by conventional emulsion polymerization with a hydrolysable emulsifier

An alkali‐hydrolyzable surfactant, (1‐tetradecyloxycarbonyl)trimethylammonium chloride, was used as an emulsifier for emulsion polymerization of styrene inwater. The polymerization yielded a high molecular‐weight polymer almost quantitatively. Addition of a small amount of NaOH to the resulting latex solution precipitated the polymer immediately. Analysis of the centrifuged solid indicated almost perfection of both recovery of the polymer and removal of surface‐active species from it. Minimization of ionic species in the polymer solid was confirmed by a high contact angle of the polymer film with water. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Accelerated controlled radical polymerization of methacrylates

BACKGROUND: Nitroxide adducts 1,1‐ditertbutyl‐1‐(1‐methyl‐1‐cyanoethoxy)‐amine (AIBN/DBN), 1,1‐ditertbutyl‐1‐(benzoylperoxy)‐amine (BPO/DBN) and 2,2,6,6,‐tetramethyl‐4‐oxo‐1‐(1‐methyl‐1‐cyanoethoxy)‐piperidine (AIBN/4‐OXO‐TEMPO) were prepared and evaluated as stabilized unimolecular initiators for controlled radical polymerization of methacrylate monomers using sulfuric acid as an accelerating additive. Their effectiveness was evaluated from polymerization rates, molecular weight control and dispersity (D) of the polymers. Thermal stabilities of the polymers were also examined. The monomers used were methyl methacrylate, triethylene glycol dimethacrylate (TEGDMA) and ethoxylated bisphenol A dimethacrylate (EBPADMA). RESULTS: Polymerization was accomplished at 70 and 130 °C in 5 min to 144 h. The value of D of poly(methyl methacrylate) (PMMA) was 1.05–1.22. The glass transition temperature (T_g) for PMMA was 122–127 °C. The activity of the chain ends was established by chain extension and controlled polymerization was established by plotting M_n versus monomer conversion. First‐order kinetics in monomer consumption was established and an electron paramagnetic resonance study was conducted. Decomposition temperature (T_d) for PMMA was 360–380 °C, for poly(TEGDMA) was 300–380 °C and for poly(EBPADMA) was 360–440 °C. Photoinitiation without additive yielded no polymer. Thermal initiation by AIBN/4‐OXO‐TEMPO was the fastest. CONCLUSIONS: The initiators are applicable in low‐temperature additive‐enhanced controlled polymerization of methacylates and dimethacrylates, producing polymers with excellent attributes and a low value of D. Copyright © 2008 Society of Chemical Industry     

烷基与酯基的引入对高吸水性树脂吸液性能的影响

以丙烯酸(AA)为单体,通过水溶液聚合法分别与丙烯酸丁酯、甲基丙烯酸、甲基丙烯酸甲酯和丙烯酸甲酯(MA)共聚合,制备了二元共聚高吸水性树脂,并采用傅里叶变换红外光谱仪、扫描电子显微镜和热重分析仪等进行了表征。结果表明:酯基与烷基的引入拓宽了树脂的三维网络结构,明显提高了树脂的吸液性能。其中,AA与MA的二元共聚物吸液性能最优,与聚丙烯酸相比,吸水倍率提高39%,吸水速率提高26%,吸CaCl2和NaCl水溶液的速率明显增强,得到的吸水性树脂结构致密、质地均匀、热稳定性好。     

Frontal polymerization of a cyanate ester

Thermal frontal polymerization is an exothermic process that uses a propagating wave to polymerize monomers via an external heat source, such as a soldering iron, to initiate front propagation. Herein, for the first time, the curing of a cyanate ester via thermal frontal polymerization is described with two different external heat sources. However, issues of bubbling due to vaporization of the amine catalyst generally resulted in incomplete frontal polymerization when a soldering iron was used as the external heat source. To counter this issue, dual‐strip polymerization systems were used, wherein the heat from the exothermic polymerization of a free‐radical system was used to initiate the frontal polymerization of a cyanate ester system with an amine catalyst. As a result, complete frontal polymerization occurred. Additionally, the effect of the width of the acrylate strip and its impact on the front temperature, initial velocity, and steady‐state velocity of the adjacent cyanate ester system were studied. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Graft copolymerization of poly(methyl methacrylate) with some alkyl methacrylates by atom transfer radical polymerization method and thermal properties

The preparation of graft copolymers of poly(methyl methacrylate) with some alkyl methacrylates were carried out via atom transfer radical polymerization method catalyzed by CuCl/2,2′-bipyridine and using a macroinitiator, poly[(methyl methacrylate)-co-(3,5-bis(chloroacetoxy)phenyl methacrylate)], including an amount of 1 mol % having α-halogeno carbonyl group in the side groups. Although the number-average molecular weights of a graft copolymer series of n-butyl methacrylate (n-ButMA) ended at different times increased from 55,700 to 99,500, the polydispersities decreased from 1.85 to 1.39 with time. The thermal degradation kinetics of macroinitiator and a two-armed graft copolymer of n-ButMA with this macroinitiator, PMMA-g-PnButMA: 4% (by mol), were carried out at different heating rates by thermogravimetric analysis and the results were compared. Using both the Flynn–Wall–Ozawa and Kissinger methods, the decomposition activation energies for macroinitiator were determined as 168 and 162 kJ/mol, respectively; they were also calculated as 233 and 239 kJ/mol for PMMA-g-PnButMA: 4%. The solid state thermodegradation mechanisms of both macroinitiator and PMMA-g-PnButMA: 4% are R₁-type mechanism, a phase boundary-controlled reaction, and F₁-type mechanism, a random nucleation with one nucleus on the individual particle, respectively. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Facile atom transfer radical homo and block copolymerization of higher alkyl methacrylates at ambient temperature using CuCl/PMDETA/quaternaryammonium halide catalyst system

Controlled polymerization of higher alkyl methacrylates, e.g. lauryl methacrylate (LMA) and stearyl methacrylate (SMA) has been successfully achieved by atom transfer radical polymerization (ATRP) at ambient temperature using CuCl/N,N,N′,N′,N″-pentamethyldiethylenetriamine (PMDETA)/tricaprylylmethylammonium chloride (Aliquat^®336) as the catalyst system and ethyl 2-bromoisobutyrate or 2,2,2-trichloroethanol as the initiator. Although the bulk polymerization gives satisfactory control, the latter becomes better when anisole or THF is added into the system. Without AQCl the control was lost. A large deviation of molecular weight from theory has been observed which has been attributed to the very high-molecular weight of the dead polymers formed during the building-up of the persistent radical. The controlled polymers have been used as macroinitiators for block (di, tri and penta) ATR copolymerization with several methacrylates.     

N-(n-Alkyl)-2-pyridinemethanimine mediated atom transfer radical polymerization of lauryl methacrylate: Effect of length of alkyl group

The article describes the polymerization of lauryl methacrylate (LMA) using Cu(I)Br as catalyst for atom transfer radical polymerization in conjunction with N-(n-propyl) [PPMI]/(n-hexyl) [HPMI]/(n-octyl) [OPMI]-2-pyridinemethanimine as complex ligands. The polymerization of LMA was investigated in bulk and solution (toluene as solvent) using Cu(I)Br as catalyst, N-(n-alkyl)-2-pyridinemethanimine as ligands and ethyl-2-bromo isobutyrate (EBiB) as initiator. The ratio of LMA : CuBr : Ligand : EBiB was kept constant in all the polymerizations. In bulk polymerization, the solubility of the catalyst complex increased with increasing the length of alkyl chain on the ligand from propyl to octyl and also gave polymers with narrow molecular weight distribution. The PDI was further narrowed by using OPMI as ligand and toluene was used as solvent. The kinetics of polymerization was also analyzed and it clearly shows that % conversion increased with time. Increase in molecular weight with % conversion without affecting PDI clearly show that the system is living and living nature can be controlled by increasing the length of alkyl group. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Nanosize polymer latices made by microemulsion copolymerization: Preparation and characterization

Polymer nanoparticles were prepared by a methyl methacrylate/butyl methacrylate/2‐hydroxyethyl methacrylate/acrylate or methyl acrylate microemulsion copolymerization process. A microemulsion copolymerization method was used. With this process high polymer : surfactant weight ratios (≥15 : 1), relatively concentrated (～ 30 wt %) lattices, and small (～ 60 nm) particle diameters were obtained. Properties of the latices were characterized in detail by TEM, DSC, dynamic light scattering, spectrophotometry, and tensile strength testing. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3625–3630, 2003     

Dispersion polymerization of methyl methacrylate with three types of comblike fluorinated stabilizers in supercritical carbon dioxide

Dispersion polymerizations of methyl methacrylate in supercritical carbon dioxide were conducted with three types of comblike fluorinate polymer stabilizers: poly(3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10‐heptadecafluorodecyl methacrylate) (PHDFDMA), poly(3,3,4,4,5,5,6,6,7,7,8,8,8‐tridecafluorooctyl methacrylate) (PTDFOMA), and poly(2,2,3,3,3‐pentafluoropropyl methacrylate) (PPFPMA). The effect of the polymerization pressure was not significant on the mean diameters of the poly(methyl methacrylate) (PMMA) particles from 20 to 40 MPa. However, the coefficients of variation of the particle diameters produced at 20 MPa ( , where is the number‐basis mean particle diameter), where the heterogeneous phase was found before polymerization, were larger than those produced at 30 and 40 MPa, where the homogeneous phase was found. The mean size of the PMMA obtained with PTDFOMA and PPFPMA strongly depended on the stabilizer concentration compared with that obtained with PHDFDMA. Moreover, the mean size decreased as the carbon dioxide‐philic side chain length increased. As shown by the results of this study, the best stabilizer among the three types of stabilizers for producing PMMA particles was PHDFDMA. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43813.     

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     

Heterocoagulation behavior of carbon black with surface encapsulation through emulsion polymerization

Nanocomposite microspheres containing styrene–acrylate resin, wax, and carbon black (CB) with desired CB dispersion were prepared through heterocoagulation. The CB surface was modified using conventional anionic emulsifier and anionic dispersants with different lengths of nonionic chains and reactivities or through polymer encapsulation via emulsion polymerization to regulate the dispersion and concentration of CB in the microspheres. Experimental results showed that anionic dispersants with long nonionic chains effectively dispersed and stabilized CB particles. Polystyrene (PS) was then encapsulated on the CB surface by using a reactive dispersant and a water‐soluble initiator of polymerization. The CB particles exhibited comparable pH stability with other heterocoagulation components. Overall, encapsulation through emulsion polymerization can be used to obtain not only high CB content but also improved CB distribution in the resulting microspheres. High coagulation efficiency can also be achieved using polystyrene‐encapsulated dispersed CB because of its high affinity to emulsifiers and reactive dispersants during dispersion. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43516.     

Tentative study on kinetics of bulk polymerization of methyl methacrylate in presence of montmorillonite

The kinetics of the bulk polymerization of methyl methacrylate (MMA) in the presence of montmorillonite (MMT) were studied. The effect of MMT on the radical polymerization of MMA was researched by determining the polymerization rate dilatometrically. It was assumed that there were both bimolecular and monomolecular termination processes involved in the termination of the radicals in the polymerization. It was found that a lower benzoyl peroxide (BPO) concentration promotes a higher fraction of monomolecular mode in chain termination. The results show that there is an optimal ratio of MMT to initiator that increases the bulk polymerization rate of MMA. The X‐ray results show that the layer structure of the formed PMMA–MMT composites was also affected by the BPO concentration. With lower initiator concentration, less pronounced layer structure will be observed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3690–3695, 2003     

Isomerization of silyl ketene acetals: Models for the propagating chain end in group transfer polymerization

The rate of E/Z isomerization for the propagating end in group transfer polymerization (GTP) of methyl methacrylate (MMA) is comparable to the rate of propagation for bifluoride catalysis, in contrast to bibenzoate catalysis where propagation is faster. Methyl 2,2,4-trimethyl-5-methoxy-5-(trimethylsiloxy)pent-4-enoate, 4 (the product of the initiation step in the GTP of MMA), was used as the model of the GTP living end. The rate of monomer addition to 4 was independent of the starting E/Z isomer ratio. The observation of random tacticity in the polymers prepared via anionically catalyzed GTP can be adequately explained by comparable rates of E/Z isomerization and propagation or in the case of bibenzoate catalysis, by the assumption that E and Z propagating ends react with similar stereochemistry. Silyl ketene acetal 2 (a model of the polyacrylate propagating end) underwent HgI₂ catalyzed E/Z isomerization at a rate comparable to the polymerization of ethyl acrylate.     

Modified emulsifier‐free emulsion polymerization of butyl methacrylate with ionic or/and nonionic comonomers

A modified emulsifier‐free emulsion polymerization of butyl methacrylate (BMA) with ionic or/and nonionic comonomers was successfully used to prepare nanosized poly(butyl methacrylate) (PBMA) latices with high polymer contents. After seeding particles were generated in an initial emulsion system, consisting of a portion of BMA, water, ionic comonomer [sodium styrenesulfonate (NaSS)] or nonionic comonomer [2‐hydroxyethyl methacrylate (HEMA)] and potassium persulfate, most of the BMA monomer or the mixture of BMA and HEMA was added dropwise to the polymerizing emulsion over a period of 6–12 h. Stable latices with high PBMA contents up to 27% were obtained. It was found that the latex particle sizes (2R_h) were largely reduced (34 nm) by the continuous addition of monomer(s) compared to those (107 nm) obtained by the batch polymerization method. The effect of comonomer concentration on the particle size, the number of PBMA particles/mL of latex (N_d), and the molar mass (M_w) of copolymer during the polymerization were discussed. The surface compositions of latex particles were analyzed by X‐ray photoelectron spectroscopy, indicating that the surface of latex particles was significantly enriched in NaSS or/and HEMA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3080–3087, 2004     

RAFT polymerization of N,N-diethylacrylamide: Influence of chain transfer agent and solvent on kinetics and induction period

RAFT polymerization of N,N-diethylacrylamide was achieved using three different chain transfer agents bringing cyanoisopropyl, cumyl, or tert-butyl R groups, in different solvents (dioxane, toluene), or in bulk. Reactions were controlled and allowed the synthesis of poly(N,N-diethylacrylamide) with targeted molecular weights. Best results were obtained with cyanoisopropyl dithiobenzoate at 80 °C in toluene. This chain transfer agent (CTA) led to the highest efficiency with a very short induction period. On the reverse, cumyl and tert-butyl dithiobenzoates led to relatively high induction periods which were explained by the slow fragmentation of the intermediate radicals and/or the presence of irreversible termination reactions. Initialization process was also discussed. Cumyl dithiobenzoate surprisingly gave the highest induction in comparison with other CTAs and the slowest polymerization rate in all reactional media. Finally, we demonstrated that the induction period was influenced by the solvent.     

Role of anionic and nonionic surfactants on the control of particle size and latex colloidal stability in the seeded emulsion polymerization of butyl methacrylate

The evolution of the main colloidal parameters in the seeded starved‐feed semi‐continuous emulsion polymerization of butyl methacrylate (BMA) was investigated, with the main purpose of assessing the effectiveness of the semi‐empirical relationship S = K · S_S · ΔA/A_S as a tool to define the surfactant/monomer feed ratio (∝ K) best suited to achieve a target particle size. In particular, the effect of the type and amount of surfactant [i.e., anionic, sodium dodecyl sulfate (SDS), or nonionic, Brij 58P] added during the semi‐continuous stage was considered. Coagulum formation was never observed under the adopted experimental conditions. To detect the occurrence of secondary nucleation or particle aggregation, or both, the particle size and number of particles, the surface tension and the particle surface coverage ratio were correlated. The best results were obtained with SDS and 0.8 ≤ K ≤ 3. In fact, under the selected experimental conditions, only with SDS did the number of particles remain nearly constant throughout the polymerization at the value defined by the seed latex; the particle size distribution was highly monodisperse, and the final particle diameter closely matched the calculated one (～ 120 nm). The above semi‐empirical relationship based on the adjustable parameter K was validated by running test polymerizations aimed at lattices with well‐defined particle size. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3083–3094, 2006     

Propylene polymerization over supported Ziegler–Natta catalysts: Effect of internal and external donors on distribution of active sites according to stereospecificity

Data on the content of fractions with different microtacticities for polypropylene (PP) samples produced over three catalysts [the “donor‐free” titanium–magnesium catalyst and catalysts with dibutyl phthalate and 1,3‐diether(fluorene) used as internal donors] upon polymerization in the absence/presence of an external donor (ED) have been obtained by preparative temperature rising elution fractionation method. The effect of internal and EDs on the distribution of PP fractions with different microtacticity is discussed. Data on molecular weight and thermophysical characteristics were obtained for individual fractions with different microtacticities. Correlations were found between microtacticity, molecular weight, and the melting points of these fractions. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46291.     

Effect of ultrasound on electrochemically initiated acrylamide polymerization

Acrylamide was polymerized under different voltages with ammonium persulfate as the initiator at room temperature. The polymerization reactions were performed in two different ways. In one case, the reaction was performed in a classical, three‐electrode electrochemistry cell, and in the other, the cell was placed in an ultrasonic bath, and ultrasound was applied during the reaction. Both reactions were performed at room temperature. The conversion was rapid; even in the normal electrochemical case, the composite rate constant was comparable to the case with free‐radical polymerization of acrylamide at 50–70°C. When ultrasound was applied, the conversion values increased more. The heterogeneity index and molecular weights of the polymers produced with and without ultrasound were measured with size exclusion chromatography. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 83–89, 2002; DOI 10.1002/app.10233     

Effect of a combination of hexamethylphosphoramide and alkyl alcohol on the stereospecificity of radical polymerization of N-isopropylacrylamide

Radical polymerization of N-isopropylacrylamide (NIPAAm) was investigated at low temperatures in the presence of both hexamethylphosphoramide (HMPA) and alkyl alcohols. Although HMPA and alkyl alcohols separately induced syndiotactic specificity in NIPAAm polymerization in toluene at low temperatures, a combination of HMPA and less bulky alkyl alcohols, such as methanol and ethanol, was found to induce isotactic specificity at −80 °C. NMR analysis of mixtures of NIPAAm, ethanol and HMPA suggested the formation of a 1:1:1 complex through O-H•••O=C and N-H•••O=P hydrogen bonding. It is believed that the steric effect of HMPA enhanced by cooperative hydrogen bonding was responsible for the combined effect of HMPA and alkyl alcohols in inducing isotactic specificity.