Nonaqueous poly(methyl methacrylate) dispersions: radical dispersion polymerization in the presence of AB block copolymers of polystyrene and poly(dimethyl siloxane)

Well defined AB block copolymers of polystyrene (PS) and poly(dimethyl siloxane) (PDMS) have been prepared with PS molecular weights in the range 8 800 to 43 600 and PDMS molecular weights in the range 2 400 to 48 000. Provided the PS and PDMS molecular weights have a ratio within the range 0.5 to 4.0, these block copolymers stabilize particles of poly(methyl methacrylate) in n-alkanes. The particle size over the range 0.1 to 0.5 μm may be varied by performing dispersion polymerizations of methyl methacrylate as a function of monomer content of the seed stage and as a function of the concentration, molecular weight and composition of the block copolymer. From silicon analyses of the poly(methyl methacrylate) particles, values of the surface area stabilized per PDMS chain were established. The results indicate complete surface coverage of the particles.     

功能性甲基丙烯酸甲酯-甲基丙烯酸缩水甘油酯嵌段聚合物ATRP合成

以2-溴代丙酸乙酯(EPN-Br)为引发剂,CuCl和2,2’-联二吡啶(BPY)为催化剂,以甲基丙烯酸甲酯(MMA)为原料,用原子转移自由基(ATRP)的方法,在80℃下合成带有卤原子的聚甲基丙烯酸甲酯大分子引发剂,在20～50℃下,以丁酮和正丙醇的混合液为溶剂,引发甲基丙烯酸缩水甘油酯(GMA)聚合,制得侧链含有环氧基团的PMMA-b-PGMA嵌段共聚物,分子量分布较窄,聚合物的分子量可通过单体与引发剂的比例进行控制。     

Morphology and thermodynamic analysis of composite polymer particles prepared by soap‐free emulsion polymerization in the presence of poly(methyl methacrylate) and polystyrene as biseeds

Biseeds emulsion polymerization was investigated with poly(methyl methacrylate) (PMMA) and polystyrene (PSt) as biseeds and styrene (St) as second‐stage monomer, as well as with thermodynamic analysis; namely, the principle of minimum interfacial free‐energy change was utilized to explain the competitiveness of different seeds for second‐stage monomer and the final equilibrium morphology of composite polymer particles. The experimental results indicated the polymeric particles prepared had bimodal size distribution and the PMMA seed particles showed a higher chance of obtaining St than that of the PSt seed particles, which was in agreement with the computational outcome by the principle of minimum interfacial free‐energy change. Owing to the kinetic factors, the equilibrium morphology could not be reached in the experiments. However, the results demonstrated that double or multiple seeds emulsion polymerization could be used as a model experiment to study the morphology of polymer particle and the morphological prediction. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2675–2680, 2004     

Characterization of some poly(methyl methacrylate) prepared by emulsion polymerization in presence of egyptian delta titano magnetite ore (EDTMO)

The emulsion polymerization of methyl methacrylate was studied in water using potassium persulphate as initiator and dedocyl–benzene sodium sulphonate as emulsifying agent at 85°C. The effect of Egyptian delta titano magnetite ore (EDTMO) upon the activation energy and on the mean average molecular weights of the obtained polymers was studied. It was found that the viscosity average molecular weights increase with decrease of reaction temperature and initiator concentration but increase with increase of monomer concentration in the reaction medium. Some of the polymer samples prepared in absence and in presence of some (EDTMO) were separated on tlc plates according to molecular weight in binary mixture, benzene:methanol (1:1.4 by volume) at 30°C. The tlc techniques were performed to give an idea about the molecular weight distribution of the polymer samples obtained.     

Characterization of some poly(methyl methacrylate)s prepared by emulsion polymerization in the presence of burnt mazot boiler deposit (BMBD)

The emulsion polymerization of MMA was studied in water using potassium persulfate as initiator and dodocyl benzene sodium sulfonate as emulsifying agent in the absence and presence of burnt mazote boiler deposit (BMBD). The BMBD has a catalytic effect on the polymerization reaction; its effect on the mean average molecular weights of the obtained polymers was also examined by viscosity measurements. The molecular weight distribution was obtained by thin layer chromatographic analysis. The polydispersity for the obtained polymers was wider when prepared in the presence of BMBD. The apparent activation energy among 65, 75, and 85°C for this system was 13.2 × 10⁴ J/mol and 9.2 × 10⁴ J/mol when the polymerization is carried out in the absence and presence of 0.1 g BMBD/20 mL of the reaction mixture, respectively. The suitable mobile phase was ethylacetate or dimethylformamide as single eluent system. In case of binary eluent systems the mobile phase was benzene + methanol (1:1.4 by volume).     

Solution blending of polystyrene and poly(methyl methacrylate)

Blends of poly(methyl methacrylate) (PMMA) and polystyrene (PS) have been investigated by differential scanning calorimetry and scanning electron microscopy. Blends were made of a low molecular weight PS with three PMMAs having number-average molecular weights of (1) 18,300, (2) 37,000, and (3) 211,000, The blend was found to be partially miscible. The composition-dependent values of the polymer-polymer interaction parameter (g₁₂) were determined and found to be from 0.015 to 0.029 for solution casting at 25°C. The interaction parameter (g₁₂) increases with increasing PMMA molecular weights in the PMMA/PS blend systems. This result is consistent with the behavior of the glass transition temperatures and with the microscopy study which indicate that compatibility is greater in the PMMA-1/PS blends having the low molecular weight of PMMA than in the PMMA-3/PS blends having the higher molecular weights of PMMA.     

Morphological characterization of attapulgite/poly(methyl methacrylate) particles prepared by soapless emulsion polymerization

BACKGROUND: The synthesis of core–shell inorganic/polymer nanocomposites, in which the polymer shell determines the chemical properties and the interaction with the environment, whereas their physical properties are governed by both the size and shape of the inorganic core and the surrounding organic layer, is an area of increasing research activity. RESULTS: Core–shell and bead–string shaped attapulgite/poly(methyl methacrylate) (ATP/PMMA) nanocomposite particles were prepared by soapless emulsion polymerization in an aqueous suspension of attapulgite organically modified with cetyltrimethylammonium bromide. CONCLUSION: Transmission electron microscopy analysis results showed that the amounts of the monomer added had no influence on the morphologies of the ATP/PMMA particles. The morphologies only depended on the length/diameter ratio of the attapulgite fibrillar single crystal used. Long ATP needles formed the bead–string structure while short ATP needles formed the core–shell structure. Copyright © 2007 Society of Chemical Industry     

Modified frontal polymerization of poly(methyl methacrylate)

In this work, we propose a modified frontal polymerization method to build a uniform reaction front by gradually immersing the reacting mixture in a thermal bath. This scheme allows uniform materials to be obtained with nearly constant molecular weights and polydispersities and a low residual monomer concentration. A comparative study of the molecular weight distributions of poly(methyl methacrylate)s obtained by bulk polymerization, frontal polymerization, and frontal polymerization with the proposed gradual immersion is presented. Samples obtained by these methods show that materials obtained by bulk polymerization and by frontal polymerization are less uniform than those obtained by frontal polymerization with gradual immersion in a thermal bath. The obtained uniformity is directly related to a stabilizing effect of the reaction front by the gradual immersion of the reactor in a constant‐temperature bath and to a reduction in the reaction rate promoted by a moderate transfer agent concentration. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Hyperbranched poly(methyl methacrylate)s prepared by miniemulsion polymerization and their (non)-Newtonian flow behaviors

Miniemulsion polymerization is most suitable for the targeted synthesis of vinyl copolymers than the conventional emulsion polymerization, because in miniemulsion polymerization each monomer nanodroplet is a nanoreactor, and the monomers in each droplet are in situ converted to the corresponding polymers. Soluble and hyperbranched poly(methyl methacrylate)s (PMMA) were prepared with quantitative monomer conversion and without gelation by the miniemulsion copolymerization with di- and tri-acrylate and mediated with 1-dodecyl thiol (DDT). DDT acted both as a gelation prohibitor and as a reactive cosurfactant. The PMMAs with varied “X” or “Ж” shaped branches, depending on the di- and tri-functional acrylate used as the branching agent, are characterized and interpreted in terms of the repeating units per part, parts and branches per macromolecule, average molecular weight, latex particle size and size distribution. Effects of topology changes of the branched PMMAs on the rheological behaviors are observed for the first time: from Newtonian flow for the densely branched PMMAs to the non-Newtonian flow with pronounced shear thickening for the PMMA samples with high-molecular-weight and longer parts.     

Controlled radical polymerization of methyl methacrylate in the presence of 2-bromoethanol

Summary The radical polymerization of methyl methacrylate (MMA) and styrene (St) initiated by 2,2’-azobis(isobutyronitrile) (AIBN) at 60 °C in the presence of haloalkyl alcohol are studied. The influence of structure and concentration of haloalkyl alcohol as a transfer agent are investigated. For the radical polymerization of MMA in the presence of large amount of 2-bromoethanol, controlled radical polymerization is proceeded. The 2-bromoethanol is, thus, one of the transfer agents for radical polymerization to control the molecular weight and the structure of poly(MMA).     

Particle features of a poly(methyl methacrylate) resin prepared by a new emulsion polymerization process

A new emulsion polymerization process, in which water acted as the dispersed phase and a mixture of methyl methacrylate (MMA) and cyclohexane acted as the continuous phase, was applied to the preparation of a poly(methyl methacrylate) (PMMA) resin. The primary (latex) particles were formed in the early stage of polymerization and coagulated as the polymerization conversion increased. Scanning electron micrographs showed that the final PMMA particles were porous and composed of loosely aggregated primary particles. The porosity characterized by cold di(2‐ethylhexyl) phthalate absorption increased as the water/oil and cyclohexane/MMA mass ratios increased. The PMMA primary particles were smaller than the primary particles in the PMMA resin prepared by suspension polymerization in the presence of cyclohexane. Because of the phase composition of the reaction system, the solubility of PMMA in a mixture of cyclohexane and MMA, and the particle morphology of PMMA, a particle formation mechanism, including the formation, growth, and coagulation of primary particles in dispersed water droplets, was proposed. The primary particles formed mainly through a homogeneous nucleation mechanism and increased in size as MMA diffused from the oil phase to the water phase to the primary particles. The coagulation of the primary particles occurred because of the lower colloidal stability and the space limitations of the primary particles. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1905–1911, 2004     

甲基丙烯酸甲酯的反向原子转移自由基沉淀聚合反应的研究

以甲基丙烯酸甲酯（MMA）为单体,偶氮二异丁腈（AIBN）为引发剂,以氯化铜（CuCl2）/2,4,6-三（二甲氨基甲基）苯酚（DMP-30）为催化体系,以乙醇为溶剂,进行了甲基丙烯酸甲酯的反向原子转移自由基沉淀聚合。聚合反应速率对单体呈一级动力学特征,数均分子量与单体转化率呈线性关系。     

Rheological properties of polystyrene and poly(methyl methacrylate) blends

Rheological properties of the polystyrene (PS) and poly(methyl methacrylate) (PMMA) blends were studied by Advanced Rheometric Expansion System (ARES). Storage modulus and loss modulus of the PS and PMMA blends were measured, and the interfacial tension of the PS and PMMA blends were obtained with various emulsion models by using the storage modulus and loss modulus of the blends. The value of interfacial tension estimated from the Palierne emulsion model was found to be 2.0 mN/m. Also, the interfacial tension between PS and PMMA was calculated by a theoretical model. The values of interfacial tension of the PS and PMMA blends obtained by the experiment and theoretical model were found to be in good agreement.     

Influence of nanozirconia on the thermal stability of poly(methyl methacrylate) prepared by in situ bulk polymerization

Nanozirconia (nano‐ZrO₂) was prepared by the sol–gel method and incorporated into poly(methyl methacrylate) (PMMA) by the in situ bulk polymerization of methyl methacrylate. The structure of the nano‐ZrO₂ was confirmed by X‐ray diffraction (XRD), transmission electron microscopy, and Fourier transform infrared (FTIR) spectroscopy. The structure of the nano‐ZrO₂ nanocomposites were studied by differential scanning calorimetry, FTIR spectroscopy, XRD, and scanning electron microscopy, and the results show that there were interactions between the nanoparticles and the polymer. The influence of the nano‐ZrO₂ on the thermal stability of PMMA was investigated by thermogravimetric analysis (TGA). The results indicate that nano‐ZrO₂ enhanced the thermal stability of the PMMA/nano‐ZrO₂ nanocomposites. The effects of the heating rate in dynamic measurements (5–30°C/min) on kinetic parameters such as apparent activation energy (E_a) in TGA both in nitrogen and air were investigated. The Kissinger method was used to determine E_a for the degradation of pure PMMA and the PMMA/nano‐ZrO₂ nanocomposites. The kinetic results show that the values of E_a for the degradation of the nanocomposites were higher than that of pure PMMA in air. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Characterization of some poly(methyl methacrylate)s prepared by emulsifier-free emulsion polymerization in presence of some organic ligands and their nickel complexes

The aqueous polymerization of methyl methacrylate (MMA) was studied using sodium bisulfite as initiator in absence and presence of tetraoxalyl urea (TOU), tetraoxalyl thiourea (TOthioU) and tetraoxalyl paraphenylene diamine (TOp-phD). The effect of their nickel complexes on the polymerization rate has also been studied. Ligands with free carboxyl groups have a retarding effect on the polymerization reaction, while their nickel complexes have a catalytic effect. The polymers obtained in presence of nickel complexes were found to have wider molecular weight distribution than those obtained in their absence; this was deduced by thin layer chromatographic analysis in a binary mixture (benzene/methanol). The apparent energy of activation was found to be 5.83 × 10⁴ J/mol, 1.87 × 10⁴ J/mol, 2.11 × 10⁴ J/mol, and 3.95 × 10⁴ J/mol in absence and in presence of 0.5 g of Ni complex of TOp-phD, TOthioU and TOU, respectively.     

Atom transfer radical coupling of polystyrene and poly(methyl acrylate) synthesized by reverse iodine transfer polymerization

Iodo-terminated polystyrene and poly(methyl acrylate) (PMA-I) were synthesized by reverse iodine transfer polymerization. The resulting polymers were coupled by atom transfer radical coupling using Cu(I)/linear amino-ligand catalysts in the presence of reducing Cu(0). The efficiency of the coupling reaction is discussed as a function of various factors, namely, the Cu(0) particle sizes, the number of nitrogen present in the ligand structure, the type of halogen associated with Cu(I) (CuX, X = I, Br, Cl), the nature of the polymer and the nature of the chain ends. In particular, a quantitative coupling (100%) was obtained with a CuBr/HMTETA system in the presence of nanosized Cu(0) for PMA-I, thus opening for the first time a facile route to telechelic and multiblock poly(acrylate)-based structures.     

Effects of reaction conditions on poly(methyl methacrylate) polymerized by living radical polymerization with iniferter

Living radical polymerization of methyl methacrylate (MMA) through the use of benzyl diethyl dithiocarbamate (BDC) was studied. The aim was to investigate the role of the concentration, BDC‐to‐MMA mol ratio, and reaction time upon the molecular weight, polydispersity, and conversion of the product. It was found that the molecular weight and the conversion increase with increase of the concentration at the expense of low polydispersity. The reaction time also played a significant role, especially at a relatively long reaction time where molecular weight, polydispersity, and conversion increased with increasing reaction time. In terms of the mol ratio effect, it was found that there was a critical mol ratio for maximum conversion. The results indicate that the kinetics of polymerization of MMA through the use of a BDC inifeter is different from that in the presence of a conventional initiator. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 938–944, 2000     

Phase behavior and properties of poly(methyl methacrylate)/poly(vinyl acetate) blends prepared via in situ polymerization

Polymer blends composed of poly(methyl methacrylate) (PMMA) and poly(vinyl acetate) (PVAc) were prepared via radical-initiated polymerization of methyl methacrylate (MMA) in the presence of PVAc. Differential scanning calorimetry and dynamic mechanical analysis were employed to investigate the miscibility and phase behavior of the blends. The PMMA/PVAc blends of in situ polymerization were found to be phase separated and exhibited a two-phase structure, although some chain transferring reaction between the components occurred. The phase separation resulted from the solvent effect of MMA during the in situ polymerization, which was confirmed by the investigation of phase behavior based on solution cast blending. Solubility analysis of the polymerized blends indicated that some chain transferring reaction between the components occurred during the polymerization. An abrupt increase in gel content from 21.2 to 72.4 wt % was observed when the inclusion of PVAc increased from 30 to 40 wt %, and the gel component consisted of the component polymers as shown by infrared spectroscopy studies. The thermogravimetric analysis study indicated that the inclusion of a small amount of PVAc gives rise to a marked stabilization effect on the thermal stability. The PMMA/PVAc blends exhibited increased notched impact properties with the inclusion of 5 wt % PVAc. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 675–684, 1998