Effect of sparteine on the photopolymerization of methyl and ethyl methacrylates with bis(cyclopentadienyl)titanium dichloride in a water–methanol mixture

The photopolymerization of methyl methacrylate (MMA) with bis(cyclopentadienyl)titanium dichloride (Cp₂TiCl₂) in a H₂O‐MeOH [1 : 1 (v/v)] mixture was examined at 40°C in the presence of 2,2′‐bipyridyl (Bipy), 1,10‐phenanthlorine (Phen) or sparteine (Spr) as the chelating reagent. The presence of these chelating reagents retarded the photopolymerization. Poly(MMA)s formed in the presence of them were found to contain a considerable fraction of the benzene‐insoluble part, in contrast to the ones in the absence of them. Spr was the most effective for formation of the insoluble part. The benzene‐insoluble poly(MMA) was insoluble in usual organic solvents including acetone, tetrahydrofuran, ethyl acetate, and dimethyl sulfoxide, suggesting crosslinking. However, poly(MMA) reproduced by hydrolysis of the insoluble part followed by methylation was soluble in usual organic solvents, indicating no crosslinking between polymer main chains. The insoluble part was thermally more stable than the soluble part. Polymerization of ethyl methacrylate in the presence of Spr gave similar results. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 815–822, 2001     

二氯二环戊二烯基锆合成方法的改进

双环戊二烯在180°C解聚为环戊二烯,冰水浴条件下环戊二烯与钠砂反应得到环戊二烯基钠,再在二甲苯为溶剂、低温下环戊二烯基钠与四氯化锆按理论摩尔比2∶1反应3h时得到二氯二环戊二烯基锆,整个过程始终要用氮气保护。产率可以达到70%。     

Optical waveguiding in doped poly(methyl methacrylate)

Poly(methyl methacrylate) doped with the photoinitiators benzil and benzildimethylketal is dissolved in the monomer MMA. From the solutions, planar waveguides and optically-recorded strip waveguides are fabricated on quartz substrates. Mode spectra and total losses are investigated and indicate a minimum loss value of about 0.015 dB mm^?1 for photoinitiator concentrations of about 10%. The results also point to a considerable influence of surface irregularities.     

Bis(cyclopentadienyl)zirconium Dichloride for Alkylation of Heteroaromatics and Synthesis of Bis(indolyl)methanes

Bis(cyclopentadienyl)zirconium dichloride catalyzed alkylation of heteroaromatics with epoxides results in the formation of 3-alkylated heteroaromatics in high yields. Cp₂ ZrCl₂ is also found to be an efficient catalyst for the electrophilic substitution reaction of indoles with aldehydes and ketones to afford the corresponding bis(indolyl)methanes in high yields with complete regioselectivity.     

Synthesis and thermal properties of poly(methyl methacrylate)‐poly(L‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer

Poly(methyl methacrylate)‐poly(L ‐lactic acid)‐poly(methyl methacrylate) tri‐block copolymer was prepared using atom transfer radical polymerization (ATRP). The structure and properties of the copolymer were analyzed using infrared spectroscopy, gel permeation chromatography, nuclear magnetic resonance (¹H‐NMR, ¹³C‐NMR), thermogravimetry, and differential scanning calorimetry. The kinetic plot for the ATRP of methyl methacrylate using poly(L ‐lactic acid) (PLLA) as the initiator shows that the reaction time increases linearly with ln[M]₀/[M]. The results indicate that it is possible to achieve grafted chains with well‐defined molecular weights, and block copolymers with narrowed molecular weight distributions. The thermal stability of PLLA is improved by copolymerization. A new wash‐extraction method for removing copper from the ATRP has also exhibits satisfactory results. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Interface and mechanical properties of poly(methyl methacrylate)–fiber composites

Long‐fiber pellets were made by an in situ pultrusion process. Fiber‐reinforced composites were prepared by an injection‐molding process and an extrusion/injection‐molding method with pellets, respectively. SEM observations showed that the strong interface was maintained during the injection process for low shearing forces, although polymer adhesion to the fiber surface was completely delaminated in the process of extrusion/injection molding for very high shearing forces. Enhanced adhesion of composites promoted substantial improvement of mechanical properties compared to those with poor adhesion. However, the enhanced adhesion between the fiber and the matrix also sacrificed the impact resistance properties. Longer fibers substantially enhanced the properties of composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2478–2483, 2004     

Electrospinning of cyclodextrin functionalized poly(methyl methacrylate) (PMMA) nanofibers

Cyclodextrin functionalized PMMA nanofibers (PMMA/CD) were successfully produced by electrospinning technique with the goal to develop functional nanowebs. Bead-free uniform electrospun PMMA/CD nanofibers were obtained from a homogeneous solution of CDs and PMMA in dimethylformamide (DMF) using three different types of CDs, α-CD, β-CD and γ-CD. The electrospinning conditions were optimized in order to form bead-free PMMA/CD nanofibers by varying the concentrations of PMMA and CDs in the solutions. The concentration of CDs was varied from 5% up to 50% w/w, with respect to the PMMA matrix. We find that the presence of the CDs in the PMMA solutions facilitates the electrospinning of bead-free nanofibers from the lower polymer concentrations and this behavior is attributed to the high conductivity and viscosity of the PMMA/CD solutions. The X-ray diffraction (XRD) spectra of PMMA/CD nanowebs did not show any significant diffraction peaks indicating that the CD molecules are homogeneously distributed within the PMMA matrix and does not form any phase separated crystalline aggregates. Furthermore, attenuated total reflection Fourier transform infrared (ATR-FTIR) studies elucidate that some CD molecules are located on the surface of the nanowebs. This suggests that these CD functionalized nanowebs may have the potential to be used as molecular filters and/or nanofilters for waste treatment purposes.     

Preparation of gold nanoparticles on poly(methyl methacrylate) nanospheres with surface-grafted poly(allylamine)

A facile method for in situ anchoring of gold nanoparticles onto the surface of polymer nanospheres was successfully developed in this study. As polymer nanospheres, amphiphilic poly(methyl methacrylate) (PMMA)/poly(allylamine) (PAA) nanospheres were prepared by graft copolymerization of methyl methacrylate from PAA. The gold nanoparticles anchored were spherically symmetric and the average sizes were ∼12 nm for all samples. It was found that surface-grafted PAA effectively anchored and stabilized gold nanoparticles for a long period of time.     

Mechanical properties of soft liner–poly(methyl methacrylate)‐based denture material

In this study, the mechanical properties of two different permanent soft lining materials and their bonding to poly(methyl methacrylate) (PMMA) were compared. Both of the soft liners were heat‐cured commercial materials. The polymerization was carried out by conventional methods suggested by manufacturer, and the curing was done at the temperature of boiling water for 5, 15, 25, and 35 min. The sample groups were tested in the computer‐aided tensile‐testing machine at a rate of 2 mm/min. The slow rate helps the collection of more and more reliable data. At this time, the stress–strain curves were used to calculate ultimate tensile strength, elastic modulus, resilience, and toughness. The measurements were carried for PMMA, Molloplast B, Flexor, and a combination of PMMA/soft liner. After introducing the soft lining material on PMMA of the same thickness, the new material structure was more elastic than the original PMMA. Flexor showed adhesive failure at studied curing periods, but Molloplast B gave larger tear strength values and cohesive rather than adhesive failure at the 25‐min and 35‐min curing times. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 467–474, 2002     

Rate enhancement of amines in the photopolymerization of methyl methacrylate under oxygen

The photopolymerization of methyl methacrylate was accelerated by amines such as N,N-dimethylbenzylamine, triethylamine, and diethylamine under nitrogen, in which additional initiating radicals were generated by the reaction of the amines with excited MMA. Enhanced rates were observed under oxygen for this photopolymerization in the presence of amines. Because UV spectra of the amines under oxygen indicated that the amines form charge-transfer complexes with oxygen, the rate enhancement was ascribed to photodecomposition of complexes that yield radical species. Molecular weights of polymers obtained in the photopolymerization in the presence of amines decreased under oxygen, supporting the assumed mechanism. © 1998 Society of Chemical Industry     

Network structure and methanol transport dynamics in poly(methyl methacrylate)

The effect of the polymer network structure on methanol transport dynamics in glassy polymers was investigated in both dry and plasticized disks of poly(methyl methacrylate) (PMMA) through gravimetric integral sorption studies. PMMA was synthesized by a controlled free radical polymerization mechanism, crosslinked in bulk with ethylene glycol dimethacrylate, and swollen in methanol under a variety of conditions. In the Case II transport regime, control over the transport rate was shown to depend on the glassy‐state properties of the polymer, and the Case II front velocity was found to be proportional to the square root of the crosslinking density. Similarities were observed in the penetrant transport behavior of both dry and plasticized samples at high degrees of crosslinking, and the activation energy of methanol transport at low degrees of crosslinking was found to be similar for both Fickian and Case II mechanisms. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Preparation and solubility of water–methanol mixtures in sulfonated poly(etherketone) containing a cardo‐ring structure

The preparation and solubility of water–methanol mixtures in sulfonated (1,3‐dihydro‐3‐oxoisobenzofuran‐1,1‐diyl‐1,4‐phenyleneoxy‐1,4‐phenylenecarbonyl‐1,4‐phenyleneoxy‐1,4‐phenylene) (C‐PEK) was systematically studied. The sulfonation was carried out by reacting C‐PEK with 98% sulfuric acid at 60°C. This reaction obeys a first‐order reaction mechanism up to 4 h. The sulfonic acid group was uniformly dispersed in a sulfonated C‐PEK (SC‐PEK) membrane. The introduction of sulfonic acid groups in C‐PEK could increase polymer segmental gaps because of the size of a bulky sulfonic acid group or decrease polymer segmental gaps as a result of polar interactions. The former effect is dominant for SC‐PEK with low sulfonic acid content, whereas the latter occurs for SC‐PEK with high sulfonic acid content. The uptake of pure water or an aqueous methanol solution (e.g., 3, 5, and 10 wt % methanol concentration) in the sulfonated C‐PEK membranes increases with increasing sulfonic acid group content. However, the sulfonated C‐PEK with high sulfonic acid content selectively sorbs water rather than methanol in the membrane. This suggests that the sulfonated C‐PEK membrane could prevent crossover of methanol through the membrane and has potential as a polymer electrolyte for the direct methanol fuel cell. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1113–1123, 2006     

Cp2ZrCl2/三异丁基铝/B(C6F5)3催化体系催化1-辛烯聚合

用Cp₂ZrCl₂/三异丁基铝/B(C₆F₅)₃催化体系对1-辛烯的聚合进行研究,考察催化剂用量、反应温度、反应时间、Al与Zr物质的量比和B与Zr物质的量比等工艺条件的影响。确定1-辛烯齐聚的最佳工艺条件为：催化剂用量0.028 7 mmol,反应温度60 ℃,反应时间60 min,Al与Zr物质的量比为110,B与Zr物质的量比为1.5。     

Structure and properties of highly stereoregular isotactic poly(methyl methacrylate) and syndiotactic poly(methyl methacrylate) blends treated with supercritical CO2

The structure and properties of highly stereoregular isotactic poly(methyl methacrylate) (it-PMMA) and syndiotactic poly(methyl methacrylate) (st-PMMA) blends with crystalline stereocomplex formed by supercritical CO₂ treatment at temperatures ranging from 35 to 130 °C were investigated by means of differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), and dynamic mechanical analysis (DMA) measurements. The melting temperature, T_m, and the heat of fusion, ΔH_m, had maximum values at about 200 °C and 25 J/g, respectively. The degree of crystallinity evaluated by WAXD ranged in value from 32 to 38%. The fringed-micellar stereocomplex crystallites were formed in case of treatment temperatures below 90 °C, and the orderliness perpendicular to the helix axis of the fringed-micellar crystallites was considered to be increased with increasing treatment temperature. In case of treatment temperature of 130 °C, the fringed-micellar crystallites and the lamellar crystallites with high orderliness parallel to the helix axis coupled with the perpendicular orderliness were formed, and the respective double endothermic peaks, T_m¹ and T_m³, were observed in DSC due to the melting of the two kinds of stereocomplex crystallites. The it-PMMA/st-PMMA blends containing the fringed-micellar crystallites maintained high values of storage modulus, E′, up to higher temperature compared with the amorphous blends. The E′ of the blend treated with CO₂ at 130 °C decreased twice at temperatures corresponding to T_m¹ and T_m³.     

Synthesis and dielectric properties of poly(methyl methacrylate)–clay nanocomposite materials

Poly(methyl methacrylate) (PMMA)–clay nanocomposite (PCN) materials were synthesized through in situ intercalative polymerization. A cationic surfactant, [2(dimethylamino)ethyl]triphenylphosphonium bromide, was used as an intercalating agent with pristine Na⁺‐montmorillonite (MMT). The synthesized PCN materials were subsequently investigated by a series of characterization techniques, including wide‐angle powder X‐ray diffraction, Fourier transform IR spectroscopy, transmission electron microscopy, thermogravimetric analysis, and differential scanning calorimetry. Compared to pure PMMA, the PCN materials exhibit higher thermal degradation temperatures and glass‐transition temperatures. The dielectric properties of PCN blending with a commercial PMMA material in film form with clay loading from 0.5 to 5.0 wt % were measured under frequencies of 100 Hz–1 MHz at 35–100°C. Significantly depressed dielectric constants and losses were observed for these PCN‐blending materials. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2175–2181, 2005     

Comparison of the phase behaviour of the liquid-crystalline polymer/poly(methyl methacrylate) and poly(vinyl acetate)/poly(methyl methacrylate) blends

The phase behaviour of blends of a liquid-crystalline polymer (LCP) and poly(methyl methacrylate) (PMMA), as well as the phase state of blends of PMMA and poly(vinyl acetate) (PVA) has been investigated using light scattering and phase-contrast optical microscopy. The blends of LCP and PMMA have been obtained by coagulation from ternary solutions. The cloud point curves were determined. It was established that both pairs demix upon heating, ie have an LCST. In the region of intermediate composition, the phase separation proceeds according to a spinodal mechanism; however for LCP/PMMA blends, the decomposition proceeds according to a non-linear regime from the very onset. In the region of small amounts of LCP, the phase separation follows a mechanism of nucleation and growth. For PMMA/PVA blends, the spinodal decomposition proceeds according to a linear regime, in spite of the molecular mobility that PVA chains develop at lower temperatures. Only after prolonged heat treatment does the process transit to a non-linear regime. The data show a similarity between the phase behaviour of blends of liquid-crystalline and of flexible amorphous polymers. The distinction consists of the absence of a linear regime of decomposition for LCP-PMMA blends. © 1999 Society of Chemical Industry     

Solvent effects on the miscibility of poly(methyl methacrylate)/poly(bisphenol a carbonate) blends

Blends of atactic or syndiotactic poly(methyl methacrylate) (designated as aPMMA or sPMMA) and poly(bisphenol A carbonate) (PC) were prepared from solution casting. Tetrahydrofuran (THF) and chloroform were used as solvent. Experimental results indicated that the as‐cast blends from THF were quite different from the chloroform‐cast ones. After film preparation, THF‐cast blends did not show any visible phase separation. However, chloroform‐cast blends formed a phase‐separated structure. The as‐cast PC from either solvent was not completely amorphous, and had a melting point at 239–242°C, indicating a certain degree of crystallinity. In contrast, the quenched samples of aPMMA/PC blends prepared from the two solvents behaved virtually the same. They both showed aPMMA dissolves better in PC, but PC solubility in aPMMA is very little. Using sPMMA instead of aPMMA to blend with PC, different results were obtained. The quenched sPMMA/PC blends cast from THF showed only one T_g. However, immiscibility (i.e., two T_gs) was found in the same blend system when cast from chloroform. THF was believed to cause the observation of single T_g due to the following kinetic reason. sPMMA and PC were still trapped together even after THF removal in a homogeneous, but nonequilibrium state below the glass transition. Therefore, the quenched sPMMA/PC blends were not truly thermodynamically miscible. From the results of aPMMA or sPMMA with PC, increasing syndiotacticity seemed to improve the miscibility between PMMA and PC. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2842–2850, 2001     

Water‐uptake kinetics in poly(methyl methacrylate) films with a fluorescent rotor probe

A fluorescence method was adapted to measure moisture‐uptake kinetics in films of poly(methyl methacrylate), and data were interpreted in the context of a Fickian diffusion model. The films, 2–60 μm thick, were supported on acid‐etched microscope slides. They were compared with several freestanding slabs about 1 mm thick. The moisture diffusion in the slabs was Fickian with a diffusivity of 3.2 × 10^?9 cm²/s. The apparent Fickian diffusivity in the films decreased substantially with decreasing film thickness; however, a careful examination revealed that the initial moisture uptake was governed by a thickness‐independent diffusivity for a wide range of film thicknesses. This suggested that the appearance of non‐Fickian behavior originated within about a micrometer of the buried interface, possibly as a result of water accumulation beneath the film or slight thickness variations. Moisture uptake in the thickest films was more rapid than in the slabs, most likely because of residual thermal stresses. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2463–2471, 2002     

Preparation of poly(methyl methacrylate)/titanium oxide composite particles via in‐situ emulsion polymerization

Poly(methyl methacrylate) (PMMA)/Titanium oxide (TiO₂) composite particles were prepared via in‐situ emulsion polymerization of MMA in the presence of TiO₂ particles. Before polymerization, the TiO₂ particles was modified by the silane coupling agent, which is crucial to ensure that PMMA reacts with TiO₂ via covalent bond bindings. The structure of the obtained PMMA/TiO₂ composite particles was characterized using Fourier transform infrared spectra (FTIR) and thermogravimetric analysis (TGA). The results indicate that there are covalent bond bindings between PMMA macromolecules and TiO₂ particles. Based on these facts, several factors affecting the resulting PMMA/TiO₂ composite system, such as the type of coupling agents, the mass ratio of the MMA to the modified TiO₂, the emulsifier concentration, and the initiator concentration, etc., were examined by the measurement of conversion of monomers, the gel content of polymers, the percentage of grafting, and the grafting efficiency, using gravity method or TGA method. As a result, the optimized recipe was achieved, and the percentage of grafting and the grafting efficiency could reach 216.86 and 96.64%, respectively. In addition, the obtained PMMA/TiO₂ composite particles were found to a stable colloidal dispersion in good solvent for PMMA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4056–4063, 2006     

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