Poly(methyl acrylate-co-methyl methacrylate)/montmorillonite nanocomposites fabricated by soap-free emulsion polymerization

The exfoliated poly(methyl acrylate-co-methyl methacrylate)/montmorillonite (MMT) nanocomposite latex solutions fabricated by soap-free emulsion polymerization were able to cast into a film. The films were transparent and ductile unless more than 5 wt% of MMT was incorporated. With the MMT content higher than 5 wt%, the inflammable residuals of nanocomposites after combustion could preserve their original film profile acting like an inflammable scaffold. Moreover, as 20 wt% MMT was incorporated, the yield strength of the films was increased up to 20 times and Young’s modulus up to 2,000 times. However, the water vapor permeability coefficient of the films was only decreased down to its half value. This unexpected behavior of permeability was associated with the decrease of T _g as the content of MMT was increased, owing to the large difference of the reactivity ratios between methyl acrylate and methyl methacrylate monomers and their differential absorption to the MMT during copolymerization.     

Effect of Clay Type on Structure and Properties of Poly(methyl methacrylate)/Clay Nanocomposites

Summary: PMMA nanocomposites using natural Cloisite 6A and synthetic Lucentite SPN clays were produced via melt blending. The degree of intercalation or exfoliation was measured for both composites using transmission electron microscopy (TEM) and the results were confirmed with small angle X‐ray scattering (SAXS). The smaller dimensions of the synthetic SPN, as well as the complete absence of Fe ion impurities allowed for the production of a composite which was optically clear and completely colorless. TEM and SAXS measurements were performed on samples heated to high temperatures. The data showed that in both cases large ribbons composed of the individual platelets were formed. We postulated that these ribbons formed a barrier against spreading of the flame and hence the smaller clays, which are more mobile, had a higher efficiency.

TEM image of a high degree of exfoliation of synthetic clay SPN in the PMMA matrix.     

聚甲基丙烯酸甲酯／纳米SiO2复合粒子的制备与表征

采用甲基丙烯酸-3-甲氧基硅丙酯（MPs）对分散于甲基丙烯酸甲酯（MMA）中的纳米SiO2粒子进行偶联改性，得到了表面改性的纳米SiO2单体分散液，用原位悬浮聚合方法制备了不同SiO2含量的PMMA／纳米SiO2复合粒子。通过红外光谱、透射电镜、差示扫描量热分析和热重分析等方法对制备的纳米复合粒子进行了表征，结果表明，纳米SiO2粒子在PMMA中分散良好；MMA可通过与MPS的共聚而有效地接枝到SiO2粒子表面，当SiO2含量为6．6％（质量分数，下同）、MPS用量为0．06g／gSiO2时，其接枝率可达73．8％；同时，纳米SiO2的引入可提高PMMA的耐热性能，当Si02含量为14.7％时，其玻璃化转变温度和最大热分解速率时的温度分别提高了11．8℃和18．8℃。     

Preparation and Characterization of Poly(benzimidazole-amide)/ZnO Nanocomposites Using Silane Coupling Agent

Some novel nanocompoites were fabricated via zinc oxide (ZnO) nanoparticles which was modified by 3-aminopropyltriethoxylsilane (KH550) as a coupling agent. Poly(benzimidazole-amide) (PBIA) was synthesized via polymerization reaction of 1,3-bis(5-amino-1H-benzimidazol-2-yl)benzene (3a) with isophthaloyl chloride (4b) and used as a polymer matrix. PBIA/ZnO nanocompoites were characterized by Fourier transform infrared spectra (FT-IR), X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM). FE-SEM and TEM analysis showed that the modified ZnO nanoparticles were homogeneously dispersed in polymer matrix. In addition, thermogravimetric analysis (TGA) data indicated an enhancement of thermal stability of nanocomposite compared with the pure polymer.     

Poly(methyl methacrylate)/clay nanocomposites by photoinitiated free radical polymerization using intercalated monomer

A series of poly(methyl methacrylate)/montmorillonite (PMMA/MMT) nanocomposite were prepared by successfully dispersing the inorganic nanolayers of MMT clay in an organic PMMA matrix via in situ photoinitiated free radical polymerization. Methyl methacrylate monomer was first intercalated into the interlayer regions of organophilic clay hosts by “click” chemistry followed by a typical photoinitiated free radical polymerization. The intercalated monomer was characterized by FT-IR spectroscopy, elemental analysis and thermogravimetric analysis methods. The intercalation ability of the modified monomer and exfoliated nanocomposite structure were confirmed by X-ray diffraction spectroscopy (XRD), transmission electron microscopy (TEM) and atomic force microscopy (AFM). Thermal stability of PMMA/MMT nanocomposites was also studied by both differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA).     

Tacticity effects on the miscibility behavior of poly(methyl methacrylate)/poly(ethylene oxide-b-dimethylsiloxane-b-ethylene oxide) blends

The miscibility of a triblock copolymer poly(ethylene oxide)-poly(dimethylsiloxane)-poly(ethylene oxide) with syndiotactic and isotactic poly(methylmethacrylate) wasstudied. Although isotactic poly(methyl methacrylate) (PMMA) was miscible with poly(ethylene oxide) (PEO) in the pure state, it was immiscible with the PEO end blocks in the copolymer. In comparison, the syndiotactic poly(methyl methacrylate) (sPMMA) was miscible with the PEO blocks as indicated by melting point depression, decrease in crystallinity, and slower rate of spherulite growth of PEO. When blends of the triblock copolymer were cooled to low temperatures, the poly(dimethylsiloxane) (PDMS) middle block which resided in the interlamellar region of PEO spherulites also crystallized; the development of PDMS crystals was clearly suppressed at high sPMMA contents.On leave from Union Chemical Laboratories, Industrial Technology Research Institute, Hsinchu, Taiwan     

Synthesis and Surface Properties of Poly(methyl methacrylate)/Poly(ethylene glycol) Binary Brushes

A new kind of binary polymer brushes was synthesized from two immiscible polymers, PMMA and PEG, on GPS‐modified silicon wafers. Surface composition, layer thickness, coverage, chain density, wetting ability, morphology and protein adsorption of the binary brushes were investigated by XPS, ellipsometry, AFM and contact angle measurements. The results show that both PMMA and PEG were successfully grafted onto the surface. The surface coverage and the chain density of PMMA and PEG brushes can be controlled by modulating the reaction temperature and time. This kind of binary polymer brushes exhibits a distinct microphase‐separated structure and excellent protein‐preventing property.

     

Damping Properties of Polyorganosiloxane/Poly(methyl methacrylate) Interpenetrating Networks

Interpenetrating polymer networks (IPNs) based on polyorganosiloxane/poly(methyl methacrylate) were prepared via sequential polymerization and the damping and mechanical properties of these materials were studied. The effects of crosslinking in both the first‐ and second‐formed networks were investigated. The experimental results show that the extent of damping of the IPNs was decreased and shifted to higher temperature as the content of poly(methyl methacrylate) was increased; the mechanical properties such as tensile strength and hardness (Shore A) were increased with increasing poly(methyl methacrylate) (PMMA) content. The loss factor peak becomes narrower with increasing crosslinker level in the first‐formed network (polysiloxane network), while increasing crosslinker content in the second‐formed network (PMMA network) results in a broadening of the IPN transition peak and moves the IPN transition to higher temperatures as well.     

Poly(methyl methacrylate) nanocomposite reinforced with graphene,graphene oxide,and graphite: a review

Poly(methyl methacrylate) (PMMA) is an important transparent thermoplastic polymer having appropriate strength, chemical, weathering, heat, and UV resistance. However, essential properties of this versatile polymer need to be enhanced for high-tech applications. Graphene has opened up a new vista for developing functional polymeric nanocomposite. Therefore, reinforcement of PMMA with graphene and related nanofiller has been focused in literature. This review basically highlights the fundamentals and characteristics of the significant classes of PMMA/graphene, PMMA/graphene oxide, and PMMA/graphite nanocomposite. Recent developments in the applications of PMMA/graphene-based nanofiller nanocomposite in biomedical, sensor, supercapacitor, flame retardant, and electromagnetic interference shielding materials were also comprehended.     

Impact,Thermal, and Morphological Properties of Poly(Lactic Acid)/Poly(Methyl Methacrylate)/Halloysite Nanotube Nanocomposites

Poly(lactic acid)/poly(methyl methacrylate) blends containing halloysite nanotube (2 and 5 phr) and epoxidized natural rubber (5–15 phr) were prepared by melt mixing. The impact strength of poly(lactic acid)/poly(methyl methacrylate) blend was slightly improved by the addition of halloysite nanotube. Adding epoxidized natural rubber further increased the impact strength of poly(lactic acid)/poly(methyl methacrylate)/halloysite nanotube nanocomposite. Single T_g of poly(lactic acid)/poly(methyl methacrylate) is observed and this indicates that poly(lactic acid)/poly(methyl methacrylate) blend is miscible. The addition of halloysite nanotube into poly(lactic acid)/poly(methyl methacrylate) slightly increased the T_g of the blends. The epoxidized natural rubber could encapsulate some of the halloysite nanotube and prevent the halloysite nanotube from breaking into shorter length tube during the melt shearing process.     

电容式湿度传感器电容式湿度传感器——交联的聚甲基丙烯酸甲酯的感湿性能

运用本体聚合法合成了聚甲基丙烯酸甲酯（ＰＭＭＡ）和分别用三种交联剂交联的ＰＭＭＡ。以ＰＭＭＡ和交联的ＰＭＭＡ为感湿膜制成电容式湿度传感器,在１０％～９０％ＲＨ范围内,这些传感器的电容随相对湿度呈线性规律变化。交联的ＰＭＭＡ传感器具有正的温度系数,但与乙酸丁酸纤维素（ＣＡＢ）传感器相比,ＰＭＭＡ的温度依赖性更小。交联的ＰＭＭＡ传感器能耐有机蒸气,在饱和丙酮蒸气中放置３０ｍｉｎ后,３次测试循环后在９０％ＲＨ下传感器电容的变化约为１％。在高温、高湿、油烟气等各种苛刻环境中放置预定时间后,传感器的漂移一般在±２％ＲＨ范围内。     

Properties of mineral filled poly(lactic acid)/poly(methyl methacrylate) blend

This study examines the influence of three different minerals, that is, clay, calcium carbonate, and quartz on the physical, thermal, and mechanical properties of poly(lactic acid) (PLA)/poly(methyl methacrylate) blend. Rheological behavior and phase structure were initially studied by small-amplitude oscillatory shear rheology. Clay- and quartz-filled materials presented an increase in viscosity at low frequency associated with the presence of a yield stress. However, this behavior was not observed for calcium carbonate filled materials due to a matrix degradation effect. To elucidate this aspect, thermal stability and thermal properties were examined by thermogravimetric analysis and differential scanning calorimetry, showing that calcium carbonate promotes degradation of the PLA phase. No nucleating effect was observed in the presence of the minerals. Dynamical mechanical analysis and mechanical characterization revealed an increase of the overall softening temperature and, a reinforcing effect for clay- and quartz-based composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 46927.     

Surface mechanical properties of transparent poly(methyl methacrylate)/zirconia nanocomposites prepared by in situ bulk polymerization

Poly(methyl methacrylate)/zirconia (PMMA/ZrO₂) nanocomposites with ZrO₂ content as high as 15 wt% were prepared by modifying non-aqueous synthesized ZrO₂ nanoparticles with methacryloxypropyltrimethoxysilane (MPS) in tetrahydrofuran, dispersing MPS-functionalized ZrO₂ nanoparticles in MMA and following in situ bulk polymerization with controlled pre-polymerization time. The MPS-functionalized ZrO₂ nanoparticles showed an efficient crosslinking role in the polymerization, leading to a complete gel of PMMA at 5 wt% of ZrO₂ content. Homogeneous dispersion of the ZrO₂ nanoparticles at primary particle size level was observed in all nanocomposites, which results in good clarity of the obtained nanocomposites. Hardness tests (pendulum hardness tests and indentation tests) and anti-scratch tests (abrasion tests and nano scratch tests) were employed to probe the surface mechanical properties of the nanocomposites. The properties of nanocomposites as a function of ZrO₂ content, revealing from various characterization techniques, are not consistent and discussed in detail. At low ZrO₂ content, the mechanical properties are enhanced by the formed crosslinking structure. However, remarkable improvements of hardness and scratch resistance of PMMA were achieved when 15 wt% of ZrO₂ content was embedded.     

A reactive molecular dynamics model of thermal decomposition in polymers: I. Poly(methyl methacrylate)

The theory and implementation of reactive molecular dynamics (RMD) are presented. The capabilities of RMD and its potential use as a tool for investigating the mechanisms of thermal transformations in materials are demonstrated by presenting results from simulations of the thermal degradation of poly(methyl methacrylate) (PMMA). While it is known that depolymerization must be the major decomposition channel for PMMA, there are unanswered questions about the nature of the initiation reaction and the relative reactivities of the tertiary and primary radicals formed in the degradation process. The results of our RMD simulations, performed directly in the condensed phase, are consistent with available experimental information. They also provide new insights into the mechanism of the thermally induced conversion of this polymer into its constituent monomers.     

抗聚结MBS的制备及性能

通过分子结构设计,合成了一系列提高MBS粉末特性的包裹剂,研究了抗聚结新型MBS的制备工艺以及包裹剂化学结构对MBS粉末特性及PVC／MBS共混物力学性能的影响。结果表明,加入包裹剂后,MBS粉末流动性及其堆积密度均有较大提高,而且显著提高PVC／MBS共混物的抗冲强度和抗拉强度。     

Poly(ethylene oxide)/clay nanocomposite: Thermomechanical properties and morphology

Poly(ethylene oxide) (PEO)/clay nanocomposites were prepared by a solution intercalation method using chloroform as a solvent. The nanocomposites were characterised by X-ray diffraction (XRD), differential scanning calorimetry (DSC), hot-stage polarized optical microscopy (POM), Fourier transform infrared spectroscopy (FT-IR), tensile analysis, dynamic mechanical analysis (DMA) characterisation techniques. Formation of nanocomposite was confirmed by X-ray diffraction (XRD) analysis. A decrease in PEO crystallinity in case of nanocomposite, was confirmed by a decrease in the heat of melting and spherulite size as indicated by DSC and POM studies, respectively. Improvement in tensile properties in all respect was observed for nanocomposites with optimum clay content (12.5 wt%). DMA studies indicate an increase in loss peak temperature and broadening of loss peak as a result of clay intercalation.     

Phase continuity and inversion in polystyrene/poly(methyl methacrylate) blends

Dual-phase continuity and phase inversion of polystyrene (PS)/poly(methyl methacrylate) (PMMA) blends processed in a twin-screw extruder was investigated using a selective extraction technique and scanning electron microscopy. Emphasis was placed on investigating the effects of viscosity ratio, blend composition, processing variables (mixing time and annealing) and diblock copolymer addition on the formation of bi-continuous phase structure (BPS) in PS/PMMA blends. The experimental results were compared with the volume fraction of phase inversion calculated with various semi-empirical models. The results showed that the formation of a BPS strongly depends on the blend composition and the viscosity ratio of the constituent components. Furthermore, BPS was found in a wide volume fraction interval. Increasing the mixing time and the addition of diblock copolymer, both led to a narrowing range of volume fraction in which BPS exists. Quiescent annealing coarsened the structure but indicated no qualitative changes. Some model predictions for phase inversion could predict qualitative aspects of the observed windows of co-continuity but none of the models could account quantitatively for the observed data.     

Hot-drawing of poly(methyl methacrylate) and simulation using a glass-rubber constitutive model

The large-deformation three-dimensional glass-rubber constitutive model for isotropic, amorphous, linear polymers near the glass transition, previously proposed, has been extended to include a spectrum of network relaxations. In addition, an experimental programme of uniaxial tension and compression tests was carried out on high molecular weight cast sheets of poly(methyl methacrylate) (PMMA), with varying strain-rate and temperature across the range from 114 to 190 °C, encompassing the thermoforming range of practical importance. The extended model was found to fit successfully the data for PMMA, provided a doublet network relaxation spectrum was employed. The original model, with only a single network relaxation, was found to be grossly inadequate when there was significant network relaxation by entanglement slippage. Parameters of the model for PMMA, obtained by fitting to the new data, were compared with values obtained by other routes.     

聚乙烯醇/蒙脱石纳米复合材料的结构与性能

通过溶液插层 流延成膜法,以聚乙烯醇和钠质蒙脱石为原料,制备出了不同蒙脱石含量的聚乙烯醇/蒙脱石纳米复合材料薄膜。用X射线衍射(XRD)、扫描电子显微镜(SEM)、热重分析(TGA)和力学性能测试对复合材料的结构和性能进行了表征。结果表明,聚乙烯醇分子成功进入蒙脱石的层间,实现了在纳米尺度上的复合;蒙脱石含量高于7 5wt%形成插层型的纳米复合材料,低于7 5wt%形成剥离型的纳米复合材料;在SEM图片上还观察到了纳米复合材料的微观结构。纳米复合材料的热稳定性、拉伸强度和直角撕裂强度均比纯聚乙烯醇有很大提高。     

Synthesis and properties of poly(methyl methacrylate)/montmorillonite (PMMA/MMT) nanocomposites

PMMA/MMT nanocomposites were successfully synthesized via in situ intercalative polymerization, and characterized by means of wide‐angle X‐ray diffractometry, transmission electron microscopy, thermal gravimetric analysis, dynamic mechanical analysis and Fourier‐transform infrared analysis. The nanocomposites possess partially exfoliated and partially intercalated structure, in which the silicate layers are exfoliated into nanometre secondary particles with thickness of less than 20 nm and uniformly dispersed in the polymer matrix. In comparison with pure PMMA, the thermal stability, glass transition temperature, and mechanical properties of the polymer are notably improved by the presence of the nanometric silicate layers. It was found that part of the PMMA chains in the nanocomposites are well immobilized inside and/or onto the layered silicates and, therefore, the unique properties of the nanocomposites result from the strong interactions between the nanometric silicate layers and the polymer chains. Copyright © 2003 Society of Chemical Industry