The effects of structure of POSS on the properties of POSS/PMMA hybrid materials

Octa‐vinyl polyhedral oligomeric silsesquioxane (V‐POSS) and octa‐(methacryloxy) propyl polyhedral oligomeric silsesquioxane (M‐POSS) were incorporated into PMMA to prepare POSS/PMMA hybrid materials at molecular level via in situ polymerization. The resulting hybrid materials showed only swelling instead of solution in ethyl acetate, while pristine PMMA completely dissolved in ethyl acetate; moreover, the M‐POSS/PMMA hybrid materials exhibited more excellent resistance to solvent stress cracking. An excellent transparency was observed for all hybrid materials. Incorporation of V‐POSS and M‐POSS significantly improved thermal properties of PMMA. The thermal decomposition temperature of hybrid materials was enhanced except a slightly compromised initial decomposition temperature. The hybrid materials prepared with 0.2–0.6 mol% M‐POSS or V‐POSS improved the reinforcing and toughening properties in comparison to pristine PMMA. Also, the incorporation of POSS decreased the dielectric constant and dielectric loss of the hybrid materials with more voids introduced into the composites no matter the structure of POSS. POLYM. ENG. SCI., 55:565–572, 2015. © 2014 Society of Plastics Engineers     

Thermal and optical properties of PMMA–titania hybrid materials prepared by sol‐gel approach with HEMA as coupling agent

A series of sol‐gel derived organic–inorganic hybrid materials consisting of organic poly(methyl methacrylate) (PMMA) and inorganic titania (TiO₂) were successfully synthesized by using 2‐hydroxyethyl methacrylate (HEMA) as coupling agent. In this work, HEMA is first copolymerized with methyl methacrylate monomer at specific feeding ratios by using benzoyl peroxide (BPO) as initiator. Subsequently, the as‐prepared copolymer (i.e., sol‐gel precursor) is then cohydrolyzed with various contents of titanium butoxide to afford chemical bondings to the forming titania networks to give a series of hybrid materials. Transparent organic–inorganic hybrid materials with different contents of titania are always achieved. Effects of the material composition on the thermal stability, optical properties, and morphology of neat copolymer and a series of hybrid materials, in the form of both coating and free‐standing film, are also studied by differential scanning calorimetry, thermogravimetric analysis, UV–Vis transmission spectra, refractometer, and atomic force microscopy, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 400–405, 2004     

Poly(methyl methacrylate) hybrid syntactic foams with hollow glass microspheres and polyhedral oligomeric silsesquioxanes

The study aims to produce poly(methyl methacrylate) (PMMA)-based lower density syntactic foams with hollow glass microspheres (HGMs) and to improve their mechanical properties by the addition of polyhedral oligomeric silsesquioxanes (POSSs) while maintaining the thermal properties of the neat polymer. First to understand the effect of POSS addition, PMMA–POSS composites with octaisobutyl and octaphenyl POSS were produced through extrusion. Higher relative flexural and impact strengths were obtained with POSS addition to PMMA. Obtaining more enhanced properties with octaphenyl POSS, PMMA-HGM-POSS hybrid syntactic foams were prepared with this additive. In general, the specific flexural strength and modulus of the PMMA syntactic foams were improved with the POSS loading, while the lower density and thermal properties of the PMMA syntactic foams were maintained. PMMA hybrid syntactic foams with 15 wt % HGMs and 0.25 wt % POSS exhibited 37.6% improvement in the specific flexural modulus with respect to the neat PMMA. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48368.     

Synthesis and characterization of poly(methyl methacrylate) using monofunctional polyhedral oligomeric silsesquioxane as an initiator

POSS/PMMA composite was synthesized by atom transfer radical polymerization (ATRP) at 110 °C using commercial POSSCl as an initiator and CuCl/2,2′-bipyridine as catalyst system. The structures of POSS/PMMA and POSSCl were characterized by Fourier transfer infrared spectroscopy, Nuclear magnetic resonance spectroscopy, Ger permeation chromatography, X-ray diffraction and X-ray photoelectron spectroscopy, which confirmed that Si–Cl bond on POSS cage could successfully initiate the ATRP of methyl methacrylate, so there is only one POSS unit in a PMMA chain. The thermal properties of POSS/PMMA were investigated by Differential scanning calorimetry and Thermogravimetric analysis, the results show that the incorporation of POSS cage results in the enhancement of the glass transition temperature and the decomposition temperature of PMMA, which is mainly attributed to the mono-dispersion of POSS in PMMA matrix at molecular lever.     

Effect of baking treatment and materials composition on the properties of bulky PMMA–silica hybrid sol–gel materials with low volume shrinkage

A series of bulky PMMA–silica hybrid sol–gel materials had been successfully prepared through the conventional HCl‐catalyzed sol–gel approach with 2‐hydroxyethyl methyl methacrylate (HEMA) as coupling agent under pumping pretreatment (i.e., exhaustive vacuum evacuation). In this work, the hydroxyl groups of HEMA monomers were first cohydrolyzed with various contents of tetraethyl orthosilicate (TEOS) to afford chemical bonding for the forming silica networks by removal of solvent and byproduct of sol–gel reactions through pumping pretreatment before gelation reactions. Subsequently, the resultant viscous solution was then copolymerized with methyl methacrylate (MMA) monomers at specific feeding ratios by using benzoyl peroxide (BPO) as free‐radical initiator. Eventually, transparent bulky organic–inorganic hybrid sol–gel materials loaded with different silica content were always achieved. The obtained bulky hybrid sol–gel materials were found to be transparent, crack‐free, and of relatively low volume shrinkages even in high silica content. The as‐prepared bulky hybrid sol–gel materials were then characterized through silicon element mapping studies of energy‐dispersive X‐ray (EDX) and transmission electron microscopy (TEM). Effect of heating process at 150°C for 5 h after polymerization and material composition on the thermal properties, mechanical strength, and optical clarity of a series of bulky PMMA–silica hybrid sol–gel materials was investigated and compared by thermogravimetric analysis (TGA), thermomechanical analysis (TMA), hardness test, dynamic mechanical analysis (DMA), and UV–vis transmission spectroscopy, respectively. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1151–1159, 2006     

Synthesis,characterization, and photochromic properties of PMMA functionalized with 4,4′‐diacryloyloxyazobenzene

Attempts to introduce the azo chromophore into poly(methyl methacrylate) (PMMA) molecular chains were made in search for a new approach to obtain functionalized‐PMMA (f‐PMMA) with high glass transition temperature and an adequate azo content. A novel functionalized monomer, 4,4′‐diacryloyloxyazobenzene (DAOAB), was synthesized and used as grafting agent in the polymerization of methyl methacrylate. ¹H‐NMR spectrum, FTIR spectrum, elemental analysis, and MDSC measurement confirmed that the proposed structure of DAOAB was synthesized successfully. Furthermore, the thermal properties and photochromic behavior of f‐PMMA samples were also analyzed by DSC, TGA, and UV–visible spectroscopy. The results have shown that f‐PMMA exhibited a better photochromic behavior and considerably improved thermal properties than pure PMMA. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1061–1068, 2002     

Preparation and thermal properties of hybrid nanocomposites of poly(methyl methacrylate)/octavinyl polyhedral oligomeric silsesquioxane blends

A series of poly(methyl methacrylate) (PMMA)/octavinyl polyhedral oligomeric silsesquioxane (POSS) blends were prepared by the solution‐blending method and characterized with Fourier transform infrared, X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, and thermogravimetric analysis techniques. The glass‐transition temperature (T_g) of the PMMA–POSS blends showed a tendency of first increasing and then decreasing with an increase in the POSS content. The maximum T_g reached 137.2°C when 0.84 mol % POSS was blended into the hybrid system, which was 28.2°C higher than that of the mother PMMA. The X‐ray diffraction patterns, transmission electron microscopy micrographs, and Fourier transform infrared spectra were employed to investigate the structure–property relationship of these hybrid nanocomposites and the T_g enhancement mechanism. The results showed that at a relatively low POSS content, POSS as an inert diluent decreased the interaction between the dipolar carbonyl groups of the homopolymer molecular chains. However, a new stronger dipole–dipole interaction between the POSS and the carbonyl of PMMA species formed at the same time, and a hindrance effect of nanosize POSS on the motion of the PMMA molecular chain may have played the main role in the T_g increase of the hybrid nanocomposites. At relatively high POSS concentrations, the strong dipole–dipole interactions that formed between the POSS and carbonyl groups of the PMMA gradually decreased because of the strong aggregation of POSS. This may be the main reason for the resultant T_g decrease in these hybrid nanocomposites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and properties of monomer casting polyamide 6/poly(methyl methacrylate) blends

We successfully synthesized monomer casting polyamide 6 (MCPA6)/poly(methyl methacrylate) (PMMA) blends in two steps: (1) radical polymerization of methyl methacrylate in ?‐caprolactam and (2) anionic ring‐opening polymerization of this ?‐caprolactam solution. The influence of PMMA on the crystallization behavior of MCPA6 was studied with differential scanning calorimetry and X‐ray diffraction, which showed that PMMA could act as a heterogeneous nucleation agent and favored the formation of the γ‐crystalline form. The rheological properties were also studied and indicated that PMMA reduced the interaction between MCPA6 chains by lowering the density of hydrogen bonding. This study used a novel and convenient method to prepare microporous MCPA6/PMMA particles that involved removing the continuous phase. Their surface area and thermal stability were characterized by the Brunauer–Emmett–Teller method and thermogravimetric analysis, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermomechanical properties and morphology of interpenetrating polymer networks of polyurethane–poly(methyl methacrylate)

Interpenetrating networks (IPNs) of polybutadiene‐based polyurethane (PU) and poly(methyl methacrylate) (PMMA) were synthesized. The effect of the incorporation of 2% glycidyl methacrylate (GMA) and 2‐hydroxyethyl methacrylate (2‐HEMA) on the thermal, mechanical, and morphological properties of IPNs was investigated. Both 2‐HEMA and GMA led to improvements in these properties. However, 2‐HEMA‐containing IPNs showed somewhat better tensile strength, elongation, and damping characteristics. The morphology of IPNs containing 2‐HEMA showed better mixing of the components. The improvement in the properties was observed for up to 40% PMMA in the IPNs. Differential scanning calorimetry thermograms showed the presence of three glass transitions. The third glass‐transition temperature was explained by possible grafting of methyl methacrylate onto PU. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1576–1585, 2002     

Microheterogeneous polymer systems prepared by suspension polymerization of methyl methacrylate in the presence of poly(ε‐caprolactone)

Poly(methyl methacrylate) – polycaprolactone (PMMA/PCL) microheterogeneous beads were synthesized by suspension polymerization starting from methyl methacrylate (MMA) monomer and PCL, which was synthesized by ring‐opening polymerization of ε‐caprolactone using ZnCl₂ as initiator. The resulting polymer was fully characterized by ¹H and ¹³C NMR, differential scanning calorimetry (DSC), gel permeation chromatography (GPC) and dynamic mechanical thermal analysis (DMTA). The size distribution and morphology of the resulting beads were investigated by optical microscopy and scanning electron microscopy (SEM). Moreover, blends of PMMA beads and PCL in different proportions were prepared and the morphology of the films was examined by optical microscopy. The low compatibility between PMMA and PCL was clearly evidenced through these experiments.     

Organic‐acid‐catalyzed sol–gel route for preparing poly(methyl methacrylate)–silica hybrid materials

In this study, a series of organic–inorganic hybrid sol–gel materials consisting of a poly(methyl methacrylate) (PMMA) matrix and dispersed silica (SiO₂) particles were successfully prepared through an organic‐acid‐catalyzed sol–gel route with N‐methyl‐2‐pyrrolidone as the mixing solvent. The as‐synthesized PMMA–SiO₂ nanocomposites were subsequently characterized with Fourier transform infrared spectroscopy and transmission electron microscopy. The solid phase of organic camphor sulfonic acid was employed to catalyze the hydrolysis and condensation (i.e., sol–gel reactions) of tetraethyl orthosilicate in the PMMA matrix. The formation of the hybrid membranes was beneficial for the physical properties at low SiO₂ loadings, especially for enhanced mechanical strength and gas barrier properties, in comparison with the neat PMMA. The effects of material composition on the thermal stability, thermal conductivity, mechanical strength, molecular permeability, optical clarity, and surface morphology of the as‐prepared hybrid PMMA–SiO₂ nanocomposites in the form of membranes were investigated with thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, gas permeability analysis, ultraviolet–visible transmission spectroscopy, and atomic force microscopy, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and properties of poly(methyl methacrylate)/clay nanocomposites using natural montmorillonite and synthetic Fe‐montmorillonite by emulsion polymerization

In this article, Fe‐montmorillonite (Fe‐MMT) was synthesized by hydrothermal method. For the first time, Fe‐MMT was modified by cetyltrimethyl ammonium bromide (CTAB), and poly(methyl methacrylate)(PMMA)/Fe‐MMT nanocomposites were synthesized by emulsion polymerization. Then poly(methyl methacrylate)(PMMA)/natural montmorillonite (Na‐MMT) and PMMA/Fe‐MMT nanocomposites were compared by Fourier transform infrared (FTIR) spectra, X‐ray diffraction (XRD) patterns, transmission electron microscopy (TEM), and thermal gravimetric analysis (TGA). By XRD and TEM, it was found out that the morphology of PMMA/Fe‐MMT nanocomposites was different from that of the PMMA/Fe‐MMT nanocomposites when the content of two types of clay was same in the PMMA matrix. It was possible that the presence of iron may lead to some radical trapping, which enhances intragallery polymerization to be developed to improve layer dispersion in PMMA/Fe‐MMT systems. In TGA curves, the thermal stability and residue at 600°C of PMMA/Fe‐MMT nanocomposites were higher than those of PMMA/Na‐MMT nanocomposites. Those dissimilarities were probably caused by structural Fe ion in the lattice of Fe‐MMT. POLYM. COMPOS., 27:49–54, 2006. © 2005 Society of Plastics Engineers     

The effect of incorporation of POSS units on polymer blend compatibility

In this work, the compatibility of poly(methyl methacrylate) (PMMA) and polystyrene (PS) polymers with their polyhedral oligomeric silsesquioxane (POSS) copolymers combined by solution blending is investigated, to determine the effect of incorporation of the POSS unit on polymer compatibility. The morphology of these tethered POSS copolymer/polymer blends was studied by electron microscopy, thermal analysis, and density. Although the basic PS/PMMA blend was clearly immiscible, it was also found that the incorporation of POSS into the PS chain led to incompatibility when the POSScoPS copolymer was blended with PS homopolymer. However, conversely, in the case where the POSS moiety was included as part of a copolymer with PMMA, the copolymer was miscible with the PMMA homopolymer. The presence of isobutyl units on the corners of POSS cage is clearly sufficient to encourage miscibility with PMMA. Interestingly, blends of the two different POSS copolymers led to an immiscible structure, despite having the common POSS units, the interactions between the POSS moieties clearly not being sufficient to drive compatibility. The POSS copolymers have also been used as interfacial agents in immiscible PS and PMMA blend, and it has been found that the appearance of the interface bonding is improved, although the phase morphology is only slightly changed. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Star‐shaped POSS–methacrylate copolymers with phenyl–triazole as terminal groups,synthesis, and the pyrolysis analysis

Star‐shaped polyhedral oligomeric silsesquioxane (POSS)–methacrylate hybrid copolymers with phenyl–triazole as terminal groups had been designed and synthesized via sequential atom transfer radical polymerization (ATRP), azidation, and phenylacetylene‐terminated procedures, and the hybrid copolymers here could be denoted as POSS–(PXMA‐Pytl)₈, where X can be M, B, L, and S, represented four different methacrylate monomers, such as methacrylate (MMA), butyl methacrylate (BMA), lauryl methacrylate (LMA), and stearyl methacrylate (SMA), respectively. Thermal gravimetric analysis (TGA) and in situ Fourier transform infrared spectroscopy (FTIR) were applied for studying the thermal stability and degradation mechanism, and it was found that all of the POSS–(PXMA‐Cl)₈ and POSS–(PXMA‐Pytl)₈ copolymers exhibited excellent thermal stabilities, which had great potential in heat‐resistant material application. Different tendencies of decomposition temperatures at 5% and 10% weight loss (T₅ and T₁₀) dependent on the side‐chain length and terminal group species were investigated respectively. The longer alkyl side chains of the monomers, the lower thermal stabilities, and enhanced T₅ and T₁₀ were also shown with the introduction of phenyl–triazole groups instead of chlorine groups. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40652.     

Montmorillonite clay/poly(methyl methacrylate) hybrid resin and its barrier property to the plasticizer within poly(vinyl chloride) composite

A poly(methyl methacrylate) (PMMA)‐clay hybrid resin was prepared via bulk polymerization methyl methacrylate monomer in the presence of montmorillonite intercalated with an ammonium salt of dctadecylamine. The products were characterized by infrared spectroscopy, X‐ray diffraction, pyrolysis gas chromatography, and transmission electron microscopy. Results confirm that the resin is intercalated with PMMA molecules. The layer spacing of montmorillonite are enlarged, whereas the silicate layers are homogeneously dispersed individually. When the PMMA‐clay hybrid was blended with plasticized poly(vinyl chloride), the resulting composite exhibited excellent barrier property in preventing the plastizer's migration from the inner matrix to the surface of the product. This is presumably caused by barrier property of the silicate layers dispersed in the composite. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 425–430, 1999     

Studies on synthesis and characterization of poly(methyl methacrylate)‐bentonite clay composite by emulsion polymerization and simultaneous in situ clay incorporation

Well‐dispersed poly(methyl methacrylate) (PMMA)–bentonite clay composite was synthesized by emulsion polymerization using methyl methacrylate (MMA) monomer and 3% sodium carbonate treated bentonite clay. The composite lost its transparency normally encountered with the neat PMMA. The composite was characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), vicat softening point (VSP), dynamic mechanical thermal analysis (DMTA), and tensile studies. The morphology was investigated by scanning electron microscopy (SEM) and atomic forced microscopy (AFM) as well. The crystallography was studied to estimate the changes in crystallographic planes by X‐ray diffraction (XRD) analysis. The particle size distribution was compared amongst neat bentonite clay, neat PMMA and the composite. The FTIR spectra reveal the fact that no new primary valence bond is formed between the clay and PMMA. The thermal stability of the composite is significantly improved, as indicated by the TGA and VSP studies. A substantial increase in glass transition temperature (T_g) approximately, 10°C was recorded from the DMTA as both the storage modulus and tan δ values underwent inflexion at higher temperatures in case of the composite compared with the pristine PMMA. The XRD pattern indicates increase in basal “d” spacing for the composite. The morphology from both the SEM and AFM is quite supportive to well‐dispersed exfoliation. The incorporation of nanosized activated clay particles in PMMA during its in situ polymerization from MMA led to the formation of nanocomposites. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

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).     

Structural characterization,thermal properties,and density functional theory studies of PMMA‐maghemite hybrid material

Maghemite (γ‐Fe₂O₃)‐poly(methyl methacrylate) (PMMA) nanocomposites were prepared by grafting 3‐(trimethoxy‐silyl) propyl methacrylate on the surface of maghemite nanoparticles, this process being followed by methyl methacrylate radical polymerization. Three different hybrids with 0.1, 0.5, and 2.5 wt% of maghemite nanoparticles were studied. The results indicate that these nanocomposites consist of a homogeneous PMMA matrix in which maghemite nanoparticles with a bimodal size distribution are embedded. The existence of covalent bonding between silane monomers and atoms on the maghemite surface was evidenced. AFM images showed a clear increase in surface roughness for increasing maghemite content. The thermal stability of PMMA‐maghemite nanocomposites is higher than that of pure PMMA and increases for increasing maghemite content. The results of our theoretical studies indicate that the electron density in the maghemite nanoparticle is not homogenous, the low electron density volumes being supposed to be radical trappers during PMMA decomposition, thus acting as a thermal stabilizer. POLYM. COMPOS., 51–60, 2016. © 2014 Society of Plastics Engineers     

Fabrication of composite films with poly(methyl methacrylate) and incompletely condensed cage‐silsesquioxane fillers

Polyhedral oligomeric silsesquioxane (POSS) is a promising nanofiller for tuning properties of optically transparent polymer materials. On the other hand, traditional completely condensed POSS (CC‐POSS) has a fundamental problem for fabricating optically transparent composite films; CC‐POSS has high crystallinity due to its symmetrical structure, resulting in aggregation in the polymer matrices. In this work, we have demonstrated that incompletely‐condensed POSS (IC‐POSS), which has an open‐cage structure, can be well dispersed in a poly(methyl methacrylate) (PMMA) matrix. IC‐POSS with various substituents were readily synthesized, and their composite films of PMMA were fabricated by solution‐casting method. High transparency was achieved with up to 30 wt % of the IC‐POSS fillers, while the CC‐POSS analogues caused phase separation with 10 wt % loading. Addition of the IC‐POSS fillers can improve thermal stability and control glass transition temperature by the substituent structure. Additionally, refractive index was tuned from 1.485 to 1.513. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46033.     

Synthesizing multi‐walled carbon nanotube‐polymethyl methacrylate conductive composites and poly(lactic acid) based composites

Multi‐walled carbon nanotube was modified with polymethyl methacrylate (MWCNT‐PMMA) by in situ solution radical polymerization in the presence of 2,2′‐Azobis (isobutyronitrile) as an initiator. The products with different addition of methyl methacrylate (MMA) were pressed into slices to prepare specimens for electrical conductivity testing. It was found that the MWCNT‐PMMA nanocomposites demonstrate excellent electrical conductivity. To investigate the microsphere morphology and the colloidal surfactant of MWCNTs in MWCNT‐PMMA composites, samples were submitted to scanning electron microscopy and transmission electron microscopy. The thermogravimetric analysis of the prepared composites confirmed that MWCNTs as a thermal stabilizer for PMMA, which could have a wide range of potential applications, such as in catalysts, sensors, environmental remediation, and energy storage. Two series of poly(lactic acid) (PLA) based biocomposites with different MMA additions and MWCNT‐PMMA composites contents were prepared with twin‐screw extruding and injection molding. The results show the mechanical properties changed a little with the MMA and MWCNT‐PMMA composites contents increasing, which suggested the well compatibility between MWCNT‐PMMA composites and PLA. POLYM. COMPOS., 37:503–511, 2016. © 2014 Society of Plastics Engineers