Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(methyl methacrylate)

Summary Poly(n-propyl methacrylate) is known to be immiscible with poly(methyl methacrylate) (PMMA). However, we have found that poly(methoxymethyl methacrylate) is miscible with PMMA, indicating the importance of ether oxygen atoms in achieving miscibility. On the other hand, poly(methylthiomethyl methacrylate) is immiscible with PMMA.     

Effect of diluents on the porous structure of crosslinked poly(methyl methacrylate) beads

Summary Copolymer beads based on methyl methacrylate (MMA) and ethylene glycol dimethacrylate (EGDM) were prepared by suspension polymerization technique. Two different solvents, namely toluene and cyclohexane, were used as the diluents in the polymerization system. It was found that toluene produces pores of radii 2 to 10 nm corresponding to the interstices between the nuclei. In the case of cyclohexane as the diluent, formation of large pores with a broad size distribution from 10 to 1000 nm were observed. These sizes correspond to the spaces between the microspheres and the aggregates forming the copolymer beads. The results indicate that, as in porous styrene-divinylbenzene copolymers, the solvating power of the diluent present during the network formation is mainly responsible for the structural characteristics of porous MMA/EGDM copolymer beads.     

Macroporous membranes,IV. Synthesis and properties of poly[(2,3-epoxypropyl methacrylate)-co-(N-vinyl-2-pyrrolidone)-co-(ethylene dimethacrylate)] membranes

Macroporous membranes based on terpolymers of 2,3-epoxypropylmethacrylate, N-vinyl-2-pyrrolidone, and ethylenedimethacrylate were prepared by radical suspension copolymerization and subsequently modified with ammonia. The membranes were characterized by their porosity, specific surface area, pore size, water permeability and mechanical properties. The low content of N-vinyl-2-pyrrolidone improves the mechanical properties of the membranes. The mechanism of formation of the macroporous structure and heterogeneities is discussed.     

Organic-inorganic hybrid materials from a new octa(2,3-epoxypropyl)silsesquioxane with diamines

Hybrid materials based on a new polyhedral oligomeric silsesquioxane, octa(2,3-epoxypropyl)silsesquioxane (OE) with diamines of 4,4′-methylenedianiline (DDM) and 5-trifluoromethyl-1,3-phenylenediamine (FPA) were prepared and characterized. OE was synthesized from cage-structured octaallylsilsesquioxane (OA) with m-chloroperbenzoicacid. The FTIR studies suggested that the N-H bond in diamines was not completely reacted with epoxy group due to steric hindrance and also extensive hydrogen bonding existed in the hybrid materials. The retention of the cage structure in the prepared hybrid materials was suggested by the FTIR and ²⁹Si NMR studies. The OE/FPA hybrid materials had superior thermal/mechanical characteristics than the OE/DDM due to the higher rigidity of the FPA than that of DDM or the silicon-fluorine interaction enhancing crosslinking reaction or hydrogen bonding. The prepared OE/FPA had a T_g of 170 °C, which was higher than diglycidyl ether of bisphenyl A (DGEBA)/DDM at the same stoichiometric ratio. It also had excellent thermal, mechanical, and dielectric characteristics with high storage modulus of 1.8 GPa (30 °C) and 0.3 GPa (250 °C), low coefficient of thermal expansion of 86 μm/m °C, and dielectric constant of 2.19. Thus, it can be high performance materials with potential applications for electronic packaging.     

Synthesis and characterization of polypropylene-based polymer hybrids linking poly(methyl methacrylate) and poly(2-hydroxyethyl methacrylate)

Isotactic polypropylene-based polymer hybrids linking poly(methyl methacrylate) (PMMA) and poly(2-hydroxyethyl methacrylate) (PHEMA) were successfully synthesized by a graft copolymerization from maleic anhydride-modified polypropylene (PP-MAH). PP-MAH reacted with ethanolamine to produce a hydroxyl group containing polypropylene (PP-OH) and the thus obtained PP-OH was treated with 2-bromoisobutyryl bromide and converted to a 2-bromoisobutyryl group containing polypropylene (PP-Br). The metal-catalyzed radical polymerization of MMA with PP-Br was performed using a copper catalyst system in o-xylene solution at 100 °C to give the PP-based polymer hybrids linking PMMA segments (PP-PMMA hybrids). Thus obtained PP-PMMA hybrids demonstrated higher melting temperature than PP-Br and microphase-separation morphology at the nanometer level owing to the chemical linkage between both segments. On the other hand, the polymer hybrids linking PHEMA segment (PP-PHEMA hybrids) were also obtained by the radical polymerization of HEMA with PP-Br in o-xylene slurry at 25 °C. TEM observation suggested that the polymerization mainly initiated on the surface of the PP-Br powder, led to the peculiar core-shell-like morphology. These PP-PHEMA hybrid powders showed a good affinity with water due to the hydrophilicity of the PHEMA segments.     

Uralkyd and poly (butyl methacrylate) interpenetrating polymer networks

ABSTRACT:: Hydroxyl terminated alkyds synthesized from castor oil, glycerol, and different dibasic acids were used to develop uralkyds and their interpenetrating polymer networks (IPNs) with polybutyl methacrylate (PBMA). Glass transition temperature measurements gave the evidence of interpenetration. The IPNs were characterized for their physicomechanical properties and their phase morphology was studied by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). As the concentration of the uralkyd in IPNs increases, a gradual increase in elongation, density, and swelling with a consequent decrease in the hardness were observed for all IPNs. Swelling is relatively more prominent in methyl ethyl ketone (MEK) and toluene than in water. From SEM it was observed that IPNs of PBMA‐uralkyd containing phthalic anhydride (UA‐P) as an acid part showed greater compatibility than those containing dimethyl terephthalate (UA‐D). From thermogravimetric analysis (TGA) no significant change was observed in the degradation behavior of the IPNs. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 825–832, 2000     

Shape memory polymer system of semi-interpenetrating network structure composed of crosslinked poly (methyl methacrylate) and poly (ethylene oxide)

Shape memory semi-interpenetrating polymer networks (semi-IPNs) composed of crystalline poly (ethylene oxide) (PEO) and crosslinked poly (methyl methacrylate) (x-PMMA) have been investigated. The selected compositions show shape memory property with a reasonable fast recovery (recovery time ∼1 min) and shape recovery ratio of 99%. Effects of composition (x-PMMA/PEO = 80/20…60/40) and crosslinker (triethyleneglycol dimethacrylate) concentration (up to 6 wt.%) on the creep property were also studied. The recovery time of the semi-IPNs increased and the creep compliance decreased with increasing crosslinker concentration. The network structure containing PEO crystal was characterized by scanning electron microscopy (SEM). Differential scanning calorimetry (DSC) indicated that the PEO, present confined in the semi-IPN, melts at a lower temperature compared to the pure PEO. Dynamic mechanical analysis (DMA) showed a decrease in the glass transition (T_g) of the semi-IPN due to the phase mixing of amorphous PEO and PMMA. Both the glassy and rubbery moduli (E_g and E_r, respectively) were lower for the semi-IPNs than for the x-PMMA network. On the other hand, the E_g/E_r ratio was markedly increased for the semi-IPNs supporting an easy shaping along with a good shape fixing.     

Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(vinylidene fluoride)

Summary The miscibility behaviour of poly(methoxymethyl methacrylate) (PMOMA) and poly(methylthiomethyl methacrylate) (PMTMA) with poly(vinylidene fluoride) (PVDF) was examined by differential scanning calorimetry. PMOMA/PVDF blend system was judged to be miscible on the bases of the presence of a single, composition-dependent glass transition for the blend and a pronounced melting point depression of the PVDF component. Furthermore, lower critical solution temperature (LCST) behaviour was observed for all PMOMA/PVDF blends. PMTMA/PVDF blends were found to be immiscible. Based on the melting point depression of PVDF in PMOMA/PVDF blends, the interaction parameter B was found to be -14.5 J/cm³.     

Study of polymer blends of poly(acetylene) with poly(methyl methacrylate) and methyl methacrylate-butadiene-styrene copolymer

Summary Electroactive polymer blends of polyacetylene (PA) with poly (methyl methacrylate) (PMMA) or methyl methacrylate-butadien-styrene (MBS) copolymer were prepared in situ as free-standing films or powders by polymerization of acetylene in the presence of PMMA or MBS-copolymer, using Luttinger's catalyst. Blends of different composition were studied by infrared spectroscopy and electrical conductivity measurements. Environmental stability of pristine and doped PA was improved to some extent in the presence of PMMA.     

Miscibility of poly(methoxymethyl methacrylate) and poly(methylthiomethyl methacrylate) with poly(styrene-co-acrylonitrile) and poly(p-methylstyrene-co-acrylonitrile)

The miscibility of poly(methoxymethyl methacrylate) (PMOMA) and poly(methylthiomethyl methacrylate) (PMTMA) with poly(styrene-co-acrylonitrile) (SAN) and poly(p-methylstyrene-co-acrylonitrile) (pMSAN) was studied by differential scanning calorimetry. PMOMA is miscible with SAN having an acrylonitrile (AN) content around 30 wt %. However, PMOMA is immiscible with any of the pMSAN having AN contents between 9 and 36 wt % and with pMSAN having AN contents between 19 and 34 wt %. The miscibility of the blends enables the evaluation of various segmental interaction parameters.     

Reactive polymers,XXXVII. An investigation of the internal structure of polymeric sorbents based on poly(2,3-epoxypropyl methacrylate-co-ethylene dimethacrylate)

The internal structure of polymeric sorbents based on 2,3-epoxypropyl methacrylateethylene dimethacrylate was investigated by means of mercury porosimetry and by employing the sorption method. The results were confronted with characteristic chromatographic data and helped to elucidate the relationships existing between the internal structure of copolymers and their chromatographic properties.     

Phase behaviour and phase separation in polymer blends of poly(methyl methacrylate) with poly(vinyl acetate)

Summary Phase behaviour and phase separation in a binary polymer blends of poly(methyl methacryate) (PMMA) with poly(vinyl acetate) (PVAc) was invistigated by cloud method and light scattering. A lower critical solution temperature (LCST) type phase diagram was found. The mixture system of PMMA/PVAc is miscible. Kinetic study on demixing at the two-phase region above the LCST was carried out by light scattering.     

Miscible blends of biobased poly(lactide) with poly(methyl methacrylate): Effects of chopped glass fiber incorporation

Poly(lactide) (PLA) and poly(methyl methacrylate) (PMMA) are melt compounded with chopped glass fiber using laboratory scale twin‐screw extrusion. Physical properties are examined using differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), thermogravimetric analysis (TGA), tensile testing, impact testing, X‐ray computed tomography (CT) scanning, and field emission scanning electron microscopy (FE‐SEM). Molecular weight is determined using gel permeation chromatography (GPC). Miscibility of the blends is implied by the presence of a single glass transition temperature and homogeneous morphology. PLA/PMMA blends tend to show positive deviations from a simple linear mixing rule in their mechanical properties (e.g., tensile toughness, modulus, and stress at break). The addition of 40 wt % glass fiber to the system dramatically increases physical properties. Across all blend compositions, the tensile modulus increases from roughly 3 GPa to roughly 10 GPa. Estimated heat distortion temperatures (HDTs) are also greatly enhanced; the pure PLA sample HDT increases from 75 °C to 135 °C. Fiber filled polymer blends represent a sustainable class of earth abundant materials which should prove useful across a range of applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44868.     

Miscible blends of poly(n-vinyl-2-pyrrolidone) with poly(3-chloropropyl methacrylate), poly(2-bromoethyl methacrylate) and poly(2-iodoethyl methacrylate)

Summary Poly(N-vinyl-2-pyrrolidone) is miscible with poly(3-chloropropyl methacrylate), poly(2-bromoethyl methacrylate) and poly(2-iodoethyl methacrylate) as shown by the optical clarity and the glass transition behaviour of the blends. The miscible blends degrade before phase separation could be induced by heating. The three T_g-composition curves can be fitted by the Gordon-Taylor equation. The implication of the Gordon-Taylor k parameters of the blends is discussed.     

Dynamic mechanical behavior of poly(vinyl chloride)/poly(methyl methacrylate) polymer blend

A poly(vinyl chloride) (PVC)/poly(methyl methacrylate) (PMMA) (80/20 w/w) polymer blend was studied by mechanical spectroscopy. Two relaxations can be distinguished: in the glassy state, a very large secondary relaxation in the range of 100 K to 325 K which results from the combination of secondary relaxations of PVC and PMMA; and only one main relaxation at 364 K associated to the glass rubber transition. The relaxation spectrum in the range of the β relaxation has been described by a relaxation time distribution function based upon a Gaussian function and a series-parallel model. The α relaxation was studied by means of a theoretical approach for the nonelastic deformation of polymers. We found that the miscibility of this blend appears to be a function of the observation scale: the PVC/PMMA blend is heterogeneous at the scale of molecular movements involved for the β relaxation process but homogeneous at the scale of the chain segments responsible for the α relaxation dynamics. © 1996 John Wiley & Sons, Inc.     

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     

Preparation of porous membranes grafted with poly(spiropyran-containing methacrylate) and photocontrol of permeability

Graft copolymerization of spiropyran-containing methacrylate (SPMMA) and acrylamide (AM) onto the surface of a porous polymer membrane was carried out. The permeability of the graft membrane varied with ultraviolet (UV) - or visible-light irradiation. It was found that the change by UV-light irradiation of the permeability of the H₂O/CH₃OH mixture through the SPMMA/AM-grafted membrane is related to the change by UV-light irradiation of the solubility, i.e., the chain extension, of the graft copolymer in the mixed solvent. When the free SPMMA/AM copolymer becomes insoluble in the H₂O/CH₃OH mixture by UV-light irradiation, the permeability of the H₂O/CH₃OH mixture through the SPMMA/AM-grafted membrane is increased. © 1994 John Wiley & Sons, Inc.     

Fabrication and apparent kinetic study of poly(methyl methacrylate)/poly(octyl acrylate) and poly(octyl acrylate)/poly(methyl methacrylate) latex interpenetrating polymer networks

Two latex interpenetrating polymer networks (LIPNs) were synthesized with methyl methacrylate (MMA) and octyl acrylate (OA) as monomers, respectively. The apparent kinetics of polymerization for the LIPNs was studied. This demonstrates that network II does not have a nucleus formation stage. The monomers of network II were diffused into the latex particles of network I and then formed network II by in situ polymerization. It indicates that the polymerization of network I obeys the classical kinetic rules of emulsion polymerization. But the polymerization of network II only appears a constant‐rate stage and a decreasing‐rate stage. The apparent activation energies (E_a) of network I and network II of PMMA/POA were calculated according to the Arrhenius equation. The E_a values of POA as network I (62 kJ/mol) is similar to that of POA as network II PMMA/POA (60 kJ/mol). However, the E_a value of PMMA as network II POA/PMMA (105kJ/mol) is higher than that of PMMA as network I (61 kJ/mol). Results show that the E_a value of the network II polymerization is related to the properties of its seed latex. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Probing the structure of polymer blends by vibrational spectroscopy: the case of poly(ethylene oxide) and poly(methyl methacrylate) blends

The blends of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) are prepared in the form of thin films from solution casting. The Fourier transform infrared spectra of the blends are recorded in the spectral range 400–4000 cm^?1. The spectra are analysed using various recent techniques of vibrational spectroscopy. It is concluded that upon blending PEO takes preferentially a planar zig-zag structure. Furthermore the intermolecular interactions between the molecules of PEO and PMMA in blends are very weak and their compatibility as blends is more ‘physical’ than ‘chemical’. Further, on the basis of the atomic charges transferred from model molecules it is seen that the blending is preferred with isotactic PMMA when compared to syndiotactic PMMA.