Synthesis and ionic conductivity studies of solid polymer electrolytes based on modified alternating maleic anhydride copolymer with oligo(oxyethylene) side chains

Comb-like polymers (CP) based on modified alternating methyl vinyl ether/maleic anhydride copolymer with oligo-oxyethylene side chains of the type-O(CH2CH2O)(n)CH3 have been synthesized and characterized, and complexed with LiNO3 to form an amorphous polymer electrolyte. CP/salt complexes showed conductivity up to 10(-5) S/cm at room temperature. The temperature dependence of ionic conductivity suggests that the ion transport is controlled by segmental motion of the polymer, shown by linear curves obtained in Vogel-Tammann-Fulcher plots. The ionic conductivity maximum moves to a higher salt concentration as the temperature increases. IR results also indicate that the ester in CP might decompose at 140 degrees C and reproduce the maleic anhydride ring.

Preparation and characterization of ethylene-propylene copolymer grafted with acrylamido tertiary butyl sulfonic acid

Grafting of acrylamido tertiary butyl sulfonic acid (ATBS) onto ethylene-polypropylene copolymer (EPM) was carried out by using a reactive processing method. The grafting copolymer was characterized by means of WAXD, FT-IR, ESCA, and DSC. Improved thermal stability was observed for graft copolymer. Effects of the monomer and the initiator concentrations, reactive temperature, and time on grafting degree were investigated. (C) 1997 John Wiley & Sons, Inc.

Crystalline behavior and critical crystalline sequence length of propylene/alpha-olefin copolymer

The melting points(T-m), crystalline temperature(T-c) and crystallinity(chi(c)) of propylene/alpha-olefin (pentene-l, octene-1 and decene-1) copolymers have been investigated, The results show that the T-m, T-c and chi(c) of the copolymers are lower than those of propylene homopolymer, indicating that lower alpha-olefin incorporation in copolymer has strongly hampered the crystallization of propylene, From critical crystalline sequence length of several propylene/alpha-olefin copolymers, it can be seen that a long chain alpha-olefin has much stronger effect on crystallization of PP than a short alpha-olefin does.

Thermal analysis of ethylene-propylene copolymer-grafted-glycidyl methacrylate

The thermal properties of ethylene-propylene copolymer grafted with glycidyl methacrylate (EP-g-GMA) were investigated by using differential scanning calorimetry (DSC). Compared to the plain ethylene-propylene copolymer (EP), peak values of melting temperature (T-m) of the propylene sequences in the grafted EP changed a little, crystallization temperature (T-c) increased about 8-12 degrees C, and melting enthalpy (Delta H-m) increased about 4-6 J/g. The isothermal and nonisothermal crystallization kinetics of grafted and ungrafted samples was carried out by DSC. Within the scope of the researched crystallization temperature, the Avrami exponent (n) of ungrafted sample is 1.6-1.8, and those of grafted samples are all above 2. The crystallization rates of propylene sequence in EP-g-GMA were faster than that in the plain EP and increased with increasing of grafted monomer content. It might be attributed to the results of rapid nucleation rate. (C) 1996 John Wiley & Sons, Inc.

Lithium ion conducting polymer electrolytes based on alternating maleic anhydride copolymer with oligo-oxyethylene side chains

A comb polymer with oligo-oxyethylene side chains of the type -(CH2CB2O)(12)CH3 was prepared from methyl vinyl ether/maleic anhydride copolymer and poly (ethylene glycol) methyl ether. The polymer can dissolve LiClO4 salt to form homogeneous amorphous polymer electrolyte. The ac ion conduction was measured using the complex impedance method, and conductivities were investigated as functions of temperatures and salt concentration. The complexes were first found to have two classes of glass transition which increase with increasing salt content, The optimum conductivity attained at 25 degrees C is in the order of 5.50 x 10(-6)Scm(-1). IR spectroscopy was used to study the cation-polymer interaction.

The miscibility of homopolymer random copolymer blends .1. Poly(styrene-co-acrylonitrile) poly(ethyl methacrylate) and poly(styrene-co-acrylonitrile) poly(methyl methacrylate) blends

The miscibility of blends of poly(styrene-co-acrylonitrile) (SAN) with poly(methyl methacrylate) (PMMA) or poly(ethyl methacrylate) (PEMA) has been investigated by means of NMR and DSC techniques. It is found that there are intermolecular interactions between the phenyl groups in SAN and carbonyl groups in PMMA or PEMA, and the strength of this intermolecular interaction strongly depends on the properties of ester side groups in PEMA or PMMA, composition of the blends and a certain composition of the copolymer. It is this specific interaction instead of the intramolecular repulsion force within the copolymer that plays a key role for the miscibility of SAN/PMMA and SAN/PEMA blends.

The miscibility of homopolymer random copolymer blends .4. Poly(vinylidene chloride-co-acrylonitrile) poly(methyl methacrylate) blends

The miscibility of blends of poly(vinylidene chloride-co-acrylonitrile) (VDC-AN) and poly(methyl methacrylate) (PMMA) has been studied with DSC, FT-IR, and NMR methods. The results indicate that the VDC-AN/PMMA blends are miscibile on a molecular level, and the dipole-dipole interactions between C=O and C-Cl-2 and/or interpolymer hydrogen bondings between COOCH3 and CN and CCl groups play the role on the miscibility of the blends. It is found that the -CCl2- groups have two different chemical environments in the pure VDC-AN copolymer, which may result from the different configurations of the copolymer, such as -CCl2- groups in the ''alternating'' segments and -CCl2- groups in the ''blocky'' segments as proposed. It is the -CCl2- group in the ''alternating'' segment that takes part in the dipole-dipole interaction with C=O group in PMMA.

The determination of ethylene-propylene copolymer-grafted-glycidyl methacrylate by the contact angle method

The contact angles theta of some liquids on ethylene-propylene copolymer-grafted-glycidyl methacrylate (EPM-g-GMA) were measured. The critical surface tensions r(c) of EPM-g-GMA were evaluated by the Zisman Plot (cos theta versus r(L)), Young-Dupre-Good-Girifalco plot (1 + cos theta versus 1/r(L)(0.5)) and log (1 + cos theta) versus log(r(L)) plot. The following results were obtained: the r(c) values varied significantly with the estimation methods. The critical surface tension r(c) decreased with the increase of the degree of grafting of EPM-g-GMA.

Rheological properties and crystallization behavior of yttrium oxide filled low ethylene content polypropylene copolymer

The rheological properties and crystallization characteristics of low ethylene content poly propylene (EPM) with and without Yittrium oxide (Y2O3) as a filler was investigated by cone-plate viscometer and differential scanning calorimetry. Yittrium oxide had a profound effect on the viscosities of the systems. To determine the nonisothermal crystallization rate of the materials, a new estimation method was used. From the results, we can conclude that Y2O3 acts as a nucleating agent, which increased the crystallization rate of the EPM. (C) 1996 John Wiley & Sons, Inc.

Properties of ethylene-propylene copolymer/PA-1010 blends using ethylene-propylene copolymer-graft-acrylic acid as a compatibilizing agent

The modification of ethylene-propylene copolymer (EP) has been accomplished by radical EP-graft-acrylic acid (EP-g-AA) has been used to obtain ternary PA/EP/EP-g-AA blends by melt mixing. Different blend morphologies were observed by scanning electron microscopy; the domain size of the EP-dispersed phase in the polyamide 1010 matrix of compatibilized blends decreased compared with that of uncompatibilized blends. It is found that EP-g-AA used as the third component has a profound effect on the mechanical properties of the resulting blends. This behavior has been attributed to serious chemical interactions taking place between the two components. Thermal analysis shows that some thermal properties of PA in compatibilized PA/EP/EP-g-AA changed because of chemical reactions taken place during the blending process. Wide angle x-ray diffraction measurements also confirmed this result. (C) 1996 John Wiley & Sons, Inc.

Crafting of glycidyl methacrylate onto ethylene-propylene copolymer: Preparation and characterization

Ethylene-propylene copolymer (EP) was functionalized with glycidyl methacrylate (GMA) by means of a radical-initiated melt grafting reaction. FTIR and ESCA were used to characterize the formation of EP-g-GMA copolymers. The content of GMA in EP-g-GMA was determined by using hydrochloric acid/xylene titration. Effects of concentrations of GMA and dicumyl peroxide on grafting rate were studied. It was found that contact angles of the water on surfaces of EP-g-GMA samples increased with increasing content of GMA in EP-g-GMA. The influence of the content of GMA on the crystallization structure of EP-g-GMA was investigated by DSC and WAXD. Compared with the plain EP, the crystallization temperature of propylene blocks of EP-g-GMA increased over 10 K, and the melting temperature and crystallinity decreased somewhat. Functionalization of EP led to the change of the crystal form of propylene blocks from the mixed form of alpha and beta into the alpha form. (C) 1996 John Wiley & Sons, Inc.

Ionic conductivity of gel electrolyte based on polydiethylene glycol dimethacrylate and its copolymer

Gel electrolytes were prepared by thermal polymerization of diethylene glycol dimethacrylate (DIEGD) or its copolymer with methoxy polyethylene glycol monomethacrylate, molecular weight 400 (PEM(400)), at a molar ratio of 3/1 in the presence of propylene carbonate (PC) and LiClO4. Conductivity was measured by impedance spectroscopy. It was found that the conductivity data follow the Arrhenius equation in the homopolymer gel system, while the VTF equation holds true in the copolymer gel system. An increase in conductivity was observed in the copolymer gel system. However, whether in the homopolymer or in the copolymer gel system, a maximum ambient temperature conductivity was found at a salt concentration near 1.50 mol/l. Further, the activation energy values calculated from Arrhenius plots for the homopolymer gel system tended to reach a minimum value with increasing salt concentration. (C) 1996 Elsevier Science Ltd

SYNTHESIS OF POLYBUTADIENE MACROINITIATOR AND POLYBUTADIENE/POLYACRYLAMIDE BLOCK-COPOLYMERS

An azo-group containing polybutadiene macroinitiator was prepared by Pinner synthesis and characterized by IR, NMR, GPC, viscosity and elemental measurements. The macroinitiator was further use to polymerize acrylamide (AAm) in benzene to form polybutadiene/polyacrylamide (PBD/PAAm) block copolymers. High conversion of AAm was obtained over a wide range of monomer/macroinitiator ratios. The PBD/PAAm block copolymers were found to have excellent solvent resistance.

IONIC-CONDUCTION OF A NOVEL COMB POLYMER ELECTROLYTE BASED ON MALEIC-ANHYDRIDE COPOLYMER WITH OLIGO-OXYETHYLENE SIDE-CHAINS

A comb-shaped polymer (BM350) with oligo-oxyethylene side chains of the type -O(CH2CH2O)(7)CH3 was prepared from methyl vinyl ether/maleic anhydride copolymer. Homogeneous amorphous polymer electrolyte complexes were made from the comb polymer and LICF(3)SO(3) by solvent casting from acetone, and their conductivities were measured as a function of temperature and salt concentration. Maximum conductivity close to 5.08 X 10(-5) Scm(-1) was obtained at room temperature and at a [Li]/[EO] ratio of about 0.12. The conductivity which displayed non-Arrhenius behaviour was analyzed using the Vogel-Tammann-Fulcher equation and interpreted on the basis of the configurational entropy model. The results of mid-IR showed that the coordination of Li+ to side chains made the C-O-C band become broader and shift slightly. X-ray photoelectron spectroscopy analysis indicated that the oxygen atoms in the two situations could coordinate to Li+ and this coordination resulted in the reduction of the electron orbit binding energy of F and S.

MODIFICATION OF PP/HDPE BLENDS BY PP-PE SEQUENTIAL POLYMERIZATION PRODUCT

The morphology and mechanical properties of polypropylene/high-density polyethylene (PP/HDPE) blends in a wide range of compositions modified by a sequential Ziegler-Natta polymerization product (PP-PE) have been investigated. PP-PE contains multiple components such as PP, ethylene-propylene copolymer (EPC), and high molecular weight polyethylene (HMWPE). The effects of PP-PE on the mechanical properties and morphology of the PP/HDPE blends are the aggregative results of all its individual components. Addition of PP-PE to the blends not only improved the tensile strength of the blends, but the elongation at break increased linearly while the moduli were nearly unchanged. Morphological studies show that the adhesion between the two phases in all the blends of different compositions is enhanced and the dispersed domain sizes of the blends are reduced monotonously with the increment of the content of PP-PE. PP-PE has been demonstrated to be a more effective compatibilizer than EPC. Based on these results, it can be concluded that the tensile strength of the blends depends most on the adhesion between the two phases and the elongation at break depends most on the domain size of the dispersed component. (C) 1995 John Wiley & Sons, Inc.