Synthesis and characterization of aromatic poly(ether sulfone)s with pendent benzoyl groups

Summary The new sulfone-activated difluoro monomers with benzoyl substituents, bis(2-benzoyl-4-fluorophenyl) sulfone and 2-benzoyl-4,4'-difluorophenyl sulfone, were synthesized and converted to the corresponding poly(aryl ether sulfone)s with bisphenol A. While homopolymerization of the two monomers gave low molecular weight polymers because of cleavage of sulfone induced by the pendent benzoyl group at ortho position, copolymerization with his(4-fluorophenyl) sulfone comonomer produced moderately high molecular weight polymers. The inherent viscosities of the synthesized polymers were 0.20–0.38 dL/g and the glass transition temperatures of the polymers were 173–195°C. Thermogravimetric analysis showed that thermal stability of the polymers decreased as the polymers contain more benzoyl substituents. Received: 15 May 1998/Revised version: 13 October 1998/Accepted: 4 November 1998     

Wide-angle X-ray scattering study of crystalline orientation in reticulate-doped polymer composites

Reticulate doping consists of casting a composite film from a solution containing both a polymer and a charge-transfer complex (CTC) and allowing the conductive free radical salt to recrystallize as the solvent is removed from the polymer. In this study, a highly branched, low molecular weight polyethylene (PE) was doped with the CTC tetrathiafulvalene–tetracyanoquinodimethane (TTF–TCNQ). Wide-angle X-ray scattering (WAXS), conductivity, optical microscopy, stress relaxation, and differential scanning calorimetry (DSC) measurements were used to show the effect of the addition of filler and uniaxial orientation on the mechanical and electrical properties of the composites. It has been shown that increasing TTF–TCNQ concentration shifts the preferential orientation of the crystalline phase of the PE from slightly perpendicular to slightly parallel to the casting surface. WAXS measurements were made on samples that were uniaxially stretched at 80°C and cooled to room temperature. These experiments showed a smaller incremental increase in crystalline orientation with increasing TTF–TCNQ. This observation was consistent with a drop in initial relaxation times calculated from room temperature stress relaxation experiments. In the unoriented composites, increasing TTF–TCNQ loading had no effect on PE crystallinity; however, the increase in crystallinity caused by uniaxial stretching was decreased by the presence of TTF–TCNQ. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1785–1794, 1998     

Synthesis and characterization of liquid crystalline ionomers with polymethylhydrosiloxane main-chain- and side-chain-containing sulfonic acid groups

A novel thermotropic side-chain liquid crystalline ionomer (LCI) containing sulfonic acid groups on the side-chain was synthesized by graft copolymerization of mesogenic monomer 4-allyloxy-benzoxy-4′-methoxyphenyl (ABM) and nonemesogenic monomer 4-allyloxy-azobenzene sulfonic acid (AABS) upon polymethylhydrosiloxane (PMHS). The chemical structures of the polymers were confirmed by IR spectroscopy. DSC and TGA were used to measure the thermal properties of those polymers and the mesogenic properties were characterized by polarized optical micrography (POM), DSC, and WAXD. The clearing point temperature (T_c) of these liquid crystalline ionomers was enhanced 50–60°C compared with the polymer without ionic groups. The LCIs exhibit a broad smectic mesogenic region of 80–90°C; the thermal stability below 200°C of the polymers decreases with increasing sulfonic acid concentration. The inherent viscosity of 0.5% solutions decreased with increasing sulfonic acid concentration in the polymer chains. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1555–1561, 1998     

Application of zirconium (IV) acetylacetonate to the copolymerization of glycolide with ɛ-caprolactone and lactide

Summary A study on the copolymerization of glycolide with lactide and glycolide with ɛ-caprolactone was performed in the presence of zirconium (IV) acetylacetonate at moderate temperatures (100° and 150°C). Zirconium acetylacetonate appeared to be an efficient initiator of copolymerization. The obtained polymers were characterized by high molecular weights. Considerable influence of transesterification on the polymer chain microstructure was found. Received: 13 October 1998/Revised version: 4 January 1999/Accepted: 4 January 1999     

Postfunctionalization of aromatic polyamine by [2+2] cycloaddition of 7,7,8,8-tetracyanoquinodimethane with side chain alkynes

Electron-rich, side chain alkynes of an aromatic polyamine were functionalized by a [2+2] cycloaddition, followed by retro-cyclization with the electron-accepting 7,7,8,8-tetracyanoquinodimethane (TCNQ). ¹H NMR studies were used to optimize the reaction conditions. Mild heating to >50?°C afforded the postfunctionalized aromatic polyamines with the desired acceptor amounts. The quantitative TCNQ addition was demonstrated by the MALDI-TOF mass spectrum and elemental analysis. Introduction of the cyano-based acceptor moieties into the polymer side chains resulted in unusually strong intermolecular interactions. In addition to the ?ШC?? interactions of the extended acceptor moieties, these intermolecular forces were supposed to improve the thermal stability of the aromatic polymers. Furthermore, the donor?Cacceptor chromophores formed by this postfunctionalization displayed low energy charge-transfer bands and redox activities in both the anodic and cathodic directions. The straightforward postfunctionalization technique using the alkyne?CTCNQ addition is useful for the preparation of narrow band gap polymers in one step.     

Gas absorption with filled polymer systems

This paper deals with the gas absorption behavior of polymer systems. The emphasis is on the difference between filled and unfilled polymers to explain heterogeneous nucleation in filled polymers. A Foaming Process Simulator has been built to study the gas absorption. It consists of a test chamber that holds the polymer samples. The chamber can be pressurized with gas up to 5000 psi and heated up to 450°F. The gas pressure is monitored by a high‐accuracy pressure transducer and recorded by a data acquisition system. The amount of gas absorbed by a polymer is determined from the pressure change in the test chamber. A rotor applies shear to the polymer melt to investigate the shear effects. Two polymer systems were tested: HDPE with/without talc, and PVC with/without calcium carbonate. The fillers were well dispersed as verified with scanning electron microscope. The tests were done at the melt temperatures from 120°C to 177°C and a saturation pressure of about 18.9 MPa. It was found that the filled polymers absorb more gas compared to the unfilled ones. It is suggested that there is a certain amount of gas accumulated in the filler‐polymer interface. This accumulated gas helps to create cells during the foaming process.     

Synthesis and characterization of poly(ether sulfone) copolymers

Poly(ether sulfone) copolymers I–V were synthesized by the nucleophilic substitution reaction of 4,4-dichlorodiphenyl sulfone with varying mole proportions of 4,4-isopropylidene diphenol (bisphenol A) and 4,4-dihydroxydiphenyl sulfone (bisphenol S) using sulfolane as the solvent in the presence of anhydrous K₂CO₃. The polymers were characterized by different physicochemical techniques. The glass transition temperature was found to decrease with increase in the concentration of bisphenol A units in the polymers. All polymers were found to be amorphous. Thermogravimetric studies showed that all the polymers were stable up to 400°C with a char yield of about 36% at 900°C in a nitrogen atmosphere. ¹³C-NMR spectral analysis reveals that bisphenol S-based triads are preferentially formed compared to bisphenol-A triads, indicating greater reactivity of bisphenol S toward dichlorodiphenyl sulfone. The overall activation energy for the thermal decomposition of bisphenol A-based polymer (1) is much higher than that of bisphenol S-based polymer ( II ). This was attributed to the modification of the backbone of polymer I during the initial cleavage of the C—CH3 bond of the isopropyledene group. Polymer II decomposes by cleavage of the C—SO2 bond. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 743–750, 1998     

Synthesis and properties of poly(phenylacetylene)s having dialkylamino groups

Summary Poly(phenylacetylene)s bearing dialkylamino groups were prepared by the polymerization of p-(N,N-dialkylamino)phenylacetylenes with [Rh(nbd)Cl]₂, and their electrochemical behavior was examined. Rh-catalyzed polymerization of p-(N,N-diethylamino)phenylacetylene (DEAPA) and p-(N,N-di-n-butylamino)phenylacetylene (DBAPA) in toluene in the presence of triethylamine gave good yields of the polymers (86 and 90%, respectively). Poly(DEAPA) was soluble in chloroform and dichloromethane, and poly(DBAPA) dissolved in various solvents such as toluene, THF, dichloromethane and chloroform. Poly(DEAPA) and poly(DBAPA) showed onset temperatures at 248 and 190°C, respectively, and absorptions around 300–400 nm. Electrochemical doping of the polymer films resulted in the shift of the absorptions to a region around 680 nm, which accompanied a color change of the polymer films from green ocher to deep blue. Received: 26 October 1998/Revised version: 6 November 1998/Accepted: 12 November 1998     

Effect of storage on film-formation property of vinylidene chloride-acrylonitrile-methyl acrylate terpolymer latex

Latex prepared from 91 : 5 : 4 wt % vinylidene chloride-acrylonitrile-methyl acrylate monomer mixture by seeded semicontinuous emulsion polymerization was investigated for a change in minimum film-formation temperature (MFFT) during storage, with focus placed on polymer crystallinity in the dispersed state. MFFT rose from 20°C to 32°C, with storage at 20°C for 49 weeks. Infrared absorption of fresh and stored latexes in the dispersed state indicated an increase in absorbance at 1048 cm⁻¹, which is characteristic of a crystalline vinylidene chloride polymer, that correlated with the MFFT rise with storage. This suggested that the MFFT rise with storage was caused by increasing crystallinity of the polymer in the dispersed state. X-ray wide-angle diffraction and infrared absorption of powder polymers obtained by lyophilization of fresh and stored latexes also indicated increasing crystallinity with latex storage. Oxygen gas permeabilities of films coated with fresh and stored latexes were measured. Latex stored for long periods exhibited poor barrier property, indicating that such latex is unsuitable as an industrial barrier coating material for films and papers. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 573–579, 1998     

Storage modulus changes with temperature in poly(vinyl alcohol), PVA,/poly(acrylic acid), PAA, blends

Summary Poly(vinyl alcohol), PVA, and poly(acrylic acid), PAA, blends were prepared by solution casting. These polymers were found to be miscible in the whole composition range as determined by DSC even though some crystallinity remains in blends with PVA concentrations above 50wt%. Dynamic mechanical measurements of these blends and PAA as a function of temperature show an increase in storage modulus, E', when they reach a temperature of 140°C that is well beyond their softening point. The E' increase in PAA beyond 140°C is attributed to an intramolecular reaction of cyclic anhydride formation that stiffens the chain. Isothermal storage modulus test as a function of time and FTIR measurements at 160°C of PAA and three blends show that this increase in E' is due to cyclic anhydride formation. Received: 4 November 1998/Revised version: 11 March 1999/Accepted: 11 March 1999     

Hyperbranched poly(arylene ether phosphine oxide)s

Summary New AB₂ and A₂B monomers, bis(4-fluorophenyl)-4'-hydroxyphenylphosphine oxide and bis(4-hydroxyphenyl)-4'-fluorophenyl-phosphine oxide were prepared and converted to corresponding hyperbranched poly(arylene ether phosphineoxide)s with hydroxyphenyl and fluorophenyl end functional groups. While the dihydroxy monomer gave a low molecular weight polymer, the difluoro monomer produced a high molecular weight hyperbranched polymer. The glass transition temperature of the obtained polymers was 266°C and 230°C, and 5% weight loss temperature was 491 °C and 391 °C, respectively. The fluorophenyl-terminated hyperbranched polymer was soluble in CHCl₃, but the hydroxyphenyl-terminated polymer was not soluble in CHCl3 even though it has lower molecular weight than the fluorophenyl-terminated polymer, indicating that properties of the hyperbranched polymers markedly depend on end functional groups as well as their molecular weight. Received: 23 August 2000/Revised version: 19 October 2000/Accepted: 31 October 2000     

Synthesis and characterization of polyimides from 9,10-dialkyloxy-1,2,3,4,5,6,7,8-octahydro-2,3,6,7-anthracenetetracarboxylic-2,3:6,7-dianhydrides and 4,4'-oxydianiline

Summary New dianhydrides having alkyloxy side chains were synthesized and polymerized with 4,4'-oxydianiline in NMP. Chemically cyclized polyimides were obtained with inherent viscosities of 0.30∼0.84 dL/g range. All the polymers were highly soluble in polar solvent such as NMP at room temperature. TGA pyrograms showed two-step degradation and in DSC thermograms the polymers exhibited T_gs between 124°C and 259°C. Wide-angle X-ray diffractograms revealed very low crystallinity and layered structure, which was better developed in the polymers with longer side chains Received: 16 October 2000/Accepted: 10 November 2000     

Synthesis,characterization, and studies on the solid-state crosslinking of functionalized vinyl cinnamate polymers

Functionalized vinyl cinnamate monomers were synthesized by the reaction between hydroxyethylacrylate (HEA) and substituted cinnamoyl chlorides possessing electron releasing and withdrawing functional groups like chloro, methoxy, and nitro groups at the para position of the aromatic ring. The structures of these monomers were characterized by Fourier transform infrared (FTIR), ¹H-, and ¹³C-NMR spectral techniques. The homopolymers of the synthesized monomers were obtained by the free radical solution polymerization in dimethylformamide (DMF) at 80°C for 12 h using azobisisobutyronitrile (AIBN) as a radical initiator. The sensitivity of these polymers towards light was studied by monitoring the photocrosslinking nature of the polymers by ultraviolet (UV) and FTIR techniques. The effect of the functional groups on the crosslinking efficiency was studied and compared with that of the unsubstituted polymer. The cyclobutane-type addition mechanism involved in the photocrosslinking phenomena was confirmed by the above spectral studies in the functionalized vinyl cinnamate polymers. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 441–448, 1998     

Characterization of poly(methyl methacrylate) from radiation-induced polymerization in the presence of a kaolin clay substrate

Two types of polymer are formed in the radiation-initiated polymerization of methyl methacrylate (MMA)–kaolin clay complexes. Homopolymer can be extracted from the complex by the use of organic solvents. Inserted polymer must be removed by dissolution of the polymer–clay complex with hydrofluoric acid. The polymers formed show no differences in structure (as determined by infrared analysis), had high molecular weights (1–5 × 10⁶), and had similar molecular weight distributions (as determined by GPC). The molecular weights of the homopolymer increased as temperature increased (25°–75°C), and dose rate decreased (24.9–7.35 rads/sec). The isotacticity of the polymers when compared to irradiated bulk polymer decreased as follows: inserted > homo > bulk. The compressive properties of the irradiated composite compared well with those of commercial bulk polymers. Degradation temperatures were 20° to 30°C higher for the composite than for the commercial chemically initiated bulk polymer.     

A new class of poly(1,6-heptadiyne)-based photorefractive materials by metathesis polymerization

SUMMARY: We utilized the first metathesis reaction to synthesize a new type of photorefractive polymers that contain both a carbazole moiety as a hole transporter and NLO chromophores. These polymers have a long tail band at above 700 nm, indicating the formation of intramolecular charge transfer complexes between the carbazole groups and the conjugated double bonds in the polymer backbone. Also, these polymers show two maximum values of photocurrent around 350 and 700 nm. The electro-optic coefficient (r ₃₃) at the wavelength of 1.3 μm for polymer thin films poled around the 85°C were in the range of 1.6 ∼6.3 pm/V. The hyperpolarizabilities, <γ>, of the resulting polymers were ca. 2.9 × 10⁻³² esu. at the incident wavelength of 1.907 μm. Received: 1 June 1998/Revised version: 27 July 1998/Accepted: 5 August 1998     

Chemical and electrochemical polymerisation of diacetylenes containing thienyl moiety as the side group

Summary Two symmetrical diacetylene monomers containing thienyl moiety as the side groups, namely 1,4-bis(2'-thienyl)butadiyne and 1,4-bis(3'-thienyl)butadiyne, are reported which have been successfully polymerised electrochemically. They have also been polymerised chemically in solution using Lewis acid as initiator. The resulting polymers have been characterised by elemental analysis, infrared spectra, absorption spectra and by solid state NMR spectra. The polymers were found to have conjugated π-electron structure and both of them show high environmental stability. The properties of the polymers have been compared with that of poly(3-methylthiophene) which is a conventional and much studied conjugated polymer. The electrical conductivity of the polymers has also been investigated. Received: 9 September 1998/Revised version: 12 November 1998/Accepted: 19 November 1998     

Polymer blends of polypropylene with polydialkylsiloxane

Polypropylene was blended with polydialkylsiloxane (alkyl : propyl and octyl). Some properties of the resultant polymer blends were investigated: the melt flow index at 230°C, bending modulus, and Izod impact strength. Furthermore, their morphology was observed using scanning and transmission electron microscopes. It was elucidated that polydipropylsiloxane and polydioctylsiloxane, which are finely dispersed as ciliated islands in the sea of polypropylene, are effective to increase the melt flow index and Izod impact strength of the polymer blends. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1853–1861, 1998     

Exploring the post-polymerization modification of side-chain amino acid containing polymers via Michael addition reactions

An efficacious protocol for the aza-Michael addition of a C-terminus modified phenylalanine side-chain containing polymer (Michael donor) was demonstrated with various Michael acceptors. The aza-Michael addition reactions were carried out at 50 °C in anhydrous methanol, which is a protic solvent, to enhance the advancement of the reactions. ¹H and inverse gated ¹³C NMR spectroscopy were utilized to qualitatively deliver comprehensive data on the reaction progress. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF) provided quantitative information about the modification of the polymer. The extent of change in the aza-Michael addition varied with different Michael acceptors and decreased in the order of acrylate > acrylamide > methacrylate. The present study opens up a library of polymers with functional modifications in the side-chain.     

Thermal behavior and morphological properties of novel magnesium salt–polyacrylamide composite polymers

Magnesium salt–polyacrylamide composite polymers have been prepared by blending magnesium chloride and magnesium hydroxide, respectively, with polyacrylamide aqueous solution. The thermal behavior of the dried magnesium salt–polyacrylamide composite polymers has been studied. Differential scanning calorimetric (DSC) analysis and thermal gravimetric analysis (TGA) were carried out to investigate the changes of the composite polymers' behavior with temperature. The kinetics of the thermal decomposition of magnesium salt–polyacrylamide composite polymers was investigated over temperature range of 35–800°C with three heating rates of 10, 20, and 40°C/min under nitrogen atmosphere. Flynn and Wall's model was usedto determine the activation energies of thermal decomposition for magnesium salt–polyacrylamide composite polymers. The activation energies needed to decompose 50 wt% of magnesium hydroxide‐polyacrylamide (MHPAM) composite polymer ranged from of 28.993–174.307 kJ/mol which are higher than the values for magnesium chloride–polyacrylamide (MCPAM) composite polymer (21.069–39.412 kJ/mol). Therefore, MHPAM composite polymer has a better thermal stability compared with MCPAM composite polymer. The morphological properties of magnesium salt–polyacrylamide composite polymers were studied using scanning electron microscopy (SEM). Energy‐dispersive X‐ray (EDX) spectroscopy was used to determine the composition of the chemical elements. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Diacetylene-containing polymers. XI. Synthesis and characterization of poly(hexa-2,4-diynylene-1,6-dioxydibenzoate) and poly(octa-3,5-diynylene-1,8-dicarboxylate) containing p-nitroaniline groups

Summary Two novel polymers containing p-nitroaniline group in the side chain and diacetylene groups in the main chain, were synthesized, and characterized. The polymers gave films of excellent optical quality by spin coating from DMF or chloroform. The one containing benzoate had a T_g of 103°C and its thermal cross-linking through the diacetylene group started at around 160°C. The one containing pentynoate had a T_g of 35°C and its cross-linking started at around 120°C. It was shown that thermosetting resins with functional groups could be obtained by using diacetylene-containing polymers. Although these two polymers have a same polar dye molecule, the second order nonlinear optical property was so different, showing that the main chains are very important for nonlinear optical property. Irradiation of UV light converted the polymer films to completely insoluble thermoset resins. Received: 13 February 2001/Revised version: 25 July 2001/Accepted: 30 July 2001