Improvement of the thermal stability of cluster‐crosslinked polystyrene and poly(methyl methacrylate) by optimization of the polymerization conditions

The polymerization conditions for polystyrene and poly(methyl methacrylate) crosslinked by 0.5 mol % of the cluster Zr₆O₄(OH)₄(methacrylate)₁₂ were optimized by applying a step polymerization procedure. The onset of thermal decomposition was thus increased up to about 50° for polystyrene and about 110° for poly(methyl methacrylate). The increase in thermal stability correlated with a higher char yield. The glass transition temperatures were also increased by about 15°. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6586–6591, 2005     

Synthesis and characterization of thermally stable and flame retardant poly (benzoxazine-co-urethane) matrices

Abstract

The flame-retardant behavior of organic polymers is considered as very important criteria to utilize them in the form of coatings, encapsulants, sealants, and matrices for high performance industrial applications. A new type of poly (benzoxazine-co-urethane) (PBZ-co-PU) matrices have been developed using dimethylol benzoxazine monomers (BZM and BZE) and tris(p-isocyanatophenyl)thiophosphate (Desmodur) through A₂?+?B₃ approach followed by thermal curing. The molecular structure of developed PBZ-co-PU was confirmed by FT-IR spectra and their thermal stability and flame retardant behavior were studied by standard methods. Data obtained from TGA and DSC, indicate that the PBZ-co-PU possesses higher Tg, better thermal stability and LOI than those of neat PBZ. Further, it was also observed that among the two matrix systems (PBZ-co-PU-1 and PBZ-co-PU-2) studied, the PBZ-co-PU-1 based system exhibited higher T_g, thermal stability and flame retardant behavior than those of PBZ-co-PU-2.     

A systematic study of stereochemical effects in homologous poly(alkenamer)s: Dewar benzene versus norbornene

Two diastereomeric derivatives of norbornene, dimethyl (1R,2R,3S,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate and dimethyl (1R,2S,3S,4S)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate, were synthesized and polymerized using ring-opening metathesis polymerization (ROMP). For comparative purposes, diastereomeric derivatives of Dewar benzene, dimethyl (1R,2S,3R,4S)-bicyclo[2.2.0]hex-5-ene-2,3-dicarboxylate and dimethyl (1R,2S,3S,4S)-bicyclo[2.2.0]hex-5-ene-2,3-dicarboxylate, were also synthesized and polymerized using ROMP. The polymerization reactions proceeded in a controlled manner as evidenced in part by linear relationships between the monomer-to-catalyst feed ratios and the molecular weights of the polymer products. Chain extension experiments were also conducted which facilitated the formation of block copolymers. Although the poly(norbornene) derivatives exhibited glass transition temperatures that were dependent on their monomer stereochemistry (cis: 115°C vs. trans: 125°C), more pronounced differences were observed upon analysis of the polymers derived from Dewar benzene (cis: 70°C vs. trans: 95°C). Likewise, microphase separation was observed in block copolymers that were prepared using the diastereomeric monomers derived from Dewar benzene but not in block copolymers of the norbornene-based diastereomers. The differential thermal properties were attributed to the relative monomer sizes as reducing the distances between the polymer backbones and the pendant stereocenters appeared to enhance the thermal effects.     

Preparation and cryogenic mechanical properties of epoxy resins modified by poly(ethersulfone)

A thermoplastic, poly(ethersulfone) (PES) was used to modify a bisphenol‐F based epoxy resin cured with an aromatic diamine. The initial mixtures before curing, prepared by melt mixing, were homogeneous. Scanning electron microscopy (SEM) micrographs of solvent‐etched fracture surfaces of the cured blends indicated that phase separation occurred after curing. The cryogenic mechanical behaviors of the epoxy resins were studied in terms of tensile properties and Charpy impact strength at cryogenic temperature (77 K) and compared to their corresponding behaviors at room temperature (RT). The addition of PES generally improved the tensile strength, elongation at break, and impact strength at both RT and 77 K except the RT tensile strength at 25 phr PES content. It was interesting to observe that and the maximum values of the tensile strength, elongation at break, and impact strength occurred at 20 phr PES content where a co‐continuous phase formed. Young's modulus decreased slightly with the increase of the PES content. Moreover, the tensile strength and Young's modulus at 77 K were higher than those at RT at the same composition, whereas the elongation at break and impact strength showed the opposite results. Finally, the differential scanning calorimetry analysis showed that the glass transition temperature (T_g) was enhanced by the addition of PES. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 612–624, 2008     

Thermal properties of biocomposites

Thermal properties of new biocomposites prepared from modified starch matrix reinforced with natural vegetable fibres were studied. DSC and TG methods were applied to study thermal behaviour of biocomposites. Biocomposites were obtained in the laboratory twin-screw extruder. Two kinds of natural fibres were used, i.e. flax and cellulose in the amount of 0–40 mass%. DSC curves of biocomposites reveal glass transition temperature, attributed to the amorphous nature of the plasticized starch matrix. In general, incorporating natural fibres into modified starch matrix leads to an increase in glass transition temperature. Thermal degradation of modified starch matrix and cellulose reinforced biocomposites proceeds in three steps, whereas the degradation process of flax reinforced biocomposites occurs in two steps. For unreinforced matrix as well as for all biocomposites, regardless of type and amount of reinforcement, the major mass loss is observed at the temperature above 300°C. The increase in thermal stability with introduction of natural fibre is observed for both flax and cellulose reinforced biocomposites.     

Cationic cyclopolymerization of divinyl ethers with norbornane‐, norbornene‐, or adamantane‐containing substituents: Synthesis of cyclopoly(divinyl ether)s with bulky rigid side chains leading to high glass transition temperature

Cationic cyclopolymerizations of 2,2‐bis(vinyloxymethyl)bicyclo[2.2.1]heptane ( 1 ), 5,5‐bis(vinyloxymethyl)‐2‐bicyclo[2.2.1]heptene ( 2 ), and 2,2‐bis(vinyloxymethyl)tricyclo[3.3.1.1]^{3, 7}decane ( 3 ), divinyl ethers with a norbornane, norbornene, or adamantane unit, respectively, were investigated with the HCl/ZnCl₂ initiating system in toluene and methylene chloride at ?30 °C. All the reactions proceeded quantitatively to give gel‐free, soluble polymers in organic solvents. The number‐average molecular weight (M_n) of the polymers increased in direct proportion to monomer conversion and further increased on addition of a fresh monomer feed to the almost completely polymerized reaction mixture. The contents of the unreacted vinyl groups in the produced soluble polymers were less than ～10 mol %, and therefore, the degree of cyclization of the polymers was determined to be over ～90%. These facts show that cyclopolymerization of 1 , 2 , and 3 exclusively occurred and the poly(vinyl ether)s with the cyclized repeating units and polycyclic pendants were obtained with their molecular weights being regulated. BF₃OEt₂ initiator also caused cyclopolymerization of 1 , 2 , and 3 to give the corresponding high‐molecular‐weight cyclopolymers quantitatively. Glass transition temperatures (T_g's) of poly( 1 ) and poly( 2 ) were 165–180 °C, and T_g's of poly( 3 ) were 211–231 °C; these values are very high as vinyl ether polymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2445–2454     

Viscoelastic properties of poly(methyl methacrylate) with high glass transition temperature by lithium salt addition

The effect of ion‐dipole interaction between lithium cations and oxygen atoms in poly(methyl methacrylate) (PMMA), which leads to the great enhancement of glass transition temperature (T_g), on the linear viscoelastic properties is studied using binary blends of PMMA and lithium trifluoromethanesulfonate (LiCF₃SO₃). The strong interaction at low temperature leads to the high modulus in the glassy region even near T_g. The interaction becomes weak as increasing the temperature. Consequently, the rheological terminal region is clearly detected without a marked enhancement of steady‐state compliance, although the zero‐shear viscosity increases by the LiCF₃SO₃ addition. The result indicates that the crosslinking due to the ion‐dipole interaction has a lifetime that decides the longest relaxation time. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2388–2394     

Energy‐damping behaviors of poly(methyl acrylate‐co‐divinylbenzene) microspheres coated with a porous nickel–phosphorus layer

Hybrid microspheres of poly(methyl acrylate‐co‐divinylbenzene) (PMADVB) with a thin and porous nickel–phosphorus (Ni–P) alloy layer were prepared via suspension polymerization and electroless nickel plating. The characterization of pristine and nickel‐coated microspheres was carried out with a differential scanning calorimeter and a scanning electron spectroscope equipped with an energy‐dispersive system. The glass‐transition range of Ni–P‐coated PMADVB was broadened and extended in the higher temperature direction. This effect allowed the PMADVB network to embrace more diversified energy states of the segment motion, this being a desired feature for damping sound waves. The low‐frequency (100–1000‐Hz) sound absorption behavior of the microspheres was tested with a sound attenuation kit. Besides the testing of their low‐frequency damping performance, an investigation into the ultrasonic‐wave (～35 kHz) absorption feature of the microspheres was conducted through chemical means; that is, the attenuation to the ultrasonic wave with respect to the unprotective situation was assessed through the chemisorption extent of copper ions on a biomass adsorbent. The Ni–P deposition layer was found to augment the damping capacity of the polymer network. The alloy layer was determined to cause an expansion of the glass‐transition range of PMADVB and its wave‐scattering capability because this layer was made up of submicrometer metallic grains. In this work, the particulars of the metal–polymer interactions were associated with a core–shell structure. The metal outer layer was thought to create a spherical temperature field inside the PMADVB network, and concerted motions of the polymer segments resulted. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2710–2723, 2004     

Thermal analysis of PMMA/gel silica glass composites

Thermal analysis of poly-methylmethacrylate (PMMA) impregnated porous gel silica glasses confirms that the PMMA chains form hydrogen bonds with the pore surface silanol groups. The adopted conditions for the insitu polymerisation result in about 4% of residual monomers trapped in the polymer, most of them in the amorphous structure. The polymer and monomer mixture takes up the whole of the free pore volume. Most of the residual monomer polymerises during the DSC scans above the glass transition temperature providing an excellent probe for the weak glass transition. Polymerisation in the gel silica glass medium affects the glass transition temperature, the length of polymer chains, and the degree of polymerisation.     

Thermal and photochemical stability of poly(methyl methacrylate) and its blends with poly(vinyl acetate)

An investigation of the thermal stability of poly(methyl methacrylate) (PMMA) blends with poly(vinyl acetate) (PVAc) revealed that PVAc acts as a stabilizer as concerns thermal and photochemical degradation when the processes take place in air. The temperatures of decomposition of these blends are higher than that of pure PMMA. The efficiency of photodegradation and photooxidation in the blends is lower than that of pure PMMA.     

Synthesis and liquid crystalline properties of new amide‐modified poly(1,4‐cyclohexanedimethylene terephthalate)

New series of cycloaliphatic poly(ester‐amide)s, poly(1,4‐cyclohexanedimethyleneterephthalate‐co‐1,3‐cyclohexanedimethylene terephthalamide), were synthesized through solution polymerization route. The compositions of ester/amide units in the copolymers were varied from 0 to 100% by varying the amount of 1,4‐cyclohexanedimethanol and 1,3‐cyclohexanebis(methylamine) in the feed. The structures of the polymers were confirmed by NMR and FTIR, and the molecular weights were determined by inherent viscosity. The composition analysis by NMR reveals that the reactivity of the diamine toward the acid chlorides is lowered than that of diol, which results in the formation of more ester content in the poly (ester‐amides). The thermal analysis indicate that the new poly(ester‐amide)s having less than 10 mol % of amide linkages are thermotropic liquid crystalline from 200 to 250 °C and a thread like nematic phases are observed under the polarizing microscope. WXRD studies suggest that the liquid crystalline domains promote the nucleation process in the polyester chains and increases the percent crystallinity of the poly(ester‐amide)s. The glass transition temperature of the copolymers initially increases with increase in amide units because of the presence of nematic phases and subsequently follows the Flory–Fox behavior. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 42–52, 2006     

Thermal properties of swollen butadiene-acrylonitrile rubber vulcanizates

The present paper discusses the results of assessing thermal properties of nitrile rubber, Perbunan NT 3945 and its peroxide vulcanizates, before and after their swelling in solvents such as benzene, toluene and dimethylformamide. The measurements were carried out by means of differential scanning calorimetry (DSC) and thermogravimetry (TG) under nitrogen. It has been found that a slight rise in the glass transition temperature due to the elastomer cross-linking is clearly revealed under the influence of its vulcanizates swelling in solvents whose solubility parameters considerably differ from the solubility parameters of the polymer. The thermal curves of swollen samples reveal processes resulting from polymer-solvent interactions and thermodesolvation processes, which accompany the initial stage of solvent evaporation.The authors would like to express their thanks to the Bayer company for providing free of charge samples of Perbunan NT 1845 and Perbunan 3945 which were used in this study.     

Thermal properties and toughness performance of hyperbranched‐polyimide‐modified epoxy resins

An amine‐terminated hyperbranched polyimide (HBPI) was prepared by the condensation polymerization of a commercially available triamine monomer with a dianhydride monomer. The effects of the HBPI content on the thermal and mechanical interfacial properties of diglycidyl ether of bisphenol A (DGEBA) epoxy resins were investigated with several techniques. The thermogravimetric analysis results showed that the thermal stability of the DGEBA/HBPI blends did not obviously change as the HBPI content increased. The glass‐transition temperature (T_g) of the DGEBA/HBPI blends increased with the addition of HBPI. Improvements in the critical stress intensity factor (K_IC) and impact strength of the blends were observed with the addition of HBPI. The K_IC value and impact strength were 2.5 and 2 times the values of the neat epoxy resins with only 4 wt % HBPI. The fractured surfaces were studied with scanning electron microscopy to investigate the morphology of the blends, and they showed that shear deformation occurred to prevent the propagation of cracks in the DGEBA/HBPI blends. These results indicated that a toughness improvement was achieved without a decrease in the thermal stability or T_g. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3348–3356, 2006     

Living/controlled cationic cyclopolymerization of divinyl ether with a cyclic acetal moiety: Synthesis of poly(vinyl ether)s with high glass transition temperature based on incorporation of cyclized main chain and cyclic side chains

Cationic cyclopolymerization of 2‐methyl‐5,5‐bis(vinyloxymethyl)‐1,3‐dioxane ( 1 ), a divinyl ether with a cyclic acetal group, was investigated with the HCl/ZnCl₂ initiating system in toluene and methylene chloride at ?30 °C. The reaction proceeded quantitatively to give gel‐free, soluble polymers in organic solvents. The number‐average molecular weight (M_n) of the polymers increased in direct proportion to monomer conversion, and further increased on addition of a fresh monomer feed to the almost completely polymerized reaction mixture, indicating that the polymerization proceeded in living/controlled manner. The contents of the unreacted vinyl groups in the produced soluble polymers were less than ～3 mol %, and therefore, the degree of cyclization was determined to be ～97%. In contrast, the pendant cyclic acetal groups remained intact in the polymers under the present cationic polymerization conditions. These facts show that cyclopolymerization of 1 almost exclusively occurred and the poly(vinyl ether)s with the cyclized repeating units and cyclic pendant acetal rings were obtained. Glass transition temperature (T_g) and thermal decomposition temperature (T_d) of poly( 1 ) (M_n = 7870, M_w/M_n = 1.57) were found to be 166 and 338 °C, respectively, indicating that poly( 1 ) had high T_g and high thermal stability. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 952–958, 2010     

Thermal and dynamic mechanical properties of poly(propylene carbonate)

Summary Thermal and dynamic mechanical properties of carbon dioxide and propylene oxide alternative copolymer, poly(propylene carbonate) (PPC), and the end-capped PPC with maleic anhydride were investigated by means of TG and DMA. A master curve of the storage modulus vs. frequency can be deduced from the isochronal curves. Physical parameters of both plain and MA end-capped PPC were discussed. The results showed that for maleic anhydride (MA) end-capping PPC, an improvement of its thermal stability and mechanical properties accompanied with some modifications of the viscoelastic behavior were obtained.     

Thermal characterization of benzylcellulose derivatives prepared from bleached pinus kraft pulp

The thermal characterization (DSC and TG) of benzylcellulose derivatives prepared from the benzylation of bleached Pinus Kraft pulp is described in this paper. The objective of this study was to examine the changes in glass transition temperature (T _g) and the thermal stability of the benzylated product as a function of the benzylation extent (degree of substitution). The DSC analysis showed that the benzylcelluloses can display glass transition temperature at two different regions and that thermal stability is slightly higher than that of the parent cellulose. This revised version was published online in August 2006 with corrections to the Cover Date.     

Synthesis and thermal properties of poly(cycloalkyl methacrylate)s bearing bridged- and fused-ring structures

Radical polymerizations of some cycloalkyl methacrylates bearing bridged- and fused-ring structures, i.e., bornyl methacrylate (BoMA), isobornyl methacrylate (IBoMA), 2-decahydronaphthyl methacrylate (DNMA), and 3-tetracyclo [4.4.0^2,5.1^7,10] dodecyl methacrylate (TCDMA), were carried out. The radical polymerization reactivities of these monomers depended on the structure of the cycloalkyl ester groups in the following order: TCDMA > BoMA > DNMA > CHMA > IBoMA > MMA, where CHMA and MMA are cyclohexyl and methyl methacrylates, respectively. The propagation and termination rate constants of these monomers were evaluated from the polymer radical concentration determined by electron spin resonance spectroscopy. The solubilities and microstructures of the resulting polymers were examined. Thermal properties, i.e., glass transition temperatures and decomposition behaviors, of the polymers were also investigated and related to the structures of the polymer side chain. © 1993 John Wiley & Sons, Inc.     

Thermal properties of fibres from a new polymer of the polyimideamide group

The paper presents the thermal properties of fibres made of a modified polyimideamide. The effects of as-spun draw ratio and deformation during the fibre drawing stage on the structure, thermal properties, moisture absorption and tenacity of the obtained fibres have been determined. Based on the findings obtained by the DTA and DSC methods, it has been found that the modification of the polymer under investigation causes its glass transition temperature to decrease through the increase of molecular mobility. At the same time, the heat-resistant fibres with the amorphous oriented structure are characterized by a tenacity of 16 cN/tex, good absorption properties and increased porosity. The thermal stability indices of the examined fibres have been determined on the basis of thermogravimetric curves obtained both under air and inert gas. This revised version was published online in July 2006 with corrections to the Cover Date.     

Oxyethylene copolymers with chloromethyl and (alkylthio)methyl or (alkylsulfonyl)methyl side groups: Syntheses and Tg/composition relationships

New classes of copolymers, poly[oxy(chloromethyl)ethylene]/poly[oxy-((alkylthio)methyl)ethylene] copolymers (CE-ATEs), poly[oxy((alkylthio)methyl)-ethylene]s (ATEs), poly[oxy(chloromethyl)ethylene]/poly[oxy((alkylsulfonyl)meth-yl)ethylene] copolymers (CE-ASEs), and poly[oxy((alkylsulfonyl)methyl)ethylene]s (ASEs) have been made for the first time. The thioether-containing polymers (CE-ATEs and ATEs) were synthesized by reacting poly[oxy(chloromethyl)ethylene] (CE, poly(epichlorohydrin)) with different amounts of sodium alkanethiolates. The sulfone-containing polymers (CE-ASEs and ASEs) were synthesized by oxidizing the CE-ATEs and ATEs using m-chloroperoxybenzoic acid. The Fox equation, a linear relationship, fit the T_g/composition data for most CE-ATEs. The T_g's of the CE-ASEs showed positive deviations from those calculated using the Fox equation. The Johnston equation, in which steric and/or polar interactions between dissimilar monomeric units are considered by using T_gAB (the T_g of the AB or BA dyad), fit the T_g/composition data for all copolymers in this study. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36 : 495–504, 1998