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61.
Francesco Acquasanta Corrado BertiMartino Colonna Maurizio FioriniSreepadaraj Karanam 《Polymer Degradation and Stability》2011,96(4):566-573
Recent regulation IEC 60335-1 ed.4 (2008) was introduced for materials used in electric appliance, establishing new limits in Glow Wire Ignition Temperature (GWIT) performance for materials used for electric connectors. Development of new products with high GWIT is possible, but the main issue is to keep good mechanical properties and processability, as well as tracking resistance (Comparative Tracking Index-CTI). Only a few patents and scientific publications exist about glow wire test performance of polymers. In this work we report GWIT and CTI properties for three engineering thermoplastic polymers (PBT, PET and PC). We have also studied the phenomena involved in this test, treating the phenomena with the parameterisation approach already used in the studies of the fire behaviour of polymers. PC, PBT and PET filled with 30% w/w glass fibres have been tested, and material properties that can be related to GWIT and CTI performance have been measured by TGA, Laser Flash Thermal Diffusivity (LFTD), Pyrolysis-GC/MS. CTI seems to be correlated with the char formation tendency of the materials, so PBT show a higher tracking resistance than PET and PC. Polycarbonate was the only material that passed the glow wire test (GWIT higher than 775 °C) but generally GWIT performance is not directly related with degradation temperature, since PET is thermally more stable compared with PBT, but less stable in glow wire test. The ignition process, together with the unsteady heat and mass transfer process characteristic of glow wire testing, are affected by many parameters at the same time. That’s why it is not easy to relate results of TGA, Laser flash, Pyrolysis-GC/MS with the glow wire ignition temperature of the materials tested, but the whole of these properties can give useful indication. 相似文献
62.
Miscible blends of poly(ethylene oxide) with brush copolymers of poly(vinyl alcohol)‐graft‐poly(l‐lactide)
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Ainhoa Lejardi Jose‐Ramon Sarasua Agustin Etxeberria Emilio Meaurio 《Journal of Polymer Science.Polymer Physics》2016,54(13):1217-1226
Even though poly(ethylene oxide) (PEO) is immiscible with both poly(l ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA), this article shows a working route to obtain miscible blends based on these polymers. The miscibility of these polymers has been analyzed using the solubility parameter approach to choose the proper ratios of the constituents of the blend. Then, PVA has been grafted with l ‐lactide (LLA) through ring‐opening polymerization to obtain a poly(vinyl alcohol)‐graft‐poly(l ‐lactide) (PVA‐g‐PLLA) brush copolymer with 82 mol % LLA according to 1H and 13C NMR spectroscopies. PEO has been blended with the PVA‐g‐PLLA brush copolymer and the miscibility of the system has been analyzed by DSC, FTIR, OM, and SEM. The particular architecture of the blends results in DSC traces lacking clearly distinguishable glass transitions that have been explained considering self‐concentration effects (Lodge and McLeish) and the associated concentration fluctuations. Fortunately, the FTIR analysis is conclusive regarding the miscibility and the specific interactions in these systems. Melting point depression analysis suggests that interactions of intermediate strength and PLOM and SEM reveal homogeneous morphologies for the PEO/PVA‐g‐PLLA blends. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1217–1226 相似文献
63.
Lidia Jasinska Cor E. Koning 《Journal of polymer science. Part A, Polymer chemistry》2010,48(24):5907-5915
A new experimental approach for preparing biobased, water‐soluble polyesters (PEs) via titanium(IV) n‐butoxide‐catalyzed bulk polycondensation is presented. In the described method polymers were obtained from isosorbide, maleic anhydride and poly(ethylene glycol) (PEG). The chemical structure of the synthesized PEs was confirmed using 2D NMR spectroscopy and by titration methods. Careful analysis of 2D NMR spectra viz. correlation spectra (COSY), heteronuclear single quantum correlation spectra (HSQC) and heteronuclear multiple‐bond correlation spectra (HMBC) allowed to accomplish the complete proton assignment of isosorbide, PEG, and unsaturated acid residues in the PEs. Moreover, by using NMR spectroscopy the transformation of maleic anhydride into fumaric acid ester and the absence of maleic acid ester units in the final polymer were proven. However, during polycondensation part of the unsaturated bonds has reacted in a Michael addition with isosorbide or PEG. Gel permeation chromatography measurements revealed that the unsaturated PEs have Mn values in the range 3000–5000 g/mol. These PEs, with a low content of carboxylic acid end groups, exhibited sufficient thermal resistance for practical applications, for example, as free radical curable coatings. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献
64.
Po‐Sheng Chen Yi‐Chang Liu Chia‐Her Lin Bao‐Tsan Ko 《Journal of polymer science. Part A, Polymer chemistry》2010,48(16):3564-3572
Two novel sulfonate phenol ligands—3,3′‐di‐tert‐butyl‐2′‐hydroxy‐5,5′,6,6′‐tetramethyl‐biphenyl‐2‐yl 4‐X‐benzenesulfonate (X?CF3, LCF3 ‐H, and X?OCH3, LOMe ‐H)—were prepared through the sulfonylation of 3,3′‐di‐tert‐butyl‐5,5′,6,6′‐tetramethylbiphenyl‐2,2′‐diol with the corresponding 4‐substituted benzenesulfonyl chloride (1 equiv.) in the presence of excess triethylamine. Magnesium (Mg) complexes supported by sulfonate phenoxide ligands were synthesized and characterized structurally. The reaction of MgnBu2 with L‐H (2 equiv.) produces the four‐coordinated monomeric complexes ( LCF3 )2Mg ( 1 ) and ( LOMe )2Mg ( 2 ). Complexes 1 and 2 are efficient catalysts for the ring‐opening polymerization of ε‐caprolactone (ε‐CL) and trimethylene carbonate (TMC) in the presence of 9‐anthracenemethanol; complex 1 catalyzes the polymerization of ε‐CL and TMC in a controlled manner, yielding polymers with the expected molecular weights and narrow polydispersity indices (PDIs). In ε‐CL polymerization, the activity of complex 1 is greater than that of complex 2 , likely because of the greater Lewis acidity of Mg2+ metal caused by the electron‐withdrawing substitute trifluoromethyl (? CF3) at the 4‐position of the benzenesulfonate group. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3564–3572, 2010 相似文献
65.
Kosuke Makiguchi Seiya Kikuchi Toshifumi Satoh Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2013,51(11):2455-2463
The ring‐opening polymerization (ROP) of cyclic esters, such as ε‐caprolactone, 1,5‐dioxepan‐2‐one, and racemic lactide using the combination of 3‐phenyl‐1‐propanol as the initiator and triflimide (HNTf2) as the catalyst at room temperature with the [monomer]0/[initiator]0 ratio of 50/1 was investigated. The polymerizations homogeneously proceeded to afford poly(ε‐caprolactone) (PCL), poly(1,5‐dioxepan‐2‐one) (PDXO), and polylactide (PLA) with controlled molecular weights and narrow polydispersity indices. The molecular weight determined from an 1H NMR analysis (PCL, Mn,NMR = 5380; PDXO, Mn,NMR = 5820; PLA, Mn,NMR = 6490) showed good agreement with the calculated values. The 1H NMR and matrix‐assisted laser desorption ionization time‐of‐flight mass spectrometry analyses strongly indicated that the obtained compounds were the desired polyesters. The kinetic measurements confirmed the controlled/living nature for the HNTf2‐catalyzed ROP of cyclic esters. A series of functional alcohols, such as propargyl alcohol, 6‐azido‐1‐hexanol, N‐(2‐hydroxyethyl)maleimide, 5‐hexen‐1‐ol, and 2‐hydroxyethyl methacrylate, successfully produced end‐functionalized polyesters. In addition, poly(ethylene glycol)‐block‐polyester, poly(δ‐valerolactone)‐block‐poly(ε‐caprolactone), and poly(ε‐caprolactone)‐block‐polylactide were synthesized using the HNTf2‐catalyzed ROP. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2455–2463 相似文献
66.
Seda Cakir René Kierkels Cor Koning 《Journal of polymer science. Part A, Polymer chemistry》2011,49(13):2823-2833
This work describes the synthesis and characterization of polyamide 6 (PA 6)‐polycaprolactone (PCL) multiblock copolymers. Low molar mass, fully amine end‐capped PA 6 was prepared by the addition of a diamine monomer during ε‐caprolactam polymerization. A low molar mass PCL was selected to be incorporated as the biodegradable block and was fully end‐capped with toluene 2,4‐diisocyanate. End group analysis and molecular weight characterizations were performed for both end‐functionalized polymers by SEC, NMR and titration analysis. Incorporation of PCL into PA 6 was mainly achieved by solution mixing of the two end‐functional blocks and, was continued after the removal of the solvent with solid state polymerization (SSP) by gradual heating until about 40 °C below the melting temperature of the PA 6. Molecular weights started to grow immediately during solution mixing and only increased marginally during the SSP treatment. FTIR and SEC studies confirmed the reaction between the two components. DSC data, in combination with the enhanced molar mass during solution mixing pointed to a blocky microstructure, for which distinct melting and crystallization temperatures were observed for the PCL and the PA 6 blocks. Hydrolytic and enzymatic degradation studies were performed at 25 °C where the degree of degradation was followed by weight loss analysis, SEM and SEC. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
67.
Toshimitsu Ichimori Shinichi Yamazaki Kunio Kimura 《Journal of polymer science. Part A, Polymer chemistry》2011,49(21):4613-4617
The influence of shear flow, especially the timing for the application of shearing, was examined to enhance the selectivity for the preparation of poly(p‐oxybenzoyl) (Pp‐OB) by using hydrodynamically induced phase separation during polymerization of 4‐(4‐acetoxybenzoyloxy)benzoic acid (p‐ABAD) and m‐acetoxybenzoic acid (m‐ABA). The polymers containing few m‐oxybenzoyl (m‐OB) moieties were obtained as precipitates even at high content of m‐OB moiety in feed (χf) under shear flow. The content of m‐OB moiety in the precipitates (χp) prepared under shearing throughout the polymerization at the shear rate (γ) of 489 s?1 was 6.3 mol % even at χf of 60 mol %. Especially, the Pp‐OB was obtained as the precipitates at χf of less than 50 mol %. The timing of the application of the shearing influenced the selectivity significantly, and the shearing just after the precipitation of the oligomers started was quite efficient to enhance the selectivity more. The χp of the precipitates prepared with shearing at γ of 489 s?1 just after the precipitation was only 3.9 mol % even at χf of 60 mol %. The shear flow reduced the difference in the reactivity between p‐ABAD and m‐ABA, resulting in the decrease in the selectivity with regard to the formation of p‐oxybenzoyl homo‐oligomer. However, the shear flow enhanced the difference in the miscibility between homo‐oligomers and co‐oligomers. This change in the miscibility by shear flow brought about the more rapid precipitation of homo‐oligomers, leading to the enhancement of the selectivity. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
68.
Ryan M. Weiss Evan M. Jones David E. Shafer Ryan M. Stayshich Tara Y. Meyer 《Journal of polymer science. Part A, Polymer chemistry》2011,49(8):1847-1855
Repeating sequence copolymers of poly(lactic‐co‐caprolactic acid) (PLCA), poly(glycolic‐co‐caprolactic acid) (PGCA), and poly(lactic‐co‐glycolic‐co‐caprolactic acid) (PLGCA) have been synthesized by polymerizing segmers with a known sequence in yields of 50–85% with Mns ranging from 18–49 kDa. The copolymers exhibited well‐resolved NMR resonances indicating that the sequence encoded in the segmers used in their preparation is retained and that transesterification is minimal. The exact sequences allowed for unambiguous assignment of the NMR spectra, and these standards were compared with the data previously reported for random copolymers. The glass transition temperatures (Tgs) of the PLCA and PGCA copolymers were found to depend primarily on monomer ratio rather than sequence. Sequence dependent Tgs were, however, noted for the PLGCA polymers with 1:1:1 L:G:C ratios; poly LGC and poly GLC exhibited Tgs that differed by nearly 8 °C. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
69.
Andreia F. Sousa Alessandro Gandini Armando J. D. Silvestre Carlos Pascoal Neto José J. C. Cruz Pinto Christer Eckerman Bjarne Holmbom 《Journal of polymer science. Part A, Polymer chemistry》2011,49(10):2281-2291
This article reports the successful synthesis and characterization of two types of completely biobased polymers prepared by the polycondensation or polytransesterification of suberin fragments, isolated by different procedures and from two different vegetable sources. These polymerizations were conducted with different experimental conditions in terms of the type of catalyst, the reaction medium and temperature, as well as the molar ratio between the reactive moieties. The ensuing linear or partly crosslinked polyesters were characterized by conventional spectroscopic techniques, SEC, DSC, XRD, DMA, and TGA. These hydrophobic materials represent an original contribution to the growing field of polymers from renewable resources. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
70.
Atsushi Sudo Yuan Zhang Takeshi Endo 《Journal of polymer science. Part A, Polymer chemistry》2011,49(3):619-624
This article describes the anionic copolymerization of glycidyl phenyl ether (GPE) and 1,2‐dihydro‐3H‐naphtho[2,1‐b]pyran‐3‐one (DHNP), a six‐membered aromatic lactone bearing naphthyl moiety. The copolymerization proceeded in a 1:1 alternating manner, to afford the corresponding polyester. The ester linkage in the main chain was cleavable by reduction with lithium aluminum hydride to give the corresponding diol that inherited the structure of the alternating sequence. The copolymerization ability of DHNP permitted its addition as a comonomer to an imidazole‐initiated polymerization of bisphenol A diglycidyl ether. The resulting networked polymer, of which main chain was endowed with the DHNP‐derived rigid naphthalene moieties, showed a higher glass transition temperature than that obtained similarly with using 3,4‐dihydrocoumarin (DHCM) as a comonomer, an analogous aromatic lactone bearing phenylene moiety instead of naphthalene moiety of DHNP. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献