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71.
Maryluz Moreno Gerard Lligadas Joan C. Ronda Marina Galià Virginia Cádiz 《Journal of polymer science. Part A, Polymer chemistry》2012,50(15):3206-3213
A novel phosphorus‐containing vegetable oil (PETR) was prepared through phospha‐Michael addition of a diphenyl phosphine oxide to the enone derivative of high‐oleic sunflower oil (ETR). The reaction was investigated using the enone derivative of methyl oleate under conventional thermal heating and microwave irradiation. The kinetic study showed a great enhancement of reaction rate for the microwave‐initiated addition. The crosslinking of ETR with diaminodiphenylmethane (DDM) via aza‐Michael addition was also investigated under microwave irradiation, showing a noticeable acceleration of the curing. The new phosphorus‐containing triglyceride was crosslinked with DDM to obtain phosphorus‐containing vegetable oil‐based thermosets of different phosphorus contents. Limiting oxygen index values from 26.4 to 35.0 for the final materials were obtained, demonstrating that the flame retardant properties of vegetable oil‐based thermosets can be improved by adding covalently bonded phosphorus to the polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
72.
E. Del Rio M. Galià V. Cádiz G. Lligadas J. C. Ronda 《Journal of polymer science. Part A, Polymer chemistry》2010,48(22):4995-5008
Ring‐opening polymerization of epoxidized methyloleate (EMO) with various ionic‐coordinative initiators have been studied and compared with other internal epoxy monomers: benzyl 9,10‐epoxyoleoylether and cis‐4,5‐epoxyoctane. The structure and molecular weight of the resulting polymers have been studied by 1H‐ and 13C‐NMR, MALDI‐TOF‐MS, and size exclusion chromatography analysis. Polymers with higher molecular weight than those obtained with conventional cationic catalyst are obtained. These materials have been found to consist of a complex mixture of cyclic and linear polymer chains with different chain ends that can be related to the catalyst nature and the occurrence of two main polymerization mechanisms, the cationic and the ionic‐coordinative. In the polymerization of EMO, transesterification by‐side reactions leading to ester linkages in the main chain have been identified. These undesired reactions have been suppressed by copolymerization with small amounts of tetrahydrofuran with no substantial decrease in the polymer yield and molecular weight. Finally, the polymerization of EMO has been tested in a larger scale to prepare a renewable resource‐based polyether as starting material to produce polyether polyols for polyurethane applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 相似文献
73.
M. Garrido M. S. Larrechi F. X. Rius J. C. Ronda V. Cdiz 《Journal of polymer science. Part A, Polymer chemistry》2006,44(16):4846-4856
The reactivity of sulfur‐based epoxy monomers was studied by monitoring of a model system involving phenylglycidylthioether and aniline. The reaction was carried out under isothermal conditions and monitored in situ by near infrared spectroscopy. Using multivariate curve resolution‐alternating least squares made it possible to obtain the concentration and spectral profiles of each species throughout the reaction. To obtain the kinetic rate constants, the values of the recovered concentration profiles were fitted to a kinetic model proposed for the reaction. Reactivity was evaluated by comparing the concentration profiles and kinetic rate constants obtained with the same parameters obtained for phenylglycidylether/aniline as a reference system. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4846–4856, 2006 相似文献
74.
L. Montero de Espinosa J. C. Ronda M. Galià V. Cádiz 《Journal of polymer science. Part A, Polymer chemistry》2008,46(20):6843-6850
A novel triglyceride containing α,β‐unsaturated ketone was prepared through photoperoxidation from high oleic sunflower oil by two steps one pot environmentally friendly procedure. This new enone‐containing triglyceride was crosslinked with diaminodiphenylmethane (DDM) via aza‐Michael addition. A kinetic study of the reaction of p‐toluidine with either enone‐containing methyl oleate or epoxidized methyl oleate, as model compounds, allowed us to establish the higher reactivity of the former, thus confirming this curing system as an alternative to amine‐cured epoxidized vegetable oils. The thermal properties of thermosets from enone‐ and epoxy‐containing triglycerides with DDM have been evaluated. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6843–6850, 2008 相似文献
75.
J. M. Montorns J. A. Reina J. C. Ronda 《Journal of polymer science. Part A, Polymer chemistry》2004,42(12):3002-3012
A set of poly[ω‐(4′‐cyano‐4‐biphenyloxy)alkyl‐1‐glycidylether]s were synthesized by the chemical modification of the corresponding poly(ω‐bromoalkyl‐1‐glycidylether)s with the sodium salt of 4‐cyano‐4′‐hydroxybiphenyl. New high‐molecular‐weight side‐chain liquid‐crystalline polymers were obtained with excellent yield and almost quantitative degree of modification. All side‐chain liquid‐crystalline polymers were rubbers soluble in tetrahydrofuran. The characterization by 1H and 13C NMR revealed no changes in the regioregular isotactic microstructure of the starting polymer and the absence of undesirable side reactions such as deshydrobromination. The liquid crystalline behavior was analyzed by DSC and polarized optical microscopy, and mesophase assignments were confirmed by X‐ray diffraction. Polymers that had alkyl spacers with n = 2 and 4 were nematic, those that had spacers with n = 6 and 8 were nematic cybotactic, and those that had longer spacers (n = 10 and 12) were smectic C and showed some crystallization of the side alkyl chains. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3002–3012, 2004 相似文献
76.
Manufacturing skills for capillary GC columns have improved to a point where the commonly used tests no longer distinguish between "adequate" and "excellent" columns. A more stringent test mixture, coupled with a more exacting procedure, was proposed for testing capillary columns in 2004. The solutes were less sterically hindered and less retained, permitting the test to be run isothermally at lower temperatures where sorptive forces are stronger. To avoid masking active sites by solvent flooding, the test used a higher boiling solvent that eluted last. This test mixture, used under the prescribed conditions, differentiated adequate from excellent columns, but removal of the late-eluting solvent prolonged run times to as long as 1 h. The new test uses the same probes proposed in 2004, but entirely eliminates the solvent. Injections utilize a plunger-in-needle microvolume syringe, and the "gas saver" feature of a contemporary gas chromatograph. The latter serves as a dynamic diluter to deliver nanogram quantities of undiluted solutes to the column. The test can be conducted isothermally at a lower temperature in less than 15 min for most of the columns. This paper summarizes the analytical approach used, and presents method performance data and test results obtained on contemporary capillary columns from leading manufacturers. 相似文献
77.
C. Martín J. C. Ronda V. Cdiz 《Journal of polymer science. Part A, Polymer chemistry》2006,44(5):1701-1710
Boron‐containing novolac resins were synthesized by the modification of a commercial novolac resin with different contents of bis(benzo‐1,3,2‐dioxaborolanyl)oxide. These novolac resins were crosslinked with diglycidyl ether of bisphenol A (DGEBA), and their thermal, thermodynamomechanical, and flame‐retardant properties were evaluated. The boron‐containing novolac resins were less thermally stable than the unmodified novolac resin. Their modification degree and DGEBA content were related to the crosslinking density of the materials. The boron‐containing novolac resins generated boric acid at high temperatures and gave an intumescent char that slowed down the degradation and prevented it from being total. They also showed good flame‐retardant properties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1701–1710, 2006 相似文献
78.
R. Andreu M. A. Espinosa M. Gali V. Cdiz J. C. Ronda J. A. Reina 《Journal of polymer science. Part A, Polymer chemistry》2006,44(4):1529-1540
Benzoxazines derived from aniline and 4‐hydroxybenzoic acid and from phenol and 4‐aminobenzoic acid were prepared with two different synthetic approaches. When the carboxylic group reacted with epichlorohydrin, glycidylic derivatives M‐1 and M‐2 , respectively, were obtained. The ring opening of benzoxazine and epoxy took place simultaneously with no catalyst for both monomers. Likewise, both ring‐opening polymerizations took place when boron trifluoride monoethylamine (BF3·MEA) or 4‐(N,N‐dimethylamino)pyridine was used as a catalyst for M‐1 . However, for M‐2 , when BF3·MEA was used as a catalyst, the epoxy and benzoxazine ring openings could be distinguished, and a polyether intermediate containing benzoxazine side chains could be obtained. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1529–1540, 2006 相似文献
79.
Mariola Calle Gerard Lligadas Juan C. Ronda Marina Galià Virginia Cádiz 《Journal of polymer science. Part A, Polymer chemistry》2014,52(21):3017-3025
A novel and efficient strategy for the synthesis of nonisocyanate polyurethanes has been developed via thiol–ene self‐photopolymerization. An aliphatic thiol–ene carbamate monomer (allyl(2‐mercaptoethyl)carbamate, AMC) was synthesized by a one‐step synthesis procedure, from cysteamine and allyl chloroformate. The urethane group was therefore incorporated directly into the monomer precursor, avoiding the problems associated to toxic isocyanates. AMC was successfully stabilized with the radical inhibitor pyrogallol (1% wt). In addition, the use of phenyl phosphonic acid as coadditive allowed its stabilization for lower concentrations of pyrogallol (0.1% wt). AMC was directly transformed into thermoplastic polyurethane (TPU) through thiol–ene photopolymerization by UV‐irradiation at 365 nm. The obtained TPU presented semi‐crystalline nature and very high thermal stability (T5% ~325 °C). It was found that high concentrations of pyrogallol decreased the reaction rate and final conversion of photopolymerization. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3017–3025 相似文献
80.
Lucas Montero de Espinosa Juan C. Ronda Marina Galià Virginia Cádiz 《Journal of polymer science. Part A, Polymer chemistry》2010,48(4):869-878
The crosslinking reaction of a triglyceride derivative containing α,β‐unsaturated ketones with diaminodiphenylmethane via aza‐Michael addition has been extensively studied. First, a model study with monofunctional compounds showed that the conjugated addition product undergoes a series of transformations leading to formation of a substituted quinoline. The proposed reaction pathway is presented as a variation of the Skraup‐Doebner‐Von Miller quinoline synthesis. The presence of quinolines as crosslinking points in the cured materials has been proved by means of different characterization techniques, and the properties derived from this aromatization process have been described. This new crosslinking approach has been successfully applied to an aldehyde‐containing triglyceride to obtain quinoline‐containing thermosets. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 869–878, 2010 相似文献