一种改性氰酸酯预聚体的合成和性能研究

将聚砜树脂(PSF)和双酚A型氰酸酯树脂(BCE)在一定条件下进行预聚反应,通过红外光谱(FT-IR)、差热扫描(DSC)、扫描电镜(SEM)对所得到的预聚体树脂及其固化后产物进行分析和表征。结果表明改性后的氰酸酯预聚体具有优异的力学性能和良好的介电性能。     

Synthesis,characterization, and properties of multifunctional naphthalene-containing epoxy resins cured with cyanate ester

Multifunctional naphthalene-containing epoxy resins derived from 2,7-dihydroxylnaphthalene were synthesized and the intermediates were characterized by Fourier transform infrared spectroscopy, elemental analysis, and mass spectrometry. The cured products from naphthalene-containing epoxy resin and the dicyanate ester of bisphenol A (DCBA) exhibited a better T_g and a lower coefficient of thermal expansion than those of the commercial epoxy system. The glass transition temperature, thermal stability, and moisture absorption were found to increase with the epoxy functionality when naphthalene-containing epoxy resins were cured with DCBA. Thermogravimetric analyses revealed that the DCBA-cured system had a better thermal stability than that of the 4,4′-diaminodiphenylsulfone (DDS)-cured system. The addition of a metallic catalyst into the epoxy resin/cyanate ester system not only facilitated the cyclotrimerization of the cyanate ester but also the polyetherification of the epoxy resin. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1611–1622, 1999     

Synthesis and characterization of novel low‐dielectric cyanate esters. II

A novel cyanate ester, 2,6‐dimethyl phenol dipentene cyanate ester (DPCY), was successfully synthesized from cyanogen bromide with 2,6‐dimethyl phenol dipentene novolac, which was synthesized from dipentene and 2,6‐dimethyl phenol. For the purpose of increasing the mobility of residual DPCY during the final stage of curing and achieving a complete reaction of cyanate groups, a small quantity of a monofunctional cyanate ester, 4‐tert‐butyl phenol cyanate ester, was added to DPCY to form a cyanate ester copolymer. The thermal properties of the cured cyanate ester resins were studied by dynamic mechanical analysis, dielectric analysis, and thermogravimetric analysis. These data were compared with those of the commercial bisphenol A cyanate ester system. The cured modified cyanate ester exhibited a dielectric constant of 2.59–2.50, a dissipation factor of 0.0055–0.0089, and moisture absorption of 0.91–1.17%; these values were all lower than those of the as‐cured bisphenol A dicyanate system. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 369–379, 2005     

Synthesis, characterization, and surface properties of sulfoxylated methyl esters

Sulfoxidation of fatty methyl esters with SO₂, O₂, and ultraviolet light of appropriate wavelength has led to a synthesis of sodium methyl ester sulfonates known as Φ-MES. The designation of Φ refers to the random positioning of SO₃ in the alkyl chain. This investigation describes for the first time the operating conditions necessary to produce these new anionic surfactants as well as the analytical methods used in their isolation, analysis, identification. Some surface properties are discussed as well.     

酚酞型氰酸酯的合成与表征

采用卤化氰-酚合成法制备了酚酞型CE(氰酸酯),并采用红外光谱(FT-IR)法、质谱法、核磁共振氢谱(1H-NMR)法、毛细管法和差示扫描量热(DSC)法等对酚酞型CE的结构和性能进行了表征和分析,同时对其热性能和热解动力学行为进行了研究。结果表明:酚酞型CE的合成条件为"-15℃搅拌反应1 h→升温至5℃搅拌反应4 h→5℃保温反应2 h";目标产物失重5%温度为435℃,最大失重速率温度为453℃,表观活化能为222.49 kJ/mol,指前因子为1013.97s-1;将酚酞型CE加入到胶粘剂的基础配方中,相应胶粘剂的综合性能略高于基础配方胶粘剂。     

A study of the thermal and dynamic mechanical properties of functionalized aryl cyanate esters and their polymers

Differential scanning calorimetry (DSC) was employed to examine the thermally initiated and catalysed polymerizations of a number of cyanate ester monomers. Rigorous purification by preparative HPLC was found to have marked effects on the thermal polymerization characteristics of these compounds as determined by DSC. The effects on the thermal behaviour of varying the heating rate and level of catalysis were also examined. The thermal polymerization of the cyanate ester monomers was found to obey a first order model over wide apparent conversion limits. Functionalized cyanate ester/bis-maleimide copolymers were prepared and the thermal stabilities of these were evaluated by thermogravimetric analysis (TGA) alongside a variety of commercial blends and homopolymers. The dynamic mechanical properties of the cured neat resins were also investigated.     

Synthesis of novel phosphorus-containing cyanate esters and their curing reaction with epoxy resin

Novel phosphorus-containing cyanate esters with phosphorus contents between 1-4% (badcyp_x, x=1-4) were synthesized from the addition reaction of 9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide (dopo) and bisphenol A dicyanate (badcy). The structures of synthesized cyanate ester resins were confirmed by NMR and IR spectra. The modified cyanate esters were either self-curing (badcy and badcyp_x series) or curing with epoxy (badcye and badcyp_xe series). Thermal properties of cured cyanate ester were evaluated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), thermal gravimetric analysis (TGA), dielectric analyzer (DEA) and UL-94 vertical test. It was found that T_g and T_d (5%) decrease markedly with the phosphorus content for the self-curing system, while T_g and T_d (5%) decrease slightly with the increase of cyanate equivalent weight for the cyanate-epoxy curing system. The flame retardancy increases with the phosphorus content and a UL-94 V-0 rating can be achieved for cured badcyp₂-badcyp₄ and badcyp₃e-badcyp₄e. These flame retardant thermosets exhibit low moisture absorption as well as low dielectric constants and dissipation factors. Experimental results indicate that introducing the flame retardant phosphorus element into cyanate ester will not sacrifice its low dielectric characteristic.     

Styrene-maleic anhydride copolymers: Synthesis,characterization, and thermal properties

Radical copolymerization of styrene and maleic anhydride have been carried out in N, N-dimethylformamide at 60°C using 2,2′-azobisisobutyronitrile as initiator. The copolymer compositions were determined using an aqueous conductometric direct titration method. Monomer reactivity ratios were calculated by Fineman-Ross, Kelen-Tudos, and conversion-based Kelen-Tudos methods. Gel permeation chromatography was used to determine molecular weights and polydispersity indexes. The thermal degradation and energy of activation of the degradation process were determined by several thermogravimetric analysis and differential scanning calorimetric models. The thermal degradation of the copolymer is a two-stage process, the major degradation being the second stage. The copolymer degrades at a lower temperature than polystyrene. © 1996 John Wiley & Sons, Inc.     

Synthesis,characterization, thermal and flame-retardant properties of silicon-based epoxy resins

A new silicon-containing oxirane triglycidyl phenyl silane oxide (TGPSO) and its corresponding silicon-containing epoxy resins are synthesized and characterized. The activation energies of TGPSO curing reaction with various curing agents, including 4,4-diaminodiphenylmethane, 4,4-diaminodiphenylsulfone, and dicyanodiaminde, are found to be 180, 196.5, and 154 kJ/mol. The curing reaction of TGPSO with diamines is determined to be a first-order reaction through means of Arrhenius plots. The introduction of the silicon-containing group results in higher curing reactivity. This silicon-containing resin possesses higher char yield as well as higher limiting oxygen index (LOI = 35) than the commercial epoxy resins, confirming the usefulness of these silicon-containing epoxy resins as flame retardants. Char yields and LOI measurements demonstrate that incorporating silicon into epoxy resins is able to improve their flame retardancy. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 1231–1238, 1999     

Synthesis,characterization and assessment thermal properties of clay based nanopigments

Nano-clay based pigments (NCP) are new type of pigments composed of organic dyes and layered silicate-clay nano-particles, and have already been used in polymeric coatings to improve mechanical thermal and stability properties. In this paper, the basic blue 41(BB41) was intercalated into Na⁺- montmorillonite in an aqueous medium. The dye-intercalated montmorillonite was centrifuged, dried, and milled to prepare the nanopigment particles. X-ray diffraction showed an increase in the basal spacing, thus confirming intercalation of the BB41 molecules within the nanostructures of the interlayer spaces. Fourier transform infrared spectroscopy was used for identifying the functional groups and chemical bounding of Na⁺-montmorillonite, BB41 and montmorillonite-BB41. The morphology of NCP was also studied by transmission electron microscopy. Finally, thermo-gravimetric analysis and differential thermograms suggested the thermal stability of the intercalated dye was improved.     

双氰乙基偶氮化合物的合成及表征

用无水AlCl3催化问甲苯胺与丙烯腈的加成反应,合成了偶合组分N,N-二氰乙基间甲苯胺,并分别与重氮组分对硝基苯胺、对硝基邻氯苯胺、2,4-二硝基-6-氯苯胺和2,4-二硝基-6-溴苯胺进行偶合反应,合成了4种双氰乙基偶氮化合物.结果表明,生成的偶氮化合物产率分别为72%、78%、91%和81%,含量均超过96%;而且...     

Aminotetryls: Synthesis,spectral characterization,thermal decomposition and explosive properties

This paper describes the synthesis and spectral investigations of two amino derivatives of N-methyl-N-(2,4,6-trinitrophenyl)nitramine (tetryl). Also discussed are the results from thermal decomposition studies on the three explosives, viz. tetryl, 3-aminotetryl (3 AT) and 3,5-diaminotetryl (3,5 DAT) and preliminary work on the explosive properties of the last two compounds. The aminotetryls have been prepared by the amination of the corresponding chlorotetryls. The yield was 87% for 3 AT, but was only 33% for 3,5 DAT, probably due to steric crowding around the benzene nucleus. The mass spectra show interesting differences in the electron impact fragmentation patterns of the three tetryls with the M⁺ ion relative intensities following the order 3,5 DAT > 3 AT > tetryl, which could be due to (a) resonance stabilization and (b) hydrogen bonding effects. Evidence for the latter is also found in the infrared spectra of these compounds. Arrhenius kinetic parameters derived from thermal decomposition studies of the three compounds are presented and show that 3,5 DAT is thermally less stable than 3 AT. Explosive sensitiveness tests indicate that the diamino compound is the most sensitive, the trend being 3,5 DAT > 3 AT > tetryl. This is contrary to the generally found desensitizing influence of NH₂ groups on the thermal stability and explosive sensitiveness of trinitroaromatic energetic molecules. Mechanisms to account for the observed thermal decomposition behaviour and explosive sensitiveness patterns are discussed.     

Synthesis, characterization, and thermal properties of poly(siloxane-carborane)s

Three exactly alternating carborane-siloxane polymers P1, P2, and P3, have been synthesized by the polycondensation of 1,7-bis(dimethylhydroxylsilyl)-m-carborane and cyclotrisilazanes in the presence of (NH₄)₂SO₄. The reaction shows a new and convenient synthesis of poly(carborane-siloxane)s, and the first example of stoichiometric polycondensation of cyclosilazanes with diols. The new polymers P2 and P3 could be converted into thermosets at elevated temperature through the cross-linking of pendant vinyl groups. The structures of the polymers were fully characterized. Thermogravimetric analysis (TGA) showed the superior thermal stability of the polymers and thermosets, with their char yields of over 83% both in air (800 °C) and nitrogen (1000 °C). The microstructure of the chars was studied by scanning electron microscopy (SEM). It was found that the cross-linking of vinyl groups helped in enhancing the thermal stabilities of the polymers and keeping the integrity of the chars. The results suggest their potential utility under severe thermal and/or thermo-oxidative conditions.     

Synthesis,characterization, and thermal properties of alkyl‐functional naphthoxazines

A series of alkyl‐functional naphthoxazine resins having various alkyl chain lengths from C1 to C18 are synthesized with a high yield and high purity by the reactions of 1,5‐dihydroxynaphthalene, formaldehyde, and aliphatic amines. The proposed chemical structures of the naphthoxazines are confirmed by high‐resolution mass spectrometry, ¹H nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy, and pyrolysis mass spectrometry studies. The alkyl‐functional naphthoxazines have shown low polymerization temperature characteristics where polymerization of these monomers is achieved in the range of 150–170°C yielding cross‐linked polynaphthoxazines. The low‐temperature polymerization characteristics and the associated thermal degradation behaviors are studied. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

The synthesis, characterization, thermal and optical properties of copper, nickel, and vanadyl complexes derived from azo dyes

Two, novel, tetradentate Schiff-base ligands, namely bis-5-phenylazosalicylaldehyde diethylenetriimine and bis-5-[(4-methoxyphenyl)azo]salicylaldehyde diethylenetriimine, as well as their Cu²⁺, Ni²⁺, and VO²⁺ complexes, were synthesized and characterized using elemental analysis, infrared and also UV–Visible spectroscopy, ¹HNMR and mass spectra. The thermal stability of the free ligands and the related metal complexes, as determined using differential scanning calorimetry and thermal gravimetric analysis, were found to be thermally stable upto 240–275 °C depending on the type of ligand and the central metal atom. The λ_max of the ligands and their transition metal complexes in the region 300–800 nm are discussed. The novel metal complexes offer potential for application as recording media owing to both their absorption spectra in the blue-violet light region and high thermal stability.     

Curing behavior and thermal mechanical properties of cyanate ester blends

Cyanate esters are a class of important thermally resistant polymers. To tailor their processability and thermomechanical properties, a series of cyanate ester blends based on a trifunctional novolac cyanate ester (HF‐5), a difunctional bisphenol E cyanate ester (HF‐9), and a reactive catalyst [2,2′‐diallyl bisphenol A (DBA)] were formulated. The effect of the blend composition on the rheology and curing behavior of these cyanate ester blends and the corresponding thermal and mechanical properties of the cured cyanate ester blends was studied. The results showed that HF‐5 contributed to good mechanical property retention at high temperatures because of its trifunctionality, whereas HF‐9 imparted processability by reducing the viscosity and extending the pot life of the formulated cyanate ester blends at the processing temperature. On the basis of the results, an optimal cyanate ester blend suitable for resin transfer molding was determined: the HF‐5/HF‐9/DBA weight ratio of 80 : 15 : 5 exhibited good processability and thermomechanical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4284–4290, 2006     

Synthesis and characterization of photopolymers with azo units. Interfacial polyaddition,photolysis, photodegradation

The synthesis of an aryl alkyl azo diisocyanate and a model azo urea is described. From the azo diisocyanate new azo polyureas were created by interfacial polyaddition. Molecular weights M_n in the range of 6000 to 9000 were determined by gel permeation chromatography (GPC). Photolysis and thermolysis of both, model compounds and polymers, were studied by UV-spectroscopy and differential scanning calorimetry (DSC), respectively, and the results were compared with those of similar azo amides. Photochemical polymer degradation was followed by GPC.     

DGEBA‐grafted polyaniline: Synthesis,characterization and thermal properties

The utilization of conducting emeraldine salt (PANI‐ES) and intrinsic leucoemeraldine polyaniline (PANI‐LEB) in the synthesis of DGEBA‐grafted PANI via anionic copolymerization is described. The structures of copolymers obtained were characterized by FTIR, ¹³C and ¹H NMR. The extent of grafting was verified by THF Soxhlet (solvent extraction). The thermal properties of these new copolymers were described and their conductivities were reported. Results obtained indicated that the graft copolymer exhibited higher electrical and thermal conductivities than that of the blend counterpart. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of inherently coloured azo polyamides

Six intrinsically coloured azo polyamides have been prepared by interfacial polycondensation and characterized by visible, ultra-violet and infra-red spectroscopy, viscometry and differential thermal analysis.     

Main-chain azo polyaramides with high thermal stability and liquid crystal properties

Two novel main-chain aromatic polyamides containing azobenzene were synthesized by polycondensation of trans-azobenzene-4,4′-dicarbonyl chloride with various aromatic diamines under low temperature. Their molecular structures were identified to be symmetric and regular by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy and elemental analysis. Polymers exhibited not only high thermal stability, but also lyotropic liquid crystal (LC) phases in N,N-dimethylacetamide solution which is due to hydrogen bonding and an ordered rigid structure. The crystal behaviours of the polymers were studied with X-ray diffraction analysis, and the photochromism was investigated with an ultraviolet–visible spectrophotometer with 365 nm ultraviolet irradiation. An abnormal change of the crystal behavior and thermal stability of polymer was found to be related with molecular structure containing ether linkage. The azo polyaramides can be applied in fields of optical techniques and potential photochromics fibres spinning in wide temperature ranges