Heat-resistant thermosetting polymers based on a novel tetrakisaminophenoxycyclotriphosphazene

Two heat-resistant thermosetting polymers ( IX and X ) have been developed based on a new cyclotriphosphazene containing tetrakisamine. These polymers were synthesized by the reaction of tetrakisamine ( IV ) with maleic anhydride followed by in situ cyclodehydration and polymerization of the maleimides ( VII and VIII ) at 235–240°C for 1.5 h and 290°C for 0.5 h. The thermogravimetric analyses (TGA) of the developed cyclotriphosphazene containing cyclomatrix polymers showed their thermal stability up to 350°C and char yield of 71% in nitrogen at 800°C and 65% in air at 700°C. The monomer, 2,2,4,4-tetrakis(4′-aminophenoxy) -6,6-diphenylcyclotriphosphazene ( IV ), useful for producing a variety of heat- and fire-resistant polymers, has been synthesized in good yield. Its syntheses involve Friedel-Crafts reaction of hexachlorocyclotriphosphazene ( I ) with benzene followed by the reaction of 2,2,4,4-tetrachloro-6,6-diphenylcyclotriphosphazene ( II ) with potassium 4-nitrophenoxide. The reduction of the obtained 2,2,4,4-tetrakis(4′-nitrophenoxy)-6,6-diphenylcyclotriphosphazene ( III ) with molecular hydrogen in presence of PtO₂ gave the tetrakisamine ( IV ). The structure of the synthesized monomer and intermediates were characterized by FT-IR, ¹H-NMR, ³¹P-NMR, mass spectroscopy, differential scanning calorimetry (DSC), and elemental analysis. These resins are potential candidates for the development of heat- and fire-resistant composites, laminates, and adhesives, useful for space, aerospace, and electronic application. © 1993 John Wiley & Sons, Inc.     

High-strength fire- and heat-resistant imide resins containing cyclotriphosphazene and hexafluoroisopropylidene groups

High-strength fire- and heat-resistant polymers were obtained by the thermally induced melt-polymerization of maleimido-phenoxy cyclotriphosphazenes linked by hexafluoroisopropyliden-ediphthalimide groups. These polymers show good thermal stability and high char yields: 78–80% at 800°C in nitrogen and 60–68% in air at 700°C. Graphite-fabric laminates did not burn in pure oxygen, even at 300°C (LOI = 100%), and were tested for shear, flexural, and tensile strengths. Two monomers were synthesized by reacting tris(4-aminophenoxy)-tris(phenoxy) cyclotriphosphazene with maleic anhydride and hexafluoroisopropylidenediphthalic anhydride. The triamine was synthesized by a stepwise reaction of hexachlorocyclotriphosphazene with phenol and 4-nitrophenol to give tris(4-nitrophenoxy)-tris(phenoxy)cyclotriphosphazene and reducing the nitro groups. The structures of cyclic phosphazene-trimeric precursors and the polymers were characterized by FT-IR, ¹H-NMR, ³¹P-NMR, and mass spectroscopy. The curing behaviors of polymer precursors were evaluated by differential scanning calorimetry and thermogravimetric analyses.     

Fire- and heat-resistant matrix resins based on ethynyl-substituted aromatic cyclotriphosphazenes

A novel class of fire- and heat-resistant matrix resins has been synthesized by thermal polymerization of ethynyl-substituted aromatic cyclotriphosphazenes. Thermal polymerization of new tris[4-(4′-ethynylbenzanilido)phenoxy]tris(phenoxy) cyclotriphosphazene ( III ) and tris[4-(4′-ethynylphthalimido)phenoxy]tris(phenoxy)cyclotriphosphazene ( VII ) at 250°C for 1–1.5 h gave tough polymers. The thermal stabilities of the polymers were evaluated in nitrogen and in air by thermogravimetric analysis (TGA). The synthesised polymers were stable to 400–410°C and showed char yield of 78–65% at 800°C in nitrogen and of 78–69% at 700°C in air. The ethynyl-substituted polymer precursor ( III ) was synthesised by the reaction of tris(4-aminophenoxy)tris(phenoxy)cyclotriphosphazene ( I ) with 4-ethynylbenzoyl chloride. The polymer precursor ( VII ) was synthesised by a solution condensation of I with 4-ethynylphthalic anhydride followed by in situ thermal cyclodehydration at 150°C. The structure of polymer precursors was characterized using proton nuclear magnetic resonance (¹H-NMR), infrared (IR) spectroscopy, and elemental analysis. The curing of polymer precursors was monitored by differential scanning calorimetery (DSC) and IR spectroscopy. The synthesised matrix resins are potential candidates for the development of heat- and fire-resistant fiber-reinforced composites. © 1993 John Wiley & Sons, Inc.     

Control of the conjugation length and solubility in electroluminescent polymers

A new type of cyclolinear polymer, poly(phenylene vinylene‐alt‐cyclotriphosphazene), was synthesized through Heck‐type coupling reactions to produce π‐conjugated macromolecules with excellent solubility and precise electronic control of the band‐gap energy. This synthesis method is capable of producing well‐defined alternating polymers. The method is highly adaptable and can be readily used for other chromophore systems. The resulting polymers were also capable of accommodating a wide variety of substituents on the cyclophosphazene rings with minimal effect on the electronic properties. The band gap and electron affinities of the polymer were varied through the manipulation of the π‐conjugated unit located between the insulating phosphazene rings. Each chromophore matched the intended conjugation length consistently throughout the macromolecules. The polymers were good film formers because of the chosen substituents on the phosphazene rings. The absorbance of the polymers indicated minimal spectral shift from the monomer absorbance. This suggested an effective insulation of each chromophore unit from its neighbors by the phosphazene rings. Solution photoluminescence efficiencies were found to be up to 44.1%. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 69–76, 2006     

Synthesis and characterization of aromatic cyclolinear phosphazene polyetherketones containing bis‐Spiro‐substituted cyclotriphosphazene unit

A novel monomer, 2,2‐bis‐(4′‐fluorobenzoylphenoxy)‐4,4,6,6‐bis[spiro‐(2′,2″‐dioxy‐1′, 1′‐biphenylyl)] cyclotriphosphazene, was synthesized and polymerized with 4,4′‐difluorobenzophenone as a comonomer and 4,4′‐isopropylidenediphenol or 4,4′‐(hexafluoroisopropylidene) diphenol in N,N‐dimethylacetamide at 162 °C for 4 h to give two series of aromatic cyclolinear phosphazene polyetherketones containing bis‐spiro‐substituted cyclotriphosphazene groups. The structure of the monomer was confirmed by ¹H, ¹³C, and ³¹P NMR. The effect of the incorporation of the bis‐spiro‐substituted cyclotriphosphazene group on the thermal properties of these polymers was investigated by DSC and thermogravimetric analysis. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 2993–2997, 2001     

Organophosphazenes 27: the Synthesis and Polymerization of (4- Ethenylphenyl)Pentafluorocyclotriphosphazene

Abstract

The synthesis and homopolymerization of a fluorocyclotriphosphosphazene with a directly bonded styrene moiety is presented. A multistep sequence was employed wherein commercially available p-bromostyrene is first converted to 1-(4-bromophenyl)-1-methoxyethene, 4-BrC₆H₄C(OCH₃)CH₂ which in turn is lithiated and added to N₃P₃F₆ to give (4-(1-methoxyethenyl)phenyl)pentafluorocyclotri phosphazene, N₃P₃F₅(4-C₆H₄C(OCH₃)?CH₂)(2). Addition of tri(n-butyl)tin hydride to 2 followed by elimination of tri(n-butyl)tin methoxide over silica produced the target monomer, (4-ethenylphenyl)- pentafluorocyclotriphosphazene, and N₃P₃F₅(4-C₆H₄CH?CH₂)(3). The new phosphazene derivatives were characterized by mass spectrometry, NMR (¹H,¹³C,¹⁹F,³¹P) and IR spectroscopy. Radical addition polymerization of 3 resulted in the formation of poly(p-pentafluorocyclotriphosphazenylstyrene)(4). Molecular weights of the new polymer were determined by GPC and membrane osmometry. The GPC data suggested the occurrence of chain transfer in the polymerization. TGA studies showed that 4 exhibits high thermal stability compared to other organophosphazene polymers. The T_g value is significantly greater than that of polystyrene.     

Polybismaleimide containing tetrakisphenoxycyclotriphosphazenes

A heat-resistant polybismaleimide was obtained by the thermal polymerization of bis(maleimidophenoxy)- tetrakis(phenoxy)cyclotriphosphazene. The thermal stabilities of the polybismaleimide were evaluated in nitrogen and in air by thermogravimetric analysis. The polybismaleimide was stable to 340°C and has char yield of 70% at 800°C in nitrogen and of 60% at 700°C in air. The monomer bismaleimide was obtained by the reaction of bis(4-aminophenoxy)tetrakis(phenoxy)cyclotriphosphazene with maleic anhydride. The diamine was synthesized by a stepwise reaction of hexachlorocyclotriphosphazene with phenol and 4-nitrophenol to give bis(4-nitrophenoxy)tetrakis(phenoxy)cyclotriphosphazene and reducing the nitro groups. The structure of the cyclotriphosphazenes were characterized using Fourier transform infrared (IR), proton nuclear magnetic resonance (¹H-NMR) spectroscopy, and elemental analysis.     

Sensitivity Enhancement of Polyorganophosphazenes to Radiation with 2,2,4,4,6,6-Hexakis(2-Hydroxyethyl Methacrylate)Cyclotriphosphazene Monomer and its Application for Negative Resists

Abstract

This work focuses on the application of a multifunctional phosphazene monomer, 2,2,4,4,6,6-hexakis(2-hydroxyethyl methacrylate)-cyclotriphosphazene (6-Hema) for enhancement of the sensitivity of polyphosphazenes to both ⁶⁰Co and E-beam radiation. Specifically, elastomeric and glassy phosphazene polymer films treated with 6-Hema were irradiated under vacuum, and the gel content was determined. The Charlesby-Pinner approach was used to compare the radiation sensitivities of these films. This served as the basis for eventually preparing SiO₂ wafers with thin films of the glassy polyphosphazenes mixed with or overcoated by the 6-Hema monomer. The SiO₂ wafers prepared with the most sensitive polymer/monomer system were patterned with an ERC electron beam accelerator/scanning electron microscope computer-driven instrument. It was determined that these negative resist films were 1-2 orders of magnitude more sensitive to radiation than the polymers without the monomer.     

Synthesis and thermal properties of crosslinkable phosphazene copolymers

Polyphosphazenes of formula [NP(OC₆H₄CN)_x(OCH₂CF₃)_2?x] (x = 0.04–2) were prepared. The copolymers were crosslinked via cyclotrimerization of the nitrilic function, using acid catalysts (chlorosulfonic acid, aluminum chloride) at elevated temperatures. The thermal properties of the crosslinked cyclomatrix polymer were compared to the linear polymer by thermogravimetric analysis and differential scanning calorimetry. When the 4-cyanophenoxy-2,2,2-trifluoroethoxy ratios were less than 0.2, the crosslinked polymers were soluble in polar organic solvents.     

Synthesis and molecular structure of platinum(II) complexes with cyclotriphosphazenes containing pyridylalkylamino and pyridylmethoxy groups

The interaction of platinum(II) nitrile complexes with polydentate ligands, pentaphenoxy(2-pyridylmethylamino)cyclotriphosphazene (L¹), pentaphenoxy(3-pyridylmethylamino)cyclotriphosphazene (L²), pentaphenoxy[2-(2-pyridyl)ethylamino]cyclotriphosphazene (L³), and pentaphenoxy(2-pyridylmethoxy)-cyclotriphosphazene (L⁴), was studied. The synthesized complexes were characterized by single-crystal X-ray diffraction, ¹H and ³¹P NMR spectroscopy, IR spectroscopy, FAB mass spectrometry, and other methods. In complexation of phosphazenes L¹-L³ with Pt(II) ions, nitrogen atoms of the pyridine ring and alkylamine fragment participate in the coordination to form chelate rings. In the complex with L⁴, the substituted phosphazene is coordinated via nitrogen atoms of the pyridyl group and cyclotriphosphazene ring to form a sevenmembered ring.     

Synthesis,Characterization, and Spectroscopic Properties of Hexa(4-Bromo-2-Formyl-Phenoxy)Cyclotriphosphazene and Hexa(4-Chloro-2-Formyl-Phenoxy)Cyclotriphosphazene and Fully Substituted Cyclotriphosphazene Derivatives Bearing a Schiff Base at Room Temperature

Abstract

Hexa(4-bromo-2-formyl-phenoxy)cyclotriphosphazene (2) and hexa(4-chloro-2- formyl-phenoxy)cyclotriphosphazene (3) were obtained from the reactions of hexachloro- cyclotriphosphazene (1) with 5-bromosalicylaldehyde and 5-chlorosalicylaldehyde in the presence of (C₂H₅)₃N and K₂CO₃ at room temperature, respectively. The new two organocyclotriphosphazenes bearing formyl groups were reacted with 4-cyano aniline, 2-phenyl aniline, 4-aceto aniline, 5-chloro-2-hydroxy aniline, 2-hydroxy aniline, 4-hydroxy aniline, 2-(4-morpholino)ethyl amine, 4-carboxy aniline, 4-carbomoyl aniline, 2-mercapto aniline, and 5-amino isoquonoline to prepare cyclotriphosphazene derivatives containing a Schiff base at room temperature. However, fully phenoxy-substituted cyclotriphosphazenes containing a Schiff base were isolated from the reactions of the compound 2 and 3 with 5-chloro-2-hydroxy aniline, 2-hydroxy aniline, 4-hydroxy aniline, and 2-(4-morpholino)ethyl amine. The structures of the synthesized compounds were characterized by elemental analysis, IR, and NMR (¹H, ¹³C, ³¹P) spectroscopy. According to the results of the analysis, all synthesized compounds were found to be fully substituted organocyclotriphosphazenes, such as hexa[4-bromo-2-(5-chloro-2-hydroxy-pheyliminomethyl)phenoxy]cyclotriphosphaze (2a). All cyclotriphosphazene derivatives synthesized gave fluorescence emission peaks in range between 300 nm and 410 nm.     

Preparation and characterization of a water resistance flame retardant and its enhancement on charring–forming for polycarbonate

Hexakis(4-nitrophenoxy) cyclotriphosphazene (HNTP) was synthesized and was added into polycarbonate (PC) functioned as intumescent flame retardant and charring agent. The chemical structure of HNTP was confirmed by hydrogen and phosphorus nuclear magnetic resonance (¹H-NMR, ³¹P-NMR), energy-dispersive spectroscopy and Fourier transform infrared (FTIR). Flame retardancy and charring–forming behaviors of HNTP- and PC-based composites were extensively investigated with the limiting oxygen index, UL-94 vertical burning test, microscale combustion calorimeter (MCC) and thermogravimetric analysis. The water resistance of PC-based composites was studied by stationary water contact angle measurements. Furthermore, TG/FTIR was used to research their gaseous products and their releasing intensity during the decomposition. The morphology and chemical structure of residual char were used to study scanning electron microscopy (SEM) analyses and FTIR spectroscopy. The mechanical properties of samples were compared by tensile and impact tests.     

Synthesis, characterization, and thermal stability of star-shaped poly(ε-caprolactone) with phosphazene core

Hexakis[p-(hydroxylmethyl)phenoxy]cyclotriphosphazene was synthesized by the reaction of hexachlorocyclotriphosphazene with the sodium salt of 4-hydroxybenzaldehyde and subsequent reduction of aldehyde groups to alcohol groups by using sodium borohydride. This compound was employed in initiating the ring-opening polymerization of ε-caprolactone. The resulting polymers were characterized using Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC). The characterization data indicated the star-shaped PCL with phosphazene core were successfully synthesized with narrow molecular weight distribution and high yields. ¹H-NMR analysis was used to calculate the number-average molecular weight. The calculated result from NMR was closer to the theoretical data than that from GPC analysis. Polarizing optical microscopy (POM) combined with differential scanning calorimetry (DSC) was used to study the crystallization behavior of the star-shaped PCL. The result indicated that the highly branched architecture of star-shaped PCL resulted in interrupted crystallization form and subsequently lower melting temperature. Thermogravimetric analysis (TGA) carried out on the star-shaped PCL suggested that introduction of phosphazene rings strengthen the thermal stability of the resulting polymers.     

QTAIM study of transition metal complexes with cyclophosphazene-based multisite ligands II. Cobalt(II) complexes

[(CoLCl)CoCl₃], [(CoMeLCl)CoCl₃], [(CoLBr)CoBr₃], [CoLBr]⁺ and [CoMeLBr₂] complexes, L = hexakis(2-pyridyloxy)cyclotriphosphazene, MeL = hexakis(4-methyl-2-pyridyloxy)cyclotriphosphazene, in the most stable high spin states are investigated at DFT level of theory using hybrid B3LYP functional. The exchange coupling parameter evaluated using a broken symmetry treatment increases with the ligands mass. Electron density is evaluated in terms of QTAIM (Quantum Theory of Atoms-in-Molecule) topological analysis of electron density. The bonds of central Co atoms with phosphazene nitrogens are shorter, stronger and more polar than with the aromatic pyridine nitrogens and their higher ellipticities may be explained by the π contribution from the phosphazene ring. The atomic charges of phosphazene nitrogens are ca. twice more negative than at the pyridine ones.     

Studies of phosphazenes. XIX. New polyorganophosphazenes derived from the friedel–crafts reactions of hexa(aryloxy)cyclotriphosphazenes with polyhaloalkanes

The reactions of hexa(aryloxy)cyclotriphosphazenes N₃P₃(OR)₆[R = C₆H₅, C₆H₄CH₃-p] with polyhaloalkanes in the presence of anhydrous aluminium chloride yield new crosslinked phosphazene polymers which are characterized by elemental analysis, IR spectroscopy, and pyrolysis—mass spectrometric measurements. Soluble “prepolymers” are obtained by using stoichiometric quantities of the phosphazene and haloalkane in nitromethane as the solvent. The ¹H and ³¹P NMR data for these “prepolymers” are presented. The thermal stability of the polymers derived from various haloalkanes decreases in the order 1,2-ClCH₂CH₂Cl < CHCl₃ > CH₂Cl₂ > CCl₄. The thermal stability also increases with increasing amounts of the catalyst, reaching a maximum at 1:10 mol ratio of N₃P₃(OPh)₆:AlCl₃. The phosphazene polymers reported here possess much greater thermal stability compared to linear polyorganophosphazenes, [NPR₂]n, as well as the polymers prepared by the Friedel–Crafts reactions of P(O)(OPh)₃ and P(O)(OC₆H₄CH₃-p)₃ with haloalkanes.     

Synthesis and Characterization of Novel Poly(Arylene Ether)s from 1,3‐bis(4‐Hydroxyphenyl) Benzene

Abstract

Several poly(aryl ether)s have been prepared by the condensation of 1,3‐bis(4‐hydroxy phenyl) benzene with different trifluoromethyl activated bis‐fluoro compounds. IR, ¹H and ¹³C NMR, and elemental analyses have established the resulting polymer structures. The properties of the polymers have been evaluated by DSC, TGA, dynamic mechanical analysis (DMA) and stress–strain analysis. The polymers 1a and 1c showed semi‐crystalline behavior as evident by sharp crystalline melting peaks at 299°C and 330°C along with glass transitions at 202°C and 216°C, respectively. The polymers showed very good thermal stability in air, high modulus, and high tensile strength with low elongation at break.     

New Acid-Polyfunctional Water-Soluble Phosphazenes: Synthesis and Spectroscopic Characterization

Poly [bis(phenoxy)] phosphazene sulfonic acid and its mixed substitution derivatives containing N-methylsulfonamide, sulfonylaminoacetic, and free sulfonic acid functions have been obtained and characterized by IR and ¹H-, ³¹P-, ¹³C-NMR spectroscopy. The polymers are all water soluble. Poly [bis(4-benzoylphenoxy)] phosphazene sulfonic acid could not be obtained due to chain degradation during the synthesis.     

Novel hexacentered phosphazene compound as selective Fe3+ ions sensor with high quantum yield: Synthesis and application

A novel compound hexa-rhodamine substituted phosphazene (HRP) with six active centers on a cyclotriphosphazene ring was synthesized using the alkyne-azide “click” reaction. The structure of HRP was characterized using spectroscopic techniques. The optical sensor properties of HRP for metal ions were investigated using UV-Vis and Fluorescence spectroscopy. It was determined that HRP is a selective sensor with colorimetric and fluorescent properties for Fe³⁺ ions. Limit of detection (LOD) of HRP was determined as 6.94?×?10^?9 M using fluorescence intensities in the presence of different concentrations of Fe³⁺ ions. It was determined that HRP-Fe³⁺ complex has high quantum yield and excellent photostability.     

SYNTHESIS AND CHARACTERIZATION OF A NOVEL ALCOHOL-SOLUBLE POLYORGANOSILOXANE CONTAINING AMINO SIDE GROUPS*

 A novel alcohol-soluble polyorganosiloxane containing amino side groups, poly[3-(4-aminophenoxy)propylmethylsiloxane] (2), was first prepared by the reduction of nitro groups on 4-nitrophenoxypropyl side chains of poly[3-(4-nitrophenoxy)propylmethylsiloxane] (1). The reaction proceeded easily with nearly 100% conversion. The synthesized alcohol-soluble polymer 2, which has potential application as a precursor for preparing advanced functional polymers, was characterized by FTIR ¹H-NMR, ¹³C-NMR, ²⁹Si-NMR, VPO and GPC, respectively.