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This paper is designated to the development of flame retardant solid polymer electrolytes based on phosphorus containing polymers. The new green technique synthesis, respectively polycondensation under microwave irradiation of hexylphosphonic dichloride (HPD) with 4,4′-(1,3-phenylenediisopropylidene) bisphenol (bisphenol M) was described. 86% yield and 0.95 dl g −1 inherent viscosity were obtained. The polyphosphonate was characterized by FT-IR, 1 H and 31 P NMR spectroscopy, gel permeation chromatography, and thermal analysis. The polymer presents thermal stability, begins to lose weight above 280 °C. The influence of the reaction temperature and reaction time on yield and inherent viscosity for MW polycondensation was studied and the results were compared with the results of polycondensation reaction under conventional heating in similar conditions. Best results were obtained under microwave irradiation. Solid polymer electrolytes were obtained from the polyphosphonate complexed with different lithium salts using casting technique and the electrochemical properties were determined. The low activation energy of conduction determined for solid polymer electrolyte membrane with bis(oxalato)borate anions overcomes the activation energy request for relaxation process and this membrane presents the best conductivity. Also, the flammability of polyphosphonate and membranes was investigated by measuring limiting oxygen index values.

Vinylphosphonic acid is homopolymerized with dimethylvinylphosphonate by radical polymerization using using UV light and photoinitiator Darocur 4265 (3 wt%). The molar ratio between vinylphosphonic acid and dimethylvinylphosphonate is varied between 1:1 and 4:1, respectively. The obtained homopolymer of vinylphosphonic acid and copolymers are characterized by Fourier transform infrared spectroscopy (FTIR), thermal analysis and size exclusion chromatography - multi angle laser light scattering. The polymerization by UV light is efficient and an average molar mass of 34,200 g/mol is obtained for poly(vinylphosphonic acid) and in the range from 12,700 to 19,120 g/mol for copolymers, which also have a good thermal stability until 320 °C. The polymers structure allows the formation of random coil conformation. The copolymers are tested as inhibitors against corrosion of iron in NaCl aqueous solution, and, as a result, it was shown that these copolymers exhibit promising anticorrosion properties.

Polyphosphoesters gained importance especially due to their use as flame retardants and as biocompatible and biodegradable materials for medicine and in the pharmaceutical industry. This paper presents the results obtained by our research group in the synthesis of polyphosphoesters by interfacial polycondensation. This reaction is rapid and irreversible polymerization at the interface between a phase containing one difunctional intermediate and another phase containing a complementary difunctional reactant. Different methods like liquid–liquid, vapor–liquid or solid

Improved ionic conductivity of solid polymer electrolytes (SPE) was achieved by adding polyaniline (PANI) in membrane formulation. SPE composite membranes contain: tris(4-hidroxybutylacrylate)-phosphate, polyphosphoester, lithium salts and small amount of PANI. The conductivity of membranes increases with PANI content and above a certain amount it decreases. The variation of the conductivity vs temperature is linear, characteristic for a thermally activated process. The activation energy for polymer matrix without PANI is 0.30 eV and 0.26 eV for polymer matrix with PANI. Conductivity enhancement in the composite polymer matrix is caused by the presence of PANI due to the increase in the concentration of free ions. PANI decreases the salt aggregation and as a consequence, the concentration of free ions was increased by improving dispersion of the lithium salt in membranes.

Two new series of solid polymer electrolytes (SPEs) based on phosphorus containing (co)polyesters (PPE) and Lithium triflate were obtained. PPEs are composed of phosphonate moeties (cyclohexyldichlorophosphonate (CHDP)) as linking agent and two diols: PEG (6000) and poly(tetramethylene glycol) (PTMG) in PPE I, and PEG (6000) and 4,4′-cyclohexylidenebisphenol (bisphenol Z, BZ) in PPE II. Polycondensation was carried out in solution in the presence of triethylamine (TEA) as scavenger of HCl side product (PPE I–IIa) and in the absence of any acid acceptor (PPE I–IIb). The Limiting Oxygen Index (LOI) and thermal analysis were performed both on polymers and membranes. The ionic conductivity of SPE membranes based on PPE-salt complexes, with various salt concentrations, was investigated at different temperature and ionic transference numbers were determined. Optimum composition was obtained for the polymer which contains in structure only alkyl units and 15% Lithium triflate.

New structures of polymers containing phosphorus in the main chain were prepared by interfacial polycondensation of phenylphosphonic dichloride with 4,4’-(1,3-phenylenediisopropylidene) bisphenol (bisphenol M) using two different methods: method I: gas–liquid interfacial polycondensation without an organic solvent and a catalyst; and method II: solid–liquid interfacial polycondensation using green solvents and without catalyst. The aim of this work was to apply these methodologies as eco-friendly and economical procedures for a green chemistry. The polymers were characterized by gel permeation chromatography (GPC), FT-IR, 1 H and 31 P-NMR spectroscopy, differential scanning calorimetry (DSC) and thermal analysis. Yields in the range of 88.0–90.0, and inherent viscosities in the range of 2.2–3.2 dl/g were obtained. High molecular weight polymers (57 600–114 400) have been successfully prepared. The polymers are self-extinguishing and begin to lose weight at around 300 °C. The flammability was investigated by measuring limiting oxygen index values (LOI).

UV-cured nanocomposite films were prepared from acrylic monomer and two types of nanomaterial: zirconium vinylphosphonate and zirconia, in the presence of a photoinitiator. The films were characterized by FTIR, SEM, and AFM. FTIR spectra showed the disappearance of band assigned to the CC group both of monomer and zirconium vinylphosphonate by polymerization and the presence of the phosphonate group in polymer. The influence of zirconium vinylphosphonate and zirconia content on thermooxidative degradation of polymeric films was studied by thermogravimetry. SEM and AFM images showed that nanomaterials are dispersed in polymer matrix with no macroscopic phase separation. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Due to a steady increase in daily life of the need for innovative products, new materials suitable to meet these requirements have to be developed. Poly(vinylphosphonic acid) and its derivatives, poly(vinylphosphonates) and poly(vinylphosphine oxides), have been developed as functional synthetic polymers and gained importance in the polymer applications. Homopolymers of vinylphosphonic acid and its copolymers show interesting properties, given by the presence of acidic functionality. The aim of this paper is to present an overview on the synthesis and applications of vinyl polymers containing functional phosphorus moieties and to emphasize their special properties.

The aminophosphonate styrene–divinylbenzene–silica hybrid materials are obtained in two step reactions: synthesis of alkoxysilane containing polymer precursors and preparation of organic/inorganic ...

p-Methoxybenzoyldialkylphosphonates, terephtaloylbis(dialkylphosphonates), (alkyl=methyl, ethyl), p-methoxybenzoyldiphenylphosphine oxide and terephtaloylbis(diphenylphosphine oxide) were synthesized by Michaelis–Arbuzov reaction. These compounds were used as photoinitiators for radical polymerization of acrylic monomer 1,6-hexandiol diacrylate. The photoinitiating activity was determined by differential photocalorimetry (DPC), in isothermal conditions, using 1,6-hexandiol diacrylate as monomer, in the absence of amines and in the presence of amines as synergist additive. The influence of amine on photoreactivity parameters was studied. The kinetic study of polymerization of 1,6-hexandiol diacrylate sensitized by these radical photoinitiators have been studied by DPC. These compounds performed good photoinitiating activity in comparison with commercial product Lucirin TPO (2,4,6-trimethylbenzoyldiphenylphosphine oxide).

Polyphosphates were synthesized by base promoted liquid-vapor polycondensation of cyclohexylphosphoric dichloride with bisphenol A. The effects of temperature, reaction time, base concentration and molar ratio of reagents on yield, inherent viscosity and molecular weight of the obtained polymer were studied. A second order, central composite, rotatable experimental design was used to find domain experimental field for optimal yields and high inherent viscosities.

Polyphosphonate esters of molecular weights ∼ 104 were synthesized by base promoted liquid-vapor polycondensation of cyclohexylphosphonic dichloride with bisphenol A. The effect of temperature, reaction time, base concentration and molar ratio of reagents on yield, inherent viscosity and molecular weight of the obtained polymer was studied. A second order, central composite, rotatable experimental design was used to find domain experimental field for optimal yields and high inherent viscosities.

Synthetic polymers, which include functional polymers bearing phosphonic acid groups at the side chain such as poly(vinylphosphonic acid) and its copolymers, are designed to yield a desired set of properties such as electrical conductivity and biomimetic behavior together with thermal, chemical, and mechanical resistance. In this chapter the synthesis of vinylphosphonic acid monomer, its polymerization, and the properties of the resulting poly(vinylphosphonic acid) are presented. In previous attempts at its synthesis the apparently simple molecule of vinylphosphonic acid involved either elaborate methods comprising many steps or high energy consumption. Nowadays, the main synthesis path is based on 2-chloroethylphosphonic acid, a plant growth regulator obtained on an industrial scale. Also, the polymerization of vinylphosphonic acid was a challenge for chemists. The deep insight into the structure of poly(vinylphosphonic acid) using modern technique was an accomplishment for scientists because it revealed the complexity of the polymerization reaction of vinylphosphonic acid. The structure of the final product influences the properties required in further applications: high proton conductivity, good mechanical and thermal properties based on low cost materials, and finally an environmentally friendly material.

This paper is directed towards the development of safe, and thermally stable solid polymer electrolytes. Linear phosphorus-containing (co)polyesters are described, including their synthesis, thermal analysis, conductivity, and non-flammability. Polycondensation of phenylphosphonic dichloride (PPD) with poly(ethylene glycol) (PEG 12000) with and without bisphenol A (BA) was carried out using solid-liquid phase transfer catalysis. Potassium phosphate is used as base. Yields in the range of 85.0–88.0%, and inherent viscosities in the range of 0.32–0.58 dL/g were obtained. The polymers were characterized by gel permeation chromatography, FT-IR, 1H- and 31P-NMR spectroscopy and thermal analysis. Their flammability was investigated by measuring limiting oxygen index values. The polymers are flame retardants and begin to lose weight in the 190 °C–231 °C range. Solid phosphorus- containing (co)polyesters were complexed with lithium triflate and the resulting ionic conductivity was determined. Conductivities in the range of 10−7–10−8 S cm−1 were obtained.

Instability of the trialkylphosphates (RO)3P(O), with R ˭ C2H11 - C8H17 has been observed when pairs of these esters were analysed on gas-chromatographic columns with silicone stationary phases, e.g., OV-17. New peaks were identified between those corresponding to the initial esters analysed separately. The Kovats retention indices were calculated for these peaks, with n-alkanes, as standards and phosphorus indices with tri-n-alkyl-phosphates as standards. The relationships between the retention indices and the number of the total carbon atoms in the molecules of the alkyl-phosphates was represented for the identification of the new peaks. The new peaks were identified as mixed phosphates with general structure (RO)z(RO)P(O), where R and R are alkyl radicals C5H11-C6H17. These phosphates are the results of interchange of alkoxy groups from the esters in the conditions of high temperature (240°C) of the chromatographic colums. The retention data of the esters examined are shown in the table.

Organophosphorus compounds containing a c h i d ccntrc at the P atom are of considerable interest fiom a stcreochemical point of view. Accordingly, trialkyl phosphates (RO)(RIO)(R20)P(0) (4) were synthesized starting from dialkyl phosphites. Thus: direct hydrolysis of dialkyl phosphites (ROhP(0)H (1) with tetraethylammonium hydroxide (20% aqueous solution), followed by extraction with dichloromethane affords the corresponding tetraethylammonium alkyl hydrogen phosphitcs (2). Good yields (q) of mixed dialkyl phosphites (3) were obtained on heating stoichiometric amounts of (2) and alkyl iodides in acetonitrile solution at 6O°C, for 6 hrs. Mixed dialkyl phosphites (3) were used in synthesis of some trialkyl phosphates (4) by PTC (see scheme).

The simultaneous influence of four factors [reaction time (I), temperature (T), base concentration (c). molar ratio of the reagents (r)] on the yield (q) and on the inherent viscosity (qIv) of the product has been studied for the liquid-vapor system pol ycondensation of cyclohexyldichlorophosphonate (CDP) with bisphenol A (BA) by second order central composite circumscribed design. For a reasonable domain of the parameters [t = 30 ÷ 70 min., T = 20 ÷ 60 °C, c = 1 ÷ 5 mol/l, r = 1 ÷ 3.5 mol(CDP)/mol(BA)], designing the experiments, the η and ηiv values where determined in 31 synthesis (7 center points were used). In order to model the response (hyper)surfaces for η and ηiv, second order equations with interaction terms were used. Analyzing these model equations, T and c appear to be the most important factors, but acting in opposite way. Higher T resulted in greater yield and inherent viscosity. In the above defined domain the hypersurface of η presents a saddle point. From the sequential inspecti...

Polyphosphonates were synthesized by interfacial alkaline polycondensation of bispheml A (BA) with phenyldichlorophosphonate (PPD) and cyclohexyl-dichlorophosphonate (CPD) in liquid-liquid[1] (1–1) and Iiquid-vapoR[2] (I-v) systems.

Background Phosphorus-containing high performance polymers have aroused wide interest, mainly due to good mechanical properties and their excellent fire resistance. The flexibility of synthetic polyphosphoesters allows the development of polymers in order to obtain solid polymer electrolytes for rechargeable lithium batteries based on solid films with superior fire resistance. Results Novel linear Phosphonate-PEG polymers were synthesized by solution polycondensation of 4-chlorophenyldichlorophosphonate as a linking agent and poly(ethylene glycol)s with different molecular weights in the presence of triethylamine or 1-methylimidazole as acid scavenger. The yields were between 54% and 88% and inherent viscosity between 0.18-0.48 dl/g. Molar masses, Mn were about 26300 g/mol for polyphosphonates with PEG 2000 and 4600 g/mol for polyphosphonates with PEG 200. The LOI values for these polymers and membranes are in the range of 26–29. The membranes based on polyphosphonate with PEG 200 and 2000 showed conductivity between 6 × 10-8 S.cm-1 and 6 × 10-7 S.cm-1 at room temperature and total ionic transference number between 0.87- 0.96. The evolution of conductivity vs. temperature is linear. Conclusions 1-methylimidazole was found to be better HCl scavenger than triethylamine, and allowed higher yields and more eco-friendly synthesis of the Phosphonate-PEG polymers for SPE. These polymers and membranes based on these polymers showed good LOI values and indicate an improvement of the safety of lithium batteries. The membranes present conductivities around 6 × 10-7 S.cm-1at room temperature and total ionic transference number is higher for membranes based on polymers with high EG unit content. Best results yield 88%, inherent viscosities 0.48 dl/g and Mn 26000 were obtained with 1-methylimidazole and PEG 2000. These membranes based on these polymers showed good LOI values (in the range 26-29%) and indicate an improvement of the safety of lithium batteries.