Phosphorus-containing Polymers Research Articles

Synthesis and photopolymerizations of phosphate-containing acrylate/(di)methacrylate monomers from 3-(acryloyloxy)-2-hydroxypropyl methacrylate

Novel phosphorus-containing acrylate/(di)methacrylate monomers based on 3-(acryloyloxy)-2-hydroxypropyl methacrylate (AHM) were prepared by two different methods. The first method involved reaction of AHM with diethylchlorophosphate to produce a phosphate-containing acrylate/methacrylate monomer followed by Michael addition of this monomer with dihexyl amine. In the second method, a hydroxyl-containing dimethacrylate monomer was prepared via Michael addition of hydroxyl amine to AHM followed by its reaction with diethylchlorophosphate. The photopolymerization kinetics of the synthesized monomers were investigated using a differential scanning calorimeter. It was shown that changing the monomer structure allows control of polymerization reactivity and new phosphorus-containing polymers can be obtained.

The Reinforcement of Calcium Carbonate Filled Papers with Phosphorus-Containing Polymers

Anionic polyelectrolytes bearing phosphate or phosphonate groups were compared to poly(acrylic acid-co-acrylamide) as reinforcing polymers for paper filled with calcium carbonate. Cationic polyvinylamine, PVAm, was used to promote adsorption of the anionic polymers onto fiber and filler surfaces in the aqueous papermaking suspension. Both poly(acrylamide-co-vinyl phosphonate), PAMVP, and phosphate esters of poly(vinyl alcohol), PVAP, gave stronger paper than did the acrylate copolymers. PAMVP bound soluble calcium ions, resulting in the formation of multichain colloidal-sized clusters. Subsequent addition of PVAm produced dispersed, cationic polyelectrolyte complexes. The polyacrylates bound less soluble calcium and formed weakly scattering clusters. It is proposed that the phosphate and phosphonate groups promote polymer adhesion to the calcium carbonate surfaces, resulting in stronger paper.

Phase transfer catalysis in the synthesis of phosphorus-containing polymers

Polyphosphonates of high molecular weights were prepared from chloromethylphosphonic dichloride (CMPD) and 4,4?-sulfonyldiphenol (SDP) by two-phase interfacial polycondensation (l?l), in an organic solvent-aqueous alkaline solution system, with a phase-transfer catalyst, at ?8 ? ? 0 ?C. Alternative method, namely vapor-liquid interfacial polycondensation (v?l) of the same reagents gave better results (higher inherent viscosities and molecular weights). The polymers were characterized by spectroscopic techniques IR and 1H-NMR. The molecular weights and thermal stability determinations were carried out by gel chromatography and thermogravimetry. The effect of reaction temperature on yield and inherent viscosity in l?l and v?l interfacial polycondensation was studied. In l?l system the highest inherent viscosities were obtained at ?8 ? ? 0 ?C, whereas in v?l system the maximum inherent viscosity was obtained at 120 ?C.

Novel thermotropic liquid crystalline polyphosphonates

Main chain liquid crystalline polyphosphonates containing semi-flexible phenylester mesogen with even number of methylene spacers (2–10) have been synthesized. The monomers and polymers were characterized by IR, 1H, 13C and 31P NMR spectroscopy. The spectral details are in accordance with the structures. All the polymers were exhibited liquid crystalline property in the Hot stage optical polarized microscope (HOPM). DSC thermal analysis confirms the mesophase formation for all the polymers. The grain size of the liquid crystalline mesophase is increasing with increasing methylene chain. T g, T m and T i of the polymers decreased with increase in spacer length. The T g of these phosphorus-containing polymers is much lower than that of non-phosphorus polymers containing triad ester mesogens. Energy minimized structures for the molecules which mimic the polymer chain suggests that the reduction in T g may be due to entanglement raised by incorporation of phosphorus heterogeneity.

Energy Characteristics of the Surface of Modified Phosphorus-Containing Epoxy Polymers

The Fowkes and van Oss-Good approaches were used for assessing the energy characteristics of the surface of the epoxy-amine systems modified with triglycidyl phosphate. Variation of these characteristics with the modifier content and polymer curing conditions was studied.

Encyclopedia of polymer science and technology

VOLUME 1. Acetylenic Polymers, Substituted. Acrylamide Polymers. Acrylic (and Methacrylic) Acid Polymers. Acrylic Ester Polymers. Acrylonitrile and Acrylonitrile Polymers. Acrylonitrile-Butadiene-Styrene Polymers. Additives. Adhesion. Adhesive Compounds. Aging, Physical. Alkyd Resins. Am,ino Resins and Plastics. Antifoaming Agents. Atomic Force Microscopy. Biotechnology Applications. Bloack Copolymers. Bloack Copolymers, Ternary Triblock. Blow Molding. Chitin and Chitosan. Chromatography, Affinity. Chromatography, HPLC. Chromatography, Size Exclusion. Coating Methods, Survey. Coatings. VOLUME 2 Coextrusion. Colorants. Coloring Processes. Composites, Fabrication. Conformation and Configuration. Critical Phase Polymerizations. Cyclohexanedimethanol Polyesters. Dendronized Polymers. Dental Applications. Diacethylene and Triacethylene Polymers. Elasticity, Rubber-Like. Electronic Packaging. Electrooptical Applications. Engineering, Thermoplastics, Overview. Enzymatic Polymerization. Ethylene Polymers, Chlorosulfonated. Ethylene Polymers, HDPE. Ethylene Polymers, LDPE. Ehtylene Polymers, LLDPE. Ethylene-Acrylic Elastomers. Ethylene-Norbornene Copolymers. Extrusion. Films, Orientation. Fluorocarbon Elastomers. Fractography. Fracture. Glass Transition. Hardness. Hydrogels. Hyperbranched Polymers. VOLUME 3 Injection Molding. Inorganic Polymers. Laser Light Scattering. Light-Emiting Diodes. Lignin. Liquid Crystalline Polymers, Main-Chain. Liquid Crystalline Thermosets. Mass Spectrometry. Membrane Technology. Methacrylic Ester Polymers. Micromechanical Properties. Modeling of Polymer Processing and Properties. Nanocomposites, Polymer-Clay. Packaging, Flexible. Perfluorinated Polymers, Perfluorinated Ethylene-Propylene Copolymers. Perfluorinated Polymers Polytetrafluoroethylene. Perfluorinated Polymers Tetrafluoroethylene-Ethylene Copolymers. Perfluorinated Polymers, Tetrafluoroethylene-Perfluorinated Copolymers. Perfluorinated Polymers. Tetrafluoroethylene-Perfluorovinyl Ether Copolymers. Phosgene. Phosphorus-Containing Polymers and Oligomers. Piezoelectric Polymers. Plasticizers. Poly(3-Hydroxyalkanoates). Poly(Trimethylene Terephthalate). Polyamides, Atomatic. Polyamides, Fibers. Polyamides, Plastics. Polycyanoacrylates. Polyesters, Fibers. Polyketones. Polynucleotides. Polysulfides. VOLUME 4 Polysulfones. Polyurethanes. Pressure-Sensitive Adhesive. Reinforcement. Release Agents. Shape-Memory Polymers. Single-Site Catalysis. Stabilization. Styrene-Butadiene Rubber (SBR). Styrene Polymers. Sulfur-Containing Polymers. Surface Properties. Syndiotactic Polystyrene. Vinyl Fluoride Polymers (PVF). Vinylidene Chloride Polymers. Vinylidene Fluoride Polymers. Viscoelasticity. Weathering.

Polyphosphates and Other Phosphorus-Containing Polymers for Drug Delivery Applications

Poly(phosphate ester)s, polyphosphonates, and polyphosphazenes are three classes of phosphorus-containing polymers that have received wide attention over the past decade for their utility in biomedicine and tissue engineering. These three families of polymers can lead to a number of subclasses of polymers with varied properties. Significant research in this area has led to niche polymers with morphologies ranging from viscous gels to amorphous microparticles for utility in drug delivery. Furthermore, the pentavalency of phosphorus offers the potential for covalent linking of the drug. The classes of polymers discussed in this review are being explored in human clinical trials for vaccine delivery as well as delivery of oncolytic and CNS therapeutics. More applications in the areas of DNA delivery and tissue engineering are also being explored.

Manufacture of Vinylidene Diphosphonic Acid and Novel Phosphorus-Containing Polymers

A novel method for the preparation of vinylidene diphosphonic acid (VDPA) is described. Incorporation of this monomer into water-soluble polymers is discussed.

Miscibility of Poly(arylene phosphine oxide) Systems and Bisphenol A Poly(hydroxy ether)

A number of new aryl phosphorus-containing polymers were found to be miscible with the commercially significant bisphenol A-based poly(hydroxy ether)s (PHE) over the entire composition range by dif...

Use of Phosphorus-Containing Polymers as Additives for Lubricants

Use of Phosphorus-Containing Polymers as Additives for Lubricants

Lithium insertion in carbons prepared from phosphorus-containing polymers

Phosphorus-containing carbon has been prepared by the pyrolysis of phenolic resin containing chemically bonded phosphorus atoms, which is synthesized through the esterification of phenolic hydroxyl group by phosphoric acid. The electrochemical insertion of lithium in as-prepared carbon is also investigated. It is found that, at a pyrolysis temperature of 500°C, the addition of phosphoric acid in the precursor lowers the reversible capacity of the resultant carbon, but at 900°C, the addition of phosphoric acid in the precursor resin increases the reversible capacity of resultant carbon. Especially, the phosphorus-containing carbon prepared by the above method at 900°C gives a capacity beyond the theoretical value of graphite and reasonable discharge/charge curves. The phosphorus-containing carbon prepared by the pyrolysis at 500°C shows a similar electrochemical behavior to that of pure carbon and the effect of phosphorus atoms is little. Its reversible capacity is mainly determined by the content of hydrogen atoms rather than phosphorus atoms. However, at a relatively high pyrolysis temperature, 900°C, more phosphorus atoms are bonded with carbon atoms and are introduced to the microcrystallite structure of carbon. Hence, phosphorus element exerts a strike effect on the electrochemical behavior of carbon and, because of its different electronic effect from carbon element, more lithium species are inserted into carbon matrix.

Radiation-Chemical Synthesis of Phosphorus-Containing Polymers in the Presence of Inorganic Additives

Radiation-Chemical Synthesis of Phosphorus-Containing Polymers in the Presence of Inorganic Additives

Flame retardance in some polystyrenes and poly(methyl methacrylate)s with covalently bound phosphorus-containing groups: initial screening experiments and some laser pyrolysis mechanistic studies

Styrene (ST) and methyl methacrylate (MMA) have been copolymerized with a variety of comonomers containing covalently-bound phosphorus-containing groups, including vinyl phosphonic acid, several dialkyl vinyl phosphonates, and various vinyl and allyl phosphine oxides. The flame retardance of these polymers has been preliminarily assessed through thermogravimetric analysis and measurements of limiting oxygen index (LOI) and char yields. All the phosphorus-containing polymers produce char on burning (and also on heating in air or nitrogen) and have LOIs higher than those of the parent homopolymers, indicating significant flame retardance involving condensed-phase mechanisms. However, despite there being general correlations between LOI, char yield and phosphorus-content, some copolymers have higher than expected LOI and/or char yield, whilst others have lower, indicating that phosphorus environment is important. In order to explore mechanisms of flame retardance in more detail, laser pyrolysis/time-of-flight mass spectrometry and mass spectrometric thermal analysis have been applied to study the decomposition behaviour of three of the MMA copolymers: those containing pyrocatecholvinylphosphonate (MMA-PCVP), diethyl- p-vinylbenzylphosphonate (MMA-DE pVBP) and di(2-phenylethyl)vinylphosphonate (MMA-PEVP) as comonomers. The laser pyrolysis experiments provide an insight into probable polymer behaviour behind the flame front in a polymer fire and show that copolymerization of MMA with the comonomers does not greatly change the pyrolysis mechanism compared with that of poly(methyl methacrylate) (PMMA). However, the amounts of MMA monomer evolved during pyrolysis are much reduced for the copolymerized samples. Since MMA is the major fuel evolved during the combustion of PMMA and its copolymers, this effect must be a major contributing factor to the reduced flammability shown by the copolymers. MMA-DE pVBP underwent the most extensive decomposition following laser pyrolysis. In particular, significant amounts of highly flammable methane and ethene were detected. Such increased amounts would occur also if the copolymer were to be exposed to high temperature conditions when burnt. Hence, its seems reasonable that the MMA-DE pVBP has a lower LOI value than expected, despite it giving a relatively high yield of char. Mass spectrometric thermal analysis studies of the MMA-PEVP provide evidence that the PEVP unit decomposes around 200°C, eliminating styrene, with evolution of MMA reaching a maximum some 50°C higher. Possible mechanisms for these processes are suggested.

Novel phosphorus-containing dicyclopentadiene-modified phenolic resins for flame-retardancy applications

2-[4-(2-hydroxyphenyl)tricyclo[5.2.1.02,6]dec-8-yl]phenol (HPTCDP) were prepared from dicyclopentadiene (DCPD) and phenol via Friedel-Crafts alkylation. DCPD-containing phenolic resin (DPR) was also synthesized by incorporating the DCPD-containing monomer HPTCDP with formaldehyde. DPR was further modified by grafting the phosphate group. The phosphorylation was confirmed by a Fourier transform infrared, 31P-NMR spectroscopy, and an element analysis. The phosphorus content in the DPR could be successfully tailored to give values of 3.46 to 7.79 wt % by varying the feeding ratios of the phosphorus group. The thermal stabilities of the phosphorus-containing polymers were identified by differential scanning calorimeter and thermogravimetric analysis. The glass transition temperature values were decreased as the content of phosphorus increased. High char yield 39–47 wt % in thermogravimetric analysis evaluation and limiting oxygen index values of 27 to 34 were found for all the phosphorylated phenolic resins. Such properties make these polymers highly promising for flame-retardant applications. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 342–349, 2001

The thermal degradation of phosphorus-containing copolyesters

Two series of phosphorus-containing copolyesters were synthesized by poly-condensation of phosphorus-containing monomers: poly(ethylene terephthalate)-co-poly(ethylene phenylphosphonate)s [PET-co-PEPPs] and poly(ethylene terephathalate)-co-poly(ethylene DDP)s [PET-co-PEDDPs]. Both series are considered as flame retardants in polyester fibers and polyester plastics. The phosphorus-containing polymers were characterized by NMR, IR, TGA and acid titration. Experimental results indicated that for the PET-co-PEPP higher phosphorus content results in lower thermal stability. However, an insignificant effect on thermal stability was observed in the case of PET-co-PEDDPs. Thus, the incorporation of the phosphorus linkage into the main chain results in less thermal stability than that having the phosphorus linkage as a pendant group, i.e. PET-co-PEDDPs are more stable than PET-co-PEPPs.

Synthesis and flame-retardant properties of phosphorus-containing polymers based on poly(4-hydroxystyrene)

Phosphorus-containing polystyrene was obtained through incorporating phosphate groups onto poly(4-hydroxystyrene). This was achieved by esterification with diethylchlorophosphate. The phosphorylation was confirmed by IR, 1H-NMR, and 31P-NMR analysis. By varying the feeding ratios of the reactants, the phosphorus content in the polymers could be successfully tailored and gave values of 12.8 to 4.9% by weight. This was further corroborated by elemental analysis. Thermal characteristics and temporal stability of the phosphorylated polymers were evaluated by DSC and TGA. High char yields (64% by weight) and LOI values of 41 were found for these polymers. Such properties make these polymers useful in flame retardants. © 1996 John Wiley & Sons, Inc.

Controlled release from poly(phosphoester) matrices

A class of biodegradable polymers, poly (phosphoesters), was studied for its potential as a matrix for controlled drug delivery. The degradability of the phosphorus ester linkage and the versatility of phosphorus-containing polymers make poly (phosphoesters) attractive candidates for development as a degradable biomaterial. The release of various drugs in vitro from a series of bisphenol-A based poly (phosphoesters) was examined. Sustained release for up to several months was achieved for cortisone acetate and model drug p-nitroaniline. The mechanism of release was found to be a combination of diffusion, swelling and degradation. The structure of the sidechain influenced the release behavior in all instances.

Synthesis of Phosphorus-Containing Polymers with Aziridine Ring

It has been established that phosphorus containing alkylammonium salts obtained by alkylation of primary amines with bis(2-chloroethyl) phosphonate or alkyl 2-chloroethyl phosphonate can be transformed into corresponding compounds with aziridine ring.

Flame and thermal resistance of phosphorus-functionalized poly(methyl methacrylate) and polystyrene

A series of phosphorus functionalized poly(methyl methacrylate) (PMMA) and polystyrene (PS) samples where the phosphorus functions are located at the chain ends, as pendant groups and as blocks in the middle of the polymer chain were evaluated for their flame and thermal resistance. The limiting oxygen index values (LOI) of the polymers revealed that the flame retardant efficiency of the phosphorus was dependent on its nature and position in the polymer chain and the type of polymer rather than on its absolute concentration. On a comparative scale, polymers with phosphorus at chain ends and in the middle of the chain exhibited better flame retardant properties. The polymers were subjected to thermogravimetric analysis (TGA) in air and N 2 under dynamic conditions and the trends in thermal behaviour with change in structure and composition have been examined and compared with that of the homopolymers. Except when located at chain ends, the phosphorus functionalization adversely affected the initial thermal characteristics of the PMMA samples, but with an improvement at elevated temperatures. For PS, phosphorus functionalization as pendant groups reduced their thermal resistance whereas chain-end and mid chain functionalization either did not affect or slightly improved their overall thermal resistance. All phosphorus-containing polymers left some char residue at higher temperatures. The activation energies for the major step of thermal decomposition were calculated from the thermograms. As the phosphorus content increased, the activation energy for a given degradation step was found to decrease except when the degradation was principally due to the phosphorus containing polymer block where a reverse trend was observed. The flame resistance of the polymers could be correlated to some extent with their thermal behaviour.

Preparation of phosphorus-containing polymers. XXVIII. Synthesis and flame resistance of phenoxaphosphine-containing copolyesters

Copolyesters containing phenoxaphosphine rings were prepared from 2,8-dichloroformyl-10-phenylphenoxaphosphine 10-oxide and isophthaloyl chloride and three bisphenols (bisphenol A, tetrabromobisphenol A, and tetrachlorobisphenol A) by interfacial polycondensation, and the flame resistance of the resulting copolyesters was investigated by measuring limiting oxygen index (LOI) values. Most of the copolyesters had good solubilities in N-methyl-2-pyrrolidone and chloroform and gave the films from the chloroform solutions. The relationship between the melting temperature of copolyesters and phenoxaphosphine content held for the Flory's equation for random copolymers over 20–30% of phenoxaphosphine content. The halogen-free copolyesters with phenoxaphosphine rings showed not only good thermostability but also good flame resistance. In contrast with these copolymers the halogen-containing copolyesters with phenoxaphosphine rings had very high LOI values and exhibited excellent flame-retardant property, but their thermostability was poor and the copolymers began to decompose at lower temperatures in comparison with the halogen-free copolyesters. The mode of action of the halogen-free copolyesters containing phenoxaphosphine rings was based on the effect of phosphorus in the solid phase, whereas the action of the copolyesters with both halogen and phenoxaphosphine ring was due to the additive effect of the solid-phase and the gas-phase mechanisms.