Organophosphorus Polymers Research Articles

One-Pot Synthesis of Polymers Containing PC Bonds in the Main Chain.

Placement of phosphorus in the polymer main chain leads to organophosphorus polymers with potentially unique chemical and physical properties. Herein, it is demonstrated that the Abramov phosphonylation reaction can be extended to the synthesis of such polymers, by reacting di- or tricarbaldehydes with phosphinic acid (PA) in the presence of N,O-bis(trimethylsilyl)acetamide (BSA). This technique affords polymers with main chain PC bonds, wherein phosphorus (V), aromatic rings, and hydroxymethylene moieties are linked by bis(α-hydroxymethylene)phosphinic acid (BHMPA) units. The resulting polymers are water soluble, display resilience against acid- and base-catalyzed hydrolysis, and exhibit superior thermal stability with high char yield in air (≈83%) and nitrogen (≈76%) atmosphere.

Ultramicroporous Organophosphorus Polymers via Self-Accelerating P-C Coupling Reactions: Kinetic Effects on Crosslinking Environments and Porous Structures.

Porous organic polymers (POPs) have drawn significant attention in diverse applications. However, factors affecting the heterogeneous polymerization and porosity of POPs are still not well understood. Herein, we report a new strategy to construct porous organophosphorus polymers (POPPs) with high surface areas (1283 m2/g) and ultramicroporous structures (0.67 nm). The strategy harnesses an efficient transition-metal-catalyzed phosphorus-carbon (P-C) coupling reaction at the trigonal pyramidal P-center, which is distinct from the typical carbon-carbon coupling reaction utilized in the synthesis of POPs. As the first kinetic study on the coupling reaction of POPs, we uncovered a self-accelerating reaction characteristic, which is controlled by the choice of bases and catalysts. The self-accelerating characteristic of the P-C coupling reaction is beneficial for the high surface area and uniform ultramicroporosity of POPPs. The direct crosslinking of the P-centers allows 31P solid-state (ss)NMR experiments to unambiguously reveal the crosslinking environments of POPPs. Leveraging on the kinetic studies and 31P ssNMR studies, we were able to reveal the kinetic effects of the P-C coupling reaction on both the crosslinking environments and the porous structures of POPPs. Furthermore, our studies show that the CO2 uptake capacity of POPPs is highly dependent on their porous structures. Overall, our studies paves the way to design new POPs with better controlled chemical and ultramicroporous structures, which have potential applications for CO2 capture and separation.

Phosphates-Containing Interpenetrating Polymer Networks (IPNs) Acting as Slow Release Fertilizer Hydrogels (SRFHs) Suitable for Agricultural Applications.

Novel, phosphorus-containing slow release fertilizer hydrogels (SRFHs) composed of interpenetrating polymer networks (IPNs) with very good swelling and mechanical properties have been obtained and characterized. It was found that introducing organophosphorus polymer based on a commercially available monomer, 2-methacryloyloxyethyl phosphate (MEP), as the IPN’s first component network results in much better swelling properties than for a terpolymer with acrylic acid (AAc), 2-methacryloyloxyethyl phosphate (MEP) and bis[2-(methacryloyloxy)ethyl] phosphate (BMEP) when the same weight ratios of monomers are employed. The procedure described in this paper enables the introduction of much larger amounts of phosphorus into polymer structures without significant loss of water regain ability, which is crucial in the application of such materials in the agricultural field.

Poly(p‐phenylenediethynylene phosphane): A Phosphorus‐Containing Macromolecule that Displays Blue Fluorescence Upon Oxidation

AbstractDespite the challenges associated with their synthesis, hybrid inorganic–organic polymers featuring heavier main‐group elements spaced by π‐conjugated organic functionalities have garnered considerable recent attention due to their chemical functionality and novel photophysical properties. We have succeeded in the preparation of an unprecedented organophosphorus polymer possessing functional phosphane‐di‐yne moieties in the main chain. Namely, poly(p‐phenylenediethynylene phosphane) (PPYP) is prepared using a nickel(II)‐catalyzed PC bond‐forming reaction. The hexyl‐substituted PPYPs are solution processible and have been thoroughly characterized (molecular weight, Mw, ca. 104 Da vs. polystyrene; degree of polymerization, DP, ca. 10). Remarkably, although PPYP shows very weak emission upon irradiation with UV light, its oxide shows blue “turn‐on” fluorescence. The present discovery bridges the areas of main‐group and polymer science and opens the door to a new class of σ‐π‐conjugated macromolecules with unique chemical functionality.

Poly(p-phenylenediethynylene phosphane): A Phosphorus-Containing Macromolecule that Displays Blue Fluorescence Upon Oxidation.

Despite the challenges associated with their synthesis, hybrid inorganic-organic polymers featuring heavier main-group elements spaced by π-conjugated organic functionalities have garnered considerable recent attention due to their chemical functionality and novel photophysical properties. We have succeeded in the preparation of an unprecedented organophosphorus polymer possessing functional phosphane-di-yne moieties in the main chain. Namely, poly(p-phenylenediethynylene phosphane) (PPYP) is prepared using a nickel(II)-catalyzed P-C bond-forming reaction. The hexyl-substituted PPYPs are solution processible and have been thoroughly characterized (molecular weight, Mw, ca. 10(4) Da vs. polystyrene; degree of polymerization, DP, ca. 10). Remarkably, although PPYP shows very weak emission upon irradiation with UV light, its oxide shows blue "turn-on" fluorescence. The present discovery bridges the areas of main-group and polymer science and opens the door to a new class of σ-π-conjugated macromolecules with unique chemical functionality.

Flammability properties of paper coated with poly (methylenephosphine), an organophosphorus polymer

SummaryThe flame retardant properties of paper coated with either poly(methylenephosphine) (PMP) or poly(methylenephosphine oxide) (PMP‐O) are evaluated. Paper sheets made from thermomechanical pulp were coated with PMP (Mn = 27,000 g mol−1, polydispersity index (PDI) = 1.47), PMP‐O (Mn = 30,000 g mol−1, PDI = 1.24), or monobasic ammonium phosphate (MAP) to achieve an approximate loading of 0.8 mmol P/g paper. Thermal stability studies by thermogravimetric analysis show that the paper degrades in two main stages, with the second thermo‐oxidative stage having a slower rate of degradation for paper treated with flame retardants. The flame retardancy of the sheets was evaluated by Technical Association of Pulp and Paper Industry Standard Method T461 cm‐00 and by limiting oxygen index (LOI) according to ASTM D2863. After leaching with water, samples coated with PMP or PMP‐O show no loss of flame retardancy, while those coated with MAP lose all flame retardancy. The LOI of paper coated with PMP (23.1%) or PMP‐O (25.9%) is higher than those of uncoated paper (19.6%), but lower than MAP‐coated paper (34.7%). Analysis of the char provided evidence that the flame retardant mechanism of PMP and PMP‐O involves the formation of phosphorus oxides and acids. Copyright © 2014 John Wiley & Sons, Ltd.

The Use of Transesterification Method for Obtaining Phosphorus‐Containing Polymers

ABSTRACTAn introduction and overview of the transesterification method is presented in this review. This method is a very convenient way to obtain polyphosphoesters (PPEs). It can be simply described as a chemical reaction in which an ester is transformed into another one by the exchange of alkoxy groups. In this review, we will refer to the synthesis of PPEs via transesterification. In other words, it is focused on the applications of the transesterification method in phosphorus chemistry to obtain polymers (PPEs). The PPEs are an interesting class of organophosphorus polymers. These compounds are important for biological applications because of their biocompatibility and similarity to biopolymers. When the products are polymers, the chemical reaction is called polytransesterification. This method has also several applications in industry (esters of oil, paint industry).

Flame retardant cotton fabrics treated with organophosphorus polymer

Organo-phosphorus compounds was prepared and applied onto cotton fabrics as flame retarding agent. methacryloloxyethylorthophoshor tetraethyl diamidate (MPD) was prepared and its structure was confirmed by IR, NMR and mass spectroscopy. Pyrovatex as commercial flame retardant was used for comparative study. Impregnation method was used as coating for the application of the organophosphorus compounds to cotton fabrics. The major factors affecting the reaction were studied. The results show that the prepared organophosphorus compound can be successfully used as flame retardant for cotton fabrics.

Reactions of elemental phosphorus and phosphine with electrophiles in superbasic systems: XX. Phosphorylation of 4-vinylbenzyl chloride with elemental phosphorus

4-Vinylbenzyl chloride reacts with white and red phosphorus, as well as with nanostructured “activated” red phosphorus (complex organophosphorus polymer prepared from white phosphorus under ionizing radiation) in the system concentrated aqueous KOH-dioxane-phase-transfer catalyst (20–50°C, argon) to form tris(4-vinylbenzyl)phosphine oxide, along with (4-vinylbenzyl)- and bis(4-vinylbenzyl)phosphinic acids, the yield and product ratio being dependent on both the reaction conditions and the nature of the phosphorylating agent. The nanostructured “activated” red phosphorus is more reactive than ordinary commercial red phosphorus.

Investigation on stilbene- and azobenzene-based liquid crystalline organophosphorus polymers

Two series of combined liquid crystalline polyphosphates bearing dual photoreactive mesogenic units (stilbene and azobenzene/α-methylstilbene and azobenzene) were synthesized by solution polycondensation method. The structures of the synthesized polymers were confirmed by various spectroscopic techniques. Thermogravimetric analysis reveals that they are stable between 230 and 320°C. Differential scanning calorimetry studies were done to study the liquid crystalline property, and glass-transition, melting, and isotropization temperatures for all the polymers. Polarizing optical microscope shows the birefringent melt for all the polymers exhibiting liquid crystalline property. The photochemical response was studied by UV–visible and fluorescence spectroscopy for all the polymers. The photocrosslinking reaction of the stilbene containing polymers was ascertained by spectroscopic and photolysis studies. The rate of the switching time for the conversion of trans to cis form of azobenzene unit was investigated by UV spectroscopy. The terminal substituents in the side chain affects the texture of liquid crystalline phase for all the polymers. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

Reactions of elemental phosphorus and phosphine with electrophiles in superbasic systems: XVIII. Phosphorylation of 1-(chloromethyl)naphthalene with the elemental phosphorus

1-Chloromethylnaphthalene reacts with white and red phosphorus, and also with the “activated red phosphorus,” the complex organophosphorus polymer of unknown structure obtained by irradiation of a solution of white phosphorus in benzene by the 60Co source, in a system including KOH water solution, dioxane or benzene, and a phase transfer catalyst (22–98°C, argon), to form bis(1-naphthylmethyl)-and tris-(1-naphthylmethyl)phosphine oxides, and also (1-naphthylmethyl)phosphonous-and bis(1-naphthylmethyl)-phosphinic acids. The yield and the ratio of the reaction products depend on reaction conditions as well as on the nature of phosphorylating agent. It is shown that the reactivity of the “activated red phosphorus” is not worse than that of the white phosphorus and significantly exceeds the reactivity of the usual technical red phosphorus.

Anionic ring-opening polymerization of a strained phosphirene: A route to polyvinylenephosphines

A strained 1-phenyl-2,3-dimethylphosphirene undergoes anionic ring-opening polymerization upon initiation with n-butyl lithium at ambient temperature to yield polyvinylenephosphine, an unsaturated organophosphorus polymer.

31P and 1H NMR studies of the transesterification polymerization of polyphosphonate oligomers

Polymeric phosphonate esters are an interesting class of organophosphorus polymers because both the polymer backbone and phosphorus substituents can be modified. These polymers have been prepared by ring-opening polymerizations of cyclic phosphites, stoichiometric polycondensations of dimethyl phosphonate with diols in conjunction with diazomethane treatment and by transesterification of polyphosphonate oligomers. Our initial attempts to prepare high molecular weight polymeric phosphonate esters by the transesterification methods were unsuccessful. Results indicate that the reactions of dimethyl phosphonate with diols to form polyphosphonate oligomers with only methyl phosphonate end groups are plagued by a serious side reaction that forms phosphonic acid end groups. These end groups do not participate in the transesterification reaction and limit the molecular weights of the polymers that can be obtained. The phosphonic acid end groups can be converted into reactive methyl phosphonate end groups by treatment with diazomethane, however diazomethane is explosive and the polymerization is slow. An alternative route for the production of high molecular weight polymers is the transesterification of the 1,12-bis(methyl phosphonato)dodecane, formed by the reaction of excess dimethyl phosphonate and 1,12-dodecanediol, with a Na 2CO 3 promoter. This allows polymers with molecular weights of up to 4.5×10 4 to be prepared, and no phosphonic acid end groups are observed in these polymers. Thermal analyses of the poly(1,12-dodecamethylene phosphonate) have shown that this polymer has reasonable thermal stability (onset of thermal decomposition at 273 °C). This polymer also undergoes a cold crystallization process at 15 °C similar to that which has been observed in some polyesters, polyamides and elastomers.

Calculating glass temperatures of polymers containing phosphorus

A universal system is used for calculating the glass temperatures T g of organophosphorus polymers. Satisfactory agreement was found between experimental and calculated values of T g. The quantitative analysis of the microstructure of diene polymers containing phosphorus, which was carried out using the method of calculation in question, is in satisfactory agreement with results of NMR of 31P spectroscopy.

Synthesis of organophosphorus oligomers and polymers by polycondensation

ONE of the methods of increasing the resistance of polymers to burning is to intr~duce phosphorus into the polymer molecule. Many organophosphorus polymers have been synthesized [1] and some are produced commercially. Our efforts have been directed mainly toward preparat ion of organophosphorus compounds containing functional groups, and of oligomers with reactive ends. The polymers and oligomers tha t we obtained were used for synthesis of polymers by polycondensation, and also for modifying the properties of polyesters and polyurethanes during the course of their preparat ion. Difunctional monomers have been obtained from di-(chloromethyl)methylphosphine oxide (DCMPO) [2] by replacement of the chlorine atoms by radicals containing functional groups [3]. Polyesters, eopolyesters, mixed polyesters, oligoesters and mixed oligoesters have been obtained from di-(carbomethoxyphenoxymethyl)methyl phosphine oxide prepared in this way. Polyurethanes were obtained from the oligoesters [4, 5]. Polymerizable products have been obtained by esterification of bis-(hydroxymethyl)phosphinic acid with acrylic or methacrylic acid [6]. Polyformamidopolyurethanes and polyurethanes containing chlorine and phosphorus have been prepared by addit ion of monoand dicondensation products of chloral and hypophosphorous acid to di-isocyanates [7]. The above phosphorus-containing monomers, oligomers and polymers are based on relat ively easily accessible phosphorus compounds and are distinguished by the fact t ha t the phosphorus a tom forms par t of the main polymer chain and is connected to it by a C P bond. Phosphonic acid esters are used to prepare polymers with C O P bonds. Oligoesters have been obtained from these by transesterification with diols [8-10], and oligoester-methaerylates have been prepared from the oligoesters [9, 10]. Oligophosphites have been synthesized by transesterifieation of diethyl phosphite with 1,6-hexanediol [11], and by using bis-(hydroxyethylene)polysulphide as the diol polyesters [12] and oligoesters [13] containing phosphorus and sulphur were obtained. The phosphorusand sulphur-containing oligophosphites and polyformamidopolyllrethanes derived from them were tested as addit ives in unfilled natura l rubber compositions [14]. They were found to be good anti-ageing additives, with special properties. In the course of s tudy of these propert ies i t was found tha t polyurethanes free from phosphorus can also be used as addit ives [15], bu t their anti-ageing properties are weaker. Oligoesters containing phosphorus and sulphur have also been prepared by reaction of hexanediol wi th P2S5, and also by reaction with P~S5 of the oligophosphite obtained by transesterification of diethyl phosphite wi th hexanediol [11]. These results are presented in greater detail in reference [16].

Organophosphorus monomers and polymers By Ya. L. Gefter (translated from the Russian by J. Burdon). Pp. vii + 302. Pergamon Press Ltd, Oxford. 1962. 70s. net

Organophosphorus monomers and polymers By Ya. L. Gefter (translated from the Russian by J. Burdon). Pp. vii + 302. Pergamon Press Ltd, Oxford. 1962. 70s. net

Organophosphorus Monomers and Polymers.

<b>Organophosphorus Monomers and Polymers.</b>

Preparation of a polymer from benzyldiphenylphosphine oxide by the polyrecombination reaction

1. It was shown that organophosphorus polymers can be prepared with the aid of the polyrecombination reaction. 2. Poly[benzyldiphenylphosphine oxide] was prepared, and its properties were studied. 3. The presence of phosphorus in the monomer molecule has a passivating effect on the mobility of the hydrogen of the methylene group. 4. Some regularities in the polyrecombination process were examined.

Investigation in organophosphorus polymers—IX. The polycondensation of phosphinyl dichlorides with dioxy compounds: V. V. Korshak, I. A. Gribova and M. A. Andreeva, Vysokomol. soedin. 2: No. 3, 427–432, 1960

Investigation in organophosphorus polymers—IX. The polycondensation of phosphinyl dichlorides with dioxy compounds: V. V. Korshak, I. A. Gribova and M. A. Andreeva, Vysokomol. soedin. 2: No. 3, 427–432, 1960

Organophosphorus polymers. I. Peroxide‐initiated polymerization of diethyl and diisopropyl vinylphosphonate

AbstractIt was shown that diethyl vinylphosphonate and diisopropyl vinylphosphonate are polymerized by peroxide initiators to clear, light‐yellow, viscous liquid polymers of low molecular weight. It was found that the yield of the isolated polymers varied directly, while the molecular weight varied inversely, with the concentration of the initiator. Infrared spectra of the monomers used and the polymers obtained established that polymerization occurs through the vinyl group. It is postulated that the low molecular weight is due to the result of chain transfer with polymer and/or monomer through the alkoxy groups attached to the phosphorus atom.