Synthesis of poly(phosphonosiloxane) and its cyclic monomer via hydrosilylation and phosphonylation of vinylbenzyl chloride

Song, Lin; Cabasso, Israel

doi:10.1002/(sici)1099-0518(19991115)37:22<4043::aid-pola3>3.0.co;2-e

Cited by 9 publications

(5 citation statements)

References 31 publications

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“…The success in growing semiconducting nanoparticles in ultrathin Langmuir-Blodgett (LB) films (being cast and oriented at water-air interfaces) of polystyrene phosphonate esters and its blends with cellulose acetate and with vinylbenzyl phosphonate (VBP) monomers and polymers (PSP) [1][2][3] lead us to the inspection of the field in which phosphonate moieties would be combined with polysiloxane matrices that could be deposited as LB films or monolayers. 4 Polymers that contain a phosphonate ester functionality, -R′-PO(OR) 2 can chelate and dissolve large quantities of metal salt (e.g., uranyl nitrate) within their matrices. [1][2][3][4] The phosphonyl group, PdO, is a strong nucleophile and interacts with water and other proton donor solvents through hydrogen bonding.…”

Section: Introductionmentioning

confidence: 99%

“…The success in growing semiconducting nanoparticles in ultrathin Langmuir−Blodgett (LB) films (being cast and oriented at water−air interfaces) of polystyrene phosphonate esters and its blends with cellulose acetate and with vinylbenzyl phosphonate (VBP) monomers and polymers (PSP) – lead us to the inspection of the field in which phosphonate moieties would be combined with polysiloxane matrices that could be deposited as LB films or monolayers …”

Section: Introductionmentioning

confidence: 99%

“…Polymers that contain a phosphonate ester functionality, −R′-PO(OR) 2 can chelate and dissolve large quantities of metal salt (e.g., uranyl nitrate) within their matrices. – The phosphonyl group, PO, is a strong nucleophile and interacts with water and other proton donor solvents through hydrogen bonding. Several phosphonate-containing polymers have been synthesized in our laboratory and were proven to produce effective LB films. –,, However, these polymers have a relatively high glass-transition temperature, T g , of ∼10−100 °C.…”

Section: Introductionmentioning

confidence: 99%

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Amphiphilic Siloxane Phosphonate Macromolecule Monolayers at the Air/Water Interface: Effects of Structure and Temperature

Cabasso

Stesikova

2008

J. Phys. Chem. B

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A comprehensive study is reported of Langmuir-Blodgett (LB) films (spread at the air/water interface using the Langmuir balance technique) composed of surface active, nonionic, and OH-free amphiphilic siloxane phosphonate ester macromolecules. Analysis is made on three molecular structures in the form of linear polymer poly(diethylphosphono-benzyl-alphabeta-ethyl methylsiloxane) (PPEMS), cyclic oligomer methylphosphonobenzyl-alphabeta-ethyl cyclosiloxane (MPECS), and copolymer poly(PEMS-co-DMS). The surface pressure-surface area (pi -A) isotherms of homopolymer at 3-40 degrees C show a clear temperature-induced phase transition (plateaus at pit approximately 17-19 mN/m) below 10 degrees C. The magnitude of the transition substantially increases upon lowering the temperature (partial differential DeltaAt/ partial differential T approximately -0.1 nm2 unit(-1) deg(-1) and partial differential pi t / partial differential T approximately -0.25 mN m(-1) deg(-1)). The positive entropy and enthalpy gain infers that strong coupling with the subphase and excess hydration attributed to hydrogen bonding between the P=O bond and the subphase prevails at low temperatures. The cyclic oligomer MPECS forms a condensed monolayer at the air/water interface that does not display a similar transition in the experimental temperature range. The temperature sensitivity of MPECS film is observed only in the collapsed region. The nature of the interaction with the subphase is similar for MPECS and PPEMS, indicating that the size and thermal mobility are the controlling factors in these processes. The elasticity plot reveals two distinct states (above and below transition). This observation is supported by BAM images that show irregular spiral structures below 10 degrees C. The transition occurring in the copolymer at 20 degrees C is due to relaxation of the PDMS component. The two maxima shown in the elasticity plot indicate additive fractions of PPEMS and PDMS. The surface areas of these macromolecules in the relaxed (1.48 nm2/unit) and packed (0.45 nm2/unit) forms obtained by PM3 modeling agree well with the experimental data and seem to indicate that the siloxane chain is being lifted off the subphase by the hydrophobic phenylic part of the molecule.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Amphiphilic Siloxane Phosphonate Macromolecule Monolayers at the Air/Water Interface: Effects of Structure and Temperature

Cabasso

Stesikova

2008

J. Phys. Chem. B

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“…Siloxane polymers containing benzyl phosphonate groups were reported by Lin and Cabasso. 27 In their work, the hydrosilylation of poly(methylhydrosiloxane), followed by phosphorylation, produced viscous oils containing pendant diethyl phosphonates. Attempts to produce polymer 6 with similar hydrosilylation techniques proved unsuccessful.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and characterization of phosphonate‐containing polysiloxanes

Gallagher¹

2002

J. Polym. Sci. A Polym. Chem.

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Phosphonate-functionalized polysiloxanes have been prepared with a new siloxane/phosphonate monomer. The reaction of 3-chloropropylmethyldimethoxysilane with trimethylphosphite or triethylphosphite produces several new monomers containing pendant phosphonate groups. Copolymerization with dimethyldimethoxysilane has produced polymers soluble in most organic solvents. The acid hydrolysis of the phosphoryl esters has produced hydrophilic siloxane polymers containing phosphonic acid groups. The thermal properties of the polymers and several related small molecules have been compared with thermogravimetric analysis. Both the monomers and the resulting polymers have been characterized with 1 H, 13 C, 31 P, and 29 Si NMR.

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“…Functionalization of macromolecules with phosphonate ester groups has been shown to impart many desirable properties such as solubility in a wide variety of organic solvents, − miscibility with other polymers, , metal coordinating ability − ,− and adhesive properties. − Most of the unique properties are due to the −C−PO group which is a proton acceptor and thus enables the macromolecule to form a hydrogen bond and interact with Lewis acids. Additionally, the polyphosphonate esters may be hydrolyzed to the corresponding polyphosphonic acids.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Mechanism of PBI Phosphonate, Poly[2,2′-(-m-phenylene)-5,5′-Bibenzimidazole Phosphonate Ester], and its Polyphosphonic Acid Derivatives

Johnson

Cabasso

2010

Macromolecules

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Polybenzimidazole diethyl phosphonates (PBIP Et ) of high phosphorus content (as high as ∼13%) have been synthesized by reacting poly[2,2 0 -(m-phenylene)-5,5 0 -bibenzimidazole] (PBI) with diethyl phosphite and a peroxide, in N,N-dimethylacetamide solution, via a free radical mechanism. The phosphonate ester groups are linked directly to the aromatic backbone thus establishing a strong -(Od)P-Phbond. The highly phosphonylated products dissolve in lower alcohols and the corresponding polyphosphonic acids (PBIP OH ) dissolve in aqueous sodium hydroxide (pH ∼ 7-8); membranes composed of either polymer are readily prepared. PBIP OH displayed high thermal stability as well as charge densities as high as ∼9 mequiv of H þ /g. Model compounds benzimidazole and 2,2 0 -diphenyl-5,5 0 -bibenzimidazole have been phosphonylated under similar conditions in order to resolve phosphonylation mechanism, and some aspects of a rather complicated oxidative substitution. Benzoic acid is a byproduct of reactions involving benzoyl peroxide supporting a mechanism that involves breakdown of the peroxide into radicals followed by reaction with the phosphite ester and subsequent attack of phosphorus centered radicals on an aromatic ring. In the case of PBI, phosphonylation appears to occur preferentially at the C 4 and C 7 positions of the benzimidazole rings (on the benzene ring adjacent to the fusion points) as well as on the m-phenylene rings ortho-to the linkage with benzimidazole. The observed substitution pattern is likely controlled by the resonance stability of the radical adduct.

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Synthesis of poly(phosphonosiloxane) and its cyclic monomer via hydrosilylation and phosphonylation of vinylbenzyl chloride

Cited by 9 publications

References 31 publications

Amphiphilic Siloxane Phosphonate Macromolecule Monolayers at the Air/Water Interface: Effects of Structure and Temperature

Amphiphilic Siloxane Phosphonate Macromolecule Monolayers at the Air/Water Interface: Effects of Structure and Temperature

Synthesis and characterization of phosphonate‐containing polysiloxanes

Synthesis and Mechanism of PBI Phosphonate, Poly[2,2′-(-m-phenylene)-5,5′-Bibenzimidazole Phosphonate Ester], and its Polyphosphonic Acid Derivatives

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