- Study on thermal degradation and combustion behavior of flame retardant unsaturated polyester resin modified with a reactive phosphorus containing monomer
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A halogen-free phosphorus-containing monomer (TAOPO) with a P-C bond was successfully synthesized and used as a co-curing agent to prepare intrinsic flame-retardant unsaturated polyester resin (FR-UPR) by radical bulk polymerization with different TAOPO content. The thermal degradation and flame retardancy of pure UPR and FR-UPR were investigated by thermogravimetric analysis (TGA), cone calorimetry tests and limiting oxygen index (LOI). As the phosphorus content increased to 3%, FR-UPR (URP-3) showed a lower peak heat release rate (PHRR) and total heat release (THR), reducing by 45.7% and 45.5% those of pure UPR, while the LOI value and char residue increased markedly. Besides, thermal-oxidative degradation behaviors of different UPR samples were characterized by real-time infrared spectrometry (RT-IR) and thermogravimetry-Fourier transform infrared (TG-FTIR) spectroscopy, revealing the degradation mechanism. Furthermore, the residual char of UPRs was investigated by scanning electron microscopy (SEM) and Raman spectroscopy. The results indicated that the incorporation of TAOPO into UPR could effectively prompt the UP matrix to form a more compact char layer which acted as a protective barrier to reduce heat release during combustion.
- Lin, Ying,Yu, Bin,Jin, Xin,Song, Lei,Hu, Yuan
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- Phosphorus-containing polymers from THPS. VII. Synthesis of phosphorus-containing trialkynes and their metal-free 1,3-dipolar cycloaddition reaction with azidated soybean-oil
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A novel hydrolysis-resistant trialkyne, namely tris(prop-2-yn-1-yloxy methyl)phosphane oxide (TPOPO) was prepared from an environmentally friendly tetrakis(hydroxymethyl)phosphonium sulfate (THPS). The chemical structure of TPOPO was characterized by FT-IR, NMR (1H, 13C, 31P) and MS. The TPOPO underwent metal-free and solvent-free 1,3-dipolar cycloaddition reaction with azidated soybean oil (AzSBO) at different alkyne/azide molar ratios. The gel contents of the cured polymers were higher than 95% and the char yields of polymers at 850 °C were over 16.4%. DMA analysis showed that the glass transition temperatures were over 45.9 °C. The cured polymers showed high dielectric constant and dielectric loss due to their high polarity.
- Guo, Gang,Sun, Jian,Zhao, Chen,Liu, Yun,Liu, Cheng-Mei
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- Phosphorus-containing polymers from tetrakis-(hydroxymethyl)phosphonium sulfate iii. A new hydrolysis-resistant tris(allyloxymethyl)phosphine oxide and its thiol-ene reaction under ultraviolet irradiation
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Two kinds of new phosphorus-containing crosslinked polymer materials were prepared via thiol-ene photopolymerization and their properties were studied. In order to prepare these crosslinked polymer materials, multifunctional monomer tris(allyloxymethyl)phosphine oxide (TAOPO) was synthesized from an eco-friendly raw material, tetrakis(hydroxymethyl) phosphonium sulfate (THPS). Crosslinked poly(phosphine oxide) networks were then produced by a thiol-ene reaction in which TAOPO reacts with the two kinds of polythiol under ultraviolet (UV) irradiation. The new crosslinked polymers possess long-term hydrolysis-resistance property because the monomer TAOPO contains a phosphorus-carbon bond. The crosslinked polymers have a high gel content, high dielectric constant, low dielectric loss, and excellent transparency with a high refractive index and high Abbe number. DMA and TGA results indicated that all cured poly(phosphine oxide) were uniform networks and exhibited a high thermal stability. This journal is
- Tan, Zhiwei,Wu, Chengyan,Zhang, Min,Lv, Wenzhong,Qiu, Jinjun,Liu, Chengmei
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- Synthesis method of tris (hydroxymethyl) phosphine oxide
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The method comprises the following steps: taking tetramethyl phosphonium chloride as a raw material, adding an alkali solution and heating to carry out reaction, and carrying out desalination and purification on the product by using an organic solvent to obtain the refined tris (hydroxymethyl) phosphine oxide. The reaction is simple in synthesis process, mild in reaction condition and high in yield. A byproduct is sodium chloride and methanol, the solvent used in the refining process can be recycled, and the whole process is green, environment-friendly and pollution-free. Trimethylol phosphine oxide is flame retardant. At present, the halogen-free compound can be used as a solvent, a raw material for synthesizing polyether polyol and a drug intermediate, and is applied to various fields such as polyurethane rigid foam insulation board flame retardation, polyurethane adhesive flame retardation and the like.
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Paragraph 0015-0019
(2021/09/26)
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- STABLE MODIFIED POLYMER POLYOL DISPERSIONS
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The present invention relates to new stable modified polymer polyol dispersions. The modified polymer polyols of the present invention comprise at least one polyol and a stable dispersion of polymeric particles in the at least one polyol. There are also disclosed processes for the preparation of the herein described modified polymer polyols, and processes for preparing polyurethane materials containing them.
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Paragraph 0340-0341; 0352-0353
(2021/06/26)
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- Synthesis of monophosphines directly from white phosphorus
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Monophosphorus compounds are of enormous industrial importance due to the crucial roles they play in applications such as pharmaceuticals, photoinitiators and ligands for catalysis, among many others. White phosphorus (P4) is the key starting material for the preparation of all such chemicals. However, current production depends on indirect and inefficient, multi-step procedures. Here, we report a simple, effective ‘one-pot’ synthesis of a wide range of organic and inorganic monophosphorus species directly from P4. Reduction of P4 using tri-n-butyltin hydride and subsequent treatment with various electrophiles affords compounds that are of key importance for the chemical industry, and it requires only mild conditions and inexpensive, easily handled reagents. Crucially, we also demonstrate facile and efficient recycling and ultimately catalytic use of the tributyltin reagent, thereby avoiding the formation of substantial Sn-containing waste. Accessible, industrially relevant products include the fumigant PH3, the reducing agent hypophosphorous acid and the flame-retardant precursor tetrakis(hydroxymethyl)phosphonium chloride. [Figure not available: see fulltext.]
- Scott, Daniel J.,Cammarata, Jose,Schimpf, Maximilian,Wolf, Robert
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p. 458 - 464
(2021/04/09)
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- RAPAMYCIN ANALOGS AND USES THEREOF
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The present invention provides compounds, compositions thereof, and methods of using the same.
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Paragraph 00417-00418
(2020/01/08)
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- A three hydroxymethyl phosphine oxide of the high-pressure oxidation synthetic process and apparatus
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The invention relates to a high-pressure oxidation synthesis process and device of tris (hydroxymethyl) phosphine oxide (THPO), wherein the production process comprises the following steps: adding an organic solvent and paraformaldehyde into a high-pressure reaction kettle, introducing nitrogen for protection, stirring, increasing the temperature to 60-100 DEG C, introducing PH3 gas for pressurization, maintaining the pressure in the kettle at 3.0-5.0MPa, reacting for 1-3h, and then reducing the pressure and the temperature to normal pressure and normal temperature; totally transferring materials into an oxidation kettle, adding an oxidant, increasing the temperature to 30-120 DEG C, stirring, reacting for 3-6h, and reducing the temperature to room temperature; and filtering the materials by a filter, transferring a filtrate into a desolventizing kettle, performing reduced pressure distillation at the desolventizing temperature of 55-85 DEG C till the moisture content in the materials is less than 2%, and transferring the materials into a finished product tank. The process provided by the invention has the advantages of simple route, few process steps and low operation strength; no catalyst is used and the production cost is low; a byproduct, namely PH3 in the production of sodium hypophosphite is comprehensively utilized; the process has no environmental pollution and is environment-friendly.
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Paragraph 0023; 0024
(2016/10/08)
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- A three hydroxymethyl phosphine oxide of the process and apparatus for catalytic oxidation synthesis
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The invention relates to a synthesis process and equipment of THPO through catalytic oxidation. The synthesis process comprises the steps as follows: PH3 gas and formaldehyde gas are processed through a dryer and a filter and are fed into a fluidized bed through a fan; dry nitrogen is fed into the fluidized bed to protect the PH3 gas and the formaldehyde gas; the PH3 gas and the formaldehyde gas enter a fluidized bed system for reacting, wherein the fluidized bed carries a solid particle catalyst and the reaction temperature is 5 DEG C below zero to 5 DEG C; generated trishydroxymethyl phosphine is heated to be molten into liquid; wherein the temperature of the liquid is 60 to 100 DEG C, liquid THP is transferred into an oxidation kettle; an oxidizing agent is fed into the oxidation kettle, wherein the reaction temperature is 30 to 120 DEG C; the THPO is obtained after stirring for reaction is performed for 3 to 6 h. According to the industrial devices and process routes for producing THPO, the catalyst can be reused, the cost is low, the by-product PH3 produced during the production of sodium hypophosphite is comprehensively utilized, no three-waste is discharged, environment pollution is avoided and the national policy of green and environment protection and the strategy of sustainable development are met.
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Paragraph 0031-0034
(2017/03/08)
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- Polymerization behaviour of butyl bis(hydroxymethyl)phosphine oxide: Phosphorus containing polyethers for Li-ion conductivity
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Synthesis of phosphorus containing polyethers and their lithium-ion conductivities for the potential use as solid polymer electrolyte (SPE) in high-energy density lithium-ion batteries have been described. Co-polymerization of butyl bis(hydroxymethyl)phosphine oxide with three different dibromo monomers were carried out to produce three novel phosphorous containing polyethers (P1-P3). These polymers were obtained via nucleophilic substitution reactions and were characterized by 1H, 31P NMR spectral data and gel permeation chromatography. SPEs were prepared using polyethers (P1 and P2) with various amounts of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The lithium-ion conductivity of SPE2 containing 40 wt% of LiTFSI was 2.1 × 10-5 S cm-1 at room temperature and 3.7 × 10-4 S cm-1 at 80°C. [Figure not available: see fulltext.]
- Babu, Heeralal Vignesh,Srinivas, Billakanti,Kumar Naik, Khevath Praveen,Muralidharan, Krishnamurthi
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p. 635 - 641
(2015/06/17)
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- The Synthesis of 2,6,7-Trioxa-1,4-diphosphabicyclo[2.2.2]octane Revisited: The Synthesis of 2,6,7-Triphenyl-2N,6N,7N-triaza-1,4-diphosphabicyclo[2.2.2]octane and the Synthesis of 1λ5-Phosphiranol
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We report herein a reliable synthesis of P(OCH2)3P in a study aimed at understanding the factors that control its formation. We also report the serendipitous synthesis of the novel phosphiranol (CH2)2PO2H and the synthesis of P(PhNCH2)3P in good yield.
- Kisanga, Philip,Verkade, John
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p. 114 - 117
(2007/10/03)
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- Facile and general synthesis of polyphosphane polyoxides with (O)PCP(O) linkages
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Polyphosphane polyoxides with (O)PCP(O) linkages are powerful chelating agents for extraction of actinides from nuclear wastes. They are obtained either by the Michaelis-Arbuzov reaction of chloromethylphosphane oxides and phosphorus(III) esters, or by the reaction of phosphane oxide carbanions with chlorophosphanes. With the latter method, the addition of a phosphane oxide carbanion in excess allowed us to overcome a transmetallation reaction and thereby obtain polyphosphane polyoxides in good yields. The 1H-NMR spectra of the PCH2P groups show the influence of the different R groups attached to the phosphorus atoms. We determined the coupling constants and the chemical shifts of these spin systems.
- Cristau, Henri-Jean,Virieux, David,Mouchet, Patrick,Fruchier, Alain
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p. 1561 - 1569
(2007/10/03)
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- NOVEL HIGH-YIELD TRANSESTERIFICATION AND TRANSAMINATION ROUTES TO P(OCH2)3CCH3 AND P3CCH3, RESPECTIVELY
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High yields (93-96percent) in a one-step syntheses of CH3C(CH2OP(o-O2C6H4))3 (3), (4) and (5) are reported.Compounds 4 and 5 at 100-110o give P(OCH2)3CCH3 (2) and P(N(CH3)CH2)3CCH3 (7) in 97 and 96percent yield, respectively, plus the diphosphite (CH3)2C(CH2O)2POCH2C(CH3)2CH2OP(OCH2)2C(CH3)2 (8).Compound 8 was also characterized as its dithiophosphate derivative.Experiments designed to synthesize the adamantane-like P(OCH)3(CH2)3 (9) and P(CH2O)3P (10) in an analogous manner met with only partial success.The tris-phosphate analogue of 4 was also synthesized but it did not thermolyze to OP(OCH2)3CCH3 under the conditions used for 4 and 5 even after prolonged heating.
- Volcko, E. J.,Verkade, J. G.
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p. 111 - 118
(2007/10/02)
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