Fireproofing of polyurethane elastomers by reactive organophosphonates

Khatib, Wassef El; Youssef, B.; Bunel, Claude; Mortaigne, B.

doi:10.1002/pi.1009

Cited by 50 publications

(36 citation statements)

References 19 publications

(22 reference statements)

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“…[22,23,26] They first showed the possibility of adding thiols to nearly all the double bonds, by using aliphatic thiols. In later studies, many functionalising thiols were used with HTPBs to obtain improvement of the mechanical properties of the final polyurethane (MTPS, [36,37] TGA, [38,39] fluorinated thiols [40,41] ) or its fireproofing (phosphonated thiols [17,37,42] ). In all the investigated systems, experimental data confirmed both the previous reactivity trend of the PB constitutive units and the anti-Markovnikov selectivity of the reaction.…”

Section: Introductionmentioning

confidence: 99%

Thiol‐Ene Radical Addition of L‐Cysteine Derivatives to Low Molecular Weight Polybutadiene

Lotti

Coiai

Ciardelli

et al. 2009

Macro Chemistry & Physics

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The functionalisation of a low molecular weight, liquid 1,2‐polybutadiene (PBL) was performed by the addition of either N‐acetyl‐L‐cysteine or its methyl ester through the thiol‐ene radical reaction. The functionalisation runs were carried out in 1,4‐dioxane solution and in the presence of a free radical initiator (2,2′‐azobisisobutyrronitrile, AIBN). The initial feed ratio polymer/cysteine derivative/initiator was varied, in order to highlight the occurrence of side reactions and to understand their possible influence on the process. The 1H NMR determination of the functionalisation degree brought out high addition degrees of thiols, regardless of the initial thiol/double bonds ratio. This caused a drastic change in the macroscopic properties of the PBL with improved solubility in hydrophilic solvents (for instance in alkaline aqueous solutions) and impressive increase of the glass transition temperature. The propagation of chiral properties from the functionalising agents to the modified polymers was evaluated by polarimetry and circular dichroism in solution.magnified image

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Section: Introductionmentioning

confidence: 99%

Thiol‐Ene Radical Addition of L‐Cysteine Derivatives to Low Molecular Weight Polybutadiene

Lotti

Coiai

Ciardelli

et al. 2009

Macro Chemistry & Physics

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“…The reasoning is based on the chemical shifts of the -CH 2 OH and -CHOH of compounds (2) [24] or its analogue, [23] and -CH 2 OCO-and -CHOCO-after esterification. For compounds (2), the 1 H NMR shows two multiplets (3.4-3.7 ppm) for CH 2 OH and a multiplet (3.95-4.15 ppm) for CHOH.…”

Section: Resultsmentioning

confidence: 99%

New Phosphonated Methacrylates: Synthesis, Photocuring and Study of their Thermal and Flame‐Retardant Properties

Youssef¹,

Lecamp²,

Khatib³

et al. 2003

Macro Chemistry & Physics

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In this work, a new methacrylate phosphonate monomer synthesis was described according to two routes: firstly, by condensation of methacrylic acid with a phosphonate epoxide and secondly by an esterification between methacryloyl chloride and a phosphonate diol. The photoinduced polymerization of this new monomer was studied as a function of reaction temperature. The optimal conversion of the photopolymerization was 81% for temperatures below 60 °C. Above 60 °C, the existence of a thermal polymerization leads to a decrease in the apparent photochemical yield. This new monomer is less reactive than the commercial dimethacrylate polyether of Bisphenol A we have used for copolymerization. Mechanical and thermal properties of the final copolymers were studied as a function of methacrylate phosphonate monomer content. Tg of the copolymers reaches a maximum when the phosphorus content is about 2%. The addition of phosphorus leads to an improvement of the thermal and flame‐retardant properties. Thus, addition of 2% phosphorus allows us to decrease the degradation rate, to increase the amount of remaining residue after combustion up to 12%, and finally to increase the Limiting Oxygen Index (LOI) from 16.8 (0% P) to 21.4 (2% P).

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“…None or quite modest improvement was gained with PA C H T U N G T R E N N U N G (C 6 F 5 ) 3 or PA C H T U N G T R E N N U N G (n-Bu) 3 (entries 6 and 7). On the other hand, addition of the bulky, basic tricyclohexylphosphine to Wilkinsons complex generated a highly active and productive catalyst (entries 8-11).…”

Section: Catalytic Hydrophosphorylationmentioning

confidence: 99%

“…Dienes 1 and 5 and HP(O)A C H T U N G T R E N N U N G (OMe) 2 (all purchased from Aldrich) were dried by standard methods and distilled before use. Ligands [PPh 3 , PCy 3 , PA C H T U N G T R E N N U N G (C 6 F 5 ) 3 , PA C H T U N G T R E N N U N G (n-Bu) 3 , dppb, dpph, dchpb] and com-…”

Section: Experimental Section General Conditionsmentioning

confidence: 99%

“…[2] Also, they can bring special properties to materials, e.g., as flame-retardants in polymers. [3] The traditional method for the preparation of organophosphonates consists in the Arbuzov reaction of phosphites with organic halides. [4] Hydrophosphorylation of alkenes provides a much more atom-economic route toward organophosphonates and usually takes place under relatively mild conditions.…”

Section: Introductionmentioning

confidence: 99%

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Efficient and Selective Rhodium‐Catalyzed Hydrophosphorylation of Dienes

2006

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Abstract:The hydrophosphorylation of a model 1,6-diene having a terminal and an internal alkene function has been investigated. Free radical protocols lead invariably to mixtures of cyclic phosphonate products, due to rapid cyclization of the intermediary radical species. Rhodium catalysis using a cyclic pinacol-derived phosphonate provides an efficient technique for the highly selective (> 99 %) hydrophosphorylation at the terminal alkene function. In situ modification of Wilkinsons complex by addition of 2-50 equivalents (vs. Rh) of a monophosphine (PCy 3 > PPh 3 ) or carbene ligand greatly improves the catalyst performances (TON up to 2250 mol phosphonate/mol Rh). An even more efficient system was obtained with 2 equivalents (vs. Rh) of the bidentate 1,6-bis(diphenylphosphino)hexane ligand, which affords so far unprecedented high catalytic productivity (TON up to 4 550 mol phosphonate/mol Rh) and activity (TOF up to 250 h À1 ).

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Fireproofing of polyurethane elastomers by reactive organophosphonates

Cited by 50 publications

References 19 publications

Thiol‐Ene Radical Addition of L‐Cysteine Derivatives to Low Molecular Weight Polybutadiene

Thiol‐Ene Radical Addition of L‐Cysteine Derivatives to Low Molecular Weight Polybutadiene

New Phosphonated Methacrylates: Synthesis, Photocuring and Study of their Thermal and Flame‐Retardant Properties

Efficient and Selective Rhodium‐Catalyzed Hydrophosphorylation of Dienes

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