Study On Synthesis And Properties Of Novel Structure Phosphorus-containing Polyester-polyurethane

The phosphorus-containing polyurethane is the introduction of phosphorus into thepolyurethane material. Compared to non-phosphorus polyurethane material, Thephosphorus-containing polyurethane have attracted tremendous attention to scientists inBiological, architectural and other fields, due to their unique properties, such asbiocompatibility, hydrophilicity, and flame resistance.In this paper, a novel phosphorus-containing polyester polyol was synthesized byusing2-phosphonic acid-1,2,4-three carboxylic acid butane (PBTCA) as phosphorusmonomer and the PPhDH was synthesized as a novel containing phosphorus chainextender, structure phosphorus-containing polyester-polyurethane was synthesized byusing the polyester polyol containing phosphorus as the soft segment. Structurephosphorus-containing polyester-polyurethane were characterized and analyzed by fouriertransform infrared spectra (FTIR), thermal gravimetric analysis (TGA), differentialscanning calorimetry (DSC) and the limiting oxygen index (LOI) and so on. The mainresearch work contents include the following aspects:1) Study on esterification reactivity of PBTCA: The esterification of PBTCA wasinvestigated with different small molecules primary alcohols by the change of acid value(Av), FTIR, and phosphorus nuclear magnetic resonance (31P NMR). The results indicatedthat there were only three types of phosphorus-containing esters formed in theesterification reaction system of PBTCA and anyone of small molecules primary alcohols.The results also showed one of hydroxyl group in the phosphonic group firstly reacted, andthen the1,4carboxylic acid groups.2) The preparation of a novel phosphorus-containing polyester polyol: The novelphosphorus-containing polyester polyol was synthesized by using adipic acid, glycol andPBTCA as raw materials. The product was characterized by FTIR,13C NMR, themeasurement of hydroxyl value, and gel permeation chromatography (GPC). The resultsindicated that above characterizations are in good agreement with the chemical structure.The hydroxy-terminated product was synthesized when the mole rate of alcohol and acid is1:6. Three phosphorus-containing polyesters were synthesized by keeping the molar ratioof constant, and changing the content of PBTCA.3) The preparation of a novel phosphorus-containing chain extender PPhDH: The novelphosphorus diol chain extender PPhDH was synthesized by three steps. The chemical structure was characterized by FTIR,1H NMR and31P NMR. The results indicated thatabove characterizations are in good agreement with the chemical structure of PPhDH.4) Study on synthesis and properties of structure phosphorus-containing polyester-polyurethane: With phosphorus-containing polyester polyols as soft segment, the softsegment phosphorus-containing polyurethane, the soft and hard segment phosphorus-containing polyurethane, the soft and hard segment and flame retardant both containingphosphorus-containing polyurethane were synthesized respectively. The results indicatedthat in the heating process, the lower bond energy C-P breaking first, lower thermalstability of the polyurethane, it can improve the flame retardant of polyurethane; Thepolyurethane char yield of the phosphorus content of1.53%of the soft segmentphosphorus-containing polyurethane of14.8%higher than polyurethane that not containingphosphorus of2.6%, the oxygen index of phosphorus-containing polyurethane of25.0%also higher than polyurethane that not containing phosphorus of17.9%; Introdution ofphosphorus in the polyurethane can increase the amount of the surface tension, the tensileproperties of the polyurethane has little effect; Introdution of phosphorus in thepolyurethane, the char yield and oxygen index of the soft segment phosphorus-containingpolyurethane superior to the hard segment phosphorus-containing polyurethane; Inpolyurethane material, the flame retardant of structure phosphorus-containing polyurethaneexcellent than additive phosphorus-containing polyurethane.