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以六氯环三聚磷腈为原料通过真空热开环聚合制得线型聚二氯磷腈(PDCP),再通过对PDCP进行亲核取代合成制备了新的聚膦腈类高分子——聚[(四氟丙氧基)2-x(三氟乙氧基)x]膦腈,聚合物经过四氢呋喃-苯反复溶解-沉淀得到纯化产物.通过31P-NMR、1H-NMR和FTIR对其结构进行了表征;DSC法测定其玻璃化转变温度Tg;,GPC测定了分子量,XRD测定其结晶度,压力法透气性能测定仪测定了聚合物膜对N2、O2、CH4、CO2、He、H2等气体的透过性能.测试结果表明,得到x值分别为1.53、1.86、1.75和0的4种聚[(四氟丙氧基)2-x(三氟乙氧基)x]膦腈;其玻璃化温度Tg为-45.2℃、-45.2℃、-50.3℃和-32.3℃;重均分子量为1.2×105、5.6×105、2.6×105和6.0×105;两种取代基比例适中时显示出较高的气体透过性能,取代比例x为1.53的聚合物PH2=55 barrer,PCO2=75 barrer,PHe=40 barrer,PO2=15 barrer,H2/N2选择系数达到11.7,在合成NH3尾气中回收H2存在发展前景;O2/N2的选择系数达3.1,是一种很有希望的富氧材料.
A novel polyphosphazene polymer (PDCP) was synthesized by vacuum thermal ring-opening polymerization using hexachlorocyclotriphosphazene as a starting material. Then, a new polyphosphazene polymer- Poly [(tetrafluoropropoxy) 2-x (trifluoroethoxy) x] phosphazene was obtained by repeated dissolution-precipitation of the polymer through tetrahydrofuran-benzene to obtain the purified product. The product was characterized by 31P-NMR, 1H-NMR and FTIR The structure of the polymer was characterized by DSC; the glass transition temperature (Tg) was measured by DSC; the molecular weight was determined by GPC; the crystallinity was measured by XRD; the permeability of the polymer membrane was measured by N2-O2, CH4, CO2, He, H2 Etc. The results showed that four poly [(tetrafluoropropoxy) 2-x (trifluoroethoxy) x] phosphazenes with x values of 1.53, 1.86, 1.75 and 0 were obtained respectively. The glass transition temperature Tg is -45.2 ° C., -45.2 ° C., -50.3 ° C. and -32.3 ° C. The weight average molecular weights are 1.2 × 10 5, 5.6 × 10 5, 2.6 × 10 5 and 6.0 × 10 5, respectively. A higher gas permeation performance was achieved in place of the polymer with a ratio x of 1.53 of PH2 = 55 barrer, PCO2 = 75 barrer, PHe = 40 barrer, PO2 = 15 barrer and H2 / N2 selectivity of 11.7. Recycle H2 In the development prospects; coefficient selecting O2 / N2 up to 3.1, is a promising oxygen-rich material.