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第 4 期                           徐   洋,等:  三(2-羟丙基)磷酸酯的合成                                 ·775·


            2.2.5    热重分析                                          flame-retardant application[J]. Fine Chemicals (精细化工), 2015,
                 对产品进行热重分析,氮气流速 100 mL/min,                        32(4): 457-460.
                                                               [2]   Babrauskas  V,  Lucas  D,  Eisenberg  D,  et al.  Flame  retardants  in
            升温速率 5 ℃/min,结果见图 6。从图 6 可以看出,                         building  insulation  a  case  for  re-evaluating  building  codes[J].
            产品的热分解大致分为 4 个阶段。第一阶段为                                 Building Research & Information, 2012, 40(6) 738-755.
                                                               [3]   Zhang Zhonghou (张忠厚), Wang Yintao (王银涛), Yang Guang (杨
            20~150 ℃,这个阶段失重主要是由于产品中少量的
                                                                   光),  et al.  Study  on  the  properties  of  composite  flame  retardant
            水分挥发引起;第二阶段为 150~250 ℃,失重是由                            flame-retardant  rigid  polyurethane  foam[J].  Engineering  Plastics
            于分子中较多不稳定的 P—O—C 断裂所致;第三阶                              Application (工程塑料应用), 2014, 42(1): 16-19.
                                                               [4]   Wang  L,  He  X,  Wilkie  C  A.  The  utility  of  nanocomposites  in fire
            段为 250~600 ℃,失重主要是因为进一步炭化所致                [16] ;
                                                                   retardancy[J]. Materials, 2010, 3(9): 4580-4606.
            第四阶段为 600~700 ℃,此时失重幅度较小。DTA                       [5]   Zhang A, Zhang Y, Lv F, et al. Synergistic effects of hydroxides and
            曲线在 249 ℃左右有一个放热峰,对应于 P—O—C                            dimethyl  methylphosphonate  on  rigid  halogen-free  and  flame-
                                                                   retarding  polyurethane  foams[J].  Journal  of  Applied  Polymer
            键断裂分解放热并伴随失重。600 ℃时,产品的残                               Science, 2013, 128(1): 347-353.
            炭率为 16.66%,比一般的磷系阻燃剂高               [17] 。所以,      [6]   Pan H, Wang W, Pan Y, et al. Formation of layer-by-layer assembled
            产品具有很好的热稳定性。                                           titanate nanotubes filled coating on flexible polyurethane foam with
                                                                   improved flame retardant and smoke suppression properties[J]. ACS
                                                                   Applied Materials & Interfaces, 2014, 7(1): 101-111.
                                                               [7]   Wu D, Zhao P, Liu Y. Flame retardant property of novel intumescent
                                                                   flame retardant rigid polyurethane foams[J]. Polymer Engineering &
                                                                   Science, 2013, 53(11): 2478-2485.
                                                               [8]   Zhang  L,  Zhang  M,  Hu  L,  et al.  Synthesis  of  rigid  polyurethane
                                                                   foams  with  castor  oil-based  flame  retardant  polyols[J].  Industrial
                                                                   Crops and Products, 2014, 52: 380-388.
                                                               [9]   Lin H, Yan H, Liu B, et al. The influence of KH-550 on properties of
                                                                   ammonium  polyphosphate  and  polypropylene  flame  retardant
                                                                   composites[J]. Polymer Degradation & Stability, 2011, 96(7): 1382-
                                                                   1388.
                                                               [10]  Chen M J, Shao Z B, Wang X L, et al. Halogen-free flame-retardant
                                                                   flexible polyurethane foam with a novel nitrogen–phosphorus flame

                        图 6    产品的 TG-DTA 曲线                       retardant[J].  Industrial  &  Engineering  Chemistry  Research,  2012,
                                                                   51(29): 9769-9776.
                      Fig. 6    TG-DTA curve of product
                                                               [11]  Liu  W,  Zhang  S,  Chen  X,  et al.  Thermal  behavior  and  fire
                                                                   performance  of  nylon-6,  6  fabric  modified  with  acrylamide  by
            3   结论
                                                                   photografting[J].  Polymer  Degradation  &  Stability,  2010,  95(9):
                                                                   1842-1848.
                 以磷酸、环氧丙烷为原料,在路易斯酸离子液                          [12]  Zhang Xiaoguang (张晓光), Wang Lieping (王列平), Ning Binke (宁
            体催化下合成了三(3-羟丙基)磷酸酯。最佳工艺                                斌科),  et al.  Research  progress  of  halogen-free  flame  retardant
                                                                   technology  for  polyurethane  foams[J].  Chemical  Engineering
            条件为:磷酸、1,2-环氧丙烷的物质的量比为 1.0∶
                                                                   Development (化工进展), 2012, 31(7): 521-1527.
            3.2,反应温度为 90 ℃,反应时间为 3  h,在此条                      [13]  Shiozawa,  Keishin,  Shinsaburo,  et al.  Phosphates  or  phosphites
            件下得到无色半透明液体,收率为 92.8%。产物折                              containing hydroxy groups: JP39030154 [P]. 1962-12-24.
                                                               [14]  Arthue  E,  Robert  A,  Lake  Jackson,  et al.  Process  for  preparing
            光率为 1.4340,酸值为 0.06 mg KOH/g,黏度为 85                    hydroxyalkyl phosphates: US3094549[P]. 1963-06-18.
            mPa·s(25 ℃),磷元素质量分数为 11.5%,羟值为                     [15]  Li Ruxiong (李汝雄), Wang Jianji (王建基). Synthesis and application
            615 mg KOH/g。该合成方法条件温和,原子经济性                           of ionic liquids[J]. Chemical Reagents(化学试剂), 2001, 23(4): 211-
                                                                   215.
            高,由于羟基的存在,三(3-羟丙基)磷酸酯可以                            [16]  Li Magang (李马刚), Li Qifeng (李其峰), Wang Junwei (王军威), et
            作为反应型阻燃剂,其在聚氨酯泡沫中不易析出,                                 al.Preparation of reactive flame retardant THPP and its application in
                                                                   PU rigid foam[J]. Polyurethane Industry (聚氨酯工业), 2015, 30(6):
            效果持久。
                                                                   12-15.
                                                               [17]  Qian Lijun (钱立军), Feng Fafei (冯发飞), Ye Longjian (叶龙健), et
            参考文献:
                                                                   al.  Manufacturing  and  application  of  new  flame  retardants[M].
            [1]   Wang Aihua (王爱华), Yang Xufeng (杨旭峰), Feng Hao (冯昊), et   Beijing:  Chemical  Industry  Press  (北京:  化学工业出版社),  2012:
                 al. One-step preparation of phenylphosphinic acid aluminum and its     129-201.
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