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植酸脒基脲的合成及其对木材的阻燃

郑书清 张益 穆佳鑫 王永娟 王奉强 张志军

郑书清, 张益, 穆佳鑫, 等. 植酸脒基脲的合成及其对木材的阻燃[J]. 复合材料学报, 2024, 42(0): 1-15.
引用本文: 郑书清, 张益, 穆佳鑫, 等. 植酸脒基脲的合成及其对木材的阻燃[J]. 复合材料学报, 2024, 42(0): 1-15.
ZHENG Shuqing, ZHANG Yi, MU Jiaxin, et al. Preparation of amidinourea phytate and its flame retardant effect on wood[J]. Acta Materiae Compositae Sinica.
Citation: ZHENG Shuqing, ZHANG Yi, MU Jiaxin, et al. Preparation of amidinourea phytate and its flame retardant effect on wood[J]. Acta Materiae Compositae Sinica.

植酸脒基脲的合成及其对木材的阻燃

基金项目: 国家自然科学基金 (31890773, 31670570)
详细信息
    通讯作者:

    张志军,博士,副教授,博士生导师,研究方向为生物质及其复合材料的制备、生物质复合材料热化学转化及材料阻燃E-mail: zzj_1003@163.com

  • 中图分类号: S781.73; TB332

Preparation of amidinourea phytate and its flame retardant effect on wood

Funds: National Natural Science Foundation of China (No. 31890773 and 31670570)
  • 摘要: 植酸(Phytic acid, PA)是一种极具潜力的磷系水性生物基阻燃剂,但其单独处理木材存在PA易流失,燃烧烟释放量大等问题,通过与其他氮、硼系阻燃剂复配,可在一定程度上缓减上述问题。然而,由于PA酸性较强,PA及其复配阻燃剂处理木材时会造成木材降解,进而影响其力学强度。以PA和双氰胺为原料合成了一类新型磷氮阻燃剂——植酸脒基脲(Amidinourea phytate,AUP)。利用FTIR、XRD、XPS及TG等手段对AUP阻燃剂理化特性进行了表征。采用TG、Py-GC/MS、氧指数测定仪、CONE等研究了AUP对杨木的热解及燃烧行为的影响,探究了其阻燃机制。结果表明:AUP阻燃材在较低的增重率(8.73%)下表现出优异的阻燃及抑烟性能,优于增重率为14.8%的PA阻燃材,且抗流失性较好;AUP阻燃材的LOI值为34.8%,较未处理材提高了54.0%;总释热量和总生烟量分别降低了57.7%、65.7%,成炭率提高了148%,残炭结构更为密实,具有凝聚相与气相协效阻燃效果。此外,AUP阻燃材冲击强度比未处理材提高了58.5%,而PA阻燃材则下降了29.2%。

     

  • 图  1  AUP-x的溶解度变化曲线

    Figure  1.  Solubility change curve of AUP-x

    图  2  PA、DCD、AUP- x的FTIR(a)及AUP- x的XRD(b)、XPS C1s(c)/N1s(d)能谱

    Figure  2.  FTIR(a) of PA, DCD, AUP-x, XRD(b) and C1s(c)/N1s(d) of XPS patterns from AUP- x

    图  3  AUP阻燃剂的合成机制

    Figure  3.  Synthesis Mechanism of AUP Flame retardant

    图  4  AUP- x阻燃剂在N2气氛下的热重分析曲线:(a) TG;(b) DTG

    Figure  4.  Thermogravimetric analysis curves of AUP-x in N2 atmosphere: (a) TG; (b) DTG

    图  5  未处理材及AUP阻燃处理材的SEM图像:(a)、(b)为未处理材的横截面;(c)、(d)为AUP处理材的横截面;(e)为AUP处理材的纵切面;(f)为附着在木材内部的AUP阻燃剂分子形貌

    Figure  5.  SEM images of untreated wood and AUP flame retardant treated wood: (a), (b) are cross section of untreated wood; (c), (d) are cross section of AUP treated wood; (e) are longitudinal section of AUP treated wood; (f) are molecular morphology of AUP flame retardant attached to wood.

    图  6  未处理材及抗流失测试前后的PA、AUP阻燃材LOI值

    Figure  6.  LOI values of control, PA/wood and AUP/wood before and after loss resistance test

    图  7  未处理材、PA阻燃材、AUP阻燃材在50 kW/m2下的锥形量热测试结果:(a)热释放速率(HRR);(b)总热释热量(THR);(c)生烟速率(SPR);(d)总烟释放(TSP);(e)CO释放速率(COP);(f)质量损失速率(MLR);

    Figure  7.  Cone calorimetric test results of of control, PA/wood and AUP/wood under 50 kW/m2: (a) HRR; (b) THR;(c) SPR; (d) TSP; (e) COP; (f) MLR

    图  8  未处理材、PA阻燃材、AUP阻燃材分别在N2气氛下的TG(a)、DTG(b)及空气气氛下的TG(c)、DTG(d);

    Figure  8.  Thermogravimetric curves of control, PA/wood, AUP/wood: TG(a) and DTG(b) in N2 atmosphere; TG(c) and DTG(d) in air

    图  9  未处理材、PA阻燃材、AUP阻燃材锥形量热测试后的残炭数码照片及SEM-EDS图像

    Figure  9.  Digital photographs and SEM-EDS images of residual carbon from control, PA/wood and AUP/wood after cone test

    图  10  未处理材、PA阻燃材、AUP阻燃材的总离子流图及各类型气态产物相对含量

    Figure  10.  TIC and relative content of each type of gas product of control, PA/wood and AUP/wood after cone test

    表  1  AUP-x的合成配方

    Table  1.   Formulation of AUP-x

    Ingre-dients DCD/g 60%PA/mL Molar ratio (PA to DCD) H2O/mL pH
    AUP-6 12.6 27.6 1∶6 10.4 3.52
    AUP-9 18.9 27.6 1∶9 21.4 4.34
    AUP-12 25.2 27.6 1∶12 32.1 5.39
    Notes: pH value is tested after reaction at 25℃; AUP—Amidinourea phytate; PA—Phytic acid; DCD—Dicyandia-mide.
    下载: 导出CSV

    表  2  AUP-x的元素原子比

    Table  2.   XPS patterns of AUP-x

    Sample AUP-6 AUP-9 AUP-12
    C /atom% 23.91 25.17 25.34
    O /atom% 38.65 37.02 30.78
    N /atom% 30.36 32.48 38.41
    P /atom% 7.08 5.33 5.47
    下载: 导出CSV

    表  3  抗流失试验相关参数

    Table  3.   Parameters related to erosion resistance test

    Sample ε/% y1 y2 I/%
    PA/wood −53.94 68.53±3.49 15.73±1.65 22.89±1.35
    AUP/wood −1.36 41.65±0.67 35.55±0.52 85.36±1.09
    Notes: ε indicates the moisture absorption rate of the flame retardant material; y1, y2 indicates the amount of drug load before and after the anti-erosion test; I indicates the loss resistance of the flame retardant.
    下载: 导出CSV

    表  4  未处理材、PA阻燃材、AUP阻燃材的力学性能

    Table  4.   Mechanical properties of Control, PA/wood and AUP/wood

    Sample Flexural strength/MPa Flexural modulus/GPa Impact strength/(kJ·m−2)
    Control 122.68±0.16 11.31±0.08 19.92±0.29
    PA/wood 91.65±0.21 10.69±0.11 14.10±0.12
    AUP/wood 113.18±0.07 10.81±0.07 31.58±0.25
    下载: 导出CSV

    表  5  未处理材、PA阻燃材、AUP阻燃材的锥形量热测试参数

    Table  5.   Cone calorimetric test parameters of control, PA/wood and AUP/wood

    Sample Pk1-HRR/
    (kW·m−2)
    Pk2-HRR/
    (kW·m−2)
    THR/
    (MJ·m−2)
    Av-EHC/
    (MJ·kg−1)
    TSP/
    (m2·m−2)
    Av-COY/
    (MJ·kg−1)
    TTI/s FPI/
    (s·m2·k−1)
    Char yield/
    (%)
    B-W A-W B-W A-W B-W A-W
    Control 161.9 201.7 58.2 12.4 3.5 0.026 31 0.154 13.5
    PA/wood 104.9 139.1 129.2 165.1 39.0 49.9 9.8 3.6 0.035 19 0.147 19.4
    AUP/wood 36.3 42.9 82.1 77.1 20.0 21.4 5.7 1.2 0.041 55 0.670 33.5
    Notes: B-W refers to before the loss resistance test; A-W refers to after the loss resistance test; Pk-HRR was the peak values of HRR with time; THR was the total heat release; Av-EHC was the average effective heat of combustion; TSP was the total smoke release; Av-COY was the average CO production; TTI was the was the time from when the cone shutter opened, exposing the sample to the set heat flux, to the moment flaming was established; FPI indicates fire performance index; Char yield was the carbon residue ratio.
    下载: 导出CSV

    表  6  未处理材、PA阻燃材和AUP阻燃材的热重特征参数

    Table  6.   Thermogravimetric parameters of control, PA/wood and AUP/wood

    Sample Atmosphere T5wt%/℃ T10wt%/℃ T50wt%/℃ Tmax/℃ W800℃/%
    Control N2 240 300 353 362 10.9
    Air 264 293 369 372 0.1
    PA/wood N2 72 194 288 264 27.9
    Air 183 233 377 298 17.2
    AUP/wood N2 200 252 322 294 29.5
    Air 213 274 369 306 16.8
    Notes: The data in the table are obtained under nitrogen and air atmosphere. T5wt% refers to the temperature at 5% weight loss; T10wt% refers to the temperature at 10% weight loss; T50wt% refers to the temperature at 50% weight loss; Tmax refers to the temperature at which the rate of heat loss is maximized; W800℃ refers to the residual rate of the sample at 800℃.
    下载: 导出CSV
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出版历程
  • 收稿日期:  2024-02-27
  • 修回日期:  2024-04-16
  • 录用日期:  2024-04-20
  • 网络出版日期:  2024-05-22

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