Page 205 - 《精细化工》2021年第9期

第 9 期 张 继，等: 低聚羟丙基磷酸乙酯阻燃剂的合成及应用 ·1919·

响见表 9。 阻燃剂的添加提高了 RPUF 热分解后的残炭
如表 9 所示，阻燃剂的添加提高了材料的阻燃 量，当阻燃剂添加量为 10%时残炭量较未添加时提
性能。当阻燃剂添加量为 10%时，便可明显改善材 高了 12.8%；当阻燃剂添加量为 30%（磷含量为
料轰燃及熔滴情况；当阻燃剂添加量为 30%时，材 1.76%）时，RPUF-3 的 LOI 值为 27.1%，UL-94 测
料极限氧指数达 27.1%，垂直燃烧达 V-0 级别，属 试达 V-0 级。阻燃剂的添加使 RPUF 的机械性能有
于难燃材料。此时材料的弯曲强度有明显下降，可 所降低，但仍在较高水平，满足使用要求。该低聚
能由于阻燃剂的大量添加增加了与异氰酸酯基团反 羟烷基磷酸酯具有高磷含量、含活性基团羟基、阻
应的空间位阻，导致体系的交联度降低，黏度降低， 燃效率高，有望替代三氯丙基磷酸酯（TCPP）等添
泡孔增大，材料密度也随之下降，但仍符合材料的 加型阻燃剂用于改性 RPUF，实现更持久更环保高
基本使用要求。且与现有研究的含磷多元醇阻燃剂 效的阻燃。
或添加型阻燃剂相比（表 10），合成的低聚羟丙基
参考文献：
磷酸乙酯具有较明显的阻燃优势。
[1] LIU L, WANG Z Z, ZHU M H. Flame retardant, mechanical and
表 9 阻燃剂添加量对材料机械性能及阻燃性能的影响 thermal insulating properties of rigid polyurethane foam modified by
nano zirconium amino-tris-(methylenephosphonate) and expandable
Table 9 Effect of adding amount of flame retardant on graphite[J]. Polymer Degradation and Stability, 2019, 170: 108997.
mechanical properties and flame retardant properties [2] JIA F C (贾丰春), BAI Z Q (白志强). Application of high efficiency
of materials and energy saving polyurethane foam in exterior wall insulation[J].
拉伸强度 弯曲强度 密度 Synthetic Resins and Plastics (合成树脂及塑料), 2015, 32(4):
样品 3 LOI/% UL-94 100-102.
/kPa /kPa /(kg/m )
[3] CHOE H, CHOI Y, KIM J H. Threshold cell diameter for high
RPUF-0 143.6 141.5 57.6 18.9 HB
thermal insulation of water-blown rigid polyurethane foams[J].
RPUF-1 143.7 135.7 58.7 21.2 V-2 Journal of Industrial and Engineering Chemistry, 2019, 73: 344-350.
RPUF-2 144.6 133.4 58.9 24.2 V-1 [4] AYDIN A A, OKUTAN H. Polyurethane rigid foam composites
incorporated with fatty acid ester-based phase change material[J].
RPUF-3 142.1 134.6 56.7 27.1 V-0 Energy Conversion and Management, 2013, 68: 74-81.
RPUF-4 140.6 133.2 55.1 28.9 V-0 [5] JELLE B P. Traditional, state-of-the-art and future thermal building
insulation materials and solutions—Properties, requirements and
RPUF-5 137.6 132.1 54.2 29.1 V-0
possibilities[J]. Energy Build Energy and Buildings, 2011. 43(10):
2549-2563.
表 10 不同阻燃剂对材料阻燃性能的影响 [6] ZHANG A Z, ZHANG Y H, LYU F Z, et al. Synergistic effects of
Table 10 Effect of different flame retardants on flame hydroxides and dimethyl methylphosphonate on rigid halogen-free
retardant properties of materials and flame-retarding polyurethane foams[J]. Journal of Applied
Polymer Science, 2013, 128(1): 347-353.
阻燃剂 添加量/% UL-94 LOI/%
[7] CHEN L M (陈立明), LIU L (刘李), CAI J K (蔡建坤), et al. Effect
OHPEP 30 V-0 27.1 of halogen-free flame retardants on the combustion properties of
PPGE [13] 30 V-1 24.5 polyurethane rigid foams[C]//Academic Meeting of China Fire
Protection Association Fire Protection Material Branch and Building
[10]
THPO 30 NR 23.0
Fire Protection Professional Committee, 2012.
OP550 [26] 30 – 23.0 [8] LIU W (刘伟). Effect of compound flame retardant on flame
ENGP [27] 30 V-2 22.5 retardant properties of rigid polyurethane foam[J]. Engineering
Plastics Application (工程塑料应用), 2016, 44(6): 110-113.
EG [28] 30 – 25.5
[9] ZHANG M (张猛), ZHOU Y H (周永红). Study on Preparation and
MCA [29] 30 V-1 22.0 properties of structural flame retardant bio-based polyurethane
foams[J]. China Flame Retardant (中国阻燃), 2016, (3): 2-6.
注：PPGE 为低聚苯基磷酰乙二醇醚；OP550 为聚磷酸酯
[10] LUO Y F, MIAO Z N, SUN T, et al. Preparation and mechanism
多元醇；ENGP 为磷酸乙基新戊二醇酯；EG 为可膨胀石墨；MCA
study of intrinsic hard segment flame-retardant polyurethane foam[J].
为三聚氰胺氰尿酸盐；–表示没有该项数据。 Journal of Applied Polymer Science, 2021, 138(9): 49920.
[11] YUAN Y, YANG H Y, SHI Y Q, et al. Phosphorus and
3 结论 nitrogen-containing polyols: Synergistic effect on the thermal
property and flame retardancy of rigid polyurethane foam
composites[J]. Industrial & Engineering Chemistry Research, 2016,
以 P 2 O 5 、TEP、磷酸（质量分数 85%）、水和
55(41): 10813-10822.
PO 为原料，PO 与中间体Ⅱ开环反应采取分段式， [12] NING L (宁磊), GUO L (郭来), WANG D (王栋), et al. Synthesis of
先低温滴加后升温加压反应制备低聚羟丙基磷酸乙 a reactive flame retardant containing phosphorus and its flame
retardancy to polyurethane[J]. New Chemical Materials (化工新型材
酯。得到的最佳工艺条件为：PO 与中间体Ⅱ的质量 料), 2015, 43(1): 159-162.
比为 0.67∶1.0，PO 滴加温度为 15 ℃，反应体系压 [13] WU N J, NIU F K, LANG W H, et al. Synthesis of reactive
phenylphosphoryl glycol ether oligomer and improved flame
力为 0.5 MPa，反应温度为 70 ℃，反应时间为 1.5 h。 retardancy and mechanical property of modified rigid polyurethane
在此条件下制备的产品酸值为 0.6 mg KOH/g，羟值 foams[J]. Materials & Design, 2019, 181: 1-10.
135 mg KOH/g，磷含量为 16.3%。 （下转第 1927 页）