Page 72 - 《精细化工》2022年第2期
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第 39 卷第 2 期                             精   细   化   工                                  Vol.39, No.2
             202 2 年 2 月                             FINE CHEMICALS                                  Feb.  2022


              功能材料
                        一种含磷自修复水性聚氨酯的合成及性能



                                                                       2
                                                          1
                                                                                   1*
                                             1
                                    翟文芮 ,丁善军 ,赵本波 ,罗运军
                      (1.  北京理工大学  材料学院,北京  100081;2.  中北大学  化工学院,山西  太原  030051)
                 摘要:采用异佛尔酮二异氰酸酯、聚丙二醇和 2,2-二羟甲基丙酸为主要原料,以无卤含磷阻燃剂 Exolit OP550
                 (记为 OP550,下同)为软段扩链剂,通过前扩链方式将二羟乙基二硫化物引入到水性聚氨酯(WPU)分子链
                 中,成功制备了兼具阻燃和自修复两种特殊功能的水性聚氨酯(记为 OHWPU)乳液。采用 FTIR 和激光粒度仪
                 对 OHWPU 结构及乳液性能进行了表征,通过热重分析仪、万能试验机、极限氧指数仪及锥形量热仪考察了
                 OP550 对 OHWPU 胶膜热性能及自修复性能的影响。结果表明,OP550 含量为反应物总质量的 20%时,制备的
                 OHWPU-20%胶膜的极限氧指数达到 29.0%,比对应的无 OP550 水性聚氨酯胶膜提高了 7.4%;在 80  ℃,修复
                 时间为 3.0 h 条件下,OHWPU-20%胶膜损伤修复后的拉伸强度为 4.64 MPa,自修复效率达到 107.9%。
                 关键词:水性聚氨酯;阻燃剂;力学性能;自修复;功能材料
                 中图分类号:TQ323.8      文献标识码:A      文章编号:1003-5214 (2022) 02-0276-06


                         Synthesis and characterization of a phosphorus-containing

                                      self-healing waterborne polyurethane

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                                 ZHAI Wenrui , DING Shanjun , ZHAO Benbo , LUO Yunjun
                 (1. School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, China; 2. College of
                 Chemical Engineering and Technology, North University of China, Taiyuan 030051, Shanxi, China)
                 Abstract: Self-healing and flame retardant waterborne polyurethane (OHWPU) emulsions were prepared
                 using isophorone diisocyanate, polypropylene glycol and 2,2-bis(hydroxymethyl)propionic acid as  main
                 raw materials,  halogen-free flame retardant Exolit  OP550 (noted as  OP550, the same below)
                 phosphorus-containing as soft section chain extender, then introducing 2-hydroxyethyl disulfide by forward
                 chain extension. The structure and emulsion properties of OHWPU samples were characterized by FTIR
                 and laser particle size analyzer. The effects of OP550 on the thermal properties and self-healing properties
                 of OHWPU films were investigated by thermogravimetric analyzer, universal testing machine, limit oxygen
                 index tester and cone calorimeter. The result showed that when OP550 content was 20% of the total mass of
                 reactants, the limiting oxygen index of the prepared OHWPU-20% film was 29.0%, 7.4% higher than that
                 of corresponding without OP550 waterborne polyurethane film. The tensile strength of OHWPU-20% film
                 after damage repair was 4.64 MPa and the self-healing efficiency reached 107.9% at 80  ℃  for 3.0 h.
                 Key words:  waterborne  polyurethane; flame retardant;  mechanical properties; self-healing; functional
                 materials


                                                                         [3]
                 自修复聚合物材料具有能够修复裂纹和缺陷以                          ZHANG 等 以动态二硫键设计了自修复水性聚氨
            及延长聚合物材料寿命等优点而成为当今极具潜力的                            酯(WPU),当二羟乙基二硫化物(HEDS)与 1,4-
                    [1]
            智能材料 。通常,聚氨酯具有优异的机械性能且能满                           丁二醇(BDO)的物质的量比为 8∶2 时,其修复效
                                                       [2]
            足多种结构设计而成为设计自修复材料的理想基材 。                           率高达 100%。WAN 等         [4-5] 不仅在分子链中接入
                 关于自修复聚氨酯材料的报道很多。例如,                           HEDS,还引入了环糊精和石墨烯等材料,赋予 WPU


                 收稿日期:2021-07-22;  定用日期:2021-10-11; DOI: 10.13550/j.jxhg.20210748
                 基金项目:国家重点研发计划(2016YFC0204400)
                 作者简介:翟文芮(1998—),女,硕士生,E-mail: zhaiwrui@foxmail.com。联系人:罗运军(1964—),男,教授,E-mail:yjluo@bit.edu.cn。
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