Page 175 - 精细化工2019年第12期
P. 175

第 36 卷第 12 期                            精   细   化   工                                 Vol.36, No.12
             2019 年 12 月                             FINE CHEMICALS                                 Dec.    2019


              粘合剂
                           HDI-BPA 酚醛树脂的合成及应用性能



                                1
                                             1*
                                                           2
                                                                       1
                                                                                                 1
                                                                                    1
                       郭   睿 ,李秀环 ,何观伟 ,刘雪艳 ,霍文生 ,冯文佩
                 (1.  陕西科技大学  教育部轻化工助剂化学与技术重点实验室,陕西  西安    710021;2.  西北化工研究院
                 有限公司,陕西  西安    710061)
                 摘要:以双酚 A(BPA)酚醛树脂和六亚甲基二异氰酸酯(HDI)为原料,在二月桂酸二丁基锡(DBTDL)催
                                                        1
                 化作用下合成了 HDI-BPA 酚醛树脂。采用 FTIR、 HNMR、GPC、有机元素分析等对 HDI-BPA 酚醛树脂的化学
                 结构和相对分子质量进行了表征,结果表明目标产物成功制备,其 M w 为 3376。探讨了反应温度、反应时间、
                 物料配比、催化剂用量等因素对目标产物中异氰酸酯基质量分数及接枝率的影响。通过建立异氰酸酯基质量分
                 数和接枝率的二次回归方程,使用响应面分析法中的 Box-Behnken Design(BBD)对 HDI-BPA 酚醛树脂的合成
                 工艺进行了优化,最佳工艺条件为:反应温度 32 ℃、反应时间为 55 min、m(BPA 酚醛树脂)∶m(HDI)∶m
                 (DBTDL)=0.2101∶1∶0.0025。在此条件下,合成产物中异氰酸酯基质量分数为 25.51%,接枝率为 48.929%。
                 最后,在 HDI-BPA 酚醛树脂中加入 E-51 固化剂,制备出 HDI-BPA 酚醛树脂胶黏剂,其最大粘结力达 283.69 N,
                 相对于 BPA 酚醛树脂胶黏剂的性能提升了 3.7 倍,表明 HDI 的加入显著提高了 BPA 酚醛树脂对低极性皮革基
                 材的粘结性能。同时,HDI-BPA 酚醛树脂胶黏剂的接触角为 93.5°,表现出较好的疏水和耐水性能。
                 关键词:BPA 酚醛树脂;HDI;胶黏剂;耐水性能;粘结性能;粘合剂
                 中图分类号:O621.3      文献标识码:A      文章编号:1003-5214 (2019) 12-2503-09



                      Synthesis and Application Properties of HDI-BPA Phenolic Resin


                                                                     1
                                                                                                     1
                                                                                      1
                            1
                                        1*
                                                       2
                   GUO Rui , LI Xiu-huan , HE Guan-wei , LIU Xue-yan , HUO Wen-sheng , FENG Wen-pei
                 (1. MOE Key Laboratory of the Chemistry and Technology of Light Auxiliary Chemicals, Shaanxi University of Science
                 & Technology, Xi'an 710021, Shaanxi, China; 2. The Northwest Research Institute of Chemical Industry Co., Ltd., Xi'an
                 710061, Shaanxi, China)
                 Abstract:  HDI-BPA  phenolic  resin  was  synthesized  from  bisphenol  A  (BPA)  phenolic  resinand
                 hexamethylene diisocyanate (HDI) in the presence of a catalytic amount of dibutyltindilaurate (DBTDL).
                 The chemical structure and relative molecular mass of HDI-BPA phenolic resin were characterize by FTIR,
                 1
                  HNMR, GPC and element analysis. The results showed that the target product was successfully prepared
                 and  its  M w  was  3376.  In  addition,  the  effects  of  reaction  temperature,  reaction  time,  material  ratio  and
                 amount  of  catalyst  on  the  content  and  grafting  ratio  of  isocyanate  groups  in  the  target  product  were
                 discussed. The synthesis process of HDI-BPA phenolic resin was optimized by Box-Behnken Design (BBD)
                 in response surface methodology by establishing a quadratic regression equation of isocyanate content and
                 grafting ratio. The optimum conditions were obtained as follows: reaction temperature 32 ℃, reaction time
                 55 min, m(BPA phenolic resin)∶m(HDI)∶m(DBTDL)= 0.2101∶1∶0.0025. Under these conditions, the
                 mass  fraction  and  graft  ratio  of  the  isocyanate  groups  in  the  final  product  were  25.51%  and  48.929%,
                 respectively.  Finally,  HDI-BPA  phenolic  resin  adhesive  was  prepare  by  adding  E-51  curing  agent  to
                 HDI-BPA phenolic resin. Its maximum adhesion was 283.69 N, which was 3.7 times higher than that of


                 收稿日期:2019-04-22;  定用日期:2019-06-05; DOI: 10.13550/j.jxhg.20190342
                 基金项目:陕西省 2017 年重点研发计划项目(2017ZDXM-GY-087);陕西省  2017  年重点研发计划项目(2017GY-185);陕西省教育
                 厅服务地方专项计划项目(15JF011)
                 作者简介:郭   睿(1959—),男,教授,硕士生导师,E-mail:365726475@qq.com。联系人:李秀环(1994—),女,硕士生,E-mail:
                 1208284741@qq.com。
   170   171   172   173   174   175   176   177   178   179   180