生物质基高邻位热塑性酚醛树脂作为树脂纤维前驱体的研究

Preparation of Biobased High Ortho Novolak Resin

以大理漾濞核桃(Juglans regia)壳液化物为原料,合成了生物基热塑性酚醛树脂(thermoplastic phenolic resin,TPPF),探讨了核桃壳液化物中苯酚(phenol,P)与甲醛(formaldehyde,F)的摩尔比、反应时间、反应温度对TPPF得率、游离酚含量和有机元素含量的影响,在获得优化合成条件的基础上,使用ZnOH为催化剂合成生物基高邻位热塑性酚醛树脂(High-Ortho TPPF),探讨了甲醛加入次数对生物基High Ortho TPPF的邻对位比值(O/P)的影响,并采用核磁共振(NMR)、红外光谱(FTIR)对生物基High Ortho TPPF进行表征。结果表明,生物基TPPF的最佳合成条件为核桃壳液化物中苯酚与甲醛的摩尔比1∶0.75、反应时间3.5h、反应温度85℃,树脂得率为75.70%,游离酚含量为9.18%;在此基础上,利用FTIR可发现采用两步甲醛法能够制备生物基High Ortho TPPF,其邻对位比值通过核磁验证为1.10。

The bio-based thermoplastic phenolic-formaldehyde resin（TPPF）was synthesized by using liquefied walnut shell product.Effects of relative parameters（such as the ratio of phenolic in liquefied product and formaldehyde,reaction time,temperature）on TPPF yield,free phenol,and organic elements were studied.Based on the optimized synthesis conditions,the influence in the formaldehyde additions on the O/Pratio of high-ortho TPPF that was synthesized by the use of zinc hydroxide as a catalyst and characterized though the methods of nuclear magnetic resonance（NMR）and infrared spectroscopy（FTIR）was examined.The optimal synthetic conditions of bio-based TPPF were the molar ratio of phenol in liquefied product to formaldehyde：1∶0.75,the reaction time：3.5 h,temperature：85℃,from which the yield of resin was 75.70%,and the content of free phenol was 9.18%.In addition,the bio-based high ortho TPPF could be prepared by two-step formaldehyde method from the FTIR,and its ortho/para position ratio was 1.10,which was proved by NMR.