桉树生物质制备高邻位酚醛树脂纤维的研究

doi:10.3969/j.issn.0253-2417.2020.06.009

林产化学与工业 ›› 2020, Vol. 40 ›› Issue (6): 70-76.doi: 10.3969/j.issn.0253-2417.2020.06.009

桉树生物质制备高邻位酚醛树脂纤维的研究

刘灿¹(), 任宇¹, 李欣¹, 刘建祥¹, 史正军¹, 郑志锋²^,*()

1. 西南地区林业生物质资源高效利用国家林业和草原局重点实验室; 林业生物质资源高效利用技术国家地方联合工程研究中心; 西南林业大学材料科学与工程学院, 云南昆明 650224
2. 厦门大学能源学院, 福建厦门 361102

收稿日期:2020-06-29 出版日期:2020-12-28 发布日期:2020-12-29
通讯作者: 郑志锋 E-mail:liucanswfu@163.com;zhifeng.zheng@xmu.edu.cn
作者简介:郑志锋, 教授, 博士生导师, 主要从事生物质能源以及生物质材料的研究; E-mail:zhifeng.zheng@xmu.edu.cn
刘灿(1982-), 男, 山东菏泽人, 讲师, 博士, 硕士生导师, 主要从事生物基材料与生物质碳材料方面的研究; E-mail:liucanswfu@163.com
基金资助:
国家重点研发计划资助项目(2017YFD0601003);云南省重大科技专项计划(农业)(2018ZG004);云南省农业联合青年基金项目(2017FG001-072)

Preparation of High-ortho Phenolic Resin Fiber from Eucalyptus Residue

Can LIU¹(), Yu REN¹, Xin LI¹, Jianxiang LIU¹, Zhengjun SHI¹, Zhifeng ZHENG²^,*()

1. Key Laboratory of National Forestry and Grassland Administration for Highly-Efficient Utilization of Forest Biomass Resources in the Southwest China; National Joint Engineering Research Center for Highly-Efficient Utilization Technology of Forest Biomass Resources; College of Materials Science and Engineering, Southwest Forestry University, Kunming 650224, China
2. College of Energy, Xiamen University, Xiamen 361102, China

Received:2020-06-29 Online:2020-12-28 Published:2020-12-29
Contact: Zhifeng ZHENG E-mail:liucanswfu@163.com;zhifeng.zheng@xmu.edu.cn

摘要/Abstract

摘要：

使用桉树树皮、桉树树杆、造纸黑液木质素为原料制备生物基高邻位酚醛树脂纤维，采用FT-IR、TG、DSC、游离酚标定、力学性能测试等方法对材料性能进行表征，对不同生物质的热塑性酚醛树脂性能、生物质的添加量对酚醛树脂热性能的影响规律、密炼工艺对生物基酚醛树脂纤维的机械性能影响进行了探讨。研究结果表明：木质素基树脂成分组成均一，结构稳定，热稳定性最佳；以木质素为原料，不同木质素和苯酚质量比(木酚比)的生物基酚醛树脂邻对位比(O/P)值相似，邻位反应比例均大于对位；木酚比为1：4时制备的树脂组分均一，性能最好；密炼时间15 min，转速为45 r/min、密炼温度为135℃条件下制备的生物基酚醛树脂纤维性能较优，拉伸强度为168.6 MPa、断裂伸长率为2.1%。

关键词: 桉树剩余物, 高邻位, 酚醛树脂, 纤维

Abstract:

Biomass-based high-ortho phenolic resin fibers were prepared from eucalyptus bark, tree stem, and lignin. FT-IR, TG, DSC and mechanical properties as well as the measurement of free phenol, were used to evaluate the properties of different biomass-based thermoplastic phenolic resins. The influence of the amount of the same kind of biomass on phenolic resins, and the mixing process on mechanical properties of bio-based phenolic resins fiber were alse investigated. The results showed that the composition of lignin-based resin was uniform, the structure was stable, and the thermal stability was the best. The bio-based phenolic resins with three lignin ratios had similar ortho-position(O/P) ratios, and the ortho-position reaction ratios were all greater than the para-position. When the ratio of lignin and phenol was 1:4, the obtained resin had uniform composition and best performance. The internal mixing process could homogenize the resin and avoid overheating, which caused by internal heat generation. Combined with mechanical properties, the optimal conditions of mixing process of bio-based fibers were internal mixing for 15 min, rotation speed of 45 r/min, and internal mixing temperature of 135 ℃. The maximum strength was 168.6 MPa and the elongation at break was 2.1%.

Key words: eucalyptus residue, high-ortho, phenolic resin, fiber

中图分类号:

TQ35

刘灿, 任宇, 李欣, 刘建祥, 史正军, 郑志锋. 桉树生物质制备高邻位酚醛树脂纤维的研究[J]. 林产化学与工业, 2020, 40(6): 70-76.

Can LIU, Yu REN, Xin LI, Jianxiang LIU, Zhengjun SHI, Zhifeng ZHENG. Preparation of High-ortho Phenolic Resin Fiber from Eucalyptus Residue[J]. Chemistry and Industry of Forest Products, 2020, 40(6): 70-76.

图/表 5

参考文献 23

1	MARLIANA M M , HASSANA A , YUZIAH M Y N , et al. Flame retardancy, thermal and mechanical properties of Kenaf fiber reinforced unsaturated polyester/phenolic composite[J]. Fibers and Polymers, 2016, 17 (6): 902- 909.
2	焦明立, 杨凯, 刘红燕, 等. 酚醛纤维的制备及改性研究进展[J]. 合成纤维工业, 2013, 36 (6): 33- 36.
	JIAO M L , YANG K , LIU H Y , et al. Research progress in preparation and modification of phenolic fibers[J]. China Synthetic Fiber Industry, 2013, 36 (6): 33- 36.
3	任东雪, 焦明立, 郑瑾, 等. 酚醛基活性炭纤维的研究进展[J]. 合成纤维工业, 2017, 40 (5): 62- 67.
	REN D X , JIAO M L , ZHENG J , et al. Research progress of phenolic resin-based activated carbon fibers[J]. China Synthetic Fiber Industry, 2017, 40 (5): 62- 67.
4	YANG L J , WANG M G . Synthesis and property of solid resol phenolic resins with high molecular weight[J]. Polymer Materials Science & Engineering, 2012, 28 (12): 24- 28.
5	LI C , BU Z Y , SUN J P , et al. New insights into high-ortho phenolic novolac:Elucidating dependence between molecular structure, curing kinetics and thermal stability[J]. Thermo Chemical Acta, 2013, 557 (7): 77- 86.
6	HAN Z Q , QI S L , LIU W , et al. Surface-modified polyimide fiber-filled ethylenepropylenediene monomer insulations for a solid rocket motor:Processing, morphology, and properties[J]. Industrial & Engineering Chemistry Research, 2013, 52, 1284- 1290.
7	马小丰, 李建华, 吴剑吴, 等. 酚醛短切纤维对EPDM绝热材料性能的影响[J]. 塑料工业, 2019, 47 (7): 31- 36.
	MA X F , LI J H , WU J W , et al. Effects of phenolic short fibers on properties of EPDM insulations[J]. China Plastics Industry, 2019, 47 (7): 31- 36.
8	陈滨.改性热塑性酚醛树脂的制备及其成纤性能研究[D].上海: 东华大学, 2016.
	CHEN B.Study on the preparation and spinnability of modified phenolic resin[D]. Shanghai: Donghua University, 2016.
9	李改云, 任海青, 秦特夫, 等. 木材液化产物制备热塑性树脂的研究[J]. 林产化学与工业, 2008, 28 (4): 23- 28.
	LI G Y , REN H Q , QIN T F , et al. Preparation of novolak-type phenolic resin from phenolated wood[J]. Chemistry and Industry of Forest Products, 2008, 28 (4): 23- 28.
10	陈玉竹, 邵慧娟, 李竞, 等. 温度和pH值对预固化脲醛树脂固化影响的评价[J]. 热固性树脂, 2017, (3): 54- 59.
	CHEN Y Z , SHAO H J , LI J , et al. Evaluation of the effects of temperature and pH on the curing of pre-curing urea-formaldehyde resins[J]. Thermosetting Resin, 2017, (3): 54- 59.
11	刘春玲, 郭全贵, 史景利, 等. 用固化反应法制备酚醛纤维[J]. 材料研究学报, 2005, 19 (1): 28- 34.
	LIU C L , GUO G Q , SHI J L , et al. The curing reaction of phenolic fibers[J]. Chinese Journal of Materials Research, 2005, 19 (1): 28- 34.
12	CHEN B , YU J R , ZHOU Y S , et al. Preparation structure and properties of boron modified high-ortho phenolic fibers[J]. Fibers and Polymers, 2016, 17 (5): 678- 686.
13	张伟. 生物炼制木质素基酚醛树脂的制备与应用(摘要)[J]. 生物质化学工程, 2014, 48 (4): 57- 58.
	ZHANG W . Preparation and application of the biorefinery lignin-based phenolic resin(Abstract)[J]. Biomass Chemical Engineering, 2014, 48 (4): 57- 58.
14	卢宇晗, 黄元波, 李欣, 等. 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[J]. 西北林学院学报, 2018, 33 (3): 1- 7.
	LU Y H , HUANG Y B , LI X , et al. Preparation of biobased high ortho novolak resin[J]. Journal of Northwest Forestry College, 2018, 33 (3): 1- 7.
15	李欣, 卢宇晗, 黄元波, 等. 木质素基碳纤维力学性能的研究进展[J]. 西南林业大学学报(自然科学版), 2019, 39 (3): 176- 182.
	LI X , LU Y H , HUANG Y B , et al. Research progress on mechanical properties of lignin-based carbon fibers[J]. Journal of Southwest Forestry University(Natural Science), 2019, 39 (3): 176- 182.
16	卢宇晗, 黄元波, 杨晓琴, 等. 核桃壳液化物合成高邻位热塑性酚醛树脂的研究[J]. 材料导报, 2018, 32 (9): 3244- 3248.
	LU Y H , HUANG Y B , YANG X Q , et al. Synthesis of high-ortho novolak resin from liquefied products of walnut shell[J]. Material Reports, 2018, 32 (9): 3244- 3248.
17	戴燕, 谭卫红, 胡立红, 等. TG-DSC-MS联用研究不同气氛下腰果壳油改性热朔性酚醛树脂的热裂解特性[J]. 分析测试学报, 2014, 33 (4): 387- 394.
	DAI Y , TAN W H , HU L H , et al. Investigation on thermal decomposition behaviors of cashew nut shell liquid modified thermos plastic phenolic resin by TG-DSC-MS coupling techniques at different atmospheres[J]. Journal of Instrumental Analysis, 2014, 33 (4): 387- 394.
18	HUSKIĆ M , ANŽLOVAR A , ŽIGON M . Montmoril-lonite-phenolic resin nanocomposites prepared by one-step in-situ intercalative polymerization[J]. Applied Clay Science, 2014, 101, 484- 489.
19	阮胜军, 左小华, 张世磊, 等. 改性热塑性酚醛树脂的制备及残炭率的影响因素[J]. 中国胶黏剂, 2012, 21 (12): 33- 36.
	RUAN S J , ZUO X H , ZHANG S L , et al. Preparation of modified thermoplastic phenol-formaldehyde resin and influence factors of residual carbon[J]. China Adhesives, 2012, 21 (12): 33- 36.
20	陈滨, 于俊荣, 王彦, 等. 钼改性高邻位酚醛纤维的制备及性能[J]. 东华大学学报(自然科学版), 2016, 42 (6): 787- 792.
	CHEN B , YU J R , WANG Y , et al. Preparation of molybdenum modified high-ortho-phenolic fibers and its properties[J]. Journal of Donghua University(Natural Science), 2016, 42 (6): 787- 792.
21	卢宇晗.核桃壳液化树脂化产物制备碳纤维的研究[D].昆明: 西南林业大学, 2018.
	LU Y H.Preparation of carbon fiber by liquefying resin from walnut shell[D]. Kunming: Southwest Forestry University, 2018.
22	徐旭东.氯化钯催化下低共熔离子液活化木质素改性酚醛树脂的研究[D].南京: 南京林业大学, 2016.
	XU X D.Study on the modification of phenolic resin using eutectic ionic liquid activated lignin catalysed under palladium chloride[D]. Nanjing: Nanjing Forestry University, 2016.
23	GAO S , TANG G , HUA D , et al. Stimuli-responsive bio-based polymeric systems and their applications[J]. Journal of Materials Chemistry B, 2019, 7 (5): 709- 729.

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桉树生物质制备高邻位酚醛树脂纤维的研究

Preparation of High-ortho Phenolic Resin Fiber from Eucalyptus Residue

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