木质素基含氮磷阻燃剂的合成及热重分析

doi:10.3969/j.issn.0253-2417.2021.03.009

林产化学与工业 ›› 2021, Vol. 41 ›› Issue (3): 63-70.doi: 10.3969/j.issn.0253-2417.2021.03.009

木质素基含氮磷阻燃剂的合成及热重分析

李卓¹(), 翁述贤¹, 宋飞², 任晓丽¹, 杨晓慧¹^,⁴, 胡立红¹^,³^,*()

1. 中国林业科学研究院林产化学工业研究所; 生物质化学利用国家工程实验室; 国家林业和草原局林产化学工程重点实验室; 江苏省生物质能源与材料重点实验室, 江苏南京 210042
2. 南京林业大学化学工程学院, 江苏南京 210037
3. 南京林业大学江苏省林业资源高效加工利用协同创新中心, 江苏南京 210037
4. 中国林业科学研究院林业新技术研究所, 北京 100091

收稿日期:2021-01-26 出版日期:2021-06-28 发布日期:2021-07-01
通讯作者: 胡立红 E-mail:19852832112@163.com;hlh@icifp.cn
作者简介:胡立红, 研究员, 硕士生导师, 主要从事生物基高分子材料的应用研究; E-mail: hlh@icifp.cn
李卓(1996-), 女, 安徽宿州人, 硕士生, 主要从事生物基高分子材料研究; E-mail: 19852832112@163.com
基金资助:
中国林科院中央级公益性科研院所基本科研业务费专项资金(CAFYBB2019SZ007);国家重点研发计划资助项目(2019YFB1503804)

Synthesis and Thermal Analysis of Lignin-based Flame Retardant Containing Nitrogen and Phosphorus

Zhuo LI¹(), Shuxian WENG¹, Fei SONG², Xiaoli REN¹, Xiaohui YANG¹^,⁴, Lihong HU¹^,³^,*()

1. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab. for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China
2. College of Chemical Engineering, Nanjing Forestry University, Nanjing 310037, China
3. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China
4. Research Institute of Forestry New Technology, CAF, Beijing 100091, China

Received:2021-01-26 Online:2021-06-28 Published:2021-07-01
Contact: Lihong HU E-mail:19852832112@163.com;hlh@icifp.cn

摘要/Abstract

摘要：

以解聚木质素（DL）为原料，采用相转移超声波法制备了席夫碱型含氮木质素（N-DL），再进一步与9，10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）反应，合成氮磷改性DL（NP-DL），NP-DL是一种新型膨胀型木质素基含氮磷阻燃剂。采用FT-IR、¹H NMR、³¹P NMR、TG、TG/FT-IR、TG/MS、GPC和XPS方法对NP-DL的结构和性能进行表征。研究结果表明：DL中成功地引入了N、P元素；TG分析表明600和800℃时NP-DL残炭率比DL残炭率分别提高了1 285.5%和362.6%。TG/FT-IR联用和TG/MS联用测试结果表明：NP-DL受热降解产生含磷物[OP⁺]（m/z=47）、[H₃PO]（m/z=50）、[O₂P⁺]（m/z=63）和[HO₂P⁺]（m/z=64），证明NP-DL在热解过程中产生的含磷化合物抑制了燃烧。

关键词: 木质素, 阻燃剂, DOPO, 席夫碱反应

Abstract:

Using depolymerized lignin(DL) as raw material, Schiff base nitrogen-containing lignin(N-DL) was prepared by phase transfer ultrasonic method, and then further reacted with 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO) to synthesize nitrogen-phosphorus modified DL(NP-DL). NP-DL was a new type of expanded lignin-based nitrogen and phosphorus flame retardant. The structure and performance of NP-DL were characterized by FT-IR, ¹H NMR, ³¹P NMR, TG, TG/FT-IR, TG/MS, GPC and XPS. The results showed that N and P were successfully introduced into the depolymerized lignin; TG analysis showed that the carbon residue rates of NP-DL at 600 and 800℃ were increased by 1 285.5% and 362.6% compared with those of DL, respectively. The test results of TG/FT-IR and TG/MS showed that NP-DL was thermally degraded to produce phosphorus: [OP⁺] with m/z=47, [H₃PO] with m/z=50, [O₂P⁺] with m/z=63 and[HO₂P⁺] with m/z=64 proved that the phosphorus-containing compounds produced during the pyrolysis of NP-DL inhibited combustion.

Key words: lignin, flame retardant, DOPO, Schiff base reaction

中图分类号:

TQ35

李卓, 翁述贤, 宋飞, 任晓丽, 杨晓慧, 胡立红. 木质素基含氮磷阻燃剂的合成及热重分析[J]. 林产化学与工业, 2021, 41(3): 63-70.

Zhuo LI, Shuxian WENG, Fei SONG, Xiaoli REN, Xiaohui YANG, Lihong HU. Synthesis and Thermal Analysis of Lignin-based Flame Retardant Containing Nitrogen and Phosphorus[J]. Chemistry and Industry of Forest Products, 2021, 41(3): 63-70.

图/表 11

图1

图2

图3

图4

图5

表1

图6

图7

表2

图8

图9

参考文献 26

1	WU M, SONG W, WU Y, et al. Preparation and characterization of the flame-retardant decorated plywood based on the intumescent flame retardant adhesive[J/OL]. Materials, 2020, 13(3): 1-13[2020-10-10]. https://pubmed.ncbi.nlm.nih.gov/32028679.DOI:10.3390/ma13030676.
2	PRICE E J , COVELLO J , TUCHLER A , et al. Intumescent, epoxy-based flame-retardant coatings based on poly(acrylic acid) compositions[J]. ACS Applied Materials & Interfaces, 2020, 12 (16): 18997- 19005.
3	WANG J, XUE L, ZHAO B, et al. Flame retardancy, fire behavior, and flame retardant mechanism of intumescent flame retardant EPDM containing ammonium polyphosphate/pentaerythrotol and expandable graphite[J/OL]. Materials, 2019, 12(24): 1-15[2020-10-10]. https://pubmed.ncbi.nlm.nih.gov/31817279.DOI:10.3390/ma12244035.
4	ZHU H , PENG Z , CHEN Y , et al. Preparation and characterization of flame retardant polyurethane foams containing phosphorus-nitrogen-functionalized lignin[J]. RSC Advances, 2014, 4 (98): 55271- 55279. doi: 10.1039/C4RA08429B
5	张金凯, 马丽, 葛维娟, 等. 膨胀型阻燃剂阻燃聚丙烯的研究进展[J]. 材料导报, 2015, 29 (5): 68- 72.
	ZHANG J K , MA L , GE W J , et al. Research status of intumescent flame-retarded polypropylene[J]. Materials Review, 2015, 29 (5): 68- 72.
6	ZHAO Q , WEI Y C , NI C J , et al. Effect of a minated nanocrystal cellulose on proton conductivity and dimensional stability of proton exchange membranes[J]. Applied Surface Science, 2019, 466 (1): 691- 702.
7	THAKUR V K , THAKUR M K , RAGHAVAN P , et al. Progress in green polymer composites from lignin for multifunctional applications: A review[J]. ACS Sustainable Chemistry, 2014, 2 (5): 1072- 1092. doi: 10.1021/sc500087z
8	OSBERT Y , KWANG H K . Lignin to materials: A focused review on recent novel lignin applications[J]. Applied Science, 2020, 10 (13): 2- 16.
9	YAN R , YANG D , ZHANG N , et al. Performance of UV curable lignin based epoxy acrylate coatings[J]. Progress in Organic Coatings, 2018, 116, 83- 89. doi: 10.1016/j.porgcoat.2017.11.011
10	WANG X , JI S , WANG X , et al. Thermally conductive, super flexible and flame-retardant BN-OH/PVA composite film reinforced by lignin nanoparticles[J]. Journal of Materials Chemistry, 2019, 7 (45): 14159- 14169.
11	VELENCOSO M M , BATTIG A , MARKWART J C , et al. Molecular firefighting: How modern phosphorus chemistry can help solve the flame retardancy task[J]. Angewandte Chemie International Edition, 2018, 57 (33): 10450- 10467. doi: 10.1002/anie.201711735
12	杨融生, 余秀芬, 张汉辉, 等. 木质素硝酸降解及其产物的生理活性[J]. 福州大学学报(自然科学版), 1999, 27 (1): 83- 85. doi: 10.3969/j.issn.1000-2243.1999.01.021
	YANG R S , YU X F , ZHANG H H , et al. Decomposition of lignin by nitric acid and physiological activation[J]. Journal of Fuzhou University(Natural Science Edition), 1999, 27 (1): 83- 85. doi: 10.3969/j.issn.1000-2243.1999.01.021
13	胡立红. 木质素酚醛泡沫保温材料的制备与性能研究[D]. 北京: 中国林业科学研究院, 2012.
	HU L H. Study on the Preparation and properties of lignin-based phenolic foam thermal insulation materials[D]. Beijing: Chinese Academy of Forestry, 2012.
14	ARSHADI M , GHIACI M , GIL A . Schiff base ligands immobilized on a nanosized SiO₂-Al₂O₃ mixed oxide as adsorbents for heavy metals[J]. Industrial & Engineering Chemistry Research, 2011, 50 (24): 13628- 13635.
15	XIONG C H , FENG Y P , ZHENG X M , et al. Synthesis and characterization of a novel chloromethylated polystyrene-g-2-adenine chelating resin and its application to preconcentrate and detect the concentration of mercury ions in edible mushroom samples[J]. Canadian Journal of Chemistry, 2016, 94 (9): 751- 758. doi: 10.1139/cjc-2016-0113
16	AKINE S , TANIGUCHI T , DONG W , et al. Oxime-based salen-type tetradentate ligands with high stability against imine metathesis reaction[J]. Journal of Organic Chemistry, 2005, 70 (5): 1704- 1711. doi: 10.1021/jo048030y
17	王志国, 梁兵, 刘徐越. 磷氮阻燃剂PiP-DOPO的制备及对环氧树脂的阻燃[J]. 高分子材料科学与工程, 2018, 34 (8): 149- 153.
	WANG Z G , LIANG B , LIU X Y . Preparation of phosphorus-nitrogen flame retardant PiP-DOPO and its flame retarded epoxy resin[J]. Polymer Materials Science & Engineering, 2018, 34 (8): 149- 153.
18	WANG P , YANG F , LI L , et al. Flame retardancy and mechanical properties of epoxy thermosets modified with a novel DOPO-based oligomer[J]. Polymer Degradation and Stability, 2016, 129, 156- 167. doi: 10.1016/j.polymdegradstab.2016.04.005
19	ZHANG Y M , ZHAO Q , LI L , et al. Synthesis of a lignin-based phosphorus-containing flame retardant and its application in polyurethane[J]. RSC Advances, 2018, 8 (56): 32252- 32261. doi: 10.1039/C8RA05598J
20	YAN L , XU Z , WANG X , et al. Preparation of a novel mono-component intumescent flame retardant for enhancing the flame retardancy and smoke suppression properties of epoxy resin[J]. Journal of Thermal Analysis & Calorimetry, 2018, 134 (3): 1505- 1519.
21	GUAN Y H , HUANG J Q , YANG J C , et al. An effective way to flame-retard biocomposite with ethanola mine modified ammonium polyphosphate and its flame retardant mechanisms[J]. Industrial & Engineering Chemistry Research, 2015, 54 (13): 3524- 3531.
22	XU Z , CHU Z , YAN L , et al. Effect of chicken eggshell on the flame-retardant and smoke suppression properties of an epoxy-based traditional APP-PER-MEL system[J]. Polymer Composites, 2018, 40, 2712- 2723.
23	VASILJEVIĆ J , JERMAN I , JAKŠA G , et al. Functionalization of cellulose fibres with DOPO-polysilsesquioxane flame retardant nanocoating[J]. Cellulose, 2015, 22 (3): 1893- 1910. doi: 10.1007/s10570-015-0599-x
24	TUDORACHI N , MUSTATA F . Thermal degradation and evolved gas analysis of some vegetable oils using TG/FT-IR/MS technique[J]. Journal of Thermal Analysis and Calorimetry, 2014, 119 (3): 1703- 1711. doi: 10.1007/s10973-014-4320-3
25	WU K , SONG L , HU Y , et al. Synthesis and characterization of a functional polyhedral oligomeric silsesquioxane and its flame retardancy in epoxy resin[J]. Progress in Organic Coatings, 2009, 65 (4): 490- 497. doi: 10.1016/j.porgcoat.2009.04.008
26	QIAN L , QIU Y , SUN N , et al. Pyrolysis route of a novel flame retardant constructed by phosphaphenanthrene and triazine-trione groups and its flame-retardant effect on epoxy resin[J]. Polymer Degradation and Stability, 2014, 107, 98- 105. doi: 10.1016/j.polymdegradstab.2014.05.007

样品 samples	M_n	M_w/M_n	N/%	C/%	H/%	P/%
DL	1748	6.99	1.04	58.37	5.47	—
N-DL	2012	7.56	4.27	57.55	5.96	—
NP-DL	2154	9.29	3.25	58.14	5.59	1.1

样品 samples	T_-5%/℃	T_max/℃			残炭率residual mass/%
样品 samples	T_-5%/℃	StepⅠ	StepⅡ	StepⅢ	600 ℃	800 ℃
DL	199.07	72.6	269.3	471.9	2.28	2.27
N-DL	158.01	78.1	242.3	512.9	10.90	4.19
NP-DL	175.88	70.6	374.8	578.5	31.59	10.50

[1]	刘金昱, 刘瑞霞, 邓萍萍, 刘德乡, 郭盟, 吴志平. 木质素离子印迹聚合物的制备及其对Cr(VI)吸附性能的研究[J]. 林产化学与工业, 2021, 41(2): 24-32.
[2]	李欣, 任宇, 刘建祥, 史正军, 郑志锋, 刘灿. 温度对木质素基酚醛树脂纤维固化行为的影响[J]. 林产化学与工业, 2021, 41(2): 33-38.
[3]	杨倩, 刘贵锋, 金灿, 孔振武. 路易斯酸复合Pt/ZrO₂协同催化碱木质素还原降解制备酚类低聚物[J]. 林产化学与工业, 2020, 40(6): 37-49.
[4]	黄勇,刘沙沙,吴益霜,周建斌,张书. 基于模型化合物的生物质半焦催化性能研究[J]. 林产化学与工业, 2020, 40(5): 63-68.
[5]	朱恩清,史正军,刘守庆,杨静,王大伟,杨海艳. 基于不同发泡剂的木质素基泡沫炭的制备及性能研究[J]. 林产化学与工业, 2020, 40(4): 63-70.
[6]	钟磊,王超,吕高金,吉兴香,杨桂花,陈嘉川. 低共熔溶剂在木质素分离方面的研究进展[J]. 林产化学与工业, 2020, 40(3): 12-22.
[7]	侯兴隆,郭奇,建晓朋,吴迪超,许伟,刘军利. 响应面法优化设计木质素基活性炭的制备[J]. 林产化学与工业, 2020, 40(3): 115-122.
[8]	储秋露,陈雪艳,宋凯,王静,张晓东,施爱平. 两步法预处理对杨木酶水解及木质素吸附性能的影响[J]. 林产化学与工业, 2019, 39(6): 68-74.
[9]	卢传巍,郭晓亮,蔡青云,王春鹏,储富祥,王基夫. 甲基丙烯酸化木质素磺酸钙/聚丙烯酰胺复合水凝胶的制备与性能研究[J]. 林产化学与工业, 2019, 39(6): 75-80.
[10]	李宁,陈智糠,张一甫. 酚化木质素改性酚醛树脂胶黏剂的制备及性能表征[J]. 林产化学与工业, 2019, 39(6): 95-101.
[11]	陈雪艳, 储秋露, 王静, 张晓东, 施爱平. 两步法预处理脱除木质素对杨木酶水解的影响[J]. 林产化学与工业, 2019, 39(5): 73-79.
[12]	王兴佳, 乔炜, 肖达明, 李淑君. 铝氧单钠固体超强碱催化降解木质素的研究[J]. 林产化学与工业, 2019, 39(5): 80-86.
[13]	张清桐,运晓静,颜德鹏,李明富,王双飞,闵斗勇. 太阳光催化木质素制备银纳米颗粒[J]. 林产化学与工业, 2019, 39(4): 35-41.
[14]	孙永昌,张冰清,刘力鸣,刘肖南,史正军. 木质素基炭材料的制备及其对Cr(Ⅵ)的吸附机制研究[J]. 林产化学与工业, 2019, 39(4): 120-128.
[15]	詹满军,陈志林,储富祥. 复合型阻燃剂对无醛超低密度纤维板性能的影响[J]. 林产化学与工业, 2019, 39(3): 87-93.

木质素基含氮磷阻燃剂的合成及热重分析

Synthesis and Thermal Analysis of Lignin-based Flame Retardant Containing Nitrogen and Phosphorus

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 26

相关文章 15

编辑推荐

Metrics

本文评价

关于本刊

投稿指南

在线期刊

相关单位

联系我们