棉纺黑液提取物基聚氨酯泡沫的制备及性能

doi:10.16085/j.issn.1000-6613.2023-1546

摘要/Abstract

摘要：

针对棉纺黑液生物质资源未被高效利用造成资源浪费的问题，本文提出了一种基于棉纺黑液提取物制备聚氨酯泡沫（PUF）的方法。首先采用酸沉法制得原料，再部分替代聚醚多元醇一步发泡法制备棉纺黑液提取物聚氨酯泡沫，并采用红外（FTIR）、光学显微镜、扫描电子显微镜（SEM）、热重量分析（TGA）、水平燃烧、降解试验等手段表征棉纺黑液提取物聚氨酯泡沫表面及残炭形貌、热稳定性、阻燃性及可降解性等。结果表明，通过棉纺黑液提取物部分替代聚醚多元醇改善了PUF材料的热稳定性能和成炭性能，当棉纺黑液提取物替代率为30%（质量分数）时，聚氨酯泡沫的表观密度为0.0439g/cm³，热导率为0.03088W/(m·K)，起始分解温度为214℃，700℃下残炭率可达45%，水平燃烧炭化长度为0.5mm，12h降解率为27.9%，聚氨酯泡沫各项性能均有一定提升。

关键词: 棉纺黑液提取物, 聚氨酯泡沫, 热稳定性, 阻燃性, 可降解性

Abstract:

In order to solve the problem that the biomass resource of cotton spinning black liquor is not efficiently utilized, which causes resource waste, this paper proposed a method to prepare polyurethane foam (PUF) based on the extract of cotton spinning black liquor. First, the raw material was prepared by acid precipitation method, and then the polyurethane foam was partially prepared by one-step foaming method instead of polyether polyol. Finally, infrared (FTIR), optical microscope, scanning electron microscope (SEM), thermogravimetric analysis (TGA), horizontal combustion, degradation test and other means were used to characterize the foam surface and carbon residue morphology, thermal stability, flame retardancy and degradation. The results showed that the partial substitution of polyether polyols with cotton spinning black liquor extract improved the thermal stability and carbonization performance of PUF materials, When the substitution rate of cotton spinning black liquor extract was 30%, the apparent density of polyurethane foam was 0.0439g/cm³, the thermal conductivity was 0.03088W/(m∙K), the initial decomposition temperature was 214℃, the carbon residue rate was 45% at 700℃, the horizontal combustion carbonization length was 0.5mm, and the 12h degradation rate was 27.9%. All properties of polyurethane foam were improved to a certain extent.

Key words: extract of cotton spinning black liquor, polyurethane foam, thermal stability, flame retardancy, degradability

中图分类号:

TQ322.4

李珍明, 李春祺, 李征光, 李秀敏, 赵俭波. 棉纺黑液提取物基聚氨酯泡沫的制备及性能[J]. 化工进展, 2024, 43(10): 5704-5711.

LI Zhenming, LI Chunqi, LI Zhengguang, LI Xiumin, ZHAO Jianbo. Preparation and properties of polyurethane foam based on extract of cotton spinning black liquor[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5704-5711.

图/表 11

表1 不同替代率棉纺黑液基聚氨酯泡沫配比

编号	聚醚多元醇/g	棉纺黑液提取物/g	替代率/%
0M-PUF	5	0	0
10M-PUF	4.5	0.5	10
20M-PUF	4	1	20
30M-PUF	3.5	1.5	30
40M-PUF	3	2	40
50M-PUF	2.5	2.5	50

图1 棉纺黑液提取物官能图含量和红外谱图

图2 不同替代率棉纺黑液提取物聚氨酯泡沫表观密度

图3 棉纺黑液提取物基聚氨酯泡沫的红外表征

图4 不同替代率棉纺黑液提取物聚氨酯泡沫表面形貌

图5 不同替代率棉纺黑液提取物聚氨酯泡沫的TGA和DTG曲线

图6 不同替代率棉纺黑液提取物聚氨酯泡沫热导率

图7 不同替代率棉纺黑液提取物聚氨酯泡沫残炭SEM图

图8 不同替代率棉纺黑液提取物聚氨酯泡沫水平燃烧火焰火势图和炭化长度

图9 不同替代率棉纺黑液提取物聚氨酯泡沫的降解

图10 不同替代率棉纺黑液提取物的降解率时间曲线

参考文献 34

1	王帅, 杨富凯, 徐新宇. 阻燃型全生物基多元醇聚氨酯泡沫的制备及性能研究[J]. 化工学报, 2023, 74(3): 1399-1408.
	WANG Shuai, YANG Fukai, XU Xinyu. Preparation and characterization of flame retardant bio-based polyols polyurethane foam[J]. CIESC Journal, 2023, 74(3): 1399-1408.
2	游怀, 严硕, 宋学霖, 等. 有机催化精准制备聚酯多元醇：环氧化物原位缓释与捕捉策略[J]. 高分子学报, 2023, 54(3): 327-335.
	YOU Huai, YAN Shuo, SONG Xuelin, et al. Precise construction of polyester polyol from organocatalysis: Epoxide slow-release and in situ capture strategy[J]. Acta Polymerica Sinica, 2023, 54(3): 327-335.
3	张佳燕, 刘博文, 王玉忠, 等. 聚氨酯泡沫无卤阻燃研究进展[J]. 高分子学报, 2022, 53(7): 842-855.
	ZHANG Jiayan, LIU Bowen, WANG Yuzhong, et al. Recent advances in halogen-free flame-retardant polyurethane foams[J]. Acta Polymerica Sinica, 2022, 53(7): 842-855.
4	张冰, 杨素洁, 杨亚东, 等. 三聚氰胺植酸/硬质聚氨酯泡沫复合材料的制备及其热解动力学特性[J]. 复合材料学报, 2021, 38(8): 2505-2516.
	ZHANG Bing, YANG Sujie, YANG Yadong, et al. Preparation and pyrolysis kinetics of melamine phytates/rigid polyurethane foam composites[J]. Acta Materiae Compositae Sinica, 2021, 38(8): 2505-2516.
5	Roberto MORALES-CERRADA, TAVERNIER Romain, CAILLOL Sylvain. Fully bio-based thermosetting polyurethanes from bio-based polyols and isocyanates[J]. Polymers, 2021, 13(8): 1255.
6	ZHENG Lei, MCCLELLAND Daniel J, REHMANN Kelsi M S, et al. Bio-based 1,5-pentanediol as a replacement for petroleum-derived 1,6-hexanediol for polyester polyols, coatings, and adhesives[J]. ACS Sustainable Chemistry & Engineering, 2022, 10(18): 5781-5791.
7	李梦雨, 王冬祥, 郑晓阳, 等. 粗甘油生物基聚氨酯材料的制备及吸附性能研究[J]. 化工学报, 2022, 73(5): 2270-2278.
	LI Mengyu, WANG Dongxiang, ZHENG Xiaoyang, et al. Preparation and adsorption properties of crude glycerol bio-based polyurethane material[J]. CIESC Journal, 2022, 73(5): 2270-2278.
8	CABULIS Ugis, IVDRE Aiga. Recent developments in the sustainability of the production of polyurethane foams from polyols based on the first- to the fourth-generation of biomass feedstock[J]. Current Opinion in Green and Sustainable Chemistry, 2023, 44: 100866.
9	STANČIN H, ŠAFÁŘ M, RŮŽIČKOVÁ J, et al. Influence of plastic content on synergistic effect and bio-oil quality from the co-pyrolysis of waste rigid polyurethane foam and sawdust mixture[J]. Renewable Energy, 2022, 196: 1218-1228.
10	CHEN Boxi, LIAO Meng, SUN Jianping, et al. A novel biomass polyurethane-based composite coating with superior radiative cooling, anti-corrosion and recyclability for surface protection[J]. Progress in Organic Coatings, 2023, 174: 107250.
11	LICONA-AGUILAR Á I, TORRES-HUERTA A M, DOMÍNGUEZ-CRESPO M A, et al. Reutilization of waste biomass from sugarcane bagasse and orange peel to obtain carbon foams: Applications in the metal ions removal[J]. Science of the Total Environment, 2022, 831: 154883.
12	RANGANATHAN Palraj, CHEN Chin-Wen, CHOU Yiling, et al. Biomass chemical upcycling of waste rPET for the fabrication of formamide-free TPEE microcellular foams via scCO₂ foaming[J]. Journal of CO₂ Utilization, 2022, 65: 102199.
13	JIANG Haoyu, LI Jun, ZHANG Ruijie, et al. Mapping the contribution of biomass burning to persistent organic pollutants in the air of the indo-china peninsula based on a passive air monitoring network[J]. Environmental Science & Technology, 2023, 57(6): 2274-2285.
14	CAO Hui, LIU Ruilin, LI Bing, et al. Biobased rigid polyurethane foam using gradient acid precipitated lignin from the black liquor: Revealing the relationship between lignin structural features and polyurethane performances[J]. Industrial Crops and Products, 2022, 177: 114480.
15	Marzena SZPIŁYK, LUBCZAK Renata, LUBCZAK Jacek. The biodegradable cellulose-derived polyol and polyurethane foam[J]. Polymer Testing, 2021, 100: 107250.
16	MOHAMED Dhey Jawad, HADI Nizar Jawad, ALOBAD Zoalfokkar Kareem. Investigation of the polyol types and isocyanate concentrations on the rheological, morphological and mechanical properties of polyurethane foams[J]. IOP Conference Series: Materials Science and Engineering, 2021, 1094(1): 012157.
17	MOHAMMADPOUR Raziye, MOHAMAD SADEGHI Gity MIR. Potential use of black liquor as lignin source for synthesis of polyurethane foam[J]. Journal of Polymer Research, 2020, 27(12): 362.
18	李鹏辉, 蒋政伟, 李家全, 等. 木质素降解产物酚羟基测定方法研究进展[J]. 光谱学与光谱分析, 2022, 42(9): 2666-2671.
	LI Penghui, JIANG Zhengwei, LI Jiaquan, et al. Research progress in quantitative determination of phenolic hydroxyl groups in lignin[J]. Spectroscopy and Spectral Analysis, 2022, 42(9): 2666-2671.
19	HONG Nanlong, WANG Jiahui, YOU Jinhua. Lignin-based polymer with high phenolic hydroxyl group content prepared by the alkyl chain bridging method and applied as a dopant of PEDOT[J]. Frontiers of Chemical Science and Engineering, 2023, 17(8): 1075-1084.
20	RUWOLDT Jost, Mihaela TANASE-OPEDAL, SYVERUD Kristin. Ultraviolet spectrophotometry of lignin revisited: Exploring solvents with low harmfulness, lignin purity, Hansen solubility parameter, and determination of phenolic hydroxyl groups[J]. ACS Omega, 2022, 7(50): 46371-46383.
21	刘芳, 赵志刚, 杨雪, 等. 热塑性聚氨酯微孔发泡材料的表观密度与其力学性能的关系[J]. 高分子学报, 2021, 52(4): 388-398.
	LIU Fang, ZHAO Zhigang, YANG Xue, et al. Relationship between apparent density and mechanical properties of microcellular thermoplastic polyurethane foam[J]. Acta Polymerica Sinica, 2021, 52(4): 388-398.
22	WANG Chunhong, ZUO Qi, LIN Tianyang, et al. Predicting thermal conductivity and mechanical property of bamboo fibers/polypropylene nonwovens reinforced composites based on regression analysis[J]. International Communications in Heat and Mass Transfer, 2020, 118: 104895.
23	刘泓吟, 杨宏宇, 陈明凤. 异氰酸酯指数对聚氨酯硬泡阻燃、热稳定性及燃烧性能的影响[J]. 材料导报, 2019, 33(12): 2071-2075.
	LIU Hongyin, YANG Hongyu, CHEN Mingfeng. Impact of isocyanate index on flame retardancy, thermal stability and combustion behaviors of rigid polyurethane foam[J]. Materials Reports, 2019, 33(12): 2071-2075.
24	赖英萍, 陈应, 赵佳佳, 等. 椰衣基聚氨酯包装缓冲泡沫的制备与性能研究[J]. 化工学报, 2021, 72(7): 3880-3889.
	LAI Yingping, CHEN Ying, ZHAO Jiajia, et al. Preparation and performance of coconut fiber based polyurethane packaging cushioning foam[J]. CIESC Journal, 2021, 72(7): 3880-3889.
25	MA Chao, ZHANG Kang, ZHOU Feng, et al. Fabrication of flexible polyurethane/phosphorus interpenetrating polymer network (IPN) foam for enhanced thermal stability, flame retardancy and mechanical properties[J]. Polymer Degradation and Stability, 2021, 189: 109602.
26	SMITH Dallin L, Danixa RODRIGUEZ-MELENDEZ, COTTON Sidney M, et al. Non-isocyanate polyurethane bio-foam with inherent heat and fire resistance[J]. Polymers, 2022, 14(22): 5019.
27	李婷, 杜少辉, 崔锦峰, 等. 磷-硼杂化预聚物嵌段水性聚氨酯纸张施胶剂的制备和性能[J]. 化工进展, 2022, 41(10): 5549-5557.
	LI Ting, DU Shaohui, CUI Jinfeng, et al. Preparation and properties of waterborne polyurethane paper sizing agents with phosphorus-boron hybrid prepolymer blocks[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5549-5557.
28	SHEN Yongxian, ZHOU Hongjun, GUO Qingbing, et al. Preparation, properties, and applications of modified polyurethane foam from persimmon tannin powder[J]. Journal of Applied Polymer Science, 2022, 139(17): 52012.
29	CHANG Chun, LIU Liwei, LI Pan, et al. Preparation of flame retardant polyurethane foam from crude glycerol based liquefaction of wheat straw[J]. Industrial Crops and Products, 2021, 160: 113098.
30	CHENG Jiaji, NIU Shaoshuai, KANG Moyun, et al. The thermal behavior and flame retardant performance of phase change material microcapsules with modified carbon nanotubes[J]. Energy, 2022, 240: 122821.
31	郑梓璇, 王德刚, 梁国杰, 等. 聚氨酯泡沫浸渍酚醛树脂溶液制备炭泡沫隔热材料研究[J]. 材料导报, 2022, 36(7): 227-233.
	ZHENG Zixuan, WANG Degang, LIANG Guojie, et al. Preparation of carbon foam insulation material from polyurethane foam impregnated with phenolic resin solution[J]. Materials Reports, 2022, 36(7): 227-233.
32	张继, 边金彩, 何珍妮, 等. 低聚羟丙基磷酸乙酯阻燃剂的合成及应用[J]. 精细化工, 2021, 38(9): 1913-1919, 1927.
	ZHANG Ji, BIAN Jincai, HE Zhenni, et al. Synthesis and application of oligohydroxypropyl ethyl phosphate flame retardant[J]. Fine Chemicals, 2021, 38(9): 1913-1919, 1927.
33	林绍铃, 罗祖获, 陈丹青, 等. 无卤阻燃硬质聚氨酯泡沫塑料研究进展[J]. 材料导报, 2021, 35(1): 1196-1202.
	LIN Shaoling, LUO Zuhuo, CHEN Danqing, et al. Research progress on halogen-free flame retardant rigid polyurethane foam[J]. Materials Reports, 2021, 35(1): 1196-1202.
34	黄文媛, 孙士杰, 唐宏震, 等. 聚氨酯泡沫固定化Alcaligenes sp. DN25去除苯酚的研究[J]. 化工学报, 2021, 72(5): 2783-2791.
	HUANG Wenyuan, SUN Shijie, TANG Hongzhen, et al. Phenol removal by the Alcaligenes sp. DN25 immobilized on the polyurethane foams[J]. CIESC Journal, 2021, 72(5): 2783-2791.

[1]	黄军, 张应娟, 林茵童, 韦雪纯, 吴雨桐, 毋高博, 莫钧麟, 赵祯霞, 赵钟兴. 蚕沙基生物多孔炭的制备及对杀虫单/呋虫胺的协同吸附与缓释性能[J]. 化工进展, 2024, 43(7): 3964-3971.
[2]	刘泽鹏, 曾纪珺, 唐晓博, 赵波, 韩升, 廖袁淏, 张伟. 四种烷基咪唑磷酸酯离子液体的热力学性质[J]. 化工进展, 2024, 43(3): 1484-1491.
[3]	李云闯, 谢方明, 席亚男, 万新月, 孙玉虎, 赵永峰, 李根, 刘宏海, 高雄厚, 刘洪涛. 高水热稳定性介孔分子筛的低成本合成研究进展[J]. 化工进展, 2023, 42(4): 1877-1884.
[4]	张晨光, 封硕, 邢玉烨, 沈伯雄, 苏立超. 柴油车用NH₃-SCR铜基分子筛催化剂孤立态Cu²⁺研究进展[J]. 化工进展, 2023, 42(3): 1321-1331.
[5]	蒋佳骏, 吴张永, 朱启晨, 蔡昌礼, 朱家军, 王志强. In-Bi-Sn基Si₃N₄/GNFs混合纳米流体的流变性和润滑性[J]. 化工进展, 2023, 42(12): 6197-6206.
[6]	罗继永, 张道海, 周密, 田琴, 秦舒浩. PBT/TPU/DOPO-MA阻燃复合材料的制备及性能[J]. 化工进展, 2020, 39(8): 3221-3229.
[7]	李均星, 郭锦棠, 张弛, 李鹏鹏. 一种新型缓凝剂的制备及其在水泥基复合材料中的应用[J]. 化工进展, 2019, 38(06): 2953-2960.
[8]	辛华, 杨江鹏, 徐敬尧, 王静会, 赵星, 郭兵. 有机硅协同改性含氟聚氨酯[J]. 化工进展, 2018, 37(11): 4444-4450.
[9]	郭亚军, 胡立红, 张娜, 周永红. 纳米SiO₂-木质素基酚醛泡沫的热稳定性及韧性表征[J]. 化工进展, 2017, 36(12): 4569-4574.
[10]	崔喜, 刘冰灵, 赫崇衡, 田恒水. 脂肪族聚醚型聚氨酯弹性体热降解机理及热稳定性[J]. 化工进展, 2016, 35(11): 3585-3589.
[11]	陈缘博, 包慧敏, 苗海龙, 李晓林, 王益庆, 郑广宇. 氧化破胶剂过硫酸钾的安全性[J]. 化工进展, 2016, 35(10): 3267-3272.
[12]	马健, 赵基钢, 王荣杰, 舒阳, 沈本贤. 基于分子模拟的不溶性硫黄稳定剂的性能[J]. 化工进展, 2016, 35(03): 706-710.
[13]	张旭, 王志, 王旭, 谢华. 磷酸盐阻燃液的制备及阻燃棉布的应用[J]. 化工进展, 2015, 34(11): 4023-4025.
[14]	郑德志, 辛梅华, 李明春. 软质聚氨酯泡沫塑料无卤阻燃技术研究进展[J]. 化工进展, 2015, 34(09): 3349-3355,3362.
[15]	钱伟1，3，李湘洲1，2，吴志平1，房丛丛4，殷凯1，贾可敬1. 茶皂素基膨胀型阻燃剂的制备及其在涂料中的应用[J]. 化工进展, 2014, 33(01): 198-203.