木质素基聚氨酯预聚体改性酚醛泡沫的制备及表征

doi:10.3969/j.issn.0253-2417.2017.01.008

林产化学与工业 ›› 2017, Vol. 37 ›› Issue (1): 63-72.doi: 10.3969/j.issn.0253-2417.2017.01.008

木质素基聚氨酯预聚体改性酚醛泡沫的制备及表征

薄采颖¹, 胡立红^1,2, 杨晓慧¹, 郑敏睿¹, 张猛¹, 周永红¹

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;国家林业局林产化学工程重点开放性实验室;江苏省生物质能源与材料重点实验室, 江苏南京 210042;
2.中国林业科学研究院林业新技术研究所, 北京 100091

收稿日期:2016-06-15 出版日期:2017-02-25 发布日期:2017-02-25
通讯作者: 周永红,研究员,博士,博士生导师,主要从事生物质化学转化与应用的研究;E-mail:yhzhou777@163.com。 E-mail:yhzhou777@163.com
作者简介:薄采颖(1984-),女,江苏东海人,助理研究员,博士生,主要从事生物质资源转化与利用研究;E-mail:newstar2002@163.com
基金资助:
国家自然科学基金资助项目（31470613）；江苏省生物质绿色燃料与化学品重点实验室开放基金（JSBGFC14002）

Preparation and Characterization of Phenolic Foams Modified by Lignin-based Polyurethane Prepolymers

BO Caiying¹, HU Lihong^1,2, YANG Xiaohui¹, ZHENG Minrui¹, ZHANG Meng¹, ZHOU Yonghong¹

1. Institute of Chemical Industry of Forest Products, CAF;National Engineering Lab. for Biomass Chemical Utilization;Key and Open Lab. of Forest Chemical Engineering, SFA;Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China;
2. Research Institute of Forestry New Technology, CAF, Beijing 100091, China

Received:2016-06-15 Online:2017-02-25 Published:2017-02-25

摘要/Abstract

摘要： 以聚乙二醇（PEG）为液化剂液化木质素，得到液化产物直接合成木质素基聚氨酯预聚体（LLPUPs），并用来改性酚醛泡沫。采用FT-IR对木质素液化产物（LLs）和LLPUPs的结构进行了表征和分析，通过SEM、万能试验机结合热重分析仪研究了LLPUPs对酚醛泡沫的形态，机械性能和热稳定性的影响。结果表明：木质素液化产物的羟值为177~286 mg/g，并随着PEG相对分子质量的增加而下降；添加LLPUPs可以增强酚醛泡沫的压缩强度和比压缩强度，当LLPUP2添加量为9%时，比压缩强度最高，为4.44（Pa·m³）/g；LLPUP1和LLPUP2添加量为9%时，酚醛泡沫泡孔均匀，当LLPUP1添加量为9%时，比弯曲强度最高，为8.23（Pa·m³）/g；LLPUPs改性酚醛泡沫与纯酚醛泡沫相比，具有相似的热稳定性。

关键词: 液化木质素, 酚醛泡沫, 聚氨酯预聚体, 表征

Abstract: Lignin was liquefied with polyethylene glycol (PEG) in a solvent-free system and then directly used with suitable PEG as a co-monomer and co-solvent to prepare liquefied lignins (LLs)-based polyurethane prepolymers (LLPUPs). The structural changes that lignin undergoes after liquefaction were studied by Fourier transform infrared spectroscopy (FT-IR), the hydroxyl number of LL is 177-286 mg/g and decreases with the increasing of molecular mass of PEG. The structures of LLPUPs were characterized by FT-IR. Then, phenolic foams (PFs) modified with different contents of LLPUPs were prepared. Morphological properties, mechanical properties and thermal stability of PFs were assessed by scanning electron microscopy (SEM), universal test and thermogravimetric analysis (TGA). Results show that uniform cells can be prepared by incorporating 9% LLPUP1 and LLPUP2 into the network. The addition of LLPUPs into foam formulations improves the compressive strength and specific compressive strength of PFs, and the highest specific compressive strength is obtained by adding 9% LLPUP2 (4.44(Pa·m³)/g). Appropriate levels of LLPUPs could improve the specific flexural strength of PFs, and the highest specific flexural strength is obtained by adding 9% LLPUP1 (8.23(Pa·m³)/g). PFs modified with different contents of LLPUPs show similar thermal resistance as pristine foam.

Key words: liquefied lignin, phenolic foams, polyurethane prepolymer, characterization

中图分类号:

TQ35

薄采颖, 胡立红, 杨晓慧, 郑敏睿, 张猛, 周永红. 木质素基聚氨酯预聚体改性酚醛泡沫的制备及表征[J]. 林产化学与工业, 2017, 37(1): 63-72.

BO Caiying, HU Lihong, YANG Xiaohui, ZHENG Minrui, ZHANG Meng, ZHOU Yonghong. Preparation and Characterization of Phenolic Foams Modified by Lignin-based Polyurethane Prepolymers[J]. Chemistry and Industry of Forest Products, 2017, 37(1): 63-72.

参考文献

[1] RANGARI V K,HASSAN T A,ZHOU Y X,et al.Cloisite clay-infused phenolic foam nanocomposites[J].Journal of Applied Polymer Science,2007,103(1):308-314.
[2] DESAI A,NUTT S R,ALONSO M V.Modeling of fiber-reinforced phenolic foam[J].Journal of Cellular Plastics,2008,44(5):391-413.
[3] AUAD M L,ZHAO L H,SHEN H B,et al.Flammability properties and mechanical performance of epoxy modified phenolic foams[J].Journal of Applied Polymer Science,2007,104(3):1399-1407.
[4] SAZ-OROZCO B DEL,OLIET M,ALONSO M V,et al.Formulation optimization of unreinforced and lignin nanoparticle-reinforced phenolic foams using an analysis of variance approach[J].Composites Science and Technology,2012,72(6):667-674.
[5] SAZ-OROZCO B DEL,ALONSO M V,OLIET M,et al.Effects of formulation variables on density,compressive mechanical properties and morphology of wood flour-reinforced phenolic foams[J].Composites Part B:Engineering,2014,56:546-552.
[6] KAYNAK C,CAGATAY O.Rubber toughening of phenolic resin by using nitrile rubber and amino silane[J].Polymer Testing,2006,25(3):296-305.
[7] YANG H Y,WANG X,YU B,et al.A novel polyurethane prepolymer as toughening agent:Preparation,characterization,and its influence on mechanical and flame retardant properties of phenolic foam[J].Journal of Applied Polymer Science,2013,128(5):2720-2728.
[8] CRITCHFIELD F E,PAPA A J,ROLLINS R L.Phenolic foam modified with phosphorus-containing isocyanate-terminated prepolymers:USA 4119584[P].1978-10-10.
[9] YUAN H X,XING W Y,YANG H Y,et al.Mechanical and thermal properties of phenolic/glass fiber foam modified with phosphorus containing polyurethane prepolymer[J].Polymer International,2013,62(2):273-279.
[10] NOWAKOWSKI D J,BRIDGWATER A V,ELLIOTT D C,et al.Lignin fast pyrolysis:Results from an international collaboration[J].Journal of Analytical and Applied Pyrolysis,2010,88(1):53-72.
[11] LAURICHESSE S,AVÉROUS L.Chemical modification of lignins:Towards biobased polymers[J].Progress in Polymer Science,2014,39(7):1266-1290.
[12] KIM K H,YU J H,LEE E Y.Crude glycerol-mediated liquefaction of saccharification residues of sunflower stalks for production of lignin biopolyols[J].Journal of Industrial and Engineering Chemistry,2016,38:175-180.
[13] LI H Q,SHAO Q,LUO H,et al.Polyurethane foams from alkaline lignin-based polyether polyol[J/OL].Journal of Applied Polymer Science,2016,133(14).[2016-03-15].DOI:10.1002/app.43261.
[14] HU L H,ZHOU Y H,LIU R J,et al.Synthesis of foaming resol resin modified with oxidatively degraded lignosulfonate[J].Industrial Crops and Products,2013,44:364-366.
[15] D'SOUZA J,YAN N.Producing bark-based polyols through liquefaction:Effect of liquefaction temperature[J].ACS Sustainable Chemistry & Engineering,2013,1(5):534-540.
[16] LEE W J,LIN M S.Preparation and application of polyurethane adhesives made from polyhydric alcohol liquefied Taiwan acacia and China fir[J].Journal of Applied Polymer Science,2008,109(1):23-31.
[17] ZHANG X,YUAN T,PENG F,et al.Separation and structural characterization of lignin from hybrid poplar based on complete dissolution in DMSO/LiCl[J].Separation Science and Technology,2010,45(16):2497-2506.
[18] JIN Y,RUAN X,CHENG X,et al.Liquefaction of lignin by polyethyleneglycol and glycerol[J].Bioresource Technology,2011,102(3):3581-3583.
[19] OPREA S.Synthesis and properties of polyurethane elastomers with castor oil as crosslinker[J].Journal of the American Oil Chemists' Society,2010,87(3):313-320.
[20] TONDI G,PIZZI A.Tannin-based rigid foams:Characterization and modification[J].Industrial Crops and Products,2009,29(2):356-363.
[21] CINELLI P,ANGUILLESI I,LAZZERI A.Green synthesis of flexible polyurethane foams from liquefied lignin[J].European Polymer Journal,2013,49(6):1174-1184.
[22] CHAUHAN M,GUPTA M,SINGH B,et al.Effect of functionalized lignin on the properties of lignin-isocyanate prepolymer blends and composites[J].European Polymer Journal,2014,52:32-43.
[23] YANG Y,HE J.Mechanical characterization of phenolic foams modified by short glass fibers and polyurethane prepolymer[J].Polymer Composites,2015,36(9):1584-1589.
[24] NAKAMURA K,MÖRCK R,REIMANN A,et al.Mechanical properties of solvolysis lignin-derived polyurethanes[J].Polymers for Advanced Technologies,1991,2(1):41-47.
[25] GONG R,XU Q,CHU Y,et al.A simple preparation method and characterization of epoxy reinforced microporous phenolic open-cell sound absorbent foam[J].RSC Advances,2015,5(83):68003-68013.
[26] ZÁRATE C N,ARANGUREN M I,REBOREDO M M.Thermal degradation of a phenolic resin,vegetable fibers,and derived composites[J].Journal of Applied Polymer Science,2008,107(5):2977-2985.
[27] MA Y F,WANG J F,XU Y Z,et al.Preparation and characterization of phenolic foams with eco-friendly halogen-free flame retardant[J].Journal of Thermal Analysis and Calorimetry,2013,114(3):1143-1151.
[28] CARVALHO G,FROLLINI E.Lignin in phenolic closed cell foams:Thermal stability and apparent density[J].Journal of Macromolecular Science,Part A,2002,39(7):643-656.
[29] LAURICHESSE S,HUILLET C,AVÉROUS L.Original polyols based on organosolv lignin and fatty acids:New bio-based building blocks for segmented polyurethane synthesis[J].Green Chemistry,2014,16(8):3958-3970.
[30] YANG C,ZHUANG Z H,YANG Z G.Pulverized polyurethane foam particles reinforced rigid polyurethane foam and phenolic foam[J/OL].Journal of Applied Polymer Science,2014,131(1).[2016-03-15].DOI:10.1002/app.39734.

木质素基聚氨酯预聚体改性酚醛泡沫的制备及表征

Preparation and Characterization of Phenolic Foams Modified by Lignin-based Polyurethane Prepolymers

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