木质素/PVA发泡材料的制备及性能表征
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摘要
目的探究木质素/PVA发泡材料的制备工艺及性能优化。方法采用控制单一变量和正交试验法对木质素、PVA溶液质量分数、甲醛、硫酸的制备工艺进行探索及优化。结果单因素试验结果显示,木质素/PVA发泡材料的最佳工艺水平,PVA溶液的质量分数为9%,木质素用量为30%(文中所提用量均表示相对于PVA的质量,下同),甲醛用量为24%,硫酸用量为39%。正交试验结果显示,发泡材料的制备工艺最优组合,PVA溶液的质量分数为9%,木质素用量为20%,甲醛用量为40%,硫酸用量为47%。FTIR结果显示,木质素与PVA在适宜的条件下发生缩醛交联反应生成木质素/PVA发泡材料,但反应程度低,以在木质素苯环5位发生的取代反应为主。SEM显示,在不考虑各因素的相互影响下,各单因素木质素用量为30%,PVA溶液的质量分数为9%,甲醛用量为24%,硫酸用量为47%时所制备的发泡材料形成了较规则、均匀分布的泡孔或数目较多的孔隙结构。结论各单因素用量对木质素/PVA发泡材料的性能有很大影响,4个因素对发泡材料性能影响的主次排序为木质素用量>PVA溶液的质量分数>硫酸用量>甲醛用量。
The work aims to study the preparation process and performance optimization of lignin/PVA foam materials. The preparation process of lignin, PVA solution mass fraction, formaldehyde and sulfuric acid were explored and optimized by the control of single variable and orthogonal experiment. The single-factor experiment results showed the technological level of lignin/PVA foam materials is optimal when the mass fraction of PVA solution was 9%, the amount of lignin was 30%(the amount proposed herein indicated the mass relative to PVA, the same below), and the amount of formaldehyde and sulfuric acid was respectively 24% and 39%. The orthogonal test results showed the preparation process of lignin/PVA foam materials was the optimal combination when the mass fraction of PVA solution was 9%, the amount of lignin was 20%, and the amount of formaldehyde and sulfuric acid was respectively 40% and 47%. According to the FTIR results, lignin and PVA underwent acetal crosslinking reaction and produced lignin/PVA foam material under the appropriate conditions, but the reaction rate was low, and the substitution reaction mainly occurred at the 5th lignin benzene ring. SEM showed that, when the amount of the single-factor lignin was 30%, the mass fraction of PVA solution was 9%, the amount of formaldehyde was 24% and the amount of sulfuric acid was 47%, without considering the influence of each factor, the prepared foam material formed regular, evenly distributed pores or a large number of pore structures. In conclusion, each single factor has a great influence on the performance of the lignin/PVA foam materials. The order of priority regarding the influence of the four factors on the performance of the foam materials was: the amount of lignin>the mass fraction of PVA solution> the amount of sulfuric acid>the amount of formaldehyde.
The work aims to study the preparation process and performance optimization of lignin/PVA foam materials. The preparation process of lignin, PVA solution mass fraction, formaldehyde and sulfuric acid were explored and optimized by the control of single variable and orthogonal experiment. The single-factor experiment results showed the technological level of lignin/PVA foam materials is optimal when the mass fraction of PVA solution was 9%, the amount of lignin was 30%(the amount proposed herein indicated the mass relative to PVA, the same below), and the amount of formaldehyde and sulfuric acid was respectively 24% and 39%. The orthogonal test results showed the preparation process of lignin/PVA foam materials was the optimal combination when the mass fraction of PVA solution was 9%, the amount of lignin was 20%, and the amount of formaldehyde and sulfuric acid was respectively 40% and 47%. According to the FTIR results, lignin and PVA underwent acetal crosslinking reaction and produced lignin/PVA foam material under the appropriate conditions, but the reaction rate was low, and the substitution reaction mainly occurred at the 5th lignin benzene ring. SEM showed that, when the amount of the single-factor lignin was 30%, the mass fraction of PVA solution was 9%, the amount of formaldehyde was 24% and the amount of sulfuric acid was 47%, without considering the influence of each factor, the prepared foam material formed regular, evenly distributed pores or a large number of pore structures. In conclusion, each single factor has a great influence on the performance of the lignin/PVA foam materials. The order of priority regarding the influence of the four factors on the performance of the foam materials was: the amount of lignin>the mass fraction of PVA solution> the amount of sulfuric acid>the amount of formaldehyde.
引文
[1]于菲.碱木质素基硬质聚氨酯泡沫制备及性能表征[D].哈尔滨:东北林业大学,2009.YU Fei.Preparation and Performance Characterization of Alkali Lignin Based Rigid Polyurethane Foam[D].Harbin:Northeast Forestry University,2009.
[2]PAN X J,SADDLER J N.Effect of Replacing Polyol by Organosolv and Kraft Lignin on the Property and Structure of Rigid Polyurethane Foam[J].Biotechnology for Biofuels,2013,6(12):2—10.
[3]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 Li-hong.Study on the Preparation and Properties of Lignin-based Phenolic Foam Thermal Insulation Material[D].Beijing:Chinese Academy of Forestry,2012.
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[7]苏玲,方桂珍.甲醛交联碱木质素-聚乙烯醇薄膜的透光性和透气性[J].农业工程学报,2014,30(4):239—246.SU Ling,FANG Gui-zhen.Transparency and Permeability of Alkaline Lignin-Polyvinyl Alcohol Films in Formaldehyde Crosslinking[J].Journal of Agricultural Engineering,2014,30(4):239—246.
[8]姜玉,魏风军.聚乙烯醇缩甲醛泡沫塑料的研究进展[J].中国塑料,2011(4):12—16.JIANG Yu,WEI Feng-jun.Advances in Polyvinyl Formaldehyde Foam Plastics[J].China Plastics,2011(4):12—16.
[9]WANG J W.Lignin Waste Polyurethane Cushion Packaging Materials Research[J].Applied Mechanics&Materials,2014(488/489):98—101.
[10]唐龙祥,王安锋,刘春华,等.聚乙烯醇缩甲醛吸水泡沫塑料的制备及性能研究[J].塑料助剂,2012(5):34—36.TANG Long-xiang,WANG An-feng,LIU Chun-hua,et al.Preparation and Properties of Polyvinyl Alcohol for Maldehyde Absorbent Foam[J].Plastics Auxiliaries,2012(5):34—36.
[11]马倩云,韩建国,鄂雷,等.甲醛交联麦草碱木质素-聚乙烯醇反应膜的制备及其性能研究[J].北京林业大学学报,2014(4):141—146.MA Qian-yun,HAN Jian-guo,E Lei,et al.Preparation and Properties of Chitin Cross-linked Wheat Straw Lignin-Polyvinyl Alcohol Reaction Membrane[J].Journal of Beijing Forestry University,2014(4):141—146.
[12]姜玉,魏风军.聚乙烯醇缩甲醛泡沫塑料的研究进展[J].中国塑料,2011(4):12—16.JIANG Yu,WEI Feng-jun.Advances in Polyvinyl Formaldehyde Foam Plastics[J].China Plastics,2011(4):12—16.
[13]罗华超,任世学,马艳丽,等.聚乙烯醇—碱木质素发泡材料的制备与性能[J].北京林业大学学报,2015,37(4):127—134.LUO Hua-chao,REN Shi-xue,MA Yan-li,et al.Preparation and Properties of Polyvinyl Alcohol-Alkali Lignin Foaming Material[J].Journal of Beijing Forestry University,2015,37(4):127—134.
[14]杨为宁,贾青青,王琴,等.发泡剂类型对聚乙烯醇发泡行为的影响[J].中国塑料,2012(8):81—84.YANG Wei-ning,JIA Qing-qing,WANG Qin,et al.Effects of Foaming Agent Types on Foaming Behavior of Polyvinyl Alcohol[J].China Plastics,2012(8):81—84.
[15]ANBARASAN R,PANDIARAJAGURU R,PRABHU R,et al.Synthesis,Characterizations,and Mechanical Properties of Structurally Modified Poly(Vinyl Alcohol)[J].Journal of Applied Polymer Science,2010,117(4):2059—2068.
[16]黄灵阁,刘培义,李新法,等.AS/PVA生物降解包装塑料的红外光谱分析[C]//第十三届全国包装工程学术会议论文集,2010:4.HUANG Ling-ge,LIU Pei-yi,LI Xin-fa,et al.AS/PVA Biodegradable Packaging Plastics Infrared Spectroscopy Analysis[C]//The 13th National Packaging Engineering Conference Proceedings,2010:4.
[17]苏玲,任世学,方桂珍.戊二醛交联碱木质素/聚乙烯醇膜的制备及其光学性能[J].生物质化学工程,2013,47(3):1—5.SU Ling,REN Shi-xue,FANG Gui-zhen.Preparation and Optical Properties of Glutaraldehyde Cross Linked Alkaline Lignin/Polyvinyl Alcohol Membrane[J].Biomass Chemical Engineering,2013,47(3):1—5.
[18]YUAN C.Study on the Structural Characteristics of Alkali Lignin from Wheat Straw[J].Paper Science&Technology,2008(2):20—23.
[19]LEWIS N G,YAMAMOTO E.Lignin:Occurrence,Biogenesis and Biodegradation[J].Plant Physiology and Plant Molecular Biology,1990,41(1):455—496.
[2]PAN X J,SADDLER J N.Effect of Replacing Polyol by Organosolv and Kraft Lignin on the Property and Structure of Rigid Polyurethane Foam[J].Biotechnology for Biofuels,2013,6(12):2—10.
[3]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 Li-hong.Study on the Preparation and Properties of Lignin-based Phenolic Foam Thermal Insulation Material[D].Beijing:Chinese Academy of Forestry,2012.
[4]LI X L,LI Y F,ZHANG S D,et al.Preparation and Characterization of New Foam Adsorbents of Poly(vinyl alcohol)/Chitosan Composites and Their Removal for Dye and Heavy Metal from Aqueous Solution[J].Chemical Engineering Journal,2012,183:88—97.
[5]罗华超,陈禾木,陈颖超,等.聚乙烯醇/改性碱木质素发泡材料的制备与性能[J].生物质化学工程,2015(2):1—6.LUO Hua-chao,CHEN He-mu,CHEN Ying-chao,et al.Preparation and Properties of Polyvinyl Alcohol/Modified Alkaline Lignin Foam Material[J].Biomass Chemical Engineering,2015(2):1—6.
[6]陈禾木,罗华超,王琛,等.有机发泡剂制备聚乙烯醇—碱木质素发泡材料及性能研究[J].北京林业大学学报,2015,37(7):109—116.CHEN He-mu,LUO Hua-chao,WANG Chen,et al.Study on Preparation and Properties of Polyvinyl Alcohol-Lignin Foam by Organic Foaming Agent[J].Journal of Beijing Forestry University,2015,37(7):109—116.
[7]苏玲,方桂珍.甲醛交联碱木质素-聚乙烯醇薄膜的透光性和透气性[J].农业工程学报,2014,30(4):239—246.SU Ling,FANG Gui-zhen.Transparency and Permeability of Alkaline Lignin-Polyvinyl Alcohol Films in Formaldehyde Crosslinking[J].Journal of Agricultural Engineering,2014,30(4):239—246.
[8]姜玉,魏风军.聚乙烯醇缩甲醛泡沫塑料的研究进展[J].中国塑料,2011(4):12—16.JIANG Yu,WEI Feng-jun.Advances in Polyvinyl Formaldehyde Foam Plastics[J].China Plastics,2011(4):12—16.
[9]WANG J W.Lignin Waste Polyurethane Cushion Packaging Materials Research[J].Applied Mechanics&Materials,2014(488/489):98—101.
[10]唐龙祥,王安锋,刘春华,等.聚乙烯醇缩甲醛吸水泡沫塑料的制备及性能研究[J].塑料助剂,2012(5):34—36.TANG Long-xiang,WANG An-feng,LIU Chun-hua,et al.Preparation and Properties of Polyvinyl Alcohol for Maldehyde Absorbent Foam[J].Plastics Auxiliaries,2012(5):34—36.
[11]马倩云,韩建国,鄂雷,等.甲醛交联麦草碱木质素-聚乙烯醇反应膜的制备及其性能研究[J].北京林业大学学报,2014(4):141—146.MA Qian-yun,HAN Jian-guo,E Lei,et al.Preparation and Properties of Chitin Cross-linked Wheat Straw Lignin-Polyvinyl Alcohol Reaction Membrane[J].Journal of Beijing Forestry University,2014(4):141—146.
[12]姜玉,魏风军.聚乙烯醇缩甲醛泡沫塑料的研究进展[J].中国塑料,2011(4):12—16.JIANG Yu,WEI Feng-jun.Advances in Polyvinyl Formaldehyde Foam Plastics[J].China Plastics,2011(4):12—16.
[13]罗华超,任世学,马艳丽,等.聚乙烯醇—碱木质素发泡材料的制备与性能[J].北京林业大学学报,2015,37(4):127—134.LUO Hua-chao,REN Shi-xue,MA Yan-li,et al.Preparation and Properties of Polyvinyl Alcohol-Alkali Lignin Foaming Material[J].Journal of Beijing Forestry University,2015,37(4):127—134.
[14]杨为宁,贾青青,王琴,等.发泡剂类型对聚乙烯醇发泡行为的影响[J].中国塑料,2012(8):81—84.YANG Wei-ning,JIA Qing-qing,WANG Qin,et al.Effects of Foaming Agent Types on Foaming Behavior of Polyvinyl Alcohol[J].China Plastics,2012(8):81—84.
[15]ANBARASAN R,PANDIARAJAGURU R,PRABHU R,et al.Synthesis,Characterizations,and Mechanical Properties of Structurally Modified Poly(Vinyl Alcohol)[J].Journal of Applied Polymer Science,2010,117(4):2059—2068.
[16]黄灵阁,刘培义,李新法,等.AS/PVA生物降解包装塑料的红外光谱分析[C]//第十三届全国包装工程学术会议论文集,2010:4.HUANG Ling-ge,LIU Pei-yi,LI Xin-fa,et al.AS/PVA Biodegradable Packaging Plastics Infrared Spectroscopy Analysis[C]//The 13th National Packaging Engineering Conference Proceedings,2010:4.
[17]苏玲,任世学,方桂珍.戊二醛交联碱木质素/聚乙烯醇膜的制备及其光学性能[J].生物质化学工程,2013,47(3):1—5.SU Ling,REN Shi-xue,FANG Gui-zhen.Preparation and Optical Properties of Glutaraldehyde Cross Linked Alkaline Lignin/Polyvinyl Alcohol Membrane[J].Biomass Chemical Engineering,2013,47(3):1—5.
[18]YUAN C.Study on the Structural Characteristics of Alkali Lignin from Wheat Straw[J].Paper Science&Technology,2008(2):20—23.
[19]LEWIS N G,YAMAMOTO E.Lignin:Occurrence,Biogenesis and Biodegradation[J].Plant Physiology and Plant Molecular Biology,1990,41(1):455—496.