酚化改性蔗渣硫酸盐木素制备酚醛树脂胶黏剂
|
摘要
本研究以蔗渣硫酸盐木素(KL)为原料,在酸性条件下对KL进行酚化改性,通过单因素实验和正交实验优化反应条件。以酚化改性硫酸盐木素(P-KL)酚羟基含量为响应值,确定最佳反应条件为:苯酚∶木素(质量比)=4∶1,催化剂(质量分数98%浓硫酸)用量4%,反应时间2. 5 h,反应温度110℃。利用凝胶渗透色谱(GPC)表征硫酸盐木素酚化改性前后相对分子质量的变化,结果表明,与KL相比,P-KL相对分子质量减小、分布变窄,酚羟基含量增加。分别用P-KL和KL代替质量分数60%的苯酚制取木素基酚醛树脂胶黏剂P-KLPF和KLPF。结果表明,P-KLPF中游离甲醛和游离酚含量均小于KLPF胶黏剂。由此可知,酚化改性能显著提高硫酸盐木素与甲醛的反应活性,降低木素基酚醛树脂胶黏剂中游离甲醛及苯酚的释放量。
In this study,sugarcane bagasse kraft lignin( KL) was phenolated by using acid as a catalyst. The phenolation process was optimized by single-factor and orthogonal experimental design where the phenolic hydroxyl group content of lignin was used as response value.The optimal conditions were found as follows: phenol∶ KL = 4∶ 1( mass ratio),t = 2. 5 h,T = 110℃,the catalyst dosage( concentrated sulphuric acid of 98 wt%) was 4%. The structural changes of KL induced by phenolation were further characterized by~31 P Nuclear Magnetic Resonance Spectroscopy(~31 P NMR),and Fourier Transform infrared spectroscopy. The results indicated that the molecular weight and the polydispersity of phenolated bagasse kraft lignin( PKL) decreased. The phenolic hydroxyl group content increased. Eventually,P-KL and KL were respectively used to replace 60 wt % of phenol to produce phenolic formaldehyde( PF) adhesives as P-KLPF and KLPF. Compared to KLPF,less formaldehyde and phenol were released from P-KLPF which indicated that phenolation was an effective way to improve the reaction activity bagasse kraft lignin lignin and formaldehyde.
In this study,sugarcane bagasse kraft lignin( KL) was phenolated by using acid as a catalyst. The phenolation process was optimized by single-factor and orthogonal experimental design where the phenolic hydroxyl group content of lignin was used as response value.The optimal conditions were found as follows: phenol∶ KL = 4∶ 1( mass ratio),t = 2. 5 h,T = 110℃,the catalyst dosage( concentrated sulphuric acid of 98 wt%) was 4%. The structural changes of KL induced by phenolation were further characterized by~31 P Nuclear Magnetic Resonance Spectroscopy(~31 P NMR),and Fourier Transform infrared spectroscopy. The results indicated that the molecular weight and the polydispersity of phenolated bagasse kraft lignin( PKL) decreased. The phenolic hydroxyl group content increased. Eventually,P-KL and KL were respectively used to replace 60 wt % of phenol to produce phenolic formaldehyde( PF) adhesives as P-KLPF and KLPF. Compared to KLPF,less formaldehyde and phenol were released from P-KLPF which indicated that phenolation was an effective way to improve the reaction activity bagasse kraft lignin lignin and formaldehyde.
引文
[1]QIN Zu.Study on Preparation and Properties of Bayberry Tannin Modified Phenolic Resin Adhesive[D].Changsha:Central South University of Forestry and Technology,2017.覃族.杨梅栲胶改性酚醛树脂胶黏剂的制备及其性能研究[D].长沙:中南林业科技大学,2017.
[2]JIA Zhuan,WAN Guang-cong,LI Ming-fu,et al.Research Progress of Chemical Modification in Preparation of Lignin-based Phenolic Resin Adhesives[J].China Pulp&Paper,2018,37(3):72.贾转,万广聪,李明富,等.化学改性在木素基酚醛树脂胶黏剂制备中的研究进展[J].中国造纸,2018,37(3):72.
[3]ZHANG Ming-yang,JIN Xiao-juan.Research Progress of Preparation of Phenolic Resin Adhesive by Black Lignosin[J].China Pulp&Paper,2012,31(7):64.张铭洋,金小娟.黑液木素制备酚醛树脂胶黏剂的研究进展[J].中国造纸,2012,31(7):64.
[4]CHEN Yan-yan.Preparation of Lignin-phenolic Resin by Enzymatic Ligand Phenolization and Its Performance[D].Guangzhou:South China University of Technology,2011.陈艳艳.酶解木素酚化制备木素-酚醛树脂及其性能研究[D].广州:华南理工大学,2011.
[5]ZHANG Yan-ru,SONG Yan-na,DONG Rui-xue,et al.Alkali Lignin-catalyzed Phenol Modification[C]//The Proceedings of the Seventeenth Annual Academic Meeting,Xi'an:China Technical Association of Paper Industry,2016.张燕如,宋艳娜,董瑞雪,等碱木质素催化酚化改性的研究[C]//中国造纸学会第十七届学术年会论文集,西安:中国造纸学会,2016.
[6]WANG Jun.Study on Modification of Enzymatic lignin Hydroxymethylation and preparation of Phenolic Resin[D].Beijing:China Academy of Forestry Sciences,2017.王钧.酶解木素羟甲基化改性及制备酚醛树脂的研究[D].北京:中国林业科学研究院,2017.
[7]HU Li-hong,ZHOU Yong-hong,PAN Hui,et al.Modification of lignin De-methylation and characterization of its structure[J].Polymer bulletin,2012(3):77.胡立红,周永红,潘晖,等.木素脱甲基化改性及产物结构表征[J].高分子通报,2012(3):77.
[8]ZHANG Zhan-ye,MU Huan-zhen,ZHANG Chun-ping,et al.Polymerization and ionization modification of amphoteric lignin graft copolymer[J].Environmental Chemistry,2007(5):654.张占业,穆环珍,张春萍,等.两性木素接枝共聚物的聚合反应与离子化改性[J].环境化学,2007(5):654.
[9]HE Jin-cun.Study on Synthesis of Phenolic Resin adhesive by PhenolModified lignin[D].Harbin:Northeast Forestry University,2013.何金存.酚化改性木素合成酚醛树脂胶黏剂的研究[D].哈尔滨:东北林业大学,2013.
[10]LIU Gang-yong,QIU Xue-qing,XING De-song.Study on phenol modification of wheat straw alkali lignin and preparation of LPF adhesive[J].Journal of chemical engineering in Colleges and Universities,2007(4):678.刘纲勇,邱学青,邢德松.麦草碱木素酚化改性及其制备LPF胶黏剂工艺研究[J].高校化学工程学报,2007(4):678.
[11]Tabarsa T S,Jahanshahi S,Ashori A.Mechanical and physical properties of wheat straw boards bonded with a tannin modified phenolformaldehyde adhesive[J].Composite Part B,2011,42:176.
[12]Granata A,Argyropouols D S.2-Chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphosp-holane,a Reagent for the Accurate Determination of the Uncondensed and Condensed Phenolic Moieties in Lignins[J].Journal of Agricultural and Food Chemistry,1995,43(6):1538.
[13]Argyropouols D S.Quantitative Phosphorus-31 NMR Analysis of Lignins,a New Tool for the Lignin Chemist[J].Journal of Agricultural and Food Chemistry,1994,14(1):45.
[14]Guerra A,Filpponen I,Lucial A,et al.Toward a better understanding of the lignin isolation process from wood[J].Journal of Agricultural and Food Chemistry,2006,54(16):5939.
[15]JIANG Xiao.Fractionation and characterization of Kraft lignin[D].Nanjing:Nanjing Forestry University,2015.蒋晓.硫酸盐木素的分级分离与性能表征[D].南京:南京林业大学,2015.
[16]Podschun J,Saake B,Lehnen R.Reactivity enhancement of organosolv lignin by phenola-tion for improved bio-based thermosets[J].European Polymer Journal,2015,67:1.
[17]Lin L Z,Yao Y G,Shiraishi N.Liquefaction mechanism ofβ-O-4lignin model compound in the presence of phenol under acidcatalysis Part 1.Identification of the reaction products[J].Holzforschunng,2001,55(6):617.
[18]Lin L Z,Yao Y G,Shiraishi N,et al.Liquefaction mechanism ofβ-O-4 lignin model compound in the presence of phenol under acidcatalysis Part 2.Reaction behavior and pathways[J].Holzforschunng,2001,55(6):625.
[2]JIA Zhuan,WAN Guang-cong,LI Ming-fu,et al.Research Progress of Chemical Modification in Preparation of Lignin-based Phenolic Resin Adhesives[J].China Pulp&Paper,2018,37(3):72.贾转,万广聪,李明富,等.化学改性在木素基酚醛树脂胶黏剂制备中的研究进展[J].中国造纸,2018,37(3):72.
[3]ZHANG Ming-yang,JIN Xiao-juan.Research Progress of Preparation of Phenolic Resin Adhesive by Black Lignosin[J].China Pulp&Paper,2012,31(7):64.张铭洋,金小娟.黑液木素制备酚醛树脂胶黏剂的研究进展[J].中国造纸,2012,31(7):64.
[4]CHEN Yan-yan.Preparation of Lignin-phenolic Resin by Enzymatic Ligand Phenolization and Its Performance[D].Guangzhou:South China University of Technology,2011.陈艳艳.酶解木素酚化制备木素-酚醛树脂及其性能研究[D].广州:华南理工大学,2011.
[5]ZHANG Yan-ru,SONG Yan-na,DONG Rui-xue,et al.Alkali Lignin-catalyzed Phenol Modification[C]//The Proceedings of the Seventeenth Annual Academic Meeting,Xi'an:China Technical Association of Paper Industry,2016.张燕如,宋艳娜,董瑞雪,等碱木质素催化酚化改性的研究[C]//中国造纸学会第十七届学术年会论文集,西安:中国造纸学会,2016.
[6]WANG Jun.Study on Modification of Enzymatic lignin Hydroxymethylation and preparation of Phenolic Resin[D].Beijing:China Academy of Forestry Sciences,2017.王钧.酶解木素羟甲基化改性及制备酚醛树脂的研究[D].北京:中国林业科学研究院,2017.
[7]HU Li-hong,ZHOU Yong-hong,PAN Hui,et al.Modification of lignin De-methylation and characterization of its structure[J].Polymer bulletin,2012(3):77.胡立红,周永红,潘晖,等.木素脱甲基化改性及产物结构表征[J].高分子通报,2012(3):77.
[8]ZHANG Zhan-ye,MU Huan-zhen,ZHANG Chun-ping,et al.Polymerization and ionization modification of amphoteric lignin graft copolymer[J].Environmental Chemistry,2007(5):654.张占业,穆环珍,张春萍,等.两性木素接枝共聚物的聚合反应与离子化改性[J].环境化学,2007(5):654.
[9]HE Jin-cun.Study on Synthesis of Phenolic Resin adhesive by PhenolModified lignin[D].Harbin:Northeast Forestry University,2013.何金存.酚化改性木素合成酚醛树脂胶黏剂的研究[D].哈尔滨:东北林业大学,2013.
[10]LIU Gang-yong,QIU Xue-qing,XING De-song.Study on phenol modification of wheat straw alkali lignin and preparation of LPF adhesive[J].Journal of chemical engineering in Colleges and Universities,2007(4):678.刘纲勇,邱学青,邢德松.麦草碱木素酚化改性及其制备LPF胶黏剂工艺研究[J].高校化学工程学报,2007(4):678.
[11]Tabarsa T S,Jahanshahi S,Ashori A.Mechanical and physical properties of wheat straw boards bonded with a tannin modified phenolformaldehyde adhesive[J].Composite Part B,2011,42:176.
[12]Granata A,Argyropouols D S.2-Chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphosp-holane,a Reagent for the Accurate Determination of the Uncondensed and Condensed Phenolic Moieties in Lignins[J].Journal of Agricultural and Food Chemistry,1995,43(6):1538.
[13]Argyropouols D S.Quantitative Phosphorus-31 NMR Analysis of Lignins,a New Tool for the Lignin Chemist[J].Journal of Agricultural and Food Chemistry,1994,14(1):45.
[14]Guerra A,Filpponen I,Lucial A,et al.Toward a better understanding of the lignin isolation process from wood[J].Journal of Agricultural and Food Chemistry,2006,54(16):5939.
[15]JIANG Xiao.Fractionation and characterization of Kraft lignin[D].Nanjing:Nanjing Forestry University,2015.蒋晓.硫酸盐木素的分级分离与性能表征[D].南京:南京林业大学,2015.
[16]Podschun J,Saake B,Lehnen R.Reactivity enhancement of organosolv lignin by phenola-tion for improved bio-based thermosets[J].European Polymer Journal,2015,67:1.
[17]Lin L Z,Yao Y G,Shiraishi N.Liquefaction mechanism ofβ-O-4lignin model compound in the presence of phenol under acidcatalysis Part 1.Identification of the reaction products[J].Holzforschunng,2001,55(6):617.
[18]Lin L Z,Yao Y G,Shiraishi N,et al.Liquefaction mechanism ofβ-O-4 lignin model compound in the presence of phenol under acidcatalysis Part 2.Reaction behavior and pathways[J].Holzforschunng,2001,55(6):625.