木质素基环氧树脂的制备及其性能研究
摘要
木质素在自然界中的含量仅次于纤维素,是复杂的芳香化合物,是化工原料重要的潜在资源。利用可再生的木质素制备高分子材料,实现木质素在高分子材料领域对石油原料的有效替代,对于有效利用生物质资源和保护环境,具有重要意义。在本研究中,通过将乙酸木质素(AAL)以不同方式和环氧树脂共混以及对AAL的分级,探讨了AAL的不同级分的结构特性对制备的环氧树脂的性质的影响。
将AAL和E-44环氧树脂按不同比例共混。木质素环氧树脂共混物的初始热分解温度(T_d)随着AAL含量的增大缓慢降低,残炭率逐渐升高,其黏结剪切强度,其拉伸强度随着AAL含量的增大而减小,其吸水率随着AAL含量的增大而增大。
将AAL和双酚A按不同比例混合经环氧化后得到木质素改性双酚A环氧树脂(LBEP)。随着木质素含量的增大,LBEP固化物的T_d逐渐降低,残炭率逐渐升高,LBEP的黏结剪切强度略有降低。延长固化时间和提高固化温度有利于提高LBEP固化物的黏结剪切强度。随着AAL含量的增大,LBEP固化物的吸水率逐渐增大,AAL在LBEP固化物里的分布变得越来越不均匀。
AAL经过酚化改性后得到酚化木质素(PL),其酚羟基含量明显提高,相对分子质量略有降低。这有利于下一步环氧化反应制备木质素基环氧树脂(LER)。将LER和E-44环氧树脂共混固化,随着LER含量的增大,环氧树脂共混物的T_d逐渐降低,但残炭率逐渐升高;黏结剪切强度首先增大,并在LER含量为20%时具有最大值,此后趋于下降;拉伸强度逐渐降低。AAL在环氧树脂共混固化物中的分布变得越来越不均匀,吸水率逐渐增大。
采用沉淀法在不同浓度的乙酸水溶液中将AAL分成具有不同相对分子质量的3个级分。其中,相对分子质量最低的级分酚羟基含量最高,而初始热分解温度和残炭率都最低。3个级分经过酚化改性后,得到3种PL,其酚羟基含量较酚化前明显提高。3种酚化产物与环氧氯丙烷反应得到3种LER。由最低相对分子质量的PL制备的LER环氧值最高,T_d最高,但残炭率最低。由相对分子质量最低的AAL级分酚化及环氧化制备的LER与E-44环氧树脂共混固化后黏结剪切强度最高,达到7.9MPa。PL作为双酚A的替代物合成环氧树脂是可行的。
Lignin, the most abundant biopolymers on earth second only to cellulose, is a kind of complicated aromatic polymer. It is thought to be a potential resource for chemical raw materials. The conversion of lignin into polymer materials is of great importance in the utilization of biomass and protection of the environment. In this study, AAL was used in preparation of epoxy resin in different ways. AAL was fractionated and the impact of structural characteristics and blending method on the properties of epoxy resin was studied.
AAL was blended with E-44 epoxy resin with different ratio. With an increase in AAL content, the initial thermal decomposition temperature (T_d) of the cured lignin epoxy blends decreased slowly, the char content and water absorption of the cured lignin epoxy blends increased, and adhesive shear strength of cured lignin epoxy blends firstly increased and then decreased, the tensile strength was decreased. AAL was distributed in lignin-based epoxy blends in more heterogeneous way.
AAL was mixed with bisphenol A with different ratio and then the mixture was epoxidised to prepare lignin modified bisphenol A epoxy resin (LBEP). The increase of the curing time and curing temperature improved the adhesive shear strength of the cured LBEP. With the increase in AAL content, the T_d and the adhesive shear strength of cured LBEP decreased, char content and water absorption of cured LBEP increased, and adhesive shear strength slightly decreased. The existence of AAL in LBEP became heterogeneous.
Lignin-based epoxy resin (LER) was prepared from phenolated lignin (PL) and epichlorohydrin (ECH) in the presence of sodium hydroxide. LER was mixed with E-44 epoxy resin. As the increase of LER content, the T_d of the cured epoxy blends decreased, and the char content increased. The existence of LER in the cured epoxy blends became heterogeneous and the water absorption of the cured epoxy blends increased.
AAL was fractionated into three fractions by precipitation at different concentration of acetic acid- water solution. The fraction with the lowest relative molecular mass showed the highest phenolic hydroxyl content, the lowest T_d and the lowest char content. The three fractions reacted with phenol and yielded the corresponding PL. The phenol hydroxyl content of phenolated lignin fraction was higher than that of corresponding fraction. Three kinds of LER were prepared from PL by reacting with ECH. LER prepared from PL with the lowest relative molecular mass showed the highest epoxy value, the highest T_d and the lowest char content. The adhesive shear strength of the cured blends of LER and E-44 epoxy resin was improved compared with E-44 epoxy resin. Furthermore, the cured blend of E-44 epoxy resin and LER prepared from the AAL fraction with lowest relative molecular mass showed the highest adhesive shear strength up to 7.9MPa. PL can be used as a substitute for bisphenol A to prepare epoxy resin.
将AAL和E-44环氧树脂按不同比例共混。木质素环氧树脂共混物的初始热分解温度(T_d)随着AAL含量的增大缓慢降低,残炭率逐渐升高,其黏结剪切强度,其拉伸强度随着AAL含量的增大而减小,其吸水率随着AAL含量的增大而增大。
将AAL和双酚A按不同比例混合经环氧化后得到木质素改性双酚A环氧树脂(LBEP)。随着木质素含量的增大,LBEP固化物的T_d逐渐降低,残炭率逐渐升高,LBEP的黏结剪切强度略有降低。延长固化时间和提高固化温度有利于提高LBEP固化物的黏结剪切强度。随着AAL含量的增大,LBEP固化物的吸水率逐渐增大,AAL在LBEP固化物里的分布变得越来越不均匀。
AAL经过酚化改性后得到酚化木质素(PL),其酚羟基含量明显提高,相对分子质量略有降低。这有利于下一步环氧化反应制备木质素基环氧树脂(LER)。将LER和E-44环氧树脂共混固化,随着LER含量的增大,环氧树脂共混物的T_d逐渐降低,但残炭率逐渐升高;黏结剪切强度首先增大,并在LER含量为20%时具有最大值,此后趋于下降;拉伸强度逐渐降低。AAL在环氧树脂共混固化物中的分布变得越来越不均匀,吸水率逐渐增大。
采用沉淀法在不同浓度的乙酸水溶液中将AAL分成具有不同相对分子质量的3个级分。其中,相对分子质量最低的级分酚羟基含量最高,而初始热分解温度和残炭率都最低。3个级分经过酚化改性后,得到3种PL,其酚羟基含量较酚化前明显提高。3种酚化产物与环氧氯丙烷反应得到3种LER。由最低相对分子质量的PL制备的LER环氧值最高,T_d最高,但残炭率最低。由相对分子质量最低的AAL级分酚化及环氧化制备的LER与E-44环氧树脂共混固化后黏结剪切强度最高,达到7.9MPa。PL作为双酚A的替代物合成环氧树脂是可行的。
Lignin, the most abundant biopolymers on earth second only to cellulose, is a kind of complicated aromatic polymer. It is thought to be a potential resource for chemical raw materials. The conversion of lignin into polymer materials is of great importance in the utilization of biomass and protection of the environment. In this study, AAL was used in preparation of epoxy resin in different ways. AAL was fractionated and the impact of structural characteristics and blending method on the properties of epoxy resin was studied.
AAL was blended with E-44 epoxy resin with different ratio. With an increase in AAL content, the initial thermal decomposition temperature (T_d) of the cured lignin epoxy blends decreased slowly, the char content and water absorption of the cured lignin epoxy blends increased, and adhesive shear strength of cured lignin epoxy blends firstly increased and then decreased, the tensile strength was decreased. AAL was distributed in lignin-based epoxy blends in more heterogeneous way.
AAL was mixed with bisphenol A with different ratio and then the mixture was epoxidised to prepare lignin modified bisphenol A epoxy resin (LBEP). The increase of the curing time and curing temperature improved the adhesive shear strength of the cured LBEP. With the increase in AAL content, the T_d and the adhesive shear strength of cured LBEP decreased, char content and water absorption of cured LBEP increased, and adhesive shear strength slightly decreased. The existence of AAL in LBEP became heterogeneous.
Lignin-based epoxy resin (LER) was prepared from phenolated lignin (PL) and epichlorohydrin (ECH) in the presence of sodium hydroxide. LER was mixed with E-44 epoxy resin. As the increase of LER content, the T_d of the cured epoxy blends decreased, and the char content increased. The existence of LER in the cured epoxy blends became heterogeneous and the water absorption of the cured epoxy blends increased.
AAL was fractionated into three fractions by precipitation at different concentration of acetic acid- water solution. The fraction with the lowest relative molecular mass showed the highest phenolic hydroxyl content, the lowest T_d and the lowest char content. The three fractions reacted with phenol and yielded the corresponding PL. The phenol hydroxyl content of phenolated lignin fraction was higher than that of corresponding fraction. Three kinds of LER were prepared from PL by reacting with ECH. LER prepared from PL with the lowest relative molecular mass showed the highest epoxy value, the highest T_d and the lowest char content. The adhesive shear strength of the cured blends of LER and E-44 epoxy resin was improved compared with E-44 epoxy resin. Furthermore, the cured blend of E-44 epoxy resin and LER prepared from the AAL fraction with lowest relative molecular mass showed the highest adhesive shear strength up to 7.9MPa. PL can be used as a substitute for bisphenol A to prepare epoxy resin.
引文
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[2]Hon D. N. S.; Shiraishi N. Wood and cellulosic chemistry[M]. 2nd edition. New York: Marcel Dekker Inc., 2001: 64-67
[3]Orlandi M.; Canevali C.; Rindone B., et al. Biomimetic approach to lignin degradation: A mechanistic study of Metallosalen catalysed oxidation of lignin and lignin model compounds[C]. 7th European Workshop on Lignocellulosics and Pulp, 2002: 369-373
[4]杨淑蕙.植物纤维化学[M].第三版.北京:中国轻工业出版社, 2006: 69-96
[5]中野准三.木质素的化学-基础与应用[M].高洁等译.北京:轻工业出版社, 1988: 264-283
[6]赵斌元,李恒德,胡克鳌,等.木质素基环氧树脂合成及表征[J].纤维素科学与技术, 2000, 8(4): 19-26
[7]Feldman, D.; Banu, D.; Natansohn, A, et al. Structure-properties relations of thermally cured epoxy-lignin polyblends[J]. Journal of Applied Polymer Science, 1991, 42(6): 1537-1550
[8]Feldman, D.; Banu, D.; Luchian, C., et al. Epoxy-lignin polyblends: correlation between polymer interaction and curing temperature[J]. Journal of Applied Polymer Science, 1991, 42(5): 1307-1318
[9]Nonaka Y.; Tomita B.; Hatano Y. Synthesis of lignin/epoxy resin in aqueous systems and their properties[J]. Holzforschung, 1997, 51(2), 183-187
[10]陈云平,程贤甦,方华书,等.高沸醇溶剂法制备松木纸浆和木质素[J].纤维素科学与技术, 2003, 11(1): 19-22
[11]林玮,程贤甦.高沸醇木质素环氧树脂的合成与性能研究[J].纤维素科学与技术, 2007, 15(2): 8-12
[12]程贤甦,陈为健,方华书.福州大学.高沸醇木质素环氧树脂的制备方法[P].中国: 200410061295.X, 2008. 01. 23
[13]程贤甦.福州大学.酶解木质素环氧树脂的原料配方及其制备方法[P].中国: 200610069529.4, 2009. 08. 19
[14]Nakamura Y.; Sawada T.; Kuno K., et al. Resinification of woody lignin and its characteristic on safety and biodegradation[J]. Journal of Chemical Engineering of Japan,2001, 34(10): 1309-1312
[15]Shiraishi N. Lignin properties and materials[M]. Washington DC: American Chemical Society, 1989: 488-495
[16]赵斌元,胡克鳌,范永忠等.木质素磺酸及其衍生物红外光谱研究[J].分析化学, 2000, 28(6): 716-719
[17]Zhao B.Y.; Fan Y.Z.; Hu K.A., et al. Development of lignin epoxide—a potential matrix of resin matrix composite[J]. Journal of Wuhan University of Technology—Material Science Edition, 2000, 15(3): 6-12
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