Lignin,a biomass crosslinker,in a shape memory polycaprolactone network

This work reports a new direction of natural lignin valorization, which utilizes lignin to produce crosslinked polycaprolactone (PCL) via a straightforward synthesis. Lignin's hydroxyl groups of its multibranched phenolic structure allow lignin to serve as crosslinkers, whereas the aromatic groups serve as hard segments. The modified natural lignin containing alkene terminals is crosslinked with a thiol‐terminal PCL via Ru‐catalyzed photoredox thiol‐ene reaction. The high rate of gel contents measured for all crosslinked polymers, with the least being 84% of gel content, indicates efficient crosslinking. The prepared flat rectangular shape lignin‐crosslinked PCL sample demonstrates rapid thermal responsive shape memory behavior at 10 °C and 80 °C showing interconversion between a permanent and temporary shape. The melting temperature of the lignin‐crosslinked PCL is tunable by varying the percent weight of lignin. The 11, 21, and 30 wt % lignin demonstrated T_m of 42 °C, 35 °C, and 26 °C, respectively. The role of lignin as a crosslinker presented in this work suggests that lignin can serve as an efficient biomass‐based functional additive to polymers. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2121–2130     

Lignin and Lignin-Derived Compounds for Wood Applications—A Review

Improving the environmental performance of resins in wood treatment by using renewable chemicals has been a topic of interest for a long time. At the same time, lignin, the second most abundant biomass on earth, is produced in large scale as a side product and mainly used energetically. The use of lignin in wood adhesives or for wood modification has received a lot of scientific attention. Despite this, there are only few lignin-derived wood products commercially available. This review provides a summary of the research on lignin application in wood adhesives, as well as for wood modification. The research on the use of uncleaved lignin and of cleavage products of lignin is reviewed. Finally, the current state of the art of commercialization of lignin-derived wood products is presented.     

Sustainable poly(ether amide)s from lignin-derived precursors

In recent years, there have been concerted efforts to replace petrochemical products with those from renewable sources due to the unsustainability of petroleum feedstock, and the continued volatility in the price. This work describes the synthesis and thermal properties of two new lignin-derived poly(ether-amide)s as alternative thermoplastics to petroleum-based commodities. Poly-4-(2-aminoethoxy)benzoate (PEAB) and poly-4-(2-aminoethoxy)-3-methoxybenzoate (PEAV) are synthesized by a melt polycondensation and characterized by ¹H NMR spectroscopy and thermal analysis. The number average molecular weight (M_n) of the polymers are estimated from the ¹H NMR spectroscopy analysis, and were shown to be 4100 and 12,000 g/mol for PEAB and PEAV respectively. The PEAB had a higher decomposition temperature (T_d) as well as glass transition temperature (T_g) compared to PEAV; albeit, with a lower molecular weight. The polymers’ T_d were in the range of 330 °C–380 °C and the T_g were between 100 °C and 120 °C. The thermal properties of the polymers are in the desirable range for thermoplastic materials used in the packaging, storage, and coating industries. Furthermore, the polymers are susceptible to degradation under acidic conditions in a short period; a property that is highly desirable for degradable polymers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2154–2160     

Lignin‐based polymers via graft copolymerization

Lignin is an important source of synthetic materials because of its abundance in nature, low cost, stable supply, and no competition to the human food supply. Lignin, a cross‐linked phenolic polymer, contains a large number of aromatic groups that can be used as a substitute for petroleum‐based aromatic fine chemicals. However, modification of lignin is necessary for its application in advanced materials due to its chemically inert nature and structural complexity. Polymeric modification of lignin via graft copolymerization represents an important avenue for modification because this method forms stable covalent bond linkages between lignin and synthetic functional polymers. In this review, we discuss recent synthetic strategies toward polymeric modification of lignin using graft copolymerization and the special properties and applications of the produced lignin copolymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3515–3528     

Carbon Fibers: Precursor Systems,Processing, Structure,and Properties

This Review gives an overview of precursor systems, their processing, and the final precursor‐dependent structure of carbon fibers (CFs) including new developments in precursor systems for low‐cost CFs. The following CF precursor systems are discussed: poly(acrylonitrile)‐based copolymers, pitch, cellulose, lignin, poly(ethylene), and new synthetic polymeric precursors for high‐end CFs. In addition, structure–property relationships and the different models for describing both the structure and morphology of CFs will be presented.     

Preparation and antimicrobial properties of LL‐37 peptide immobilized lignin/caprolactone polymer film

The use of biopolymers has gained priority in tissue engineering and biotechnology, both as dressing material and for enhancing treatment efficiency. There is a demand for new biopolymers designed with protease inhibitors and antimicrobials. LL‐37 is an important antimicrobial peptide in human skin and exhibits a broad spectrum of antimicrobial activity against bacteria, fungi, and viral pathogens. Using lignin which is an abundant carbohydrate polymer in nature and a polyacrylic acid, we prepared a lignin/caprolactone biodegradable film by plastifying caprolactone and polyacyrlic acid. Lignin/caprolactone biodegradable film was activated with CDI and then immobilized LL‐37 peptide. The structure was elucidated in terms of its functional groups by attenuated total reflectance‐fourier transform infrared spectroscopy (ATR‐FTIR), and the morphology of the lignin/caprolactone biodegradable film was characterized by scanning electron microscopy (SEM) before and after the immobilization process. The amount of LL‐37 immobilized was determined by ELISA method. It was found that 97% of LL‐37 peptide was successfully immobilized onto the lignin/caprolactone biodegradable film. Antimicrobial activity was determined in the lignin/caprolactone biodegradable film samples by quantitative antimicrobial activity method. According to the results, LL‐37 immobilized lignin/caprolactone biodegradable film samples were effective on test organisms; Gram‐positive Staphylococcus aureus and Gram‐negative Escherichia coli. In bio‐compatibility assays, the ability to support tissue cell integration was detected by using 3 T3 mouse fibroblasts. Samples were examined under transverse microscope, non‐immobilized sample showed a huge cellular death, whereas LL‐37 immobilized lignin/caprolactone biodegradable film had identical cellular growth with the control group. This dual functional lignin/caprolactone biodegradable film with enhanced antibacterial properties and increased tissue cell compatibility may be used to design new materials for various types of biological applications.     

Improving the Yield and Rate of Acid-Catalyzed Deconstruction of Lignin by Mechanochemical Activation

Lignin is a potential biomass feedstock from plant material, but it is particularly difficult to economically process. Inspired by recent ball-milling results, state-of-the-art quantum mechanochemistry calculations have been performed to isolate and probe the purely mechanochemical stretching effect alone upon acid-catalyzed deconstruction of lignin. Effects upon cleavage of several exemplary simple ethers are examined first, and with low stretching force they all are predicted to cleave substantially faster, allowing for use of milder acids and lower temperatures. Effects upon an experimentally known lignin fragment model (containing the ubiquitous β-O-4 linkage) are next examined; this first required a mechanism refinement (3-step indirect cleavage, 1-step side reaction) and identification of the rate-limiting step under zero-force (thermal) conditions. Mechanochemical activation using very low stretching forces improves at first only yield, by fully shutting off the ring-closure side reaction. At only somewhat larger forces, in stark contrast, a switch in mechanism is found to occur, from 3-step indirect cleavage to the direct cleavage mechanism of simple ethers, finally strongly enhancing the cleavage rate of lignin. It is concluded that mechanochemical activation of the common β-O-4 link in lignin would improve the rate of its acidolysis via a mechanism switch past a low force threshold. Relevance to ball-milling experiments is discussed.     

磁性碱木素胺稳定的Ru纳米粒子催化α-蒎烯加氢反应

通过Mannich反应在碱木素结构中引入胺源,再结合共沉淀法制备了包裹Fe₃O₄磁核的稳定金属粒子的碱木素胺载体,并进一步构建了催化可再生资源α-蒎烯加氢反应的Ru纳米粒子催化剂.通过元素分析、粉末X射线衍射、傅里叶变换红外光谱、电感耦合等离子体原子发射光谱、透射电子显微镜、热重分析和X射线光电子能谱等方法对该催化剂进行表征.结果表明,碱木素中的苯环和含氧基团均对金属粒子有稳定作用,但胺源的引入可更加有效地稳定金属粒子.经过对催化剂制备工艺、木质素类型、胺源类型和胺源含量的筛选,得到活性最优的催化剂Fe₃O₄@0.8ALN₁-Ru,Ru负载量为1.92 mmol/g,Ru粒子粒径为（2.1±0.5）nm.该催化剂在n（α-蒎烯）/n（Ru）=65.8,1 MPa H₂条件下70℃催化1 mL α-蒎烯加氢反应2 h,可获得99.64%的α-蒎烯转化率和96.52%的顺式蒎烷选择性,并表现出良好的重复使用稳定性.     

羟甲基化木质素磺酸盐添加剂对钻井液性能的影响

为了进一步优化木质素磺酸盐作为钻井液处理剂的效能,利用其与甲醛的羟甲基化反应制备了羟甲基化木质素磺酸盐;采用红外光谱仪、X射线粉末衍射仪、扫描电镜等分析了其结构;测定了改性前后的木质素磺酸盐对钻井液流变性、降滤失性、黏土水化膨胀抑制性等性能的影响.结果显示,改性后的羟甲基化木质素磺酸盐的整体结构变化不大,但羟基数量增加,与水的相溶性增强.与木质素磺酸盐相比,羟甲基化木质素磺酸盐在室温下对基浆有较强的提黏作用,经180℃高温老化后降黏、降滤失作用有所增强,形成的泥饼厚度降低,对黏土水化膨胀的抑制作用增强.