Rapid determination of lignosulfonate depolymerization products by advanced polymer chromatography

Depolymerized lignin products are very complex mixtures. Based on a depolymerization solution of commercially available sodium lignosulfonate under mild conditions, a fast and efficient method for the separation and direct characterization of the degree and efficiency of the acid‐catalyzed depolymerization of lignin was developed in this study. Using an ultraviolet detector, the depolymerized lignosulfonate products were well separated and characterized according to the relative molar mass distribution on an advanced polymer chromatographic system with three ethylene‐bridged hybrid columns having small pore sizes (45 Å) in series and tetrahydrofuran as the mobile phase. The developed advanced polymer chromatography method enabled the detection of low‐molecular‐weight lignin degradation products (M_n = 260–1100 Da) with high peak resolutions in less than 7.2 min. Furthermore, preliminary advanced polymer chromatography studies to determine the influence of reaction temperature on the depolymerized products indicated that the depolymerized aromatics fell in several molecular weight ranges with an extremely low dispersity. This new approach can be used for the rapid analysis of lignin depolymerization products.     

Recycling of End-of-Life Poly(bisphenol A carbonate) via Alkali Metal Halide-Catalyzed Phenolysis

The chemical recycling of end-of-life plastic waste streams can contribute to a resource-conserving and sustainable society. This matter of recycling is composed of a sequence of depolymerization and subsequent polymerization reactions. In this regard, we have studied the chemical recycling of end-of-life poly(bisphenol A carbonate) applying phenol as depolymerization reagent. In the presence of catalytic amounts of alkali metal halides as products bisphenol A and diphenyl carbonate were obtained in excellent turnover frequencies of up to 1392 h⁻¹ and short reaction times. These depolymerization products offer the straightforward possibility to close the cycle by producing new poly(bisphenol A carbonate) and as second product phenol, which can be reused for further depolymerizations.     

Effect of Two-Step Formosolv Fractionation on the Structural Properties and Antioxidant Activity of Lignin

The formosolv fractionation process has been demonstrated to be an effective approach toward lignin recovery as an antioxidant from lignocellulosic biomass. In this study, four lignin fractions, FL-88%, FSL-70%, FIL-70% and FL-EtAc, were isolated from Phragmites australis biomass through two-step formosolv fractionation (88% formic acid delignification followed by 70% aqueous formic acid fractionation). To better understand the structural properties of the lignin obtained from this fractionation process, four isolated lignins were successfully characterized by gel permeation chromatography (GPC), Fourier transform infrared (FT-IR), two-dimensional heteronuclear single quantum coherence nuclear magnetic resonance (2D-HSQC NMR) spectroscopy, thermogravimetric analysis (TGA) and gas chromatograph-mass spectroscopy (GC/MS). It was found that lignin depolymerization via β-O-4 cleavage occurred via a formylation, elimination and hydrolysis mechanism, accompanied by a competitive condensation reaction. Noteworthily, two-step formosolv fractionation can produce specific lignin fractions with different ABTS and DPPH radical scavenging activities. The FL-EtAc fraction with low molecular weight (M_w = 2748 Da) and good homogeneity (PDI = 1.5) showed excellent antioxidant activity, compared with the other three isolated lignin fractions, even equal to that of commercial antioxidant BHT at the same concentration of 2.0 mg·mL⁻¹. These findings are of great help for specific lignin from biomass as a natural antioxidant in the future.     

Excess volumes of the binary mixtures of trichloroethylene withn-alcohols at 30 and 40°C

Volumes of mixing binary systems formed by trichloroethylene with n-alcohols (1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-heptanol, and 1-octanol) were measured as a function of composition at 30 and 40°C, by dilatometric measurements. All the systems show a change of sign for V ^E from negative to positive as the mole fraction trichloroethylene increases at both temperatures The positive value of the excess volumes increase as carbon chain length increases. The results are explained in terms of depolymerization of hydrogen bonded alcohol aggregates and weak hydrogen-bonding interaction of the type Cl-H–O between unlike molecules.     

煤的化学降解研究——Ⅰ.煤的氯化降解

用水介质中氯化的方法对煤进行降解研究,考察了降解后煤的化学组成和在有机溶剂中抽提性质的变化。降解后,煤中碳、氢含量下降,氯、氧含量增加,腐植酸及活性官能团增多,使煤具有一系列新的性质。如在极性溶剂中抽出量显著增加,其中丙酮抽出率高达86.4%。     

Readily hydrolysable cellulose esters as intermediates for the regioselective derivatization of cellulose; II. Soluble,highly substituted cellulose trifluoroacetates

Cellulose trifluoroacetate (CTFA) with DS values of 1.5 and 2.1 and DP values ranging from 170 to 800 have been prepared free from impurities of the reaction mixture (weakly bound trifluoroacetic acid) and of the procedure of isolation (diethyl ether). The CTFAs are soluble in DMSO, DMF, pyridine, and THF and thermostable up to 250 °C. A convenient synthetic method for CTFAs with DS 1.5 involves the acylation of cellulose with mixtures of trifluoroacetic acid (TFA) and trifluoroacetic anhydride (TFAA, 33% v/v) at room temperature for 4 h and subsequent treatment of the crude polymer at 150 °C and 80 Pa for 40 min. The preparation of CTFAs with DS-values up to 2.1 requires the addition of chloroform and 16 h reaction time.¹³ C-NMR studies as well as HPLC analyses after methylation and chain degradation show a preferred trifluoroacetylation of the primary hydroxy groups of the cellulose. The extent of depolymerization during the trifluoroacetylation was investigated for various cellulose materials. The cleavage of the trifluoroacetyl groups is possible by treating the derivative with a protic medium like water. Total hydrolysis of CTFA dissolved in DMF with water (room temperature) takes 6 min. The first paper on this topic was concerned with cellulose formates (Schnabelrauchet al., 1992).     

Ionic Liquids for the Chemical Recycling of Polymeric Materials and Control of Their Solubility

Plastics are wonderful materials that have modernized our daily life; however, importance of effective recycling of plastics is gradually recognized widely. In this account, we describe our discovery of new and efficient methods for the chemical recycling of plastics using ionic liquids (ILs). Since the chemical recycling usually requires high temperature conditions to breakdown chemical bonds in polymeric materials, we thought that less-flammability and non-volatility of ionic liquids are the most suitable physical properties for this purpose. Ionic liquids successfully depolymerized polyamides and unsaturated polyesters smoothly and corresponding monomeric materials were obtained in good yields. To the best of our knowledge, this was the first use of Ionic liquids for such reactions. However, we encountered another difficult problem-separation. To solve the problem, we developed solubility-switchable ionic liquids, a new type of ionic liquids in which solubility is readily changed using the chemistry of protective groups. Conversion between hydrophilic and lipophilic forms was readily achieved using a simple chemical treatment under mild conditions, and the complete separation of products was achieved by liquid-liquid-extraction. The robustness of either form unlocks their wide use as reaction solvents.     

Protection Group Effects During α,γ‐Diol Lignin Stabilization Promote High‐Selectivity Monomer Production

Protection groups were introduced during biomass pretreatment to stabilize lignin's α,γ‐diol group during its extraction and prevent its condensation. Acetaldehyde and propionaldehyde stabilized the α,γ‐diol without any aromatic ring alkylation, which significantly increased final product selectivity. The subsequent hydrogenolysis catalyzed by Pd/C generated lignin monomers at near‐theoretical yields based on Klason lignin (48 % from birch, 20 % from spruce, 70 % from high‐syringyl transgenic poplar), and with high selectivity to a single 4‐n‐propanolsyringol product (80 %) in the case of the poplar. Unlike direct hydrogenation of native wood, hydrogenolysis of protected lignin with Ni/C also led to high selectivity to this single product (78 %), paving the way to high‐selectivity lignin upgrading with base metal catalysts. The use of extracted lignin facilitated valorization of polysaccharides, leading to high yields of all three major biomass polymers to a single major product.     

Hydrogenative Depolymerization of End-of-Life Polycarbonates by an Iron Pincer Complex

Chemical recycling processes can contribute to a resource-efficient plastic economy. Herein, a procedure for the iron-catalyzed hydrogenation of the carbonate function of end-of-life polycarbonates under simultaneous depolymerization is presented. The use of a straightforward iron pincer complex leads to high rate of depolymerization of poly(bisphenol A carbonate) and poly(propylene carbonate) yielding the monomers bisphenol A and 1,2-propanediol, respectively, as products under mild reaction conditions. Furthermore, the iron complex was able to depolymerize polycarbonates containing goods and mixture of plastics containing polycarbonates.     

Measurement of the Average Molecular Weight of Cotton Cellulose Crosslinked by a Polycarboxylic Acid at Different pH Using Multiple Angle Light Scattering Photometer in a DMAc/LiCl Solvent System

Durable press finishing of cotton fabrics with polycarboxylic acid increases fabric wrinkle-resistance at the expense of its mechanical strength. Severe tensile strength loss is the major disadvantage for wrinkle resistant cotton fabrics. Tensile strength loss of cotton fabric crosslinked by a polycarboxylic acid can be attributed to depolymerization and crosslink of cellulose molecules. Measurement of the molecular weight of cotton fabric before and after crosslinked by polycarboxylic acids can offer a possibility of direct understanding of the depolymerization. In this research, a multiple angle laser light scattering photometer was used to determine the absolute molecular weight of cotton fabric treated with BTCA at different pH and then hydrolyzed with 0.5 M NaOH solution at 50℃ for 144 h. The results indicate that average molecular weights of cotton fabric treated with polycarboxylic acids at different pH are almost the same.