The isolation and characterization of lignin of kenaf fiber

In this article, milled wood lignin (MWL) was isolated and purified from retted kenaf fiber, the lignin obtained was characterized by elemental analysis, FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopy. The C₉ formula is calculated for kenaf fiber MWL as C₉H_9.32O_3.69(OCH₃)_1.30. The spectra of FTIR, ¹H‐NMR, and ¹³C‐NMR show the kenaf fiber lignin to be of the G/S type with high proportion of syringyl (S) unit. The numbers of phenolic and aliphatic hydroxyl groups in the kenaf fiber MWL are estimated to be 0.14 and 1.31, respectively, per C₉ unit. The OH_aliph is 90.3% in total numbers of hydroxyl groups of kenaf fiber MWL, and the OH_ph is 9.7%. It is evident that the β‐O‐4 structures are mainly linkage in the MWL of kenaf fiber, which contain more erythro stereochemistry type in β‐O‐4 units than thero stereochemistry type. In general, the characteristics of lignin of kenaf fiber are similar to that of hardwood. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

烟煤和白煤结构表征及煤净洁添加剂的研制

运用远红外傅立叶变换光谱、超导核磁、光栅发射光谱、元素分析、X射线荧光光谱等分析测试手段,对烟煤和白煤的基本结构单元进行了表征。研究表明,白煤骨架中的芳环聚合度比烟煤大,碳支链较烟煤少;而且在白煤骨架中部分三维碳骨架中可能存在C—O—Si—O—C化学键。研制出了型煤净洁剂,将其与白煤粉、烟煤粉进行拌合,冷压后制成的型煤着火点降低,燃烧速度加快,不仅燃煤效率提高了20%,而且消烟除尘效果已达排放标准,有害气体二氧化硫降低了48%。     

Synthesis and properties of poly ether nitrile sulfone copolymers with pendant methyl groups

Poly ether nitrile and poly ether nitrile sulfone copolymers with pendant methyl groups were prepared by the nucleophilic substitution reaction of 2,6′‐dichlorobenzonitrile with methyl hydroquinone and with varying mole proportions of methyl hydroquinone and 4,4′dihydroxydiphenylsulfone using N‐methyl pyrrolidone as solvent in the presence of anhydrous K₂CO₃. The polymers were characterized by different physicochemical techniques. Copolymer composition was determined using FTIR technique. Thermogravimetric data reveals that all the polymers were stable up to 420°C with a char yield above 40% at 900°C in N₂ atmosphere. The glass transition temperature was found to increase and the activation energy and inherent viscosities were found to decrease with increase in concentration of the 4,4′‐dihydroxydiphenylsulfone units in the polymer. Trimerization reactions are found to be favorable with increase in concentration of methyl hydroquinone units in the polymer. Crystallinity of the polymer was also studied using wide angle X‐ray diffraction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1303–1309, 2006     

Synthesis and properties of poly(ether nitrile sulfone) copolymers with pendant methyl groups

Poly(ether nitrile) and poly(ether nitrile sulfone) copolymers with pendant methyl groups were prepared by the nucleophilic substitution reaction of 2,6′‐dichlorobenzonitrile with methyl hydroquinone and with varying mole proportions of methyl hydroquinone and 4,4′‐dihydroxydiphenylsulfone using N‐methyl pyrrolidone as a solvent in the presence of anhydrous K₂CO₃. The polymers were characterized by different physicochemical techniques. Copolymer composition was determined using the FTIR technique. Thermogravimetric data revealed that all polymers were stable up to 420°C with a char yield above 40% at 900°C in a nitrogen atmosphere. The glass‐transition temperature increased and the activation energy and inherent viscosities decreased with an increase in the concentration of the 4,4′‐dihydroxydiphenylsulfone units in the polymer. Trimerization reactions were favorable with an increase in the concentration of methyl hydroquinone units in the polymer. The crystallinity of the polymer was also studied using wide‐angle X‐ray diffraction. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1987–1994, 2005     

纤维素酯在涂料中的研究与应用

重点介绍了纤维素结构与性质的关系及其对所得到的纤维素酯在特殊领域应用性能的影响。同时也概述了纤维素酯在涂层、控制释放、塑料(尤其是生物降解塑料)、复合材料方面以及在丁酸酯、光学胶片、膜材料及相关隔离中介等领域的应用。     

Simplified method for estimation of composition of alginates by FTIR

A modified method of preparing highly purified polymannuronic acid and polyguluronic acid was developed wherein acid hydrolysis was carried out using oxalic acid and separation was made using the difference of solubility with pH value. The simplified method using FTIR measurement to estimate the M/G ratio of alginate was investigated using Ca or Mn salts of alginate. The developed method appears to offer enhanced accuracy compared to that of previous techniques. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1372–1377, 2004     

The Molecular Origin of Nuclear Magnetic Relaxation in Methyl Cellulose and Hydroxypropylmethyl Cellulose

Nuclear magnetic relaxation processes in methyl cellulose (MC) and hydroxypropylmethyl cellulose (HPMC) were studied by proton spin-lattice NMR relaxation. The proton relaxations were measured in the temperature range 90–420 K at 90 MHz. At low temperature the proton spin-lattice relaxation is caused by the modulation of the methyl proton-proton dipole-dipole interactions by the reorientation of the methyl groups. In this temperature range the spin relaxation vs. temperature data were interpreted with the model of dynamical inequivalence of methyl groups: two in MC and three in HPMC. The dynamical parameters were calculated for each of these groups. The segmental motion of the MC and HPMC chain via the glucosidic bond which corresponds to the local chain motion of these polymers is the dominant mechanism of the proton spin-lattice relaxation time above 250 K.     

Investigations on esterification reactions of starches in 1‐N‐butyl‐3‐methylimidazolium chloride and resulting substituent distribution

The ionic liquid (IL) 1‐N‐butyl‐3‐methylimidazolium chloride ([C₄mim]⁺Cl^?) was used as solvent for different esterification reactions of the biopolymer starch. Therefore, maize starches with varying content of amylose were used. Different carboxylic acid anhydrides were applied to esterify starch with a degree of substitution (DS) in the range of 0.7–3.0. For example, starch acetates with the mentioned DS are accessible within 30 min at a 105°C‐reaction temperature. The DS distribution of starch acetates synthesized in IL was compared with the common starch acetate synthesis of Mark and Mehltretter. Also, a consideration of starch acetates and cellulose acetates synthesized in [C₄mim]⁺Cl^? is given. The starch esters were characterized by means of Raman spectroscopy for qualitative‐ and nuclear magnetic resonance spectroscopy for quantitative determination of the functionalization pattern. Moreover, the molecular mass distribution was determined after saponification by means of GPC‐MALLS. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal oxidative and photo‐oxidative degradation of polytetrahydrofuran studied using 1H NMR, 13C NMR and GPC

The products and mechanism of the thermal oxidative degradation at 180 °C and the photo‐oxidative degradation at 40 °C of polytetrahydrofuran have been investigated using ¹H NMR, ¹³C NMR and GPC. The NMR analysis was assisted by the use of DEPT ¹³C spectra, two‐dimensional NMR spectroscopy (COSY, HMQC and HMBC) and chemical shift simulation software. The NMR spectra of both thermally and photolytically degraded samples were similar showing that the degradation mechanisms were similar. GPC indicated that both chain scission, leading to lower molar mass products, and chain extension, leading to higher molar mass products, occurred initially. NMR analysis of the initial soluble degraded polymers showed that chain scission resulted in formate, aldehyde, propyl ether, butyl ether and propanoyl chain ends, and in‐chain ester groups were also formed. For longer periods of degradation, crosslinked gels were formed but these were not amenable to detailed structural characterisation by high‐resolution NMR to determine the crosslink mechanism. Copyright © 2004 Society of Chemical Industry     

4‐Acetamidophenyl acrylate copolymers with acrylonitrile and N‐vinyl‐2‐pyrrolidone: Synthesis,characterization, and reactivity ratios

4‐Acetamidophenyl acrylate (APA) was synthesized and characterized by IR, ¹H and ¹³C NMR spectroscopies. Homo‐ and copolymers of APA with acrylonitrile (AN) and N‐vinyl‐2‐pyrrolidone (NVP) were prepared by a free radical polymerization. All the copolymer compositions have been determined by ¹H NMR technique, and the reactivity ratios of the monomer pairs have been evaluated using the linearization methods Fineman–Ross, Kelen–Tudos, and extended Kelen–Tudos. Nonlinear error‐in‐variable model (EVM) method was used to compare the reactivity ratios. The reactivity ratios for copoly(APA–AN) system were APA(r₁) = 0.70 and AN(r₂) = 0.333, and for copoly(APA–NVP) system the values were APA(r₁) = 4.99 and NVP(r₂) = 0.019. Thermal stability and molecular weights of the copolymers are reported. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1919–1927, 2006     

甘蔗渣纤维素磷酸酯的合成与应用研究

甘蔗渣纤维素为原料 ,用尿素作催化剂 ,研究了甘蔗渣纤维素磷酸酯合成的最佳工艺条件。将 5 .0g甘蔗渣纤维素与w(NaOH) =2 0 %的 3 0mL水溶液反应 1h ,水洗至中性 ,制得碱纤维 ,5 .0g碱纤维再用w (H3PO4) =2 0 %的水溶液 4 0mL进行预膨润 12h ,将滤饼用 5mLw(H3PO4) =85 %的水溶液、0 .3g催化剂尿素、甲苯作溶剂 ,5 0℃下反应 1h。产品对Ag+、Pb2 +、Fe3+、Zn2 +离子的平衡交换吸附量比活性炭平均增加 7.15mg/g ,对X -GRRL阳离子蓝染料的交换吸附性能比活性炭提高了 15 .7%。     

13C‐NMR study on cure‐accelerated phenol–formaldehyde resins with carbonates

Both liquid‐ and solid‐state ¹³C‐NMR spectroscopies were employed to investigate the cure‐acceleration effects of three carbonates [propylene carbonate (PC), sodium carbonate (NC), and potassium carbonate (KC)] on liquid and cured phenol–formaldehyde (PF) resins. The liquid‐phase ¹³C‐NMR spectra showed that the cure‐acceleration mechanism in the PC‐added PF resin seemed to be involved in increasing reactivity of the phenol rings, while the addition of both NC and KC into PF resin apparently resulted in the presence of ortho–ortho methylene linkages. Proton spin‐lattice rotating frame relaxation time (T_1ρH) measured by solid‐state ¹³C‐CP/MAS‐NMR spectroscopy was smaller for the cure‐accelerated PF resins than for that of the control PF resin. The result indicated that cure‐accelerated PF resins are less rigid than the control PF resin. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 841–851, 2000     

13C‐NMR study on cure‐accelerated phenol‐formaldehyde resins with carbonates

Both liquid‐ and solid‐state carbon‐13–nuclear magnetic resonance (¹³C‐NMR) spectroscopies were used to investigate the cure acceleration effects of three carbonates (propylene carbonate, sodium carbonate, and potassium carbonate) on liquid and cured phenol‐formaldehyde (PF) resins. The liquid‐phase ¹³C‐NMR spectra showed that the cure acceleration mechanism in the propylene carbonate‐added PF resin seemed to be involved in increasing reactivity of the phenol rings, whereas the addition of both sodium carbonate and potassium carbonate into PF resin apparently resulted in the presence of ortho–ortho methylene linkages. Proton spin‐lattice rotating frame relaxation time (T_1ρH) measured by solid‐state ¹³C cross polarization/magic‐angle spinning NMR spectroscopy was smaller for the cure‐accelerated PF resins than that of the control PF resin. The result indicated that the cure‐accelerated PF resins are less rigid than the control PF resin. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1284–1293, 2000     

Oxidation and crosslinking processes during thermal aging of low‐density polyethylene films

This work analyzes the influence of thermal degradation on the microstructure and the mechanical properties of low‐density polyethylene subjected to aging at 70°C in the dark for times up to 21 months. It is found that the polymer shows a gradual increase of its elastic modulus and a dramatic reduction of its ductility, due to secondary crystallization. Infrared spectroscopy (FTIR) reveals the autoaccelerated oxidation of the polymer after 5 months aging. It is observed that the unsaturated vinylidene groups initially present in the material are gradually overridden by vinyl groups and, eventually, by t‐vinylene groups. Nuclear magnetic resonance (¹³C NMR) shows that the initial butyl chain branches are progressively completed by shorter ramifications, namely ethyl branches. These results are discussed in term of macromolecular mechanisms: (i) oxidation, (ii) chain scission, and (iii) crosslinking. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Influence of climatic ageing on the mechanical properties and the microstructure of low‐density polyethylene films

Blown extruded films of low‐density polyethylene (LDPE) have been subjected to climatic ageing in a sub‐Saharan facility at Laghouat (Algeria) with direct exposure to sun. Samples were characterized by complementary techniques after prescribed amounts of time up to 8 months. It was shown by tensile testing that the mechanical properties are quite sensitive to ageing: (i) the elastic modulus increases and saturates, (ii) the tensile stress increases slightly, and (iii) the rupture energy decreases dramatically after 4 months weathering. Fourier‐transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (¹³C NMR) were performed to identify the evolution of the polymer microstructure. The FTIR spectra reveal the initial presence of vinylidene groups that exhaust rapidly after 4 months ageing. Also, it detects the progressive multiplication of vinyl groups and oxidation products of many kinds. The NMR technique revealed specifically the carbon–carbon configurations in the polymer chains. By contrast to the original film that contained almost exclusively butyl chain branches, the aged specimens presented shorter ramifications, namely ethyl branches. Also, the presence of quaternary atoms was detected after long ageing times. The discussion of these complementary results in the light of current literature makes possible to identify the leading mechanisms that control the decay of LDPE film properties. Although these mechanisms are numerous and complex, they can be schematically summarized within three main classes: oxidation, scission, and crosslinking. Each class is discussed in details. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

酸处理后纤维素分子结构的显微红外光谱分析

摘要：应用显微红外光谱技术分析了经不同浓度硫酸处理后纤维素分子结构的变化,通过对红外特征谱带吸光度和位置的分析,证实经酸处理后纤维素的分子结构发生了变化。当硫酸质量分数达到15％时,纤维素分子链遭到严重破坏。由此可见,应用显微红外光谱可以准确地对纤维素分子结构变化进行分析和表征。     

An NMR spectroscopic investigation of the oxidation reactions of DL-selenomethionine

Oxidation reactions of DL -selenomethionine (DL -SeMet) with hydrogen peroxide and ozone were investigated by ¹H and ¹³C NMR spectroscopy. Chemical shifts of the reaction products were measured at different pD values in D₂O solutions. In the moderate (4–8) pD range, a pair of singlets of equal intensity appeared at 2·71 and 2·80 ppm, with the disappearance of the DL -SeMet methyl peak at 2·04 ppm. As the pD of the solution decreased, the chemical shifts of both peaks increased relative to 3-trimethylsilylpropionic acid-d₄ sodium salt. In strongly acidic solutions (pD<3), the pair collapsed to one singlet at 3·18 ppm. As pD values increased the chemical shifts decreased in numerical value with only a singlet at 2·69 ppm observed in strongly basic solutions (pD>10). These data were assigned to Met selenoxide in basic solution, stabilized by intermolecular hydrogen bonding, and to the hydration of Met selenoxide to Met dihydroxyselenide in acidic solutions. In moderate pD solutions (pD = 4–8), both forms of the selenoxide can exist. For the reaction of DL -SeMet with CNBr, two parallel reactions occur, i.e. oxidation and bond cleavage with cyanization: the bond cleavage giving the expected products, i.e. 2-amino-4-butyrolactone and methyl selenocyanate, with an additional singlet observed at 2·54 ppm. © 1988 SCI     

霍林河褐煤化学结构特性的13C NMR与FTIR对比分析

采用¹³C NMR及FTIR对霍林河褐煤的化学结构特性进行深入分析,通过¹³C NMR计算得到霍林河褐煤包含34.32%的脂肪族碳、61.25%的芳香族碳以及4.43%的羰基碳。平均每个芳环团簇包含1~2个芳香环,每个芳香环中平均碳原子取代数为3~4。平均亚甲基碳链数为1.4,烷链支化度为25.47%,说明脂肪族多以短链分支形式存在。通过对霍林河褐煤红外光谱进行分峰拟合,计算得到煤的FTIR结构参数（平均亚甲基碳链数、芳香环取代度、烷链支化度）与¹³C NMR计算结果相吻合。虽然芳碳率（f_ar-F=55.37%）与¹³C NMR计算结果存在一定的偏差,但是FTIR很大程度上仍然可以反映煤的碳骨架结构特性。     

Nuclear Magnetic Resonance Spectroscopy: A Versatile Tool for Qualitative and Quantitative Analysis of an Emulsifier Mixture of Soybean Oil

Finding a fast, reliable, and reproducible approach for an accurate analysis of complex lipid mixtures of emulsifiers is crucial for the food and beverages, pharmaceuticals, personal care products, cosmetics, and agrochemicals industries. In the current study, a comprehensive qualitative and quantitative nuclear magnetic resonance (NMR) spectroscopy analysis of a high monoester mixture of soybean oil (HMMS) was conducted using ¹H, ¹³C, and ³¹P NMR of 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane (CTDP) derivatives. The HMMS was produced by enzymatic alcoholysis of soybean oil and 1.2-propanediol in a supercritical CO₂ system. Compositional distribution analysis, quantified by aliphatic carbons with ¹³C NMR, showed that HMMS is composed of more unsaturated fatty acids, comprised of polyunsaturated fatty acids (PUFA) (60 ± 1.1%) and monounsaturated fatty acids (MUFA) (22 ± 0.8%), than saturated fatty acids (18 ± 0.9%). The ³¹P NMR quantification of HMMS demonstrated that, out of the total amount of monoacylglycerols (MAG), they are composed of 21 ± 2.9% of 2-MAG and 4 ± 0.3% of 1-MAG. Among the three techniques, ³¹P NMR spectroscopy proved to be a practical methodology with high reproducibility for the precise detection and quantification of partially esterified glycerols and free fatty acids in complex lipid mixtures.     

FTIR, 1H‐NMR spectra,and thermal characterization of water‐based polyurethane/acrylic hybrids

Polyurethane (PU) polymer was synthesized following a prepolymer mixing process, by polyaddition of isophorone diisocyanate (IPDI), poly(propylene glycol) (PPG), 2‐hydroxyethyl methacrylate (HEMA), and 2,2‐bis(hydroxymethyl)propionic acid (DMPA). The PU anionomer having 2‐ethoxymethacrylate terminal groups was dispersed in water by prior neutralization of carboxylic acid groups of DMPA with triethylamine (TEA), chain extended with hydrazine (HZM) in water and a dispersion polymerization with methyl methacrylate/n‐butyl acrylate/acrylic acid mixture was performed. The above polymerization reactions lead to the formation of PU/acrylic hybrids having a chemical bond between PU and acrylic moieties. Acrylic content was varied from 0 to 50 wt % and samples were purified to eliminate oligomers and impurities before characterization. The FTIR and ¹H‐NMR spectra of these purified hybrid samples were obtained and bands and peaks assignments were discussed. Thermal properties (DSC and TGA) were also discussed. Breaking hydrogen bonds is the main reason for changes in properties with increasing acrylic content. Particle size data of dispersions is also presented and discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008