HPMC水凝胶溶胀性能的影响因素研究

制备了一系列具有不同相对分子质量和取代度的羟丙基甲基纤维素(HPMC)水凝胶,并用称重的方法对凝胶的溶胀性能进行了研究,考察了温度、pH值、溶剂类型、取代度和相对分子质量对HPMC水凝胶溶胀性能的影响。结果显示,HPMC水凝胶的平衡溶胀度随温度的升高而减小;其溶胀行为受溶剂影响显著,而受溶液pH值的影响不明显;而取代度和相对分子质量都对凝胶溶胀行为有较大的影响。     

Homogenous carboxymethylation of cellulose in the NaOH/urea aqueous solution

In this work, the carboxymethylation of cellulose in the alkaline cellulose solvent, 7 wt% NaOH/12 wt% urea aqueous solution, was investigated. Carboxymethyl cellulose (CMC) samples were characterized with FT-IR, NMR, HPLC, and viscosity measurements. Water-soluble CMC with DS = 0.20–0.62 was prepared from both Avicel cellulose and cotton linters. Thus, carboxymethylation of cellulose in NaOH/urea leads to a polymer with the lowest DS value for water solubility (0.20) of CMC known. The total DS of CMC could be controlled by varying the molar ratio of reagents and NaOH to AGU and the reaction temperature. Structure analysis by means of HPLC after complete depolymerization showed that the mole fractions of the different carboxymethylated repeating units as well as those of unmodified glucose follow the simple statistic pattern. A distribution of the carboxymethyl groups at the level of the AGU in the order O-6 > O-2 > O-3 was determined. The results were similar with findings for CMC obtained by totally homogeneous reaction of cellulose in aqueous solvents such as Ni[tris(2-aminoethyl)amine](OH)₂.     

羧甲基多糖对羟丙基甲基纤维素溶液性能的影响

利用羧甲基淀粉、羧甲基纤维素与羟丙基甲基纤维素进行复配,研究羧甲基类多糖与羟丙基甲基纤维素的协同作用,并对其增稠作用的机理进行研究。结果表明:羧甲基淀粉钠和羧甲基纤维素钠对非离子型纤维素混合醚都有一定的增黏协同效应,且淀粉羧甲基物比纤维素羧甲基物的增黏效应更明显。     

Influence of wood pulp quality on the structure of carboxymethyl cellulose

The quality of carboxymethyl cellulose (CMC) prepared from different wood-derived market pulps is examined. The pulps represent kraft and sulfite qualities with different levels of hemicellulose (1.5–22.8 wt %), intrinsic viscosity (391–780 mL g⁻¹), and content of extractives (0.04–0.13 wt %). The pulps are carboxymethylated in aqueous medium at three different levels of sodium hydroxide concentration, resulting in three levels of degree of substitution (DS), 0.3, 0.7–0.8, and 1.3–1.4 (according to nuclear magnetic resonance spectroscopy and high-performance liquid chromatography). CMC with DS 0.7–0.8 is found to be near the limit for water solubility and the resulting ranking for that solubility is shown to be correlated to DS. The DS is found to be impaired by a high content of impurities and high degree of Cellulose II in the pulp. The sulfite pulps yield CMC with the best solubility in water. A high level of extractives does not interfere with reactivity. Moreover, it is found that impurities, such as lignin and xylan, inhibit thickening behavior even at high DS, and that the ratio of substitution on Position 3 is a measure of the xylan content, which suggests that this position in xylan has extremely high reactivity. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47862.     

Experimental study on carboxymethylation of cellulose extracted from Posidonia oceanica

The production of carboxymethylcellulose (CMC) from bleached cellulose pulps obtained from Posidonia oceanica was explored. The optimal reaction conditions were studied for the carboxymethylation of cellulose in organic liquids. The carboxymethylation reaction was carried out with NaOH and monochloroacetic acid (MAC) as the reagent. Different alcohols were compared in terms of the degree of substitution (DS). The highest DS was obtained with n‐butanol. For this alcohol, the effects of the temperature, alkali concentration, and MAC concentration were studied. The reaction was also carried out in three consecutive steps. The resulting CMC had a DS of about 2.75. The functionalization of cellulose was checked using FTIR spectroscopy and ¹³C‐NMR. The X‐ray analysis showed that the crystalline structure of cellulose decreased when the DS increased and the structure was totally amorphous in high DS material. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1808–1816, 2006     

羧甲基纤维素钠取代度测定的新方法

对测定羧甲基纤维素（CMC）的取代度（DS）方法进行了探讨，发现虽然电导滴定法可较快地和较准确地测定DS，但是易受反应副产物的影响。采用红外光谱法可达到快速测定DS，并且可直观地大致判断出样品的纯度，以决定是否需要对样品进行提纯精制。     

Formation of polyelectrolyte complexes between cellulose derivatives and their blood compatibility

Formation of polyelectrolyte complexes (PECs) between cellulose derivatives in aqueous solution and their blood compatibility were examined. To this end, two types of quaternary ammonium cellulose derivatives, Q-Cell and Q-HEC, were prepared by treating cellulose and hydroxyethyl cellulose (HEC), respectively, with glycidyl trimethylammonium chloride. Anionic derivatives were carboxymethyl cellulose (CMC) with different degrees of substitution (DS) and cellulose sulfate (CS). In vivo blood tests were made by a method of peripheral vein indwelling suture. The results showed that the complex formation of Q-Cell did not follow a stoichiometric reaction, but Q-HEC reacted stoichiometrically with CMC and CS. It was also found that water-insoluble cellulosic PECs are soluble in formic acid, showing that the cellulosic PEC films can be prepared from formic acid solutions. The blood tests revealed that by the criteria of the test method employed in this work, cellulosic PECs had a good blood compatibility.     

Preparation of sodium carboxymethyl cellulose from paper sludge

BACKGROUND: This paper describes the reuse of paper sludge, an industrial solid waste, for the preparation of sodium carboxymethyl cellulose (CMC). The process includes pretreatment, basification and etherification. RESULTS: The optimal pretreatment condition involved the addition of 6.7% hydrochloric acid to the paper sludge for 30 min at 70 °C. The order of factors influencing the effect of reaction was: etherification temperature > sodium hydroxide dose > basification temperature > etherification time > sodium chloroacetate dose. The optimal preparation condition of CMC was: m_papersludge: m_{sodiumhydroxide}: m_{sodiumchloroacetate} = 0.9:0.8:1.15; basification at 40 °C; etherification at 60 °C for 1 h. Under these conditions, certified CMC with viscosity less than 20 mPa· s, DS more than 0.50 and purity more than 90% was produced. The results of Fourier transform infrared (FTIR) and X‐ray diffraction (XRD) spectra analyses indicated that the product has characteristics of high degree of substitution (DS) and low crystallinity. The coated paper using CMC prepared from paper sludge as a water retention agent can meet the quality standards of GB/T 10335.1‐2005. CONCLUSION: Preparation of CMC from paper sludge can be considered a feasible alternative, generating value‐added product and contributing to solving environmental problems resulting from paper sludge. Copyright © 2008 Society of Chemical Industry     

蔗渣再生纤维素制备高取代度羧甲基纤维素钠的研究

先以NaOH/H2O2水溶液对蔗渣进行预处理,再用预冷至-12℃的7%NaOH/12%尿素水溶液对预处理蔗渣进行分离,获得结构蓬松的蔗渣再生纤维素。以蔗渣再生纤维素为原料,以氯乙酸钠为醚化剂,在85%乙醇水溶液中,采用一次碱化、二次醚化的工艺,制备了羧基取代度达1.45的羧甲基纤维素钠(CMC)。利用红外光谱(FTIR)、扫描电镜(SEM)、X-射线衍射(XRD)、热重分析(TGA)等手段对样品的结构进行了表征,并研究了羧甲基纤维素钠样品的黏度性能。     

Effect of organic solvent on morphology and mechanical properties of electrospun syndiotactic polypropylene nanofibers

We study the stress–strain behaviors of the electrospun sPP single nanofibers as well as nonwoven mats, which were electrospun from sPP solutions using two different solvents (decalin and cyclohexane) by electrospinning. The effects of organic solvents were explored on the morphologies and the mechanical properties of the corresponding electrospun sPP single nanofibers and nonwoven mats. It was found that the nature of organic solvents dramatically affected the surface morphologies, the circular and looping deposition of the electrospun sPP fibers, and the mechanical properties. The tensile strength of both electrospun sPP single nanofibers and nonwoven mats prepared from decalin-base solution was stronger than that of cyclohexane-base solution.     

Optimization of nanofiber-caproate/laurate esters synthesis,their characterization,and usage as emulsifier in o/w emulsion

The aim of this study is to optimize the esterification of nanofibers with caproyl/lauroyl chlorides at different substitution degrees' (DS) and to investigate the usage of nanofiber derivatives in model emulsions. First, cellulosic material was obtained and milled into nanofibers using a micro-fluidizer. Then, these nanofibers were esterified with caproyl/lauroyl chlorides in a solvent of DMAc/LiCl with DMAP as an acid scavenger. The esterification of nanofibers with caproyl/lauroyl chlorides was optimized for fatty acid chloride mole and reaction time. Esterification reactions were carried out at 80°C with various molar ratios of acyl chlorides (3–15 moles) versus anhydroglucose unit of nanofibers and for various time durations (30–360 min). The hydrophobic derivatives with DS in the range of 0.34–2.77 were successfully obtained. Using the data obtained as a result of the optimization, nanofiber-fatty acid esters with different DS (0.50–2.75) were produced and characterized. Analyzes showed that the esterification process was successful and as the degree of esterification increased, the crystallinity index and thermal stability of the derivatives decreased. Then, the nanofiber-caproate/laurate esters with different DS were used as emulsifier (0.5 wt%) in an oil-in-water model emulsion containing 25 wt% oil and the emulsions were analyzed. The nanofiber caproate/laurate esters with a DS of 0.50–1.25 were suitable for o/w emulsions, while samples with a DS of 2.00 and above were not found suitable. Emulsions prepared by using nanofiber derivatives with 1.25 DS had higher G′ and G″ and viscosity values and lower droplet sizes than those of other group.     

Factors influencing molecular weights of methylcelluloses prepared from annual plants and juvenile eucalyptus

We studied the factors that influenced the molecular weights (M_w) of water‐soluble methylcelluloses prepared from annual plants and juvenile eucalyptus. Miscanthus and cardoon stalks, and bleached pulps of abaca, jute, sisal, hemp, and flax were the annual plant materials studied. A higher concentration of NaOH solution during the impregnation led to a spring cardoon methylcellulose having a lower molecular weight. As the impregnation times increased, so did the molecular weights of the water‐soluble methylcelluloses of spring cardoon. The impregnation conditions had less influence on the methylcelluloses of summer cardoon than on the methylcelluloses of spring cardoon. As the cooking times increased, so did the molecular weights of miscanthus methylcelluloses. A lower pulping severity increased the molecular weight of eucalyptus methylcellulose. The preliminary treatments (water soaking, premercerization, mercerization under pressure, and steam explosion) improved the molecular weights of water‐soluble abaca methylcelluloses. The steam explosion method was the best of the preliminary treatments for the abaca pulp. Different species led to different molecular weights for methylcelluloses synthesized from ECF bleached pulps, and these were further improved by preliminary mercerization. The molecular weight of α‐cellulose methylcellulose changed as the ratio of the methylation reagent was varied. To synthesize an optimum M_w of methylcellulose, the different raw materials can be chosen, the pulping parameters adjusted (including impregnation and cooking), the cellulose pretreated, and the methylcellulose conditions changed. The plant species is the decisive factor for the M_w of methylcellulose. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1785–1793, 2006     

Effects of hard and soft components on the structure formation,crystallization behavior and mechanical properties of electrospun poly(l-lactic acid) nanofibers

The effects of multi-wall carbon nanotubes (MWCNTs) and poly(ethylene oxide) (PEO) on the structure formation, morphology, crystallization behavior and mechanical property of electrospun poly (l-lactic acid) (PLLA) nanofiber mats were investigated by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), differential scanning calorimeter (DSC) and mechanical test. If incorporate hard filler, MWCNTs into electrospun PLLA nanofiber, the crystallinity, chain orientation, and crystallization behaviors were almost not influenced by the MWCNTs content owing to the MWCNTs mainly acted as impeding the crystal growth and chain diffusion. If incorporate small content of soft and miscible component, PEO (10 wt%) into the electrospun PLLA and PLLA/MWCNTs nanofibers, the crystallinity and crystallization rate of PLLA in nanofibers were obviously enhanced. The synergistic effect of PEO and MWCNTs in PLLA nanofibers was observed during melt-crystallization behaviors of PLLA/MWCNTs fibers. Based on those results, we found that the chain mobility is an important factor to influence the structure formation and crystallization behaviors in the electrospun nanofibers. Our results indicated that the structure and properties of electrospun nanofibers could be optimized by compounding with hard inorganic filler and soft polymer components.     

不同碱金属氢氧化物对纤维素羧甲基化的影响

以不同碱金属氢氧化物(NaOH,KOH)为碱化剂,利用淤浆法合成CMC,对纤维素的碱化及羧甲基化进行了研究。结果表明,NaOH质量分数为25%,纤维素达到最大的润胀,KOH质量分数在20%~35%,纤维素的润胀率出现平台区;同一质量分数下,纤维素在NaOH溶液中的润胀率和吸附碱量都比在KOH中高;CMC的取代度随NaOH用量的增加急剧增加,而随KOH量的增加较为缓慢;取代度相近时,羧甲基纤维素钾的耐酸性和耐盐性比羧甲基纤维素钠差。     

Polybenzimidazole nanofiber produced by electrospinning

Nanofibers of aromatic heterocyclic PBI (poly(2,2′(m-phenylene)-5,5′ bibenzimidazole)) polymer were made by an electrospinning process. The diameter of the fibers was around 300 nanometers. A liquid jet of a polymer solution, formed when electrical force overcame surface tension, stretched and dried as the solvent evaporated. The resulting electrically charged nanofibers were attracted to and collected on a rotating cylinder covered with aluminum foil that was electrically grounded. The fibers were collected in non-woven sheets about 20 centimeters wide and 100 centimeters long, with a compressed thickness of a few tens of microns. The mass per unit area of the nonwoven sheets was 15 to 50 g/m². The nonwoven fabric of PBI nanofibers was treated with sulfuric acid, and then washed, dried and heated to improve its strength. Optical microscopy showed that electrospun PBI nanofibers fibers were birefringent. Other morphological features of these fibers were observed with scanning electron microscopy, transmission electron microscopy and atomic force microscopy.     

Solvent-free Synthesis of Cellulose Acetate by Solid Superacid Catalysis

Herein a novel process to synthesize cellulose acetate (CA) is reported in a solvent-free ball-milling reactor in the presence of solid superacid SO₄ ²⁻/ZrO₂ as green catalyst. FT-IR and H¹-NMR spectra reveal that the maximum degree of substitution (DS) of formed cellulose acetate can achieve 1.8, and the DS depends on the reaction time. This method provides a new environmental benign and simple way to synthesize cellulose acetate.     

植物胶囊用药用辅料流变性研究

利用安东帕Physica MCR 301型流变仪,研究了日本信越、湖州展望和山东瑞泰低黏羟丙基甲基纤维素(HPMC)、羧甲基纤维素(CMC)和明胶的流变性能。结果表明,各公司低黏HPMC溶液均表现为牛顿性流体,CMC和明胶溶液表现为假塑性流体;20%低黏HPMC黏度越大,触变环交叉面积越大,10%、20%低黏CMC和10%明胶溶液触变环无交叉;HPMC在凝胶点以前表现出较好的黏弹性,明胶在30℃解冻之后和70℃因水分挥发凝固之前表现出优越的黏弹性;CMC溶液具有较好的流动性,需加入更多的卡拉胶才能在胶囊成型时快速定型而不漏胶。随着人们对植物胶囊的了解,以及国内外公众用药理念的转变,植物胶囊的市场需求将迅速增长。     

羟丙基甲基纤维素生产技术与市场发展现状

综述了国内外羟丙基甲基纤维素(HPMC)生产技术、应用技术与市场发展的现状。目前欧美等发达国家更多地采用气相法工艺生产HPMC,单批产量高,反应时间短,劳动强度小;国内生产以液相法工艺为主,反应器通常在15 m3以下,劳动强度大,但对设备承压要求低,危险性小。欧美的HPMC市场已较为成熟,羧甲基纤维素(CMC)与HPMC消费量各占50%;随着中国经济的发展和技术水平的提高,国内HPMC市场处于快速增长阶段,消费量会逐步追平CMC。欧美由于生产HPMC较早,应用技术较为丰富;国内HPMC应用技术刚刚起步,但随着国内城镇化进程的加快和人民生活水平的提高,建筑、食品和医药将是HPMC应用增长最快的领域。随着技术的发展和市场的拓宽,在未来10年内,国内将会出现像美国道化学公司和赫克力士公司一样的大企业或跨国公司,并带领国内各纤维素醚企业向前发展,形成百花齐放,百家争鸣的局面。     

The influence of electrospinning parameters on the structural morphology and diameter of electrospun nanofibers

Electrospinning is a simple method of producing nanofibers by introducing electric field into the polymer solutions. We report an experimental investigation on the influence of processing parameters and solution properties on the structural morphology and average fiber diameter of electrospun poly ethylene oxide (PEO) polymer solution. Experimental trials have been conducted to investigate the effect of solution parameters, such as concentration, molecular weight, addition of polyelectrolyte in PEO solution, solvent effect, as well as governing parameter, such as applied voltage. The concentration of the aqueous PEO solution has shown noteworthy influence on the fiber diameter and structural morphology of electrospun nanofibers. At lower concentrations of PEO polymer solution, the fibers showed irregular morphology with large variations in fiber diameter, whereas at higher concentrations, the nanofibers with regular morphology and on average uniform fiber diameter were obtained. We find that the addition of polyelectrolytes, such as sodium salt of Poly acrylic acid (PAA) and Poly allylamine hydrochloride (PAH), increases the conductivity of PEO solutions and thereby decreases the bead formation in electrospun nanofibers. The increase in applied voltage has been found to affect the structural morphology of nanofiber while the addition of ethanol in PEO solution diminishes the bead defects. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and characterization of cellulose ethers/Eu(III)

The coordination complexes of the crystalline structure of cellulose ethers/Eu(III) with fluorescence emission, viz CMC/Eu(III), MC/Eu(III), and HEC/Eu(III), were synthesized and characterized. Results showed the emission spectra of Eu³⁺ ions in these coordination compounds, which originates from electric dipole transition. The main emission peak at 615 nm generated from ⁵D₀→⁷F₂ transition of Eu³⁺ ions. Their absorption and excitation spectra were different, because the effect of the high polarity of water and having both hydrogen bond donor and acceptor properties on the excited molecule is different from the effect on the ground state of the molecule. Our study demonstrated that the Degree of Substitute (DS) of CMC could influence the fluorescence intensity (FI) of CMC/Eu(III). The emission intensity of CMC/Eu(III) varies with the DS of CMC. For example, when the DS of CMC was 0.89, the FS (fluorescent spectra) of solid CMC/Eu(III) displayed three emission peaks Eu(III): the strongest emission peak at 615 nm (⁵D₀→⁷F₂ transition) and other two weaker peaks at 583 nm (⁵D₀→⁷F₁ transition) and at 652 nm (⁵D₀→⁷F₃ transition), respectively. The concentration of Eu(III) could also affect the FI of these coordination complexes. The FI of the coordination complexes peaked at 615 nm all reached maximum when Eu³⁺ concentration was at 5% (wt/wt). © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 743–747, 2005