微波强化碱预处理对二次纤维结构及其氰乙基化反应的影响

研究了微波强化碱预处理对二次纤维(SF)化学结构、超分子结构、物理特性的影响,并通过与丙烯腈反应分析微波强化对二次纤维氰乙基化反应性能的影响,初步探讨了微波强化作用机理。结果表明,微波强化碱预处理二次纤维(WASF)的化学组分和晶型没有发生改变,但纤维素分子中的氢键受到部分破坏,结晶度下降,纤维变得疏松,表面和内部结构受到一定的损伤,保水值和可及度增大,反应活性提高。与碱预处理相比,微波强化碱预处理显著提高了二次纤维的氰乙基化反应性能,在同一辐射功率下,延长微波强化时间有利于氰乙基化反应,微波强化碱预处理氰乙基化二次纤维的含氮率由10.85%提高至17.80%。     

微晶纤维素氰乙基化及其反应动力学研究

通过微晶纤维素的氰乙基化试验,研究了反应温度和反应时间对氰乙基化产物取代度(DS)的影响,表明在50℃以下,微晶纤维素的氰乙基化取代度随反应温度的升高和反应时间的延长而增加。傅里叶红外光谱分析显示微晶纤维素氰乙基化后羟基峰明显减弱,并形成了新的碳氮三键吸收峰,证明纤维素中的部分羟基氢被氰乙基所取代。X射线衍射分析显示微晶纤维素中原有的结晶结构被破坏。X4显微熔融温度测定仪、维卡软化点测定仪等的分析表明微晶纤维素氰乙基化产物的热塑性先随取代度的升高而提高,取代度超过1.43后,产物的热塑性又随取代度的升高而下降。确定了微晶纤维素氰乙基化在不同温度(30、35、40和45℃)下的反应速率常数(分别为1.30、1.61、1.94和2.26 s-1),计算出了微晶纤维素氰乙基化反应的表观活化能为29.8 kJ/mol。     

木材氰乙基化改性研究（Ⅱ）

利用ＮａＳＣＮ饱和的低浓度ＮａＯＨ水溶液作预润胀剂和催化剂，以丙烯腈作醚化剂对杉木进行氰乙基化改性。研究了丙烯腈用量、反应温度和时间、ＮａＯｈ浓度等对氰乙基化反应的影响。利用ＦＴＩＲ－Ｘ－ｒａｙ、ＴＭＡ、ＳＥＭ等对氰乙基化木材的微观结构和热塑性进行了研究和表征。     

马来酸乙基纤维素的制备与表征

为提高乙基纤维素的进一步应用,以乙基纤维素为原料,马来酸酐为衍生化试剂,制备了马来酸乙基纤维素,通过红外、核磁、X射线衍射、差示扫描量热(DSC)等手段对其结构及性质进行了表征,研究了反应各因素对产物取代度的影响,确定了马来酸乙基纤维素(ECMA)最佳反应条件为:马来酸酐与乙基纤维素中羟基总量物质的量之比为4:1,反应...     

微波辐射法竹浆纤维素的中性TEMPO氧化及表征

采用微波辐射法和中性2,2,6,6-四甲基哌啶-1-氧化物(TEMPO)自由基氧化工艺来预处理竹浆纤维素,之后用超声波机械处理制备微纤化纤维素。实验结果表明,在60℃下,TEMPO用量为0.15 mmol/g(以绝干浆计,下同),Na Cl O2用量为10 mmol/g,Na Cl O用量为1 mmol/g,微波氧化2 h,其羧基含量最高到达0.729 mmol/g,氧化效果最佳,超声波处理后微纤化纤维素得率高达85.7%。FT-IR分析表明纤维素氧化后引入羧基官能团;XRD结果揭示纤维素氧化反应只发生在纤维素的无定型区或结晶区表面;纤维素氧化前后的聚合度(Dp)结果表明相对于碱性氧化,微波辐射和中性TEMPO氧化对纤维的降解程度低,从而有效地保持了纤维素原本的长度。     

纸浆纤维素苄基化及其反应动力学

通过纸浆纤维素的苄基化试验,研究反应温度和反应时间对苄基化产物取代度的影响,证明适当延长反应时间、提高反应温度有利于提高产物的取代度。傅里叶红外光谱仪、差示扫描量热仪、X射线衍射仪等对纸浆纤维素苄基化产物的分析表明:原料中的部分羟基被苄基取代,原有的结晶结构被破坏,产物热稳定性略有下降。维卡软化点和熔融温度测试显示产物的热塑性随取代度的增加而增加。本文还确定纸浆纤维素苄基化在4个不同温度下的反应速度常数,计算出纸浆苄基化反应的表观活化能为46.1kJ·mol-1。     

ATRP法制备纤维素-油脂-糠醛热塑性弹性体及性能表征

通过"从主链接枝"原子转移自由基聚合(ATRP)法,采用分步聚合策略,成功制备了一种乙基纤维素接枝嵌段共聚物乙基纤维素-g-甲基丙烯酸月桂酯-b-甲基丙烯酸四氢糠基酯(EC-g-P(LMA-b-THFMA))。对聚合物的热力学性能研究发现:共聚物中存在两个热转变,分别发生在-35℃和49～56℃时,表明该共聚物存在微相分离;机械性能分析表明该共聚物具有优异的热塑性弹性体行为,伸长率为89%～147%,拉伸强度为1.7～9.5 MPa。循环拉伸机械性能研究表明EC-g-P(LMA-b-THFMA200)的弹性恢复系数高达92%以上。乙基纤维素接枝共聚物的机械性能具有明显的增强作用,较线性聚合物P(LMA-b-THFMA)的机械强度提高了1.36倍。     

Effects of Microwave Pretreatment on Liquefaction in the Preparation of Biomass Polyurethane

为提高液化效率,以水为介质,将麦秆纤维在不同的微波条件下进行预处理,研究微波处理对液化效率的影响,利用FT-IR、SEM、XRD等仪器分析方法对微波处理前后的麦秆化学结构、纤维形貌和聚集态结构等进行对比分析,研究了微波加速液化反应的机理.结果表明:其他备件相同时,微波预处理3 min可将液化反应时间由未处理时的60min降低至处理后的40 min,效果明显;研究发现微波预处理不会改变液化反应的历程.但适当的微波作用使麦秆纤维的结晶度由未处理前的46.35％下降到30.7％,麦秆纤维表面变得疏松,可及度变大,因此反应活性增强.     

马尾松微波间歇干燥对干燥效率与速率的影响

分析马尾松木材微波干燥速率随时间的变化规律,比较微波连续辐射和间歇辐射对木材干燥速率和微波能利用效率的影响.结果表明:木材微波干燥过程可以分成加速段、恒速段和减速段3个阶段;在微波干燥过程中,木材含水率在纤维饱和点以上时,其平均干燥速率和水分蒸发效率比在纤维饱和点以下时的高;采用适当间歇辐射对木材输入微波能,微波能利用率较高.     

天然纤维材料内部塑化研究综述

天然纤维具有来源广、价格低、可再生、能降解等特征,是当前资源开发的热点。热塑性转化是农林废弃类天然纤维资源有效利用的新途径。介绍天然纤维的塑化原理、热塑化方法、研究现状以及今后发展方向等。     

Cyanoethylation of several fiber materials and their utilization as adhesive in wood-based panels

This study examines the cyanoethylation and thermoplasticity of several cyanoethylated fiber materials. Cyanoethylated pulps with a degree of substitution of 1.43 have the lowest Vicat softening point. Cyanoethylated poplar with a weight gain of 18.2 % has the lowest melting temperature. Instead of traditional adhesives, cyanoethylated materials can be used to produce wood-based panels because of their good thermoplasticity. Plywood bonded with cyanoethylated pulp has a bonding strength of 2.06 MPa and an average wood failure of 62.7 %. Wheat straw particle board containing 40 % cyanoethylated pulp has an internal bonding strength of 0.49 MPa, a modulus of rupture (MOR) of 33 MPa, and a density between 0.5 and 0.6 g cm^?3. Fiberboard containing 40 % cyanoethylated pulp has an internal bonding strength of 0.53 MPa, MOR of 38 MPa, modulus of elasticity of 4,200 MPa, and a density between 0.7 and 0.8 g cm^?3. Its swelling in thickness is 41 %.     

13种食用菌对稻草生物降解能力的研究

通过对13种食用菌对稻草生物降解能力的研究,结果表明除蒙古白蘑(Tricholamamongolicum)外,其他12菌株对稻草中的木素及纤维素均有一定的降解能力。其中侧耳(Pleurotus.ostreatus)表现出了很强的木素降解能力及较低的综纤维素降解能力,其木素降解率为17.86%,综纤维素降解率为2.44%,SF指数为7.97,为理想的木素降解菌。其他菌株木素降解率为2.30%~16.54%,综纤维素降解率为5.60%~17.32%,而SF指数均较低,介于0.14~2.24。通过线性回归得出菌落直径与变色圈直径比值(d1/d2)和选择性指数(SF)为负相关,其相关系数r=-0.1476,相关性不大。表5参9。     

微波处理对稻草表面特性的影响

利用FEIXG型电子自旋共振波谱仪和Nicolet Nexus 670型傅立叶变换红外光谱仪(FTIR)研究了微波处理对稻草表面特性的影响。研究结果表明,经微波处理后的稻草表面自由基浓度显著增加,最高可以达到处理前自由基浓度的7倍左右。且随着处理时间的延长和微波强度的增加,稻草表面自由基浓度的增加幅度有所上升。经微波处理后,稻草外表面的化学成分(包括SiO2、羟基、木素和纤维素)变化都不明显,而稻草内表面SiO2略有减少,羟基显著增加,木素和纤维素也有一定变化。微波处理可以改善稻草内表面的特性,使之比外表面更具活性,有利于稻草与胶黏剂之间的交联。     

Fundamental characteristics of microwave explosion pretreatment of wood I. Properties of temperature development

In this study,the effects of microwave radiation intensity,radiation time and initial wood moisture content (MC) on the properties of temperature development in Eucalyptus urophylla wood samples during the microwave explosion pretreatment have been investigated using a new microwave pretreatment equipment.The results show that 1) with the increase of microwave radiation intensity and a decrease in initial wood MC,both the average temperature and its rate of increase in wood rise rapidly;2) with an increase ...     

Piezoelectric effect of cyanoethylated hydroxyethylcellulose

The piezoelectricity of cyanoethylated hydroxyethylcellulose was investigated. Elastic, piezoelectric, and dielectric relaxations were observed at –80° to –60°C and 0° to 20°C at a frequency of 10Hz. The activation energy is about 9–15 kcal/mol in the low temperature region and about 30–45 kcal/mol at room temperature. These relaxations in the low temperature region may be caused by the motion of the cyanoethyl group and those at room temperature mostly by the motions of the main chain. Cyanoethylated hydroxyethylcellulose has a high piezoelectric strain constant (d ₂₅), which is the largest value among the cellulose derivatives and is almost the same as the value for polyvinylidene fluoride. The electromechanical coupling factor for cyanoethylated hydroxyethylcellulose was small.     

Study on biodegradated ability of thirteen edible fungi to straw

The biodegradated abilities of 13 edible fungi to straw were studied. The results showed that all the experimental fungi except Tricholama mongolicum had definite biodegradated abilities to the lignin and cellulose of straw. The Ideal fungus for straw degradation was screened out as Pleurotus ostreatus, which showed a higher degradation ability for lignin (17.86%) and lower degradation rate for cellulose (2.24%), with a Selection Factor (SF) of 7.97. The degradation rates of lignin and cellulose for other fungi ranged from 2.30% to 16.54% and 5.60% to 17.32%, respectively, and the SF was very low in range of 0.14 to 2.24.The ratio of colony‘s diameters to the color-zone (d1/d2) and SF are negative correlation, with a correlation coefficient of -0.1476.     

基于微波液化的木质纤维素组分分离和转化——纤维素组分的理化和酶解性质

【目的】将微波加热与甘油利用相结合的综合炼制工艺用于木质纤维素生物质预处理,探索其在燃料乙醇制备中的可行性,为实现经济可行、经济有效的木质纤维素生物质酶解预处理技术和生物燃料生产提供基础信息。【方法】以银腺杨、日本落叶松、刚竹和柳枝稷为试验材料,采用微波液化法对其进行液化处理,将液化产物分为纤维素、半纤维素和木质素组分,并对纤维素纤维组分进行综合表征。【结果】化学分析结果表明,纤维素纤维具有较高的葡聚糖含量;红外光谱显示,木质素和半纤维素的信号逐渐减弱,说明半纤维素和木质素经液化处理后有效脱除;XRD分析结果表明,纤维素纤维结晶度高、表面积大。【结论】相比原木质纤维素生物质,银腺杨、日本落叶松、刚竹和柳枝稷4种原材料纤维素纤维的酶解糖化效率均有不同程度提升(最高酶解转化率可达70%),液化固体产物--纤维素纤维在制备燃料乙醇中具有广阔的潜力和前景。     

新型转极性离子化合物对香樟木屑的溶解和再生性能研究

为实现生物质的溶解,同时克服传统离子液体溶解生物质的缺点,制备了新型转极性离子化合物1,8-二氮杂二环十一碳-7-烯(DBU)/CH3OH/CO_2(DCC)的甲醇溶液,考察了不同温度、时间和溶液浓度对香樟木屑的溶解性能和再生效果,分析了溶解前后香樟木屑中纤维素、半纤维素和木质素的溶解率及结晶度的变化,并对溶解前后的木屑进行FT-IR、XRD和SEM表征,对溶解液中再生的物质进行FT-IR和UV分析。结果表明:较高温度(≥120℃)下,香樟木屑在DCC的甲醇溶液中的溶解率随温度升高和时间延长而有所增加;DCC甲醇溶液对半纤维素和木质素的溶解能力较强,对纤维素的溶解能力较弱;2.5 mol/L的DCC甲醇溶液在溶解温度180℃,溶解时间6 h时,木屑溶解率达到48.6%,半纤维素溶解率达62.4%,木质素溶解率为55.7%,纤维素溶解率为19.6%,溶解效果与传统离子液体相当。FT-IR、XRD和SEM分析表明,DCC甲醇溶液溶解木屑时,主要溶解木屑中无定形的半纤维素、木质素和少量非晶态的纤维素。FT-IR和UV分析表明溶解液中再生的物质是木质素,其质量分数在90%以上。DCC甲醇溶液重复使用3次时,每溶解一次其溶解能力下降2~3个百分点。     

Fabrication of pulverized cellulosics by ultra high-pressure water jet treatment and usage in polymer nanocomposites and graft copolymerization

Cellulose powders were pulverized by an ultra high-pressure counter-collision treatment in an aqueous suspension state, and then used in composites with vinyl polymers and graft copolymerized with methyl methacrylate using ceric ion initiator. The influence of freeze-drying methods after microfibrillation of cellulose was visualized by scanning electron microscopy (SEM). The coalescence of microfibrillar structures was observed to increase easily reflecting the freeze-drying conditions. While the degree of microfibrillation was unsatisfactory for use as fillers in preparing polymer-nanocellulose composites, the situation was found to be rectified with the use of a proper kneading technique. The roles of microfibrillated cellulose in processes producing bio-nano-composites suitable for practical uses were studied through SEM observations and measurements of physical properties. The characteristics of the successive graft copolymerization were studied through examining the monomer conversion and the grafting effi- ciency. The significant improvement in the grafting became apparent in response to the counter-collision pretreatment. Dynamic viscoelastic properties of the molded sheets of the grafted products were studied to measure the effects of the graft copolymerization compared with the corresponding physically blended material and neat poly(methyl methacrylate). The grafting reaction resulted in composites with much higher heat-resisting properties than those obtained for the latter two.