稀土金属氧化物催化松香酯化反应的研究

研究了稀土金属氧化物 (NdnOm,SmnOm,GdnOm,LanOm)对松香酯化反应的催化作用 ,系统探讨了各种反应因素对松香酯化反应的影响 ,研究结果表明 :稀土金属氧化物催化松香与各种醇的酯化时 ,具有催化剂用量少 (仅占原料松香的 0 .33 %～0 .83 % )、反应时间短 ( 2～ 6h)、反应温度低 ( 2 0 0～ 2 60℃ )等优点 ;酯化完成后不需碱中和等后处理过程 ,酯化产品性能较佳     

过渡金属氧化物对木粉/PVC复合材料燃烧性能的影响

用锥形量热仪(CONE)和热重分析法(TGA)研究金属氧化物CuO、La2O<,3>和TiO2对木粉/PVC复合材料(WF-PVC)燃烧性能的影响.结果表明,这3种过渡金属氧化物的加入对WF-PVC均有阻燃作用.其中,CuO使热释放速率(HRR)和总热释放量(THR)降低较多,阻燃效果明显;加入金属氧化物使WF-PVC的烟释放速率(SPR)和总烟释放量(TSP)都有所降低,其中,CuO在有焰燃烧阶段烟释放量最低,抑烟效果最好.这3种氧化物都能增加成炭量.结合热重分析的结果,3种金属氧化物对WF-PVC的热降解影响是不同的.PVC和木粉之间存在相互作用,PVC显著促进了木粉的热降解,木粉的加入推迟了PVC的降解,明显提高了PVC体系的成炭量;WF-PVC的热降解行为,具有更多的PVC降解的特征.     

Investigation on the Catalysis in the Oxidation of α-Pinene

概述了近20年来国内外对催化α-蒎烯氧化反应过程的研究,重点分析了α-蒎烯氧化中催化剂的性能特点及产物分布规律,总结了过渡金属盐、氧化物、配合物、分子筛及杂多酸在α-蒎烯氧化中的催化作用,比较了催化活性及选择性的特点,并初步探讨了发展趋势.提出在已有的α-蒎烯氧化反应催化剂中,分子筛类催化剂在制备方法和工业化发展上有一定的优势,深入研究过渡金属化合物在α-蒎烯氧化反应的催化性能及调变方法,应是α-蒎烯氧化反应中值得重点关注的研究内容.     

-蒎烯氧化中的催化作用研究进展

概述了近20年来国内外对催化α-蒎烯氧化反应过程的研究,重点分析了α-蒎烯氧化中催化剂的性能特点及产物分布规律,总结了过渡金属盐、氧化物、配合物、分子筛及杂多酸在α-蒎烯氧化中的催化作用,比较了催化活性及选择性的特点,并初步探讨了发展趋势。提出在已有的α-蒎烯氧化反应催化剂中,分子筛类催化剂在制备方法和工业化发展上有一定的优势,深入研究过渡金属化合物在α-蒎烯氧化反应的催化性能及调变方法,应是α-蒎烯氧化反应中值得重点关注的研究内容。     

双酚A及四溴双酚A的热分解动力学研究

采用热分析方法(TG,DTA)、热分解气相色谱和红外光谱等联合手段,对双酚A(4-4'-二羟基二苯基丙烷)和四溴双酚A(2,2-二[3,5-二溴-4-羟基苯基]丙烷)的热稳定性及热分解反应动力学进行了研究,发现它们的稳定性和分解机理与取代基性质、分子结构的对称性有明显关系,并对其稳定性、热解机理从电荷分布出发进行了理论分析.     

1-(β,γ-环氧丙氧甲基)-7-异丙基-4-甲基的合成及结构鉴定

在相转移催化作用下,将7-异丙基-4-甲基-1-甲醇(2)和环氧氯丙烷进行反应,成功地合成了新的反应型类化合物1-(β,γ-环氧丙氧甲基)-7-异丙基-4-甲基(1).本反应条件比较简单,较佳条件下分离的目的物摩尔得率达到了64%.目的物(1)的化学结构(Fig.2)经过UV-Vis、IR、HR-MS和1H NMR等数据分析得到了完满的鉴定.     

林产工业专利选摘

专利名称:一种抗流失高效阻燃木材及处理方法专利申请号:CN200910075032.7公开号:CN101623886申请日:2009.08.03公开日:2010.01.13申请人:河北大学本发明提供一种抗流失高效阻燃木材,含有碳酸盐或酸式碳酸盐与氧化物溶胶复合物。所述的氧化物溶胶包括SiO_2溶胶、Al_2O_3溶胶或SiO_2/Al_2O_3复合溶胶或过渡金属氧化物溶胶或稀土氧化物溶胶。本发明利用无机阻燃剂阻燃效率高、价格便宜、配制简单的优点,与氧化物溶胶共用,克服无机阻燃剂吸潮、耐候性差、遇水或环境湿度大时容易流失等缺点,在提高了     

一种合成蒎酮酸新方法的研究

为了解决蒎酮酸传统合成方法的条件苛刻和反应时间太长等问题 ,提出用表面活性剂催化氧化α 蒎烯的新方法。主要研究了用十二烷基硫酸钠 (以下简称K1 2 )作催化剂对KMnO4氧化α 蒎烯合成蒎酮酸的反应的催化作用 ,系统探讨了各种反应因素对α 蒎烯氧化反应的影响。研究结果表明 :用表面活性剂K1 2作催化剂对KMnO4氧化α 蒎烯时 ,具有催化剂用量少 (2 % )、反应条件温和 (3 0℃ )、反应时间短 (5 .0～ 5 .5h)和蒎酮酸产率较高 (>60 % )等优点。     

微氧下低浓度磷化氢在浸渍活性炭上的吸附及表征

要利用富含高浓度CO的工业尾气(如黄磷尾气)生产甲酸、乙酸以及甲醇等高附加值产品,净化处理成为制约其应用的瓶颈问题.采用浸渍法改性活性炭吸附净化低浓度PH3,研究了HCl、KNO3和己二醇改性活性炭吸附净化磷化氢(PH3)的性能,研究表明:质量分数7%的HCl是最佳浸渍液,70℃和氧体积分数0.8%是改性活性炭的最佳反应条件.改性后的活性炭用氮气吸附的方法测定其孔结构特征.结果表明,改性使吸附剂总孔容的减少主要发生在2nm以下的微孔直径范围内,特别是在0.3～1.5nm的微孔范围内,孔容积减小明显,经改性后,微孔容的减少占总孔容减少的87%,吸附后,微孔容减少29%,表面积减少28%.HCl改性可以显著增加活性炭对PH3的吸附能力.分析表明,存在于微孔中的HCl起了催化作用,使PH3迅速氧化成磷的氧化物(P2O3或P2O5),而磷的氧化物能较强地吸附在活性炭0.3～1.5nm的微孔中.     

水可分散型松香基聚酯多元醇的制备及耐热性研究

以马来海松酸(MPA)、新戊二醇(NPG)、三羟甲基丙烷(TMP)、间苯二甲酸(IPA)、己二酸(AA)、间苯二甲酸-5-磺酸钠(5-SSIPA)为原料,采用先分步熔融后溶剂回流法制得水可分散型松香基聚酯多元醇(WDRPP)。探讨了反应时间、催化剂用量、n(—OH)∶n(—COOH)和亲水单体用量对反应的影响,并利用傅里叶红外光谱(FT-IR)和~(13) C NMR对产物进行了表征。利用热重分析(TG)研究了WDRPP的耐热性,并采用Coats-Redfem法对WDRPP的热分解动力学试验数据进行拟合分析,得到动力学参数。结果表明,当反应时间为5.5 h(熔融反应3 h,溶剂回流2.5 h),催化剂用量为0.10%,n(—OH)∶n(—COOH)为1.4∶1,亲水单体用量为2.86%时,制备的WDRPP的热稳定性和WDRPP水分散体的稳定性最佳;WDRPP的最大失重速率温度(Tmax)为406.7℃、热解反应活化能为64.65 k J/mol,且热分解动力学曲线线性良好(R~2=0.997 3),表明WDRPP热分解过程符合一级反应动力学规律;FT-IR和~(13) C NMR的分析结果表明WDRPP制备成功。     

TGA modeling of the thermal decomposition of CCA treated lumber waste

 To guide the development of thermal decomposition methods for disposal of CCA treated wood, reactions during the thermal decomposition of CCA treated wood were modeled using thermogravimetric analysis (TGA), with special focus placed on arsenic volatilization. Simple inorganic compounds, such as As₂O₅, CuO, and Cr₂O₃, were used to model the thermal behavior of the inorganics in CCA treated wood. In air and nitrogen, arsenic (V) oxide began to volatilize at 600 °C during temperature ramps at 5 °C/min. During a 5 °C/min ramp in a hydrogen mix, arsenic (V) oxide began decomposition at 425 °C. Arsenic volatile loss from CCA treated wood can depend strongly on the gases produced by wood thermal decomposition. In the presence of As₂O₅, chromium (III) oxide and copper (II) oxide formed arsenates in air and nitrogen. Chromium arsenates began decomposition as low as 790 °C. This suggested that chromium arsenates in CCA treated wood formed during original preservative fixation may decompose as low as 790 °C. Copper arsenates were stable up to 900 °C in air, but showed only a limited range of stability in nitrogen. Depending on process conditions, the formation of copper arsenates may limit arsenic loss during thermal decomposition of CCA treated wood up to 900 °C. The thermal decomposition of inorganic oxides was influenced by interactions with wood and wood decomposition products. In a dry YP sawdust/As₂O₅ mix, arsenic (V) oxide volatilized at 370 °C during inert pyrolysis at 5 °C/min and at 320 °C during smoldering combustion at 5 °C/min. Thermal dwells of a dry YP/As₂O₅ mix showed no arsenic loss at 250 °C, but significant loss occurred during higher temperature dwells. During inert pyrolysis at 5 °C/min, the formation of complexes and hydrates were shown to prevent arsenic loss up to 400 °C. Received 14 July 1999     

橡胶原木蓝变及防治方法初步研究

新鲜橡胶原木最易感染蓝变菌而引起木材蓝变。试验结果表明,造材后即用２％ＴＭＯ防霉剂喷涂端面,若在雨季喷药后再涂刷防水ＴＭＯ,一个月内效果良好,适用于鲜橡胶原木的短期保存。     

竹材中密度纤维板（MDF）防霉研究

用厘竹、青皮竹、篙竹制成的MDF为试材,以国产TMO、DD及比利时的MECT三种防霉剂对其进行处理后,从板的物理力学性能及抗霉效力等方面进行比较表明,对木材有效的防霉剂并非对竹材MDF也有效。MECT与TMO比较,前者抗霉效力略高于后者,但前者使板的强度下降幅度较大,而价格约为后者的5倍。如果用法得当,TMO对竹材MDF的抗霉效力仍可达到100%。工艺试验结果表明,合适的制板工艺将使板的抗霉效果得到充分发挥,而且可以保证板的物理力学指标处于高水平前提下,确定其最低的原料及防霉剂消耗水平。     

羟基酪醇的热稳定性和分解动力学研究

研究不同升温速率(β=5、10、20、40 K/min)下羟基酪醇的热稳定性、分解动力学和贮存期。利用热重分析得到羟基酪醇在氮气氛围中不同升温速率(β)下的热分解曲线,运用3种多升温速率法Kissinger法、Friedman法和Flynn-Wall-Ozawa法以及2种单升温速率方法 Coats-Redfern法和Achar法进行动力学分析,计算热分解的表观活化能(Ea)和指前因子(A),且根据Ea和A推算羟基酪醇的贮存期。结果显示:羟基酪醇的热分解过程一步完成,在升温速率为10 K/min时,从260~409℃为羟基酪醇的主要失重阶段;TG曲线随着温度的升高而迅速出现陡峭明显的失重台阶,DTG曲线亦出现负值,且随着温度的升高而急剧下降,在305.2℃达到了DTG的峰值,此时达到最大热失重速率为-12.91%/min;升温速率的变化对羟基酪醇的分解有影响,随着速率的升高,羟基酪醇的热分解温度逐渐升高,热分解曲线略微向高温移动,呈现了分解滞后现象。羟基酪醇的热分解机制符合一维扩散(D1)模型。测得平均Ea为122.40 k J/mol,A为3.37×1010min-1。根据Ea和A可推断,在室温25℃下,羟基酪醇在氮气氛围下的理论贮存期为4~5年。     

八种防霉剂对橡胶木和竹材霉菌及蓝变菌的毒性试验

霉菌和蓝变菌是橡胶木和竹材变质的主要原因之一。八种防霉荆对上述木竹材霉菌及蓝变菌的毒性试验结果表明：祛霉乐防霉剂对霉菌的最低抑制浓度为２～１０ＰＰｍ，和ＭＥＣＴ相当，对蓝变菌有特效，防治橡胶木或竹材霉菌和蓝变菌的最低有效浓度为０．２％，可替代五氯酚钠和进口防霉剂。     

Effects of <Emphasis Type="Italic">Ips typographus</Emphasis> (L.) damage on litter quality and decomposition rates of Oriental Spruce [<Emphasis Type="Italic">Picea Orientalis</Emphasis> (L.) Link.] in Hatila Valley National Park,Turkey

This study investigated the effects of Ips typographus (L.) damage on initial litter quality parameters and subsequent decomposition rates of oriental spruce tree species [Picea orientalis (L.) Link]. The needle litter was collected from highly damaged, moderately damaged and control stands on two aspects (north and south) and two slope position (top and bottom) on each aspect. The litter was analyzed for initial total carbon, lignin and nutrient (nitrogen, phosphorus, potassium, calcium, magnesium and manganese) concentrations. The variability in nitrogen and calcium concentrations and ratios of C:N, lignin:N and lignin:Ca was significantly affected by the insect damaged levels. While nitrogen concentrations in needle litter increased with increasing insect damage (and consequently the ratios of C:N and lignin:N decreased), calcium concentrations decreased (and consequently the ratio of lignin:Ca increased). Aspect and slope positions explained most of the variability in carbon, lignin, phosphorus, potassium, magnesium and manganese concentrations and lignin:P ratio between all studied stands. Litter decomposition was studied in the field using the litterbag technique. The litter from highly damaged stands showed highest decomposition rates followed by moderately damaged and control stands. The mass loss rates were significantly positively correlated with initial nitrogen concentration and negatively with C:N and lignin:N ratios. The effects of microclimate resulting from canopy damage on litter decomposition was also examined at the same time using standard litter with the same litter quality parameters, but they showed no significant differences among the insect damage levels indicating that alteration of the litter quality parameters produced by I. typographus damage played a more important role than altered microclimate in controlling needle litter decomposition rates. However, changes in microclimate factors due to topography influenced decomposition rates.     

点击反应制备木质素-纳米SiO_2复合微粒及其结构表征

以竹木质素为原料,利用Cu(Ⅰ)催化的炔基-叠氮环加成点击反应将木质素修饰到纳米SiO_2材料表面,制备木质素-纳米SiO_2复合微粒(LS-NPs)。首先采用硅烷基化反应在纳米SiO_2微粒表面引入叠氮结构,并由竹木质素制备炔基木质素,再通过Cu(Ⅰ)催化炔基木质素与叠氮基纳米SiO_2的点击反应生成含三氮唑结构单元的LS-NPs。采用红外光谱(FT-IR)、元素分析(EA)、X射线光电子能谱(XPS)等分析手段表征了LS-NPs的化学结构,并通过扫描电镜(SEM)、透射电镜(TEM)、Zeta电位分析仪和热重分析(TGA)等表征方法考察了LS-NPs的形貌结构和理化性质。结果表明,点击反应成功将木质素结构通过三氮唑单元接枝到纳米SiO_2表面,LS-NPs微粒为球形,粒径为50~100 nm,分散性能和热稳定性能均有明显提高。     

人工林珍贵树种柚木和楸木的热解特性及动力学

木材阻燃体系的选择应考虑其热解特性，选取人工林珍贵树种柚木、楸木和速生材杉木、辐射松为研究对象，通过化学成分和热重（TG）分析试验，研究热解特性、热解动力学模型和参数，为阻燃体系选择提供理论依据。结果表明：四种木材的热解过程均可分为失水、过渡、剧烈降解和成炭等四个阶段；柚木、楸木的最大热解速率温度、活化能和活化因子均低于杉木和辐射松，适用于热解温度相对较低的阻燃体系。     

Decomposition and nutrient release in needle litter from nitrogen‐fertilized scots pine (pinus sylvestris) stands

Decomposition of Scots pine needle litter originating from five stands treated with different amounts of nitrogen fertilizer was measured over a 4‐year period in a mature Scots pine forest. The litter types, which differed in initial concentrations of nitrogen, phosphorus, potassium, and sulfur, but not in gross organic composition, were studied with respect to mass loss, ingrowth of total fungal mycelium, and net release of nutrients. During the first year of decomposition, rates of mass loss and ingrowth of fungal mycelium were highest in the nutrient‐rich litter. Phosphorus concentration was found to be the main factor affecting mass‐loss rate, and the rate of fungal ingrowth was positively correlated with initial nitrogen concentration. After this initial period, decomposition rates decreased, and after 4 years, accumulated mass loss and amounts of fungal mycelium were similar in all five litter types. These findings may be due, in part, to a lower rate of lignin decomposition in nitrogen‐enriched litter. Of the elements, potassium and magnesium were most rapidly lost from the litter, and their release was most pronounced during the first year. Calcium release was proportional to the loss in organic matter. Initially, the release of nitrogen and phosphorus was positively related to their concentrations in litter, however, during later stages of decomposition the differences among litter types levelled out. There was a tendency for concentrations of all elements, except nitrogen, in the different litters to approach similar levels as decomposition proceeded. Thus, after 4 years the nutrient composition of the various litter types was very similar, except for higher nitrogen concentrations in the originally most nutrient‐rich litters. The importance of the results in terms of substrate quality in fertilized as well as in non‐fertilized forests is discussed.