【作者】 李志强；

【导师】 蒋明亮；

【作者基本信息】 中国林业科学研究院 ， 木材科学与技术， 2010， 博士

【摘要】 与加铬砷酸铜(CCA)相比,含硼木材防腐剂环保、无毒、无色、成本低廉、不抗流失,目前含硼防腐剂处理的木材只能用于室内,不能用于室外。开展室外用硼酸盐化合物的合成及其处理材的抗流失性和耐腐性研究,具有重要的理论意义及应用价值。本文通过化学合成得到硼酸盐化合物,并制备成制剂;通过实验室抗流失试验对不同含硼化合物及处理方法处理木材后硼元素水流失性进行了测定;并对其抑菌性能、部分硼酸盐化合物的室内外耐腐性能和含硼季铵盐类化合物的固着机理进行了研究,主要结果如下:(1)合成出难溶于水的无机硼酸盐、四氟硼酸季铵盐类、四苯基硼酸季铵盐类和二(水杨酸)硼酸季铵盐类化合物,通过化学元素分析和化合物熔点测定鉴定确认。化学元素分析值与化学式理论计算值一致。化合物熔点与有文献报道的值相吻合,无文献报道值的化合物熔程较窄,纯度较高。(2)采用无机硼和金属盐或聚乙烯醇等两步法处理木材,处理材的硼流失率显著降低,最低至39.6%。疏水成分能够有效的降低处理材中硼的流失率,且两步法处理木材硼的流失率低于一步处理法。透明清漆处理的木材,硼的流失率可以达到50%以下。复分解反应制备的无机硼酸盐的水溶型制剂处理木材的硼的流失率在83.2%～96.8%之间。有机溶剂型的ZB(油酸)处理材中硼的流失率低至2.7%。四氟硼季铵盐化合物处理材的硼流失率随着碳原子数的增多而降低。当化合物中碳原子数>19时,化合物处理材的硼的流失率明显降低,最低可达19.8%。四苯基硼酸季铵盐处理材的硼流失率2.1%～24.7%。二癸基二甲基-二(水杨酸)硼酸铵的处理材硼的流失率降至11.3%～16.5%。十二烷基二甲基苄基-二(水杨酸)硼酸铵处理材的硼流失率降至33.2%～38.4%。(3)四氟硼酸季铵盐类有较好的抑菌效果,其中效果最好的为含有C8～C12基团的季铵盐。实验室白蚁试验结果表明,二癸基二甲基四氟硼酸铵(DBF)和十二烷基二甲基苄基四氟硼酸铵(BBF)抗白蚁效果好。(4)DBF和BBF处理后的杨木有很好的耐腐效果。当载药量为7.0 Kg/m3左右时,试样的白腐和褐腐质量损失率均在4%以内。野外埋地试验(10个月)后,这两种化合物初步表现出良好的耐腐和抗白蚁效果,加入溴氰菊酯,能够明显改善抗白蚁性能。(5)建立了含硼季铵盐类化合物的高效液相色谱分析方法。色谱条件为:Venusil SCX (100 mm×4.6 mm , 5μm)强阳离子交换柱,溶有氯化铵的V (甲醇): V (乙腈): V (水) = 1:1:1混合液作为流动相,检测波长262 nm,在质量浓度10～500 mg/L的相关系数为0.998 9,相对标准偏差0.397%,平均加标回收率为100.44 % ,检出限2.0mg/L。(6)含硼季铵盐化合物处理材中,硼和季铵盐的流失率并不一致,硼的流失率要远远大于季铵盐的流失率。含硼季铵盐类化合物处理材的流失率与其在水中的溶解度有关。溶解度大的化合物,其硼的流失就高,反之就低。当含硼季铵盐化合物的饱和水溶液质量分数低于0.036%时,其处理材中硼的流失率可降至40%以内。更多还原

【Abstract】 Inorganic borates are effective and environmental friendly as wood preservatives and offer good protection to timber in indoor applications. But these compounds can not be used in exterior circumstance for they are likely to leach out from treated wood. For finding new boron preservatives of leach resistance, some kinds of borates were synthesized and laboratory leaching performance, fungicidal activity and termite resistance of these borates were conducted in this paper.Insoluble inorganic borates, quaternary ammonium tetrafluoroborate, quaternary ammonium tetraphenylborate and quaternary ammonium bis(salicylato)borate were synthesized by the metathesis reaction in water. Each of those resulting compounds has been confirmed by micro-elemental analysis and melting point. The results of the elemental analysis are consistent with the theoretical calculation of the same chemical formula.The boron leaching rates of wood treated by different formulations and post-treatment were determined according to AWPA standard E11-06. The results show that: The boron leaching rates of treated samples are decreased significantly by two-step method, wood treated by borax firstly, and then by calcium chloride, polyvinyl alcohol(PVA P1763) or hydrophobic materials. The boron leaching rates are as low as 39.6% to 55.5%. The leaching rates of water insoluble inorganic borate prepared by metathesis reaction are between 83.2% ~ 96.8%. The boron leaching rate of wood samples treated by organic solvent-based ZB (oleic acid) is as low as 2.7%. The boron leaching rates of wood treated by quaternary ammonium tetrafluoroborate compounds increase with the number of carbon atoms of the compounds decrease. When the numbers of carbon atoms of the compounds are more than 19, the boron leaching rates by the compounds decrease significantly, the minimum up to 19.8%. The leaching rates of boron treated by quaternary ammonium tetraphenylborates are 2.1% ~ 24.7%, and 11.3% ~ 16.5% by didecyl dimethyl ammonium bis(salicylato) borates, and from 33.2% to 38.4% by dodecyl dimethyl benzyl ammonium bis(salicylato) borates.The inhibition zone test of quaternary ammonium tetrafluoroborate, quaternary ammonium tetraphenylborate and quaternary ammonium bis(salicylato) borate compounds were conducted, test fungus included white rot fungi, brown rot fungi and mold, etc. The results show that quaternary ammonium tetrafluoroborate have the best inhibitory effect, the best of them containing C8 ~ C12 alkyl groups. Termite test results show that, didecyl dimethyl ammonium tetrafluoroborate(DBF) and benzyl dodecyl dimethyl ammonium tetrafluoroborate (BBF) are effective against termites.The anti-fungi performance of DBF and BBF was evaluated by laboratory sand block test and field stake test. Different formulations of preservatives based on DBF and BBF were tested. In laboratory accelerated test, the brown rot fungi Gloeophyllum trabeum (G.T) and white rot fungi Coriolus versicolor (C.V) were used. The result shows that there is no significant difference of anti-fungi performance between DBF and BBF. DBF is just a little better than BBF, the weight loss of specimens by the two fungi were both less than 4% at the retention about 7.0 Kg/m3 of the two compounds. After field trial test for about 10 months, the stakes of DBF at the retention of 11.1Kg/m3, perform a good resistance to decay. Termite resistance of treated stakes by both DBF and BBF were poor and could be efficiently improved by adding pyrethroid in treating solution.An analytical method for determining boron-containing quaternary ammonium compounds in preservative or treated wood by HPLC is established. The apparatus and reagents: Elite P230 pump with 20μL loop injector; the column is Venusil SCX (100 mm×4.6 mm, 5μm) strong cation exchange column; UV detector with a measuring wavelength of 262 nm; EC2000 workstation; HPLC mobile phase is the mixture of acetonitrile, methanol and water in a volume ratio of 1:1:1, within appropriate amount of ammonium chloride; the flow rate is kept at 1.5 mL per minute. The linear correlation of this method is 0.9989 at concentration of the activities from 10 mg/L to 500 mg/L. The average recovery of spiked samples is 100.44%, and relative standard deviation is 0.397%. The detection limit of method was 2.0 mg/L.For quaternary ammonium borate compounds, the leaching rates of boron and quaternary ammonium are uncoordinate, the leaching rate of boron is much higher than the leaching rate of quaternary ammonium. The leaching rate of boron-containing quaternary ammonium compounds in treated wood have a relationship with their solubility in water. The higher solubility in water, the higher leaching rate of boron. When the concentration of saturated aqueous solution of boron-containing quaternary ammonium compound is less than 0.036%, the leaching rates of boron of its treated wood could be reduced to less than 40%.更多还原