【作者】 苏文强；

【导师】 李坚；

【作者基本信息】 东北林业大学 ， 林产化学加工工程， 2008， 博士

【摘要】 树木提取物用于木材防腐是现代开发新型木材防腐剂重要研究方向,树木提取物中的部分化合物对木材腐朽菌具有不同程度的抑制活性,将其用于木材防腐,与传统防腐剂相比,具有鲜明的优点。本研究按照化学药剂的极性大小,选用水、甲醇、丙酮、氯仿和乙醚等5种试剂,对怀槐心材、树皮分别进行了提取,得出实验和分析结果:其心材提取物的总得率为12.59%;树皮提取物的总得率为57.68%。分别对怀槐心材的甲醇提取物、丙酮提取物、怀槐树皮的氯仿提取物、乙醚提取物进行了GC-MS检测分析。在怀槐心材提取物中确定的化学成分有25种,其中含量较多的为苯酚类物质,如苯酚、间苯二酚、邻苯二酚、邻甲氧基苯酚、间甲氧基苯酚等,此外还含有少量烯类、蒽类与菲类化合物;在怀槐树皮提取物中的化学成分有5种,其中多为脂肪酸类与脂类物质,如9-十六碳烯酸甲酯、辛酸等;辛酸在怀槐树皮氯仿提取物中所占比例为3.826%,在乙醚提取物中所占比例为8.260%。对提取物的混合物进行了大量的抑菌实验,在此基础上,采用滤纸片法,用9-十六碳烯酸甲酯、苯酚、间苯二酚、角鲨烯类化合物、邻苯二酚、邻甲氧基苯酚、辛酸对白腐菌[采绒革盖菌（Coriolus versicolor）]、褐腐菌[密粘褶菌（Gloeophyllum trabeum）]、软腐菌[球毛壳菌（Chaetomium globosum）]、霉菌[宛氏拟青霉菌（Paecilomyces variot Bainier）]做抑制实验。结果显示:在4%药物浓度下,9-十六烯酸甲酯仅对宛氏拟青霉菌有一定的抑制效果。在2%药物浓度下,9-十六烯酸甲酯、苯酚、角鲨烯、邻甲氧基苯酚对4种木材腐朽菌没有抑制效果;间苯二酚对白腐菌抑制效果较好,对球毛壳菌和宛氏拟青霉菌的抑制效果略差,对褐腐菌没有抑制效果;邻苯二酚对4种菌的抑制效果依次为:褐腐菌>球毛壳菌>宛氏拟青霉菌>白腐菌;对4种菌抑制效果最好的药物为辛酸,其效果依次为:白腐菌>褐腐菌>球毛壳菌>宛氏拟青霉菌。为进一步提高辛酸对木材腐朽菌的抑制活性以及作为木材防腐剂的适用性,本研究以辛酸、羟乙基乙二胺、二乙烯三胺、苄基氯和硫酸二甲酯为原料功能性合成了2种咪唑啉和4种咪唑啉系列季铵盐:（1）1-羟乙基-2-庚基咪唑啉（1-hydroxyethyl-2-heptylimidazolines,HOI）;（2）1-氨乙基-2-庚基咪唑啉（1-Aminoethyl-2-heptylimidazoline;EOI）;（3）1-苄基-1-羟乙基-2-庚基咪唑啉（1-hydroxyethyl-1-benzyl-2-heptylimidazolines,HOIB）;（4）1-甲基-1-羟乙基-2-庚基咪唑啉（1-hydroxyethyl-1-methyl-2-heptylimidazolines,HOIM）;（5）1-苄基-1-氨乙基-2-庚基咪唑啉（1-Aminoethyl-1-benzyl-2-heptylimidazoline;EOIB,）;（6）1-甲基-1-氨乙基-2-庚基咪唑啉（1-Aminoethyl-1-methyl-2-hept）,limidazoline;EOIM)。经过CA检索,尚未发现与HOIB和EOIB结构相同的化合物。采用菌悬浮液法,以浓度梯度的HOIB、HOIM、EOIB、EOIM溶液,混合白腐菌、褐腐菌的孢子溶液,并与碱性季铵铜（ACQ-C）、酸溶性铬酸铜（ACC）、二甲基二癸基氯化铵（DDAC）、十二烷基二甲基苄基氯化铵（1227）、铜唑（CA-B）等木材防腐剂作对比进行实验室培养实验。结果显示:HOIM、HOIB两种季铵盐抑菌效果较差,EOIB、EOIM的抑菌效果比ACQ-C、DDAC、1227、CA-B略差,但优于ACC。采用实验室木块防腐实验方法,以大青杨为试材,选用EOIB、EOIM、ACQ-C、DDAC、ACC、CA-B做对比实验。检测了防腐剂的防腐性能、抗流失性能、对环境的急性毒性以及防腐木材的尺寸稳定性、弹性模量和表观颜色等指标。实验室木材防腐试验结果显示:1、EOIB对白腐菌和褐腐菌,浓度为2%时,可达到Ⅱ级防腐标准,浓度为4%时,均可达到Ⅰ级防腐标准。2、EOIM对白腐菌,浓度为2%时,可达到Ⅱ级防腐标准,浓度为4%时,可达到Ⅰ级防腐标准;对褐腐菌,浓度为2%时,可达到Ⅲ级防腐标准,浓度为4%- 6%时,可达到Ⅱ级防腐标准,浓度为8%时,可达到Ⅰ级防腐标准。3、CA-B对白腐菌和褐腐菌,浓度为2%时,均可达到Ⅰ级防腐标准。4、ACQ-C对白腐菌和褐腐菌,浓度为2%时,均可达到Ⅰ级防腐标准。5、DDAC对白腐菌和褐腐菌,浓度为2%时,均可达到Ⅰ级防腐标准。6、ACC对白腐菌,浓度为2%时,可达到Ⅰ级防腐标准;对褐腐菌,浓度为2%- 8%时,可达到Ⅱ级防腐标准,浓度为10%时,可达到Ⅰ级防腐标准。各种防腐剂的流失率:ACQ-C,20.43%;CA-B,17.23%;EOIM,10.22%;EOIB,10.05%;DDAC,8.31%;ACC,7.57%。对环境的急性毒性试验结果为:安全浓度/(mg·L^-1):DDAC为2.47,EOIB为2.02,CA-B为0.63,ACC为0.46,ACQ-C为0.01。半致死浓度LC₅₀/(mg·L^-1):24h,DDAC为10.20,EOIB为7.15,CA-B为3.60,ACC为3.20,ACQ-C为2.59;48h以上,DDAC为9.50,EOIB为7.01,CA-B为3.00,ACC为2.50,ACQ-C为0.66。木材经过真空浸注防腐剂药液处理后,其防腐木材的抗弯强度（MPa）从高到低依次为EOIM>空白试样>ACC>CA-B>ACQ-C>DDAC>EOIB;抗弯弹性模量（MPa）从高到低依次为EOIM>ACC>CA-B>ACQ-C>空白试样>EOIB>DDAC。防腐木材的尺寸稳定性实验结果显示:从全干至气干,线湿胀率从高到低依次为:CA-B>EOIB>空白试样>DDAC>ACC>EOIM>ACQ-C;体积湿胀率从高到低依次为:DDAC>EOIB>EOIM>ACQ-C>空白试样>CA-B>ACC。从全干至吸水,线湿胀率从高到低依次为:空白试样>CA-B>EOIB>DDAC>EOIM>ACQ-C>ACC;体积湿胀率从高到低依次为:空白试样>ACC>DDAC>EOIM>CA-B>EOIB>ACQ-C。综合大量的实验室试验和科学研究结果表明:（1）部分树木提取物成分对木腐菌具有抑制活性;（2）树木提取物经功能性合成后,可适于做某种环境下的木材防腐剂;（3）以树木提取物作为新型木材防腐剂具有对环境无污染,对人畜无害,师法自然等特点。选择合适的树木提取物成分为原料,进行功能性合成,可作为研究、开发新型木材保护剂的有效途径之一。更多还原

【Abstract】 It is an important research direction that tree extractives are used as wood preservatives, because some compounds of tree extractives have good resistance to wood preservation fungi. Extractives were prepared from the bark and heartwood of Wild Siris （Maackia amurensis Rupr.et.Maxim） with water, methanol, acetone, chloroform and ether, respectively. The total extractives with all different solvents took up 12.59% （w/w） of the heartwood and 57.68% of the bark. Among the heartwood extractives, 25 compounds were identified by the analysis of GC/MS. Most of them are phenolic compounds, such as phenol, resorcinol, catechol, 2-methoxy-phenol, 3-methoxy-phenol etc. Besides, there are also a small amount of alkene, anthracene, phenanthrene and their derivatives. From the bark extractives of Wild Siris, 5 compounds were identified by the same method. They are fatty acid, fat and their derivatives etc., such as 9-hexadecenoic acid methyl ester and octanoic acid. Octanoic acid took up 3.826% of the chloroform extractive from the bark of Wild Siris, and 8.260% of the ether extractive.In this study, the resistance of 9-hexadecenoic acid methyl ester, phenol, catechol, resorcinol, triacontahexaene, 2-methoxy-l,2-benzenediol, octanoic acid to a white rot fungus （Paecilomyces variot Bainier）, a brown rot fungus （Gloeophyllum trabeum）, a soft rot fungus （Chaetomium globosum） and a penicillium fungus （Coriolus versicolor） were determined respectively by filter paper disk method on the basis of the mixtures resistance experiments. The results showed that 4% 9-hexadecenoic acid methyl ester is resistant to Penicillium. At 2% of the concentration, 9-Hexadecenoic acid methyl ester, Phenol, Triacontahexaene, 2-Methoxy-1,2-Benzenediol have no resistance to all the tested fungi. The resistance of resorcinol is high to the white rot fungus, low to the brown rot fungus and the penicillium fungus, and no effect to the brown rot fungus. Catechol is resistant to all of the 4 fungi. Its bioactivity to the fungi in turn is: to the brown rot fungus greater than the soft rot fungus, greater than the penicillium fungus, and greater than the white rot fungus. Octanoic acid has the best resistance to all the tested fungi and its bioactivity to the fungi in turn is: to the white rot fungus better than the brown rot fungus, better than the soft rot fungus, and better than the penicillium fungus. In order to improve the resistance of octanoic acid to wood decay fungi and the its applicability as a wood preservative, 6 imidazolines derivatives include 4 quaternary ammonium salt（OIQ） were synthesized:（1） （1-hydroxyethyl-2-heptylimidazolines, HOI）;（2） （1-Aminoethyl-2-heptylimidazoline, EOI）;（3） （1-hydroxyethyl-1- benzyl -2-heptylimidazolines, HOIB）; （4） （1-hydroxyethyl-1- methyl -2-heptylimidazolines, HOIM）;（5） （1-Aminoethyl-1- benzyl -2-heptylimidazoline, EOIB）;（6） （1-Aminoethyl-1- methyl -2-heptylimidazoline, EOIM ）.In Chemistry Abstract （CA）, the same structure compounds with HOIB or EOIB have notbeen found.Then, the cultivation experiments were done by the suspension method of white rot fungusspore and brown rot fungus spore with HOIM, HOIB, EOIM, EOIB, ACQ-C, DDAC, ACC,BAC（1227） and CA-B separately. The results display that the resistance of HOIM and HOIB towhite and brown rot fungi is not good. The resistance of EOIM and EOIB to the white andbrown rot fungi is not as good as that of ACQ-C, DDAC, 1227 and CA-B, but better than thatofACC.By the method of wood block preservation in laboratory, we finished the wood block [（UssuriPoplar）, （Populus ussuriiensis Kom.）] preservation experiments with EOIM, EOIB, ACQ-C,DDAC, ACC and CA-B to the white rot fungus and brown rot fungus.The wood decay resistance, leachability, toxicity to the environment, dimensional stability,modulus of elasticity, and color was determined. The results were as follows:1. To the white and brown rot fungi, the wood treated with 2% EOIB could meet the demand of DegreeⅡof preservation, and the wood treated with 4% EOIB could be ranked DegreeⅠ.2. To the white rot fungus, the wood treated with 2% EOIM could meet the demand of DegreeⅡof preservation, and the wood treated with 4% EOIM reached Degree I . To the brown fungus, the wood treated with 2% EOIM could meet the demand of DegreeⅢof preservation, and the wood treated with 4%-6% EOIM reached DegreeⅡ, and the wood treated with 8% EOIM reached DegreeⅠ.3. To the white and brown rot fungi, the wood treated with 2% CA-B could meet the demands of DegreeⅠof preservation.4. To the white and brown rot fungi, the wood treated with 2% ACQ-C could meet the demands of DegreeⅠof preservation.5. To the white and brown rot fungi, the wood treated with 2% DDAC could meet the demands of DegreeⅠof preservation.6. To the white rot fungus, the wood treated with 2% ACC could meet the demands of Degree I of preservation. To the brown rot fungus, the wood treated with 2%-8% ACC could meet the demands of DegreeⅡof preservation and the wood treated with 10% could reach DegreeⅠ.The leachability was 20.43% for ACQ-C, 17.23% for CA-B, 10.22% for EOIM, 10.05% for EOIB, 8.31% for DDAC and 7.57% for ACC. The safety concentration (mg·L^-1) is 2.47 for DDAC, 2.02 for EOIB, 0.625 for CA-B, 0.46 forACC and 0.01 for ACQ-C.The half lethal concentration [LC₅₀ /(mg·L^-1)] is 10.20（the time of operation at less than 24h）and 9.50（the time of operation above 48h ） for DDAC, 7.15 （less than 24h） and 7.01 （above48h ） for EOIB, 3.60（less than 24h） and 3.00（above 48h ） for CA-B, 3.20 （less than 24h） and2.50 （above 48h） for ACC, 2.59（less than 24h） and 0.66（above 48h ） for ACQ-C.The wood samples were impregnated with preservatives by vacuum and pressure method.Their bending strength and elastic modulus of bending was tested. According to the results, theorder of bending strength from high to low is EOIM, Control, ACC, CA-B, ACQ-C, DDACand EOIB and the elastic modulus of bending from high to low is EOIM, ACC, CA-B, ACQ-C,Control, EOIB and DDAC.The results of the treated wood dimensional stability are as follows:From oven-dry to air-dry, the line expansivity of the treated wood from high to low is CA-B,EOIB, Control, DDAC, ACC, EOIM and ACQ-C. The volume expansivity of the treatedwood from high to low is DDAC, EOIB, EOIM, ACQ-C, Control, CA-B, ACC.From oven-dry to sopping water, the line expansivity of the treated wood from high to low isControl, CA-B, EOIB, DDAC, EOIM, ACQ-C and ACC. The volume expansivity of thetreated wood from high to low is Control, ACC, DDAC, EOIM, CA-B, EOIB and ACQ-C.As the results from a mass of experiments and the research, some compounds of treeextractives have resistant ability to wood decay fungi. After functional synthesis, thecompounds of tree extractives are feasible to be used as wood preservatives in someenvironment. As a new type wood preservative, the tree extractives have the characters of nopollution to environment, innocuity to human and domestic animal. The compounds imitatenature. It is an effective approach to develope the new type wood preservetives by using themethod of functional synthesis compounds of tree extractives.更多还原