【作者】 席丽霞；

【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， 2014， 博士

【摘要】 与传统防腐剂相比，三唑类化合物对人畜低毒，符合安全、环保的要求，对担子菌、部分变色菌等具有较好的抑制效果，在木材保护中有很大的应用潜力。但三唑类化合物难溶于水，而三唑有机溶剂型制剂存在成本较高、挥发性有机物（VOC）存在危害环境等问题。因此，对水溶性三唑类木材防腐剂的制备及其性能研究，具有重要的应用价值。本研究首先对几种三唑化合物的抗菌性进行了初筛，确定了抗腐朽及变色菌的有效成分及复配制剂的配比；再对溶剂及乳化剂进行筛选，制备出含三唑的水溶性制剂；为提高制剂的抗流失性能，对不同乳化剂制备制剂的抗流失性能进行测定及评价；并对所制备的水溶性三唑制剂的金属的腐蚀性能、处理材的防腐、防白蚁、防霉、防变色性能进行评价，主要研究结论归纳如下：（1）三唑类化合物中，除已应用于木材防腐剂的丙环唑（PPZ）、戊唑醇（TEB）和环丙唑醇（CY）外，己唑醇（Hex）、氟环唑（Epo）和三唑醇（Tri）对腐朽菌具有较好的抑制效果，且与CY效果相当，可作为三唑类木材防腐剂的有效成分。三唑与铜（Cu）复配，优化的质量配比：Cu/Hex为99:1~70:1，Cu/Epo为124:1~70:1，Cu/Tri为49:1~32:1。除PPZ、TEB、CY外，单一成分各三唑类化合物对木材霉菌和变色菌较差。（2）制备出均一、稳定的PPZ、TEB、CY、Hex和Tri的水溶性制剂。优选乳化剂为阳离子型表面活性剂（CE-2），或其与十二烷基二甲基氧化胺（OA-12）、十二烷基二羟乙基氧化胺（OAE-12），及CE-4的复配乳化剂。采用CE-2作为乳化剂制备PPZ/TEB制剂,乳化剂用量与三唑用量之比约为0.9:1。（3）对不同种类三唑制剂及不同乳化剂制备制剂的抗流失性能测定结果为：PPZ和Hex的抗流失性能相当，且最好，固着率均达70%以上，TEB固着率均较PPZ和Hex低，CY的固着率基本在60~70%之间，而Tri的抗流失性能最差，在较高载药量下，固着率不足60%。相同三唑制备的不同配方制剂中的抗流失性能相当。三唑与Cu复配后，抗流失性能增强，固着率基本能达到80%以上，Cu的固着率在90%以上；三唑与多菌灵（CBZ）复配后，三唑固着率均在90%以上，而CBZ固着率在70%左右。采用一定处理工艺添加疏水试剂可有效提高三唑及CBZ在处理材中的固着率。（4）采用与防腐剂接触时金属的腐蚀性测定方法，三唑类木材防腐剂对金属的腐蚀性结果为：铜唑对Q235A钢和紫铜的腐蚀性均低于水溶季铵铜（ACQ），尤其是对Q235A钢几乎无腐蚀；不含铜三唑制剂对Q235A钢的腐蚀较铜唑严重。多菌灵盐酸盐溶液，以及三唑与CBZ的复合制剂对Q235A钢和紫铜的腐蚀均较严重。（5）在室外地上(C3)使用条件下，铜/三唑复合制剂在处理材中的合理载药量为1.0kg/m3左右，不含铜三唑制剂PT（PPZ和TEB混合制剂，质量比为1:1）为0.2kg/m3，CY、Hex和Tri在0.05~0.08kg/m3之间。更多还原

【Abstract】 Triazole fungicides are low toxic to human and animals, safe and environmental friendly,and effective against basidiomycetes and some wood-stain fungi, triazole fungicides have greatpotential for application in the wood protection. However, The solubility of triazoles in water isvery low and organic solvent-triazole formulations have high cost, emmission of volatileorganic compounds (VOC) and other problems. Therefore, the preparation and properties ofwater-soluble triazole formulations were conducted in the study.In order to prepare water-soluble triazole wood preservatives, the effective triazolecompounds, solvents and emulsifiers were selected firstly, as well as the best ratio of the activeingredients of the triazole formulations were determined. Then the leaching properties ofdifferent kinds of triazole and different kinds of emulsifiers were deterimined and compared forimproving the leaching rate of the formulations. Finally, the corrosion rate, the resistancesagainst decay, mold and sapstain fungi by triazole formulations were evaluated. The mainfindings and conclusions are summarized as follows.1) In addition to propiconazole (PPZ), tebuconazole (TEB) and cyproconazole (CY)which have been used in wood preservatives, the hexaconazole (Hex), epoxiconazole (Epo)and triadimenol (Tri) had better inhibitory effects against decay fungi, and the effects wereequivalent to CY. Therefore, these triazoles could be used as active ingredients of noveltriazole wood preservatives. For the mixture of triazole/copper (Cu) formulations, the optimalratio: Cu/Hex was99:1~70:1, Cu/Epo was about124:1~70:1, Cu/Tri was49:1~32:1. Whenused alone, some triazoles had poor inhibitory effect against sapstain fungi except PPZ, TEBand CY.2) Several kinds of water-soluble triazole formulations were prepared successfully,including PPZ, TEB, CY, Hex and Tri. The appropriate emulsifiers were including a kind ofcationic surfactant (CE-2) and the mixture of CE-2with lauryl dimethyl amine oxide (OA-12) or lauryl dihydroxyethyl amine oxide (OAE-12) or CE-4. The optimum amount of emulsifierswas0.9times of PPZ/TEB.3) The leachabilities of different triazoles and different emusfers were tested. the fixationrates of PPZ and Hex were higher and more than70%. The fixation rate of TEB was littlelower than PPZ and Hex. The fixation rate of CY in treated wood was between60%to70%and that of Tri was less than60%at the highest retention. The leach resistances of the samekind of triazole in different foumulations were equal. After compounding with Cu or CBZ, Theleach resistances of triazole were improved with the fixation rate of more than80%or90%. Inaddition, the fixation rate of Cu in wood treated with the mixtures of Cu/triazole was morethan90%and that of CBZ was about70%. The fixation rates of triazole and CBZ in treatedwood could be improved effectively through brushing hydrophobic agent on wood surface.4) The method for determining corrosion rates of metals in contact with treating solutionwas used to evaluate the corrosiveness of triazole formulations. The corrosion rates of Q235Asteel and red copper in the compound preservative containing Cu, PPZ and TEB (CuPT) wereboth lower than in ACQ, especially for Q235A steel with a corrosion rate of about zero inCuPT. The corrosions of Q235A steel in free of copper triazole preservatives or in carbendazimhydrochloride solution or in their were all serious and that of red copper were also serious incarbendazim hydrochloride solution or the mixed solution.5) When used in the condition of on the ground outdoor, the rational retention should beabout1.0kg/m3of mixtures of Copper/triazoles or0.2kg/m3of PPZ/TEB (mass ratio1:1) orbetween0.05~0.08kg/m3of CY, Hex and Tri.更多还原