抗流失硼基木材防腐剂配方遴选及优选配方处理材的性能
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摘要
随着人们环保意识的提高,一些对环境和人畜有危害的木材防腐剂的使用逐步受到限制或禁止。硼酸盐是一类性能优良的木材防腐剂,且对人畜和环境没有毒害,然而其抗水流失性很差,因而其应用范围受到了很大的限制。为了提高硼酸盐的抗流失性,本研究中用了二十几种助剂与硼酸盐复合处理木材,得到了两个对硼的固着效果较好的优选配方。并对两个优选配方进行深入实验,测定了其处理材的各项性能。最后以优选配方的组分为中间介质,将经过有机改性的蒙脱土引入到木材中,制备了蒙脱土复合防腐木材。本研究的结果归纳如下:
(1)本研究中所使用的多种助剂如蛋白质、乙二醛/丙三醇、醇类化合物、金属盐以及乙烯单体等都能通过各种形式,不同程度的提高三种硼酸盐(硼酸、硼砂、四水合八硼酸二钠)的抗流失性,但效果均不是特别明显。
(2)四苯硼钠(TPBNa)自身的耐腐及抗流失效果较好,并且经过改进之后,抗流失效果更好,但其价格较贵,不适合工业化生产使用,但在某些特定用途中仍有一定的应用前景。
(3)优选配方一:首次提出将水溶性酚醛树脂与硼酸盐混合后处理木材以提高处理材中硼的保持率;在室内耐腐及抗白蚁实验中,硼酸盐浓度较高时处理材几乎没有质量损失;处理材的尺寸稳定性、吸水性以及力学强度都得到了很大程度的改善;FTIR分析表明酚醛树脂与纤维素、半纤维素以及木素中的一些基团发生了作用;SEM分析表明所合成的水溶性酚醛树脂对木材的渗透性很好,能够到达木材内的各个部位,并且酚醛树脂在高温固化之后,牢牢的附着在木材的细胞壁上,从而将硼酸盐很好的固定在木材内。
(4)优选配方二:创新采用一种无机硼酸盐与季铵盐用两步法处理木材,不仅大大提高了这种硼酸盐的抗水流失性,还对处理材的各项物理力学性能都起到了积极的作用。硼的保持率随着这种硼酸盐与季铵盐浓度的增加而上升,且实验中最低浓度的硼酸盐与季铵盐复合处理材的耐腐及抗白蚁性能表现仍然很好;FTIR分析表明季铵盐以及硼酸盐与季铵盐反应生成的季铵硼盐主要是通过与木材中的纤维素和木素上的羟基、羧基等发生阳离子交换作用固定在木材上;SEM分析表明硼酸盐与季铵盐在木材内部反应生成的部分季铵硼盐以非常细小的颗粒分布在木材细胞内。
(5)在两个优选配方实验的基础之上,分别用季铵盐和酚醛树脂溶液为载体,将经过有机改性后的蒙脱土(OMMT)引入木材中,制得蒙脱土复合防腐木材。结果表明,引入OMMT以后,对于处理材中硼的保持率没有太大影响;通过SEM可观察到OMMT不规则的分布在管胞壁上,很多OMMT都沉积在纹孔内及纹孔周围。但从整体来看OMMT引入木材内部的量比较有限,未能对木材细胞壁、细胞腔等空隙产生非常有效的填充及插层效应,因此对提高木材物理力学性能的贡献不是很明显。
With the increase of the environmental awareness of people,some wood preservatives with potential risk to the environment and human health have been or will be gradually restricted or prohibited. Borates are efficient wood preservatives and safe for the mammals and environment.However,the use of their treated wood in outdoor is limited because of the migration of boron.In order to improve the leaching resistance of borates,more than twenty kinds of additives were used to in cooperation with borates.Two optimized formulations were selected and the properties of their treated wood were determined.Then,the component of the two optimized formulations was used as the intermediate medium to introduce organo-modified montmorillonite(OMMT) into wood to prepare the OMMT composite preservation wood and the properties of the composite wood were measured.The results of this study are summarized below.
1) A variety of additives such as proteins,glyoxal / glycerol,alcohols,metal salts,as well as ethylene monomer were used in this study and all of them could improve the leaching resistance of the three kinds of borate(boric acid,borax,disodium octaborate tetrahydrate) in different extents through variety forms.But the results were not very evident.
2) Sodium tetraphenylborate(TPBNa) has better water leaching resistance and good decay resistance. And the leaching resistance was improved after amelioration.But its prices were very expensive and not suitable for industrial production.But it were be used in some specific applications.
3) Optimized formula 1:A method to treat wood with the mixed solution of water-soluble PF and borate is first put forward to increase the retention of boron;in the decay and termite resistant tests,the specimens treated with high concentration of borates and PF had no mass loss;the dimensional stability and water absorption and mechanical strength of treated wood have been improved a lot;FTIR analysis showed that the PF reacted with certain groups of the wood cell wall material(cellulose,hemiceilulose and lignin).SEM analysis showed that the PF had nice permeability to the wood and could reach all parts of the wood.PF could attach to the cell wall of wood firmly after curing at high temperature, which would fix borate in the timber commendably.
4) Optimized formula 2:A new method to treated wood with quaternary ammonium salt(QAS) and inorganic borate(IB) in two steps is posted for the first time.This optimized formula displayed high leaching resistance of boron and the physical and mechanical material properties were improved. Retention of boron increased with the increasing of concentration of QAS and IB.And even wood treated with the lowest concentration of IB and QAS showed excellent resistance to fungi and termites. FTIR analysis showed that QAS and the reaction products of IB and QAS would be fixed on wood mainly through the cation exchange reaction with the hydroxyl,carboxyl etc.of the cellulose and lignin; SEM analysis showed that the reaction products of IB and QAS distributed in the wood cells with the form of very small particle.
5) On the basis of the experiments of the two optimization formulas,QAS and PF were used as the intermediate medium to introduce organo-modified montmorillonite(OMMT) into wood to prepare OMMT composite preservation wood.The results showed that the immission of OMMT didn't impact the retention of boron.Through SEM,the irregular distribution of OMMT on the tracheids and around the pits was observed.But on the whole the amount of OMMT introduced into wood was relatively limited and failed to fill the interstice of wood such as cell wall and cell cavities very effectively.So its contribution to improve the physical and mechanical properties of wood is not very clear.
(1)本研究中所使用的多种助剂如蛋白质、乙二醛/丙三醇、醇类化合物、金属盐以及乙烯单体等都能通过各种形式,不同程度的提高三种硼酸盐(硼酸、硼砂、四水合八硼酸二钠)的抗流失性,但效果均不是特别明显。
(2)四苯硼钠(TPBNa)自身的耐腐及抗流失效果较好,并且经过改进之后,抗流失效果更好,但其价格较贵,不适合工业化生产使用,但在某些特定用途中仍有一定的应用前景。
(3)优选配方一:首次提出将水溶性酚醛树脂与硼酸盐混合后处理木材以提高处理材中硼的保持率;在室内耐腐及抗白蚁实验中,硼酸盐浓度较高时处理材几乎没有质量损失;处理材的尺寸稳定性、吸水性以及力学强度都得到了很大程度的改善;FTIR分析表明酚醛树脂与纤维素、半纤维素以及木素中的一些基团发生了作用;SEM分析表明所合成的水溶性酚醛树脂对木材的渗透性很好,能够到达木材内的各个部位,并且酚醛树脂在高温固化之后,牢牢的附着在木材的细胞壁上,从而将硼酸盐很好的固定在木材内。
(4)优选配方二:创新采用一种无机硼酸盐与季铵盐用两步法处理木材,不仅大大提高了这种硼酸盐的抗水流失性,还对处理材的各项物理力学性能都起到了积极的作用。硼的保持率随着这种硼酸盐与季铵盐浓度的增加而上升,且实验中最低浓度的硼酸盐与季铵盐复合处理材的耐腐及抗白蚁性能表现仍然很好;FTIR分析表明季铵盐以及硼酸盐与季铵盐反应生成的季铵硼盐主要是通过与木材中的纤维素和木素上的羟基、羧基等发生阳离子交换作用固定在木材上;SEM分析表明硼酸盐与季铵盐在木材内部反应生成的部分季铵硼盐以非常细小的颗粒分布在木材细胞内。
(5)在两个优选配方实验的基础之上,分别用季铵盐和酚醛树脂溶液为载体,将经过有机改性后的蒙脱土(OMMT)引入木材中,制得蒙脱土复合防腐木材。结果表明,引入OMMT以后,对于处理材中硼的保持率没有太大影响;通过SEM可观察到OMMT不规则的分布在管胞壁上,很多OMMT都沉积在纹孔内及纹孔周围。但从整体来看OMMT引入木材内部的量比较有限,未能对木材细胞壁、细胞腔等空隙产生非常有效的填充及插层效应,因此对提高木材物理力学性能的贡献不是很明显。
With the increase of the environmental awareness of people,some wood preservatives with potential risk to the environment and human health have been or will be gradually restricted or prohibited. Borates are efficient wood preservatives and safe for the mammals and environment.However,the use of their treated wood in outdoor is limited because of the migration of boron.In order to improve the leaching resistance of borates,more than twenty kinds of additives were used to in cooperation with borates.Two optimized formulations were selected and the properties of their treated wood were determined.Then,the component of the two optimized formulations was used as the intermediate medium to introduce organo-modified montmorillonite(OMMT) into wood to prepare the OMMT composite preservation wood and the properties of the composite wood were measured.The results of this study are summarized below.
1) A variety of additives such as proteins,glyoxal / glycerol,alcohols,metal salts,as well as ethylene monomer were used in this study and all of them could improve the leaching resistance of the three kinds of borate(boric acid,borax,disodium octaborate tetrahydrate) in different extents through variety forms.But the results were not very evident.
2) Sodium tetraphenylborate(TPBNa) has better water leaching resistance and good decay resistance. And the leaching resistance was improved after amelioration.But its prices were very expensive and not suitable for industrial production.But it were be used in some specific applications.
3) Optimized formula 1:A method to treat wood with the mixed solution of water-soluble PF and borate is first put forward to increase the retention of boron;in the decay and termite resistant tests,the specimens treated with high concentration of borates and PF had no mass loss;the dimensional stability and water absorption and mechanical strength of treated wood have been improved a lot;FTIR analysis showed that the PF reacted with certain groups of the wood cell wall material(cellulose,hemiceilulose and lignin).SEM analysis showed that the PF had nice permeability to the wood and could reach all parts of the wood.PF could attach to the cell wall of wood firmly after curing at high temperature, which would fix borate in the timber commendably.
4) Optimized formula 2:A new method to treated wood with quaternary ammonium salt(QAS) and inorganic borate(IB) in two steps is posted for the first time.This optimized formula displayed high leaching resistance of boron and the physical and mechanical material properties were improved. Retention of boron increased with the increasing of concentration of QAS and IB.And even wood treated with the lowest concentration of IB and QAS showed excellent resistance to fungi and termites. FTIR analysis showed that QAS and the reaction products of IB and QAS would be fixed on wood mainly through the cation exchange reaction with the hydroxyl,carboxyl etc.of the cellulose and lignin; SEM analysis showed that the reaction products of IB and QAS distributed in the wood cells with the form of very small particle.
5) On the basis of the experiments of the two optimization formulas,QAS and PF were used as the intermediate medium to introduce organo-modified montmorillonite(OMMT) into wood to prepare OMMT composite preservation wood.The results showed that the immission of OMMT didn't impact the retention of boron.Through SEM,the irregular distribution of OMMT on the tracheids and around the pits was observed.But on the whole the amount of OMMT introduced into wood was relatively limited and failed to fill the interstice of wood such as cell wall and cell cavities very effectively.So its contribution to improve the physical and mechanical properties of wood is not very clear.
引文
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