CN105622828A - 载药聚合物木竹材改性剂及生产和使用方法 - Google Patents

载药聚合物木竹材改性剂及生产和使用方法 Download PDF

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CN105622828A
CN105622828A CN201610056195.0A CN201610056195A CN105622828A CN 105622828 A CN105622828 A CN 105622828A CN 201610056195 A CN201610056195 A CN 201610056195A CN 105622828 A CN105622828 A CN 105622828A
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wood
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bamboo wood
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孙芳利
鲍滨福
张艳
陈安良
于红卫
杜春贵
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Zhejiang A&F University ZAFU
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Abstract

一种载药聚合物木竹材改性剂由下列原料及其重量份配制而成：杀真菌剂和杀虫剂0.5-5.0份、单体0.0～30.0份、水溶性聚合物0.0～15.0份、引发剂0.05～0.5份、交联剂0.1～0.5份、有机溶剂5.0～15.0份、表面活性剂0.5～15.0份、水60.0～100.0份；配制改性剂的具体方法有三个步骤：1、水溶性原料混合后加水溶解；2、油溶性原料混合后加杀真菌剂和杀虫剂，在有机溶剂中搅拌至全溶，再加入表面活性剂搅拌至全溶；3、将步骤1和2制成的两种溶液混合搅拌即得本改性剂，用时选用喷、涂、浸泡或真空加压对木竹材进行改性处理，沥干后在60-100℃中固化1-4h即成。经本改性剂处理的木竹材尺寸稳定性好、抗菌与杀虫长效、稳定，生产工艺简单、成本低，使用方便。

Description

载药聚合物木竹材改性剂及生产和使用方法
技术领域
本发明涉及一种采用浸渍、喷、涂等方式在木竹材内部原位构建具有物理缠结和化学交联的载药聚合物，主要用于提高木竹材的尺寸稳定性和抗菌及防虫性。
背景技术
木竹材作为一种可再生的天然高分子材料，以纤维素、半纤维素和木质素为主要成分，同时含有糖和淀粉等营养成分，因此易受菌虫危害而腐朽、霉变和虫蛀。目前，解决此问题的主要方法是采用防腐、防霉或防虫剂处理木竹材。但是，不断拓展的木竹产品种类和应用领域对这些保护剂的持效性提出了新的要求，尤其是户外用材。户外材会受到光照、雨淋、风沙和尘土等影响，保护剂不仅要高效，还要抗流失性、不因光和热而降解。本发明提供一种将保护剂负载于具有物理缠结和化学交联的聚合物中，达到可控或缓释药剂，提高保护剂对菌虫的作用效力。本发明不同于将保护剂加入胶黏剂和油漆等物质中，保护剂如果加入胶黏剂或油漆中，固化后的胶黏剂或油漆将很难释放药剂，从而大大降低了保护剂对木竹材的保护效果。而本发明的聚合物是在木竹材中原位构建，在构建过程中同时负载保护剂，且能可控或者缓慢释放药剂。
本发明的另一目的是提高木竹材的尺寸稳定性。研究中发现，木竹材表面微裂和开裂为菌虫侵入和滋生提供了便利。因此，要真正解决木竹材的腐朽、霉变和虫蛀，需要提高木竹材的尺寸稳定性，减少开裂。木竹材的易裂性除与其化学组成中的大量游离羟基有关外，还与其各向异性关系密切。木材的横纹抗拉强度仅为顺纹抗拉强度的1/65～1/35，竹材因缺乏横向的木射线，横纹抗拉强度更低。本发明在木竹材中原位构建一种能提高木竹材尺寸稳定性、与木竹材互穿和交联聚合物，并同时载入防腐、防霉和/或防虫药剂，拓宽木竹材的应用领域。
发明内容
本发明要解决的技术问题是提供一种在木竹材中原位构建载药聚合物的木竹材改性剂及其生产和使用方法。
解决上述技术问题采用如下技术方案：
本载药聚合物木竹材改性剂，由下列原料及其重量份配制而成：
所述的杀真菌剂由丙环唑、戊唑醇、百菌清、碘代丙炔基氨基甲酸丁酯、二硫氰基甲烷、4，5-二氯-2-正辛基-4-异噻唑啉-3-酮中任意一种或两种组成；所述的杀虫剂是高效氯氰菊酯、吡虫啉、甲维盐、溴氰菊酯、阿维菌素、噻虫啉中的任何一种。
所述的单体分为水溶性单体和油溶性单体，水溶性单体为丙烯酸、丙烯酰胺、衣康酸、N-异丙基丙烯酰胺、甲基丙烯酸羟乙酯中的0或1-2种；油溶性单体为甲基丙烯酸甲酯、醋酸乙烯酯、叔碳酸乙烯酯、苯乙烯中的0或1-2种。
所述的水溶性聚合物为壳聚糖、壳聚糖季铵盐、聚乙二醇、聚乙烯醇、聚乙烯吡咯烷酮、共聚维酮、海藻酸钠等化合物中的0或1-2种。
所述的引发剂分为水溶性引发剂和油溶性引发剂，水溶性引发剂为过硫酸铵或过硫酸钾，油溶性引发剂为过氧化苯甲酰、偶氮二异丁腈和过氧化苯甲酸叔丁酯中的0或任意一种。
所述的交联剂为N，N′-亚甲基双丙烯酰胺、N-羟甲基丙烯酰胺、乙二醛、戊二醛和1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐中的1-2种。
所述的有机溶剂为乙醇、丙酮、丁醇、丙醇、丙二醇中至少一种。
所述的表面活性剂为壬基酚聚氧乙烯醚、十二烷基苯磺酸钠、烷基酚聚氧乙烯醚、月桂醇聚氧乙烯醚磷酸酯、三苯乙烯基酚聚氧乙烯醚磷酸酯、烷基酚聚氧乙烯醚磷酸酯、十二烷基苯磺酸钙和中的一种或两种。
本载药聚合物木竹材改性剂的生产方法按如下步骤进行：
①先将水溶性单体和/或水溶性聚合物、水溶性引发剂和交联剂分别溶解于水中，搅拌，直至完全溶解；
②将油溶性单体、油溶性引发剂、杀真菌剂和杀虫剂分别溶解于有机溶剂中，搅拌，直至完全溶解，加入表面活性剂，搅拌直至完全溶解；
③将两种配好的溶液混合并搅拌均匀，即制得本专利所述的木竹材改性剂。
本载药聚合物木竹材改性剂的使用是按如下步骤进行：
使用时先选择喷、涂、浸泡或真空加压浸渍方式对木竹材及其制品进行改性处理，取出沥干至不滴液，再在60-100℃的环境中固化反应1-4小时，干燥到用户所需含水率，即完成了木竹材的尺寸稳定化和抗菌、虫处理。对于较易渗透的木竹材或小竹木制品，也可用喷、涂方式处理，热固化和干燥可参考上法变通处理。
本发明的有益效果是：本处理所选水溶性单体和聚合物对木竹材渗透性好，能够对细胞壁增容和改性，而少量的油溶性单体也能够同时进入增容后的木材细胞壁，在引发剂和交联剂的作用下聚合和交联，显著降低木竹材的吸水和吸湿性，提高其尺寸稳定性。同时，杀真菌剂和杀虫剂被负载于具有物理缠结和化学交联的聚合物，在外界环境和菌虫作用下缓慢释放或控制释放，达到长效和稳定的抗菌杀虫目的。本技术生产工艺简单，成本低，使用方便，无毒、不污染环境，也不会改变木竹材的加工性能。
附图说明
图1为毛白杨改性处理材和未处理材的扫描电子显微图(a、b为处理材，c、d为未处理材)。
图2为毛白杨改性处理材(a和c)和竹材改性处理材(b和d)抗缩率和阻湿率的效果图。
图3为毛竹材改性处理材的防霉效果图。
具体实施方式
本发明下面结合实施例作进一步详述：
下面本发明将各原料及其重量份配比值按八项实施例列于表1：
实施例1(对照表1中实施例1对应的原料与重量份配比值)：
先将作为水溶性单体的25.0份丙烯酸、作为水溶性聚合物的6.0份聚乙二醇、作为水溶性引发剂的0.45份过硫酸铵和作为交联剂的0.2份N，N′-亚甲基双丙烯酰胺和0.15份1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐分别溶于57.6mL水中；再将作为油溶性单体的5.0份叔碳酸乙烯酯、作为杀菌剂的0.2份丙环唑和0.1份碘代丙炔基氨基甲酸丁酯、作为杀虫剂的0.1份甲维盐溶解于作为有机溶剂的5.0份丁醇溶液中，搅拌至完全溶解，加入作为表面活性剂的0.2份壬基酚聚氧乙烯醚和0.4份月桂醇聚氧乙烯醚磷酸酯中，再次搅拌至完全溶解；混合以上两个步骤得到的溶液，得到木竹材尺寸稳定化和抗菌虫的木竹材改性剂。采用喷、涂、浸泡或真空加压浸渍方式对竹木材及其制品进行处理，在80℃的环境中固化反应2小时，然后干燥到用户所需含水率，即完成了对木竹材的尺寸稳定化和抗菌、防虫处理工作。
表1的八项实施例中均有权利要求1指明的8类原料，但对权利要求2-8中明确的各类具体原料的加入情况不甚一致，有不加的，有加入一种或两种的，对于不加的是基于以下考虑：不加水溶性单体的，如实施例6，是因水溶性聚合物能够替代水溶性单体，达到同等或较好的改性效果；不加水溶性聚合物的，如实施例3、4和8，是因水溶性单体聚合后能够替代水溶性聚合物，达到同等或较好的改性效果。不加油溶性单体的，如实施例2、3和6，是因水溶性单体和/或水溶性聚合物反应后能达到同等或较好的改性效果；不加油溶性引发剂，是因水溶性引发剂能够满足引发需要。
其余实施例2-8，均对照表中对应实施例的原料和重量份配比值，与实施例1相同的方法制得本尺寸稳定化和抗菌虫木竹材改性剂，均能达到所述的技术效果，其中以实施例2、4和6优选。
用本发明制得的尺寸稳定化和抗菌、防虫改性剂对较易渗透的木竹材及其制品进行改性处理，可采用喷、涂的方式，对较难渗透的木竹材及其制品采用常压浸渍、真空加压浸渍的方式处理0.5-1.0小时，之后再通过固化和干燥处理完成木竹材的尺寸稳定化和抗菌、防虫处理。
本发明处理材抗缩率达到40.0％以上，阻湿率达60.0％以上；对黑曲霉、木霉、桔青霉、变色菌等菌的抵抗力达79％以上；对白腐菌、褐腐菌的耐腐能力可达到强耐腐等级。
说明：上表因受格子局限，原料名称有的用简称，其中碘代丙炔基氨基甲酸丁酯称为氨基甲酸酯，4，5-二氯-2-正辛基-4-异噻唑啉-3-酮称为异噻唑啉酮，N-异丙基丙烯酰胺称为丙烯酰胺，甲基丙烯酸羟乙酯称为羟乙酯，N，N′-亚甲基双丙烯酰胺称为双丙烯酰胺，1-乙基-(3-二甲基氨基丙基)碳二亚胺称为碳二亚胺，十二烷基苯磺酸钠称为苯磺酸钠，月桂醇聚氧乙烯醚磷酸酯称为月桂醇醚磷酯，三苯乙烯基酚聚氧乙烯醚磷酸酯称为三苯酚醚磷酯。
下面选用实施例2所制得的改性剂对木竹材进行处理后该材的形貌、尺寸稳定性、防腐、防霉效果介绍如下。
图1中a和b为实施例2处理材的形貌。与未处理材(图1中c和d)相比，改性处理后木材的孔隙如管孔和细胞壁均填充有聚合物，细胞壁膨胀，且因膨胀使细胞相互挤压而变形，说明所选改性剂渗透性好，能够对细胞壁进行改性。
参考LY/T2490-2015标准，对改性木竹材尺寸稳定性测试，测试处理材尺寸稳定性见图2所示。图2中的a和b分别为毛白杨和竹材处理材经过三次干燥-浸水循环后的抗缩率ASE(Anti-swellingefficiency)。可以看出，改性后毛白杨和竹材抗缩率均可达到50％以上。图c和d分别为毛白杨和竹材处理材经过三次干燥-调湿循环后的阻湿率MEE(MoistureExcludingEfficiency)，调湿在恒温恒湿箱中操作，温度28℃，相对湿度90％。可以看出，改性后毛白杨和竹材阻湿率≥55％。以上数据说明，该木竹材改性处理能够明显提高木竹材的尺寸稳定性，从而减少因水分和湿度变化造成的开裂，试验中也发现改性材在干湿交替的极端环境中没有出现开裂现象。
以实施例2、4和6为例，按照《木材防腐剂对腐朽菌毒性实验室试验方法》(LY/T1283-2011)中规定的方法测试供试木材试块的耐腐性，结果见表2，白腐菌采用彩绒革盖菌，褐腐菌采用棉腐卧孔菌。结果表明，各实施例改性处理材经过室内耐腐性测试后，重量损失率≤6.18％，均达到强耐腐等级，即I级。
表2改性处理材的室内耐腐性
以实施例2、4和6为例，采用《防霉剂防治木材霉菌及蓝变菌的试验方法》(GB/T18261-2000)测试毛竹材处理材的防霉性能，结果见图3。图3显示，所测实施例2、4和6处理后竹材的综合防霉效力≥79％，远高于直接使用防霉剂的防霉效果，且能够长效保护竹材不霉变。
参考《GB/T18260-2000木材防腐剂对白蚁毒效实验室试验方法》和美国AWPAE1297(AWPA1999)测试马尾松处理材经过12个月试验后的防白蚁性能，结果见表3。结果表明，所选实施例能够较好地保护木材不受白蚁危害。
表3马尾松改性材防白蚁效果

Claims (10)

1.一种载药聚合物木竹材改性剂，由下列原料及其重量份配制而成：
。
2.如权利要求1所述的载药聚合物木竹材改性剂，其特征是所述的杀真菌剂由丙环唑、戊唑醇、百菌清、碘代丙炔基氨基甲酸丁酯、二硫氰基甲烷、4，5-二氯-2-正辛基-4-异噻唑啉-3-酮中任意一种或两种组成；所述的杀虫剂是高效氯氰菊酯、吡虫啉、甲维盐、溴氰菊酯、阿维菌素、噻虫啉中的任何一种。
3.如权利要求1所述的载药聚合物木竹材改性剂，其特征是所述的单体分为水溶性单体和油溶性单体，水溶性单体为丙烯酸、丙烯酰胺、衣康酸、N-异丙基丙烯酰胺、甲基丙烯酸羟乙酯中的0或1-2种；油溶性单体为甲基丙烯酸甲酯、醋酸乙烯酯、叔碳酸乙烯酯、苯乙烯中的0或1-2种。
4.如权利要求1所述的载药聚合物木竹材改性剂，其特征是所述的水溶性聚合物为壳聚糖、壳聚糖季铵盐、聚乙二醇、聚乙烯醇、聚乙烯吡咯烷酮、共聚维酮、海藻酸钠化合物中的0或1-2种。
5.如权利要求1所述的载药聚合物木竹材改性剂，其特征是所述的引发剂分为水溶性引发剂和油溶性引发剂，水溶性引发剂为过硫酸铵或过硫酸钾，油溶性引发剂为过氧化苯甲酰、偶氮二异丁腈和过氧化苯甲酸叔丁酯中的0或任意一种。
6.如权利要求1所述的载药聚合物木竹材改性剂，其特征是所述的交联剂为N,N'-亚甲基双丙烯酰胺、N-羟甲基丙烯酰胺、乙二醛、戊二醛和1-乙基-(3-二甲基氨基丙基)碳二亚胺盐酸盐中的1-2种。
7.如权利要求1所述的载药聚合物木竹材改性剂，其特征是所述的有机溶剂为乙醇、丙酮、丁醇、丙醇、丙二醇中的1-2种。
8.如权利要求1所述的载药聚合物木竹材改性剂，其特征是所述的表面活性剂为壬基酚聚氧乙烯醚、十二烷基苯磺酸钠、烷基酚聚氧乙烯醚、月桂醇聚氧乙烯醚磷酸酯、三苯乙烯基酚聚氧乙烯醚磷酸酯、烷基酚聚氧乙烯醚磷酸酯、十二烷基苯磺酸钙中的一种或两种。
9.生产权利要求1所述的载药聚合物木竹材改性剂的方法，其特征是按如下步骤进行：
①先将水溶性单体和/或水溶性聚合物、水溶性引发剂和交联剂分别溶解于水中，搅拌，直至完全溶解；
②将油溶性单体、油溶性引发剂、杀真菌剂和杀虫剂分别溶解于有机溶剂中，搅拌，直至完全溶解，加入表面活性剂，搅拌直至完全溶解；
③将两种配好的溶液混合并搅拌均匀，即制得本专利所述的木竹材改性剂。
10.使用权利要求1所述的载药聚合物木竹材改性剂是按如下步骤进行：
使用时先选择喷、涂、浸泡或真空加压浸渍方式对木竹材及其制品进行处理，取出沥干至不滴液，再在60-100℃的环境中固化反应1-4小时，干燥到用户所需含水率，即完成了木竹材的尺寸稳定化和抗菌、防虫处理。对于较易渗透的木竹材或小竹木制品，可用喷、涂方式处理，热固化和干燥可参考上法变通处理。
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CN109705261A (zh) * 2017-10-26 2019-05-03 中国林业科学研究院木材工业研究所 一种环保型木材改性剂及其应用和木材改性处理方法
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CN111452172A (zh) * 2020-04-16 2020-07-28 浙江孚林家居有限公司 一种防虫复合地板及其制备工艺
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