CN116587385B - 一种乙二醛-丙烯酰胺复配物液的用途 - Google Patents
一种乙二醛-丙烯酰胺复配物液的用途 Download PDFInfo
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Abstract
本发明公开了一种乙二醛‑丙烯酰胺复配物液的用途，用于霉菌和白蚁的防治；乙二醛‑丙烯酰胺复配物液的组成为：乙二醛4‑8％，丙烯酰胺8‑12％，乙醇胺0.1‑0.2％和余量的水。本发明乙二醛‑丙烯酰胺复配物液的用途，对霉菌和白蚁等具有效的防治功能，利用乙二醛‑丙烯酰胺复配物液对木材进行浸渍和热处理后，对桔青霉、绿色木霉、黑曲霉和可可球二孢菌等霉菌的防治效力为100％，对白蚁的防治效力达9.5等级以上。
Description
技术领域
本发明涉及一种乙二醛-丙烯酰胺复配物液的用途，属于木材处理技术领域。
背景技术
木材作为一种自然资源，由于其良好的机械性能、易于加工和令人愉悦的美学外观，已被广泛用于工具、家具、装饰和建筑等领域。然而，木材的天然特性使其在使用过程中受到限制。如尺寸不稳定，当周围温湿度条件发生变化时，容易产生开裂、变形等问题；易受真菌侵袭，木材主要由纤维素、半纤维素和木质素组成，且存在非常多的孔隙，容易被霉菌、腐朽菌及白蚁侵蚀，导致产品使用寿命缩短。为了克服这些缺点，人们开发了不同的木材处理方法。主要可归纳为三类：浸渍毒杀性防护药剂、热处理和化学改性。其中，浸渍毒杀性防护药剂，效果好、成本相对较低，但存在药剂流失和使用寿命结束时难以处理等不环保问题。比较而言，热处理更为绿色环保，木材经过160～210℃的高温热处理后，亲水性羟基明显减少，尺寸稳定性和防腐耐久性显著改善，但温度过高或处理时间过长，会出现部分力学强度显著降低的问题。木材化学改性主要采用有机单体或低聚物浸渍木材，经过热固化热干燥等工艺，单体或低聚物在木材细胞腔、细胞壁及其他孔道中原位聚合，甚至与细胞壁组份发生交联反应，润胀木材细胞壁，但容易导致木材脆化。因此，寻找合适的、绿色环保、可再生、可持续的改性剂非常重要。
乙二醛又称草醛、甘醛，具有反应活性高和摩尔体积小等特点，可制备许多系列精细化工产品，在纺织印染、造纸、皮革、香料、建材、医药、农药、水处理及洗涤业、国防、卫生及化妆品、石油和冶金工业、食品工业、环保等方面具有广泛用途；丙烯酰胺是一种重要的化工原料，丙烯酰胺固体在室温下很稳定，当处于熔点或氧化条件下，则很容易发生聚合反应。目前，关于乙二醛和丙烯酰胺复配物用途的报道主要是用于湿强剂使用，关于其用作木材改性剂鲜有报道。
发明内容
本发明提供一种乙二醛-丙烯酰胺复配物液的用途，其改性木材对桔青霉、绿色木霉、黑曲霉和可可球二孢菌等霉菌的防治效力为100％，防白蚁蛀蚀能力达9.5级以上，可用于木材改性，安全，环保。
为解决上述技术问题，本发明所采用的技术方案如下：
一种乙二醛-丙烯酰胺复配物液的用途，用于霉菌的防治；乙二醛-丙烯酰胺复配物液的组成为：乙二醛4～6％，丙烯酰胺8～12％，乙醇胺0.1～0.2％和余量的水，前述百分比为质量百分比。
上述乙醇胺用作表面活性剂，其作用之一是起到增溶作用。
发明人经实验意外发现，乙二醛-丙烯酰胺复配物液可对木材常见霉菌起到有有效的防治，对桔青霉、绿色木霉、黑曲霉和可可球二孢菌等霉菌的防治效力为100％，相比于乙二醛或丙烯酰胺单独使用，防治效力显著提升。
需要说明的是，物料用量的选择是非常关键的，如当乙二醛用量小于4％时，乙二醛与木材细胞壁纤维素分子的交联作用不明显；乙二醛含量从4％增至6％过程中，增容率逐步增加，当乙二醛含量继续增加，增容率增量平缓，甚至出现下降；当丙烯酰胺用量过低时，丙烯酰胺自聚合量较低，达不到改善木材耐久性的效果；当丙烯酰胺用量在8％～12％范围时，丙烯酰胺自聚合量逐步增加，木材耐久性获得显著改善，进一步增加，改善趋势平缓，综合考虑成本和效果，选择上述范围。
上述乙二醛-丙烯酰胺复配物液可用于桔青霉的防治，对其防治效力可达到100％。
上述乙二醛-丙烯酰胺复配物液可用于绿色木霉的防治，对其防治效力可达到100％。
上述乙二醛-丙烯酰胺复配物液可用于黑曲霉的防治，对其防治效力可达到100％。
上述乙二醛-丙烯酰胺复配物液可用于可可球二孢菌的防治，对其防治效力可达到100％。
一种乙二醛-丙烯酰胺复配物液的用途，用于白蚁的防治；乙二醛-丙烯酰胺复配物液的组成为：乙二醛4～8％，丙烯酰胺8～12％，乙醇胺0.1～0.2％和余量的水，前述百分比为质量百分比。
上述乙二醛-丙烯酰胺复配物液改性木材防白蚁蛀蚀能力达9.5级以上。
一种乙二醛-丙烯酰胺复配物液的用途，用于木材的防霉改性；乙二醛-丙烯酰胺复配物液的组成为：乙二醛4～6％，丙烯酰胺8～12％，乙醇胺0.1～0.2％和余量的水，前述百分比为质量百分比。
发明人发现，利用乙二醛和丙烯酰胺的高反应活性，将其复配物液通过空细胞法浸渍到木材细胞壁中，辅以160℃短时热处理，使其在木材细胞壁中完成高效聚合，充分润胀木材细胞壁，可实现改善木材尺寸稳定性和防霉、抗白蚁等耐久性能的目的，同时不会降低木材的力学强度。
上述木材的改性方法为：将乙二醛-丙烯酰胺复配物液空细胞法浸渍处理木材，再经热处理，改性剂固化在木材细胞壁上，得到的改性木材。
本申请制得的改性木材对桔青霉、绿色木霉、黑曲霉和可可球二孢菌等霉菌(变色菌)的防治效力为100％，防白蚁蛀蚀能力达9.5级以上。
作为其中一种具体的实现方案，木材的改性方法优选为：将木材试件置于处理罐中，将压缩空气引入处理罐，直到压力达到0.15～0.25MPa，保压10～30min，目的是将空气压入并占据木材细胞腔，然后加入药剂，在加入药剂的过程中，保持处理罐内压力不变，当药剂充满处理罐，5min内将处理罐中的压力升至1.40～1.60MPa，保持20～30min，泄压，取出木材试件，室温下晾至含水率低于15％(此处百分比为质量百分比)，热处理，得到的改性木材。
上述热处理为：用蒸汽热处理罐进行100～108℃烘干，烘干时间为20～25min，再用蒸汽8～10bar吹扫5～10min，然后将温度升至150～160℃保持40min～1h，得到的改性木材。
本研究选择无毒害、无污染的乙二醛为交联剂，丙烯酰胺为助剂，进行木材交联化反应，通过乙二醛与木材细胞壁纤维素分子交联，丙烯酰胺在木材细胞中发生自聚合、并与细胞壁组分发生交联等，实现木材交联改性处理，安全性好，且不存在流失问题。
本发明未提及的技术均参照现有技术。
本发明乙二醛-丙烯酰胺复配物液的用途，对霉菌和白蚁等具有效的防治功能，利用乙二醛-丙烯酰胺复配物液对木材进行浸渍和热处理后，对桔青霉、绿色木霉、黑曲霉和可可球二孢菌等霉菌的防治效力为100％，防白蚁蛀蚀能力达9.5级以上。
附图说明
图1为不同药剂浸渍后木材的吸药率条形图；
图2为白蚁测试前的样品形态(E是实施例1样品，F是空白对照)；
图3为白蚁测试后的样品形态(E是实施例1样品，F是空白对照)；
图4为试样经黑曲霉防霉测试结束的形貌；
具体实施方式
为了更好地理解本发明，下面结合实施例进一步阐明本发明的内容，但本发明的内容不仅仅局限于下面的实施例。
各例中，木材试件规格尺寸：6cm(宽)×2.5cm(厚)×34cm(长)，木材为南方松木材，每3块一组进行药剂处理。
各例中，未特别说的，均在室温(20～25℃)下操作。
实施例1
所用药剂组成为：丙烯酰胺6％、乙二醛4％、乙醇胺0.1％和余量的水，其处理的木材试件，取代号为E；
上述药剂的制备方法为：称取9公斤丙烯酰胺，15公斤40％乙二醛和200克乙醇胺，加入125.8公斤水中，搅拌溶解。
对比例1
所用药剂为质量浓度为6％的丙烯酰胺水溶液，其处理的木材试件，取代号为G。
上述药剂的制备方法为：称取9公斤丙烯酰胺，加入141公斤水中，搅拌溶解。
对比例2
所用药剂为质量浓度为4％的乙二醛水溶液，其处理的木材试件，取代号为H。
上述药剂的制备方法为：15公斤40％乙二醛，加入135公斤水中，搅拌溶解。
对比例3
将未用药剂处理的南方松木材试件，作为空白对照，取代号为F。
每组木材试件3个重复，并进行编号，实施例1样品编号为E-1，E-2，E-3；对比例1样品编号为G-1，G-2，G-3；对比例2样品编号为H-1，H-2，H-3；对比例3样品编号为F-1，F-2，F-3。
各例药剂均按照如下方法对木材试件进行处理：
1)将木材试件置于处理罐中，将压缩空气引入处理罐，直到压力达到0.2MPa，保压10min，然后加入药剂，在加入药剂的过程中，保持处理罐内压力0.2MPa不变，当药剂充满处理罐，5min内将处理罐中的压力升至1.5MPa，保持30min，泄压，取出木材试件；
2)将取出的木材试件，室温下晾干至含水率低于15％，然后用蒸汽热处理罐进行108℃烘干，烘干时间为25分钟，再用蒸汽10bar吹扫10min，然后将温度升至160℃保持1h，得到的改性木材。
实施例1所得的改性木材相比于改性前，力学强度没有任何降低，也没有任何脆化倾向。
如图1所示，不同处理木材试件吸药率差异明显，4％的乙二醛水溶液处理材吸药率最高，8％丙烯酰胺、4％乙二醛与0.1％乙醇胺复配液处理材吸药率次之，8％的丙烯酰胺水溶液处理材吸药率最低，这主要是因为不同组分分子量大小决定了其渗透能力。
将改性后的木材试件锯制尺寸为25mm×25mm×6mm(顺纹)大小的样品，每组5个重复，参照GB/T 18260—2015木材防腐剂对白蚁毒效实验室试验方法，进行室内抗白蚁测试，并评定白蚁蛀蚀等级。测试结果如表1和图2-3所示。
表1.白蚁测试结果
| 样品名称 | 质量损失率(％) | 白蚁存活率(％) | 蚁蛀等级 |
| E | 0.2 | 0 | 9.5 |
| G | 0.9 | 0 | 9 |
| H | 7.1 | 0 | 8 |
| F | 67.6 | 32.4 | 4 |
将改性后的木材试件锯制尺寸为20mm×5mm×50mm(顺纹)大小的样品，每组24块，参照GB/T 18261-2013防霉剂对木材霉菌及变色菌防治效力的试验方法，进行防霉防变色测试，并评定防治效力。测试结果如表2和图4所示所示。
表2.防霉测试结果
Claims (5)
1.一种乙二醛-丙烯酰胺复配物液的用途，其特征在于：用于木材的防霉和防白蚁改性；乙二醛-丙烯酰胺复配物液的组成为：乙二醛4~8%，丙烯酰胺8~12%，乙醇胺0.1~0.2%和余量的水，前述百分比为质量百分比；
木材的防霉和防白蚁改性方法为：将木材试件置于处理罐中，将压缩空气引入处理罐，直到压力达到0.15~0.25MPa，保压10~30 min，目的是将空气压入并占据木材细胞腔，然后加入药剂，在加入药剂的过程中，保持处理罐内压力不变，当药剂充满处理罐，5 min内将处理罐中的压力升至1.40~1.60MPa，保持20~30 min，泄压，取出木材试件，室温下晾至含水率低于15%，热处理，得到的改性木材；
热处理为：用蒸汽热处理罐进行100~108℃烘干，烘干时间为20~25 min，再用蒸汽8~10bar吹扫5~10 min，然后将温度升至150~160℃保持40min~1 h，得到的改性木材。
2.如权利要求1所述的用途，其特征在于：用于桔青霉的防治。
3.如权利要求1所述的用途，其特征在于：用于绿色木霉的防治。
4.如权利要求1所述的用途，其特征在于：用于黑曲霉的防治。
5.如权利要求1所述的用途，其特征在于：用于可可球二孢菌的防治。
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