CN112431021B - 一种阻燃天然丝瓜络的制备方法 - Google Patents
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Abstract
本发明属于耐火纤维领域，具体涉及一种阻燃天然丝瓜络的制备方法。将天然丝瓜络分别用氢氧化钠和双氧水进行预处理备用，再利用三聚氰胺和磷酸组成的磷氮阻燃体系对预处理后的丝瓜络进行阻燃处理，得到阻燃型丝瓜络。本发明通过正交试验方法确定了阻燃丝瓜络的最优制备条件，所得产品可以达到难燃级别，极限氧指数达到27.5，垂直燃烧测试可以做到离火即灭，具有良好的阻燃性能，有广泛的应用前景。
Description
技术领域
本发明属于耐火纤维领域，具体涉及一种阻燃天然丝瓜络的制备方法。
背景技术
丝瓜络是成熟丝瓜果实除去外皮和种子后、具有多层丝状纤维质网状结构的天然纤维管束组织，主要由纤维素、半纤维素和木质素组成。丝瓜络纤维纵横交织、孔隙率高、比表面积大，吸水性能极佳，具有体轻、质韧、耐磨、弹性好等不同于其他生物质纤维材料的优异力学性能，单根丝瓜络纤维杨氏模量和断裂强度可达2.3GPa和103MPa，与木质纤维相当。
近年来，环境的压力越来越大，自然资源的短缺也日益明显，使得人们在注重科技和经济发展的同时，更加注意对自然环境的保护以及新能源、新材料的开发和研究，绿色化、减量化逐渐成为包装行业的发展趋势和要求。
丝瓜络别名丝瓜筋、丝瓜布，国外叫植物海绵，为葫芦科植物丝瓜成熟后去皮和种子的丝瓜果实维管束，具有网状纤维管系统，并且在其预期寿命中相对稳定，在堆肥条件下处理后可生物降解。由于其具备质轻、高强、低成本、可生物降解性和可再生性等优异性能，使得拥有多级孔隙结构的天然丝瓜络材料引起很多研究人员的关注。丝瓜为葫芦科丝瓜属一年生攀缘性草本植物，作为一种新兴的经济作物，在国内外热带、亚热带地区均有广泛种植。丝瓜络具有独特的天然网状多孔结构、亲水亲油的化学结构和优良的韧性，还具有质轻且机械强度高、耐酸碱性能好、吸附性能强等优点。近年来，随着科技的发展，丝瓜络经科学开发，已悄然成为一种新型的天然工业材料，在包装、消声、过滤、保温、减震和抗冲击缓冲器等工程领域获得应用。但原生丝瓜络纤维作为生物质材料，干燥状态下易于燃性，因此，用于保温隔热的丝瓜络纤维复合材料在保持材料良好力学性能时，亟需提高丝瓜络纤维的阻燃性，解决制约其高值化开发利用的技术瓶颈问题。
发明内容
为了解决上述问题，本发明的目的在于提供一种阻燃丝瓜络纤维的制备方法，并通过正交试验的方法优化制备条件。
为了实现上述目的，本发明的技术方案如下：
以氧指数为评价指标，采用L9(34)正交试验，以三聚氰胺质量浓度、反应时间、丝瓜络浴比、反应温度为考察因素，每个因素取3个水平，优化阻燃丝瓜络的制备方法。
一种基于正交试验的阻燃天然丝瓜络的制备方法，包括以下步骤：
(1)将天然丝瓜络经粉碎机粉碎后于烘箱中60～90℃烘干备用，称取一定量粉碎后的丝瓜络放置于装有氢氧化钠水溶液的圆底烧瓶中，然后将烧瓶放置在温度为98℃的油浴锅中回流搅拌反应4h，抽滤，多次水洗直至中性后放置于温度为60～90℃的干燥箱中干燥处理6～12h；
其中，氢氧化钠水溶液的质量浓度为10％，丝瓜络的浴比为1:50。
(2)称取一定量干燥后的丝瓜络放置于装有双氧水溶液的圆底烧瓶中，然后将烧瓶放置在温度为80℃的油浴锅中回流搅拌反应4h，抽滤水洗2-3次，放置于温度为60～90℃的干燥箱中干燥处理6～12h；从而去除天然丝瓜络表面的木质素表层、蜡质层和灰分，得到表面富含大量羟基的丝瓜络；
其中，双氧水溶液的质量体积浓度为2g/L，丝瓜络的浴比为1:50。
(3)称取一定量的三聚氰胺和磷酸加入水溶液中，称取步骤(2)中一定量的预处理后的丝瓜络加入圆底烧瓶中，使之浸没在三聚氰胺-磷酸溶液中，然后将烧瓶放置在温度为80～100℃的油浴锅中回流搅拌反应1～3h。反应结束后，趁热抽滤，放置于温度为60～90℃的干燥箱中干燥处理6～12h，得到阻燃丝瓜络。
其中，三聚氰胺与磷酸的物质的量之比为1：3，趁热抽滤需要保持液体温度为80℃以上。
所述正交试验方法为确定阻燃丝瓜络制备中三聚氰胺质量浓度、反应时间、丝瓜络浴比、反应温度中四因素的三水平进行多次试验设计；并根据正交试验设计结果，利用极差分析四因素对材料阻燃性能的影响程度。
所述三聚氰胺质量浓度的三水平为2g/L、6g/L、10g/L，所述反应时间的三水平为1h、2h、3h，所述丝瓜络浴比的三水平为1：50、1：75、1：100，所述反应温度的三水平为80℃、90℃、100℃。
有益效果：
1.本发明以多孔三维网状结构的生物质基原料天然丝瓜络为基材，通过浸渍-烘焙的方式，利用三聚氰胺和磷酸组成的磷氮阻燃体系对天然丝瓜络进行阻燃处理，该制备方法简单，快速，所用原料经济易得且易于降解，具有广泛的社会效益和经济效益。
2.本发明制备的阻燃丝瓜络，具有良好的阻燃效果，极限氧指数达到27.5，空气中可以做到离开火源立即熄灭，达到了难燃的级别。
3.本发明采用正交试验方法确定了制备阻燃丝瓜络的最优制备条件，可以以更低的能耗获得更好的阻燃效果。
附图说明
图1为原生丝瓜络、预处理后的丝瓜络以及6号正交实验产物在氮气气氛下的TGA曲线图。
图2为原生丝瓜络、预处理后的丝瓜络以及6号正交实验产物在氮气气氛下的DTG曲线图。
图3为样条燃烧前后形貌的对比图。
图4为原生丝瓜络、预处理后的丝瓜络以及6号正交实验产物的烟密度测试结果曲线图。
具体实施方式
下面结合附图对本发明的具体实施方式作进一步描述，在此需要说明的是，对于这些实施方式的说明用于帮助理解本发明，但并不构成对本发明的限定。
实施例1
(1)将天然丝瓜络经粉碎机粉碎后于烘箱中80℃烘干备用，称取一定量粉碎后的丝瓜络放置于装有质量浓度为10％的氢氧化钠水溶液的圆底烧瓶中，然后将烧瓶放置在温度为98℃的油浴锅中回流搅拌反应4h，抽滤多次水洗直至中性后放置于温度为80℃的干燥箱中干燥处理10h；丝瓜络的浴比为1:50。
(2)称取一定量干燥后的丝瓜络放置于装有质量体积浓度为2g/L的双氧水溶液的圆底烧瓶中，然后将烧瓶放置在温度为80℃的油浴锅中回流搅拌反应4h，抽滤水洗3次，将双氧水洗净，放置于温度为80℃的干燥箱中干燥处理10h；从而去除天然丝瓜络表面的木质素表层、蜡质层和灰分，得到表面富含大量羟基的丝瓜络；丝瓜络的浴比为1:50。
(3)称取一定量的三聚氰胺和磷酸加入水溶液中，称取步骤(2)中一定量预处理后的丝瓜络加入圆底烧瓶中，使之浸没在三聚氰胺-磷酸溶液中，然后将烧瓶放置在温度为80～100℃的油浴锅中回流搅拌反应1～3h。反应结束后，趁热抽滤，放置于温度为70℃的干燥箱中干燥处理12h，得到阻燃丝瓜络。
其中，三聚氰胺与磷酸的物质的量之比为1：3，趁热抽滤需要保持液体温度为80℃以上。
所述正交试验方法为确定阻燃丝瓜络制备中三聚氰胺质量浓度、反应时间、丝瓜络浴比、反应温度中四因素的三水平进行多次试验设计；并根据正交试验设计结果，以极限氧指数为参考指标，利用极差分析四因素对材料阻燃性能的影响程度。因素水平表见表1。
表1因素水平表
表2正交试验结果分析表
实验结果，由表2正交试验结果分析表可知，通过实验发现各因素对丝瓜络吸附阻燃剂的吸附率的影响程度为三聚氰胺质量浓度>反应温度>反应时间>丝瓜络浴比。根据K值分析并结合实际情况，由于当三聚氰胺浓度为10g/L时，滤液冷却后会有大量三聚氰胺的结晶体析出，而当浓度为6g/L时则几乎没有晶体析出；三聚氰胺+磷酸在水溶液中完全溶解的最低温度为80℃；丝瓜络浴比变化所导致的影响结果较小，进一步缩小浴比实际意义不大，故选择最优吸附率的实验条件为三聚氰胺质量浓度6g/L、丝瓜络浴比1:100、反应温度80℃、反应时间2h，即正交实验6号实验条件，极限氧指数为27.5％，也是最佳的阻燃性能。
对原生丝瓜络以及预处理后的丝瓜络进行极限氧指数测试，测得数据分别为16％和17％，进行阻燃吸附后的丝瓜络极限氧指数相较这两者分别提升了11.5％和10.5％，阻燃性能显著提高。
分别对原生丝瓜络、预处理后的丝瓜络以及9组正交实验产物进行垂直燃烧测试，测试结果见表3。4号、5号实验产物达到V1级别；6～9号实验产物均已达到V0燃烧级别，其中最优实验条件产物，即6号样条余焰燃烧时间总和(t1+t2)最短，在空气中点燃可以做到瞬间自熄，表明其阻燃性能良好。通过对6号样条燃烧过程及燃烧后形貌的观察(如图3所示)可以发现，完全损毁长度仅1.5cm，为外部火源燃烧所致，其余部分仅表面发生燃烧，内部并无燃烧迹象，也可体现阻燃型丝瓜络良好的阻燃性能。
通过吸附率与样条余焰燃烧时间总和(t1+t2)进行对比可知，二者数值呈现负相关，即吸附率越高，余焰燃烧时间总和越短。
表3垂直测试结果与吸附率对照表
材料热稳定性分析：选取原生丝瓜络、预处理后的丝瓜络以及6号正交实验产物在氮气气氛下进行同步热分析测试，TGA和DTG曲线如图1和图2所示，热降解参数见表4。由于丝瓜络有极佳的吸水性，所以初始质量下降是由于丝瓜络中的水分导致的，后续可以发现阻燃型丝瓜络与原生丝瓜络和预处理后的丝瓜络相比有更低的最初分解温度。原生丝瓜络在235℃左右开始发生分解，阻燃型丝瓜络在165℃左右开始发生分解，这是因为P-O-C的稳定性低于C-C的稳定性。阻燃剂含磷组分优先分解，促进了炭层的形成。对比最终残碳率发现：阻燃型丝瓜络>原生丝瓜络>预处理后的丝瓜络，分别为36.74％、19.53％、13.52％。添加磷氮阻燃剂后比原生丝瓜络提高了88.12％，比预处理后的丝瓜络提高了171.75％。可见吸附磷氮系阻燃剂可促进热分解过程中残炭的形成，提高丝瓜络热稳定性。预处理后的丝瓜络最终残碳率相较于原生丝瓜络有所降低，这是由于预处理使得原生丝瓜络当中的胶质和木质素等物质被除去所致。
从三组样品的DTG曲线图可以看出，阻燃型丝瓜络的最大热失重速率和其对应温度比原生丝瓜络和预处理后的丝瓜络有所降低和减少，三者的最大热失重速率和其对应温度分别为296.1℃，9.87％/min；365.7℃，13.81％/min；361.6℃，11.86％/min，进一步说明三聚氰胺和磷酸所组成的磷氮系阻燃剂改变了丝瓜络的热分解过程，抑制了高温下纤维素分子链的降解，提高了丝瓜络的热稳定性。
表4热降解参数
烟密度分析：由于丝瓜络燃烧很大的一个危险性在于持续时间长，产烟量大。因此选取原生丝瓜络、预处理后的丝瓜络以及正交实验6号样品进行无焰烟密度测试。测试结果如图4和表5所示。
原生丝瓜络产生烟雾速度迅速。4min时透光率(Ts4，％)仅为6.16％，最大比光密度(Ds_max)为159.72。预处理后的丝瓜络烟释放速度缓慢，Ts4为67.56％，Ds_max为30.62，相比于原生丝瓜络，Ts4增加了61.4％，Ds_max减少了129.1。从图3中不难发现，预处理后的丝瓜络在加热一开始便产生了烟雾，而原生丝瓜络则是到55s后才开始产生烟雾，这是由胶质和蜡质相较于纤维素的热分解需要更高的能量所导致的。
经过阻燃处理后的丝瓜络Ts4为60.35％，Ds_max为31.32，相比于预处理后的丝瓜络，Ts4减少了7.21％，Ds_max增加了0.7。从图3中也可以明显看出，相较于预处理后的丝瓜络，经过阻燃处理的丝瓜络有着更加缓慢的烟气释放速率，也体现了良好的抑烟性能。
表5烟密度测试结果数据表
综上所述，由实验结果和分析验证可知，经正交试验优化后的阻燃丝瓜络的制备方法可行性好，阻燃性能优异，为后续丝瓜络应用提供了一定的前提条件。
对比实施例1
步骤(1)-步骤(2)同实施例1。
取三聚氰胺甲醛树脂和纳米级氢氧化镁阻燃剂加入到丙酮溶液中，在35℃下超声分散3h，将预处理后的丝瓜络浸没在丙酮分散液中，超声浸涂2h，取出在60℃下烘干即得产物。其中，三聚氰胺甲醛树脂和纳米级氢氧化镁的质量占丙酮分散液质量的5％，三聚氰胺甲醛树脂与纳米级氢氧化镁的质量比为1:3，丝瓜络浴比为1:100。
制得的阻燃丝瓜络氧指数仅19，且随储藏时间增加，阻燃剂脱附现象严重，1周左右，取用3-5次，阻燃剂基本就脱附完了，脱附后几乎无阻燃效果。
对比实施例2
取三聚氰胺甲醛树脂和聚磷酸铵阻燃剂加入到丙酮溶液中，在35℃下超声分散3h，将预处理后的丝瓜络浸没在丙酮分散液中，超声浸涂2h，取出在60℃下烘干即得产物。其中，三聚氰胺甲醛树脂和聚磷酸铵阻燃剂的质量占丙酮分散液质量的5％，三聚氰胺甲醛树脂与聚磷酸铵的质量比为1:3，丝瓜络浴比为1:100。
制得的阻燃丝瓜络氧指数为21，但随储藏时间增加，阻燃剂脱附现象严重，1周左右，取用3-5次，阻燃剂基本就脱附完了，脱附后几乎无阻燃效果。
Claims (5)
1.一种阻燃天然丝瓜络，其特征在于，所述阻燃天然丝瓜络的制备方法步骤如下：
（1）将天然丝瓜络经粉碎机粉碎后于烘箱中60~90℃烘干备用，称取粉碎后的丝瓜络放置于装有氢氧化钠水溶液的圆底烧瓶中，然后将烧瓶放置在油浴锅中回流搅拌反应，抽滤水洗直至中性后，放置于干燥箱中干燥处理；
（2）称取步骤（1）碱处理干燥后的丝瓜络放置于装有双氧水溶液的圆底烧瓶中，然后将烧瓶放置在油浴锅中回流搅拌反应，抽滤水洗2-3次后放置于干燥箱中干燥处理，得到表面富含大量羟基的丝瓜络；
所述双氧水的质量体积浓度为2g/L；回流搅拌反应温度为80℃，回流搅拌反应时间为4h；干燥温度为60~90℃，干燥时间为6~12h；
（3）称取三聚氰胺和磷酸加入水溶液中，称取步骤（2）预处理后的丝瓜络加入圆底烧瓶中，使之浸没在三聚氰胺-磷酸溶液中，然后将烧瓶放置在油浴锅中回流搅拌反应，反应结束后，趁热抽滤，放置于干燥箱中干燥处理，得到阻燃丝瓜络；
所述三聚氰胺质量浓度为2g/L-10g/L，所述丝瓜络浴比为1：50-1：100；
所述三聚氰胺与磷酸的物质的量之比为1：3。
2.如权利要求1所述的阻燃丝瓜络，其特征在于：步骤（1）所述氢氧化钠的质量浓度为10%；回流搅拌反应温度为98℃，回流搅拌反应时间为4h；干燥温度为60~90℃，干燥时间为6~12h。
3.如权利要求1所述的阻燃丝瓜络，其特征在于：步骤（1）和步骤（2）所述丝瓜络的浴比均为1:50。
4.如权利要求1所述的阻燃丝瓜络，其特征在于：步骤（3）所述油浴反应温度为80~100℃，反应时间为1~3h。
5.如权利要求1所述的阻燃丝瓜络，其特征在于：步骤（3）所述趁热抽滤需要保持液体温度为80℃以上；干燥温度为60~90℃，干燥时间6~12h。
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