CN105780172A - 一种植物基发光纤维及其制备方法 - Google Patents

一种植物基发光纤维及其制备方法 Download PDF

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CN105780172A
CN105780172A CN201610198087.7A CN201610198087A CN105780172A CN 105780172 A CN105780172 A CN 105780172A CN 201610198087 A CN201610198087 A CN 201610198087A CN 105780172 A CN105780172 A CN 105780172A
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陈港
张俊奇
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South China University of Technology SCUT
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Abstract

本发明公开了一种植物基发光纤维及其制备方法,涉及防伪荧光纤维技术领域。制备方法包括如下步骤:1、以纳米纤维素为原料制备再生纤维;2、再生纤维交联改性;3、再生纤维荧光改性,得植物基发光纤维。本发明制备的植物基发光纤维直径、长度尺寸可控,可根据需求制备不同规格的纤维长丝、短丝,同时本发明制备的发光纤维具有优异的荧光性能及抄造性能。

Description

一种植物基发光纤维及其制备方法
技术领域
本发明涉及防伪荧光纤维技术领域,尤其涉及一种植物基发光纤维及其制备方法。
背景技术
随着科技的不断进步和经济的飞速发展,防伪领域对新型、高效防伪技术的需求愈加强烈,同时由于目前多数防伪纤维的原料为化学纤维,在制备防伪纸张时抄造性能不佳,因此,开发能有效的与传统造纸技术结合、使用方便的防伪材料及技术是防伪纤维发展的主要方向。
目前市场上常见的荧光防伪纤维为化学纤维,通过纺丝方法制备,目前披露的该类荧光纤维制备技术包括熔融纺丝(专利CN200780048275.0、专利CN201210197075.4)、湿法纺丝(专利CN200810042269.0)、干法纺丝(专利CN201410398215.3)。以化学纤维为原料制备的荧光纤维应用于防伪纸张领域,具有分散性差,纤维间结合力弱的缺点,极大的限制了其应用。因此,近年来植物基荧光纤维的研究得到了广泛的关注。
植物纤维来源丰富,具有可再生,反应性好,可生物降解等特点。以植物纤维为原料制备荧光防伪纤维具有广阔的市场前景和发展潜力。
目前国内公开的植物基荧光纤维的发明技术较少,主要包括以下几个方面:东华大学公开了一种荧光防伪Lyocell纤维的制备方法,技术方案为将荧光物质分散到4-甲基吗啉-N-氧化物水溶液中,与纤维素浆粕混合制备Lyocell纺丝原液,经干湿法纺丝制备荧光纤维(专利CN201210006299.2);发明人赵兵公开了一种荧光沙柳再生纤维素纤维的制备方法,技术方案为以沙柳为原料制备沙柳浆粕,将水溶性上转换纳米颗粒与沙柳纤维素混合制备纺丝液,经纺丝后得到荧光纤维(专利CN201410701957.9)。以上方法均以纤维素浆粕为原料,将发光物质与浆粕混合制备纺丝液,通过纺丝方法制备荧光纤维,但纺丝液制备工艺条件较为苛刻,操作复杂。此外,由于纤维素纤维具有较强的吸水润胀性,以纤维素浆粕为原料制备的再生纤维,应用于潮湿或有水存在的环境下将受到很大的限制,会导致再生纤维吸水润胀,强度损失甚至纤维断裂破碎。
发明内容
本发明的目的在于克服现有技术存在的不足,以纳米纤维素为原料制备发光纤维,在赋予纤维优异荧光性能的同时,有效解决了纤维吸水润胀的问题,提高了纤维物理强度,从而更适用于防伪纸张的抄造,具体技术方案如下。
一种植物基发光纤维的制备方法,该制备方法包括以下步骤:
(1)以纳米纤维素为原料制备再生纤维;
(2)将步骤(1)得到的再生纤维交联改性;
(3)将步骤(2)交联改性后的再生纤维荧光改性,得植物基发光纤维。
进一步地,步骤(1)所述再生纤维的制备方法为将纳米纤维素配制成凝胶,将凝胶注入到容器中,加压使凝胶通过容器中的微孔挤出,在凝固浴中反应后烘干,得到再生纤维。
更进一步地,所述纳米纤维素为细菌纤维素、微纤化纤维素或纳米晶体纤维素;所述凝胶质量浓度为0.5%~3.0%;所述凝固浴为乙醇、丙酮、1,4-二氧六环、四氢呋喃、异丙醇中的一种以上;所述反应时间为5~30min;所述烘干方式为热风干燥,干燥温度为50~110℃。
进一步地,再生纤维首先通过交联剂改性降低纤维的吸水润胀度,步骤(2)所述再生纤维交联改性的具体步骤为将再生纤维浸渍于交联剂溶液中,再取出烘干,得到交联改性纤维。
更进一步地,所述交联剂为异氰酸酯、醛类化合物、乙烯砜类化合物、硼酸、硼砂类化合物、金属离子类化合物或碳酸锆盐;所述浸渍时间为5~30min;所述烘干方式为热风干燥,干燥温度为50~110℃。
进一步地,交联改性处理后的再生纤维通过荧光剂进行荧光改性,具体步骤为将交联改性处理后的再生纤维浸渍于荧光溶液中,再取出烘干,得到植物基发光纤维。
更进一步地,所述荧光溶液包括荧光剂和有机溶剂,荧光溶液质量浓度为0.5%~20%;所述荧光剂为芳香烃、芳香烃取代物、芳基乙烯化合物、芳基乙炔化合物、带有环外CN基团的化合物、五元杂环化合物、六元杂环化合物、羰基化合物、萘二甲酸衍生物、苯并蒽酮衍生物、蒽醌衍生物、罗丹明和罗丹明衍生物中的一种;所述有机溶剂为甲醇、乙醇、异丙醇、丙酮、乙酸乙酯、氯仿、冰醋酸、二氧六环、四氯化碳、苯、石油醚、甲苯、硝基甲烷、乙醚、二甲基甲酰胺和二甲亚砜中的一种;所述浸渍时间为5~30min;所述烘干方式为热风干燥,干燥温度为50~110℃。
由上述的制备方法制得的一种植物基发光纤维。
本发明制得的植物基发光纤维在相应的激发光下观察,纤维发光性能良好。将植物基发光纤维应用于纸张抄造,得到的纸张中发光纤维分布均匀,且无荧光物质脱落。
与现有技术相比,本发明具有如下优点和技术效果:
本发明制备的植物基发光纤维除了具有普通荧光纤维所具备的荧光性能,同时通过对纤维的交联改性,大大降低了纤维的吸水润胀度,提高了纤维的物理强度,使发光纤维可以应用于潮湿或有水存在的环境,并赋予发光纤维良好的抄造性能,此外,还可以根据需要制备不同直径、长度规格的发光纤维应用于防伪纸张的抄造,发光纤维与纸浆纤维可以形成良好的结合,不易从纸张表面剥落,具有优异的防伪特性。
具体实施方式
以下结合实例对本发明的具体实施作进一步说明,但本发明的实施和保护范围不限于此。
实施例1
1)纤维素再生纤维的制备:将细菌纤维素置于烧杯中,加水调节其质量浓度为0.5%,磁力搅拌30min后得到细菌纤维素凝胶,再把凝胶通过容器微孔挤入到乙醇凝固浴中,反应5min后,取出在60℃下热风干燥,得到纤维素再生纤维。
2)再生纤维交联改性:将步骤1)制备得到的纤维素再生纤维浸渍于二苯基甲烷二异氰酸酯溶液中进行交联反应(二苯基甲烷二异氰酸酯溶液的溶质为二苯基甲烷二异氰酸酯,溶剂为丙酮,溶液质量浓度为10%),反应10min后取出,在80℃下热风干燥。交联改性后的再生纤维吸水润胀度为6%。
3)再生纤维荧光改性:将罗丹明B有机荧光物质溶解于乙醇溶剂中,配制成质量浓度为15%的有机荧光溶液,将步骤2)交联改性后的再生纤维浸渍于有机荧光溶液中5min,取出后在50℃下热风干燥,得植物基发光纤维。
通过以上步骤得到植物基发光纤维,该发光纤维在波长为540nm激发光下,纤维呈红色荧光,纤维发光性能良好。将该发光纤维与浆料混合,发光纤维在浆料中均匀分散,抄纸得到的纸张中发光纤维分布均匀,且不脱落。
实施例2
1)纤维素再生纤维的制备:将纳米晶体纤维素加水配制成质量浓度为3.0%的凝胶,再把凝胶通过容器微孔挤入到四氢呋喃凝固浴中,反应30min后,取出在110℃下热风干燥,得纤维素再生纤维。
2)再生纤维交联改性:将步骤1)制备得到的纤维素再生纤维浸渍于质量浓度为40%的乙二醛溶液中进行交联反应,反应5min后取出,在50℃下热风干燥。交联改性后的再生纤维吸水润胀度为8%。
3)再生纤维荧光改性:将有机荧光物质赫斯特荧光染料33258(属于五元杂环化合物)溶解于二甲亚砜溶剂中,配制成质量浓度为20%的有机荧光溶液,将步骤2)交联改性后的再生纤维浸渍于有机荧光溶液中10min,取出后在110℃下热风干燥,得植物基发光纤维。
通过以上步骤得到植物基发光纤维,该发光纤维在波长为346nm激发光下,纤维呈青色荧光,纤维发光性能良好。将该发光纤维与浆料混合,发光纤维在浆料中均匀分散,抄纸得到的纸张中发光纤维分布均匀,且不脱落。
实施例3
1)纤维素再生纤维的制备:将微纤化纤维素加水配制成质量浓度为2.0%的凝胶,再把凝胶通过容器微孔挤入到丙酮凝固浴中,反应15min后,取出在50℃下热风干燥,得到纤维素再生纤维。
2)再生纤维交联改性:将步骤1)制备得到的纤维素再生纤维浸渍于质量浓度为15%的碳酸锆铵溶液中进行交联反应,反应30min后取出,在110℃下热风干燥。交联改性后的再生纤维吸水润胀度为6%。
3)再生纤维荧光改性:将有机荧光物质N-苯基-1-萘胺-8-磺酸(属于芳香烃取代物)溶解于石油醚溶剂中,配制成质量浓度为0.5%的有机荧光溶液,将步骤2)交联改性后的再生纤维浸渍于有机荧光溶液中30min,取出后在50℃下热风干燥,得植物基发光纤维。
通过以上步骤得到植物基发光纤维,该发光纤维在波长为365nm激发光下观察,纤维呈青色荧光,纤维发光性能良好。将该发光纤维与浆料混合,发光纤维在浆料中均匀分散,抄纸得到的纸张中发光纤维分布均匀,且不脱落。
实施例4
1)纤维素再生纤维的制备:将微纤化纤维素加水配制成质量浓度为1.0%的凝胶,再把凝胶通过容器微孔挤入到丙酮凝固浴中,反应5min后,取出在100℃下热风干燥,得到纤维素再生纤维。
2)再生纤维交联改性:将步骤1)制备得到的纤维素再生纤维浸渍于质量浓度为5%的硼酸溶液中进行交联反应,反应10min后取出,在50℃下热风干燥。交联改性后的再生纤维吸水润胀度为5%。
3)再生纤维荧光改性:将有机荧光物质4-甲基伞形酮(属于羰基化合物)溶解于二甲基甲酰胺溶剂中,配制成质量浓度为10%的有机荧光溶液,将步骤2)交联改性后的再生纤维浸渍于有机荧光溶液中150min,取出后在50℃下热风干燥,得植物基发光纤维。
通过以上步骤得到植物基发光纤维,该发光纤维在波长为365nm激发光下观察,纤维呈蓝色荧光,纤维发光性能良好。将该发光纤维与浆料混合,发光纤维在浆料中均匀分散,抄纸得到的纸张中发光纤维分布均匀,且不脱落。

Claims (8)

1.一种植物基发光纤维的制备方法,其特征在于,该制备方法包括以下步骤:
(1)以纳米纤维素为原料制备再生纤维;
(2)将步骤(1)得到的再生纤维交联改性;
(3)将步骤(2)交联改性后的再生纤维荧光改性,得植物基发光纤维。
2.根据权利要求1所述的一种植物基发光纤维的制备方法,其特征在于,步骤(1)所述再生纤维的制备方法为将纳米纤维素配制成凝胶,将凝胶注入到容器中,加压使凝胶通过容器中的微孔挤出,在凝固浴中反应后烘干,得到再生纤维。
3.根据权利要求2所述的一种植物基发光纤维的制备方法,其特征在于,所述纳米纤维素为细菌纤维素、微纤化纤维素或纳米晶体纤维素;所述凝胶质量浓度为0.5%~3.0%;所述凝固浴为乙醇、丙酮、1,4-二氧六环、四氢呋喃和异丙醇中的一种以上;所述反应时间为5~30min;所述烘干方式为热风干燥,干燥温度为50~110℃。
4.根据权利要求1所述的一种植物基发光纤维的制备方法,其特征在于,步骤(2)所述再生纤维交联改性的具体步骤为将再生纤维浸渍于交联剂溶液中,再取出烘干,得到交联改性纤维。
5.根据权利要求4所述的一种植物基发光纤维的制备方法,其特征在于,所述交联剂为异氰酸酯、醛类化合物、乙烯砜类化合物、硼酸、硼砂类化合物、金属离子类化合物或碳酸锆盐;所述浸渍时间为5~30min;所述烘干方式为热风干燥,干燥温度为50~110℃。
6.根据权利要求1所述的一种植物基发光纤维的制备方法,其特征在于:交联改性处理后的再生纤维通过荧光剂进行荧光改性,具体步骤为将交联改性处理后的再生纤维浸渍于荧光溶液中,再取出烘干,得到植物基发光纤维。
7.根据权利要求6所述的一种植物基发光纤维的制备方法,其特征在于,所述荧光溶液包括荧光剂和有机溶剂,荧光溶液质量浓度为0.5%~20%;所述荧光剂为芳香烃、芳香烃取代物、芳基乙烯化合物、芳基乙炔化合物、带有环外CN基团的化合物、五元杂环化合物、六元杂环化合物、羰基化合物、萘二甲酸衍生物、苯并蒽酮衍生物、蒽醌衍生物、罗丹明和罗丹明衍生物中的一种;所述有机溶剂为甲醇、乙醇、异丙醇、丙酮、乙酸乙酯、氯仿、冰醋酸、二氧六环、四氯化碳、苯、石油醚、甲苯、硝基甲烷、乙醚、二甲基甲酰胺和二甲亚砜中的一种;所述浸渍时间为5~30min;所述烘干方式为热风干燥,干燥温度为50~110℃。
8.由权利要求1-7任一项所述的制备方法制得的一种植物基发光纤维。
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