CN108425244A - 一种壳聚糖改性蚕丝纤维制品的制备方法 - Google Patents
一种壳聚糖改性蚕丝纤维制品的制备方法 Download PDFInfo
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Abstract
本发明涉及纺织材料制备技术领域,具体涉及一种壳聚糖改性蚕丝纤维制品的制备方法。本发明以蚕丝纤维为基材,硝酸银溶液和自制纳米氧化锌粉末作为促进剂,并辅以琥珀粉和无水乙醇等制备得到壳聚糖改性蚕丝纤维制品,首先以蚕丝纤维和去离子水为原料处理得到脱胶蚕丝纤维,再将虾壳和河底淤泥、醋酸溶液混合发酵得到自制壳聚糖醋酸溶液,利用自制壳聚糖醋酸溶液对脱胶蚕丝纤维进行改性,提高蚕丝纤维制品的吸湿性,将自制纳米氧化锌粉末与基材共混,有利于蚕丝纤维制品的抗老化性能得到提高,继续将硝酸银溶液与葡萄糖溶液共混,使基材表面电阻明显下降,从而提高蚕丝纤维制品的抗静电性,具有广泛的应用前景。
Description
技术领域
本发明涉及纺织材料制备技术领域,具体涉及一种壳聚糖改性蚕丝纤维制品的制备方法。
背景技术
我国是蚕丝的主要生产国,蚕丝产量占世界产量的70%以上。蚕丝是熟蚕结茧时所分泌丝液凝固而成的连续长纤维,也称天然丝,是一种天然纤维,是丝绸织造最主要的原料。蚕丝主要由丝素蛋白和丝胶蛋白组成,丝素蛋白是蚕丝的主要部分,约占总量的75%,其余大部分是丝胶蛋白约有25%。
蚕丝作为一种来源于自然界的天然高分子生物材料,具有优良的力学和生物性能。近来,随着生物医学和生物材料的发展,蚕丝蛋白已经研究于诸多领域,例如生物支架、外科敷料、组织工程、伤口愈合、酶稳定剂等。由于其良好的机械性能和生物相容性,它在新兴领域的许多方面如美容面膜、防伪材料、光电子器件、生物追踪标记,光动力治疗等领域也有相关应用。
蚕丝的应用虽然十分广泛,但是目前的蚕丝纤维制品还存在以下缺陷:1、由于蚕丝主要成分是由动物蛋白,质地较为脆弱,长时间光照后容易发黄、发硬;2、蚕丝纤维容易遭受微生物、虫类的侵蚀,不仅影响美观和手感,而且还会使蚕丝纤维加速老化,强度下降,容易破损;3、蚕丝纤维的吸湿性不高,回潮率仅为11%,大大限制了蚕丝纤维在吸湿领域的应用;4、由于蚕丝等天然纤维在加工过程中的静电问题日益严重,蚕丝等天然纤维在服装及各个领域的应用都受到了一定的局限。
因此,急需寻求一种简单方便的制备高吸湿、耐拉伸、抗菌、耐老化的天然蚕丝纤维制品的方法。
发明内容
本发明所要解决的技术问题:针对目前普通蚕丝纤维制品存在吸湿性差、抗静电性差以及抗老化性能差,满足不了市场要求的缺陷,提供了一种壳聚糖改性蚕丝纤维制品的制备方法。
为解决上述技术问题,本发明采用如下所述的技术方案是:
一种壳聚糖改性蚕丝纤维制品的制备方法,其特征在于具体制备步骤为:
(1)称取0.1~0.2kg虾壳研磨粉碎,得到虾壳粉末,向虾壳粉末中加入虾壳粉末质量0.9%的河底淤泥,装入发酵罐中,密封发酵,待发酵结束后,取出发酵产物,继续将发酵产物和质量分数为8%的醋酸溶液混合,搅拌,得到自制壳聚糖醋酸溶液;
(2)将蚕丝纤维和去离子水混合浸泡,取出浸泡蚕丝纤维,再将浸泡蚕丝纤维、双氧水和硅酸钠混合,搅拌处理后,得到预处理蚕丝纤维;
(3)用去离子水冲洗预处理蚕丝纤维,干燥出料,得到脱胶蚕丝纤维,将脱胶蚕丝纤维和自制壳聚糖醋酸溶液混合搅拌,得到改性脱胶蚕丝纤维;
(4)量取32~36mL氯化锌溶液倒入烧杯中,并将烧杯置于水浴锅中,搅拌,向烧杯中滴加24~32mL氢氧化钠溶液,待滴加结束后,继续保温搅拌反应,反应结束后离心分离,去除上清液,得到沉淀物;
(5)用无水乙醇清洗沉淀物,最后将清洗后的沉淀物置于烘箱中干燥,自然冷却至室温,并研磨后过80目筛,得到自制纳米氧化锌粉末;
(6)按重量分数计,分别称取35~42份改性脱胶蚕丝纤维、6~8份质量分数为18%的硝酸银溶液、4~6份质量分数为21%的葡萄糖溶液、12~16份自制纳米氧化锌粉末、21~24份去离子水、2~4份琥珀粉和3~5份无水乙醇,先将改性脱胶蚕丝纤维、质量分数为18%的硝酸银溶液和质量分数为21%的葡萄糖溶液混合置于搅拌机中搅拌,再添加自制纳米氧化锌粉末、去离子水、琥珀粉和无水乙醇,继续保温混合搅拌,得到混合料,继续将混合料倒入双螺杆挤出机中挤压成型,冷却出料,即得壳聚糖改性蚕丝纤维制品。
步骤(1)所述的研磨粉碎时间为18~21min,发酵温度为36~45℃,发酵时间为9~10天,含有壳聚糖的产物和质量分数为8%的醋酸溶液的质量比为4:1,搅拌温度为42~45℃,搅拌时间为12~15min。
步骤(2)所述的蚕丝纤维和去离子水的质量比为1:5,浸泡时间为1~2h,浸泡蚕丝纤维、质量分数为30%的双氧水和硅酸钠的质量比为5:2:1,搅拌处理温度为96~100℃,搅拌处理时间为45~60min。
步骤(3)所述的冲洗次数为3~5次,脱胶蚕丝纤维和自制壳聚糖醋酸溶液的质量比为4:1,混合搅拌时间为16~20min。
步骤(4)所述的氯化锌溶液的质量分数为24%,搅拌温度为81~85℃,搅拌时间为18~21min,氢氧化钠溶液的质量分数为21%,继续搅拌反应时间为35~42min。
步骤(5)所述的清洗次数为5~6次,干燥温度为95~100℃,干燥时间为2~3h,研磨时间为15~18min。
步骤(6)所述的搅拌温度为45~50℃,搅拌时间为1~2h,继续搅拌时间为16~20min,挤压成型温度为127~135℃,挤压成型压力为3~5MPa。
本发明与其他方法相比,有益技术效果是:
本发明以蚕丝纤维为基材,硝酸银溶液和自制纳米氧化锌粉末作为促进剂,并辅以琥珀粉和无水乙醇等制备得到壳聚糖改性蚕丝纤维制品,首先将蚕丝纤维和去离子水混合浸泡,用双氧水和硅酸钠对其进一步脱胶处理,处理后得到脱胶蚕丝纤维,再将虾壳和河底淤泥混合,并在一定温度下密封发酵得到发酵产物,将其与醋酸溶液混合搅拌得到自制壳聚糖醋酸溶液,利用自制壳聚糖醋酸溶液对脱胶蚕丝纤维进行改性,其中自制壳聚糖醋酸溶液中含有大量的亲水基团-羟基和氨基,使得脱胶蚕丝纤维表面的亲水基团增多,从而提高蚕丝纤维制品的吸湿性,接着将氯化锌溶液和氢氧化钠溶液混合,在一定温度条件下搅拌反应并研磨得到自制纳米氧化锌粉末,将其与基材共混,由于自制纳米氧化锌粉末能吸收强烈的紫外线,也能散射强烈的紫外线,当强烈的紫外线照射在基材表面时,基材表面的自制纳米氧化锌能够散射强烈的紫外线,从而降低照射方向的紫外线强度,有利于蚕丝纤维制品的抗老化性能得到提高,继续将硝酸银溶液与葡萄糖溶液共混,诱导银离子还原生成银单质,并吸附于基材表面,形成了微粒,使基材表面电阻明显下降,从而提高蚕丝纤维制品的抗静电性,具有广泛的应用前景。
具体实施方式
称取0.1~0.2kg虾壳研磨粉碎18~21min,得到虾壳粉末,向虾壳粉末中加入虾壳粉末质量0.9%的河底淤泥,装入发酵罐中,在温度为36~45℃的条件下密封发酵9~10天,待发酵结束后,取出发酵产物,继续将发酵产物和质量分数为8%的醋酸溶液按质量比为4:1混合,在温度为42~45℃的条件下搅拌12~15min,得到自制壳聚糖醋酸溶液;按质量比为1:5将蚕丝纤维和去离子水混合浸泡1~2h,取出浸泡蚕丝纤维,再将浸泡蚕丝纤维、质量分数为30%的双氧水和硅酸钠按质量比为5:2:1混合,在温度为96~100℃的条件下搅拌处理45~60min后,得到预处理蚕丝纤维;用去离子水冲洗预处理蚕丝纤维3~5次,干燥出料,得到脱胶蚕丝纤维,按质量比为4:1将脱胶蚕丝纤维和自制壳聚糖醋酸溶液混合搅拌16~20min,得到改性脱胶蚕丝纤维;量取32~36mL质量分数为24%的氯化锌溶液倒入烧杯中,并将烧杯置于水浴锅中,在温度为81~85℃的条件下搅拌18~21min,向烧杯中滴加24~32mL质量分数为21%的氢氧化钠溶液,待滴加结束后,继续保温搅拌反应35~42min,反应结束后离心分离,去除上清液,得到沉淀物;用无水乙醇清洗沉淀物5~6次,最后将清洗后的沉淀物置于烘箱中,在温度为95~100℃下干燥2~3h,自然冷却至室温,并研磨15~18min后过80目筛,得到自制纳米氧化锌粉末;按重量分数计,分别称取35~42份改性脱胶蚕丝纤维、6~8份质量分数为18%的硝酸银溶液、4~6份质量分数为21%的葡萄糖溶液、12~16份自制纳米氧化锌粉末、21~24份去离子水、2~4份琥珀粉和3~5份无水乙醇,先将改性脱胶蚕丝纤维、质量分数为18%的硝酸银溶液和质量分数为21%的葡萄糖溶液混合置于搅拌机中,在温度为45~50℃的条件下搅拌1~2h,再添加自制纳米氧化锌粉末、去离子水、琥珀粉和无水乙醇,继续保温混合搅拌16~20min,得到混合料,继续将混合料倒入双螺杆挤出机中,在温度为127~135℃、压力为3~5MPa的条件下挤压成型,冷却出料,即得壳聚糖改性蚕丝纤维制品。
称取0.1kg虾壳研磨粉碎18min,得到虾壳粉末,向虾壳粉末中加入虾壳粉末质量0.9%的河底淤泥,装入发酵罐中,在温度为36℃的条件下密封发酵9天,待发酵结束后,取出发酵产物,继续将发酵产物和质量分数为8%的醋酸溶液按质量比为4:1混合,在温度为42℃的条件下搅拌12min,得到自制壳聚糖醋酸溶液;按质量比为1:5将蚕丝纤维和去离子水混合浸泡1h,取出浸泡蚕丝纤维,再将浸泡蚕丝纤维、质量分数为30%的双氧水和硅酸钠按质量比为5:2:1混合,在温度为96℃的条件下搅拌处理45min后,得到预处理蚕丝纤维;用去离子水冲洗预处理蚕丝纤维3次,干燥出料,得到脱胶蚕丝纤维,按质量比为4:1将脱胶蚕丝纤维和自制壳聚糖醋酸溶液混合搅拌16min,得到改性脱胶蚕丝纤维;量取32mL质量分数为24%的氯化锌溶液倒入烧杯中,并将烧杯置于水浴锅中,在温度为81℃的条件下搅拌18min,向烧杯中滴加24mL质量分数为21%的氢氧化钠溶液,待滴加结束后,继续保温搅拌反应35min,反应结束后离心分离,去除上清液,得到沉淀物;用无水乙醇清洗沉淀物5次,最后将清洗后的沉淀物置于烘箱中,在温度为95℃下干燥2h,自然冷却至室温,并研磨15min后过80目筛,得到自制纳米氧化锌粉末;按重量分数计,分别称取35份改性脱胶蚕丝纤维、6份质量分数为18%的硝酸银溶液、4份质量分数为21%的葡萄糖溶液、12份自制纳米氧化锌粉末、21份去离子水、2份琥珀粉和3份无水乙醇,先将改性脱胶蚕丝纤维、质量分数为18%的硝酸银溶液和质量分数为21%的葡萄糖溶液混合置于搅拌机中,在温度为45℃的条件下搅拌1h,再添加自制纳米氧化锌粉末、去离子水、琥珀粉和无水乙醇,继续保温混合搅拌16min,得到混合料,继续将混合料倒入双螺杆挤出机中,在温度为127℃、压力为3MPa的条件下挤压成型,冷却出料,即得壳聚糖改性蚕丝纤维制品。
称取0.1kg虾壳研磨粉碎20min,得到虾壳粉末,向虾壳粉末中加入虾壳粉末质量0.9%的河底淤泥,装入发酵罐中,在温度为39℃的条件下密封发酵9天,待发酵结束后,取出发酵产物,继续将发酵产物和质量分数为8%的醋酸溶液按质量比为4:1混合,在温度为43℃的条件下搅拌13min,得到自制壳聚糖醋酸溶液;按质量比为1:5将蚕丝纤维和去离子水混合浸泡1h,取出浸泡蚕丝纤维,再将浸泡蚕丝纤维、质量分数为30%的双氧水和硅酸钠按质量比为5:2:1混合,在温度为98℃的条件下搅拌处理53min后,得到预处理蚕丝纤维;用去离子水冲洗预处理蚕丝纤维4次,干燥出料,得到脱胶蚕丝纤维,按质量比为4:1将脱胶蚕丝纤维和自制壳聚糖醋酸溶液混合搅拌18min,得到改性脱胶蚕丝纤维;量取34mL质量分数为24%的氯化锌溶液倒入烧杯中,并将烧杯置于水浴锅中,在温度为84℃的条件下搅拌19min,向烧杯中滴加28mL质量分数为21%的氢氧化钠溶液,待滴加结束后,继续保温搅拌反应38min,反应结束后离心分离,去除上清液,得到沉淀物;用无水乙醇清洗沉淀物5次,最后将清洗后的沉淀物置于烘箱中,在温度为98℃下干燥2h,自然冷却至室温,并研磨17min后过80目筛,得到自制纳米氧化锌粉末;按重量分数计,分别称取39份改性脱胶蚕丝纤维、7份质量分数为18%的硝酸银溶液、5份质量分数为21%的葡萄糖溶液、14份自制纳米氧化锌粉末、23份去离子水、3份琥珀粉和4份无水乙醇,先将改性脱胶蚕丝纤维、质量分数为18%的硝酸银溶液和质量分数为21%的葡萄糖溶液混合置于搅拌机中,在温度为48℃的条件下搅拌1h,再添加自制纳米氧化锌粉末、去离子水、琥珀粉和无水乙醇,继续保温混合搅拌18min,得到混合料,继续将混合料倒入双螺杆挤出机中,在温度为130℃、压力为4MPa的条件下挤压成型,冷却出料,即得壳聚糖改性蚕丝纤维制品。
称取0.2kg虾壳研磨粉碎21min,得到虾壳粉末,向虾壳粉末中加入虾壳粉末质量0.9%的河底淤泥,装入发酵罐中,在温度为45℃的条件下密封发酵10天,待发酵结束后,取出发酵产物,继续将发酵产物和质量分数为8%的醋酸溶液按质量比为4:1混合,在温度为45℃的条件下搅拌15min,得到自制壳聚糖醋酸溶液;按质量比为1:5将蚕丝纤维和去离子水混合浸泡2h,取出浸泡蚕丝纤维,再将浸泡蚕丝纤维、质量分数为30%的双氧水和硅酸钠按质量比为5:2:1混合,在温度为100℃的条件下搅拌处理60min后,得到预处理蚕丝纤维;用去离子水冲洗预处理蚕丝纤维5次,干燥出料,得到脱胶蚕丝纤维,按质量比为4:1将脱胶蚕丝纤维和自制壳聚糖醋酸溶液混合搅拌20min,得到改性脱胶蚕丝纤维;量取36mL质量分数为24%的氯化锌溶液倒入烧杯中,并将烧杯置于水浴锅中,在温度为85℃的条件下搅拌21min,向烧杯中滴加32mL质量分数为21%的氢氧化钠溶液,待滴加结束后,继续保温搅拌反应42min,反应结束后离心分离,去除上清液,得到沉淀物;用无水乙醇清洗沉淀物6次,最后将清洗后的沉淀物置于烘箱中,在温度为100℃下干燥3h,自然冷却至室温,并研磨18min后过80目筛,得到自制纳米氧化锌粉末;按重量分数计,分别称取42份改性脱胶蚕丝纤维、8份质量分数为18%的硝酸银溶液、6份质量分数为21%的葡萄糖溶液、16份自制纳米氧化锌粉末、24份去离子水、4份琥珀粉和5份无水乙醇,先将改性脱胶蚕丝纤维、质量分数为18%的硝酸银溶液和质量分数为21%的葡萄糖溶液混合置于搅拌机中,在温度为50℃的条件下搅拌2h,再添加自制纳米氧化锌粉末、去离子水、琥珀粉和无水乙醇,继续保温混合搅拌20min,得到混合料,继续将混合料倒入双螺杆挤出机中,在温度为135℃、压力为5MPa的条件下挤压成型,冷却出料,即得壳聚糖改性蚕丝纤维制品。
对比例以东莞市某公司生产的蚕丝纤维制品作为对比例
对本发明制得的壳聚糖改性蚕丝纤维制品和对比例中的蚕丝纤维制品进行检测,检测结果如表1所示:
参照《絮用纤维制品通用技术要求》(GB18383-2007)进行检测。
表1性能测定结果
由表1数据可知,本发明制得的壳聚糖改性蚕丝纤维制品,具有吸湿性好、抗静电效果好、抗老化性强以及抑菌效果好等优点,且本发明的制备工艺简单,操作控制方便,质量稳定,生产效率高,可大规模工业化生产。因此,明显优于对比例产品,具有广阔的使用前景。
Claims (7)
1.一种壳聚糖改性蚕丝纤维制品的制备方法,其特征在于具体制备步骤为:
(1)称取0.1~0.2kg虾壳研磨粉碎,得到虾壳粉末,向虾壳粉末中加入虾壳粉末质量0.9%的河底淤泥,装入发酵罐中,密封发酵,待发酵结束后,取出发酵产物,继续将发酵产物和质量分数为8%的醋酸溶液混合,搅拌,得到自制壳聚糖醋酸溶液;
(2)将蚕丝纤维和去离子水混合浸泡,取出浸泡蚕丝纤维,再将浸泡蚕丝纤维、双氧水和硅酸钠混合,搅拌处理后,得到预处理蚕丝纤维;
(3)用去离子水冲洗预处理蚕丝纤维,干燥出料,得到脱胶蚕丝纤维,将脱胶蚕丝纤维和自制壳聚糖醋酸溶液混合搅拌,得到改性脱胶蚕丝纤维;
(4)量取32~36mL氯化锌溶液倒入烧杯中,并将烧杯置于水浴锅中,搅拌,向烧杯中滴加24~32mL氢氧化钠溶液,待滴加结束后,继续保温搅拌反应,反应结束后离心分离,去除上清液,得到沉淀物;
(5)用无水乙醇清洗沉淀物,最后将清洗后的沉淀物置于烘箱中干燥,自然冷却至室温,并研磨后过80目筛,得到自制纳米氧化锌粉末;
(6)按重量分数计,分别称取35~42份改性脱胶蚕丝纤维、6~8份质量分数为18%的硝酸银溶液、4~6份质量分数为21%的葡萄糖溶液、12~16份自制纳米氧化锌粉末、21~24份去离子水、2~4份琥珀粉和3~5份无水乙醇,先将改性脱胶蚕丝纤维、质量分数为18%的硝酸银溶液和质量分数为21%的葡萄糖溶液混合置于搅拌机中搅拌,再添加自制纳米氧化锌粉末、去离子水、琥珀粉和无水乙醇,继续保温混合搅拌,得到混合料,继续将混合料倒入双螺杆挤出机中挤压成型,冷却出料,即得壳聚糖改性蚕丝纤维制品。
2.根据权利要求1所述的一种壳聚糖改性蚕丝纤维制品的制备方法,其特征在于:步骤(1)所述的研磨粉碎时间为18~21min,发酵温度为36~45℃,发酵时间为9~10天,含有壳聚糖的产物和质量分数为8%的醋酸溶液的质量比为4:1,搅拌温度为42~45℃,搅拌时间为12~15min。
3.根据权利要求1所述的一种壳聚糖改性蚕丝纤维制品的制备方法,其特征在于:步骤(2)所述的蚕丝纤维和去离子水的质量比为1:5,浸泡时间为1~2h,浸泡蚕丝纤维、质量分数为30%的双氧水和硅酸钠的质量比为5:2:1,搅拌处理温度为96~100℃,搅拌处理时间为45~60min。
4.根据权利要求1所述的一种壳聚糖改性蚕丝纤维制品的制备方法,其特征在于:步骤(3)所述的冲洗次数为3~5次,脱胶蚕丝纤维和自制壳聚糖醋酸溶液的质量比为4:1,混合搅拌时间为16~20min。
5.根据权利要求1所述的一种壳聚糖改性蚕丝纤维制品的制备方法,其特征在于:步骤(4)所述的氯化锌溶液的质量分数为24%,搅拌温度为81~85℃,搅拌时间为18~21min,氢氧化钠溶液的质量分数为21%,继续搅拌反应时间为35~42min。
6.根据权利要求1所述的一种壳聚糖改性蚕丝纤维制品的制备方法,其特征在于:步骤(5)所述的清洗次数为5~6次,干燥温度为95~100℃,干燥时间为2~3h,研磨时间为15~18min。
7.根据权利要求1所述的一种壳聚糖改性蚕丝纤维制品的制备方法,其特征在于:步骤(6)所述的搅拌温度为45~50℃,搅拌时间为1~2h,继续搅拌时间为16~20min,挤压成型温度为127~135℃,挤压成型压力为3~5MPa。
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CN111088550A (zh) * | 2019-12-19 | 2020-05-01 | 湖州旧馆四发服装砂洗厂 | 一种防静电涤纶面料的制备及其染色方法 |
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