CN112647317A - 一种提高羊毛纤维强力的生物酶促染色方法 - Google Patents

一种提高羊毛纤维强力的生物酶促染色方法 Download PDF

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CN112647317A
CN112647317A CN202011510926.7A CN202011510926A CN112647317A CN 112647317 A CN112647317 A CN 112647317A CN 202011510926 A CN202011510926 A CN 202011510926A CN 112647317 A CN112647317 A CN 112647317A
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CN112647317B (zh
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苏静
王鸿博
李洁
李宇
李楠楠
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Jiangnan University
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Abstract

本发明公开了一种提高羊毛纤维强力的生物酶促染色方法,属于纺织材料改性技术领域。本发明利用蛋白质纤维大分子中含有大量的羟基、氨基和羧基等活性基团,易与酶催化酚类化合物形成的聚酚类色素反应形成共价结合的特点,实现羊毛纤维低温上染的同时提升纤维强力。本发明操作条件温和,易控制,在日益强调环保的今天,利用生物酶对羊毛纤维染色安全、环保、高效、有着长远的发展前景。

Description

一种提高羊毛纤维强力的生物酶促染色方法
技术领域
本发明涉及一种提高羊毛纤维强力的生物酶促染色方法,属于纺织材料改性技术。
背景技术
蛋白质纤维如羊毛纤维具有优良的吸湿性、保暖性,穿着柔软,在纺织行业应用广泛。在加工过程中,如洗毛、纺纱、织造、染色等,纤维会受到损伤,机械性能变差,值得注意的是,因羊毛表面鳞片层具有疏水性,常使用高温工艺进行染色,造成强力损伤,严重影响纤维的后续加工和织物的服用性能,且能耗大,对环境不利。因此寻求一种温和有效的染色方法预防和修复羊毛纤维损伤具有重要意义。
现有技术中,对羊毛纤维强力损伤修复的报道较少,有报道使用化学交联剂,如乙二醛、戊二醛、二辛酯和碳二亚胺等,这些交联剂便宜,且容易提高纤维的拉伸性能,但对环境、对使用者的健康构成极大的威胁。目前,针对转谷氨酰胺酶(TG酶)修复羊毛强力损伤的研究较广泛,TG酶具有吸收伯胺和将肽链(含谷氨酰胺或赖氨酸残基)嫁接到蛋白质中的能力,可修复羊毛的化学损伤、生物损伤等多重损伤,但用途单一。
蛋白质纤维染色主要以酸性染料与活性染料为主,通过与纤维发生物理或化学结合上染。但随着世界能源枯竭及环境问题的日益恶化,合成染料和印染工业的发展面临着环境污染、高人工成本等众多问题,寻找新型生态友好型染料成为新的发展方向。
发明内容
解决的技术问题:
本发明的生物酶促染色及提高羊毛纤维强力的方法,首先用物理或化学方法对羊毛纱线进行预处理,然后使经预处理的羊毛纱线在漆酶-酚类化合物的反应体系中进行染色,蛋白质纤维大分子中含有大量的羟基、氨基和羧基等活性基团,易与有色酶促酚类聚合产物反应形成共价结合,从而实现对羊毛纤维低温染色并赋予纤维良好的染色性能与力学性能,反应条件温和,易控制,绿色环保,有广阔的发展前景。
本发明使用天然的动植物染料代替化学染料。漆酶是一种含铜的氧化还原酶,存在于许多植物、真菌和微生物中。在纺织加工中,漆酶被用于提高漂白过程中织物的白度、有色废水的脱色以及纤维的精练、羊毛防毡缩等,但未有用于改善增强羊毛纤维强力的报道,本发明利用漆酶可催化底物反应生成有色聚合产物,与蛋白质纤维大分子中大量的羟基、氨基和羧基等活性基团反应形成共价结合,在完成原位上染的同时提升羊毛纤维强力。
技术方案:
本发明的第一个目的是提供一种生物酶促提高羊毛纤维强力并染色的方法,所述生物酶促染色及提高羊毛纤维强力的方法是:将漆酶-酚类化合物加入到缓冲溶液中,羊毛纤维在含有漆酶-酚类化合物的反应体系中进行染色。
在本发明的一种实施方式中,所述酚类化合物为邻苯二酚、对苯二酚、没食子酸、香草醛、愈创木酚等。
在本发明的一种实施方式中,酶催化酚类化合物与羊毛反应前,羊毛纤维需经过预处理:所述预处理包括化学法、酶法或物理法。
在本发明的一种实施方式中,所述预处理可采用碳酸钠进行预处理,所述处理工艺处方及条件:称取羊毛纤维和碳酸钠,将碳酸钠溶解在去离子水中配制成0.5-1g/L的碳酸钠溶液,浴比为1:20~1:50。将羊毛纤维浸泡在30-80℃的碳酸钠溶液中处理15-30min,然后用40℃的无水乙醇清洗5-15min,去离子水漂洗多次,将洗净的羊毛纤维在40-60℃下烘干。
在本发明的一种实施方式中,所述预处理可采用低温等离子体进行预处理,所述处理工艺处方及条件:将羊毛纤维置于低温等离子体处理机内架子上,开启真空泵,通入一路氧气,点击自动模式对羊毛纤维进行低温等离子体处理,处理功率100-150W,处理时间5-10min。
在本发明的一种实施方式中,所述生物酶促染色及提高羊毛纤维强力的方法为:将生物催化剂漆酶、酚类化合物依次加入到缓冲溶液中,配制成pH为4.0-6.0的反应体系,将经过预处理的羊毛纤维加入到反应体系中,于30-80℃下反应2-10小时。
在本发明的一种实施方式中,所述缓冲溶液为乙酸-乙酸钠缓冲液。
在本发明的一种实施方式中,所述乙酸-乙酸钠缓冲溶液浓度为0.1-0.3mol/L。
在本发明的一种实施方式中,所述生物酶促染色及提高羊毛纤维强力的工艺处方及条件:配制pH为4.0-6.0的乙酸-乙酸钠缓冲溶液,向缓冲溶液中依次加入催化剂漆酶与底物,使漆酶浓度为25~125U/mL,酚类化合物浓度为0.04-0.20mol/L,将经过预处理的羊毛纤维加入到反应体系中,浴比为1:20-1:50,升温至30-80℃保温反应2~10小时。
在本发明的一种实施方式中,所述漆酶的用量为(25~125U)U/(0.04-0.20)mmol酚类化合物。
本发明的第二个目的是提供一种采用上述方法制备得到的蛋白质纤维。
在本发明的一种实施方式中,所述蛋白质纤维为羊毛。
本发明的第三个目的是提供一种含有上述羊毛的纱、线和织物。
有益效果:
本发明利用生物催化剂--漆酶催化氧化酚类化合物生成有色聚合产物,蛋白质纤维大分子中含有大量的羟基、氨基和羧基等活性基团,易与酶促酚类有色聚合产物反应形成共价结合,从而实现羊毛纤维染色,并赋予羊毛良好的染色性能,染色后的羊毛强力显著提高,耐碱性能改善,且具有抗氧化性能。该反应条件温和,易控制,对环境友好,有良好的发展前景。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案,下面将对具体的实施方式或现有技术描述中所使用的附图做简单地介绍,显而易见地,下面描述中的附图是本发明的一些实施方式,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他附图。
图1为未改性羊毛纱线和改性羊毛纱线的SEM图,标尺均为10μm,其中,a为空白对照组,b为实施例1,c为实施例2。
图2为未改性羊毛纱线和改性羊毛纱线横截面(放大1000倍)图,其中,a为空白对照组,b为实施例1,c为实施例2。
图3为未改性羊毛纱线和改性羊毛纱线染色图,其中,a为空白对照组,b为实施例1,c为实施例2。
图4为生物酶促染色过程示意图。
具体实施方式
以下对本发明的优选实施例进行说明,应当理解实施例是为了更好地解释本发明,不用于限制本发明。
断裂强力测试:在拉伸试验机上进行,选择加持长度180mm,拉伸拉伸速度为100mm/min,,测试多次,取平均值。碱溶性测定:用碱处理后纱线的重量和溶解度公式计算纱线的溶解度,测试纱线抗碱损伤性能。抗氧化性测定:采用ABTS法测定纱线的抗氧化性能。羊毛纱线的K/S值用测色仪测试。
实施例1
(1)预处理:
所述处理工艺处方及条件:称取1g羊毛纱线和碳酸钠,将碳酸钠溶解在去离子水中配制成1g/L的碳酸钠溶液,浴比为1:30。将羊毛纤维浸泡在40℃的碳酸钠溶液中处理15min,然后用40℃的无水乙醇清洗10min,去离子水漂洗,将洗净的羊毛纤维在40℃下烘干。
(2)酶催化酚类化合物与羊毛反应:
配制溶液:配制0.2mol/L的乙酸-乙酸钠缓冲液,调节pH至5.0,依次加入0.04mol/L邻苯二酚和75U/mL漆酶,浴比1:30,置于反应器中震荡均匀,将经预处理过的羊毛纱线放入配制好的缓冲液中,于40℃下恒温振荡反应5h。
(3)后处理:
将步骤(3)得到的羊毛纱线取出后,在-50℃条件下冷冻12h灭酶,用去离子水清洗,自然晾干。
实施例2
(1)预处理:
所述处理工艺处方及条件:将1g羊毛纱线置于低温等离子体处理机内,开启真空泵,通入一路氧气,点击自动模式,对蛋白质纤维进行低温等离子体处理,处理功率100W,处理时间5min。
(2)酶催化酚类化合物与羊毛反应:
配制溶液:配制0.2mol/L的乙酸-乙酸钠缓冲液,调节pH至5.5,依次加入0.04mol/L邻苯二酚和75U/mL漆酶,浴比1:50,置于反应器中震荡均匀,将经预处理过的羊毛纱线放入配制好的缓冲液中,于40℃下恒温振荡反应5h。
(3)后处理:
将步骤(3)得到的羊毛纱线取出后,在-40℃条件下冷冻12h灭酶,然后用去离子水清洗,自然晾干。
对实施例1-2所得的羊毛的性能进行检测,结果见表1和表2。
表1实施例1-2所得的羊毛纤维的性能检测结果
Figure BDA0002846377280000041
表2实施例1-2中不同处理方法所得的羊毛纤维的染色参数
Figure BDA0002846377280000042
Figure BDA0002846377280000051
根据表中数据可见,经不同预处理的羊毛纱线进行酶促聚合染色都可得到较好的染色深度,且羊毛纱线强力均得到不同程度的提高,碱溶性降低,抗氧化性提高。较为明显的是,经等离子体预处理后的酶法染色羊毛纱线强力提升了26%,较化学预处理的酶促聚合染色羊毛纱线力学性能好。
实施例3探究漆酶用量对羊毛纤维染色的影响
参照实施例1,将步骤(2)中的漆酶的用量分别替换为25U/mL、50U/mL、100U/mL、125U/mL,其他条件不变:
(1)预处理:
所述处理工艺处方及条件:称取1g羊毛纱线和碳酸钠,将碳酸钠溶解在去离子水中配制成1g/L的碳酸钠溶液,浴比为1:30。将羊毛纤维浸泡在40℃的碳酸钠溶液中处理15min,然后用40℃的无水乙醇清洗10min,去离子水漂洗,将洗净的羊毛纤维在40℃下烘干。
(2)酶催化酚类化合物与羊毛反应:
配制溶液:配制0.2mol/L的乙酸-乙酸钠缓冲液,调节pH至5.0,依次加入0.04mol/L邻苯二酚和25U/mL、50U/mL、75U/mL、100U/mL、125U/mL漆酶,浴比1:30,置于反应器中震荡均匀,将经预处理过的羊毛纱线放入配制好的缓冲液中,于40℃下恒温振荡反应5h。
(3)后处理:
将步骤(3)得到的羊毛纱线取出后,在-50℃条件下冷冻12h灭酶,用去离子水清洗,自然晾干。
所得的羊毛的性能进行检测,结果见表3、4。
表3不同酶浓度所得染色羊毛纤维的结果
Figure BDA0002846377280000052
Figure BDA0002846377280000061
表4不同酶浓度所得的羊毛纤维的染色参数
Figure BDA0002846377280000062
根据表中数据可见,当酶浓度较低时,纱线即可得到较高的染色深度和断裂强度,L*值逐渐降低(明度降低),a*、b*均为正值,纱线呈现棕褐色。随着酶浓度增加,纱线碱溶性减少,抗氧化性虽略有增加,但效果也不佳。当酶浓度超过75U/mL,断裂强力和染色深度均趋于稳定。漆酶浓度太高时(150U/mL),染色深度稍有变深、但强力改善效果下降,且浪费试剂,不经济。
实施例4探究邻苯二酚浓度对羊毛纤维染色的影响
参照实施例1,将步骤(2)中的酚类底物的反应浓度分别替换为0.08mol/L、0.12mol/L、0.16mol/L、0.20mol/L,其他条件不变:
(1)预处理:
所述处理工艺处方及条件:称取1g羊毛纱线和碳酸钠,将碳酸钠溶解在去离子水中配制成1g/L的碳酸钠溶液,浴比为1:30。将羊毛纤维浸泡在40℃的碳酸钠溶液中处理15min,然后用40℃的无水乙醇清洗10min,去离子水漂洗,将洗净的羊毛纤维在40℃下烘干。
(2)酶催化酚类化合物与羊毛反应:
配制溶液:配制0.2mol/L的乙酸-乙酸钠缓冲液,调节pH至5.0,依次加入0.08mol/L、0.12mol/L、0.16mol/L、0.20mol/L邻苯二酚和75U/mL漆酶,浴比1:30,置于反应器中震荡均匀,将经预处理过的羊毛纱线放入配制好的缓冲液中,于40℃下恒温振荡反应5h。
(3)后处理:
将步骤(3)得到的羊毛纱线取出后,在-50℃条件下冷冻12h灭酶,用去离子水清洗,自然晾干。
所得的羊毛的性能进行检测,结果见表5、6。
表5不同邻苯二酚浓度所得染色羊毛纤维的结果
Figure BDA0002846377280000071
表6不同邻苯二酚浓度所得的羊毛纤维的染色参数
Figure BDA0002846377280000072
根据表中数据可见,在漆酶的催化作用下,随着邻苯二酚单体浓度的增加,羊毛纱线的染色深度逐渐增加,纱线呈现棕褐色,且耐碱性与抗氧化性改善。但随着酚用量的增加,纱线的断裂强力先增加后减小,断裂伸长率随着酚用量增加而减小。当底物浓度低(比如0.02mol/L)时,染色及强力没有显著改善效果;底物浓度过高(比如0.4mol/L)时,染色深度变大,但染色不匀,纱线强力下降、断裂伸长下降,手感***弹性变差。
实施例5探究反应温度对羊毛纤维染色的影响
参照实施例1,将步骤(2)中的反应温度分别替换为30℃、50℃、60℃、70℃、80℃,其他条件不变:
(1)预处理:
所述处理工艺处方及条件:称取1g羊毛纱线和碳酸钠,将碳酸钠溶解在去离子水中配制成1g/L的碳酸钠溶液,浴比为1:30。将羊毛纤维浸泡在40℃的碳酸钠溶液中处理15min,然后用40℃的无水乙醇清洗10min,去离子水漂洗,将洗净的羊毛纤维在40℃下烘干。
(2)酶催化酚类化合物与羊毛反应:
配制溶液:配制0.2mol/L的乙酸-乙酸钠缓冲液,调节pH至5.0,依次加入0.04mol/L邻苯二酚和75U/mL漆酶,浴比1:30,置于反应器中震荡均匀,将经预处理过的羊毛纱线放入配制好的缓冲液中,于不同温度下恒温振荡反应5h。
(3)后处理:
将步骤(3)得到的羊毛纱线取出后,在-50℃条件下冷冻12h灭酶,用去离子水清洗,自然晾干。
所得的羊毛的性能进行检测,结果见表7、8。
表7不同温度所得染色羊毛纤维的结果
Figure BDA0002846377280000081
表8不同温度所得的羊毛纤维的染色参数
Figure BDA0002846377280000082
根据表中数据可见,当温度低于50℃时,染色纱线染色深度和断裂强度随着温度的升高而增加,温度高于50℃后,羊毛纱线的断裂强度、染色深度随温度升高缓慢降低。
虽然本发明已以较佳实例公开如上,但其并非用以限定本发明,任何熟悉此技术的人,在不脱离本发明的精神和范围内,都可做各种的改动与修饰,因此本发明的保护范围应该以权力书所界定的为准。

Claims (10)

1.一种生物酶促提高羊毛纤维强力的方法,其特征在于,所述方法是将漆酶、酚类化合物加入到缓冲溶液中,形成混合体系;然后将羊毛纤维放置在所得混合体系中,30-80℃下保温进行反应。
2.根据权利要求1所述的方法,其特征在于,所述酚类化合物为邻苯二酚、对苯二酚、没食子酸、香草醛、愈创木酚。
3.根据权利要求1所述的方法,其特征在于,所述缓冲溶液为乙酸-乙酸钠缓冲液。
4.根据权利要求3所述的方法,其特征在于,所述乙酸-乙酸钠缓冲溶液浓度为0.1-0.3mol/L;pH为4.0-6.0。
5.根据权利要求1所述的方法,其特征在于,所述混合体系中漆酶浓度为25~125U/mL。
6.根据权利要求1所述的方法,其特征在于,所述混合体系中酚类化合物浓度为0.04-0.20mol/L。
7.根据权利要求1所述的方法,其特征在于,按照浴比为1:20-1:50,将羊毛纤维加入到混合体系中。
8.根据权利要求1-7任一项所述的方法,其特征在于,所述反应是在30-80℃保温反应2~10小时。
9.权利要求1-8任一项所述方法制备得到的羊毛纤维。
10.含有权利要求9所述的羊毛纤维的纱、线或者织物。
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