CN112227064A - 醛亲核加成络合抗菌纤维、制备方法及应用 - Google Patents
醛亲核加成络合抗菌纤维、制备方法及应用 Download PDFInfo
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- CN112227064A CN112227064A CN202011169048.7A CN202011169048A CN112227064A CN 112227064 A CN112227064 A CN 112227064A CN 202011169048 A CN202011169048 A CN 202011169048A CN 112227064 A CN112227064 A CN 112227064A
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- fiber
- aldehyde
- antibacterial
- nucleophilic addition
- reaction
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- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
- D06M11/30—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with oxides of halogens, oxyacids of halogens or their salts, e.g. with perchlorates
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- D—TEXTILES; PAPER
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Abstract
本发明涉及纺织品领域，尤其涉及一种抗菌纤维。一种醛亲核加成络合抗菌纤维制备方法，选取糖单元上至少含有一个醛活性基团的待改性纤维作为原料，交联反应，将待改性纤维浸轧于交联剂和催化剂的溶液中得到改性纤维中间体；所述交联剂至少含有一个和待改性纤维上的醛活性基团和一个络合活性基团；交联剂洗涤；络合反应，得到抗菌纤维。本发明采用醛加成反应将双功能的交联剂交联到纤维上，然后再络合抗菌离子，形成键能较高的共价键，不是一般洗涤强度可以断裂，因而产品抗菌能力耐久，经洗涤50次抗菌能力依然达到3A级标准；另外此加工技术较为简单，工业大规模生产上容易实现，具有很好的技术可行性和经济价值。
Description
技术领域
本发明涉及纺织品领域，尤其涉及一种抗菌纤维。
背景技术
随着社会经济的发展和人民生活水平的提高，人们对纺织品的要求，已从基本的保暖、舒适等要求，上升到希望纺织品同时兼具保健、安全等多功能。许多致病性微生物不仅会引起皮肤感染，分解人体代谢产物产生异味，危害人类身体、心理健康，而且会在人际之间传播，引发传染病，如院内感染。在病原的传播中，纺织品是重要的媒介之一。因而纺织品的抗菌加工技术就应运而生，现有的抗菌纤维一般是靠添加抗菌剂来实现的。抗菌加工方法分为两种：
一种是将抗菌剂加到成纤前的聚合物中，采用共混纺丝来制得抗菌纤维。这种抗菌剂可以是纳米金属及其氧化物，如纳米银、纳米铜、纳米氧化亚铜、纳米氧化锌等，或负载等处理后的纳米材料，如专利“一种十字异型铜抗菌纤维(CN107779981A)”，通过将纳米铜、添加剂和聚酯混合，制得功能性母粒，将母粒与聚酯混合后进行发纺丝。这种方法抗菌耐久性较好，但具有两项相冲突的特征导致实用性不强：一、抗菌性与添加剂含量有关，抗菌添加剂含量越高抗菌性越强，但是抗菌添加剂含量越高，纤维的物理指标会越差，因此添加量不能太大。二、因为抗菌添加剂是在纺丝前添加在母粒中，使得抗菌添加剂在母粒中均匀分布，而实际起到抗菌作用的仅有纺丝后纤维表面位置的添加剂才能起作用，纤维内部的抗菌剂实际上毫无用处，起不到抗菌作用，进一步增加纤维中添加剂的含量，则影响到纤维物理性能。
抗菌加工的另一种方法是使用抗菌剂对纤维进行后加工整理，也就是在纤维成纤纺丝完成后，用抗菌加工整理剂再处理，使抗菌剂与纤维结合，从而使纺织品获得抗菌性能。如发明专利“一种抗菌功能性纤维素纤维的制备方法（CN103422339B）”，该发明利用纤维上的环糊精对抗菌药物进行包合然后接枝到纤维素上制备抗菌纤维素。这种加工方法使用的有机抗菌剂用量少且效果显著，但多数属于溶出性抗菌剂，一经洗涤就会脱落，抗菌性能很快丧失，甚至还可能导致过敏等反应，这是标准FZ/T 73023-2006不允许的。后整理法使用无机抗菌剂时，多数是靠涂覆或者范德华力吸附。涂覆的涂层不耐洗涤，而且使纤维和纺织品显得僵硬。范德华力吸附（比如浸渍法，如专利 “HAP掺合银和铜抗菌剂复合涂层的制备方法(CN201410366746.4)”）加工的纺织品结合力不够强，不耐洗涤，较容易在盐存在的情况下脱附而丧失持久抗菌性能,且纤维僵硬，织物柔软度下降。另有中国专利CN108239881A中公开了一种抗菌纤维制备方法，在该方法中虽然采用了中间体（甲基丙烯酸二甲氨基乙酯）接枝方式将纤维与杀菌离子通过化学键连接在一起，解决了涂层式杀菌层不耐洗涤的缺陷；但是中间体一端到的接枝方式为采用辐射高能与纤维端接枝，这种方式不但具有能耗高，接枝率低、经济性差，无法应用于大规模工业生产以外，其中间产物（季胺化纤维产物）还可能具有一定的人体毒性，影响生育和胎儿发育（Toxicol. Sci. 2019,DOI:10.1093/toxsci/kfz139），需要进一步研究观察，不适合直接应用于直接穿戴的纺织品上；同时，中间体另一端通过离子键与高锰酸根结合实现杀菌效果，但是高锰酸根具有很强的氧化性，极易被还原而导致抗菌性流失；并且离子键不耐盐，而汗液和洗涤剂中盐是必然存在的，从而使得该产品的抗菌性有效期不长，另外高锰酸根离子本身带有紫红色，影响后续纺织品的染色过程。
发明内容
本发明所要解决的技术问题是提供一种醛亲核加成络合抗菌纤维、制备方法及应用，利用醛活性基团，采用醛亲核加成反应将双功能的交联剂交联到纤维上，然后再络合抗菌离子如Ag+、Cu2+、Zn2+，形成的强化学键（共价键）连接到纤维或纺织品上，解决了现有技术中抗菌有效成份不耐水洗、易融出，抗菌有效期短的缺陷。
本发明是这样实现的：一种醛亲核加成络合抗菌纤维制备方法，选取待改性纤维作为原料，所述待改性纤维素的糖单元上至少含有一个醛活性基团，制备方法包括以下步骤：
S1.交联反应，将待改性纤维浸轧于交联剂和催化剂的溶液中，通过醛与交联剂亲核加成反应得到改性纤维中间体；
所述交联剂至少含有一个和待改性纤维上的醛活性基团发生反应的亲核加成反应活性基团，同时交联剂还至少另含有一个络合活性基团与抗菌金属离子发生络合反应；
所述交联剂上亲核加成反应活性基团选自胺基-NH2、亚胺基-NH-或巯基-SH；
S2.交联剂洗涤，选用交联剂洗涤剂洗涤改性纤维中间体，使得改性纤维中间体上未成功交联到纤维上的交联剂被充分洗涤干净；
S3.络合反应，将洗涤后的改性纤维中间体浸轧于抗菌金属离子的盐溶液中，进行络合反应，得到抗菌纤维，最后洗涤、干燥得到抗菌纤维成品。
所述交联剂为如下所示的式(1)化合物或其盐：
其中:
R1代表碳C、氮N或磷P；
R2代表巯基-SH、胺基-NH2、亚胺基-NH-；
R3代表H、-CH3、-CH2CH3、-CH2CH2CH3、芳基、烯基或他们的卤素、硝基取代物；
R4、R5、R6相同或不同，各自代表亚甲基-CH2-、烯基团-CH=CH-、芳香基团，或以上基团的N、P、卤素、硝基取代基团；
R7、R8相同或不同，各自代表羧基羟基、羧基胺基、羧基巯基、多羧酸、多羧基羟基、多羧基胺基、多羧基巯基、多磷酸，或以上基团的盐；
n为0~20的自然数，m、k为0~5的自然数。
当所述R2代表巯基-SH、胺基-NH2、亚胺基-NH-时，所述交联剂洗涤剂为质量百分比浓度为0.001%～1%的十二烷基聚氧乙烯醚和碳酸钠的混合水溶液，所述混合水溶液中十二烷基聚氧乙烯醚与碳酸钠的质量比为10：1～1：1。
所述待改性纤维为纤维素纤维。
所述纤维素纤维包括棉、麻、再生纤维素基纤维。
所述步骤S1之前还包括步骤BS1，氧化处理，使用氧化剂对纤维素纤维进行氧化处理，将纤维素纤维上的末端易异构醛“-CHO”或2,3位仲羟基氧化处理为醛基“-HC=O”，得到预处理纤维；BS2.洗涤预处理纤维，使得预处理纤维上的氧化剂被充分洗涤干净。
所述步骤BS1中所述氧化剂选自高碘酸或其盐的水溶液；氧化催化剂选自磷酸、磺酸；溶液的质量百分比浓度为0.1%～30%，氧化催化剂用量为高碘酸的5%~30%；反应温度为室温至80℃，反应时间为1~60 min；BS2.洗涤预处理纤维，使得预处理纤维上的氧化剂被充分洗涤干净。
所述步骤S1之前还包括染色步骤，选用偶氮苯磺酸盐类或蒽醌类染色剂对纤维进行染色。
所述染色剂选择直接冻黄g或对氯磺酸蒽醌；染色采用轧染工艺，将织物在染液中经过短暂的浸渍后，随即用压辊轧压，将染液挤入纺织品的组织空隙中，并除去多余染液，使染料均匀分布在织物上，然后通过汽蒸过程进行固色处理，汽蒸温度80℃。
所述交联剂和催化剂的溶液质量百分比浓度为1%～10%；其中，交联剂与催化剂的质量比为1:1～10：1；所述交联反应的条件是：反应时间1min～60min；反应温度20～90℃。
所述催化剂选自硼酸类化合物、镍类催化剂、二氯二茂铪、FeCl3、AlCl3、吡啶、三乙胺。
所述抗菌金属离子选自Ag+、Cu2+、Zn2+或其中任意一种或多种的任意比例混合。
所述抗菌金属离子的质量为抗菌纤维成品干重的0.1%～30%。
所述步骤S3和BS2中的洗涤方式为使用清水进行浸轧洗涤或逆流洗涤，所述洗涤水用量为，水：抗菌纤维的体积比40:1～2:1；洗涤时间为30～50min；所述干燥时间为15～60min，温度为35℃～80℃的热风吹干。
一种醛亲核加成络合抗菌纤维。
一种醛亲核加成络合抗菌纤维的应用，将醛亲核加成络合抗菌纤维应用在纺织品上。
本发明醛亲核加成络合抗菌纤维、制备方法及应用中利用纤维上的醛活性基团，采用醛亲核加成反应将双功能的交联剂交联到纤维上，然后再络合抗菌离子如Ag+、Cu2+、Zn2+，形成的强化学键（共价键）连接到纤维或纺织品上。共价键键能较高，不是一般洗涤强度可以断裂，因而产品抗菌能力耐久，经洗涤50次抗菌能力依然达到3A级标准；另外此加工技术较为简明简单，工业大规模生产上容易实现，具有很好的技术可行性和经济价值。
附图说明
图1为本发明中纤维素纤维基本结构示意图；
图2为纤维素纤维中的2,3位仲羟基氧化为醛基示意图；
图3为本发明中纤维上的醛基与胺基的加成反应机理示意图；
图4为本发明中纤维上的醛基与含巯基亲核试剂的加成反应机理示意图；
图5为本发明中纤维提供醛基发生醛胺加成反应时所用的交联剂结构示意图；
图6为本发明中纤维提供醛基发生醛硫加成反应时所用的交联剂结构示意图；
图中：R和括号中的基团代表-(R0)i-H，R0代表亚甲基-CH2-、烯基团-CH=CH-、芳香基团，或以上基团的N、P、卤素、硝基取代基团；
R´代指双功能交联剂上除-NH2、-SH以外的其它基团、R1´代指纤维上糖单元其余基团；
i=0~20的自然数；j指代聚合度，其值为20~200000之间自然数。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明表述的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例
在本说明书中，除非另有说明，所有份数都是重量份。
一种醛亲核加成络合抗菌纤维制备方法，选取待改性纤维作为原料，所述待改性纤维素的糖单元上至少含有一个醛活性基团；
如图1所示，在本发明中，纤维素纤维可分为天然纤维素纤维如棉、麻类和再生纤维素纤维如Lyocell、Modal纤维、竹纤维、铜氨纤维等。这类纤维是由纤维素组成，纤维素（cellulose）是由葡萄糖组成的大分子多糖，不溶于水及一般有机溶剂。其还原性末端易异构为醛（-CHO），具有较好的反应活性。另外，如图2所示，2,3位的仲羟基也具有较强的活性，可在适宜的条件下氧化为醛基。
包括以下步骤：
S1.交联反应，将待改性纤维浸轧于交联剂和催化剂的溶液中，通过醛与交联剂亲核加成反应得到改性纤维中间体；
所述交联剂至少含有一个和待改性纤维上的醛活性基团发生反应的亲核加成反应活性基团，同时交联剂还至少另含有一个络合活性基团与抗菌金属离子发生络合反应，以提高抗菌金属离子附着在纤维上的牢固性，实现长效、抗洗涤的抗菌能力；所述交联剂上的醛亲核加成反应活性基团选自巯基-SH、胺基-NH2或亚胺基-NH-；
在本发明中，所述交联剂为如下所示的式(1)化合物或其盐：
其中:
R1代表碳C、氮N或磷P；
R2代表巯基-SH、胺基-NH2、亚胺基-NH-；
R3代表H、-CH3、-CH2CH3、-CH2CH2CH3、芳基、烯基或他们的卤素、硝基取代物；
R4、R5、R6相同或不同，各自代表亚甲基-CH2-、烯基团-CH=CH-、芳香基团，或以上基团的N、P、卤素、硝基取代基团；
R7、R8相同或不同，各自代表羧基羟基、羧基胺基、羧基巯基、多羧酸、多羧基羟基、多羧基胺基、多羧基巯基、多磷酸，或以上基团的盐；
n为0~20的自然数，m、k为0~5的自然数。
在本发明中，当待改性纤维为纤维素纤维时，为了提高易异构为醛-CHO的亲核加成反应的活性，确保最终产品的杀菌效果，所述步骤S1之前还包括预处理步骤BS1，氧化处理，使用氧化剂对纤维素纤维进行氧化处理，将纤维素纤维上的末端易异构醛“-CHO”氧化处理为醛基-HC=O，得到预处理纤维，经过氧化处理后的纤维素纤维活性位点更多，更易于进行后续的交联反应，能有效提高抗菌金属离子的负载量；BS2.洗涤预处理纤维，使得预处理纤维上的氧化剂被充分洗涤干净；氧化处理后需要充分洗涤，是因为氧化剂具有亲电性，氧化剂会与后续添加的交联剂中的络合活性基团发生反应，影响后续双功能交联剂中的络合活性基团与抗菌金属离子的络合反应。
所述步骤BS1中所述氧化剂选自高碘酸或其盐的水溶液；氧化催化剂选自磷酸、磺酸；溶液的质量百分比浓度为0.1%～30%，氧化催化剂用量为高碘酸的5%~30%；反应温度为室温至80℃，反应时间为1~60 min；BS2.洗涤预处理纤维，使得预处理纤维上的氧化剂被充分洗涤干净。
本发明中，所述的醛亲核加成反应分为如下两种情况：
情况一、如图3所示，当利用纤维上的羰基（醛、酮）与胺基、亚胺基发生加成反应时，形成的共价连接健为：
、
。
情况二、如图4所示，当利用纤维上的羰基（醛、酮）与含硫亲核试剂发生加成反应时，形成的共价连接健为：
。
S2.洗涤交联剂，选用交联剂洗涤剂洗涤改性纤维中间体，使得改性纤维中间体上未成功交联到纤维上的交联剂被充分洗涤干净；
这是因为未反应的交联剂也会络合金属离子，这部分未被交联上的交联剂即使可以络合金属离子，但将会被洗涤带出，既影响后续络合反应的效率，也影响处理后抗菌纤维抗菌性能的耐久性。因而需要将改性纤维中间体用交联剂洗涤剂清洁干净后再进行络合反应，因此交联剂洗涤剂的选用与交联剂有关；
在本发明中，所述交联剂洗涤剂通常包括表面活性剂C与助剂D混合而成；所述表面活性剂C选自磺酸盐类、硫酸盐类、苯磺酸盐类阴离子表面活性剂；聚氧乙烯醚类、烷醇酰胺类非离子表面活性剂；甜菜碱两性表面活性剂；所述助剂D选自三聚磷酸钠、硅酸钠、硫酸钠或碳酸钠；所述助剂D的选用与表面活性剂C相配合；
在本实施例中，作为优选，
当所述亲电加成反应交联基团为巯基-SH、胺基-NH2、亚胺基-NH-时，所述交联剂洗涤剂为质量百分比浓度为0.001%～1%的十二烷基聚氧乙烯醚和碳酸钠的混合水溶液，所述混合水溶液中十二烷基聚氧乙烯醚与碳酸钠的质量比为10：1～1：1；优选比例为3:1。
S3络合反应，将洗涤后的改性纤维中间体浸轧于抗菌金属离子的盐溶液中，进行络合反应，得到抗菌纤维，最后洗涤、干燥得到抗菌纤维成品；通常抗菌金属离子的盐溶液选自硫酸铜水溶液、硫酸锌水溶液、氯化锌水溶液、硝酸银水溶液。
在本实施例中，所述抗菌金属离子选自Ag+、Cu2+、Zn2+或其中任意一种或多种的任意比例混合，抗菌金属离子的质量为抗菌纤维成品干重的0.1%～30%。
氧化处理和络合反应后的洗涤方式优选为，使用清水进行浸轧洗涤或逆流洗涤，所述洗涤水用量为，水：抗菌纤维的体积比40:1～2:1；洗涤时间为30～50min；所述干燥时间为15～60min，温度为35℃～80℃的热风吹干。
在发生如图3所示的醛胺加成反应时，交联剂上的NH2、-NH-有孤对电子，易进攻呈正电性的醛基碳而发生亲核加成反应而交联起来。如图5所示，在本实施例中，所述交联剂选自以下化合物及其盐：聚羧酸胺类（I）（II）、羟基胺基羧酸类（III）（IV）（IX）、有机多元磷酸胺类（改性多元膦酸）（V）（VI）、多胺类（VII）（VIII）、硫醇基胺基羧酸类（X）、硫醇基多胺类（XI）、氨基羧酸类（改性氨基柠檬酸、改性酒石酸）（XII）、氨基巯基醇（XIII）（XIV）；这些物质都含有胺基（-NH2）或亚胺基（-NH-）。作为优选，通常情况下选用的交联剂为N-2(2-乙酰氨基)亚胺基二乙酸盐、羟乙基乙二胺二乙酸、3-氨基-1-羟基丙亚基-1,1-二磷酸、二甲基二烯丙基氯化铵-丙烯酸共聚物、乙胺乙二酸萘、二硫代氨基乙酸钠。
在发生如图4所示的醛硫加成反应时，交联剂上的-SH有孤对电子，易进攻呈正电性的醛基碳而发生亲核加成反应而交联起来。如图6所示，在本实施例中，所述交联剂选自以下化合物及其盐：羧基硫醇类（I）、巯基羧酸酯类（II）胺基羧基硫醇类（III）羧基羟基胺基硫醇类（IV）、巯基（氨基）有机多元磷酸类（改性多元膦酸）（V）（VI）多胺基硫醇类（VII、VIII）、多羟基硫醇类（IX）、胺基巯基硫醇类（XI）、多羟基硫醇类（XII）巯基羟基硫醇类（XIII），这些物质都含有巯基-SH基团作为反应官能团。作为优选，通常情况下选用的交联剂为2,3二巯基琥珀酸、季戊四醇四硫代乙醇酸酯、N-(羟甲基)-N-(2-巯基乙基)甘氨酸、三氮杂-2-基甲硫醇、(2-巯基丁烯-1,1-二基)双(膦酸)、4,5-二氨嘧啶-2-硫醇、3-巯基丙烷-1,2-二醇、丙烷1,2,3-三硫醇、2-(氨基甲基)丙烷-1,3-二硫醇、2,3-巯基丙酸、1,4-二巯基丁烷-2,3-二醇、2-氨基-3-巯基丙烷-1-醇。
在本发明中，所用的催化剂与交联剂相配合，在本实施例中，所述催化剂选自硼酸类化合物、镍类催化剂、二氯二茂铪、FeCl3、AlCl3、吡啶、三乙胺。所述交联剂和催化剂的溶液质量百分比浓度为1%～10%；
其中，交联剂与催化剂的质量比为1:1～10：1；所述交联反应的条件是：反应时间1min～60min；反应温度20～90℃；反应环境为水热反应、微波反应、超声反应。
本发明需要特别说明的是，考虑到成品的实际商用性，成品纤维不可能采用原色直接制作各类纺织品，必然需要对纤维进行染色，而成品络合后的纤维再进行染色时，某些染料会破坏络合的抗菌金属离子，而有些染色后的染料本身会覆盖住抗菌金属离子等等原因最终都会使得染色工艺可能影响到已经络合抗菌金属离子的纤维的抗菌性能，因此在本发明中，所述步骤S1之前还包括染色步骤，选用偶氮苯磺酸盐类或蒽醌类染色剂对纤维进行染色，当待改性纤维为纤维素纤维时，为了避免氧化剂对染色步骤的影响，所述染色步骤在BS2步骤之后。
在本实施例中，作为优选，所述染色剂选择直接冻黄g或对氯磺酸蒽醌；染色步骤中的染色采用轧染工艺，将预处理纤维浸轧于染色剂溶液中，浸泡10～60分钟后烘干，再汽蒸1～10分钟后，洗净、冷却至室温。
通过选用合适的染色剂，并控制染色工艺的参数，使得纤维能够被顺利上色且不会影响到后续的交联反应，以提高本发明醛亲核加成络合抗菌纤维的商业价值。
本发明中的醛亲核加成络合抗菌纤维的应用，可以单独或与其他纤维一起混纺应用在纺织品上。
下表1为实施例1～5中分别采用具体的参数，表2为所采用的交联剂的分子结构：
表1
表2
将实施例3所得的醛亲核加成络合抗菌纤维纺织成毛巾大小的织物后进行如下抗菌实验：
抗菌物质溶出性测试：
洗涤程序：根据FZ/T73023-2006抗菌针织品附录C.3标准化洗涤条件及程序进行1次洗涤后，抗菌织物中的抗菌物质的溶出性测试，结果如表3所示：
检测要求:安全性试验（抑菌圈法）
检测方法:安全性试验：FZ/T73023-2006抗菌针织品附录E抗菌物质的溶出性测试方法
| 检测菌种 | 大肠杆菌8099 | 金黄色葡萄球菌ATCC6538 | 白色念珠菌ATCC10231 |
| 培养时间(小时) | 18h | 18h | 48h |
| 抑菌圈宽度D(mm) | 0 | 0 | 0 |
表3为抗菌织物中的抗菌物质的溶出性测试结果
抗菌测试：
洗涤程序：根据FZ/T73023-2006抗菌针织品附录C.4简化洗涤条件及程序进行50次（10个完整洗涤循环）洗涤后的抗菌效果试验结果，如表4所示：
检测要求:抗菌效果试验
检测方法:抗菌效果试验：FZ/T73023-2006抗菌针织品附录D.8抗菌织物测试方法:振荡法
表4洗涤后的抗菌效果试验结果
备注: 标准空白样为100%纯棉布，样品灭菌方式为高压蒸汽灭菌（121℃,15min）。
Claims (18)
1.一种醛亲核加成络合抗菌纤维制备方法，其特征是，选取待改性纤维作为原料，所述待改性纤维素的糖单元上至少含有一个醛活性基团，制备方法包括以下步骤：
S1.交联反应，将待改性纤维浸轧于交联剂和催化剂的溶液中，通过醛与交联剂亲核加成反应得到改性纤维中间体；
所述交联剂至少含有一个和待改性纤维上的醛活性基团发生反应的亲核加成反应活性基团，同时交联剂还至少另含有一个络合活性基团与抗菌金属离子发生络合反应；
所述交联剂上亲核加成反应活性基团选自胺基-NH2、亚胺基-NH-或巯基-SH；
S2.交联剂洗涤，选用交联剂洗涤剂洗涤改性纤维中间体，使得改性纤维中间体上未成功交联到纤维上的交联剂被充分洗涤干净；
S3.络合反应，将洗涤后的改性纤维中间体浸轧于抗菌金属离子的盐溶液中，进行络合反应，得到抗菌纤维，最后洗涤、干燥得到抗菌纤维成品。
2.如权利要求1所述的醛亲核加成络合抗菌纤维制备方法，其特征是：所述交联剂为如下所示的式(1)化合物或其盐：
其中:
R1代表碳C、氮N或磷P；
R2代表巯基-SH、胺基-NH2、亚胺基-NH-；
R3代表H、-CH3、-CH2CH3、-CH2CH2CH3、芳基、烯基或他们的卤素、硝基取代物；
R4、R5、R6相同或不同，各自代表亚甲基-CH2-、烯基团-CH=CH-、芳香基团，或以上基团的N、P、卤素、硝基取代基团；
R7、R8相同或不同，各自代表羧基羟基、羧基胺基、羧基巯基、多羧酸、多羧基羟基、多羧基胺基、多羧基巯基、多磷酸，或以上基团的盐；
n为0~20的自然数，m、k为0~5的自然数。
3.如权利要求2所述的醛亲核加成络合抗菌纤维制备方法，其特征是：当所述R2代表巯基-SH、胺基-NH2、亚胺基-NH-时，所述交联剂洗涤剂为质量百分比浓度为0.001%～1%的十二烷基聚氧乙烯醚和碳酸钠的混合水溶液，所述混合水溶液中十二烷基聚氧乙烯醚与碳酸钠的质量比为10：1～1：1。
4.如权利要求2所述的醛亲核加成络合抗菌纤维制备方法，其特征是：所述待改性纤维为纤维素纤维。
5.如权利要求4所述的醛亲核加成络合抗菌纤维制备方法，其特征是：所述纤维素纤维包括棉、麻、再生纤维素基纤维。
6.如权利要求5所述的醛亲核加成络合抗菌纤维制备方法，其特征是：所述步骤S1之前还包括步骤BS1，氧化处理，使用氧化剂对纤维素纤维进行氧化处理，将纤维素纤维上的末端易异构醛“-CHO”或2,3位仲羟基氧化处理为醛基“-HC=O”，得到预处理纤维；BS2.洗涤预处理纤维，使得预处理纤维上的氧化剂被充分洗涤干净。
7.如权利要求6所述的醛亲核加成络合抗菌纤维制备方法，其特征是：所述步骤BS1中所述氧化剂选自高碘酸或其盐的水溶液；氧化催化剂选自磷酸、磺酸；溶液的质量百分比浓度为0.1%～30%，氧化催化剂用量为高碘酸的5%~30%；反应温度为室温至80℃，反应时间为1~60 min；BS2.洗涤预处理纤维，使得预处理纤维上的氧化剂被充分洗涤干净。
8.如权利要求1～7中任意一权利要求所述的醛亲核加成络合抗菌纤维制备方法，其特征是：所述步骤S1之前还包括染色步骤，选用偶氮苯磺酸盐类或蒽醌类染色剂对纤维进行染色。
9.如权利要求8所述的醛亲核加成络合抗菌纤维制备方法，其特征是：所述染色剂选择直接冻黄g或对氯磺酸蒽醌；染色采用轧染工艺，将织物在染液中经过短暂的浸渍后，随即用压辊轧压，将染液挤入纺织品的组织空隙中，并除去多余染液，使染料均匀分布在织物上，然后通过汽蒸过程进行固色处理，汽蒸温度80℃。
10.如权利要求8所述的醛亲核加成络合抗菌纤维制备方法，其特征是：所述交联剂和催化剂的溶液质量百分比浓度为1%～10%；其中，交联剂与催化剂的质量比为1:1～10：1；所述交联反应的条件是：反应时间1min～60min；反应温度20～90℃。
11.如权利要求8所述的醛亲核加成络合抗菌纤维制备方法，其特征是：所述催化剂选自硼酸类化合物、镍类催化剂、二氯二茂铪、FeCl3、AlCl3、吡啶、三乙胺。
12.如权利要求8所述的醛亲核加成络合抗菌纤维制备方法，其特征是：所述抗菌金属离子选自Ag+、Cu2+、Zn2+或其中任意一种或多种的任意比例混合。
13.如权利要求8所述的醛亲核加成络合抗菌纤维制备方法，其特征是：所述抗菌金属离子的质量为抗菌纤维成品干重的0.1%～30%。
14.如权利要求8所述的醛亲核加成络合抗菌纤维制备方法，其特征是：所述步骤S3和BS2中的洗涤方式为使用清水进行浸轧洗涤或逆流洗涤，所述洗涤水用量为，水：抗菌纤维的体积比40:1～2:1；洗涤时间为30～50min；所述干燥时间为15～60min，温度为35℃～80℃的热风吹干。
15.一种如权利要求1～7中任意一权利要求所述的制备方法所制得的醛亲核加成络合抗菌纤维。
16.一种如权利要求15所述的醛亲核加成络合抗菌纤维的应用，其特征是：将醛亲核加成络合抗菌纤维应用在纺织品上。
17.一种如权利要求8所述的制备方法所制得的醛亲核加成络合抗菌纤维。
18.一种如权利要求17所述的醛亲核加成络合抗菌纤维的应用，其特征是：将醛亲核加成络合抗菌纤维应用在纺织品上。
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