CN106415086A - 活性颗粒至基质中的引入 - Google Patents

活性颗粒至基质中的引入 Download PDF

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CN106415086A
CN106415086A CN201580009729.8A CN201580009729A CN106415086A CN 106415086 A CN106415086 A CN 106415086A CN 201580009729 A CN201580009729 A CN 201580009729A CN 106415086 A CN106415086 A CN 106415086A
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G·W·哈格奎斯特
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Cocona Co Ltd
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Abstract

活性颗粒结合体系，其包括活性颗粒，化学地键合至活性颗粒的材料，和包埋至所述活性颗粒和所述材料的至少一个的基质。

Description

活性颗粒至基质中的引入
发明领域
本发明涉及包括活性颗粒的材料。特别是，但不仅限于，本发明涉及使用染色方法将活性颗粒引入纺织品和聚合物中。
发明背景
使用各种各样的方法将活性颗粒引入织物。这些方法从在薄膜上印刷到在织物自身上引入活性颗粒，到通过产生纱线的母料将活性颗粒引入纱线。在所有这些方法中，为了实现来自产生最终产品时的活性颗粒的全部益处，应该防止所述活性颗粒失活、涂覆或覆盖。此外，为了实现添加活性颗粒的全部益处，所有这些方法需要在外部环境与活性颗粒表面之间的相互作用从而有利于活性颗粒存在于最终的产品中。
发明简述
为了产生包括未失活的活性颗粒的织物最终产品，开发了体系、织物和纤维。一个这样的实施方案包括活性颗粒结合体系。一种活性颗粒结合体系包括活性颗粒、化学地键合至活性颗粒的材料(即聚合物锚定物)和包埋有活性颗粒或聚合物锚定物的基质。该活性颗粒和/或聚合物锚定物的包埋发生在织物染色过程中。
另一个实施方案包括将一个或更多个活性颗粒偶联至作为织物产品一部分的纤维的方法。一个这样的方法包括将材料(聚合物锚定物)化学地键合至一个或更多个活性颗粒并使纤维溶胀。发生所述一个或更多个活性颗粒和该材料的至少一个至所述纤维的扩散。在这一点上，纤维体积减小，在该点上，将一个或更多个活性颗粒可操作地偶联至所述纤维或包埋在所述纤维中。
本发明的又一个实施方案包括纤维。一种这样的纤维包括可操作地偶联至活性颗粒的基质和化学地键合至活性颗粒的材料。在一个这样的实施方案中，所述材料可与基质混合，其中通过化学扩散使所述活性颗粒和所述材料的至少一个偶联至所述基质。
附图简述
当结合附图时，通过参考以下发明详述和所附的权利要求，本发明的各种目的和有利之处和更完整地理解是显而易见的并且更容易意识到的，其中：
图1描绘了根据本发明的一个实施方案的活性颗粒结合体系；
图1A描绘了根据本发明的一个实施方案的图1的140区域在溶胀状态下的近摄；
图1B描绘了根据本发明的一个实施方案的图1的140区域在非溶胀状态下的近摄；
图2描绘了可以采用本文中描述的实施方案进行的方法；和
图3描绘了根据本发明的一个实施方案的纤维。
发明详述
给出以下段落中位于引号(“”)中的术语和短语的定义。这些定义意在应用到贯穿该文件(包括在权利要求中，除非在上下文中另有明确指示)的术语和短语。此外，可适用的是，不管所述词语和短语的情形，所定义的词语或短语的时态、任意单数或复数变化，应用所阐明的定义。
如在该说明书和所附的权利要求中使用的术语“或”并不意味着具有排他性；然而该术语包括“两者之一或两者都有”的意思。在说明书中提及“一个实施方案”、“实施方案”、“优选的实施方案”、“可替代的实施方案”、“变型”、“一个变型”和相似的短语意指将与所述实施方案有关而描述的具体特征、结构或特性包括在本发明的至少一个实施方案中。在说明书的各种位置的短语的形态如“在一个实施方案中”、“在实施方案中”或“在变型中”并非必然意指涉及相同的实施方案或变型。
现在转向图1，所见的是用于产生织物和纺织品、在其中的其它产品中的活性颗粒结合体系100的一个实施方案。一个活性颗粒结合体系100包括活性颗粒110、材料120和基质130。活性颗粒110是具有孔或凹坑的颗粒，该孔或凹坑具有吸附或解吸呈固、液和/或气相和/或其组合的物质的空间。这些孔可以根据所使用的活性颗粒110的类型在尺寸、形状和数量方面变化。例如，一些活性颗粒110天然具有孔，例如火山岩，以及可以将其它活性颗粒110(如碳)用极端温度和活化试剂(如氧气)产生孔。
活性颗粒110可以性能增强性质提供给其中包括它们的物品。这样的性能增强特性包括气味吸附、水分处理、湿气捕获和释放、紫外线保护、红外线吸收率、化学试剂保护性质、生物危害保护性质、阻燃、抗菌保护性质、抗病毒保护性质、抗真菌保护性质、抗微生物保护性质、干燥剂性质及其组合。活性颗粒110可以包括，但是不限于活性炭、碳纳米管、卡宾、石墨、氧化铝(活性氧化铝)、硅胶、纯碱、铝三水合物、小苏打、对甲氧基-2-乙氧基乙基酯肉桂酸(西诺沙酯)、氧化锌、沸石、二氧化钛、二氧化硅、分子过滤类型材料和其它合适的材料。
在一个实施方案中，使材料120化学地键合至活性颗粒110。例如，可以使活性颗粒100初始用材料120处理或与其反应，以形成化学键。可以使用与活性颗粒100化学地键合并且也可与基质130混合的任意材料120。例如，材料的一部分可以结合至活性颗粒，而材料的另一部分可以偶联至基质130，如下文所示。材料120可以包括末端官能化的长链基团并且可以在本文中被称为长链基团、官能团、反应性基团、胺基团、锚定物或锚定基团。其它材料120类型包括涉及一个或更多纤维素、聚醚、末端官能化的胺基团、聚酯、聚乙烯醇、聚苯乙烯、聚丙烯酸系、改性聚丙烯酸系、聚丙烯、聚氨酯(脂族的和芳族的)、芳族聚酰胺和聚酰胺的长链基团。
基质130可以包括聚合物、聚合物共混物或天然纤维。此外，在本文中可以将基质130称为聚合物、聚合物纤维、天然纤维或纤维。在一个实施方案中，基质130可以包括一个或更多个聚酯或天然纤维基团。在这样的实施方案中，材料120可以包括具有末端官能化的胺基团的聚醚。在这样的实施方案中的活性颗粒110可以首先与末端官能化的胺基团的第一部分反应。一个第一部分可以包括末端官能化的胺基团的第一末端。第二部分(例如，末端官能化的胺基团的第二末端)可以偶联至基质130，如下文所述。因此，每个末端官能化的胺基团可以化学地键合至活性颗粒110并且偶联至基质130。
例如，在化学地键合至活性颗粒110时，将材料120(和/或活性颗粒110)引入基质130。在一个这样的实施方案中，在染色过程期间将长链基团用作锚定物而将活性颗粒110连接至纤维。本领域已知的各种染色方法，溶胀纤维(即基质130)保证这样的锚定物偶联至基质130。如图1A所示，看到在纤维溶胀期间的从图1的区域140的近摄。如所示，在这样的纤维130溶胀期间，在纤维颗粒125之间的空间135或体积足够大，以保证长链基团120匹配在纤维颗粒125之间。也可以在本文中将这样的体积称为“自由体积”。也可以在本文中将纤维颗粒125称为纤维分子。尽管空间135可以足够大，以容纳材料120，甚至在溶胀期间，空间135可以不足够大而保证活性颗粒110匹配在活性颗粒125之间。
现转向图1B，所见的是在纤维溶胀减退之后的图1的区域140的近摄。如所见的，图1B中在纤维颗粒125之间的空间135比如图1A中所见的在纤维溶胀期间的纤维颗粒125之间的空间135小。由于在基质130内的这种收缩，长链基团在微观上变成在纤维内缠结，锁定材料120和如图1所示的附接的活性颗粒110至纤维。当材料120可与基质130混合时，即当基质130和材料120包括相似或匹配的溶解度时，发生材料120和基质130的缠结。尽管未在图1A-1B中显示，但还设想空间135可以足够大，图1中所见的活性颗粒可以变成缠结，并且因此在微观上锁定或锚定在基质130的聚合物链中。
在溶胀期间，空间135的尺寸保证包括在约1至约100nm之间的粒度145的长链颗粒变成缠结在基质130中。随着额外溶胀，空间135可以包括保证包括约100nm直至约1微米的粒度145的长链颗粒变成缠结在基质130中的尺寸，并且随着另外的额外溶胀，空间135可以包括保证包括约1微米至约5微米的粒度145的长链颗粒缠结至基质130中的尺寸。
基质130可以包括一种或更多种以下材料来用于制造织物、丝线或任意其它的产品：聚酯、聚酰胺、芳族聚酰胺棉制品、羊毛、聚氨酯、改性丙烯酸系、聚丙烯酸系、人造纤维、聚丙烯，其它纺织纤维或本领域中已知的任意其它材料。可以考虑图1所示的基质130可以包括如图1B所示的预先溶胀的基质130，其包括偶联至材料120的基质。然而，基质130也可以或可替换地连接至活性颗粒110。如图1所示，通过使用长链基团作为锚定物将活性颗粒110偶联至基质130，与直接偶联至纤维的活性颗粒110’相比，将活性颗粒110的更大的表面积暴露至周围环境。在本文中也可以将活性颗粒110称为第一活性颗粒110并且在本文中可以将活性颗粒110’称为第二活性颗粒110’。
现在转向图2，可见将一个或更多个活性颗粒偶联至纤维的方法250。例如，一个或更多个活性颗粒可以包括图1中所示的活性颗粒110，并且纤维可以包括图1中所示的基质130。一种这样的方法在255处开始并且在260处包括将材料化学地键合至一个或更多个活性颗粒110。例如，如本文中所讨论，图1中所示的材料120可以化学地键合至活性颗粒110。在265处，方法250包括使纤维溶胀。例如，可以在本领域已知的纤维着色或染色过程中使纤维溶胀。然而，也考虑本领域已知的其它过程来使纤维溶胀。在270处，方法250包括使一个或更多个活性颗粒110和材料120的至少一个扩散至纤维中。例如，如以上关于图1A和1B所描述，在使纤维溶胀期间，空间135可以保证一个或更多个活性颗粒110和材料120扩散至纤维中并且可以发生长链颗粒120和纤维颗粒125的微观缠结。例如，缠结可以在步骤275处发生，其包括减少纤维体积。如关于图1A和1B所描述，在随着纤维从如图1A中所示的经溶胀状态转换到如图1B中所示的非溶胀状态，纤维颗粒125之间的空间135减小时，可以发生纤维体积的减少。将一个或更多个活性颗粒110可操作地偶联至纤维的在285处的步骤也如上文参考图1A和1B以及长链材料120和/或活性颗粒110(如图1中所示)与纤维颗粒125的微观缠结的随附的公开所描述。
随着在265处使纤维溶胀，在270处使一个或更多个活性颗粒和材料的至少一个扩散至纤维中，在275处减少纤维体积且在285处在染色过程期间也可以发生可操作地将一个或更多个活性颗粒偶联至纤维。纤维染色可以通过一个或更多个常规的、分散体或超临界二氧化碳(CO2)染色方法来进行。因此，在一个实施方案中，可以将超临界CO2染色过程用于帮助执行方法250的步骤265、270、275和285并且通过使用材料120将活性颗粒100引入纤维110。一种这样的材料120可以是在这样的过程期间存在的CO2。因此，使用超临界CO2的一个有利之处在于这样的过程可以不需要超出CO2的任何其它化学品来执行活性颗粒100至纤维110的结合。采用这样的实施方案，所述CO2可以起本文中所描述的材料120的作用。此外，通过仅使用CO2，因为在过程中没有其它化学品存在，所以更可能防止活性颗粒100在染色过程中失活。
当将材料偶联至活性颗粒的孔和/或表面区域时发生活性颗粒的失活，并且阻断它们的吸收，吸附和解吸物质的能力。活性颗粒是包括可以吸收、吸附和解吸物质的或具有吸收、吸附和解吸物质的潜力的孔或其它表面区域特征的颗粒。当阻断或抑制活性颗粒的孔和/或表面区域吸附某些分子尺寸的物质时，活性颗粒可以以识货的状态离开。然而，这并不总是意味着永久地排出这些孔/表面区域吸附所述物质。活性颗粒的孔/表面区域可以通过再活化或复原而解锁或解禁(即一般地或基本上返回到它们的原始状态)。再活化或复原除去了活性颗粒的孔中捕限的物质，阻断它们的活性。然而，如果有害物质被活性颗粒吸附，则再活化或复原可以使活性颗粒的吸附能力还原是不太可能的。
在一个实施方案中，在具有或不具有保护层辅助以防止活性颗粒永久失活的织物染色过程期间，可以将活性颗粒施加至基质。一种这样的保护层可以包括密封剂。密封剂是可除去的物质，其通过阻止过早失活(例如，防止吸附有害或无意的物质或通过其它不利的条件失活)保持与活性颗粒有关的性质。在预定的时间并且当经受施加一个或更多个预定条件(例如热、时间等)或物质(例如水、光、分散剂、溶剂等)时，可以将密封剂从活性颗粒移除。所述密封剂可以包括，但是不仅限于，水溶性表面活性剂、其它表面活性剂类型、盐(例如，氯化钠、氯化钙)、聚合物盐、聚乙烯醇、蜡(例如，石蜡、巴西棕榈蜡等)、光反应性材料、可生物降解材料、不同于可生物降解材料的可降解材料、乙氧基化的炔属二醛和任意其它合适的物质。然而通过使用CO2染色过程，因为在所述过程期间不存在有害物质，所以可以不需要这样的密封剂。
可以考虑将材料120化学地键合至一个或更多个活性颗粒110的步骤260可以包括在使纤维溶胀之前将材料120化学地键合至一个或更多个活性颗粒110，在使纤维溶胀期间将材料120化学地键合至一个或更多个活性颗粒110，或二者。例如，在使纤维溶胀之前(例如，在染色过程(例如但不限于超临界CO2过程)开始之前)可以通过单独的化学键合过程将活性颗粒110化学地键合至上述一个或更多个材料120。在发生活性颗粒110和材料120的结合之后，活性颗粒/材料组合可以在染色过程开始之前或在所述过程的任意点进入染色过程。
如先前所描述，材料120可以包括一个或更多个长链基团。在这样的实施方案中，使一个或更多个活性颗粒110和材料120的至少一个扩散至纤维中的步骤270可以包括通过一个或更多个活性颗粒110和一个或更多个长链基团的尺寸自动选择一个或更多个活性颗粒110和一个或更多个扩散至纤维中的长链基团。例如，参考图1A和1B如上所示和描述，可以基于空间135的尺寸和纤维颗粒125之间的体积发生扩散。如果在使纤维溶胀期间空间/容积展开并且足够大，则可以使活性颗粒110在基质130内扩散。然而，如果活性颗粒110比体积/空间更大，则将不会使活性颗粒110在基质130内扩散。因此，活性颗粒越大，越难于扩散。类似地，在使纤维溶胀期间，空间/体积可以足够大以发生长链基团和基质130的扩散。然而，如果纤维并未溶胀，则因为空间/容积可能不足以使长链基团变得与纤维颗粒125缠结，所以不太可能发生长链基团和基质130之间的扩散。因此，长链基团和活性颗粒110的尺寸决定是否使活性颗粒110和/或长链基团偶联至基质130，其中自动地选择适当尺寸的长链基团和活性颗粒110(变得缠结的那个)作为锚。因此，通过一个或更多个活性颗粒110和一个或更多个长链基团的尺寸自动选择一个或更多个活性颗粒110和一个或更多个扩散至纤维中的长链基团包括基于适应于匹配在基于基质130中的空间135(即体积)的在经溶胀的纤维中的一个或更多个区域中的一个或更多个活性颗粒110和一个或更多个长链基团的尺寸容纳一个或更多个活性颗粒110和一个或更多个长链基团。减少纤维体积包括消除多个纤维颗粒125之间的空间。在一个这样的实施方案中，基质130可以包括聚酯并且材料120可以包括具有用于将聚醚连接至纤维的末端官能化的胺基团的聚醚。
如图1中所示，通过材料120扩散至纤维中而偶联至纤维的第一活性颗粒110的暴露至周围环境(围绕体系100的区域)的表面积比通过第二活性颗粒110′扩散至纤维中而偶联至纤维的第二活性颗粒110′的暴露至周围环境的表面积更大。所述方法250在290处结束。
本发明的另一个实施方案在本文中被称为纤维。图3所见的纤维305类似于上文参考图1描述的体系100，并且在此引入本文中涉及体系100的描述和适用图3中对纤维305的全部描述。类似地，纤维305的以下描述可以适用于图1所见的体系100。
在一个实施方案中，纤维305包括具有基质330的聚合物材料和至少一个活性颗粒310。可以将材料320化学地键合至活性颗粒310。如上文所描述，材料320应该是与基质330可混溶的(相容地可溶的)，包括与活性颗粒310化学地键合的反应性基团，且活性颗粒310和材料320的至少一个通过扩散偶联至基质。例如，使图3中所见的活性颗粒310′偶联至基质330。此外，反应性基团可以包括具有末端官能化的胺基团的聚醚。如上文所描述，活性颗粒310和/或材料320可以在染色过程(例如但不限于超临界CO2染色过程)期间通过使基质330溶胀时的扩散而偶联至基质330。可以考虑末端官能化的胺基团可以包括大量长链基团并且至少其中一个长链基团化学地键合至活性颗粒。在这样的实施方案中，可以发生至少其中一个长链基团至基质中的扩散。
一种锚定基团可以包括活性部分或位点，其化学地键合至活性颗粒100。可以在开始染色方法之前包括这样的锚定基团或长链基团120可以在染色方法期间连接至活性颗粒100。一种长链基团120可以与纤维110相容和可混溶。此外，染色方法可以充分溶胀纤维110以使得活性颗粒100或锚定基团扩散至纤维110中。不需要粒度预分级。过程本身将会对可以扩散至经溶胀的纤维中的颗粒进行尺寸选择。在发生染色之后的超临界CO2程序中回收未使用的活性颗粒。
本领域技术人员可以容易认识到可以对本发明进行的很多变型和替代，其用途及其结构实现本文中所描述的实施方案所实现的基本相同的结果。因此，并不意图本发明限制在所公开的示例性形式。许多变型、改变和替代性结构落入如权利要求中所阐述的本公开的发明的范围和精神之内。

Claims (21)

1.活性颗粒结合体系，包括：
活性颗粒；
化学地键合至活性颗粒的材料；和
包埋至所述活性颗粒和所述材料的至少一个的基质。
2.根据权利要求1所述的活性颗粒结合体系，其中，
所述基质包括包含多个聚合物链的预先溶胀的基质；和
使多个聚合物链的至少一部分通过微观缠结连接至所述活性颗粒和所述材料的至少一个。
3.根据权利要求2所述的活性颗粒结合体系，还包括存在于基质中的多个聚合物链之内的自由体积。
4.根据权利要求3所述的活性颗粒结合体系，其中在基质从溶胀状态转换至非溶胀状态时，多个聚合物链之间的体积减少。
5.根据权利要求1所述的活性颗粒结合体系，其中所述材料与预先溶胀的基质是可混溶的。
6.根据权利要求1所述的活性颗粒结合体系，其中使预先溶胀的基质在染色过程期间连接至所述活性颗粒和所述材料的至少一个。
7.将一个或更多个活性颗粒偶联至纤维的方法，包括：
将材料化学地键合至一个或更多个活性颗粒；
使所述纤维溶胀；
使所述一个或更多个活性颗粒和所述材料的至少一个扩散至所述纤维中；
减少纤维体积；和
可操作地将一个或更多个活性颗粒偶联至纤维。
8.根据权利要求7所述的方法，其中将材料化学地键合至一个或更多个活性颗粒包括以下之一：
在使所述纤维溶胀之前将所述材料化学地键合至一个或更多个活性颗粒；和
在使所述纤维溶胀期间将所述材料化学地键合至一个或更多个活性颗粒。
9.根据权利要求7所述的方法，其中使所述纤维溶胀发生在超临界CO2过程期间以使所述纤维染色。
10.根据权利要求7所述的方法，其中使所述纤维溶胀发生在分散过程期间以使所述纤维染色。
11.根据权利要求7所述的方法，其中
所述材料包括一个或更多个长链基团；
使所述一个或更多个活性颗粒和所述材料中的至少一个扩散至所述纤维中包括通过所述一个或更多个活性颗粒和所述一个或更多个长链基团的尺寸自动选择所述一个或更多个活性颗粒和所述一个或更多个长链基团以扩散至所述纤维中。
12.根据权利要求11所述的方法，其中，通过所述一个或更多个活性颗粒和所述一个或更多个长链基团的尺寸自动选择所述一个或更多个活性颗粒和所述一个或更多个长链基团以扩散至所述纤维中包括容纳适应于匹配在经溶胀的纤维中的一个或更多个区域中的所述一个或更多个活性颗粒和所述一个或更多个长链基团的尺寸。
13.根据权利要求12所述的方法，其中，在经溶胀的纤维中的一个或更多个区域适应于容纳所述一个或更多个活性颗粒和所述一个或更多个长链基团。
14.根据权利要求7所述的方法，其中，
减少纤维体积包括减小多个纤维颗粒之间的空间；
所述纤维包括聚酯；
所述材料包括与纤维素、聚醚、改性聚丙烯酸系、末端官能化的胺基团、聚酯、聚乙烯醇、聚苯乙烯、聚丙烯酸系、聚丙烯、聚氨酯(脂族的和芳族的)、芳族聚酰胺和聚酰胺的一个或更多个相关的末端官能化的长链基团的至少一个；和
将所述材料用于使聚醚连接至所述纤维。
15.根据权利要求7所述的方法，其中，
通过将所述材料扩散至纤维中而偶联至纤维的第一活性颗粒的暴露至周围环境的第一表面积比通过将第二活性颗粒扩散至所述纤维中而偶联至所述纤维的第二活性颗粒的暴露至周围环境的第二表面积更大。
16.引入一个或更多个纤维的纺织品，其中一个或更多个纤维包括：
基质；
活性颗粒；
化学地键合至所述活性颗粒的材料；其中，
所述材料与所述基质是可混溶的；和
所述活性颗粒和所述材料的至少一个通过扩散偶联至所述基质。
17.根据权利要求16所述的纺织品，其中，
使所述活性颗粒和所述材料的至少一个在纺织品染色过程期间在使所述基质溶胀时通过扩散偶联至所述基质；和
所述材料包括反应性基团。
18.根据权利要求17所述的纺织品，其中，
所述染色过程包括超临界CO2染色过程；和
所述纤维包括聚合物材料。
19.根据权利要求17的纺织品，其中所述反应性基团包括与纤维素、聚醚、改性聚丙烯酸系、末端官能化的胺基团、聚酯、聚乙烯醇、聚苯乙烯、聚丙烯酸系、聚丙烯、聚氨酯(脂族的和芳族的)、芳族聚酰胺和聚酰胺的一个或更多个相关的末端官能化的长链基团的至少一个。
20.根据权利要求19所述的纺织品，其中
所述末端官能化的胺基团包括多个长链基团；
使所述长链基团的至少一个化学地键合至所述活性颗粒；和
发生所述长链基团的至少一个至基质中的扩散。
21.根据权利要求16所述的纺织品，其中，使所述材料偶联至所述基质。
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