CN112533871B - 包括5种不同类型的铜化合物的具有抗菌和/或杀生物活性的微结构化多复合铜微米颗粒 - Google Patents
包括5种不同类型的铜化合物的具有抗菌和/或杀生物活性的微结构化多复合铜微米颗粒 Download PDFInfo
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Abstract
一种具有抗菌和/或杀生物活性的铜微米颗粒,其中每个微米颗粒具有规则、结晶且微结构化的组合物,所述规则、结晶且微结构化的组合物包括5种不同的铜化合物:块铜矾Cu3 +2(SO4)(OH)4、水胆矾Cu4 +2SO4(OH)6、胆矾Cu+2SO4·5H2O、钠铜矾NaCu2 +2(SO4)2OH·H2O和水合氢氧化硫酸铜Cu3(SO4)2(OH)2·4H2O/2CuSO4·Cu(OH)2·4H2O,其中所述微米颗粒的大小介于5μm与50μm之间。一种用于制备具有抗菌和/或杀生物活性的铜微米颗粒的方法。一种具有抗菌和/或杀生物活性的浓缩的聚合物组合物(母料),所述浓缩的聚合物组合物(母料)在挤出过程期间并入到熔融聚合物中以形成如纤维、细丝和片材等刚性或柔性产物。一种具有抗菌和/或杀生物活性的铜微米颗粒的用途。一种具有抗菌和/或杀生物活性的浓缩的聚合物组合物(母料)的用途。
Description
技术领域
本发明涉及一种具有抗菌和/或杀生物活性的微结构化多复合铜微米颗粒,在其结构上包括5种不同类型的铜化合物,所有铜化合物均为规则的且结晶的,所述铜化合物解释了以下微米颗粒的有利结构特性:块铜矾Cu3 +2(SO4)(OH)4、水胆矾Cu4 +2SO4(OH)6、胆矾Cu+ 2SO4·5H2O、钠铜矾NaCu2 +2(SO4)2OH·H2O、水合氢氧化硫酸铜Cu3(SO4)2(OH)2·4H2O/2CuSO4·Cu(OH)2·4H2O。微结构化多复合微米颗粒的均质组成使5种不同铜化合物中的每一种铜化合物的差异释放速度特性在其所并入的整个材料中均能够为均匀的,并且每种铜化合物在微米颗粒结构所存在的所有地方中同时单独执行其抗菌和/或杀生物作用。由于在同一微结构化微米颗粒中包含了五种铜化合物,因此具有这些化合物的均质且均匀的分布,所述分布也使得能够使用更少的剂量,从而有助于材料的半透明特性。
微结构化多复合微米颗粒的产生过程在于由处于凝胶状态的氢氧化铜的分散体的制备,所述分散体是用硫酸铜于水中溶液作为溶剂乳化的,紧接着此分散体/溶液之后为热空气流中的喷雾干燥过程。
还公开了微米颗粒在具有抗菌和/或杀生物活性的材料的产生中的用途。
本发明的范围还包含浓缩的聚合物组合物(母料(masterbatch)),所述浓缩的聚合物组合物包括可以包含在其它/各种材料中以赋予其抗菌和/或杀生物活性的所描述的微结构化多复合铜微米颗粒和聚合物或树脂。特别地,所述母料可以用于具有抗菌和/或杀生物活性的多层片材的结构化中。
背景技术
在聚合物和树脂中应用铜盐和铜微米颗粒,以用于控制生长增殖。
多药抗性微生物的出现已经引发了对能够对抗细菌增殖而又不会如目前所使用的药剂那样获得抗性的新型化合物的研究(Betancourt等人,2016)。
纳米技术的发展已允许创建尺寸在微米和纳米范围内的材料,所述材料作为抗微生物剂显示出了非常有前途的特性(Chatterjee等人,2014)。纳米颗粒和微米颗粒具有独立或作为其它分子的转运蛋白而起作用的能力,并且借助于其表面积、体积和结构的特性,可以触发生物响应(Chatterjee等人,2014)。
铜是用于形成纳米颗粒和微米颗粒的化学元素之一。铜化合物和络合物在调配物和产物中已经用于对液体、固体和人类组织进行消毒(Delgado等人,2011)。
来自现有技术的不同文献已经描述了将铜化合物和铜纳米颗粒/微米颗粒并入到固体中,目的是产生具有抗菌和/或杀生物特性的产物。
在纺织型材料和纤维的情况下,文献US 8183167(B1)公开了与示出抗微生物活性的铜和/或银纳米颗粒共价结合的织物底物。
文献US 5458906A呈现了一种用于用抗菌化合物(其中包括铜)处理可生物降解底物的方法。US 7754625B2描述了一种抗微生物织物,所述抗微生物纺织品包括与抗微生物剂组合的一种或多种天然或合成纤维或细丝,其中所述抗微生物剂包括主要量的水溶性锌盐与至少一种抗微生物银离子源和至少一种铜离子源的组合。
文献US 7169402B2呈现了一种抗微生物和抗病毒聚合物材料,所述抗微生物和抗病毒聚合物材料具有包封在其中的离子化铜的微观颗粒,所述抗微生物和抗病毒聚合物材料包含在要形成的产物的表面中。
在文献CL201300332(WO 2014117286A1)中,公开了一种植物、动物或合成来源的可浸渍底物或占不同比例的含有对应于Cu4SO4(OH)6的抗微生物化合物的其混合物。
文献CL201500921公开了一种纤维素基材料,所述纤维素基材料并入了对应于铜化合物、混合的铜微米颗粒或纳米颗粒的抗菌剂。还包含一种用于制造纤维素基材料的方法,所述方法包含添加铜微米颗粒或纳米颗粒的步骤。
文献CL 201503652进而呈现了一种显示出表面保护抗菌活性的半透明粘合剂膜,所述粘合剂膜包括铜、壳聚糖、明胶和戊二醛的纳米颗粒。
已经为食品工业专门开发了用于包装食品的各种材料。文献WO 2014001541 A1、WO 2012127326 A1和WO 2000053413 A1描述了含有铜颗粒的聚合物材料的产生,所述铜颗粒出于在食品包装中使用的目的,具有抗菌和/或杀生物特性。这些文献中设想的材料包含铜化合物或铜颗粒,其中主要为氧化铜。
尽管有关于将支撑在不同类型的载体上的铜化合物和铜微米颗粒或其混合物添加在底物和聚合物材料中以赋予抗菌特性的几个先前的先决条件,但是关于铜的氧化状态的提议却有所不同。铜的氧化状态将影响此类铜的溶解度,以及因此其在从聚合物材料中的释放行为中的溶解度;而且,所使用的不同载体往往会使必要的颗粒膨大。
关于用于包装或容器的抗菌和/或杀生物材料,需要在容器中产生快速且瞬时的释放,以抑制微生物在食品上的表面生长,所述表面生长会使食物变质并且在包装时就存在(RAM细菌)。中期释放对于抑制由对每个操作的特定处理、温度变化和存储等引起的爆发也是必要的。因此,在实践中,必要的是材料包含具有一定溶解度(Kps)并维持铜的浓度的铜微米颗粒,所述溶解度使其能够随着时间的推移而立即释放、持续释放和残留释放,所述浓度允许其具有抗菌和/或杀生物作用,但是所述浓度也为允许避免与此化合物相关联的毒性或过量迁移到接触的食品中的铜浓度。换句话说,需要在铜的较低浓度下具有改进的抗菌和/或杀生物作用的材料。
本发明的微米颗粒的具体组成使得能够产生半透明材料,这在食品包装材料的情况下是重要特性,因为颗粒不具有任何载体来支撑其并使其膨大,给予材料半透明性。
在本发明的情况下,提出了产生包括5种类型的铜化合物,每种化合物具有不同溶解度(Kps)的铜的微米颗粒的方法。在一方面,在与水分接触时会瞬时解离的硫酸铜化合物(Kps=4x10-36)-快速释放铜化合物-将使其可能在接触其的材料中产生直接且立即的抗菌和/或杀生物作用。在另一方面,氢氧化铜化合物(Kps=2.2x10-14)-具有较低溶解度的化合物-的存在将赋予其随着时间的推移而持续的杀菌和/或杀生物作用。此微米颗粒提供其能够提供5种不同的铜化合物的优势以及其各自的不可转让的品质和优势,所述品质和优势在被引入到最终聚合物或其所放置的任何地方时提供在同一地方或物理空间中,从而在同一地方和物理空间中同时提供单独化合物中的每一个化合物的所有品质和优势,这在以下时是必不可少的条件:需要低剂量,以避免半透明性的损失和可能传递到接触的产物的铜的释放,而不会减少其抗菌和/或杀生物功效,随着时间的推移、全部在同一地方中、在均质形式下并且与食品或其它类型的产物或不需要高水平的自由循环铜离子的表面接触时有效。因此,由于根据本发明的微米颗粒的具体组成,可以均质地且以低剂量提供5种铜化合物中的每种铜化合物的抗菌和/或杀生物作用。
附图说明
图1-本发明的铜微米颗粒的样本的扫描电子显微镜图像。a)以10.00KX的放大率获得的图像;b)2.50KX的放大率下图像,c)500X y的放大率下图像,d)以100X的放大率获得的图像。
图2-借助与EDS检测器耦接的扫描电子显微镜确定本发明的铜微米颗粒的元素组成。在a)中,呈现了构成微米颗粒的以下元素的映射结果:碳、氧、硫和铜;b)示出了本发明的铜微米颗粒的元素组成的图。
图3-本发明的铜微米颗粒的样本的X射线衍射图谱。由表示的衍射图对应于块铜矾Cu3 +2(SO4)(OH)4,对应于水胆矾Cu4 +2SO4(OH)6,对应于胆矾Cu+2SO4·5H2O,对应于钠铜矾NaCu2 +2(SO4)2OH·H2O,并且对应于水合氢氧化硫酸铜Cu3(SO4)2(OH)2·4H2O/2CuSO4·Cu(OH)2·4H2O。
具体实施方式
本发明涉及一种微结构化多复合铜微米颗粒,在其组成中包括5种不同类型的铜化合物:块铜矾Cu3 +2(SO4)(OH)4、水胆矾Cu4 +2SO4(OH)6、胆矾Cu+2SO4·5H2O、钠铜矾NaCu2 +2(SO4)2OH·H2O和水合氢氧化硫酸铜Cu3(SO4)2(OH)2·4H2O/2CuSO4·Cu(OH)2·4H2O,其在形状上均为规则的且结晶的,这给予微米颗粒有利的结构特性。作为本发明的范围的一部分的微米颗粒的限定的大小介于5μm与50μm之间,具体地介于10与40之间,并且更具体地介于10μm与15μm之间。
以上描述的微米颗粒通过包括以下步骤的方法的方式产生:
a)以1:10w/w的比率制备溶解的硫酸铜于蒸馏水的溶液;
b)向在步骤a)中获得的溶液中添加10%w/v氢氧化钠溶液和蒸馏水,直到获得pH介于4与6之间的溶液为止;
c)24小时后,分离上清液和沉淀物,所述沉淀物为氢氧化铜凝胶;
d)将在步骤c)中获得的处于凝胶状态的沉淀物在以1:5w/v的比率制备的硫酸铜于蒸馏水中的溶液中乳化;
e)在优选地介于220℃与280℃之间的入口温度以及优选地介于80℃与100℃之间的出口温度下,优选地借助于喷雾干燥器使在步骤d)中获得的乳液经受干燥过程。
在执行使用温度处于所指示的范围内的类型喷雾干燥器的干燥器的步骤d)时,会产生微米颗粒,其中所述微米颗粒中的每个微米颗粒均含有5种不同类型的铜化合物:块铜矾Cu3 +2(SO4)(OH)4、水胆矾Cu4 +2SO4(OH)6、胆矾Cu+2SO4·5H2O、钠铜矾NaCu2 +2(SO4)2OH·H2O和水合氢氧化硫酸铜Cu3(SO4)2(OH)2·4H2O/2CuSO4·Cu(OH)2·4H2O,其与组分的混合物或其附聚物没有可比性,而是相反,其为包括5种化合物的单个微结构化微米颗粒。
本发明的范围包含用于塑料行业或用于其它材料的浓缩的聚合物复合物(被称为母料),所述浓缩的聚合物复合物包括可以包含在材料中从而赋予其抗菌和/或杀生物活性的所描述的铜微米颗粒和聚合物或树脂。特别地但非排他性地,所述母料可以用于具有抗菌和/或杀生物活性的多层片材的形成。
本发明旨在解决的技术问题是提供包括5种类型的铜的新颖类型的微米颗粒,所述铜均为规则的、结晶的,并且微结构化组成实现了对给予其抗菌和/或杀生物特性的铜离子的控制释放。包含在微米颗粒中的5种不同铜化合物的差异释放的动力学使接触时的主要抗菌和/或杀生物作用以及随着时间的推移由于存在于其中的其它种类的铜的二次释放和随后释放而持续的抗菌和/或杀生物作用成为可能。另一方面,具有这些特性的铜微米颗粒可以形成浓缩的聚合物组合物或母料的一部分,所述一部分可以在挤出过程期间并入到用于形成刚性模具、纤维、细丝和片材的熔融聚合物中,以用于产生并入微米颗粒并且具有抗菌和/或杀生物活性以及以上所描述的技术特性和优点的膜、片材或结构的目的。
此结构化微米颗粒也可以直接或以混合物形式使用,以在其所放置的地方产生抗菌和/或杀生物作用。
5种类型的铜作为一种微米颗粒和相同微米颗粒的一部分的目标放置提供了关于其解离和释放的程度的实质技术优势。此外,包括此多组成的此铜微米颗粒的添加改进了微米颗粒的分散性,因为块铜矾Cu3 +2(SO4)(OH)4、水胆矾Cu4 +2SO4(OH)6、胆矾Cu+2SO4·5H2O、钠铜矾NaCu2 +2(SO4)2OH·H2O和水合氢氧化硫酸铜Cu3(SO4)2(OH)2·4H2O/2CuSO4·Cu(OH)2·4H2O将以以相同的比例存在于整个材料中,这使得能够实现抗菌和/或杀生物活性连同有利地非常小的剂量以及5种类型的均质分布,这还有有助于其所并入的材料,如包装膜、覆盖膜或刚性模具等的半透明性。另外,构成微米颗粒的化合物中的所有化合物均呈结晶形式,从而维持有序的、非无定形结构,所述有序的、非无定形结构实现了具有要限定的特定特性的特定通用结构。
本发明还提供了铜微米颗粒和浓缩的聚合物组合物(母料)的用途,所述铜微米颗粒和浓缩的聚合物组合物如适用于在接触时具有抗菌和/或杀生物活性并且持续作用的材料的制备。微米颗粒所包括的组分的微结构配置允许当材料与细菌和/或病原体剂接触时,其同时与铜化合物直接接触,从而在接触时发挥立即抗菌和/或杀生物作用。具有不同溶解度和/或解离度的5种不同铜化合物的存在还使得所公开的微米颗粒的抗菌和/或杀生物活性的持续作用能够存在。
当在本发明中提到材料具有“杀生物活性”时,其意指微米颗粒能够抑制细菌和真菌的发展和生长。
当说明材料具有“抗菌活性”时,其意指微米颗粒抑制或阻止细菌的增殖。
在本发明中,术语“微结构化”意指材料-在此情况下为微米颗粒-是由形成其的一组相或组分组成的。在材料科学的领域中,据说材料的微结构决定其特性。
在本发明中,术语“多复合”意指微米颗粒同时包括某种不同化合物组。
术语“母料”是指浓缩的聚合物组合物,所述浓缩的聚合物组合物包括将并入到要产生的材料中的元素的预混物。
落入本发明的范围内的材料可以包含但不限于聚合物、纤维、织物、各类型的玻璃、树脂等。聚合物包含但不限于聚丙烯(PP)、聚乙烯(PE)、聚对苯二甲酸乙二酯(PET)、乙烯-乙酸乙烯酯(EVA橡胶)等。
在本发明的一个实施例中,微米颗粒可以进一步包括具有抗菌作用的其它金属和非金属化合物。这些化合物包含但不限于锌化合物、铅化合物、镉化合物、银化合物等。
以下呈现的示例性应用展示了本发明的但未限制其范围的一个实施例。
示例性应用
实例1:铜微米颗粒的产生
通过将含有100g/l的五水化硫酸铜的硫酸铜溶液碱化来制备构成微米颗粒的氢氧化铜,所述硫酸铜溶液应产生完全可溶的溶液。然后需要将氢氧化钠或具有OH碱的另一种碱稀释成含10%的水;将此溶液缓慢地并且在搅动下添加到所制备的硫酸铜溶液中,直至达到介于4与6之间的pH值为止,其中产生以下反应:
CuSO4(ac)+2Na(OH)(ac)→Cu(OH)2(s)+Na2SO4(ac)
反应产生含氢氧化铜的溶液的凝胶状态的沉淀物,并且在24小时之后去除上清液。
以1:5的比率将含有氢氧化铜的所得沉淀物在硫酸铜溶液中乳化。在介于220℃与280℃之间的入口温度以及80℃到100℃的出口温度下,使用喷雾干燥器使含有硫酸铜的溶解的离子相和呈凝胶形式的另一种相(如氢氧化铜)的此悬浮液经受干燥过程。
实例2:铜微米颗粒的表征
为了表征借助于实例1中所描述的协议的方式产生的铜微米颗粒的结构、大小和分布,执行了扫描电子显微镜(SEM)分析。
所述SEM分析是使用扫描电子显微镜(SEM)、使用EDS模式的具有Penta FET精确检测器的Zeiss型EVO MA 10、牛津仪器公司(Oxford Instruments)X-act执行的。此分析在于扫描(固体)铜微米颗粒的粉末的代表性样本以及选择代表性区域,以确定微米颗粒的元素组成。
根据不同放大率下的SEM图像,观察到颗粒具有规则的球形形状和非均质的大小分布(图1a-d)。借助于与显微镜耦接的EDS检测器,确定了微米颗粒的元素组成,并且确立了其是由元素铜、硫和氧构成的(图2a-b)。
关于颗粒的大小,评估了从两个独立的颗粒样本提取的图像的四个独立的代表性区域。确定了颗粒的测微大小介于7微米-22微米之间(参见表1)。
表1-铜颗粒的代表性大小
样本MB-1(μm) | 样本MB-2(μm) | |
测量结果1 | 10.52 | 7.480 |
测量结果2 | 19.44 | 10.88 |
测量结果3 | 7.61 | 21.94 |
测量结果4 | 7.363 | 13.61 |
平均值 | 11.23 | 13.48 |
为了确定微米颗粒的具体化学组成并确定所含有的铜的类型的氧化状态,执行了X射线衍射分析。基于此分析,通过各种化合物的存在确定了X射线衍射图谱(图3)。
为了限定微米颗粒存在中的化合物,咨询了结晶粉末PDF-2数据库,并将其与获得的图谱进行了比较。确定了本发明的微米颗粒是由5种类型的铜化合物构成的:块铜矾、水胆矾、胆矾、钠铜矾和水合氢氧化硫酸铜(表2)。
表2-铜微米颗粒的化学组成
化合物名称 | 化学结构 |
块铜矾 | <![CDATA[Cu<sub>3</sub><sup>+2</sup>(SO<sub>4</sub>)(OH)<sub>4</sub>]]> |
水胆矾 | <![CDATA[Cu<sub>4</sub><sup>+2</sup>SO<sub>4</sub>(OH)<sub>6</sub>]]> |
胆矾 | <![CDATA[Cu<sup>+2</sup>SO<sub>4</sub>·5H<sub>2</sub>O]]> |
钠铜矾 | <![CDATA[NaCu<sub>2</sub><sup>+2</sup>(SO<sub>4</sub>)<sub>2</sub>OH·H<sub>2</sub>O]]> |
水合氢氧化硫酸铜 | <![CDATA[Cu<sub>3</sub>(SO<sub>4</sub>)<sub>2</sub>(OH)<sub>2</sub>·4H<sub>2</sub>O/2CuSO<sub>4</sub>·Cu(OH)<sub>2</sub>·4H<sub>2</sub>O]]> |
实例3:母料的制备铜微米颗粒到多层聚合物片材的添加
实施例2中所描述的微米颗粒可以包含在不同的聚合物材料和树脂中,以形成多层纤维和片材。在此实施例中,描述了在制备浓缩的聚合物组合物(母料)时遵循的方案以及将其包含在树脂和聚合物中的条件。
a)浓缩的聚合物组合物(母料)的制备
为了制备母料,制备了聚合物材料和微米颗粒的预混物。为此,将树脂或聚合物材料在磨机中经受粉碎,然后与微米颗粒冷混合。
根据以下树脂或聚合物的类型,将预混物在介于120℃与250℃之间的温度下熔融:聚丙烯(PP)、聚乙烯(PE)、PET,EVA橡胶,并使其传递通过粒料挤出机,这会产生被称为母料的粒料。
b)将母料包含在熔融聚合物的挤出过程中以形成多层材料。
可以将母料添加到用于形成刚性或柔性聚合物,如纤维、细丝和片材的熔融聚合物的挤出过程中。借助于此程序产生的片材可以对应于多层结构,其中每个片材的厚度介于5μm与120μm之间,更具体地介于5μm与30μm之间;也就是说,可能形成可以含有聚合物树脂,如PE、PA、PP和/或PET的这些层中的2个、3个以及甚至5个层的最终材料。
实例4:具有微结构化铜微米颗粒的多层聚合物材料的抗菌和/或杀生物作用。
为了评估具有微结构化铜微米颗粒的多层材料的抗菌和/或杀生物作用,执行了由细菌培养物的添加构成的测试,所述细菌培养物先前已在由不同聚合物构成的多层材料的表面上生长。评估了对大肠杆菌(Escherichia coli)和金黄色葡萄球菌(Staphylococcus aureus)的抗菌和/或杀生物作用。
将多层材料在细菌生长所需的温度下温育24小时。一旦温育期结束,就对材料上的菌落形成单位执行计数,并将其与不含有铜微米颗粒的材料进行比较。根据添加到母料中的聚合物的类型对两种类型的片材进行了测试:1)由聚丙烯和铜微米颗粒制成的片材(添加到母料中的2%w/w);以及2)由乙烯-乙酸乙烯酯(EVA橡胶)制成的片材,其具有添加到母料中的微结构化铜微米颗粒。
结果表明,当将由聚丙烯和微结构化铜微米颗粒(添加到母料中的2%w/w)构成的片材的菌落形成单位(CFU)计数与不包含母料的组分的对照片材进行比较时,具有铜微米颗粒的片材显示出CFU的数量减少了99%,并且细菌计数已减少了3个数量级(表3)。在由乙烯-乙酸乙烯酯(EVA橡胶)和铜微米颗粒构成的片材的情况下,观察到等效现象,这反映出相对于对照材料而言,在包括母料的片材上测试的细菌的CFU计数降低(表4)。
表3:由聚丙烯和铜微米颗粒(2%w/w)制成的片材上的菌落形成单位的计数。
表4-由乙烯-乙酸乙烯酯(EVA橡胶)和铜微米颗粒构成的片材上的菌落形成单位的计数。
Claims (13)
1.一种具有抗菌和/或杀生物活性的铜微米颗粒,其特征在于,每个微米颗粒具有规则、结晶且微结构化的组合物,所述规则、结晶且微结构化的组合物包括5种不同的铜化合物:块铜矾Cu3 +2(SO4)(OH)4、水胆矾Cu4 +2SO4(OH)6、胆矾Cu+2SO4·5H2O、钠铜矾NaCu2 +2(SO4)2OH·H2O和水合氢氧化硫酸铜Cu3(SO4)2(OH)2·4H2O/2CuSO4·Cu(OH)2·4H2O,
其中所述微米颗粒的大小介于5μm与50μm之间。
2.根据权利要求1所述的具有抗菌和/或杀生物活性的铜微米颗粒,其特征在于,所述微米颗粒的大小介于5μm与50μm之间。
3.根据权利要求1所述的具有抗菌和/或杀生物活性的铜微米颗粒,其特征在于,所述微米颗粒的大小介于10μm与40μm之间。
4.根据权利要求1所述的具有抗菌和/或杀生物活性的铜微米颗粒,其特征在于,所述微米颗粒的大小介于10μm与15μm之间。
5.根据权利要求1至4中任一项所述的具有抗菌和/或杀生物活性的铜微米颗粒,其特征在于,其能够进一步包括其它金属抗菌化合物和非金属抗菌化合物。
6.根据权利要求5所述的具有抗菌和/或杀生物活性的铜微米颗粒,其特征在于,所述其它金属抗菌化合物选自锌化合物、铅化合物、镉化合物和银化合物。
7.一种用于制备根据权利要求1所述的具有抗菌和/或杀生物活性的铜微米颗粒的方法,其特征在于,其包括以下步骤:
a)以1:10w/w的比率制备溶解的硫酸铜于蒸馏水中的溶液;
b)向在步骤a)中获得的所述溶液中添加10%w/v氢氧化钠溶液和蒸馏水,直到获得pH介于4与6之间的溶液为止;
c)24小时之后,分离上清液和沉淀物,所述沉淀物为氢氧化铜凝胶;
d)将在步骤c)中获得的处于凝胶状态的所述沉淀物在以1:5w/v的比率制备的硫酸铜于蒸馏水中的溶液中乳化;
e)在介于220℃与280℃之间的入口温度以及介于80℃与100℃之间的出口温度下,通过喷雾干燥器使在步骤d)中获得的乳液经受干燥过程。
8.一种具有抗菌和/或杀生物活性的浓缩的聚合物组合物,所述浓缩的聚合物组合物在挤出过程期间并入到熔融聚合物中以形成刚性或柔性产物,其特征在于,其包括根据权利要求1至4中任一项所述的铜微米颗粒以及至少一种聚合物或树脂。
9.根据权利要求8所述的浓缩的聚合物组合物,其特征在于,所述刚性或柔性产物选自纤维、细丝和片材。
10.根据权利要求8所述的浓缩的聚合物组合物,其特征在于,所述聚合物或树脂对应于但不限于聚丙烯(PP)、聚乙烯(PE)、聚对苯二甲酸乙二醇酯(PET)、乙烯-乙酸乙烯酯(EVA橡胶)、聚苯乙烯(PS)、丁苯橡胶(SBR)、聚氯乙烯(PVC)、聚四氟乙烯(PTFE)、甲基丙烯酸酯(PMMA)、聚酯、脂肪族聚酰胺、聚对苯二甲酰胺、芳酰胺(芳香族聚酰胺)、刚性和柔性聚氨酯、硅树脂。
11.一种根据权利要求1至6中任一项所述的具有抗菌和/或杀生物活性的铜微米颗粒的用途,其特征在于,所述具有抗菌和/或杀生物活性的铜微米颗粒用于制备在接触时具有抗菌和/或杀生物活性并且具有持续作用的材料。
12.一种根据权利要求8-10中任一项所述的具有抗菌和/或杀生物活性的浓缩的聚合物组合物的用途,其特征在于,所述具有抗菌和/或杀生物活性的浓缩的聚合物组合物用于制备在接触时具有抗菌活性并且具有持续作用的材料。
13.一种根据权利要求8-10中任一项所述的具有抗菌和/或杀生物活性的浓缩的聚合物组合物的用途,其特征在于,所述具有抗菌和/或杀生物活性的浓缩的聚合物组合物用于制备在接触时具有抗菌活性并且具有持续作用的多层片材。
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