CN101384679B - 响应性涂覆颗粒 - Google Patents

响应性涂覆颗粒 Download PDF

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CN101384679B
CN101384679B CN2007800051548A CN200780005154A CN101384679B CN 101384679 B CN101384679 B CN 101384679B CN 2007800051548 A CN2007800051548 A CN 2007800051548A CN 200780005154 A CN200780005154 A CN 200780005154A CN 101384679 B CN101384679 B CN 101384679B
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V·加尔斯坦
D·S·萨鲁姆
F·F·舍曼
R·M·鲁皮特斯基
S·米科
M·莫托诺夫
R·B·谢帕洛维奇
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Abstract

本发明公开了一种包括至少一种颗粒的响应性涂覆颗粒，所述颗粒包括响应性涂层连接到其上的面间表面，所述响应性涂层包括：(a)至少一种基于硅氧烷的基本疏水的聚合物和(b)至少一种基本亲水的聚合物，其中所述响应性涂覆颗粒处于第一状态。

Description

响应性涂覆颗粒
发明领域
本发明涉及在颗粒的面间表面上提供的响应性涂层。具体地讲，本发明涉及在颗粒的面间界面上形成的响应性涂层，所述响应性涂层包括至少一种基本疏水的聚合物和至少一种基本亲水的聚合物。更具体地讲，本发明涉及当暴露于外部刺激(环境条件或时间的改变)时可从第一状态转换为至少第二状态(例如从基本亲水状态转换为基本疏水状态)的响应性涂层。
发明背景
固/液界面处的交互作用，例如蛋白质吸附、细胞粘着和生物污染，可由基质的最外表面决定。为了改善产品的界面性能，希望增强或阻止与特定基质有关的润湿属性。例如，为了改善舒适性，已希望推进有关特定产品的可润湿特性的技术，所述特定产品包括例如女性护理制品和失禁制品、婴儿护理产品、织物护理产品以及一般来讲一次性制品。已采用多种技术来解决这些问题，但未能提供商业上可行的基质，该基质提供消费者护理产品内的各种用途。
例如，2005年左右开发的Nanopin薄膜拥有高度不寻常的疏水性。此类技术特征在于具有“荷叶效应”，据此所述表面表现出疏水特性，即，极差的可润湿特性与高的液体接触角。接触Nanopin薄膜表面的水滴形成具有大约178°的润湿接触角的几乎完美的球体。
尽管诸如Nanopin薄膜的疏水表面可提供大量的商业优点，但涂覆基质表面以提供此类疏水条件未能解决用于各种用途的商业上可行的问题。例如，可期望将表面形成或涂覆成在第一场合表现出亲水性，但是当施加外部刺激时，可转换为在第二场合表现出疏水性。另一个实例可包括期望将表面形成或涂覆成在最终场合表现出疏水性，但需要涂层在初始时为亲水状态，以便允许物质分散在含水介质中。不受理论的约束，消费者可期望一种包括亲水性颗粒并且为了清洁目的而被施用到家用表面上的液体溶液。当被沉积并干燥时，亲水性颗粒可从第一亲水状态转换为第二疏水状态，以防止诸如生物流体的生物污垢物质粘附到表面上。
为了增强基质的润湿性来用于如上所示的商业用途，必需提出允许此类亲水与疏水状态之间的转换发生，尤其是当施加外部刺激和/或环境条件改变时。由于现有技术未能公开此类结构，更不用说形成此类结构的方法，因此本发明通过本文所公开的颗粒克服了此类不足和缺点。
发明概述
本发明涉及一种包括至少一种颗粒的响应性涂覆颗粒，所述颗粒包括响应性涂层连接到其上的面间表面，所述响应性涂层包括：(a)至少一种基于硅氧烷的基本疏水的聚合物和(b)至少一种基本亲水的聚合物，其中所述响应性涂覆颗粒处于第一状态。
发明详述
虽然在说明书之后提供了特别指出和清楚地要求保护本发明的权利要求书，但是据信，通过下面的描述可以更好地理解本发明。
除非另有说明，在本文中描述的所有百分比份数和比例都是基于组合物的总重量计的。除非另外指明，有关所列成分的所有这些重量都是基于活性水平，并因此不包括市售材料中可能包括的载体或副产物。本文中，术语“重量百分比”可表示为“％重量”。除了提出的实际测量值的具体实施例之外，本文所参考的数值应视为受单词“约”限制。
除非另外指明，本文所用的所有分子量均为重量平均分子量，以克/摩尔表示。
如本文所用，“包含”是指可加入不影响最终结果的其它步骤和其它成分。该术语包括术语“由...组成”和“基本上由...组成”。本发明的组合物和方法/工艺可以包括本文描述的本发明的必需部件和限制以及本文描述的任何另外的或任选的成分、组分、步骤或限制，由它们组成，或者基本上由它们组成。
如本文所用，术语“基质”是指任何有机的、无机的、合成的或非合成的表面。基质的实例包括但不限于半导体晶片、皮肤、组织、硬表面和软表面、细胞、机织材料和非织造材料、毛发、衣服、纺织物、以及它们的组合。
术语“颗粒”被理解为单个颗粒或颗粒的聚集体。
如本文所用，术语“面间表面”是指隔开单相或多相的任何区域。此类多相包括但不限于固-液相、液-气相、固-气相和固-固相。尽管本发明的面间表面涉及固-气相，但据理解其它相在存在时也将满足需要。
本发明涉及在颗粒的部分表面或整个表面上的响应性涂层。该响应性涂层由连接到颗粒的面间表面上的一种或多种聚合物构成。此类颗粒可用来与基质的界面相互作用，其中可润湿性得以增强。
本发明的颗粒可为软质、硬质、有机的、无机的、或它们的混合物，并且可选自由下列物质组成的组：氧化物、金属和金属合金。例如，本发明的硬质无机颗粒可包括但不限于氧化铝、氧化镁、铁、氧化铁、二氧化钛、二氧化硅、锌、氧化铁锌、氧化锌。本发明的软质有机颗粒可包括但不限于具有表面基团的树状高分子，例如聚磷(酰氨基胺)(PAMAM)和聚丙烯亚胺；硅倍半氧烷聚合物；聚苯乙烯；聚甲基丙烯酸甲酯；聚乙烯；尼龙；三聚氰胺(聚亚甲基三聚氰胺)；聚乳酸；葡聚糖；以及脱乙酰壳多糖。本发明的颗粒可根据其杨氏模量值(GPa)选择。本发明的颗粒可具有约0.01GPa至约1000GPa的杨氏模量值。本发明的软质有机颗粒可具有约0.01GPa至约10GPa的杨氏模量值。本发明的硬质无机颗粒可具有约50GPa至约1000GPa的杨氏模量值。
响应性涂覆颗粒应足够小，以便最大程度地减少对所述颗粒粘附到其上的基质的视觉表面属性的干涉作用。因此，所述颗粒可具有约1nm、约10nm、约20nm或者约50nm且不超过约1μm、不超过约500nm、不超过250nm、或不超过约100nm的粒度。所述颗粒也可为圆形、片状、椭圆形、球形、圆柱形、管状或不规则形状。
本发明的聚合物可为基本疏水的、基本亲水的、基本疏油的、基本亲油的、或它们的混合物。本发明的基本疏水的聚合物可选自硅氧烷基团、氟基、或它们的混合物。具体地讲，本发明的基于硅氧烷的基本疏水的聚合物可包含硅氧烷聚合物，具体地讲聚二甲基硅氧烷(PDMS)或氨丙基封端的PDMS。本发明的基本亲水的聚合物可为高分子电解质，具体地讲聚氮丙啶(PEI)。具体地讲，基本亲水的聚合物可选自由下列物质组成的组：聚环氧乙烷及其衍生物、聚丙烯酰胺及其衍生物、聚烷基(丙烯酸)及其盐、聚苯乙烯磺酸及其盐、以及它们的混合物。聚合物可以不同的量连接到颗粒上。例如，基本疏水的聚合物的70％可包含PDMS，而基本亲水的聚合物的剩余30％可包含PEI。
不受理论的约束，本发明的响应性涂层可包含聚二甲基硅氧烷(PDMS)作为基本疏水的聚合物。PDMS具有大约负125℃(-125℃)的玻璃化转变温度(Tg)，和大约负40℃(-40℃)的熔点(Tm)。PDMS含有非常柔韧的硅氧烷键，并且PDMS的玻璃化转变温度使得在PDMS主链的设计和改性中具有附加柔韧性。例如，可将功能聚合物添加到PDMS主链中以改变PDMS的玻璃化转变温度。PDMS还具有比大多数其它弹性体材料更高的气体渗透性。PDMS提供的一个重要特征是由硅氧烷聚合物表面产生的非常低的表面能。PDMS具有大约20达因/厘米的表面能。由于具有可用性和在理想pH下的良好溶解度，聚氮丙啶(PEI)可以被选作基本亲水的聚合物。其提供用于接枝到颗粒表面上的反应基团(胺基)。
基本疏水的聚合物与基本亲水的聚合物的质量比率可大于约0.01，大于约0.05，大于约1.0，大于约2.0或小于约100，小于约50.0，小于约10.0，小于约8.0或小于约2.0。例如，基本疏水的聚合物与基本亲水的聚合物的质量比率可为约0.01至约100。
本发明的聚合物通过接枝连接到颗粒的面间表面上以形成响应性涂层。诸如聚合物的选择、连接到所选聚合物上的官能团以及聚合物的质量比率等特定因素的组合是用于设计本发明颗粒的响应性涂层的多种因素之一。所谓“设计”是指响应性涂层由上述因素规定，以存在于诸如基本疏水性、基本亲水性、基本疏油性、基本亲油性或它们的组合的特定状态下。“第一状态”被认为是颗粒存在的第一状态。之后状态可相应接续(第二状态、第三状态等等)。术语“响应”用于描述涂覆颗粒在暴露于外部刺激时的行为，所述刺激包括但不限于环境、pH、极性、温度以及基质表面(纹理、类型(固体、液体、气体)、材料等等)。颗粒可沉积在基质上，其中所述基质将存在于特定第一状态下。由于基质上颗粒的存在，所述基质将对任何外部刺激作出响应以提供有利的可润湿性。
不受理论的约束，响应性涂覆颗粒可包括含有PDMS和PEI的涂层，其中由于基本亲水的聚合物(PEI)，所述涂层使得颗粒基本处于亲水的第一状态。当包含此类颗粒的组合物暴露于诸如热量的外部刺激时，所述颗粒可通过从基本亲水的第一状态转换为基本疏水的第二状态而作出“响应”。这些颗粒还可暴露于具有约5.5pH的酸性溶液，其中所述颗粒可通过从基本疏水的第二状态转换为基本亲水的第三状态而再次作出“响应”。
本发明的颗粒也可作为响应的一部分经受反转或者从一个状态转换为另一状态。例如，包含本发明的基本疏水颗粒的组合物可暴露于诸如紫外线、pH或温度的外部刺激下，使得颗粒从第一基本疏水状态转换为第二基本亲水状态。一段时间之后，颗粒可回复至基本疏水的状态而无需另外暴露于外部刺激。
因此，本发明的颗粒可保持在特定状态直到暴露于外部刺激。然而，时间也可作为担当触发物的有意或无意的因素，以使得颗粒转换。然而，颗粒的响应由其设计决定。此类行为是涂层的示例，并因此是本发明的响应性涂覆颗粒的示例。
实例
以下实例进一步描述和说明了本发明保护范围内的实施例。所给的这些实例仅仅是说明性的，不可理解为是对本发明的限制，因为在不背离本发明精神和范围的条件下可以进行许多更改。
实例1
二氧化硅纳米颗粒(粒度：0.014μ，表面积：200±25m2/g)在真空烘箱中于120℃下干燥12小时，随后立即用于硅烷化(参见下文)。将1g的二氧化硅颗粒在超声波浴槽中分散到200mL的甲苯中，持续2小时。将2mL的GPS(3-(环氧丙氧)丙基三甲氧基硅烷)添加到分散体中并在室温下搅拌混合物12小时。然后，颗粒通过离心从硅烷化混合物中分离出，再次分散到甲苯中，并再次离心。用甲苯再一次重复该洗涤过程。最终离心之后，将颗粒再次分散到MEK(甲基乙基酮)中，颗粒浓度为1％。在下一步中，将GPS改性的颗粒(20mL的1％MEK中分散体)与4g PDMS(带末端氨基官能团的聚二甲基硅氧烷，分子量30K)混合，接下来在低于50℃的温度下蒸发溶剂。将聚合物颗粒混合物分成三份。将混合物在真空烘箱中于90℃下加热3小时(样本#1)，在80℃下加热1小时(样本#2)，在70℃下加热1小时(样本#3)以实现PDMS层三种不同的接枝密度。颗粒通过离心分离出，再次分散到MEK中，并再次离心。重复该洗涤过程三次以移除未接枝的PDMS。以与PDMS的接枝相同的方式进行PEI(聚乙烯亚胺，分子量25K)的接枝。接枝温度为90℃，每个样本的接枝时间为3小时。在移除未接枝的PEI之后，将颗粒在pH2下分散到水中。随后通过添加NaOH溶液调节混合物的pH至pH5。改性的可转换颗粒最终存在于水分散体中。
实例2
合成步骤开始于将GPS共价接枝到聚甲基倍半硅氧烷颗粒(300nm)上，接下来是聚(二甲基硅氧烷)(PDMS)和聚乙烯亚胺(PEI)的随后接枝。将0.4mL的GPS添加到40mL的1％甲基乙基酮(MEK)中颗粒分散体溶液中，并在室温下搅拌混合物12小时。然后，颗粒通过离心从硅烷化混合物中分离出，再次分散到MEK中，并再次离心。再次重复该洗涤过程三次。在下一步中，将GPS改性的颗粒(40mL的1％MEK中分散体)与10％氨丙基封端的聚(二甲基硅氧烷)(分子量30000)混合。在水浴中于70℃下加热混合物6小时，同时剧烈搅拌。之后，通过上述离心方法洗涤掉分散体的未反应聚合物。将PDMS接枝的颗粒分散体(MEK中1％)分成四份。每份与无水PEI(分子量25000)混合，浓度按重量计为10％。在水浴中于70℃下加热混合物，同时剧烈搅拌多次，以便实现不同的PEI层接枝密度。通过上述离心方法洗涤掉颗粒的未反应PEI，随后分散到包含按重量计1％固体的超纯水中。
本文所公开的尺寸和数值不应理解为严格局限于所引用的精确数值。相反，除非另外指明，每个这样的尺寸是指所引用数值和围绕那个数值的功能上等同的范围。例如，公开为“40mm”的尺寸是指“约40mm”。在发明详述中引用的所有文件都在相关部分中引入以供参考。对于任何文件的引用不应当解释为承认其是有关本发明的现有技术。当本发明中术语的任何含义或定义与引入以供参考的文件中术语的任何含义或定义矛盾时，应当服从在本发明中赋予该术语的含义或定义。
虽然已经举例说明和描述了本发明的具体实施方案，但是对于本领域技术人员来说显而易见的是，在不背离本发明实质和范围的情况下可以做出多个其他改变和变型。因此，权利要求书意欲包括在本发明范围内的所有这样的改变和变型。

Claims (13)

1.一种包括至少一种颗粒的响应性涂覆颗粒，所述颗粒包括响应性涂层，所述响应性涂层包括：
a.至少一种基于硅氧烷的基本疏水的聚合物；和
b.至少一种基本亲水的聚合物，
一旦涂覆所述颗粒，所述聚合物连接到所述颗粒的面间表面，使得所述颗粒被规划处于第一状态，一旦接触外部刺激，所述颗粒产生响应并从其第一状态转化为可区别的第二状态。
2.如权利要求1所述的响应性涂覆颗粒，其中所述基于硅氧烷的基本疏水的聚合物包含PDMS。
3.如权利要求1所述的响应性涂覆颗粒，其中所述基本亲水的聚合物包含PEI。
4.如权利要求1所述的响应性涂覆颗粒，其中所述基于硅氧烷的基本疏水的聚合物与所述基本亲水的聚合物的质量比为约0.01至约100。
5.如权利要求4所述的响应性涂覆颗粒，其中所述基于硅氧烷的基本疏水的聚合物与所述基本亲水的聚合物的质量比为约0.05至约10.0。
6.如权利要求1所述的响应性涂覆颗粒，其中所述颗粒为约1nm至约1μm。
7.如权利要求1所述的响应性涂覆颗粒，其中所述第一状态是亲水状态。
8.如权利要求1所述的响应性涂覆颗粒，其中所述颗粒具有约0.01GPa至约1000GPa的杨氏模量值。
9.如权利要求8所述的响应性涂覆颗粒，其中所述颗粒为具有约0.01GPa至约10GPa杨氏模量值的软质有机颗粒。
10.如权利要求8所述的响应性涂覆颗粒，其中所述颗粒为具有约50GPa至约1000GPa杨氏模量值的硬质无机颗粒。
11.一种将如权利要求1所述的响应性涂覆颗粒从所述第一状态转换为至少第二状态的方法，所述方法包括以下步骤：
使所述颗粒接触至少一种外部刺激以产生转化，其中所述颗粒处于不同于所述第一状态的第二状态。
12.如权利要求11所述的方法，其中不接触附加的刺激所述颗粒从所述第二状态回到所述第一状态。
13.如权利要求12所述的方法，其中所述颗粒接触附加的刺激，使得所述处于第二状态的颗粒处于不同于所述第一和第二状态的第三状态。
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