CN102802421A - 用于输送次卤酸盐的聚合物系统 - Google Patents
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Abstract
本发明涉及用于稳定、存储和输送次卤酸盐的聚合物系统。一种系统包括涂覆有两个层的材料:一个层由聚乙二醇环氧化物和三聚氰胺溶液备,另一个层由无机次卤酸盐溶液制备。该材料可以是织物、棉、竹、纤维素材料、纤维素与合成纤维的混合。还描述了包括该系统的杀菌材料。另一系统包括具有预先成形的空间的材料,其涂覆有次卤酸盐的水-聚乙二醇溶液并由成膜聚合物包裹。两个系统内的次卤酸盐在一些情况下稳定存储至少三个月。
Description
相关申请的交叉引用
本申请要求于2010年1月21日提出的名称为“用于输送次卤酸盐的聚合物系统”的美国临时专利申请序列号61/297,129的权益,并在此全文引用作为参考。
技术领域
本公开总体上涉及无机次氯酸盐和次溴酸盐,特别涉及固体次氯酸盐和次溴酸盐的聚合物输送系统。
背景技术
无机次氯酸盐,诸如次氯酸钠和次氯酸钙,以及次溴酸盐,诸如次溴酸钠和次溴酸钙,是非常优秀的消毒剂,已证明对于广泛的微生物有效并具有突出的安全记录。但是,在一般实践中,这些盐很难操作、储存、运输和/或应用。有些情况下,这些材料的储存稳定性很差,因而保质期一般很短。如果暴露于大气中,这些材料的保质期以天来计,甚至以小时来计。有些情况下,这些盐或者溶于溶液中,或者以固体颗粒或片剂的形式存在,这在许多应用中难以使用。
发明内容
本发明的一个实施方式是一种输送稳定储存的次卤酸盐的方法,其中,使含有聚乙二醇环氧化物(polyethylene glycol epoxide)和三聚氰胺的第一水溶液与材料接触。第一水溶液在该材料上干燥。使该材料与含有次卤酸盐的第二水溶液接触并干燥。该材料中的次卤酸盐在暴露于大气时可以稳定达至少3个月。在一些实施方式中,所得到的材料在与大气接触3个月后,仍保留至少约90%的最初保存的次卤酸盐。
本发明的另一实施方式是一种输送稳定储存的次卤酸盐的方法,其中,将含有预先成形的空间的多种材料与含有次卤酸盐和聚乙二醇的水溶液接触,来形成含有次卤酸盐的具有预先成形的空间的材料。将这些材料加入到由成膜聚合物和溶剂构成的溶液中,形成成膜混合物。从成膜混合物中挥发溶剂,形成含有具有次卤酸盐的材料的薄膜。薄膜中的次卤酸盐在暴露于大气时,至少稳定达约3个月。
本发明的另一实施方式是一种杀菌材料,其包括在材料之上形成的第一涂层,该第一涂层通过将材料与聚乙二醇环氧化物和三聚氰胺的水溶液接触而形成。在第一涂层之上形成含有次卤酸盐第二涂层。该次卤酸盐至少稳定3个月。
尽管公开了多个实施方式,基于以下说明和描述的本发明的示例性实施方式的详细说明,仍有其他实施方式对于本领域技术人员是明显的。相应地,这些详细说明应被认为是示例性质的,而不是限制性的。
具体实施方式
本公开提供改进的无机次卤酸盐,诸如次氯酸盐和次溴酸盐的稳定性和储存。在一些实施方式中,本公开提供用于稳定、储存、携带和输送无机次卤酸盐的水不溶性的聚合物系统。水不溶性的聚合物系统的例子包括但不限于织物(fabric)、薄板(sheet)、微珠(bead)、涂层等。
聚合物系统包括能够吸收和稳定次氯酸盐(诸如次氯酸钠和次氯酸钙)和/或次溴酸盐(诸如次溴酸钠和次溴酸钙)的材料,诸如物品(article)、化合物和/或官能团。这些材料的例子包括但不限于具有预先形成空间的材料以及包含树脂或粘合剂的材料。具有预先形成空间的材料的例子包括基底(substrate)、中空纤维、泡沫、胶囊、中空或多孔无机微珠或聚合物微珠、沸石、纤维、非织材料等。在一些实施方式中,该材料可以是纤维素、合成纤维或纤维素与合成纤维的组合。
在一些实施方式中,纤维可被视为是将纤维通过纺织(weaving)、针织(knitting)、钩织(crocheting)、打结(knotting)或将纤维挤压在一起而形成的天然或人造的丝或纱的网络。单独的纤维可以通过在纺车上对原材料,诸如毛、麻、棉、尼龙、聚酯、腈纶、聚丙烯、聚乙烯、聚氯乙烯(PVC)或其他材料纺织来形成纤维来形成。包含树脂或粘合剂的材料的例子包括环氧树脂、三聚氰胺粘合剂或树脂、丙烯酸乳液或树脂、聚氨酯树脂或乳液以及这些的组合。
在一些实施方式中,将这些材料浸渍于或对其喷洒次氯酸盐(诸如次氯酸钠和次氯酸钙)和/或次溴酸盐(诸如次溴酸钠和次溴酸钙)的溶液或粉末。然后,用惰性聚合物基质来涂覆、浸渍、吸附、层叠、共价结合和/或混合该材料来形成聚合物系统,用于携带、稳定和输送无机次氯酸盐和/或次溴酸盐。
在一些实施方式中,包括上述物品、化合物和/或官能团的该材料被惰性聚合物基质涂覆、浸渍、吸附、层叠、共价结合和/或混合来形成聚合物系统,然后,该系统被浸渍于或对其喷洒无机次氯酸盐和/或次溴酸盐的溶液或粉末。
在任一种方式中,在所得的聚合物系统中的无机次氯酸盐(诸如次氯酸钠和次氯酸钙)和次溴酸盐(诸如次溴酸钠和次溴酸钙)与其在溶液中、粉末或片剂的形式具有相同的杀菌/消毒潜力。但是,在新的聚合物系统中的保质期相比于在溶液中、粉末或片剂的形式显著地提高了,可以以周来计甚至以年来计。而且,该聚合物系统在许多杀菌/消毒应用中更易于操作、储存、运输和/或应用/使用。
在一些实施方式中,使织物片与含有聚乙二醇环氧化物和三聚氰胺的第一水溶液接触,并将第一水溶液在织物上干燥。在一些实施方式中,可以将织物浸渍于和/或对其喷第一水溶液。织物可以与含有丙烯酸材料和次卤酸盐(诸如次氯酸钠)的第二水溶液接触,并将第二水溶液干燥。在一些实施方式中,可用第二水溶液对织物进行喷洒。
在一些情况下,织物在接触第二水溶液之前可以与第一水溶液接触。在一些情况下,织物在接触第一水溶液之前可以与第二水溶液接触。在一些实施方式中,第一水溶液还可以含有水基树脂或粘合剂。该次卤酸盐在暴露于大气时可以稳定达至少3个月。
在一些实施方式中,多个多孔微珠可以与含有次卤酸盐(诸如次氯酸钠)和聚乙二醇的水溶液接触,来形成含有次卤酸盐的微珠。然后,可以将该微珠加入到由成膜聚合物和溶剂构成的溶液中,来形成成膜混合物。该溶剂可以从成膜混合物中挥发来形成薄膜,该薄膜中包含含有次卤酸盐的微珠。薄膜中的次卤酸盐在暴露于大气时可以稳定达至少3个月。
在一些实施方式中,多孔微珠可以包括具有约300~约1200微米的粒径和100埃的平均孔径的微珠。在一些情况下,多孔微珠可以包括聚(4-乙基苯乙烯-co-二乙烯苯)微珠。
在一些实施方式中,水溶液可以含有约0.01~约30wt.%的次卤酸盐。在一些实施方式中,水溶液可以含有约1~约10wt.%的次卤酸盐。在一些实施方式中,水溶液可以含有约10wt.%的次卤酸钠。
在一些实施方式中,由成膜聚合物和溶剂构成的溶液可以含有约0.01~约40wt.%的成膜聚合物,余量为溶剂。在一些情况下,该溶液可以含有约15wt.%的成膜聚合物,余量为溶剂。在一些实施方式中,该溶液可以含有约0.1~约5wt.%的成膜聚合物。在一些实施方式中,成膜聚合物可以包括乙烯醋酸乙烯酯,且溶剂可以包括二氯甲烷。
在一些实施方式中,诸如纤维素材料的杀菌织物可以含有自由的羟基、氨基、酰胺基、羧酸酯官能团。通过将织物与含有聚乙二醇环氧化物和三聚氰胺的水溶液接触可以在织物上形成第一涂层。在第一涂层之上可以形成含有次卤酸(诸如次氯酸钠)的第二涂层。次卤酸盐可以稳定达至少约3个月。
在一些实施方式中,水溶液中的每约100mL的溶液含有约0.1~约30g的聚乙二醇环氧化物和约0.01~约10g的三聚氰胺。在一些实施方式中,水溶液中的每约100mL的溶液含有约2~约5g的聚乙二醇环氧化物和约0.5~约2g的三聚氰胺。在一些实施方式中,将第一涂层与次卤酸盐和可选择的丙烯酸材料的水溶液接触来形成第二涂层。
在一些实施方式中,杀菌的竹织物可以包括用100%的源自竹子的粘胶制成的织物。可以通过将织物与次卤酸盐(诸如次氯酸钠)和可选择的丙烯酸材料的水溶液接触来在织物上形成第一涂层。可以通过将第一涂层与聚乙二醇环氧化物、三聚氰胺和可选择的聚氨酯的水溶液接触来在第一涂层之上形成第二涂层。次卤酸盐稳定达至少约3个月。
试验部分
碘量滴定测试
在这种新的输送系统中的次氯酸钠的耐久性通过碘量滴定进行测定。在该测试中,将0.05g的新的输送系统分散于含有1.0wt%醋酸的40mL的无水乙醇中。加入1g的碘化钾,将混合物在室温的N2气氛中搅拌1h。释放的碘用0.01mol/L的硫代硫酸钠水溶液滴定。对相同量的纯棉/聚酯混纺织物进行相同的步骤作为对照。根据以下公式计算氯含量的百分比(表明次氯酸钠含量):
其中,VCl和V0分别是在对样品和对照进行滴定时消耗的硫代硫酸钠溶液的体积(mL),WCl是样品的重量(g)。每一测试重复三次,记录平均值。
实施例1
将一片(50cmx30cm)棉/聚酯混纺织物(60/40)浸渍于含有2g聚乙二醇环氧化物和0.5g三聚氰胺的100ml水溶液中1min。拍打该织物使之达到100%的吸收,然后,将其在120℃干燥至恒重。冷却该织物至室温后,在该织物上喷洒5ml的含有2%次氯酸钠的水基的丙烯酸涂层/粘合剂溶液,然后将该织物在空气中干燥一夜。
在刚刚处理完之后,通过上述的碘量测试,发现织物含有2000百万分率(ppm)的次氯酸钠。在室温暴露于大气3个月后,该织物仍含有多于约1800ppm的次氯酸钠,表明保留了超过约90%的最初的次氯酸钠。因而,该织物可以被用于次氯酸钠的储存和输送。
作为比较例,对一片(50cmx30cm)棉/聚酯混纺织物(60/40)直接喷洒5ml的2%次氯酸钠,而不进行将织物与含有聚乙二醇环氧化物和三聚氰胺的水溶液接触的初始步骤。该织物在空气中干燥一夜,然后储存于室温下的开放空气。在3天之内,已经损失了超过95%的喷洒到织物上的最初的次氯酸钠。
这些结果表明树脂方式对于延长次氯酸钠的寿命和次氯酸钠和其他无机次氯酸盐和/或次溴酸盐的储存和输送的广泛潜在用途是非常有效的。
实施例2
在另一实施例中,将一片(50cmx30cm)的竹织物(由100%的由有机竹纤维获得的粘胶制成的针织织物)浸渍于含有10%的水基的丙烯酸涂层/粘合剂溶液和2%次氯酸钠的100ml水溶液中,拍打以得到100%湿吸收。将含有2%的水基的聚氨酯和1%的环氧化物/三聚氰胺树脂的5ml水溶液喷洒到该织物上。将该织物在40℃真空干燥至恒重。碘量滴定测试显示,该处理之后,该织物含有约580ppm的次氯酸钠。在室温的大气中暴露2个月后,保留超过约540ppm的次氯酸钠。这意味着保留了超过约90%的最初的次氯酸钠。因而,该织物可以被用于次氯酸钠的储存和输送。
作为对比,将相同织物直接浸渍于2%次氯酸钠而不施加含有聚氨酯、聚乙二醇环氧化物和三聚氰胺的水溶液。拍打该织物并空气干燥。在室温的开放空气中3天后,损失了超过95%的次氯酸钠。
实施例3
将具有300-1200μm的粒径和的中位孔径的10g聚(4-乙基苯乙烯-co-二乙烯苯)多孔微珠加入到含有10%次氯酸钠的500mL次氯酸钠水溶液中。在混合物中加入1g聚乙二醇(MW:5000),将混合物在室温下搅拌24hr以使得次氯酸钠吸收进多孔微珠的孔隙中。通过过滤来收集微珠,在暗室的真空干燥器中干燥一夜。将这些微珠称为含有次氯酸钠的微珠。
在一个实施例中,将1g上述含有次氯酸钠的微珠加入到200ml的二氯甲烷中的15wt%的乙烯醋酸乙烯酯(EVA)共聚物溶液中。搅拌该混合物30min,然后将10ml混合物倒入玻璃培养皿(直径10cm)。在通风橱中挥发溶剂之后,可以将含有EVA薄膜的微珠用于次氯酸钠的储存和输送。碘量滴定测试显示,在处理后,通过上述的碘量测试发现织物含有2000ppm的次氯酸钠。在室温暴露于大气3个月后,保留了超过90%(大于1800ppm)的最初的次氯酸钠。该织物可以用于次氯酸钠的储存和输送。
在另一实施例中,将1g上述含有次氯酸钠的微珠加入到200ml的水中的市售丙烯酸背涂层溶液。搅拌该混合物30min,然后,将10ml混合物倒向一片丙烯酸毯的背面并涂抹均匀。在室温干燥一夜后,该毯可以用于次氯酸钠的储存和输送。碘量滴定测试显示,在处理之后,毯背面(backing)含有约800ppm的次氯酸钠。在室温暴露于大气3个月后,保留了超过90%(大于约720ppm)的原始保存的次氯酸钠。
在不脱离本发明的范围的基础上可以对讨论过的示例性实施方式进行各种改进和添加。例如,当上述的实施方式设计特定特征时,本发明的范围还包括具有不同的特征组合的实施方式和不包括全部上述特征的实施方式。
Claims (19)
1.一种输送稳定储存的次卤酸盐的方法,其特征在于,该方法包括以下步骤:
将材料与含有聚乙二醇环氧化物和三聚氰胺的第一水溶液接触;
在该材料上干燥第一水溶液;
将该材料与含有次卤酸盐的第二水溶液接触;以及
在该材料上干燥第二水溶液;
其中,该材料中的次卤酸盐在暴露于大气时稳定达至少3个月。
2.根据权利要求1所述的方法,其中,所得到的材料在与大气接触约3个月后,具有至少约90%的材料中原始保存的次卤酸盐。
3.根据权利要求1所述的方法,其中,该材料包括织物。
4.根据权利要求1所述的方法,其中,该材料包括棉、竹、纤维素材料或纤维素与合成纤维的混合。
5.根据权利要求1所述的方法,其中,该材料与第一水溶液的接触包括将该材料浸渍于第一水溶液或用第一水溶液喷洒该材料。
6.根据权利要求1所述的方法,其中,第二水溶液中的次卤酸盐包括次氯酸盐和次溴酸盐中的至少一种。
7.根据权利要求1所述的方法,其中,第二水溶液还含有水基的树脂或粘合剂。
8.根据权利要求1所述的方法,其中,该材料与第二水溶液的接触包括将该材料浸渍于第二水溶液或用第二水溶液喷洒该材料。
9.一种输送稳定储存的次卤酸盐的方法,其特征在于,该方法包括以下步骤:
将具有预先成形的空间的多种材料与含有次卤酸盐和聚乙二醇的水溶液接触,以形成含有次卤酸盐的具有预先成形的空间的材料;
将含有次卤酸盐的具有预先成形的空间的材料加入到由成膜聚合物和溶剂构成的溶液,来形成成膜混合物;以及
从成膜混合物中使溶剂挥发,形成薄膜,其具有含有次卤酸盐的材料;
其中,薄膜中的次卤酸盐在暴露于大气时稳定达至少约3个月。
10.根据权利要求9所述的方法,其中,具有预先成形的空间的材料选自中空纤维、泡沫、胶囊、中空或多孔无机或聚合物微珠、沸石及其组合。
11.根据权利要求9所述的方法,其中,水溶液含有约0.01~约30wt.%的次卤酸盐。
12.根据权利要求9所述的方法,其中,由成膜聚合物和溶剂构成的溶液含有约0.01~约40wt.%的成膜聚合物和余量的溶剂。
13.一种杀菌材料,包括:
通过将该材料与聚乙二醇环氧化物和三聚氰胺的水溶液接触而在该材料上形成的第一涂层;以及
在第一涂层之上形成的含有次卤酸盐第二涂层;
其中,次卤酸盐稳定达至少约3个月。
14.根据权利要求13所述的杀菌材料,其中,该材料包括织物。
15.根据权利要求13所述的杀菌材料,其中,该材料包括含有自由的羟氨基、酰胺基或羧酸酯官能团的棉、纤维素材料、纤维素/合成纤维混纺或其他织物。
16.根据权利要求13所述的杀菌材料,其中,第一涂层中在每约100mL溶液中含有约0.1~约30g的聚乙二醇环氧化物和约0.01~约10g的三聚氰胺。
17.根据权利要求13所述的杀菌材料,其中,通过将第一涂层与次卤酸盐的水溶液接触来形成第二涂层。
18.根据权利要求13所述的杀菌材料,其中,第二涂层包含次卤酸盐。
19.根据权利要求18所述的杀菌材料,其中,次卤酸盐包括次氯酸钠、次氯酸钙、次溴酸钠、次溴酸钙及其组合的一种或多种。
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AU2011207194B2 (en) | 2014-11-27 |
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US9700040B2 (en) | 2017-07-11 |
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US20130115259A1 (en) | 2013-05-09 |
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AU2011207194A1 (en) | 2012-08-09 |
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