CN1902125B - 释放二氧化氯的复合制品 - Google Patents

释放二氧化氯的复合制品 Download PDF

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CN1902125B
CN1902125B CN2004800221920A CN200480022192A CN1902125B CN 1902125 B CN1902125 B CN 1902125B CN 2004800221920 A CN2004800221920 A CN 2004800221920A CN 200480022192 A CN200480022192 A CN 200480022192A CN 1902125 B CN1902125 B CN 1902125B
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clo
composite product
activation
organic substrate
produce
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CN1902125A (zh
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B·K·斯佩罗内罗
L·赫拉特科
M·S·科克伦
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BASF Catalysts LLC
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Engelhard Corp
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/40—Peroxides
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/02—Oxides of chlorine
    • C01B11/022—Chlorine dioxide (ClO2)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B11/00—Oxides or oxyacids of halogens; Salts thereof
    • C01B11/02—Oxides of chlorine
    • C01B11/022—Chlorine dioxide (ClO2)
    • C01B11/023—Preparation from chlorites or chlorates
    • C01B11/024—Preparation from chlorites or chlorates from chlorites

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Abstract

描述了一种包含结合到有机基质中的ClO2产生材料的复合制品及使用该制品的方法。所述复合制品的有机基质可在低于约150℃的温度下成形，当复合制品暴露于活化刺激下时允许活化刺激(如水蒸气和/或电磁能)与ClO2产生材料之间的接触，并且其可渗透ClO2。

Description

释放二氧化氯的复合制品
发明领域
本发明涉及一种在暴露于活化刺激如环境湿分或光下可产生ClO2气体的制品及使用该制品的方法。
发明背景
现有技术公开了在多种条件下产生ClO2气体的多种粉末状组合物。其中包括用于受控持续释放ClO2的材料(CSR材料)，该材料暴露于水蒸气下时释放出ClO2。还包括暴露于光下时产生ClO2的材料。
为了便于使用和处理，对于这些材料，有利的是以包含所述粉末于多孔袋状物(即香袋)中的方式将其容纳或包装，或者将这些材料挤出入聚合物基质膜如聚乙烯中。这样可避免使用者与所述粉末直接接触，并且可以更容易地从被处理的区域移走用过的粉末。
不幸地，袋包相对宽大且造价昂贵，小尺寸的袋包非常轻且难以操作。因此，将粉末包装于小袋包中(尺寸小于约2克)的成本通常不切合实际地高。
挤出聚合物片材可以相对廉价地制成小尺寸，因为可以以经济的大尺寸制备所述片材，然后可以廉价地从较大的片材上切割下较小尺寸的片体。然而，由于引入所有ClO2产生材料中的亚氯酸盐阴离子的分解温度低，因此ClO2释放聚合物片材的挤出温度不能高于约150-160℃。如果该温度高于上述温度，则挤出过程中由于分解损失的亚氯酸盐的量会不可接受的高。这已经限制选择聚合物基质为含有相当大量的熔点相对低的低密度聚乙烯的聚合物基质。但是聚乙烯不是理想的基质材料，原因是聚乙烯不能高度渗透用于从大多数二氧化氯释放材料中引发二氧化氯释放的水蒸气。另外，聚乙烯的挤出温度为约150℃，其恰好处在亚氯酸盐阴离子会发生分解的边界。由于亚氯酸盐分解会导致聚乙烯的爆炸氧化，因此所述挤出片材与许多粉末状材料相比通常包含浓度较低的亚氯酸盐阴离子。因此，较低的亚氯酸盐含量反过来会限制其ClO2最高产率。
发明概述
本发明一般涉及包含结合到有机基质中的在暴露于活化刺激时能够产生ClO2的材料的复合制品及使用该制品的方法。所述有机基质可在低于约150℃、优选低于约135℃、最优选低于约110℃的温度下成形。当所述复合制品暴露于活化刺激如水或光下时，该有机基质允许所述ClO2产生材料与活化刺激之间的至少部分接触，这反过来导致所述材料产生ClO2。该有机基质也可渗透ClO2以使得至少一部分由所述ClO2产生材料生成的ClO2从该复合制品中逸出。优选地，该制品在暴露于所述刺激之前的贮存期间是稳定的。
优选实施方案详述
本发明涉及一种包含结合到有机基质中的ClO2产生材料的复合制品及使用该制品方法。
ClO2产生材料是暴露于某些活化刺激时能够产生ClO2的任何材料或材料组合。所述活化刺激可以是水蒸气、电磁能或可实现由所述ClO2产生材料形成ClO2的任何其它引发体。典型地，ClO2产生材料包含含有亚氯酸盐例如亚氯酸钠的化合物和酸化剂。美国专利US6,294,108和WO03/056951A2中描述了ClO2产生材料的实例，通过引用将这两份专利并入本文。
所述有机基质含至少一种有机材料并且：a)可在低于约150℃、优选低于约135℃、最优选低于约110℃的温度下成形；b)在所述复合制品暴露于活化刺激下时允许活化刺激与所述ClO2产生材料之间的至少部分接触从而产生ClO2；和c)可渗透ClO2。所述有机基质的低温可成型性与温度敏感的ClO2产生材料相适应。当暴露于活化刺激下时，所述有机基质使得活化刺激接触被结合的ClO2产生材料，并允许产生的ClO2逸出到制品周围的空间中。
适用于所述有机基质的一类材料是低熔点分子固体。尤其是，低熔点亲水性分子固体。低熔点分子固体材料的实例是聚乙二醇蜡(如DowChemical Co.以商标CARBOWAX出售的聚乙二醇蜡)、聚乙二醇蜡与石腊的混合物、硬酯酸、和聚乙二醇蜡与硬酯酸的混合物。仅包含石腊作为有机材料的所述有机基质优选与湿分激活的ClO2释放材料一起使用以及与引入到该配方中用于促进湿分侵入的成孔剂一起使用。
适用于所述有机基质的另一类材料是低熔点可热成型或热固化的官能聚合物，如EVA(乙烯乙酸乙烯酯)。这些材料通常用于配制于相对较低温度下软化和流动(即可以被挤出)的热熔胶制品。其它热熔胶型配方也适于此目的。如果通过暴露于光下而引发ClO2释放，那么所述基质材料优选是可有效透光的。
可以通过以下步骤形成该复合制品：将所述ClO2释放材料与所述有机基质材料混合、加热至低于150℃的温度以使基质材料软化或熔化、和将该混合物挤出成棒状物、片状物、球状物等。作为选择，可以在与所述ClO2产生材料混合之前将所述基质材料加热至低于150℃的温度并软化/熔化。
作为选择，可以通过以下方式形成复合制品：通过将混合物注入模具中并冷却；通过将混合物涂覆到平坦表面上以形成薄片(如刮涂工艺)；或者通过将混合物通过两个辊之间的辊隙空间以形成片材。同样，可以使用本领域技术人员已知的若干其它方法中的任一种来形成制品。
所述复合制品可以包含其它提供所需特性的组分。例如，可以向所述复合物中添加纤维材料以提高硬度和强度，或可以添加增塑剂以提高柔韧性。可以添加成孔剂如硅胶和硅藻土以提高制品的孔隙率。提高的孔隙率有助于水蒸气进入所述制品和/或ClO2逸出所述制品。可以添加色彩和香味以增强美感。可以添加干燥剂以限制贮存期间的水暴露。
可以在任何需要ClO2并将暴露于活化刺激下的场合使用该复合制品。一些具体的应用包括：延长食品保存期、运输和/或贮存期间物品(如鞋)的微生物致劣保护、抗微生物包装、除味装置和除味涂层。
现在将描述优选实施方式的非限制性实施例。
实施例
在低于100℃的温度下将十三点三(13.3)克与美国专利US6,294,108实施例7中描述的材料相似的二氧化氯释放粉末混入20克熔化的聚乙二醇蜡(CARBOWAX 4000品牌)。将五点三(5.3)克该混合物注入小铝盘中以制得直径约2英寸和厚1/8英寸的盘状物。在相对湿度80％下，使用美国专利US6,294,108中描述的测试方法测试该盘状物的ClO2释放作用，其在约20h时产生5ppm的ClO2。

Claims (7)

1.一种包含结合到有机基质中的ClO2产生材料的复合制品，其中ClO2产生材料基本由亚氯酸钠和酸化剂组成，并且其中所述ClO2产生材料在与活化刺激接触时释放ClO2，以及其中所述有机基质：
a)可在低于150℃的温度下成形；
b)在所述复合制品暴露于所述活化刺激下时允许所述活化刺激与所述ClO2产生材料之间的至少部分接触；和
c)可渗透ClO2。
2.如权利要求1所述的复合制品，其中所述有机基质可在低于135℃的温度下成形。
3.如权利要求1所述的复合制品，其中所述有机基质可在低于110℃的温度下成形。
4.如权利要求1所述的复合制品，其中所述活化刺激是水蒸气。
5.如权利要求1所述的复合制品，其中所述有机基质为聚乙二醇蜡、聚乙二醇蜡与石蜡的混合物、硬脂酸、聚乙二醇蜡与硬酯酸的混合物、石蜡或乙烯乙酸乙烯酯。
6.一种产生ClO2的方法，其包括将权利要求1的复合制品暴露于活化刺激下。
7.如权利要求6所述的方法，其中所述活化刺激是水蒸气。
CN2004800221920A 2003-08-04 2004-07-30 释放二氧化氯的复合制品 Expired - Fee Related CN1902125B (zh)

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US49243103P 2003-08-04 2003-08-04
US60/492,431 2003-08-04
US10/902,735 2004-07-29
US10/902,735 US8137581B2 (en) 2003-08-04 2004-07-29 Chlorine dioxide releasing composite article
PCT/US2004/024865 WO2005019101A2 (en) 2003-08-04 2004-07-30 Chlorine dioxide releasing composite article

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AT (1) ATE463464T1 (zh)
AU (1) AU2004267046B2 (zh)
CA (1) CA2535002C (zh)
DE (1) DE602004026480D1 (zh)
ES (1) ES2341251T3 (zh)
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US20090238872A9 (en) 2009-09-24
US20060024369A1 (en) 2006-02-02
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WO2005019101A2 (en) 2005-03-03
AU2004267046B2 (en) 2010-03-25
EP1708962B1 (en) 2010-04-07
ATE463464T1 (de) 2010-04-15
AU2004267046A1 (en) 2005-03-03
EP1708962A2 (en) 2006-10-11
ES2341251T3 (es) 2010-06-17
CA2535002A1 (en) 2005-03-03
CN1902125A (zh) 2007-01-24
US8137581B2 (en) 2012-03-20
CA2535002C (en) 2013-10-29
PT1708962E (pt) 2010-04-29
DE602004026480D1 (de) 2010-05-20

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