CN101396017A - 对聚合物分散体进行蒸汽汽提以提高杀微生物剂的稳定性 - Google Patents

对聚合物分散体进行蒸汽汽提以提高杀微生物剂的稳定性 Download PDF

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CN101396017A
CN101396017A CNA2008102131666A CN200810213166A CN101396017A CN 101396017 A CN101396017 A CN 101396017A CN A2008102131666 A CNA2008102131666 A CN A2008102131666A CN 200810213166 A CN200810213166 A CN 200810213166A CN 101396017 A CN101396017 A CN 101396017A
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microbicide
steam
polymer dispersions
aqueous polymer
isothiazolinone
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J·K·卡朋特
C·古维亚
Z·卢迪克
J·J·文特尔
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Rohm and Haas Co
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Abstract

一种用来对聚合物分散体中的杀微生物剂进行稳定化的方法,该方法包括:提供水性聚合物分散体和蒸汽;在汽提塔中使得所述水性聚合物分散体和蒸汽接触;将所述蒸汽与所述水性聚合物分散体分离;向所述水性聚合物分散体中加入至少一种杀微生物剂。

Description

对聚合物分散体进行蒸汽汽提以提高杀微生物剂的稳定性
技术领域
本发明涉及一种对聚合物分散体(或者在本文中称为“分散体”)进行汽提的方法,该方法作为对杀微生物剂进行稳定化的处理方式。
背景技术
在本文中,杀微生物剂表示下式所示的3-异噻唑啉酮(3-Isothiazolone):
Figure A200810213166D00031
其中Y是包含1-18个碳原子的烷基或取代烷基;包含约2-8个碳原子的未取代的或卤代的烯基或炔基;包含约3-12个碳原子的环烷基或取代环烷基或取代的环烷基;最高包含约10个碳原子的芳烷基或卤代、低级烷基取代或低级烷氧基取代的芳烷基;或者包含最高约10个碳原子的芳基或卤代、低级烷基取代或低级烷氧基取代的芳基,或氢;X和X’是氢,卤素或(C1-C4)烷基;X和X’合并起来为稠合芳基。
存在一些非常重要的杀微生物剂种类。一些物质已经产业化,广泛用来抑制细菌、真菌和藻类的生长。一些例子是甲基异噻唑啉酮和5-氯-2-甲基-3-异噻唑啉酮,2-甲基-3-异噻唑啉酮,2-正辛基-3-异噻唑啉酮和1,2-苯并-3-异噻唑啉酮。
使用异噻唑啉酮化合物作为杀微生物剂,特别是使用3-异噻唑啉酮来控制乳液中微生物的生长,是本领域普通技术人员众所周知的。但是在聚合物分散体中使用异噻唑啉酮的一个问题在于,这些化合物会被聚合物分散体中发现的氧化剂和还原剂破坏,从而降低异噻唑啉酮防止微生物生长的功效。
作为一种解决该问题的方法,本领域的人们施涂对这些杀微生物剂进行稳定化。一般来说,人们通过使用无机金属化合物在分散环境下对异噻唑啉酮化合物进行稳定化。这些无机金属化合物包括但不限于金属硝酸盐和金属的硝酸盐。另外,人们众所周知可以将铜用作稳定剂。尽管这些金属有助于使得杀微生物剂组分稳定化,但是在许多应用中经常不希望使用这些金属。具有较高价态的金属化合物会降低分散体的稳定性。使得分散体稳定性降低会产生凝聚物,这些凝聚物被称为凝胶,其会降低分散体的性能。
本发明通过对分散体进行汽提,从而改进异噻唑啉酮的稳定性,从而缓解了对这些金属化合物的需要。
发明内容
在本发明中提供了一种用来对水性聚合物分散体中的杀微生物剂进行稳定化的方法,该方法包括:
提供水性聚合物分散体和蒸汽(steam);
在汽提塔中使得所述水性聚合物分散体和蒸汽接触;
将所述蒸汽与所述水性聚合物分散体分离;
其中在所述水性聚合物分散体和蒸汽在所述汽提塔中接触之后,加入至少一种杀微生物剂。
本发明的水性聚合物分散体可通过乳液聚合、微乳液聚合或悬浮聚合制备。特别的,通过溶液聚合法形成的聚合物不包括在本发明中。
在本文中,蒸汽定义为惰性气体,或者用水蒸气饱和的非冷凝的惰性气体的组合。
所述聚合物分散体和蒸汽混合物可以在间歇式或连续式汽提设备中接触。如果采用连续方式,进料可以并流或逆流的。在本文中,“并流”表示分散体和蒸汽一起流入和流出汽提塔。在本文中,逆流表示分散体从蒸汽流出的位置流入汽提塔,蒸汽从分散体流出的位置流入汽提塔。
汽提塔设备可以以间歇式、单步连续式或多步连续式工艺进行操作。为此,可以将单独的汽提塔、多个汽提塔、单独的冷凝器或多个冷凝器用作所述汽提设备。本领域普通技术人员目前所知的任意汽提设备均可用于本发明。可用于本发明的汽提设备的非限制性例子包括间歇式真空容器、有夹套的单通过壳管式热交换器,多通过壳管式热交换器和螺旋热交换器。在汽提设备的壳内可具有单独的管或多个管。
在本发明的一个实施方式中,在将物料加入汽提塔之前,将至少一种杀微生物剂加入所述聚合物分散体和蒸汽混合物中。在本发明的第二个实施方式中,在所述聚合物分散体和蒸汽混合物已进行过汽提之后,再将至少一种杀微生物剂加入所述聚合物分散体和蒸汽混合物中。可用于本发明的杀微生物剂的非限制性例子包括甲基异噻唑啉酮和5-氯-2-甲基-3-异噻唑啉酮,2-甲基-3-异噻唑啉酮,2-正辛基-3-异噻唑啉酮和1,2-苯并-3-异噻唑啉酮或其混合物。
本发明的分散体聚合物在低于80℃的温度下进行汽提。在更高温度(例如高于80℃)下进行汽提会造成不希望出现的性质,例如形成凝胶以及分散体聚合物使得设备结垢。
化合物混合物中剩余的杀微生物剂的量可以随时间测量。这被称为杀微生物剂稳定性。本发明的一个优点是在50℃储存7天之后,在汽提过的稳定化的材料中发现的初始的异噻唑啉酮的量比类似处理的未汽提的样品中的量高最多达80重量%。在50℃保持14天之后,在汽提过的稳定化的材料中发现的初始异噻唑啉酮的量比类似处理的没有经过汽提的样品中的量高最多达45重量%。
以下给出了用来说明本发明一些优点的非限制性实施例。
实施例
测试方法
热稳定化测试
将28克分散体样品置于50℃的烘箱中。7天之后,取出1克样品,根据以下方法进行活性成分分析。在14天末,再对1克样品进行分析。通过以下方法测量材料中异噻唑啉酮化合物的含量。结果与0时间的参比样相比较。所述参比样是未置于烘箱中的样品。参比样一收到就立刻分析。
异噻唑啉酮含量测量
用去离子水,以9份水:1份分散体的比例稀释分散体样品。混合样品,将异噻唑啉酮萃取入水(水性)相。对样品进行离心,提取清澈的液相。将清澈的液体注入HPLC测试仪器,例如Agilent 1100 Series,以测量异噻唑啉酮的含量。
实施例:汽提的样品与未汽提的样品的异噻唑啉酮稳定性的比较
在5加仑的间歇式反应器中制备了聚合物分散体。该分散体是丙烯酸丁酯/苯乙烯水基分散体。该分散体聚合物用表面活性剂和丙烯酸单体稳定化。
所得分散体的固体含量未53-54重量%。分散体的最终pH值为6.8-7.8,粘度小于200cp。
所述聚合物样品分成四份。每一份包括通过以下方式加入的甲基异噻唑啉酮(MIT)和氯代甲基异噻唑啉酮(CMIT)的组合:
第1份 批料聚合后加入异噻唑啉酮。
第2份 批料聚合后2小时之后加入异噻唑啉酮。
第3份 批料完成后加入异噻唑啉酮,然后分散体样品进行蒸汽汽提。
第4份 样品进行蒸汽汽提,然后加入异噻唑啉酮。
汽提过的样品通过单步连续汽提塔三次进行汽提。汽提过程中蒸汽与分散体的相对流速为1:5。如果汽提过的样品表现出改进的稳定性,则在热稳定性测试之后,作为比较的未汽提的样品将具有较低的杀微生物剂浓度。
再将样品置于50℃的烘箱中2周。在第0天、处于烘箱内第7天、第14天测量每种样品中的MIT含量和CMIT含量,以测试分散体中杀微生物剂的稳定性。
上面的第2份是参比样品,保持时间用来表示汽提所需的时间。
实验结果列于下表:
表1
正常的杀微生物剂加入
 
MIT含量(ppm) CMIT含量(ppm)
0 271.2 29.6
7 42.1 0
14 41.9 0
表2
保持2小时,加入杀微生物剂
 
MIT含量(ppm) CMIT含量(ppm)
0 272.5 30.7
7 40.5 0
14 41 0
表3
加入杀微生物剂,然后汽提
 
MIT含量(ppm) CMIT含量(ppm)
0 247.4 28.2
7 243 10.2
14 148.9 0
表4
汽提然后加入杀微生物剂
 
MIT含量(ppm) CMIT含量(ppm)
0 270.9 33.6
7 242.2 6.6
14 74.3 0
7天之后,两种未汽提的样品中的MIT含量都降至40-43ppm。7天之后,这些样品中的CMIT含量都降至0ppm。相比之下,7天之后,汽提过的样品中的MIT含量为243和242ppm,CMIT含量为10.2和6.6ppm。14天后,未检测到CMIT,但是检测到汽提过的样品中剩余一些MIT。很显然,两种汽提过的样品的异噻唑啉酮的稳定性都获得提高。在加入异噻唑啉酮之前保持2小时的未汽提的样品的杀微生物剂含量或杀微生物剂稳定性与聚合完成后即加入异噻唑啉酮的样品没有差异。

Claims (8)

1.一种用来对水性聚合物分散体中的杀微生物剂进行稳定化的方法,该方法包括:
提供水性聚合物分散体和蒸汽;
在汽提塔中使得所述水性聚合物分散体和蒸汽接触;
将所述蒸汽与所述水性聚合物分散体分离;
至少一种杀微生物剂被加入所述水性聚合物分散体。
2.如权利要求1所述的方法,其特征在于,在使得所述水性聚合物分散体和蒸汽在汽提塔中接触之前,加入所述至少一种杀微生物剂。
3.如权利要求1所述的方法,其特征在于,在使得所述水性聚合物分散体和蒸汽在汽提塔中接触之后,加入所述至少一种杀微生物剂。
4.如权利要求1所述的方法,其特征在于,在使得所述水性聚合物分散体和蒸汽在汽提塔中接触的同时,加入所述至少一种杀微生物剂。
5.如权利要求2所述的方法,其特征在于,所述至少一种杀微生物剂选自甲基异噻唑啉酮、氯代甲基异噻唑啉酮、或其混合物。
6.如权利要求3所述的方法,其特征在于,所述至少一种杀微生物剂选自甲基异噻唑啉酮、氯代甲基异噻唑啉酮、或其混合物。
7.如权利要求4所述的方法,其特征在于,所述至少一种杀微生物剂选自甲基异噻唑啉酮、氯代甲基异噻唑啉酮、或其混合物。
8.如权利要求1所述的方法,其特征在于,所述汽提塔温度低于80℃。
CNA2008102131666A 2007-09-24 2008-09-16 对聚合物分散体进行蒸汽汽提以提高杀微生物剂的稳定性 Pending CN101396017A (zh)

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