CN101563140B - 可抑制泡沫的水性季铵和/或季磷组合物 - Google Patents

可抑制泡沫的水性季铵和/或季磷组合物 Download PDF

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CN101563140B
CN101563140B CN2007800473501A CN200780047350A CN101563140B CN 101563140 B CN101563140 B CN 101563140B CN 2007800473501 A CN2007800473501 A CN 2007800473501A CN 200780047350 A CN200780047350 A CN 200780047350A CN 101563140 B CN101563140 B CN 101563140B
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菲利普·哲顿·斯维尼
米夏埃尔·吕策勒
沃尔克·兰夫特
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Chuangxin Water Care Co ltd
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Abstract

通过以0.001到0.2的阴离子表面活性剂与季化合物的摩尔比例添加阴离子表面活性剂,降低含有具生物杀灭性能的季铵和/或季磷化合物的水性系统的发泡倾向。根据本发明的该水性系统的优选应用是在游泳池和水疗(spa)用水中作为除藻剂。

Description

可抑制泡沫的水性季铵和/或季磷组合物
技术领域
本发明涉及在含有具生物灭活功能的季铵和/或季磷化合物(“quats”)的水性系统中抑制泡沫形成的方法。本发明同时也涉及含有季铵和/或季磷化合物的低泡水性配方,和所述配方化合物来杀灭或者抑制微生物、藻类和真菌的生长的用途。
背景技术
几种季铵和/或季磷化合物(“quats”)显示出显著的生物灭活性能,因此已经做为消毒剂、保鲜剂或其他用于杀灭或者抑制微生物如细菌、病毒、藻类和真菌的生长的化合物中的活性组分而应用多年。然而,因为多数季铵和/或磷化合物同时也具有表面活性剂的特性,其在水性系统中的用途经常由于大量起泡而遭到破坏,即使其在溶液中的浓度已低至百万分之一(ppm)等级,这对于当水性系统暴露在空气中且处于被搅动状态时(比如游泳池、spa用水或是冷却塔中的水体)的应用特别具有危害性。
发明内容
该问题可通过本发明中提出的抑制在含有至少一种具生物灭活性能季铵和/或季磷化合物(quats)的水性系统中产生泡沫的方法得以解决。
如本发明所述,该问题可应用权利要求1的法得到解决。申请者已发现在含有至少一种生物灭活功能季铵和/或季磷化合物的水性系统中,以0.001至0.2(即为0.001∶1到0.2∶1),优选0.001至0.09的阴离子表面活性剂与季铵和/或季磷化合物的摩尔比例添加至少一种阴离子表面活性剂,在该水性系统使用期间可显著减少泡沫形成的体积和持续时间。
因为阴离子表面活性剂被认为会降低季铵化合物生物灭活的效能,通过远低于摩尔当量的量添加阴离子表面活性剂,以减少观测到的泡沫量,对于季铵和/或磷化合物作用功效角度来说非常重要。由于只需添加少量的,例如0.1或者0.02摩尔当量的阴离子表面活性剂,因此该组合物还分别保留了其大约90%或者98%的活性季铵和/或季磷化合物浓度。
在更优选的实施方式中,阴离子表面活性剂和季铵和/或季磷化合物的摩尔比例范围为0.001至0.05。
优选地,至少一种季铵和/或季磷化合物选自:
(i)具有式[QR1R2R3R4]+X-(I)的化合物,其中Q是氮或磷,R1和R2是独立的未被取代的或者被羟基取代的直链或者支链的C1-4烷基;-(CH2CH2O)MCH2CH2OH,或者-(CH2CH(CH3)O)MCH2CH(CH3)OH,其中m在每个分子中分别为从1到10的整数;
R3是可选地取代的苯甲基、乙苯基、萘甲基或者直链或支链的C6-22烷基基团;
R4是可选地取代的苯甲基、乙苯基、甲萘基或者直链或支链的C1-22烷基基团,或-R5(O)n(C6H4)R6,其中n是0或1;
R5是取代的或未取代的C1-8亚烷基(alkanediyl)或-(CH2)p-O-(CH2)q-,其中p和q分别为从1至8的整数;
R6是氢或经取代或未取代的直链或支链的C1-12烷基基团;X-是单价的或一当量的多价阴离子;
(ii)具有式R19R20R21R22Q+X-(II)的化合物,其中Q是氮或磷,R19、R20、R21和R22是独立的直链、支链、环状或其任意组合的饱和或不饱和的烃基基团,X-是单价的或一当量的多价阴离子,同时R19、R20、R21和R22中碳原子的总数在10至50范围中;
(iii)聚合季铵或季磷生物灭活剂,和
(iv)由任意(i)至(iii)中的两种或多种季化合物组成的混合物。
更优选的是,具有式[QR1R2R3R4]+X-(I)的季铵和/或季磷化合物,其中Q如上述定义,R1和R2均为C1-4烷基,R3是直链或支链的C6-22烷基,R4是苯甲基或直链或支链的C1-22烷基,X-是氯。
更优选的是,具有式[QR1R2R3R4]+X-(I)的季铵和/或季磷化合物,其中Q如上述定义,R1和R2均为甲基,R3是直链或支链的C6-22烷基,R4是苯甲基或直链或支链的C6-22烷基,X-是氯。
最优选的是,Q为氮。
特别优选的是,铵和磷化合物,例如烷基二甲苄基氯化铵或三丁基-十四烷基氯化磷。
另一优选的实施方式中,式(I)和/或(II)中的X-可选自1/2CO3 2-,HCO3 -和OH-
另一优选的实施方式中,至少一种阴离子表面活性剂是磺酸盐。
另一优选的实施方式中,至少一种阴离子表面活性剂是二酯。
在特别优选的实施方式中,至少一种阴离子表面活性剂选自磺基琥珀酸二戊酯、磺基琥珀酸二己酯、磺基琥珀酸二辛酯、双十三烷磺基琥珀酸酯、以及任意前述化合物的钾盐、钠盐和钙盐,和任意前述磺基琥珀酸酯及其盐类混合物。
在一种最优选的实施方式中,至少一种阴离子表面活性剂选自磺基琥珀酸二己酯以及其磺酸盐中的钾盐、钠盐和钙盐组合。
另一种最优选的实施方式中,至少一种阴离子表面活性剂选自磺基琥珀酸二辛酯以及其钾盐、钠盐和钙盐。
另一最优选的实施方式中,至少一种阴离子表面活性剂选自磺基琥珀酸二戊酯以及其钾盐、钠盐和钙盐。
在上述磺基琥珀酸酯盐中,特别优选钠盐。
上述磺酸盐可被观测到在保持季铵和/或季磷化合物(quat)高度活性的同时,显著减少泡沫。
优选地,该水性系统中包含了具有生物灭活性质的季铵和/或季磷化合物,含量为0.1至100ppm,更优选0.5至50ppm。
本发明的另一目标是低泡配方,其包含了至少一种具生物灭活性质的季铵和/或季磷化合物和至少一种阴离子表面活性剂,其中阴离子表面活性剂与季铵和/或磷化合物的摩尔比例为0.001至0.2,优选0.001至0.09,更优选0.001至0.05.
优选地,基于100%总配方质量,低泡配方包含了占5%至80wt.%,更优选占10%至50wt.%的至少一种具生物灭活性质的季铵和/或季磷化合物。
本发明的低泡配方是稳定的单相的澄清溶液。
优选地,该低泡配方含有至少一种性能添加剂,例如染料或香水。
本发明另一个目标是杀灭或抑制微生物、浮游动物、藻类和/或真菌的生长的方法,包括向水性系统或多孔或硬质表面使用上述的配方。
在优选的实施方式中,该多孔或硬质表面为木材、金属或塑料。
在另一种优选的实施方式中,该配方用于作为木质防腐剂。
在其它一种优选的实施方式中,该配方用于作为硬质表面的消毒剂或清洁杀菌剂。
在其它另一种优选的实施方式中,该水性系统选自冷却水、废水、油田注入、检测或回收用水、娱乐池或水疗(spa)用水、压舱水,和纸浆或造纸浆。
更优选地,该水性系统是冷却水、压舱水或娱乐池水或水疗用水。
特别优选在游泳池或水疗用水中作为除藻剂的应用。
优选地,该水性系统含有0.1至100ppm,更优选0.5至50ppm的具生物灭活性质的季铵和/或季磷化合物浓度。
本发明将通过以下非限制性实施例进一步阐述。
实施例
方法:
测试溶液用选定的季铵化合物和选定的阴离子表面活性剂加入20℃自来水(pH=7-8,总硬度=相当160-300ppm CaCO3的含量,总碱度=相当150-250ppmCaCO3的含量)中进行制备。每份150毫升的测试溶液加入到250毫升用塞子塞紧的带刻度混合量筒中,通过颠倒量筒十次对其中的溶液进行搅拌,搅拌后立即测量泡沫的体积,沉降30秒后再次测量泡沫的体积。然后测定泡沫完全消失需要的时间(“完全消泡所需的时间”)。除非另行指出,所有的季铵和磷化合物浓度用ppm或百分比表示均基于重量,所指的都是活性组分的实际含量。
实施例1(参考实施例)
烷基(67%C12,25%C14,7%C16,1%C8,10,18)二甲基苄基氯化铵(ADBAC;Barquat
Figure G2007800473501D00061
,50-65B,Lonza Inc.,Allendale,NJ)被选为代表性的季铵化合物用于泡沫评估。如下表1所示,ADBAC产生了大量的泡沫,其产生的初始泡沫量为25毫升,在30秒钟之后泡沫量仍保持10毫升。作为比较,聚合季化合物聚[氧亚乙基(二甲基亚胺基)亚乙基(二甲基亚胺基)亚乙基二氯化物](WSCP,Buckman Laboratories International,Inc.,Memphis,TN)的发泡表现也被测定。
实施例2
使用上述方法测定阴离子表面活性剂磺基琥珀酸二辛酯钠(NaDOSS)对ADBAC起泡的影响。结果如下表1所示。相对活性季化合物,仅添加浓度0.1摩尔当量NaDOSS便将起始的泡沫体积减少了85%,从25毫升降至4毫升。甚至仅添加浓度0.02摩尔当量的NaDOSS,导致的起始泡沫体积仅6毫升,而且泡沫在10秒钟内完全消失。
实施例3
由于低浓度季铵经常在水处理中得到应用,例如作为游泳池中的杀藻剂,所以使用实施例2中的方法,以2ppm的季铵化合物浓度,测试NaDOSS控制低浓度的季铵化合物起泡的能力。作为对照,另一个测试在不添加NaDOSS的情况下进行。结果如下表1所示。结果显示,低至0.05ppm的NaDOSS浓度便可控制2ppm季铵化合物的起泡。
实施例4
其它的阴离子表面活性剂磺基琥珀酸二己酯钠(NaDHSS)和双十三烷磺基琥珀酸酯钠(NaDTSS)同样使用实施例2所述方法作为泡沫消除剂进行测试。结果如下表1所示。结果显示NaDHSS浓度低至1.1ppm时便可抑制季铵和/或季磷化合物浓度为10ppm时溶液的起泡(相当于阴离子表面活性剂和季铵和/或季磷化合物(quat)的摩尔比例为0.10),当其浓度低至0.2ppm时仍显示少量抑泡效果。相似的结果可以在NaDTSS浓度在1.7ppm(相当于阴离子表面活性剂和季铵和/或季磷化合物(quat)的摩尔比例为0.10)和0.4ppm时分别得到。优选NaDHSS,因为其所有被测浓度在实验中都呈现澄清的溶液。
表1
Figure G2007800473501D00081
实施例5
如前述的实施例所显示,NaDOSS可被分别应用于含有季铵和/或季磷化合物的溶液中达到期望的消泡效果。然而,出于应用的原因,特别是为了便于应用,想要含有最优化的季铵和/或季磷化合物和阴离子表面活性剂摩尔比例的单种配方(浓缩物)。因此实验对含有Barquat
Figure G2007800473501D00082
50-65B和NaDOSS的两种配方的相稳定性进行了检测。结果如下表2所示。
表2
  NaDOSS/Quat摩尔比例   Quat含量(%)   NaDOSS含量(%)   外观
  0.02   49.2   1.2   单相,澄清
  0.10   46.1   5.8   单相,澄清
据发现可制备含有0.02和0.10摩尔比例的NaDOSS与ADBAC的澄清相稳定配方。含有10ppm季铵和/或季磷化合物(quat)的待测溶液根据这个配方比例进行制备,且基本显示出和实施例2结果相同的起泡表现。
实施例6
对磺基琥珀酸二辛酯钠(NaDOSS)和磺基琥珀酸二己酯钠(NaDHSS)在为模拟冷却水系统应用而设计的动态再循环泡沫实验中进行测试。该动态泡沫实验包括使1.5升水样以5.7升/分钟(1.5加仑/分钟)的速度循环通过大型带刻度量筒。水的条件:总硬度(相当于CaCO3)280ppm,总碱度(相当于CaCO3)164ppm,温度22℃,pH=7.3。待测配方的主溶液添加以达到报告浓度。结果如下表3所示。
表3
  样品  5分钟后稳定的泡沫高度(厘米)
  LF  7.25~8.0
  LF+0.02mol NaDOSS  4.0
  LF+0.02mol NaDHSS  6.0
两种被测的化合物均显著降低了90ppm活性二辛基二甲基氯化铵(BardacLF18,Lonza Inc.)的发泡特性。如表3结果所示,添加NaDOSS(磺基琥珀酸酯/Bardac
Figure G2007800473501D00092
LF18)到其摩尔浓度达到0.02可将泡沫高度降低50%,从8厘米降至4厘米,而添加相同摩尔浓度NaDHSS将泡沫高度降低25%。
实施例7
两种含有Bardac
Figure G2007800473501D00093
LF18和NaDOSS的配方的相稳定性被测定。如下表4结果所示,配方中含有NaDOSS的摩尔质量浓度为0.02和0.05时相容,可产生澄清,单相的溶液。
表4
  NaDOSS/Quat摩尔比例   Quat含量[%]   NaDOSS含量[%]   外观
  0.02   51.0   1.5   单相,澄清
  0.05   50.0   3.6   单相,澄清

Claims (21)

1.一种在含有至少一种生物灭活功能季铵和/或季磷化合物的水性系统中抑制泡沫形成的方法,所述方法包括以0.001到0.05的阴离子表面活性剂与季铵和/或季磷化合物的摩尔比例向该水性系统添加至少一种阴离子表面活性剂,其中所述阴离子表面活性剂为二酯磺酸盐。
2.如权利要求1所述的方法,其中该至少一种季铵和/或季磷化合物选自
(i)具有式[QR1R2R3R4]+X-(I)的化合物,其中Q是氮或磷;
R1和R2是独立的未被取代的或者被羟基取代的直链或支链的C1-4烷基;-(CH2CH2O)mCH2CH2OH或者-(CH2CH(CH3)O)mCH2CH(CH3)OH,其中m在每个分子中分别为从1到10的整数;
R3是取代或未取代的苯甲基、乙苯基、萘甲基或者直链或支链的C6-22烷基;
R4是取代的或未取代的苯甲基、乙苯基、甲萘基或者直链或支链的C1-22烷基,或-R5(O)n(C6H4)R6,其中n是0或1;
R5是取代的或未取代的C1-8亚烷基(alkanediyl)或-(CH2)p-O-(CH2)q-,其中p和q分别为从1至8的整数;
R6是氢或取代或未取代的直链或支链的C1-12烷基;X-是单价的或一当量的多价阴离子;
(ii)具有式R19R20R21R22Q+X-(II)的化合物,其中Q定义同上,R19、R20、R21和R22是独立的直链、支链、环状或其任意组合的饱和的或不饱和的烃基基团,
X-是单价的或一当量的多价阴离子,
且R19、R20、R21和R22中碳原子的总数在10至50范围中;
(iii)聚合季铵或季磷生物灭活剂,和
(iv)任意(i)至(iii)中两种或多种季化合物的混合物。
3.如权利要求2所述的方法,其中该季化合物具有式[QR1R2R3R4]+X-,Q如权利要求2中定义,R1和R2均为C1-4烷基,R3是直链或支链的C6-22烷基;R4是苯甲基或直链或支链的C1-22烷基,且X-是氯离子。
4.如权利要求2所述的方法,其中X-选自1/2CO3 2-,HCO3 -和OH-
5.如权利要求1所述的方法,其中该至少一种阴离子表面活性剂选自磺基琥珀酸二戊酯、磺基琥珀酸二己酯、磺基琥珀酸二辛酯、双十三烷磺基琥珀酸酯,以及任意前述化合物的钾盐、钠盐和钙盐,和任意前述磺基琥珀酸酯及其盐类的混合物。
6.如权利要求5所述的方法,其中该至少一种阴离子表面活性剂选自磺基琥珀酸二己酯以及其钾盐、钠盐和钙盐。
7.如权利要求5所述的方法,其中该至少一种阴离子表面活性剂选自磺基琥珀酸二辛酯以及其钾盐、钠盐和钙盐。
8.如权利要求1-3以及5-7任意一项所述的方法,其中该水性系统含有0.1至100ppm的具生物灭活性质的季铵和/或季磷化合物。
9.如权利要求1-3以及5-7任意一项所述的方法,其中该水性系统含有0.5至50ppm的具生物灭活性质的季铵和/或季磷化合物。
10.单相液体低泡配方,其包含了至少一种具生物灭活性质的季铵化合物和至少一种阴离子表面活性剂,其中该阴离子表面活性剂与该季铵化合物的摩尔比例为0.001至0.05,且该阴离子表面活性剂为二酯磺酸盐。
11.如权利要求10所述的配方,其包含了以100wt%总配方为基础,占5%至80wt%的至少一种具生物灭活性质的季铵和/或季磷化合物。
12.如权利要求10所述的配方,其包含了以100wt%总配方为基础,占10%至50wt%的至少一种具生物灭活性质的季铵和/或季磷化合物。
13.如权利要求10-12任一项所述的配方,其包含了染料或香水或其他性能添加剂。
14.杀灭或抑制微生物、藻类和/或真菌的生长的方法,该方法包含在水性系统或多孔或硬质表面应用如权利要求9至11任一项所述的配方。
15.如权利要求14所述的方法,其中该多孔或硬质表面为木材、金属或塑料。
16.如权利要求15所述的方法,其中该配方用作木材防腐剂。
17.如权利要求14所述的方法,其中该配方用作硬质表面的消毒剂或清洁杀菌剂。
18.如权利要求14所述的方法,其中该水性系统选自冷却水、废水、用于油田注入、检测或回收用的水、娱乐池或水疗用水、压舱水以及造纸浆。
19.如权利要求18所述的方法,水性系统是冷却水、压舱水或娱乐池水或水疗用水。
20.如权利要求18或19所述的方法,其中该水性系统含有0.1至100ppm的具生物灭活性质的季铵和/或季磷化合物。
21.如权利要求18或19所述的方法,其中该水性系统含有0.5至50ppm的具生物灭活性质的季铵和/或季磷化合物。
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