CN105968043B - 双子座季铵盐及其用途 - Google Patents
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Abstract
Description
技术领域
本发明涉及一种双子座(Gemini)季铵盐及其用途,具体地说,涉及一种双子座(Gemini)季铵盐及其在制备水性涂料的抗菌防腐剂中的应用。
背景技术
涂料是一种施工方便、价格低廉、效果明显和附加价值率高的化工产品。它不仅能装饰建筑、船舶、机械等表面,且具有防止其表面锈蚀,延长使用寿命之功能,还有装饰环境给人以美的享受和醒目标记的功能,随着科技的不断发展,涂料逐步成为一种专用性强、功能性强的精细化学产品。
为了提高涂料的施工性能和漆膜性能,所添加的助剂往往含有微生物所必须的营养物,为细菌,霉菌和酵母菌等微生物提高了良好的生长环境。因此,在水性涂料的贮存过程中,常常因为细菌的繁殖,使产品性能遭到破坏,质量下降,导致出现涂料表面变色,黏度下降,pH值变化,颜料沉淀,乳液絮凝、破乳,产生异味甚至表面长霉等现象。最终造成涂料的废弃,给使用者和生产者造成损失。因此,在生产和贮存涂料时,必须添加一定的抗菌、防腐剂来抑制和阻止微生物的生存,以保证产品的质量。
早期开发的抗菌防腐剂中,包括甲醛、重金属盐、苯酚、五氯酚钠等,由于对人体和环境都有一定的危害,现在已经禁止使用。随后发展的缓释甲醛型罐内抗菌防腐剂,如氯化3-氯烯丙基六亚甲基四胺(季铵盐-15)、1,3-二羟甲基-5,5-二甲基海因(DMDMH)、咪唑烷基脲等也因为甲醛的挥发性、刺激性和致癌作用,使其使用受到一定限制。
近年来,水性涂料中常用的罐内抗菌防腐剂已被尼泊金酯类及异塞唑啉酮类等高效抗菌剂替代。然而这些抗菌剂仍然对人体和环境也有一定的危害,其使用也日益受到限制。
鉴于此,研制一种安全、环保及高效的水性涂料的罐内抗菌防腐剂成为本发明需要解决的技术问题。
发明内容
本发明的发明人设计并合成了一种结构新颖的双子座(Gemini)季铵盐。将所制备双子座(Gemini)季铵盐用于水性涂料中,发现其具有安全、环保及高效的抗菌防腐性能。
因此,本发明一个目的在于,提供一种结构新颖的双子座(Gemini)季铵盐。
本发明所述双子座(Gemini)季铵盐,为式Ⅰ所示化合物:
式Ⅰ中,R1和R2分别独立选自:C6~C18的直链或支链烷基或含氟C6~C12直链或支链烷基中一种,Y为C1~C12的烃基,X为卤素(F、Cl、Br或I)或含氧酸根(如TfO、HSO4或HNO3等)。
本发明另一个目的在于,提供一种组合物,所述组合物包括:式Ⅰ所示化合物,杀菌剂和水;
其中,所述杀菌剂为2,2-二溴-3-次氮基丙酰胺(DBNPA),陶氏快速杀菌剂(QK-20)或苯丙异塞唑啉酮(VFB-1)。
本发明还有一个目的在于,揭示式Ⅰ所示化合物的一种用途,即:式Ⅰ所示化合物在制备水性涂料的罐内抗菌防腐剂中的应用。
此外,本发明还提供一种制备式Ⅰ所示化合物的方法,所述方法包括如下步骤:
(1)3-羟基吡啶与溴代或/和碘代烷(BrR1,BrR2,IR1或/和IR2)反应,制备式Ⅱa所示化合物和Ⅱb所示化合物的步骤;
(2)式Ⅱa所示化合物或/和Ⅱb所示化合物与二卤代化合物(X1—Y—X1)反应,得到目标化合物的步骤;
其中,X1为卤素(F、Cl、Br或I),R1,R2和Y的含义与前文所示相同。
具体实施方式
在本发明一个优选的技术方案中,R1和R2相同,均为C6~C18的直链或支链烷基或含氟C6~C12直链或支链烷基。
在本发明另一个优选技术方案中,Y为二价的C1~C5的脂烃基或二价的C6~C12芳烃基;
进一步优选的技术方案是:Y为二价的C1~C5直链或支链的烷基或链烯基,或二价的C6~C12芳烃基;
更进一步优选的技术方案是:Y为亚甲基(CH2),二价的乙烯基,二价苯基或二价联苯基;
在本发明又一个优选技术方案中,所述(杀菌)组合物包括:3.0重量份数~10.0重量份数的式Ⅰ所示化合物和0.1重量份数~1.0重量份数的杀菌剂(DBNPA、QK-20或VFB-1),余量为水。
本发明所述双子座(Gemini)季铵盐可用于水性涂料体系。所述水性涂料体系,除含本发明提供双子座(Gemini)季铵盐外,还包括下列组分:
成膜物质组分,如:粒径为150nm~240nm,玻璃化温度Tg为18℃~26℃,最低成膜温度(MFFT)为9℃~15℃的醋丙(共聚)乳液;
颜/填料组分,所述颜料组分包括:金红石型钛白粉;所述填料包括:硅灰石、硅宝、滑石粉、煅烧高岭土和/或重钙;
HASE助剂组分,所述HASE助剂如:HASE疏水分散剂助剂等;
水性蜡乳液组分,所述水性蜡乳液如:水性微细氧化聚乙烯蜡乳化液等;
助溶剂组分,所述助溶剂如:二醇类抗冻剂等;
成膜助剂组分,所述成膜助剂如:醇酯类溶剂等;
涂料助剂组分,其包括:消泡剂、pH调节剂、增稠剂和防霉剂等;
其中,所述消泡剂为有机硅类消泡剂或矿物油类消泡剂,所述增稠剂为聚氨酯类流变调节剂或无机膨润土,所述pH调节剂为有机醇胺pH调节剂。
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。下列实施例中未注明具体条件的实验方法,通常按照国家标准测定。若没有相应的国家标准,则按照通用的国际标准、常规条件、或按照制造厂商所建议的条件进行。除非另外说明,否则所有的份数为重量份数,所有的百分比为重量百分比,所述的聚合物分子量为数均分子量。
实施例1
式Ⅰ-1所示化合物的制备:
(1)在插有温度计的250ml三口烧瓶中,加入1份的3-羟基吡啶,溶剂N,N-二甲基甲酰胺(DMF),磁力搅拌。再加入3份的NaH,有气泡产生,待气泡消去后,加入1.5份的1-溴-十二烷,加热至70℃。磁力搅拌,用TLC跟踪反应至原料点消失,停止搅拌,得到深棕色液体,用水洗涤该深棕色液体(3次),合并水相,再用二氯甲烷(DCM)萃取3次,合并有机相,用无水Na2SO4干燥,过滤,滤液经蒸除溶剂后,得到深棕色液体,再通过硅胶柱柱层析(石油醚/乙酸乙酯=20/1(v/v)),得到淡黄色固体(式Ⅱ-1所示化合物)。
(2)在100ml耐压反应管中投入3份式Ⅱ-1所示化合物与1份的1,4-二溴-2-丁烯,无水乙腈作为溶剂,加热至90℃,使乙腈回流。磁力搅拌反应,用TLC跟踪反应至原料点消失,停止加热,冷却后有大量淡黄色固体析出,抽滤,滤饼用乙酸乙酯/乙醇体系重结晶,得到的白色固体(式Ⅰ-1所示化合物),得率为95%。
1H NMR(400MHz,CDCl3)δ9.42(s,2H),9.29(d,J=4.0Hz,2H),7.99-7.96(m,2H),7.89-7.86(m,2H),6.81(s,2H),5.89(d,J=4.0Hz,4H),4.34(t,J=8.0Hz,4H),1.85-1.78(m,4H),1.49-1.42(m,4H),1.30-1.26(m,32H),0.88(t,J=8.0Hz,6H).
13C NMR(100MHz,CDCl3)δ158.5,138.0,132.3,131.4,130.9,128.5,71.8,61.4,31.9,29.7,29.63,29.60,29.5,29.36,29.35,28.8,25.8,22.7,14.1。
实施例2
式Ⅰ-2所示化合物的制备:
除以1,3-二溴丙烷替换实施例1中1,4-二溴-2-丁烯外,其它步骤及条件与实施例1相同,得到标题化合物,得率为55%。
1H NMR(400MHz,CDCl3)δ9.68(s,2H),9.34-9.32(m,2H),7.88-7.83(m,4H),5.23(t,J=8.0Hz,4H),4.34(t,J=8.0Hz,4H),3.30-3.22(m,2H),1.86-1.83(m,4H),1.48-1.47(m,4H),1.34-1.26(m,32H),0.88(t,J=8.0Hz,6H).
13C NMR(100MHz,CDCl3)δ158.7,137.9,132.6,131.1,128.2,71.9,57.8,35.6,31.9,29.63,29.60,29.54,29.46,29.33,29.27,28.7,25.8,22.7,14.1。
实施例3
式Ⅰ-3所示化合物的制备:
除以联苯二溴苄替换实施例1中1,4-二溴-2-丁烯外,其它步骤及条件与实施例1相同,得到标题化合物,得率为60%。
1H NMR(400MHz,CDCl3)δ9.72(s,2H),9.36-9.34(m,2H),8.88-8.83(m,2H),8.56-8.53(m,2H),7.43-7.41(m,4H),7.35-7.33(m,4H),6.06(s,4H),4.26-4.23(m,4H),1.77-1.75(m,4H),1.44-1.43(m,4H),1.31-1.26(m,32H),0.88(t,J=8.0Hz,6H).
13C NMR(100MHz,CDCl3)δ158.6,142.8,140.2,138.1,134.5,133.5,132.8,131.5,131.1,130.9,130.3,71.8,62.4,31.9,29.71,29.63,29.62,29.52,29.38,29.32,28.7,25.8,22.7,14.1。
实施例4
式Ⅰ-4所示化合物的制备:
除以1-碘-2-全氟正丁基乙烷(CF3CF2CF2CF2CH2CH2I)替换实施例1中1-溴-十二烷外,其它步骤及条件与实施例1相同,得到标题化合物,得率为25%。
1H NMR(400MHz,CDCl3)δ9.43(s,2H),9.28-9.26(m,2H),7.99-7.96(m,2H),7.89-7.86(m,2H),6.81(s,2H),5.90-5.88(m,4H),4.34(t,J=8.0Hz,4H),2.03-1.76(m,4H).
13C NMR(100MHz,CDCl3)δ158.7,138.1,132.3,131.5,130.9,128.5,122.5,119.7,118.5,123.3,61.4,58.7,31.4.
19F NMR(376MHz,CDCl3)δ-80.97~-81.03(m,6F),-114.66~-114.73(m,4F),-124.37~-124.45(m,4F),-125.97~-126.04(m,4F)。
实施例5~12
根据实施例1~4的教导,采用相应原料做替换,可以制得表1.所列化合物。
表1.
本发明提供的双子座(Gemini)季铵盐在水性涂料中性能测试
实施例13
(1)将由实施例1~12制备双子座季铵盐分别与常用工业杀菌剂DBNPA、QK-20、VFB-1和水做成复配物(所述复配物的具体物组分及含量见表2.),得到水性涂料罐内防腐剂(表2中简记为“罐内防腐剂”):H1~H36。
表2
续表2
续表2
(2)分别将水性涂料罐内防腐剂H1~H36与其它组分(具体见表3.(水性涂料组分表))按下列步骤制得水性涂料,采用行业内常用的CTFA细菌挑战实验标准和方法测试所得水性涂料的抗菌防霉性能,及按照国标(GB/T 9756-2009内墙涂料国家标准)对所得水性涂料的耐水、耐碱等涂料全性能进行测试,结果见表4.(水性涂料性能测试结果)。
表3.水性涂料组分表
制备所述水性涂料的方法,包括以下步骤:
(1)将水放入分散罐内,转速控制在400转/分钟;
(2)然后依次将消泡剂、HASE疏水分散剂助剂加入到分散罐内,搅拌3分钟;
(3)将颜填料加入分散罐内,提高转速至1200转/分钟,高速分散12分钟;
(4)高速分散后降转速至600转/分钟,加入水,搅拌4分钟;
(5)缓慢加入成膜物质,搅拌3分钟;
(6)接着加入助溶剂和成膜助剂,搅拌3分钟;
(7)再依次加入防霉剂和新型罐内抗菌防腐剂,搅拌2分钟;
(8)缓慢加入水性微细氧化聚乙烯蜡乳化液,搅拌3分钟;
(9)再加入含氟表面活性剂,搅拌4分钟;
(10)然后加入pH调节剂,将pH值调节为8-10;
(11)最后加入水调节粘度,得到所述涂料组合物。
表4.水性涂料性能测试结果
由上述表4.可知,本发明提供的双子座(Gemini)季铵盐在水性涂料中抗菌性能优异,高效,符合工业生产化要求,可替代传统,目前常用的异塞唑啉酮类罐内防腐剂。且本发明产品对涂料本身性能无影响,真正保证了水性涂料在罐内存贮的质量性能。
Claims (6)
3.一种组合物,其包括:权利要求1或2所述的双子座季铵盐,杀菌剂和水;
其中,所述杀菌剂为2,2-二溴-3-次氮基丙酰胺,陶氏快速杀菌剂或苯丙异塞唑啉酮。
4.如权利要求3所述的组合物,其特征在于,所述组合物包括:3.0重量份数~10.0重量份数的权利要求1或2所述的双子座季铵盐和0.1重量份数~1.0重量份数的杀菌剂。
5.如权利要求1所述的双子座季铵盐在制备水性涂料的罐内抗菌防腐剂中的应用。
6.如权利要求3所述组合物作为水性涂料的罐内抗菌防腐剂的应用。
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