CN114573762B - 一种具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物及制备方法 - Google Patents
一种具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物及制备方法 Download PDFInfo
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Abstract
一种具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物及制备方法，属于有机抗菌聚合物技术领域。聚氨酯丙烯酸酯主链上枝接了苯并异噻唑啉酮衍生物，聚氨酯丙烯酸酯主链上枝接了苯并异噻唑啉酮衍生物，结构式中包括如下嵌段；主要是利用含有双键的N‑取代苯并异噻唑酮抗菌剂与聚氨酯丙烯酸酯低聚物、活性稀释剂、光引发剂按照一定比例混合，通过紫外光固化反应聚合而成。本发明以化学键嵌入到材料主链中的方式实现对材料的功能化改性，既避免了小分子抗菌剂流失的问题，又扩大了抗菌剂的使用范围。嵌段A嵌段B嵌段C嵌段D和基团
Description
技术领域
本发明公开一种具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物的结构及其制备方法，属于有机抗菌聚合物技术领域。
背景技术
卫生健康的重要性已经得到越来越多的重视，与微生物斗争不仅仅发生在医疗领域，在日常办公用品、家具、电器表面也极容易滋生细菌，细菌长时间附着在其表面，会导致表面涂层收到细菌侵蚀引发剥落，影响美观的同时还会导致涂层的使用价值大打折扣。为了解决这种问题，在涂层中引入抗菌单元，通过将高效、低毒或无毒的抗菌剂利用化学方法连接到涂料基材主链，合成功能化抗菌涂料。
杂环类小分子存在于许多具有药理领域的生物活性化合物之中，含杂环的药物小分子已经被认为是非常优异的抗菌剂。苯并异噻唑啉酮(BIT)类化合物热稳定性较好，具有很好的杀菌性能和很好的安全性能，是国际上公认的高效、低毒、广谱性的新型杀菌剂。其抗菌机理主要因为其能够扩散穿过细菌细胞膜，N-S键的缺电子硫可以与细胞组分的亲核基团反应，如蛋白质活性位点半胱氨酸的硫醇，阻止它们的酶活性，最终导致细胞死亡(Isothiazolinone Biocides:Chemistry,Biological,and Toxicity Profiles[J].Molecules 2020,25(4),991)。
中国专利CN11068423报道一种5-氯-烷基异噻唑啉酮制备方法，获得了单氯代烷基异噻唑啉酮抗菌剂，可广泛应用于杀菌防腐领域；中国专利CN111887256报道苯并异噻唑啉酮在预防或灭杀害虫中应用广泛；中国专利111635374报道了一种含N-烯丙基-(苯并异噻唑啉-3-酮-2-基)甲酰胺单体的丙烯酸树脂的结构和制备方法，可在海洋防污涂料领域广泛应用。然而将含有烯烃长链的N-取代苯并异噻唑啉酮利用紫外光固化合成聚氨酯丙烯酸酯涂膜的方法还未见到相关报道。
发明内容
本发明所要解决的技术问题是提供一种具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物的结构及其制备方法。所制备的苯并异噻唑啉酮衍生物抗菌剂不仅具备一般异噻唑啉酮高效、低毒、广谱抗菌的特点，而且分子具有碳碳双键，可与其他化合物利用紫外光固化反应后通过化学键嵌入材料中，既避免了小分子抗菌剂流失的问题，又扩大了抗菌剂的使用范围。
本发明提供一种具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物，其特征在于，所述苯并异噻唑啉酮衍生物指的是含有双键的N-取代苯并异噻唑啉酮，聚氨酯丙烯酸酯主链上枝接了苯并异噻唑啉酮衍生物，结构式中包括如下嵌段：嵌段A嵌段B/>嵌段C/>嵌段D/>和基团/>进一步由上述嵌段和/>基团构成；/>在具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物中的质量百分含量为30-60％；
其中，所述R1为具有三分支结构且每个分支末端为双键的聚氨酯聚合物，三分支结构末端至少有两个在具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物中进行单碳键连接，典型结构之一如式(1)所示，其中的m、n取值范围为1-30；所述R2可选C1～C10的脂肪基团；a、b、c、d为聚合度可根据需要调节，如取值范围为2-50等；
具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物的一种结构式表达如下式(2)：
波浪线代表未写出的化学键连接。
R1的一种结构式即式(3)
本发明提供了具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物的制备方法，其特征在于，包括以下步骤：
(1)按照公开报道方法制备R1聚合物，典型结构之一如式(3)所示；
(2)选取比R2多一个碳对应的溴代长链烯烃的苯并异噻唑啉酮溶解于乙腈中，进行有机合成方法合成后，通过柱层析技术进行产物提纯、除去有机溶剂后，即得式(4)所示结构的苯并异噻唑啉酮衍生物淡黄色油状液体产物；
(3)将R1聚合物、式(3)所示苯并异噻唑啉酮衍生物、嵌段A对应的活性稀释剂单体A、嵌段B对应的活性稀释剂单体B、嵌段B对应的活性稀释剂单体B、光引发剂混合得到聚氨酯丙烯酸酯预聚体；
(4)由步骤(3)所得的聚氨酯丙烯酸酯预聚体，经紫外光固化后成膜。
上述举例如聚氨酯聚合物R1：活性稀释剂单体(A+B+C)：苯并异噻唑啉酮衍生物＝5：4.7：0.6；其中活性稀释剂的质量比a:b:c＝5:3:2。
本发明以化学键嵌入到材料主链中的方式实现对材料的功能化改性，既避免了小分子抗菌剂流失的问题，又扩大了抗菌剂的使用范围。
附图说明
图1为实施例1中N取代苯并异噻唑啉酮抗菌剂的核磁共振氢谱图。
图2为实施例1中N取代苯并异噻唑啉酮抗菌剂的核磁共振碳谱图。
图3为实施例2-4中制备得到的嵌入不同的苯并异噻唑啉酮衍生物抗菌聚氨酯丙烯酸酯涂膜的全反射衰减红外光谱图。
图4为实施例2-4中制备得到的嵌入不同的苯并异噻唑啉酮衍生物抗菌聚氨酯丙烯酸酯涂膜在N2条件下的热重曲线示意图。所制备的涂膜均有较良好的热稳定性。
图5为实施例2-4中制备得到的嵌入不同的苯并异噻唑啉酮衍生物抗菌聚氨酯丙烯酸酯涂膜对大肠杆菌和金黄色葡萄球菌的结果示意图。随着添加的N取代苯并异噻唑啉酮的侧链长度的增加，其抗菌性能降低。但是与未添加抗菌剂的聚氨酯丙烯酸酯的涂膜相比，其涂膜对于革兰氏阳性菌金黄色葡萄球菌和革兰氏阴性菌大肠杆菌均有抗菌效果。
具体实施方式(将实施例中的)
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。
实施例1
将10mmol化合物A和10mmol K2CO3分别添加到100mL三口烧瓶中，向其中加入50mLDMF，在N2条件下磁力搅拌5min，再加入20mmol B。在90℃中回流，通过TLC点板监测反应的进程。待反应完全后，冷却至室温，向三口烧瓶中加入去离子水，然后用乙酸乙酯萃取混合溶液，用无水硫酸钠进行干燥，过滤收集滤液，后旋蒸除去乙酸乙酯。用色谱层析柱(石油醚和乙酸乙酯)进行进一步提纯，得到的淡黄色油状物即为目标产物C。
实施例2
将异佛尔酮二异氰酸酯(1.25g)和50mg催化剂二月桂酸二丁基锡加入到50mL三口烧瓶中，在45℃逐滴加入聚醚多元醇HSH330N(8.39g)，机械搅拌反应2h，后向体系中滴加丙烯酸-2-羟基乙酯(0.36g)，对体系中的-NCO进行封端。反应1h后即得到了聚氨酯丙烯酸酯低聚物。
将聚氨酯丙烯酸酯、活性稀释剂(1,6-己二醇二丙烯酸酯，三羟甲基丙烷三丙烯酸酯，丙烯酸异冰片酯)和光引发剂2-羟基-2-甲基-1-苯基-1-丙酮以5:4.7:0.3质量比加入烧杯中搅拌均匀，随后加入质量分数为6wt％的式(4)所示苯并异噻唑啉酮衍生物(R2为C4烷基)，将混合物超声处理1h后将其在涂抹到50mm×50mm聚碳酸酯板上，再覆盖一层聚乙烯薄膜以抑制光照时氧阻聚的发生。在高压汞灯下曝光一定时间获得紫外光固化聚氨酯丙烯酸酯涂膜PABITC6-6wt％。
实施例3
将异佛尔酮二异氰酸酯(1.25g)和50mg催化剂二月桂酸二丁基锡加入到50mL三口烧瓶中，在45℃逐滴加入聚醚多元醇HSH330N(8.39g)，机械搅拌反应2h，后向体系中滴加丙烯酸-2-羟基乙酯(0.36g)，对体系中的-NCO进行封端。反应1h后即得到了聚氨酯丙烯酸酯低聚物。
将聚氨酯丙烯酸酯、活性稀释剂(1,6-己二醇二丙烯酸酯，三羟甲基丙烷三丙烯酸酯，丙烯酸异冰片酯)和光引发剂2-羟基-2-甲基-1-苯基-1-丙酮以5:4.7:0.3质量比加入烧杯中搅拌均匀，随后加入6wt％的式(4)所示苯并异噻唑啉酮衍生物(R2为C6烷基)，将混合物超声处理1h后将其在涂抹到50mm×50mm聚碳酸酯板上，再覆盖一层聚乙烯薄膜以抑制光照时氧阻聚的发生。在高压汞灯下曝光一定时间获得紫外光固化聚氨酯丙烯酸酯涂膜PABITC8-6wt％。
实施例4
将异佛尔酮二异氰酸酯(1.25g)和50mg催化剂二月桂酸二丁基锡加入到50mL三口烧瓶中，在45℃逐滴加入聚醚多元醇HSH330N(8.39g)，机械搅拌反应2h，后向体系中滴加丙烯酸-2-羟基乙酯(0.36g)，对体系中的-NCO进行封端。反应1h后即得到了聚氨酯丙烯酸酯低聚物。
将聚氨酯丙烯酸酯、活性稀释剂(1,6-己二醇二丙烯酸酯，三羟甲基丙烷三丙烯酸酯，丙烯酸异冰片酯)和光引发剂2-羟基-2-甲基-1-苯基-1-丙酮以5:4.7:0.3质量比加入烧杯中搅拌均匀，随后加入质量分数为6wt％的式(4)所示苯并异噻唑啉酮衍生物(R2为C8烷基)，将混合物超声处理1h后将其在涂抹到50mm×50mm聚碳酸酯板上，再覆盖一层聚乙烯薄膜以抑制光照时氧阻聚的发生。在高压汞灯下曝光一定时间获得紫外光固化聚氨酯丙烯酸酯涂膜PABITC10-6wt％。
将上述实施例2-4中所得抗菌涂膜和没有嵌入抗菌剂的涂膜对大肠杆菌和金黄色葡萄球菌分别进行热稳定性测试，用没有嵌入N-取代苯并异噻唑酮抗菌剂的涂膜作为对照组。
将上述实施例2-4中所得抗菌涂膜和没有嵌入抗菌剂的涂膜对细菌浓度均为107CFU·mL-1的大肠杆菌和金黄色葡萄球菌进行抗菌测试，用没有嵌入N取代苯并异噻唑酮抗菌剂的涂膜作为对照组。
Claims (6)
1.一种具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物涂膜，其特征在于，所述苯并异噻唑啉酮衍生物指的是含有双键的N-取代苯并异噻唑啉酮，聚氨酯丙烯酸酯聚合物为：聚氨酯丙烯酸酯主链上枝接了苯并异噻唑啉酮衍生物，聚氨酯丙烯酸酯聚合物结构式中包括如下嵌段：嵌段A嵌段B嵌段C/>嵌段D
和基团/>所述R1为具有三分支结构且每个分支末端为双键的聚氨酯聚合物，三分支结构末端至少有两个在具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物中进行单碳键连接，所述R2选自C1～C10的脂肪基团；a、b、c、d为聚合度；在具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物中的质量百分含量为30-60％；
具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物的制备方法，包括以下步骤：
(1)按照公开报道方法制备R1聚合物；
(2)选取比R2多一个碳对应的溴代长链烯烃的苯并异噻唑啉酮溶解于乙腈中，进行有机合成方法合成后，通过柱层析技术进行产物提纯、除去有机溶剂后，即得苯并异噻唑啉酮衍生物淡黄色油状液体产物；
(3)将R1聚合物、步骤(2)所得苯并异噻唑啉酮衍生物、嵌段A对应的活性稀释剂单体A、嵌段B对应的活性稀释剂单体B、嵌段C对应的活性稀释剂单体C、光引发剂混合得到聚氨酯丙烯酸酯预聚体；
(4)由步骤(3)所得的聚氨酯丙烯酸酯预聚体，经紫外光固化后成膜。
2.按照权利要求1所述的一种具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物涂膜，其特征在于，a、b、c、d取值范围为2-50。
3.按照权利要求1所述的一种具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物涂膜，其特征在于，R1结构之一如式(1)所示，其中m、n的取值范围为1-30。
4.按照权利要求1所述的一种具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物涂膜，其特征在于，具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物的一种结构式表达如下式(2)：
波浪线代表未写出的化学键连接。
5.权利要求1或2所述的一种具有抗菌性的含有苯并异噻唑啉酮衍生物的聚氨酯丙烯酸酯聚合物涂膜的制备方法，其特征在于，包括以下步骤：
(1)按照公开报道方法制备R1聚合物，进一步典型结构之一如式(3)所示；
(2)选取比R2多一个碳对应的溴代长链烯烃的苯并异噻唑啉酮溶解于乙腈中，进行有机合成方法合成后，通过柱层析技术进行产物提纯、除去有机溶剂后，即得式(4)所示结构的苯并异噻唑啉酮衍生物淡黄色油状液体产物；
(3)将R1聚合物、式(4)所示苯并异噻唑啉酮衍生物、嵌段A对应的活性稀释剂单体A、嵌段B对应的活性稀释剂单体B、嵌段C对应的活性稀释剂单体C、光引发剂混合得到聚氨酯丙烯酸酯预聚体；
(4)由步骤(3)所得的聚氨酯丙烯酸酯预聚体，经紫外光固化后成膜；
R1的一种结构式即式(3)
A：
B：
C：
6.按照权利要求5所述的制备方法，其特征在于，聚氨酯聚合物R1：活性稀释剂单体(A+B+C)：苯并异噻唑啉酮衍生物的质量比＝5：4.7：0.6；其中活性稀释剂的质量比a:b:c＝5:3:2。
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030733A (zh) * | 2012-12-06 | 2013-04-10 | 青岛大学 | 一种侧链含苯异噻唑啉酮的聚丙烯酸酯防污共聚树脂及其制备方法 |
| CN109942629A (zh) * | 2019-03-21 | 2019-06-28 | 北京化工大学 | 一种含有三羟基的六季鏻阳离子抗菌剂及其制备方法 |
| CN111635374A (zh) * | 2019-09-28 | 2020-09-08 | 海南大学 | 一种含苯并异噻唑啉酮甲酰胺功能单体的丙烯酸树脂的结构及制备方法 |
| CN112279957A (zh) * | 2019-07-22 | 2021-01-29 | 广东迪美生物技术有限公司 | 水性聚丙烯酸酯抗菌乳液及其制备方法和在涂料中的应用 |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030733A (zh) * | 2012-12-06 | 2013-04-10 | 青岛大学 | 一种侧链含苯异噻唑啉酮的聚丙烯酸酯防污共聚树脂及其制备方法 |
| CN109942629A (zh) * | 2019-03-21 | 2019-06-28 | 北京化工大学 | 一种含有三羟基的六季鏻阳离子抗菌剂及其制备方法 |
| CN112279957A (zh) * | 2019-07-22 | 2021-01-29 | 广东迪美生物技术有限公司 | 水性聚丙烯酸酯抗菌乳液及其制备方法和在涂料中的应用 |
| CN111635374A (zh) * | 2019-09-28 | 2020-09-08 | 海南大学 | 一种含苯并异噻唑啉酮甲酰胺功能单体的丙烯酸树脂的结构及制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| 含不饱和侧链异噻唑啉类抗菌剂的合成及其抗菌性能初步评价;衡士芳等;纺织学报;第第30卷卷(第第9期期);第87-92页 * |
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