CN114736221B - 一种稀土基配合物海洋防污剂及其制备方法 - Google Patents
一种稀土基配合物海洋防污剂及其制备方法 Download PDFInfo
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- CN114736221B CN114736221B CN202210327705.9A CN202210327705A CN114736221B CN 114736221 B CN114736221 B CN 114736221B CN 202210327705 A CN202210327705 A CN 202210327705A CN 114736221 B CN114736221 B CN 114736221B
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
本发明公开了一种稀土基配合物海洋防污剂及其制备方法,其有效成分的结构式包括其中,R为H、烷基、杂环基或巯基,Re选自镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、钇和钪稀土元素。本发明由吡啶硫酮钠、酸性α‑氨基酸与可溶性稀土盐三元通过配位构成,降低海洋生物对防污剂的排斥性,使得抗菌防污效果明显,又增加防污剂渗透性,更好渗入细胞内,与细胞内结构结合,从而有效抑制细菌的新陈代谢,具有抗菌广谱、抗菌能力强、抗菌效力持久和生态安全风险低等优点。
Description
技术领域
本发明属于海洋防污剂技术领域,具体涉及一种稀土基配合物海洋防污剂及其制备方法。
背景技术
海洋污损是指海洋生物在海上设施设备上生长,造成设施设备损毁或增加而外的燃料消耗,导致巨大的经济损失和能源浪费。因此,人们通过各种技术手段防止海生物的附着生长。目前,最经济最有效的防治手段是在设施设备上涂敷一层防污涂料,通过防污涂料释放毒性防污剂实现防止海生物生长的目的。当前,防污涂料主要由氧化亚铜、氧化锌和有机防污剂复配,自抛光树脂等构成。随着研究的深入,人们发现重金属铜容易在海生物体内富集,存在潜在生态风险,因此,替代重金属铜新型防污剂的研究成为了全球科研工作者重点研究方向。
由于稀土离子和Ca2+的离子半径接近,化学性质相似,,均属硬酸,对不同配位数的配位空间都具有较大的适应性,所以稀土可以结合在钙结合蛋白或钙依赖蛋白的钙结合位点上,从而干预Ca2+所介导的信号转导过程,诱导和影响细胞内钙信号,抑制细胞新陈代谢活动;此外,稀土毒性要比氧化亚铜低很多,生态安全性风险较低,现已作为各种抑菌剂杀菌剂以及抗癌药物被广泛应用,因此,以稀土及其衍生物为防污剂成为研究新方向。
CN 112175434A公开了一种含稀土/防污剂的防污凝胶粒子及其制备方法,该技术方案将稀土与白炭黑结合,再通过自由基共聚法将稀土抗菌白炭黑及防污剂共包覆,使制备的防污凝胶兼具亲水特性抗菌附着及防污剂杀菌双重功效。CN 101921530 A公开了一种无毒生物防污涂料及其制备方法,该技术方案提供了一种无毒生物防污涂料,主要是通过稀土元素激发碱土硅铝酸盐的夜光材料为光抑制剂,提供昼夜不休的环境照明,从而降低海洋生物的附着,该材料无毒无放射,减少对环境的不良作用。以上现有技术均将稀土离子以稀土盐的形式加入作为防污剂,所涉及的机制均不同。
发明内容
本发明目的在于提供一种稀土基配合物海洋防污剂。
本发明的另一目的在于提供上述稀土基配合物海洋防污剂的制备方法。
本发明的技术方案如下:
一种稀土基配合物海洋防污剂,其有效成分的结构式包括其由吡啶硫酮钠、酸性α-氨基酸与可溶性稀土盐配位构成,其中,R为H、烷基、杂环基或巯基,Re选自镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、钇和钪稀土元素。
在本发明的一个优选实施方案中,其有效成分的结构式为
在本发明的一个优选实施方案中,所述可溶性稀土盐为硝酸盐或氯化盐,其中的稀土元素选自镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、钇和钪。
在本发明的一个优选实施方案中,所述酸性α-氨基酸选自甘氨酸、丙氨酸、缬氨酸、亮氨酸、异亮氨酸、甲硫氨酸、脯氨酸、丝氨酸、酪氨酸、半胱氨酸、苯丙氨酸、苏氨酸和谷氨酸。
上述稀土配合物海洋防污剂的制备方法,包括如下步骤:
(1)将可溶性稀土盐与水混合,获得稀土盐溶液;
(2)将吡啶硫酮钠与无水乙醇混合,获得吡啶硫酮钠溶液;
(3)将酸性α-氨基酸与水混合,获得酸性α-氨基酸溶液;
(4)边搅拌,边将上述吡啶硫酮钠溶液滴加入上述稀土盐溶液中,滴加时间为5-20min,滴加完毕后继续搅拌20-40min;
(5)边搅拌,边将上述酸性α-氨基酸溶液滴加入步骤(4)所得的物料中,滴加时间为5-20min,滴加完毕后继续搅拌20-40min;
(6)将步骤(5)所得的物料进行离心,获得沉淀,将该沉淀用无水乙醇离心洗涤,然后烘干;
(7)将步骤(6)所得的物料研磨至粒径50-200nm,即得。
在本发明的一个优选实施方案中,所述可溶性稀土盐、吡啶硫酮钠和酸性α-氨基酸的质量比为2∶5-7∶2-3。
进一步优选的,所述步骤(1)中,可溶性稀土盐与水的质量比为1∶9。
进一步优选的,所述步骤(2)中,吡啶硫酮钠与无水乙醇的质量比为5-7∶13-15。
进一步优选的,所述步骤(3)中,酸性α-氨基酸与水的质量比为2-3∶17-18。
进一步优选的,所述步骤(1)中,可溶性稀土盐与水的质量比为1∶9;所述步骤(2)中,吡啶硫酮钠与无水乙醇的质量比为5-7∶13-15;所述步骤(3)中,酸性α-氨基酸与水的质量比为2-3∶17-18。
本发明的有益效果是:
1、本发明由吡啶硫酮钠、酸性α-氨基酸与可溶性稀土盐三元通过配位构成,稀土离子由于其类钙化学性质,可抑制菌类的代谢活动,具有抗菌、消炎、镇痛等作用;吡啶硫酮含氮杂环结构,氮杂环具有良好抑菌作用;酸性α-氨基酸是生物体必需元素之一,三者协同效应可降低海洋生物对防污剂的排斥性,使得抗菌防污效果明显,又增加防污剂渗透性,更好渗入细胞内,与细胞内蛋白活性中心结合,从而有效抑制细菌的新陈代谢,具有抗菌广谱、抗菌能力强、抗菌效力持久和生态安全风险低等优点。
2、本发明的制备方法工艺简单,环保,施工简便,所制备的配合物产率较高,具有良好的应用和推广前景,可应用于海洋防污涂料、塑料、橡胶、胶粘剂、纤维、日化品等材料中。
附图说明
图1为本发明实施例2中的镧三元配合物的红外图谱(纵坐标:%透过率,横坐标:波数(cm-1))。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
实施例1
(1)稀土盐溶液的制备:称取20g氯化铈,加入180g的水中,搅拌溶解,备用。
(2)吡啶硫酮钠溶液的制备:称取吡啶硫酮钠50g,加入150g的无水乙醇中,搅拌溶解,备用。
(3)酸性α-氨基酸溶液的制备:称取甘氨酸25g,加入175g的去离子水中,搅拌溶解,备用。
(4)在搅拌条件下,将上述吡啶硫酮钠溶液滴加入上述稀土盐溶液中,滴加时间约10min,滴加完成后继续搅拌20min。
(5)在搅拌条件下,将上述酸性α-氨基酸溶液滴加入步骤(4)所得的物料中,滴加时间约5min,滴加完成后继续搅拌40min。
(6)将步骤(5)所得的物料倒入离心管中,进行离心操作,倒去上清液;并用无水乙醇清洗5次,重复离心操作;最后,取出沉淀物,在105℃烘箱中干燥4.5h。
(7)将步骤(6)所得的物料研磨至50-190nm,密封,阴凉处保存。
实施例2
(1)稀土盐溶液的制备:称取20g硝酸镧,加入180g的水中,搅拌溶解,备用。
(2)吡啶硫酮钠溶液的制备:称取吡啶硫酮钠60g,加入140g的无水乙醇中,搅拌溶解,备用。
(3)酸性α-氨基酸溶液的制备:称取丝氨酸20g,加入180g的去离子水中,搅拌溶解,备用。
(4)在搅拌条件下,将上述吡啶硫酮钠溶液滴加入上述稀土盐溶液中,滴加时间约20min,滴加完成后继续搅拌30min。
(5)在搅拌条件下,将上述酸性α-氨基酸溶液滴加入步骤(4)所得的物料中,滴加时间约20min,滴加完成后继续搅拌30min。
(6)将步骤(5)所得的物料倒入离心管中,进行离心操作,倒去上清液;并用无水乙醇清洗4次,重复离心操作;最后,取出沉淀物,在105℃烘箱中干燥3h。
(7)将步骤(6)所得的物料研磨至50-180nm,密封,阴凉处保存,其有效成分,即镧三元配合物的红外图谱如图1所示。
实施例3
一种稀土基配合物海洋防污剂制备方法:
(1)稀土盐溶液的制备:称取20g硝酸铕加入180g的水中,搅拌溶解,备用。
(2)吡啶硫酮钠溶液的制备:称取吡啶硫酮钠70g,加入130g的无水乙醇中,搅拌溶解,备用。
(3)酸性α-氨基酸溶液的制备:称取谷氨酸30g,加入170g的去离子水中,搅拌溶解,备用。
(4)在搅拌条件下,将上述吡啶硫酮钠溶液滴加入上述稀土盐溶液中,滴加时间约5min,滴加完成后继续搅拌40min。
(5)在搅拌条件下,将上述酸性α-氨基酸溶液滴加入步骤(4)所得的物料中,滴加时间约20min,滴加完成后继续搅拌20min。
(6)将步骤(5)所得的物料倒入离心管中,进行离心操作,倒去上清液;并用无水乙醇清洗3次,重复离心操作;最后,取出沉淀物,在105℃烘箱中干燥6h。
(7)将步骤(6)所得的物料研磨至50-200nm,密封,阴凉处保存。
实施例4
一种稀土基配合物海洋防污剂制备方法:
(1)稀土盐溶液的制备:称取20g硝酸镧,加入180g的水中,搅拌溶解,备用。
(2)吡啶硫酮钠溶液的制备:称取吡啶硫酮钠60g,加入140g的无水乙醇中,搅拌溶解,备用。
(3)酸性α-氨基酸溶液的制备:称取天冬氨酸20g,加入180g的去离子水中,搅拌溶解,备用。
(4)在搅拌条件下,将上述吡啶硫酮钠溶液滴加入上述稀土盐溶液中,滴加时间约20min,滴加完成后继续搅拌30min。
(5)在搅拌条件下,将上述酸性α-氨基酸溶液滴加入步骤(4)所得的物料中,滴加时间约20min,滴加完成后继续搅拌30min。
(6)将步骤(5)所得的物料倒入离心管中,进行离心操作,倒去上清液;并用无水乙醇清洗4次,重复离心操作;最后,取出沉淀物,在105℃烘箱中干燥3h。
(7)将步骤(6)所得的物料研磨至50-180nm,密封,阴凉处保存。
实施例5
(1)稀土盐溶液的制备:称取20g氯化钆,加入180g的水中,搅拌溶解,备用。
(2)吡啶硫酮钠溶液的制备:称取吡啶硫酮钠55g,加入145g的无水乙醇中,搅拌溶解,备用。
(3)酸性α-氨基酸溶液的制备:称取甘氨酸25g,加入175g的去离子水中,搅拌溶解,备用。
(4)在搅拌条件下,将上述吡啶硫酮钠溶液滴加入上述稀土盐溶液中,滴加时间约14min,滴加完成后继续搅拌22min。
(5)在搅拌条件下,将上述酸性α-氨基酸溶液滴加入步骤(4)所得的物料中,滴加时间约12min,滴加完成后继续搅拌26min。
(6)将步骤(5)所得的物料倒入离心管中,进行离心操作,倒去上清液;并用无水乙醇清洗5次,重复离心操作;最后,取出沉淀物,在105℃烘箱中干燥2.6h。
(7)将步骤(6)所得的物料研磨至50-120nm,密封,阴凉处保存。
对比例1
(1)稀土盐溶液的制备:称取20g硝酸镧,加入180g的水中,搅拌溶解,备用。
(2)吡啶硫酮钠溶液的制备:称取吡啶硫酮钠60g,加入140g的无水乙醇中,搅拌溶解,备用。
(3)在搅拌条件下,将上述吡啶硫酮钠溶液滴加入上述稀土盐溶液中,滴加时间约20min,滴加完成后继续搅拌30min。
(4)将步骤(3)所得的物料倒入离心管中,进行离心操作,倒去上清液;并用无水乙醇清洗4次,重复离心操作;最后,取出沉淀物,在105℃烘箱中干燥3h。
(5)将步骤(4)所得的物料研磨至50-180nm,密封,阴凉处保存。
对比例2
(1)稀土盐溶液的制备:称取20g硝酸镧,加入180g的水中,搅拌溶解,备用。
(2)酸性α-氨基酸溶液的制备:称取丝氨酸60g,加入140g的无水乙醇中,搅拌溶解,备用。
(3)在搅拌条件下,将上述酸性α-氨基酸溶液滴加入上述稀土盐溶液中,滴加时间约20min,滴加完成后继续搅拌30min。
(4)将步骤(3)所得的物料倒入离心管中,进行离心操作,倒去上清液;并用无水乙醇清洗4次,重复离心操作;最后,取出沉淀物,在105℃烘箱中干燥3h。
(5)将步骤(4)所得的物料研磨至50-180nm,密封,阴凉处保存。
实施例和对比例所制得的样品的抗菌性能采用培养基扩散法测试评估:
培养基扩散法原理:利用抗菌剂不断溶解经琼脂扩散形成不同浓度梯度,以显示其抗菌作用。
操作步骤:将实施例和对比例所制得的样品用去离子水溶解,配制成0.005mol/L的溶液,分别试验对大肠杆菌和金黄葡萄球菌的抑菌作用。采用培养基扩散法,在37℃培养箱中经18-24h培养后,用游标卡尺测定其抑菌圈直径。
抑菌圈结果评判规定和抗菌性能评价:进行平行3次重复实验,抗菌剂样品片均有抑菌效果的,判为合格;否则实验无效。根据《中华人民共和国化工行业标准》,通过抑菌圈直径大小来判断抗菌剂能力。抑菌圈直径小于或等于7mm者,判为无抑菌作用;抑菌圈直径大于7mm者,有弱抑菌作用;抑菌圈在10-20mm者,有中等抑菌作用;抑菌圈直径大于20mm者,有强抑菌作用。
表1实施例及对比例的效果
以上所述,仅为本发明的较佳实施例而已,故不能依此限定本发明实施的范围,即依本发明专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明涵盖的范围内。
Claims (7)
1.一种稀土基配合物海洋防污剂,其特征在于:其有效成分的结构式为
其由吡啶硫酮、酸性α-氨基酸与可溶性稀土盐配位构成,其中,R为H、CH2OH或CH2CH2COOH,Re选自镧、铈、铕和钆,可溶性稀土盐为硝酸盐或氯化盐,其中的稀土元素选自镧、铈、铕和钆,酸性α-氨基酸选自甘氨酸、丝氨酸和谷氨酸;
其制备方法包括如下步骤:
(1)将可溶性稀土盐与水混合,获得稀土盐溶液;
(2)将吡啶硫酮钠与无水乙醇混合,获得吡啶硫酮钠溶液;
(3)将酸性α-氨基酸与水混合,获得酸性α-氨基酸溶液;
(4)边搅拌,边将上述吡啶硫酮钠溶液滴加入上述稀土盐溶液中,滴加时间为5-20min,滴加完毕后继续搅拌20-40min;
(5)边搅拌,边将上述酸性α-氨基酸溶液滴加入步骤(4)所得的物料中,滴加时间为5-20min,滴加完毕后继续搅拌20-40min;
(6)将步骤(5)所得的物料进行离心,获得沉淀,将该沉淀用无水乙醇离心洗涤,然后烘干;
(7)将步骤(6)所得的物料研磨至粒径50-200nm,即得。
2.如权利要求1所述的一种稀土基配合物海洋防污剂,其特征在于:所述可溶性稀土盐、吡啶硫酮钠和酸性α-氨基酸的质量比为2:5-7:2-3。
3.如权利要求2所述的一种稀土基配合物海洋防污剂,其特征在于:所述步骤(1)中,可溶性稀土盐与水的质量比为1:9。
4.如权利要求2所述的一种稀土基配合物海洋防污剂,其特征在于:所述步骤(2)中,吡啶硫酮钠与无水乙醇的质量比为5-7:13-15。
5.如权利要求2所述的一种稀土基配合物海洋防污剂,其特征在于:所述步骤(3)中,酸性α-氨基酸与水的质量比为2-3:17-18。
6.如权利要求2所述的一种稀土基配合物海洋防污剂,其特征在于:所述步骤(1)中,可溶性稀土盐与水的质量比为1:9;所述步骤(2)中,吡啶硫酮钠与无水乙醇的质量比为5-7:13-15;所述步骤(3)中,酸性α-氨基酸与水的质量比为2-3:17-18。
7.一种稀土基配合物海洋防污剂,其特征在于:其有效成分的结构式为其由吡啶硫酮、天冬氨酸与可溶性稀土盐配位构成,其中,R为CH2COOH,Re为镧,可溶性稀土盐为硝酸镧;
其制备方法包括如下步骤:
(1)稀土盐溶液的制备:称取20g硝酸镧,加入180g的水中,搅拌溶解,备用;
(2)吡啶硫酮钠溶液的制备:称取吡啶硫酮钠60g,加入140g的无水乙醇中,搅拌溶解,备用;
(3)天冬氨酸溶液的制备:称取天冬氨酸20g,加入180g的去离子水中,搅拌溶解,备用;
(4)在搅拌条件下,将上述吡啶硫酮钠溶液滴加入上述稀土盐溶液中,滴加时间约20min,滴加完成后继续搅拌30min;
(5)在搅拌条件下,将上述天冬氨酸溶液滴加入步骤(4)所得的物料中,滴加时间约20min,滴加完成后继续搅拌30min;
(6)将步骤(5)所得的物料倒入离心管中,进行离心操作,倒去上清液;并用无水乙醇清洗4次,重复离心操作;最后,取出沉淀物,在105℃烘箱中干燥3h;
(7)将步骤(6)所得的物料研磨至50-180nm,密封,阴凉处保存。
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