CN115340626A - 一种接枝酚异噻唑啉酮丙烯酸酯单体的杀菌防污树脂及其制备方法 - Google Patents
一种接枝酚异噻唑啉酮丙烯酸酯单体的杀菌防污树脂及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种接枝酚异噻唑啉酮丙烯酸酯单体的防污杀菌树脂及其制备方法，用于海洋防污杀菌材料领域。将2，4，6‑三甲酰基均苯三酚还原成2，4，6‑三羟甲基均苯三酚，再与固体光气、丙烯酰氯、异噻唑啉酮类化合物反应，制得接枝酚异噻唑啉酮丙烯酸酯单体，单体与丙烯酸酯共聚，制得接枝酚异噻唑啉酮丙烯酸酯防污杀菌树脂。本发明的树脂具有优异的抑藻、杀菌、自抛光性能，通过酯键的缓慢水解，控制活性物质的释放，达到长期防污杀菌目的，有效延长海洋建筑、船舶、海洋设施的寿命。
Description
技术领域
本发明属于海洋防污防腐杀菌涂料领域，尤其涉及一种接枝酚异噻唑啉酮丙烯酸酯单体的防污杀菌树脂及其制备方法。
背景技术
自全球禁止使用有机锡防污涂料以来，现有防污涂料应用效果较差，急需开发新型高效环保的防污涂料。
异噻唑啉酮类化合物是一种广谱、高效、低毒的新型工业杀菌防腐剂，具有突出的抑制细菌、霉毒、真菌和藻类等微生物的繁殖的作用，是较理想的防污杀菌防腐剂。CN111574658公开了一种接枝苯并异噻唑啉酮甲酸酯单体的丙烯酸酯类防污树脂，具有良好的防污性能和自抛光性能，且对海洋环境友好，但该树脂不具备抑菌功能。CN104761667公开了一种改性苯并异噻唑啉酮接枝的丙烯酸锌树脂，具有较好的抑菌、抑制海洋生物的附着和生长、水解抛光的功能，能延缓防污剂的释放。但是，目前可使用的性能较好的海洋防污杀菌树脂种类仍然较少。同时接枝抑菌、抑藻的酚基、异噻唑啉酮基活性成分制备的丙烯酸酯树脂并用于海洋防污杀菌未见报道。
发明内容
为解决上述问题，本发明提供一种接枝酚异噻唑啉酮丙烯酸酯单体的防污杀菌树脂及其制备方法，可以获得同时含有抑菌、抑藻的酚基、异噻唑啉酮基活性成分的丙烯酸酯树脂，该树脂不仅具有杀菌作用，还能够抑制海洋生物的附着和生长，具有水解抛光功能。所述树脂能延缓防污剂的释放，有效延长海洋固体建筑、设施和船舶涂层的防污寿命。所述树脂环境友好，绿色高效、经济。
本发明还提供了一种接枝酚异噻唑啉酮丙烯酸酯单体的制备方法。
本发明再提供了一种接枝酚异噻唑啉酮丙烯酸酯单体的杀菌防污树脂，用于海洋防污杀菌涂料，其对海洋藻类、菌类、藤壶和贻贝等大型污损生物表现出了非常好的抑制能力，具有高效、环保、经济的特点。
本发明采用如下技术方案：
所述一种接枝酚异噻唑啉酮丙烯酸酯单体的杀菌防污树脂，其结构如下所示：
其中，R1独立选自H，CH3；R2独立选自
，
；R3独立选自CH3, C4H9。
所述的一种接枝丙烯酸酯的酚异噻唑啉酮丙烯酸酯单体，其结构如下所示：
其中，R1独立选自H，CH3；R2独立选自
，
；
所述一种接枝酚异噻唑啉酮丙烯酸酯单体的杀菌防污树脂的制备方法，包括以下步骤：
酚异噻唑啉酮丙烯酸酯单体的制备：
N2氛围下，将2，4，6-三甲酰基均苯三酚溶于甲醇中，加入3倍摩尔量的NaBH4，室温反应3h，加入适量水，减压蒸出甲醇，乙酸乙酯萃取，无水硫酸钠干燥，过滤，浓缩，硅胶柱层析纯化，制得2，4，6-三羟甲基均苯三酚，收率91.2%。
N2氛围下，将1摩尔量的2，4，6-三羟甲基均苯三酚溶于二氯甲烷中，加入5.5摩尔量的三乙胺，降温至0℃以下，加入2摩尔量的固体光气，搅拌，再分别加入2摩尔量的苯并[d]异噻唑啉-3-酮或4，5-二氯异噻唑啉酮，保温反应1h，再分别加入1摩尔量的丙烯酰氯或3-甲基丙烯酰氯，保温反应1h，升温至室温，反应2h，加水猝灭反应，分层，二氯甲烷萃取，有机相用无水硫酸钠干燥，过滤，浓缩，硅胶柱层析纯化，制得酚异噻唑啉酮丙烯酸酯单体。
接枝酚异噻唑啉酮丙烯酸酯单体的杀菌防污树脂的制备：
将酚异噻唑啉酮丙烯酸酯单体10-20份溶于有机溶剂中，滴加到丙烯酸酯20-40份和有机溶剂40-60份的溶液中，再加入引发剂0.1-1.0份，60-120℃反应6-12h，冷至室温，得到接枝酚异噻唑啉酮丙烯酸酯单体的杀菌防污树脂。
其中，所述有机溶剂为氯仿、甲苯、二甲苯、二氧六环、DMF的一种或几种的混合物。
所述的一种接枝酚异噻唑啉酮丙烯酸酯单体的杀菌防污树脂用于制备海洋防污、防腐、杀菌、水解抛光涂料，能单独或与其它涂料混合涂覆于海洋固体建筑、设施和船舶表面，用于海洋防污防腐，抑制包括海藻、藤壶、牡蜗在内的生物的生长，用于抑制海洋中常见的菌的繁殖。所述树脂环境友好，绿色高效、经济。
本发明的有益之处：本发明将具有较强抗菌能力的活性成分苯并[d]异噻唑啉-3-酮或4，5-二氯异噻唑啉酮、具有好的聚合性能的丙烯酸基同时接枝到含3个酚羟基的具有强的杀菌抑藻作用的2，4，6-三羟甲基均苯三酚分子上，再与丙烯酸酯聚合，使防污剂以共价键与树脂结合，经水解缓慢释放出防污杀菌活性成分，加上酚羟基的直接杀菌、抑藻功能，确保了所述树脂的高效、持久、环境友好的杀菌、抑藻功能。
下面举例对本发明做更详细的描述。但这并非是对本发明的限制，本领域技术人员根据本发明的基本思想，可以做出各种变型或改性，只要不脱离本发明的基本思想，均在本发明之内。
实施例1
酚异噻唑啉酮丙烯酸酯单体1的制备：
N2氛围下，将21g (0.1mol)2，4，6-三甲酰基均苯三酚溶于100mL甲醇中，加入11.3g (0.3mol)NaBH4，室温反应3h，加入50mL水，减压蒸出甲醇，乙酸乙酯萃取，无水硫酸钠干燥，过滤，浓缩，硅胶柱层析纯化，制得2，4，6-三羟甲基均苯三酚，收率91.2%。
N2氛围下，将21.6g (0.1mol)2，4，6-三羟甲基均苯三酚溶于100mL二氯甲烷中，加55.6g (0.55mol)三乙胺，降温至0℃以下，加入2摩尔量的59.4g (0.2mol)固体光气，搅拌，加入30.2g (0.2mol)苯并[d]异噻唑啉-3-酮，保温反应1h，再加入9.0g (0.1mol)丙烯酰氯，保温反应1h，升温至室温，反应2h，加水猝灭反应，分层，二氯甲烷萃取，有机相用无水硫酸钠干燥，过滤，浓缩，硅胶柱层析纯化，制得酚异噻唑啉酮丙烯酸酯单体1。
实施例2
酚异噻唑啉酮丙烯酸酯单体2的制备：
以10.4g (0.1mol)3-甲基丙烯酰氯代替9.0g (0.1mol)丙烯酰氯，其它操作与实施例1相同，制得酚异噻唑啉酮丙烯酸酯单体2。
实施例3
酚异噻唑啉酮丙烯酸酯单体3的制备：
以34g (0.2mol)4，5-二氯异噻唑啉酮代替30.2g (0.2mol)苯并[d]异噻唑啉-3-酮，其它操作与实施例1相同，制得酚异噻唑啉酮丙烯酸酯单体3。
实施例4
酚异噻唑啉酮丙烯酸酯单体4的制备：
以10.4g (0.1mol)3-甲基丙烯酰氯代替9.0g (0.1mol)丙烯酰氯，其它操作与实施例3相同，制得酚异噻唑啉酮丙烯酸酯单体4。
实施例5
接枝酚异噻唑啉酮丙烯酸甲酯单体的杀菌防污树脂1的制备：
将20份酚异噻唑啉酮丙烯酸酯单体1溶于30份二甲苯中，滴加到丙烯酸甲酯40份和二甲苯50份的溶液中，再加入偶氮异丁腈0.1份，120℃反应6h，冷至室温，得到接枝酚异噻唑啉酮丙烯酸酯单体的杀菌防污树脂1。
实施例6
接枝酚异噻唑啉酮丙烯酸甲酯单体的杀菌防污树脂2的制备：
将10份酚异噻唑啉酮丙烯酸酯单体2溶于15份氯仿中，滴加到丙烯酸丁酯20份和氯仿35份的溶液中，再加入偶氮异丁腈1份，60℃反应12h，冷至室温，得到接枝酚异噻唑啉酮丙烯酸酯单体的杀菌防污树脂2。
实施例7
接枝酚异噻唑啉酮丙烯酸甲酯单体的杀菌防污树脂3的制备：
将12份酚异噻唑啉酮丙烯酸酯单体3溶于15份二氧六环中，滴加到丙烯酸丁酯30份和氯仿35份的溶液中，再加入偶氮异丁腈0.5份，100℃反应10h，冷至室温，得到接枝酚异噻唑啉酮丙烯酸酯单体的杀菌防污树脂3。
实施例8
接枝酚异噻唑啉酮丙烯酸甲酯单体的杀菌防污树脂4的制备：
将15份酚异噻唑啉酮丙烯酸酯单体4溶于20份甲苯中，滴加到丙烯酸甲酯40份和甲苯40份与DMF10份的混合溶液中，再加入过氧苯甲酰0.5份，110℃反应9h，冷至室温，得到接枝酚异噻唑啉酮丙烯酸酯单体的杀菌防污树脂4。
实施例9
采用吸光度法测试防污杀菌树脂的抑菌性能。制备的防污杀菌树脂1-4对金黄色葡萄球菌、溶珊瑚弧菌和副溶血弧菌在12h的抑菌率如表1所示。与空白样品对照，涂有防污杀菌树脂1-4的样品的孔板中菌的数量显著减少，说明防污杀菌树脂1-4具有很好的抑制海洋细菌的生长能力。
实施例10
采用吸光度法测试防污杀菌树脂的抑藻性能。制备的防污杀菌树脂1-4对小球藻、球等鞭金藻和旋链角毛藻在7d的抑制率如表2所示。与空白样品对照，加有防污杀菌树脂样品板的塑料杯中，藻液颜色非常浅，说明防污杀菌树脂1-4具有很好的抑制海洋藻类的生长能力。
上述实施例仅例示性说明发明的原理及其功效，而非用于限制本发明。举凡所属领域的中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。
Claims (4)
1.一种接枝酚异噻唑啉酮丙烯酸酯单体的防污杀菌树脂及其制备方法，其特征在于，树脂的结构如下所示：
其中，R1独立选自H，CH3；R2独立选自
，
；R3独立选自CH3, C4H9。
2.根据权利要求要求1所述的一种接枝酚异噻唑啉酮丙烯酸酯单体的防污杀菌树脂及其制备方法，其特征在于，所述接枝丙烯酸酯的酚异噻唑啉酮丙烯酸酯单体的结构如下所示：
其中，R1独立选自H，CH3；R2独立选自
，
。
3.根据权利要求1所述的一种接枝酚异噻唑啉酮丙烯酸酯单体的防污杀菌树脂的制备方法，其特征在于，包括以下步骤：
酚异噻唑啉酮丙烯酸酯单体的制备：
N2氛围下，将2，4，6-三甲酰基均苯三酚溶于甲醇中，加入3倍摩尔量的NaBH4，室温反应3h，加入适量水，减压蒸出甲醇，乙酸乙酯萃取，无水硫酸钠干燥，过滤，浓缩，硅胶柱层析纯化，制得2，4，6-三羟甲基均苯三酚，收率91.2%；
N2氛围下，将1摩尔量的2，4，6-三羟甲基均苯三酚溶于二氯甲烷中，加入5.5倍摩尔量的三乙胺，降温至0℃以下，加入2倍摩尔量的固体光气，搅拌，再分别加入2摩尔量的苯并[d]异噻唑啉-3-酮或4，5-二氯异噻唑啉酮，保温反应1h，再分别加入1摩尔量的丙烯酰氯或3-甲基丙烯酰氯，保温反应1h，升温至室温，反应2h，加水猝灭反应，分层，二氯甲烷萃取，有机相用无水硫酸钠干燥，过滤，浓缩，硅胶柱层析纯化，制得酚异噻唑啉酮丙烯酸酯单体；
接枝酚异噻唑啉酮丙烯酸酯单体的防污杀菌树脂的制备：将酚异噻唑啉酮丙烯酸酯单体10-20份溶于有机溶剂中，滴加到丙烯酸酯20-40份和有机溶剂40-60份的溶液中，再加入引发剂0.1-1.0份，60-120℃反应6-12h，冷至室温，得到接枝酚异噻唑啉酮丙烯酸酯单体的杀菌防污树脂，其中，所述有机溶剂为氯仿、甲苯、二甲苯、二氧六环、DMF的一种或几种的混合物。
4.根据权利要求1所述的一种接枝酚异噻唑啉酮丙烯酸酯单体的防污杀菌树脂及其制备方法，其特征在于，所述接枝酚异噻唑啉酮丙烯酸酯单体的杀菌防污树脂用于制备海洋防污、防腐、杀菌、水解抛光涂料，能单独或与其它涂料混合涂覆于海洋固体建筑、设施和船舶表面，用于海洋防污防腐，抑制包括海藻、藤壶、牡蜗在内的生物的生长，用于抑制海洋中常见的菌的繁殖，环境友好，绿色高效、经济。
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Effective date of registration: 20240419 Address after: No.61, Fuqiang Road, Hecheng Town, Heshan City, Jiangmen City, Guangdong Province, 529700 Applicant after: Guangdong paint color new material Co.,Ltd. Country or region after: China Address before: Room 801, 85 Kefeng Road, Huangpu District, Guangzhou City, Guangdong Province Applicant before: Yami Technology (Guangzhou) Co.,Ltd. Country or region before: China |
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