CN111808481B - 一种单原子灭藻杀菌水池涂料及其制备方法 - Google Patents
一种单原子灭藻杀菌水池涂料及其制备方法 Download PDFInfo
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Abstract
本发明涉及水池涂料领域，具体公开了一种单原子灭藻杀菌水池涂料及其制备方法。一种单原子灭藻杀菌水池涂料，包括以下比例份的原料：产品包含以下重量百分比的组分：去离子水20‑30%、分散剂2.0‑3.0%、消泡剂0.2‑1.0%、丙二醇1.5‑2.5%、填料20‑35%、增稠剂1.0‑2.0%、成膜助剂1.0‑3.0%、超细苯丙乳液35‑45%、pH调节剂0.1‑0.5%、单原子灭藻杀菌剂1.0‑8.0%；其制备方法为：先加去离子水，搅拌下加入分散剂、消泡剂、丙二醇、填料、单原子灭藻杀菌剂，搅拌，研磨，再依次加入增稠剂、去离子水、成膜助剂、超细苯丙乳液、消泡剂、pH调节剂搅拌制得成品。本发明应用于水池涂料，其具有灭藻防藻、抗菌杀毒、持久净化的优点。
Description
技术领域
本发明涉及内墙涂料领域，更具体地说，它涉及一种单原子灭藻杀菌水池涂料及其制备方法。
背景技术
水是生命之源，水资源的安全利用对人类生存发展至关重要，在生活中，常见的绿藻、蓝藻等水体藻类和金黄色葡萄球菌、大肠杆菌、H1N1病毒、沙门氏菌等常见水体致病微生物对水体生态平衡的严重破坏，进而影响饮水安全、水体感观、水产养殖业等方方面面。传统的灭藻杀菌化学药剂存在毒性大、有效期短、污染严重、不可回收等致命缺陷，因此开发新型、实用、长效的灭藻防藻、抗菌杀毒、持久净化的材料对水的安全利用具有重大的意义。
近年来，单原子催化迅速发展为催化科学领域最热门的前沿领域，广泛地应用在能源、材料、化工、医疗、生物等领域，在科学领域掀起一股热烈地研究热潮。相对于纳米尺度催化剂而言，单原子催化剂以单个原子为活性中心，催化活性材料利用率达到了100％，极大地降低了催化剂成本。单原子催化剂活性位点清晰均匀，具有高活性和高选择性。单原子催化剂在杀菌消毒、防霉除藻等领域表现出巨大的潜力，且结构非常稳定，对生物体无毒害作用，不污染环境，自身不消耗，长效持久。
发明内容
针对常见的水体藻类和常见水体致病微生物对水体生态平衡的严重破坏，进而影响饮水安全、水体感观、水产养殖业，特此提供一种具有灭藻防藻、抗菌杀毒、持久净化多重特殊功能的单原子灭藻杀菌水池涂料。
本发明的第二个目的在于提供一种单原子灭藻杀菌水池涂料的制备方法，所述制备方法具有操作简单，可进行大规模工业化生产的优点。
为实现上述第一个目的，本发明提供了如下技术方案：一种单原子灭藻杀菌水池涂料，产品包含以下重量百分比的组分：去离子水20-30％、分散剂2.0-3.0％、消泡剂0.2-1.0％、丙二醇1.5-2.5％、填料20-35％、增稠剂1.0-2.0％、成膜助剂1.0-3.0％、超细苯丙乳液35-45％、pH调节剂0.1-0.5％、单原子灭藻杀菌剂1.0-8.0％。
通过采用上述技术方案，由于采用单原子抗菌消毒剂，在杀菌消毒、防霉除藻等领域表现出巨大的潜力，且结构非常稳定，对生物体无毒害作用，不污染环境，自身不消耗，长效持久，因此，获得灭藻防藻、抗菌杀毒、持久净化多重功能。
进一步地，产品包含以下重量百分比的组分：产品包含以下重量百分比的组分：去离子水25-30％、分散剂2.0-3.0％、消泡剂0.2-1.0％、丙二醇1.5-2.5％、填料20-35％、成膜助剂1.5-2.0％、超细苯丙乳液35-40％、pH调节剂0.2％、单原子灭藻杀菌剂2.0-5.0％。
通过采用上述技术方案，在保证本发明灭藻防藻、抗菌杀毒、持久净化的效果下，控制单原子灭藻杀菌剂添加量，可节约生产成本。
进一步地，超细苯丙乳液粒径为100-200nm；消泡剂为非硅酮矿物油系；所述分散剂为聚羧酸铵盐；所述成膜助剂为醇酯十二；所述增稠剂为缔合型聚氨酯；所述pH调节剂为二甲基乙醇胺。
通过采用上述技术方案，由于采用聚羧酸铵盐，因此，获得对填料粉体有良好的分散效果好；由于采用缔合型聚氨酯，因此，获得了可调节粘度，起到稳定增稠作用；采用二甲基乙醇胺可调节pH同时作水溶性涂料助溶剂；醇酯十二可有效降低其最低成膜温度，便于涂料使用。
进一步地，单原子抗菌消毒剂由载体和过渡金属组成，其中载体为钛白粉、硅藻土、碳酸钙、高岭土、氧化铝、沸石分子筛中的一种或多种，过渡金属选自铁、钴、镍、铜、锌、银、锰中的一种或多种。
通过采用上述技术方案，可制备得到无需其他辅助条件，即可高效活化空气或水中的氧，产生活性氧物种，氧化细菌的细胞膜、蛋白质、遗传物质，并将其杀死的单原子抗菌消毒剂。
进一步地，单原子抗菌消毒剂过渡金属以单原子形式锚定在载体表面的缺陷位点中；所述单原子抗菌消毒剂中过渡金属和载体的质量比为1:10-1:100。
通过采用上述技术方案，对起到抗菌消毒的过渡金属有效成分进行控制，当过渡金属和载体的质量比为1:10-1:100时，运用到本申请的水池内墙涂料中，不仅可以与填料均匀混合，使其在长时间使用过程中，单原子抗菌消毒剂析出释放，保证生产的单原子抗菌消毒剂的质量，还可降低单原子抗菌消毒剂在涂料配方中的质量百分比，降低工业生产成本；且单原子抗菌消毒剂结构稳定，自身不消耗，可以重复多次使用，对环境无污染，对生物体无副作用。
进一步地，所述填料由占配料总质量15-25％的钛白粉、2.0-5.0％的高岭土、2.0-5.0％的沉淀硅酸铝组成；钛白粉粒径为200nm，高岭土粒径为1μm，沉淀硅酸铝粒径为50nm。
通过采用上述技术方案，填料的粒径处于纳米级，纳米分散相具有较大的表面积和强的界面相互作用，可有效的与单原子抗菌消毒剂结合，可保证填料较细度均匀同时保障涂料的耐候性和抗菌持久性；钛白粉的使用可使本内墙涂料在日光照射下,耐日晒,不开裂、不变色，伸展率大、耐酸碱；高岭土良好的结合性，可使得钛白粉、沉淀硅酸铝更好混合在一起，保证填料混合均匀度；沉淀硅酸铝起到提升储存稳定性和降低钛白粉用量的作用。
进一步地，填料粉体还包括0.5-1％辣椒碱、0.2-1％的氧化锌晶须。
通过采用上述技术方案，辣椒碱接枝连接于苯丙乳液中的苯乙烯-丙烯酸酯链上，涂覆于水池壁上可缓慢释放处辣椒碱起到防污抗菌的作用，辅助增强抗藻杀菌作用；氧化锌晶须高度形态规整和尺寸均一性，可有效改善涂料墙面的耐老化性能和耐热性，同时因氧化锌晶须高密度的特性，涂了本申请的墙面的吸波减振性能良好，有效降低水池中水波对水池壁上涂料的冲击，提升本申请涂料的使用寿命；氧化锌晶须呈四脚三维空间结构，可有效与单原子抗菌消毒剂的结合，降低单原子抗菌消毒剂在使用过程中，从涂料层中脱离的概率，起到辅助强度抗菌消毒作用；为了水池水质，水池会用到紫外线杀菌对水体消毒，氧化锌晶须在紫外光区具有显著的吸收特征，可起到良好的抗紫外线作用，可保证本申请涂料对紫外线的抵抗强度，从而保证本申请具有长久的使用寿命。
为实现上述第二个目的，本发明提供了如下技术方案：一种单原子灭藻杀菌水池涂料的制备方法，包括以下步骤：
步骤1：容器中加入15-20％的去离子水，在持续搅拌下，依次加入分散剂、消泡剂、丙二醇，搅拌5-8分钟；
步骤2：调节搅拌转速至500-600转/分钟，依次加入填料、单原子灭藻杀菌剂，搅拌10-15分钟，将转速调至1000-1200转/分钟持，续搅拌30分钟；
步骤3：将步骤2的浆料进行搅拌10-15分钟，调节搅拌转速至1200转/分钟，加入增稠剂、持续搅拌，随后依次加入剩余的去离子水、成膜助剂、超细苯丙乳液、消泡剂、pH调节剂，充分搅拌10-15分钟，制得涂料成品。
通过采用上述技术方案，涂料配制操作简单，可进行大规模工业化生产。
进一步地，步骤1中，搅拌状态下转速200-400转/分钟；步骤2中，填料的添加顺序为依次加入辣椒碱、钛白粉、高岭土、沉淀硅酸铝、氧化锌晶须；步骤3：将步骤2的浆料进行搅拌10-15分钟，搅拌转速为1200-1400转/分钟。
通过采用上述技术方案，步骤1中通过控制搅拌转速，可使得分散剂、消泡剂、丙二醇三者低速混合均匀；步骤2中在低速搅拌下先添加辣椒碱，可使得辣椒碱分散于物料中，与后加入的填料均匀混合，便于后续接枝于苯乙烯-丙烯酸酯链上；步骤3对步骤2的浆料进行搅拌10-15分钟是为了调节浆料的细度，使各组分物料之间混合均匀，便于后续处理。
进一步地，步骤3中，加入增稠剂后，持续搅拌5-10分钟以形成均匀的漩涡状，搅拌为600-800转/分钟。
通过采用上述技术方案，进一步使各组分物料之间混合均匀，便于后续处理。
综上所述，本发明具有以下有益效果：
1、本发明使用新研发的单原子灭藻杀菌剂，采用全新的原子灭藻杀菌技术，无需任何辅助条件，可广谱杀灭常见水体致病微生物，全天候净化水质。
2、本发明的单原子灭藻杀菌水池涂料的持续作用时间较长，且自身不产生任何耐药性，可取代传统毒性大、有效期短、污染严重的灭藻杀菌药剂。
3、本发明可广泛用于饮用蓄水池、游泳池、景观池、水产养殖常见水池领域，具有灭藻杀菌、净化水质、长效持久、绿色环保、安全无毒等优势功能，是一种较优异的功能型水池涂料。
具体实施方式
以下结合和实施例对本发明作进一步详细说明。
原料
原料的制备例
制备例1：
单原子抗菌消毒剂的制备，步骤1，将5g/L硝酸银的水溶液加入硅藻土中，其中过渡金属盐与载体的质量比为1:20，所得溶液100kHz的条件下超声30min分散均匀，然后再将混合溶液100r/min搅拌12h；
步骤2，将步骤1得到的混合溶液升温至水的沸点，高温挥发，蒸干溶剂，并用球磨机于50r/min转速下充分研磨0.5小时，得到固体粉末；
步骤3，将步骤2得到的固体粉末在空气气氛和400℃的温度条件下加热处理2h，冷却到室温，球磨机于50r/min转速下研磨20min，即得所需的催化剂。
实施例
实施例1
一种单原子灭藻杀菌水池涂料，包含以下重量百分比的组分：去离子水23.5％、聚羧酸铵盐2.5％、非硅酮矿物油系0.5％、丙二醇1.8％、填料23％、缔合型聚氨酯1.5％、醇酯十二2％、超细苯丙乳液40％、二甲基乙醇胺0.2％、单原子灭藻杀菌剂5％；填料由占配料总重量18％的钛白粉、3％的高岭土、2％的沉淀硅酸铝组成。
一种单原子灭藻杀菌水池涂料的制备方法，包含以下步骤：
1)在选用不锈钢铁通中，先加入14.5kg的去离子水，搅拌转速300转/分钟，在持续搅拌下，依次加入2.5kg聚羧酸铵盐、0.2kg非硅酮矿物油消泡剂、1.8kg丙二醇，搅拌5分钟，使所有物料均匀混合；
2)将搅拌转速调到500转/分钟，依次缓慢加入18kg钛白粉、3kg高岭土、2kg沉淀硅酸铝、5kg单原子灭藻杀菌剂，充分搅拌15分钟，将转速调至1000转/分钟，持续搅拌30分钟；
3)搅拌转速调至1400转/分钟，将上述浆料均匀搅拌15分钟后，搅拌转速调至1200转/分钟，在该搅拌速度下，依次加入1.5kg缔合型聚氨酯，调整搅拌转速为600转/分钟，持续搅拌10分钟以形成均匀的漩涡状，随后依次加入9kg去离子水、2kg醇酯十二、40kg超细苯丙乳液、0.3kg非硅酮矿物油系、0.2kg二甲基乙醇胺，充分搅拌10分钟制得涂料成品。
实施例二
实施例二与实施例一的区别在于：单原子灭藻杀菌水池涂料配方中去离子水25.5％、超细苯丙乳液42％、单原子灭藻杀菌剂1％，其他组分均相同。
实施例三
实施例三与实施例一的区别在于：单原子灭藻杀菌水池涂料配方中去离子水24.5％、超细苯丙乳液42％、单原子灭藻杀菌剂2％，其他组分均相同。
实施例四
实施例四与实施例一的区别在于：单原子灭藻杀菌水池涂料配方中去离子水22.5％、超细苯丙乳液38％、单原子灭藻杀菌剂8％，其他组分均相同。
实施例五
一种单原子灭藻杀菌水池涂料，包含以下重量百分比的组分：去离子水23.5％、聚羧酸铵盐2.5％、非硅酮矿物油系0.5％、丙二醇1.8％、填料23％、缔合型聚氨酯1.5％、醇酯十二2％、超细苯丙乳液40％、二甲基乙醇胺0.2％、单原子灭藻杀菌剂5％；填料由钛白粉17％、高岭土3％、沉淀硅酸铝2％和1％辣椒碱组成。
一种单原子灭藻杀菌水池涂料的制备方法，包含以下步骤：
1)在不锈钢铁通中，先加入14.5kg的去离子水，搅拌转速300转/分钟，在持续搅拌下，依次加入2.5kg聚羧酸铵盐、0.2kg非硅酮矿物油系、1.8kg丙二醇，搅拌5分钟，使所有物料均匀混合；
2)将转速调到500转/分钟，依次缓慢加入1kg辣椒碱、17kg钛白粉、3kg高岭土、2kg沉淀硅酸铝、5kg单原子灭藻杀菌剂，其中辣椒碱添加速度为200g/分钟，充分搅拌15分钟，将转速调至1000转/分钟，持续搅拌30分钟；
3)搅拌转速调至1400转/分钟，将上述浆料均匀研磨15分钟后，搅拌转速调至1200转/分钟，在该搅拌速度下，依次加入1.5kg缔合型聚氨酯，持续搅拌10分钟以形成均匀的漩涡状，随后依次加入9kg去离子水、2kg醇酯十二、40kg超细苯丙乳液、0.3kg非硅酮矿物油系、0.2kg二甲基乙醇胺，充分搅拌10分钟制得涂料成品。
实施例六
实施例六与实施例五的区别在于：原子灭藻杀菌水池涂料配方中填料由占原料总质量16.7％的钛白粉、3％的高岭土、2％的沉淀硅酸铝、0.3％的氧化锌晶须和1％的辣椒碱组成。
对比例
对比例1
与实施例一的区别在于：单原子抗菌消毒内墙涂料配方中的超细苯丙乳液43％，去离子水25.5％，不添加单原子抗菌消毒剂，其他组分均相同。
对比例2
与实施例一的区别在于：单原子抗菌消毒内墙涂料配方中去离子水25.5％、超细苯丙乳液42.5％，单原子抗菌消毒剂0.5％，其他组分均相同。
性能检测试验
1.抗细菌测试方法：按照GB/T21866-2008标准要求测试。
2.抗霉菌测试：试验菌种：黑曲霉AS3.4463、土曲霉AS3.3935、宛氏拟青霉AS3.4253、绳状青霉AS3.3875、出芽短梗霉AS3.3984、球毛壳霉AS3.4254。试验条件：时间28天，湿度90％RH，温度28℃。
检测方法/试验方法
表1实施例1-6和对比例1-3的抗细菌测试参数
表2实施例1-7和对比例1-3的抗霉菌测试参数
结合实施例1-6和对比例1-2并结合表1可以看出，添加单原子抗菌消毒剂的涂料具有较好的抗细菌性能；且单原子抗菌消毒剂用量在2-5％抗细菌效果可保证杀菌效果同时降低生产成本。
结合表1可以看出，实施例5和6的测试抗菌率大于实施例1-3的测试抗菌率，抗菌效果与实施例4相同，因此，添加氧化锌晶须和辣椒碱对涂料的抗菌性能有积极作用。
结合实施例1-6和对比例1-2并结合表2可以看出，添加单原子抗菌消毒剂的涂料具有较好的抗霉菌性能。
综上所述，本发明使用新研发的单原子灭藻杀菌剂，采用全新的原子灭藻杀菌技术，无需任何辅助条件，可广谱杀灭常见水体致病微生物，全天候净化水质。本发明可广泛用于饮用蓄水池、游泳池、景观池、水产养殖常见水池领域，具有灭藻杀菌、净化水质、长效持久、绿色环保、安全无毒等优势功能，是一种较优异的功能型水池涂料。
本具体实施例仅仅是对本发明的解释，其并不是对本发明的限制，本领域技术人员在阅读完本说明书后可以根据需要对本实施例做出没有创造性贡献的修改，但只要在本发明的权利要求范围内都受到专利法的保护。
Claims (5)
1.一种单原子灭藻杀菌水池涂料，其特征在于，所述产品包含以下重量百分比的组分：去离子水25-30%、聚羧酸铵盐2.0-3.0%、非硅酮矿物油系消泡剂0.2-1.0%、丙二醇1.5-2.5%、填料20-35%、缔合型聚氨酯1.0-2.0%、醇酯十二1.5-2.0%、粒径为100-200nm的超细苯丙乳液35-40%、二甲基乙醇胺0.2%、单原子灭藻杀菌剂2.0-5.0%；单原子灭藻杀菌剂由载体和过渡金属组成，其中载体为硅藻土，过渡金属选自银；所述单原子灭藻杀菌剂过渡金属以单原子形式锚定在载体表面的缺陷位点中；所述单原子灭藻杀菌剂中过渡金属和载体的质量比为1:20；所述单原子灭藻杀菌剂的制备方法，步骤 1，将 5g/L 硝酸银的水溶液加入硅藻土中，其中硝酸银与硅藻土的质量比为 1:20，所得溶液 100kHz 的条件下超声 30min分散均匀，然后再将混合溶液 100r/min 搅拌 12h；步骤 2，将步骤 1 得到的混合溶液升温至水的沸点，高温挥发，蒸干溶剂，并用球磨机于 50r/min 转速下充分研磨 0.5 小时，得到固体粉末；步骤 3，将步骤 2 得到的固体粉末在空气气氛和 400℃的温度条件下加热处理 2h，冷却到室温，球磨机于 50r/min 转速下研磨 20min，即得所需的单原子灭藻杀菌剂；填料由占配料总质量15-25%的钛白粉、2.0-5.0%的高岭土、2.0-5.0%的沉淀硅酸铝组成；钛白粉粒径为200nm，高岭土粒径为1μm，沉淀硅酸铝粒径为50nm。
2.根据权利要求1所述的一种单原子灭藻杀菌水池涂料，其特征在于，所述填料还包括0.5-1%辣椒碱、0.2-1%的氧化锌晶须。
3.权利要求2所述的一种单原子灭藻杀菌水池涂料的制备方法，其特征在于，包括以下步骤：
步骤1：容器中加入15-20%的去离子水，在持续搅拌下，依次加入聚羧酸铵盐、非硅酮矿物油系消泡剂、丙二醇，搅拌5-8分钟；
步骤2：调节搅拌转速至500-600转/分钟，依次加入填料、单原子灭藻杀菌剂，搅拌10-15分钟，将转速调至1000-1200转/分钟持续搅拌30分钟；
步骤3：将步骤2的浆料进行搅拌10-15分钟，调节搅拌转速至1200转/分钟，加入缔合型聚氨酯持续搅拌，随后依次加入剩余的去离子水、醇酯十二、粒径为100-200nm的超细苯丙乳液、剩余的非硅酮矿物油系消泡剂、二甲基乙醇胺，充分搅拌10-15分钟，制得涂料成品。
4.权利要求3所述的一种单原子灭藻杀菌水池涂料的制备方法，其特征在于，步骤1中，搅拌状态下转速200-400转/分钟；步骤2中，填料的添加顺序为依次加入辣椒碱、钛白粉、高岭土、沉淀硅酸铝、氧化锌晶须；步骤3：将步骤2的浆料进行搅拌10-15分钟，搅拌转速为1200-1400转/分钟。
5.权利要求4所述的一种单原子灭藻杀菌水池涂料的制备方法，其特征在于，步骤3中，加入增稠剂后，持续搅拌5-10分钟以形成均匀的漩涡状，搅拌为600-800转/分钟。
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