CN108795243B - 一种添加疏水改性氧化亚铜制备渔网用防污防腐涂料的方法 - Google Patents
一种添加疏水改性氧化亚铜制备渔网用防污防腐涂料的方法 Download PDFInfo
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Abstract
本发明公开了一种添加疏水改性氧化亚铜制备渔网用防污防腐涂料的方法,将石墨烯分散液、混酸氧化修饰的碳纳米管加入到水性环氧树脂中搅拌均匀,加入固化剂,搅拌至树脂和固化剂完全混合后,再与氯磺化聚乙烯树脂、松香、增塑剂及辐照改性三聚磷酸铝、改性氧化亚铜加入带有密封盖的铁桶中,密封后,快速分散振荡,过滤分装涂料。采用gamma射线对三聚磷酸铝进行辐射改性,高辐照剂量改性三聚磷酸铝的腐蚀抑制性能得到明显提高,以其为填料制备防腐涂料,长期防腐蚀性能优异。石墨烯具备优异的隔水性能,可以提高环氧树脂的阻抗模值,增大涂层耐腐蚀性能。
Description
技术领域
本发明属于渔网防污防腐领域,具体涉及一种添加疏水改性氧化亚铜制备渔网用防污防腐涂料的方法。
背景技术
与其它海洋设施相同,水产养殖业也面临着同样严重的生物污损问题。污损生物不仅对于养殖生物产生严重危害,而且使得网衣网箱等渔用设备的使用寿命大大缩短,从而带来巨大的经济损失。针对水产养殖业的污损问题的防污措施主要有三种,物理去除、生物法和化学防污涂料。其中人工或物理机械的去除费时费力,生物控制方法利用生物之间的竞争达到防污目的也只适用于少量的特定生物,而较为长期有效的方法是防污涂料的使用。
腐蚀现象遍及国民经济和国防建设各个领域,石墨烯作为一种理想的二维片状纳米材料,在防腐功能涂料中有着非常诱人的潜在前景,而涂层保护是腐蚀控制最常用也是最直接的保护措施。碳纳米材料自发现以来,由于其独特的结构特性,引起了众多领域的研究者的广泛研究。近几年来,许多人将碳纳米材料应用到防腐涂料中以增强涂料的防腐性能。
发明内容
本发明的目的是针对现有的问题,提供了一种添加疏水改性氧化亚铜制备渔网用防污防腐涂料的方法,依照该方法制备的涂料具有良好的防污防腐性能,长期防污防腐蚀性能优异。
本发明是通过以下技术方案实现的:
一种添加疏水改性氧化亚铜制备渔网用防污防腐涂料的方法,其特征在于,包括如下步骤:
(1)三聚磷酸铝的辐照改性:
将15-25份三聚磷酸铝装入聚乙烯密封袋中,置于辐射场中,对其进行总辐照量为100-150kGy的gamma射线辐照;
(2)无机防污剂氧化亚铜的改性:
向10-20份氧化亚铜中加入2-4份改性剂KH570、100-150份蒸馏水,超声震荡10-15min后,在80-82℃下回流加热磁力搅拌反应4-5h,减压抽滤、用无水乙醇洗涤2-3次,在50-53℃烘箱中干燥过夜,制得改性氧化亚铜;
(3)防污防腐涂料:
将石墨烯分散液、混酸氧化修饰的碳纳米管加入到90-100份水性环氧树脂E44中搅拌均匀,加入30-33份固化剂DF1228,搅拌至树脂和固化剂完全混合后,再与30-40份氯磺化聚乙烯树脂、6-10份松香、2-5份增塑剂及(1)、(2)中所得物料加入带有密封盖的铁桶中,密封后,快速分散振荡,过滤分装涂料。
进一步的,步骤(1)中三聚磷酸铝为ZnO/SiO2改性三聚磷酸铝,辐射源为60Co,剂量率为1kGy/h。
进一步的,步骤(3)中石墨烯分散液的制备:
将1-2份聚吡咯烷酮溶解在水中,配制成浓度为1mg/mL的溶液,加入5-10份质量分数为4%的石墨烯浆料、1-2份防沉剂硅藻土,在10000rpm的高速离心机中离心3-4h,再用功率为200W、超声频率为50Hz的超声波清洗机超声分散30-35min,制得石墨烯分散液。
进一步的,步骤(3)中混酸氧化修饰的碳纳米管:
向1-2份碳纳米管中1:100加入混酸(98%的浓硫酸和65%的浓硝酸按体积比3:1混合),超声30-35min分散均匀,然后在80-82℃油浴中冷凝回流反应2-3h,冷却后,缓慢加入去离子水稀释,抽滤、洗涤产物至滤液为中性,在70-73℃干燥箱中干燥20-24h,制得混酸氧化修饰的碳纳米管。
本发明相比现有技术具有以下优点:
(1)采用gamma射线对三聚磷酸铝进行高辐照剂量辐射改性,改性后的三聚磷酸铝的腐蚀抑制性能得到明显提高,以其为填料制备防腐涂料,长期防腐蚀性能优异。
(2)使用硅烷偶联剂KH570对于防污剂氧化亚铜进行表面疏水改性,改性后的氧化亚铜的疏水性能增加,粒径整体增大,在树脂溶液中的分散性变差,经研磨分散后,涂料的沉降性显著改善,且铜离子的渗出率减小,且使得涂料具有缓释功能,防污期效延长,提升了其在渔网及防污涂料领域的适用性。
(3)以石墨烯分散液、混酸氧化修饰的碳纳米管为填料,添加到双组份水性环氧树脂中,再与氯磺化聚乙烯树脂、松香、增塑剂、辐照改性三聚磷酸铝、改性氧化亚铜防污剂混合,振荡分散制备渔网防污防腐涂料,明显提高耐蚀性;石墨烯具备优异的隔水性能,可以提高环氧树脂的阻抗模值,增大涂层耐腐蚀性能。
具体实施方式
实施例1
一种添加疏水改性氧化亚铜制备渔网用防污防腐涂料的方法,其特征在于,包括如下步骤:
(1)三聚磷酸铝的辐照改性:
将15份三聚磷酸铝装入聚乙烯密封袋中,置于辐射场中,对其进行总辐照量为100kGy的gamma射线辐照;
(2)无机防污剂氧化亚铜的改性:
向10份氧化亚铜中加入2份改性剂KH570、100份蒸馏水,超声震荡10min后,在80-82℃下回流加热磁力搅拌反应4h,减压抽滤、用无水乙醇洗涤2次,在50-53℃烘箱中干燥过夜,制得改性氧化亚铜;
(3)防污防腐涂料:
将石墨烯分散液、混酸氧化修饰的碳纳米管加入到90份水性环氧树脂E44中搅拌均匀,加入30份固化剂DF1228,搅拌至树脂和固化剂完全混合后,再与30份氯磺化聚乙烯树脂、6份松香、2份增塑剂及(1)、(2)中所得物料加入带有密封盖的铁桶中,密封后,快速分散振荡,过滤分装涂料。
进一步的,步骤(1)中三聚磷酸铝为ZnO/SiO2改性三聚磷酸铝,辐射源为60Co,剂量率为1kGy/h。
进一步的,步骤(3)中石墨烯分散液的制备:
将1份聚吡咯烷酮溶解在水中,配制成浓度为1mg/mL的溶液,加入5份质量分数为4%的石墨烯浆料、1份防沉剂硅藻土,在10000rpm的高速离心机中离心3h,再用功率为200W、超声频率为50Hz的超声波清洗机超声分散30min,制得石墨烯分散液。
进一步的,步骤(3)中混酸氧化修饰的碳纳米管:
向1份碳纳米管中1:100加入混酸(98%的浓硫酸和65%的浓硝酸按体积比3:1混合),超声30min分散均匀,然后在80-82℃油浴中冷凝回流反应2h,冷却后,缓慢加入去离子水稀释,抽滤、洗涤产物至滤液为中性,在70-73℃干燥箱中干燥20h,制得混酸氧化修饰的碳纳米管。
实施例2
一种添加疏水改性氧化亚铜制备渔网用防污防腐涂料的方法,其特征在于,包括如下步骤:
(1)三聚磷酸铝的辐照改性:
将25份三聚磷酸铝装入聚乙烯密封袋中,置于辐射场中,对其进行总辐照量为150kGy的gamma射线辐照;
(2)无机防污剂氧化亚铜的改性:
向20份氧化亚铜中加入4份改性剂KH570、150份蒸馏水,超声震荡15min后,在80-82℃下回流加热磁力搅拌反应5h,减压抽滤、用无水乙醇洗涤3次,在50-53℃烘箱中干燥过夜,制得改性氧化亚铜;
(3)防污防腐涂料:
将石墨烯分散液、混酸氧化修饰的碳纳米管加入到100份水性环氧树脂E44中搅拌均匀,加入33份固化剂DF1228,搅拌至树脂和固化剂完全混合后,再与40份氯磺化聚乙烯树脂、10份松香、5份增塑剂及(1)、(2)中所得物料加入带有密封盖的铁桶中,密封后,快速分散振荡,过滤分装涂料。
进一步的,步骤(1)中三聚磷酸铝为ZnO/SiO2改性三聚磷酸铝,辐射源为60Co,剂量率为1kGy/h。
进一步的,步骤(3)中石墨烯分散液的制备:
将2份聚吡咯烷酮溶解在水中,配制成浓度为1mg/mL的溶液,加入10份质量分数为4%的石墨烯浆料、2份防沉剂硅藻土,在10000rpm的高速离心机中离心4h,再用功率为200W、超声频率为50Hz的超声波清洗机超声分散35min,制得石墨烯分散液。
进一步的,步骤(3)中混酸氧化修饰的碳纳米管:
向2份碳纳米管中1:100加入混酸(98%的浓硫酸和65%的浓硝酸按体积比3:1混合),超声35min分散均匀,然后在80-82℃油浴中冷凝回流反应3h,冷却后,缓慢加入去离子水稀释,抽滤、洗涤产物至滤液为中性,在70-73℃干燥箱中干燥24h,制得混酸氧化修饰的碳纳米管。
对比实施例1
本对比实施例1与实施例1相比,在步骤(1)中未对三聚磷酸铝进行辐照改性,除此外的方法步骤均相同。
对比实施例2
本对比实施例2与实施例2相比,在步骤(2)中未对防污剂氧化亚铜进行疏水改性,除此外的方法步骤均相同。
对照组
申请号为:2010105950587公开的一种水性渔网防污涂料及其制备方法。
为了对比本发明制得的涂料的防污防腐性能,对上述实施例1、实施例2、对比实施例1、对比实施例2制备的涂料,以及对照组的涂料,渔网防污防腐涂料采用浸涂施工,进行常规性能测试,具体采用以下方法及评价标准对附着力进行测试评价:
①附着力:将涂有防污涂料并完全干燥的渔网来回对折25次,肉眼观察渔网:网线上涂层无脱落,无裂纹,则认为附着力为1级,涂膜轻微裂纹,无脱落,则认为附着力为2级,涂层少量脱落,则认为附着力为3级,涂层裂纹、脱落明显,则认为附着力为4级。
②防污期效:实海挂网后,考察防污性能。海生物附着面积小于10%,认为防污涂料有效果。
③贮存稳定性:60℃下放置15天,涂料不结块,沉淀后搅拌均匀、不返粗。
本发明的防污防腐涂料各实施例的应用测试结果如下:
表1
Claims (1)
1.一种添加疏水改性氧化亚铜制备渔网用防污防腐涂料的方法,其特征在于,包括如下步骤:
(1)三聚磷酸铝的辐照改性:
将15-25份三聚磷酸铝装入聚乙烯密封袋中,置于辐射场中,对其进行总辐照量为100-150kGy的gamma射线辐照;
(2)无机防污剂氧化亚铜的改性:
向10-20份氧化亚铜中加入2-4份改性剂KH570、100-150份蒸馏水,超声振荡10-15min后,在80-82℃下回流加热磁力搅拌反应4-5h,减压抽滤、用无水乙醇洗涤2-3次,在50-53℃烘箱中干燥过夜,制得改性氧化亚铜;
(3)防污防腐涂料:
将石墨烯分散液、混酸氧化修饰的碳纳米管加入到90-100份水性环氧树脂E44中搅拌均匀,加入30-33份固化剂DF1228,搅拌至树脂和固化剂完全混合后,再与30-40份氯磺化聚乙烯树脂、6-10份松香、2-5份增塑剂及(1)、(2)中所得物料加入带有密封盖的铁桶中,密封后,快速分散振荡,过滤分装涂料;
其中,步骤(1)中三聚磷酸铝为ZnO/SiO2改性三聚磷酸铝,辐射源为60Co,剂量率为1kGy/h;
其中,步骤(3)中石墨烯分散液的制备:将1-2份聚吡咯烷酮溶解在水中,配制成浓度为1mg/mL的溶液,加入5-10份质量分数为4%的石墨烯浆料、1-2份防沉剂硅藻土,在10000rpm的高速离心机中离心3-4h,再用功率为200W、超声频率为50kHz的超声波清洗机超声分散30-35min,制得石墨烯分散液;
其中,步骤(3)中混酸氧化修饰的碳纳米管:向1-2份碳纳米管中1:100加入混酸,超声30-35min分散均匀,然后在80-82℃油浴中冷凝回流反应2-3h,冷却后,缓慢加入去离子水稀释,抽滤、洗涤产物至滤液为中性,在70-73℃干燥箱中干燥20-24h,制得混酸氧化修饰的碳纳米管;所述混酸为98%的浓硫酸和65%的浓硝酸按体积比3:1混合制成。
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