CN109370365A - 一种船舶用防腐防污双功能涂料 - Google Patents
一种船舶用防腐防污双功能涂料 Download PDFInfo
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Abstract
本发明公开了一种船舶用防腐防污双功能涂料,由组分A、固化剂、甲基有机硅树脂按质量比7~10:1:2~3组成;其中,组分A由以下质量份数的各组分组成:分散液30~60份,填料10~20份,助剂0.1~0.5份;所述分散液由聚四氟乙烯、全氟聚醚与聚硅烷改性双酚A型环氧树脂按质量比1~2:1:15~20组成。本发明制备得到的防腐防污双功能涂料的固体含量大于85%,无挥发性有机物,非常环保,实现了防腐防污的双功能。同时,本发明工艺简单,所述反应均为室温下完成,大大节约了成本,适合大规模生产。
Description
技术领域
本发明属于化工涂料技术领域。更具体地,涉及一种船舶用防腐防污双功能 涂料。
背景技术
腐蚀和污损一直是海洋船舶所面临的主要问题。当今大多数船只的船体都是 由金属材料制作而成的,而海水中的金属材料受大气、海水温度及盐碱度的影响, 易引起腐蚀,进而破坏船体结构,严重时将威胁船上人员的生命。因此,采取一 定防腐和保养措施对船舶进行防护是非常有必要的。
据报道,目前常见的海洋污损生物多达2000种,最常见的是藻类、水螅、 藤壶、牡蛎等,它们附着在船舶和海洋设施上,增加了船体自重和航海摩擦力, 电力和燃料的消耗量也随之增加。统计显示,由海洋污损导致的燃料消耗增加可 达40%,航次总成本增加可达77%。海洋运输费用在过去的三十年内翻了两番, 给世界贸易和海运贸易带来了严重的损失,因此,开发环境友好型船舶防污涂料 具有广泛的应用前景。
目前,船舶涂料通常采用外层防污和内层防腐的不同涂层,这种涂层不仅厚 度大,成本高,而且两种涂料还难以兼容。另外,传统的船舶防污涂料通常含有 有机锡防污剂,易对环境造成污染。因此,开发兼具防腐与防污功能的环境友好 型涂料成为大势所趋。然而,尚未见有关防腐防污双功能涂料的相关报道。
发明内容
本发明要解决的技术问题是克服现有船舶涂料功能单一的缺陷和不足,提供 一种防腐防污二合一的船舶用环保涂料。以甲基有机硅树脂、聚四氟乙烯为原料 制备低表面能的防污涂料,符合环保的要求,同时硅烷改性环氧树脂和填料的加 入,改善了涂料的防腐效果,实现了防腐防污的双功能,大大节约了成本。
本发明的目的是提供一种船舶用防腐防污双功能涂料。
本发明的另外一个目的是提供一种船舶用防腐防污双功能涂料的制备方法。
本发明上述目的通过以下技术方案实现:
一种船舶用防腐防污双功能涂料,该涂料由组分A、固化剂、甲基有机硅树 脂按质量比7:1:2~10:1:3组成;其中,组分A的配方为:分散液30~60份,填 料10~20份,助剂0.1~0.5份;组分A中的分散液由聚四氟乙烯、全氟聚醚与 聚硅烷改性环氧树脂按质量比1:1:20~2:1:30组成。
本发明的聚硅烷改性双酚A型环氧树脂作为主要成膜物质,具有优异的防 腐性能,耐化学品性优良,尤其是耐碱性;显著增强漆膜附着力;增加涂料的柔 韧性;具有较好的耐热性和电绝缘性;提高漆膜保色性。而甲基有机硅树脂可以 增强漆膜的憎水性,增加漆膜的接触角,大幅降低涂层的表面能,增加漆膜的柔 韧性和化学稳定性,同时具有耐高温、耐潮防水、防腐蚀性能。聚硅烷改性双酚 A型环氧树脂含有Si-O键,能够与甲基有机硅树脂的Si-O键发生交联反应,从 而提高涂料的各项性能。
优选地,所述固化剂为三乙烯四胺。
优选地,所述填料由钛白粉和云母粉组成,其质量比1:1~2。
优选地,所述助剂由分散剂、流平剂和消泡剂组成,其质量比1:1:1~2。
更优选地,所述助剂由分散剂为6212,流平剂为BYK346,消泡剂为B-943。
优选地,所述聚硅烷改性双酚A型环氧树脂通过硅烷偶联剂改性双酚A型 环氧树脂制备得到。
进一步优选地,所述硅烷偶联剂为KH-550,所述硅烷与所述环氧树脂的体 积比为1:10~1:15。
更优选地,所述双酚A型环氧树脂的制备方法为将双酚A:环氧氯丙 烷:NaOH=3:10:1(按质量比)混合,90℃反应3h得到淡黄、透明的双酚A型环氧 树脂。
同时,所述涂料的制备方法,包括如下步骤:
S1.按质量比,聚四氟乙烯:全氟聚醚:聚硅烷改性双酚A型环氧树脂=1~ 2:1:15~20,向聚硅烷改性双酚A型环氧树脂中加入聚四氟乙烯和全氟烷基聚醚, 混匀得到分散液;
S2.按分散液30~60份,填料10~20份,助剂0.1~0.5份,将分散液与填 料、助剂混匀得到组分A;
S3.将组分A与固化剂、甲基有机硅树脂按质量比7~10:1:2~3混匀,即得。
优选地,所述混匀为搅拌混匀,转速为1000~1500rpm,搅拌时间为1~2h。
与现有技术相比,本发明具有以下有益效果:
本发明制备得到的防污涂料接触角可达120度,涂层的表面能低于1.5×10-4 N/m。经过挂板实验发现硅藻、藤壶、海洋细菌的附着较传统防污涂层明显减少; 经两个生物旺季的海水实验发现,海生物附着面积≤5%,涂层附着力可达10Mpa, 硬度达到6H。另外,经检测本发明制备得到的船舶用防腐防污双功能涂料耐盐 雾超过3000h、耐5%H2SO41000h、耐5%NaOH 500h、耐3%NaCl 720h、耐 93#汽油600h、抗氯离子渗透性为0.65×10-3mg/(cm2·d),具有良好的防腐性能。 此外,该涂料的固体含量大于85%,无挥发性有机物,非常环保,实现了防腐防 污的双功能。同时本发明工艺简单,所述反应均为室温下完成,大大节约了成本, 适合大规模生产。
具体实施方式
以下结合具体实施例来进一步说明本发明,但实施例并不对本发明做任何形 式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试 剂、方法和设备。
除非特别说明,以下实施例所用试剂和材料均为市购。
实施例1
1、制备方法
(1)双酚A型环氧树脂的制备
在500mL三口瓶上装好搅拌器、回冷凝管和温度计,加入11.4g双酚A、 46.5g环氧氯丙烷4.1g NaOH,混合搅拌,缓慢加热至80℃,反应3h后结束反 应,产物为浅黄色;将反应液过滤除去副产物NaCl,减压下蒸馏除去过量的环 氧氯丙烷(回收)(60~70℃),停止蒸馏,将剩余物趁热倒入小烧杯中,得到淡 黄色、透明、粘稠的双酚A型环氧树脂。
(2)聚硅烷改性双酚A型环氧树脂的制备
将硅烷偶联剂KH-550制备的双酚A型环氧树脂按照体积比为1:12进行混 合,1000rpm下搅拌2h得到聚硅烷改性双酚A型环氧树脂。
(3)防腐防污涂料的制备
10g聚四氟乙烯、10g全氟聚醚加入到200g聚硅烷改性双酚A型环氧树脂 中,1500rpm下搅拌1h,再加入60g云母粉、30g钛白粉、2g分散剂BYK9076、 2g流平剂BYK346、2g消泡剂B-943在1000rpm下搅拌1h;得到防腐防污涂 料组分A;将组分A与固化剂三乙烯四胺、甲基有机硅树脂按照质量比7:1:2配 比使用。
实施例2
1、制备方法
(1)双酚A型环氧树脂的制备
在500mL三口瓶上装好搅拌器、回冷凝管和温度计,加入12.4g双酚A、 48.5g环氧氯丙烷、4.2g NaOH,混合搅拌,缓慢加热至80℃,反应3h后结束 反应,产物为浅黄色;将反应液过滤除去副产物NaCl,减压下蒸馏除去过量的 环氧氯丙烷(回收)(60~70℃)。停止蒸馏,将剩余物趁热倒入小烧杯中,得到 淡黄色、透明、粘稠的双酚A型环氧树脂。
(2)聚硅烷改性双酚A型环氧树脂的制备
将硅烷偶联剂KH-550制备的双酚A型环氧树脂按照体积比为1:15进行混 合1000rpm下搅拌1h得到聚硅烷改性双酚A型环氧树脂。
(3)防腐防污涂料的制备
20g聚四氟乙烯、10g全氟聚醚加入到150g聚硅烷改性环氧树脂中,1500 rpm下搅拌0.5h进行分散,再加入50g云母粉、30g钛白粉、1g分散剂BYK9076、 1g流平剂BYK346、1g消泡剂B-943在1500rpm下搅拌1h;得到防腐防污涂 料组分A;将组分A与四乙烯三胺、甲基有机硅树脂按照质量比10:1:3配比使 用。
实施例3
1、制备方法
(1)双酚A型环氧树脂的制备
在500mL三口瓶上装好搅拌器、回冷凝管和温度计,加入10.4g双酚A、 42.5g环氧氯丙烷3.8g NaOH,混合搅拌,缓慢加热至80℃,反应3h后结束反 应,产物为浅黄色;将反应液过滤除去副产物NaCl,减压下蒸馏除去过量的环 氧氯丙烷(回收)(60~70℃),停止蒸馏,将剩余物趁热倒入小烧杯中,得到淡 黄色、透明、粘稠的双酚A型环氧树脂。
(2)聚硅烷改性双酚A型环氧树脂的制备
将硅烷偶联剂KH-550制备的双酚A型环氧树脂按照体积比为1:10进行混 合,1500rpm下搅拌2h得到聚硅烷改性双酚A型环氧树脂。
(3)防腐防污涂料的制备
10g聚四氟乙烯、5g全氟聚醚加入到100g聚硅烷改性环氧树脂中,1000rpm 下搅拌1h进行分散,再加入30g云母粉、20g钛白粉、0.5g分散剂BYK9076、 0.5g流平剂BYK346、1g消泡剂B-943在1500rpm下搅拌2h;得到防腐防污 涂料组分A;将组分A与四乙烯三胺、甲基有机硅树脂按照质量比8:1:2配比使 用。
性能测试
1、测试方法
将实施例1~3防腐防污涂料的相关指标根据HG/T 5177-2017,GB 13351-1992,JG/T224-2007,JTJ275-2000进行检测。
2、测试结果
实施例1~3所述防腐防污涂料的相关指标如下表1所示
表1防腐防污涂料的相关指标
同时,将实施例1~3所述涂料经过挂板实验发现,硅藻、藤壶、海洋细菌 的附着较传统防污涂层明显减少,海水实验两个生物旺季,海生物附着面积≤5%, 涂层附着力最大可达10Mpa,硬度最高达到6H。表明本发明制备得到的涂料具 有防腐防污的双功能,具有较大的应用前景。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施 例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替 代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (8)
1.一种船舶用防腐防污双功能涂料,其特征在于,由组分A、固化剂、甲基有机硅树脂按质量比7~10:1:2~3组成;其中,组分A由以下质量份数的各组分组成:分散液30~60份,填料10~20份,助剂0.1~0.5份;所述分散液由聚四氟乙烯、全氟聚醚与聚硅烷改性双酚A型环氧树脂按质量比1~2:1:15~20组成。
2.根据权利要求1所述的涂料,其特征在于,所述固化剂为三乙烯四胺。
3.根据权利要求1所述的涂料,其特征在于,所述填料由钛白粉和云母粉组成,其质量比1:1~2。
4.根据权利要求1所述的涂料,其特征在于,所述助剂由分散剂、流平剂和消泡剂组成,其质量比1:1:1~2。
5.根据权利要求1所述的涂料,其特征在于,所述聚硅烷改性双酚A型环氧树脂通过硅烷偶联剂改性双酚A型环氧树脂制备得到。
6.根据权利要求1所述涂料,其特征在于,所述硅烷偶联剂为KH-550,所述硅烷与所述环氧树脂的体积比为1:10~1:15。
7.权利要求1~6任一项所述涂料的制备方法,其特征在于,包括如下步骤:
S1.按质量比,聚四氟乙烯:全氟聚醚:聚硅烷改性双酚A型环氧树脂=1~2:1:15~20,向聚硅烷改性双酚A型环氧树脂中加入聚四氟乙烯和全氟烷基聚醚,混匀得到分散液;
S2.按分散液30~60份,填料10~20份,助剂0.1~0.5份,将分散液与填料、助剂混匀得到组分A;
S3.将组分A与固化剂、甲基有机硅树脂按质量比7~10:1:2~3混匀,即得。
8.根据权利要求7所述涂料的制备方法,其特征在于,所述混匀为搅拌混匀,转速为1000~1500 rpm,搅拌时间为1~2 h。
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