CN106634243A - 一种防锈性能良好的高氯化聚乙烯混合防腐涂料及其制备方法 - Google Patents

一种防锈性能良好的高氯化聚乙烯混合防腐涂料及其制备方法 Download PDF

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CN106634243A
CN106634243A CN201611007650.4A CN201611007650A CN106634243A CN 106634243 A CN106634243 A CN 106634243A CN 201611007650 A CN201611007650 A CN 201611007650A CN 106634243 A CN106634243 A CN 106634243A
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chlorinated polyethylene
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申继东
鲁廷涛
芮鸿迎
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Ma'anshan Ruidong Instrument Co Ltd
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Abstract

本发明公开一种防锈性能良好的高氯化聚乙烯混合防腐涂料,由以下重量份的原料组成:高氯化聚乙烯65‑85,壳聚糖26‑37,过氧化二苯甲酰0.8‑2,甲基丙烯酸‑β‑羟乙酯10‑18,乙酸乙酯适量,去离子水适量,叔丁基过氧化氢1‑2,甲基丙烯酸六氟丁酯14‑22,无水乙醇适量,氯化石蜡2‑3,钛白粉2‑6,消泡剂1‑2,二甲苯适量,复合铁钛粉2‑5份,片状氧化铁3‑8份,甲乙酮肟1‑4。本发明使用甲基丙烯酸‑β‑羟乙酯接枝高氯化聚乙烯,之后与甲基丙烯酸六氟丁酯单体共聚引入含氟基团,然后与壳聚糖接枝复配制备了壳聚糖接枝含氟丙烯酸酯/高氯化聚乙烯三元共聚物,使得防腐涂料具有较高的抗污性、极佳的防腐性和优异的附着力。

Description

一种防锈性能良好的高氯化聚乙烯混合防腐涂料及其制备方法
技术领域
[0001] 本发明属于防腐漆领域,具体涉及一种防锈性能良好的高氯化聚乙烯混合防腐涂料及其制备方法。
背景技术
[0002] 高氯化聚乙烯含氯量高,又称HCPE树脂。白色轻质小颗粒,氯含量>61%,热分解温度>130°C,热稳定时间180°C>3min。由于分子结构中不含双键,氯原子又是无规分布,因此具有良好的耐候性、耐臭氧性、耐热老化性、耐燃性、耐化学药品性和耐油性,但以此为单一成膜物的涂层很脆、附着力较差,因此在实际应用过程中常常添加柔性树脂以改善涂膜的性能,提高涂膜的耐候性能,同时提高涂膜的附着力和光泽等物理机械性能,如加入醇酸树脂、丙烯酸树脂、氯化石蜡等进行改性。
[0003]周耿槟、杨卓如等人在其《含氟丙烯酸酯共聚物的制备及其涂膜表面疏水疏油性能的研究》一文中,以单体甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸、含氟(甲基)丙烯酸酯为原料,合成了一系列的含氟丙烯酸酯共聚物。通过侧链引入全氟基团来改变丙烯酸酯聚合物的结构,这样既保持了丙烯酸酯聚合物原有的优点,又赋予含氟聚合物特有的疏水、疏油、耐候性及自清洁性能,使其综合性能指标大大提高。
[0004] 壳聚糖具有一定的杀菌作用对微生物腐蚀有抑制作用,起到一定的防污功能,而其本身无毒,可以说是一种既防腐又防污的绿色环保材料。壳聚糖的结构与纤维素很相似,同样具有良好的成膜性,结构中的羟基和氨基使分子链间存在较强的氢键,能承受一定的机械强度和拉伸强度,而且分子中存在羟基和氨基这样的极性基团,尤其是氨基,带上正电荷后具有与铁的外层空轨道形成配位的孤对电子或η电子,使吸附层与金属表面作用力增强,吸附膜稳定性提高。
[0005]因此本发明使用甲基丙烯酸-β_羟乙酯接枝高氯化聚乙烯,之后采用水相悬浮聚合法将甲基丙烯酸-β_羟乙酯、甲基丙烯酸六氟丁酯单体成功接枝到壳聚糖分子上,制备了壳聚糖接枝含氟丙烯酸酯/高氯化聚乙烯三元共聚物,使得防腐涂料具有较高的抗污性、极佳的防腐性、优良的涂覆性和优异的附着力。
发明内容
[0006] 针对现有技术的不足,本发明提供一种防锈性能良好的高氯化聚乙烯混合防腐涂料及其制备方法,提供涂料的防腐性能、抗污性和附着力。
[0007] —种防锈性能良好的高氯化聚乙烯混合防腐涂料,由以下重量份的原料组成:高氯化聚乙烯65-85份,壳聚糖26-37份,过氧化二苯甲酰0.8-2份,甲基丙烯酸-β-羟乙酯10-18份,乙酸乙酯适量,去离子水适量,叔丁基过氧化氢1-2份,甲基丙烯酸六氟丁酯14-22份,无水乙醇适量,氯化石蜡2-3份,钛白粉2-6份,消泡剂1-2份,二甲苯适量,复合铁钛粉2-5份,片状氧化铁3-8份,甲乙酮肟1-4份。
[0008] 具体步骤如下:
(1)高氯化聚乙烯接枝甲基丙烯酸-β-羟乙酯的制备:
依次将1/5份的高氯化聚乙烯、过氧化二苯甲酰、甲基丙烯酸-β-羟乙酯加入到含有二甲苯与乙酸乙酯混合液的三口烧瓶中,搅拌使高氯化聚乙烯充分溶胀,然后剧烈搅拌并缓慢加入去离子水,待其分散均匀稳定后,通入氮气至85-95°C反应2-4小时,之后用热水洗涤,于55-65°C真空干燥至恒温,即得接枝产物;
(2)壳聚糖接枝含氟丙烯酸酯/高氯化聚乙烯三元共聚物:
将干燥处理后的壳聚糖置于装有回流冷凝管、搅拌器、温度计的三口烧瓶中,加去离子水,浸泡,溶胀过夜,置于恒温水浴锅中,55-65°C搅拌5-10分钟,滴加叔丁基过氧化氢,搅拌
8-15分钟,加入步骤(I)高氯化聚乙烯接枝甲基丙烯酸-β-羟乙酯、甲基丙烯酸六氟丁酯,回流状态下反应4-5小时,冷却至室温,过滤,用无水乙醇洗涤后,烘干至恒重,得壳聚糖接枝含氟丙烯酸酯/高氯化聚乙烯三元共聚物;
(3)配制涂料:
①、将余下的高氯化聚乙烯树脂溶于二甲苯溶剂中,边搅拌、边投入,搅拌速度控制在60-80r/min,直至完全溶解成透明粘稠液体,再将搅拌速度升至300_500r/min,加入复合铁钛粉、片状氧化铁、钛白粉,搅拌20-40分钟;
②、加入步骤(2)制备的三元共聚物搅拌混合均匀,升温到45-52°C,依次加入甲乙酮肟、氯化石蜡、消泡剂,高速1500-3000r/min搅拌3-5小时,用20目滤网粗滤;
(4)粗滤的物料进入砂磨机研磨,研磨至细度为彡40μπι,砂磨机出口温度控制在彡60°C,再使用二甲苯调整粘度在160-220 (S)涂-4杯,用120目振动筛过滤、包装。
[0009] 其中,所述的步骤(I)中的二甲苯与乙酸乙酯混合液是由二甲苯与乙酸乙酯按体积比为3:1混合而成。
[0010]与现有技术相比,本发明具有如下优点:
(I)本发明利用悬浮溶胀接枝法制备了高氯化聚乙烯接枝甲基丙烯酸-β-羟乙酯,之后与甲基丙烯酸六氟丁酯单体共聚引入含氟基团,得到含氟丙烯酸酯/高氯化聚乙烯复合物,由于氟电负性大,C-F键能高,紫外线对其没有任何影响,显示该涂料具有超耐候性,通过改性后的含氟丙烯酸酯不仅保持了丙烯酸酯原有特性,还有效提高了防腐涂层的耐候性、抗污性、耐油耐水性。
[0011] (2)本发明利用水相悬浮聚合法将含氟丙烯酸酯接枝到壳聚糖分子上,利用壳聚糖的杀菌作用,提高了涂料的抗污防腐性能;利用壳聚糖分子中存在的极性基团,增强防腐涂料与金属表面的作用力,提高吸附膜稳定性,增强防腐涂料的附着力;另外本发明防腐涂料在保护金属使用时,当有铁离子或其它金属离子溶出时,壳聚糖上的极性基团也会将其络合住,形成致密的“钝化膜”,防止进一步腐蚀的进行。
[0012] (3)片状氧化铁具有独特的鳞片结构,化学性质稳定,耐高温,抗紫外线,有良好的防锈性、耐碱性、耐盐雾性、耐候性等优良性能,由于片状氧化铁的片状粒子能定向地平行重叠排列,在涂料中形成一个惰性阻挡层,可有效地减少大气、水、紫外线对钢制结构的侵蚀,与复合铁钛粉复配进一步提高涂层的防锈、防腐性能,另外添加甲乙酮肟有效防止防腐涂料在贮存过程中结皮,提高其使用寿命。
具体实施方式
[0013] 一种防锈性能良好的高氯化聚乙烯混合防腐涂料,由以下重量份的原料组成:高氯化聚乙烯78,壳聚糖34,过氧化二苯甲酰1.5,甲基丙烯酸-β-羟乙酯16,乙酸乙酯适量,去离子水适量,叔丁基过氧化氢2,甲基丙烯酸六氟丁酯20,无水乙醇适量,氯化石蜡3,钛白粉4,消泡剂I,二甲苯适量,复合铁钛粉3,片状氧化铁5,甲乙酮肟2。
[0014] 具体步骤如下:
(1)高氯化聚乙烯接枝甲基丙烯酸-β-羟乙酯的制备:
依次将1/5份的高氯化聚乙烯、过氧化二苯甲酰、甲基丙烯酸-β-羟乙酯加入到含有二甲苯与乙酸乙酯混合液的三口烧瓶中,搅拌使高氯化聚乙烯充分溶胀,然后剧烈搅拌并缓慢加入去离子水,待其分散均匀稳定后,通入氮气至90°C反应3小时,之后用热水洗涤,于60°C真空干燥至恒温,即得接枝产物;
(2)壳聚糖接枝含氟丙烯酸酯/高氯化聚乙烯三元共聚物:
将干燥处理后的壳聚糖置于装有回流冷凝管、搅拌器、温度计的三口烧瓶中,加去离子水,浸泡,溶胀过夜,置于恒温水浴锅中,60°C搅拌8分钟,滴加叔丁基过氧化氢,搅拌13分钟,加入步骤(I)高氯化聚乙烯接枝甲基丙烯酸-β-羟乙酯、甲基丙烯酸六氟丁酯,回流状态下反应4.5小时,冷却至室温,过滤,用无水乙醇洗涤后,烘干至恒重,得壳聚糖接枝含氟丙烯酸酯/高氯化聚乙烯三元共聚物;
(3)配制涂料:
①、将余下的高氯化聚乙烯树脂溶于二甲苯溶剂中,边搅拌、边投入,搅拌速度控制在80r/min,直至完全溶解成透明粘稠液体,再将搅拌速度升至500r/min,加入复合铁钛粉、片状氧化铁、钛白粉,搅拌30分钟;
②、加入步骤(2)制备的三元共聚物搅拌混合均匀,升温到50°C,依次加入甲乙酮肟、氯化石蜡、消泡剂,高速2500r/min搅拌4小时,用20目滤网粗滤;
(4)粗滤的物料进入砂磨机研磨,研磨至细度为彡40μπι,砂磨机出口温度控制在彡60°C,再使用二甲苯调整粘度在160-220 (S)涂-4杯,用120目振动筛过滤、包装。
[0015] 其中,所述的步骤(I)中的二甲苯与乙酸乙酯混合液是由二甲苯与乙酸乙酯按体积比为3:1混合而成。
[0016] 涂料性能测试结果:
耐冲击性:多46kg/cm,柔韧性SI.2mm,附着力:I级;
干燥时间(h):表干彡0.5,实干彡4;
常温下耐腐蚀性能:
10%HC1水溶液多360h,涂层不起泡、不脱落;
20%H2S04水溶液多360h,涂层不起泡,不脱落;
20%Na0H水溶液多360h,涂层不起泡,不脱落;
耐盐雾腐蚀试验多50次,涂层不起泡,无变质、软化现象。

Claims (3)

1.一种防锈性能良好的高氯化聚乙烯混合防腐涂料,其特征在于,由以下重量份的原料组成:高氯化聚乙烯65-85份,壳聚糖26-37份,过氧化二苯甲酰0.8_2份,甲基丙烯酸-β-羟乙酯10-18份,乙酸乙酯适量,去离子水适量,叔丁基过氧化氢1-2份,甲基丙烯酸六氟丁酯14-22份,无水乙醇适量,氯化石蜡2-3份,钛白粉2-6份,消泡剂1-2份,二甲苯适量,复合铁钛粉2-5份,片状氧化铁3-8份,甲乙酮肟1-4份。
2.根据权利要求书I所述的一种防锈性能良好的高氯化聚乙烯混合防腐涂料的制备方法,其特征在于,具体步骤如下: (1)高氯化聚乙烯接枝甲基丙烯酸-β-羟乙酯的制备: 依次将1/5份的高氯化聚乙烯、过氧化二苯甲酰、甲基丙烯酸-β-羟乙酯加入到含有二甲苯与乙酸乙酯混合液的三口烧瓶中,搅拌使高氯化聚乙烯充分溶胀,然后剧烈搅拌并缓慢加入去离子水,待其分散均匀稳定后,通入氮气至85-95°C反应2-4小时,之后用热水洗涤,于55-65°C真空干燥至恒温,即得接枝产物; (2)壳聚糖接枝含氟丙烯酸酯/高氯化聚乙烯三元共聚物: 将干燥处理后的壳聚糖置于装有回流冷凝管、搅拌器、温度计的三口烧瓶中,加去离子水,浸泡,溶胀过夜,置于恒温水浴锅中,55-65°C搅拌5-10分钟,滴加叔丁基过氧化氢,搅拌8-15分钟,加入步骤(I)高氯化聚乙烯接枝甲基丙烯酸-β-羟乙酯、甲基丙烯酸六氟丁酯,回流状态下反应4-5小时,冷却至室温,过滤,用无水乙醇洗涤后,烘干至恒重,得壳聚糖接枝含氟丙烯酸酯/高氯化聚乙烯三元共聚物; (3)配制涂料: ①、将余下的高氯化聚乙烯树脂溶于二甲苯溶剂中,边搅拌、边投入,搅拌速度控制在60-80r/min,直至完全溶解成透明粘稠液体,再将搅拌速度升至300_500r/min,加入复合铁钛粉、片状氧化铁、钛白粉,搅拌20-40分钟; ②、加入步骤(2)制备的三元共聚物搅拌混合均匀,升温到45-52°C,依次加入甲乙酮肟、氯化石蜡、消泡剂,高速1500-3000r/min搅拌3-5小时,用20目滤网粗滤; (4)粗滤的物料进入砂磨机研磨,研磨至细度为彡40μπι,砂磨机出口温度控制在彡60°C,再使用二甲苯调整粘度在160-220 (S)涂-4杯,用120目振动筛过滤、包装。
3.根据权利要求书2所述的一种防锈性能良好的高氯化聚乙烯混合防腐涂料的制备方法,其特征在于,所述的步骤(I)中的二甲苯与乙酸乙酯混合液是由二甲苯与乙酸乙酯按体积比为3:1混合而成。
CN201611007650.4A 2016-11-16 2016-11-16 一种防锈性能良好的高氯化聚乙烯混合防腐涂料及其制备方法 Pending CN106634243A (zh)

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CN102863854A (zh) * 2012-10-18 2013-01-09 山东聊城齐鲁特种涂料有限责任公司 一种高氯化聚乙烯防腐涂料及其制备方法

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CN102863854A (zh) * 2012-10-18 2013-01-09 山东聊城齐鲁特种涂料有限责任公司 一种高氯化聚乙烯防腐涂料及其制备方法

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