CN106010106B - 一种大型发电机用抑晕三防绝缘涂料及其制备方法 - Google Patents
一种大型发电机用抑晕三防绝缘涂料及其制备方法 Download PDFInfo
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Abstract
本发明属于涂料研究领域,特别涉及一种大型发电机用抑晕“三防”绝缘涂料及其制备方法。该绝缘涂料包括组分A和组分B,组分A包括氟硅氧烷聚合物、氨烃基硅烷改性修饰处理的纳米SiO2粒子混合物、改性树脂、颜填料、复配广谱防霉防藻剂;组分B为固化体系,包括固化剂和助溶剂。所制备的涂层具有强烈的憎水性,对灰尘、油污具有较大的润湿角和低附着性,实现了对水、汽、灰等污染物的低附着和不透过,避免了此类物质对抑制电晕、绝缘、腐蚀等的不利影响。
Description
技术领域
本发明属于涂料研究领域,特别涉及一种大型发电机用抑晕“三防”绝缘涂料及其制备方法。
背景技术
表面绝缘涂料是涂敷于发电机组定子、转子、壳体表面的功能涂料,除具有良好的绝缘性能外,还应具有优异的“三防”功能,即具有优异的防盐雾性、防湿热和防霉菌性能。
以大功率和高压为特征的电机已广泛应用于风力、水利、火电、大型动力牵引系统、超高压输变系统等各工业领域。由于大功率发电机具有单机容量大(可达兆瓦级以上)、绝缘等级要求高的特点,对发电机定子用表面绝缘涂料提出了更高要求,为适应不同使用工况环境要求,表面绝缘涂料要兼具有高的绝缘性、耐电弧性、防盐雾、防湿热、防霉菌。
在设备运行过程中,易受到水汽、灰尘等物质的侵蚀,对绝缘性、抑制电晕性及“三防”性能带来不利影响,从而降低设备运行的可靠性。表面绝缘涂料要涂敷的基材复杂多变,既包括硅钢片、铜等金属,还包括了云母带、绝缘薄膜复合材料等,这也对绝缘涂料对不同基材表面的良好附着力带来了较大技术挑战。
发明内容
本发明的目的在于提供一种大型发电机用抑晕“三防”绝缘涂料,该涂料具有优异防盐雾腐蚀、耐湿热、抗霉菌性等“三防”性能的同时,漆膜可实现颗粒、飞尘、泥土、水等污染物的抗附着性和自清洁性,能够持续有效地为防护表面提供优良的绝缘性、抗电晕性、耐候性等性能,
本发明的绝缘涂料包括组分A和组分B,
组分A包括氟硅氧烷聚合物、氨烃基硅烷改性修饰处理的纳米SiO2粒子混合物、改性树脂、颜填料、复配广谱防霉防藻剂,
组分B为固化体系,包括固化剂和助溶剂,
组分A中氟硅氧烷聚合物、氨烃基硅烷改性修饰处理的纳米SiO2粒子混合物通过以下工艺制备:
将氨烃基硅烷加入到溶剂中,升温至50~65℃,加入纳米SiO2粒子,保温状态下磁力搅拌0.5h;再加入氟硅氧烷聚合物,升温至75~85℃,保温状态下磁力搅拌1.5h,降至常温,
其中,氨烃基硅烷为氨甲基甲氧基硅烷、氨乙基氨丙基三甲氧基硅烷、氨甲基三甲氧基硅烷中的一种或几种的混合,
氟硅氧烷聚合物为聚甲基三氟丙基硅氧烷、聚十七氟癸基甲基硅氧烷、聚甲基九氟己基硅氧烷中的一种或几种的混合,
溶剂为二甲苯、正丁醇或环己酮,
氟硅氧烷聚合物、氨烃基硅烷中均含有可水解的烷氧基,水解形成硅醇(含羟基),然后与二氧化硅粒子表面的羟基形成氢键,进一步缩合成含Si-O键与粒子表面进行结合,
一方面,经过上述处理的纳米SiO2粒子具有了适度聚集体粒径,具体为200nm~2um不同尺寸的聚集体,从微观来看,不同尺寸聚集体在涂层表面体现为微突起形态,具体表现为大的突起结构上还有小的突起结构,大突起和小突起混杂,这些微突起结构可以实现对水、油具有高的接触角(接触角大于150度)和低附着性,
并且,由于上述微突起形态是经过氟硅氧烷聚合物、氨烃基硅烷双重处理后而形成的,因此通过对氟硅氧烷聚合物、氨烃基硅烷添加比例及处理工艺的调控,所形成的微突起的尺寸范围具有可控制性,
另一方面,本发明中还充分利用了氟硅氧烷聚合物、氨烃基硅烷自身的极性链段和非极性链段的定向排布,使得改性后的纳米SiO2粒子在有机物涂料体系中也能够随着固化的进行而顺利向空气界面处迁移,从而在涂层表面聚集形成一层致密且微观粗糙的界面,该界面层中的氟硅氧烷聚合物、氨烃基硅烷低表面能物质具有强烈的憎水性;适度聚集体粒径的纳米SiO2粒子形成的微观粗糙界面对灰尘、油污实现较大的润湿角和低附着性;同时氨烃基硅烷的氨基可以与环氧基体的环氧基发生化学交联,从而使涂层外表面迁移层与涂层基体具有较强的结合强度,增强了对水、汽、灰等污染物的防止透过性,并且作用效果持久,
本发明的涂料层正是通过上述机理,实现了对水、汽、灰等污染物的低附着和不透过来提高相关性能,避免了此类物质对抑制电晕、绝缘、腐蚀等的不利影响;
另外,组分A中的改性树脂由环氧值0.41~0.56eq/100g的双酚A环氧树脂、环氧值0.32~0.48eq/100g的双酚F环氧树脂、增韧改性环氧树脂组成,
其中,增韧改性环氧树脂为端羧基丁腈橡胶(CTBN)增韧环氧树脂;
颜填料为纳米氧化锌、云母氧化铁、云母粉、碳化硅、炭黑、氧化铁红、氧化铁黑、聚磷酸铝、硫酸钡中的一种或几种的组合;
组分B中的固化剂为脂肪胺加成固化剂、DMP-10或DMP-30酚醛胺、聚酰胺固化剂(胺值200~400mgKOH/g)中的一种或几种的组合,
组分B中的助溶剂为二甲苯、正丁醇或环己酮。
本发明还提供了一种上述大型发电机用抑晕“三防”绝缘涂料的制备方法:
将组分A中的各成分混合,经高速搅拌后泵入砂磨机中进行研磨,研磨粒径小于30μm后出料,包装;再将将组分B中的各成分混合搅拌均匀、包装。
具体实施方式
实施例1
A组分:将2重量份的氨甲基甲氧基硅烷加入到8重量份的正丁醇中,升温至65℃,加入9重量份的纳米SiO2粒子,保温状态下搅拌0.5h;再加入1重量份的粘度为2.5mPas的聚甲基九氟己基硅氧烷,升温至80℃,保温状态下搅拌1.5h,降至常温后再向上述混合体系中加入4重量份的双酚A环氧树脂(环氧值0.5eq/100g)、2重量份的双酚F环氧树脂(环氧值0.42eq/100g)、6重量份的CTBN增韧改性环氧树脂、2.5重量份的纳米氧化锌、7重量份的云母氧化铁、2重量份的碳化硅、0.4重量份的炭黑、10重量份的氧化铁红、5重量份的氧化铁黑、5重量份的聚磷酸铝、3重量份的硫酸钡、1.5重量份的复配广谱防霉防藻剂、4重量份的正丁醇进行混合,经高速搅拌后,泵入砂磨机中进行研磨,研磨粒径小于30μm后出料,包装;
B组分:将3重量份的T31固化剂、2重量份的聚酰胺固化剂(胺值300mgKOH/g)、12重量份的正丁醇混合,搅拌均匀,包装。
实施例2
A组分:将1.5重量份的氨乙基氨丙基三甲氧基硅烷加入到8重量份的环己酮中,升温至58℃,加入8重量份的纳米SiO2粒子,保温状态下搅拌0.5h;再加入1.5重量份的粘度为7mPas的聚十七氟癸基甲基硅氧烷,升温至76℃,保温状态下搅拌1.5h,降至常温后再向上述混合体系中加入3重量份的双酚A环氧树脂(环氧值0.45eq/100g)、4重量份的双酚F环氧树脂(环氧值0.45eq/100g)、7重量份的CTBN增韧改性环氧树脂、4重量份的纳米氧化锌、6重量份的云母氧化铁、2重量份的碳化硅、0.4重量份的炭黑、10重量份的氧化铁红、3重量份的氧化铁黑、5重量份的聚磷酸铝、3重量份的硫酸钡、1.5重量份的复配广谱防霉防藻剂、4重量份的正丁醇进行混合,经高速搅拌后,泵入砂磨机中进行研磨,研磨粒径小于30μm后出料,包装;
B组分:将2重量份的T31固化剂、4重量份的DMP-30酚醛胺、12重量份的环己酮混合,搅拌均匀,包装。
实施例3
A组分:将1.2重量份的氨甲基三甲氧基硅烷加入到7重量份的二甲苯中,升温至60℃,加入8重量份的纳米SiO2粒子,保温状态下搅拌0.5h;再加入1.8重量份的粘度为14mPas的聚甲基三氟丙基硅氧烷,升温至82℃,保温状态下搅拌1.5h,降至常温后再向上述混合体系中加入4重量份的双酚A环氧树脂(环氧值0.52eq/100g)、2重量份的双酚F环氧树脂(环氧值0.36eq/100g)、6重量份的CTBN增韧改性环氧树脂、2.5重量份的纳米氧化锌、6重量份的云母氧化铁、2重量份的碳化硅、0.5重量份的炭黑、12重量份的氧化铁红、3重量份的氧化铁黑、5重量份的聚磷酸铝、4重量份的硫酸钡、1.2重量份的复配广谱防霉防藻剂、4重量份的二甲苯进行混合,经高速搅拌后,泵入砂磨机中进行研磨,研磨粒径小于30μm后出料,包装;
B组分:将2重量份的DMP-30酚醛胺、4重量份的DMP-10酚醛胺、12重量份的二甲苯混合,搅拌均匀,包装。
实施例4
A组分:将2重量份的氨乙基氨丙基三甲氧基硅烷加入到8重量份的环己酮中,升温至62℃,加入10重量份的纳米SiO2粒子,保温状态下搅拌0.5h;再加入1.7重量份粘度为8mPas的聚十七氟癸基甲基硅氧烷,升温至75℃,保温状态下搅拌1.5h,降至常温后再向上述混合体系中加入4重量份的双酚A环氧树脂(环氧值0.48eq/100g)、4重量份的双酚F环氧树脂(环氧值0.42eq/100g)、8重量份的CTBN增韧改性环氧树脂、3重量份的纳米氧化锌、6重量份的云母氧化铁、2重量份的碳化硅、0.3重量份的炭黑、9重量份的氧化铁红、3重量份的氧化铁黑、4重量份的聚磷酸铝、4重量份的硫酸钡、1.5重量份的复配广谱防霉防藻剂、4重量份的正丁醇进行混合,经高速搅拌后,泵入砂磨机中进行研磨,研磨粒径小于30μm后出料,包装;
B组分:将2重量份的聚酰胺固化剂(胺值300mgKOH/g)、4重量份的DMP-10酚醛胺、12重量份的环己酮混合,搅拌均匀,包装。
成膜工艺:
将A、B两组分混合搅拌均匀,刷涂成膜,室温干燥,所得漆膜表面较为粗糙。
本发明所制备的多功能涂料,可以在硅钢、铜、云母带、聚酯薄膜等不同基材上实现良好附着,具有良好的耐盐雾、耐湿热、耐霉菌性,同时漆膜表面具有较小的表面能,能够实现灰尘、油污、水等污染物的低沾附,具有自洁性,具体检测性能请见表1:
表1
对比实施例1
对纳米SiO2粒子仅采用氨烃基硅烷进行改性,其余步骤、组分及后续的成膜工艺均同实施例2,具体操作为:
A组分:将1.5重量份的氨乙基氨丙基三甲氧基硅烷加入到8重量份的环己酮中,升温至58℃,加入8重量份的纳米SiO2粒子,保温状态下搅拌0.5h;再升温至76℃,保温状态下搅拌1.5h,降至常温后再向上述混合体系中加入3重量份的双酚A环氧树脂(环氧值0.45eq/100g)、4重量份的双酚F环氧树脂(环氧值0.45eq/100g)、7重量份的增韧改性环氧树脂、4重量份的纳米氧化锌、6重量份的云母氧化铁、2重量份的碳化硅、0.4重量份的炭黑、10重量份的氧化铁红、3重量份的氧化铁黑、5重量份的聚磷酸铝、3重量份的硫酸钡、1.5重量份的复配广谱防霉防藻剂、4重量份的正丁醇进行混合,经高速搅拌后,泵入砂磨机中进行研磨,研磨粒径小于30μm后出料,包装;
B组分:将2重量份的T31固化剂、4重量份的DMP-30酚醛胺、12重量份的环己酮混合,搅拌均匀,包装。
将A、B两组分混合搅拌均匀,刷涂成膜,室温干燥。
经检验,漆膜耐沾污性测试(GB/T9755)不合格,这说明:氨烃基硅烷改性的纳米SiO2粒子在有机物体系中具有良好的相容性,而由于对纳米SiO2粒子未采用氟硅氧烷聚合物改性,从而无法在SiO2粒子表面形成氟硅氧烷聚合物和氨烃基硅烷的自身极性链段和非极性链段的定向排布来促进纳米SiO2粒子在有机物涂料固化过程中向涂层表面迁移,因此无法在涂层表面形成微突起形态,导致漆膜对污染物的拒止性不高。
对比实施例2
对纳米SiO2粒子仅采用氟硅氧烷聚合物进行改性,其余步骤、组分及后续的成膜工艺均同实施例2,具体操作为:
A组分:将8重量份的环己酮升温至58℃,加入8重量份的纳米SiO2粒子,保温状态下搅拌0.5h;再加入1.5重量份粘度为7mPas的聚十七氟癸基甲基硅氧烷,升温至76℃,保温状态下搅拌1.5h,降至常温后再向上述混合体系中加入3重量份的双酚A环氧树脂(环氧值0.45eq/100g)、4重量份的双酚F环氧树脂(环氧值0.45eq/100g)、7重量份的增韧改性环氧树脂、4重量份的纳米氧化锌、6重量份的云母氧化铁、2重量份的碳化硅、0.4重量份的炭黑、10重量份的氧化铁红、3重量份的氧化铁黑、5重量份的聚磷酸铝、3重量份的硫酸钡、1.5重量份的复配广谱防霉防藻剂、4重量份的正丁醇进行混合,经高速搅拌后,泵入砂磨机中进行研磨,研磨粒径小于30μm后出料,包装;
B组分:将2重量份的T31固化剂、4重量份的DMP-30酚醛胺、12重量份的环己酮混合,搅拌均匀,包装。
将A、B两组分混合搅拌均匀,刷涂成膜,室温干燥。
经检验,漆膜耐沾污性测试(GB/T9755)不合格。
Claims (10)
1.一种大型发电机用抑晕“三防”绝缘涂料,其特征在于:所述的涂料包括组分A和组分B,
组分A包括氟硅氧烷聚合物、氨烃基硅烷改性修饰处理的纳米SiO2粒子混合物,改性树脂,颜填料,复配广谱防霉防藻剂;
组分B为固化体系,包括固化剂和助溶剂。
2.如权利要求1所述的绝缘涂料,其特征在于:所述的氟硅氧烷聚合物、氨烃基硅烷改性修饰处理的纳米SiO2粒子混合物的制备工艺为,
将氨烃基硅烷加入到溶剂中,升温至50~65℃,加入纳米SiO2粒子,保温状态下磁力搅拌0.5h;再加入氟硅氧烷聚合物,升温至75~85℃,保温状态下磁力搅拌1.5h,降至常温。
3.如权利要求1或2所述的绝缘涂料,其特征在于:所述的氨烃基硅烷为氨甲基甲氧基硅烷、氨乙基氨丙基三甲氧基硅烷、氨甲基三甲氧基硅烷中的一种或几种的混合。
4.如权利要求1或2所述的绝缘涂料,其特征在于:所述的氟硅氧烷聚合物为聚甲基三氟丙基硅氧烷、聚十七氟癸基甲基硅氧烷、聚甲基九氟己基硅氧烷中的一种或几种的混合。
5.如权利要求2所述的绝缘涂料,其特征在于:所述的溶剂为二甲苯、正丁醇或环己酮。
6.如权利要求1所述的绝缘涂料,其特征在于:所述的改性树脂由环氧值0.41~0.56eq/100g的双酚A环氧树脂、环氧值0.32~0.48eq/100g的双酚F环氧树脂、增韧改性环氧树脂组成。
7.如权利要求6所述的绝缘涂料,其特征在于:所述的增韧改性环氧树脂为端羧基丁腈橡胶增韧环氧树脂。
8.如权利要求1所述的绝缘涂料,其特征在于:所述的颜填料为纳米氧化锌、云母氧化铁、云母粉、碳化硅、炭黑、氧化铁红、氧化铁黑、聚磷酸铝、硫酸钡中的一种或几种的组合。
9.如权利要求1所述的绝缘涂料,其特征在于:所述的固化剂为脂肪胺加成固化剂、DMP-10酚醛胺、DMP-30酚醛胺、聚酰胺固化剂中的一种或几种的组合。
10.一种如权利要求1所述的绝缘涂料的制备方法,其特征在于:将组分A中的各成分混合,经高速搅拌后泵入砂磨机中进行研磨,研磨粒径小于30μm后出料,包装;再将将组分B中的各成分混合搅拌均匀、包装。
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