CN111286126A - 一种防覆冰组合物 - Google Patents
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Abstract
一种防覆冰组合物,属于高分子防覆冰材料技术领域。其组成为结构材料和吸水膨胀离子型疏冰添加剂,吸水膨胀离子型疏冰添加剂质量分数为5%‑40%,吸水膨胀离子型疏冰添加剂均匀分布在结构材料中,其吸水膨胀率在100‑400倍,其粒径为20‑75μm。所述的结构材料由聚丙烯、聚乙烯、聚氯乙烯、聚乙烯、聚对苯二甲酸酯、聚苯乙烯、ABS树脂,聚碳酸酯、PA塑料中的一种或多种构成。本发明具有优异的防覆冰效果,延迟水滴在表面的结冰达30小时,覆冰在表面的粘附力13.1kPa;该防覆冰组合物无须依赖其他基底材料可直接作为构件使用,凝胶润滑层耐久度高,不会出现防覆冰层流失等问题,可反复使用,具有优异的长久防冰、疏冰效果。
Description
技术领域
本发明涉及一种防覆冰组合物,属于高分子防覆冰材料技术领域。
背景技术
冰雪在表面的积累会影响许多重要系统的正常工作,甚至造成损坏,如航空运输、风力发电机、输电线、海岸线工作平台、光伏器件、车辆船舶等等,不仅带来了经济损失,而且还会危及生命。冰的积累会改变风力发电机叶片的形状和表面粗糙度,导致电力损耗甚至是设备损毁,许多风涡轮机如果出现冰雪堆积就会减小功率或者完全关停。根据对中国气象灾害年鉴统计分析,冰、霜冻、低温近十年来,年平均直接损失达290亿人民币,严重地影响了国民经济以及人民正常生活。
覆冰的去处方法主要分为两大类:主动法和被动法。主动法是目前广泛应用的方法,包括在出现冰层后机械刮除、加热除冰和使用除冰剂。然而,这些方法由于需要耗费大量能量,价格昂贵。被动法包括形成疏冰或防冰表面,来阻止冰层黏附在表面或者使冰层在风力、振动或吸收阳光辐射热下从表面滑落。疏冰性能是冰雪不能在表面上粘附力和堆积的能力。对于某一表面,其疏冰性可以从延迟结冰时间的长短和覆冰粘附力的大小两个角度进行描述。国际防覆冰研究领域相关报道的延迟结冰时间最长约为2小时,一般认为覆冰粘附力在100kPa以下的材料表面具有防覆冰功能,材料表面的覆冰粘附力在20kPa以下则表明其具有优异的防覆冰功能。
目前,传统防覆冰材料的防覆冰机理都是基于降低材料表面的表面能,从而使水滴在材料表面有较大的接触角,减少水滴在表面停留时间以达到防覆冰目的。专利CN105969177公布了一种涂料组合物及其制备方法与应用,其通过涂料中控制纳米颗粒的质量分数获得了超疏水材料,具有接触角达到150°以上的接触角和190s延迟结冰时间剪切覆冰粘附力210kPa,但是其延迟时间太短不能充分利用日照能保持不冻,其覆冰粘附力较大,自然条件下自动脱附困难,且涂料只能依附其他材料使用才能呈现出疏冰性,与基材的粘合匹配性差和耐久性短、粘附力大不易脱落等严重制约该类技术的推广。上述专利CN105969177虽然对防覆冰有一定效果,仍存在覆冰粘附力大、延迟结冰时间短、阻止覆冰能力差、防覆冰层易流失、使用寿命短、本体强度低等急待解决的难题。
发明内容
与传统降低表面能、增大接触角的防覆冰表面涂料不同,本发明提供了一种防覆冰组合物,其在冰/水相与材料表面(固相)之间形成一层润滑层,润滑层降低了水相的蒸汽压,低温下,水相在材料表面保持不结冰可长时间保持流动状态,使冰层浮在基底上;吸水膨胀离子型疏冰添加剂含有多个羧基,具有亲水性,吸水后形成稳定的离子型凝胶,同时,凝胶能缓缓吸水膨胀百倍以上,改变冰层内部的膨胀力方向,使得冰层内部及与基材材料表面之间的不断地产生微小的裂纹,延迟覆冰的同时还降低了冰层与表面之间的粘附力,可保持超长时间不结冰,润滑层的存在使冰层与材料表面的粘附力急剧下降,可降至20kPa以下。由于润滑层厚度为数百纳米,且吸水膨胀离子型疏冰添加剂镶嵌在结构材料连续相中,所以在除冰过程中几乎不会造成疏冰添加剂的损失。不需要主动除冰,在自然环境下,冰层升华或融化成水层后再蒸发的物理过程均不会造成对疏冰添加剂的损失。本发明由于结构材料具有刚性,对实施环境的选择性低,耐久度高且防覆冰效果明显。
一种防覆冰组合物,其组成为:结构材料和吸水膨胀离子型疏冰添加剂,吸水膨胀离子型疏冰添加剂质量分数为5%-40%,吸水膨胀离子型疏冰添加剂均匀分布在结构材料中,其吸水膨胀率在100-400倍,其粒径为20-75μm。所述的结构材料由聚丙烯、聚乙烯、聚氯乙烯、聚乙烯、聚对苯二甲酸酯、聚苯乙烯、ABS树脂,聚碳酸酯、PA塑料中的一种或多种构成,结构材料作为防覆冰的主体刚性材料,结构材料质量分数为60%-95%。
吸水膨胀离子型疏冰添加剂由超高分子量的聚丙烯酸钠、超高分子量的聚丙烯酸铵、甲基乙烯基醚和马来酸酐的交替共聚物的钠盐、甲基乙烯基醚和马来酸酐的交替共聚物的钙盐中的一种或多种构成,超高分子量的范围为500万-3000万。
甲基乙烯基醚和马来酸酐的交替共聚物的钠盐、甲基乙烯基醚和马来酸酐的交替共聚物的钙盐化学结构式为:
式中:n+m=2000-12000。
结构材料作为连续相,吸水膨胀离子型疏冰添加剂作为分散相,均匀分散于连续相基内,吸水膨胀离子型疏冰添加剂的分散尺度20-75μm。
吸水膨胀离子型疏冰添加剂含有多个羧基,具有亲水性,吸水后形成稳定的离子型凝胶。
具体实施方法
以下结合具体实施例对本发明进一步说明。下列实施例为本发明优选的实施方式,但本发明的实施方式并不受下述实施例的限制,其他的任何未背离本发明所作的所有改变均为等效的置换方式,都在本发明的保护范围之内。
实施例1:
结构材料选用聚丙烯(PP)粒料,吸水膨胀离子型疏冰添加剂选用Mn=30,000,000g/mol的聚丙烯酸钠(PAAS3000w),质量分数为10%。将两者充分混合后倒入密炼机中,加热至190℃搅拌30分钟,得到混合物,将其注塑成直径15cm、厚度2mm的PP-PAAS3000w防覆冰材料。
将PP-PAAS3000w防覆冰材料切割成1cm×1cm的小方块,放置于低温接触角测试仪上,设置测试温度为-10℃,使用自动进液器在防覆冰材料小方块上滴加8uL的二次水,延迟结冰时间为29.9小时。
在PP-PAAS3000w防覆冰材料与直径50mm的锭子之间注满厚2mm的二次水层,放置于温度为-10℃,冷冻48小时。利用垂直拔脱装置将锭子从防覆冰材料表面拔脱,测得垂直覆冰粘附力为13.1kPa。
实施例2:
结构材料选用聚乙烯(PE)粒料,吸水膨胀离子型疏冰添加剂选用Mn=12,000,000g/mol的聚丙烯酸钠(PAAS1200w),质量分数为20%。混合均匀后倒入螺杆挤出机,直接注塑成直径15cm、厚度2mm的PP-PAAS1200w防覆冰材料。
将PP-PAAS1200w防覆冰材料切割成1cm×1cm的小方块,放置于低温接触角测试仪上,设置测试温度为-10℃,使用自动进液器在防覆冰材料小方块上滴加8uL的二次水,延迟结冰时间为8.4小时。
实施例3:
结构材料选用聚氯乙烯(PVC)粒料,吸水膨胀离子型疏冰添加剂选用甲基乙烯基醚和马来酸酐的交替共聚物的钠盐(CPMVE/MAS),Mn=2500000g/mol质量分数为10%。将两者混合均匀后倒入密炼机中,160℃混炼30分钟,混炼料加入模具中压制成直径15cm、厚度2mm的PVC-CPMVE/MAS防覆冰材料。
将PVC-CPMVE/MAS防覆冰材料切割成1cm×1cm的小方块,放置于低温接触角测试仪上,设置测试温度为-10℃,使用自动进液器在防覆冰材料小方块上滴加8uL的二次水,延迟结冰时间为9.9小时。
由以上实施例可知,相较于已经公开的防覆冰材料,本发明所述防覆冰制备方法可采用常规的塑料加工手段,实施简便,结构材料和吸水膨胀离子型疏冰添加剂可以自由选择组合,灵活适应应用环境,吸水膨胀离子型疏冰添加剂的质量分数为5%-40%,优选质量分数10-25%;制备出的防覆冰材料具有优异的防覆冰效果,显著延迟了水滴在表面的结冰时间,明显降低了覆冰在表面的粘附力;该组合物具有一定的刚度无须依赖其他基底材料可直接作为构件使用,凝胶润滑层耐久度高,不会出现防覆冰层流失等问题,可反复使用,具有优异的长久防冰、疏冰效果。
以上所述,仅为本发明的说明实施例,并非对本发明任何形式上和实质上的限制,应当指出,对于本技术领域的普通技术人员,在不脱离本发明方法的前提下,做出的若干改进和补充也应视为本发明的保护范围;凡熟悉本专业的技术人员,在不脱离本发明机理和范围的情况下,利用以上所揭示的技术内容做出的些许更改、修饰与演变的等同变化,均为本发明的等效实施例;同时,凡依据本发明的实质技术对上述实施例所做的任何等同变化的更改、修饰与演变,均仍属于本发明的保护范围。
Claims (3)
1.一种防覆冰组合物,其特征在于组成为:结构材料和吸水膨胀离子型疏冰添加剂;吸水膨胀离子型疏冰添加剂质量分数为5%-40%,吸水膨胀离子型疏冰添加剂均匀分布在结构材料中,其吸水膨胀率在100-400倍,其粒径为20-75μm;结构材料由聚丙烯、聚乙烯、聚氯乙烯、聚乙烯、聚对苯二甲酸酯、聚苯乙烯、ABS树脂,聚碳酸酯、PA塑料中的一种或多种构成,结构材料质量分数为60%-95%。
2.根据权利要求1所述的防覆冰组合物,其特征在于吸水膨胀离子型疏冰添加剂由超高分子量聚丙烯酸钠、超高分子量聚丙烯酸铵、甲基乙烯基醚和马来酸酐的交替共聚物的钠盐、甲基乙烯基醚和马来酸酐的交替共聚物的钙盐中的一种或多种构成,超高分子量的范围为500万-3000万。
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CN104693544A (zh) * | 2015-02-08 | 2015-06-10 | 北京化工大学 | 一种输送带表面低粘附力防覆冰配方 |
CN105885778A (zh) * | 2015-01-12 | 2016-08-24 | 刘艳娇 | 一种纳米热电薄膜的制备方法 |
CN109943162A (zh) * | 2019-03-07 | 2019-06-28 | 师红 | 一种能使各组分间热膨胀系数有效匹配的防结冰涂料 |
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CN102134475A (zh) * | 2010-01-21 | 2011-07-27 | 中国科学院化学研究所 | 防结冰添加剂及其制备方法 |
CN105885778A (zh) * | 2015-01-12 | 2016-08-24 | 刘艳娇 | 一种纳米热电薄膜的制备方法 |
CN104693544A (zh) * | 2015-02-08 | 2015-06-10 | 北京化工大学 | 一种输送带表面低粘附力防覆冰配方 |
CN109943162A (zh) * | 2019-03-07 | 2019-06-28 | 师红 | 一种能使各组分间热膨胀系数有效匹配的防结冰涂料 |
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