CN112029170A - 一种核电专用气相防锈塑料薄膜及其制备方法 - Google Patents
一种核电专用气相防锈塑料薄膜及其制备方法 Download PDFInfo
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- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
本发明公开了一种核电专用气相防锈塑料薄膜及其制备方法，所述塑料薄膜从内到外分为三层结构，外层包括74％～96％聚烯烃树脂、1％～5％改性石墨烯、1％～5％马来酸酐、1％～8％分散剂、1％～7％润滑剂、0.1％～1％抗氧化剂，所述外层的重量占所述塑料薄膜总重的30～40％；中层包括91～97％聚烯烃树脂、2～6％气相防锈母粒、1～3％的助剂，所述中层的重量占所述塑料薄膜总重的20～40％；内层包括90～95％聚烯烃树脂、5～10％气相防锈母粒，所述内层的重量占所述塑料薄膜总重的30～40％。本发明提高薄膜的物理性能、阻隔性能及热稳定性能；适用于多种金属的防锈，具有优异的气相防锈能力；具备适用于核电金属部件及设备设施在贮存和运输过程中的防锈包装。
Description
技术领域
本发明属于防锈技术领域，特别涉及气相防锈塑料薄膜技术领域。
背景技术
核电站在建设的过程中，大量的核电金属部件或设备设施在核岛就位前需经历工厂预制及现场贮存阶段，有时还会受到项目核准影响，核电金属部件或设备设施在现场存放时间较长，尤其在南方沿海地区，长期处于高温、高湿、高盐等恶劣环境条件，对核电金属部件或设备设施造成不同程度的锈蚀，这就需要采用长效的综合防锈防护包装方式。
在此之前，核电物项多采用防锈油等临时防护方式，未考虑长周期防护要求，同时在长期防护时，防护产品中所包含的有害元素可能会对物项带来其他方面的不利影响，特别是用于核岛内部使用的物项。这就要求防护产品严格控制卤素、重金属等有害元素含量。
气相防锈塑料薄膜是一种由聚烯烃树脂和防锈成分合成的气相防锈包装材料，主要用于包装容易发生锈蚀的金属部件及设备设施等。聚烯烃材料因综合性能良好、价格低廉和易加工而在工业生产中应用广泛，但是聚烯烃材料也存在强度不够、耐热性差、成型收缩率大等缺陷，严重限制了聚烯烃的应用拓展。
为了避免污染以及长效的综合防锈防护，有必要研发一种气相防锈塑料薄膜，使其中磷、硫、铟、汞、氯、氟等元素的含量，满足核电金属部件及设备设施的防污染要求。
发明内容
针对以上现有技术存在的不足之处，本发明提供了一种核电专用气相防锈塑料薄膜及其制备方法。
一种核电专用气相防锈塑料薄膜，所述塑料薄膜从内到外分为三层共挤形成紧密结合结构，按重量百分比计，外层包括74％～96％聚烯烃树脂、1％～5％改性石墨烯、1％～5％马来酸酐、1％～8％分散剂、1％～7％润滑剂、0.1％～1％抗氧化剂，所述外层的重量占所述塑料薄膜总重的30～40％；中层包括91～97％聚烯烃树脂、2～6％气相防锈母粒、1～3％的助剂，所述中层的重量占所述塑料薄膜总重的20～40％；内层包括90～95％聚烯烃树脂、5～10％气相防锈母粒，所述内层的重量占所述塑料薄膜总重的30～40％。
优选的，所述改性石墨烯是通过按重量百分比计的0.4～0.5％氧化石墨烯分散在90～92％去离子水中，在常温下通过超声波震荡的方式进行剥离和溶解，得到氧化石墨烯—-水分散液；将所述的氧化石墨烯—-水分散液与7.5～9％乙醇、0.1～3％改性剂进行混合，将该混合溶液加热回流，得到改性氧化石墨烯溶液；然后将所述的改性氧化石墨烯溶液过滤，过滤得到的粉末在无水乙醇中搅拌冲洗，再过滤；将过滤后的产物置于烘箱中烘干至恒重制成。
优选的，所述气相防锈母粒，包括65～80％的聚烯烃树脂，17～30％的气相防锈剂，3～5％的助剂，按重量百分比计。
优选的，所述气相防锈剂包括30～40％苯甲酸钠、20～30％钼酸钠、10～18％钼酸铵、5～18％苯并三氮唑、4～10％酒石酸钠、3～12％肉桂酸钠，按照质量百分比计。
优选的，所述聚烯烃树脂包括低密度聚乙烯LDPE、线性低密度聚乙烯LLDPE、茂金属线型低密度聚乙烯mLLDPE、高密度聚乙烯HDPE、聚丙烯PP中的一种或几种。
优选的，所述分散剂为甲醇、乙醇、硬脂酸酰胺中的一种或多种。
优选的，所述润滑剂为硬脂酸、硬脂酸钙、硬脂酸镁、硅酸酯、聚乙烯蜡、聚丙烯蜡中的一种或多种。
优选的，所述抗氧剂为双十二碳醇酯、双十四碳醇酯、双十八碳醇酯中的一种或多种。
优选的，所述助剂包括色母粒、低分子量聚乙烯、硬脂酸、硅酸酯、硬脂酸酰胺、油酸酰胺、二氧化硅中的一种或几种。
优选的，所述改性剂为聚乙烯醇、聚环氧乙烷、聚丙烯酸、聚甲基丙烯酸、聚甲基丙烯酸甲酯、聚丙烯酰胺、壳聚糖、聚赖氨酸中的一种或几种。
一种核电专用气相防锈塑料薄膜的制备方法，其特征在于，包括权利要求1-10所述的一种核电专用气相防锈塑料薄膜，其制备方法如下：
1)混料，分别混合所述外层、所述中层和所述内层的制备原料，制备所述气相防锈塑料薄膜的外层原料混合物、中层原料混合物和内层原料混合物；
2)配料，将步骤1)制备的气相防锈塑料薄膜的外层原料混合物、中层原料混合物、内层原料混合物按配比进行配料；
3)吹膜，将步骤2)配料后的混合原料采用三层共挤的方式吹塑成型。
优选的，所述步骤3)中的共挤吹塑过程为，将所述外层原料混合物、所述中层原料混合物和所述内层原料混合物按配比加入三层共挤吹塑薄膜机的外、中、内层料斗中，加热并逐渐升温，所述外层、所述中层和所述内层的挤出温度控制在170～205℃，经挤出吹塑成型制得。
本发明提高气相防锈塑料薄膜的物理性能、阻隔性能及热稳定性能；适用于钢、铁、铝、铜等多种金属的防锈，具有优异的气相防锈能力；满足核电的防污染要求，并具备适用于核电金属部件及设备设施在贮存和运输过程中的防锈包装。
附图说明
图1为本发明一种核电专用气相防锈塑料薄膜的结构示意图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合附图和具体实施方式对本发明作进一步详细的说明。
实施例1
一种核电专用气相防锈塑料薄膜是通过三层共挤形成紧密结合结构，外层的制备原料包括93.5％聚烯烃树脂、1％改性石墨烯、1％马来酸酐、2％分散剂、2％润滑剂、0.5％抗氧化剂，重量占膜总重的30％；中层的制备原料包括96％聚烯烃树脂、3％气相防锈母粒、1％的助剂，重量占膜总重的40％；所述内层的制备原料包括93％聚烯烃树脂、7％气相防锈母粒，重量占膜总重的30％。经以下步骤，将所述原材料经混料、配料、吹膜三个步骤，即制得核电专用气相防锈塑料薄膜1。
实施例2
一种核电专用气相防锈塑料薄膜，其是通过三层共挤形成紧密结合结构，外层的制备原料包括86％聚烯烃树脂、3％改性石墨烯、2.5％马来酸酐、4％分散剂、4％润滑剂、0.5％抗氧化剂，重量占膜总重的40％；中层的制备原料包括94％聚烯烃树脂、4％气相防锈母粒、2％的助剂，重量占膜总重的20％；内层的制备原料包括95％聚烯烃树脂、5％气相防锈母粒，重量占膜总重的40％。经以下步骤，将所述原材料经混料、配料、吹膜三个步骤，即制得核电专用气相防锈塑料薄膜2。
实施例3
一种核电专用气相防锈塑料薄膜，其是通过三层共挤形成紧密结合结构，外层的制备原料包括77.5％聚烯烃树脂、5％改性石墨烯、4.5％马来酸酐、7％分散剂、5％润滑剂、1％抗氧化剂，重量占膜总重的40％；中层的制备原料包括95％聚烯烃树脂、2％气相防锈母粒、3％的助剂，重量占膜总重的25％；内层的制备原料包括94％聚烯烃树脂、6％气相防锈母粒，重量占膜总重的35％。经以下步骤，将所述原材料经混料、配料、吹膜三个步骤，即制得核电专用气相防锈塑料薄膜3。
对实施例1、2、3制备所得目标产物进行气相缓蚀能力试验、相容性试验、接触腐蚀试验和交变湿热试验。其中，气相缓蚀能力试验参照GB/T16267-2008《包装材料试验方法气相缓蚀能力》进行测试，相容性试验参照GB/T16265-2008《包装材料试验方法相容性》进行测试，接触腐蚀试验参照GB/T16266-2019《包装材料试验方法接触腐蚀》进行测试，交变湿热试验参照GB/T2423.4-2008《电工电子产品环境试验第2部分：试验方法试验Db交变湿热(12h+12h循环)试验》进行测试。具体测试结果见表1。
表1
通过测试结果可知，实施例1、2、3具有良好的气相缓蚀能力，对钢和铝无接触腐蚀，与紫铜和铝具有良好的相容性，与10#钢和H62铜交变湿热试验7周期合格。
综上，实施例1、2、3对黑金属和有色金属均具有良好的防锈性能。
根据核电金属部件及设备设施的防污染要求，气相防锈塑料薄膜中磷、硫、铟、汞、氯、氟等元素的含量必需在规定的有害物质浓度限值以下。经第三方检测机构通标标准技术服务(天津)有限公司(SGS)检测，完全满足核电金属部件及设备设施的防污染要求。
显然，本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样，倘若对本发明的这些修改和变型属于本发明权利要求及其同等技术的范围之内，则本发明意图包含这些改动和变型在内。上述实施例或实施方式只是对本发明的举例说明，本发明也可以以其它的特定方式或其它的特定形式实施，而不偏离本发明的要旨或本质特征。因此，描述的实施方式从任何方面来看均应视为说明性而非限定性的。本发明的范围应由附加的权利要求说明，任何与权利要求的意图和范围等效的变化也应包含在本发明的范围内。
Claims (12)
1.一种核电专用气相防锈塑料薄膜，其特征在于，所述塑料薄膜从内到外分为三层共挤形成紧密结合结构，按重量百分比计，外层包括74％～96％聚烯烃树脂、1％～5％改性石墨烯、1％～5％马来酸酐、1％～8％分散剂、1％～7％润滑剂、0.1％～1％抗氧化剂，所述外层的重量占所述塑料薄膜总重的30～40％；中层包括91～97％聚烯烃树脂、2～6％气相防锈母粒、1～3％的助剂，所述中层的重量占所述塑料薄膜总重的20～40％；内层包括90～95％聚烯烃树脂、5～10％气相防锈母粒，所述内层的重量占所述塑料薄膜总重的30～40％。
2.根据权利要求1所述的一种核电专用气相防锈塑料薄膜，其特征在于，所述改性石墨烯是通过按重量百分比计的0.4～0.5％氧化石墨烯分散在90～92％去离子水中，在常温下通过超声波震荡的方式进行剥离和溶解，得到氧化石墨烯—-水分散液；将所述的氧化石墨烯—-水分散液与7.5～9％乙醇、0.1～3％改性剂进行混合，将该混合溶液加热回流，得到改性氧化石墨烯溶液；然后将所述的改性氧化石墨烯溶液过滤，过滤得到的粉末在无水乙醇中搅拌冲洗，再过滤；将过滤后的产物置于烘箱中烘干至恒重制成。
3.根据权利要求1所述的一种核电专用气相防锈塑料薄膜，其特征在于，所述气相防锈母粒，包括65～80％的聚烯烃树脂，17～30％的气相防锈剂，3～5％的助剂，按重量百分比计。
4.根据权利要求3中所述的一种核电专用气相防锈塑料薄膜，其特征在于，所述气相防锈剂包括30～40％苯甲酸钠、20～30％钼酸钠、10～18％钼酸铵、5～18％苯并三氮唑、4～10％酒石酸钠、3～12％肉桂酸钠，按照质量百分比计。
5.根据权利要求1所述的一种核电专用气相防锈塑料薄膜，其特征在于，所述聚烯烃树脂包括低密度聚乙烯LDPE、线性低密度聚乙烯LLDPE、茂金属线型低密度聚乙烯mLLDPE、高密度聚乙烯HDPE、聚丙烯PP中的一种或几种。
6.根据权利要求1所述的一种核电专用气相防锈塑料薄膜，其特征在于，所述分散剂为甲醇、乙醇、硬脂酸酰胺中的一种或多种。
7.根据权利要求1所述的一种核电专用气相防锈塑料薄膜，其特征在于，所述润滑剂为硬脂酸、硬脂酸钙、硬脂酸镁、硅酸酯、聚乙烯蜡、聚丙烯蜡中的一种或多种。
8.根据权利要求1所述的一种核电专用气相防锈塑料薄膜，其特征在于，所述抗氧剂为双十二碳醇酯、双十四碳醇酯、双十八碳醇酯中的一种或多种。
9.根据权利要求1或3中所述的一种核电专用气相防锈塑料薄膜，其特征在于，所述助剂包括色母粒、低分子量聚乙烯、硬脂酸、硅酸酯、硬脂酸酰胺、油酸酰胺、二氧化硅中的一种或几种。
10.根据权利要求2所述的一种核电专用气相防锈塑料薄膜，其特征在于，所述改性剂为聚乙烯醇、聚环氧乙烷、聚丙烯酸、聚甲基丙烯酸、聚甲基丙烯酸甲酯、聚丙烯酰胺、壳聚糖、聚赖氨酸中的一种或几种。
11.一种核电专用气相防锈塑料薄膜的制备方法，其特征在于，包括权利要求1-10所述的一种核电专用气相防锈塑料薄膜，其制备方法如下：
1)混料，分别混合所述外层、所述中层和所述内层的制备原料，制备所述气相防锈塑料薄膜的外层原料混合物、中层原料混合物和内层原料混合物；
2)配料，将步骤1)制备的气相防锈塑料薄膜的外层原料混合物、中层原料混合物、内层原料混合物按配比进行配料；
3)吹膜，将步骤2)配料后的混合原料采用三层共挤的方式吹塑成型。
12.根据权利要求11所述的一种核电专用气相防锈塑料薄膜的制备方法，其特征在于，所述步骤3)中的共挤吹塑过程为，将所述外层原料混合物、所述中层原料混合物和所述内层原料混合物按配比加入三层共挤吹塑薄膜机的外、中、内层料斗中，加热并逐渐升温，所述外层、所述中层和所述内层的挤出温度控制在170～205℃，经挤出吹塑成型制得。
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| CN113829711A (zh) * | 2021-09-23 | 2021-12-24 | 沈阳防锈包装材料有限责任公司 | 一种耐候性气相防锈包装材料及其制备方法 |
| CN113846328A (zh) * | 2021-09-23 | 2021-12-28 | 沈阳防锈包装材料有限责任公司 | 一种缓释型气相防锈剂及其制备方法 |
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