CN109651902B - 聚醚酮酮增强氟树脂耐高温防腐涂层 - Google Patents

聚醚酮酮增强氟树脂耐高温防腐涂层 Download PDF

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CN109651902B
CN109651902B CN201811405679.7A CN201811405679A CN109651902B CN 109651902 B CN109651902 B CN 109651902B CN 201811405679 A CN201811405679 A CN 201811405679A CN 109651902 B CN109651902 B CN 109651902B
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polyether ketone
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王帅坡
李光辉
孙庆民
张泰铭
张际亮
贾亚非
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Shandong Kaisheng New Materials Co Ltd
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Abstract

本发明涉及一种聚醚酮酮增强氟树脂耐高温防腐涂层，属于高分子技术领域。所述的涂层，包括含聚醚酮酮的氟树脂底漆和聚醚酮酮改性氟树脂面漆，含聚醚酮酮的氟树脂底漆由下列质量分数的物质组成：聚醚酮酮10‑15％；聚酰胺酰亚胺5‑10％；PFA 20‑35％；表面活性剂0.5‑5％；增粘胶体1‑5％；有机溶剂45‑60％；颜料0.5‑1％；聚醚酮酮改性氟树脂面漆由氟树脂、聚醚酮酮和交联剂组成，其中，聚醚酮酮质量为氟树脂质量的7‑15％，交联剂质量为氟树脂质量的0.1‑0.5％。本发明所提供的聚醚酮酮增强氟树脂耐真空耐高温涂层，具有耐真空、耐高温和耐腐蚀的特点。

Description

聚醚酮酮增强氟树脂耐高温防腐涂层
技术领域
本发明涉及一种聚醚酮酮增强氟树脂耐高温防腐涂层，属于高分子技术领域。
背景技术
聚醚酮酮(PEKK)作为一种高性能热塑性工程塑料，具有出色的耐热性，优良的机械性能。目前将聚醚酮酮作为涂料来使用，具有多种优异的性能，如与基材优异的结合性，良好的耐化学性，耐高温等，非常适用于耐高温、防腐蚀涂层的应用。传统涂覆方法中四氟乙烯-全氟烷氧基乙烯基醚共聚物(PFA)涂覆在金属表面，因为氟材料本身的不粘性，导致涂层结合力差。传统的氟树脂底漆，对涂层结合有一定结合力，但结合仅仅局限在物理结合，在高温状态或者高真空状态下，会出现涂层脱落等问题。
因此，在防腐涂层领域，氟树脂与金属基材结合方面，亟待开发一种具有高结合，耐高温防腐性能的涂层。
发明内容
针对现有技术的不足，本发明的目的是提供一种聚醚酮酮增强氟树脂耐真空耐高温涂层，具有耐真空、耐高温和耐腐蚀的特点。
本发明所述的聚醚酮酮增强氟树脂耐高温防腐涂层，包括含聚醚酮酮的氟树脂底漆和聚醚酮酮改性氟树脂面漆，含聚醚酮酮的氟树脂底漆由下列质量分数的物质组成：
Figure BDA0001877278420000011
聚醚酮酮改性氟树脂面漆由氟树脂、聚醚酮酮和交联剂组成，其中，聚醚酮酮质量为氟树脂质量的7-15％，交联剂质量为氟树脂质量的0.1-0.5％。
所述的聚醚酮酮粘度为0.6-0.8dl/g，粒径尺寸D90不大于10um。
所述的聚酰胺酰亚胺粒径尺寸D90不大于10um。
所述的PFA为聚四氟乙烯-全氟烷氧基乙烯基醚共聚物，粒径尺寸D90不大于10um。
所述的表面活性剂为非离子型表面活性剂。
优选的，所述的表面活性剂为异构醇聚氧乙烯醚类。
所述的增粘胶体为羟甲基纤维素醚。
所述的有机溶剂为N-甲基吡咯烷酮。
所述的颜料为炭黑。
所述的聚醚酮酮增强氟树脂耐高温防腐涂层的组合方式，是在金属基材上涂覆含聚醚酮酮的氟树脂底漆，在含聚醚酮酮的氟树脂底漆上涂覆聚醚酮酮改性氟树脂面漆，得到聚醚酮酮增强氟树脂耐高温防腐涂层。
所述的含聚醚酮酮的氟树脂底漆的制备方法：将表面活性剂，有机溶剂，按配比量依次加入到搅拌桶内，设置搅拌转速为1500r/min搅拌10-15min，待溶液混合均匀，依次将聚酰胺酰亚胺细粉、聚醚酮酮树脂、PFA和颜料按配比量加入到溶液中，转速1500r/min搅拌30-60min，待溶液体系分散均匀后，向溶液体系中加入配比量的增粘胶体，设置搅拌转速1000r/min搅拌，得到均匀稳定的底漆。
所述的聚醚酮酮改性氟树脂面漆：向氟树脂中加入聚醚酮酮，交联剂，在三维混合机中混合30min后，即得。
所述的交联剂为4,4-二氨基二苯醚；氟树脂为PFA。
所述聚醚酮酮增强氟树脂耐高温防腐涂层的制备过程：是先在金属基材上涂覆含聚醚酮酮的氟树脂底漆，待底漆烘干后，用静电喷涂的方式喷涂聚醚酮酮改性氟树脂面漆，即得到聚醚酮酮增强氟树脂耐高温防腐涂层。
聚醚酮酮应用在底漆中，聚醚酮酮结构中的醚键以及酮基等含氧基团对金属有极强的亲和性，可以保证聚醚酮酮树脂和金属基材紧密结合在一起。PFA树脂中添加交联剂4,4-二氨基二苯醚，交联剂先与PFA树脂进行分散均匀，在高温状态下，一方面交联剂可以有助于打开PFA结构中的烷氧基团，与改性氟树脂中的PEKK中的活性基团进行连接，聚醚酮酮的苯环结构穿插在PFA氟树脂结构中，提升了PFA的性能，另一方面，交联剂结构中的氨基可以与底漆中PEKK树脂上的活性位点发生化学反应。
含聚醚酮酮树脂的氟树脂底漆中的聚醚酮酮树脂作为过渡层，一方面通过化学键与金属键的优良结合保证了树脂与金属通过化学键结合在一起，另一方面聚醚酮酮树脂与PFA树脂中的交联剂发生化学反应，紧紧结合在一起，进而保证了涂层之间通过彼此之间的化学键紧密结合在一起，突破了原有涂层之间物理结合的局限性，提升了涂层的使用寿命和实用性。
与现有技术相比，本发明具有如下有益效果：
1.所述的含聚醚酮酮的氟树脂底漆，具有粘结性强、耐热性好和耐化学性优的特点；
2.通过含聚醚酮酮的氟树脂底漆与改性氟树脂之间化学交联的方式，解决了传统氟树脂防腐涂层与金属基材结合力差、耐温性差、易剥离和不耐真空性的问题，使涂层的适用范围和使用寿命得到显著改善；
3.所述的聚醚酮酮增强氟树脂耐高温防腐涂层可在200℃长时间使用；
4.所述涂层经化学浸泡实验，涂层外观良好，涂层结合力未受影响；
5.所提供的制备方法，科学合理，简单易行。
具体实施方式
下面结合实施例对本发明做进一步的说明。
实施例1
将表面活性剂APEO 40g，N-甲基吡咯烷酮578g，依次加入到搅拌桶内，搅拌设置转速1500r/min，搅拌10min，待溶液混合均匀，依次将聚酰胺酰亚胺细粉55g，聚醚酮酮细粉120g，PFA树脂220g，炭黑6g，加入到溶液中，设置转速为1500r/min搅拌50min，待溶液体系分散均匀后，向溶液体系中加入30g羟甲基纤维素醚，设置转速为1000r/min搅拌体系，得到均匀稳定的底漆，用150目过滤网进行过滤，静止，使用。
称取10g 4,4-二氨基二苯醚，300g聚醚酮酮细粉和2990gPFA树脂，在三维混合机中混合30min，取出物料，先在金属基材上涂覆含聚醚酮酮的氟树脂底漆，待底漆烘干后，用静电喷涂的方式喷涂聚醚酮酮改性PFA树脂面漆于底漆上面。
实施例2
将表面活性剂APEO 40g，N-甲基吡咯烷酮578g，依次加入到搅拌桶内，搅拌设置转速1500r/min搅拌15min，待溶液混合均匀，依次将聚酰胺酰亚胺细粉105g，聚醚酮酮细粉140g，PFA树脂240g，炭黑6g，加入到溶液中，低速搅拌60min，待溶液体系分散均匀后，向溶液体系中加入30g羟甲基纤维素醚，设置转速为1000r/min搅拌体系，得到均一稳定的底漆，用150目过滤网进行过滤，静止，使用。
称取10g4,4-二氨基二苯醚，300g聚醚酮酮细粉和2990gPFA树脂，在三维混合机中混合30min，取出物料。先在金属基材上涂覆含聚醚酮酮的氟树脂底漆，待底漆烘干后，用静电喷涂的方式喷涂聚醚酮酮改性PFA树脂面漆于底漆上面。
实施例3
将表面活性剂APEO 40g，N-甲基吡咯烷酮536g，依次加入到搅拌桶内，搅拌设置转速1500r/min搅拌15min，待溶液混合均匀，依次将聚酰胺酰亚胺细粉100g，聚醚酮酮细粉110g，PFA树脂220g，炭黑6g，加入到溶液中，设置转速1500r/min搅拌40min，待溶液体系分散均匀后，向溶液体系中加入30g羟甲基纤维素醚，设置转速1000r/min搅拌体系，得到均匀稳定的底漆，用150目过滤网进行过滤，静止使用。
称取10g4,4-二氨基二苯醚，300g聚醚酮酮细粉和2990gPFA树脂，在三维混合机中混合30min，取出物料，先在金属基材上涂覆含聚醚酮酮的氟树脂底漆，待底漆烘干后，用静电喷涂的方式喷涂聚醚酮酮改性PFA树脂面漆于底漆上面。
采用拉开法附着力实验对实施例1-3产品在不同温度下的结合力和防腐性能进行测定评估，结果如表1所示。
实验方法如下：
用胶黏剂将试柱粘结到涂层表面，胶黏剂固化后，将粘结的实验组合置于合适的压力实验机上，粘接的实验组合经可控的拉力实验测出破坏涂层/底材间所需拉力，用破坏涂层的拉力大小来表示结合力强弱，具体实验结果如下：
表1实施例1-3产品和不使用底漆产品涂层结合力实验结果
Figure BDA0001877278420000041
胶黏剂拉断极限为5MPa。
用不同的化学试剂在不同温度下进行浸泡测试，浸泡条件150℃，浸泡时间30天；防腐性测试结果如表2所示。
表2实施例1产品防腐性测试结果
Figure BDA0001877278420000042

Claims (8)

1.一种聚醚酮酮增强氟树脂耐高温防腐涂层，包括含聚醚酮酮的氟树脂底漆和聚醚酮酮改性氟树脂面漆，其特征在于：含聚醚酮酮的氟树脂底漆由下列质量分数的物质组成：
Figure FDA0002704746550000011
聚醚酮酮改性氟树脂面漆由氟树脂、聚醚酮酮和交联剂组成，其中，聚醚酮酮质量为氟树脂质量的7-15％，交联剂质量为氟树脂质量的0.1-0.5％；
PFA为聚四氟乙烯-全氟烷氧基乙烯基醚共聚物；
所述的交联剂为4,4-二氨基二苯醚。
2.根据权利要求1所述的聚醚酮酮增强氟树脂耐高温防腐涂层，其特征在于：聚醚酮酮粘度为0.6-0.8dl/g，粒径尺寸D90不大于10μm。
3.根据权利要求1所述的聚醚酮酮增强氟树脂耐高温防腐涂层，其特征在于：聚酰胺酰亚胺粒径尺寸D90不大于10μm。
4.根据权利要求1所述的聚醚酮酮增强氟树脂耐高温防腐涂层，其特征在于：PFA粒径尺寸D90不大于10μm。
5.根据权利要求1所述的聚醚酮酮增强氟树脂耐高温防腐涂层，其特征在于：表面活性剂为非离子型表面活性剂。
6.根据权利要求1所述的聚醚酮酮增强氟树脂耐高温防腐涂层，其特征在于：增粘胶体为羟甲基纤维素醚。
7.根据权利要求1所述的聚醚酮酮增强氟树脂耐高温防腐涂层，其特征在于：有机溶剂为N-甲基吡咯烷酮。
8.根据权利要求1所述的聚醚酮酮增强氟树脂耐高温防腐涂层，其特征在于：颜料为炭黑。
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