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CN110062793B - 基于含氟聚合物的粉末涂料 - Google Patents

基于含氟聚合物的粉末涂料 Download PDF

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CN110062793B
CN110062793B CN201780076548.6A CN201780076548A CN110062793B CN 110062793 B CN110062793 B CN 110062793B CN 201780076548 A CN201780076548 A CN 201780076548A CN 110062793 B CN110062793 B CN 110062793B
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powder coating
coating composition
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fluoropolymer
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CN110062793A (zh
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F.阿布格拉尔
A.邦内特
S.德维斯姆
T.法恩
T.福山
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Arkema France SA
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Abstract

本发明涉及氟化丙烯酸类热塑性组合物，由这类组合物制成的粉末涂层，以及制备所述粉末涂层的方法。

Description

基于含氟聚合物的粉末涂料
技术领域
本发明涉及氟化丙烯酸类热塑性组合物，由这类组合物制成的粉末涂层(涂料，coatings)，以及制备所述粉末涂层的方法。
背景技术
通常的热塑性含氟聚合物粉末涂层的特征在于机械性能的程度和与涂饰(finish)相关的表面粗糙度或“橘皮皱(orange peel)”。可通过各种方法减少“橘皮”。虽然可降低树脂熔体粘度以对抗橘皮皱，但是熔体粘度降低通常对涂层的机械性质，特别是抗冲击性、柔韧性和抗裂性具有不利影响。
U.S.4,770,939中公开了聚偏二氟乙烯(PVDF)和含有至少90重量％VDF的偏二氟乙烯(VDF)的共聚物的粉末涂料。在上述粉末涂料的专利中公开的基于PVDF的树脂根据ASTM D3835的熔体粘度在230℃下为6至7千泊。需要少量的低分子量丙烯酸类聚合物作为流动改进剂。
文献US 5,177,150公开了由PVDF配制的粉末涂料，其特征在于熔体粘度低至1至4千泊，声称因此不需要包含流动改进剂。然而，粉末涂料组合物需要低温研磨以获得高产量的小粒度粉末(20μm或更小)。
因此，需要开发在不使用流动改进剂，并且借助于不再需要使用液氮进行研磨步骤的简化的制造方法的情况下，呈现出良好机械性质和耐风化性的粉末涂料组合物。现已发现，通过使用由熔融粘度低于1千泊的氟化聚合物和丙烯酸类聚合物制成的组合物，粉末涂料在室温下可被有效地研磨，同时显示出良好的机械性质和优异的耐风化(weather)性(耐候性)。
发明内容
本发明首先涉及由以下组成的组合物：
a.50-95重量％的热塑性含氟聚合物，和
b.5-50重量％的丙烯酸类聚合物，
其中含氟聚合物通过使用ASTM D3835在100sec-1和230℃下测量的熔体粘度为0.04至低于1千泊(kP)。
本发明的另一个主题是粉末涂料组合物，其包含上述组合物、至少一种颜料和任选地一些选自UV吸收剂、光稳定剂、消光剂、流平剂、脱气剂、流动剂、润湿剂和抗冲改性剂的添加剂。
本发明的另一个主题是使用本发明的粉末涂料组合物制备粉末涂层的方法。
本发明的另一个主题是由至少一种根据本发明的粉末涂料组合物的固化获得的涂层。
具体实施方式
现在更详细地描述本发明，并且在以下的描述中没有暗示的限制。
本发明首先涉及由以下组成的组合物：
a.50-95重量％的热塑性含氟聚合物，和
b.5-50重量％的丙烯酸类聚合物，
其中含氟聚合物通过使用ASTM D3835在100sec-1和230℃下测量的熔体粘度为0.04至低于1千泊。
因此，术语含氟聚合物表示以下的任何聚合物或聚合物的共混物，即其在其链中具有至少一种选自含有能够打开以便聚合的乙烯基的分子的单体，并且其含有直接连接至该乙烯基的至少一个氟原子、至少一个氟代烷基或至少一个氟代烷氧基。
作为单体的实例，可提及氟乙烯；偏二氟乙烯(VDF)；三氟乙烯(VF3)；氯三氟乙烯(CTFE)；1,2-二氟乙烯；四氟乙烯(TFE)；六氟丙烯(HFP)；全氟(烷基乙烯基)醚，例如全氟(甲基乙烯基)醚(PMVE)、全氟(乙基乙烯基)醚(PEVE)和全氟(丙基乙烯基)醚(PPVE)；全氟(1,3-二氧杂环戊烯)；全氟(2,2-二甲基-1,3-二氧杂环戊烯)PDD)；式CF2＝CFOCF2CF(CF3)OCF2CF2X的产品(产物)，其中X为SO2F、CO2H、CH2OH、CH2OCN或CH2OPO3H；式CF2＝CFOCF2CF2SO2F的产品；式F(CF2)nCH2OCF＝CF2的产品，其中n为1、2、3、4或5；式R1CH2OCF＝CF2的产品，其中R1为氢或F(CF2)z并且z为1、2、3或4；式R3OCF＝CH2的产品，其中R3为F(CF2)z-并且z为1、2、3或4；全氟丁基乙烯(PFBE)；3,3,3-三氟丙烯和2-三氟甲基-3,3,3-三氟-1-丙烯。
含氟聚合物可为均聚物或共聚物；其也可含有非氟化单体，例如乙烯。
例如，含氟聚合物选自：
-偏二氟乙烯(VDF)的均聚物和共聚物，优选含有至少50重量％的VDF，共聚单体选自氯三氟乙烯(CTFE)、六氟丙烯(HFP)、三氟乙烯(VF3)和四氟乙烯(TFE)；
-三氟乙烯(VF3)的均聚物和共聚物；和
-组合了以下的残基的共聚物，且尤其是三元共聚物：氯三氟乙烯(CTFE)、四氟乙烯(TFE)、六氟丙烯(HFP)和/或乙烯单元和任选地VDF和/或VF3单元。
有利地，含氟聚合物是聚偏二氟乙烯(PVDF)均聚物或共聚物。优选地，PVDF含有至少50重量％、更优选至少75重量％且甚至更优选至少85重量％的VDF。在一个实施方案中，共聚单体是HFP。在另一个实施方案中，共聚单体是TFE。
特征在于，含氟聚合物的粘度为0.04至小于1千泊，使用ASTM D3835在100sec-1和230℃下测量。
术语“丙烯酸类聚合物”表示甲基丙烯酸甲酯的均聚物或甲基丙烯酸甲酯(MMA)和至少一种可与MMA共聚的其他单体的共聚物，这些共聚物含有至少50重量％的MMA。作为可与MMA共聚的共聚单体的实例，可提及(甲基)丙烯酸烷基酯、衣康酸、(甲基)丙烯腈、叔碳酸乙烯酯(vinyl versatate)、丁二烯、苯乙烯和异戊二烯。有利地，丙烯酸类聚合物含有按重量计优选5至15％的(甲基)丙烯酸C1-C20烷基酯，其优选为丙烯酸甲酯和/或丙烯酸乙酯。丙烯酸类聚合物也可为官能化的；也就是说，共聚物含有MMA单元和以下通式的第二种共聚单体：
Figure BDA0002090376110000031
其中：
R1表示H或–CH3；
R2表示H或含有1至20个碳原子的连接有官能团的直链或支链烷基。这类官能团(其在大多数情况下含有杂原子(既不是碳也不是氢的原子))的实例包括羧酸、磺酸或硫酸、膦酸或磷酸、羟基、酯、酮、酮酯、酰胺、氨基甲酸酯、硫醇、硅氧烷、氟代烷基、乙酰乙酸酯、环氧乙烷；以及乙烯基形式的不饱和基团例如乙烯基酯或醚、烯丙基酯或醚，乙炔基，二烯，丙二酸酯(malonates)等。
尤其有利的是含有0.5至20重量％的酸官能单体或其酸酐衍生物的丙烯酸类共聚物，例如：
Figure BDA0002090376110000041
其中：
R3表示H或甲基；或对于酸酐衍生物，以下形式的结构：
Figure BDA0002090376110000042
其中R4和R5相同或不同，表示H或甲基。官能共聚单体的比例可为包括可能的官能团的丙烯酸类聚合物的0至25重量％，优选5至20重量％。
根据第二主题，本发明涉及粉末涂料组合物，其包含上述热塑性组合物、至少一种颜料和任选地一些选自UV吸收剂、光稳定剂、消光剂、流平剂、脱气剂、流动剂、润湿剂和抗冲改性剂的添加剂。
粉末涂料组合物含有一种或多种颜料。颜料可为有机的或无机的。根据一个实施方案，颜料组分可包含二氧化钛，或二氧化钛与一种或多种其它无机颜料的组合，其中二氧化钛构成组合的主要部分。可单独使用或与二氧化钛组合使用的无机颜料包括例如二氧化硅；各种颜色的铁氧化物；钛酸铅；和各种硅酸盐，例如滑石、硅藻土石棉、云母、粘土和碱式硅酸铅。可与二氧化钛组合使用的颜料包括例如氧化锌、硫化锌、氧化锆、白铅、炭黑、铬酸铅、漂浮型(leafing)和非漂浮型(non-leafing)金属颜料、钼酸橙、碳酸钙和硫酸钡。颜料组分在粉末涂料组合物中有利地以约5至约30重量份的量存在。
粉末涂料组合物可含有一种或多种非颜料的添加剂。这些添加剂的实例是UV吸收剂、光稳定剂、消光剂、流平剂、脱气剂、流动剂、润湿剂和抗冲改性剂。
粉末涂料中所含的任何添加剂均可为有机的或无机的。其可以一种类型单独使用，或以两种或更多种类型的组合使用。UV吸收剂的一些实例包括苯并三唑、草酸二芳基酰胺和2-羟基二苯甲酮。合适的光稳定剂包括例如位阻胺，例如聚(链烷酰基哌啶醇)，例如琥珀酸二甲酯与4-羟基四甲基哌啶乙醇的低聚物，位阻酚，或其组合。消光剂的一些实例包括二氧化硅和蜡。流平剂的实例包括熔点低于130℃的VDF和HFP的共聚物、酯胶和硅油。脱气剂的实例包括苯偶姻。流动剂的实例包括二氧化硅和气相氧化铝。二氧化硅也可用作润湿剂。抗冲改性剂可优选为核-壳类型的。
粉末涂料组合物由平均尺寸为10至50μm、优选15至30μm的颗粒组成。
本发明的另一个主题是使用本发明的粉末涂料组合物制备粉末涂层的方法，所述方法包括以下步骤：
i.通过将热塑性含氟聚合物、丙烯酸类聚合物、颜料和任选地添加剂共混制备这些组分的混合物，然后将混合物造粒或片材挤出；
ii.在室温下在锤磨机中研磨由此获得的粒料，以获得粉末；
iii.通过使用开口为50μm的筛子收集粉末；
iv.将粉末施加至基底然后对其进行热处理以形成涂层。
含氟聚合物、丙烯酸类树脂和颜料的粉末涂料组合物通过挤出而被熔融混合，例如在160℃至210℃范围内运行的双螺杆挤出机中。然后通过常规技术将挤出的混合物造粒或挤出成片。
在下一步骤中，根据常规技术将粒料研磨成粉末，优选通过使用锤磨机。通过穿过适当尺寸的筛子将所得原料粉末分级为期望的粒度，其范围为10至100μm，优选15至80μm，更优选15至30μm。
根据本发明的粉末涂料可在室温下有效地研磨成平均尺寸为10至50μm的颗粒，而无需使用低温研磨技术。这允许更容易地处理粒料，并且确保降低整个过程的成本。
然后根据适合获得均匀粉末分布的任何方法将所得粉末施加至基底。电压在25和100V之间的静电施加是优选的施加方法。
基底选自金属，例如铁、铝和锰，并且优选由铝制成。铝基底的表面可被氧化或化学处理，但优选经铬酸盐处理以与根据本发明的粉末涂料(涂层)具有最佳粘附性。在以含氟聚合物的粉末涂料涂覆之前，可用底漆例如环氧型树脂涂覆基底。
施加之后，对粉末涂料进行足以使粉末涂料熔化的热处理。使用的温度应高于粉末的熔点。
在一个实施方案中，涂料在220和260℃之间的温度下烘烤，持续时间为5至20分钟。然后通过任何合适的方法冷却涂层(涂料)及其基底。
在另一个实施方案中，热处理包括将经涂覆的基底浸入沸水中4至6小时。
本发明的另一个主题是涂覆有根据本发明的如上定义的涂层的基底。涂层厚度优选但不限于30～1000μm。基底可用于诸如高层建筑的幕墙、交通标志和空调的室外单元的应用中。
实施例
实施例1
将52.5重量％的根据ASTM D3835在100sec-1，230℃下测量的熔体粘度为0.2kP的PVDF均聚物添加至22.5重量％的包含90:10甲基丙烯酸甲酯和戊二酸酐共聚物的PMMA树脂中。还向混合物中添加25重量％的TiO2。在160℃至210℃的范围内运行的双螺杆混合器中将混合物共混，并且造粒。在室温下在锤磨机中将粒料直接研磨。通过Microtrac 3000装置以水作为介质测量所得粉末的粒度分布。将粉末在50kV下以静电方式施加到经铬酸盐处理的铝的基底上。然后将板材在250℃下烘烤15分钟。
通过以下表1中所示的方法评估经涂覆的板材。
Figure BDA0002090376110000071
表1
实施例2
与实施例1中的步骤相同，不同之处在于含氟聚合物的组成。47.5重量％的制剂保持为根据ASTM D3835在100sec-1，230℃下测量的熔体粘度为0.2kP的PVDF均聚物，并且5重量％用根据ASTM D3835在100sec-1，230℃下测量的熔体粘度为25kP的VDF/HFP共聚物替代。含氟聚合物相的总粘度为0.9kP(根据ASTM D3835在100sec-1，230℃下测量)。
对比实施例3
使用与实施例1中的步骤相同，不同之处在于根据ASTM D3835在100sec-1，230℃下测量的熔体粘度为6kP的PVDF均聚物替代0.2kP的PVDF均聚物，并且使用MMA和丙烯酸乙酯的共聚物代替MMA/戊二酸酐90/10丙烯酸类共聚物。
对比实施例4
使用与实施例1中的步骤相同，不同之处在于根据ASTM D3835在100sec-1，230℃下测量的熔体粘度为3.5kP的PVDF均聚物替代0.2kP的PVDF均聚物。
评估结果在表2中给出。
Figure BDA0002090376110000081
表2
这些数据表明低于1kP的含氟聚合物粘度(如实施例1和2中)允许比对比实施例3和4更好的可研磨性。凭借室温下的研磨过程可实现低粒度，这在研磨成本和生产率方面是主要优点。令人感兴趣地注意到用实施例1和2的组合物仍然实现了涂层(涂料)的主要应用性质。

Claims (21)

1.粉末涂料组合物，其含有由以下组成的组合物：
a. 50-95重量%的一种或多种热塑性含氟聚合物，和
b. 5-50重量%的丙烯酸类聚合物，
其中含氟聚合物通过使用ASTM D3835在100 sec-1和230℃下测量的熔体粘度为0.04至低于1 kP，
其中所述粉末涂料组合物还包含5至30重量%的颜料。
2.根据权利要求1所述的粉末涂料组合物，其中所述含氟聚合物选自偏二氟乙烯(VDF)的均聚物和含有至少50重量% VDF的偏二氟乙烯(VDF)的共聚物，共聚单体选自氯三氟乙烯、六氟丙烯、三氟乙烯和四氟乙烯。
3.根据权利要求1所述的粉末涂料组合物，其中所述含氟聚合物选自三氟乙烯的均聚物和共聚物。
4.根据权利要求1所述的粉末涂料组合物，其中所述含氟聚合物选自组合了以下的残基的共聚物：氯三氟乙烯、四氟乙烯、六氟丙烯和/或乙烯单元和任选地VDF和/或三氟乙烯单元。
5.根据权利要求4所述的粉末涂料组合物，其中所述共聚物为三元共聚物。
6.根据权利要求1或2中任一项所述的粉末涂料组合物，其中含氟聚合物是聚偏二氟乙烯(PVDF)均聚物，或偏二氟乙烯与六氟丙烯或四氟乙烯的共聚物。
7.根据权利要求1至5中任一项所述的粉末涂料组合物，其中所述丙烯酸类聚合物是甲基丙烯酸甲酯(MMA)的均聚物或甲基丙烯酸甲酯与至少一种可与MMA共聚的其他单体的共聚物，这些共聚物含有至少50重量%的MMA。
8.根据权利要求1至5中任一项所述的粉末涂料组合物，其中所述颜料选自二氧化钛、铁氧化物、钛酸铅和硅酸盐。
9.根据权利要求1至5中任一项所述的粉末涂料组合物，其中所述组合物还包含至少一种选自光稳定剂、消光剂、流平剂、脱气剂、流动剂、润湿剂和抗冲改性剂的添加剂。
10.根据权利要求9所述的粉末涂料组合物，其中光稳定剂为UV吸收剂。
11.根据权利要求1至5中任一项所述的粉末涂料组合物，其中所述组合物由平均尺寸为10至100 μm的颗粒组成。
12.根据权利要求1至5中任一项所述的粉末涂料组合物，其中所述组合物由平均尺寸为15至80 μm的颗粒组成。
13.根据权利要求1至5中任一项所述的粉末涂料组合物，其中所述组合物由平均尺寸为15至30 μm的颗粒组成。
14.使用根据权利要求1至13中任一项所述的粉末涂料组合物制备粉末涂层的方法，所述方法包括以下步骤：
i. 通过将热塑性含氟聚合物、丙烯酸类聚合物、颜料和任选地添加剂共混来制备这些组分的混合物，然后将混合物造粒或片材挤出；
ii. 在室温下在锤磨机中研磨由此获得的粒料，以获得粉末；
iii. 通过使用开口为50 μm的筛子收集粉末；
iv.将粉末施加至基底，然后对其进行热处理以形成涂层。
15.根据权利要求14所述的方法，其中在25和100 V之间的电压下将粉末以静电方式施加至所述基底。
16.根据权利要求14或15中任一项所述的方法，其中基底由铝制成。
17.根据权利要求14或15中任一项所述的方法，其中基底由经铬酸盐处理的铝制成。
18.根据权利要求14或15中任一项所述的方法，其中热处理包括在220和260℃之间的温度下烘烤经涂覆的基底，持续时间在5至20分钟之间。
19.根据权利要求14或15中任一项所述的方法，其中热处理包括将经涂覆的基底浸入沸水中4至6小时。
20.根据权利要求14或15中任一项所述的方法，其中所获得的涂层的厚度为30至1000μm。
21.涂层，其特征在于其由至少一种如权利要求1至13中任一项所定义的粉末涂料组合物的固化产生。
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