CN111497227A - 酚酞聚芳醚酮/砜3d打印专用料及其制备方法 - Google Patents

酚酞聚芳醚酮/砜3d打印专用料及其制备方法 Download PDF

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CN111497227A
CN111497227A CN202010465361.9A CN202010465361A CN111497227A CN 111497227 A CN111497227 A CN 111497227A CN 202010465361 A CN202010465361 A CN 202010465361A CN 111497227 A CN111497227 A CN 111497227A
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sulfone
phenolphthalein
phenolphthalein polyaryletherketone
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高新帅
王红华
周光远
栾世芳
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Changchun Institute of Applied Chemistry of CAS
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Abstract

本发明公开了一种酚酞聚芳醚酮/砜3D打印专用料及其制备方法，本发明属于3D打印材料技术领域。该方法是将无定形酚酞聚芳醚酮/砜粉料在双螺杆中熔融挤出，并在牵引装置的作用下得到丝径均一的3D打印专用丝材；所述的无定形酚酞聚芳醚酮/砜的结构如式(Ⅰ)所示；将3D打印专用丝材干燥，然后通过高温3D打印机喷嘴出丝进行熔融沉积成型，打印速度为30～50mm/s，打印层厚为0.2mm，在打印底板上得到酚酞聚芳醚酮/砜3D打印专用料。本发明得到的专用料具有更高的强度和性能。

Description

酚酞聚芳醚酮/砜3D打印专用料及其制备方法
技术领域
本发明属于3D打印材料技术领域，具体公开了一种酚酞聚芳醚酮/砜3D打印专用料及其制备方法。
背景技术
凭借成型速度快、成本低、精度高等优势，3D打印技术在航空航天、电子电气、建筑和医疗等领域得到了广泛的应用。其中，熔融沉积成型工艺(FDM)通过高温喷嘴熔融热塑性丝材，在底板逐层成型，操作简单，成本低，原料利用率高且来源范围广，成为应用最广的3D打印工艺之一。然而，可使用的3D打印材料成熟度跟不上3D打印市场的发展速度，3D打印材料是制约3D打印技术发展的重要因素，因此开发新型、高性能3D打印材料成为重要的研究方向。
聚芳醚酮(砜)作为特种工程塑料具有优异的力学、电学性能，耐热耐化学腐蚀，阻燃性能好，在航空航天、电子信息、国防军工等领域具有广泛的应用。聚醚醚酮(PEEK)是目前在3D打印领域应用最广泛的聚芳醚酮，作为一种半结晶态聚合物，其具有优异的强度和较好的热稳定性、化学稳定性，广泛应用于医疗、汽车等领域。
CN 107756783 A公开了一种3D打印PEEK修补材料二次加工定型方法，采用控性3D打印方法制造出具有高韧性和可塑性的低结晶度PEEK原材料，通过后处理来提高材料的结晶度和强度。然而，通过熔融沉积成型的结晶PAEK的层间粘结性难以满足3D打印成型件的强度，因此需要对结晶PAEK进行改性增强层间强度。但对结晶型的PAEK进行改性的过程中，很可能会破坏其排列规整的序列结构而影响树脂性能。CN 108424605 A公开了一种PEEK-MBA-PEI共混物3D打印材料及其3D打印成型方法，通过共混无定形PEI的方式在一定程度上增强了打印件的强度。CN 108291083 A提出了用于积层制造的无定形聚芳醚酮(PAEK)及其共混物，将无定形PAEK添加到半结晶PAEK中，可增强3D打印成型件的热稳定性和尺寸稳定性，减少翘曲变形。因此，没有晶格限制、易于改性、强度高且可塑性和尺寸稳定性好的无定形聚芳醚酮(砜)的研发显得尤为重要。
发明内容
本发明的目的是为了提供一种酚酞聚芳醚酮/砜3D打印专用料及其制备方法，本发明3D打印成型件层间强度高、尺寸稳定性好。
本发明首先提供一种酚酞聚芳醚酮/砜3D打印专用料的制备方法，该方法包括：
步骤一：将无定形酚酞聚芳醚酮/砜粉料在双螺杆中熔融挤出，并在牵引装置的作用下得到丝径均一的3D打印专用丝材；所述的无定形酚酞聚芳醚酮/砜的结构如式(Ⅰ)所示：
Figure BDA0002512440120000021
式(Ⅰ)中，n>0；
所述X选自下列结构(A)或(B)中的一种：
Figure BDA0002512440120000022
步骤二：将步骤一中所述的3D打印专用丝材干燥，然后通过高温3D打印机喷嘴出丝进行熔融沉积成型，打印速度为30～50mm/s，打印层厚为0.2mm，在打印底板上得到酚酞聚芳醚酮/砜3D打印专用料。
优选的是，所述的步骤一中熔融挤出温度为320～360℃，螺杆转速为60～110rpm。
优选的是，所述的步骤一中的3D打印专用丝材的直径为1.75±0.05mm。
优选的是，所述的步骤二中的3D打印底板温度为250～270℃。
优选的是，所述的步骤二中的3D打印喷嘴温度为360～400℃。
优选的是，所述的无定形酚酞聚芳醚酮/砜粉料的制备方法，包括：将酚酞、4,4’-二卤二苯酮或4,4’-二卤二苯砜、封端剂、催化剂和带水剂在溶剂中加热反应，先进行冷凝回流，带水剂将反应过程中产生的水带出反应装置，再升温，进行缩聚反应，得到无定形酚酞聚芳醚酮/砜粉料。
优选的是，所述的4,4’-二卤二苯酮为4,4’-二氟二苯酮或4,4’-二氯二苯酮；所述的4,4’-二卤二苯砜为4,4’-二氟二苯砜或4,4’-二氯二苯砜。
优选的是，所述的封端剂为4-氟二苯甲酮、4-氯二苯甲酮、4-(对氟苯酰基)联苯、4-(对氯苯酰基)联苯、4-(对氟苯酰基)二苯醚、4-(对氯苯酰基)二苯醚中的一种。
优选的是，所述的酚酞与封端剂的摩尔比为100:(1～5)。
本发明还提供上述制备方法得到的酚酞聚芳醚酮/砜3D打印专用料。
本发明的有益效果
本发明提供一种酚酞聚芳醚酮/砜3D打印专用料及其制备方法，本发明的酚酞聚芳醚酮/砜为无定形聚合物，没有晶格的限制、易于改性，可塑性好，3D打印成型件层间强度高、尺寸稳定性好。合成过程中通过调整单体的比例和封端，能改变聚合物的分子量和粘度，从而使树脂的流动性与3D打印工艺相匹配。基于特种工程塑料的高温熔融沉积成型，通过调节打印速度和底板温度，能使打印件具有更高的强度和更好的性能。方法简单，易于操作，原料易得，成本低。
附图说明
图1为本发明实施例1制备得到的无定形酚酞聚芳醚酮的核磁谱图；
图2为本发明实施例1制备得到的无定形酚酞聚芳醚酮的红外谱图。
具体实施方式
本发明首先提供一种酚酞聚芳醚酮/砜3D打印专用料的制备方法，该方法包括：
步骤一：将无定形酚酞聚芳醚酮/砜粉料在双螺杆中熔融挤出，并在牵引装置的作用下得到丝径均一的3D打印专用丝材；所述的无定形酚酞聚芳醚酮/砜的结构如式(Ⅰ)所示：
Figure BDA0002512440120000041
式(Ⅰ)中，n>0；
所述X选自下列结构(A)或(B)中的一种：
Figure BDA0002512440120000042
步骤二：将步骤一中所述的3D打印专用丝材优选在150℃下干燥24h，然后通过高温3D打印机喷嘴出丝进行熔融沉积成型，打印速度为30～50mm/s，打印层厚为0.2mm，在打印底板上得到酚酞聚芳醚酮/砜3D打印专用料。
按照本发明，步骤一中，所述的熔融挤出温度优选为320～360℃，螺杆转速优选为60～110rpm，所述的3D打印专用丝材的直径优选为1.75±0.05mm。步骤二中，所述的3D打印底板温度优选为250～270℃，所述的3D打印喷嘴温度优选为360～400℃。
本发明的无定形酚酞聚芳醚酮/砜粉料的制备方法优选包括：将酚酞、4,4’-二卤二苯酮或4,4’-二卤二苯砜、封端剂、催化剂和带水剂在溶剂中加热反应，先进行冷凝回流，带水剂将反应过程中产生的水带出反应装置，再升温，进行缩聚反应，得到无定形酚酞聚芳醚酮/砜粉料。
按照本发明，所述的4,4’-二卤二苯酮优选为4,4’-二氟二苯酮或4,4’-二氯二苯酮，所述的4,4’-二卤二苯砜优选为4,4’-二氟二苯砜或4,4’-二氯二苯砜；所述的封端剂优选为4-氟二苯甲酮、4-氯二苯甲酮、4-(对氟苯酰基)联苯、4-(对氯苯酰基)联苯、4-(对氟苯酰基)二苯醚、4-(对氯苯酰基)二苯醚中的一种；所述的催化剂为无水碳酸钾或无水碳酸钠，所述的带水剂为甲苯或二甲苯，所述的溶剂为环丁砜或二甲基亚砜。
按照本发明，所述的酚酞、4,4’-二卤二苯酮或4,4’-二卤二苯砜、封端剂和催化剂的摩尔比优选为100:100:(1～5)：(100-150)。按照本发明，所述的冷凝回流温度优选为130～160℃，回流时间优选为2h～3h；所述的缩聚反应的温度优选为150～230℃，反应时间优选为1h～5h。
下面结合具体实施例对本发明做进一步详细的描述，这些描述只是示例性的，而并非要限制本发明的范围，本发明可以由权利要求限定和覆盖的多种不同方式实施。
实施例1
向三口烧瓶中加入酚酞(400mmol)、4,4’-二氟二苯甲酮(400mmol)、4-氟二苯甲酮(4mmol)、碳酸钾(460mmol)、环丁砜(560ml)、甲苯(80ml)，在氮气保护下，边搅拌边将上述混合物加热到150℃共沸除水，恒温2.5h，除去甲苯和水，继续加热到210℃反应2.5h，停止加热，将反应物转移到乙醇/水中沉淀，沉淀物经过滤、粉碎，并用去离子水反复煮洗5次除去无机盐和残留溶剂，在真空烘箱中150℃下干燥24h，即得到具有(Ⅱ)结构的聚合物粉料。核磁氢谱图如图1所示，红外谱图如图2所示。
Figure BDA0002512440120000051
将聚合得到的粉料在双螺杆中330℃下熔融挤出，并在牵引装置的作用下得到丝径为1.75mm、粗细均一的3D打印专用丝材。将3D打印专用丝材在150℃下干燥24h，然后通过高温3D打印机喷嘴出丝进行熔融沉积成型，喷嘴温度为380℃，打印速度为40mm/s，打印层厚为0.2mm，打印底板温度为260℃，在打印底板上得到无定形酚酞聚芳醚酮3D打印产品，经后处理完成3D打印成型。
实施例2
将实施例1制备聚合得到的粉料在双螺杆中340℃下熔融挤出，并在牵引装置的作用下得到丝径为1.76mm、粗细均一的3D打印专用丝材。将3D打印专用丝材在150℃下干燥24h，然后通过高温3D打印机喷嘴出丝进行熔融沉积成型，喷嘴温度为390℃，打印速度为40mm/s，打印层厚为0.2mm，打印底板温度为270℃，在打印底板上得到无定形酚酞聚芳醚酮3D打印产品，经后处理完成3D打印成型。
实施例3
向三口烧瓶中加入酚酞(400mmol)、4,4’-二氟二苯砜(400mmol)、4-(对氟苯酰基)联苯(4mmol)、碳酸钾(460mmol)、环丁砜(580ml)、甲苯(60ml)，在氮气保护下，边搅拌边将上述混合物加热到150℃共沸除水，恒温2.5h，除去甲苯和水，继续加热到210℃反应2.5h，停止加热，将反应物转移到乙醇/水中沉淀，沉淀物经过滤、粉碎，并用去离子水反复煮洗5次除去无机盐和残留溶剂，在真空烘箱中150℃下干燥24h，即得到具有(Ⅲ)结构的聚合物粉料。
Figure BDA0002512440120000061
将聚合得到的粉料在双螺杆中360℃下熔融挤出，并在牵引装置的作用下得到丝径为1.75mm、粗细均一的3D打印专用丝材。将3D打印专用丝材在150℃下干燥24h，然后通过高温3D打印机喷嘴出丝进行熔融沉积成型，喷嘴温度为390℃，打印速度为40mm/s，打印层厚为0.2mm，打印底板温度为260℃，在打印底板上得到无定形酚酞聚芳醚砜3D打印产品，经后处理完成3D打印成型。
实施例4
将实施例3聚合得到的粉料在双螺杆中330℃下熔融挤出，并在牵引装置的作用下得到丝径为1.75mm、粗细均一的3D打印专用丝材。将3D打印专用丝材在150℃下干燥24h，然后通过高温3D打印机喷嘴出丝进行熔融沉积成型，喷嘴温度为370℃，打印速度为40mm/s，打印层厚为0.2mm，打印底板温度为250℃，在打印底板上得到无定形酚酞聚芳醚砜3D打印产品，经后处理完成3D打印成型。

Claims (10)

1.一种酚酞聚芳醚酮/砜3D打印专用料的制备方法，其特征在于，该方法包括：
步骤一：将无定形酚酞聚芳醚酮/砜粉料在双螺杆中熔融挤出，并在牵引装置的作用下得到丝径均一的3D打印专用丝材；所述的无定形酚酞聚芳醚酮/砜的结构如式(Ⅰ)所示：
Figure FDA0002512440110000011
式(Ⅰ)中，n>0；
所述X选自下列结构(A)或(B)中的一种：
Figure FDA0002512440110000012
步骤二：将步骤一中所述的3D打印专用丝材干燥，然后通过高温3D打印机喷嘴出丝进行熔融沉积成型，打印速度为30～50mm/s，打印层厚为0.2mm，在打印底板上得到酚酞聚芳醚酮/砜3D打印专用料。
2.根据权利要求1所述的一种酚酞聚芳醚酮/砜3D打印专用料的制备方法，其特征在于，所述的步骤一中熔融挤出温度为320～360℃，螺杆转速为60～110rpm。
3.根据权利要求1所述的一种酚酞聚芳醚酮/砜3D打印专用料的制备方法，其特征在于，所述的步骤一中的3D打印专用丝材的直径为1.75±0.05mm。
4.根据权利要求1所述的一种酚酞聚芳醚酮/砜3D打印专用料的制备方法，其特征在于，所述的步骤二中的3D打印底板温度为250～270℃。
5.根据权利要求1所述的一种酚酞聚芳醚酮/砜3D打印专用料的制备方法，其特征在于，所述的步骤二中的3D打印喷嘴温度为360～400℃。
6.根据权利要求1所述的一种酚酞聚芳醚酮/砜3D打印专用料的制备方法，其特征在于，所述的无定形酚酞聚芳醚酮/砜粉料的制备方法，包括：将酚酞、4,4’-二卤二苯酮或4,4’-二卤二苯砜、封端剂、催化剂和带水剂在溶剂中加热反应，先进行冷凝回流，带水剂将反应过程中产生的水带出反应装置，再升温，进行缩聚反应，得到无定形酚酞聚芳醚酮/砜粉料。
7.根据权利要求1所述的一种酚酞聚芳醚酮/砜3D打印专用料的制备方法，其特征在于，所述的4,4’-二卤二苯酮为4,4’-二氟二苯酮或4,4’-二氯二苯酮；所述的4,4’-二卤二苯砜为4,4’-二氟二苯砜或4,4’-二氯二苯砜。
8.根据权利要求1所述的一种酚酞聚芳醚酮/砜3D打印专用料的制备方法，其特征在于，所述的封端剂为4-氟二苯甲酮、4-氯二苯甲酮、4-(对氟苯酰基)联苯、4-(对氯苯酰基)联苯、4-(对氟苯酰基)二苯醚、4-(对氯苯酰基)二苯醚中的一种。
9.根据权利要求1所述的一种酚酞聚芳醚酮/砜3D打印专用料的制备方法，其特征在于，所述的酚酞与封端剂的摩尔比为100:(1～5)。
10.根据权利要求1-9任何一项所述的制备方法得到的酚酞聚芳醚酮/砜3D打印专用料。
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