CN106046631B - 一种静电纺丝法填料规则排列的多层氟醚橡胶制备方法 - Google Patents
一种静电纺丝法填料规则排列的多层氟醚橡胶制备方法 Download PDFInfo
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Abstract
本发明涉及一种静电纺丝法填料规则排列的多层氟醚橡胶制备方法,将炭黑、碳纳米管等填料混入氟醚橡胶,配制成溶液后,将混合溶液,通过静电纺丝的方法制备高度定向排列的填料/氟醚橡胶纤维,将该纤维引入到氟醚橡胶薄膜表面,将含有定向排列纤维的橡胶薄膜层层复合后加压硫化得到具有多层级结构的氟醚橡胶材料,该发明方法将填料在氟醚橡胶中高度定向排列,突破了传统各向同性橡胶材料的制备方法,制备得到的氟醚橡胶材料为各向异性的橡胶,充分发挥各个方向上的优异性能,显著提高橡胶密封性能,具有良好的密封应用前景。
Description
技术领域
本发明涉及氟醚橡胶领域,特别涉及一种静电纺丝法填料规则排列的多层氟醚橡胶制备方法。
背景技术
氟醚橡胶作为高性能的氟橡胶,保持了普通氟橡胶良好的耐化学性和耐高温性,且兼顾良好的低温弹性。随着我国经济发展,特别是航空航天、高端汽车行业的推动和化工仪器仪表等工业产品可靠性的要求增加,氟醚橡胶逐渐成为不可替代的密封材料。然而,制备高性能的氟醚橡胶是困难的:氟醚橡胶的分子组成阻挡了它与大多数聚合物的相容性,因此,传统的橡胶并用制备方法不能有效提高功能性氟醚橡胶的长期稳定性;另一方面,它的耐高温特性也限制了特定配合剂(如增塑剂)使用。因此,如何提高氟醚橡胶性能成为一个迫切解决的问题。
目前提高氟醚橡胶性能的方法主要延续了上述传统氟橡胶的低温改性手段,因此,无法综合提高氟醚橡胶的性能。而进一步采用分子设计技术提高氟醚橡胶的性能也是困难的,因为缺少了合适的化学组成。因此,必须寻找新的方法去制备高性能氟醚橡胶材料。
发明内容
本发明的目的在于克服现有技术的上述不足,提供一种静电纺丝法填料规则排列的多层氟醚橡胶制备方法,该方法制备得到的氟醚橡胶材料为各向异性的橡胶,充分发挥各个方向上的优异性能,显著提高橡胶密封性能。
本发明的上述目的主要是通过如下技术方案予以实现的:
一种静电纺丝法填料规则排列的多层氟醚橡胶制备方法,包括如下步骤:
步骤(1):将填料与氟醚橡胶进行混炼,并将混炼好含有填料的氟醚橡胶配制成溶液,作为纺丝液备用;
步骤(2)、将氟醚橡胶与硫化剂、助硫化剂进行混炼,混炼好后采用溶液流延法或压延法制备橡胶薄膜备用;
步骤(3)、将步骤(1)制备的纺丝液加入静电纺丝仪中,将步骤(2)制备的橡胶薄膜包裹在静电纺丝仪滚筒表面,进行静电纺丝,静电纺丝仪滚筒高速旋转进行纺丝缠绕收集,形成表面含有纺丝的橡胶薄膜,其中静电纺丝仪的高压喷丝端的移动方向与滚筒转动方向垂直;
步骤(4)、将表面含有纺丝的橡胶薄膜取下,重复步骤(3),制备多个表面含有纺丝的橡胶薄膜;
步骤(5)、将所述多个表面含有纺丝的橡胶薄膜层层叠放,叠放的方向始终保持一致,将叠放好的橡胶薄膜放入模具中,进行加压硫化和二段硫化,得到橡胶产品。
在上述静电纺丝法填料规则排列的多层氟醚橡胶制备方法中,步骤(1)中的填料为纳米级的各种碳黑、白炭黑、碳纳米管、石墨烯或蒙脱土中的一种或组合。
在上述静电纺丝法填料规则排列的多层氟醚橡胶制备方法中,步骤(1)中填料质量占填料与氟醚橡胶总质量的百分比含量为20%以下。
在上述静电纺丝法填料规则排列的多层氟醚橡胶制备方法中,步骤(1)中溶剂为四氢呋喃THF或N,N-二甲基甲酰胺DMF中的一种或组合,所述配制的溶液的质量浓度为5~10%。
在上述静电纺丝法填料规则排列的多层氟醚橡胶制备方法中,步骤(2)中氟醚橡胶与硫化剂、助硫化剂的质量比为100:1~5:1~4。
在上述静电纺丝法填料规则排列的多层氟醚橡胶制备方法中,硫化剂为2,5-二甲基-2,5-二(叔丁基过氧基)己烷或过氧化二异丙苯中的一种或组合;所述助硫化剂为氰尿酸三烯丙酯、异氰脲酸三烯丙酯、二乙烯基苯、邻苯二甲酸二烯丙酯、三羟甲基丙烷三甲丙烯酸酯或二甲基丙烯酸乙二醇中的一种或组合。
在上述静电纺丝法填料规则排列的多层氟醚橡胶制备方法中,步骤(1)、(2)中的氟醚橡胶为氟含量高于60%以上,玻璃化转变温度为-30℃以下的非全氟类氟醚橡胶。
在上述静电纺丝法填料规则排列的多层氟醚橡胶制备方法中,步骤(2)中制备的橡胶薄膜的厚度为0.02~0.1mm。
在上述静电纺丝法填料规则排列的多层氟醚橡胶制备方法中,步骤(3)中静电纺丝的工艺参数为:滚筒直径为5~10cm,滚筒转速为300~600r/min;纺丝电压为10~20KV,与滚筒顶端的接收距离为80~100mm,纺丝速率为0.1~3mL/h,湿度控制在20%以下;高压喷丝端往返移动,速度在0.01~15cm/s,移动距离为1~20cm。
在上述静电纺丝法填料规则排列的多层氟醚橡胶制备方法中,步骤(5)中加压硫化的硫化压力为0.1~3MPa,硫化温度为160~180℃,硫化时间为10~30min;二段硫化的硫化温度为200~230℃,硫化时间为5~15h。
本发明与现有技术相比具有如下有益效果:
(1)、本发明将炭黑、碳纳米管等填料混入氟醚橡胶,配制成溶液后,将混合溶液,通过静电纺丝的方法制备高度定向排列的填料/氟醚橡胶纤维,将该纤维引入到氟醚橡胶薄膜表面,将含有定向排列纤维的橡胶薄膜层层复合后加压硫化得到具有多层级结构的氟醚橡胶材料,本发明设计制备的氟醚橡胶密封材料为各向异性的橡胶,发挥各个方向上的优异性能,显著提高橡胶的密封性能;
(2)、本发明采用静电纺丝的工艺方法,将填料在氟醚橡胶内部形成高度取向的排列结构,并采用多“层”复合硫化方法,将填料的排列结构稳定在橡胶内部,从而提高氟醚橡胶在密封产品中的应用性能;
(3)、本发明突破了传统各向同性橡胶材料的制备方法,制备得到的氟醚橡胶沿着周向方向有良好的拉伸强度、拉断伸长率和耐介质性能,满足不同密封结构的密封要求,具有良好的密封应用前景。
(4)、本发明所用设备常规,操作工艺简单,产物性能优良,具有良好的应用前景。
附图说明
图1为本发明静电纺丝法填料规则排列的多层氟醚橡胶制备方法的示意图。
具体实施方式
下面结合附图和具体实施例对本发明作进一步详细的描述:
如图1所示为本发明静电纺丝法填料规则排列的多层氟醚橡胶制备方法的示意图,本发明静电纺丝法填料规则排列的多层氟醚橡胶制备方法包括如下步骤:
步骤(1):将填料与氟醚橡胶混炼,并将混炼好的含有填料的氟醚橡胶配制成溶液,作为纺丝液备用。配制溶液的溶剂为四氢呋喃THF或N,N-二甲基甲酰胺DMF中的一种或组合,配制的溶液的质量浓度为5~10%。
填料为纳米级的各种碳黑、白炭黑、碳纳米管、石墨烯或蒙脱土中的一种或组合。填料质量占填料与氟醚橡胶总质量的百分比含量为20%以下。
氟醚橡胶为氟含量高于60%以上,玻璃化转变温度为-30℃以下的非全氟类氟醚橡胶。
步骤(2)、将氟醚橡胶与硫化剂、助硫化剂进行混炼,氟醚橡胶与硫化剂、助硫化剂的质量比为100:1~5:1~4。混炼好后采用溶液流延法或压延法制备橡胶薄膜备用,制备的橡胶薄膜的厚度为0.02~0.1mm。
其中硫化剂为2,5-二甲基-2,5-二(叔丁基过氧基)己烷或过氧化二异丙苯中的一种或组合;助硫化剂为氰脲酸三烯丙酯、异氰脲酸三烯丙酯、二乙烯基苯、邻苯二甲酸二烯丙酯、三羟甲基丙烷三甲丙烯酸酯或二甲基丙烯酸乙二醇中的一种或组合。氟醚橡胶为氟含量高于60%以上,玻璃化转变温度为-30℃以下的非全氟类氟醚橡胶。
步骤(3)、将步骤(1)制备的纺丝液加入静电纺丝仪中,将步骤(2)制备的橡胶薄膜包裹在静电纺丝仪滚筒表面。在一定电压下进行静电纺丝,静电纺丝仪滚筒高速旋转进行纺丝缠绕收集,形成表面含有纺丝的橡胶薄膜,其中静电纺丝仪的高压喷丝端的移动方向与滚筒转动方向垂直。
静电纺丝的工艺参数为:滚筒直径为5~10cm,滚筒转速为300~600r/min;纺丝电压为10~20KV,与滚筒顶端的接收距离为80~100mm,纺丝速率为0.1~3mL/h,湿度控制在20%以下;高压喷丝端往返移动,速度在0.01~15cm/s,移动距离为1~20cm。
步骤(4)、将表面含有纺丝的橡胶薄膜取下,重复步骤(3),制备多个表面含有纺丝的橡胶薄膜。
步骤(5)、将所述多个表面含有纺丝的橡胶薄膜层层叠放,叠放的方向始终保持一致,即按照薄膜-纺丝-薄膜-纺丝…的方式叠放,相邻两个橡胶薄膜上的纺丝不接触,纺丝在薄膜上的排布保持一致。将叠放好的橡胶薄膜放入模具中,进行加压硫化和二段硫化,得到橡胶产品。模具形状根据橡胶产品的形状设计。
加压硫化的硫化压力为0.1~3MPa,硫化温度为160~180℃,硫化时间为10~30min;二段硫化不加压,在烘箱内200~230℃下硫化5~15h。
实施例1
1.称取炭黑N330 10g与氟醚橡胶100g进行混炼。将混炼好的橡胶放入为四氢呋喃THF溶剂中,配制6wt%(质量浓度)含量的溶液,作为纺丝液。
2.按配方(质量份):氟醚橡胶100份,2,5-二甲基-2,5-二(叔丁基过氧基)己烷4份,异氰脲酸三烯丙酯2份进行混炼。炼制好的氟醚橡胶配成20wt%(质量浓度)的DMF溶液,采用流延法制备厚度为0.05mm的橡胶薄膜。随后将其包裹固定在静电纺丝仪的滚筒表面。
3.称取4mL的纺丝液进行静电纺丝:室温下,湿度控制为20%以下,将纺丝电压设置为15KV,推进泵的推进速度为0.2mL/h,纺丝用滚筒进行接收。滚筒转速为500r/min,喷丝端与滚筒上端接收距离为10cm。高压喷丝端往返移动,移动距离为5cm,移动速度为0.02cm/s。
4.将富集纺丝的橡胶薄膜取下,重复步骤(3),制备多个相同的富集纺丝的橡胶薄膜,将橡胶薄膜裁成面积为30cm×15cm的橡胶胶块。将裁好的橡胶胶块按照相同方向进行叠加,叠加层数为30层。将叠好的橡胶胶块放入模具中进行硫化。一段硫化压力为0.5MPa,硫化温度为170℃,时间为20min。二段硫化条件为在230℃的烘箱内放置15h。
实施例2
1.称取石墨烯1g与氟醚橡胶100g进行混炼。将混炼好的橡胶放入四氢呋喃THF溶剂中,配制8wt%(质量浓度)含量的溶液,作为纺丝液。
2.橡胶薄膜的制备方法同实施例1。
3.称取1.5mL的纺丝液进行静电纺丝:室温下,湿度控制为20%以下,将纺丝电压设置为10KV,推进泵的推进速度为0.5mL/h,纺丝用滚筒进行接收转速为300r/min,接收距离为8cm。高压喷丝端往返移动,移动距离为5cm,速度为1cm/s。
4.将富集纺丝的橡胶薄膜,重复步骤(3),制备多个相同的富集纺丝的橡胶薄膜,将橡胶薄膜裁成面积为25cm×30cm的橡胶胶块。将裁好的橡胶胶块按照相同方向进行叠加,叠加层数为20层。将叠好的橡胶胶块放入模具中进行硫化。一段硫化压力为0.8MPa,硫化温度为180℃,时间为10min。二段硫化条件为在220℃的烘箱内放置5h。
实施例3
1.称取多壁碳纳米管(长径比为20,直径越为10nm)3g与氟醚橡胶100g进行混炼。将混炼好的橡胶放入THF溶剂中,配制5wt%(质量浓度)含量的溶液,作为纺丝液。
2.按配方(质量份):氟醚橡胶100份,2,5-二甲基-2,5-二(叔丁基过氧基)己烷4份,异氰脲酸三烯丙酯4份进行混炼。炼制好的氟醚橡胶采用压延法制备厚度为0.08mm的橡胶薄膜。随后将其包裹固定在静电纺丝仪的滚筒表面。
3.称取5mL的纺丝液进行静电纺丝:室温下,湿度控制为20%以下,将纺丝电压设置为10KV,推进泵的推进速度为0.9mL/h,纺丝用滚筒进行接收转速为400r/min,接收距离为9cm。高压喷丝端往返移动,移动距离为10cm,速度为5cm/s。
4.将富集纺丝的橡胶薄膜,重复步骤(3),制备多个相同的富集纺丝的橡胶薄膜,将橡胶薄膜裁成面积为20cm×20cm的橡胶胶块。将裁好的橡胶胶块按照相同方向进行叠加,叠加层数为50层。将叠好的橡胶胶块放入模具中进行硫化。一段硫化压力为2.5MPa,硫化温度为175℃,时间为15min。二段硫化条件为在200℃的烘箱内放置10h。
实施例4
1.称取气相法白碳黑15g与氟醚橡胶100g进行混炼。将混炼好的橡胶放入THF溶剂中,配制5wt%(质量浓度)含量的溶液,作为纺丝液。
2.按配方(质量份):氟醚橡胶100份,过氧化二异丙苯4份,异氰脲酸三烯丙酯1.5份进行混炼。炼制好的氟醚橡胶采用压延法制备厚度为0.09mm的橡胶薄膜。随后将其包裹固定在静电纺丝仪的滚筒表面。
3.称取3mL的纺丝液进行静电纺丝:室温下,湿度控制为20%以下,将纺丝电压设置为20KV,推进泵的推进速度为2mL/h,纺丝用滚筒进行接收,滚筒转速为450r/min,接收距离为9cm。高压喷丝端往返移动,移动距离为18cm,速度为0.2cm/s。
4.将富集纺丝的橡胶薄膜,重复步骤(3),制备多个相同的富集纺丝的橡胶薄膜,将橡胶薄膜裁成面积为20cm×20cm的橡胶胶块。将裁好的橡胶胶块按照相同方向进行叠加,叠加层数为35层。将叠好的橡胶胶块放入模具中进行硫化。一段硫化压力为0.3MPa,硫化温度为177℃,时间为20min。二段硫化条件为在230℃的烘箱内放置15h。
实施例5
1.称取蒙脱土3g与氟醚橡胶100g进行混炼。将混炼好的橡胶放入DMF溶剂中,配制8wt%(质量浓度)含量的溶液,作为纺丝液。
2.按配方(质量份):氟醚橡胶100份,过氧化二异丙苯5份,邻苯二甲酸二烯丙酯1.5份进行混炼。炼制好的氟醚橡胶采用压延法制备厚度为0.1mm的橡胶薄膜。随后将其包裹固定在静电纺丝仪的滚筒表面。
3.称取2mL的纺丝液进行静电纺丝:室温下,湿度控制为20%以下,将纺丝电压设置为10KV,推进泵的推进速度为1mL/h,纺丝用滚筒进行接收,滚筒转速为600r/min,接收距离为10cm。高压喷丝端往返移动,移动距离为10cm,速度为5cm/s。
4.将富集纺丝的橡胶薄膜,重复步骤(3),制备多个相同的富集纺丝的橡胶薄膜,将橡胶薄膜裁成面积为15cm×15cm的橡胶胶块。将裁好的橡胶胶块按照相同方向进行叠加,叠加层数为50层。将叠好的橡胶胶块放入模具中进行硫化。一段硫化压力为2.5MPa,硫化温度为175℃,时间为15min。二段硫化条件为在210℃的烘箱内放置10h。
如下表1给出了实施例1-5的力学性能。由表可知,实施例1-5显示了明显的力学各向异性性能。
表1实施例1-5的力学性能
*注:方向主要根据橡胶薄膜叠合过程确定的。平行方向是指成型过程中平行与橡胶薄膜水平方向;垂直方向指垂直橡胶薄膜方向。拉伸强度和拉断伸长率按照GB528,恒定压缩永久变形按照GB7759,测试试样由实施例中的样品裁切获得。
以上所述,仅为本发明最佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到的变化或替换,都应涵盖在本发明的保护范围之内。
本发明说明书中未作详细描述的内容属于本领域专业技术人员的公知技术。
Claims (10)
1.一种静电纺丝法填料规则排列的多层氟醚橡胶制备方法,其特征在于:包括如下步骤:
步骤(1):将填料与氟醚橡胶进行混炼,并将混炼好含有填料的氟醚橡胶配制成溶液,作为纺丝液备用;
步骤(2)、将氟醚橡胶与硫化剂、助硫化剂进行混炼,混炼好后采用溶液流延法或压延法制备橡胶薄膜备用;
步骤(3)、将步骤(1)制备的纺丝液加入静电纺丝仪中,将步骤(2)制备的橡胶薄膜包裹在静电纺丝仪滚筒表面,进行静电纺丝,静电纺丝仪滚筒高速旋转进行纺丝缠绕收集,形成表面含有纺丝的橡胶薄膜,其中静电纺丝仪的高压喷丝端的移动方向与滚筒转动方向垂直;
步骤(4)、将表面含有纺丝的橡胶薄膜取下,重复步骤(3),制备多个表面含有纺丝的橡胶薄膜;
步骤(5)、将所述多个表面含有纺丝的橡胶薄膜层层叠放,叠放的方向始终保持一致,将叠放好的橡胶薄膜放入模具中,进行加压硫化和二段硫化,得到橡胶产品。
2.根据权利要求1所述的一种静电纺丝法填料规则排列的多层氟醚橡胶制备方法,其特征在于:所述步骤(1)中的填料为纳米级的各种碳黑、白炭黑、碳纳米管、石墨烯或蒙脱土中的一种或组合。
3.根据权利要求1或2所述的一种静电纺丝法填料规则排列的多层氟醚橡胶制备方法,其特征在于:所述步骤(1)中填料质量占填料与氟醚橡胶总质量的百分比含量为20%以下。
4.根据权利要求1所述的一种静电纺丝法填料规则排列的多层氟醚橡胶制备方法,其特征在于:所述步骤(1)中溶剂为四氢呋喃THF或N,N-二甲基甲酰胺DMF中的一种或组合,所述配制的溶液的质量浓度为5~10%。
5.根据权利要求1所述的一种静电纺丝法填料规则排列的多层氟醚橡胶制备方法,其特征在于:所述步骤(2)中氟醚橡胶与硫化剂、助硫化剂的质量比为100:1~5:1~4。
6.根据权利要求1或5所述的一种静电纺丝法填料规则排列的多层氟醚橡胶制备方法,其特征在于:所述硫化剂为2,5-二甲基-2,5-二(叔丁基过氧基)己烷或过氧化二异丙苯中的一种或组合;所述助硫化剂为氰尿酸三烯丙酯、异氰脲酸三烯丙酯、二乙烯基苯、邻苯二甲酸二烯丙酯、三羟甲基丙烷三甲丙烯酸酯或二甲基丙烯酸乙二醇酯中的一种或组合。
7.根据权利要求1所述的一种静电纺丝法填料规则排列的多层氟醚橡胶制备方法,其特征在于:所述步骤(1)、(2)中的氟醚橡胶为氟含量高于60%以上,玻璃化转变温度为-30℃以下的非全氟类氟醚橡胶。
8.根据权利要求1所述的一种静电纺丝法填料规则排列的多层氟醚橡胶制备方法,其特征在于:所述步骤(2)中制备的橡胶薄膜的厚度为0.02~0.1mm。
9.根据权利要求1所述的一种静电纺丝法填料规则排列的多层氟醚橡胶制备方法,其特征在于:所述步骤(3)中静电纺丝的工艺参数为:滚筒直径为5~10cm,滚筒转速为300~600r/min;纺丝电压为10~20KV,与滚筒顶端的接收距离为80~100mm,纺丝速率为0.1~3mL/h,湿度控制在20%以下;高压喷丝端往返移动,速度在0.01~15cm/s,移动距离为1~20cm。
10.根据权利要求1所述的一种静电纺丝法填料规则排列的多层氟醚橡胶制备方法,其特征在于:所述步骤(5)中加压硫化的硫化压力为0.1~3MPa,硫化温度为160~180℃,硫化时间为10~30min;二段硫化的硫化温度为200~230℃,硫化时间为5~15h。
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