CN109056336A - 一种碳纤维用耐热型水性上浆剂及其制备方法和应用 - Google Patents
一种碳纤维用耐热型水性上浆剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种碳纤维用耐热型水性上浆剂及其制备方法和应用,所述的制备方法为:将还原氧化石墨烯‑磁性粒子添加到聚酰胺酸水性分散体中,超声分散处理,得到聚酰胺酸/还原氧化石墨烯‑磁性粒子水性上浆剂。本发明利用磁性粒子在磁场下的取向作用带动石墨烯按照一定的方向排列,有效地削弱了石墨烯的团聚效应,本发明制备得到的上浆剂耐热性能优异且具有环境友好性,适用于聚酰亚胺、聚醚砜、聚醚醚酮等耐高温工程塑料。
Description
技术领域
本发明属于碳纤维制造领域,具体涉及一种碳纤维用耐热型水性上浆剂及其制备方法和应用。
背景技术
碳纤维具有耐高温、耐腐蚀、高比强度、高比模量和热膨胀系数小等一系列优异性能,常用作复合材料的增强体。碳纤维属于脆性材料,在生产和深加工过程中较易产生毛丝,不仅污染工作环境,还会影响树脂对纤维的浸润性。毛丝的出现使复合材料界面处产生孔隙等缺陷,严重影响复合材料的力学性能。而且,毛丝的产生往往伴随着单丝的断裂,致使碳纤维强度下降。所以,为提高碳纤维强度和表面活性,需要进行上浆处理。
上浆剂一般分为三类:溶剂型、乳液型和水性。其中,溶剂型上浆剂在制备过程中使用了大量的有机溶剂,存在安全隐患和资源浪费的缺点,所以目前已经不再大批量生产。水性上浆剂采用水为溶剂,具有环境友好性,是将来上浆剂领域的一个重要研究方向。
近年来,碳纤维增强热塑性树脂基复合材料发展迅速,但现在常用的上浆剂与热塑性树脂基体相容性差且耐高温稳定性差,不适用于碳纤维增强热塑性树脂复合材料。所以,研究适用于热塑性树脂的耐热性上浆剂对提高碳纤维增强热塑性树脂基复合材料的性能具有重要的意义。CN101858038A公开了以缩水甘油醚型环氧树脂和环氧脂肪族聚烯烃为主浆料的乳液型上浆剂。该上浆剂制备工艺简单,成本低且不污染环境,但主浆料为环氧树脂,耐热性能较差,不适用于热塑性树脂基体。CN107022901A公开了一种水性聚酰胺酰亚胺/环氧树脂复合型碳纤维上浆剂及其制备方法和使用方法,上浆后碳纤维增强环氧树脂基复合材料的层间剪切强度增加了50%左右。但上浆剂中的环氧树脂在200℃左右就开始热分解,将该上浆剂涂覆的碳纤维用于工艺温度较高的树脂基体时,环氧树脂的分解将会影响复合材料的界面性能。CN107299531A公开了一种碳纤维用耐温性乳液上浆剂及其制备方法,主浆料由聚芳醚酮树脂和有机溶剂组成,制备工艺简单且性能稳定。但是,主浆料中有机溶剂占有较大的比重(70%以上),所以使用该上浆剂会对环境造成一定的污染。以上的技术均没有很好的解决现在常用的上浆剂无法用于耐高温热塑性树脂基复合材料的问题。
发明内容
为了解决现有技术中存在的上述问题,本发明提供一种碳纤维用耐热型水性上浆剂及其制备方法和应用,所述的制备方法为:将还原氧化石墨烯-磁性粒子添加到聚酰胺酸水性分散体中,超声分散处理,得到聚酰胺酸/还原氧化石墨烯-磁性粒子水性上浆剂。本发明利用磁性粒子在磁场下的取向作用带动石墨烯按照一定的方向排列,有效地削弱了石墨烯的团聚效应,本发明制备得到的上浆剂耐热性能优异且具有环境友好性,适用于聚酰亚胺、聚醚砜、聚醚醚酮等耐高温工程塑料。
进一步的,将还原氧化石墨烯-磁性粒子添加到聚酰胺酸水性分散体中,并用去离子水稀释,超声分散处理,得到聚酰胺酸/还原氧化石墨烯-磁性粒子水性碳纤维上浆剂,其中所述的还原氧化石墨烯-磁性粒子在上浆剂中的质量分数为0.01~9%;所述的聚酰胺酸水性分散体在上浆剂中的质量分数为1~9%;所述的磁性粒子为Fe3O4、Fe2O3或两者的混合物。
进一步的,所述的还原氧化石墨烯-磁性粒子的制备方法为:
(1) 将氧化石墨烯分散在去离子水中并室温下超声处理0.5~3h;
(2) 将含铁化合物分散在去离子水中,再加入到步骤(1)的溶液中得到悬浮液;
(3) 向悬浮液中滴加氢氧化钠溶液,调整悬浮液的ph值为9~13,在磁场存在的情况下控制反应温度为55~75℃,搅拌1~3h;
(4) 加入水合肼,并在80~100℃下搅拌4~8h,保证氧化石墨烯完全还原;
(5) 将得到的固体产物用乙醇洗涤三次,并在60~80℃的烘箱干燥12~36h。
更进一步的,步骤(2)中,所述的含铁化合物为FeCl3·6H2O、FeSO4·7H2O或FeCl2·4H2O中的一种或多种。
更进一步的,步骤 (3)中,氢氧化钠的浓度为0.3~0.6mol/l。
更进一步的,氧化石墨烯与含铁化合物的质量比为0.1~0.4。
更进一步的,氧化石墨烯与水合肼的质量比为0.1~1。
更进一步的,含铁化合物中Fe3+和Fe2+的摩尔比为1.5~3。
进一步的,所述聚酰胺酸水性分散体的制备方法为:
(a) 向容器中滴加一定量的有机溶剂,并向有机溶剂中加入等摩尔比的二酐单体和二胺单体;
(b) 惰性气氛下,在室温下搅拌2~7h,得到黄绿色的聚酰胺酸溶液;
(c) 将黄绿色的聚酰胺酸溶液放入烘箱中干燥以除去有机溶剂,得到固体聚酰胺酸树脂;
(d) 将固体聚酰胺酸树脂加入到有机溶剂的水溶液中,在温度为5~15℃下搅拌0.5~2h,使聚酰胺酸树脂反应完全,得到聚酰胺酸水性分散体。
更进一步的,所述的步骤(a)中,有机溶剂为N,N-二甲基甲酰胺或N,N-二甲基乙酰胺中的一种;所述的有机溶剂的体积为40~120ml;所述的二酐单体为3,3’,4,4’-二苯甲酮四羧酸二酐、联苯四甲酸二酐(BPDA)、均苯四甲酸二酐(PMDA)或二苯醚四甲酸二酐中的一种;所述的二胺单体为对苯二胺、联苯二胺或4,4’-二氨基二苯醚中的一种。
更进一步的,所述的步骤(b)中,惰性气氛为氮气或氩气;步骤(b)中,聚酰胺酸溶液的固含量为15~30%,数均分子量为1.8×106~2.6×106g/mol。
更进一步的,所述的步骤 (c)中,黄绿色溶液在真空烘箱中的干燥温度为60~100℃,干燥时间为5~10h。
更进一步的,所述的步骤 (d)中,所述的有机溶剂为三乙胺、二甲基乙醇胺或三乙醇胺中的一种;所述的有机溶剂和固体聚酰胺酸树脂的摩尔比值为1~4;所述的有机溶剂的水溶液浓度为4~20%;所述的固体聚酰胺酸树脂的粒径为0.2~1微米。
本发明还保护上述制备方法制备得到的碳纤维用耐热型水性上浆剂。
本发明还保护所述的碳纤维用耐热型水性上浆剂的应用方法,将所述的上浆剂用水稀释2~30倍,在磁场条件下,利用上浆装置对碳纤维丝束进行上浆,浸渍时间为5~60秒,随后在100~400℃下进行烘干,烘干时间为3~20min,碳纤维表面的上浆量为0.05~4%。
与现有技术相比,本发明的有益效果在于:
1. 本发明的碳纤维用耐热型水性上浆剂具有优异的耐热性能,可以满足碳纤维增强热塑性树脂基复合材料的加工温度要求,有效的解决了现在常用的上浆剂无法用于耐高温热塑性树脂基复合材料的问题。
2. 本发明的碳纤维用耐热型水性上浆剂中磁性粒子在磁场下的取向作用有效地改善了石墨烯的团聚现象,使该上浆剂的柔韧性和耐热性都得到一定程度的提高。
3. 本发明的碳纤维用耐热型水性上浆剂,具有环境友好性。
4. 本发明的碳纤维用耐热型水性上浆剂,可以提高碳纤维和树脂的浸润性,改善两者的界面性能。
附图说明
下面结合附图进一步说明:
图1是本发明实例1得到的上浆剂上浆后碳纤维和环氧上浆剂上浆后的碳纤维的热失重曲线。
具体实施方式
为了使本发明的目的、技术方案及有益效果更加清楚,本发明用以下具体实施例进行说明,但本发明绝非限于这些例子。
实施例1
步骤1:还原氧化石墨烯-磁性粒子的制备
(1) 0.2g氧化石墨烯分散在100ml去离子水中并超声处理0.5h;
(2) 0.81g FeCl3·6H2O和0.42gFeSO4•7H2O分散在100ml去离子水中,然后加入到(1)溶液中;
(3) 向悬浮液中滴加0.5mol/l的氢氧化钠溶液,调整悬浮液的ph值为9,在磁场存在的情况下调整反应温度为75℃,搅拌2h;
(4) 加入1ml水合肼,并将新的混合物在90℃下搅拌4h,保证氧化石墨烯完全还原;
(5) 将得到的固体产物用乙醇洗涤三次,并在烘箱中60℃干燥12h。
步骤2:聚酰胺酸(PAA)水性分散体的制备
(1) 在250ml三口烧瓶里加入160ml N,N-二甲基甲酰胺,将0.05mol 3,3’,4,4’-二苯甲酮四羧酸二酐和0.05mol 4,4’-二氨基二苯醚溶于上述溶剂中;
(2) 氮气气氛下,室温搅拌2h,得到黄绿色PAA溶液;
(3) 将PAA溶液放入真空烘箱,在60℃下干燥5h除去有机溶剂,得到固体PAA树脂;
(4) 将2ml三乙胺滴入40ml去离子水中,向三乙胺的水溶液添加2.5g PAA固体,在室温下搅拌30min,得到PAA水性分散体。
步骤3:复合型水性上浆剂的制备
将0.105g还原氧化石墨烯-磁性粒子添加到PAA水性分散体中,并用去离子水稀释至210ml;超声分散处理,得到聚酰胺酸的质量分数为1%、还原氧化石墨烯-磁性粒子的浓度为0.5mg/ml的聚酰亚胺/还原氧化石墨烯-磁性粒子水性碳纤维上浆剂。
图1为本发明实施例1得到的上浆剂上浆后碳纤维和环氧上浆剂上浆后的碳纤维的热失重曲线,从图1曲线可以看出,本发明上浆碳纤维的耐热性较好。经检测,将碳纤维丝束置于上浆装置中,使碳纤维在上浆剂中浸渍30s,然后在200℃的干燥炉中干燥10分钟,得到碳纤维的上浆量为0.4%。该水性上浆剂上浆后的碳纤维增强聚醚砜树脂基复合材料的层间剪切强度为32.1MPa,与环氧上浆剂上浆后碳纤维增强聚醚砜复合材料的层间剪切强度26.8MPa比,增加了19.7%。
实施例2
一种碳纤维用耐热型水性上浆剂及其制备方法,同实施例1,不同之处在于,步骤2(4)中所用的有机溶剂为二甲基乙醇胺。
经检测,将碳纤维丝束置于上浆装置中,使碳纤维在上浆剂中浸渍30s,然后在200℃的干燥炉中干燥10分钟,得到碳纤维的上浆量为0.5%。该水性上浆剂上浆的碳纤维增强聚醚砜树脂基复合材料的层间剪切强度为32.8MPa,与环氧上浆剂上浆后碳纤维增强聚醚砜复合材料的层间剪切强度26.8MPa比,增加了22.4%。
实施例3
一种碳纤维用耐热型水性上浆剂及其制备方法,同实施例1,不同之处在于,称取0.237g还原氧化石墨烯-磁性粒子固体添加到PAA水性分散体中,并用去离子水稀释至158ml。上浆剂中聚酰胺酸的质量分数为1.5%,还原氧化石墨烯-磁性粒子的浓度为1.5mg/ml。
经检测,将碳纤维丝束置于上浆装置中,使碳纤维在上浆剂中浸渍30s,然后在200℃的干燥炉中干燥10分钟,得到碳纤维的上浆量为1%。该水性上浆剂上浆的碳纤维增强聚醚砜树脂基复合材料的层间剪切强度为35.2MPa,与环氧上浆剂上浆后碳纤维增强聚醚砜复合材料的层间剪切强度26.8MPa比,增加了31.3%。
实施例4
一种碳纤维用耐热型水性上浆剂及其制备方法,同实施例1,不同之处在于,称取0.234g还原氧化石墨烯-磁性粒子固体添加到PAA水性分散体中,并用去离子水稀释至117ml。上浆剂中聚酰胺酸的质量分数为2%,还原氧化石墨烯-磁性粒子的浓度为2mg/ml。
经检测,将碳纤维丝束置于上浆装置中,使碳纤维在上浆剂中浸渍30s,然后在200℃的干燥炉中干燥10分钟,得到碳纤维的上浆量为1.6%。该水性上浆剂上浆的碳纤维增强聚醚砜树脂基复合材料的层间剪切强度为34.1MPa,与环氧上浆剂上浆后碳纤维增强聚醚砜复合材料的层间剪切强度26.8MPa比,增加了27.2%。
虽然,上文中已经用一般性说明、具体实施方式及试验,对本发明作了详尽的描述,但在本发明基础上,可以对之作一些修改或改进,这对本领域技术人员而言是显而易见的。因此,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本发明要求保护的范围。
Claims (9)
1.一种碳纤维用耐热型水性上浆剂的制备方法,其特征在于,所述的制备方法为:将还原氧化石墨烯-磁性粒子添加到聚酰胺酸水性分散体中,超声分散处理,得到聚酰胺酸/还原氧化石墨烯-磁性粒子水性上浆剂。
2.根据权利要求1所述的制备方法,其特征在于,将还原氧化石墨烯-磁性粒子添加到聚酰胺酸水性分散体中,并用去离子水稀释,超声分散处理,得到聚酰胺酸/还原氧化石墨烯-磁性粒子水性碳纤维上浆剂,其中所述的还原氧化石墨烯-磁性粒子在上浆剂中的质量分数为0.01~9%;所述的聚酰胺酸水性分散体在上浆剂中的质量分数为1~9%;所述的磁性粒子为Fe3O4、Fe2O3或两者的混合物。
3.根据权利要求2所述的制备方法,其特征在于,所述的还原氧化石墨烯-磁性粒子的制备方法为:
(1) 将氧化石墨烯分散在去离子水中并室温下超声处理0.5~3h;
(2) 将含铁化合物分散在去离子水中,再加入到步骤(1)的溶液中得到悬浮液;
(3) 向悬浮液中滴加氢氧化钠溶液,调整悬浮液的ph值为11~13,在磁场存在的情况下控制反应温度为55~75℃,搅拌1~3h;
(4) 加入水合肼,并在80~100℃下搅拌4~8h,保证氧化石墨烯完全还原;
(5) 将得到的固体产物用乙醇洗涤三次,并在60~80℃的烘箱干燥12~36h。
4.根据权利要求3所述的制备方法,其特征在于,步骤(2)中,所述的含铁化合物为FeCl3·6H2O、FeSO4·7H2O或FeCl2·4H2O中的一种或多种;步骤 (3)中,氢氧化钠的浓度为0.3~0.6mol/l。
5.根据权利要求4所述的制备方法,其特征在于,氧化石墨烯与含铁化合物的质量比为0.1~0.5;氧化石墨烯与水合肼的质量比为0.1~1;含铁化合物中,Fe3+和Fe2+的摩尔比为1.5~3。
6.根据权利要求2所述的制备方法,其特征在于,所述聚酰胺酸水性分散体的制备方法为:
(a) 向容器中滴加一定量的有机溶剂,并向有机溶剂中加入等摩尔比的二酐单体和二胺单体;
(b) 惰性气氛下,在室温下搅拌2~7h,得到黄绿色的聚酰胺酸溶液;
(c) 将黄绿色的聚酰胺酸溶液放入烘箱中干燥以除去有机溶剂,得到固体聚酰胺酸树脂;
(d) 将固体聚酰胺酸树脂加入到有机溶剂的水溶液中,在温度为5~15℃下搅拌0.5~2h,使聚酰胺酸树脂反应完全,得到聚酰胺酸水性分散体。
7.根据权利要求6所述的制备方法,其特征在于,所述的步骤(a)中,有机溶剂为N,N-二甲基甲酰胺或N,N-二甲基乙酰胺中的一种;所述的有机溶剂的体积为40~120ml;所述的二酐单体为3,3’,4,4’-二苯甲酮四羧酸二酐、联苯四甲酸二酐(BPDA)、均苯四甲酸二酐(PMDA)或二苯醚四甲酸二酐中的一种;所述的二胺单体为对苯二胺、联苯二胺或4,4’-二氨基二苯醚中的一种;所述的步骤(b)中,惰性气氛为氮气或氩气;步骤(b)中,聚酰胺酸溶液的固含量为15~30%,数均分子量为1.8×106~2.6×106g/mol;所述的步骤 (c)中,黄绿色溶液在真空烘箱中的干燥温度为60~100℃,干燥时间为5~10h;所述的步骤 (d)中,所述的有机溶剂为三乙胺、二甲基乙醇胺或三乙醇胺中的一种;所述的有机溶剂和固体聚酰胺酸树脂的摩尔比值为1~4;所述的有机溶剂的水溶液浓度为4~20%;所述的固体聚酰胺酸树脂的粒径为0.2~1微米。
8.权利要求1-7中任一项所述的制备方法制备得到的碳纤维用耐热型水性上浆剂。
9.权利要求8所述的碳纤维用耐热型水性上浆剂的应用方法,其特征在于,将所述的上浆剂用水稀释2~30倍,在磁场条件下,利用上浆装置对碳纤维丝束进行上浆,浸渍时间为5~60秒,随后在100~400℃下进行烘干,烘干时间为3~20min,碳纤维表面的上浆量为0.05~4%。
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