CN109183416B - 一种水性碳纤维上浆剂及其制备方法和应用 - Google Patents
一种水性碳纤维上浆剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及碳纤维上浆剂领域，特别涉及一种水性碳纤维上浆剂，按重量份计算，包含丙烯酸类聚合物2.5～10份；含呋喃基的环氧化合物1～5份；表面活性剂1～10份；水100份；抗氧化剂0.2～2份；流平剂0.2～2份；防冻剂0.2～2份；还含有金属氧化物粉末1～5份。按照以下步骤制备：S1：将含呋喃基的环氧化合物与表面活性剂在反应釜中混合均质；S2：将均质混合物冷却后加入水，高速剪切分散乳化；S3：加入丙烯酸类聚合物，混合均匀得到水性碳纤维上浆剂。本发明水性碳纤维上浆剂能有效减少有机溶剂对环境的污染，提高碳纤维和上浆剂的耐高温、耐腐蚀、耐溶剂性，经上浆计上浆处理后的碳纤维仍能保持良好的导热性能。
Description
技术领域
本发明涉及碳纤维上浆剂领域，特别涉及一种水性碳纤维上浆剂。
背景技术
碳纤维是含碳质量分数在90％以上的无机纤维材料，具有高强度、高比模量、耐高温腐蚀、导电导热性能好等优点，广泛运用于航空航天、交通运输等各行各业。但是，碳纤维是脆性材料，在加工过程中容易起毛和断裂，导致碳纤维产品力学性能的下降。因此，为了解决这一问题，在碳纤维的生产工艺中都要对碳纤维进行表面上浆处理，通过上浆剂浸润碳纤维而在它表面包裹一层有机薄膜材料，这样可以提高碳纤维的集束性和耐磨性，减少起毛和断裂的情况发生，同时上浆后也会提高树脂对碳纤维的浸润性，增强界面粘附力，提高碳纤维复合材料的力学性能，特别是层间剪切强度。
现阶段，碳纤维的上浆剂都是有机物溶液。并且这些上浆剂必须通过在上浆助剂如表面活性剂等材料提高上浆效果。它们都需要溶解分散在易挥发的有机溶剂中，通过碳纤维浸泡在这些溶液中，再经过高温除去有机溶剂才能完成上浆。但是有机溶剂的挥发去除会造成空气中挥发性有机物的污染。
为此，人们想到运用水溶性高分子溶于水形成水溶性上浆剂，来解决有机溶剂对环境的污染。如中国专利CN102691211A提出了一种由水溶性魔芋低聚糖水溶胶和氧化淀粉水溶胶组成的水溶性上浆剂，溶剂为水，可以消除挥发性有机污染。但是，水溶性上浆剂在空气中易吸水，降低碳纤维储存时间，并影响碳纤维材料的力学性能。中国专利CN105332285A公布了一种水性上浆剂，是由环氧树脂、环氧树脂改性剂、水和助剂组成，通过改性剂改性环氧树脂，提高环氧树脂的水溶性。改性环氧树脂在水中的溶解度不高，并且在储存时间达到一定时间就会团聚甚至沉淀，影响储存时间和上浆效果。
发明内容
为解决上述问题，本发明提供了一种水性碳纤维上浆剂，包含按重量比计的以下组份：
丙烯酸类聚合物2.5～10重量份；
含呋喃基的环氧化合物1～5重量份；
表面活性剂1～10重量份；
水100重量份。
其中，丙烯酸类聚合物是由丙烯酸及其衍生物聚合得到的高分子化合物或其混合物，作为上浆剂主要成分，具有良好的水溶性，制成水溶性上浆剂，消除有机溶剂对环境的污染。
优选的，丙烯酸类聚合物为呋喃改性丙烯酸聚合物，由呋喃基取代的丙烯酸类单体均聚或与其他丙烯酸单体共聚得到的共聚物或混合物组成，呋喃基可以增强与碳纤维的粘附力以及高导热、耐高温、耐腐蚀性和耐溶剂性等优良性能，且分子中呋喃基的含量越多，性能越好。当丙烯酸类聚合物小于2.5重量份，碳纤维上上浆剂的量不够，对碳纤维的保护和性能改进达不到要求；当丙烯酸类聚合物大于10重量份，溶液粘度过大，有机物无法分散均匀，影响上浆效果。优选为4～8重量份。
含呋喃基的环氧化合物是指含有呋喃基和环氧基团的化合物。其中，呋喃基可以增强与碳纤维的粘附力以及高导热、耐高温、耐腐蚀性和耐溶剂性等优良性能。环氧基团可以在一定温度下与丙烯酸类聚合物反应而交联固化，提高碳纤维的力学强度。含呋喃基的环氧化合物含量根据丙烯酸丙烯酸类聚合物聚合物的量决定，小于1重量份，丙烯酸聚合物交联固化不完全，力学性能不够；含量大于5重量份，丙烯酸聚合物交联已经固化完全而不会增加上浆剂的力学性能，造成原料的浪费并影响体系的稳定性；优选的，含呋喃基的环氧化合物的含量为2～4重量份。
表面活性剂是能明显改变体系中界面状态的物质，能溶于水并降低水的表面能，提高有机物在水中的溶解度。一般具有亲水基团和亲油基团，可分为离子型表面活性剂、非离子型表面活性剂、两性表面活性剂、复配型表面活性剂等，具体如羧酸或羧酸盐、氨基或铵盐、酰胺基等。可以提高丙烯酸等有机物在水中的溶解性并使其分散均匀。其含量根据丙烯酸类聚合物等其他有机物的量决定，含量太少，体系不稳定，分散不均匀，均一性不够；含量太多，并不会提高性能，浪费原料。优选为3～8重量份。
进一步的，按水100重量份计，所述的水性碳纤维上浆剂中还含有0.2～2重量份的抗氧化剂、0.2～2重量份的流平剂、0.2～2重量份的防冻剂，保证上浆剂体系更加稳定，不团聚、不变质，保存时间更加长。优选的，所述的抗氧化剂为2,6-二叔丁基对甲酚，所述的流平剂为聚醚改性聚硅氧烷BNKLK380，所述的防冻剂为乙二醇丁醚。优选的，流平剂、抗氧化剂和防冻剂含量分别优选0.5～1.5重量份。
进一步的，所述的含呋喃基的环氧化合物包括如式1所示结构的环氧化合物：
式1中，R为C1～C12的烷基或为如式2所示结构：
式2中，n＝1～20，R1为H、甲基或乙基。
优选的，含呋喃基的环氧化合物是式2中R1为H的式1所示环氧化合物；更优选的，含呋喃基的环氧化合物是式2中，R1为H，n＝5～10的式1所示环氧化合物。
进一步的，按水含量为100重量份计，还含有1～5重量份的直径小于100nm的金属氧化物粉末。金属氧化物可以提高碳纤维上浆剂的导热性，优选氧化镁、氧化钙、氧化铝、氧化锌、氧化铋、氧化铜中的一种或多种。含量小于1重量份，导热性的提高不足，含量大于5重量份，降低碳纤维的韧性。并且金属氧化物粉末直径为数均直径，当直径大于100nm，不利于提高导热性。优选的，金属氧化物粉末的直径小于80nm，含有2～4重量份。优选的，金属氧化物粉末为氧化铝、氧化铋、氧化锌中的一种或多种，更优选为氧化铝和氧化铋的混合物，混合物中氧化铝和氧化铋的质量比为(3:1)～(1:3)，优选为(1:1)～(1:2)。
进一步的，本发明还提供了一种水性碳纤维上浆剂的制备方法，包含以下步骤：
S1：将含呋喃基的环氧化合物与表面活性剂在反应釜中混合均质，混合温度控制在60～110℃；
S2：将S1制得的均质混合物冷却至20～50℃，加入水后，高速剪切分散乳化；
S3：在S2制得的产物中加入丙烯酸类聚合物，混合均匀得到水性碳纤维上浆剂。
优选的，S1混合溶液中还加入抗氧化剂，混合温度为80～110℃。S3后还加入流平剂和防冻剂并混合均匀。
进一步的，所述的碳纤维上浆剂的运用中，将碳纤维在上浆剂中浸渍走丝后，依次经过第一热处理过程、第二热处理过程得到上浆后的碳纤维。第一热处理过程的温度范围为90～110℃，用于去除上浆剂中的水分，处理时间以水分除尽为准，优选大于5min。第二热处理过程的温度范围为110～180℃，让含呋喃基的环氧化合物与丙烯酸类聚合物反应，使上浆剂交联固化提高上浆剂和碳纤维性能，处理温度优选130～150℃，处理时间优选大于20min。
进一步的，经本发明上浆剂上浆后的碳纤维中，上浆剂的质量为上浆后的碳纤维总质量的5％～20％。超过这个范围，碳纤维的综合性能都会变差。优选的，上浆剂的质量为上浆后的碳纤维总质量的8％～15％。优选的，碳纤维在上浆剂中浸润时间为0.5～20min。
经过本发明上浆剂上浆后的碳纤维适用于环氧树脂、不饱和树脂、酚醛树脂等的热固性树脂复合材料，尤其适用于环氧树脂、不饱和树脂的复合材料。
本发明的有益效果：
1、运用丙烯酸类聚合物可以溶于水的特点制备出水性碳纤维上浆剂代替含有有机溶剂的溶剂型上浆剂，减少有机污染溶剂对环境的污染。
2、含呋喃基的环氧化合物可与丙烯酸类聚合物反应而使其交联固化，提高碳纤维和上浆剂的耐高温、耐腐蚀、耐溶剂性和优异的力学性能。
3、呋喃基和金属氧化物可以提高有机物的导热性能，提升上浆剂的导热系数，保证经过本发明上浆计上浆处理后的碳纤维仍能保持良好的导热性能。
具体实施方式
一、原料选择
【丙烯酸聚合物】
A1，一种呋喃改性丙烯酸聚合物，参考CN200710011054.8，由以下方法制备：
单体：
丙烯酸65g；
丙烯酸丁酯15g；
α-呋喃丙烯酸20g。
先在单体中加入0.15g引发剂偶氮二异丁腈，在80℃下反应2h，继而降温至65℃，缓慢滴加0.35g偶氮二异丁腈，反应2h即可。
A2，一种呋喃改性丙烯酸聚合物，制备方法参考A1，仅把单体替换为：
丙烯酸45g；
丙烯酸丁酯15g；
α-呋喃丙烯酸40g。
A3，一种丙烯酸类聚合物，制备方法参考A1，仅把单体替换为：
丙烯酸85g；
丙烯酸丁酯15g。
【含呋喃基的环氧化合物】
B1：式1所示化合物，其中R是正癸基；按照专利CN 105906644A中实施例3的制备得到，环氧值为0.40。
B2：式1所示化合物，其中R是羟乙基氧乙基；按照专利CN105906644A中实施例5的制备得到，环氧值为0.45。
B3：式1所示化合物，其中R1是H，n＝8；先以聚合度n＝8的聚乙二醇和邻苯二甲酸酰胺混合溶于四氢呋喃中，在偶氮二甲酸乙二酯的作用下制备得到聚乙二醇单端邻苯二甲酰亚胺；再将聚乙二醇单端邻苯二甲酰亚胺与无水乙醇中与水合肼反应制备出单端基氨基聚乙二醇。参照专利CN105906644A中实施例5的制备方法，用单端基氨基聚乙二醇代替(2-氨基乙氧基)乙醇，得到产物，环氧值为0.27。
【表面活性剂】
C1：十二烷基苯磺酸钠，重庆赛普那斯科技有限公司产；
C2：苄索氯胺，武汉联商网科技有限公司产；
【流平剂】
D：聚醚改性聚硅氧烷BNK-LK380，美国BNK公司生产；
【抗氧化剂】
E：2,6-二叔丁基对甲酚，国药集团生产；
【防冻剂】
F：乙二醇丁醚，国药集团生产；
【金属氧化物】
G1：氧化铝，南京爱普瑞纳米材料有限公司售，粒径为50nm，比表面为60m2/g。
G2：氧化铋，南京爱普瑞纳米材料有限公司售，粒径为40nm，比表面为25.8m2/g。
G3：氧化镁，南京爱普瑞纳米材料有限公司售，粒径为20nm，比表面为100m2/g。
二：性能检测及方法
数均粒径：用激光粒度仪测定。
碳纤维上浆后上浆剂质量分数：以测量碳纤维上浆前后质量差值与上浆后碳纤维的质量的比值表征。
拉伸强度：按GB/T1447-2005测定，将样品裁成Ⅱ型式样，长度为250mm，长度为碳纤维长丝的排列方向。拉伸速率5mm/min。
导热系数：按GB/T3139-2005测定，将样品裁成长100mm、宽100mm的试样。
实施例1～13
按照表1中原料和配方按照如下办法制备得到本发明碳纤维上浆剂：
S1：将表1中含呋喃基的环氧化合物、表面活性剂和抗氧化剂在反应釜中在100℃混合均质；
S2：将均质混合物冷却至30℃，加入100重量份的水后，高速剪切分散乳化；
S3：再水乳液中加入丙烯酸类聚合物、流平剂、防冻剂混合均匀得到水性碳纤维上浆剂。
表1：水性碳纤维上浆剂原料及其重量份(以水为100重量份计)
对比例1
在实施例1的基础上，不添加含呋喃基环氧化合物，按照相同的方法制备得到水性碳纤维上浆剂。
对比例2
在实施例1的基础上，只是将B1替换成等重量份的聚乙二酸二缩水甘油醚(武汉远成共创科技有限公司产，环氧值为0.5)，按照相同的方法制备得到水性碳纤维上浆剂。
将实施例和对比例制备的碳纤维表面上浆剂浸润碳纤维长丝(日本东丽株式会社产T300-12000，纤度为800g/1000m，使用前先将碳纤维长丝在氮气气氛下，于350℃下加热4小时，以除去原有的上浆剂)10min，然后在100℃热处理10min除去上浆剂中的水分、再在150℃热处理30min得到上浆后的碳纤维，并测定碳纤维表面上浆剂的含量。
将上述制备的碳纤维长丝，按照如下方法制备碳纤维增强环氧树脂复合材料。
1、将混合均匀的双酚A型环氧树脂E-51和固化剂乙二胺(约为10g/KG环氧树脂)注入4mm厚模具中，并于80℃预固化1h形成1.5mm预固化环氧树脂层。
2、在预固化环氧树脂层上按一个方向均匀紧密铺设一层上述实施例和对比例得到的碳纤维长丝，并加压使其粘连其上。
3、混合均匀的双酚A型环氧树脂E-51和固化剂乙二胺(约为10g/KG环氧树脂)注入并填满模具中，于80℃固化8h，得到碳纤维增强环氧树脂复合板。
对比例3
将碳纤维丝(日本东丽株式会社产T300-12000，纤度为800g/1000m，使用前先将碳纤维长丝在氮气气氛下，于350℃下加热4小时，以除去原有的上浆剂)不经过上浆剂上浆处理，按照上述方法制备出8mm碳纤维增强环氧树脂板。
对制备的环氧树脂板进行纤维长丝方向拉伸强度和厚度方向导热系数的测试。测试结果如表2所示。
表2碳纤维增强环氧树脂板的性能测试数据
从表2中可以看出，与对比例相比本发明的碳纤维上浆剂与碳纤维的粘附力强，大大提高碳纤维的韧性和碳纤维复合材料的力学性能。本发明的上浆剂有很好的导热系数，有助于保持并提高上浆剂后的碳纤维的导热性能，并大大提高碳纤维复合材料的导热性能，能用作导热材料。此外，本发明的上浆剂使用水代替有机液体作为溶剂，消除挥发性有机物进入大气中，减少对环境的污染和污染治理费用。
以上所述，仅为本发明较佳的具体实施方式，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，根据本发明的技术方案及其发明构思加以等同替换或改变，都应涵盖在本发明的保护范围之内。
Claims (6)
1.一种水性碳纤维上浆剂，其特征在于，按重量份数计，包含以下组份：
丙烯酸类聚合物 2.5~10重量份；
含呋喃基的环氧化合物 1~5重量份；
表面活性剂 1~10重量份；
水 100重量份；
金属氧化物粉末 1~5重量份；
其中，所述含呋喃基的环氧化合物为含有如下式1结构的环氧化合物，
式1中，R为C1~C12的烷基或为如下式2所示结构：
式2中，n＝1~20，R1为H、甲基或乙基；
所述金属氧化物粉末的直径小于100nm。
2.根据权利要求1所述的水性碳纤维上浆剂，其特征在于，还含有0.2~2重量份的抗氧化剂、0.2~2重量份的流平剂、0.2~2重量份的防冻剂。
3.根据权利要求1所述的水性碳纤维上浆剂，其特征在于，所述丙烯酸类聚合物为呋喃改性丙烯酸聚合物。
4.根据权利要求1所述的水性碳纤维上浆剂，其特征在于，所述金属氧化物粉末为氧化铝、氧化铋、氧化锌中的一种或多种。
5.根据权利要求1-4任一项所述的水性碳纤维上浆剂在碳纤维中的应用，其特征在于，将碳纤维在上浆剂中浸渍走丝后，经过第一热处理过程、第二热处理过程得到上浆后的碳纤维，其中，第一热处理过程的温度范围为90~110℃，第二热处理过程的温度范围为110~180℃。
6.权利要求5所述的水性碳纤维上浆剂在碳纤维中的应用，上浆后的碳纤维中，上浆剂的质量为上浆后的碳纤维总质量的5%~20%。
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