CN110924137A - 一种基于芳纶纳米纤维的聚苯乙烯增韧剂及其制备方法 - Google Patents
一种基于芳纶纳米纤维的聚苯乙烯增韧剂及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种基于芳纶纳米纤维的聚苯乙烯增韧剂及其制备方法。该增韧剂呈纳米球状,表面富含C=C和苯环等含π电子的基团,与苯乙烯基体界面作用良好,在不降低聚苯乙烯材料强度的同时,可使其韧性大幅提高500%以上。本发明将具有高强度、高模量、高韧性的芳纶纤维引入到PS增韧应用领域,将对位芳纶纤维在DMSO(二甲基亚砜)体系中经KOH溶解后,制得对位芳纶纳米纤维(ANFs),然后将其进行烯丙基化或苄基化处理,从而得到功能化ANFs纳米材料。该纳米材料对PS的增韧效果显著,且在增韧的同时,还可保持甚至提高PS的强度。
Description
技术领域
本发明涉及一种基于芳纶纳米纤维的聚苯乙烯增韧剂及其制备方法。
背景技术
聚苯乙烯(PS)是世界上应用最广泛的五大通用塑料之一,由苯乙烯单体聚合而成。聚苯乙烯具有高刚性、良好的尺寸稳定性及易加工成型等优点而受到人们的日益关注。但是由于其硬而脆、耐冲击性能差以及较低的断裂伸长率(2%),影响了其在高抗冲制品方面的应用。
对聚苯乙烯进行增韧改性的研究始于20世纪60年初美国的DOW化学公司对HIPS的研发。目前,PS增韧改性技术主要包括物理法和化学法两大类,物理改性技术包括填充改性、共混改性和增强增韧改性;化学改性技术包括共聚改性、接枝改性和交联改性。其中,聚合法和共混法是工业上常用方法,即将顺丁橡胶等橡胶等通过化学或物理的方法加入到聚苯乙烯体系中,以达到增韧的目的。但是这些方法的工艺条件较为苛刻,容易出现交联过度等现象,橡胶在聚苯乙烯基体中的形态难以有效控制,且有时为了达到韧性指标,往往橡胶添加量过大,反而降低了PS的刚性和强度。
发明内容
本发明针对上述现有技术存在的不足,提供一种基于芳纶纳米纤维的聚苯乙烯增韧剂及其制备方法。该增韧剂呈纳米球状,表面富含C=C和苯环等含π电子的基团,与苯乙烯基体界面作用良好,在不降低聚苯乙烯材料强度的同时,可使其韧性大幅提高500%以上。本发明将具有高强度、高模量、高韧性的芳纶纤维引入到PS增韧应用领域,将对位芳纶纤维在DMSO(二甲基亚砜)体系中经KOH溶解后,制得对位芳纶纳米纤维(ANFs),然后将其进行烯丙基化或苄基化处理,从而得到功能化ANFs纳米材料。该纳米材料对PS的增韧效果显著,且在增韧的同时,还可保持甚至提高PS的强度。
具体技术方案如下:
本发明的目的之一是公开一种基于芳纶纳米纤维的聚苯乙烯增韧剂,其为苄基改性对位芳纶纳米纤维或烯丙基改性对位芳纶纳米纤维。
本发明的改性对位芳纶纳米纤维在透射电镜下呈纳米颗粒状。
本发明的另一个目的是公开一种如前述的基于芳纶纳米纤维的聚苯乙烯增韧剂的制备方法,包括以下步骤:
(1)将KOH加入二甲基亚砜中,50~80℃搅拌1~5h后加入对位芳纶纤维,继续30~50℃搅拌反应1~8天,制得ANFs溶液;
(2)向步骤(1)所得ANFs溶液中加入苄基溴或烯丙基溴,25~50℃下反应5~20h后得橙黄色透明溶液;
(3)将步骤(2)所得橙黄色溶液加入到去离子水中沉淀、过滤,并用去离子水和丙酮交替洗涤后,过滤、干燥,得到淡黄色粉末,即得聚苯乙烯增韧剂。
通过上述制备方法获得的聚苯乙烯增韧剂为苄基改性对位芳纶纳米纤维或烯丙基改性对位芳纶纳米纤维。
优选的,步骤(1)中KOH与二甲基亚砜的用量比为1g:(200~600)mL,KOH与对位芳纶纤维的质量比为1:0.5~1:2。
优选的,步骤(2)中的苄基溴与步骤(1)获得的ANFs溶液的体积比为1:125~1:200;烯丙基溴与步骤(1)获得的ANFs溶液的体积比为1:125~1:250。
优选的,所述的对位芳纶纤维为Kevlar-964C对位芳纶纤维。
本发明的有益效果如下:
本发明将对位芳纶纳米纤维进行苄基化或烯丙基化改性,改性后的纳米材料呈纳米球状,表面富含苄基或烯丙基,添加到聚苯乙烯基体中后,其中所含的苯环(或C=C)可以和基体苯环之间产生π-π相互作用,从而增强了其界面间的作用力。且对位芳纶纳米纤维本身的高强度、高韧性、高模量也赋予聚苯乙烯更优异的力学性能。在实施例中,当烯丙基增韧剂添加量为0.15%时,聚苯乙烯的韧性最高可增大到原来的9.69倍。
此外,本发明工艺简单,反应条件温和,易控制,合成效率高。
附图说明
图1为本发明实施例1的产品透射电镜图片;
图2为本发明实施例2的产品透射电镜图片;
图3为聚苯乙烯复合膜的拉伸测试曲线。
具体实施方式
以下结合实例对本发明的原理和特征进行描述,所举实例只用于解释本发明,并非用于限定本发明的范围。
本发明实施例中使用的试剂与物料均为市售普通商品。
实施例1
制备苄基改性的芳纶纳米纤维。
一种基于芳纶纳米纤维的聚苯乙烯增韧剂的制备方法,包括以下步骤:
(1)将干燥的500mL三口瓶用氮气吹扫5min,向其内部加入0.5g KOH和200mL DMSO(二甲基亚砜),70℃机械搅拌2h后,加入0.5g Kevlar-964C对位芳纶纤维,35℃下保持搅拌反应7天,制得ANFs溶液;
(2)在氮气保护下,量取步骤(1)所得ANFs溶液50mL于150mL三口烧瓶中,加入苄基溴0.4mL,在30℃恒温水浴下机械搅拌17h,得到橙黄色透明溶液;
(3)将步骤(2)所得橙黄色溶液加入到150mL去离子水中沉淀、过滤;然后将所得固体产物用去离子水和丙酮交替洗涤2次后,再次过滤;最后将过滤所得固体产物在60℃真空烘箱中干燥5h后,即得到淡黄色粉末状PS增韧剂—苄基化ANFs。
实施例2
制备烯丙基改性的芳纶纳米纤维。
一种基于芳纶纳米纤维的聚苯乙烯增韧剂的制备方法,包括以下步骤:
(1)将干燥的500mL三口瓶用氮气吹扫5min,向其内部加入0.5g KOH和200mL DMSO(二甲基亚砜),70℃机械搅拌2h后,加入0.5g Kevlar-964C对位芳纶纤维,35℃下保持搅拌反应7天,制得ANFs溶液;
(2)在氮气保护下,量取步骤(1)所得ANFs溶液50mL于150mL三口烧瓶中,滴加烯丙基溴0.3mL,在30℃恒温水浴下机械搅拌17h,得到橙黄色透明溶液;
(3)将步骤(2)所得橙黄色溶液加入到150mL去离子水中沉淀、过滤;然后将所得固体产物用去离子水和丙酮交替洗涤2次后,再次过滤;最后将过滤所得固体产物在60℃真空烘箱中干燥5h后,即得到淡黄色粉末状PS增韧剂—烯丙基化ANFs。
实施例3
制备苄基改性的芳纶纳米纤维。
一种基于芳纶纳米纤维的聚苯乙烯增韧剂的制备方法,包括以下步骤:
(1)将干燥的500mL三口瓶用氮气吹扫5min,向其内部加入1g KOH和200mL DMSO(二甲基亚砜),50℃机械搅拌5h后,加入0.5g Kevlar-964C对位芳纶纤维,50℃下保持搅拌反应1天,制得ANFs溶液;
(2)在氮气保护下,量取步骤(1)所得ANFs溶液50mL于150mL三口烧瓶中,加入苄基溴0.25mL,在50℃恒温水浴下机械搅拌5h,得到橙黄色透明溶液;
(3)将步骤(2)所得橙黄色溶液加入到150mL去离子水中沉淀、过滤;然后将所得固体产物用去离子水和丙酮交替洗涤2次后,再次过滤;最后将过滤所得固体产物在60℃真空烘箱中干燥5h后,即得到淡黄色粉末状PS增韧剂—苄基化ANFs。
实施例4
制备烯丙基改性的芳纶纳米纤维。
一种基于芳纶纳米纤维的聚苯乙烯增韧剂的制备方法,包括以下步骤:
(1)将干燥的500mL三口瓶用氮气吹扫5min向其内部加入0.4g KOH和200mL DMSO(二甲基亚砜),80℃机械搅拌1h后,加入0.8g Kevlar-964C对位芳纶纤维,30℃下保持搅拌反应8天,制得ANFs溶液;
(2)在氮气保护下,量取步骤(1)所得ANFs溶液50mL于150mL三口烧瓶中,滴加烯丙基溴0.2mL,在25℃恒温水浴下机械搅拌20h,得到橙黄色透明溶液;
(3)将步骤(2)所得橙黄色溶液加入到150mL去离子水中沉淀、过滤;然后将所得固体产物用去离子水和丙酮交替洗涤2次后,再次过滤;最后将过滤所得固体产物在60℃真空烘箱中干燥5h后,即得到淡黄色粉末状PS增韧剂—烯丙基化ANFs。
实验
通过透射电镜验证本发明的微观形态,并验证本发明应用于PS复合膜后对其韧性的优化。
实施例1制备获得的苄基改性ANFs(ANFs-C7H7)的透射电镜图见图1,实施例2制备获得的烯丙基改性ANFs(ANFs-C3H5)的透射电镜图见图2。由图1和图2可见,所得产品呈细小的纳米颗粒状。
分别将实施例1制备获得的ANFs-C7H7与实施例2制备获得的ANFs-C3H5添加于聚苯乙烯复合膜作为增韧剂,添加量均为0.15wt%,与未添加本发明增韧剂的聚苯乙烯复合膜进行拉伸测试对比。除添加增韧剂外,参与测试的三种聚苯乙烯复合膜的制备方法与成分相同,为本领域常规制备方法与成分。其拉伸测试曲线见图3。由图3可见,添加了本发明所得增韧剂ANFs-C7H7和ANFs-C3H5后,PS膜的韧性有了大幅提升。
以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种基于芳纶纳米纤维的聚苯乙烯增韧剂,其特征在于,为苄基改性对位芳纶纳米纤维或烯丙基改性对位芳纶纳米纤维。
2.根据权利要求1所述的聚苯乙烯增韧剂,其特征在于,呈纳米颗粒状。
3.一种如权利要求1或2所述的聚苯乙烯增韧剂的制备方法,其特征在于,包括以下步骤:
(1)将KOH加入二甲基亚砜中,50~80℃搅拌1~5h后加入对位芳纶纤维,继续30~50℃搅拌反应1~8天,制得ANFs溶液;
(2)向步骤(1)所得ANFs溶液中加入苄基溴或烯丙基溴,25~50℃下反应5~20h后得橙黄色透明溶液;
(3)将步骤(2)所得橙黄色溶液加入到去离子水中沉淀、过滤,并用去离子水和丙酮交替洗涤后,过滤、干燥,得到淡黄色粉末,即得聚苯乙烯增韧剂。
4.根据权利要求3所述的制备方法,其特征在于,步骤(1)中KOH与二甲基亚砜的用量比为1g:(200~600)mL,KOH与对位芳纶纤维的质量比为1:0.5~1:2。
5.根据权利要求3所述的制备方法,其特征在于,步骤(2)中的苄基溴与步骤(1)获得的ANFs溶液的体积比为1:125~1:200;烯丙基溴与步骤(1)获得的ANFs溶液的体积比为1:125~1:250。
6.根据权利要求3~5任一项所述的制备方法,其特征在于,获得的聚苯乙烯增韧剂为苄基改性对位芳纶纳米纤维或烯丙基改性对位芳纶纳米纤维。
7.根据权利要求3~5任一项所述的制备方法,其特征在于,所述的对位芳纶纤维为Kevlar-964C对位芳纶纤维。
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