CN111379058A - 一种环形高性能合成纤维束 - Google Patents
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Abstract
本发明的一种环形高性能合成纤维束,为由未改性合成纤维和改性合成纤维环形相连而成的纤维束,所述改性合成纤维包括极性改性合成纤维、官能团接枝改性合成纤维、填料改性合成纤维和母粒改性合成纤维。不仅实现了牢固联合上述不同纤维的构想,相对单根纤维整体强度得到提高,而且纤维束具有各种性能优势,更重要的是可使强度、分散性和界面结合力都能更好的发挥改性作用,使得在纤维强度相同的情况下,纤维的分散性和界面结合均分别明显提高,因此纤维束在混凝土中的增强效果也大幅提高。
Description
技术领域
本发明涉及一种高性能合成纤维束,具体的涉及一种用于纤维增强领域的环形纤维束,可被纤维束增强的材料包括但不限于水泥、混凝土、塑料、树脂、橡胶等。
背景技术
合成纤维是一种由合成树脂通过熔融拉丝或熔融纺丝制备而成的纤维。这种纤维具有较高的强度,可用于增强水泥、混凝土、塑料、树脂、橡胶等材料。与玻璃相比,合成纤维耐碱、耐腐蚀、安全、对人体没有任何伤害。与钢纤维相比,合成纤维不扎人、质量轻、不生锈、耐腐蚀、成本较低。
然而,合成纤维也有自身的缺陷,从而大大限制了纤维的应用。首先,合成纤维耐热性差,在塑料或者橡胶高温成型的材料中,如果合成纤维的耐热温度低于塑料、橡胶的成型温度,在成型过程中合成纤维就会因为高温而丧失掉强度。第二,合成纤维的分散性差。合成纤维在基体中的分散性取决于基体(水泥、混凝土、塑料、树脂、橡胶等)的性能,纤维的极性需要与基体的极性相匹配,极性差异过大或者过小,极性太高或太低,都会导致分散困难。第三,合成纤维的强度普遍不高,通常低于玻璃纤维或者钢纤维,这就导致了合成纤维的增强效果比玻璃纤维和钢纤维要差。第四,合成纤维与基体的粘结性,普遍不好。例如,非极性合成纤维与极性的橡胶基体、无官能团的合成纤维与含SiO2的水泥和混凝土、极性的纤维与非极性的塑料基体等,都会有较差的粘结性,这也导致了纤维的增强效果较差。
因此,当前技术中很难找到一种合成纤维,将耐高温、高分散性、高强度、高粘结性、可调节的极性与非极性、可调节的官能团引入等优势,融为一体。
发明内容
为了解决这样的缺陷,让合成纤维将尽可能多的优势融为一体,同时让合成纤维可根据所增强基体的性质进行改变和调节,本发明提供一种环形高性能合成纤维束。
本发明的技术方案如下:
由未改性的合成纤维和改性合成纤维分别形成纤维圈,且未改性合成纤维圈和改性合成纤维圈通过环形相套形成纤维束。
优选的由多组纤维圈单元首尾环形相套而成,每组纤维圈单元包括多种纤维圈,所述多种纤维圈分别为未改性合成纤维圈和不同类型的改性合成纤维圈,且每组的未改性合成纤维圈同时与本组和相邻组的改性合成纤维圈环形相套。
优选的所述合成纤维的合成树脂原料为聚丙烯、聚乙烯、聚丙烯腈纤维、聚酯、超高分子量聚乙烯、聚酰胺、聚甲醛、聚乙烯醇、聚乙烯醇缩甲醛、聚对苯二甲酸乙二酯、聚苯咪唑、聚四氟乙烯、聚对苯二甲酰对苯二胺、聚酰亚胺中的一种或一种以上混合物。
优选的所述改性合成纤维包括极性改性合成纤维、官能团接枝改性合成纤维、填料改性合成纤维和/或母粒改性合成纤维。
进一步优选的所述改性合成纤维的改性剂为硅烷偶联剂Si-69、KH570、KH560、KH550、KH151、硅胶抗粘连剂、钛酸酯偶联剂、铝酸酯偶联剂、正硅酸乙酯、成核剂母粒、色母粒、增塑母粒、耐高温母粒、防腐母粒、消泡母粒、氯化聚丙烯、马来酸酐接枝聚丙烯、马来酸酐接枝聚乙烯、马来酸二烯丙烯酯、四甲基丙烯酸季戊四醇、聚乙二醇、聚己二酸丁二醇酯、聚己内酯、二丙二醇丁醚、二乙烯基苯、过氧化二异丙苯、硅油、表面活性剂、乙醇、二甲苯、无机物超细颗粒、炭黑、碳酸钙、TiO2、滑石粉、高岭土、二氧化硅、硅土、硅灰石、云母、硫酸钡、玻璃微珠、玻璃纤维、硅藻土、蒙脱土、水滑石、木粉、淀粉中的任一种或一种以上的混合物。
优选的所述纤维圈的直径为0.001-5mm。
前述的纤维束的制备方法,其特征在于包括以下步骤:
制备改性合成纤维,将改性剂与合成树脂按比例混合后,进行熔融拉丝或熔融纺丝后,制成改性合成纤维;或,先将合成树脂通过熔融拉丝或熔融纺丝的方法制成纤维,然后使用改性剂对纤维进行改性后,制成改性合成纤维;或,先将改性剂与合成树脂按比例混合后,进行熔融拉丝或熔融纺丝,然后再次使用改性剂对纤维进行改性后,制成改性合成纤维;
制备未改性的合成纤维,由合成树脂熔融纺丝或熔融拉丝制备而成;
将所述未改性的合成纤维与所述改性合成纤维以纤维圈相套的形式环形连接形成纤维束。
优选的所述纤维圈的制备过程为:在两根同样的纤维上分别选取纤维圈周长一半的长度部分,并将两个部分的两端分别对齐,然后在对齐处分别用高温刀切除,切口处由于高温融化则自动发生粘合,形成纤维圈。
本发明的技术效果如下:
本发明的一种环形高性能合成纤维束,开拓性地将经过多种改性处理后的改性合成纤维与未改性的合成纤维共同以环形相连的形式形成纤维束,具有以下效果:
未改性的合成纤维可以保持其原始的性能,包括强度、韧性、极性和官能团等。这些性能不会因改性剂而改变,强度不会因改性剂而降低,加工性性能不会因改性剂而变差,同时减少使用改性剂,还会降低纤维的成本。
改性纤维,通常包括但不限于以下四类:
(1)极性改性合成纤维,该纤维是通过改性剂对纤维进行极性与非极性的调节,使纤维与增强基体的极性进行匹配,从而提高纤维的分散性。所用改性剂为马来酸酐接枝聚丙烯、马来酸酐接枝聚乙烯、马来酸二烯丙烯酯、四甲基丙烯酸季戊四醇、聚乙二醇、聚己二酸丁二醇酯、聚己内酯、二丙二醇丁醚、二乙烯基苯、过氧化二异丙苯、硅油、表面活性剂、乙醇、二甲苯中的一种或一种以上的混合物。
(2)官能团接枝改性合成纤维,该纤维是通过改性剂为纤维引入适当的官能团,如Si、Si-O、-OH、-COOH等,使纤维与基体产生较强的粘结力,以及其他特殊功能。所用改性剂为硅烷偶联剂Si-69、KH570、KH560、KH550、KH151、硅胶抗粘连剂、钛酸酯偶联剂、铝酸酯偶联剂、正硅酸乙酯、氯化聚丙烯中的一种或一种以上的混合物。
(3)填料改性合成纤维,该纤维是通过填料对纤维进行增强,从而提高纤维刚性、弹性模量、拉伸强度等,部分无机填料还可以提高纤维的耐高温性。所用改性剂为无机物超细颗粒、炭黑、碳酸钙、TiO2、滑石粉、高岭土、二氧化硅、硅土、硅灰石、云母、硫酸钡、玻璃微珠、玻璃纤维、硅藻土、蒙脱土、水滑石、木粉、淀粉中的一种或一种以上的混合物。
(4)母粒改性合成纤维,母粒的加入可以使纤维在熔融拉丝或熔融纺丝时,具有相应的性能和功能,也可以使制备纤维时所用的两种或两种以上合成树脂产生更好的相容性。所用改性剂为成核剂母粒、色母粒、增塑母粒、耐高温母粒、防腐母粒、消泡母粒中的一种或一种以上的混合物。
本发明的纤维束使多种不同的改性纤维和未改性纤维很好的结合起来。不同特性的改性剂可以对纤维分开进行改性,这样改性效率就会大大提升,不但有效节约了改性剂,还可以使改性剂单独发挥各自的作用,而不会互相干扰,例如使纤维束整体可以同时具有亲水、有含硅官能团、高强度、耐高温且成本低等性质。如果将这些不同功能的该行进混在一起同时加入到一种纤维中,会导致很多问题,例如改性剂互相反应、改性剂过多无法均匀分散、官能团互相覆盖导致改性效率不高、浪费改性剂、过多改性剂导致纤维无法成型等等。
通过环形相连成为纤维束,不仅实现了牢固联合上述不同纤维的构想,相对单根纤维整体强度得到提高,而且纤维束具有各种性能优势,更重要的是可使强度、耐高温性、分散性和界面粘结力都能更好的发挥改性作用,使得在纤维强度相同的情况下,纤维的耐高温性、分散性和界面粘结力均分别明显提高,或者说可以在保持纤维强度较高的情况下同时保持更高的耐高温性、分散性和界面粘结力,因此纤维束在各种基体中的增强效果也大幅提高。
环形相连式的纤维束,由于每种纤维持续保持互相嵌套,保证了纤维束沿轴向整体长度上的表面基本上能保持有不同纤维存在,即改性和未改性纤维都均匀分布,不同纤维也交替暴露在表面,这样未改性合成纤维、极性改性合成纤维、官能团接枝改性合成纤维、填料改性合成纤维以及母粒改性合成纤维各自的优势性能即强度、分散性和界面结合力性能都能够得到最大化利用。
环形相连的做法有很多,常用的方法是将两股或多股纤维交叉并排在一起,然后用高温刀切纤维,纤维的边缘边切边会被融化粘结,从而形成环形相连的状态。环形相连的特殊形状,可以让基体(如水泥、混凝土等)裂纹两侧都被环形的纤维相连,极大提高纤维与基体的粘结力。此外,每个环之间的拉力也相比单纯的条状纤维在增强上有了进一步的优势和功能性。另外,纤维环的大小可根据具体需求进行调节。例如,如需高粘结力的纤维环,可提高官能团接枝改性合成纤维环的大小;如需高分散性、适中粘结力和低成本的纤维环,可提高极性改性合成纤维环的大小,适中减小官能团接枝改性合成纤维环的大小,提高未改性合成纤维环的大小。
优选的,将一个未改性合成纤维圈与两个不同改性合成纤维圈进行环形相连形成一个单元,并将每个单元首尾相连,以一个强度较高的未改性合成纤维圈作为基础连接两个改性合成纤维圈,在保证强度的基础上用尽可能少的纤维综合了三种性能,且基本尽量保持轴向的每个截面均有三种性能的纤维,使纤维束整体可以既保持纤维的高强度,又易分散,还可以实现与增强基体更好的结合,从而达到更好的增强作用;同时保持纤维束的直径为合理范围,且成束工艺简便。
附图说明
图1为本发明的一种环形高性能合成纤维束的实施例1示意图;
图2为本发明的一种环形高性能合成纤维束的实施例2示意图;
图中各标号列示如下:
1-纤维束,11-未改性合成纤维圈,12-极性剂改性合成纤维圈,13-填料改性合成纤维圈,14-官能团接枝改性合成纤维圈。
具体实施方式
为了更好的理解本发明,下面结合附图1-2和实施例对本发明进行进一步的解释。
实施例1
本实施例的一种环形高性能合成纤维束,为由未改性合成纤维圈11和填料改性合成纤维圈13按照环形相连的方式编织成纤维束,如图1所示。
上述一种环形高性能合成纤维束的制造方法,如下:
高强度未改性合成纤维的制备:将尼龙6颗粒加入到单螺杆挤出机中,在100-200度中熔融挤出,并经过冷水冷却,再经80度高温牵引,制得高强度聚酰胺纤维,其拉伸强度为1000MPa。
填料改性合成纤维的制备:将玻璃纤维和聚丙烯颗粒按照3:7的比例混合,经过熔融拉丝后,制得填料改性的聚丙烯纤维。该纤维由于玻璃纤维的增强,刚性提高了200%,耐高温性提高了80%。由于增强聚丙烯基体是在200度左右的温度中加工成型,故纤维需要具有耐高温性。该改性聚丙烯纤维,与增强基体是同类树脂,故分散性有了明显提高。
纤维束1的制备:上述两种纤维每种分别取两根,在两根同样的纤维上分别选取纤维圈周长一半的长度部分,并将两个部分的两端分别对齐,然后在对齐处分别用高温刀切除,切口处由于高温融化则自动发生粘合,形成纤维圈。
将未改性的尼龙纤维圈11和填料改性纤维圈13按照环形相连彼此相间编织成纤维束。质量分数20%该纤维束增强聚丙烯的拉伸强度为300MPa,比单用尼龙6纤维增强聚丙烯提高130%。
实施例2
本实施例的一种环形高性能合成纤维束,为由高强度未改性合成纤维圈11、极性剂改性合成纤维圈12和官能团接枝改性合成纤维圈14按照环形相连的方式编织成纤维束,如图2所示。
上述一种环形高性能合成纤维束的制造方法,如下:
高强度未改性合成纤维的制备:将聚丙烯颗粒加入到单螺杆挤出机中,在200-250度中熔融挤出,并经过冷水冷却以及熔融拉丝后,制得高强度聚丙烯纤维,其拉伸强度为600MPa。
极性剂改性合成纤维的制备:将聚丙烯颗粒和亲水剂马来酸酐接枝聚丙烯按7:3的比例加入到单螺杆挤出机中,在200-250度中熔融挤出,并经过冷水冷却以及熔融拉丝后,制得改性聚丙烯纤维。由于极性的纤维会与混凝土中的外加剂相互作用,纤维会随着外加剂的分散,进一步分散开来,因此其分散性提高80%。
官能团接枝改性合成纤维的制备:将聚丙烯颗粒和聚乙烯颗粒按5:1的比例加入到单螺杆挤出机中,在200-250度中熔融挤出,并经过冷水冷却以及熔融拉丝后,再用硅烷偶联剂Si69对纤维进行改性,制得偶联剂改性聚丙烯纤维,其与混凝土的粘结力比未改性的纤维提高了100%。
纤维束1的制备:由多组纤维圈单元首尾环形相连而成,纤维圈的制备与实施例1相同。每组纤维圈单元包括三种纤维圈,所述三种纤维圈分别为未改性高强度合成纤维圈11、极性剂改性合成纤维圈12和官能团接枝改性合成纤维圈13,且未改性合成纤维圈同时与本组和相邻组的两个改性合成纤维圈环形相连。由于纤维束由高强度聚丙烯纤维、高分散性的马来酸酐改性聚丙烯纤维和与混凝土高粘结力的硅烷偶联剂改性聚丙烯纤维组成,因此可以使用高用量的纤维增强混凝土,故大大提高了纤维对混凝土的增强效果。此外,由于环形结构的引入,进一步有效提高了纤维与混凝土的粘结力。18kg/m3的纤维束增强混凝土圆饼,根据ASTM C1550,测试得到在40mm曲挠时能量吸收为1500J,比单用18kg/m3聚丙烯纤维提高了200%。
此指明,以上叙述有助于本领域技术人员理解本发明的内容,但并非限制本发明的保护范围。任何没有脱离本发明实质内容的对以上叙述的等同替换、修饰改进和/或删繁从简而进行的实施,均落入本发明的保护范围。
Claims (8)
1.一种环形高性能合成纤维束,其特征在于由未改性的合成纤维和改性合成纤维分别形成纤维圈,且未改性合成纤维圈和改性合成纤维圈通过环形相套形成纤维束。
2.根据权利要求1所述的纤维束,其特征在于由多组纤维圈单元首尾环形相套而成,每组纤维圈单元包括多种纤维圈,所述多种纤维圈分别为未改性合成纤维圈和不同类型的改性合成纤维圈,且每组的未改性合成纤维圈同时与本组和相邻组的改性合成纤维圈环形相套。
3.根据权利要求1所述的纤维束,其特征在于所述合成纤维的合成树脂原料为聚丙烯、聚乙烯、聚丙烯腈纤维、聚酯、超高分子量聚乙烯、聚酰胺、聚甲醛、聚乙烯醇、聚乙烯醇缩甲醛、聚对苯二甲酸乙二酯、聚苯咪唑、聚四氟乙烯、聚对苯二甲酰对苯二胺、聚酰亚胺中的一种或一种以上混合物。
4.根据权利要求1所述的纤维束,其特征在于所述改性合成纤维包括极性改性合成纤维、官能团接枝改性合成纤维、填料改性合成纤维和/或母粒改性合成纤维。
5.根据权利要求4所述的纤维束,其特征在于所述改性合成纤维的改性剂为硅烷偶联剂Si-69、KH570、KH560、KH550、KH151、硅胶抗粘连剂、钛酸酯偶联剂、铝酸酯偶联剂、正硅酸乙酯、成核剂母粒、色母粒、增塑母粒、耐高温母粒、防腐母粒、消泡母粒、氯化聚丙烯、马来酸酐接枝聚丙烯、马来酸酐接枝聚乙烯、马来酸二烯丙烯酯、四甲基丙烯酸季戊四醇、聚乙二醇、聚己二酸丁二醇酯、聚己内酯、二丙二醇丁醚、二乙烯基苯、过氧化二异丙苯、硅油、表面活性剂、乙醇、二甲苯、无机物超细颗粒、炭黑、碳酸钙、TiO2、滑石粉、高岭土、二氧化硅、硅土、硅灰石、云母、硫酸钡、玻璃微珠、玻璃纤维、硅藻土、蒙脱土、水滑石、木粉、淀粉中的任一种或一种以上的混合物。
6.根据权利要求1所述的纤维束,其特征在于所述纤维圈的直径为0.001-5mm。
7.权利要求1-6任一所述的纤维束的制备方法,其特征在于包括以下步骤:
制备改性合成纤维,将改性剂与合成树脂按比例混合后,进行熔融拉丝或熔融纺丝后,制成改性合成纤维;或,先将合成树脂通过熔融拉丝或熔融纺丝的方法制成纤维,然后使用改性剂对纤维进行改性后,制成改性合成纤维;或,先将改性剂与合成树脂按比例混合后,进行熔融拉丝或熔融纺丝,然后再次使用改性剂对纤维进行改性后,制成改性合成纤维;
制备未改性的合成纤维,由合成树脂熔融纺丝或熔融拉丝制备而成;
将所述未改性的合成纤维与所述改性合成纤维以纤维圈相套的形式环形连接形成纤维束。
8.根据权利要求7所述的方法,其特征在于所述纤维圈的制备过程为:在两根同样的纤维上分别选取纤维圈周长一半的长度部分,并将两个部分的两端分别对齐,然后在对齐处分别用高温刀切除,切口处由于高温融化则自动发生粘合,形成纤维圈。
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