CN101532244B - 等离子体处理超高分子量聚乙烯纤维改性的方法 - Google Patents
等离子体处理超高分子量聚乙烯纤维改性的方法 Download PDFInfo
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- CN101532244B CN101532244B CN2008102074112A CN200810207411A CN101532244B CN 101532244 B CN101532244 B CN 101532244B CN 2008102074112 A CN2008102074112 A CN 2008102074112A CN 200810207411 A CN200810207411 A CN 200810207411A CN 101532244 B CN101532244 B CN 101532244B
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- molecular weight
- weight polyethylene
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Abstract
本发明涉及一种等离子体处理超高分子量聚乙烯纤维改性的方法,包括:(1)将二氧化硅纳米颗粒经超声波震荡技术配制成质量百分比为0.01~15%的有机溶剂或水的溶胶液;或(2)将有机-无机纳米颗粒的先驱液与二氧化硅纳米颗粒经杂化反应制得的纳米二氧化硅溶胶液;(3)将上述溶胶溶液涂覆在超高分子量聚乙烯纤维表面,涂覆方法为喷涂或浸轧的方法;(4)在10~150℃将超高分子量聚乙烯纤维烘干并收集溶剂,然后超高分子量聚乙烯纤维经等离子发生装置被引入等离子体氛围区进行等离子体表面改性。经本发明处理过的超高分子量聚乙烯纤维与有机基体材料之间的复合性能得到了大大提高,该工艺简单、、处理效果好、成本低、不易引起环境污染,并且还可以降低能耗。
Description
技术领域
本发明属超高分子量聚乙烯纤维表面改性的制备领域,特别是涉及一种等离子体处理超高分子量聚乙烯纤维改性的方法。
背景技术
超高分子量聚乙烯(UHMWPE)纤维是是继碳纤维、芳纶纤维之后出现的一种高性能纤维。它是以超高分子量聚乙烯为原料,经过高压固态挤压法、增塑熔融纺丝法、表面结晶生长法、超拉伸或局部超拉伸法、凝胶纺丝-热拉伸法等工艺制备的,一种具有高强度、高模量的高性能纤维。它的相对分子质量为100万~600万,分子形状为线型伸直链结构,取向度接近100%,强度相当于优质钢材的15倍左右,比碳纤维高2倍,比芳纶高40%,密度为0.97g/cm3,还具有耐紫外线辐射、耐化学腐蚀、比能量吸收高、介电常数低、电磁波透射率高、摩擦系数低及突出的抗冲击、抗切割等优异性能。因此,UHMWPE纤维是制作软质防弹服、防刺衣、轻质防弹头盔、运钞车防弹装甲、直升机防弹装甲、轻质高压容器、航天航空结构件、渔网、赛艇、帆船、滑雪撬等的理想材料。但是,由于UHMWPE纤维本身是由非极性的亚甲基形成的线性长链,纤维分子间没有较强的分子间作用力;纤维表面呈化学惰性,难以与树脂形成化学键合;在生产中经高倍拉伸形成的高度结晶和高度取向而导致的光滑表面。所有这些因素的共同作用使纤维的表面能很小,用作复合材料的增强材料时难以与基体树脂形成良好的界面粘接。
提高UHMWPE纤维与树脂基体间的界面粘接强度,可以通过表面涂覆法、化学试剂浸蚀、等离子体处理改性、电晕放电处理、光氧化表面改性处理、辐射接枝处理等方法对纤维进行改性,使纤维惰性表面层活化,在非极性的纤维表面引入羧基、羰基、羟基等极性基团。以及低温等离子处理法等。其中低温等离子处理法由于其高效迅速,对材料基本性能不造成损伤以及环境友好,受到广泛的关注。
中国专利CN 1431358A同时提高高强聚乙烯纤维耐热、抗蠕变和粘接性的方法利用光敏剂和交联剂组成的有机溶液浸渍聚乙烯纤维,然后再将纤维进行紫外光辐照交联;专利Int.C1D01MI5/00(2006.01)提出用本征导电聚合物单体吡咯或噻吩在真空中处理浸泡过有机磺酸铁盐的超高分子量聚乙烯纤维获得纤维表面改性。
中国专利文献CN1035308A公开了一种提高UHMWPE纤维表面粘接性的方法。它采用UHMWPE纤维表面进行等离子体处理的方法。此方法可有效提高纤维对树脂基体的浸润性和表面粘接强度。但该法设备条件要求高,工业化难度较大,且处理不当会使纤维力学性能显著下降。
SilVerstein M.S.等用铬酸试剂处理UHMWPE纤维的表面改性方法,粘接性能提高了6倍。但该方法使纤维表面受到了腐蚀,对纤维强度影响较大。
美国专利文献USP6172163也公开了一种提高纤维表面粘接性能的方法。此方法是利用聚乙烯的高结晶性能,采用纯物理的方法,使纤维表面的无定型区发生溶解后重新结晶而在纤维表面形成一层“分子刷”。用这种方法处理的UHMWPE纤维与树脂复合后,纤维粘接性能得到了很大的提高。但该方法同样工序繁琐,工艺条件苛刻,且处理不当也会造成UHMWPE纤维力学性能的显著下降。
中国专利文献CN1693544A公开了一种提高UHMWPE纤维表面粘接性的方法。此方法是将极性聚合物溶解在UHMWPE冻胶纤维的常规萃取剂中,制成复合萃取剂,再将UHMWPE冻胶纤维在复合萃取剂中萃取,然后经拉伸等后工序处理制成粘接性能有较大提高的UHMWPE纤维。该方法虽能较好的保持UHMWPE纤维的原有强度,但纤维粘接强度提高程度有限,没有达到理想和实用的目标。
美国专利文献LJSP5039549和USP5755913公开的方法是在等离子体、臭氧、电晕放电或紫外辐照下,将UHMWPE纤维表面接枝上一些含极性基团单体(如丙烯酸、丙烯酰胺、丙烯腈等)的表面改性方法,可大大提高UHMWPE纤维的表面粘接性能,但该方法工序繁琐,且接枝处理的最佳工艺条件难以掌握,工业化前景渺茫。
中国专利CN1035308A公开了一种提高UHMWPE纤维表面粘结性能的方法,它是将UHMWPE纤维表面进行等离子体处理,此方法可有效提高纤维对常用基料的润湿性和表面粘结强度,但对纤维的热性能和蠕变性能没有影响。但该专利没有利用纳米材料制备溶胶技术,更没有提到利用纳米二氧化硅溶胶技术涂覆UHMWPE纤维,特别是经纳米二氧化硅溶胶涂覆后的UHMWPE纤维再经等离子体技术进行表面改性的方法以上专利没有涉及。
低温等离子体是一种处于非热力学平衡状态下的等离子体,其中粒子的能量一般约为几个至十几电子伏特,大于材料的结合键能,完全可以破坏材料的化学键而形成新键,其能量又远低于高能放射性射线,只涉及材料表面,不影响材料的本体性能。因此,常温,常压等离子体能提高纳米粒子的化学反应活性,使用等离子体对涂敷纳米二氧化硅溶胶的UHMWPE纤维材料表面进行处理可引起传统物理与化学方法无法实现的材料表面的物理化学改性。
发明内容
本发明所要解决的技术问题是提供一种等离子体处理超高分子量聚乙烯纤维改性的方法,经本发明处理过的超高分子量聚乙烯纤维与有机基体材料之间的复合性能得到了大大提高,该工艺简单、处理效果好、成本低、不易引起环境污染,并且还可以降低能耗。
本发明的一种等离子体处理超高分子量聚乙烯纤维改性的方法,包括:
(1)将二氧化硅纳米颗粒经超声波震荡技术配制成质量百分比浓度为0.01~15%的有机溶剂或水的溶胶液;
或(2)将有机-无机纳米颗粒的先驱液与二氧化硅纳米颗粒经杂化反应制得质量百分比浓度为0.01~15%的纳米二氧化硅溶胶液;
(3)将上述溶胶溶液涂覆在超高分子量聚乙烯纤维表面,涂覆方法为喷涂或浸轧的方法;
(4)在10~150℃下将超高分子量聚乙烯纤维烘干并收集溶剂,然后超高分子量聚乙烯纤维被经等离子发生装置引入等离子体氛围区进行等离子体表面改性,处理功率为10~15000w,时间为0.5~300秒;将处理后的超高分子量聚乙烯纤维在自动收卷机中进行在线收卷,通过调节收卷轴的速度来调节超高分子量聚乙烯纤维的走线速度,根据不同加工工艺的需要,超高分子量聚乙烯纤维经过等离子体喷嘴的距离,速度进行相应的调整。
所述步骤(1)中的有机溶剂为己烷,异戊烷,正戊烷,石油醚,环己烷,异辛烷,三氟乙酸,三甲基戊烷,环戊烷,庚烷,丁基氯,丁酰氯,三氯乙烯,四氯化碳,三氯三氟代乙烷,,甲苯,对二甲苯,氯苯,邻二氯苯,二乙醚,苯,异丁醇,二氯甲烷,二氯化乙烯,正丁醇,甲基异丁酮,四氢呋喃,乙酸乙酯,异丙醇,氯仿,甲基乙基酮,二恶烷,吡啶,丙酮,硝基甲烷,乙酸,乙腈,苯胺,二甲基甲酰胺,甲醇,乙二醇,正辛醇,正己醇,环己醇,正丙醇,二丙酮醇,二甲亚砜DMSO,二硫化碳,三氯乙烷,丁酮,乙二醇二甲醚,乙二醇一甲醚或乙酸丁酯。
所述步骤(2)中的有机纳米颗粒为带反应性基团的有机化合物,蒽、苝、聚二乙炔、吡唑啉衍生物有机纳米晶PDDP、DPP、DAP、聚对苯乙烯撑PPV、噻吩齐聚物、1,4-二-(2-(5-苯基氧氮唑基))苯、芘有机小分子、蒽的纳米线、有机小分子芘的纳米管、芘-聚吡咯、有机荧光染料Nile红、酞菁氧钒、聚对苯乙烯撑PPV、苯乙烯St、油酸、羧酸、异氰酸、聚异丁烯酸、聚丁基丙烯酸、聚甲基丙烯酸PMA、甲基丙烯酸、聚甲基丙烯、硅烷、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、多异氰酸苯酯、甲苯二异氰酸酯聚醋酸乙烯酯、聚丙烯酸酯ACR、脂肪酸盐,甲基丙烯酸甲酯MMA、铝酸酯、钛酸酯等含酯基团酯类、PVA聚乙烯醇等醇类、有机分子十六烷基三甲基溴化铵、氨基化硅、聚苯胺、N,N-二甲基乙酰胺、二甲基甲酰胺等酰氨类、聚氧乙烯十二烷基醚、聚N一异丙基丙烯酸胺接枝聚苯乙烯、PEG接枝聚苯乙烯、PEG接枝聚甲基丙烯酸甲酯、聚乙二醇接枝聚苯乙烯;
所述的无机纳米颗粒选自纳米级金属、纳米级金属氧化物、纳米级非金属、纳米级非金属氧化物中的一种或几种;
所述的纳米级金属为银、铜或其混合物;
所述的纳米级金属氧化物选自钛、铝、锆、铁、锡、锌、钡、镍的氧化物中的一种或几种的混合物;
所述的纳米级非金属及其氧化物选自碳纳米管、二氧化硅、蒙脱土、磷氧化物等中的一种或几种的混合物;
所述的等离子体发生装置是各类等离子体发生器,等离子体氛围由等离子体发生器产生,并经由喷嘴机构喷射到常温、常压的大气环境中形成的等离子体氛围,应用于工业化大批量生产;
所述的等离子体选自氦气、氩气或功能性气体中的一种或几种,其中氦气、氩气摩尔比为50%-99.99%,功能性气体为0.001~30%,同时流经等离子体形成区形成等离子体氛围;
所述的功能性气体为SO2、氨气、氧气、氢气、氮气、四氟化碳、二氧化碳、甲烷CH4、乙烷C2H6、丙烷C3H8、丁烷C4H10、戊烷C5H12、己烷C6H14、庚烷C7H16、辛烷C8H18、壬烷C9H20、癸烷C10H22、十一烷C11H24、十二烷C12H26、十三烷C13H28、乙烯(C2H4)、丙烯(C3H6)、丁烯(C4H8)、戊烯(C5H10)、己烯(C6H12)、丙二烯(C3H4)、丁二烯(C4H6)、异戊二烯(C5H8)、己三烯(C6H8)、乙炔(C2H2)、丙炔(C3H4)、丁炔(C4H6)、戊炔(C5H8)、己炔(C6H10)、庚炔(C7H12)、辛炔(C8H14)、壬炔(C9H16)、癸炔(C10H18)、十一炔(C11H20)、四氟乙烯和硅烷、各种硅氧烷气体、丙烯酸,甲基丙烯酸的蒸汽或它们组合气体。
通过等离子体表面处理,涂敷纳米二氧化硅溶胶的UHMWPE纤维材料表面发生多种物理、化学变化,或产生刻蚀而粗糙,或形成致密的交联层,或引入含氧极性基团,使亲水性、粘结性及电性能等分别得到改善,使材料表面由非极性、难粘性转为有一定极性、易粘结性,有利于粘结、涂敷。
本发明的超高分子量聚乙烯纤维经等离子体处理后表面发生如下的物理化学变化:(1)超高分子量聚乙烯纤维表面以及表面涂敷的纳米材料表面的部分化学键断开,形成化学活性高的自由基;(2)以等离子体状态存在的自由基,迅速与超高分子量聚乙烯纤维表面以及表面涂敷的纳米材料表面的自由基结合,形成新的化学键;(3)超高分子量聚乙烯纤维表面以及表面涂敷的纳米材料表面受到轰击和刻蚀,微观结构由光滑变粗糙,有利于有机基体材料如树脂的渗透。
有益效果
(1)本发明处理过的超高分子量聚乙烯纤维与基体树脂的浸润速度得到提高,浸润量增大,浸润效果改善,使其复合材料的成型工艺性和整体综合性能更优化;
(2)该方法操作方便、工艺简单、加工速度快、处理效果好、成本低、不易引起环境污染,并且还可以降低能耗。
附图说明
图1为超高分子量聚乙烯纤维的表面处理方法的工艺流程图;
图2为经氦等离子体处理的超高分子量聚乙烯纤维的接触角照片;
图3为经氦等离子体处理的超高分子量聚乙烯纤维的红外图谱;
图4为经氧等离子体处理的超高分子量聚乙烯纤维的接触角照片
图5为经氧等离子体处理的超高分子量聚乙烯纤维的红外图谱;
图6为经氦等离子与氧等离子体处理的超高分子量聚乙烯纤维的红外差谱。
具体实施方式
下面结合具体实施例,进一步阐述本发明。应理解,这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解,在阅读了本发明讲授的内容之后,本领域技术人员可以对本发明作各种改动或修改,这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
氦等离子体处理纳米二氧化硅溶胶涂覆超高分子量聚乙烯纤维
如图1所示,将待处理的超高分子量聚乙烯纤维1沿溶胶浸轧装置2的花篮外圆线浸入百分比浓度为0.05%纳米二氧化硅溶胶,进行浸轧加工,而后超高分子量聚乙烯纤维被导入烘干装置3,在60℃下烘干并收集溶剂,然后超高分子量聚乙烯纤维1被引入等离子体喷嘴4的等离子体氛围区进行等离子体表面改性处理,纤维束上表面距喷嘴距离5MM,纤维束下表面距离喷嘴<20MM,功率40瓦,处理时间2秒,将处理后的超高分子量聚乙烯纤维1在自动收卷机5进行在线收卷,通过调节收卷轴的转速来调节超高分子量聚乙烯纤维的走线速度。根据不同加工工艺的需要,超高分子量聚乙烯纤维经过等离子体喷嘴的距离,速度进行相应的调整。
超高分子量聚乙烯纤维表面处理效果:接触角照片如图2,红外图谱如图3。
实施例2
氧等离子体处理纳米二氧化硅溶胶涂覆超高分子量聚乙烯纤维
如图1所示,将待处理的超高分子量聚乙烯纤维1沿溶胶浸轧装置2的花篮外圆线浸入百分比浓度为0.05%纳米二氧化硅溶胶,进行浸轧加工,而后超高分子量聚乙烯纤维被导入烘干装置3,在110℃下烘干并收集溶剂。然后超高分子量聚乙烯纤维1被引入等离子体喷嘴4的等离子体氛围区进行等离子体表面改性处理,纤维束上表面距喷嘴距离5MM,纤维束下表面距离喷嘴<20MM,功率40瓦,处理时间2秒,将处理后的超高分子量聚乙烯纤维1在自动收卷机5进行在线收卷,通过调节收卷轴的转速来调节碳纤维的走线速度。根据不同加工工艺的需要,超高分子量聚乙烯纤维经过等离子体喷嘴的距离,速度进行相应的调整。
超高分子量聚乙烯纤维表面处理效果:接触角照片如图4,红外图谱如图5。
Claims (2)
1.一种等离子体处理超高分子量聚乙烯纤维改性的方法,包括:
(1)将二氧化硅纳米颗粒经超声波震荡技术配制成质量百分比浓度为0.01~15%的有机溶剂或水的溶胶液;
(2)将上述溶胶液涂覆在超高分子量聚乙烯纤维表面,涂覆方法为喷涂或浸轧的方法;
(3)在10~150℃将超高分子量聚乙烯纤维烘干并收集溶剂,然后超高分子量聚乙烯纤维经等离子发生装置被引入等离子体氛围区进行等离子体表面改性,处理功率为10~15000w,时间为0.5~300秒;将处理后的超高分子量聚乙烯纤维在自动收卷机中进行在线收卷,通过调节收卷轴的速度来调节超高分子量聚乙烯纤维的走线速度;其中等离子体发生装置是各类等离子体发生器,等离子体氛围由等离子体发生器产生,并经由喷嘴机构喷射到常温、常压的大气环境中形成的等离子体氛围。
2.根据权利要求1所述的一种等离子体处理超高分子量聚乙烯纤维改性的方法,其特征在于:所述步骤(1)中的有机溶剂为己烷,异戊烷,正戊烷,石油醚,环己烷,异辛烷,三氟乙酸,三甲基戊烷,环戊烷,庚烷,丁基氯,丁酰氯,三氯乙烯,四氯化碳,三氯三氟代乙烷,甲苯,对二甲苯,氯苯,邻二氯苯,二乙醚,苯,异丁醇,二氯甲烷,二氯化乙烯,正丁醇,甲基异丁酮,四氢呋喃,乙酸乙酯,异丙醇,氯仿,甲基乙基酮,二恶烷,吡啶,丙酮,硝基甲烷,乙酸,乙腈,苯胺,二甲基甲酰胺,甲醇,乙二醇,正辛醇,正己醇,环己醇,正丙醇,二丙酮醇,二甲亚砜DMSO,二硫化碳,三氯乙烷,丁酮,乙二醇二甲醚,乙二醇一甲醚或乙酸丁酯。
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