CN111187449A - 一种适用于复合橡胶体系的碳纳米管功能化修饰方法 - Google Patents
一种适用于复合橡胶体系的碳纳米管功能化修饰方法 Download PDFInfo
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Abstract
本发明提出一种适用于复合橡胶体系的碳纳米管(CNTs)功能化修饰的方法。首先采用共价键改性方法—双氧水(H2O2)氧化处理CNTs,在CNTs表面氧化形成羟基官能团,然后采用硅烷偶联剂十七氟癸基三乙氧基硅烷(CF3(CF2)7CH2CH2Si(OC2H5)3)(AC‑FAS)与CNTs表面的羟基进行脱水缩合反应,将硅烷偶联剂成功引入到CNTs表面。接触角测试结果表明,采用本方法功能化的CNTs表面由亲水性转变为疏水性,从而有效改善其与橡胶基体的相容性。采用5phr该功能化碳纳米管制备炭黑/碳纳米管复合橡胶材料,发现力学性能优异,导热性能可提高11.9%。源于CNTs的分散性及其与基体之间的相容性得到很好的改善,且CNTs的分散有效促进炭黑的分散,两种填料在橡胶基体内构建了良好的填料网络。本发明提出的功能化修饰方法有效解决了碳纳米管在橡胶中的应用问题。
Description
技术领域
本发明属于材料科学领域,具体涉及一种适用于复合橡胶体系的碳纳米管(CNTs)功能化修饰方法。
背景技术
CNTs是由单层或多层石墨片卷曲而成的无缝纳米级管状壳层结构。其独特的结构和优异的力学性能、导热性能、导电性能,成为一种重要的填料。CNTs作为碳材料的同素异形体之一,因其高纵横比和良好的固有导热性能而被举证为提高聚合物导热性能的有效材料。人们在许多不同领域应用CNTs的兴趣日益浓厚,但CNTs本身易团聚,难分散性限制了CNTs的应用。与CNTs自身高性能相比,CNTs/聚合物复合材料性能远远低于CNTs自身。CNTs/聚合物复合材料的性能取决于CNTs在基体材料中的分散,以及CNTs和聚合物的界面融合性。由于CNTs是由非常稳定sp2杂化碳原子构成,因此,CNTs在化学性质方面是惰性的,并且其较强范德华力与周围基体材料很难发生相互作用,研究新的分散方法和功能化技术成为研究学者的关注焦点。针对CNTs在聚合物基体材料中应用难的问题,通过对CNTs进行共价键和非共价键改性,降低其范德华力,改善其在基体中的分散性以及界面黏附性。化学改性方法是CNTs表面的碳原子以共价键连接的方式接枝上特定的官能团,这些官能团可以连接在CNTs的末端或者管壁上。对CNTs管壁的功能化改性可以通过与一些高化学反应活性的分子反应来进行。
Kelly K F等人在Insight into the mechanism of sidewallfunctionalization of single-walled nanotubes中指出,他们已经成功实现通过氨基,烷基和羟基取代氟原子,完成了CNTs的侧壁氟化。有其他类似的方法,包括环加成,如Diels-Alder反应,氯化,溴化,催化加氢( S,Kulawik D,et al.A review ofprocedures of purification and chemical modification of carbon nanotubes withbromine[J].Fullerenes,Nanotubes and Carbon Nanostructures,2017,25(10):563-569.)。然而,上述研究制得的CNTs方法非常复杂,并且制得的CNTs不利于所填充的聚合物导热性能的提高。
缺陷官能化是CNTs共价功能化的另一种方法。(Zakharychev E A,Razov E N,Semchikov Y D,et al.The influence of functionalization time of carbonnanotube on the mechanical properties of the epoxy composites[J].Journal ofComposite Materials,2017,51(12):1693-1701.)该过程利用CNTs上的缺陷位点进行化学反应接枝新的官能团。然而,这种方法会使CNTs被碎裂成较小的碎片,降低了CNTs的机械性能,导致所填充聚合物的力学性能严重下降。同时,还会导致CNTs中π电子的破坏,缺陷位置增多,造成导热声子的散射,CNTs本身导热能力严重下降。
中国专利(CN106185861A)公布了一种新的氧化体系功能化CNTs的方法,该专利也是一种缺陷官能化方法。该专利通过加入强氧化剂浓硫酸H2SO4对CNTs进行氧化,加入强氧化剂KMnO4在CNTs的侧壁和端口处产生缺陷,通过与羧酸(-COOH)或羟基(-OH)官能团的化学反应来稳定由氧化剂所产生的CNTs上的缺陷。然而,该专利用于CNTs功能化的浓酸以及强氧化剂会对环境造成不利影响且浓酸会破坏CNTs的结构。
到目前为止聚合物应用中所涉及的碳纳米管功能化方法,大多针对树脂材料,如中国专利(CN107177165A)。且功能化对于聚合物基体的导热性能利弊说法不一。同一种功能化方法,有的有利于性能提高,有的不利于性能提高,原因在于不同基体材料,与碳纳米管的相互作用不同,而且基体内不同填料间相互影响。近年来碳纳米管在绿色轮胎和高性能橡胶制品中的应用成为热点,然而由于碳纳米管的易团聚及其与橡胶基体相容性差的原因,导致碳纳米管的分散和界面难以掌控,使其在橡胶中的应用受限。而上述方法均不适用于CNTs在橡胶中的应用,尤其是提高橡胶复合材料的导热性能。对于橡胶制品,高温会导致降解等破坏性变化,对于轮胎甚至引发爆胎等安全事故,导热性能至关重要。
中国专利(CN 109651622 A)公开了一种用于压敏胶体系的CNTs功能化修饰方法,目的是提高压敏胶保护膜的抗静电和导电效果。该专利使用化学方法将含有活性基团的有机硅大分子接枝到CNTs上,以促进CNTs在溶剂中的分散性。但是该专利针对压敏胶的抗静电效果,而且该功能化修饰方法仅适用于长度范围在5-10μm的CNTs,对于更长的CNTs难以分散均匀。综上所述,针对橡胶行业开发一种新的功能化修饰碳纳米管的方法迫在眉睫。
发明内容
本发明所要解决的技术问题是提供一种CNTs的功能化修饰方法,达到有效改善其在橡胶基体中的分散和界面粘附的目的,同时还能促进橡胶的传统填料CB的分散,如此最终在保证橡胶复合材料力学性能的前提下有效提高橡胶复合材料的导热性能,解决CNTs在橡胶中的应用瓶颈问题。
本发明所涉及的功能化修饰CNTs的方法原料安全简单,操作方便。本发明采取的技术方案包括下列步骤:
(1)按照1:1的比例制备H2O2和H2O混合溶液。
(2)将原始CNTs分散在(1)中制备的H2O2和H2O混合溶液中,浓度0.005g/ml。
(3)将(2)制得的混合物放入水浴中进行超声处理,水浴温度为80℃,超声时间1小时。超声结束后,将混合物用蒸馏水洗涤数次,放入50℃-60℃真空干燥箱中干燥48h以上,制得羟基化CNTs。
(4)分别制备体积分数范围为0%-2%,2%-4%,4%-6%,6%-8%的AC-FAS和乙醇混合溶液,然后用冰醋酸将混合溶液的pH值调整到3.5。
(5)将羟基化CNTs添加到(4)制得的混合溶液中配置成溶质质量分数1.7%的羟基化CNTs溶液,将其进行混合磁搅拌,搅拌时间2小时,搅拌温度40℃。然后将搅拌后的CNTs从上清液中过滤分离出来,用乙醇进行洗涤,次数至少5次。将洗涤干净后的CNTs放入真空干燥箱,干燥温度50℃-60℃,干燥时间至少48h。
步骤(2)中的原始CNTs由CCVD法制备,但不限于此,同时也包括单壁CNTs、双壁CNTs、多壁CNTs、短直径CNTs或者是这些的混合物。
步骤(3)中H2O2在超声条件能够分解生成羟基自由基(HO·),由于羟基自由基具有较强的亲电加成和氧化性能,羟基自由基与CNTs接触时,会攻击CNTs表面的不饱和双键,发生亲电加成反应,使得羟基连接在CNTs表面的碳原子上,导致CNTs表面的羟基含量大大提升,制得羟基化CNTs。
步骤(5)采用硅烷偶联剂十七氟癸基三乙氧基硅烷(CF3(CF2)7CH2CH2Si(OC2H5)3)(AC-FAS)与CNTs表面的羟基进行脱水缩合反应。在羟基化CNTs表面连接上硅烷偶联剂。硅烷偶联剂的通式为Y(CH2)nSiX3,而其中n=0、1、2、3,X表示可水解的基团,Y则表示不参与水解的有机官能团。通常X为氯基、甲氧基、乙氧基、乙酰氧基等基团,这些基团在一定条件下可发生水解反应,生成硅醇(Si(OH)3)。这些基团可与CNTs表面的大量羟基发生脱水缩合反应形成硅氧烷((R2SiO)x)。而Y通常为乙烯基、环氧基、氨基、甲基丙烯酰氧基等,而这些基团具有亲油性。正是因为在CNTs上引入了这些亲油性的基团,使得CNTs由亲水性转变为亲油性,因此CNTs与各类聚合物具有良好的相容性,可以大大提高CNTs在聚合物中的分散性。
通过上述改性方法制备得到的CNTs,具有如下特点:羟基化CNTs共价修饰是通过对管壁缺陷或管壁进行化学修饰来实现CNTs的功能化,使其表面羟基含量增加。采用AC-FAS与CNTs表面羟基进行脱水缩合,不仅能够提高CNTs在橡胶基体中的分散,同时还增强了CNTs与橡胶基体间的界面作用。
与现有技术相比,本发明主要存在以下优点:
1、连接在CNTs表面羟基上的乙烯基、环氧基、氨基、甲基丙烯酰氧基等亲油基团能够显著提高CNTs在橡胶基体内的分散性及其与橡胶基体之间的相容性。具体见后面的实施例。
2、通过本发明功能化修饰的CNTs,其长度和原始CNTs几乎一样,也就说明,改性处理的过程并不会对CNTs的结构造成破坏,不会减短CNTs的长度,见电镜图。CNTs经过功能化修饰后,仍可保持着原始CNTs的优异特性。
3、本发明涉及的功能化修饰方法适用于CNTs的长度达100um。
4、通过本发明功能化修饰的CNTs,不仅其自身在橡胶基体内的分散性得到有效改善,也促进了橡胶基体内的传统填料-炭黑(CB)的分散,CNTs和CB二者构建了良好的填料网络,而这种填料网络使得橡胶复合材料获得优异的性能。解决了CNTs在橡胶中的应用瓶颈问题。
附图说明
图1为本发明中原始CNTs和经过第一次双氧水表面改性后的羟基化CNTs的傅里叶红外光谱图。
图2为本发明中的羟基化CNTs和AC-FAS改性羟基化CNTs的傅里叶红外光谱图。
图3为本发明中的原始CNTs和AC-FAS改性羟基化CNTs的接触角结果图。
图4为本发明中的原始CNTs和AC-FAS改性羟基化CNTs在乙醇溶液中的透射电镜图。
图5为本发明中的原始CNTs和AC-FAS改性羟基化CNTs与CB混合填充天然橡胶复合材料透射电镜图。
具体实施方式
本发明通过下列实施例作进一步说明,根据下列实施例,可以更好地理解本发明。然而,本领域的技术人员容易理解,实施例所描述的具体的体积比,填充比例及其结果仅用于说明本发明,而不应当也不会限制权利要求书中所详细描述的本发明。
实施例1
功能化修饰CNTs的方法,包括以下步骤。
(1)将2.0g CNTs分散在200ml:200ml的H2O2和H2O混合溶液中。在80℃的水浴中超声处理1小时。
(2)将上述处理过的CNTs用蒸馏水洗涤数次,在50℃真空干燥箱中干燥48小时,制得羟基化CNTs。
(3)制备体积分数为1.8%的AC-FAS乙醇溶液,在20℃-25℃温度范围内迅速混合。然后用冰醋酸调节溶液的pH值为3.5。
(4)将步骤(2)制备的羟基化CNTs添加到步骤(3)制备的AC-FAS乙醇溶液中,配置成溶质质量分数为1.7%的混合溶液,40℃下混合磁搅拌2小时。然后将改性后CNTs从上清液中过滤分离出来,用乙醇至少洗涤5次。洗涤干净后,真空干燥箱60℃条件下干燥48h,制得AC-FAS改性羟基CNTs。
实施例2
功能化修饰CNTs的方法,包括以下步骤。
(1)将2.0g CNTs分散在200ml:200ml的H2O2和H2O混合溶液中。在80℃的水浴中超声处理1小时。
(2)将上述处理过的CNTs用蒸馏水洗涤数次,在60℃真空干燥箱中干燥48小时,制得羟基化CNTs。
(3)制备体积分数为3.2%的AC-FAS乙醇溶液,在20℃-25℃温度范围内迅速混合。然后用冰醋酸调节溶液的pH值为3.5。
(4)将步骤(2)制备的羟基化CNTs添加到步骤(3)制备的AC-FAS乙醇溶液中,配置成溶质质量分数为1.7%的混合溶液,40℃下混合磁搅拌2小时。然后将改性后CNTs从上清液中过滤分离出来,用乙醇至少洗涤5次。洗涤干净后,真空干燥箱60℃条件下干燥48h,制得AC-FAS改性羟基CNTs。
实施例3
功能化修饰CNTs的方法,包括以下步骤。
(1)将2.0g CNTs分散在200ml:200ml的H2O2和H2O混合溶液中。在80℃的水浴中超声处理1小时。
(2)将上述处理过的CNTs用蒸馏水洗涤数次,在60℃真空干燥箱中干燥48小时,制得羟基化CNTs。
(3)制备体积分数为4.7%的AC-FAS乙醇溶液,在20℃-25℃温度范围内迅速混合。然后用冰醋酸调节溶液的pH值为3.5。
(4)将步骤(2)制备的羟基化CNTs添加到步骤(3)制备的AC-FAS乙醇溶液中,配置成溶质质量分数为1.7%的混合溶液,40℃下混合磁搅拌2小时。然后将改性后CNTs从上清液中过滤分离出来,用乙醇至少洗涤5次。洗涤干净后,真空干燥箱50℃条件下干燥50h,制得AC-FAS改性羟基CNTs。
实施例4
功能化修饰CNTs的方法,包括以下步骤。
(1)将2.0g CNTs分散在200ml:200ml的H2O2和H2O混合溶液中。在80℃的水浴中超声处理1小时。
(2)将上述处理过的CNTs用蒸馏水洗涤数次,在60℃真空干燥箱中干燥48小时,制得羟基化CNTs。
(3)制备体积分数为6.1%的AC-FAS乙醇溶液,在20℃-25℃温度范围内迅速混合。然后用冰醋酸调节溶液的pH值为3.5。
(4)将步骤(2)制备的羟基化CNTs添加到步骤(3)制备的AC-FAS乙醇溶液中,配置成溶质质量分数为1.7%的混合溶液,40℃下混合磁搅拌2小时。然后将改性后CNTs从上清液中过滤分离出来,用乙醇至少洗涤5次。洗涤干净后,真空干燥箱50℃条件下干燥48h,制得AC-FAS改性羟基CNTs。
图1为原始CNTs和羟基化CNTs的傅里叶红外光谱图(FT-IR)。FT-IR表明,原始CNTs表面成功引入了羟基官能团。
图2为本发明中的羟基化CNTs和实施例2制得的AC-FAS改性羟基化CNTs的傅里叶红外光谱图。约在3443cm-1处为CNTs表面的羟基(-OH)特征吸收峰,但经过AC-FAS处理过的CNTs羟基峰明显要比原始CNTs的羟基峰小。说明AC-FAS与羟基化CNTs表面的羟基反应,使其数量减少。在1054cm-1处为C-O-Si吸收峰,在883cm-1处的Si-C吸收峰,证明FAS中的亲油长链成功引入到CNTs的表面。
图3为本发明中的原始CNTs和实施例2制得的AC-FAS改性羟基化CNTs的接触角结果图。可以看出图(a)中原始CNTs呈现亲水特性;而图(b)中FAS改性羟基化CNTs呈现疏水特性,说明FAS中的亲油长链成功接枝到羟基化碳纳米管表面。
图4为本发明中的原始CNTs和实施例2制得的AC-FAS改性羟基化CNTs在乙醇溶液中的透射电镜图。结果显示,图(b)中AC-FAS改性羟基CNTs的分散情况明显优于图(a)中未改性的原始CNTs,改性后CNTs甚至成单根呈现。
将5phr本实施例2制得的AC-FAS改性羟基CNTs、羟基CNTs和原始未经处理的CNTs加入到橡胶中,30phr炭黑,制备CNTs/CB/NR复合材料。制备方法如下:将天然橡胶薄通塑炼数次成片状,在Haake密炼机中进行橡胶与小料的共混,设定初始温度为70℃,转速70r/min,混炼共混时间设定为10min。具体为,先将天然橡胶加入模腔内,混炼2min;然后加入硬脂酸、氧化锌、防老剂、抗氧剂、微晶蜡,共混2min;再将CB和CNTs分成两份加入,共混2min;再加剩下的CB和CNTs,共混4min,排胶。混合胶料凉至室温,在双辊开炼机上薄通数次,加入橡胶硫化促进剂CBS和硫化剂S,割刀,打5次三角包,调辊距至1.8mm下片,制备成混炼胶。
混炼胶的硫化特性按照GB/T 16584-1996和ISO 6502-1991进行测试。混炼胶在MDR2000无转子流变仪中,温度150℃来测定硫化时间。橡胶硫化机中采用无转子流变仪测定的t90+2min,硫化温度是150℃,硫化压力是15.0MPa,硫化样品约为2mm的薄片,停放至少6个小时进行后续性能测试。
硫化胶的导热性能测试采用DTC-300导热仪。测试试样为圆形,直径约50.0mm,厚度约1.9mm。
原始CNTs、羟基化CNTs和AC-FAS改性羟基CNTs填充的复合橡胶的导热系数与导热系数提高率见下表:
可见,经过AC-FAS功能化修饰后,填充胶的导热系数比羟基CNTs填充胶高很多,尤其是高温导热系数,相对于羟基CNTs提高了9.6%,相对于原始CNTs提高了11.9%。
硫化胶的力学性能测试按照GB/T-529-2009标准进行。将试样裁成哑铃形状,在德国Zwick公司生产的Z005型万能电子拉力试验机上,以500mm/min的速度进行测试。每个样品测试5个样条,取中值。
原始CNTs、羟基化CNTs和AC-FAS改性羟基CNTs填充的复合橡胶的力学性能见下表:
可见,相对于羟基化CNTs和原始CNTs的填充胶,经过AC-FAS功能化修饰后CNTs填充胶力学性能依旧优异。
图5为本发明中的原始CNTs和AC-FAS改性羟基CNTs与CB混合填充天然橡胶复合材料透射电镜图。图(a)原始CNTs填充的复合橡胶中,填料团聚现象明显。图(b)中,AC-FAS改性羟基CNTs在橡胶中分散更均匀,且在一定程度上减少CB的聚集,形成了更好的三维填料网络,从而复合橡胶的性能得到提高。
上面结合具体实施例对本发明进行了示例性的描述,显然本发明的实现并不受上述方式的限制,只要采用了本发明的方法构思和技术方案进行的各种改进,或未经改进将本发明的构思和技术方案直接应用于其它场合的,均在本发明的保护范围内。
Claims (7)
1.一种适用于复合橡胶体系的碳纳米管功能化修饰方法,其特征在于,包括步骤:
1)将CNTs分散在H2O2和H2O制成的混合溶液中。
2)将步骤1)制得的混合物放入水浴中进行超声处理,之后将混合物用蒸馏水洗涤数次,直至洗去表面的杂质。再在真空干燥箱中干燥,制得羟基化碳纳米管。
3)制备AC-FAS和乙醇的混合溶液,然后用冰醋酸等酸类物质将AC-FAS和乙醇的混合溶液的pH值调整到3.5。
4)将步骤2)制得的羟基化碳纳米管加入到步骤3)制备的AC-FAS和乙醇的混合溶液中,配置成溶质为羟基化碳纳米管的溶液。对配置好的溶液进行混合磁搅拌。
5)将步骤4)制得的碳纳米管从上清液中过滤分离出来,用乙醇洗涤至少5次。洗涤干净后,将其置于真空干燥箱干燥,制得FAS功能化羟基碳纳米管。
2.根据权利要求1所述的改性方法,其特征在于,碳纳米管包括单壁碳纳米管、双壁碳纳米管、多壁碳纳米管、短直径碳纳米管或者是这些的混合物。
3.根据权利要求1所述的改性方法,其特征在于,步骤1)中,H2O2和H2O混合溶液的体积比例为1:1。CNTs在步骤1)制得的混合水溶液中的浓度为0.005g/ml。
4.根据权利要求1所述的改性方法,其特征在于,步骤2)中,制备CNTs与H2O2混合水溶液的CNTs的分散条件是玻璃棒先进行初步搅拌,目的使CNTs与混合溶液充分接触。超声水浴温度为80℃,超声时间为1小时,干燥箱内干燥温度为50℃-60℃,干燥时间为48小时以上。
5.根据权利要求1所述的改性方法,其特征在于,步骤3)中,AC-FAS与乙醇混合溶液的混合条件为20℃-25℃温度范围下迅速混合,AC-FAS乙醇混合溶液的体积分数范围为0%-2%,2%-4%,4%-6%,6%-8%。
6.根据权利要求1所述的改性方法,其特征在于,步骤4)中,混合磁搅拌的搅拌时间为2小时,搅拌温度为40℃。
7.根据权利要求1所述的改性方法,其特征在于,步骤5)中,干燥箱内干燥温度为50℃-60℃,干燥时间为48小时以上。
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