CN112479185A - 一种聚单宁酸氨酯稳定的碳纳米管水分散体及其制备方法 - Google Patents
一种聚单宁酸氨酯稳定的碳纳米管水分散体及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种聚单宁酸氨酯稳定的碳纳米管水分散体及其制备方法,制备方法为:以单宁酸和芳香族异氰酸酯类单体为原料,逐步聚合成聚单宁酸氨酯;然后加入碱的水溶液中和聚单宁酸氨酯中未反应的酚羟基,得到水溶性聚单宁酸氨酯。将其用作超分散剂分散碳纳米管,聚单宁酸氨酯中含有的芳香环能够通过π‑π相互作用锚定在碳纳米管表面,促进碳纳米管分散,同时高分子量的聚单宁酸氨酯带来的空间位阻效应避免了碳纳米管的二次团聚;水溶性聚单宁酸氨酯的结构特性和自身的体积位阻效应,实现了碳纳米管在水体系中的高度均匀分散,可应用于导电、抗静电、电磁屏蔽等领域。且本方法工艺简单、易于控制,适合于工业化生产。
Description
技术领域
本发明属于高分子材料的制备领域,具体涉及一种聚单宁酸氨酯稳定的碳纳米管水分散体及其制备方法。
背景技术
近年来,碳纳米管(CNT)由于其优异的电性能、重量轻、机械性能好等优点能够以比球形颗粒低得多的浓度在聚合物基体中形成导电网络,在电子元件领域得到了广泛的应用。然而碳纳米管具有高纵横比和大比表面积的特性,具有极强的疏水性,易于在水中聚集和沉积。所以,对碳纳米管的聚集体打开并保持稳定的研究具有极其重要的意义。
超分散剂是一种新型、高效的聚合物型分散剂,在分散固体颗粒时,具有显著的空间屏蔽作用和电斥力,可以快速充分地润湿碳纳米管,大幅度提高分散体系中的固体颗粒含量,使得分散体系更加均匀,且稳定性良好。
Wang等(Wang T,Geng H-Z.Tannic acid modified graphene/CNT three-dimensional conductive network for preparing high-performance transparentflexible heaters[J].Journal of Colloid and Interface Science,2020,577.)具体步骤为:单壁碳纳米管和单宁酸以质量比1:2分散在去离子水中,搅拌、离心、洗涤和冷冻干燥获得单宁酸功能化的碳纳米管分散液(TCNTs)。随后,用十二烷基苯磺酸钠(SDBS)作为分散剂将得到的TCNTs粉体分散在去离子水中;继而超声、离心,仔细收集80%上清液。其工艺繁琐,不易于工业化生产。该单宁酸功能化的碳纳米管冻干后再分散,易团聚且无法做到在水中快速分散,最终应用效果大大减弱。而高分子量的聚单宁酸氨酯带来的空间位阻效应避免了碳纳米管的二次团聚。
Tan等(Tan Kan,Luo Jing.Tannic acid functionalized UV-curable carbonnanotube:Effective reinforcement of acrylated epoxidized soybean oil coating[J].Progress in Organic Coatings,2019,130:214-220.)以单宁酸和甲基丙烯酸缩水甘油酯为原料,磷酸三苯酯为催化剂,对苯二酚为抑制剂,采用开环加成反应合成光敏单宁酸,经沉淀、洗涤、干燥后用于分散多壁碳纳米管。继而超声、离心、干燥后得到光敏化多壁碳纳米管。将其在四氢呋喃中超声处理、高度分散各2h,以实现均匀分散。整体操作步骤繁琐,不易于工业化生产。
CN 108192137A公布了一种用做橡胶填料高分散碳纳米管的制备方法,采用强氧化性酸和多元胺对碳纳米管表面进行胺基化处理,而后采用不饱和乙烯基类酰胺极性单体和芳基乙烯类单体进行原位聚合,在碳纳米管表面形成一层具有聚苯乙烯分子结构特点的包覆层来制备高分散型碳纳米管。此工艺中使用强氧化性酸,难以除去,且聚苯乙烯包覆层只适用于在油相中分散碳纳米管,应用范围受限。
发明内容
针对现有技术的不足,本发明的目的是提供一种聚单宁酸氨酯稳定的碳纳米管水分散体及其制备方法,在第一步聚合物的合成后,不需要提纯、干燥等步骤直接进行下一步的共混。制备的聚单宁酸氨酯作为超分散剂,可用于不同体系中分散碳纳米管,得到高度分散的碳纳米管。且此工艺简单,操作易行,反应条件温和易于控制,成本低廉,易于工业化。
本申请专利与以往报道对比,创新性在于合成高分子量的聚单宁酸氨酯,充分利用了单宁酸和芳香族二异氰酸酯的芳香环通过π-π相互作用锚定在碳纳米管表面促进其分散,同时高分子量的聚单宁酸氨酯带来的空间位阻效应避免了碳纳米管的二次团聚,水溶性聚单宁酸氨酯的结构特性和自身的体积位阻效应,实现了碳纳米管在水体系中的高度均匀分散。
为实现上述目的,本发明采用的技术方案为:
一种聚单宁酸氨酯稳定的碳纳米管水分散体的制备方法,包括以下步骤:
S1、将单宁酸溶解在有机溶剂中,然后向有机溶剂中加入芳香族二异氰酸酯类单体,单宁酸的酚羟基和芳香族二异氰酸酯类单体的异氰酸酯基团进行聚合反应,生成高分子量(用注射器从反应体系中取样,采用GPC测试聚合物的分子量)的聚单宁酸氨酯;然后加入碱的水溶液中和聚单宁酸氨酯中未反应的酚羟基,得到水溶性聚单宁酸氨酯。值得注意的是:芳香族二异氰酸酯类单体需要缓慢加入,可通过注射器或者蠕动泵滴加到反应体系中。聚合反应的温度和时间不做具体的限定,可以根据所需聚单宁酸氨酯的分子量大小进行调整,在本发明的一些实施例中优选的聚合温度为40-80℃,比如40℃、60℃、65℃或80℃,反应时间为2-3h。而其中的加工参数也属于逐步聚合反应的常规调整,本领域技术人员可以根据需要进行调整,这里也不再具体的限定。
S2、将碳纳米管与水溶性聚单宁酸氨酯、去离子水混合均匀后,经分散即得到聚单宁酸氨酯稳定的碳纳米管水分散体。
进一步的,步骤S1中,所述单宁酸在使用前需真空干燥,以去除水分。
进一步的,步骤S1中,所述芳香族二异氰酸酯类单体的分子结构中同时含有苯环和异氰酸酯基团;所述碱的水溶液中碱为氢氧化钠、氢氧化钾、氢氧化钙、氢氧化钡中的一种。更进一步的,所述芳香族二异氰酸酯类单体优选甲苯二异氰酸酯或二苯基甲烷二异氰酸酯中的至少一种。
进一步的,步骤S1中,所述单宁酸、芳香族二异氰酸酯类单体、碱的摩尔比为1:(0.5~1.0):(22.5~23)。
进一步的,步骤S2中分散采用高速分散,高速分散的速率为10000~20000rpm,时间为3~5min。
进一步的,所述碳纳米管种类不设限制。步骤S2中所用碳纳米管直径为10~20nm,长度为20~100μm。所述碳纳米管与聚单宁酸氨酯的质量比为1:10~10:1。
本发明中优选上述范围是由于这样反应更加有效及快速,且使得药品得到最大程度的利用。
本发明的另一个目的是提供上述制备方法制得的聚单宁酸氨酯稳定的碳纳米管水分散体。利用单宁酸和芳香族二异氰酸酯的芳香环通过π-π相互作用锚定在碳纳米管表面促进其分散,同时高分子量的聚单宁酸氨酯带来的空间位阻效应避免了碳纳米管的二次团聚,水溶性聚单宁酸氨酯结构实现了碳纳米管在水体系中的高度均匀分散。
与现有技术相比,本发明具有以下有益效果:
(1)本发明在第一步由单宁酸和芳香族二异氰酸酯类单体聚合生成聚合物后,不需要沉降、干燥等步骤,直接进行下一步的共混,操作简易,适于工业化生产。
(2)本发明所用的单宁酸和芳香族二异氰酸酯类单体均来源于天然植物,价格低廉,且绿色环保,具有商业价值。此外,本发明制得的碳纳米管水分散体具有浓度高、分散度高和高稳定性的特点,可应用于导电,抗静电,抗电磁屏蔽,荧光标记等领域。
(3)碳纳米管是由多个苯环结构衔接而成的管状物,化学键完全由sp2碳键组成。而聚单宁酸氨酯的单体单宁酸本身含有10个苯环、芳香族二异氰酸酯类单体也含有苯环。碳纳米管和聚单宁酸氨酯在结构上存在相似性。与单宁酸比较,聚单宁酸氨酯增加分子量、扩大表面积、增大了空间位阻;芳香环通过π-π相互作用更易于锚定在碳纳米管结构上,促进了碳纳米管在水中的分散性,避免了管与管之间的团聚。这样的结构不仅可以形成稳定的导电网络,还可以提高对基体的附着力。当与碳纳米管混合时,聚合物的疏水性部分将与碳纳米管的侧壁相互作用,使其亲水性部分延伸到水中,水溶性聚单宁酸氨酯促进碳纳米管在水中的分散,获得均匀分散的分散体。
(4)通过聚合物包裹以促进其分散的碳纳米管非共价功能化优于有机功能化,因为原始sp2杂化状态得以保存。与含有亲水和疏水结构的聚单宁酸氨酯构建的非共价相互作用可以保持碳纳米管的碳主链完整,不破坏固有电子管的结构和电子性质。
附图说明
图1为实施例1中碳纳米管水分散体在不同放大倍数下的透射电镜图;
图2为实施例1中加入聚单宁酸氨酯前后的碳纳米管的粒径分布图;
图3为实施例1中单宁酸、聚单宁酸氨酯的红外光谱图;
图4为实施例1中碳纳米管水分散体的紫外光谱图
具体实施方式
为了便于理解本发明,下面将结合具体的实施例对本发明进行更全面的描述。但是,本发明可以以许多不同的形式来实现,并不限于本文所描述的实施方式。相反地,提供这些实施方式的目的是使对本发明的公开内容理解的更加透彻全面。
除非另有定义,本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施方式的目的,不是旨在于限制本发明。
实施例1
取真空干燥后的单宁酸2g于三口烧瓶中,加入10g N,N-二甲基甲酰胺,磁力搅拌使二者充分混匀成均一溶液。然后通氮气,冷凝、在油浴中加热至40℃;利用注射器向三口瓶内缓慢滴加甲苯二异氰酸酯。单宁酸的酚羟基和芳香族二异氰酸酯类单体的异氰酸酯基团相互反应而逐步增长成多聚体,当达到所需的聚合物分子量(7.65×103)时,终止反应,加入氢氧化钠的水溶液中和聚单宁酸氨酯中未反应的酚羟基,得到水溶性聚单宁酸氨酯。其中,单宁酸、甲苯二异氰酸酯和氢氧化钠的摩尔比为1:0.5:23.5。称取1g碳纳米管,加入5.7g的聚单宁酸氨酯、93.3g去离子水,共混、然后在10000rpm下高速分散5min后得到固含量1%的碳纳米管水分散体。
测试例
图1为实施例1中碳纳米管水分散体在不同放大倍数下的透射电镜图,从图中可以看出碳纳米管为长管状结构,直径约为10~15nm。
图2中a为实施例1中碳纳米管的粒径分布图,图2中b为实施例1中所得聚单宁酸氨酯加入碳纳米管后的粒径分布图,从图中可以看出:碳纳米管的粒径约为730.7nm,加过聚单宁酸氨酯后碳纳米管的粒径约为91.8nm。可以看出:聚单宁酸氨酯的加入,使得碳纳米管的粒径尺寸明显变小。这是因为聚单宁酸氨酯可以有效减少碳纳米管的团聚。
图3为实施例1中单宁酸、聚单宁酸氨酯的红外光谱图,图中可以看出:与纯单宁酸的红外光图谱相比,聚单宁酸氨酯在3450和1656cm-1处出现了新峰,分别表示亚氨基和酯基。从而可以得出:单宁酸和异氰酸酯基团逐步聚合生成聚单宁酸氨酯。
以实施例1制得的聚单宁酸氨酯为分散剂,将其加入碳纳米管中,配制浓度为25mg/L的碳纳米管水分散体,其紫外光谱图如图4所示,可知,在224nm处的吸光度为1.025。由此可以得出该分散剂所能稳定的颗粒数目较多,分散性能较好。
取0.3g碳纳米管(XFQ041)加入到30mL去离子水中,在12000rpm下高速分散3min,得溶液A;同时,取0.3g碳纳米管(XFQ041)和实施例1制备的聚单宁酸氨酯(0.06g、0.18g、0.3g)一同加入到30mL去离子水中,在12000rpm下高速分散3min,分别得溶液B(20wt%)、C(60wt%)、D(100wt%)。将溶液A、B、C、D静置24h,观察其变化(如下表1所示)。再分别取4mL溶液A、B、C、D,在5000r/min下离心10min,观察离心之后的状态,测其离心稳定性(如下表2)。
表1
表2
从上表1、2可看出,未添加分散剂的溶液,静置一段时间后,碳纳米管沉积到样品瓶底部,呈明显的分层状态,而不能分散在水中。对其进行离心,发现碳纳米管全部沉积到离心管底部。而随着分散剂质量的增加,碳纳米管可以逐渐分散在水中,当分散剂的质量分数达到60wt%时,无分层现象,且离心管底部只沉积了极少量的碳纳米管。当分散剂的质量分数达到100wt%时,对其进行离心稳定性测试,发现碳纳米管全部分散在水中。因此,进一步证明聚单宁酸氨酯可以有效减少碳纳米管的团聚,从而达到分散碳纳米管的效果。
实施例2
取真空干燥后的单宁酸3g于三口烧瓶中,加入18g丙酮,磁力搅拌使二者充分混匀成均一溶液。然后通氮气,冷凝、在油浴中加热至50℃;利用蠕动泵向三口瓶内缓慢滴加二苯基甲烷二异氰酸酯。单宁酸的酚羟基和芳香族二异氰酸酯类单体的异氰酸酯基团相互反应而逐步增长成多聚体,当达到所需的聚合物分子量(8.5×103)时,终止反应,加入氢氧化钾中和聚单宁酸氨酯中未反应的酚羟基,得到水溶性聚单宁酸氨酯。其中,单宁酸、二苯基甲烷二异氰酸酯和氢氧化钾的摩尔比为1:0.6:23.4。称取1g碳纳米管,加入6.7g的聚单宁酸氨酯、42.3g去离子水,共混,然后在11000rpm下高速分散5min后得到固含量2%的碳纳米管分散液。
实施例3
取真空干燥后的单宁酸4g于三口烧瓶中,加入28g二甲基亚砜,磁力搅拌使二者充分混匀成均一溶液。然后通氮气,冷凝、在油浴中加热至60℃;利用注射器向三口瓶内缓慢滴加甲苯二异氰酸酯。单宁酸的酚羟基和芳香族二异氰酸酯类单体的异氰酸酯基团相互反应而逐步增长成多聚体,当达到所需的聚合物分子量(1.02×104)时,终止反应,加入氢氧化钡中和聚单宁酸氨酯中未反应的酚羟基,得到水溶性聚单宁酸氨酯。其中,单宁酸、甲苯二异氰酸酯和氢氧化钡的摩尔比为1:0.7:23.3。称取1g碳纳米管,加入7.5g的聚单宁酸氨酯、24.8g去离子水,共混,然后在12000rpm下高速分散4min后得到固含量3%的碳纳米管分散液。
实施例4
取真空干燥后的单宁酸5g于三口烧瓶中,加入40g环丁砜,磁力搅拌使二者充分混匀成均一溶液。然后通氮气,冷凝、在油浴中加热至65℃;利用蠕动泵向三口瓶内缓慢滴加二苯基甲烷二异氰酸酯。单宁酸的酚羟基和芳香族二异氰酸酯类单体的异氰酸酯基团相互反应而逐步增长成多聚体,当达到所需的聚合物分子量(1.6×104)时,终止反应,加入氢氧化钙中和聚单宁酸氨酯中未反应的酚羟基,得到水溶性聚单宁酸氨酯。其中,单宁酸、二苯基甲烷二异氰酸酯和氢氧化钙的摩尔比为1:0.8:23.2。称取1g碳纳米管,加入8.3g的聚单宁酸氨酯、90.7g去离子水,共混,然后在13000rpm下高速分散4min后得到固含量1%的碳纳米管分散液。
实施例5
取真空干燥后的单宁酸6g于三口烧瓶中,加入54g苯甲醚,磁力搅拌使二者充分混匀成均一溶液。然后通氮气,冷凝、在油浴中加热至70℃;利用注射器向三口瓶内缓慢滴加甲苯二异氰酸酯。单宁酸的酚羟基和芳香族二异氰酸酯类单体的异氰酸酯基团相互反应而逐步增长成多聚体,当达到所需的聚合物分子量(2.1×104)时,终止反应,加入氢氧化钠中和聚单宁酸氨酯中未反应的酚羟基,得到水溶性聚单宁酸氨酯。其中,单宁酸、甲苯二异氰酸酯和氢氧化钠的摩尔比为1:0.9:23.1。称取1g碳纳米管,加入9.1g的聚单宁酸氨酯、39.9g去离子水,共混,然后在15000rpm下高速分散3min后得到固含量2%的碳纳米管分散液。
实施例6
取真空干燥后的单宁酸7g于三口烧瓶中,加入70g N,N-二甲基甲酰胺,磁力搅拌使二者充分混匀成均一溶液。然后通氮气,冷凝、在油浴中加热至80℃;利用蠕动泵向三口瓶内缓慢滴加二苯基甲烷二异氰酸酯。单宁酸的酚羟基和芳香族二异氰酸酯类单体的相互反应而逐步增长成多聚体,当达到所需的聚合物分子量(2.5×104)时,终止反应,加入氢氧化钾中和聚单宁酸氨酯中未反应的酚羟基,得到水溶性聚单宁酸氨酯。其中,单宁酸、二苯基甲烷二异氰酸酯和氢氧化钾的摩尔比为1:1:23。称取1g碳纳米管,加入10g的聚单宁酸氨酯、22.3g去离子水,共混,然后在20000rpm下高速分散3min后得到固含量3%的碳纳米管分散液。
以上所述实施例的各技术特征可以进行任意的组合,为使描述简洁,未对上述实施例中的各个技术特征所有可能的组合都进行描述,然而,只要这些技术特征的组合不存在矛盾,都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本发明的几种实施方式,其描述较为具体和详细,但并不能因此而理解为对发明专利范围的限制。应当指出的是,对于本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进,这些都属于本发明的保护范围。因此,本发明专利的保护范围应以所附权利要求为准。
Claims (7)
1.一种聚单宁酸氨酯稳定的碳纳米管水分散体的制备方法,其特征在于:包括以下步骤:
S1、将单宁酸溶解在有机溶剂中,然后向有机溶剂中加入芳香族二异氰酸酯类单体,单宁酸的酚羟基和芳香族二异氰酸酯类单体的异氰酸酯基团进行聚合反应,生成聚单宁酸氨酯;然后向聚单宁酸氨酯中加入碱的水溶液以中和聚单宁酸氨酯中未反应的酚羟基,得到水溶性聚单宁酸氨酯;
S2、将碳纳米管与水溶性聚单宁酸氨酯、去离子水混合均匀后,经分散后即得到聚单宁酸氨酯稳定的碳纳米管水分散体。
2.根据权利要求1所述的制备方法,其特征在于:步骤S1中,所述单宁酸在使用前需真空干燥;所述单宁酸、芳香族二异氰酸酯类单体、碱的摩尔比为1:(0.5~1.0):(23~23.5)。
3.根据权利要求1所述的制备方法,其特征在于:步骤S1中,所述有机溶剂为N,N-二甲基甲酰胺、丙酮、二甲基亚砜、环丁砜、苯甲醚中的一种;所述有机溶剂的质量是单宁酸质量的5~10倍;所述碱的水溶液中碱为氢氧化钠、氢氧化钾、氢氧化钙、氢氧化钡中的一种。
4.根据权利要求1所述的制备方法,其特征在于:步骤S1中,所述芳香族二异氰酸酯类单体的分子结构中同时含有苯环和异氰酸酯基团,为甲苯二异氰酸酯或二苯基甲烷二异氰酸酯中的至少一种。
5.根据权利要求1所述的制备方法,其特征在于:步骤S1中,所述聚合反应的温度为40~80℃;分散的速率为10000~20000rpm,时间为3~5min。
6.根据权利要求1所述的制备方法,其特征在于:步骤S2中,所述碳纳米管与聚单宁酸氨酯的质量比为1:10~10:1。
7.如权利要求1-6任一项所述的制备方法制得的聚单宁酸氨酯稳定的碳纳米管水分散体。
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