CN106432671A - 一种碳基海绵及泡沫材料的制备方法 - Google Patents

一种碳基海绵及泡沫材料的制备方法 Download PDF

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CN106432671A
CN106432671A CN201610836632.0A CN201610836632A CN106432671A CN 106432671 A CN106432671 A CN 106432671A CN 201610836632 A CN201610836632 A CN 201610836632A CN 106432671 A CN106432671 A CN 106432671A
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沈文
沈寒松
蒋益鑫
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Jiangsu Gaime Nano Mstar Technology Ltd
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Abstract

本发明涉及一种碳基海绵及泡沫材料的制备方法,将低温氧等离子体表面枝接技术预处理的或表面活性剂修饰的碳基材料均匀分散到海绵及泡沫的预聚体或海绵及泡沫的聚合单体原料和溶剂中,通过海绵及泡沫的发泡工艺实现已分散的碳基材料对海绵及泡沫底材骨架的原位掺杂,制得碳基原位掺杂的海绵及泡沫材料。本发明将亲水性预处理后的碳基材料直接分散于海绵及泡沫的预聚体或聚合单体和溶剂中,再通过传统的发泡工艺,实现碳基材料对海绵及泡沫材料骨架的原位掺杂,提高碳基材料在海绵及泡沫基材中的分布均匀性和结合牢度。

Description

一种碳基海绵及泡沫材料的制备方法
技术领域
本发明属于新型功能海绵及泡沫的技术领域,具体涉及一种碳掺杂海绵及泡沫材料的制备方法。
背景技术
海绵及泡沫塑料,由于其质轻、多孔、坚固、吸音、减震、易成型、良好的透气性及绝热性、价格低等特点,世界范围内,其在汽车工业、电池工业、化妆品行业、服饰制造业、餐饮业、环保行业及高档家具制造业等领域获得了越来越广泛的应用。
碳素材料在硬度、耐热性、光学特性、耐辐射特性、耐化学药品特性、电绝缘性、导电性、表面与界面特性等方面有着优异的特性表现,如最硬-最软,绝缘体-半导体-良导体,绝热-良导热,全吸光-全透光等,因此碳材料功能多样,用途广泛。
作为碳素材料的典型代表,二维材料石墨烯自2004年发现以来,就以其超高的电导率、高强度、高弹性、超轻、超薄、超硬、高光透过率等独特优势而受到极大的关注。近年来,大量研究表明,石墨烯及其衍生物,如氧化石墨、氧化石墨烯、还原氧化石墨烯、石墨微片等碳基材料在电子学、光学、磁学、生物医学、催化、储能、环保和传感等领域有着广阔的应用前景。
在环保领域,如专利CN 103342827 B公开了一种疏水亲油性聚氨酯海绵的制备方法,该发明将经丙酮和去离子水超声清洗的聚氨酯海绵浸泡入少层石墨烯纳米片层的乙醇溶液中,以制备疏水亲油性聚氨酯海绵,尽管其吸油倍率为43,但紧靠浸泡而使石墨烯负载于聚氨酯海绵骨架的表层,其结合度并不牢固,在使用过程中石墨烯片层容易脱离,尤其在当通过挤压方式实现油品回收的情况,不但造成海绵使用寿命的降低,更由于石墨烯的脱落,造成水体及回收油品的二次污染。再如专利CN 103626171 B公开了一种油水分离材料的制备方法,即将海绵材料浸泡于氧化石墨烯溶液中,经离心后得氧化石墨烯包覆海绵材料,再把所得包覆海绵材料在还原剂的作用下将氧化石墨烯还原,最终得到油水分离材料,虽然氧化石墨烯经过还原,但使用过程中负载物的脱离问题同样不可避免。
通过浸泡、浸渍、喷涂、涂覆等非原位的方式,将石墨烯及其衍生物或其他碳素材料负载于海绵或泡沫内部孔道及骨架表面以制备功能性海绵及泡沫材料,负载物与载体的结合不牢固问将题伴随着材料的整个使用过程,不但降低了材料的使用寿命及性能的快速衰减,也带来了如二次污染等新问题。鉴于此,发明一种避免负载物脱离载体的方法来制备碳基功能海绵及泡沫材料,无疑将会带来良好的经济效益和社会效益。
发明内容
本发明所要解决的技术问题是针对上述现有技术提供一种碳基海绵及泡沫材料的制备方法,通过将碳基材料先直接掺杂聚合预聚体或聚合单体,而后再进行聚合实现将一种或多种碳基材料均匀地掺杂于海绵及泡沫材料的骨架内,提高碳基材料和海绵及泡沫骨架结合的牢度,避免掺杂碳基材料脱落。以期实现所制备的碳基海绵及泡沫材料可直接或加工后用于油水分离、防静电、吸波、吸音、阻燃、防护、电容去离子脱盐、超级电容器、催化剂载体、海水淡化、电磁屏蔽等领域。
本发明解决上述问题所采用的技术方案为:一种碳基海绵及泡沫材料的制备方法,将低温氧等离子体表面枝接技术预处理的或表面活性剂修饰的碳基材料均匀分散到海绵及泡沫的预聚体或海绵及泡沫的聚合单体原料和溶剂中,通过海绵及泡沫的发泡工艺实现已分散的碳基材料对海绵及泡沫底材骨架的原位掺杂,制得碳基原位掺杂的海绵及泡沫材料。
优选地,所述碳基材料选自石墨烯、氧化石墨、氧化石墨烯、还原氧化石墨烯、石墨粉、石墨微片、碳纳米管、活性炭、介孔碳、碳纤维、富勒烯、炭黑、乙炔黑、科琴黑、Super P炭黑中的一种或两种以上。
优选地,所述的海绵选自聚酯海绵、聚醚海绵、聚乙烯醇海绵、橡胶海绵、三聚氰胺海绵的海绵预聚体。
优选地,所述的泡沫选自聚氨酯泡沫、聚苯乙烯泡沫、聚氯乙烯泡沫、聚乙烯泡沫、酚醛树脂泡沫。
优选地额,所述的聚合单体原料和溶剂,其中溶剂为醇与水的混合溶剂或甲醛,醇选自异丙醇、甲醇或乙醇,接枝效果:异丙醇>甲醇>乙醇。
上述的碳基海绵及泡沫材料的制备方法具体包括如下步骤:
(1)碳基材料的亲水性预处理:采用低温等离子体表面枝接技术对碳基材料预处理,辐照功率为50-320 W,辐照时间为1 min -10 min,真空度为20 Pa-100 Pa;
(2)碳基材料的分散:将亲水性预处理的碳基材料的一种或两种以上的混合物加入到海绵及泡沫的预聚体或海绵及泡沫的聚合单体原料和溶剂中,碳基材料的添加量相对于海绵及泡沫预聚体或海绵及泡沫聚合单体的0.01% - 10%的质量比例,搅拌5-250 min,超声5-150min,过程温度保持在5-80℃;
(3)依照传统海绵及泡沫的发泡工艺,将步骤2所得物料进行发泡制备碳基海绵及泡沫材料。
与现有技术相比,本发明的优点在于:
(1)本方法属于制备碳基材料掺杂的海绵及泡沫的一种通用方法,即将预处理后的碳基材料直接分散于海绵及泡沫的预聚体或聚合单体和溶剂中,再通过传统的发泡工艺,实现碳基材料对海绵及泡沫材料骨架的原位掺入,提高碳基材料在海绵及泡沫基材中分布均匀性和结合牢度。
(2)本发明使用低温氧等离子体表面枝接技术对碳基材料进行预处理,氧等离子的处理会改变或活化碳基材料表面的基团,提高亲水性活性基团的数量及种类,由此使其与海绵或泡沫的预聚体或聚合单体和溶剂的相容性增强,进而提高碳基材料在预聚体或溶剂中的分散性,为发泡后获得碳基材料均匀分布的海绵或泡沫提供了前提。此外,重要的一点,氧等离子处理后的碳基材料与预聚体或聚合单体的不饱和键或支链之间的接枝率会进一步显著提高,形成化学结合,提高整个泡沫或海绵材料的活性效果。
(3)本方法可实现一种或多种碳基材料同时均匀地掺入海绵及泡沫的材质中,且所得材料的机械性能好,尤其避免了在使用过程中掺入碳质的脱落问题。
(4)本方法工艺简单、成本低廉、利用传统的海绵及泡沫材料的发泡工艺即可实施。
具体实施方式
以下结合实施例对本发明作进一步详细描述。
实施例1
在25℃温度条件下,首先使用聚醚型表面活性剂对氧化石墨烯进行表面修饰,以提高其亲水性,后加入聚醚海绵预聚体-聚醚多元醇中,快速搅拌30 min并超声20 min,该过程温度控制为25℃,使氧化石墨烯均匀分散,其中氧化石墨烯的质量分数为1 %,再按传统的聚醚海绵的发泡工艺发泡,制备氧化石墨烯原位掺杂的碳基聚醚海绵。
实施例2
在25℃温度条件下,将还原氧化石墨烯粉末加入聚酯多元醇中,剧烈搅拌20 min并超声10 min,使还原氧化石墨烯均匀的分散,其中还原氧化石墨烯的质量分数为0.5 %,以聚酯多元醇为发泡原料之一,添加异氰酸酯、水、催化剂、表面活性剂及其他添加剂等后继续搅拌,按传统的聚酯海绵的发泡工艺进行发泡,制备还原氧化石墨烯原位掺杂的还原氧化石墨烯基聚酯海绵。
实施例3
在25℃温度条件下,将亲水性预处理后的石墨烯及碳纳米管按质量比1:1进行混合,加入三聚氰胺海绵预聚体-三聚氰胺-甲醛树脂中,快速搅拌30 min并超声10 min,使石墨烯及碳纳米管均匀的分散,其中石墨烯及碳纳米管的总质量分数为2 %,再按传统的三聚氰胺海绵的发泡工艺发泡,制备石墨烯及碳纳米管混合物原位掺杂的石墨烯及碳纳米管基三聚氰胺海绵。
石墨烯及碳纳米管的混合物的预处理是采用低温氧等离子体表面枝接技术的预处理,其工艺参数为辐照功率240 W,辐照时间3 min,真空度70 Pa。
实施例4
具体实施参照实施例3,不同之处在于将石墨烯及碳纳米管的1:1混合物,加入到甲醛溶液或三聚氰胺溶液中,再制备石墨烯及碳纳米管混合物均匀分散的三聚氰胺-甲醛树脂用于三聚氰胺海绵的发泡。
实施例5
在25℃温度条件下,将Super P炭黑加入甲阶可发性酚醛树脂经充分搅拌后使其均匀分散其中,其中Super P炭黑的质量分数为2.5 %,按传统的酚醛树脂泡沫塑料的发泡工艺制备石Super P炭黑原位掺杂的Super P炭黑基三聚氰胺海绵。
该实施例中Super P炭黑的氧低温离子体的预处理条件:辐照功率为180 W,辐照时间2 min,真空度60 Pa。
实施例6
具体实施参照实施例5,不同之处在于将质量分数为1.5 %石墨烯微片均匀分散到苯酚或甲醛溶液中,经碱催化缩合,制备石墨微片分散的甲阶可发性酚醛树脂,再经发泡工艺获得石墨烯微片基酚醛树脂泡沫。
本实施例中的石墨烯微片的低温氧等离子预处理过程参照实施例3进行。
除上述实施例外,本发明还包括有其他实施方式,凡采用等同变换或者等效替换方式形成的技术方案,均应落入本发明权利要求的保护范围之内。

Claims (6)

1.一种碳基海绵及泡沫材料的制备方法,其特征在于:将低温氧等离子体表面枝接技术预处理的或表面活性剂修饰的碳基材料均匀分散到海绵及泡沫的预聚体或海绵及泡沫的聚合单体原料和溶剂中,通过海绵及泡沫的发泡工艺实现已分散的碳基材料对海绵及泡沫底材骨架的原位掺杂,制得碳基原位掺杂的海绵及泡沫材料。
2.根据权利要求1所述的碳基海绵及泡沫材料的制备方法,其特征在于:所述碳基材料选自石墨烯、氧化石墨、氧化石墨烯、还原氧化石墨烯、石墨粉、石墨微片、碳纳米管、活性炭、介孔碳、碳纤维、富勒烯、炭黑、乙炔黑、科琴黑、Super P炭黑中的一种或两种以上。
3.根据权利要求1所述的碳基海绵及泡沫材料的制备方法,其特征在于:所述的海绵选自聚酯海绵、聚醚海绵、聚乙烯醇海绵、橡胶海绵、三聚氰胺海绵的海绵预聚体。
4.根据权利要求1所述的碳基海绵及泡沫材料的制备方法,其特征在于:所述的泡沫选自聚氨酯泡沫、聚苯乙烯泡沫、聚氯乙烯泡沫、聚乙烯泡沫、酚醛树脂泡沫。
5.根据权利要求1所述的碳基海绵及泡沫材料的制备方法,其特征在于:所述的聚合单体原料和溶剂,其中溶剂为醇与水的混合溶剂或甲醛,醇选自异丙醇、甲醇或乙醇。
6.根据权利要求1至5中任一权利要求所述的碳基海绵及泡沫材料的制备方法,其特征在于:包括如下步骤
(1)碳基材料的亲水性预处理:采用低温等离子体表面枝接技术对碳基材料预处理,辐照功率为50-320 W,辐照时间为1 min -10 min,真空度为20 Pa-100 Pa;
(2)碳基材料的分散:将亲水性预处理的碳基材料的一种或两种以上的混合物加入到海绵及泡沫的预聚体或海绵及泡沫的聚合单体原料和溶剂中,碳基材料的添加量相对于海绵及泡沫预聚体或海绵及泡沫聚合单体的0.01% - 10%的质量比例,搅拌5-250 min,超声5-150min,过程温度保持在5-80℃;
(3)依照传统海绵及泡沫的发泡工艺,将步骤2所得物料进行发泡制备碳基海绵及泡沫材料。
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