CN106986978A - 一种疏水性高吸油聚氨酯泡沫材料及制备方法 - Google Patents
一种疏水性高吸油聚氨酯泡沫材料及制备方法 Download PDFInfo
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Abstract
本发明公开了一种疏水性高吸油聚氨酯泡沫材料及制备方法,它是以聚醚多元醇、交联剂、泡沫稳定剂、阻燃剂、发泡剂去离子水、催化剂、表面活性剂和异氰酸酯为原料,通过一步法聚合反应得到的互穿网络结构型低密度聚氨酯泡沫材料,这种材料的吸油倍率在30分钟内高达到90g·g‑1,吸水倍率低3g·g‑1,强度高0.3‑0.4Mpa,密度范围为10~40kg/m3。本发明主要利用吸油材料表面、间隙以及孔洞的毛细管现象吸油,将油品保存在空隙间。另外其反应生成物氨基甲酸酯含有极性键,会与油发生反应,且加入的含氟的表面活性剂可以明显的增加其憎水性,从而促进吸油性能提高。
Description
技术领域
本发明属于高分子吸油材料合成及对水体油污染治理的环保领域,尤其涉及高吸油性聚氨酯泡沫材料。
背景技术
随着世界工业的不断发展和人民生活水平的提高,全球范围内对石油产品的需求不断增大,随之而来的,油污排放日益增加,石油泄漏的途径和机会也在逐渐增多,特别是海上航运造成的大规模泄露事故,对海洋生态环境和人类的生活造成了严重的威胁。这一问题已引起公众极大的关注。因此高吸油性材料的开发具有重要的现实意义。
用吸油材料吸附泄漏石油是处理油污染的理想方法。传统的吸油材料中的无机材料或天然有机材料虽然价格便宜而且容易获得,但是无机材料存在吸油率低、不易作业、回收不方便等缺点;而天然有机材料则存在易下沉、吸附能力弱、对油水的分辨率低等缺点,被逐渐淘汰。而有机合成材料因其疏水性或亲油性好,成为近期科研工作者研究的重点。用高吸油性聚氨酯泡沫吸收油污具有吸油量较大,吸油速率较快,易回收等优点,是一种比较有发展前途的方法。
在应对在大环境污染事故中,研究开发合成对典型有毒有机污染物的快速分离、高效吸附材料,吸油及含油工业废水净化材料势在必行。聚氨酯泡沫可以用于处理油船、油罐泄漏的油及含油废水,操作简单、处理量大、回收率高、不沉入水中、可以焚烧和回收。利用聚氨酯泡孔大小的不同,还可以有选择的吸收油污,大孔吸收重油,小孔吸收轻油及有毒有机污染物,可通过简单的挤压分类回收。
陈建东等人(铁道劳动安全卫生与环保,1990,4,49-51)研究了商品软质聚氨 酯泡沫材料的吸油性能,发现软质聚氨酯泡沫材料吸油率在9.1~38.6g/g之间,吸油能力优于商品聚丙烯吸油毡,但是并没有对材料组成和吸油性能间的关系展开研究。
T.Shimazu等人(J.Appl.Polymer Sci.,1997,65,179-186)提出了一种吸油性聚氨酯泡沫材料,最大吸油率达60g/g。该材料可以现场发泡成型,有效地解决了泡沫材料因体积蓬松造成储运不便的问题。该材料是一种部分闭孔的聚氨酯泡沫材料,为了使材料具有吸油能力,需要通过机械力反复挤压,将材料内部封闭的孔洞转化成开放性的孔洞。此步操作需要专用的挤压设备,费时费力,难以胜任突发性事件应急处置的需求。此外,软质聚氨酯泡沫材料泡沫体较软,易发生因形变导致所吸收油重新渗出的现象,其保持油的能力有待加强。
WO2004/113238公开一种硬质聚氨酯泡沫材料,吸油率大于30g/g。材料制成后被切割成小块,直接投放至水面上进行浮油的吸收,可实现现场发泡成型,快速处置溢油等突发性事件。不仅解决了泡沫材料因体积蓬松造成储运不便的问题,而且提高了应急处置工作的效率。该材料为开孔型硬质聚氨酯泡沫材料,存在开孔率不高、吸油效率有限等问题,为提高吸油效率,需要将泡沫切割成体积为0.3~1ml的小块,增加了应急处置工作的复杂性。此外,该材料经挤压回收所吸收油之后,泡沫块形状难以恢复,不能反复使用。
中国专利申请公布号CN105315431A于2016.2.10公开了一种高倍吸油凝胶材料,它是以聚醚多元醇、复合催化剂、泡沫稳定剂、有机低分子凝胶、去离子水、发泡剂为原料,通过一步法聚合反应得到的。其优点是吸原油倍率达到60-100g/g,保油率大于90%,但是还存在以下缺点:一是凝胶型吸油材料的吸油推动力靠油分子与高聚物中的亲油基的相互亲和作用力,要想提高它的吸油储油能力,就必 须降低高聚物的交联度,从而增加内部的网络空间,但与此同时较低的交联度将导致高聚物在油中的溶解度增大,因此,只有采用适度交联的高聚物才能既保证较高的吸油能力,又不会发生溶解而破坏交联结构,这对高聚物原料要求较高,在实际工程中很难操作。二是它的吸油能力再高,吸附性还是有限的,在水面吸附溢油时,难免会由于吸水而导致结构塌陷,从而降低了吸油储油能力。三是,这种凝胶性吸油材料无法拿来即用,需要在使用现场加热熔融或者现场即做即用,操作复杂且吸附时间长,无法应对应急情况。
中国专利公开号CN101942190A公开了一种聚氨酯泡沫及其制备方法,本发明通过制备聚合物多元醇,与催化剂、泡沫稳定剂、发泡剂、开孔剂和经过处理的膨胀石墨经过混合、发泡、熟化制成聚氨酯泡沫,该聚氨酯泡沫具有高吸油率低吸水率的特点。但是还存在以下缺陷:膨胀石墨处理操作复杂,制备工艺费时费力;加入膨胀石墨后材料的空隙可能会增大但是相应的强度会降低。
发明内容
为了克服现有凝胶性吸油材料对高聚物原料要求较高、操作复杂且吸附时间长,无法应对应急情况以及强度低的技术缺陷,本发明提供一种在30分钟内吸油倍率达到90g/g的疏水性高吸油聚氨酯泡沫材料及其制备方法。该疏水性高吸油聚氨酯泡沫可用于各种油品及有机溶剂,如:四氯化碳、丙酮、甲苯、柴油、机油等的吸附回收,适用于地面、动态水面各种油品大量泄漏的回收,且在动态水面和在纯油体系中两者吸油率没有明显差别,使之更适于溢油等突发性事件的应急处置。
为达到上述目的,本发明采取的技术方案是:
一种疏水性高吸油聚氨酯泡沫材料,其特征在于,它是以聚醚多元醇、交联 剂、泡沫稳定剂、阻燃剂、发泡剂、催化剂、表面活性剂和异氰酸酯为原料,通过一步法聚合反应得到的互穿网络结构型低密度聚氨酯泡沫材料,材料密度范围为10~40kg/m3;上述各组分的重量份数为:
聚醚多元醇90份
交联剂1-3份
泡沫稳定剂0.3-1.5份
阻燃剂5-10份
发泡剂2-12份
催化剂1-8份
表面活性剂1-4份
异氰酸酯20-50份
所述的聚醚多元醇为聚四氢呋喃二醇、聚乙二醇/三醇、聚丙二醇/三醇、聚四亚甲基醚二醇/三醇中的一种或多种的混合物,其羟值范围为20-180mgKOH·g-1。
所述的交联剂为二乙醇胺、丙三醇、三羟甲基丙烷、间苯二酚二羟乙基醚等的一种或几种的混合物。
所述的发泡剂为去离子水。
所述的泡沫稳定剂为有机硅油。
所述的阻燃剂为聚磷酸胺、磷酸三苯酯、三(氯异丙基)磷酸酯等的一种或几种混合物。
所述的催化剂为胺类催化剂或/和有机锡类催化剂。胺催化剂包括:二甲基环己胺、二甲基乙醇胺、三乙烯二胺、四甲基乙二胺、五甲基二乙烯三胺等;有机 锡催化剂包括:辛酸锡、辛酸亚锡、二丁基二月桂酸锡等。
所述的表面活性剂为含氟的表面活性剂,为全氟三乙胺,全氟丁基磺酸钾,全氟辛基季胺碘化物中的一种或多种的混合物。
所述的异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、多亚甲基苯基多异氰酸酯等中的一种或多种的混合物。
本发明的疏水性高吸油聚氨酯泡沫材料制备方法为:
将聚醚多元醇、交联剂、泡沫稳定剂、阻燃剂、发泡剂、催化剂和表面活性剂按配方比例称量搅拌混合均匀,然后加入混合均匀的异氰酸酯,用电动搅拌器以1000-1600r/min的速度快速搅拌6-8s,立刻倒入模具中自由发泡2-5min,再熟化2-5h后切割成适宜尺寸即可。
本发明疏水性高吸油聚氨酯泡沫材料的使用方法是:可在岸上或船上直接投放至水面上进行浮油的吸收。最好将聚氨酯泡沫直接投放在溢油上,尽量向溢油多的地方投放,应适量投放,使聚氨酯泡沫处于吸油饱和状态,即要使溢油得到彻底清除,又使聚氨酯泡沫充分发挥作用,当吸油量达到饱和后,应尽快捞出水面,避免长时间的留在水中。
下面结合吸油机理说明本发明的优点。
1、本发明是具有疏松多孔,有互穿网络结构的物质,主要利用吸油材料表面、间隙以及孔洞的毛细管现象吸油,将油品保存在空隙间;另外其反应生成物聚氨基甲酸酯含有大量的极性基团,会与油发生反应;且加入的含氟的表面活性剂可以明显的增加其憎水性,从而促进吸油性能提高,吸油倍率在30分钟内高达到90g·g-1、吸水倍率低约3g·g-1、强度高0.3-0.4Mpa,具有很好的应用价值和推广前景。
2、与现有一般的吸油材料相比,本发明的高吸油性聚氨酯材料具有良好的吸油选择性和环境友善性。本发明所涉及的疏水性高吸油软质聚氨酯泡沫材料能吸附多种油品及有机溶剂,如:四氯化碳、丙酮、甲苯、柴油、机油。可以用于油船、油罐泄漏的油及含油废水等各种油品。以及陆岸上泄露的油品或是化学吸附回收;机械设备的油污的清理和擦拭;储油池,排油管道,船底仓等油污清理,适用范围较广。
3、本发明的高吸油性聚氨酯材料可以事先制备好备用,当出现紧急情况时,可以立即投入使用,尤其适合江河湖海水面溢油应急处理,因此,能够有效的解决处理水体油污染的的操作复杂性问题。
4、另外,本发明的高吸油性聚氨酯材料具有良好的弹性,经挤压后可以恢复,这与加入的交联剂芳族二醇间苯二酚二羟乙基醚有关,其能够最大限度的维持弹性体的持久性和弹性,而同时又可以将收缩率限制到最小。因此可以有效的解决吸油后泡沫块形状难以恢复,不能反复使用的问题。
5、异氰酸酯和水反应剧烈,先生成不稳定的氨基甲酸,随后分解为大量的CO2和脲,产生最大压力时由于反应形成的泡孔壁强度不高,不能承受气体压力升高引起的壁膜拉伸,气泡壁膜便被拉破,气体从破裂处逸出,从而形成开孔泡沫,吸油性能增强。
6、本发明的高吸油性聚氨酯材料的发泡剂只采用了水,相比凝胶吸油材料,发泡剂环保且价格低廉。
7、本发明的高吸油性聚氨酯材料的发泡剂,能快速吸附及拦截泄露的石油及液态有机污染物,可有效的控制污染范围扩大。吸附一定时间后,可将油挤出,重复使用。用离心脱油机离心2-5分钟或是挤压机挤压一次即可脱油,经挤压回 收溢油后,泡沫材料具有一定恢复原始形状的能力,可重新用于溢油的收集。最终采用燃烧法集中处理,防止二次污染。
经测试,本发明疏水性高吸油聚氨酯泡沫材料的各项性能如下:
它是一种低密度聚氨酯泡沫材料,密度范围为10~40kg/m3;泡沫密度的测试方法为:采用带锯切割泡沫块,制作3cm×3cm×3cm立方体试样。用游标卡尺分别测量泡沫块的长、宽、高,分别测定三次,取平均值,计算泡沫表观体积。用万分之一天平准确称量泡沫重量,重量除以表观体积得泡沫密度。
表面具有一定的疏水性,材料表面与水的接触角大于95°;
材料的发泡倍率大于30倍;
它具有很强的吸油能力,吸油倍率达到90g·g-1。测试方法是:采用带锯切割泡沫块,制作3cm×3cm×3cm立方体试样,用万分之一天平准确称量泡沫重量M1。在烧杯中倒入需要测试的机油适量,将泡沫试样投入到烧杯中,吸附30min后取出,放在滤网上静置4-6分钟,用万分之一天平准确称重,得重量M2。按下列算式计算吸油率即可:吸油率=(M2-M1)/M1.
附图说明
图1a是本发明在光学显微镜下看的放大100倍数的微观结构图;
图1b是本发明在光学显微镜下看的放大200倍数的微观结构图;
图2a是本发明疏水性接触角为95.7°的实验图;
图2b是本发明疏水性接触角为99.5°的实验图。
具体实施方式
下面通过四个实施例进一步说明本发明的技术方案。
实施例1
实施例1中的聚醚多元醇为聚四氢呋喃二醇、聚乙三醇和聚四亚甲基醚二醇的混合物,异氰酸酯为甲苯二异氰酸酯和二苯基甲烷二异氰酸酯的混合物。各组分配比如下:
组分Ⅱ:甲苯二异氰酸酯 25份
二苯基甲烷二异氰酸酯 15份
制备方法是:将组分Ⅰ中各成分用电动搅拌器混合均匀,制成组分Ⅰ。将组分Ⅱ中各成分混合均匀后倒入组分Ⅰ中。用电动搅拌器快速搅拌5s,倒入自制模具中自由发泡成型,等到熟化后进行切割,测试材料的性能。
经测试对四氯化碳、丙酮、甲苯、柴油、机油的吸油倍率分别为:80g·g-1、70g·g-1、63g·g-1、49g·g-1、13g·g-1。
实施例2
实施例2中的聚醚多元醇为聚四氢呋喃二醇、聚丙二醇和聚丙三醇的混合物。异氰酸酯为六亚甲基二异氰酸酯和多亚甲基苯基多异氰酸酯的混合物,各组分配 比如下:
组分Ⅱ:六亚甲基二异氰酸酯 20份
多亚甲基苯基多异氰酸酯 20份
实施例2的制备方法见实施例1,经测试实施例2制备的材料对四氯化碳、丙酮、甲苯、柴油、机油的吸油倍率分别为:82g·g-1、70g·g-1、66g·g-1、47g·g-1、13g·g-1。
实施例3:
实施例3中的聚醚多元醇为聚四氢呋喃二醇、聚乙三醇和聚四亚甲基醚二醇的混合物。异氰酸酯为甲苯二异氰酸酯和二苯基甲烷二异氰酸酯的混合物,各组分配比如下:
组分Ⅱ:甲苯二异氰酸酯 25份
二苯基甲烷二异氰酸酯 15份
制备方法见实施例1,制备的材料经测试对四氯化碳、丙酮、甲苯、柴油、机油的吸油倍率分别为:83g·g-1、72g·g-1、66g·g-1、49g·g-1、14g·g-1。
实施例四
实施例4中的聚醚多元醇为聚四氢呋喃二醇、聚丙二醇和聚丙三醇的混合物。异氰酸酯为六亚甲基二异氰酸酯和多亚甲基苯基多异氰酸酯的混合物,去离子水的量增加到10份,各组分配比如下:
组分Ⅱ:甲苯二异氰酸酯 25份
二苯基甲烷二异氰酸酯 15份
实施例4制备方法见实施例一,经测试制备的材料对四氯化碳、丙酮、甲苯、柴油、机油的吸油倍率分别为:83g·g-1、72g·g-1、67g·g-1、50g·g-1、15g·g-1。
实施例制备的材料微观结构见图1a和图1b,从图1a和1b可以看出,本发明材料的结构为空洞状,具有很强的吸油能力;从图2a和2b所示的接触角可以看出,本发明材料表面具有一定的疏水性。
Claims (10)
1.一种疏水性高吸油聚氨酯泡沫材料,其特征在于,它是以聚醚多元醇、交联剂、泡沫稳定剂、阻燃剂、发泡剂去离子水、催化剂、表面活性剂和异氰酸酯为原料,通过一步法聚合反应得到的互穿网络结构型低密度聚氨酯泡沫材料,这种材料的吸油倍率在30分钟内高达到90g·g-1,吸水倍率低3g·g-1,强度高0.3-0.4Mpa,密度范围为10~40kg/m3;上述各组分的重量份数为:
2.如权利要求1所述的疏水性高吸油聚氨酯泡沫材料,其特征在于,所述的聚醚多元醇为聚四氢呋喃二醇、聚乙二醇/三醇、聚丙二醇/三醇、聚四亚甲基醚二醇/三醇中的一种或多种的混合物,其羟值范围为20-180mgKOH·g-1。
3.如权利要求1所述的疏水性高吸油聚氨酯泡沫材料,其特征在于,所述的阻燃剂为聚磷酸胺、磷酸三苯酯、三(氯异丙基)磷酸酯中的一种或几种混合物。
4.如权利要求1所述的疏水性高吸油聚氨酯泡沫材料,其特征在于,所述的催化剂为胺类催化剂或/和有机锡类催化剂。
5.如权利要求1所述的疏水性高吸油聚氨酯泡沫材料,其特征在于,所述的表面活性剂为含氟的表面活性剂。
6.如权利要求5所述的疏水性高吸油聚氨酯泡沫材料,其特征在于,所述的表面活性剂为全氟三乙胺、全氟丁基磺酸钾、全氟辛基季胺碘化物中的一种或多种的混合物。
7.如权利要求1所述的疏水性高吸油聚氨酯泡沫材料,其特征在于,所述的泡沫稳定剂为有机硅油。
8.如权利要求1所述的疏水性高吸油聚氨酯泡沫材料,其特征在于,所述的交联剂为二乙醇胺、丙三醇、三羟甲基丙烷、间苯二酚二羟乙基醚中的一种或几种的混合物。
9.如权利要求1所述的疏水性高吸油聚氨酯泡沫材料,其特征在于,所述的异氰酸酯为甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、多亚甲基苯基多异氰酸酯中的一种或多种的混合物。
10.一种如权利要求1-8任一所述的所述的疏水性高吸油聚氨酯泡沫材料的制备方法,其特征在于,首先将聚醚多元醇、交联剂、泡沫稳定剂、阻燃剂、发泡剂、催化剂和表面活性剂按配方比例称量搅拌混合均匀,然后加入混合均匀的异氰酸酯,用电动搅拌器以1000-1600r/min的速度快速搅拌6-8s,立刻倒入模具中自由发泡2-5min,再熟化2-5h后切割成要求的尺寸即可。
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