CN113388154A - 一种生物可降解且具有吸附功能的亲水疏油泡沫 - Google Patents
一种生物可降解且具有吸附功能的亲水疏油泡沫 Download PDFInfo
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Abstract
本发明提供一种生物可降解且具有吸附功能的亲水疏油泡沫，以聚乳酸开孔泡沫为基体材料，利用壳聚糖，单宁酸和硅烷偶联剂改性聚乳酸开孔泡沫，得到能吸附水中的甲基橙、罗丹明B，亚甲基蓝混合染料以及能吸附重金属离子的泡沫材料。此泡沫材料亲水疏油，可以在吸附水中染料的过程中不被油相污染，且具有循环吸附能力，可以反复使用。
Description
技术领域
本发明属于高分子材料领域，具体涉及一种生物可降解的可以吸附多种染料和重金属离子的泡沫，此具有油水分离功能。
技术背景
工业化发展导致水污染加剧，其中又以印染和矿物开采行业带来的水体污染较为严重，含染料和重金属离子的水污染物由于其多数有毒、不可生物降解，肆意排放会危害动植物，还会通过生物蓄积对人体健康产生威胁。现如今，已有许多方法来去除水中的有害染料和重金属离子，其中，吸附法因其成本低、使用便捷而成为备受欢迎的污水处理方法之一，各种类型的吸附剂层出不穷，如Gopakumar等人证明了改性聚偏氟乙烯微滤膜可用于吸附结晶紫；Sujoy等人通过苯胺的原位聚合法制备出了多三维多孔的叶酸-聚苯胺混合水凝胶，可同时吸附Cr(VI)和阴离子染料；Guo等人报道了一种新型改性纤维素，具有高效吸附Cd2+，Zn2+，Ni2+，Pb2+和Cu2+等重金属离子的能力。虽然这些吸附剂都有较好的吸附效果，但也存在膜的成本高，凝胶的强度低，粉末颗粒难回收等问题而难以大规模使用。也有人选用改性泡沫作为吸附剂来解决这些问题，如Li等人合成氮化硼泡沫，可从水溶液中快速去除罗丹明B和Cd(II)污染物；Su等人制备了MOF衍生的多孔ZnO纳米笼/rGO/碳海绵，对有机污染物具有优异的吸附和光催化降解性。
因此同时具备能吸附水中多种染料和重金属离子且能亲水输油可循环使用的生物可降解泡沫还是有很大的应用前景。
发明内容
本发明针对现有染料吸附材料不好回收，功能单一且不可生物降解的问题，提供一种生物可降解且具有吸附功能的疏油型泡沫。
本发明以开孔的聚乳酸(PLA)泡沫为载体，通过将壳聚糖(CS)、单宁酸(TA)和硅烷偶联剂(KH550)对PLA泡孔表面进行改性处理，使得所制备得到的泡沫亲水疏油，可以同时吸附废水中带不同种电荷的染料和重金属离子，且具有较好的循环吸附能力。
本发明的目的通过以下技术方案实现：
一种生物可降解且具有吸附功能的亲水疏油泡沫，其特征在于此泡沫能吸附水中的甲基橙、罗丹明B、亚甲基蓝和铜离子，且具有循环吸附能力，其制备过程包括以下步骤：
(1)PLA开孔泡沫的制备；
(2)TA/CS复合溶液改性PLA开孔泡沫：配置TA/CS混合溶液：首先，分别配置质量分数为1-2％的壳聚糖的水溶液，和质量分数0.2-0.8％的单宁酸水溶液，将单宁酸溶液加入到溶解的壳聚糖中，配置TA/CS的复合溶液，继续搅拌后置于室温中备用。将PLA泡沫放入TA/CS复合溶液中，反复挤压后静置12小时，取出完全浸润的PLA泡沫真空干燥后即得TA/CS改性的PLA泡沫，称为TA/CS PLA泡沫。
(3)KH550改性TA/CS PLA泡沫：配置KH550的无水乙醇溶液，将TA/CS PLA泡沫放入KH550溶液中浸渍12h，取出后置于50℃真空干燥2h后，即得TA/CS@KH550改性的PLA泡沫，称为TA/CS@KH550 PLA泡沫。
其中，所述步骤(1)中PLA开孔泡沫的制备方式可以为超临界发泡法，溶胶凝胶-热致相分离法，溶蚀法等方法的任一种或者两种方式相结合；其中超临界发泡法中所用到的PLA为扩链改性的PLA，且超临界发泡条件为110-140℃，20-30Mpa，超临界流体为CO2，饱和时间2-4h，泄压速率1-2s，得到PLA开孔材料；溶胶凝胶-热致相分离法中需要在加热的条件下用溶剂先溶解PLA固体颗粒，然后加入相分离剂，形成相分离液，在经过凝胶、溶剂置换、干燥的过程得到PLA的开孔材料；溶蚀法是将糖、NaCl、PEO等可溶性小分子加入到PLA固体中，混炼成型，然后加入能溶解这些小分子的溶剂反复洗涤，将材料中可溶性物质洗去，得到开孔材料。
其中，所述步骤(1)中PLA开孔泡沫的孔隙率为70-95％。
其中，所述步骤(2)中壳聚糖的水溶液的配置过程为先将冰乙酸(质量分数98％)加入到去离子水中，二者的体积比为0.01-0.02，然后将壳聚糖加入到含有冰乙酸的去离子水中，配置得到壳聚糖的溶液；步骤(2)中TA/CS复合溶液中TA/CS质量比为0.1～0.8。
其中，所述步骤(2)中PLA泡沫放入TA/CS复合溶液反复挤压的过程为将PLA泡沫放入TA/CS复合溶液中，每隔4h挤压一次，重复三次后再静置12h。
其中，所述步骤(3)中KH550在无水乙醇溶液中的质量分数为0.1-0.2％。
所得泡沫吸附性能的测试方法如下:
静态吸附实验：本发明中，以阴离子染料甲基橙(MO)，中性染料罗丹明B(RB)和阳离子染料亚甲基蓝(MB)溶液模拟带不同种电荷的染料废水，硫酸铜溶液模拟重金属铜离子(Cu2+)。分别配置10，20，30，40，50mg/L的甲基橙(MO)，罗丹明B(RB)，亚甲基蓝(MB)和Cu2+标准溶液，采用紫外可见分光光度计(UV-3010)在最大吸收波长处测定标准溶液的吸光度，其中铜离子需要测量铜离子溶液稀释50倍后与铜试剂(三水合二乙基二硫代氨基甲酸钠)在碱性缓冲液中生成黄色络合物(λmax＝450)的吸光度，测得标准曲线，之后通过标准曲线计算不同吸光度下的溶液浓度。
温度、pH对泡沫吸附能力的影响：分别以纯PLA开孔泡沫和TA/CS@KH550改性的PLA开孔泡沫为吸附材料。标准条件下选择相同浓度的溶液，分别改变温度(10℃，20℃，30℃，40℃，50℃)，溶液的初始pH值(用5M HCl和5M NaOH分别调节染料pH为4，6，8，10；Cu2+pH分别为2，3，4，5，6。)来测量温度和pH对改性前后泡沫材料吸附能力的影响。
循环使用实验：染料吸附实验结束后，将载有MO和RB的改性PLA开孔泡沫分别加入到NH4Cl/NH4OH洗脱液中，载有MB和Cu2+的吸附剂分别加入到HCl/HNO3洗脱液中，然后在室温下搅拌3h。解吸后，将PLA开孔泡沫洗涤并于50℃真空干燥以供循环使用。
接触角测试：在室温条件下，以水作为测试液滴，利用光学接触角测量仪测定改性处理前后PLA开孔泡沫的接触角，测量时水滴的体积大小约为5.0μL，每个测试表面上取3个不同的位置作测试点，最后取这三个结果的均值为最终接触角。
与现有技术相比，本发明具有以下优点：
(1)TA/CS@KH550 PLA泡沫亲水疏油，可用于油水分离。
(2)TA/CS@KH550 PLA泡沫可吸附水中带不同电荷的染料和重金属离子。
(3)TA/CS@KH550 PLA泡沫能循环使用。
(4)本发明中PLA开孔泡沫质量轻、孔隙率大，吸附性能好。
附图说明
图1是实施例1中步骤(1)中制备的PLA开孔泡沫的扫描电镜图；
图2是实施例1中步骤(1)中制备的PLA开孔泡沫的接触角；
图3是实施例1中步骤(2)中制备的TA/CS PLA泡沫的接触角；
图4是实施例1中步骤(3)中制备的TA/CS@KH550 PLA泡沫的接触角；
图5是实施例1中PLA开孔泡沫和TA/CS@KH550 PLA泡沫在不同温度下对MO吸附性能的影响；
图6是实施例1中PLA开孔泡沫和TA/CS@KH550 PLA泡沫在不同温度下对RB吸附性能的影响；
图7是实施例1中PLA开孔泡沫和TA/CS@KH550 PLA泡沫在不同温度下对MB吸附性能的影响；
图8是实施例1中PLA开孔泡沫和TA/CS@KH550 PLA泡沫在不同温度下对Cu2+吸附性能的影响；
图9是实施例1中接触时间对TA/CS@KH550 PLA泡沫吸附能力的影响；
图10是实施例1中TA/CS@KH550 PLA泡沫的循环吸附性能；
图11实施例1-5中不同TA含量对TA/CS@KH550PLA泡沫吸附能力的影响；
图12是实施例6中步骤(1)中制备的PLA开孔泡沫的扫描电镜图；
图13是实施例7中步骤(1)中制备的PLA开孔泡沫的扫描电镜图；
具体实施方式
下面结合实施例对本发明作进一步说明。
实施例1：
(1)聚乳酸(PLA)开孔泡沫的制备：将PLA进行扩链改性，将扩链剂分散在乙醇溶液中，均匀的包覆在PLA粒料表面，将包覆有扩链剂的PLA粒料投入挤出机中，进行扩链改性-挤出-造粒，得到扩链后PLA粒料；将扩链后PLA粒料投入注塑机中，注塑成板材；将PLA板放入超临界反应釜中，设置反应釜温度为130℃，通入CO2，达到25MPa时停止加压，进行超临界饱和，饱和2h快速卸压(＜2s)得到PLA开孔泡沫，简称PLA泡沫，其扫描电镜图见图1，接触角见图2，此泡沫的密度为0.023g/cm3，孔隙率为88.67％；
(2)TA/CS PLA泡沫的制备：配置TA/CS复合溶液：首先，将0.3g单宁酸溶于50mL去离子水中，常温下搅拌溶解后。然后，将1g壳聚糖(CS)溶于含有1mL冰乙酸(质量分数98％)的50mL的去离子水中，并于50℃搅拌2h溶解，将等体积的单宁酸溶液加入到壳聚糖溶液中进行混合，配置成TA/CS质量比为0.3的混合溶液，将其在50℃持续搅拌半小时后置于室温中备用。将提前切割好的大小接近的PLA泡沫放入TA/CS复合溶液中，每隔4h挤压一次，重复三次后静置12h，取出完全浸润的PLA泡沫在50℃真空干燥4h，即得TA/CS PLA泡沫，其接触角见图3；
(3)TA/CS@KH550 PLA泡沫的制备：将TA/CS改性的PLA泡沫放入含0.1g硅烷偶联剂KH550的无水乙醇中浸渍12h，取出后置于50℃真空干燥2h，即得TA/CS@KH550改性的PLA泡沫，其接触角见图4；
之后研究了实施例1中TA/CS@KH550 PLA泡沫对水中甲基橙(MO)、罗丹明B(RB)、亚甲基蓝(MB)和铜离子(Cu2+)的吸附性能(图5-图9)和循环吸附能力(图10)。
实施例2-实施例5：
(1)PLA开孔泡沫的制备：同实施例1步骤(1)；
(2)TA/CS PLA泡沫的制备：制备过程同实施例1步骤(2)但是TA/CS复合溶液中TA与CS的质量比不同，分别为0.1(实施例2)、0.2(实施例3)、0.4(实施例4)、0.5(实施例5)；
(3)TA/CS@KH550 PLA泡沫的制备：同实施例1步骤(3)。
不同TA占比下的TA/CS@KH55改性的PLA泡沫对四种目标污染物的吸附能力见图11。
实施例6：
(1)PLA开孔泡沫的制备：将PLA溶解在二氯甲烷中，打开加热和搅拌使PLA颗粒完全溶解，之后加入部分无水乙醇，搅拌半个小时后倒出至小烧杯中，随后将剩余无水乙醇倒入烧杯中并用保鲜膜将其密封，放进冰箱冷藏室内，温度为4℃，经过24h后，将材料倒出，放置在真空烘箱中，通过梯度升温法对其升温及抽真空，最终制得PLA开孔材料，此开孔材料的密度为0.267g/cm3，孔隙率为79.13％，其扫描电镜图见图12；
(2)TA/CS PLA泡沫的制备：同实施例1步骤(2)；
(3)TA/CS@KH550 PLA泡沫的制备：同实施例1步骤(3)。
实施例7：
(1)PLA开孔泡沫的制备：将100份PLA与40份PEO在密炼机中共混，然后模压成型，将共混物样品进行超临界发泡，设置超临界发泡反应釜温度为125℃，通入CO2，达到22MPa时停止加压，饱和1h后快速卸压(＜2s)得到PLA泡沫，然后将发泡后样品放入水浴锅中进行反复洗涤进行溶蚀，制得PLA开孔材料，此开孔材料的密度为0.163g/cm3，孔隙率为93.58％，其扫描电镜图见图13；
(2)TA/CS PLA泡沫的制备：制备过程同实施例1步骤(2)但是TA/CS复合溶液中TA与CS的质量比0.8；
(3)TA/CS@KH550 PLA泡沫的制备：同实施例1步骤(3)。
表1实施例1-7对不同污染物的吸附量。
Claims (6)
1.一种生物可降解且具有吸附功能的亲水疏油泡沫，其特征在于此泡沫能吸附水中的甲基橙、罗丹明B、亚甲基蓝和铜离子，且具有循环吸附能力，其制备过程包括以下步骤：
(1)PLA开孔泡沫的制备；
(2)TA/CS复合溶液改性PLA开孔泡沫：配置TA/CS混合溶液：首先，分别配置质量分数为1-2％的壳聚糖的水溶液，和质量分数0.2-0.8％的单宁酸水溶液，将单宁酸溶液加入到溶解的壳聚糖中，配置TA/CS的复合溶液，继续搅拌后置于室温中备用；将PLA泡沫放入TA/CS复合溶液中，反复挤压后静置12小时，取出完全浸润的PLA泡沫真空干燥后即得TA/CS改性的PLA泡沫，称为TA/CS PLA泡沫；
(3)KH550改性TA/CS PLA泡沫：配置KH550的无水乙醇溶液，将TA/CS PLA泡沫放入KH550溶液中浸渍12h，取出后置于50℃真空干燥2h后，即得TA/CS@KH550改性的PLA泡沫，称为TA/CS@KH550 PLA泡沫。
2.根据权利要求书1所述的一种生物可降解且具有吸附功能的亲水疏油泡沫，其特征在于，所述步骤(1)中PLA开孔泡沫的制备方式可以为超临界发泡法，溶胶凝胶-热致相分离法，溶蚀法等方法的任一种或者两种方式相结合；其中超临界发泡法中所用到的PLA为扩链改性的PLA，且超临界发泡条件为110-140℃，20-30Mpa，超临界流体为CO2，饱和时间2-4h，泄压速率1-2s，得到PLA开孔材料；溶胶凝胶-热致相分离法中需要在加热的条件下用溶剂先溶解PLA固体颗粒，然后加入相分离剂，形成相分离液，在经过凝胶、溶剂置换、干燥的过程得到PLA的开孔材料；溶蚀法是将糖、NaCl、PEO等可溶性小分子加入到PLA固体中，混炼成型，然后加入能溶解这些小分子的溶剂反复洗涤，将材料中可溶性物质洗去，得到PLA开孔材料。
3.根据权利要求书1所述的一种生物可降解且具有吸附功能的亲水疏油泡沫，其特征在于，所述步骤(1)中PLA开孔泡沫的孔隙率为70-95％。
4.根据权利要求书1所述的一种生物可降解且具有吸附功能的亲水疏油泡沫，其特征在于，所述步骤(2)中壳聚糖的水溶液的配置过程为先将冰乙酸(质量分数98％)加入到去离子水中，二者的体积比为0.01-0.02，然后将壳聚糖加入到含有冰乙酸的去离子水中，配置得到壳聚糖的水溶液；步骤(2)中TA/CS复合溶液中TA/CS质量比为0.1～0.8。
5.根据权利要求书1所述的一种生物可降解且具有吸附功能的亲水疏油泡沫，其特征在于，所述步骤(2)中PLA泡沫放入TA/CS复合溶液反复挤压的过程为将PLA泡沫放入TA/CS复合溶液中，每隔4小时挤压一次，重复三次后再静置12小时。
6.根据权利要求书1所述的一种生物可降解且具有吸附功能的亲水疏油泡沫，其特征在于，所述步骤(3)中KH550在无水乙醇溶液中的质量分数为0.1-0.2％。
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115155528A (zh) * | 2022-08-04 | 2022-10-11 | 成都开飞高能化学工业有限公司 | 一种高吸附容量颗粒型铝盐提锂吸附剂的制备方法 |
| CN115418858A (zh) * | 2022-09-22 | 2022-12-02 | 浙江大学 | 一种抗油污的界面水净化织物及其制备方法和应用 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921394A (zh) * | 2012-10-30 | 2013-02-13 | 江苏大学 | 聚氨酯/壳聚糖复合泡沫的制备方法及其应用 |
| US8975387B1 (en) * | 2010-03-22 | 2015-03-10 | North Carolina State University | Modified carbohydrate-chitosan compounds, methods of making the same and methods of using the same |
-
2021
- 2021-06-09 CN CN202110657892.2A patent/CN113388154A/zh active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8975387B1 (en) * | 2010-03-22 | 2015-03-10 | North Carolina State University | Modified carbohydrate-chitosan compounds, methods of making the same and methods of using the same |
| CN102921394A (zh) * | 2012-10-30 | 2013-02-13 | 江苏大学 | 聚氨酯/壳聚糖复合泡沫的制备方法及其应用 |
Non-Patent Citations (2)
| Title |
|---|
| LIYAN QIU等: ""Multifunctional Adsorbent: Oleophobic Latex Sponge for Removing Dyes and Cu2+ from Sewage Waste"" * |
| 何丁: ""超临界二氧化碳发泡法制备聚乳酸开孔泡沫材料的研究"" * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115155528A (zh) * | 2022-08-04 | 2022-10-11 | 成都开飞高能化学工业有限公司 | 一种高吸附容量颗粒型铝盐提锂吸附剂的制备方法 |
| CN115155528B (zh) * | 2022-08-04 | 2023-11-10 | 成都开飞高能化学工业有限公司 | 一种高吸附容量颗粒型铝盐提锂吸附剂的制备方法 |
| CN115418858A (zh) * | 2022-09-22 | 2022-12-02 | 浙江大学 | 一种抗油污的界面水净化织物及其制备方法和应用 |
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