CN106633027B - 一种苯胺分子印迹聚合物的制备方法 - Google Patents

一种苯胺分子印迹聚合物的制备方法 Download PDF

Info

Publication number
CN106633027B
CN106633027B CN201610883252.2A CN201610883252A CN106633027B CN 106633027 B CN106633027 B CN 106633027B CN 201610883252 A CN201610883252 A CN 201610883252A CN 106633027 B CN106633027 B CN 106633027B
Authority
CN
China
Prior art keywords
aniline
preparation
polymer
tannic acid
room temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201610883252.2A
Other languages
English (en)
Other versions
CN106633027A (zh
Inventor
靳利娥
曹青
安丽萍
张青兰
巴丽思
曹健
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Taiyuan University of Technology
Original Assignee
Taiyuan University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Taiyuan University of Technology filed Critical Taiyuan University of Technology
Priority to CN201610883252.2A priority Critical patent/CN106633027B/zh
Publication of CN106633027A publication Critical patent/CN106633027A/zh
Application granted granted Critical
Publication of CN106633027B publication Critical patent/CN106633027B/zh
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2615Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen the other compounds containing carboxylic acid, ester or anhydride groups
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26Synthetic macromolecular compounds
    • B01J20/268Polymers created by use of a template, e.g. molecularly imprinted polymers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/04Condensation polymers of aldehydes or ketones with phenols only of aldehydes
    • C08G8/08Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
    • C08G8/20Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with polyhydric phenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00Foams characterised by the foaming process
    • C08J2201/04Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/042Elimination of an organic solid phase
    • C08J2201/0424Elimination of an organic solid phase containing halogen, nitrogen, sulphur or phosphorus atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2361/00Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
    • C08J2361/04Condensation polymers of aldehydes or ketones with phenols only
    • C08J2361/06Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08J2361/12Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols with polyhydric phenols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Analytical Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

本发明公开了一种苯胺分子印迹聚合物的制备方法,所述制备方法是将单宁酸和苯胺混合进行反应,制备成以氢键结合的洋盐,然后加入交联剂进行交联聚合反应,最后利用乙醇洗涤,得到以单宁酸为功能单体的苯胺分子印迹聚合物。本方法使用的功能单体单宁酸为植物的次生物质,可再生,来源广泛,成本低,为废水中苯胺的去除提供了一种有效的手段。

Description

一种苯胺分子印迹聚合物的制备方法
技术领域
本发明涉及一种苯胺分子印迹聚合物的制备方法,属于高分子功能材料与环境领域。
背景技术
苯胺对高等动物的血液,肝及中枢神经有毒害作用。染料、纺织、油漆、制药和有机合成等企业排放的污水中含有大量的苯胺,苯胺在水相中较稳定,不易降解,是环境优先控制污染物之一。处理废水中苯胺的方法有生物法、萃取法、膜分离法、超临界氧化法、吸附法和电化学法等。其中吸附法是去除水中苯胺最有效的方法。所以,研究开发新型吸附苯胺功能材料具有重要的意义。
分子印迹技术是近年来迅速发展起来的一项新型技术,分子印迹聚合物因具有特定的分子识别能力而获得广泛的应用,是目前使用的比较有效的吸附分离方法,具有高度专一性和稳定性。文献报道有使用丙烯酰胺、丙烯酸、甲基丙烯酸为功能单体合成苯胺分子印迹聚合物,存在的问题是使用的功能单体均来源于化石原料,由于化石原料不可再生导致制备成本高,且有毒,易产生二次污染,不易大面积推广。单宁酸是植物代谢过程的次生物质,含有大量的酚羟具有一定的亲水性,不易直接用于吸附水体中的有机污染物,但是酚羟基可以进行化学修饰,制备成不同功能的单宁酸衍生物。本发明一种以单宁酸作为功能单体,苯胺为模板分子,加入一定量的交联剂进行交联聚合反应,乙醇除去模板分子,制备了一种单宁酸基苯胺分子印迹聚合物。
发明内容
本发明的目的是为了克服现有技术中的不足,提供一种有效吸附废水中苯胺的聚合物制备方法。
实现本发明上述目的的具体思路为:将单宁酸和苯胺按一定的摩尔比进行混合,在室温下反应30min后,加入一定量的交联剂,调节溶液的pH为10-11,40-60℃反应2-6h,迅速加入含有Span80的液体石蜡中,缓慢升温回流反应6h,冷却至室温,抽滤,用石油醚洗去液体石蜡,再用乙醇洗涤直至545nm处检查不到苯胺分子,水洗2-3次,50℃真空干燥得到制备的聚合物,利用制备的聚合物静态吸附水体中苯胺,吸附容量可达200mg/g以上。
上述苯胺分子印迹聚合物的制备方法中,所述功能单体单宁酸与模板分子苯胺的物质量比为1:2-6。
上述苯胺分子印迹聚合物的制备方法中,所述交联剂是甲醛和乙二醇二缩水甘油醚的一种,其中甲醛用量为4-8ml,乙二醇二缩水甘油醚用量为0.5-2ml。
本发明上述所提供的一种苯胺分子印迹聚合物的制备方法,所使用的功能单体单宁酸为天然产物,来源广泛,成本低;可再生,残留后低毒,不存在二次污染;单宁酸和苯胺以氢键特异性结合,制备成苯胺分子印迹聚合物,对水体中的苯胺吸附具有专一性,吸附容量至少为200mg/g。
图1是本发明具体实施方式中步骤一的反应示意图。
图2是本发明具体实施方式中步骤二中交联剂为乙二醇二缩水甘油醚的反应示意图。
图3是本发明具体实施方式中步骤二中交联剂为甲醛的反应示意图。
具体实施方式
实施本发明上述所提供的一种单宁酸基苯胺分子印迹聚合物制备方法,是以天然产物单宁酸作为功能单体,苯胺为模板分子,制备成以氢键结合的洋盐,加入一定量的交联剂和致孔剂进行交联聚合反应,乙醇除去模板分子,得到以单宁酸为功能单体的苯胺分子印迹聚合物。其具体制备方法如下。
步骤一:单宁酸和苯胺按一定的摩尔比进行混合,在室温下反应30min,反应见附图1。
步骤二:加入一定量的交联剂,调节溶液的pH为10-11,然后加入一定量40-60℃反应2-6h,迅速加入含有Span80的液体石蜡中,缓慢升温回流反应6h,冷却至室温,抽滤,用石油醚洗去液体石蜡,最后利用乙醇洗涤直至545nm处检查不到苯胺,水洗2-3次,50℃真空干燥得到制备的聚合物。附图2和附图3分别为交联剂为乙二醇二缩水甘油醚和甲醛的反应示图。
利用制备的聚合物静态吸附水体中苯胺,吸附容量可达200mg/g以上。
本发明上述具体实施方式能够有效地吸附苯胺废水中的苯胺,并且易于脱附和重复利用,使用的功能单体单宁酸为植物的次生物质,可再生,来源广泛,成本较低。
为了证实实验结果,没有进行印迹反应,直接将单宁酸和交联剂反应,然后在上述步骤二相同条件下制备聚合物,利用制备的聚合物静态吸附水体中苯胺,吸附容量为140mg/g左右。
苯胺浓度的测定参照GB11889-1989《水质苯胺类化合物的测定N-(1-萘基)乙二胺偶氮分光光度法》。
下面用实施例进一步对本发明的具体实施方式作出详细说明。
实施例1
将单宁酸和苯胺按摩尔比为1:3进行混合,在室温下反应30min后,加入8ml的甲醛,调节溶液的pH为10,60℃反应2h,迅速加入含有Span80的液体石蜡中,缓慢升温回流反应6h,冷却至室温,抽滤,用石油醚洗去液体石蜡,最后利用乙醇洗涤直至545nm处检查不到苯胺,水洗2-3次,50℃真空干燥得到制备的聚合物。利用制备的聚合物静态吸附水体中苯胺,吸附容量高达213mg/g。
实施例2
将单宁酸和苯胺按摩尔比为1:4进行混合,在室温下反应30min后,加入6ml的甲醛,调节溶液的pH为11,50℃反应2h,迅速加入含有Span80的液体石蜡中,缓慢升温回流反应6h,冷却至室温,抽滤,用石油醚洗去液体石蜡,最后利用乙醇洗涤直至545nm处检查不到苯胺,水洗2-3次,50℃真空干燥得到制备的聚合物。利用制备的聚合物静态吸附水体中苯胺,吸附容量高达216mg/g。
实施例3
将单宁酸和苯胺按摩尔比为1:4进行混合,在室温下反应30min后,加入0.5ml乙二醇二缩水甘油醚,调节溶液的pH为10,50℃反应2h,迅速加入含有Span80的液体石蜡中,缓慢升温回流反应6h,冷却至室温,抽滤,用石油醚洗去液体石蜡,最后利用乙醇洗涤直至545nm处检查不到苯胺,水洗2-3次,50℃真空干燥得到制备的聚合物。利用制备的聚合物静态吸附水体中苯胺,吸附容量高达210mg/g。
实施例4
将单宁酸和苯胺按摩尔比为1:3进行混合,在室温下反应30min后,加入2ml乙二醇二缩水甘油醚,调节溶液的pH为11, 40℃反应2h,迅速加入含有Span80的液体石蜡中,缓慢升温回流反应6h,冷却至室温,抽滤,用石油醚洗去液体石蜡,最后利用乙醇洗涤直至545nm处检查不到苯胺,水洗2-3次,50℃真空干燥得到制备的聚合物。利用制备的聚合物静态吸附水体中苯胺,吸附容量高达208mg/g。
实施例5
将单宁酸和苯胺按摩尔比为1:4进行混合,在室温下反应30min后,加入4ml的甲醛,调节溶液的pH为10,50℃反应2h,迅速加入含有Span80的液体石蜡中,缓慢升温回流反应6h,冷却至室温,抽滤,用石油醚洗去液体石蜡,最后利用乙醇洗涤直至545nm处检查不到苯胺,水洗2-3次,50℃真空干燥得到制备的聚合物。利用制备的聚合物静态吸附水体中苯胺,吸附容量高达213mg/g。
实施例6
将单宁酸和苯胺按摩尔比为1:4进行混合,在室温下反应30min后,加入1ml乙二醇二缩水甘油醚,调节溶液的pH为10,50℃反应2h,迅速加入含有Span80的液体石蜡中,缓慢升温回流反应6h,冷却至室温,抽滤,用石油醚洗去液体石蜡,最后利用乙醇洗涤直至545nm处检查不到苯胺,水洗2-3次,50℃真空干燥得到制备的聚合物。利用制备的聚合物静态吸附水体中苯胺,吸附容量高达203mg/g。

Claims (1)

1.一种苯胺分子印迹聚合物的制备方法,所述制备方法是将功能单体单宁酸和模板分子苯胺按1: 2-6的摩尔比进行混合,在室温下反应30min后,加入交联剂,调节溶液的pH为10-11,40-60℃反应2-6h,然后迅速加入含有Span80的液体石蜡中,缓慢升温至沸腾,回流反应6h,冷却至室温,抽滤,用石油醚洗去液体石蜡,再用乙醇洗涤直至545nm处检查不到苯胺分子,水洗2-3次,50℃真空干燥得到制备的聚合物,利用制备的聚合物静态吸附水体中苯胺,吸附容量至少为200mg/g;
所述交联剂是甲醛和乙二醇二缩水甘油醚的一种,其中甲醛用量为4-8ml,乙二醇二缩水甘油醚用量为1-2ml。
CN201610883252.2A 2016-10-10 2016-10-10 一种苯胺分子印迹聚合物的制备方法 Expired - Fee Related CN106633027B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610883252.2A CN106633027B (zh) 2016-10-10 2016-10-10 一种苯胺分子印迹聚合物的制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610883252.2A CN106633027B (zh) 2016-10-10 2016-10-10 一种苯胺分子印迹聚合物的制备方法

Publications (2)

Publication Number Publication Date
CN106633027A CN106633027A (zh) 2017-05-10
CN106633027B true CN106633027B (zh) 2018-06-08

Family

ID=58854405

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610883252.2A Expired - Fee Related CN106633027B (zh) 2016-10-10 2016-10-10 一种苯胺分子印迹聚合物的制备方法

Country Status (1)

Country Link
CN (1) CN106633027B (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108864418B (zh) * 2018-07-09 2020-09-15 中国海洋石油集团有限公司 一种老化原油破乳剂及其制备方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SG47174A1 (en) * 1995-09-18 1998-03-20 Ibm Cross-linked biobased materials and fabricating methods thereof
CN103613758B (zh) * 2013-12-03 2016-05-11 江南大学 自组装法制备分子印迹聚苯胺纳米复合物
CN103868966B (zh) * 2014-03-21 2016-08-24 上海出入境检验检疫局工业品与原材料检测技术中心 一种分子印迹聚合物-石墨烯复合材料修饰电极及其制备方法和应用

Also Published As

Publication number Publication date
CN106633027A (zh) 2017-05-10

Similar Documents

Publication Publication Date Title
Saha et al. Batch and continuous (fixed-bed column) biosorption of crystal violet by Artocarpus heterophyllus (jackfruit) leaf powder
CN101298039B (zh) 一种壳聚糖分子印迹吸附剂的制备方法
CN101759808B (zh) 一种多胺改性多孔淀粉的制备方法
CN101759809A (zh) 一种二硫代氨基甲酸基改性多孔淀粉的制备方法
CN102188957A (zh) 聚乙烯亚胺修饰的磁性多孔吸附剂及其制备方法和应用
CN103223333B (zh) 一种含双偕胺肟基的改性硅胶吸附剂及其制备方法
CN102000549B (zh) 一种三聚氰胺分子印迹吸附材料的制备方法及应用
CN101423612A (zh) 一种硅胶表面酚类分子印迹聚合物的制备方法
CN106957435A (zh) 一种用于水体中铀提取的聚合物及其制备方法
CN107552007A (zh) 离子液体改性镁铝层状双氢氧化物吸附剂及其制备和应用
CN103657600A (zh) 一种改性水处理吸附剂及其制备方法与应用
CN106699952A (zh) 一种苯硼酸基型的磁性印迹聚合物的制备方法
CN106633027B (zh) 一种苯胺分子印迹聚合物的制备方法
CN108031453A (zh) 微波辅助磁性粉煤灰负载对硝基苯酚分子印迹固相萃取材料
CN107376874A (zh) 重金属吸附剂及其制备方法
CN107126938B (zh) 一种丝瓜络表面原花青素分子印迹吸附材料的制备方法
CN108404885A (zh) 一种纤维素季铵盐吸附剂及其制备方法与应用
CN106592214A (zh) 一种两性离子交换纤维的制备方法
CN101851318B (zh) 安石榴甙分子印迹聚合物微球的制备方法
CN101215366A (zh) 一种单宁螯合树脂及其制备方法
CN114225924B (zh) 一种利用植物多酚改性的吸附树脂回收铋的方法
CN103936982B (zh) 一种主链型偶氮苯聚合物及其制备方法
CN102336869A (zh) 一种甲巯咪唑分子印迹聚合物的制备方法
CN102731684B (zh) 氨基甲酸乙酯分子印迹聚合物制备方法
CN115888419A (zh) 一种利用太阳光照射实现可持续再生超快水通道的氨基苯酚氧化石墨烯膜的制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180608

CF01 Termination of patent right due to non-payment of annual fee