CN109261136B - 一种磁性三聚氰胺脲醛树脂整体材料的制备方法 - Google Patents
一种磁性三聚氰胺脲醛树脂整体材料的制备方法 Download PDFInfo
- Publication number
- CN109261136B CN109261136B CN201811054398.1A CN201811054398A CN109261136B CN 109261136 B CN109261136 B CN 109261136B CN 201811054398 A CN201811054398 A CN 201811054398A CN 109261136 B CN109261136 B CN 109261136B
- Authority
- CN
- China
- Prior art keywords
- formaldehyde resin
- magnetic
- integral material
- melamine
- resin integral
- 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.)
- Active
Links
- 229920001807 Urea-formaldehyde Polymers 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 47
- HANVTCGOAROXMV-UHFFFAOYSA-N formaldehyde;1,3,5-triazine-2,4,6-triamine;urea Chemical compound O=C.NC(N)=O.NC1=NC(N)=NC(N)=N1 HANVTCGOAROXMV-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000011553 magnetic fluid Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 11
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 21
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 238000004140 cleaning Methods 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 229920000877 Melamine resin Polymers 0.000 claims description 12
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000006249 magnetic particle Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 229940093429 polyethylene glycol 6000 Drugs 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 14
- 150000002500 ions Chemical class 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 abstract description 7
- 239000002245 particle Substances 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000013590 bulk material Substances 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- -1 hydroxymethyl compound Chemical class 0.000 description 2
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000008118 PEG 6000 Substances 0.000 description 1
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
本发明涉及磁性树脂制备技术领域,公开了一种磁性三聚氰胺脲醛树脂整体材料的制备方法,通过在摩尔比为2:1的Fe3+与Fe2+溶液中加入氢氧化钠溶液制得纳米Fe3O4,再将纳米Fe3O4加入聚乙二醇中充分搅拌制得亲水性磁流体;将亲水性磁流体加入三聚氰胺脲醛树脂整体材料中合成制得磁性三聚氰胺脲醛树脂整体材料。本发明所制得的磁性脲醛树脂材料拥有成本较低,且材料为纳米级,粒径分布均匀,含有较多亲水性基团,对重金属离子具有较强的选择吸附能力。
Description
技术领域
本发明涉及磁性树脂制备技术领域,具体是一种磁性三聚氰胺脲醛树脂整体材料的制备方法。
背景技术
随着我国经济快速发展,矿冶、机械制造、化学工艺等生产过程中都会产生重金属废水,造成严重的重金属离子污染,成为水资源污染三大原因之一。由于重金属离子具有毒性和非生物降解性,饮用水中很低浓度的重金属离子借助生物链,经过生物浓缩、生物体内积累和生物放大过程,不仅会对人类造成危害,同时对水生动、植物而也会产生毒性和危害[3]。
目前,重金属离子污染的处理方法有物理吸附法,如碳吸附、膜处理,除去工艺主要有化学沉淀法、离子交换法、膜分离法、电解法等。其中离子交换法采用离子交换树脂对重金属进行交换,达到除去重金属的目的。
三聚氰胺脲醛树脂整体材料是通过三聚氰胺对脲醛树脂进行改性,可用于对重金属离子的吸附。但现有的三聚氰胺脲醛树脂整体材料对重金属离子的选择吸附能力较差,且三聚氰胺脲醛树脂整体材料在合成过程中链状的脲醛树脂聚合物的活性基团较多,通过三聚氰胺改性后得到的产物孔径不一致,且分布不均匀,对重金属离子的选择吸附性能较差。
发明内容
基于以上问题,本发明提供一种磁性三聚氰胺脲醛树脂整体材料的制备方法,通过本发明所制得的磁性三聚氰胺脲醛树脂整体材料成本较低,且材料为纳米级,粒径分布均匀,含有较多亲水性基团,对重金属离子具有较强的选择吸附能力。
为解决以上技术问题,本发明提供了以下技术方案:
一种磁性三聚氰胺脲醛树脂整体材料的制备方法,包括如下步骤:
S1、制备亲水性磁流体:
a1:在摩尔比为2:1的Fe3+与Fe2+的混合溶液中通入N2除去混合液中的氧气后,向混合液中加入NaOH溶液调节混合液pH值在9-10,将混合液加热到80℃恒温搅拌1h,分离出固体,清洗得到纳米Fe3O4;
a2:将a1中所得的纳米Fe3O4按质量比1:1加入聚乙二醇中,通过搅拌器搅拌24h后,用去离子水和无水乙醇反复洗涤至清洗液呈中性,然后用去离子水定容至纳米Fe3O4的质量分数为0.08g/ml,再用超声波充分打散30min形成亲水性磁流体;
S2:按质量份数取9份三聚氰胺脲醛树脂整体材料、1份步骤S1所制得的亲水性磁流体,充分混合均匀,加入甲酸调节pH为3.5-4,再在50摄氏度下恒温16h;
S3:将经S2处理后的材料取出,加入甲醇浸没,放在振荡器中震荡30min后将甲醇倾倒;重复加入甲醇并震荡、倾倒操作2-3次;之后再用去离子水震荡清洗30min,直至清洗液呈中性;
S4:将S3中所得材料置于50℃真空干燥箱干燥12h,得到磁性三聚氰胺脲醛树脂整体材料。
进一步地,步骤S1中的所用的聚乙二醇的平均相对分子量为900-1100。
进一步地,步骤S2中的三聚氰胺脲醛树脂整体材料通过如下操作步制得:
b1:按摩尔比1.4~1.6:1:0.2~0.3的比例分别称取甲醛、尿素、三聚氰胺备用;
b2:向带有搅拌器的三口烧瓶中分别加入b1中称取的50%三聚氰胺、85%的尿素,再将b1中称量好的甲醛加入三口烧瓶中,启动搅拌并通过加入20%的NaOH溶液调节pH值为9-10;维持溶液温度为45℃,搅拌1h;
b3:向所述三口烧瓶中分别加入b1中剩余的15%的尿素、50%的三聚氰胺,加热至85℃,并在恒温下调节在pH 7.5,持续搅拌2.5h;
b4:将b3中三口烧瓶内的混合物降温至45℃,加入混合物总质量8~10%的甲醇,并恒温30min,得到三聚氰胺脲醛树脂整体材料的前驱体凝胶;
b5:取b4中所得的前驱体凝胶,向其中加入前驱体凝胶总质量10~15%的乙腈的混合均匀,再将前驱体凝胶总质量25~35%的聚乙二醇6000溶解在前驱体凝胶与乙腈的混合液中;在溶液搅拌10min后加入前驱体凝胶总量10~20%的丙三醇,将混合物超声处理5min,并用氮气鼓泡5分钟以除去气体,得到三聚氰胺脲醛树脂整体材料。
进一步地,操作步S1与步骤S3中含有纳米Fe3O4的溶液在清洗后清洗液的倾倒过程中,均使用外加磁场对清洗液进行倾倒。
与现有技术相比,本发明的有益效果是:通过共沉淀法将亲水性磁流体与三聚氰胺脲醛树脂整体材料合成制得磁性三聚氰胺脲醛树脂整体材料,所制得的磁性三聚氰胺脲醛树脂整体材料具有很强的机械稳定性和耐强碱、强酸及有机试剂的能力;同时,固体表面大量氨基、羟基等亲水基团,对重金属离子具备较高的交换容量和较好的选择性,且可通过再生处理使之重复利用,在保证较高萃取和富集效率的同时又大幅节约了处理成本。
附图说明
图1为三聚氰胺脲醛树脂整体材料的SEM形貌图;
图2为核壳结构的磁性三聚氰胺脲醛树脂整体材料的SEM形貌图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白,下面结合实施例和附图,对本发明作进一步的详细说明,本发明的示意性实施方式及其说明仅用于解释本发明,并不作为对本发明的限定。
本实施例通过如下操作步骤进行磁性脲醛树脂的合成:
第一步:制备亲水性磁流体
称取9.3569g FeCl3·6H2O和3.4431g FeCl2·4H2O放入250mL烧瓶中,加入160mL纯水,向烧瓶中通入N230min,待除去混合液中的氧气后向其中加入20mL质量分数为25%的NaOH溶液,将混合液加热到80℃继续以600rpm转速恒温搅拌1h。结束后将成品分别用甲醇和水超声洗涤多次,借助外加磁场分离出纳米Fe3O4;
将所得的纳米Fe3O4加入2.0mL相对分子量为1000的聚乙二醇,在转速1000rpm条件下老化24h后,在磁场下用去离子水和无水乙醇反复洗涤,最后用去离子水定容至50mL,利用超声30min充分打散形成亲水性磁流体。
在高速机械搅拌下分别用聚乙二醇1000与磁性纳米Fe3O4充分混合,由于聚乙二醇表面含有羟基(—OH),在氢键和弱分子间力作用下与纳米Fe3O4上的O原子发生瞬间相互作用。经过长时间多次作用将纳米Fe3O4包覆其中;由于包覆一层聚乙二醇大分子,相对降低磁粒子吸引作用。同时在超声作用下充分打散,使得粒子之间不宜团聚,从而形成软核壳结构亲水性磁流体。
在清洗液的倾倒过程中,在烧瓶底部外加磁场,因磁场的作用使亲水性磁流体汇集于烧瓶底部,清洗液倾倒时不会使亲水性磁流体被倒出。
第二步:制备三聚氰胺脲醛树脂整体材料
将3.06g尿素,1.26g三聚氰胺和9.5mL 37%甲醛溶液放入三颈瓶中并搅拌混合,用20%NaOH溶液将混合物调节至pH 9.0,然后加热至45℃并保持1h;向混合物中加入0.54g尿素和1.26g三聚氰胺,加热至85℃,并在恒温下保持在pH 7.5,持续2.5h;将混合物降温至45℃,加入2mL甲醇,并恒温30min,得到三聚氰胺脲醛树脂整体材料的前驱体凝胶。
将0.90g PEG-6000溶解在3.0g前驱体凝胶和0.60mL乙腈的混合物中;在溶液搅拌10min后加入0.45g丙三醇,将混合物超声处理5min,并用氮气鼓泡5分钟以除去气体,得到三聚氰胺脲醛树脂整体材料。
在此过程中,甲醛与尿素在碱性条件下生成羟甲基化合物,当调节pH值5-6时,生成的羟甲基化合物在酸性条件下发生缩合反应,由活泼的羟甲基与尿素,或者羟甲基自身脱水缩聚生成脲醛树脂单体;当调节pH至酸性条件下时,脲醛树脂单体脱水缩聚生成线性的脲醛树脂聚合物;三聚氰胺的加入可以提高聚合物的机械稳定性和耐强碱、强酸能力,同时还大大减小了聚合物中游离甲醛的含量。与此同时,甲醛与三聚氰胺反应生成粘稠状的物质,并与聚合物反应生成三聚氰胺脲醛树脂整体材料的前驱体凝胶。
前驱体凝胶在聚乙二醇、乙腈和丙三醇组成的三元致孔剂作用下,形成空间网状结构的三聚氰胺脲醛树脂整体材料。其中,三元致孔剂的加入可以有效规避磁性三聚氰胺脲醛树脂整体材料在酸性条件下聚合成较大微球而影响后序对亲水性磁流体的包覆性能。
第三步:合成磁性三聚氰胺脲醛树脂整体材料
将约18g由第二步制得的三聚氰胺脲醛树脂整体材料加入至烧杯中,向其中加入1mL制备好的亲水性磁流体,搅拌均匀后加入甲酸调节pH至3.5-4.0,待混合均匀后,放入塑料管中封口,在50℃中水浴中恒温16h。
将塑料管中的材料从塑料管中取出,研碎。加入10mL甲醇放在恒温振荡器,震荡半小时,再外加磁场作用下将甲醇倾倒,再次加入10mL甲醇,按上述操作重复三次;之后再用10mL水清洗30min,重复三次,将致孔剂和未反应的溶剂除去,并将材料洗至中性后,置于50℃真空干燥箱干燥12h,得到具有核壳结构的磁性三聚氰胺脲醛树脂整体材料。
在此过程中,纳米Fe3O4外层包裹有聚乙二醇形成的亲水性磁流体,由于亲水性磁流体表面的羟基具有极性,易于和三聚氰胺脲醛树脂整体材料表面的极性基团相互作用,当在三聚氰胺脲醛树脂整体材料溶胶中分散亲水性磁流体后,调整好适当三聚氰胺脲醛树脂整体材料与亲水性磁流体质量比能够形成包覆磁核的磁性三聚氰胺脲醛树脂整体材料。
在室温下,通过将该方法制得的磁性三聚氰胺脲醛树脂整体材料进行Pb2+吸附实验,在Pb2+离子溶液pH值为7.5、吸附时间为60min时,最大吸附可达到33.8mg/g。
如上即为本发明的实施例。上述实施例以及实施例中的具体参数仅是为了清楚表述发明验证过程,并非用以限制本发明的专利保护范围,本发明的专利保护范围仍然以其权利要求书为准,凡是运用本发明的说明书及附图内容所作的等同结构变化,同理均应包含在本发明的保护范围内。
Claims (3)
1.一种磁性三聚氰胺脲醛树脂整体材料的制备方法,其特征在于,包括如下步骤:
S1、制备亲水性磁流体:
a1:在摩尔比为2:1的Fe3+与Fe2+的混合溶液中通入N2除去混合液中的氧气后,向混合液中加入NaOH溶液调节混合液pH值在9-10,将混合液加热到80℃恒温搅拌1h,分离出固体,清洗得到纳米Fe3O4;
a2:将a1中所得的纳米Fe3O4按质量比1:1加入聚乙二醇中,通过搅拌器搅拌24h后,用去离子水和无水乙醇反复洗涤至清洗液呈中性,然后用去离子水定容至纳米Fe3O4的浓度为0.08g/ml,再用超声波充分打散30min形成亲水性磁流体;
S2:按质量份数取9份三聚氰胺脲醛树脂整体材料、1份步骤S1所制得的亲水性磁流体,充分混合均匀,加入甲酸调节pH为3.5~4,再在50摄氏度下恒温16h;所述步骤S2中所采用的三聚氰胺脲醛树脂整体材料通过如下操作步骤 制得:
b1:按摩尔比1.4~1.6:1:0.2~0.3的比例分别称取甲醛、尿素、三聚氰胺备用;
b2:向带有搅拌器的三口烧瓶中分别加入b1中称取的50%三聚氰胺、85%的尿素,再将b1中称量好的甲醛加入三口烧瓶中,启动搅拌并通过加入20%的NaOH溶液调节pH值为9-10;维持溶液温度为45℃,搅拌1h;
b3:向所述三口烧瓶中分别加入b1中剩余的15%的尿素、50%的三聚氰胺,加热至85℃,并在恒温下调节pH在7.5,持续搅拌2.5h;
b4:将b3中三口烧瓶内的混合物降温至45℃,加入混合物总质量8~10%的甲醇,并恒温30min,得到三聚氰胺脲醛树脂整体材料的前驱体凝胶;
b5:取b4中所得的前驱体凝胶,向其中加入占前驱体凝胶总质量10~15%的乙腈并混合均匀,再将前驱体凝胶总质量25~35%的聚乙二醇6000溶解在前驱体凝胶与乙腈的混合液中;在溶液搅拌10min后加入前驱体凝胶总量10~20%的丙三醇,将混合物超声处理5min,并用氮气鼓泡5分钟以除去气体,得到三聚氰胺脲醛树脂整体材料;
S3:将经S2处理后的材料取出,加入甲醇浸没,放在振荡器中震荡30min后将甲醇倾倒;重复加入甲醇并震荡、倾倒操作2-3次;之后再用去离子水震荡清洗30min,直至清洗液呈中性;
S4:将S3中所得材料置于50℃真空干燥箱干燥12h,得到磁性三聚氰胺脲醛树脂整体材料。
2.根据权利要求1所述的一种磁性三聚氰胺脲醛树脂整体材料的制备方法,其特征在于:所述步骤S1中的所用的聚乙二醇的平均相对分子量为900-1100。
3.根据权利要求1所述的一种磁性三聚氰胺脲醛树脂整体材料的制备方法,其特征在于:所述步骤S1与步骤S3中含有Fe3O4的溶液在清洗后清洗液的倾倒过程中,均使用外加磁场对清洗液进行倾倒。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811054398.1A CN109261136B (zh) | 2018-09-11 | 2018-09-11 | 一种磁性三聚氰胺脲醛树脂整体材料的制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811054398.1A CN109261136B (zh) | 2018-09-11 | 2018-09-11 | 一种磁性三聚氰胺脲醛树脂整体材料的制备方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109261136A CN109261136A (zh) | 2019-01-25 |
CN109261136B true CN109261136B (zh) | 2021-07-23 |
Family
ID=65188284
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811054398.1A Active CN109261136B (zh) | 2018-09-11 | 2018-09-11 | 一种磁性三聚氰胺脲醛树脂整体材料的制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109261136B (zh) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115074084B (zh) * | 2022-06-08 | 2023-11-17 | 南京信息工程大学 | 一种四氧化三铁、碳核壳结构复合微粒的制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1480476A (zh) * | 2003-07-21 | 2004-03-10 | 天津大学 | 铁磁性脲醛树脂微球介质及其制备方法 |
CN101574637A (zh) * | 2008-05-08 | 2009-11-11 | 南京理工大学 | 磁性相变微胶囊及其制备方法 |
CN102188957A (zh) * | 2011-04-26 | 2011-09-21 | 湖南大学 | 聚乙烯亚胺修饰的磁性多孔吸附剂及其制备方法和应用 |
CN103130973A (zh) * | 2011-11-28 | 2013-06-05 | 同济大学 | 一种合成三聚氰胺脲醛树脂微球的方法 |
-
2018
- 2018-09-11 CN CN201811054398.1A patent/CN109261136B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1480476A (zh) * | 2003-07-21 | 2004-03-10 | 天津大学 | 铁磁性脲醛树脂微球介质及其制备方法 |
CN101574637A (zh) * | 2008-05-08 | 2009-11-11 | 南京理工大学 | 磁性相变微胶囊及其制备方法 |
CN102188957A (zh) * | 2011-04-26 | 2011-09-21 | 湖南大学 | 聚乙烯亚胺修饰的磁性多孔吸附剂及其制备方法和应用 |
CN103130973A (zh) * | 2011-11-28 | 2013-06-05 | 同济大学 | 一种合成三聚氰胺脲醛树脂微球的方法 |
Non-Patent Citations (2)
Title |
---|
Functionalized Fe3O4 nanoparticles for the removal and remediation of CrVI metal ions from synthetic solutions;A. Sivaraman et al.;《J. Indian Chem. Soc.》;20150531;第92卷;第673页实验和结论部分 * |
Synthesis and characterization of superparamagnetic poly(urea-formaldehyde) adsorbents and their use for adsorption of flavonoids from Glycyrrhiza uralensis Fisch;B. Zhang et al.;《Adsorption》;20071120;第14卷;第66-67页第2.2.1-2.2.2节 * |
Also Published As
Publication number | Publication date |
---|---|
CN109261136A (zh) | 2019-01-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN101314123B (zh) | 一种磁性生物吸附剂及其制备方法 | |
CN111004411B (zh) | 一种用于选择性分离四环素的生物质基分子印迹复合膜的制备方法 | |
Chen et al. | Immobilization of a thiol-functionalized ionic liquid onto HKUST-1 through thiol compounds as the chemical bridge | |
CN103709340B (zh) | 粉末活性炭表面接枝聚(n-异丙基丙烯酰胺)的方法 | |
CN101071669A (zh) | 电子束辐照制备具有核壳结构的磁性复合微球的方法 | |
CN105237586A (zh) | 新型双核有机骨架材料MIL-100(Fe-Mn)的制备和应用 | |
CN110227419B (zh) | 一种腐植酸/β-环糊精聚合物、复合微球及其制备方法 | |
CN106220866B (zh) | 一种对铜离子具有高吸附性磁性水凝胶的制备方法 | |
CN106745317A (zh) | 一步法制备多孔四氧化三铁磁性纳米微球的方法及其应用 | |
CN107952481B (zh) | 一种负载贵金属纳米粒子的多孔材料催化剂及其制备方法 | |
CN111468076A (zh) | 富氨基化合物修饰的壳聚糖-锆复合凝胶球及制备与应用 | |
CN113750968A (zh) | 一种不溶于水的环糊精基金属有机骨架材料及其制备方法 | |
CN107999019B (zh) | 一种两亲性磁性纳米球及其制备方法和吸附应用 | |
CN109261136B (zh) | 一种磁性三聚氰胺脲醛树脂整体材料的制备方法 | |
KR20120065848A (ko) | 금속 이온 각인된 미세다공성 고분자 입자의 제조방법 | |
CN105037630B (zh) | 一种亲水性聚合物微球及其简易制备方法 | |
CN113083236A (zh) | 一种磁性MOFs-生物炭复合材料的制备方法及应用 | |
CN108636379A (zh) | 一种带正电聚苯乙烯微球及其制备方法和应用 | |
Li et al. | A Substrate‐Selective Nanoreactor Made of Molecularly Imprinted Polymer Containing Catalytic Silver Nanoparticles | |
CN101670275B (zh) | 一种三维有序大孔螯合树脂的制备方法 | |
CN1195305C (zh) | 一种Fe3O4微粒及其制备方法 | |
CN113122938A (zh) | 含MOFs的壳聚糖/聚乙烯醇纳米纤维膜的制备方法及应用 | |
CN102921393B (zh) | 一种颗粒状三维有序大孔螯合树脂的制备方法 | |
CN108722360A (zh) | 一种复合壳聚糖的制备方法 | |
AU2021100127A4 (en) | A preparation method of magnetic melamine urea-formaldehyde resin monolithic material |
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 | ||
EE01 | Entry into force of recordation of patent licensing contract | ||
EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20190125 Assignee: Meidou Technology Service Zhangjiakou Co.,Ltd. Assignor: HEBEI NORTH University Contract record no.: X2023980053195 Denomination of invention: Preparation method of magnetic melamine urea formaldehyde resin as a whole material Granted publication date: 20210723 License type: Common License Record date: 20231219 |