CN114426682B - 一种MXene高强度复合水凝胶及其制备方法和应用 - Google Patents
一种MXene高强度复合水凝胶及其制备方法和应用 Download PDFInfo
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- CN114426682B CN114426682B CN202210116414.5A CN202210116414A CN114426682B CN 114426682 B CN114426682 B CN 114426682B CN 202210116414 A CN202210116414 A CN 202210116414A CN 114426682 B CN114426682 B CN 114426682B
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 109
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002135 nanosheet Substances 0.000 claims abstract description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 15
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical group NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 9
- 239000003999 initiator Substances 0.000 claims abstract description 7
- 229960003638 dopamine Drugs 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- 238000004873 anchoring Methods 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 20
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical group C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 10
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 6
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 4
- 150000004673 fluoride salts Chemical class 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- 239000004328 sodium tetraborate Substances 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
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- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 abstract description 12
- 125000006325 2-propenyl amino group Chemical group [H]C([H])=C([H])C([H])([H])N([H])* 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 6
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- 239000010936 titanium Substances 0.000 description 52
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- 238000001291 vacuum drying Methods 0.000 description 21
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- 230000000052 comparative effect Effects 0.000 description 18
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 4
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000008272 agar Substances 0.000 description 3
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- 229910010293 ceramic material Inorganic materials 0.000 description 3
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000009878 intermolecular interaction Effects 0.000 description 2
- 229910052757 nitrogen Chemical group 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
- 239000002158 endotoxin Substances 0.000 description 1
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- 238000000605 extraction Methods 0.000 description 1
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- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920006008 lipopolysaccharide Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
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- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- 239000000047 product Substances 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
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- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种Mxene高强度复合水凝胶及其制备方法和应用,属于纳米复合材料技术领域。该制备方法为:将原始Mxene加入到水中,空气气氛下低温超声处理得到剥离后的Mxene纳米片溶液;向该溶液加入4‑((烯丙氨基)甲基)苯‑1,2‑二醇、无水乙醇,通过多巴胺基团的锚固作用,得到表面功能化的Mxene纳米片;将其分散到水中,然后再加入单体、交联剂,混合均匀得到水凝胶预聚液,在水凝胶预聚液中加入引发剂,室温静置发生聚合反应,得到Mxene高强度复合水凝胶。通过本发明的制备方法,MXene在水凝胶中均匀分布,且制备得到的Mxene高强度复合水凝胶力学性能大幅提高的同时赋予其功能化特性。
Description
技术领域
本发明涉及纳米复合材料技术领域,更具体的涉及一种Mxene高强度复合水凝胶及其制备方法和应用。
背景技术
水凝胶材料是一种具有三维交联网络的湿软材料,具有极强的亲水性,其组分中水的含量占相当大的比重,具有优异的生物相容性,在生物材料、可穿戴器件、智能传感器等领域有广泛的应用前景。然而传统化学交联的水凝胶力学性能较差且缺乏功能性,限制了水凝胶在许多方面的应用。
纳米微粒是一种广泛应用的聚合物填充材料,将纳米颗粒添加到聚合物系统,得到的纳米复合材料可以使得机械性能,热稳定性,抗老化性等发生明显的提高。水凝胶系统是一种含水量高的聚合物系统,因此选择亲水性高的纳米颗粒可以有效提升水凝胶的物理化学性能。
MXene是一类新型的二维过渡金属碳/氮化物,通过对其前驱体MAX陶瓷材料刻蚀,去掉其中的金属元素得到,其化学式可表示为Mn+1XnTx,M代表过渡金属元素(如钛、钼、钒等),X代表碳或氮元素,T代表刻蚀过程中在表面产生的官能团(如-F、-OH、=O等),n一般为1、2、3。MXene具有出色的机械强度、高亲水性和比表面积、丰富的表面活性位点,将MXene加入到水凝胶中是一种改善水凝胶力学性能,拓宽水凝胶应用范围的良好且高效的方法。但是高浓度的MXene添加到水凝胶中易发生自聚集、难以得到均匀分布的MXene复合水凝胶。
发明内容
针对以上问题,本发明提供一种Mxene高强度复合水凝胶及其制备方法和应用,MXene在水凝胶中均匀分布,且制备得到的Mxene高强度复合水凝胶力学性能大幅提高的同时赋予其功能化特性。
本发明的第一个目的是提供一种Mxene高强度复合水凝胶的制备方法,按照以下步骤制备:
步骤1、将原始Mxene加入到水中,空气气氛下低温超声处理得到剥离后的Mxene纳米片溶液;
向剥离后的Mxene纳米片溶液加入4-((烯丙氨基)甲基)苯-1,2-二醇、无水乙醇,通过多巴胺基团的锚固作用,得到表面功能化的Mxene纳米片;
步骤2、将表面功能化的Mxene纳米片分散到水中,然后再加入单体、交联剂,混合均匀得到水凝胶预聚液,在水凝胶预聚液中加入引发剂,室温静置发生聚合反应,得到Mxene高强度复合水凝胶。
优选的,步骤1中Mxene为Ti3C2Tx,所述Ti3C2Tx是通过HCl和氟化物盐溶液对Ti3AlC2刻蚀得到。
优选的,步骤1中,原始Mxene与水的比例为4-6mg:1mL;超声时间为30-40min;
原始Mxene纳米片、4-((烯丙氨基)甲基)苯-1,2-二醇、无水乙醇的比例为4-6mg:2-12mg:1mL,反应时间为12-24h。
优选的,步骤1中,4-((烯丙氨基)甲基)苯-1,2-二醇是由盐酸多巴胺与丙烯酰氯在硼砂水溶液中发生取代反应得到的;反应温度为室温,反应时间为12-48h。
优选的,步骤2中、所述水凝胶预聚液中,表面功能化的Mxene纳米片、单体、交联剂、水的比例为20-40mg:60-70mmol:0-9.24mg:10mL。
优选的,步骤2中,所述单体为丙烯酰胺、N-异丙基丙烯酰胺、N,N-二甲基丙烯酰胺、丙烯酸、甲基丙烯酸中的一种或几种。
优选的,步骤2中,所述交联剂为N,N-亚甲基双丙烯酰胺。
优选的,步骤2中,所述引发剂为过硫酸铵、过硫酸钾、过硫酸钠中的一种,所述引发剂的质量为单体添加量的0.2-1%。
本发明的第二个目的是提供一种根据上述制备方法制备得到的Mxene高强度复合水凝胶。
本发明的第三个目的是提供上述Mxene高强度复合水凝胶在制备生物润滑剂及抗菌涂层中的应用。
本发明的机理为:
本发明首先通过HCl和氟化物盐溶液刻蚀MAX材料得到MXene,并将盐酸多巴胺与丙烯酰氯在硼砂水溶液中发生取代反应得到含多巴胺结构的丙烯酰胺—4-((烯丙氨基)甲基)苯-1,2-二醇。通过多巴胺基团的锚固作用,使4-((烯丙氨基)甲基)苯-1,2-二醇接枝在MXene表面,得到表面功能化的MXene纳米片。将表面功能化的MXene纳米片加入水凝胶预聚液中,通过聚合反应得到MXene复合水凝胶,高比表面积的MXene纳米片和聚合物具有分子间相互作用,起到动态交联的效果,产生密集缠结的聚合物网络结构。
与现有技术相比,本发明具有以下有益效果:
(1)、本发明的水凝胶力学性能优异,具有较宽的应变范围,拉伸应变最大可达1070%,拉伸应力最大可达73kPa
(2)、本发明的水凝胶具有良好的抗菌效果及自修复性能
(3)、本发明的水凝胶制备工艺简单,不需要光热引发,室温下可快速凝胶。
附图说明
图1为实施例1-2及对比例2-3制备的水凝胶的扫描电镜图,其中图1a为对比例2制备的水凝胶的扫描电镜图,图1b为实施例1制备的水凝胶的扫描电镜图,图1c为对比例3制备的水凝胶的扫描电镜图,图1d为实施例2制备的水凝胶的扫描电镜图;
图2为不同水凝胶的力学性能图;
图3为不同水凝胶及生理盐水对大肠杆菌的抗菌结果,其中,图3a为生理盐水的抗菌效果,图3b为对比例1制备的PAA+NIPAM的抗菌效果,图3c为对比例2制备的Ti3C2Tx/PAA+PNIPAM的抗菌效果,图3d为实施例1制备的AMBD-Ti3C2Tx/PAA+PNIPAM的抗菌效果;
图4为不同水凝胶及生理盐水对金黄色葡萄球菌的抗菌结果,其中,图4a为生理盐水的抗菌效果,图4b为对比例1制备的PAA+NIPAM的抗菌效果,图4c为对比例2制备的Ti3C2Tx/PAA+PNIPAM的抗菌效果,图4d为实施例1制备的AMBD-Ti3C2Tx/PAA+PNIPAM的抗菌效果;
图5为实施例3制备的MXene高强度复合水凝胶的自修复性能。
具体实施方式
下面将结合本发明实施例中的附图,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
本发明所用Mxene为Ti3C2Tx,所述Ti3C2Tx通过对Ti3AlC2经过HCl和氟化物盐溶液刻蚀得到,具体的制备方法为将5gNaF和5gNH4F加入100mL 12M盐酸中,在55℃条件下搅拌72h以剥离Al相得到手风琴状的多层Ti3C2Tx纳米片。将剥离产物在超纯水中反复离心(3500r/min,5min)洗涤至上清液pH值大于6。
实施例1
将100mg Ti3C2Tx加入20mL超纯水中定向超声(超声时间30min,功率320w,温度5℃)。超声结束后加入20mL无水乙醇与50mg表面修饰剂AMBD,在室温下搅拌24h,分别用超纯水和无水乙醇离心洗涤3次(离心转速10000r/min,离心时间5min),然后在真空干燥箱中40℃烘干12h,得到表面功能化的MXene纳米片,记为AMBD-Ti3C2Tx。
将40mgAMBD-Ti3C2Tx加入25mL烧杯中,加入10mL超纯水定向超声(超声时间30min,功率320w,温度5℃),然后加入4.32g(60mmol)丙烯酸,1.13g(10mmol)N-异丙基丙烯酰胺,9.24mgN,N-亚甲基双丙烯酰胺,混合均匀后补加适量超纯水配制成20mL的水凝胶预聚液,在真空干燥箱中抽负压保持30min除去预聚液中的气泡后加入54.5mg(单体添加量的1%)的过硫酸铵,然后以两块间隔为2mm的玻璃板为模具将预聚液加入玻璃板间,室温下静置30min得到MXene高强度复合水凝胶,记为AMBD-Ti3C2Tx/PAA+PNIPAM。
本实施例中表面修饰剂AMBD的制备方法为:
在250mL的圆底烧瓶中加入3.83g(10mmol)硼砂后加入100mL超纯水,使用氮气脱气30min后加入1.90g(10mmol)盐酸多巴胺,搅拌15min使盐酸多巴胺完全溶解后加入3.99g(10mmol)Na2CO3·10H2O以调节pH至9-10。之后将圆底烧瓶放置在冰水浴装置中,缓慢加入0.81mL(10mmol)丙烯酰氯,在氩气保护下反应24h,在反应开始6h后补加1.50gNa2CO3·10H2O(2.9mmol)以维持pH在9-10。反应结束后使用2M稀盐酸酸化溶液使pH达到2后使用乙酸乙酯萃取三次,收集上层有机提取物,用无水硫酸镁干燥后在旋转蒸发仪上旋蒸得到棕黄色的粗产物。将粗产物通过硅胶柱层析(甲醇:三氯甲烷=1:20)后旋蒸得到白色粉末状表面修饰剂AMBD。
实施例2
将100mg Ti3C2Tx加入20mL超纯水中定向超声(超声时间30min,功率320w,温度5℃)。超声结束后加入20m L无水乙醇与50mg表面修饰剂AMBD,在室温下搅拌24h,分别用超纯水和无水乙醇离心洗涤3次(离心转速10000r/min,离心时间5min),然后在真空干燥箱中烘干12h(温度40℃)即得到表面功能化的MXene纳米片,记为AMBD-Ti3C2Tx。
将40mgAMBD-Ti3C2Tx加入25mL烧杯中,加入10mL超纯水定向超声(超声时间30min,功率320w,温度5℃),然后加入4.26g(60mmol)丙烯酰胺,1.13g(10mmol)N-异丙基丙烯酰胺,9.24mg N,N-亚甲基双丙烯酰胺,混合均匀后补加适量超纯水配制成20mL的水凝胶预聚液,在真空干燥箱中抽负压保持30min除去预聚液中的气泡后加入54.5mg(单体添加量的1%)的过硫酸铵,然后以两块间隔为2mm的玻璃板为模具将预聚液加入玻璃板间,室温下静置30min得到MXene高强度复合水凝胶,记为AMBD-Ti3C2Tx/PAAm+PNIPAM。
本实施例中所用表面修饰剂AMBD的制备方法与实施例1相同。
实施例3
将100mg Ti3C2Tx加入20mL超纯水中定向超声(超声时间30min,功率320w,温度5℃)。超声结束后加入20m L无水乙醇与50mg表面修饰剂AMBD,在室温下搅拌24h,分别用超纯水和无水乙醇离心洗涤3次(离心转速10000r/min,离心时间5min),然后在真空干燥箱中烘干12h(温度40℃)即得到表面功能化的MXene纳米片AMBD-Ti3C2Tx。
将40mgAMBD-Ti3C2Tx加入25mL烧杯中,加入10mL超纯水定向超声(超声时间30min,功率320w,温度5℃),然后加入4.32g(60mmol)丙烯酸,1.13g(10mmol)N-异丙基丙烯酰胺,混合均匀后补加适量超纯水配制成20mL的水凝胶预聚液,在真空干燥箱中抽负压保持30min除去预聚液中的气泡后加入54.5mg(单体添加量的1%)的过硫酸铵,然后加入到玻璃培养皿中,室温下静置30min得到MXene高强度复合水凝胶。
本实施例中所用表面修饰剂AMBD的制备方法与实施例1相同。
实施例4
将80mg Ti3C2Tx加入20mL超纯水中定向超声(超声时间40min,功率320w,温度5℃)。超声结束后加入20mL无水乙醇与80mg表面修饰剂AMBD,在室温下搅拌24h,分别用超纯水和无水乙醇离心洗涤3次(离心转速10000r/min,离心时间5min),然后在真空干燥箱中40℃烘干12h,得到表面功能化的MXene纳米片,记为AMBD-Ti3C2Tx。
将20mgAMBD-Ti3C2Tx加入25mL烧杯中,加入10mL超纯水定向超声(超声时间30min,功率320w,温度5℃),然后加入6.94g(70mmol)N,N-二甲基丙烯酰胺,5.76mg N,N-亚甲基双丙烯酰胺,混合均匀后补加适量超纯水配制成20mL的水凝胶预聚液,在真空干燥箱中抽负压保持30min除去预聚液中的气泡后加入13.9mg(单体添加量的0.2%)的过硫酸铵,然后以两块间隔为2mm的玻璃板为模具将预聚液加入玻璃板间,室温下静置30min得到MXene高强度复合水凝胶。
本实施例中所用表面修饰剂AMBD的制备方法与实施例1相同。
实施例5
将60mg Ti3C2Tx加入10mL超纯水中定向超声(超声时间30min,功率320w,温度5℃)。超声结束后加入10mL无水乙醇与120mg表面修饰剂AMBD,在室温下搅拌12h,分别用超纯水和无水乙醇离心洗涤3次(离心转速10000r/min,离心时间5min),然后在真空干燥箱中40℃烘干12h,得到表面功能化的MXene纳米片,记为AMBD-Ti3C2Tx。
将20mgAMBD-Ti3C2Tx加入25mL烧杯中,加入10mL超纯水定向超声(超声时间30min,功率320w,温度5℃),然后加入4.32g(60mmol)丙烯酸,9.24mgN,N-亚甲基双丙烯酰胺,混合均匀后补加适量超纯水配制成20mL的水凝胶预聚液,在真空干燥箱中抽负压保持30min除去预聚液中的气泡后加入43.2mg(单体添加量的1%)的过硫酸铵,然后以两块间隔为2mm的玻璃板为模具将预聚液加入玻璃板间,室温下静置30min得到MXene高强度复合水凝胶。
本实施例中所用表面修饰剂AMBD的制备方法与实施例1相同,区别仅在于,在氩气保护下反应12h。
实施例6
将80mg Ti3C2Tx加入20mL超纯水中定向超声(超声时间35min,功率320w,温度5℃)。超声结束后加入20mL无水乙醇与40mg表面修饰剂AMBD,在室温下搅拌24h,分别用超纯水和无水乙醇离心洗涤3次(离心转速10000r/min,离心时间5min),然后在真空干燥箱中40℃烘干12h,得到表面功能化的MXene纳米片,记为AMBD-Ti3C2Tx。
将30mgAMBD-Ti3C2Tx加入25mL烧杯中,加入10mL超纯水定向超声(超声时间30min,功率320w,温度5℃),然后加入5.60g(65mmol)甲基丙烯酸,9.24mgN,N-亚甲基双丙烯酰胺,混合均匀后补加适量超纯水配制成20mL的水凝胶预聚液,在真空干燥箱中抽负压保持30min除去预聚液中的气泡后加入44.8mg(单体添加量的0.8%)的过硫酸铵,然后以两块间隔为2mm的玻璃板为模具将预聚液加入玻璃板间,室温下静置30min得到MXene高强度复合水凝胶。
本实施例中所用表面修饰剂AMBD的制备方法与实施例5相同,区别仅在于,在氩气保护下反应24h。
实施例7
将100mg Ti3C2Tx加入20mL超纯水中定向超声(超声时间30min,功率320w,温度5℃)。超声结束后加入20mL无水乙醇与200mg表面修饰剂AMBD,在室温下搅拌18h,分别用超纯水和无水乙醇离心洗涤3次(离心转速10000r/min,离心时间5min),然后在真空干燥箱中40℃烘干12h,得到表面功能化的MXene纳米片,记为AMBD-Ti3C2Tx。
将40mgAMBD-Ti3C2Tx加入25mL烧杯中,加入10mL超纯水定向超声(超声时间30min,功率320w,温度5℃),然后加入4.32g(60mmol)丙烯酸,1.13g(10mmol)N-异丙基丙烯酰胺,9.24mg N,N-亚甲基双丙烯酰胺,混合均匀后补加适量超纯水配制成20mL的水凝胶预聚液,在真空干燥箱中抽负压保持30min除去预聚液中的气泡后加入54.5mg(单体添加量的1%)的过硫酸钠,然后以两块间隔为2mm的玻璃板为模具将预聚液加入玻璃板间,室温下静置30min得到MXene高强度复合水凝胶。
本实施例中所用表面修饰剂AMBD的制备方法与实施例5相同,区别仅在于,在氩气保护下反应48h。
实施例8
将90mg Ti3C2Tx加入15mL超纯水中定向超声(超声时间30min,功率320w,温度5℃)。超声结束后加入15mL无水乙醇与60mg表面修饰剂AMBD,在室温下搅拌20h,分别用超纯水和无水乙醇离心洗涤3次(离心转速10000r/min,离心时间5min),然后在真空干燥箱中40℃烘干12h,得到表面功能化的MXene纳米片,记为AMBD-Ti3C2Tx。
将40mgAMBD-Ti3C2Tx加入25mL烧杯中,加入10mL超纯水定向超声(超声时间30min,功率320w,温度5℃),然后加入4.32g(60mmol)丙烯酸,1.13g(10mmol)N-异丙基丙烯酰胺,9.24mg N,N-亚甲基双丙烯酰胺,混合均匀后补加适量超纯水配制成20mL的水凝胶预聚液,在真空干燥箱中抽负压保持30min除去预聚液中的气泡后加入54.5mg(单体添加量的1%)的过硫酸钾,然后以两块间隔为2mm的玻璃板为模具将预聚液加入玻璃板间,室温下静置30min得到MXene高强度复合水凝胶。
本实施例中所用表面修饰剂AMBD的制备方法与实施例5相同,区别仅在于,在氩气保护下反应18h。
对比例1
本对比例制备的是未添加MXene的水凝胶
在10mL超纯水加入4.32g(60mmol)丙烯酸,1.13g(10mmol)N-异丙基丙烯酰胺,9.24mg N,N-亚甲基双丙烯酰胺,混合均匀后补加适量超纯水配制成20mL的水凝胶预聚液,在真空干燥箱中抽负压保持30min除去预聚液中的气泡后加入54.5mg(单体添加量的1%)的过硫酸铵,然后以两块间隔为2mm的玻璃板为模具将预聚液加入玻璃板间,室温下静置30min得到水凝胶,记为PAA+PNIPAM。
对比例2
将100mg Ti3C2Tx加入20mL超纯水中定向超声(超声时间30min,功率320w,温度5℃)。超声结束后分别用超纯水和无水乙醇离心洗涤3次(离心转速10000r/min,离心时间5min),然后在真空干燥箱中烘干12h(温度40℃)即得到未表面功能化的单层及少层MXene纳米片。
将40mg未表面功能化的单层及少层MXene纳米片加入25mL烧杯中,加入10mL超纯水定向超声(超声时间30min,功率320w,温度5℃),然后加入4.32g(60mmol)丙烯酸,1.13g(10mmol)N-异丙基丙烯酰胺,9.24mgN,N-亚甲基双丙烯酰胺,混合均匀后补加适量超纯水配制成20mL的水凝胶预聚液,在真空干燥箱中抽负压保持30min除去预聚液中的气泡后加入54.5mg(单体添加量的1%)的过硫酸铵,然后以两块间隔为2mm的玻璃板为模具将预聚液加入玻璃板间,室温下静置30min得到MXene高强度复合水凝胶,记为Ti3C2Tx/PAA+PNIPAM。
对比例3
将100mg Ti3C2Tx加入20mL超纯水中定向超声(超声时间30min,功率320w,温度5℃)。超声结束后分别用超纯水和无水乙醇离心洗涤3次(离心转速10000r/min,离心时间5min),然后在真空干燥箱中烘干12h(温度40℃)即得到未表面功能化的单层及少层MXene纳米片。
将40mg未表面功能化的单层及少层MXene纳米片加入25mL烧杯中,加入10mL超纯水定向超声(超声时间30min,功率320w,温度5℃),然后加入4.26g(60mmol)丙烯酰胺,1.13g(10mmol)N-异丙基丙烯酰胺,9.24mg N,N-亚甲基双丙烯酰胺,混合均匀后补加适量超纯水配制成20mL的水凝胶预聚液,在真空干燥箱中抽负压保持30min除去预聚液中的气泡后加入54.5mg(单体添加量的1%)的过硫酸铵,然后以两块间隔为2mm的玻璃板为模具将预聚液加入玻璃板间,室温下静置30min得到MXene高强度复合水凝胶,记为Ti3C2Tx/PAAm+PNIPAM。
图1为实施例1-2及对比例2-3制备的水凝胶的扫描电镜图,其中图1a为对比例2制备的水凝胶的扫描电镜图,即添加未表面修饰MXene的PAA+PNIPAM水凝胶(Ti3C2Tx/PAA+PNIPAM),图1b为实施例1制备的水凝胶的扫描电镜图,即为添加表面修饰剂MXene的PAA+PNIPAM水凝胶(AMBD-Ti3C2Tx/PAA+PNIPAM),图1c为对比例3制备的水凝胶的扫描电镜图,即为添加未表面修饰MXene的PAAm+PNIPAM水凝胶(Ti3C2Tx/PAAm+PNIPAM),图1d为实施例2制备的水凝胶的扫描电镜图,即为添加表面修饰剂MXene的PAAm+PNIPAM水凝胶(AMBD-Ti3C2Tx/PAAm+PNIPAM)。从图1中可以看出所制备的MXene高强度复合水凝胶具有均匀的三维交联网络,说明MXene纳米片均匀的分布在水凝胶系统中。
图2为不同水凝胶的力学性能图,可以看出未添加MXene时,PAA+NIPAM水凝胶发生断裂时的拉伸应力为40.30kPa,拉伸应变为513.5%。添加未进行表面修饰的MXene时,Ti3C2Tx/PAA+PNIPAM水凝胶发生断裂时的拉伸应力升高到71.53kPa,相比于PAA+NIPAM水凝胶增加了31.23kPa,拉伸应变升高到812.8%,相比于PAA+NIPAM水凝胶提升了300.3%。添加表面修饰后的MXene时,AMBD-Ti3C2Tx/PAA+PNIPAM水凝胶发生断裂时的拉伸应力增加至73.62kPa,相比于PAA+NIPAM水凝胶增加了33.32kPa,拉伸应变进一步增加至1070.4%,相比于PAA+NIPAM水凝胶提升了556.9%,显示出良好的形变能力,说明表面修饰MXene的加入显著提升了水凝胶的力学性能。
图3为不同水凝胶及生理盐水对大肠杆菌的抗菌结果,其中,图3a为生理盐水的抗菌效果,生理盐水作为空白对照样,图3b为对比例1制备的PAA+NIPAM的抗菌效果,图3c为对比例2制备的Ti3C2Tx/PAA+PNIPAM的抗菌效果,图3d为实施例1制备的AMBD-Ti3C2Tx/PAA+PNIPAM的抗菌效果。
图4为不同水凝胶及生理盐水对金黄色葡萄球菌的抗菌结果,其中,图4a为生理盐水的抗菌效果,生理盐水作为空白对照样,图4b为对比例1制备的PAA+NIPAM的抗菌效果,图4c为对比例2制备的Ti3C2Tx/PAA+PNIPAM的抗菌效果,图4d为实施例1制备的AMBD-Ti3C2Tx/PAA+PNIPAM的抗菌效果。
从图3和图4可以看出,空白对照样的琼脂表面出现了大量且密集的菌落,使用PAA+PNIPAM水凝胶培养的琼脂表面出现菌落,但数量明显减少,而Ti3C2Tx/PAA+PNIPAM和AMBD-Ti3C2Tx/PAA+PNIPAM培养的琼脂表面几乎未见菌落出现,说明MXene的加入产生了良好的抗菌效果。MXene纳米片与水凝胶网络中的其他聚合物之间可以通过离子相互作用、氢键和/或共价键的方式连接,起到提高力学性能的作用,高亲水性可以确保MXene在水凝胶中均匀分散,高比表面积且边缘锋利的MXene纳米片可以破坏细菌的细胞膜使其失活,MXene表面的含氧基团与细胞膜的脂多糖链之间的氢键可通过阻止营养摄入的方式来抑制细菌的生长,因此具有良好的抗菌效果。
图5为实施例3所制备水凝胶的自修复性能。将圆片状的水凝胶用美工刀切割成两片,然后将水凝胶的断面相接触,放置一段时间后发现水凝胶发生自修复,用手拉伸发现断面重新连接在了一起。具有自修复效果的原因是MXene在水凝胶中起到物理交联剂的作用,MXene表面具有的-OH官能团和活性位点与聚合物具有分子间相互作用,作为物理交联剂加入到水凝胶中能够与聚合物发生动态交联使其具有了自修复性能。
尽管已描述了本发明的优选实施例,但本领域内的技术人员一旦得知了基本创造性概念,则可对这些实施例作出另外的变更和修改。所以,所附权利要求意欲解释为包括优选实施例以及落入本发明范围的所有变更和修改。
显然,本领域的技术人员可以对本发明进行各种改动和变型而不脱离本发明的精神和范围。这样,倘若本发明的这些修改和变型属于本发明权利要求及其等同技术的范围之内,则本发明也意图包含这些改动和变型在内。
Claims (8)
1.一种Mxene高强度复合水凝胶的制备方法,其特征在于,按照以下步骤制备:
步骤1、将原始Mxene加入到水中,空气气氛下低温超声处理得到剥离后的Mxene纳米片溶液;
向剥离后的Mxene纳米片溶液加入N-(3,4-二羟基苯乙基)丙烯酰胺、无水乙醇,通过多巴胺基团的锚固作用,得到表面功能化的Mxene纳米片;
步骤1中,原始Mxene与水的比例为4-6mg:1mL;超声时间为30-40mi n;
原始Mxene纳米片、N-(3,4-二羟基苯乙基)丙烯酰胺、无水乙醇的比例为4-6mg:2-12mg:1mL,反应时间为12-24h;
步骤2、将表面功能化的Mxene纳米片分散到水中,然后再加入单体、交联剂,混合均匀得到水凝胶预聚液,在水凝胶预聚液中加入引发剂,室温静置发生聚合反应,得到Mxene高强度复合水凝胶;
所述水凝胶预聚液中,表面功能化的Mxene纳米片、单体、交联剂、水的比例为20-40mg:60-70mmol:0-9.24mg:10mL。
2.根据权利要求1所述的一种Mxene高强度复合水凝胶的制备方法,其特征在于,步骤1中Mxene为Ti3C2Tx,所述Ti3C2Tx是通过HCl和氟化物盐溶液对Ti3AlC2刻蚀得到。
3.根据权利要求1所述的一种Mxene高强度复合水凝胶的制备方法,其特征在于,步骤1中,N-(3,4-二羟基苯乙基)丙烯酰胺是由盐酸多巴胺与丙烯酰氯在硼砂水溶液中发生取代反应得到的;反应温度为室温,反应时间为12-48h。
4.根据权利要求1所述的一种Mxene高强度复合水凝胶的制备方法,其特征在于,步骤2中,所述单体为丙烯酰胺、N-异丙基丙烯酰胺、N,N-二甲基丙烯酰胺、丙烯酸、甲基丙烯酸中的一种或几种。
5.根据权利要求1所述的一种Mxene高强度复合水凝胶的制备方法,其特征在于,步骤2中,所述交联剂为N,N-亚甲基双丙烯酰胺。
6.根据权利要求1所述的一种Mxene高强度复合水凝胶的制备方法,其特征在于,步骤2中,所述引发剂为过硫酸铵、过硫酸钾、过硫酸钠中的一种,所述引发剂的质量为单体添加量的0.2-1%。
7.一种权利要求1-6任一项所述的制备方法制备得到的Mxene高强度复合水凝胶。
8.一种权利要求7所述的Mxene高强度复合水凝胶在制备生物润滑剂及抗菌涂层中的应用。
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