CN106633001A - 聚2,5‑二巯基‑1,3,4‑噻二唑纳米片的制备方法 - Google Patents
聚2,5‑二巯基‑1,3,4‑噻二唑纳米片的制备方法 Download PDFInfo
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- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 239000007800 oxidant agent Substances 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 230000001590 oxidative effect Effects 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000011067 equilibration Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 29
- 229920000642 polymer Polymers 0.000 abstract description 18
- 238000003786 synthesis reaction Methods 0.000 abstract description 12
- 238000006116 polymerization reaction Methods 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000003381 stabilizer Substances 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000002861 polymer material Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 230000005611 electricity Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000002604 ultrasonography Methods 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- -1 2,5-dimercapto-1,3,4- thiadiazole–gold Chemical compound 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- YXOLAZRVSSWPPT-UHFFFAOYSA-N Morin Chemical compound OC1=CC(O)=CC=C1C1=C(O)C(=O)C2=C(O)C=C(O)C=C2O1 YXOLAZRVSSWPPT-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000005708 Sodium hypochlorite Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 2
- UXOUKMQIEVGVLY-UHFFFAOYSA-N morin Natural products OC1=CC(O)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)O)=C1 UXOUKMQIEVGVLY-UHFFFAOYSA-N 0.000 description 2
- 235000007708 morin Nutrition 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 150000004867 thiadiazoles Chemical class 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical class SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002152 aqueous-organic solution Substances 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/11—Homopolymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3229—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing nitrogen and sulfur as heteroatoms
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Abstract
本发明公开了一种聚2,5‑二巯基‑1,3,4‑噻二唑纳米片的制备方法，属于有机功能高分子材料领域；该方法是将2,5‑二巯基‑1,3,4‑噻二唑单体和氧化剂分别溶于有机溶剂中，然后将氧化剂溶液逐滴加入到单体溶液中，在搅拌的条件下使氧化剂和单体充分接触反应；本发明无需添加任何外加稳定剂，只需要控制聚合反应条件，就可以合成出厚度为30～700nm的自稳定的聚合物纳米片，该合成一步完成，具有合成方法和后处理工序简单、不涉及到任何稳定剂和表面活性剂、产物纯净、所得产物分子量大、合成成本低廉且可普遍适用等优点。
Description
技术领域
本发明属于有机功能高分子材料领域，具体地说，涉及一种聚2,5-二巯基-1,3,4-噻二唑纳米片的制备方法。
背景技术
2,5-二巯基-1,3,4-噻二唑聚合物是含有S、N原子的杂环芳香聚合物，可作为高储能阴极材料应用于二次锂离子电池，也可作为电极修饰材料用于高灵敏度、高选择性的电化学探测铅离子、镉离子、桑色素等，同时也是优良的重金属离子吸附剂和抗菌杀毒剂。
在过去的研究中，2,5-二巯基-1,3,4-噻二唑聚合物的制备方法以电化学聚合法为主，通过循环伏安法制得。美国学者Shouji等人(Shouji E,Buttry D A,Aninvestigation of the effect of pyridine derivatives on the oxidativepolymerization process of 2,5-dimercapto-1,3,4-thiadiazole and its disulfidedimer[J],Journal of Physical Chemistry B,1998,102:1444-1449)使用三电极电解池，以玻碳电极为工作电极、铂丝电极为对电极、Ag/AgCl电极为参比电极，0.2mol L-1LiClO4的乙腈、二甲亚砜或N-甲基吡咯烷酮溶液为电解液，以50mV s-1的扫描速度在-0.8～+1.1V范围内连续循环扫描，制得聚2,5-二巯基-1,3,4-噻二唑膜。巴西学者Davoglio等人(Davoglio R A,Biaggio S R,Rocha-Filho R C,Bocchi N,Bilayered nanofilm ofpolypyrrole and poly(DMcT)for high-performance battery cathodes[J],Journal ofPower Sources,2010,195(9):2924-2927)以碳纤维电极作为工作电极，铂片电极作为对电极，饱和甘汞电极(SCE)作为参比电极，以0.1mol L-1LiClO4的乙腈溶液为电解液，电解液中2,5-二巯基-1,3,4-噻二唑的浓度达到饱和，以100mV s-1的扫描速度在-1.0～+0.69V范围内循环扫描30次，得到聚2,5-二巯基-1,3,4-噻二唑纳米薄膜。此外，印度学者Varghese等人(Varghese A,Chitravathi S,Munichandraiah N,Electrocatalytic oxidation anddetermination of morin at a poly(2,5-dimercapto-1,3,4-thiadiazole)modifiedcarbon fiber paper electrode[J],Journal of The Electrochemical Society,2016,163(8):B471-B477)在含有1mmol L-12,5-二巯基-1,3,4-噻二唑的磷酸盐缓冲液(pH＝9.0)中碳纤维纸电极表面电化学聚合制备了聚合物膜。电化学聚合的优势是可以在电极表面直接成膜，并且膜的厚度可以通过动电位扫描的循环次数(循环伏安法)或者固定通过工作电极的总电量(恒电位法和恒电流法)来控制，缺陷是受电极面积影响不能大规模合成，并且得到产物不够纯净，大量的电解废液会对环境造成污染。
由于2,5-二巯基-1,3,4-噻二唑单体分子为五元杂环并且含有3个硫原子和2个氮原子，一方面五元环与强氧化剂作用容易导致开环反应而得不到聚合物，另一方面易与过渡金属盐氧化剂反应只能得到金属络合物；所以迄今为止通过化学氧化聚合法制备得到聚2,5-二巯基-1,3,4-噻二唑的报道为数不多。也门学者El-Shekeil等人(El-Shekeil A G,Al-Maydama H M,Al-Shuja'a O M,The synthesis,characterization,and DCelectrical conductivity of poly[di(2,5-dimercapto-1,3,4-thiadiazole)-metal]complexes[J],Journal of Applied Polymer Science,2007,106(4):2427-2435)将2,5-二巯基-1,3,4-噻二唑与钴、镍、铜和锌的氯化物在无水乙醇中回流反应得到了相应的聚[二(2,5-二巯基-1,3,4-噻二唑)-金属]络合物，其颜色分别为绿色、深棕色、深黄色和白色，产率分别只有38％、30％、63％和33％。类似地，印度学者Tiwari等人(Tiwari M,GuptaS,Prakash R,One pot synthesis of coordination polymer 2,5-dimercapto-1,3,4-thiadiazole–gold and its application in voltammetric sensing of resorcinol[J],RSC Advances,2014,4:25675-25682)在氮气的保护和室温条件下，将2,5-二巯基-1,3,4-噻二唑乙醇溶液与四氯金酸乙醇溶液混合反应，最终得到产率为64％的浅黄色的配位聚合物。对于2,5-二巯基-1,3,4-噻二唑的化学氧化聚合，一般以甲醇、水-甲醇(体积比1:1)、水-乙醇(体积比1:2)、或0.1mol L-1醋酸-醋酸钠水溶液为反应介质，碘、过氧化氢、或过硫酸铵为氧化剂，产物为浅黄色，但一般产率较低，聚合物的分子量也不高。并且，迄今为止，尚没有发现采用化学氧化聚合法制备聚2,5-二巯基-1,3,4-噻二唑纳米片的报道。
发明内容
有鉴于此，本发明针对上述的问题，提供了一种聚2,5-二巯基-1,3,4-噻二唑纳米片的制备方法，该方法采用化学氧化聚合法，制备工艺简单。
为了解决上述技术问题，本发明公开了一种聚2,5-二巯基-1,3,4-噻二唑纳米片的制备方法，包括以下步骤：
1)按摩尔体积比1.46～2.61：10mmol/mL将2,5-二巯基-1,3,4-噻二唑单体溶于有机溶剂中，制备得到2,5-二巯基-1,3,4-噻二唑单体有机溶液；按摩尔体积比3.29～16.46：30mmol/mL将氧化剂溶解在有机溶剂中，制备得到氧化剂有机溶液；将2,5-二巯基-1,3,4-噻二唑单体有机溶液和氧化剂有机溶液分别进行平衡；
2)在搅拌和恒温的条件下将氧化剂有机溶液逐滴加入到2,5-二巯基-1,3,4-噻二唑单体有机溶液中进行反应，其中2,5-二巯基-1,3,4-噻二唑单体在整个反应体系中的终浓度为0.0356～0.0652mol L-1，反应后加入去离子水沉降、离心，沉淀再依次用去离子水和无水乙醇洗涤直至洗涤溶剂无色为止，然后干燥至恒重即得到聚2,5-二巯基-1,3,4-噻二唑纳米片。
进一步地，溶解2,5-二巯基-1,3,4-噻二唑单体和氧化剂的有机溶剂是N,N-二甲基甲酰胺、N-甲基-2-吡咯烷酮、甲醇、乙醇中的一种。
进一步地，氧化剂有机溶液为I2、(NH4)2S2O8、NaClO、FeCl3、H2O2中一种或几种混合物的有机溶液。
进一步地，I2溶液、(NH4)2S2O8溶液和FeCl3溶液是有机溶液，H2O2溶液和NaClO溶液是直接量取的水溶液或有机溶液。
进一步地，2,5-二巯基-1,3,4-噻二唑单体有机溶液和氧化剂有机溶液的平衡时间为10～30min；平衡温度为0～50℃。
进一步地，步骤2)中搅拌时间为10～24h；搅拌温度为0～50℃。
进一步地，步骤2)中氧化剂与2,5-二巯基-1,3,4-噻二唑单体固体的摩尔比为0.5:1～7.06:1。
与现有技术相比，本发明可以获得包括以下技术效果：
1)本发明中所述的有机溶剂能很好地溶解2,5-二巯基-1,3,4-噻二唑单体和氧化剂，所制得的聚2,5-二巯基-1,3,4-噻二唑产率较高、聚合效果较好。在众多的氧化剂中过氧化氢、碘、过硫酸铵都对2,5-二巯基-1,3,4-噻二唑具有较好的聚合效果。
2)本发明得到的聚2,5-二巯基-1,3,4-噻二唑，其分子链结构重复单元如下：
本发明利用2,5-二巯基-1,3,4-噻二唑结构单元上的氮和硫原子的负电排斥效应，使其作为内稳定剂在一定程度上有效地阻止了颗粒之间的聚合和团聚，成功地合成出了表面纯净、自稳定好的、纳米片状的聚2,5-二巯基-1,3,4-噻二唑。
3)本发明方法所制得的聚合物有较高的分子量和产率，同时制得的聚合物具有较高的纯度，通过化学氧化合成的方法，可以对2,5-二巯基-1,3,4-噻二唑聚合物进行大规模的合成，且有利于获得纳米尺寸的聚合物。
当然，实施本发明的任一产品并不一定需要同时达到以上所述的所有技术效果。
附图说明
此处所说明的附图用来提供对本发明的进一步理解，构成本发明的一部分，本发明的示意性实施例及其说明用于解释本发明，并不构成对本发明的不当限定。在附图中：
图1为本发明实施例1制备得到的聚2,5-二巯基-1,3,4-噻二唑纳米片的透射电镜照片；
图2为本发明实施例1制备得到的聚2,5-二巯基-1,3,4-噻二唑纳米片的扫描电镜照片；
图3为本发明实施例1制备得到的聚2,5-二巯基-1,3,4-噻二唑纳米片的另一种形式的扫描电镜照片；
图4为本实验实施例2制备得到的聚2,5-二巯基-1,3,4-噻二唑纳米片的透射电镜照片；
图5为本实验实施例2制备得到的聚2,5-二巯基-1,3,4-噻二唑纳米片的扫描电镜照片；
图6为本发明中25℃时，不同的氧化剂合成的PBT与BT的红外光谱图；
图7为本发明中25℃时，不同的氧化剂合成的PBT与BT的广角X射线衍射图；
图8为本发明实施例3制备得到的聚2,5-二巯基-1,3,4-噻二唑纳米片的紫外可见光谱图；
图9为本发明实施例4制备得到的聚2,5-二巯基-1,3,4-噻二唑纳米片的紫外可见光谱图；
图10为本实验实施例8制备得到的聚2,5-二巯基-1,3,4-噻二唑纳米片的透射电镜照片；
图11为本实验实施例8制备得到的聚2,5-二巯基-1,3,4-噻二唑纳米片的扫描电镜照片。
具体实施方式
以下将配合实施例来详细说明本发明的实施方式，藉此对本发明如何应用技术手段来解决技术问题并达成技术功效的实现过程能充分理解并据以实施。
实施例1：化学氧化聚合制备聚2,5-二巯基-1,3,4-噻二唑纳米片的方法，具体操作如下：
(1)准确称量2.33mmol(0.3497g)2,5-二巯基-1,3,4-噻二唑单体，将其加入到10mL的无水乙醇中超声至完全溶解，配成2,5-二巯基-1,3,4-噻二唑的有机溶液；准确称量6.99mmol(0.8861g)I2单质，将其加入到30mL的无水乙醇中超声至完全溶解，配成I2的有机溶液；
(2)将I2的有机溶液和2,5-二巯基-1,3,4-噻二唑的有机溶液分别置于25℃恒温水浴中平衡20min后，然后用滴管逐滴将氧化剂溶液滴加到2,5-二巯基-1,3,4-噻二唑有机溶液中，整个过程在磁力搅拌的条件下进行，恒温下反应24h，反应结束后加入200mL去离子水沉降、离心，然后沉淀依次分别用去离子水和无水乙醇洗涤至洗涤溶液为无色为止，然后沉淀置80℃下恒温烘干至恒重，制得聚2,5-二巯基-1,3,4-噻二唑纳米片，产率为92.91％，其透射电镜如图1所示，可以看出聚合物为纳米片状，其扫描电镜如图2、3，其纳米片厚度大小为89～535nm。溶解性实验发现聚2,5-二巯基-1,3,4-噻二唑纳米片不溶于去离子水、甲醇、乙醇、1mol L-1HCl水溶液，微溶于DMF、NMP、四氢呋喃(THF)，部分溶于1mol L-1氨水，说明具有良好的耐有机溶剂和耐酸性水溶液性质，可推测具有高分子量。
实施例2：化学氧化合成聚2,5-二巯基-1,3,4-噻二唑纳米片的方法，具体操作如下：
本实施例方法同实例1，不同的是氧化剂由I2的有机溶液换成H2O2的有机溶液，所得的聚2,5-二巯基-1,3,4-噻二唑纳米片的产率为82.13％,其透射电镜如图4所示，可以看出聚合物为片状，其扫描电镜如图5，其片状厚度大小为133～666nm。
图6为聚2,5-二巯基-1,3,4-噻二唑(PBT)和BT单体的红外光谱图，图中显示PBT在1045、1385、1643和3447cm-1处有强烈的吸收峰，而单体BT在713、1045、1255和1498cm-1处有强烈的吸收峰。
图7为聚2,5-二巯基-1,3,4-噻二唑的广角X射线衍射图，图中显示单体BT与聚合物PBT都在20°到25°呈现多个尖锐的衍射峰，但明显可以看出BT与PBT的衍射峰位置不一样，而两个PBT聚合物的衍射峰都一致，一方面说明BT和PBT不是同一个物质和聚合反应的发生，另一方面说明了生成的聚合物具有类似的结构，同时PBT的尖锐衍射峰又与透射电镜观察到的规整的纳米片结果一致。
实施例3：化学氧化合成聚2,5-二巯基-1,3,4-噻二唑纳米片的方法，具体操作如下：
本实施例方法同实例1，不同的是溶解2,5-二巯基-1,3,4-噻二唑单体的溶剂换成DMF、甲醇、80％乙醇，所得的聚2,5-二巯基-1,3,4-噻二唑纳米片的产率分别为38.75％、92.23％和73.71％。
不同介质中合成的PBT和单体BT紫外可见光谱见图8，可以看出单体BT分别在267和358nm处有强烈的吸收峰；而PBT都在259和358nm处有强烈的吸收峰，其中以乙醇为反应介质制备的聚合物在421nm处有明显吸收峰。
实施例4：化学氧化合成聚2,5-二巯基-1,3,4-噻二唑纳米片的方法，具体操作如下：
(1)准确称量2mmol(0.3065g)2,5-二巯基-1,3,4-噻二唑单体，将其加入到10mL的甲醇中超声至完全溶解，配成2,5-二巯基-1,3,4-噻二唑的有机溶液；而氧化剂分别用4mmol的次氯酸钠、三氯化铁和过氧化氢，溶解在30mL的甲醇中超声至完全溶解，配成各氧化剂的有机溶液；
(2)将氧化剂的有机溶液和2,5-二巯基-1,3,4-噻二唑分别置于25℃恒温水浴中平衡20min后，然后用滴管逐滴将氧化剂溶液滴加到2,5-二巯基-1,3,4-噻二唑有机溶液中，整个过程在磁力搅拌的条件下进行，恒温下反应24h，反应结束后加入200mL去离子水沉降、离心，然后沉淀依次分别用去离子水和无水乙醇洗涤5次，至洗涤溶液为无色为止，然后沉淀置80℃下恒温烘干至恒重，以次氯酸钠、三氯化铁和过氧化氢为氧化剂制得聚2,5-二巯基-1,3,4-噻二唑纳米片，产率分别为18.08％、0.8766％和91.80％。
实施例4的紫外可见光谱图见图9，看图可得出单体2,5-二巯基-1,3,4-噻二唑的吸收峰在270和355nm处；聚2,5-二巯基-1,3,4-噻二唑的吸收峰在255和364nm处。
实施例5：化学氧化合成聚2,5-二巯基-1,3,4-噻二唑纳米片的方法，具体操作如下：
本实施例方法同实例1，单体的量不变，但是不同的是改变氧化剂用量，即：改变氧化剂与单体的摩尔比，分别为0.5:1、1:1、3:1、4:1和7.06:1，所得的聚2,5-二巯基-1,3,4-噻二唑纳米片的产率分别为8.72％、68.56％、98.47％、96.45％和93.16％。
实施例6：化学氧化合成聚2,5-二巯基-1,3,4-噻二唑纳米片的方法，具体操作如下：
本实施例方法同实例1，氧化剂与单体的摩尔比不变，改变单体浓度，单体浓度分别是0.03065、0.04375、0.05和0.06525mol L-1，所得的聚2,5-二巯基-1,3,4-噻二唑纳米片的产率分别为8.72％、68.56％、80.20％和96.45％。
实施例7：化学氧化合成聚2,5-二巯基-1,3,4-噻二唑纳米片的方法，具体操作如下：
本实施例方法同实例1，不同的是反应温度由最初的25℃分别变为0℃、5℃、40℃和50℃，平衡温度与反应温度相同，所得的聚2,5-二巯基-1,3,4-噻二唑纳米片的产率分别为31.17％、72.17％、77.85％和56.18％。
实施例8：化学氧化合成聚2,5-二巯基-1,3,4-噻二唑纳米片的方法，具体操作如下：
(1)准确称量2.33mmol(0.3497g)2,5-二巯基-1,3,4-噻二唑单体，将其加入到10mL的DMF中超声至完全溶解，配成2,5-二巯基-1,3,4-噻二唑的有机溶液；准确称量6.99mmol(1.5971g)过硫酸铵，将其加入到30mL的DMF中超声至完全溶解，配成过硫酸铵的有机溶液；
(2)然后用滴管逐滴的将过硫酸铵的有机溶液滴加到2,5-二巯基-1,3,4-噻二唑的有机溶液中，整个过程在磁力搅拌的条件下进行，25℃恒温下反应24h，反应结束后加入200mL去离子水沉降、离心，然后沉淀依次分别用去离子水和无水乙醇洗涤，至洗涤溶液为无色为止，然后80℃恒温烘干至恒重，制得聚2,5-二巯基-1,3,4-噻二唑纳米片，产率为80.42％，其透射电镜如图10所示，可以看出聚合物为片状，其扫描电镜如图11，其片状厚度大小为30～333nm。
实施例9
本实施案例与实施例1相同，不同的是平衡时间由最开始的20min变成10min和30min，所得的聚2,5-二巯基-1,3,4-噻二唑纳米片的产率由92.91％变为87.64％和92.75％。
实施例10
本实施案例与实施例1相同，不同的是反应时间由最开始的24h变成10h和18h，所得的聚2,5-二巯基-1,3,4-噻二唑纳米片的产率分别为84.15％和90.32％。
上述说明示出并描述了发明的若干优选实施例，但如前所述，应当理解发明并非局限于本文所披露的形式，不应看作是对其他实施例的排除，而可用于各种其他组合、修改和环境，并能够在本文所述发明构想范围内，通过上述教导或相关领域的技术或知识进行改动。而本领域人员所进行的改动和变化不脱离发明的精神和范围，则都应在发明所附权利要求的保护范围内。
Claims (7)
1.一种聚2,5-二巯基-1,3,4-噻二唑纳米片的制备方法，其特征在于，包括以下步骤：
1)按摩尔体积比1.46～2.61：10mmol/mL将2,5-二巯基-1,3,4-噻二唑单体溶于有机溶剂中，制备得到2,5-二巯基-1,3,4-噻二唑单体有机溶液；按摩尔体积比3.29～16.46：30mmol/mL将氧化剂溶解在有机溶剂中，制备得到氧化剂有机溶液；将2,5-二巯基-1,3,4-噻二唑单体有机溶液和氧化剂有机溶液分别进行平衡；
2)在搅拌和恒温的条件下将氧化剂有机溶液逐滴加入到2,5-二巯基-1,3,4-噻二唑单体有机溶液中进行反应，其中2,5-二巯基-1,3,4-噻二唑单体在整个反应体系中的终浓度为0.0356～0.0652mol L-1，反应后加入去离子水沉降、离心，沉淀再依次用去离子水和无水乙醇洗涤直至洗涤溶剂无色为止，然后干燥至恒重即得到聚2,5-二巯基-1,3,4-噻二唑纳米片。
2.根据权利要求1所述的聚2,5-二巯基-1,3,4-噻二唑纳米片的制备方法，其特征在于，所述的溶解2,5-二巯基-1,3,4-噻二唑单体和氧化剂的有机溶剂是N,N-二甲基甲酰胺、N-甲基-2-吡咯烷酮、甲醇、乙醇中的一种。
3.根据权利要求1所述的聚2,5-二巯基-1,3,4-噻二唑纳米片的制备方法，其特征在于，氧化剂有机溶液为I2、(NH4)2S2O8、NaClO、FeCl3、H2O2中一种或几种混合物的有机溶液。
4.根据权利要求3所述的聚2,5-二巯基-1,3,4-噻二唑纳米片的制备方法，其特征在于，所述的I2溶液、(NH4)2S2O8溶液和FeCl3溶液是有机溶液，H2O2溶液和NaClO溶液是直接量取的水溶液或有机溶液。
5.根据权利要求1所述的聚2,5-二巯基-1,3,4-噻二唑纳米片的制备方法，其特征在于，所述的2,5-二巯基-1,3,4-噻二唑单体有机溶液和氧化剂有机溶液的平衡时间为10～30min；平衡温度为0～50℃。
6.根据权利要求1所述的聚2,5-二巯基-1,3,4-噻二唑纳米片的制备方法，其特征在于，步骤2)中搅拌时间为10～24h；搅拌温度为0～50℃。
7.根据权利要求1所述的聚2,5-二巯基-1,3,4-噻二唑纳米片的制备方法，其特征在于，步骤2)中氧化剂与2,5-二巯基-1,3,4-噻二唑单体的摩尔比为0.5:1～7.06:1。
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| US4246126A (en) * | 1979-05-29 | 1981-01-20 | The Lubrizol Corporation | 2,5-Dimercapto-1,3,4-thiadiazole derivatives and lubricants containing them |
| CN103012788A (zh) * | 2012-12-11 | 2013-04-03 | 昆明理工大学 | 界面化学氧化聚合制备聚(1-氨基-5-氯蒽醌)纳米纤维的方法 |
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2016
- 2016-11-29 CN CN201611071101.3A patent/CN106633001B/zh not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4246126A (en) * | 1979-05-29 | 1981-01-20 | The Lubrizol Corporation | 2,5-Dimercapto-1,3,4-thiadiazole derivatives and lubricants containing them |
| CN103012788A (zh) * | 2012-12-11 | 2013-04-03 | 昆明理工大学 | 界面化学氧化聚合制备聚(1-氨基-5-氯蒽醌)纳米纤维的方法 |
Non-Patent Citations (1)
| Title |
|---|
| LIFENG JIN ET AL.: "Poly(2,5-dimercapto-1,3,4-thiadiazole)/sulfonated grapheme composite as cathode material for rechargeable lithium batteries", 《J APPL ELECTROCHEM》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115945172A (zh) * | 2023-02-20 | 2023-04-11 | 中山大学 | 一种复合纳米纤维材料及其制备方法与应用 |
| CN115945172B (zh) * | 2023-02-20 | 2023-10-13 | 中山大学 | 一种复合纳米纤维材料及其制备方法与应用 |
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| CN106633001B (zh) | 2020-08-11 |
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