Synthesis of Ferrocene--based Polythiophenes and Preparation of Their Fibers and Composite Films.pdf

1、Even though ferrocene-based polythiophenes have been discovered from many years,the research into ferrocene-based polythiophenes continues, because of theirincorporation into a wide variety of applications in the modem l

2、ife.These applicationshave been based on the individual properties of ferrocene and thiophene as well theircombined properties.Together these two moieties are known for chemical andbiochemical sensing, and memory storage

3、 devices.
　　Ferrocene and thiophene individually have incredible properties and importantapplications.During the last two decades, scientists synthesized polythiophenescontaining ferrocene in the main chain and in the

4、 side chain.Polythiophenes have redox,conducting, and optical properties.Because of these properties the polythiophenes havebeen used in sensing applications.On the other hand, ferrocene has reversible redoxproperties an

5、d due to this property, it has been used in a lot of sensing devices.Ferrocenecan has +2 and +3 oxidation states which can be correspond to the “0” and “1” and dueto this property, it can be used as memory storage materi

6、al.When these two moieties(ferrocene and thiophene) are combined together, they show good compatibility andtherefore the resulting polymers have been used as memory storage and chemicalsensing materials.Therefore, we car

7、efully selected the articles which are associated withferrocene-based polythiophenes only.In this study, we tried to focus on the synthesisand applications of ferrocene-based polythiophenes.For the fabrication of differe

8、nt devices,electrospinning and spin-coating like techniques are used for polythiophenes/ferrocene-based polythiophenes.
　　(1)Ferrocene-based polythiophenes are the promising class of materials but, usually, thepolythi

9、ophenes have poor solubility in common solvents.Herein two new ferrocene-based thiophene monomers, 2-(thiophene-3-yl) ethyl ferrocenoate (TEF) and 2-(thiophene-3-yl) methyl ferrocenoate (TMF) were synthesized by the reac

10、tion of 3-ethanolthiophene (3ET) and 3-mathnol thiophene (3MT) with ferrocenecarbonylchloride, respectively.The synthesized monomers were polymerized byoxidative polymerization using FeCl3 as oxidizing agent.The resultin

11、g polymers werenot soluble in a considerable amount.Moreover, the molecular weight of the solublepolymers was very low.
　　(2)In this study we synthesized P3HT, ferrocene-based thiophene (TEF) and copolymerof 3HT and T

12、EF using oxidative polymerization.Series of reactions were performed (C1-C7).First, effect of the oxidant (FeCl3) on the soluble yield of P3HT was studied (C 1-C4).For this purpose different ratios of FeCl3 were used (40

13、/20/15/10 mmol) with 3HT (10mmol) in reactions C1-C4 respectively.The soluble yields of these reactions (C1-C4) were45.6％, 48.3％, 52％ and 51.5％ respectively.Following these results, monomer to tooxidant (FeCl3) ratio was

14、 kept 1∶1.5 for next reactions.After determining the effect ofoxidant on solubility of P3HT, the effect of ratio of 3HT on soluble yield of the copolymerwas determined.Here, the reason of using 3HT was the good solubilit

15、y of P3HT.To checkthe effect of alkyl chain ratio on the copolymer, different ratios of TEF and 3HT (1∶1, 1∶1.5and 1∶2) were used in polymerization reactions (C5-C7).
　　(3)In this study ferrocene based thiophene monom

16、er (TEF) was synthesized andcopolymerized with 3-hexylthiophene (3HT) using oxidative polymerization.P3HT wasalso synthesized separately.Synthesized monomer was characterized by 1H-NMR andsynthesized polymers were charac

17、terized by 1H-NMR and GPC.The resulting polymerswere electrospun in different conditions in order to obtain fibers.Moreover, theircomposites with poly (methyl methacrylate) (PMMA) were also prepared and electrospun.The f