Auswahl der wissenschaftlichen Literatur zum Thema „Ni-initiator“

The carbon aerogels doped with nickel were produced by sol-gel, supercritical ethanol drying, and high-temperature carbonization, using resorcinol-furfural as carbon source, nickel nitrate as nickel source, absolute ethanol as dispersion medium, 1,2-epoxypropane as gel initiator, polyacrylic acid as the chelating agent. The carbon aerogels were characterized by nitrogen adsorption and XRD. The effects of the molar ratio of 1,2-epoxypropane to nickel on porosity of the Ni-doped carbon aerogels were investigated. It is found that the Ni-doped carbon aerogels have abundant mesopores and the doped nickel is dispersed in samples in metallic state and oxide or pure metal depending on the preparation conditions. The mesopore volume and average mesopore size all increase with the ratio of 1,2-epoxypropane to nickel.

A novel synthesis strategy on styrene-butadiene di-block copolymer (PS-b-PB) with high cis-1,4 unit content was developed, based on a transfer technique from anionic to coordination polymerization. Firstly, the styrene monomer was initiated by n-butyllithium (Li) utilizing anionic polymerization at 50 °C, which resulted in a macromolecular alkylating initiator (PSLi). Secondly, PSLi was aged with nickel naphthenate (Ni) and boron trifluoride etherate (B) for obtaining a complex catalyst system (Ni/PSLi/B). Then, Ni/PSLi/B was applied to initiate the butadiene (Bd) polymerization. Following this new strategy, a series of PS-b-PBs were successfully synthesized. The experimental results indicated that under the molar ratio combination of [Li]/[Ni] = 5 and [B]/[Li] = 1, styrene-butadiene di-block copolymers could be easily achieved with high cis-1,4 unit content (>97%) and controlled molecular weight as well as narrow molecular weight distribution (Mw/Mn < 1.5). Furthermore, the copolymer’s block ratio could also be effectively controlled by controlling the two components’ monomer feed ratio.

Crush initiators are the weakest points to reduce initial peak load force with significant energy absorption ability. The objective of this paper is to study the effects of square tube thickness and crush initiators position for impact energy absorber (IEA) performance on thin-walled square tubes. Two square tubes having thickness about 0.6 mm (specimen code A) and 1 mm (specimen Code C) were tested under dynamic load. The crushing initiator is designed around the shape of the tube wall and has eight holes with a fixed diameter of 6.5 mm. In the experiment, the crushing initiator was determined at 5 different locations on the specimen wall. These locations are 10 mm, 20 mm. 30 mm, 40 mm, and 50 mm measured from the initial collision position of the specimen tested. The impact load mass was about 80 kg and had a drop height of about 1.5 m. Using the simulation program of the LabVIEW Professional Development System 2011 and National Instrument (NI) 9234 software equipped with data acquisition hardware NI cDAQ-9174 the signal from the load cell was sent to a computer. By controlling the thickness of the thin-walled square tube, the peak loading force can be decreased by approximately 56.75% and energy absorption ability of IEA can be increased approximately to 11.83%. By using different thin-walled square tube can produce different best crush initiators position with the lowest peak load force.

In this article, graft copolymerization of styrene (St) onto cassava starch via potassium diperiodatonickelate (IV)–starch redox system as an initiator was investigated in an alkaline medium. The effects of reaction variables were investigated, and the grafting conditions were optimized. The equation of the polymerization rate were obtained, Rp= k•C1.02 (St)•C0.53 (Ni（IV）). The graft copolymer was characterized with Fourier-transform infrared spectra analysis (FTIR) and scanning electron microscopy (SEM). FTIR spectra indicated the presence of PSt-g-starch copolymer. SEM micrographs also showed PSt adhering on the starch.

4-vinyl pyridine nickel complex containing polymerizable vinyl group, prepared by condensing (4:1 molar ratio) of 4-vinylpyridine with Nickel chloride, then polymerized with methyl methacrylate at 70 °C using AIBN as initiator. Metal complexand polymer metal complex have been characterized by elemental analyses, molar conductance, IR, 1H-NMR , Massspectra and thermal analyses (DTA and TGA). Conductivity measurement reveals the nonelectrolytic nature of thecomplex. This confirms that, the anion is coordinated to the metal ion. The IR reveal the metal ion is coordinated via thenitrogen atom of 4-VP. Nickel complex and polymer nickel complex have been tested invitro against number of tumor andnumber of microorganisms in order to assess their anti tumor and antimicrobial properties. The antimicrobial activity wasobserved by compounds VP-Ni and MMA-VP-Ni under the screening conditions. The activity against HCT-116 cells wasdetected for compound VP-Ni (with IC50 value 9.8±0.6 µg/ml), compared with reference standard (24.6±0.3 µg/ml) followedby MMA-VP-Ni (48.3±1.5). In conclusion, this study highlighted the synthesis of polymer nickel complex, and proved thepromising biological activity of the synthesized compounds.

A styrene–butadiene–styrene tri-block copolymer (SBS) with a high cis -1,4 unit content (greater than 97%) was synthesized by a novel synthetic strategy based on changing the catalytic active centres using n -butyllithium and a nickel-based catalyst. Firstly, styrene was polymerized via anionic polymerization using butyllithium as the initiator (Li, activity centre Li) at 50°C. The obtained alkylated macroinitiator (PSLi) was aged with nickel naphthenate (Ni) and boron trifluoride etherate (B) to prepare a second reactive centre (Ni-F), which was used to initiate the polymerization of butadiene (Bd). Finally, triphenyl phosphine (PPh 3 ) was added to adjust the electron density of the third active centre (P-Ni-F), and styrene monomer was added again to synthesize the second polystyrene block to obtain SBS. The polymerization technique presented here is simple and has an efficient initiation effect due to the high initiation activities for the different monomers. It also exhibits excellent control over the stereo-structure of the butadiene segments in the prepared copolymers, and the SBS polymers with high cis -1,4 unit content were easily achieved.

A novel hydroxyl-terminated π-allyl nickel initiator is synthesized for the first time. Hydroxyl-terminated PB-b-P3HT block copolymer and hydroxyl-terminated P3HT are synthesized by using the initiator to improve the workability of P3HT.

Nanoparticles comprising chitosan-graft-poly (methyl methacrylate) (CS-g-PMMA) copolymer were successfully synthesized in aqueous solution by using potassium diperiоdatоnickelate (Ni (IV)) as an initiator. The nanoparticles were characterized in terms of Fourier transform infrared (FTIR), dynamic light scattering (DLS) and transmission electron microscopy (TEM). The results indicated that chitosan was covalently linked to poly (methyl methacrylate) (PMMA) and the particles were uniform, spherical and well dispersed with narrow size distribution. Paclitaxel-loaded nanoparticles were prepared and in vitro release showed that these nanoparticles provided an initial burst release followed by a slowly sustained release for more than 16 days. Therefore, this process method would be used for synthesizing natural polymer graft copolymer nanoparticles with wide prospect.

The aim of the present work was to screen the main methods for the synthesis of conjugated polymers for their suitability in the preparation of conductive polymer brushes. The main focus was put on the grafting of intrinsically soluble substituted regioregular polyalkylthiophenes because of their excellent optoelectronic properties. The resulting polymer films were characterized and their optoelectrical properties studied. For the first time, a synthesis of conductive polymer brushes on solid substrates using “grafting-from” method was performed. The most important, from my opinion, finding of this work is that regioregular head-to-tail poly-3-alkylthiophenes – benchmark materials for organic electronics - can be now selectively grafted from appropriately-terminated surfaces to produce polymer brushes of otherwise soluble polymers - the architecture earlier accessible only in the case of non-conductive polymers. In particular, we developed a new method to grow P3ATs via Kumada Catalyst Transfer Polymerization (KCTP) of 2-bromo-5-chloromagnesio-3-alkylthiophene. Exposure of the initiator layers to monomer solutions leads to selective chain-growth polycondensation of the monomers from the surface, resulting into P3AT brushes in a very economical way. The grafting process was investigated in detail and the structure of the resulting composite films was elucidated using several methods. The obtained data suggests that the grafting process occurs not only at the poly(4-bromstyrene) (PS-Br)/polymerization solution interface, but also deeply inside the swollen PS-Br films, penetrable for the catalyst and for the monomer The grafting process was investigated in detail and the structure of the resulting composite film was elucidated using ellipsometry, X-ray Photoelectron Spectroscopy (XPS), Rutherford backscattering spectroscopy (RBS), and Conductive atomic force microscopy (C-AFM). The obtained data suggests that the grafting process occurs not only at the poly(4-bromostyrene), PS-Br/polymerization solution interface, but also deeply inside the swollen PS-Br film, which is penetrable for the catalyst and the monomer. The process results in an interpenetrated PS-Br/P3HT network, in which relatively short poly(3-hexylthiophene), P3HT grafts emanate from long, cross-linked PS-Br chains. A further method investigated during our work was to covalently graft regioirregular P3HT to substrates modified by macromolecular anchors using oxidative polymerization of 3HT with FeCl3. P3HT layers with variable thicknesses from 30 nm up to 200 nm were produced using two steps of polymerization reaction. The P3HT obtained by oxidative polymerization had always an irregular structure, which was a result of the starting monomer being asymmetric, which is undesired for electronic applications. The third method for the production of conductive polymer brushes was to graft regioregular poly(3,3''-dioctyl-[2,2';5',2'']terthiophene) (PDOTT) by electrochemical oxidative polycondensation of symmetrically substituted 3,3''-dioctyl-[2,2';5',2'']terthiophene (DOTT). A modification of the supporting ITO electrode by the self-assembled monolayers (SAMs) of compounds having polymerizable head-groups with properly adjusted oxidative potentials was found to be essential to achieve a covalent attachment of PDOTT chains. The polymer films produced show solvatochromism and electrochromism, as well as the previous two methods. After polymerization, the next step towards building organic electronic devices is applying the methods obtained in nano- and microscale production. Block copolymers constitute an attractive option for such surface-engineering, due to their ability to form a variety of nanoscale ordered phase-separated structures. However, block copolymers containing conjugated blocks are less abundant compared to their non-conjugated counterparts. Additionally, their phase behaviour at surfaces is not always predictable. We demonstrated in this work, how surface structures of non-conductive block copolymers, such as P4VP-b-PS-I, can be converted into (semi)conductive P4VP-b-PS-graft-P3HT chains via a surface-initiated polymerization of P3HT (Kumada Catalyst Transfer Polymerization (KCTP) from reactive surface-grafted block copolymers. This proves that our method is applicable to develop structured brushes of conductive polymers. We believe that it can be further exploited for novel, stimuli-responsive materials, for the construction of sensors, or for building various opto-electronic devices. The methods developed here can in principle be adapted for the preparation of any conductive block copolymers and conductive polymers, including other interesting architectures of conductive polymers, such as block copolymers, cylindrical brushes, star-like polymers, etc. To this end, one needs to synthesize properly-designed and multi-functional Ni-initiators before performing the polycondensation.

The aim of the present work was to screen the main methods for the synthesis of conjugated polymers for their suitability in the preparation of conductive polymer brushes. The main focus was put on the grafting of intrinsically soluble substituted regioregular polyalkylthiophenes because of their excellent optoelectronic properties. The resulting polymer films were characterized and their optoelectrical properties studied. For the first time, a synthesis of conductive polymer brushes on solid substrates using “grafting-from” method was performed. The most important, from my opinion, finding of this work is that regioregular head-to-tail poly-3-alkylthiophenes – benchmark materials for organic electronics - can be now selectively grafted from appropriately-terminated surfaces to produce polymer brushes of otherwise soluble polymers - the architecture earlier accessible only in the case of non-conductive polymers. In particular, we developed a new method to grow P3ATs via Kumada Catalyst Transfer Polymerization (KCTP) of 2-bromo-5-chloromagnesio-3-alkylthiophene. Exposure of the initiator layers to monomer solutions leads to selective chain-growth polycondensation of the monomers from the surface, resulting into P3AT brushes in a very economical way. The grafting process was investigated in detail and the structure of the resulting composite films was elucidated using several methods. The obtained data suggests that the grafting process occurs not only at the poly(4-bromstyrene) (PS-Br)/polymerization solution interface, but also deeply inside the swollen PS-Br films, penetrable for the catalyst and for the monomer The grafting process was investigated in detail and the structure of the resulting composite film was elucidated using ellipsometry, X-ray Photoelectron Spectroscopy (XPS), Rutherford backscattering spectroscopy (RBS), and Conductive atomic force microscopy (C-AFM). The obtained data suggests that the grafting process occurs not only at the poly(4-bromostyrene), PS-Br/polymerization solution interface, but also deeply inside the swollen PS-Br film, which is penetrable for the catalyst and the monomer. The process results in an interpenetrated PS-Br/P3HT network, in which relatively short poly(3-hexylthiophene), P3HT grafts emanate from long, cross-linked PS-Br chains. A further method investigated during our work was to covalently graft regioirregular P3HT to substrates modified by macromolecular anchors using oxidative polymerization of 3HT with FeCl3. P3HT layers with variable thicknesses from 30 nm up to 200 nm were produced using two steps of polymerization reaction. The P3HT obtained by oxidative polymerization had always an irregular structure, which was a result of the starting monomer being asymmetric, which is undesired for electronic applications. The third method for the production of conductive polymer brushes was to graft regioregular poly(3,3''-dioctyl-[2,2';5',2'']terthiophene) (PDOTT) by electrochemical oxidative polycondensation of symmetrically substituted 3,3''-dioctyl-[2,2';5',2'']terthiophene (DOTT). A modification of the supporting ITO electrode by the self-assembled monolayers (SAMs) of compounds having polymerizable head-groups with properly adjusted oxidative potentials was found to be essential to achieve a covalent attachment of PDOTT chains. The polymer films produced show solvatochromism and electrochromism, as well as the previous two methods. After polymerization, the next step towards building organic electronic devices is applying the methods obtained in nano- and microscale production. Block copolymers constitute an attractive option for such surface-engineering, due to their ability to form a variety of nanoscale ordered phase-separated structures. However, block copolymers containing conjugated blocks are less abundant compared to their non-conjugated counterparts. Additionally, their phase behaviour at surfaces is not always predictable. We demonstrated in this work, how surface structures of non-conductive block copolymers, such as P4VP-b-PS-I, can be converted into (semi)conductive P4VP-b-PS-graft-P3HT chains via a surface-initiated polymerization of P3HT (Kumada Catalyst Transfer Polymerization (KCTP) from reactive surface-grafted block copolymers. This proves that our method is applicable to develop structured brushes of conductive polymers. We believe that it can be further exploited for novel, stimuli-responsive materials, for the construction of sensors, or for building various opto-electronic devices. The methods developed here can in principle be adapted for the preparation of any conductive block copolymers and conductive polymers, including other interesting architectures of conductive polymers, such as block copolymers, cylindrical brushes, star-like polymers, etc. To this end, one needs to synthesize properly-designed and multi-functional Ni-initiators before performing the polycondensation.