Summary: The use of microwave heating in polymer science is a rapidly growing field of research leading to faster and cleaner polymerization procedures. However, the majority of the investigations are performed at small scales (≈1 mL), which is far away from potential commercial applications of microwave‐assisted polymerizations. In addition, it has been shown in organic chemistry that microwave‐assisted reaction protocols can be directly scaled without the need for process optimization. In this contribution, we have investigated the direct scaling of microwave‐assisted polymerization procedures under pressure conditions using the cationic ring‐opening polymerization of 2‐ethyl‐2‐oxazoline as the model system. This polymerization was performed at scales ranging from 4.0 mmol (1 mL) to 1.0 mol (250 mL) in different microwave synthesizers covering both monomode and multimode devices.
Scale‐up of microwave‐assisted polymerizations in batch mode: the cationic ring‐opening polymerization of 2 ethyl‐2‐oxazoline. 相似文献
The synthesis of water soluble star‐block copolypeptides and their encapsulation properties are described. The star‐block copolypeptides, obtained by ring‐opening polymerization of amino acid N‐carboxyanhydrides, consist of a PEI core, a hydrophobic polyphenylalanine or polyleucine inner shell, and a negatively charged polyglutamate outer shell. The encapsulation study showed that these water soluble, amphiphilic star‐block copolypeptides could simultaneously encapsulate versatile compounds ranging from hydrophobic to anionic and cationic hydrophilic guest molecules.
It is the general consensus that in Gilch polymerizations the 1,4‐bis(chloromethylene)benzene starting material first changes into p‐quinodimethane intermediates which then act as the real monomers. However, direct observation of these intermediates has not been possible so far. This is because usually the p‐quinodimethane auto‐initiates its rapid radical polymerization instantaneously, keeping its concentration extremely low throughout the whole process. Here it is shown that, when the reaction is carried out at very low temperatures, the formation of p‐quinodimethane still proceeds but chain growth is suppressed. Hence, the concentration of the active monomer reaches a level sufficient for NMR analysis.
Poly(L ‐lactic acid)‐block‐poly(poly(ethylene glycol) monomethacrylate) (PLLA‐b‐PPEGMA) has been prepared by the ring‐opening polymerization of lactide with a double‐headed initiator, 2‐hydroxyethyl 2′‐methyl‐2′‐bromopropionate (HMBP), followed by atom transfer radical polymerization (ATRP) of poly(ethylene glycol) monomethacrylate (PEGMA). PLLA‐b‐PPEGMA nanoparticles with encapsulated Fe3O4 are prepared by a solvent evaporation/extraction technique, and then further functionalized with folic acid, a cancer targeting ligand. Our results show that such functionalized PLLA‐b‐PPEGMA nanoparticles have good potential as carriers for targeted drug delivery in cancer treatment.
The dual self‐assembling polycondensation of p‐acetoxybenzoic acid (ABA) and p‐acetamidobenzoic acid in Therm S 800 was examined at 300 °C. Needle‐like crystals and lath‐like crystals were formed simultaneously through reaction‐induced crystallization of oligomers at a molar ratio of 30–50 mol‐% ABA in the feed. The needle‐like crystals comprised more p‐oxybenzoyl units, whereas the lath‐like ones contained higher amounts of p‐benzamide moieties.
Oxygen is shown to act as an efficient molar‐mass regulating agent in Gilch syntheses of PPV. As a scavenger, it undergoes instantaneous recombination with the initiating diradicals as soon as they appear in the system. Regular polymer formation can only start when all oxygen has been used, proceeding predominantly as chain‐growth polymerization of the p‐quinodimethane monomers. Since all radical species involved in this Gilch process are diradicals, some polyrecombination events occur in parallel. Therefore the initially formed peroxy diradicals are also incorporated into the resulting chains. Later, they break under very mild conditions, thereby causing a systematic decrease of the final molar mass of PPV.
This communication details the successful synthesis of low polydispersity core cross‐linked star (CCS) polymers via DPE‐mediated polymerisation. We demonstrate the ability to produce poly(methyl methacrylate) and poly(acrylonitrile) CCS polymers that are currently inaccessible via the two most common non‐metal‐based controlled radical polymerisation techniques (NMP and RAFT polymerisations).
High‐molecular‐weight PTeMC and PHMC were prepared by the lipase‐catalyzed polymerization of butane‐1,4‐diol or hexane‐1,6‐diol and diphenyl carbonate via the formation of a cyclic dimer by a green process. Cyclic carbonate dimers were prepared by the lipase‐catalyzed condensation of diphenyl carbonate with butane‐1,4‐diol or hexane‐1,6‐diol in dilute toluene solution using an immobilized lipase from Candida antarctica, and was followed by the ring‐opening polymerization of the cyclic dimer in bulk with the same lipase to produce PTeMC with = 119 000 g · mol?1 and PHMC with = 399 000 g · mol?1, respectively. Additionally, enzymatic polymerization of cyclic carbonate dimer was analyzed with respect to the Km and Vmax for the lipase.
A poly(methyl methacrylate)‐block‐poly(acrylic acid)‐block‐poly(2‐vinyl pyridine)‐block‐poly(acrylic acid)‐block‐poly(methyl methacrylate) (PMMA‐PAA‐P2VP‐PAA‐PMMA), pentablock terpolymer has been synthesized by anionic polymerization with sequential addition of monomers and studied in aqueous media at low pH. The system exhibits combined properties and adopts the behavior of ‘telechelic’ polyelectrolytes and that of double hydrophilic polyampholytes. This complex behavior leads to the pentablock terpolymer forming a pH and temperature sensitive reversible hydrogel at very low polymer concentration.
Reversible addition fragmentation chain transfer (RAFT) polymerization is one of the most extensively studied reversible deactivation radical polymerization methods for the production of well‐defined polymers. After polymerization, the RAFT agent end‐group can easily be converted into a thiol, opening manifold opportunities for thiol modification reactions. This review is focused both on the introduction of functional end‐groups using well‐established methods, such as thiol‐ene chemistry, as well as on creating bio‐cleavable disulfide linkages via disulfide exchange reactions. We demonstrate that thiol modification is a highly attractive and efficient chemistry for modifying RAFT polymers.
Low‐molecular weight amphiphilic diblock copolymers, polystyrene‐block‐poly (2‐vinylpyridine) (PS‐b‐P2VP), and (P2VP‐b‐PS) with different block ratios were synthesized for the first time via organotellurium‐mediated living radical polymerization (TERP). For both the homo‐ and block copolymerizations, good agreement between the theoretical, and experimental molecular weights was found with nearly 100% yield in every case. The molecular weight distribution for all the samples ranged between 1.10 and 1.24, which is well below the theoretical lower limit of 1.50 for a conventional free radical polymerization. Furthermore, a very simple approach to producing highly dense arrays of titania nanoparticles (TiO2) is presented using a site‐selective reaction of titanium tetraisopropoxide within the P2VP domains of micellar film of P2VP‐b‐PS in toluene through the sol–gel method.
Well‐controlled radical polymerization of methyl methacrylate can be achieved by in situ photochemical generation of copper (I) complex from air‐stable copper (II) species without using any reducing agent at room temperature. The living character of this polymerization was confirmed by both the linear tendency of molecular weight evolution with conversion and a chain extension experiment.
New multifunctional copoly(2‐oxazoline) nanoparticles were prepared for cell studies. The polymer contains double‐bond side chains as potential reaction sites for “thio”‐click reactions as well as a fluorescein label covalently bound to the polymer backbone. Using the nanoprecipitation technique, spherical nanoparticles of 200–800 nm were obtained. Confocal laser scanning microscopy measurements revealed the cellular uptake of the nanoparticles.
Highly efficient and well‐controlled ambient temperature reversible addition–fragmentation chain transfer (RAFT) polymerization is readily carried out under environmentally friendly mild solar radiation. This discovery has significantly extended studies from man‐made separated‐spectroscopic‐emission UV‐vis radiation (Macromolecules 2006 , 39, 3770) to natural continuous‐spectroscopic‐emission solar radiation for ambient temperature RAFT polymerization.
A novel α,ω‐heterofunctional poly(ethylene oxide) (PEO) macromonomer possessing methacryloyl and thienyl end groups was prepared by ring‐opening polymerization of ethylene oxide initiated by potassium thienylethoxide and termination of the living PEO ends with methacryloyl chloride. Incorporation of methacryloyl and thienyl groups was confirmed by free‐radical and oxidative polymerization processes, respectively, and by means of 1H NMR analysis.
The helical mechanoclinic deformation of a main‐chain chiral smectic elastomer, which is prepared by a crosslinking reaction under twist deformation, is investigated. The twist deformation induces a layer tilt angle that depends on the handedness of twist. The layer tilt angle in the right‐handedly twisted elastomer, of which the handedness is consistent with that of the helix in the SmC* phase of the non‐crosslinked backbone polymer, is estimated to be up to 16° at room temperature, although that in the left‐handedly twisted elastomer is less than several degrees. The experiments provide evidence of chiral coupling between tilt and twist for helical mechanoclinic deformation in the chiral smectic system.
Binary reactive/inert antifouling polymer brushes were grafted via a two step surface initiated polymerization from printed initiator monolayer and provided robust, effective polymeric surfaces for bioattachment with distinguishably reduced non‐specific adsorption. This synthetic strategy can be harnessed to build complex binary polymeric structures on substrate surfaces and the polymer brush surfaces reported in the present paper can be widely used for versatile biological study.
We report the first example of the synthesis and the “schizophrenic” micellization behavior of a multi‐responsive double hydrophilic ABC miktoarm star terpolymer. A well‐defined miktoarm star terpolymer consisting of poly(ethylene glycol), poly(2‐(diethylamino)ethyl methacrylate), and poly(N‐isopropylacrylamide) arms, PEG(‐b‐PDEA)‐b‐PNIPAM, was synthesized via the combination of atom transfer radical polymerization (ATRP) and click reaction. Containing pH‐responsive PDEA and thermo‐responsive PNIPAM arms, this novel type of miktoarm star terpolymer molecularly dissolves in aqueous solution at acidic pH and room temperature, but supramolecularly self‐assembles into PDEA‐core micelles at alkaline pH and room temperature, and PNIPAM‐core micelles at acidic pH and elevated temperatures. Most importantly, both types of micellar aggregates possess well‐solvated hybrid coronas.
Summary: The ring‐opening polymerizations of 2‐phenyl‐5,6‐dihydro‐4H‐1,3‐oxazine (PhOZI) with methyl tosylate (MeOTs) and butyl iodide (BuI) as initiators were performed in refluxing butyronitrile. Reaction kinetics under microwave irradiation was compared with conventional oil bath heating. The polymerization rates, under microwave irradiation, showed an acceleration by a factor of 1.8 (independently from the used initiator). The investigation of the thermal properties of the obtained poly(N‐benzoyl‐trimethyleneimine) showed the influence of molecular weight and end‐groups on the glass transition temperature.
The ring‐opening polymerizations of 2‐phenyl‐5,6‐dihydro‐4H‐1,3‐oxazine performed in refluxing butyronitrile. 相似文献
