2-methyl-2-oxazoline polymerization

The type of propagating species is mainly determined by the nucleophilicity of the monomer and basicity of the leaving group of the initiator, whereby covalent propagating species are present when the basicity of the counterion is higher than the nucleophilicity of the monomer and cationic propagating species are present if the basicity of the counterion is lower than the monomer nucleophilicity. The most nucleophilic monomer, 2-methyl-2-oxazoline, polymerizes via cationic propagating species with all counterions except... 

Well-defined amphiphilic block copolymers can be prepared by various controlled polymerization reactions, such as atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT), and nitroxide mediated polymerization (NMP). The amphiphilic copolymers most frequently used in bio-inspired strategies consist of hydrophilic blocks, such as poly(aciylic acid) (PAA), poly(ethylene oxide) (PEO), or poly(2-methyl oxazoline) (PMOXA), and a hydrophobic block, such as... 

Oxazolines are versatile structures that can undergo chemical transformation into dendrimeric and polymeric systems. Structures (26-28) show cyclotriphosphazenes with phenoxy-oxazoline pendant groups. Both oxazoline and methyl oxazoline groups can be attached to the cyclotriphosphazene ring. Methyl group attachment results in a chiral oxazoline. In a brief report, 1,3,4-oxadiazole substituted cyclotriphosphazene and linear polyphosphosphazene also were synthesized and characterized. ... 

The methyl oxazoline of 3,6-di-O-benzyl-D-glucosamine was used as a monomer for the synthesis of a dibenzylchitin-type polysaccharide. The polymerization under 10-camphorsulfonic acid catalysis provided the polyaminosaccharide [138]. 

Ring-opening polymerization of 2-methyl-2-oxazoline produces poly( V-acetyl-ethylenimine) (Scheme 2) [24-27], The resulting polymer can be regarded as a... 

The polymerization of 2-methyl-2-oxazoline is a clean reaction, which is not disturbed by chain transfer and termination. In this polymerization, the propagating species having the structure of an oxazolinium salt is not fragile, which is conveniently utilized for syntheses of block copolymers and end-reactive polymers [28],... 

Thus, the ring-opening polymerization of 2-methyl-2-oxazoline followed by the treatment of the resulting oxazolinium propagating end group with 3-aminopropyltriethoxysilane produced successfully triethoxysilyl-terminated poly-oxazoline as shown in Scheme 3 [29]. 

The relative rate of cationic homopolymerization is governed by three factors, ie. the concentration of the propagating species, the ring-opening reactivity of the growing species and the nucleophilic reactivity of the monomer. From kinetic studies196 197 of the polymerization of oxazolines and oxazines it was found that the second factor was the most important. On the other hand, the relative reactivity in the cationic copolymerization is mainly determined by the nucleophilicity of the monomer and for 2-substituted 2-oxazolines this is in the order of benzyl > methyl > > isopropyl > H > phenyl195. ... 

Symmetric triblock copolymers of the ABA type, where B was PTHF and A poly(2-methyl-2-oxazoline), PMeOx, were prepared by cationic polymerization with trifluoromethanesulfonic anhydride as a difunctional initiator [58]. Subsequent hydrolysis of the PMeOx blocks with HC1 in a methanol/ water mixture resulted in the formation of the corresponding polyethylen-imine blocks (Scheme 20). Samples with relatively low molecular weight distributions were obtained. 

The grafting from methodology was also utilized for the synthesis of poly(4-methylphenoxyphosphazene-g-2-methyl-2-oxazoline) graft copolymers [187]. The synthetic approach involved the thermal polymerization of hexachlorophosphazene, in the presence of aluminum chloride, to give low molecular weight poly(dichlorophosphazene). The chloro groups were subsequently replaced by 4-methylphenoxy groups, followed by partial bromi-... 

Much research has already been devoted in the past couple of years to (i) the immobilization of ATRP active metal catalysts on various supports to allow for catalyst separation and reycycling and (ii) ATRP experiments in pure water as the solvent of choice [62]. A strategy to combine these two demands with an amphiphilic block polymer has recently been presented. Two types of polymeric macroligands where the ligand was covalently linked to the amphiphilic poly(2-oxazo-line)s were prepared. In the case of ruthenium, the triphenylphosphine-functiona-lized poly(2-oxazoline)s described in section 6.2.3.2 were used, whereas in the case of copper as metal, 2,2 -bipyridine functionalized block copolymers were prepared via living cationic polymerization [63] of 2-methyl-2-oxazoline and a bipyridine-functionalized monomer as shown in Scheme 6.8. 

The living cationic ring opening polymerization (CROP) of 2-oxazolines was first reported in the 1960s [61, 62]. The polymerization can be initiated by an electrophile such as benzyl halides, acetyl halides, and tosylate or triflate derivatives. The typical polymerization mechanism for 2-alkyl-2-oxazoline initiated by methyl tosylate is shown in Scheme 6. 

A library of 4 chain extended homopolymers and 12 diblock copoly(2-oxazoline)s was prepared from 2-methyl, 2-ethyl, 2-nonyl, PheOx in a very short period of time [90]. The CROP was initiated by methyl tosylate and performed in acetonitrile at 140 °C in a single-mode microwave synthesizer. A total number of 100(50 + 50) repeating units was incorporated into the respective polymer chains. The concentration of the solutions and predefined polymerization times for each monomer and comonomer are summarized in Table 11. 

Synthesis of a Linear, iV-Acylated Polyethyleneimine Through Cationic Polymerization of 2-Methyl-2-Oxazoline in Bulk... 

In a 100 ml three-necked flask with stirrer and thermometer 1 mol% of p-toluenesul-fonic acid methyl ester (methyl tosylate) are added to 3 g (0.03 mol) of anhydrous 2-methyl-2-oxazoline.The reaction mixture is stirred under nitrogen at 100-120 °C.The bulk polymerization sets in immediately. After 30 min. the viscous polymer melt is poured in a dish where it solidifies within minutes. After cooling to room temperature about 2 grams are dissolved in 20 ml ethanol and precipitated in 500 ml THF.The collected precipitate is dried under vacuum. 

For (c), a macromonomer that has a pendant group accustomed to the solvent is used as a comonomer in the dispersion polymerization of a monomer that composes the particle. The surface of resulting particles is covered with the pendant group and consequently stabilized by a steric stabilization effect (14,15). In this sense the macromonomer is a kind of stabilizer that shows its effect through polymerization, and it could be called as a stabilizer formed in situ. A copolymer of macromonomer and particle-composing monomer, which joins the polymer particle, is much more effective for dispersion than a soluble stabilizer. With the dispersion polymerization of methyl methacrylate, which uses a macromonomer composed of an oligo-oxazoline pendant group, it is possible to cut the amount of stabilizer used to one-tenth or less compared to the oxazoline homopolymer stabilizer (16). 

Tsubokawa et al. (44) have reported the grafting of polymeric cationic species of vinyl butyl ether or 2-methyl-2-oxazoline onto aminated silica particles via the termination. However, it is ordinarily difficult to apply the surface termination reac-... 

A very recent paper by Saegusa, 7) describes a method of synthesizing polyoxyethylene macromonomers bearing a polymerizable heterocycle at the chain end. Here again the method involves initiation of the oxirane polymerization by means of an alcoholate (derived from 2-p-hydroxyphenyl)-oxazoline). As metalation agent butyllithium, was used since lithium alcoholates are not very reactive towards oxirane. Indeed, the macromonomers obtained exhibit very low degrees of polymerization. Deactivation was performed with methyl iodide ... 

Macromonomers were prepared by polymerizing oxazolines with monofunctional initiators (e.g., methyl p-toluenosulfonate) and terminating the polymerization with salts of acrylic or methacrylic acid. Macromonomers with M varying from M — 500 to —2500 and MJM - 1.2-1.4 were obtained functionalities, however, depended strongly on reaction conditions and the values between 0.99 down to —0.5 and lower were reported [280]. 

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