Advances in Ionic Polymerization of Vinyl-Type Monomers

Schildknecht, C. E.

doi:10.1021/ie50577a046

Cited by 36 publications

(6 citation statements)

References 22 publications

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“…13 On the other hand, the polymerizability of the residual group in a 314 linear polymer obtained by the cationic polymerization of IPOZ is considered to be similar to that of N-methacrylamide derivatives susceptible to an anionic initiator, but unsusceptible to a cationic initiator. 14 The reason why the isopropenyl group in IPOZ monomer and the methacryloyl group in the N-methacryloyl polyethylenimine are not susceptible to cationic polymerization may be due to the electrondeficient character of these polymerizable groups with a considerable positive e-value.…”

Section: Mechanism Of Cationic Selective Polymerizationmentioning

confidence: 99%

Selective Polymerization of 2-Isopropenyl-2-oxazoline and Cross-linking Reaction of the Polymers

Kagiya

Matsuda

1972

Polym J

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ABSTRACT:The selective polymerization of 2-isopropenyl-2-oxazoline possessing two polymerizable sites in molecule was studied. Due to a marked difference in .polymerizability between the isopropenyl and oxazoline groups, this monomer provided soluble linear polymers by radical and cationic polymerization. The former was poly(2-isopropenyl-2-oxazoline) with the oxazoline group as a side chain, and the latter N-methacryloyl polyethylenimine. The cross-linking reactions of reactive pendant groups in both polymers, which resulted from the radical and cationic polymerizations, gave cross-linked, insoluble products.KEY WORDS Difunctional Monomer / 2-Isopropenyl-2-oxazoline / Selective Polymerization/ Poly(2-isopropenyl-2-oxazoline) / N-Methacryloyl Polyethylenimine / Cross-linking Reaction / Gelation / 2-Isopropenyl-2-oxazoline is a difunctional monomer possessing an isopropenyl group and oxazoline heterocycle as the polymerizable sites in molecule. It is reported by T. Kagiya, et al.,1 and several other investigators 2 -5 that 2-oxazolines can be polymerized by cationic catalysts such as stannic chloride or boron trifluoride etherate to give N-acyl or N-aryloyl polyethylenimine. Kagiya, et al.,6 reported that 2-isopropenyl-2-oxazoline gave poly(2-isopropenyl-2-oxazoline) by radical vinyl polymerization.The purpose of this paper is to report the selective cationic and radical polymerization of 2-isopropenyl-2-oxazoline, and the cross-linking reaction of the linear polymer having a polymerizable functional group as pendant side chain. EXPERIMENT AL MaterialN-Methacryloylethylenimine was prepared from the Schotten-Baumann reaction of ethylenimine and methacryloyl chloride in acetone media at -30°C, according to the method of Watanabe, et al. 7 2-Isopropenyl-2-oxazoline (IPOZ) was obtained from the isomerization reaction of N-methacryloylethylenimine with the use of sodium iodide as catalyst at 60°C for 15 hours according to the literature,8 and purified by careful distillation under reduced pressure [bp 50.5°C (17.5 mm)]. The identification was carried out by the infrared and NMR spectra of the product.Adipic acid as a cross-linker and a,a'-azobisisobutyronitrile (AIBN), which were commercially available products (G. R. Grade reagents), were used without further purification. Oxazolinium PerchloratePerchloric acid (70-% aqueous solution) ought not to be used as an initiator in the cationic polymerization of 2-oxazolines, because 2-oxazolines can be readily hydrolyzed. 9 The oxazolinium perchlorates of 2-isopropenyl-2-oxazoline and 2-phenyl-2-oxazoline as cationic initiators were prepared in the same manner as previously described. 11 The perchlorate salt of poly(2-isopropenyl-2-oxazoline) (Poly-IPOZ) was prepared by the same manner as above. From the elementary analysis and infrared spectrum, the following polyfunctional oxazolinium perchlorates were identified. Perchlorate salt of 2-isopropenyl-2-oxazoline (IPOZ-HC1O 4), mp 98.5-99.0°C.

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Section: Mechanism Of Cationic Selective Polymerizationmentioning

confidence: 99%

Selective Polymerization of 2-Isopropenyl-2-oxazoline and Cross-linking Reaction of the Polymers

Kagiya

Matsuda

1972

Polym J

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“…These methods vary in their compatibility with certain monomers, solvents, polymerization conditions, and mechanic pathways , Since 1956, pioneering work with radical anions led to the polymerization of styrene with exhibited negligible chain transfer or termination reactions and is termed as living anionic polymerization . It revolutionized the field of ionic polymerizations due to the technique’s ability to form stereoregular and stereospecific polymerizations and provides conditions which inhibit free radical polymerization . Specifically, styrene and conjugated dienes are the most prominent monomers used in this type of polymerization.…”

Section: Block Copolymers From Vinyl Polymersmentioning

confidence: 99%

Linear Block Copolymer Synthesis

et al. 2022

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Block copolymers form the basis of the most ubiquitous materials such as thermoplastic elastomers, bridge interphases in polymer blends, and are fundamental for the development of high-performance materials. The driving force to further advance these materials is the accessibility of block copolymers, which have a wide variety in composition, functional group content, and precision of their structure. To advance and broaden the application of block copolymers will depend on the nature of combined segmented blocks, guided through the combination of polymerization techniques to reach a high versatility in block copolymer architecture and function. This review provides the most comprehensive overview of techniques to prepare linear block copolymers and is intended to serve as a guideline on how polymerization techniques can work together to result in desired block combinations. As the review will give an account of the relevant procedures and access areas, the sections will include orthogonal approaches or sequentially combined polymerization techniques, which increases the synthetic options for these materials.

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“…However, ethyl, isopropyl, and π-butyl vinyl ethers do not yield crystalline polymers. Branched alkyl vinyl ethers, other than isobutyl vinyl ether, and benzyl ether also yield crystalline polymers [20]. The crystallinity of the polymers (isotactic) is similar in soluble and insoluble catalyst systems [21].…”

Section: Cationi C Polymerizatio Nmentioning

confidence: 99%

“…[20] Additional examples of the free radical polymerization of vinyl ethers is shown in Table V. To a reactor bomb are added 385 gm (500 ml, 5.35 moles) of vinyl isobutyl ether, 500ml of cyclohexane, and 23.8 gm of di-/er/-butyl peroxide.…”

Section: Free-radical Polymerizationmentioning

confidence: 99%