Initiation via Haloboration in Living Cationic Polymerization. 4. The Polymerization of α-Methylstyrene

Koroskenyi, Balint; Wang, Linfu; Faust, Rudolf

doi:10.1021/ma9708149

Cited by 22 publications

(16 citation statements)

References 15 publications

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“…7) is quite similar to those obtained by Faust et al for the polymerization via haloboration. [44][45][46] Moreover, from our preliminary data the reaction order with respect to the Lewis acid for the pmethoxystyrene polymerization without initiator was calculated to be 2, indicating that two molecules of B(C 6 F 5 ) 3 participate in the initiation and propagation, that is in discrepancy with obtained above [see Fig. 6(b)] value near 1 for the 1/ B(C 6 F 5 ) 3 initiating system.…”

Section: Polymerization Without Initiatormentioning

confidence: 75%

Kinetic study on the living/controlled cationic polymerization of p‐methoxystyrene coinitiated by tris(pentafluorophenyl)borane

Radchenko

Kostjuk

Vasilenko

et al. 2008

J. Polym. Sci. A Polym. Chem.

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A kinetic study of the living cationic polymerization of p-methoxystyrene using 1-(4-methoxyphenyl)ethanol (1)/B(C 6 F 5 ) 3 initiating system in a mixture of CH 3 CN with CH 2 Cl 2 1:1 (v/v) at room temperature was carried out utilizing a wide variety of conditions. The polymerization proceeded in a living fashion even in the presence of a large amount of water ([H 2 O]/[B(C 6 F 5 ) 3 ] ratio up to 20) to afford polymers whose M n increased in direct proportion to monomer conversion with fairly narrow MWDs (M w /M n 1.3). The investigation revealed that the rate of polymerization was first-order in B(C 6 F 5 ) 3 concentration, while a negative order in H 2 O concentration close to À2 was obtained. It was also found that the rate of polymerization decreased with lowering temperature, which could be attributed to a decreased concentration in free Lewis acid, the true coinitiator of polymerization. A mechanistic scheme to explain the kinetic behavior of living p-methoxystyrene polymerization is proposed, which has been validated by PREDICI simulation on multiple-data curves obtained by 1 H NMR in situ polymerization experiment. V V C 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: [6928][6929][6930][6931][6932][6933][6934][6935][6936][6937][6938][6939] 2008

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Section: Polymerization Without Initiatormentioning

confidence: 75%

Kinetic study on the living/controlled cationic polymerization of p‐methoxystyrene coinitiated by tris(pentafluorophenyl)borane

Radchenko

Kostjuk

Vasilenko

et al. 2008

J. Polym. Sci. A Polym. Chem.

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“…High-molecular-weight PAMS is known as a useful starting material for the preparation of Inertial Confinement Fusion Targets [4][5][6]. To produce the material of required quality, the low-temperature cationic polymerization approach was chosen [7].…”

Section: Methodsmentioning

confidence: 99%

Hollow poly(alpha-methylstyrene) shells for inertial confinement fusion targets

Пастухов

Davankov

Akunets

et al. 2017

J. Phys.: Conf. Ser.

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Abstract. Using a low-temperature cationic polymerization technique, a number of poly(alpha-methylstyrene) samples with molecular masses of 300000-400000 were prepared, and their structural parameters were examined via nuclear magnetic resonance and X-ray diffraction techniques. It was found that all synthesized polymers display a stereoregular syndiotactic structure of macro chains and are amorphous. Using these polymers and the microencapsulation technique, hollow shells were obtained that were 2.4 mm in diameter and had a wall thickness of 10 to 60 µm. The quality of walls and surfaces of the shells was analyzed using scanning electron microscopy and optical profilometry. The hollow shells are intended for the preparation of inertial confinement fusion targets and for the laser plasma research.

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“…16 Metallocene, 17 metathesis, 18,19 and living cationic polymerization [20][21][22] have been employed to incorporate terminal organoboron functionality, generally by initiation with or chain transfer to a boron-containing compound, though few have resulted in specifically boronic acid-terminated polymers.…”

Section: Introductionmentioning

confidence: 99%

Boronic Acid-Terminated Polymers: Synthesis by RAFT and Subsequent Supramolecular and Dynamic Covalent Self-Assembly

De¹,

Gondi²,

Roy³

et al. 2009

Macromolecules

103

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Well-defined homopolymers and block copolymers with boronic acid-functional end groups were prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization and subsequently investigated for the potential to undergo model supramolecular and dynamic covalent self-assembly in aqueous and organic media. By employing a boronic acid-functionalized RAFT chain transfer agent, endfunctional polymers were prepared without recourse to postpolymerization functionalization. The polymerizations of styrene, N,N-dimethylacrylamide, and N-isopropylacrylamide all led to homopolymers of controlled molecular weight that were capable of subsequent chain extension to form well-defined block copolymers. The amphiphilic and stimuli-responsive block copolymers were capable of self-assembly into micellar aggregates. Quantitative retention of the boronic acid chain termini during polymerization was spectroscopically demonstrated, and two types of dynamic covalent transformations involving these moieties were investigated. The formation of boronic esters with a model 1,2-diol proved to be a highly efficient process in nonaqueous media. Additionally, Lewis base-promoted trimerization of the boronic acid end groups led to three-arm star polymers with boroxine junction points. Both of these covalent interactions were readily reversible upon the introduction of water, suggesting the potential application of these polymers to construct dynamic covalent macromolecular assemblies.

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Initiation via Haloboration in Living Cationic Polymerization. 4. The Polymerization of α-Methylstyrene

Cited by 22 publications

References 15 publications

Kinetic study on the living/controlled cationic polymerization of p‐methoxystyrene coinitiated by tris(pentafluorophenyl)borane

Kinetic study on the living/controlled cationic polymerization of p‐methoxystyrene coinitiated by tris(pentafluorophenyl)borane

Hollow poly(alpha-methylstyrene) shells for inertial confinement fusion targets

Boronic Acid-Terminated Polymers: Synthesis by RAFT and Subsequent Supramolecular and Dynamic Covalent Self-Assembly

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