Polymerization of α,α-Dimethylbenzyl Methacrylate and Its Copolymerization with Methyl Methacrylate by Anionic Initiators

Yuki, Heimei; Ohta, Koji; Hatäda, Koichi

doi:10.1295/polymj.9.511

Cited by 7 publications

(1 citation statement)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…(RS)-MBMA, diphenylmethyl methacrylate (DPMMA, mp 80-82°C), 5 and a,a-dimethylbenzyl methacrylate [DMBMA, bp 70°C (0.4 mmHg)] 6 were prepared from the corresponding alcohols and methacryloyl chloride in the presence of triethylamine in diethyl ether.…”

Section: Methodsmentioning

confidence: 99%

Alternating Copolymerization of Methyl α-Phenylacrylate and Various Methacrylates

Yuki

Ohta

Hatäda

et al. 1979

Polym J

Self Cite

View full text Add to dashboard Cite

Methyl a-phenylacrylate (MPhA) was copolymerized with methacrylates which have ester groups of various sizes, such as benzyl, a-methylbenzyl, diphenylmethyl, a,a-dimethylbenzyl, 1,1-diphenylethyl, and trityl groups. The copolymerization was carried out with butyllithium in toluene and tetrahydrofuran at various temperatures with an initial monomer ratio of 1 : 1. In both solvents the copolymers with highly alternating structure were obtained at O and 30°C, except for the case in which 1,1-diphenylethyl methacrylate was used as the comonomer in toluene. In general the copolymers were atactic. However, the coisotacticity of the alternating copolymers increased with increasing bulkiness of methacrylate and reached about 60% in the copolymer of MPhA and trityl methacrylate regardless of the polymerization medium. At-40 and-78°C MPhA was more reactive than the methacrylates. The optical activity of the copolymer of MPhA and (S)-a-methylbenzyl methacrylate was lower than the calculated value, and the difference increased as the content of the alternating sequence increased. The circular dichroism spectrum of the optically active copolymer was also measured.

show abstract

Section: Methodsmentioning

confidence: 99%

Alternating Copolymerization of Methyl α-Phenylacrylate and Various Methacrylates

Yuki

Ohta

Hatäda

et al. 1979

Polym J

Self Cite

View full text Add to dashboard Cite

show abstract

Chirality of poly(vinyl compounds), 13. Sterical requirements in analogues of trityl methacrylate for the preparation of optically active, single‐sense helical polymers

Wulff

1990

Makromol. Chem.

View full text Add to dashboard Cite

s t y 1 methacrylate possesses two different substituents at the olefinic double bond. The larger one containing the trityl group forms the outside sphere of the helix in the corresponding polymers. In this paper the role of the second, smaller substituent is discussed. For this purpose four new monomers, methyl a-(trityloxymethy1)acrylate (3, ethyl a-(trityloxymethy1)acrylate (6), a-(trityloxymethyl)styrene (7). and trityl a-ethylacrylate (3), were prepared. Polymerizationexperiments showed that this substituent should be of minimum size to obtain a stable helix. More extended substituents though do not fit into the helical arrangement and therefore neither anionic nor radical polymerization was achieved.

show abstract

Microstructure of the copolymers of methyl methacrylate with other methacrylates obtained by radical and anionic copolymerizations in tetrahydrofuran

Yuki

Shimada

Ohta

et al. 1979

J. Polym. Sci. Polym. Chem. Ed.

View full text Add to dashboard Cite

Monomer reactivity ratios r1 and r2 were determined in the copolymerizations of methyl methacrylate (MMA, M1) with 1, 1‐diphenylethyl (DPEMA), α,α‐dimethylbenzyl (DMBMA), tert‐butyl (t‐BuMA), diphenylmethyl (DPMMA), phenyl (PhMA), and 1‐naphthyl (NpMA) methacrylates (M2) in tetrahydrofuran (THF) by azobisisobutyronitrile (AIBN) at 60°C and butyllithium (n‐BuLi) at −78°C. The reactivities of the monomers were explained in terms of the polar effect of the ester groups in both copolymerizations. All the copolymers isolated in low yields were converted to PMMA either directly or by copoly(MMA—methacrylic acid) to determine the triad tacticities of the copolymers. Coisotactic parameters σ12 and σ21 were determined by assuming the terminal model statistics. The σ21 values always accorded to the σ21 values within experimental error, and in radical copolymerizations they were between isotactic parameters σ11 and σ22 of the homopolymerizations of MMA and M2 monomers. In anionic copolymerizations, however, the σ12 = σ21 values varied, depending on the M2 monomers. In copolymerization with DPEMA the values were less than both σ11 and σ22 with DMBMA they were between σ11 and σ22, with DPMMA, nearly equal to σ11, and with PhMA and NpMA, greater than both σ11 and σ22. The application of these parameters to copolymerizations performed at high conversion was also investigated.

show abstract

Polymerization of α,α-Dimethylbenzyl Methacrylate and Its Copolymerization with Methyl Methacrylate by Anionic Initiators

Cited by 7 publications

References 18 publications

Alternating Copolymerization of Methyl α-Phenylacrylate and Various Methacrylates

Alternating Copolymerization of Methyl α-Phenylacrylate and Various Methacrylates

Chirality of poly(vinyl compounds), 13. Sterical requirements in analogues of trityl methacrylate for the preparation of optically active, single‐sense helical polymers

Microstructure of the copolymers of methyl methacrylate with other methacrylates obtained by radical and anionic copolymerizations in tetrahydrofuran

Contact Info

Product

Resources

About