Structure and physical properties of “comb-like” polymers

Platè, N.A.; Shibayev, V.P.

doi:10.1016/0032-3950(71)90015-3

Polymer Science U.S.S.R.

1971

DOI: 10.1016/0032-3950(71)90015-3

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Structure and physical properties of “comb-like” polymers

N.A. Platè

V.P. Shibayev

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1977

1987

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Cited by 26 publications

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“…14 The distances associated with the major mobile peaks are far larger than the length of the fully extended side chains, the latter being 0.127 nm times n. This was repeatedly taken to indicate that the variable d spacings are somehow dependent on the length of two side chains. 14,17,18 Calculating on the basis of two side chains, the slope of the line describing the d spacings of the variable major peak yields increments of 0.1044 nm per carbon atom in the side chains of poly(n-alkyl isocyanates). This is very close to the increments of 0.1047 nm calculated by us for the polymaleimides.…”

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confidence: 99%

Rigid-backbone polymers. 8. X-ray studies of poly(n-alkyl isocyanates)

Aharoni¹

1981

Macromolecules

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confidence: 99%

Rigid-backbone polymers. 8. X-ray studies of poly(n-alkyl isocyanates)

Aharoni¹

1981

Macromolecules

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Glass transition temperatures of poly N — (N — alkyl)—maleimides

1977

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The glass transition temperatures (T,s) of a series of poly N-(n-alkyl) maleimides covering only the even members with side chains ranging in length from ethyl to n-octadecyl have been studied from room temperature to above T,. T,s and thermal quantities have been determined from the specific volume-temperature relations only for the higher (n = 8, 10, 12, 14, 16 and 18, where n = n o of CH2) members of the series. However for the lower ones (n = 2 , 4 , 6 , 8 and 10) T,s have been detected from heat capacitytemperature traces of differential scanning calorimetry diagrams by extrapolation to zero rate of heating. Accurate consistency was found in the values (n = 8 and 10) determined by both experimental methods. T,s of these polymers continuously decrease as the number of methylene groups in the side chain is increased, and they have been correlated with the size of the n-alkyl group in the side chain. The results are in accord with a previously studied series concerning the effect of a long side chain on the T, of a comb-like polymer in the amorphous state. T,s of poly N-(n-alkyl) maleimides encompassing a wide range of methylene group content (n = 2 , 4 , 6 , 8 , 10 and 12) have been examined according to the Gordon-Taylor-Wood extrapolation with the objective of ascertaining the T, of polyethylene (PE). Our approach of ignoring higher members of the homologous series in this extrapolation appears to be old and well known and it has been variously ascribed to d i f p n t authors. Extrapolation of T, values t o 100% amorphous PE gives a T, of 200 f 10 K in complete agreement with recent predictions made by Boyer from different sources of data.The Simha-Boyer free volume quantity Au . T, decreases slowly with the methylene group content in the longer terms (n = 8, 10, 12, 14, 16 and 18) of the series presumably because of a reduction in the polarity or an in-chain crankshaft loss mechanism which generates free volume in the glassy state, as stated by Boyer. T,s do not correlate very well with the contributions of the atomic groups to the cohesive energy density (c.e.d.) so it can be concluded that c.e.d. is not the only factor determining T,. However, a somewhat improved relationship might be obtained by taking into account the steric hindrance effect according to an approach made by Hayes.

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Glass transitions and relaxations in comb‐branch poly(di‐p‐alkoxyphenyl itaconate)s

Cowie¹,

Ho²

1987

Brit. Poly. J.

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A series of poly(diphenyl itaconate)s, in which the phenyl ring has been substituted in the para position by alkoxy units containing up to seven carbon atoms, has been synthesised and characterised. Glass transition temperatures were observed to decrease as the number of atoms in the p‐substituent rose to six, but increased when the chain became longer. Heat capacity changes, ΔCP, at Tg were measured and the value of the Wunderlich parameter ΔCp/bead was found to lie between 7 0 and 10 3 JK−1mol−1 depending on the size of the alkoxy unit. Dynamic mechanical analysis revealed up to three sub‐glass‐transition damping peaks centred on 290 K, 200 K and 110 K. These have been assigned respectively to (a) oxycarbonyl group rotation, (b) motion involving the pendant phenyl rings and (c) limited bond reorientation in the p‐alkoxy groups when these contain four or more atoms.

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Structure and physical properties of “comb-like” polymers

Cited by 26 publications

References 16 publications

Rigid-backbone polymers. 8. X-ray studies of poly(n-alkyl isocyanates)

Rigid-backbone polymers. 8. X-ray studies of poly(n-alkyl isocyanates)

Glass transition temperatures of poly N — (N — alkyl)—maleimides

Glass transitions and relaxations in comb‐branch poly(di‐p‐alkoxyphenyl itaconate)s

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