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Polymer Classification: Crystallinity

Polymer Classification: Crystallinity

Unlike ionic or small covalent molecules, polymers do not form crystalline solids due to the diffusion limitations of their long-chain structures. However, polymers contain microscopic crystalline domains separated by amorphous domains.
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Polymerization generates chiral centers along the entire backbone of a polymer chain. Accordingly, the stereochemistry of the substituent group has a significant effect on polymer properties. Polymers formed from monosubstituted alkene monomers feature chiral carbons at every alternate position in the polymer backbone. Relative to the predominant orientation of substituents at the adjacent chiral carbons, the polymer can exist in three different configurations: isotactic, syndiotactic, and...

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Polymers are classified as linear or branched on the basis of their chain architecture. The polymer chains in linear polymers have a long chain-like structure with minimal to no branching at all. Even if a polymer features large substituent groups on the monomer, which appear as branches to the skeleton, it is not considered a branched polymer. A branched polymer contains secondary polymer chains that arise from the main polymer chain. The branching occurs when the polymer growth shifts from...

Free-Radical Chain Reaction and Polymerization of Alkenes

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The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.

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The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the π bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the π bond generates a carbocation stabilized by the electron‐donating group. In the propagation step, the π bond of the second monomer acts as a nucleophile and attacks the generated carbocation,...

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Updated: Jul 2, 2026

Self-assembling Morphologies Obtained from Helical Polycarbodiimide Copolymers and Their Triazole Derivatives

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Published on: February 7, 2017

Partial crystallinity in alkyl side chain polymers dictates surface freezing.

Shishir Prasad¹, Zhang Jiang, Sunil K Sinha

¹Department of Polymer Science, The University of Akron, Akron, Ohio 44325, USA.

Physical Review Letters

|September 4, 2008

Summary

This summary is machine-generated.

Polymer side chains partially crystallize at the surface, affecting transition temperatures. Shorter alkyl chains increase the difference between surface and bulk melting points.

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Area of Science:

Polymer Science
Materials Science
Surface Chemistry

Background:

Polymer melts exhibit complex surface behavior.
Understanding surface structure is crucial for material properties.

Purpose of the Study:

Investigate the structure of a crystalline surface monolayer on poly(n-alkyl acrylate)s.
Determine the factors influencing surface order-to-disorder transition temperature.

Main Methods:

Grazing incidence x-ray diffraction.
Surface tension measurements.
Bulk latent heat analysis.

Main Results:

A novel crystalline surface monolayer was identified.
Polymer side chains exhibit partial crystallization, excluding units near the backbone.
Surface layer thickness increases with linker group length.

Conclusions:

Partial crystallinity and increased surface layer thickness influence transition temperatures.
The difference between surface and bulk transition temperatures is sensitive to alkyl side chain length.