Packing Length Influence in Linear Polymer Melts on the Entanglement, Critical, and Reptation Molecular Weights
Abstract
We have shown in previous studies that the entanglement molecular weight for a polymer melt, M e, is related by a power law to p, the packing length of the polymer species. We now find that power laws also describe the molecular weights characterizing the melt viscosity, M c marking the onset of entanglement effects and M r the crossover to the reptation form. The packing length exponents for M e, M c, and M r differ significantly, however. The long-held notion that the ratio M c / M e has the same value for all species is therefore incorrect. Further, the observed and predicted values of M r for two species, 1,4-polybutadiene and polyisobutylene, have been found to agree, within the uncertainties, with the projected values. Finally, the variations with packing length are such that all three characteristic molecular weights would appear to converge on the same value near p = 9 Å. As yet, no species with such a large packing length has been completely studied rheologically. But the range is not outlandish and is clearly reachable by appropriate synthetic methods.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
By introducing n-alkyl substituents of different sizes, it is possible to tune entanglement molar mass without significantly elevating the glass transition temperature.
“We have shown in this work that by introducing nalkyl substituents of di ff erent sizes it is possible to tune entanglement molar mass without signi fi cantly elevating the glass transition temperature. 78”
From Aliphatic Polyester Block Polymer Design (2016) · cites this paper as [78]
Cites
Fetters, L. J., Lohse, D. J., Richter, D., Witten, T. A., & Zirkel, A. (1994) · Macromolecules · doi:10.1021/ma00095a001 · Cited by 1,999 · see citing works
Self-citationViscosity and self-diffusion coefficient of hydrogenated polybutadiene
Pearson, D. S., Fetters, L. J., Graessley, W. W., Ver Strate, G., & von Meerwall, E. (1994) · Macromolecules · doi:10.1021/ma00081a014 · Cited by 198 · see citing works
Self-citation
Flagged first, then by citations
Cited by
Sorted by citations
Rheology and microscopic topology of entangled polymeric liquids
Everaers, R., Sukumaran, S. K., Grest, G. S., Svaneborg, C., Sivasubramanian, A., & Kremer, K. (2004) · Science · doi:10.1126/science.1091215 · Cited by 832 · see citing works
Quantitative theory for linear dynamics of linear entangled polymers
Likhtman, A. E., & McLeish, T. C. B. (2002) · Macromolecules · doi:10.1021/ma0200219 · Cited by 666 · see citing works
Hoy, R. S., Foteinopoulou, K., & Kröger, M. (2009) · Physical Review E · doi:10.1103/physreve.80.031803 · Cited by 335 · see citing works
Time and length scales of polymer melts studied by coarse-grained molecular dynamics simulations
Padding, J. T., & Briels, W. J. (2002) · The Journal of Chemical Physics · doi:10.1063/1.1481859 · Cited by 317 · see citing works
Simple models for complex nonequilibrium fluids
KROGER, M. (2004) · Physics Reports · doi:10.1016/j.physrep.2003.10.014 · Cited by 302 · see citing works
Aliphatic Polyester Block Polymer Design
Schneiderman, D. K., & Hillmyer, M. A. (2016) · Macromolecules · doi:10.1021/acs.macromol.6b00211 · Cited by 290 · see citing works
Identifying the primitive path mesh in entangled polymer liquids
Sukumaran, S. K., Grest, G. S., Kremer, K., & Everaers, R. (2005) · Journal of Polymer Science Part B: Polymer Physics · doi:10.1002/polb.20384 · Cited by 277 · see citing works
Kröger, M., & Hess, S. (2000) · Physical Review Letters · doi:10.1103/physrevlett.85.1128 · Cited by 237 · see citing works
Yeh, I.-C., Andzelm, J. W., & Rutledge, G. C. (2015) · Macromolecules · doi:10.1021/acs.macromol.5b00697 · Cited by 146 · see citing works
Translationally invariant slip-spring model for entangled polymer dynamics
Chappa, V. C., Morse, D. C., Zippelius, A., & Müller, M. (2012) · Physical Review Letters · doi:10.1103/physrevlett.109.148302 · Cited by 128 · see citing works
Stephanou, P. S., Baig, C., Tsolou, G., Mavrantzas, V. G., & Kröger, M. (2010) · The Journal of Chemical Physics · doi:10.1063/1.3361674 · Cited by 118 · see citing works
Degradable Polystyrene via the Cleavable Comonomer Approach
Gil, N., Caron, B., Siri, D., Roche, J., Hadiouch, S., Khedaioui, D., Ranque, S., Cassagne, C., Montarnal, D., Gigmes, D., et al. (2022) · Macromolecules · doi:10.1021/acs.macromol.2c00651 · Cited by 87 · see citing works
Structure, dimensions, and entanglement statistics of long linear polyethylene chains
Foteinopoulou, K., Karayiannis, N. C., Laso, M., & Kröger, M. (2009) · The Journal of Physical Chemistry B · doi:10.1021/jp808287s · Cited by 74 · see citing works
Why is understanding glassy polymer mechanics so difficult?
Hoy, R. S. (2011) · Journal of Polymer Science Part B: Polymer Physics · doi:10.1002/polb.22276 · Cited by 53 · see citing works
- Authors
- Fetters, L. J., Lohse, D. J., Milner, S. T., & Graessley, W. W.
- Affiliations
- ExxonMobil (United States) (US)
- Princeton University (US)
- ORCID
- Milner, Scott T.
- Venue
- Macromolecules
- Publisher
- American Chemical Society (ACS)
- Published
- 1999-09-09
- Volume
- 32
- Issue
- 20
- Pages
- 6847-6851
- ISSN
- 0024-9297 (ISSN-L)
- 1520-5835
- OpenAlex
- W2057831455
- Cited by
- 487
- References
- 2
- Citations by year
- 2026: 20 · 2025: 23 · 2024: 15 · 2023: 18 · 2022: 25 · 2021: 15 · 2020: 26 · 2019: 31 · 2018: 25 · 2017: 25 · 2016: 21 · 2015: 21 · 2014: 13 · 2013: 12 · 2012: 13
- FWCI
- 18.32
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Macromolecules (publishedVersion)
- Topics
- Physical Sciences › Chemical Engineering › Fluid Flow and Transfer Processes › Rheology and Fluid Dynamics Studies
- Physical Sciences › Materials Science › Materials Chemistry › Material Dynamics and Properties
- Physical Sciences › Materials Science › Polymers and Plastics › Polymer crystallization and properties
- Keywords
- entanglement molecular weight, critical molecular weight, melt viscosity, power-law scaling, 1,4-polybutadiene, polyisobutylene, polymer rheology, chain conformation
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
