Unusual contributions of molecular architecture to rheology and flow birefringence in hyperbranched polystyrene melts

Semen B. Kharchenko, Kannan Rangaramanujam, Jeff J. Cernohous, Shivshankar Venkataramani, Gaddam N. Babu

Research output: Contribution to journalArticle

Abstract

With the increase in sophisticated synthesis methods, it appears that polymer architecture may be a tunable property. Therefore, the role of architecture in rheological and processing properties has received renewed attention, mainly because of dendrimer synthesis and metallocene-catalyst technology. Linear polymers and hyperbranched polymers represent two ends of branching complexity. Some previous studies have suggested that hyperbranched polymers may behave like unentangled polymers, whereas others have proposed that they exhibit the properties of soft colloids. In an effort to compare the responses of linear and hyperbranched polymers, we synthesized starlike hyperbranched polystyrenes (HBPSs) of various branch lengths and numbers of branches. The HBPSs used in this study were unentangled or weakly entangled, allowing us to study the effect of branch density more readily. Two linear polystyrene (L-PS) melts and two HBPSs were studied. Using a custom-built rheooptical apparatus, we characterized the theology and flow birefringence of these materials. To our knowledge, these are the first flow birefringence measurements on highly branched polymer melts. Our results suggest that the flow behaviour of HBPS is significantly different from that of L-PS: (1) HBPS shows nonterminal behaviour in the low-frequency theological response; (2) when the stress-optical rule (SOR) holds, the stress-optical coefficient of HBPS is much lower than those of analogous linear polymers; and (3) when the branch density is high and the branch length is sufficiently low, the SOR fails for these homopolymer melts. A significant increase in the birefringence for a given amount of stress in the low-frequency region suggests that there may be a soft core in these materials due to the strong preferential radial orientation of chain segments near the center of a molecule versus those near the periphery. The predominantly elastic response of the soft structures may be responsible for the enhanced form birefringence. Our preliminary results indicate that these materials may exhibit both polymeric and soft-colloid natures.

Original languageEnglish (US)
Pages (from-to)2562-2571
Number of pages10
JournalJournal of Polymer Science, Part B: Polymer Physics
Volume39
Issue number21
DOIs
StatePublished - Nov 1 2001
Externally publishedYes

Fingerprint

Polystyrenes
Birefringence
Rheology
rheology
birefringence
polystyrene
Polymers
dendrimers
polymers
Colloids
colloids
low frequencies
Dendrimers
Polymer melts
synthesis
Homopolymerization
frequency response
Frequency response
catalysts
Catalysts

Keywords

  • Birefringence
  • Hyperbranched
  • Polystyrene
  • Rheooptics
  • Star polymers

ASJC Scopus subject areas

  • Polymers and Plastics
  • Materials Chemistry

Cite this

Unusual contributions of molecular architecture to rheology and flow birefringence in hyperbranched polystyrene melts. / Kharchenko, Semen B.; Rangaramanujam, Kannan; Cernohous, Jeff J.; Venkataramani, Shivshankar; Babu, Gaddam N.

In: Journal of Polymer Science, Part B: Polymer Physics, Vol. 39, No. 21, 01.11.2001, p. 2562-2571.

Research output: Contribution to journalArticle

Kharchenko, Semen B. ; Rangaramanujam, Kannan ; Cernohous, Jeff J. ; Venkataramani, Shivshankar ; Babu, Gaddam N. / Unusual contributions of molecular architecture to rheology and flow birefringence in hyperbranched polystyrene melts. In: Journal of Polymer Science, Part B: Polymer Physics. 2001 ; Vol. 39, No. 21. pp. 2562-2571.
@article{2729142498784ede978a05740ac4b3ba,
title = "Unusual contributions of molecular architecture to rheology and flow birefringence in hyperbranched polystyrene melts",
abstract = "With the increase in sophisticated synthesis methods, it appears that polymer architecture may be a tunable property. Therefore, the role of architecture in rheological and processing properties has received renewed attention, mainly because of dendrimer synthesis and metallocene-catalyst technology. Linear polymers and hyperbranched polymers represent two ends of branching complexity. Some previous studies have suggested that hyperbranched polymers may behave like unentangled polymers, whereas others have proposed that they exhibit the properties of soft colloids. In an effort to compare the responses of linear and hyperbranched polymers, we synthesized starlike hyperbranched polystyrenes (HBPSs) of various branch lengths and numbers of branches. The HBPSs used in this study were unentangled or weakly entangled, allowing us to study the effect of branch density more readily. Two linear polystyrene (L-PS) melts and two HBPSs were studied. Using a custom-built rheooptical apparatus, we characterized the theology and flow birefringence of these materials. To our knowledge, these are the first flow birefringence measurements on highly branched polymer melts. Our results suggest that the flow behaviour of HBPS is significantly different from that of L-PS: (1) HBPS shows nonterminal behaviour in the low-frequency theological response; (2) when the stress-optical rule (SOR) holds, the stress-optical coefficient of HBPS is much lower than those of analogous linear polymers; and (3) when the branch density is high and the branch length is sufficiently low, the SOR fails for these homopolymer melts. A significant increase in the birefringence for a given amount of stress in the low-frequency region suggests that there may be a soft core in these materials due to the strong preferential radial orientation of chain segments near the center of a molecule versus those near the periphery. The predominantly elastic response of the soft structures may be responsible for the enhanced form birefringence. Our preliminary results indicate that these materials may exhibit both polymeric and soft-colloid natures.",
keywords = "Birefringence, Hyperbranched, Polystyrene, Rheooptics, Star polymers",
author = "Kharchenko, {Semen B.} and Kannan Rangaramanujam and Cernohous, {Jeff J.} and Shivshankar Venkataramani and Babu, {Gaddam N.}",
year = "2001",
month = "11",
day = "1",
doi = "10.1002/polb.10013",
language = "English (US)",
volume = "39",
pages = "2562--2571",
journal = "Journal of Polymer Science, Part B: Polymer Physics",
issn = "0887-6266",
publisher = "John Wiley and Sons Inc.",
number = "21",

}

TY - JOUR

T1 - Unusual contributions of molecular architecture to rheology and flow birefringence in hyperbranched polystyrene melts

AU - Kharchenko, Semen B.

AU - Rangaramanujam, Kannan

AU - Cernohous, Jeff J.

AU - Venkataramani, Shivshankar

AU - Babu, Gaddam N.

PY - 2001/11/1

Y1 - 2001/11/1

N2 - With the increase in sophisticated synthesis methods, it appears that polymer architecture may be a tunable property. Therefore, the role of architecture in rheological and processing properties has received renewed attention, mainly because of dendrimer synthesis and metallocene-catalyst technology. Linear polymers and hyperbranched polymers represent two ends of branching complexity. Some previous studies have suggested that hyperbranched polymers may behave like unentangled polymers, whereas others have proposed that they exhibit the properties of soft colloids. In an effort to compare the responses of linear and hyperbranched polymers, we synthesized starlike hyperbranched polystyrenes (HBPSs) of various branch lengths and numbers of branches. The HBPSs used in this study were unentangled or weakly entangled, allowing us to study the effect of branch density more readily. Two linear polystyrene (L-PS) melts and two HBPSs were studied. Using a custom-built rheooptical apparatus, we characterized the theology and flow birefringence of these materials. To our knowledge, these are the first flow birefringence measurements on highly branched polymer melts. Our results suggest that the flow behaviour of HBPS is significantly different from that of L-PS: (1) HBPS shows nonterminal behaviour in the low-frequency theological response; (2) when the stress-optical rule (SOR) holds, the stress-optical coefficient of HBPS is much lower than those of analogous linear polymers; and (3) when the branch density is high and the branch length is sufficiently low, the SOR fails for these homopolymer melts. A significant increase in the birefringence for a given amount of stress in the low-frequency region suggests that there may be a soft core in these materials due to the strong preferential radial orientation of chain segments near the center of a molecule versus those near the periphery. The predominantly elastic response of the soft structures may be responsible for the enhanced form birefringence. Our preliminary results indicate that these materials may exhibit both polymeric and soft-colloid natures.

AB - With the increase in sophisticated synthesis methods, it appears that polymer architecture may be a tunable property. Therefore, the role of architecture in rheological and processing properties has received renewed attention, mainly because of dendrimer synthesis and metallocene-catalyst technology. Linear polymers and hyperbranched polymers represent two ends of branching complexity. Some previous studies have suggested that hyperbranched polymers may behave like unentangled polymers, whereas others have proposed that they exhibit the properties of soft colloids. In an effort to compare the responses of linear and hyperbranched polymers, we synthesized starlike hyperbranched polystyrenes (HBPSs) of various branch lengths and numbers of branches. The HBPSs used in this study were unentangled or weakly entangled, allowing us to study the effect of branch density more readily. Two linear polystyrene (L-PS) melts and two HBPSs were studied. Using a custom-built rheooptical apparatus, we characterized the theology and flow birefringence of these materials. To our knowledge, these are the first flow birefringence measurements on highly branched polymer melts. Our results suggest that the flow behaviour of HBPS is significantly different from that of L-PS: (1) HBPS shows nonterminal behaviour in the low-frequency theological response; (2) when the stress-optical rule (SOR) holds, the stress-optical coefficient of HBPS is much lower than those of analogous linear polymers; and (3) when the branch density is high and the branch length is sufficiently low, the SOR fails for these homopolymer melts. A significant increase in the birefringence for a given amount of stress in the low-frequency region suggests that there may be a soft core in these materials due to the strong preferential radial orientation of chain segments near the center of a molecule versus those near the periphery. The predominantly elastic response of the soft structures may be responsible for the enhanced form birefringence. Our preliminary results indicate that these materials may exhibit both polymeric and soft-colloid natures.

KW - Birefringence

KW - Hyperbranched

KW - Polystyrene

KW - Rheooptics

KW - Star polymers

UR - http://www.scopus.com/inward/record.url?scp=0035504808&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0035504808&partnerID=8YFLogxK

U2 - 10.1002/polb.10013

DO - 10.1002/polb.10013

M3 - Article

AN - SCOPUS:0035504808

VL - 39

SP - 2562

EP - 2571

JO - Journal of Polymer Science, Part B: Polymer Physics

JF - Journal of Polymer Science, Part B: Polymer Physics

SN - 0887-6266

IS - 21

ER -