Langmuir-Schaefer (LS) macroinitiator film control on the grafting of a thermosensitive polymer brush via surface initiated-ATRP

Nicel C. Estillore, Jin Young Park, Rigoberto C. Advincula

Research output: Contribution to journalArticle

28 Citations (Scopus)

Abstract

A novel surface modification based on the Langmuir-Schaefer (LS) monolayer technique was utilized for controlled surface-initiated atom transfer radical polymerization (SI-ATRP) of polymer brushes. The fabrication of these films was prepared by spreading an insoluble monolayer of an amphiphilic macroinitiator, poly(styrene-copolymer-hydroxyethyl methacrylate-2-bromoisobutyryl bromide) (p(St-co-HeBiB)), capable of initiating the ATRP polymerization of n-isopropylacrylamide (NIPAM). During the LS monolayer deposition, the surface pressure was varied in order to probe its effect on the initiator distribution and subsequent grafting density and thickness. The surface-bound macroinitiator ranged from a loosely (low surface pressure) to a densely (high surface pressure) crowded initiation sites on a monolayer. Increasing LS macroinitiator film thicknesses were observed with deposition at increasing surface pressures, i.e. 5, 15, 20, 30, and 50 mN/m using ellipsometry. However, based on the XPS data, there was a decrease in the bromine signal for the 50 mN/m LS macroinitiator film. Contrary to this result, there was a higher nitrogen signal and thicker pNIPAM brushes obtained for the 50 mN/m LS brush film. This was explained by a macroinitiator surface rearrangement during polymerization accounting for the difference. Moreover, wetting measurements by static water contact angle and an in situ atomic force microscopy (AFM) experiment were performed to investigate the temperature dependence of the pNIPAM brush surface wettability and morphology, respectively.

Original languageEnglish
Pages (from-to)6588-6598
Number of pages11
JournalMacromolecules
Volume43
Issue number16
DOIs
Publication statusPublished - 2010 Aug 24
Externally publishedYes

Fingerprint

Atom transfer radical polymerization
Brushes
Polymers
Monolayers
Wetting
Polymerization
Bromine
Ellipsometry
Bromides
Contact angle
Film thickness
Surface treatment
Styrene
Atomic force microscopy
Nitrogen
X ray photoelectron spectroscopy
Copolymers
Fabrication
Water

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Langmuir-Schaefer (LS) macroinitiator film control on the grafting of a thermosensitive polymer brush via surface initiated-ATRP. / Estillore, Nicel C.; Park, Jin Young; Advincula, Rigoberto C.

In: Macromolecules, Vol. 43, No. 16, 24.08.2010, p. 6588-6598.

Research output: Contribution to journalArticle

Estillore, Nicel C. ; Park, Jin Young ; Advincula, Rigoberto C. / Langmuir-Schaefer (LS) macroinitiator film control on the grafting of a thermosensitive polymer brush via surface initiated-ATRP. In: Macromolecules. 2010 ; Vol. 43, No. 16. pp. 6588-6598.
@article{89201c1f1677473ebbb84f34465410ea,
title = "Langmuir-Schaefer (LS) macroinitiator film control on the grafting of a thermosensitive polymer brush via surface initiated-ATRP",
abstract = "A novel surface modification based on the Langmuir-Schaefer (LS) monolayer technique was utilized for controlled surface-initiated atom transfer radical polymerization (SI-ATRP) of polymer brushes. The fabrication of these films was prepared by spreading an insoluble monolayer of an amphiphilic macroinitiator, poly(styrene-copolymer-hydroxyethyl methacrylate-2-bromoisobutyryl bromide) (p(St-co-HeBiB)), capable of initiating the ATRP polymerization of n-isopropylacrylamide (NIPAM). During the LS monolayer deposition, the surface pressure was varied in order to probe its effect on the initiator distribution and subsequent grafting density and thickness. The surface-bound macroinitiator ranged from a loosely (low surface pressure) to a densely (high surface pressure) crowded initiation sites on a monolayer. Increasing LS macroinitiator film thicknesses were observed with deposition at increasing surface pressures, i.e. 5, 15, 20, 30, and 50 mN/m using ellipsometry. However, based on the XPS data, there was a decrease in the bromine signal for the 50 mN/m LS macroinitiator film. Contrary to this result, there was a higher nitrogen signal and thicker pNIPAM brushes obtained for the 50 mN/m LS brush film. This was explained by a macroinitiator surface rearrangement during polymerization accounting for the difference. Moreover, wetting measurements by static water contact angle and an in situ atomic force microscopy (AFM) experiment were performed to investigate the temperature dependence of the pNIPAM brush surface wettability and morphology, respectively.",
author = "Estillore, {Nicel C.} and Park, {Jin Young} and Advincula, {Rigoberto C.}",
year = "2010",
month = "8",
day = "24",
doi = "10.1021/ma100726z",
language = "English",
volume = "43",
pages = "6588--6598",
journal = "Macromolecules",
issn = "0024-9297",
publisher = "American Chemical Society",
number = "16",

}

TY - JOUR

T1 - Langmuir-Schaefer (LS) macroinitiator film control on the grafting of a thermosensitive polymer brush via surface initiated-ATRP

AU - Estillore, Nicel C.

AU - Park, Jin Young

AU - Advincula, Rigoberto C.

PY - 2010/8/24

Y1 - 2010/8/24

N2 - A novel surface modification based on the Langmuir-Schaefer (LS) monolayer technique was utilized for controlled surface-initiated atom transfer radical polymerization (SI-ATRP) of polymer brushes. The fabrication of these films was prepared by spreading an insoluble monolayer of an amphiphilic macroinitiator, poly(styrene-copolymer-hydroxyethyl methacrylate-2-bromoisobutyryl bromide) (p(St-co-HeBiB)), capable of initiating the ATRP polymerization of n-isopropylacrylamide (NIPAM). During the LS monolayer deposition, the surface pressure was varied in order to probe its effect on the initiator distribution and subsequent grafting density and thickness. The surface-bound macroinitiator ranged from a loosely (low surface pressure) to a densely (high surface pressure) crowded initiation sites on a monolayer. Increasing LS macroinitiator film thicknesses were observed with deposition at increasing surface pressures, i.e. 5, 15, 20, 30, and 50 mN/m using ellipsometry. However, based on the XPS data, there was a decrease in the bromine signal for the 50 mN/m LS macroinitiator film. Contrary to this result, there was a higher nitrogen signal and thicker pNIPAM brushes obtained for the 50 mN/m LS brush film. This was explained by a macroinitiator surface rearrangement during polymerization accounting for the difference. Moreover, wetting measurements by static water contact angle and an in situ atomic force microscopy (AFM) experiment were performed to investigate the temperature dependence of the pNIPAM brush surface wettability and morphology, respectively.

AB - A novel surface modification based on the Langmuir-Schaefer (LS) monolayer technique was utilized for controlled surface-initiated atom transfer radical polymerization (SI-ATRP) of polymer brushes. The fabrication of these films was prepared by spreading an insoluble monolayer of an amphiphilic macroinitiator, poly(styrene-copolymer-hydroxyethyl methacrylate-2-bromoisobutyryl bromide) (p(St-co-HeBiB)), capable of initiating the ATRP polymerization of n-isopropylacrylamide (NIPAM). During the LS monolayer deposition, the surface pressure was varied in order to probe its effect on the initiator distribution and subsequent grafting density and thickness. The surface-bound macroinitiator ranged from a loosely (low surface pressure) to a densely (high surface pressure) crowded initiation sites on a monolayer. Increasing LS macroinitiator film thicknesses were observed with deposition at increasing surface pressures, i.e. 5, 15, 20, 30, and 50 mN/m using ellipsometry. However, based on the XPS data, there was a decrease in the bromine signal for the 50 mN/m LS macroinitiator film. Contrary to this result, there was a higher nitrogen signal and thicker pNIPAM brushes obtained for the 50 mN/m LS brush film. This was explained by a macroinitiator surface rearrangement during polymerization accounting for the difference. Moreover, wetting measurements by static water contact angle and an in situ atomic force microscopy (AFM) experiment were performed to investigate the temperature dependence of the pNIPAM brush surface wettability and morphology, respectively.

UR - http://www.scopus.com/inward/record.url?scp=77955725025&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=77955725025&partnerID=8YFLogxK

U2 - 10.1021/ma100726z

DO - 10.1021/ma100726z

M3 - Article

VL - 43

SP - 6588

EP - 6598

JO - Macromolecules

JF - Macromolecules

SN - 0024-9297

IS - 16

ER -