2012141122

I. Introduction

anostructured Thermoset Blends

Self-Assembly

Reaction induced-Phase Separation(R

Factors influencing the Blending:

Flory Huggins Interaction Parameter(), Chain Lengths, Statistical Chain length
: Describing Repulsive (bad) interactions
: Describing Attractive (interactions)

System 1: A-b-B/ C (C is miscible with B but immiscible with A)

Hashimoto et al. found miscible systems but it did not have these nanostructu
ex) PS-b-PI/poly(phenylene oxide) and PS-b-PB/ Poly( methyl vinyl ether) -> PS
System 2: A-b-B/ C(C is miscible with A and B)
Lee et al.
ex) P2VP-b-PEO/PVPh and PVPh-co-PMMA/PEO
2

I. Introduction

Nanostructured Thermoset Blends

Self-Assembly

Reaction induced-Phase Separation(

Q. Guo et al. Polymer ,Vol 49, 2008

Chen et al. Macromolecules, Vol. 41, No. 4

2008
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II. Experimental Methods

Materials and Preparation of Samples.
The block copolymer employed in this work, poly(-caprolactone)-block-poly(2-vinylpyridine) (PCL-bP2VP) with Mn(P2VP) = 20 500, Mn(PCL) = 28 000 and Mw/Mn = 1.10 was from Polymer Source, Inc.
The polymers were used as received. Diglycidyl ether of bisphenol A (DGEBA) with epoxide
equivalent weight of 172176 and 4,4-methylenedianiline (MDA) curing agent were purchased from
Aldrich Co. The chemical structures of epoxy resin (ER) and the curing agent are given in Scheme 1.
The value of n = 0.15 in that scheme indicates the number of times the structure within the
brackets is repeated
The ER precursor DGEBA and the PCL-b-P2VP diblock copolymer were mixed together, stirred and
heated at 100 C until the mixtures were homogeneous. A stoichiometric amount of the curing
agent MDA was added to the mixtures with vigorous stirring until homogeneous solutions were
obtained. The ternary mixture was poured into preheated molds and cured at 150 C for 12 h and
postcured at 180 C for 2 h.
Differential Scanning Calorimetry (DSC).
The glass transition temperatures of the blends were determined by a TA Q200 differential scanning
calorimeter using 510 mg of the sample under nitrogen atmosphere. A heating rate of 20 C/min
was employed. All samples were first heated to 250 C and maintained at that temperature for 3
min; they were subsequently cooled to 80 C at 20 C/min, held for
5 min, and heated to 200 C. The midpoints of the second heating scan of the plot were taken as
the glass transition temperatures (Tgs).
Transmission Electron Microscopy (TEM).
TEM analysis was carried out on a JEOL JEM-2100 transmission electron microscope operating at an
acceleration voltage of 100 kV. The samples were cut into ultrathin sections of about 70 nm
thickness at room temperature with a diamond knife using a Leica EM UC6 ultramicrotome machine.
The ultrathin sections were collected on 400 mesh copper grids and
stained with ruthenium tetroxide (RuO4) for observation.
Small Angle X-ray Scattering (SAXS).
SAXS experiments were conducted at the Australian Synchrotron on the small/wide-angle Xray
scattering beamline, utilizing an undulator source4that allowed measurement at a very high flux to
moderate scattering angles and a good flux at the minimum q limit (0.012 nm1). The intensity

II. Experimental Methods

K. Van Butsele et al. / Journal of Colloid and Interface Science 329

(2009) 235243

Reactants used as Epoxy Resins.

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III. Experimental Methods

Basic Interaction in the Hydrogen Bonding Concept

III. Results and Discussion

Figure 2. FTIR spectra corresponding

to the pyridine region of ER/PCL-bP2VP thermosets at room
temperature.

Figure 1. Hydroxyl region of

ER/PCL-b-P2VP blends in the
infrared spectra observed at
room temperature.

III. Results and Discussion

Figure 3. Carbonyl region of ER/PCL-bP2VP thermosets at room temperature.

III. Results and Discussion

Figure S1. IR spectra of the carbonyl

stretching region of ER/PCL blends at
room temperature.

Figure S2.DSC thermograms of the

heating curves of neat epoxy and
EP/PCL blends.
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III. Results and Discussion

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III. Results and Discussion

Self-Assembly of Nanostructure
Thermosets(SEM)

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III. Results and Discussion

Self-Assembly of Nanostructure
Thermosets(SAXS Profile)

Siril et al. New J. Chem., 2012,36, 2135-2139

van der Beek, et al. Eur. Phys. J. E 16 (3) 253-258 (2005)

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III. Results and Discussion

Self-Assembly of Nanostructure Thermosets

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III. Results and Discussion

Self-Assembly of Nanostructure Thermosets

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Conclusions
Fabrication of nanostructured thermosets via CHIPS in
ER/PCL-b-P2VP was studied.
Hydroxyl groups of ER selectively interact with both P2VP
and PCL Blocks
The disparity of strongly interacting ER/P2VP pairs and
weakly associated ER/PCL pairs results in compositionally
dependent microphase separation and the formatioin of
cylindrical, hexagonal cylinders with core-shell structures,
and lamellae at lower ER content.
ER/PCL increases at higher concentrations, which results in
twisted lamellae and homogeneous blends.

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References
Nisa V. Salim, Nishar Hameed, Bronwyn L. Fox, and Tracey
L. Hanley, Novel Approach to Trigger Nanostructures
in Thermosets Using Competitive Hydrogen-BondingInduced Phase Separation (CHIPS), Macromolecules
Article ASAP
Q. Guo et al. Polymer ,Vol 49, 2008
Chen et al. Macromolecules, Vol. 41, No. 4, 2008
van der Beek, et al. Eur. Phys. J. E 16 (3) 253-258 (2005)
Siril et al. New J. Chem., 2012,36, 2135-2139

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