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Introduction
From chemical point of view, segmented thermo-
plastic polyurethanes (TPUs) are linear multiblock
copolymers consisting of alternating soft polyether
or polyester segments (SS) and hard urethane seg-
ments (HS). The thermodynamic incompatibility
between the low polarity SS, which are rubbery at
usage temperatures, and the high polarity HS, which
are vitreous in the same conditions [13], induces a
micro-phase separation and the formation of HS
domains and SS domains, with ill-defined inter-
phases. At usage temperatures, the HS domains act
as both physical cross-links and filler particles
embedded within the SS matrix [3]. In these condi-
tions, the segmented TPUs behave as elastomers.
However, the physical cross-links disappear under
heating or in presence of an efficient solvent, and in
that case, the multiblock copolymers behave as
classical linear thermoplastics.
Basically, TPUs are produced from petroleum-based
raw materials, i.e., diisocyanates, polyols and chain
extenders. However, it has been demonstrated that
at least part of the conventional petroleum-based
polyols can be replaced by renewable resources-
based equivalent compounds such as vegetable oils
[47], and now, a major part of bio-based raw mate-
852
Development of bio-based thermoplastic polyurethanes
formulations using corn-derived chain extender for reactive
rotational molding
B. J. Rashmi, D. Rusu, K. Prashantha
*
, M-F. Lacrampe, P. Krawczak
Mines Douai, Department of Polymers and Composites Technology & Mechanical Engineering, 941 rue Charles
Bourseul, CS 10838, F-59508 Douai Cedex, France
Received 25 April 2013; accepted in revised form 24 June 2013
Abstract. Partly bio-based segmented thermoplastic polyurethane (TPU) formulations were developed to fulfill the
requirements of the reactive rotational molding process. They were obtained by one-shot bulk polymerization between an
aliphatic diisocyanate (1,6-hexamethylene diisocyanate), a polyether polyol as macrodiol (polyethylene glycol) and a bio-
based corn-derived 1,3-propanediol as chain extender (CE), in presence of a catalyst, at an initial temperature of 45C.
Equivalent TPU formulations with classical petroleum-based 1,3-propanediol were also prepared for a purpose of compar-
ison. TPU with different soft to hard segment (SS/HS) ratios were synthesized by varying the macrodiol and CE concentra-
tions in the formulations. For each formulation, the evolution of the reaction temperature as a function of time was
monitored and the kinetics of polymerization was studied by Fourier Transform infrared spectroscopy in attenuated total
reflection mode (FTIR-ATR). The morphology, thermal properties, solubility in different solvents and tensile properties of
the final products were analyzed. All synthesized polyurethanes are 100% linear polymers and the extent of microphase
separation, as well as the thermal and mechanical properties highly depends on the HS content, and glass transition temper-
ature and Young modulus can be tuned by adjustment of the SS/HS ratio. All results indicate that petrochemical CE can be
replaced by its recently available corn-derived homologue, without sacrificing any use properties of the final polyurethanes.
Keywords: processing technologies, thermoplastic polyurethanes, bio-based polymers, thermal behavior, mechanical prop-
erties
eXPRESS Polymer Letters Vol.7, No.10 (2013) 852862
Available online at www.expresspolymlett.com
DOI: 10.3144/expresspolymlett.2013.82
*
Corresponding author, e-mail: kalappa.prashantha@mines-douai.fr
BME-PT
rials derived from plant oils and natural fats is dedi-
cated to polyurethane industry [4, 5]. However, most
of the reported bio-based polyurethanes are chemi-
cally cross-linked networks (thermosets) [69],
except for a very few reports on syntheses of ther-
moplastics using either methanolysis, metathesis or
an ozonolysis pathway, which means some parts of
the original triacylglycerol were not utilized [10,
13], and for the very recent renewable-sourced ther-
moplastic polyurethanes Pearlthane
ECO from
Merquinsa [9].
The approach adopted in this paper aims at devel-
oping partially bio-based TPU formulations suit-
able for reactive rotational molding (RRM), as pre-
viously achieved for TPU foams [5]. To the best of
our knowledge, the following report is the first to
address this approach in the case of bulk TPUs. The
chosen polymerization system is based on the syn-
thesis of segmented TPUs starting from an aliphatic
diisocyanate, a polyether polyol as macrodiol and a
bio-based short diol as chain extender (CE), in pres-
ence of a catalyst. For further application, the sys-
tem should be suitable for RRM and thus the poly-
merization has to be made in one-step at ambient or
slightly higher temperature, the product should be
formed in relatively short time (~20 minutes). More-
over, the final product should be thermoplastic, to
allow easy recycling. TPUs with synthetic CE are
also going to be synthesized and the thermal and
mechanical properties of the petrochemical and bio-
based materials will be compared.
2. Experimental
2.1. Materials
The TPU formulations are based on 1,6-hexameth-
ylene diisocyanate (HDI, Sigma Aldrich, France),
polyethylene glycol (PEG 1000, VWR Interna-
tional, France) as macrodiol, 1,3-propanediol (PDO,
Sigma Aldrich, France) as petrochemical CE or
Susterra