Blends and Graft Copolymers Of: Cellulosics Toward The Design and Development of Advanced Films and
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SPRINGER BRIEFS IN MOLECULAR SCIENCE
BIOBASED POLYMERS
Yoshiyuki Nishio
Yoshikuni Teramoto
Ryosuke Kusumi
Kazuki Sugimura
Yoshitaka Aranishi
Biobased Polymers
Series editor
Patrick Navard, Sophia Antipolis cedex, France
Published under the auspices of EPNOE*Springerbriefs in Biobased polymers
covers all aspects of biobased polymer science, from the basis of this field starting
from the living species in which they are synthetized (such as genetics, agronomy,
plant biology) to the many applications they are used in (such as food, feed,
engineering, construction, health, …) through to isolation and characterization,
biosynthesis, biodegradation, chemical modifications, physical, chemical, mechan-
ical and structural characterizations or biomimetic applications. All biobased
polymers in all application sectors are welcome, either those produced in living
species (like polysaccharides, proteins, lignin, …) or those that are rebuilt by
chemists as in the case of many bioplastics.
Under the editorship of Patrick Navard and a panel of experts, the series will
include contributions from many of the world’s most authoritative biobased
polymer scientists and professionals. Readers will gain an understanding of how
given biobased polymers are made and what they can be used for. They will also be
able to widen their knowledge and find new opportunities due to the multidisci-
plinary contributions.
This series is aimed at advanced undergraduates, academic and industrial
researchers and professionals studying or using biobased polymers. Each brief will
bear a general introduction enabling any reader to understand its topic.
*EPNOE The European Polysaccharide Network of Excellence (www.epnoe.eu)
is a research and education network connecting academic, research institutions
and companies focusing on polysaccharides and polysaccharide-related research
and business.
Yoshitaka Aranishi
123
Yoshiyuki Nishio Kazuki Sugimura
Division of Forest and Biomaterials Science, Division of Forest and Biomaterials Science,
Graduate School of Agriculture Graduate School of Agriculture
Kyoto University Kyoto University
Kyoto Kyoto
Japan Japan
Ryosuke Kusumi
Division of Forest and Biomaterials Science,
Graduate School of Agriculture
Kyoto University
Kyoto
Japan
v
vi Preface
vii
viii Contents
xi
xii Abbreviations
TH
1q Proton spin–lattice relaxation time in the rotating frame
Tg Glass transition temperature
Tic Isothermal crystallization temperature
Tmeq Equilibrium melting temperature
VAc Vinyl acetate
VL d-Valerolactone
VP N-Vinyl pyrrolidone
WAXD Wide-angle X-ray diffraction
wi Weight fraction of component i
Xc Crystallinity index
b Non-exponential parameter indicating the degree of distribution
of relaxation time
eʺ Imaginary part of a complex dielectric function
e′ Real part of a complex dielectric function
l Viscometric interaction parameter
re Fold surface free energy per unit area of chain-folded crystal
Chapter 1
General Remarks on Cellulosic Blends
and Copolymers
Yoshiyuki Nishio
Abstract This chapter is a general introduction to the present monograph and first
describes the significance of the studies on “Blends and Graft Copolymers of
Cellulosics” in the research field of compositional materials based on cellulose and
related polysaccharides. Secondly, some technical key-terms and methods used for
characterizing cellulosic blends and graft copolymers are explained. Finally, the
outline of this book is provided by summarizing the main subjects of the consti-
tuting chapters with a perspective to tie together the subjects.
Keywords Blends
Cellulose Cellulose esters
Functionality
Graft
copolymers Microcomposition Miscibility
Multicomponent materials
Synergistic effect
Today, polysaccharides represented by cellulose and its relatives (glucans) are well
recognized as sustainable bioresources and high-potential polymers to be further
materialized for both commodity and specialty uses. For instance, cellulosic
polymers exhibit various characteristics at the molecular and supramolecular levels;
e.g., the polymer molecules have side-group reactivity (allowing further derivati-
zation), hydrogen-bonding formability, enzymatic degradability, semi-rigidity, and
chirality, and they can form distinct higher-order structures, such as fibrous crys-
talline entities (conditionally extractable in a nano-sized section), lyo-gels, and even
liquid crystals. Only one class of polymers (generically cellulosics) is endowed with
so many fascinating characteristics. This drives many researchers to make advanced
use of cellulosics in diverse fields involving functional materials, although accurate
understanding is still required for the individual characteristics or attributes.
A viable approach to multifaceted applications utilizing the natural bioresource,
cellulose, involves designing multifunctional or high-performance materials based
on cellulosics via microcomposition at the single-molecule level or nanofibrils with
(a) (b)
1
3
A
Undesired Property
B
Desired Property
2
X Y
4
Fig. 1.1 Illustrations of the synergistic behavior in property idealized for a material system
composed of components C-I and C-II. Patterns 1 and 2 depicted in part a are concerned with
desired properties A and X, respectively. Patterns 3 and 4 in part b refer to undesired properties
B and Y, respectively
1.1 Introduction: In the Stream of Microcomposition Research 3
system is a gross bulk mixture, the possible variation in a usable property would be
limited and hardly show such a welcome deviation from the simple additive rule,
even though the C-I/C-II composition is changed; actually, the wide compositional
change is often difficult for the fabrication process into dimensioned materials.
Instead, the more intimate incorporation at a hyperfine structural level (usually
<10−8 m) of at least one component will increase the chance of discovering that
kind of synergism in material properties. This approach can hold good in com-
posing cellulosics as the component, and the research is interesting and significant
in view of their ready availability with diverse structural features.
Among the extensive studies on microcompositions of cellulosics, the present
monograph focuses on the blends that are miscible or compatible with other
polymers and on the graft copolymers, the trunk chain of which is made up of a
carbohydrate backbone. The terms of polymer blending and copolymerization are
rather trite compared to that for the nanocomposite or nanohybrid, but are basically
pivotal and far-reaching for designing polymer-based multicomponent materials. In
fact, the knowledge of miscibility, domain formation, interaction, etc., is useful for
enhancing the performance of various gross- and nano-composites, for example, by
improving the adhesion of ingredient interfaces by chemical modification of the
bulk surfaces of the raw materials.
This monograph is not a comprehensive review, and the cellulosic polymers
covered herein are mainly organic esters of cellulose (CEs), such as cellulose
acetate, propionate, and butyrate. Concerning blends of unmodified cellulose with
synthetic polymers, a general scheme for their preparation and characterization has
been concisely described in previous reviews [1, 12, 13]. This monographic book
will summarize the total recent progress in fundamental characterization and
functional development of CE blends and copolymers, although the constitutive
chapters center on the authors’ research achievements. Synergistic effects will be
demonstrated for some properties, including thermal processability, in connection
with the practical applications of the cellulose-core materials to new advanced
films, membranes, fibers, and so forth.
1.2 Terminology
Several key specialty terms are common to the study of cellulosic blends and
copolymers. The definition or usage of these terms in this treatise is clarified below.
Cellulose is a b(1 ! 4)-linked glucan and has three hydroxyl groups in the
anhydroglucose unit (AGU) (Fig. 1.2a). Because of the hydroxyl reactivity, a
variety of cellulose derivatives can be synthesized, and industrially established
4 1 General Remarks on Cellulosic Blends and Copolymers
(b) substituent X
hydroxyl group
DS = 1.5
MS = 4
(DS = 2)
substituent Y
1.2 Terminology 5
A=3
DS ¼ ð1:1Þ
B=7
From the spectrum of CB-g-PCL (Fig. 1.3b), the MS value (= 2.33) of this graft
copolymer is determined from the following equation:
3C
MS ¼ DS ð1:2Þ
2A
where C is a resonance peak area from the Cc methylene protons of the PCL
side-chains, and DS refers to the butyryl substituent. Using the MS data and cal-
culated formula weights of the CB repeating unit and PCL-oxycaproyl unit, the
weight fraction of the grafted PCL component, WPCL, can also be determined;
WPCL = 0.46 for the example given in Fig. 1.3b.
The degree of polymerization of the side chains, DPs, is an additional important
parameter for the molecular characterization of graft copolymers. The average value
may be simply estimated from MS/DSgraft, where DSgraft indicates the DS of the
introduced grafts. It is easy to quantify DSgraft (and therefore DPs) from the NMR
6 1 General Remarks on Cellulosic Blends and Copolymers
data when a 1H NMR signal reflecting the side-chain terminal can be distinguished.
This is the case for cellulose acetate-graft-poly(L-lactic acid) [14] (see Chap. 4), but
not for CB-g-PCL. In the latter case, an apparent value of DPs is calculated by
assuming DSgraft = 3 − (butyryl DS). Again, using the example shown in
Fig. 1.3b, we find a value of 2.59 for the apparent DPs.
1.3.1 Tg Measurements
(a) (b)
A B A/B (50/50)
A B
miscible
E′
< Endothermic
Log Modulus
A/B (50/50)
immiscible
miscible
E″
immiscible
Fig. 1.4 Schematic representation of the glass transition behavior as observed by a DSC and
b DMA measurements for a miscible polymer blend (A/B = 50/50), in comparison with the
behaviors of unblended constituents A and B. In counterpoint, the case expected for an immiscible
(two-phase) blend is illustrated using a dotted line-curve
8 1 General Remarks on Cellulosic Blends and Copolymers
two Tgs of the constituent polymers (A and B). For an immiscible blend, we should
observe the two separate Tgs, as illustrated by the dotted line.
In DMA, a polymer material is subjected to a small-amplitude cyclic tensile (or
shear) deformation, and its viscoelastic response provides information on the glass
transition and other sub-transitions. The dynamic storage modulus E′ (or G′ for
shear) and loss modulus E′′ (or G′′ for shear), and the loss tangent (tan d) are
obtained as a function of temperature at a nominal frequency, typically 0.5–100 Hz.
The glass transition appears as a so-called primary dispersion signal corresponding
to the a relaxation of an amorphous material, reflecting the segmental
micro-Brownian motions of the polymer main-chain. Figure 1.4b illustrates ideal E′
and E′′ data associated with the principal relaxation for a miscible polymer blend
(again, A/B = 50/50), indicating a single glass transition situated between those of
unblended A and B. The Tg of the blend is defined as the temperature at which tan d
or E′′ assumes a maximum value within the transition range. Strictly, the use of the
peak position of E″ may be preferable. The loss factor, tan d (= E′′/E′), is formally a
ratio of the two dynamic moduli, both rapidly changeable with temperature in the
transition range; the maximum position as Tg is sometimes indiscernible.
In estimation of the miscibility for a pair of polymers, it is important to make a
plot of Tg versus blend composition. Observation of a single, composition-
dependent Tg over the whole composition range is the right sign of total miscibility,
and the presence of two Tg values indicates immiscibility or partial miscibility. DSC
excels in facility of the collection of Tg data. In this instrumentation, accurate
control of the thermal history of the used sample (typically 5–20 mg) can be
maintained by programmed heating and cooling cycles; additionally, analysis of the
melting and crystallization behavior is feasible for polymer blends showing crys-
tallinity. With DMA, only films or filamentous objects made from polymer mix-
tures are usable in the Tg measurement, and attention should be paid to the
treatment history of the test sample. An advantage of DMA is that we can discuss
the effect of blending on the low-temperature secondary relaxations associated with
local-part motions of the component polymers. Besides this, DMA can form a
general estimate of the thermo-mechanical performance of the objective material.
In many studies of polymer blends, we find good qualitative agreement in the
Tg–composition dependence between the DSC and DMA results. However, there is
a case of conflict; e.g., a particular blend may be judged miscible by DSC but
heterogeneous by DMA. This fact indicates that, regarding Tg detection, the two
techniques are responsive to similar molecular relaxations occurring over different
region sizes [19]. According to a generally accepted opinion [15, 16, 19, 20], the
level of molecular mixing to yield a single Tg in DMA for polymer blends may be
*15 nm as an upper limit of the possible domain size. In DSC, the limit would
increase to a certain larger value, e.g., *25 nm.
1.3 Methods for Miscibility Estimation 9
L ffi ð6DtÞ1=2 ð1:3Þ
DMA DSC
FT-IR (L ≤ ~15 nm) (L ≤ ~25 nm)
CP-MAS spectra
(L ≤ 1 nm) H
T1ρ (L ≤ 2–5 nm) Tg T1H (L ≤ 25–50 nm)
L (nm)
miscible immiscible
Fig. 1.5 Standard ruler to estimate the homogeneity scale in multicomponent polymer systems.
The approximate limits of heterogeneity examined by various techniques are marked on a
logarithmic coordinate axis of the domain size L
site of the polymer main-chain and/or attached side-chains has a permanent dipole
moment. A small fluctuation of polar units (e.g., -C-O-O-C-) can be detected in
dielectric relaxation spectra, whereas it is hard to detect such a small motion by
DMA and NMR techniques.
Dielectric relaxations are generally described as a combination of the real (e′)
and imaginary (e″) parts of a complex dielectric function. The relaxation processes
are each detected as a discrete dispersion signal and can be simulated using the
following Havriliak-Negami equation [29]:
ai
e* ¼ e1 þ (es e1 )/ 1 þ (ixs)bi ð1:4Þ
where e* is the complex permittivity, e∞ and es denote the limits of e′ to higher and
lower frequencies, x is the angular frequency of the measurement (x = 2pf with
normal frequency f), s is the dielectric relaxation time, and ai and bi are parameters
that characterize the shape of the relaxation time distribution (0 < bi 1,
0 < aibi 1). If ai is normalized to 1, Eq. (1.4) is reduced to a Cole-Cole rela-
tionship [30], in which bi indicates the degree of distribution of the relaxation time
associated with a dynamic process. A situation of ai = bi = 1 leads to the simplest
Debye function considering no distribution of the relaxation time. Figure 1.6
illustrates frequency dependences of e′ and e″ simulated in terms of these two types
of functions.
If a dispersion signal partly overlaps with an ascent of direct current (dc) con-
ductivity (this is often observed for the primary a relaxation), the following
equation including a correction term (−i(rdc/xe0)) should be adopted to extract the
net relaxation process:
Fig. 1.6 Dielectric relaxation curves that follow the Havriliak-Negami equation (Eq. 1.4) with
a ai = bi = 1 (Debye type) and b different bis under ai = 1 (Cole-Cole type)
12 1 General Remarks on Cellulosic Blends and Copolymers
ai
e* ¼ e1 þ (es e1 )/ 1 þ (ixs)bi i(rdc /xe0 ) ð1:5Þ
where rdc and e0 are the dc conductivity and the permittivity of a vacuum,
respectively. In the DRS study conducted for a series of CE-graft-aliphatic
polyesters (Chap. 4), the major quantities of the dielectric relaxation, e″, s, and bi,
are discussed through determination using Eqs. (1.4) or (1.5) with ai = 1.
(a) M
4,4'-bis(2-benzoxazolyl)stilbene (BBS)
M P2
ω
O
F1 Y
φ polarized component Iij
P1 X
of fluorescence (λf > λex)
P2
sample
F2
probability of excitation and that of detection are related, virtually, to the square of
a scalar product (MP1) and that of (MP2), respectively. Because of the two-fold
selectivity, the overall intensity (Iij) of the polarized component of fluorescence
obtained from the system is a function of the second and fourth moments
(<cos2x> and <cos4x>) of molecular orientation, which is defined as follows:
Z2p Zp
\cos x [ ¼
k
cosk x N(x,u) sinx dx du ðk ¼ 2; 4Þ ð1:6Þ
0 0
This monograph is organized into five chapters. Altogether, the main purpose is to
survey the fundamental aspects associated with molecular mixing, molecular
motions, and possible supramolecular structuring (e.g., crystallization) for cellulosic
blends and graft copolymers, and to demonstrate functional aspects linked to their
practical applications as advanced films and fibers. Industrially established CEs,
namely, cellulose acetate (CA), cellulose propionate (CP), and cellulose butyrate
(CB), are employed to represent the cellulosic component. The five chapters each
accomplish the above purpose in cooperation with each other.
This chapter describes the general background and common technical terms and
methods for studying cellulosic blends and graft copolymers and provides the
outline of this monograph (see Fig. 1.8).
In Chap. 2, the blend miscibility of CA, CP, and CB with vinyl copolymers
(mainly comprising the N-vinyl pyrrolidone (VP) unit) is characterized as a function
of the acyl DS of the respective CE components and the copolymer composition of
the counter component. Inter- or intra-molecular interactions that contribute to the
miscible pairings are clarified. Applications of the miscible blends to functional
optical films (e.g., film elements in the displays) and permeation-selective mem-
branes are suggested.
14 1 General Remarks on Cellulosic Blends and Copolymers
Fig. 1.8 Framework of this monograph, displaying major topics of chapters correlated to each
other
(2) miscible blending of the modified cellulose with a highly flexible polymer as a
viscosity controller.
A sequence of results compiled into this book will provide useful suggestions for
designing functionality-rich multicomponent materials based on cellulosics.
References
18. Coleman MM, Graf JF, Painter PC (1991) Specific interactions and the miscibility of polymer
blends: practical guides for predicting & designing miscible polymer mixtures. Lancaster,
Technomic Pub
19. MacKnight WJ, Karasz FE, Fried JR (1978) Solid state transition behavior of blends, chap. 5.
In: Paul DR, Newman S (eds) Polymer blends, vol 1. Academic Press, New York
20. Kaplan DS (1976) Structure–property relationships in copolymers to composites: molecular
interpretation of the glass transition phenomenon. J Appl Polym Sci 20:2615–2629.
doi:10.1002/app.1976.070201001
21. Ohno T, Nishio Y (2006) Cellulose alkyl ester/vinyl polymer blends: effects of butyryl
substitution and intramolecular copolymer composition on the miscibility. Cellulose
13:245–259. doi:10.1007/s10570-005-9014-3
22. Ohno T, Nishio Y (2007) Estimation of miscibility and interaction for cellulose acetate and
butyrate blends with N-vinylpyrrolidone copolymers. Macromol Chem Phys 208:622–634.
doi:10.1002/macp.200600510
23. Masson J-F, Manley RSJ (1991) Cellulose/poly(4-vinylpyridine) blends. Macromolecules
24:5914–5921. doi:10.1021/ma00022a004
24. Ohno T, Yoshizawa S, Miyashita Y, Nishio Y (2005) Interaction and scale of mixing in
cellulose acetate/poly(N-vinyl pyrrolidone-co-vinyl acetate) blends. Cellulose 12:281–291.
doi:10.1007/s10570-004-5836-7
25. MacBriety VJ, Douglass DC (1981) Recent advances in the NMR of solid polymers. J Polym
Sci Macromol Rev 16:295–366. doi:10.1002/pol.1981.230160105
26. Masson J-F, Manley RSJ (1992) Solid-state NMR of some cellulose/synthetic polymer
blends. Macromolecules 25:589–592. doi:10.1021/ma00028a016
27. Miyashita Y, Kimura N, Suzuki H, Nishio Y (1998) Cellulose/poly(acryloyl morpholine)
composites: synthesis by solution coagulation/bulk polymerization and analysis of phase
structure. Cellulose 5:123–134. doi:10.1023/A:1009224931504
28. Hedvig P (1977) Dielectric spectroscopy of polymers. Hilger, Bristol
29. Havriliak S, Negami S (1967) A complex plane representation of dielectric and mechanical
relaxation processes in some polymers. Polymer 8:161–210. doi:10.1016/0032-3861(67)
90021-3
30. Cole KS, Cole RH (1941) Dispersion and absorption in dielectrics I. Alternating current
characteristics. J Chem Phys 9:341–351. doi:10.1063/1.1750906
31. Nishijima Y (1970) Fluorescence methods in polymer science. J Polym Sci Part C Polym
Symp 31:353–373. doi:10.1002/polc.5070310128
32. Nishio Y, Suzuki H, Sato K (1994) Molecular orientation and optical anisotropy induced
by the stretching of poly(vinyl alcohol)/poly(N-vinyl pyrrolidone) blends. Polymer 35:
1452–1461. doi:10.1016/0032-3861(94)90345-X
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