Blends and Graft Copolymers of Cellulosics: Toward the Design and Development of Advanced Films and Fibers

136 Pages·2017·7.909 MB·English

by  Yoshiyuki Nishio, Yoshikuni Teramoto, Ryosuke Kusumi, Kazuki Sugimura, Yoshitaka Aranishi (auth.)

SPRINGER BRIEFS IN MOLECULAR SCIENCE
BIOBASED POLYMERS
Yoshiyuki Nishio
Yoshikuni Teramoto
Ryosuke Kusumi
Kazuki Sugimura
Yoshitaka Aranishi
Blends and Graft
Copolymers of
Cellulosics
Toward the Design
and Development of
Advanced Films and
Fibers
SpringerBriefs in Molecular Science
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 theliving speciesinwhichthey are synthetized (such asgenetics,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
givenbiobasedpolymersaremadeandwhattheycanbeusedfor.Theywillalsobe
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
researchersandprofessionalsstudyingorusingbiobasedpolymers.Eachbriefwill
bear a general introduction enabling any reader to understand its topic.
*EPNOETheEuropean PolysaccharideNetwork ofExcellence(www.epnoe.eu)
is a research and education network connecting academic, research institutions
and companies focusing on polysaccharides and polysaccharide-related research
and business.
More information about this series at http://www.springer.com/series/15056
Yoshiyuki Nishio Yoshikuni Teramoto
(cid:129)
Ryosuke Kusumi Kazuki Sugimura
(cid:129)
Yoshitaka Aranishi
Blends and Graft Copolymers
of Cellulosics
Toward the Design and Development
of Advanced Films and Fibers
123
YoshiyukiNishio Kazuki Sugimura
DivisionofForestandBiomaterialsScience, DivisionofForestandBiomaterialsScience,
GraduateSchool ofAgriculture GraduateSchool ofAgriculture
KyotoUniversity KyotoUniversity
Kyoto Kyoto
Japan Japan
YoshikuniTeramoto Yoshitaka Aranishi
DepartmentofAppliedLifeScience,Faculty Fibers andTextiles Research Laboratories
ofApplied Biological Sciences Toray Industries, Inc.
GifuUniversity Mishima, Shizuoka
Gifu Japan
Japan
Ryosuke Kusumi
DivisionofForestandBiomaterialsScience,
GraduateSchool ofAgriculture
KyotoUniversity
Kyoto
Japan
ISSN 2191-5407 ISSN 2191-5415 (electronic)
SpringerBriefs inMolecular Science
ISSN 2510-3407 ISSN 2510-3415 (electronic)
BiobasedPolymers
ISBN978-3-319-55320-7 ISBN978-3-319-55321-4 (eBook)
DOI 10.1007/978-3-319-55321-4
LibraryofCongressControlNumber:2017934614
©TheAuthor(s)2017
Thisworkissubjecttocopyright.AllrightsarereservedbythePublisher,whetherthewholeorpart
of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations,
recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission
orinformationstorageandretrieval,electronicadaptation,computersoftware,orbysimilarordissimilar
methodologynowknownorhereafterdeveloped.
The use of general descriptive names, registered names, trademarks, service marks, etc. in this
publicationdoesnotimply,evenintheabsenceofaspecificstatement,thatsuchnamesareexemptfrom
therelevantprotectivelawsandregulationsandthereforefreeforgeneraluse.
The publisher, the authors and the editors are safe to assume that the advice and information in this
book are believed to be true and accurate at the date of publication. Neither the publisher nor the
authorsortheeditorsgiveawarranty,expressorimplied,withrespecttothematerialcontainedhereinor
for any errors or omissions that may have been made. The publisher remains neutral with regard to
jurisdictionalclaimsinpublishedmapsandinstitutionalaffiliations.
Printedonacid-freepaper
ThisSpringerimprintispublishedbySpringerNature
TheregisteredcompanyisSpringerInternationalPublishingAG
Theregisteredcompanyaddressis:Gewerbestrasse11,6330Cham,Switzerland
Preface
Today, cellulose and related polysaccharides are well recognized as high-potential
polymers to be further materialized for both commodity and specialty uses. The
currently more vital research on microscopic composition of cellulosics may be
demonstrative of the general recognition. As a part of the compositional research,
the present monograph covers basic and applied studies of cellulosic blends and
graftcopolymers.Polymerblendingandgraftingtechniquescanofferopportunities
not only to improve the processability and original physical properties of cellu-
losics, but also to design new, cellulose-core polymeric materials exhibiting
wide-ranging orsynergistic functions unattainableingross mechanical mixtures as
well as in single-component materials.
The main purpose of this monograph is to survey the fundamental aspects
associated with molecular mixing, molecular motions, and supramolecular struc-
turing for cellulosic blends and graft copolymers, and to demonstrate functional
aspects linked to their practical applications as advanced films and fibers, as well.
Industrially important organic esters of cellulose, such as cellulose acetate, propi-
onate, and butyrate, are employed as representative of the cellulosic component.
The monograph is organized into five chapters, each written in a measure com-
mensurate to the respective subject matters as follows: methods for miscibility
estimation and structural designing (Chap. 1); typical examples of detailed char-
acterization (Chaps. 2–4); embodiment of high-functional optical films (Chaps. 2
and 4), biodegradable/biocompatible moldings (Chaps. 3 and 4), and melt-spun
green fibers (Chap. 5).
The constitutive chapters have their own share to accomplish the above main
purpose in reasonable correlation with each other. A sequence of results compiled
intothisbookwillprovideusefulsuggestionsonthedesigningoffunctionality-rich
multicomponentmaterialsbasedoncellulosics,whichinturnwillcontributetoward
moreexpandingtheavailabilityofcellulose.Therefore,thisbookwillhopefullybe
helpful to many scientists and technologists engaged on cellulose and renewable
materialsresearchinacademiaandinindustry,and,ofcourse,tograduatestudents
touching bio-based polymers in universities.
v
vi Preface
Finally, I would like to express my sincere gratitude to Dr. Patrick Navard of
Ecole des Mines de Paris, CNRS, France, who is the president of the European
Polysaccharide Network of Excellence (EPNOE), for his encouragement and
helpfuldiscussionsaswellasforhiskindinvitationtocontributetothisinteresting
series of SpringerBriefs. I am also grateful to the Springer staff involved in coor-
dinating this publication, for their kind assistance to the overall editing work.
Kyoto, Japan Yoshiyuki Nishio
November 2016 On behalf of the authors
Contents
1 General Remarks on Cellulosic Blends and Copolymers . ..... .... 1
Yoshiyuki Nishio
1.1 Introduction: In the Stream of Microcomposition
Research... .... .... ..... .... .... .... .... .... ..... .... 1
1.2 Terminology.... .... ..... .... .... .... .... .... ..... .... 3
1.2.1 Structural Parameters of Cellulose Derivatives . ..... .... 3
1.2.2 Miscibility of Polymer Blends.. .... .... .... ..... .... 6
1.3 Methods for Miscibility Estimation.... .... .... .... ..... .... 7
1.3.1 T Measurements.... .... .... .... .... .... ..... .... 7
g
1.3.2 Spectroscopic Measurements... .... .... .... ..... .... 9
1.4 Supplementary Techniques.. .... .... .... .... .... ..... .... 10
1.4.1 Dielectric Relaxation Spectroscopy.. .... .... ..... .... 10
1.4.2 Fluorescence Polarization Measurement .. .... ..... .... 12
1.5 Outline of the Monograph .. .... .... .... .... .... ..... .... 13
References.. .... .... .... ..... .... .... .... .... .... ..... .... 15
2 Cellulosic Polymer Blends 1: With Vinyl Polymers . .... ..... .... 17
Kazuki Sugimura and Yoshiyuki Nishio
2.1 Introduction .... .... ..... .... .... .... .... .... ..... .... 17
2.2 Cellulose Ester Blends with N-Vinyl Pyrrolidone
Copolymer . .... .... ..... .... .... .... .... .... ..... .... 19
2.2.1 Miscibility Maps as a Function of DS
and Copolymer Composition... .... .... .... ..... .... 20
2.2.2 Intermolecular Interaction and Homogeneity Scale... .... 27
2.2.3 Application to Functional Films .... .... .... ..... .... 33
vii
viii Contents
2.3 Other Prominent Systems of Cellulose Ester/Vinyl Polymer
Blend . .... .... .... ..... .... .... .... .... .... ..... .... 38
2.3.1 Enhancement of Thermomechanical Performance.... .... 39
2.3.2 Intimate Mixing of Cellulosic Blend by In Situ
Polymerization of Vinyl Monomer .. .... .... ..... .... 39
2.4 Concluding Remarks . ..... .... .... .... .... .... ..... .... 40
References.. .... .... .... ..... .... .... .... .... .... ..... .... 41
3 Cellulosic Polymer Blends 2: With Aliphatic Polyesters.. ..... .... 45
Ryosuke Kusumi and Yoshikuni Teramoto
3.1 Introduction .... .... ..... .... .... .... .... .... ..... .... 45
3.2 Cellulose Ester Blends with Poly(e-caprolactone). .... ..... .... 47
3.2.1 Dependence of Miscibility on Alkyl Side-Chain
Length and DS ..... .... .... .... .... .... ..... .... 47
3.2.2 Miscibility of Cellulose Mixed Ester Series ... ..... .... 49
3.2.3 Miscibility Factors in CE/PCL Blends ... .... ..... .... 50
3.2.4 Crystallization Behavior .. .... .... .... .... ..... .... 51
3.2.5 Spherulite Growth Observation. .... .... .... ..... .... 55
3.3 Acylated Chitin Blends with PCL .... .... .... .... ..... .... 56
3.3.1 Molecular Characterization of Acyl-Chs.. .... ..... .... 57
3.3.2 Miscibility Maps of Acyl-Ch/PCL Blends and
Comparison with CE Systems.. .... .... .... ..... .... 59
3.3.3 Availability as Cytocompatible Flexible Films . ..... .... 61
3.4 Concluding Remarks . ..... .... .... .... .... .... ..... .... 68
References.. .... .... .... ..... .... .... .... .... .... ..... .... 69
4 Cellulosic Graft Copolymers.... .... .... .... .... .... ..... .... 75
Yoshikuni Teramoto and Ryosuke Kusumi
4.1 Introduction .... .... ..... .... .... .... .... .... ..... .... 75
4.2 Graft Copolymers with Aliphatic Polyester Side-Chains..... .... 76
4.2.1 Synthesis and Molecular Characterization. .... ..... .... 77
4.2.2 Thermal Properties: General Transition Scheme ..... .... 79
4.2.3 Thermal Treatment Effect on Development
of Supramolecular Structures... .... .... .... ..... .... 86
4.2.4 Molecular Dynamics Characterized by Various
Relaxation Measurements . .... .... .... .... ..... .... 92
4.2.5 Tensile Properties and Orientation Characteristics
of Films . .... ..... .... .... .... .... .... ..... .... 99
4.2.6 Biodegradation Control... .... .... .... .... ..... .... 101
4.3 Other Prominences Attained by ATRP: Synthesis
and Selected Properties..... .... .... .... .... .... ..... .... 105
4.4 Conclusion and Prospect.... .... .... .... .... .... ..... .... 106
References.. .... .... .... ..... .... .... .... .... .... ..... .... 107
Contents ix
5 Cellulosic Fiber Produced by Melt Spinning... .... .... ..... .... 109
Yoshitaka Aranishi and Yoshiyuki Nishio
5.1 Introduction .... .... ..... .... .... .... .... .... ..... .... 109
5.2 Strategy for Melt Spinning Process.... .... .... .... ..... .... 112
5.2.1 Thermoplasticization of Cellulose... .... .... ..... .... 112
5.2.2 Rheological Conditioning . .... .... .... .... ..... .... 115
5.3 Industrial Example of Success ... .... .... .... .... ..... .... 116
5.3.1 Manufacturing Process ... .... .... .... .... ..... .... 116
5.3.2 Flow Properties..... .... .... .... .... .... ..... .... 117
5.4 Fiber and Textile Properties . .... .... .... .... .... ..... .... 119
5.4.1 General Properties for Clothing. .... .... .... ..... .... 119
5.4.2 Shape Variation and Functional Diversity. .... ..... .... 121
5.5 Concluding Remarks . ..... .... .... .... .... .... ..... .... 123
References.. .... .... .... ..... .... .... .... .... .... ..... .... 124