Synthesis, Structure and Properties of Poly(lactic acid)

354 Pages·2018·11.71 MB·English

by  Maria Laura Di Lorenzo

Advances in Polymer Science 279
Maria Laura Di Lorenzo
René Androsch Editors
Synthesis, Structure
and Properties of
Poly(lactic acid)
279
Advances in Polymer Science
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Maria Laura Di Lorenzo • Rene´ Androsch
Editors
Synthesis, Structure and
Properties of Poly(lactic acid)
With contributions by
(cid:1) (cid:1) (cid:1)
M.A. Abdel-Rahman R. Androsch A.B. Biernesser
(cid:1) (cid:1) (cid:1)
J.A. Byers A. Czerniecka-Kubicka K.R. Delle Chiaie
(cid:1) (cid:1) (cid:1)
M.L. Di Lorenzo S. Domenek V. Ducruet
(cid:1) (cid:1) (cid:1) (cid:1)
S. Fernandes-Nassar G. Gorrasi A. Kaur J.A. Kehl
(cid:1) (cid:1) (cid:1) (cid:1) (cid:1)
Y. Kimura B. Lotz K. Masutani R. Pantani M. Pyda
(cid:1) (cid:1) (cid:1)
M.C. Righetti C. Schick K. Sonomoto J. Tan
Editors
MariaLauraDiLorenzo Rene´Androsch
InstituteofPolymers,Composites InterdisciplinaryCenterforTransfer-Oriented
andBiomaterials ResearchinNaturalSciences
NationalResearchCouncil MartinLutherUniversityHalle-Wittenberg
Pozzuoli(NA),Italy Halle/S.,Germany
ISSN0065-3195 ISSN1436-5030 (electronic)
AdvancesinPolymerScience
ISBN978-3-319-64229-1 ISBN 978-3-319-64230-7 (eBook)
https://doi.org/10.1007/978-3-319-64230-7
LibraryofCongressControlNumber:2017952941
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Preface
Poly (L-lactic acid) (PLLA) is a thermoplastic aliphatic polyester of steadily
increasing importance, since it is produced from annually renewable resources,
withpotentialtoreplacetraditionalpetroleum-basedpolymericmaterials.PLLAis
acompostableandbiocompatible/bioresorbablepolymerusedfordisposableprod-
ucts,forbiomedicalapplications,forpackagingfilm,intheautomotiveindustry,for
electronicdevicecomponents,andformanyotherapplications.Amongthevarious
polymers produced from short-term renewable resources, PLLA has received the
most attention in recent years, with global suppliers now able to produce several
kilotonsperyear.
Thisvolumeprovidesstate-of-the-artknowledgeaboutPLLA,fromsynthesisto
structure to ultimate properties. An introductory chapter presents a general over-
viewofthevarioustypesofpoly(lacticacid),whosechainstructurecanbetailored
tocontroltheprocessingbehavior/rheology,thestructureformationfromthemelt
or solution, and, with that, the properties. The next two chapters summarize
synthesisroutes.Themonomer,lacticacid,isproducedfromrenewableresources.
Recent advancements, prospects, and limitations of lactic acid production via
biomass refining and other fermentation processes are detailed in the chapter
“Biorefinery-Based Lactic Acid Fermentation: Microbial Production of Pure
Monomer Product,” together with an overview of separation and purification
techniques needed to obtain purified lactic acid monomer. The different synthesis
routesdevelopedtoproducePLLAfromthepurifiedmonomerarereviewedinthe
chapter“CatalyticSystemsfortheProductionofPoly(lacticacid).”Thereempha-
sisisplacedonthedevelopmentofcatalystsforthering-openingpolymerizationof
lactide,whichisusedforthesynthesisofhigh-molar-massPLLA.Hydrolysisand
biodegradation of PLLA are thoroughly discussed in the chapter “Hydrolysis and
BiodegradationofPoly(lacticacid).”Hydrolyticdegradationisthemostimportant
route to control biodegradation of PLLA, and the main factors that influence the
hydrolyticdegradationofPLLA–includingtemperature,pHvalue,semicrystalline
morphology, and molar mass – are considered and analyzed. Moreover, an over-
viewofbiodegradationincompostingconditionsisalsoprovided.
v
vi Preface
The next four chapters focus on the structure and thermal properties of PLLA.
The thermodynamic properties of PLLA are presented in the chapter “Thermal
PropertiesandThermodynamicsofPoly(L-lacticacid).”Thechapter“Amorphous
FractionsofPoly(lactic acid)” summarizes thephysical propertiesofthedifferent
amorphous fractions in semicrystalline PLLA, including both the mobile and the
rigidamorphousfractions,aswellasthephysicalpropertiesofamorphousPLLA.
The crystallization kinetics of PLLA is reviewed in the chapter “Kinetics of
Nucleation and Growth of Crystals of Poly(L-lactic acid).” Here the effects of
molarmassandopticalpurityonthekineticsofthenucleationandgrowthofPLLA
crystals are covered. The crystal polymorphism and morphology of PLLA are
addressed in the chapter “Crystal Polymorphism and Morphology ofPolylactides.”
PLLA can develop a variety of crystal structures and morphologies, which can be
attained not only by imposing a specific thermomechanical history on the melt, as
formostsemicrystallinepolymers,butalsobychangingthemoleculararchitecture,
due to the availability of L- and D-stereoisomers and the formation of a
stereocomplex–arareoccurrenceinpolymers.
Thevolumeendswithachapterthatdetailstherheologyandthemechanicaland
barrier properties of PLLA. PLLA is a rather rigid polymer with a poor melt
strength, which can be improved by proper design of the polymer chain. At room
temperature,PLLAisbrittle,andanumberofstrategiescurrentlyusedtotoughen
PLLAarereviewed.ThebarrierpropertiesofPLLAarealsodiscussed,withspecial
attention given to gases and vapors that are of importance for a number of
applicationsofthispolymer.
Editingthisvolumeaboutthesynthesis,structure,andpropertiesofPLLAonly
became possible with the excellent contributions from the authors of the various
chapters. We want to express our sincere gratitude to them for sharing their
scientific points of view on the different aspects of PLLA. We are also equally
thankfultothemanycolleagueswhoactivelyparticipatedinthereviewprocessand
investedtimeandefforttoreviseandcommentoneachchapter.
Being aware that science and research are permanently ongoing processes, we
hopethatthisbookisconsideredusefulforbothstudentsandscientistsinindustry
and academia, providing a base to gain knowledge about the present state of
research, as well as to develop new ideas for understanding the link between the
moleculararchitecture,thesupermolecularstructure,andthefinalpropertiesofone
ofthemostchallengingpolymersofrecentdecades.
Pozzuoli,Italy MariaLauraDiLorenzo
Halle/Saale,Germany Rene´ Androsch
Contents
PresentSituationandFuturePerspectivesofPoly(lacticacid). . . . . . . 1
KazunariMasutaniandYoshiharuKimura
Biorefinery-BasedLacticAcidFermentation:MicrobialProduction
ofPureMonomerProduct. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
JiamingTan,MohamedAliAbdel-Rahman,andKenjiSonomoto
CatalyticSystemsfortheProductionofPoly(lacticacid). . . . . . . . . . . 67
JefferyA.Byers,AshleyB.Biernesser,KaylaR.DelleChiaie,AmanKaur,
andJeffreyA.Kehl
HydrolysisandBiodegradationofPoly(lacticacid). . . . . . . . . . . . . . . 119
GiulianaGorrasiandRobertoPantani
ThermalPropertiesandThermodynamicsofPoly(L-lacticacid). . . . . 153
MarekPydaandAnnaCzerniecka-Kubicka
AmorphousFractionsofPoly(lacticacid). . . . . . . . . . . . . . . . . . . . . . 195
MariaCristinaRighetti
KineticsofNucleationandGrowthofCrystalsofPoly(L-lacticacid). . . 235
Rene´ Androsch,ChristophSchick,andMariaLauraDiLorenzo
CrystalPolymorphismandMorphologyofPolylactides. . . . . . . . . . . 273
BernardLotz
Rheology,MechanicalProperties,andBarrier
PropertiesofPoly(lacticacid). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 303
SandraDomenek,SamiraFernandes-Nassar,andVioletteDucruet
Index. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 343
vii
AdvPolymSci(2018)279:1–26
DOI:10.1007/12_2016_16
©SpringerInternationalPublishingAG2017
Publishedonline:25May2017
Present Situation and Future Perspectives
of Poly(lactic acid)
KazunariMasutaniandYoshiharuKimura
Abstract Of the biobased polymers developed to date, poly(L-lactide) (PLLA) is
the most widely used in many application fields because of its excellent cost–
property balance. However, PLLA is slightly inferior to conventional petroleum-
basedpolymersintermsofthermalresistanceandfunctionality.Variousmodified
polylactides (PLAs consisting of enantiomeric D- and L-lactide units in different
sequences and ratios) have recently been proposed and should expand the market
for these polymers. The new developments involve polymers of high melting
temperature (high-T polymers) based on stereocomplex-type PLAs (sc-PLA)
m
and stereoblock-type PLAs (sb-PLA) as well as those of high glass transition
temperature(high-T polymers)obtainedbyunitmodificationandpolymerblend-
g
ing.Variousspecialtyderivativeshavingexcellentflexibilityandfunctionalityhave
also been developed by controlled crystallization, polymer blending, organic–
inorganic hybridization, and copolymerization. The molecular weight, terminal
groups, copolymer composition, and functionalities must be precisely controlled
toenable control ofthe propertiesofthese PLA polymers.Ordinary PLLA, being
biodegradable, is widely used in commodity and agricultural fields as well as
biomedicalfields,mainlyintheformofafilmorasanon-wovenfabric.Thenew
specialty and high-performance PLA polymers can be used as functional and
durable materials. Especially interesting is the applicability of PLLA polymers to
3Dprinting,particularlyinfuseddepositionmanufacturing(FDM).
Keywords Biobsed polymers (cid:129) Poly(lactic acid) (cid:129) Stereoblock polylactides (cid:129)
Stereocomplexedpolylactides
K.Masutani(*)andY.Kimura
CenterforFiberandTextileScience,KyotoInstituteofTechnology,Hashigami-cho,
Matsugasaki,Kyoto606-8585,Japan
e-mail:[email protected];[email protected]
2 K.MasutaniandY.Kimura
Contents
1 PolylactidesasBiodegradableandBiobasedPolymers..................................... 2
2 IndustrializationofPLLA.................................................................... 5
2.1 StructuralVarietyofPLAPolymers................................................... 5
2.2 ManufacturingofPLLA................................................................ 6
3 MacromolecularandMaterialDesignofPLAPolymers................................... 8
3.1 ControllingtheCrystallizationofPLLAforHigherPerformance................... 9
3.2 StereocomplexedPolylactidesasHigh-T Polymers................................. 12
m
3.3 StereoblockPolylactides............................................................... 12
3.4 High-T PLAPolymers................................................................. 14
g
3.5 FlexiblePLAPolymers................................................................ 16
3.6 Hybrid-PLAPolymers.................................................................. 17
3.7 PEG-PLACopolymersUndergoingSol–GelTransition.............................. 18
4 ApplicationofPLAandFutureTrend....................................................... 19
4.1 PLLAResinsforFDM................................................................. 20
4.2 FutureTrend............................................................................ 21
5 Summary...................................................................................... 22
References........................................................................................ 22
1 Polylactides as Biodegradable and Biobased Polymers
Polymericmaterialsderivedfrombiomassresourcesarecalledbiobasedpolymers.
These polymers have been attracting attention as renewable materials that can
replace conventional polymeric materials, which are synthesized from fossil
resources and not sustainable [1, 2]. Some of the biobased polymers currently
produced were once developed as bioabsorbable polymers for medical use [3]
and as biodegradable plastics for waste management [4]. Bioabsorbable polymers
arenowcontributingtothedevelopmentoftissueengineering,whereasbiodegrad-
ableplasticsareutilizedaspackagingmaterialsandagriculturalmulchingfilmsthat
canbeassimilatedintotheenvironmentorartificialcompostingsystems.Biobased
polymers should have a much wider spectrum of application than traditional
polymers.
Table 1 compares the historical classification of bioabsorbable, biodegradable,
andbiobasedpolymers.Inthefirstgeneration,bioabsorbablepolymerssuchaspoly
(glycolide) (PGA) and poly(L-lactide) (PLLA) were utilized for fabrication of
sutures, prostheses [6], and scaffolds for tissue engineering [7]. In the second
generation, biodegradable polymers such as poly(3-hydroxyalkanoates) (PHA),
poly(butylenesuccinate)(PBS),andPLLAweredevelopedtoreplace commodity
plastics for short-life applications involving daily appliances and garbage bags.
Oil-based copolymers such as poly(butylene adipate/terephthalate) (PBAT) and
poly(ethylene adipate/terephthalate) (PBET) are also included in this category. In
fact, the biodegradability of PLLA materials was confirmed by the composting
experiments established by the International Organization for Standardization
(ISO). The standard ISO 14855 stipulates that a test sample must be assimilated
to a degree higher than 70 wt% after composting at 58(cid:1)C for 6 months as a