Lignin in Polymer Composites

250 Pages·2016·25.149 MB·English

by  Faruk, Omar, Sain, Mohini

LIGNIN IN POLYMER
COMPOSITES
Omar Faruk
Mohini Sain
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Dedicated
to
My Beloved Wife
“Shaila Shumi”
and
My Beloved Daughter
“Ornela Suhiya”
Omar Faruk, Canada
Contributors
Umesh P. Agarwal USDA Forest Service, Forest Emilia Regina Inone-Kauffmann Fraunhofer-ICT,
Products Laboratory, One Gifford Pinchot Drive, Germany
Madison, WI, USA
John F. Kadla Department of Forest Biomaterials,
Abdullah Al Mamun Institute for Materials North Carolina State University, Raleigh, NC, USA
Engineering, Polymer Engineering, University of
Adel R. Kakroodi Centre for Biocomposites and
Kassel, Kassel, Germany
Biomaterials Processing, Faculty of Forestry,
PriyankaBhattacharya ProtonPower,Inc.,Lenoir University of Toronto, Toronto, ON, Canada
City, TN, USA
Muzaffer A. Karaaslan Department of Materials
Sabornie Chatterjee Chemical Sciences Division, Engineering, The University of British Columbia,
Oak Ridge National Laboratory, Oak Ridge, Vancouver, BC, Canada
TN, USA
Simon Kleinhans Institute for Materials
Hoyong Chung Department of Chemical and Engineering, Polymer Engineering, University of
Biomedical Engineering, Florida State University, Kassel, Kassel, Germany
FAMU-FSU College of Engineering, Tallahassee,
FrankK.Ko DepartmentofMaterialsEngineering,
FL, USA
TheUniversityofBritishColumbia,Vancouver,BC,
Norbert Eisenreich Fraunhofer-ICT, Germany Canada
Gunnar Engelmann Fraunhofer Institute for Mark T. Kortschot Department of Chemical
Applied Polymer Research IAP, Potsdam-Golm, Engineering and Applied Chemistry, Advanced
Germany Materials Group, University of Toronto,
Toronto, ON, Canada
Omar Faruk Centre for Biocomposites and
Biomaterials Processing, Faculty of Forestry, Yingjie Li Department of Materials Engineering,
University of Toronto, Toronto, ON, Canada TheUniversityofBritishColumbia,Vancouver,BC,
Canada
Maik Feldmann Institute for Materials
Engineering, Polymer Engineering, University of Li-Ting Lin Department of Materials Engineering,
Kassel, Kassel, Germany TheUniversityofBritishColumbia,Vancouver,BC,
Canada
Johannes Ganster Fraunhofer Institute for Applied
Polymer Research IAP, Potsdam-Golm, Germany Helmut Naegele Tecnaro GmbH, Germany
Azadeh Goudarzi Department of Materials Mohammad Ali Nikousaleh Institute for Materials
Engineering, The University of British Columbia, Engineering, Polymer Engineering, University of
Vancouver, BC, Canada Kassel, Kassel, Germany
Shayesteh Haghdan Department of Wood Science, Numaira Obaid Department of Chemical
Forest Sciences Centre, The University of British Engineering and Applied Chemistry, Advanced
Columbia, Vancouver, BC, Canada Materials Group, University of Toronto, Toronto,
ON, Canada
Hans-Peter Heim Institute for Materials
Engineering, Polymer Engineering, University of Nikhil D. Patil Faculty of Forestry, University of
Kassel, Kassel, Germany Toronto, Toronto, ON, Canada
xiii
xiv CONTRIBUTORS
Juergen Pfitzer Tecnaro GmbH, Germany Nicolas R. Tanguy Faculty of Forestry, University
of Toronto, Toronto, ON, Canada
Scott Renneckar Department of Wood Science,
Forest Sciences Centre, The University of British Jimi Tjong Centre for Biocomposites and
Columbia, Vancouver, BC, Canada Biomaterials Processing, Faculty of Forestry,
University of Toronto, Toronto, ON, Canada
Annette Ru¨ppel Institute for Materials
Engineering, Polymer Engineering, University of Newell R. Washburn Department of Chemistry,
Kassel, Kassel, Germany Carnegie Mellon University, Pittsburgh, PA,
USA; Department of Biomedical Engineering,
Mohini Sain Centre for Biocomposites and
Carnegie Mellon University, Pittsburgh,
Biomaterials Processing, Faculty of Forestry,
PA, USA
UniversityofToronto,Toronto,ON,Canada; Centre
of Advanced Chemistry, Adjunct, King Abdulaziz Ning Yan Faculty of Forestry, University of
University, Jeddah, Saudi Arabia Toronto, Toronto, ON, Canada; Department of
Chemical Engineering and Applied Chemistry,
Tomonori Saito Chemical Sciences Division, Oak
University of Toronto, Toronto, ON, Canada
Ridge National Laboratory, Oak Ridge, TN, USA
Daniel J. Yelle USDA Forest Service, Forest
Viola Sauer Institute for Materials Engineering,
Products Laboratory, One Gifford Pinchot Drive,
Polymer Engineering, University of Kassel, Kassel,
Madison, WI, USA
Germany
Lars Ziegler Tecnaro GmbH, Germany
Gregory D. Smith Department of Wood Science,
Forest Sciences Centre, The University of British
Columbia, Vancouver, BC, Canada
Nicole M. Stark USDA Forest Service, Forest
Products Laboratory, One Gifford Pinchot Drive,
Madison, WI, USA
Editor’s Biography
OmarFaruk Mohini Sain
Dr Omar Faruk Mohini Sain is
completed his BS and dean and professor at
MS in chemistry at Faculty of Forestry,
theUniversityofChit- University of Toronto.
tagong, Bangladesh. He specializes in ad-
With a DAAD vanced nanocellulose
(German Academic technology, biocom-
Exchange Service) posites, and bio-nano-
scholarship, he joined composites. He is
atUniversityofKassel, cross-appointed to the
Germany.Heachieved Department of Chemical Engineering and Applied
hisPhDinmechanical Chemistry. He is a fellow of Royal Society of
engineering at 2005. Chemistry,UK.Besides,heisalsoanadjunctprofessor
He worked at the of the Chemical Engineering Departments at the
Department of Forestry, Michigan State University, University of New Brunswick, Canada; King
USA as a visiting research associate from 2006 to Abdulaziz University, Jeddah, Saudi Arabia; Univer-
2009. Since 2010, he was working at the Centre sityofGuelph,Canada,UniversityofLulea,Sweden,
for Biocomposites and Biomaterials Processing, honorary professor at Slovak Technical University
University of Toronto, Canada. He joined Ford and Instituteof EnvironmentalScience atthe Univer-
Motor Co. Canada as research and development sity of Toronto, and collaborates with American and
engineer on January, 2015. He has more than European research institutes and universities. Prof.
70 publications to his credits which have been Sainholdsseveralawards;mostrecentoneisthePlastic
published in different international journals and InnovationAwardandKalevPugiAwardforhisinno-
conferences. He also edited one book, titled Biofiber vation and contribution to industry. Author of more
reinforcement in composites materials published than300papers,6booksandhi-citedresearcherProf.
from Woodhead Publishing Ltd. In addition, he Sain hugely contributed to the society at large by
is invited reviewer of 58 international reputed translating research to commercialization which led
journals, government research proposals, and book to three new companies making products ranging
proposals. frompackagingtoautomotivetobuildingconstruction.
xv
Preface
Lignin is a complex polymer abundantly found in opportunity in the use of lignin as a substitute for
plantsanditisthefibrouspartoftheplant.Tradition- fossil-based raw materials and it could be used in
ally, lignin is used in a wide range of low-volume, the manufacture of a wide range of products such
niche applications. Industrial lignins are currently as plastics, chemical products, and carbon fibers.
obtained as coproducts of the manufacture of cellu- Recently extensive ongoing research focusing on
lose pulp for paper, as well as from other biomass- lignin drawbacks is increasing the application scope
basedindustriesandtherearevarioustypesoflignin of lignin in the market.
dependingontheirprocessandpurity.Ligninmarket In recent years, there have been a number of
isstilllimitedinitsapplicationinawiderangeoflow- review papers published on lignin covering lignin
volume,nicheapplications,butlignincanbeusedin chemistry, modification, polymer composites from
awiderangeofapplicationssuchas inthemanufac- lignin, oxidative upgrade of lignin, biocomposites
ture of vanillin, animal feed, dye dispersants, and nanocomposites with lignin, industrial lignin
micronutrients, resins, and cleaning chemicals. In production and applications, and carbon fibers
addition, low awareness about lignin among manu- from lignin. This book focuses specifically on
facturers is the key restraint to this market. It is also lignin-based polymer composites (thermoplastic,
found that there is a weak link between the industry thermoset, and biopolymer, rubber, nano, carbon),
and research institutes which results in the low lignin-based aerogels, lignin-based foaming mate-
exposure of manufacturers to the developments of rials, as well as sources and types of lignin, lignin
lignin in different applications. Furthermore, the interunit linkages and model compounds, extraction
extraction and modification techniques and applica- of lignin, characterization and properties of lignin,
tion of lignin are still at a primary stage, which and applications of lignin. The book will be helpful
hampers the lignin market also. Another obstacle of to researchers, engineers, chemists, technologists,
lignin expansion in value-added applications is and professionals who would like to know more
mainly due to their low-purity standards, heteroge- about the development and potential of lignin and
neity, smell and color problems of the existing lignin-based composites.
commerciallignins.
Omar Faruk and Mohini Sain
Currently, environmental pollution and increasing
awareness of limited resources, there is growing
xvii
1 Sources of Lignin
Shayesteh Haghdan, Scott RenneckarandGregoryD. Smith
Department ofWood Science,Forest SciencesCentre, The Universityof British Columbia, Vancouver,BC,Canada
O U T L I N E
1. Introduction toLignin 1 3.3 Sugarcane Bagasse 6
3.4 AgriculturalResidues 7
2. LigninFunctions 4
4. LigninPotential 8
3. Sourcesof Lignin 5
3.1 Wood 5 References 8
3.2 Pulp and Paper Industry 6
1. Introduction to Lignin etal.,2014).Hence,ligninhasthepotentialtobean
important source of aromatic chemicals for the
The term lignin is derived from the latin name chemical industry, arising from the conversion of
lignum meaning wood (Mccarthy and Islam, 1999). modern era CO , and its efficient utilization solves
2
It was first isolated from wood in a scientific report apotentialpuzzleincreatingvaluableby-productsin
by the French scientist Payen (1838) and later given a biorefinery scheme. This reasoning is because if
its current name in 1857 by Schulze. Lignin was woodisconvertedtothebilliontonscaleforbiofuels
initially described as an incrustant of cellulose, and and biochemicals, then there will be greater than
thispointisinsightfulaslignificationoccursafterthe 300million tons of lignin potentially available. To
deposition of the polysaccharide framework. In an put this in perspective it is roughly the size of the
extremely simplified view it is analogous to the global polymer market.
matrix material for a fiber-reinforced composite. As mentioned above, lignin is an aromatic poly-
Ligninhasseveralfunctionswiththecellwallsuchas mer.Themonomericprecursorshaveaphenolicring
changingthepermeabilityandthermalstability,butit withathreecarbonsidechainprovidingabasicnine
has the primary function to serve as a structural carbon structure commonly referred to as a C -unit
9
material that adds strength and rigidity to plant and/or phenylpropane unit as shown in Figure 1.
tissue. In the sense lignin distinguishes lignocellu- The side chain is terminated with a primary
losic biomass from other polysaccharide-rich mate- hydroxyl group on the C , while the C and C are
g a b
rials,byreinforcingthepolysaccharidescaffoldingof connected together with an unsaturated bond. The
the cell wall. Its performance is so effective that it phenolic ring is methoxylated (eOCH ) to various
3
allows trees to outcompete other plants for sunlight degrees, dependent upon the species; p-coumaryl
forming the largest organisms on the planet. alcohol, coniferyl alcohol, and sinapyl alcohol have
As lignin constitutes 15e40% of dry weight of none, one, or two methoxyl groups at the 3- and
woody plants, it is the most abundant aromatic 5-positions, respectively. Based on the lignin mono-
polymer on the earth and the second most abundant meric composition involved in polymerization, the
organic polymer after cellulose. Based on yearly resultingligninisclassifiedintothreetypes:(1)lignin
biomass growth rates, the overall production of that contains mainly coniferyl alcohol is called
ligninisontheorderof5e36(cid:1)108tons(dosSantos guaiacyl (G) lignin and is found predominantely in
LignininPolymerComposites. http://dx.doi.org/10.1016/B978-0-323-35565-0.00001-1
Copyright©2016ElsevierInc.Allrightsreserved. 1
2 LIGNIN IN POLYMER COMPOSITES
Figure 1 Examples of C monomers: p-coumaryl alcohol, coniferyl alcohol, and syringyl alcohol.
9
gymnosperms;(2)ligninformedfromsinapylalcohol Lignification is initiated when a phenolic hydroxyl
is called syringyl lignin (S) and mixtures of G and S hydrogen atom is abstracted by the enzyme peroxi-
are found in angiosperm lignin; and (3) lignin which dase to form a phenoxy free radical, typically
incorporates p-coumaryl alcohol is p-hydroxyphenyl referred to as dehydrogenative polymerization, as
(H) lignin, and the three types of monomers are described by Freudenberg and Neish (1968). This
commonly found in grasses. Overall hardwoods have phenoxy-free radical will then delocalize to both
a G:S ratio that approaches 1:2 and softwoods have aromaticandsidechaincarbonatomsbytheprocess
approximately 95% G lignin (Lin and Dence, 1992). of resonance stabilization (Figure 2).
One simpleway of determining this ratio is based on Coupling of these radicals may form ether link-
the methoxy content of the lignin, while other tech- ages, carbonecarbon bonds, and bonds occasionally
niques can be used to identify the specific C struc- tomorethanoneotherphenylpropaneunit.Basedon
9
tures either directly using nuclear magnetic the stability of the radical at each location, there is
spectroscopy or determined from the derivatized ahigherprobabilitythatcertaincarbonswillhostthe
thioacidolysis products using gas chromatography. free radical. This, in turn, will provide preferred
The monomeric units are built into the macro- linkagesbetweenligninunits.Ithasbeendetermined
molecule lignin from the oxidative radical coupling that approximately 50% of these bonds are b-O-4
ofthesesubstructures(Adametal.,2011;Dinisetal., ether type (De la Cruz, 2014; Bowyer et al., 2007)
2009; De la Cruz, 2014; Bowyer et al., 2007). with other bonds associated such as b-5, b-1, b-b,
Figure 2 Resonance stabilization of radicals that lead to interunit linkages in lignin.
1: SOURCES OF LIGNIN 3
Figure 3 Examples of interunit connections in lignin. Note, the diagram is to simply illustrate possible linkages
and this structure is not a representative “segment” of lignin.
and5-5(Figure3).ItisevidentthattheC retainsits When analyzed using quantitative nuclear magnetic
g
hydroxyl group through this process, providing the resonance (NMR) spectroscopy, it reveals that the
nativeligninopportunitytoalsoretainacertainlevel quantityoffunctionalgroupsisbasedonthequantity
of hydrophilicity. Furthermore, as indicated in oflignin(GranataandArgyropoulos,1995).Itisalso
Figure 3, the benzylic carbon (at the C ) is typically revealed that most lignins have w4mmol aliphatic
a
highly unstable and undergoes reactions with nucle- hydroxyl groups attached to the side chain per gram
ophilic compounds. These reactions can lead to the of lignin and 0.2e1mmol free phenolic groups per
formationofasecondaryhydroxylgroupattheC by gram of lignin (Pu et al., 2011). Furthermore, it is
a
reaction with water which is a reactive site for link- possible to analyze lignin within thewhole cell wall
ages to carbohydrates creating ligninecarbohydrate withouttheneedforisolation.Thisapproachrequires
complexes. These linkages formed to the poly- themillingofwoodintoafinepowderandthenusing
saccharides are both ether and ester linkages special solvents for cell wall dissolution. Dissolved
dependent upon the functional groups of the mono- wood material is analyzed using two-dimensional
saccharide (Fengel and Wegener, 1983). (2D) 13Ce1H heteronuclear single quantum coher-
Analysis of lignin impacts several changes to its enceNMRspectroscopy(Mansfieldetal.,2012).The
native state making it difficult to have an exact technique can determine the relative concentrations
structure of lignin within the cell wall. However, ofinterunitligninstructuresprovidinganinsightinto
there are isolation methods that can be used to get the structure of lignin.
a better idea of the characteristics of a less severely Asmaybeinferredfromtheabovedescriptionof
modified lignin. One such method involves the isolating EMAL, there are two processes that occur
resizingofwoodintoafineflourthroughballmilling, duringdelignification.Thefirstinvolvesbreakageof
using cellulose-degrading enzymes to remove the key ligninecarbohydrate linkages. This bond
bulk of the polysaccharides and then an acidolysis breakage will allow extractability of the lignin as
reaction to break several of the lignin carbohydrate seen during mild acidolysis of lignin where dilute
linkages(WuandArgyropoulos,2003).Theisolation hydrochloric acid is used to break these linkages.
of this enzymatic mild acidolysis lignin (EMAL) The second process involves cleavage of some of
preserves several aspects about lignin and is used as the interunit bonds of lignin that may reduce
astandardtocompareotherligninisolationmethods. the molecular weight. Hence, delignification