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C

PAN Polyacrylonitrile
Chitin as a Resource for Eco-
PCL Poly-Ɛ-caprolactone
Friendly Bioplastics
PHBV Polyhydroxybutyrate-co-valerate
PLA Polylactic acid
Julia L. Shamshina1, Paula Berton2 and
PPG Polypropylene glycol
Robin D. Rogers3
1
Mari Signum, Mid-Atlantic, LLC, Rockville,
MD, USA
2
Chemical and Petroleum Engineering
Introduction
Department, University of Calgary,
Bioplastics
Calgary, Canada
3 The definition of “bioplastic(s)” has originated
525 Solutions, Inc., Tuscaloosa, AL, USA
from the European Association of Producers, Sup-
pliers and Consumers of Bioplastics and Other
Abbreviations
Biodegradable Materials [1]. This Association
defines bioplastics as a “material that is of biolog-
ASTM American Society for Testing and
ical origin and/or is biodegradable” [1]. Such a
Materials
definition is in fact tricky – use of an “and/or”
CAGR Compound Annual Growth Rate
grammatical conjunction indicates that not both
DNA Deoxyribonucleic Acid
biological origin and biodegradability are require-
EDPMD Environmentally Degradable
ments for bioplastics, but either one is satisfactory
Polymeric Materials and Plastics
enough. As a result, even though one expects from
EN European Standard
the name that bioplastics are safer than synthetic
FTC Federal Trade Commission
plastics, this is not always the case. In fact,
IUPAC International Union of Pure and
top bioplastics include 1,4-butanediol [2, 3]; poly-
Applied Chemistry
ethylene terephthalate (PET) [2, 4]; buta-1,3-
N-GAG N-Glycosaminoglycans
diene [2, 4]; polyethylene furanoate [2, 5]; poly-
RNA Ribonucleic acid
lactic acid [2, 6–8]; polyhydroxyalkanoate [2, 9];
DA Degree of Acetylation
polybutylene terephthalate [2]; polybutylene suc-
DP Degree of Polymerization
cinate [8]; plastic from 1,3-propanediol [8]; bio-
MW Molecular Weight
polyurethanes [8]; polytrimethylene terephthalate
VOCs Volatile Organic Solvents
[8]; and bio-polyamides [8]. Chemically speak-
PET Polyethylene terephthalate
ing, these plastics are structurally exactly the same
PVDF Poly(vinylidene fluoride)
as synthetic plastics, except for the fact that the

© Springer Nature Singapore Pte Ltd. 2019


S. Zhang (ed.), Encyclopedia of Ionic Liquids,
https://doi.org/10.1007/978-981-10-6739-6_43-1
2 Chitin as a Resource for Eco-Friendly Bioplastics

raw materials for the synthesis of those have been a specified timeframe, with formation of harmless
derived from biomass and not from oil. products.
This is both the blessing and the curse; these
so-called bioplastics do diminish our dependence What Is the Plastic Catastrophe?
on oil, but in terms of the ecological plastic catas- There is no need to talk here about the plastic
trophe they are by no means safer than their syn- catastrophe – there is abundant information out
thetic analogs. The International Union of Pure there and it is hard to keep up with every new
and Applied Chemistry (IUPAC) thus disap- academic article, TV show, or broadcast on why
proves of the use of the term bioplastics and synthetic plastics require replacement. In a single
considers it misleading because the general public year (2015), total plastic production constituted
without proper chemical education assumes that a 448 mln tons [14], with about 1/3 just for packag-
material with the prefix “bio-” is ultimately eco- ing meant to be wasted within minutes after pur-
logically safe. Instead, IUPAC advises using the chase. Thus, the now well-established production
definition “polymers of biological origin” for of “bioplastic” using a biorefinery model, in
these plastic types [10], since they are not any which biomass is converted into commodity
better in degradation rates than conventional syn- chemicals for high-volume global markets to pro-
thetic plastics. duce the same deep-rooted plastic types, but much
smaller number of high-value products, suffers
More to the Story: Biodegradation when one considers protecting the environment.
The term “biodegradable” has also been mis- This model can eventually replace the use of
treated. According to Federal Trade Commission petroleum with a renewable and carbon neutral
(FTC) Green Guides [11], the term “biodegrad- resource, biomass, but it otherwise leaves the cur-
able” should be applied to products, “which will rent global “plastic catastrophe” unsolved.
completely break down and return to nature (i.e., Realizing the problem, many industries, com-
decompose into elements found in nature) within panies, and academics work on a number of pro-
a reasonably short period of time after customary jects with the aim to urge an international
disposal.” This term, however, does not specify a movement towards decreasing plastic production
time of degradation nor does it define the degra- and keeping plastic out of the environment (see
dation conditions. Thus, time might vary from for example [15]). The movement has spread
months to tens of years under certain environmen- around the globe albeit slowly; Montreal
tal settings (e.g., require sunlight for (Quebec, Canada) banned single use of plastic
photodegradation). bags in 2018, following Los Angeles’ 2014- ini-
The correct term for defining environmentally tiative prohibiting usage of plastic at checkout
friendly products is “compostable.” “Compost- counters. Just recently, Seattle initiated a ban on
able” materials require “scientific evidence that plastic straws and utensils that went into effect
the materials break down, or become part of, July 1, 2018 [16].
usable compost in a safe and timely manner” Recognizing that paradigms take generations
[12]. As a result, because of misuse in marketing to shift, many institutions initiated an effective
and advertising, the State of California barred the chemistry curriculum which is now designed
use of the terms “biodegradable,” “degradable,” around Societal needs, with missions of the insti-
or “decomposable,” starting in 2013 [13]. More- tutions not only to educate students on the current
over, in order to use the term “Compostable” on a state of our planet, but also provide them with
company’s website and in product labeling, a tools to cope with the problems. Beyond Benign
third-party certification must be conducted in Green Chemistry Fellows program [17] was initi-
accordance to US Standard ASTM D6400 ated for various age groups, from K-12 through
(or European standard EN 13432) [13]. This higher educational, in order “to make green chem-
requires that biodegradable/compostable products istry an integral part of chemistry education.”
completely decompose in a composting setting in Colby College, participating in this program,
Chitin as a Resource for Eco-Friendly Bioplastics 3

educates their students on plastics and biodegra- expected to grow to 984.8 kilotons by 2022, at a
dation, and teaches that plastic objects could alter- compound annual growth rate (CAGR) of 15.2%
natively be created from environmentally benign for the period of 2017–2022 [20]. The market is
polymers such as chitin and chitosan, obtained expected to grow because of the high demand in a
from lobster, shrimp, or crab. They even devel- broad range of high-value applications. Mostly
oped durable plastic toys for kids to take the market growth is dominated by the medical
home [18]. application segment of biodegradable polymers
This legacy of World War II when scarcity and which is anticipated to experience the highest
cost of raw materials during the war led to inten- growth rate among all the biodegradable polymers
sified efforts of many industrial giants to find applications in coming years.
synthetic alternatives to natural polymers, led to
an enormous surge in plastic manufacture. The
main concern today is that plastics need to be Looking to the Future: Chitin
substituted with something – and this “some- Biomaterials
thing” needs to have economy of scale, consis-
tency of supply, and be suitable for preparation of Within polysaccharides, cellulose and chitin are
goods currently made of synthetic plastics. the first and second most abundant biopolymers
[21, 22], sourced from lignocellulosic plants
Biopolymers to Save the World? (cellulose) and exoskeletons of shellfish, insects,
Use of conventional plastics that create serious or cell wall of fungi (chitin). Chemically, cellulose
environmental problems requires that Society is a linear polymer made of repeated D-glycose
seek alternative compostable materials, and bio- units, while chitin is made of repeated 2-(ace-
polymers might be the answer. Biopolymers are tylamino)-2-deoxy-D-glucose units; in both poly-
polymers produced by living organisms (i.e., are mers, the units are connected by b-(1!4) linkages
“of natural origin”) and include polysaccharides, (Fig. 1). Scientific studies confirming biodegrad-
nucleic acids (RNA and DNA), polypeptides, ability of both polymers were conducted to con-
etc. [19]. firm that the biopolymers disintegrate during a
The reason that most of plastics are still of composting process. These studies of biodegrad-
synthetic origin is that biopolymeric alternatives ability and compostability of cellulose-based
have not been commercially available at scale and materials showed their biodegradability according
that large-scale commercialization of some is lim- to the European standard EN 13432 requirements
ited by significantly higher price comparing to [23]. Similarly, chitin also belongs to the list of
old-fashioned petroleum-based plastics. How- Environmentally Degradable Polymeric Materials
ever, when production scaled up, the polymer and Plastics (EDPMD list) [24].
cost should significantly drop. Yet, commercialization of chitin-based tech-
There are still a couple questions which remain nologies is overlooked in favor of its deacetylated
on how much the price of biopolymers will derivative, chitosan. The main reason for this is
decrease and whether it will be competitive with the insolubility of chitin in “traditional” volatile
existing petroleum-based plastics. The second organic solvents. Complex solvent systems
question that remains is that biopolymer-produced (i.e., N,N-dimethylacetamide/lithium chloride
materials have not yet met many performance (DMAc/LiCl) [25, 26], 2,2,2-trifluoroethanol
expectations (e.g., moisture sensitivity, insuffi- [27], NaOH-urea [28, 29] are typically used for
cient strength or even fragility, and low elasticity). the preparation of chitin materials. Thus, even
Major obstacles (high cost of production, price though the global chitin market was worth $803
competitiveness, and limited functionality) must mln in 2016, rose to $893 mln in 2017, and is
be considered when establishing new markets. predicted to triple to $2,941 mln by 2027 [30], not
Indeed, the global market for biodegradable poly- many technologies are currently on the market;
mers reached 484.7 kilotons in 2017 and is however, there are many for chitosan. The lack of
4 Chitin as a Resource for Eco-Friendly Bioplastics

Chitin as a Resource for Eco-Friendly Bioplastics, Fig. 1 Structure of chitin (left) and chitosan (right)

chitin supply and difficulties associated with its biomaterial, chitin can be used “as is” or com-
solubility have prevented its commercial develop- bined with other polymers (e.g., alginate, PLA) or
ment [31]. Nonetheless, advancements in the chi- molecular additives (e.g., drugs, polymers, and
tin field are significant, especially for medical inorganics), as well as, with cells or other mate-
applications which constitute the highest growing rials of biological origin with resultant synergistic
market segment for chitin. action.
Chitin is biocompatible and can serve as a At the same time, chitin has been shown to be
matrix for 3D tissue growth [32] due to the superior to known materials in multiple examples
structural similarity between chitin and [50, 51]. The initial assessments of bio-related
N-glycosaminoglycans (GAGs) which are respon- chitin properties in order to provide a useful sci-
sible for protein regulation and binding [33, 34]. entific basis for clinical applications: biocompati-
Chitin is a healing accelerator [35], promotes bility, cytotoxicity, intracutaneous reactivity,
rapid dermal regeneration [36], and can be used wound healing efficacy, histological evaluation
for producing different biomaterials, including of the wounds treated with chitin dressings, and
sutures, wound healing gauges, drug delivery antibacterial activity. However, “side-by-side”
vehicles, and scaffolds (Table 1) [37, 38]. comparison studies with chitosan have not been
conducted.
Part of the reason for the use of chitosan in
place of chitin is that there are no chitin producing
Commercial Deployment
plants in North America, and thus, there is no raw
supply of this polymer with consistent properties
As mentioned above, the chitin and chitosan mar-
at scale. Polymers coming from chemically and
ket is expanding at a fast pace and forecasted to
energy intensive pulping processes, conducted
triple to $2941 mln by 2027. This increase is,
outside of the USA, provide the product with
however, mostly attributed to development of
unsatisfactory characteristics (such as low MW
technologies using the well-known chemically
and unknown degree of acetylation) and these
deacetylated chitin derivative, chitosan. At the
products differ in properties depending on sup-
same time, properties of chitosan depend on a
plier and/or manufacturing process. It would be
great number of factors, such as its molecular
unreasonable to start a business based on a raw
weight (MW), degree of deacetylation, pattern of
materials supply with inconsistent properties.
deacetylation, etc., and it is difficult to control
The second reason is that companies utilizing
all the factors responsible for its properties
chitin prefer to utilize it in its soluble form,
[48]. Chitin, on the other hand, consists solely of
chitosan, rather than follow academic advances
N-acetylglucosamine units and is a strong poly-
on processing nonderivatized chitin.
mer that requires no chemical modification; in
This said, there are only a few examples of
addition, the surface of chitin materials can be
chitin use on a commercial scale. There are few
chemically functionalized when necessary. As a
Chitin as a Resource for Eco-Friendly Bioplastics 5

Chitin as a Resource for Eco-Friendly Bioplastics, Table 1 Emerging chitin-based medical applications
Type Architecture Application/Reference
Surgical sutures Fibers Chitin suture is typically absorbed in about
3–4 months in muscles, with no tissue reaction
observed [39]. Satisfactory biocompatibility
was observed and no acute toxicity,
pyrogenicity, or mutagenicity was found
Wound care/ Woven and non-woven bandages, foam Chitin promotes rapid dermal regeneration,
bleeding control dressings, hydrocolloid dressings (hydrogels, accelerating wound healing process [36], and is
both 2D and 3D), dried films a hemostatic agent [40]
Cell seeding/ Porous chitin matrixes (e.g., aerogels and Mouse and human fibroblast cell cultures
tissue beads) exposed to a porous chitin matrix were found to
engineering be growing and proliferating [41, 42],
applications indicating the feasibility of using these
architectures as cell transplants in tissue
regeneration
Orthopedic and Chitin composites with minerals such as In orthopedics, chitin can be used as an agent to
periodontics hydroxyapatite heal bones. Composites based on
Dental chitin–minerals (such as hydroxyapatites) have
scaffolding potential to be used as hard tissue substitute
materials [41, 43]. Chitin also can be used in
dental tissue engineering applications, and is a
possible temporary scaffolding/bone substitute
while pending resorption of the implant
Implant surface Coatings (e.g., layer-by-layer (LBL) methods) Chitin is able to enhance bone growth and
modifier achieve osseointegration when implanted in
osseous sites [44]. Chitin used together with
calcium phosphate on titanium (Ti6Al4V)
implants improved biocompatibility with no
observed adverse effects
Drug-delivery Beads, loaded hydrogels, and aerogels Chitin has been used as a carrier for various
active pharmaceutical ingredients
[45, 46]
Medical device Dried chitin films A nanowhiskers pre-concentrate can be
packaging compounded directly into polymers (e.g., PLA).
Specific target benefits are moisture and oxygen
barrier improvements
[47]

commercial chitin-based biomedical materials The process of chitin extraction based on


such as a nasal packing material Beschitin F [51] microwave-assisted extraction of chitin from
and a nonwoven fabric dressing Beschitin W crustacean biomass with the help of the ionic
[52]. A composite nonwoven fabric of polyester liquid (IL) 1-ethyl-3-methylimidazolium acetate
and chitin, Chitipack P [53], focuses on the appli- ([C2mim][OAc]) [55] is currently under commer-
cation of chitin nanofibers for the manufacture of cialization [56]. The scaled-up process is based on
films and rigid packaging for the food and medical the ability of certain ILs to dissolve biopolymers
industry. These chitin/chitosan dressings are used and provides a reliable and inexpensive method
for wound and burn treatments and have shown for chitin isolation (subject to successful solvent
superior performance in speed of healing and scar recovery). The method was developed and scaled
minimization. Results have also been demon- to a 20L pilot stage in 2015 [49].
strated in clinical trials showing good biocompat- When fully implemented, “economy of scale”
ibility and efficacy [54]. will decrease the cost of raw chitin material and
6 Chitin as a Resource for Eco-Friendly Bioplastics

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