polymers

Review
Bio-Polyethylene (Bio-PE), Bio-Polypropylene
(Bio-PP) and Bio-Poly(ethylene terephthalate)
(Bio-PET): Recent Developments in Bio-Based
Polymers Analogous to Petroleum-Derived Ones for
Packaging and Engineering Applications
Valentina Siracusa 1, * and Ignazio Blanco 2
1 Department of Chemical Science (DSC), University of Catania, Viale A. Doria 6, 95125 Catania (CT), Italy
2 Department of Civil Engineering and Architecture, University of Catania an UdR-Catania Consorzio INSTM,
Viale Andrea Doria 6, 95125 Catania, Italy; iblanco@unict.it
* Correspondence: vsiracus@dmfci.unict.it; Tel.: +39-3387275526




Received: 27 June 2020; Accepted: 18 July 2020; Published: 23 July 2020


Abstract: In recent year, there has been increasing concern about the growing amount of plastic waste
coming from daily life. Different kinds of synthetic plastics are currently used for an extensive range of
needs, but in order to reduce the impact of petroleum-based plastics and material waste, considerable
attention has been focused on “green” plastics. In this paper, we present a broad review on the
advances in the research and development of bio-based polymers analogous to petroleum-derived
ones. The main interest for the development of bio-based materials is the strong public concern
about waste, pollution and carbon footprint. The sustainability of those polymers, for general and
specific applications, is driven by the great progress in the processing technologies that refine biomass
feedstocks in order to obtain bio-based monomers that are used as building blocks. At the same time,
thanks to the industrial progress, it is possible to obtain more versatile and specific chemical structures
in order to synthetize polymers with ad-hoc tailored properties and functionalities, with engineering
applications that include packaging but also durable and electronic goods. In particular, three types
of polymers were described in this review: Bio-polyethylene (Bio-PE), bio-polypropylene (Bio-PP)
and Bio-poly(ethylene terephthalate) (Bio-PET). The recent advances in their development in terms
of processing technologies, product development and applications, as well as their advantages and
disadvantages, are reported.

Keywords: bio-based polymers; bio-based plastics; Bio-polyethylene (Bio-PE); bio-polypropylene

(Bio-PP); Bio-poly(ethylene terephthalate) (Bio-PET); bio-polyolefins; packaging; food packaging

1. Introduction
Today, the public interest in the environment, climate change and the limited resources of
fossil fuel are driving governments, companies and scientists to find interesting and ecofriendly
resource alternatives to petroleum. Polymers, that is to say plastics, that are obtained from petroleum
are used for diverse and/or specific application, by tailoring their chemical structure well to the
specific required performances. 85–90% are standard plastics, each one with its preferred application,
but only seven types of polymers cover approximatively two thirds of the total plastics demand in
all applications (packaging, building and construction, automotive, electric and electronics, others),
and these are: Low Density Polyethylene (LDPE), Low Linear Density Polyethylene (LLDPE),
High Density Polyethylene (HDPE), Polypropylene (PP), Polystyrene (PS), Polyvinyl chloride (PVC)

Polymers 2020, 12, 1641; doi:10.3390/polym12081641 www.mdpi.com/journal/polymers

Polymers 2020, 12, 1641 2 of 17

and polyethylene terephthalate (PET) [1]. A general distribution of such commodity plastics is reported
in Figure
Polymers 1: 12, x FOR PEER REVIEW
2020, 2 of 17

Figure 1. General
General distribution
distribution and
and application
application of plastics.

Polyolefins, followed by polyesters, comprise the major part of plastics, corresponding to about
45%, and are used especially for packaging applications, [1]. As As still
still highlighted
highlighted by by Nguyen
Nguyen et et al.
al. [1],
[1],
depletion of 5% of petroleum and natural gas per year for their production, the continuous and
the depletion
dramatic rise in plastic consumption in view of the importance importance of considering
considering the final final destination of
these materials
materials(where
(wherearearethethe
300+ billion
300+ kg of
billion kgplastic produced
of plastic producedeach year?), and the
each year?), interest
and in finding
the interest in
renewable
finding resourcesresources
renewable to build our indispensable
to build plastics must
our indispensable be followed.
plastics must be As an example,
followed. As aninexample,
the United in
States, 60% of plastics are landfilled, 10% are recycled and 30% are unaccounted
the United States, 60% of plastics are landfilled, 10% are recycled and 30% are unaccounted for, for, contributing
to terrestrial and
contributing aquatic environmental
to terrestrial concern. Furthermore,
and aquatic environmental as is also reported
concern. Furthermore, as is by
alsoNguyen
reported et al.,
by
the weight of plastic accumulated in the ocean will exceed the weight of
Nguyen et al., the weight of plastic accumulated in the ocean will exceed the weight of fishes by 2050fishes by 2050 probably,
considering
probably, that 10 tons
considering of PE,
that PP and
10 tons foamed
of PE, PP andPS (floating
foamed PS plastics)
(floatingareplastics)
discarded areevery minute
discarded into
every
the ocean.
minute intoInthethis context,
ocean. bio-based
In this context,plastics could
bio-based offer an
plastics important
could offer an contribution
important to reducing the
contribution to
use of and dependence on limited petroleum resources and to decreasing
reducing the use of and dependence on limited petroleum resources and to decreasing the related the related environmental
impacts. As reported
environmental impacts.by AsNiaounakis
reported byand by Shen and
Niaounakis et al.by[2,3],
Shenbio-based
et al. [2,3],plastics
bio-basedcanplastics
be defined
can be as
defined as or
“man-made man-processed
“man-made organic macromolecules
or man-processed derived from biological
organic macromolecules resources
derived from and for
biological plastic and
resources andfibre
for
applications”.
plastic and fibre They can be biodegradable
applications”. They can beorbiodegradable
not, sometimes orcompostable
not, sometimes andcompostable
can be synthesized
and can frombe
renewable resources
synthesized or from resources coming
from renewable or fromfrom plantscoming
resources and/or from
animals,
plants andand/or
sometime theyand
animals, can
return to nature
sometime they can asreturn
water,tocarbon
naturedioxide,
as water,inorganic compounds
carbon dioxide, and compounds
inorganic biomass via and the composting
biomass via
process,
the leavingprocess,
composting no toxicleaving
and/orno distinguishable residues [4–8],residues
toxic and/or distinguishable according to ISO
[4–8], and ASTM
according to ISOrules.
and
The biodegradability
ASTM depends on the
rules. The biodegradability chemical
depends structure
on the of the
chemical polymers
structure butpolymers
of the not on thebut sources
not onusedthe
for the monomers’ collection.
sources used for the monomers’ collection.
The bio-based plastic that has been investigated up to now could be divided divided into three principal
groups [9]:
1. bio-plastics that are based on renewable resources and that are biodegradable, like starch plastic,
1. bio-plastics that are based on renewable resources and that are biodegradable, like starch plastic,
cellulose polymers, proteins, lignin and chitosan plastics, polylactic acid (PLA), polyhydroxy
cellulose polymers, proteins, lignin and chitosan plastics, polylactic acid (PLA), polyhydroxy
alkanoates (PHAs), but also polyhydroxybutyrates (PHBs), polyhydroxyvalerate (PHV) and
alkanoates (PHAs), but also polyhydroxybutyrates (PHBs), polyhydroxyvalerate (PHV) and their
their copolymers in different percentages (PHBV); this class now includes polymers such as
copolymers in different percentages (PHBV); this class now includes polymers such as PVC, PE,
PVC, PE, PP, PET, nylon and polyamides (PA), named as bio-plastics because the starting
PP, PET, nylon and polyamides (PA), named as bio-plastics because the starting monomers could
monomers could be obtained from biological resources;
be obtained from biological resources;
2. bio-plastics based on petroleum resources, which are 100% biodegradable, like polycaprolactone
(PCL), polybutylene succinate (PBS), polybutylene adipate (PBA) and its copolymers with
synthetic polyesters like polybutylene adipate-terephthalate (PBAT) and polyvinyl alcohol
(PVOH);
 Polymers 2020, 12, 1641 3 of 17

2. bio-plastics based on petroleum resources, which are 100% biodegradable, like polycaprolactone
(PCL), polybutylene succinate (PBS), polybutylene adipate (PBA) and its copolymers with synthetic
polyesters like polybutylene adipate-terephthalate (PBAT) and polyvinyl alcohol (PVOH);
Polymers 2020, 12, x FOR PEER REVIEW 3 of 17
3. bio-plastics obtained by using monomers coming from mixed biological and petroleum resources
like polyesters
3. bio-plastics obtained
obtained with petroleum-derived
by using monomers coming terephthalic
from mixedacid and biologically
biological and derived ethanol,
petroleum
1,4-butanediol and 1,3-propanediol, such as polybutylene terephthalate (PBT), polytrimethylene
resources like polyesters obtained with petroleum-derived terephthalic acid and biologically
derivedterephthalate (PTT), polyethylene-co-isorbite
ethanol, 1,4-butanediol terephthalate
and 1,3-propanediol, (PEIT), polyurethane
such as polybutylene (PUR)(PBT),
terephthalate and epoxy
resins (thermoset
polytrimethylene plastic).
terephthalate (PTT), polyethylene-co-isorbite terephthalate (PEIT),
polyurethane (PUR)personal
A summarized and epoxy resins (thermoset
overview plastic).
of these plastics is reported in Figure 2:
A summarized personal overview of these plastics is reported in Figure 2:

Biodegradable
(PCL, PBS, PBAT, PVOH)

Petroleum based

Not biodegradable
(bio-PE, bio-PP, bio-PET,
bio-PVC, nylon)

PLA, PHAs, PHB, PHV,

PHBV

Bio-based plastics Renewable Resource based

Starch plastics (from
wheat, potato, corn),
cellulosic plastics and
proteineous plastics (from
plant and animal proteins)

Polyesters
(bio-PBT, bio-PTT, bio-
PEIT)
Mixed Resorces based
(Biosources/petroleum)
Thermosets
(bio-based Epoxy, bio-
based PUR)

Figure 2. Classification of bio-based plastics.

Figure 2. Classification of bio-based plastics.

Starting from 2000, bio-based plastics have attracted great interest thanks to the fact that in the
Starting from 2000, bio-based plastics have attracted great interest thanks to the fact that in the
last few years the development of new technological approaches has driven an interest in emerging
last few years the development of new technological approaches has driven an interest in emerging
new plastics obtained from renewable feedstocks [10–13]. Many old processes have been modified
new plastics obtained from renewable feedstocks [10–13]. Many old processes have been modified
and revised in order to be used to produce chemical intermediates for polymer production, such
and revised in order to be used to produce chemical intermediates for polymer production, such as,
as, for example, the chemical dehydration of ethanol, which could be used to produce Bio-PE and
for example, the chemical dehydration of ethanol, which could be used to produce Bio-PE and other
other plastics. Despite some of the plant capacities still being small when compared with the
plastics. Despite some of the plant capacities still being small when compared with the petrochemical
petrochemical ones, such as, for example, in the production of PHAs polymers, others are very big
ones, such as, for example, in the production of PHAs polymers, others are very big in size, such as
in size, such as the bio-based PE production plant. New materials with improved properties and
the bio-based PE production plant. New materials with improved properties and special
special functionalities could be obtained thanks to the continuous advancements and innovations
functionalities could be obtained thanks to the continuous advancements and innovations of the
of the bioplastics industry [14,15]. Today, it is even almost possible to have a bio-plastic alternative
bioplastics industry [14,15]. Today, it is even almost possible to have a bio-plastic alternative to
to conventional plastic material, with nearly the same properties and performance but with the
conventional plastic material, with nearly the same properties and performance but with the great
great advantage of reducing the carbon footprint or of being able to provide additional waste
advantage of reducing the carbon footprint or of being able to provide additional waste management
management options, such as industrial composting [9,16]. Furthermore, the growing concerns about
options, such as industrial composting [9,16]. Furthermore, the growing concerns about the
the environmental impact of plastics and the interest to reduce the dependency on fossil fuel resources
environmental impact of plastics and the interest to reduce the dependency on fossil fuel resources
have increased the interest in such bio-plastics even more, with a steady increment in the number of
have increased the interest in such bio-plastics even more, with a steady increment in the number of
materials, applications, products, manufacturers, converters and end-users. Regarding the economic,
materials, applications, products, manufacturers, converters and end-users. Regarding the economic,
political and social development, this field is of great interest, especially for single-use plastics goods,
political and social development, this field is of great interest, especially for single-use plastics goods,
the object of the Single-Use Plastics Directive implementation, of the new EU Commission’s European
the object of the Single-Use Plastics Directive implementation, of the new EU Commission’s European
Green Deal of 2020, of the Circular Economy Action Plan and the framework for bio-based and
biodegradable plastics [17–19]. A life cycle assessment (LCA) study could be a good tool to evaluate
the environmental sustainability of materials and technology [20–22]. An interesting paper, presented
by Chen et al. [23], reports a comparative LCA study on petroleum-based and bio-based PET bottles
Polymers 2020, 12, 1641 4 of 17

Green Deal of 2020, of the Circular Economy Action Plan and the framework for bio-based and
biodegradable plastics [17–19]. A life cycle assessment (LCA) study could be a good tool to evaluate
the environmental sustainability of materials and technology [20–22]. An interesting paper, presented
by Chen
Polymers et al.
2020, 12, x[23],
FORreports a comparative LCA study on petroleum-based and bio-based PET bottles
PEER REVIEW 4 of 17
within the context of the United States. The consumer-use phase as well as the end-of-life phase
(recycling and/or
considered, from disposal) were excluded
fossil resources and from from the study,
biomass while for
feedstock the PET
production phasesrespectively.
and bio-PET, were considered, For
from fossil resources and from biomass feedstock for PET and bio-PET, respectively.
the polymer production, fossil-based ethylene glycol (EG), fossil-based terephthalic acid (PTA), corn, For the polymer
production, and
switchgrass fossil-based ethylene
wheat straw raw glycol (EG),
materials forfossil-based
bio-EG, and terephthalic
corn stoveracidand(PTA),
forest corn, switchgrass
residues for bio-
and wheat
PTA straw raw
were selected materials
as the building forblock
bio-EG, and corn
materials. stover
12 PET and scenarios
bottles forest residues for bio-PTAand
were established, were 1
selected as the building block materials. 12 PET bottles scenarios were established,
kg of PET bottles was chosen as the functional unit [23]. The researchers found that biomass feedstock and 1 kg of PET
bottles wasand
extraction chosen as the functional
processing showed unit [23]. The
a greater impactresearchers
in termsfound that biomass feedstock
of environmental emissionextraction
than the
and processingfossil
corresponding showed a greater
processes impact
did, due to inthe
terms
extraof energy
environmental
requiredemission than theoperations
for agricultural corresponding and
fossil processes did, due to the extra energy required for agricultural operations
due to the chemicals requested as fertilizers for the production. The results are highly sensitive to iso- and due to the
chemicals
butanol requested[23].
production as fertilizers for the production. The results are highly sensitive to iso-butanol
production [23].
Considering the emerging interest in the synthesis of traditional polymers by using biological
Considering
low-cost resourcesthe andemerging
thanks tointerest in thein
the advances synthesis of traditional
biotechnologies, in thispolymers
review we byhave
using biological
focused our
low-cost on
attention resources and thanks
bio-plastics belonging to the advances
to the in biotechnologies,
first category, named Bio-PE, in this review
Bio-PP and we have focused
Bio-PET, and we
our attention
chose on bio-plastics
these because they are the belonging
most used topolymers
the first category,
in the world,named Bio-PE,
especially as Bio-PP
packaging andmaterials
Bio-PET,
and we
[24]. chose these
As reported because
in the they are
literature, the most used
PE dominates milkpolymers
packaging in and
the world, especially aspackaging,
cosmetic/detergent packaging
materials
PP dominates[24]. many
As reported in the literature,
sub-segments but as minor PE dominates
player, and milk packaging
PET dominates andthecosmetic/detergent
carbonated/non-
packaging, drinks
carbonated PP dominates many sub-segments but as minor player, and PET dominates the
market [25,26].
carbonated/non-carbonated drinks market [25,26].
2. Bioplastics Market and General Application
2. Bioplastics Market and General Application
As reported by European Bioplastic [9], the total bioplastics production capacity is set to increase
from As reported
around 2.11 by European
million tons in Bioplastic [9], the total bioplastics
2019 to approximately 2.43 millionproduction capacity
tons in 2024, is set toinincrease
as reported Figure
from
3: around 2.11 million tons in 2019 to approximately 2.43 million tons in 2024, as reported in Figure 3:

2024

2023

2022
Years

2021

2020

2019

2018

0 200 400 600 800 1000 1200 1400 1600

tonnes of plastics production

Bio-based non-biodegradable plastics Bio-based biodegradable plastics

Figure 3. Forecast of the bioplastics production in tons from 2019 to 2024.

Figure 3. Forecast of the bioplastics production in tons from 2019 to 2024.
Actually, bioplastic production represents about 1% of the 360 million tons of plastic produced
annually in thebioplastic
Actually, world, but the marketrepresents
production is in continuous increase
about 1% of thethanks to eventons
360 million better technologies
of plastic and
produced
emergingin
annually fields
the of interest
world, butand
theapplication
market is in[9].continuous
Some polymers showed
increase theto
thanks highest
even growth rate, such as
better technologies
PHAs and bio-PP, with great industrial interest for their application in even
and emerging fields of interest and application [9]. Some polymers showed the highest growthmore sectors. Thanks to
rate,
this, the
such Bio-PPand
as PHAs production is destined
bio-PP, with to grow by
great industrial a factor
interest foroftheir
about six by 2024,
application in while for thesectors.
even more PHAs
family the
Thanks growth
to this, the was estimated
Bio-PP to beisthree
production timesto
destined higher
growin byfive years,ofstarting
a factor from
about six by2019
2024,[9].
while for
the PHAs family the growth was estimated to be three times higher in five years, starting from 2019
[9].
In particular, the global production capacities of bio-based non-biodegradable plastics account
for about 45% of the total, while bio-based biodegradable plastics account for about 55% of the total,
as following reported in Figure 4, by material type:
 Polymers 2020, 12, 1641 5 of 17

In particular, the global production capacities of bio-based non-biodegradable plastics account

for about 45% of the total, while bio-based biodegradable plastics account for about 55% of the total,
as following reported in Figure 4, by material type:
PolymersPolymers
2020, 12, 2020,
x FOR12,
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x FOR PEER REVIEW 5 of 17 5 of 17

21 21
% of production by type

% of production by type

13 14 14
13
12 12
12 12
9 10 10
9

4 4
1 1 1 1 1 1 1 1

Bio-PP Bio-PTT
Bio-PP Bio-PET Bio-PA Bio-PA
Bio-PTT Bio-PET Bio-PE others
Bio-PE others PHA PBS
PHA PBAT
PBS PLA
PBAT Starch
PLA others
Starch others
PolymerPolymer
type type

Figure 4. Percent (%) of global bio-based plastics production, by type.

Figure 4. Percent
Figure (%) of global
4. Percent (%) ofbio-based plastics plastics
global bio-based production, by type.by type.
production,
The largest field of application for bio-based plastics is packaging (both flexible and rigid
The largest
packaging), field ofaccounts
The largest
which application
field for bio-based
of application
for over 50% plastics
forofbio-based
1.14 million istons
packaging
plastics (both plastic
is bio-based
of packaging flexible and rigid
(both production
flexible and(inrigid
2019),
packaging), which
packaging),
followed accounts for
which consumer
by textile, over 50%
accounts forgoods,of 1.14
over 50% million tons
of 1.14 million
agriculture of bio-based plastic
tons of bio-based
and horticulture, productionand(in
plastic production
automotive 2019),
(in 2019),
transport goods,
followed by textile,
followed
coatings and consumer
byadhesives,
textile, goods, goods,
consumer
buildingagriculture and horticulture,
and agriculture
construction, andelectrics automotive
horticulture, and transport
automotive
and electronics, goods,
and others
and transportlikegoods,
toys [9].
coatings and
coatingsadhesives,
and building
adhesives, and
buildingconstruction,
and electrics
construction,
The percentage distribution is reported in Figure 5. and electronics,
electrics and and others
electronics, and like toys
others [9].
like toys [9].
The percentage distribution
The percentage is reported
distribution in Figure
is reported 5.
in Figure 5.
others others
Electrics/Electronics
Electrics/Electronics
Building/Construction
Building/Construction
1% 1% 2% 2% 4% 4%
Coatings/Adhesives
Coatings/Adhesives
6% 6%
FlexibleFlexible
packaging
packaging
31% 31% Automotive/Transport
Automotive/Transport
7% 7%

Agriculture/Horticul
Agriculture/Horticul
ture ture
8% 8%

Consumer goods goods

Consumer
8% 8%

Textile Textile
Rigid packaging
Rigid packaging 11% 11%
22% 22%
Figure 5. Market segments for bio-based plastics.
Figure 5. Market
Figure segments
5. Market for bio-based
segments plastics.plastics.
for bio-based

Asia is Asia
the major
is theproduction hub in hub
major production the world
in the (45%),
world followed by Europe
(45%), followed (25%), North
by Europe (25%), America
North America
(18%) and South America (12%). The land used for the renewable feedstock for the production of bio- of bio-
(18%) and South America (12%). The land used for the renewable feedstock for the production
Polymers 2020, 12, 1641 6 of 17

Polymers 2020, 12, x FOR PEER REVIEW 6 of 17

Asia is the major production hub in the world (45%), followed by Europe (25%), North America
plastics actually comprises 0.016% of the total agricultural land, corresponding to 0.79 million
(18%) andout
hectares South America
of 4.8 (12%). The
billion hectares. 97%land usedhectares
of those for the are
renewable
dedicatedfeedstock
to pasturefor the
(3.3 production of
billion
bio-plastics actually
hectares), feed and foodcomprises 0.016%
(1.24 billion of the
hectares), and total
othersagricultural land,
such as material usescorresponding to 0.79 million
(106 million hectares)
hectares out of(53
and biofuels 4.8million
billionhectares).
hectares.Despite
97% ofthethose hectares
growing are dedicated
production to pasture
of bio-plastics, (3.3the
in 2024 billion
land hectares),
dedicated
feed and foodto them
(1.24will reach
billion a value of
hectares), 0.021%,
and otherscorresponding to 1.00
such as material million
uses (106hectares, highlighting
million hectares) and biofuels
even more the absence of competition between renewable feedstock used for the
(53 million hectares). Despite the growing production of bio-plastics, in 2024 the land dedicated production of to
plastics and that used for food and feed [9].
them will reach a value of 0.021%, corresponding to 1.00 million hectares, highlighting even more the
absence of competition
3. Bio-Based Polyethylene between
(Bio-PE)renewable feedstock used for the production of plastics and that used
for food and feed [9].
Thanks to its great performance, PE is the largest polymer used in the world. The starting
monomer
3. Bio-Based used for synthesis (Bio-PE)
Polyethylene is ethylene, which is also the case for other polymers such as PVC and
PS, and it is generally obtained from petroleum feedstock by distillation. However, great interest is
nowThanks to its to
being shown great performance,
obtain this polymer PEfromisbiological
the largest polymer
resources, and,used
as ofin the the
now, world. The starting
followed
approachused
monomer has been
for to synthetize
synthesis is the ethylene
ethylene, monomer
which by dehydration
is also the case for of bio-ethanol,
other polymers obtained
such asfrom
PVC and PS,
glucose,
and following obtained
it is generally the generalfrom
scheme reported in
petroleum Figure 6: by distillation. However, great interest is now
feedstock
being shown to obtain this polymer from biological resources, and, as of now, the followed approach
has been to synthetize the ethylene monomer by dehydration of bio-ethanol, obtained from glucose,
following the general scheme reported in Figure 6:

others Bio-based
by anaerobic by dehydration, high
polymer (PVC, PER, PS,
• Sugra cane fermentatiion • bio-ethanol (CH3CH2OH temperature, catalyst
PUR)
• sugar beet and CO2) • bio-ethylene (CH2=CH2
and water) • bio-Polyethylene (bio-
• strach crops
• Glucose (C6H12O6) as • azeotropic mixture of HDPE, bio-LDPE, bio-
• lignocellulosic LLDPE)
juice and fibers (bagasse) hydrous ethanol and
vinasse

by cleaning, slicing,
by distillation by polymerization
shredding, milling

Figure 6. General scheme for Bio-PE production.

The glucose could be obtained from different biological feedstocks, such as sugar cane, sugar beet,
starch crops coming from maize, wheat or other grains and lignocellulosic materials. When starting
from sugar cane, for example, processes like cleaning, slicing, shredding and milling are used to obtain
Figure 6. General scheme for Bio-PE production.
the main sugar cane juice product and the sugar cane fiber by-product (bagasse). The juice, containing
12–13% Theofglucose
sucrose, is anaerobically
could be obtained from fermented in order feedstocks,
different biological to obtain ethanol. Thecane,
such as sugar ethanol
sugaris distilled
inbeet,
order to remove
starch water,from
crops coming giving an wheat
maize, azeotropic
or othersolution of hydrous
grains and ethanol,
lignocellulosic at 95.5When
materials. vol.-%, and a
starting from
by-product sugar cane,
named for example,
vinasse. processes like
The subsequent cleaning, slicing,
polymerization ofshredding and milling
the ethylene monomer are used
obtained this
wayto obtain
is the the
same main sugar
that cane juicewhen
is followed product and ethylene
using the sugar cane fiberfrom
derived by-product (bagasse).
petroleum, andThethe juice,
corresponding
containing 12–13%
bio-polymer of sucrose,
is identical in itsischemical,
anaerobically fermented
physical, in order to
mechanical obtain ethanol.
properties The ethanolPE,
to fossil-based is also with
distilled in order to remove water, giving an azeotropic solution of hydrous ethanol, at 95.5 vol.-%,
regards to the mechanical recycling processes [27]. From polymerization, different types of bio-PE
and a by-product named vinasse. The subsequent polymerization of the ethylene monomer obtained
could be obtained:
this way is the same bio-HDPE with a low
that is followed whendegree
usingofethylene
short-chain branching
derived (about seven
from petroleum, branches per
and the
1000 C atoms), bio-LLDPE with a high degree of short-chain branching and bio-LDPE
corresponding bio-polymer is identical in its chemical, physical, mechanical properties to fossil-based with a high
degree of short-chain branching + long-chain branching (about 60 branches per
PE, also with regards to the mechanical recycling processes [27]. From polymerization, different types 1000 C atoms). For a
Polymers 2020, 12,
couldx FOR
be PEER REVIEW
better understanding of this, Figure 7 shows the chemical structures of such polymers:
of bio-PE obtained: bio-HDPE with a low degree of short-chain branching (about seven 7 of 17
branches per 1000 C atoms), bio-LLDPE with a high degree of short-chain branching and bio-LDPE
with a high degree of short-chain branching + long-chain branching (about 60 branches per 1000 C
atoms). For a better understanding of this, Figure 7 shows the chemical structures of such polymers:

Figure 7. General chemical structure of (a) HDPE, (b) LLDPE and (c) LDPE polymers.
Figure 7. General chemical structure of (a) HDPE, (b) LLDPE and (c) LDPE polymers.

All chemical, physical and mechanical characteristics are well reported in the literature, as are
their engineering applications [28]. LLDPE is obtained by copolymerization of ethylene and butene,
hexane or octane. For its processing, the same plant and machinery can be used [27]. Of course, bio-
PE is not biodegradable. The bagasse by-product is used as a primary fuel source in the sugar mill
Polymers 2020, 12, 1641 7 of 17

All chemical, physical and mechanical characteristics are well reported in the literature, as are
their engineering applications [28]. LLDPE is obtained by copolymerization of ethylene and butene,
hexane or octane. For its processing, the same plant and machinery can be used [27]. Of course, bio-PE
is not biodegradable. The bagasse by-product is used as a primary fuel source in the sugar mill process
because its combustion produces an amount of heat that can cover the energy needs. A surplus of heat
and/or electricity can also be produced, depending on the plant dimension. Vinasse by-product can
instead be used as fertilizer [29].
From 2010, on a commercial scale, the first companies for the production of bio-PE have been the
Brazilian company Braskem [30,31] for food packaging, cosmetics, personal care, automotive and toys
applications (in this case in a joint venture with Brinquedos Estrela, a major Brazilian toy company),
and the joint venture Dow and Crystalsev [32] for food packaging, as well as agricultural and industrial
purposes. Dow is the second largest chemical manufacturer in the world, while Crystalsev is the major
Brazilian ethanol producer. Their joint venture was born in order to produce bio-LLDPE. Furthermore,
the chemical companies Solvay, Nova Chemicals and Petrobras are in the bio-PE market, contributing
to the production of about 20% of the world’s bio-based plastics production. Braskem will cover 10%
of the worldwide plastic market by the year 2020 [32].
At the beginning, bio-ethylene production was not considered to be cost-competitive when
compared with petrochemical-derived ethylene, but starting from 2008 the price of one barrel of
ethanol derived from sugar cane has become competitive with the price of one barrel of crude oil
(about $115 US versus $80 US; 1 L = 0.0085 barrel). The price of 1 kg of bio-PE is about 30% higher than
petrochemical PE [32].
Actually, as mentioned before, bio-ethylene derived from bio-ethanol is used for the synthesis
of other polymers like PVC (used in the construction and building industry), due to severe criticism
concerning impacts on the environment, human health and safety, especially in the packaging field,
due to the difficulty of separating PVC from post-consumer waste. PS, epoxy resins and rubbers like
ethylene propylene diene monomer rubber (EPDM) could be further bio-based candidates for the use
of bio-based ethylene. Enriquez et al. [33] reported a study where Bio-PE (in particular Bio-HDPE)
was used in blends with bio-PTT (37% bio-based) in order to obtain a copolymer with a good balance
between stiffness and toughness. Bio-PE, with the trade name SHC7260, was produced by Braskem
company (Brazil) and provided by Competitive Green Technologies (Ontario, Canada) and was used as
received. Blends were mechanically obtained by melt processing in a co-rotating twin screw extruder
and then injected in a mold at 30 ◦ C. Different PPT/Bio-PE blends were obtained (0, 20, 40, 50, 60, 80,
100 wt.% of Bio-PE). From thermal analyses via differential scanning calorimetry, immiscibility was
observed due to the presence of individual melting peaks at 230 ◦ C for PPT and 118 ◦ C for Bio-PE,
showing a poor interfacial adhesion with a decreasing stiffness [33].
Brito et al. [34] investigated the mechanical performance of PLA/Bio-PE blends, while Castro
et al. [35] and Kuciel at al. [36] investigated the performance of Bio-PE after the addition of natural
fibers, used to increase the stiffness of the resulting materials. In particular, Kuciel et al. explored
the mechanical performance of bio-composite materials obtained with bio-PE and synthetized using
ethanol coming from sugarcane (Braskem, Brazil) and four different natural fillers (wood flour, ultrafine
cellulose powder, kenaf chopper fibers and microparticles of mineral tuff filler) at a percentage of
25%, in comparison to net bio-PE. These composites were obtained via compounding extrusion
molding followed by injection molding. Natural fibers and particles, with a low environmental
impact and low cost, were used in order to improve the mechanical strength and modulus [37–39],
while bio-PE was chosen as a bio-based polyolefin green matrix for structural Natural Fibre Composites
(NFC) and Wood Plastic Composites (WPC). The disadvantage of using such fillers for a structural
application is that PE-based WPC or NFC becomes hygroscopic if in contact with moisture and a water
environment, leading to dimensional changes and accelerated ageing [36]. This behavior is attributed
to a water-swollen filler, as well as the degradation of the fillers and of the interfacial adhesion between
 contact with moisture and a water environment, leading to dimensional changes and accelerated
ageing [36]. This behavior is attributed to a water-swollen filler, as well as the degradation of the
fillers and of the interfacial adhesion between the filler and the polyolefin matrix. The use of fine
cellulose microparticles and tuff microparticles, which are the easiest to process, showed a higher
elongation
Polymers at 1641
2020, 12, break and a lower water uptake. 8 of 17

4. Bio-Based Polypropylene (Bio-PP)

the filler and the polyolefin matrix. The use of fine cellulose microparticles and tuff microparticles,
whichAfter
are theethylene,
easiest topropylene is the a most
process, showed higherimportant
elongationorganic
at breakbuilding block
and a lower for uptake.
water poly-olefin
production. PP is the second most important polymer after PE [40]. Bio-PP could be obtained from
4.biological
Bio-Basedresources by butylene
Polypropylene (Bio-PP)dehydration of bio-isobutanol obtained from glucose and
subsequent polymerization, following the general scheme reported in Figure 8:
After ethylene, propylene is the most important organic building block for poly-olefin production.
PP is the second most important polymer after PE [40]. Bio-PP could be obtained from biological
resources by butylene dehydration of bio-isobutanol obtained from glucose and subsequent
polymerization, following the general scheme reported in Figure 8:

by
by dehydration
polymerization
• Glucose •bio- • bio-PP
• iso- butylene • bio-
butanol propylene
by intermediate not yet fully
by fermentation
steps commercialized

Figure 8. General scheme for Bio-PP.

With respect to the production of Bio-PE, the process followed to obtain bio-PP has been less
explored, which explains why bio-PP has not yet been commercialized. As for bio-PE, the first company
that produced Bio-PP on a pilot-plant scale was Braskem, but their process route is still confidential. The
most promising route to obtain propylene Figure 8. is probably
General through
scheme methanol, further processed to obtain
for Bio-PP.
propylene monomer via Lurgi’s methanol-to-propylene (MTP) process or UOP’s methanol-to-olefins
processWith
[32],respect
using theto the
sameproduction
industrialofplants
Bio-PE, the petrochemical
as for process followed to obtain bio-PP has been less
methanol.
explored, which explains why bio-PP has not yet been commercialized.
As reported by Chen and Patel [41], another route could be the production As of
for1,2-propanediol
bio-PE, the firstor
company
acetone that produced
through fermentationBio-PP
andon a pilot-plant
a further scale to
conversion was Braskem, by
2-propanol butdehydration
their processto route is still
propylene.
confidential. The most promising route to obtain propylene is probably through methanol, further
5.processed
Bio-Based toPolyethylene
obtain propylene Terephthalate
monomer via (Bio-PET)
Lurgi’s methanol-to-propylene (MTP) process or UOP’s
methanol-to-olefins process [32], using the same industrial plants as for petrochemical methanol.
Polyesters represent a large group of polymers that have the potential to be produced from
As reported by Chen and Patel [41], another route could be the production of 1,2-propanediol
bio-based feedstocks [42,43]. The most relevant for a shift towards bio-based chemicals are PET,
or acetone through fermentation and a further conversion to 2-propanol by dehydration to propylene.
PBT, PBS, PBA and the copolymers PBAT, poly(butylene succinate-co-lactate) (PBSL), poly(butylene
succinate adipate) (PBSA) and poly(butylene succinate terephthalate) (PBST), but also polyvinylacetate
5. Bio-Based Polyethylene Terephthalate (Bio-PET)
(PVAc), polyacrylates, poly(trimethylene naphthalate) (PTN), poly(trimethylene isophthalate) (PTI) and
Polyesters
thermoplastic represent
polyester a large group
elastomer, of polymers
as reported by the that have the
European potential
Bioplastic to be produced
Report [9]. Those from bio-
polymers
based feedstocks [42,43]. The most relevant for a shift towards bio-based chemicals
are produced from a bio-based diol, while diacid or diester could be either bio-based (like succinic or are PET, PBT,
PBS, acid)
adipic PBA or and the copolymers PBAT,
petrochemical-based poly(butylene
(like PTA succinate-co-lactate)
and/or di-methyl terephthalate, (PBSL),
DMT). poly(butylene
succinate adipate) (PBSA) and poly(butylene succinate
Among them, PET is the largest used polyester, with physical and mechanicalterephthalate) (PBST), but also
properties that
polyvinylacetate (PVAc), polyacrylates, poly(trimethylene naphthalate) (PTN),
make it suitable to be used for fibers (65%) and packaging (35%) applications. This last applicationpoly(trimethylene
isophthalate)
regards (PTI) and
bottles (76%), thermoplastic
containers (11%) andpolyester elastomer,
films (13%). It playsasan
reported by role
important the European Bioplastic
in the plastic market,
but due to its poor sustainability due to a much slower degradability, it poses serious environmental
issues, especially for waste treatment, when it is used for short time applications, as for example
when it is employed as food packaging. It was first commercialized in 1940, especially for synthetic
fibers and film applications. From 1970 onwards, it was used to produce bottles, with a continuous
growing development. Since 2010, in order to realize a sustainable plastic, both starting chemicals
such as ethylene glycol (EG) and PTA and/or DMT monomers have to be obtained from biological
sources [44–47]. The general scheme of synthesis is reported in Figure 9:
for synthetic fibers and film applications. From 1970 onwards, it was used to produce bottles, with a
continuous growing development. Since 2010, in order to realize a sustainable plastic, both starting
chemicals such as ethylene glycol (EG) and PTA and/or DMT monomers have to be obtained from
biological sources [44–47]. The general scheme of synthesis is reported in Figure 9:
Polymers 2020, 12, 1641 9 of 17

100% biobased
by dehydration
monomer
• Glucose • bio-
•bio-etholol ethylene • bio-EG

by fermentation by oxidation

by catalytic 100% bio-based

by dehydration
conversation monomer
• Glucose • bio-ethylene • bio-
• Bio-etholol • bio-ethylene paraxylene • bio-PTA
glucolsugar
by catalytic
by fermentation by oxidation
conversation

Figure 9. General scheme for Bio-EG and Bio-PTA monomers production.

The aliphatic monomer Bio-EG could be synthetized from the hydrolysis of ethylene oxide,
obtained via the oxidization of bio-ethylene obtained from the fermentation of glucose, followed
by dehydration [48,49]. Another route could be via sorbitol, based on hydrogenolysis [32,50].
The percentage of bio-based monomers can be varied, according to the stoichiometry of the reaction,
obtaining a partial bio-based polymer. In 2009, the Coca-Cola Company introduced a 30% bio-based
beverage bottle, named “PlantBottle”, made of 100% bio-based EG and petroleum-derived TA [51].
Toyota Tsusho Corporation, Japane Future Polyesters, Coca-Cola—Gevo Venture, PepsiCo-Virent
Venture are actually the producers of Bio-PET [45]. Another route to synthetize EG from biomass is
that proposed by Salvador et al. [52], via the use of different types of microorganisms. Among them,
the bio-synthesis of EG could be achieved in bacteria, in high yields, by a pentose pathway, using xylose
as a substrate. As reported by them, “xylose is first transformed into xylonate by the action of a dehydrogenase;
after the subsequent action
Figure of a dehydratase
9. General and
scheme for an aldolase,
Bio-EG glycoaldehyde
and Bio-PTA monomersis production.
obtained, which is finally reduced
to EG by a reductase”. This procedure, with a yield of 98%, could be considered a promising alternative
for the synthesis of bio-EG. Other approaches, such as through glucose in Saccharomyces cerevisiae
using glycolytic enzymes [53], through the synthesis of serine in an engineered pathway in E. coli [54],
using synthesis gas through the Wood–Ljungdahl pathway of carbon fixation present in acetogenic
bacterial species such as Moorella thermoacetica and Clostridium ljungdahlii [55], and through gaseous
alkenes using a strain of E. coli [56] could be used in a similar way.
Following a different route, but always starting from biomass feedstock, a bio-PTA could also be
synthetized, as schematically reported in Figure 8. In this case, different methods could be followed:
the iso-butanol method, the muconic acid method, the limonene method or the furfural method [46].
The iso-butanol method was developed by Gevo, starting from sugar, which is considered a key
building block for different chemicals such as isooctane, ethyl tert-butyl ether, methyl methacrylate and
other alkanes. Following this method, p-xylene is first produced by the cyclization of two isooctane
molecules, via the dehydrogenation route; second, via oxidation, the p-xylene is converted to TA.
Carraher et al. and Matthiesen et al. [57,58] proposed a route starting from cis,cis-Muconic acid as
the starting building block, obtained from sugar (through a combination of chemical processes and
biorefining). After a sequence of cis-cis to trans-trans transition steps of muconic acid, a tetrahydro
 Polymers 2020, 12, 1641 10 of 17

terephthalic acid (THTA) is obtained by ethylene addiction reactions, and, subsequently, bio-PTA is
obtained by dehydrogenation. Colonna et al. [59] started the synthesis of terephthalate polyesters
from limonene. As a starting building block, p-cymene was used, obtained by the chemical refining of
limonene. They reached an 85% conversion from limonene by the oxidation of the iso-propyl group with
potassium permanganate in concentrated nitric acid. Several researchers considered the possibility of
converting furan derivate chemicals into PTA monomer (furfural method) [60–64] via the well-known
Diels–Alder chemical reaction. First, furfural or other furan derivatives obtained by an inedible
cellulose biomass is converted to maleic anhydride by oxidization and dehydration reactions; maleic
anhydride is then involved in the reaction with furan in order to obtain a Diels–Alder adduct. By the
subsequent dehydration of the adduct, a phthalic anhydride is obtained, finally converted into bio-PTA
through phthalic acid and dipotassium phthalate. The process is still not industrialized. Tachibana et
al. [65] also measured the bio-based carbon content through a mass spectroscopy analysis, measuring
the ratios of the three carbon isotopes (14 C, 13 C, 12 C). The proposed methods are schematically shown
in Figure
Polymers 2020, 10:
12, x FOR PEER REVIEW 11 of 17

Figure 10. Schematic representation

Figure 10. of the methods
Schematic representation used
of the to achieve
methods usedbio-TA: (a) Bio-PTA.
to achieve from iso-buthanol; (b)
from muconic acid; (c) from limonene; and (d) from furfural.
An interesting advantage of furfural is that it can be easily converted into other chemicals used
forAn
theinteresting
synthesis ofadvantage
bio-based ofpolymers,
furfuralsuch as PBS
is that it canand
bepolyoxabicyclates
easily converted [65].
into other chemicals used
for the synthesis of bio-based polymers, such as PBS and polyoxabicyclates [65]. of the bio-based
Another interesting result was presented by Avantium, the developer
furandicarboxylic acid (FDCA).
Another interesting Starting
result was from fructose,
presented they obtained
by Avantium, a hydroxymethylfurfural
the developer of the bio-based
chemical molecule (HMF), which was converted to dimethyl furane (DMF) by a hydrogenation
furandicarboxylic acid (FDCA). Starting from fructose, they obtained a hydroxymethylfurfural reaction.
Then, after several chemical steps, p-xylene was obtained and subsequently converted to bio-PTA,
chemical molecule (HMF), which was converted to dimethyl furane (DMF) by a hydrogenation
as previously described. Schenk et al. [66] reported about the BioBTX pilot plant, which is used to
reaction. Then, after several chemical steps, p-xylene was obtained and subsequently converted to
produce aromatic molecules such as benzene, toluene and terephthalate by means of biomass catalytic
bio-PTA, as previously described. Schenk et al. [66] reported about the BioBTX pilot plant, which is
pyrolysis (wood and lignin-rich resources).
used to produce aromatic molecules such as benzene, toluene and terephthalate by means of biomass
Following research by Chen et Patel [41], the aromatic monomer terephthalic acid or dimethyl
catalytic pyrolysis (wood and lignin-rich resources).
terephthalate ester could be produced using lignin, the most abundant bio-renewable resource,
Following
which research
can be found byvascular
in all Chen etplants
Pateland
[41], the aromatic
which monomer
is the second terephthalic
most abundant acid
organic or dimethyl
polymer [67].
terephthalate ester could be produced using lignin, the most abundant bio-renewable resource,
which can be found in all vascular plants and which is the second most abundant organic polymer
[67]. The aromatic aldehydes vanillin and syringaldehyde could be obtained by lignin extraction in
order to further obtain bio-based p-xylene and then subsequently convert it into terephthalic acid.
The bio-based PET obtained this way can be processed by injection molding, blow molding and
extrusion, and it is identical to petrochemical PET. Of course, it is not biodegradable, but an
Polymers 2020, 12, 1641 11 of 17

The aromatic aldehydes vanillin and syringaldehyde could be obtained by lignin extraction in order to
further obtain bio-based p-xylene and then subsequently convert it into terephthalic acid.
The bio-based PET obtained this way can be processed by injection molding, blow molding
and extrusion, and it is identical to petrochemical PET. Of course, it is not biodegradable, but an
interesting paper, presented by Salvador et al., described a microbial degradation of PET due to
the action of microbial polyester hydrolase, considered a key alternative for recycling PET [52].
Actually, the glycolysis method is advantageous for depolymerizing opaque and colored PET that
cannot be recycled due to the presence of pigments, but the high energy cost associated with the high
temperature required and the long reaction times needed for depolymerization make this process
not economic and environmentally sustainable. The resulting EG and PTA monomers could be
reused in the synthesis of PET, as well as for other polymers [68]. As an alternative to chemical PET
depolymerization methods, a series of enzymes coming from different microorganisms could be used
for a more sustainable strategy.
An interesting method to determine the amount of biogenic fraction was presented by Jou et al. [69]
in their short communication on the use of Radiocarbon Accelerator Mass Spectroscopy for the isotopic
fraction determination, according to ASTM-D6866 (Standard Test Methods for Determining the
Biobased Content of Solid, Liquid, and Gaseous Samples Using Radiocarbon Analysis). As reported by
Montava-Jorda et al. [70], bio-based polymers, either biodegradable or non-biodegradable, are certified
as bio-based according to international standards such as EN 16640:2015, ISO 16620-4:2016, ASTM
6866-18 and EN 16785-1:2015. In particular, EN 16640:2015, ISO 16620-4:2016 and ASTM 6866-18
measure the bio-based carbon content in a material through 14 C measurements, while EN 16785-1:2015
measures the bio-based content of a material using radiocarbon and elemental analyses.
An alternative approach is to replace terephthalic acid by different compounds derived from
biomass, such as 2,5-furandicarboxylic acid (FDCA) for the production of polyethylene furanoate
(PEF), which is not the object of this review [71–73].

6. Discussions
The use of bio-feedstock in the polymer sector is of great interest. Starch, cellulose, but also
alkyd resins and some polyamides have been obtained from natural resources on an industrial
scale, with an estimated worldwide production of 20 Mt/year (7% of the total plastics production).
In contrast, the production of bio-based materials is estimated to be less than 2% of the total plastic
production, despite the industry having demonstrated a great ability to process large amounts of
biomass. Nevertheless, it is difficult to estimate the amount of such biomass that is necessary to
replace petrochemical polymers by bio-based ones and whether this substitution would lower the
environmental footprint. From a technological point of view, the progress in the plants processes have
been spectacular. Some plants still have a rather small capacity, but others are comparable to typical
petrochemical plants, like Braskem’s bio-based PE plant. With the continuous growing demand for
bio-based plastics, plants with a bigger capacity production will be even more commercially available.
From a geographic point of view, the United States and Europe are the most important areas for
bio-based plastic production, followed by the Asia Pacific region and South America, with important
investments [9].
Figure 11 shows the actual development stage of emerging bio-based polymers:
have been spectacular. Some plants still have a rather small capacity, but others are comparable to
typical petrochemical plants, like Braskem’s bio-based PE plant. With the continuous growing
demand for bio-based plastics, plants with a bigger capacity production will be even more
commercially available. From a geographic point of view, the United States and Europe are the most
important areas for bio-based plastic production, followed by the Asia Pacific region and South
Polymers 2020, 12, 1641 12 of 17
America, with important investments [9].
Figure 11 shows the actual development stage of emerging bio-based polymers:
• Bio-PP, Bio-PA(6 and 6,6), same new starch plastics (acetylated starch)

R&D
• Partially Bio-PET, Partially Bio-PEIT, Partially Bio-PBS, Partially Bio-PBA,
stage Partially Bio-PBSA, Partially bio-PBT

•Bio-succinic acid, Bio-PLA heat resistant

Pilot plant
stage •Partially Bio-PUR

•Bio-PHA, Bio-PE
Medium stage
•Partially Bio-epoxy resin, Partially Bio-PVC

•Bio-PLA, Plastic from Starch, Bio-PA(11)

Large stage • Partually Bio-PTT, Partially Bio-PA (11)

Commercial scale •Plastics from cellulose, alkyd resisns

Figure
Figure 11.
11. Development
Developmentstages
stagesfor
foremerging
emergingbio-based
bio-basedpolymers.
polymers.

As can be observed,
As observed, the
the largest
largest number
number of of bio-based
bio-basedplastics
plasticsareareininthe
theR&D
R&Dand andpilot
pilotplant
plant
stage, while only few
stage, few materials
materials are
are in
in large
largeand
andcommercial
commercialstages.
stages.InInthe
thefirst
firstcase,
case,different
differentkinds
kindsofof
technological challenges
technological challenges are
are only
only possible.
possible. For Forthetheproduction
productionofofpartial
partialBio-PBS,
Bio-PBS,no notechnological
technological
barriers are present, because the production of succinic acid is technically ready. The esterificationofof
barriers are present, because the production of succinic acid is technically ready. The esterification
succinic acid
succinic acidwith
withbutanol
butanol to obtain
to obtain PBS PBS is performed
is performed at ascale
at a large largebutscale but via petrochemical
via petrochemical precursors.
With respect to PBS, the production of partial Bio-PET is even more easy. Meanwhile, the production of
Bio-PP requires several steps that present limited knowledge, making the scale-up even more difficult
and more demanding. Thus, depending on the type of plastics, between 20% and 100% of the actual
volume could be replaced by bio-based alternatives, but not in the short/medium term due to economic
problems related to cost production and capital availability, technical scale-up, the great amounts of
bio-based feedstocks and the industrial conversion to the new plastics. It has been estimated that from
2030 onwards, the substitution of petrochemical plastics with bio-based plastics is expected to be even
higher, thanks to the replacement of the monomers by chemically identical bio-based compounds or
bio-based compounds with the same equivalent functionality. However, if the technology becomes
ready in plants, there are still several factors that can influence the speed of commercialization: financial,
technology, personnel involved, interaction with other sectors, collaboration with other plants and
companies from the agroindustry chain, market concerns related to the demand for bio-based goods
by retailers and producers of consumer products, and, finally, regulation factors related to fiscal policy
measures and public procurement.
Another important factor to take into consideration in the production of bio-based materials is the
competition with food, feed and bio-fuels for the supply of raw materials. Today, starch and sugar
crops are the sole feedstocks supply, but a second generation of bio-ethanol, based on lignocellulosic
feedstocks, can be used as future starting chemicals in the production of bio-PE, as well as for other
biopolymers (like PLA) [74].
Lignocellulose is cheap, abundant and not competitive with food with respect to starch and
sugar crops, but the biotechnology to transform cellulose into sugar monomers, via microorganisms,
requires processing steps that are more complicated. For the next two decades, the biomass demand for
bio-based plastics production will remain smaller than that demanded for human food and animal feed.
Polymers 2020, 12, 1641 13 of 17

The major influencing factors for the development of bio-based plastics are the technological
barriers that must be overcome in order to reach a large-scale production, the suitability of these materials
to be used as bulk materials, their competitiveness in terms of cost with respect to petroleum-derived
ones and the availability of raw materials for their synthesis. A very interesting paper is that of
Volanti et al. [75], which reports a sustainable analysis used to estimate the environmental performance
of three routes followed to obtain bio-PTA for the synthesis of bio-PET: from sweet corn, from sugar
beet and maize grain, and from orange peels. The results were compared with traditional technology.
The production using sugar beet and maize grain was closest to the current fossil technology,
the production with sweet corn was found to be the most impactful, while the production using
orange peels was the greenest one. The researchers found that the bio-routes for synthetizing PTA
could only be very competitive if organic waste streams were converted into raw materials for the
production of building blocks; however, if dedicated crops were used, some limitations were observed
on the mitigation of climate change. From this research, it is clear that an early stage evaluation is
fundamental in order to identify the benefits and the disadvantages of bio-based plastic production
and commercialization. It was pointed out that an important impact is recorded when crops are
used, even when compared to fossil fuels use. Meanwhile, waste is a very interesting and valuable
building blocks resource, showing two advantages: first, wastes are available while biomass requires
dedicated cultivation, and, second, there are economical and environmental savings that result from
the non-disposal of waste itself.
The potentiality of these bio-based polymers to be used in bulk applications is not a problem,
thanks to the fact that they are chemically identical with their petrochemical counterparts. Within the
bio-based plastics sector, PLA, bio-PE, starch plastics and bio-based epoxy resins are the four key
materials. PLA and starch plastics are candidates for fast growth thanks to their production cost
reduction and bulk application. Bio-based epoxy resins will only grow if the bio-based glycerol starting
monomer is available and its costs are lowered. Meanwhile, the key factor for the growth of Bio-PE is
related to its production costs. Bio-PP is still in its lab/pilot-plant stage due to technological barriers
that include conversion technologies and downstream processing technology. When considering an
optimistic future scenario, it is expected that it will leave the pilot stage and enter the commercialization
stage from 2021 onwards.

7. Conclusions
Bio-based plastics represent a very interesting and emerging field, and the even larger growth
in the use of biomass feedstock for non-food purposes has demonstrated the technical possibility of
producing these materials on a million-ton scale, substituting petrochemical plastics in meaningful
quantities. Actually, the most important polymers in terms of production volumes are PLA and starch
plastics, but the intended trend is to promote and increase the world-wide capacity of different types
of bio-based plastics. In view of the most important and representative company announcements,
bio-based PE and PHA, will also become as important as PLA and starch plastics by this year.
Since 1980, interest in bio-based plastics, especially biodegradable plastics, has been driven by
ever more sizeable waste management problems, but now much more attention is being focused
on durable plastics as a means of reducing wastes. The interest is to take advantage of the use of
biomass coming from food and agricultural wastes, choosing monomers and polymers that can be
easily processed within existing structures. Ethylene and propylene are a great example of this interest.
In the next decade, the interest in such bio-based durable plastics will grow much more than bio-based
biodegradable plastics, partly due to the fact that the management of bio-based biodegradable plastics
requires major changes and investments in the waste management infrastructure with respect to
petroleum-like polymers. Nevertheless, bio-based biodegradable plastics will grow continuously,
occupying their own position in the plastic market.
Small and medium enterprises (SMEs), such as Novamont, Biotec, Rodemburg Biopolymers,
Cereplast, Tianan and so on, as well as large chemical companies, such as Braskem and Dow, are very
Polymers 2020, 12, 1641 14 of 17

active in the field of bio-based plastics. Actually, for big companies, many projects on bio-based
polymers represent a relatively small share of their interests, but in a near future they will have the
opportunity to convert their production in order to avoid environmental impact problems, such as
CO2 emissions, non-renewable energy saving, greenhouse gas reduction, and waste reduction and
management. Despite the existence of numerous plastic materials with a high bio-renewability, only a
small fraction of these have found a place in commercial applications. The heaviest challenges will
be to reduce the high cost of production and processing, minimize agricultural land use and forests,
avoid competition with food production, and, of course, reduce the environmental impacts.

Author Contributions: V.S. and I.B. were both authors and writers of this paper. All authors have read and agreed
to the published version of the manuscript.
Funding: This research received no external funding.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Nguyen, H.T.H.; Qi, P.; Rostagno, M.; Feteha, A.; Miller, S.A. The quest for high glass transition temperature
bioplastics. J. Mater. Chem. A 2018, 6, 9298–9331. [CrossRef]
2. Niaounakis, M. Recycling of biopolymers—The patent perspective. Eur. Polym. J. 2019, 114, 464–475.
[CrossRef]
3. Shen, L.; Haufe, J.; Patel, M.K. Product Overview and Market Projection of Emerging Biobased Plastics; Report No:
NWS-E-2009-32; Utrecht University: Utrecht, The Netherlands, 2009; pp. 1–243.
4. Muniyasamy, S.; Reddy, M.M.; Misra, M.; Mohanty, A. Biodegradable green composites from bioethanol
co-product and poly(butylene adipate-co-terephthalate). Ind. Crops Prod. 2013, 43, 812–819. [CrossRef]
5. Ebnesajjad, S. Handbook of Biopolymers and Biodegradable Plastics: Properties, Processing and Applications; William
Andrew: Norwich, NY, USA, 2012; pp. 1–462.
6. Mulhaupt, R. Green Polymer Chemistry and Bio-based Plastics: Dreams and Reality. Macromol. Chem. Phys.
2013, 214, 159–174. [CrossRef]
7. Iwata, T. Biodegradable and Bio-Based Polymers: Future Prospects of Eco-Friendly Plastics. Angew. Chem.
Int. Ed. 2015, 54, 3210–3215. [CrossRef]
8. Molina-Besch, K.; Palsson, H. A Supply Chain Perspective on Green Packaging Development-Theory Versus
Practice. Pack. Technol. Sci. 2016, 29, 45–63. [CrossRef]
9. European Bioplastics—Report Bioplastics. Available online: https://docs.europeanbioplastics.org/
publications/market_data/Report_Bioplastics_Market_Data_2019.pdf (accessed on 25 May 2020).
10. van Beilen, J.B.; Poirier, Y. Plants as factories for bioplastics and other novel biomaterials. In Plant Biotechnology
and Agriculture; Academic Press: Cambridge, MA, USA, 2012; pp. 481–494.
11. Kimura, Y. Molecular, Structural, and Material Design of Bio-Based Polymers. Polym. J. 2009, 41, 797–807.
[CrossRef]
12. Nakajima, H.; Kimura, Y. Chapter 1, General introduction: Overview of the current development of biobased
polymers. In Bio-Based Polymers, 1st ed.; Kimura, Y., Ed.; CMC Publishing Co., Ltd.: Tokyo, Japan, 2013;
pp. 1–23. ISBN 978-4-7813-0271-3.
13. Pion, F.; Ducrot, P.-H.; Allais, F. Renewable Alternating Aliphatic–Aromatic Copolyesters Derived from
Biobased Ferulic Acid, Diols, and Diacids: Sustainable Polymers with Tunable Thermal Properties. Macromol.
Chem. Phys. 2014, 215, 431–439. [CrossRef]
14. Philp, J.C.; Ritchie, R.J.; Allan, J.E.M. Biobased chemicals: The convergence of green chemistry with industrial
Biotechnology. Trends Biotechnol. 2013, 31, 219–222. [CrossRef]
15. Cooper, T.A. Developments in bioplastic materials for packaging food, beverages and other fast- moving
consumer goods. In Trends in Packaging of Food, Beverages and Other Fast-Moving Consumer Goods (FMCG);
Woodhead Publishing: Cambridge, UK, 2013; pp. 108–152.
16. Hottle, T.A.; Bilec, M.M.; Landis, A.E. Sustainability assessments of bio-based polymers. Polym. Deg. Stab.
2013, 98, 1898–1907. [CrossRef]
17. Philp, J.C.; Ritchie, R.J.; Guy, K. Biobased plastics in a bioeconomy. Trends Biotechnol. 2013, 31, 65–67.
[CrossRef]
Polymers 2020, 12, 1641 15 of 17

18. Philp, J.C.; Bartsev, A.; Ritchie, R.J.; Baucher, M.-A.; Guy, K. Bioplastics science from a policy vantage point.
New Biotechnol. 2013, 30, 635–646. [CrossRef]
19. Chen, Y.J. Bioplastics and their role in achieving global sustainability. J. Chem. Pharm. Res. 2014, 6, 226–231.
20. Blanco, I.; Ingrao, C.; Siracusa, V. Life-Cycle Assessment in the Polymeric Sector: A Comprehensive Review
of Application Experiences on the Italian Scale. Polymers 2020, 12, 1212. [CrossRef] [PubMed]
21. Ingrao, C.; Gigli, M.; Siracusa, V. An attributional Life Cycle Assessment application experience to highlight
environmental hotspots in the production of foamy polylactic acid trays for fresh-food packaging usage.
J. Clean. Prod. 2017, 150, 93–103. [CrossRef]
22. Ingrao, C.; Siracusa, V. Quality and sustainability-related issues associated with biopolymers for food
packaging applications: A comprehensive review. In Biodegradable and Biocompatible Polymer Composites:
Processing, Properties and Applications; Shimpi, N.G., Ed.; Elsevier: Amsterdam, The Netherlands, 2017;
pp. 1–433. ISBN 978-008100970-3/978-008101058-7. [CrossRef]
23. Chen, L.; Pelton, R.E.O.; Smith, T.M. Comparative life cycle assessment of fossil and bio-based polyethylene
terephthalate (PET) bottles. J. Clean. Prod. 2016, 137, 667–676. [CrossRef]
24. Lackner, M. Biopolymers. In Handbook of Climate Change Mitigation and Adaptation, 2nd ed.; Springer:
New York, NY, USA, 2016; Volume 4, pp. 3211–3230.
25. Whitehouse, R.S. New bio-based polymers for extrusion blow molding. In Proceedings of the Society of
Plastics Engineers—27th Annual Blow Molding Conference, ABC, Chicago Marriott O’Hare, Chicago, IL,
USA, 12–13 October 2011.
26. Miller, S.A. Sustainable Polymers: Opportunities for the Next Decade. ACS Macro Lett. 2013, 2, 550–554.
[CrossRef]
27. Morschbacker, A. Bio-Ethanol Based Ethylene. Polym. Rev. 2009, 49, 79–84. [CrossRef]
28. Robertson, G.L. Food Packaging: Principles and Practice, 2nd ed.; Marcel Dekker: New York, NY, USA, 2006.
29. Wheals, A.E.; Basso, L.C.; Alves, D.M.G.; Amorim, H.V. Fuel Ethanol after 25 years. Trends Biotechnol. 1999,
17, 482–487. [CrossRef]
30. Braskem Report. Development of Bio-Based Olefins. Available online: http://www.inda.org/BIO/vision2014_
659_PPT.pdf (accessed on 22 August 2017).
31. Alvarenga, R.A.F.; Dewulf, J. Plastic vs. fuel: Which use of the Brazilian ethanol can bring more environmental
gains? Renew. Energy 2013, 59, 49–52. [CrossRef]
32. Available online: https/www.uu.nl/sites/default/files/copernicus_probip2009_final_june_2009_revised_in_
november_09 (accessed on 2 June 2020).
33. Enriquez, E.; Mohanty, A.K.; Misra, M. Biobased polymer blends of poly(trimethylene terephthalate) and
high density polyethylene. Mater. Des. 2016, 90, 984–990. [CrossRef]
34. Brito, G.F.; Agrawal, P.; Araújo, E.M.; de Mélo, T.J.A. Polylactide/biopolyethylene bioblends. Polímeros 2012,
22, 427–429. [CrossRef]
35. Castro, D.O.; Ruvolo-Filho, A.; Frollini, E. Materials prepared from biopolyethylene and curaua fibers:
Composites from biomass. Polym. Test. 2012, 31, 880–888. [CrossRef]
36. Kuciel, S.; Jakubowska, P.; Kuźniar, P. A study on the mechanical properties and the influence of water
uptake and temperature on biocomposites based on polyethylene from renewable sources. Compos. Part B
Eng. 2014, 64, 72–77. [CrossRef]
37. Mohanty, A.K.; Misra, M.; Drzal, L.T. Natural Fibers, Biopolymers, and Their Biocomposites; CRC Press: Boca
Raton, FL, USA, 2005.
38. Czaplicka-Kolarz, K.; Burchart-Korol, D.; Korol, J. Environmental assessment of biocomposites based on
LCA. Polimery 2013, 58, 476–481. [CrossRef]
39. Wambua, P.; Ivens, J.; Verpoest, I. Natural fibres: Can they replace glass in fibre reinforced plastics? Comp.
Sci. Technol. 2003, 63, 1259–1264. [CrossRef]
40. European Bioplastics. Available online: https://www.europeanbioplastics.org/bioplastics/materials/biobased/
(accessed on 28 May 2020).
41. Chen, G.Q.; Patel, M.K. Plastics derived from biological sources: Present and future: A technical and
environmental review. Chem. Rev. 2012, 112, 2082–2099. [CrossRef]
42. Guidotti, G.; Soccio, M.; Lotti, N.; Gazzano, M.; Siracusa, V.; Munari, A. Poly(propylene
2,5-thiophenedicarboxylate) vs. Poly(propylene 2,5-furandicarboxylate): Two examples of high gas barrier
bio-based polyesters. Polymers 2018, 10, 785. [CrossRef]
Polymers 2020, 12, 1641 16 of 17

43. Rabnawaz, M.; Wyman, I.; Auras, R.; Cheng, S. A roadmap towards green packaging: The current status and
future outlook for polyesters in the packaging industry. Green Chem. 2017, 19, 4737–4753. [CrossRef]
44. Xiao, B.; Zheng, M.; Pang, J.; Jiang, Y.; Wang, H.; Sun, R.; Wang, A.; Wang, X.; Zhang, T. Synthesis
and Characterization of Poly(ethylene terephthalate) from Biomass-Based Ethylene Glycol: Effects of
Miscellaneous Diols. Ind. Eng. Chem. Res. 2015, 54, 5862–5869. [CrossRef]
45. Reddy, M.M.; Vivekanandhan, S.; Misra, M.; Bhatia, S.K.; Mohanty, A.K. Biobased plastics and
bionanocomposites: Current status and future opportunities. Prog. Polym. Sci. 2013, 38, 1653–1689.
[CrossRef]
46. Nakajima, H.; Dijkstra, P.; Loos, K. The Recent Developments in Biobased Polymers toward General and
Engineering Applications: Polymers that Are Upgraded from Biodegradable Polymers, Analogous to
Petroleum-Derived Polymers, and Newly Developed. Polymers 2017, 9, 523. [CrossRef] [PubMed]
47. Collias, D.I.; Harris, A.M.; Nagpal, V.; Cottrell, I.W.; Schultheis, M.W. Biobased Terephthalic Acid Technologies:
A Literature Review. Ind. Biotech. 2014, 10, 91–105. [CrossRef]
48. Rebsdat, S.; Mayer, D. Ethylene oxide. In Ullmann’s Encyclopedia Industrial Chemistry; Wiley-VCH: Weinheim,
Germany, 2001; Volume 13, pp. 547–572.
49. Kopnick, H.; Schmidt, M.; Brugging, W.; Ruter, J.; Kaminsky, W. Polyesters. In Ullmann’s Encyclopedia
Industrial Chemistry; Wiley-VCH: Weinheim, Germany, 2000; Volume 28, pp. 623–649.
50. Petersen, G. Top Value Added Chemicals from Biomass Volume I: Results of Screening for Potential Candidates from
Sugars and Synthesis Gas; Pacific Northwest National Laboratory (PNNL): Richland, WA, USA; National
Renewable Energy Laboratory (NREL): Golden, CO, USA; 2004.
51. The Coca Cola Company Website. Available online: http://www.coca-colacompany.com/plantbottle-
technology (accessed on 14 June 2020).
52. Salvador, M.; Abdulmutalib, U.; Gonzalez, J.; Kim, J.; Smith, A.A.; Faulon, J.-L.; Wei, R.; Zimmermann, W.;
Jimenez, J.I. Microbial Genes for a Circular and Sustainable Bio-PET Economy. Genes 2019, 10, 373. [CrossRef]
53. Uranukul, B.; Woolston, B.M.; Fink, G.R.; Stephanopoulos, G. Biosynthesis of monoethylene glycol in
Saccharomyces cerevisiae utilizing native glycolytic enzymes. Metab. Eng. 2019, 51, 20–31. [CrossRef]
54. Pereira, B.; Zhang, H.; De Mey, M.; Lim, C.G.; Li, Z.-J.; Stephanopoulos, G. Engineering a novel biosynthetic
pathway in Escherichia coli for production of renewable ethylene glycol. Biotechnol. Bioeng. 2016, 113,
376–383. [CrossRef]
55. Islam, M.A.; Hadadi, N.; Ataman, M.; Hatzimanikatis, V.; Stephanopoulos, G. Exploring biochemical
pathways for mono-ethylene glycol (MEG) synthesis from synthesis gas. Metab. Eng. 2017, 41, 173–181.
[CrossRef]
56. Desai, S.H.; Koryakina, I.; Case, A.E.; Toney, M.D.; Atsumi, S. Biological conversion of gaseous alkenes to
liquid chemicals. Metab. Eng. 2016, 38, 98–104. [CrossRef]
57. Carraher, J.M.; Pfennig, T.; Rao, R.G.; Shanks, B.H.; Tessonnier, J.-P. Cis,cis-Muconic acid isomerization and
catalytic conversion to biobased cyclic-C6-1,4-diacid monomers. Green Chem. 2017, 19, 3042–3050. [CrossRef]
58. Matthiesen, J.E.; Carraher, J.M.; Vasiliu, M.; Dixon, D.A.; Tessonnier, J.-P. Electrochemical Conversion of
Muconic Acid to Biobased Diacid Monomers. ACS Sustain. Chem. Eng. 2016, 4, 3575–3585. [CrossRef]
59. Colonna, M.; Berti, C.; Fiorini, M.; Binassi, E.; Mazzacurati, M.; Vannini, M.; Karanam, S. Synthesis and
radiocarbon evidence of terephthalate polyesters completely prepared from renewable resources. Green
Chem. 2011, 13, 2543–2548. [CrossRef]
60. Shiramizu, M.; Toste, F.D. On the Diels-alder Approach to Solely Biomass-derived Polyethylene terephthalate
(PET): Conversion of 2,5-Dimethylfuran and Acrolein into p-Xylene. Chem. Eur. J. 2011, 17, 12452–12457.
[CrossRef]
61. Agirrezabal-Telleria, I.; Gandarias, I.; Arias, P.L. Heterogeneous acid-catalysts for the production of
furan-derived compounds (furfural and hydroxymethylfurfural) from renewable carbohydrates. Rev.
Catal. Today 2014, 234, 42–58. [CrossRef]
62. Tachibana, Y.; Kimura, S.; Kasuya, K. Synthesis and Verification of Biobased Terephthalic Acid from Furfural.
Sci. Rep. 2015, 5, 8249. [CrossRef]
63. Eerhart, A.J.J.E.; Patel, M.K.; Faaij, A.P.C. Fuels and plastics from lignocellulosic biomass via the furan
pathway: An economic analysis. Biofuels Bioprod. Bioref. 2015, 9, 307–325. [CrossRef]
Polymers 2020, 12, 1641 17 of 17

64. Pacheco, J.J.; Labinger, J.A.; Sessions, A.L.; Davis, M.E. Route to Renewable PET: Reaction Pathways and
Energetics of Diels−Alder and Dehydrative Aromatization Reactions Between Ethylene and Biomass-Derived
Furans Catalyzed by Lewis Acid Molecular Sieves. ACS Catal. 2015, 5, 5904–5913. [CrossRef]
65. Tachibana, Y.; Yamahata, M.; Kasuya, K. Synthesis and characterization of renewable polyester containing
oxabicyclic dicarboxylate derived from furfural. Green Chem. 2013, 15, 1318–1325. [CrossRef]
66. Schenk, N.J.; Biesbroek, A.; Heeres, A.; Heeres, H.J. Process for the Preparation of Aromatic Compounds.
Patent WO 2,015,047,085 A1, 2 April 2015.
67. Blanco, I.; Cicala, G.; Latteri, A.; Saccullo, G.; El-Sabbagh, A.M.M.; Ziegmann, G. Thermal characterization of
a series of lignin-based polypropylene blends. J. Therm. Anal. Calorim. 2017, 127, 147–153. [CrossRef]
68. Furtwengler, P.; Avérous, L. Renewable polyols for advanced polyurethane foams from diverse biomass
resources. Polym. Chem. 2018, 9, 4258–4287. [CrossRef]
69. Ju, R.M.; Macario, K.D.; Carvalho, C.; Dias, R.S.; Brum, M.C.; Cunha, F.R.; Ferreira, C.G.; Chanca, I.S. Biogenic
fraction in the synthesis of polyethylene terephthalate. Int. J. Mass Spectrom. 2015, 388, 65–68. [CrossRef]
70. Montava-Jorda, S.; Lascano, D.; Quiles-Carrillo, L.; Montanes, N.; Boronat, T.; Martinez-Sanz, A.V.;
Ferrandiz-Bou, S.; Torres-Giner, S. Mechanical Recycling of Partially Bio-Based and Recycled Polyethylene
Terephthalate Blends by Reactive Extrusion with Poly(styrene-co-glycidyl methacrylate). Polymers 2020, 12,
174. [CrossRef] [PubMed]
71. Guidotti, G.; Soccio, M.; Garcia-Guitiérrez, M.-C.; Guitiérrez-Fernandez, E.; Ezquerra, T.A.; Siracusa, V.;
Munari, A.; Lotti, N. Evidence of a 2D-Ordered Structure in Biobased Poly(pentamethylene furanoate)
Responsible for Its Outstanding Barrier and Mechanical Properties. ACS Sustain. Chem. Eng. 2019, 7,
17863–17871. [CrossRef]
72. Guidotti, G.; Soccio, M.; Lotti, N.; Siracusa, V.; Gazzano, M.; Munari, A. New multi-block copolyester
of 2,5-furandicarboxylic acid containing PEG-like sequences to form flexible and degradable films for
sustainable packaging. Polym. Degrad. Stab. 2019, 169, 108963. [CrossRef]
73. Genovese, L.; Lotti, N.; Siracusa, V.; Munari, A. Poly(neopentyl glycol furanoate): A member of the
furan-based polyester family with smart barrier performances for sustainable food packaging applications.
Materials 2017, 10, 1028. [CrossRef]
74. Frollini, E.; Rodrigues, B.V.M.; Da Silva, C.G.; Castro, D.O.; Ramires, E.C.; De Oliveira, F.; Santos, R.P.O.
Polymeric materials from renewable resources. In AIP Conference Proceedings; AIP Publishing LLC: Melville,
NY, USA, 2016.
75. Volanti, M.; Cespi, D.; Passarini, F.; Neri, E.; Cavani, F.; Mizsey, P.; Fozer, D. Terephthalic acid from renewable
sources: Early-stage sustainability analysis of a bio-PET precursor. Green Chem. 2019, 21, 885–896. [CrossRef]

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