530 CHAPTER 13 Biopolymers

Monomer O O

HO HO Condensation Polymerization Reaction

OH OH

H CH3 H3C H • low Mw

L-Lactide acid D-Lactide acid

Dimer • increased susceptibility to biodegradation

O O O

CH3 CH3 CH3 Ring Opening Polymerization (ROP) Reaction

O O O

O O O • high Mw
H3C H3C H3C

O O O • decreased susceptibility to biodegradation

L-Lactide Meso Lactide D-Lactide

FIGURE 13.5
Monomer and dimer conformations of lactic acid before polymerization reaction.

fermentation of agricultural by products [6,14,18]. PLA can be polymerized by either

or a combination of condensation polymerization and ring opening polymerization
(ROP), shown in Fig. 13.5 [18]. Condensation polymerization reactions produce
low-molecular-weight PLA versus ROP reactions which yield high-molecular-weight
PLA corresponding to increased mechanical properties as well as a higher glass tran-
sition temperature (Tg) and temperature of degradation [18]. Also, molecular weight
(Mw) of PLA has an impact on susceptibility to microbial attack. Low-molecular-
weight PLA tends to be more susceptible than high-molecular-weight PLA [18].
Another factor that influences PLA’s properties is the degree of crystallinity.
Depending on how PLA is synthesized, three stereochemical forms can exist:
poly(L-lactide) (PLLA), poly(D-lactide) (PDLA), and poly(DL-lactide) (PDLLA).
PLLA and PDLA are semicrystalline materials and are optically pure forms. A
mixture of these stereochemical configurations leads to the resulting material
being more amorphous. The crystallinity of the polymer has a noticeable impact
on degradation rates for both water and biodegradation [18]. Amorphous PLA
degrades more easily than the crystalline form [19,20]. Crystallinity is controlled
by slow cooling or annealing it above the glass transition temperature, Tg. PLA is
the most abundant bioplastic on the market, with trademark Ingeo (produced by
NatureWorks LLC) having the largest market share.

13.3.3 Production of Polymers by Microorganisms

Bioplastics in this category are polymers produced within the microorganism,
bacteria. The bacteria produce the polymers when a carbon source is in excess
and at least one other nutrient essential for growth has been depleted [21]. The
polymers accumulate in the form of intercellular granules as a carbon reserve for
energy [22]. The bacteria use sugar from plant feed stocks to fuel this cellular
process [6]. This growth and accumulation of polymers within the bacteria occur
in a bioreactor during the fermentation process [6]. The polymer from the micro-
organism is extracted by a sequence of isolating the bacteria by means of
 13.4 Biopolymer Blends and Biocomposites 531

centrifugation followed by press filtration and subsequent drying of the final bio-
plastic [21]. Bacteria used for this purpose are sometimes genetically engineered
to metabolize different feed stocks as well as to increase conversion efficiency of
feedstock into polymer. Important variables in choosing bacteria strains include
high density growth, high polymer content, rapid growth rate as well as the ability
to produce controllable structures [21]. The most widely studied bioplastics pro-
duced from this process are polyhydroxylalkanoates (PHAs).
PHAs are the most widely studied types of polyesters that are produced by
bacteria [22]. The most common type of PHA is poly(hydroxybutyrate) (PHB)
and poly(hydroxyvalerate) (PHV). PHAs are classified in terms of short chain
length (PHAscl) possessing thermoplastic properties and medium chain length
(PHAmcl) with elastomeric properties [22]. PHAs have the potential to be a com-
petitive bioplastic due to the range of possible monomers that can be polymerized
by the microorganisms. The range of material substrates allows the possibility of
tailoring the mechanical properties for a particular application. Types of PHAs
that are produced commercially include poly-(R)-3-hydroxybutyrate (PHB),
copolymer of (R)-3-hydroxybutyrate (3HB) and (R)-hydroxyvalerate (3HV)
termed PHBV, copolymer of (R)-3-hydroxybutyrate (3HB) and (R)-hydroxyhex-
anoate (3HHx) termed PHBHHx [21].

13.4 Biopolymer Blends and Biocomposites

Many other uses of biopolymers exist than are discussed in the previous sections.
A biopolymer can be blended with (1) another biopolymer, (2) a biodegradable
synthetic polymer, or (3) a non-degradable synthetic polymer. Also biopolymers
can be combined with different reinforcing materials such as mineral particles or
natural fibers to create a bio-polymer matrix composite. In fact, natural rubbers
are usually compounded with various inorganic fillers, antioxidants, pigments, to
name a few, to make it more useful.

13.4.1 Biopolymer Blends

As mentioned in Chapter 5, blending is a useful strategy to modify the materials
properties for specific applications. Biopolymers are no exception. Biopolymers are
often blended with one another to improve total degradation time as well as
mechanical properties. For instance, TPS is more susceptible to microbial action
and is more ductile compared to PLA, and a blend leads to intermediate properties.
Bioplastics are often blended with synthetic polymers in order to reduce the
cost of the material. Along with the reduction of cost, if the bioplastic chosen is
biodegradable, the overall material may be considered biodegradable depending
on the particle size of the remaining synthetic plastic once biodegradation has
been completed.
532 CHAPTER 13 Biopolymers

13.4.2 Biocomposites
A biocomposite is a material composed of two or more distinct constituent mate-
rials (one being naturally derived) which are combined to yield a new material
with improved performance over individual constituent materials. The constituent
materials are the matrix and reinforcing component. The reinforcing component is
the primary load-carrying element, which can be in the form of fibers, whiskers,
particles and flakes [23]. The matrix serves to bind the reinforcing components
together and provide mechanical support [24].
A frequently studied biocomposite is natural-fiber-reinforced biopolymer com-
posite. The reinforcing component is natural fiber or cellulose extracts combined
with a bioplastic matrix. The natural fiber adds further strength to the weaker bio-
polymer matrix, allowing for the material to be used in more applications [25 27].
Significant research is being conducted in embedding nanoparticles or particu-
lates such as layered silicates, carbon nanotubes, hydroxyapaptite, cellulose, and
talc into bioplastics [14]. The most commonly used in PLA bioplastics is layered
silicate clay, as it has been attributed to a dramatic increase in material properties
such as improved tensile and flexural properties, elevated heat distortion tempera-
ture, enhanced barrier properties, and accelerated biodegradation. Processing
issues associated with these nano-biocomposites are distribution and dispersion of
the reinforcement within the biopolymer [14].

13.5 Future of Bioplastic Products

Bioplastics, bioplastic blends, and biocomposites have the potential to be a green
solution in the future. The potential of these materials is based on their ability to
decrease CO2 emissions, producing a material which is sustainable without petro-
leum as well as reducing environmental impact after product use. Each of these
aspects will be discussed with the potential of the products as well as the reality.
Bioplastics pose the ability to achieve a near neutral carbon process, closing
the carbon cycle since CO2 is captured during photosynthesis (making the plant
material as a substrate or feedstock) and released during biodegradation. The total
amount of carbon emissions associated with the energy needed to produce and
dispose of the products should be taken into account. Currently, few processes
have emerged that use less energy in the production process. Researchers are
working on optimizing the efficiency of the processes in order to make bioplastics
a viable alternative in terms of energy consumption.
Bioplastics have the potential to reduce dependence on petroleum-based plas-
tics. The depletion of fossil fuels and the rising cost of petroleum is a growing
concern for long-term sustainability of the plastics industry. Along with the dwin-
dling petroleum supply, the other side of the production cycle, agricultural pro-
ducts, needs to be considered. Depending on the feedstocks required for the
specific bioplastics synthesis, there would be need to be a balance between the