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olylactic acid

From Wikipedia, the free encyclopedia

Polylactic acid

Identifiers

CAS Number 26100-51-6

ChemSpider none

ECHA InfoCard 100.128.355

Properties

Density 1.2101.430 gcm3 [1]

Melting point 150 to 160 C (302 to 320 F; 423 to

433 K)[1]

Solubility in water Insoluble in water[2]

Hazards

NFPA 704

1
0
0
Except where otherwise noted, data are given for materials in
their standard state (at 25 C [77 F], 100 kPa).
Infobox references

Poly(lactic acid) or polylactic acid or polylactide (PLA) is a biodegradable and


bioactive thermoplastic aliphatic polyester derived from renewable resources, such as corn starch (in
the United States and Canada), cassava roots, chips or starch (mostly in Asia), or sugarcane (in the
rest of the world). In 2010, PLA had the second highest consumption volume of any bioplastic of the
world.[3]
The name "polylactic acid" does not comply with IUPAC standard nomenclature, and is potentially
ambiguous or confusing, because PLA is not a polyacid (polyelectrolyte), but rather a polyester.[4]

Contents
[hide]

1Production
o 1.1Manufacturers
2Chemical and physical properties
3Applications
4Recycling
5Degradation
6See also
7References
8External links

Production[edit]
Producers have several industrial routes to usable (i.e. high molecular weight) PLA. Two main
monomers are used: lactic acid, and the cyclic di-ester, lactide. The most common route to PLA is
the ring-opening polymerization of lactide with various metal catalysts(typically tin octoate) in
solution, in the melt, or as a suspension. The metal-catalyzed reaction tends to
cause racemization of the PLA, reducing its stereoregularity compared to the starting material
(usually corn starch).[5]
Another route to PLA is the direct condensation of lactic acid monomers. This process needs to be
carried out at less than 200 C; above that temperature, the entropically favored lactide monomer is
generated. This reaction generates one equivalent of water for every condensation (esterification)
step, and that is undesirable because water causes chain-transfer leading to low molecular weight
material. The direct condensation is thus performed in a stepwise fashion, where lactic acid is first
oligomerized to PLA oligomers. Thereafter, polycondensation is done in the melt or as a solution,
where short oligomeric units are combined to give a high molecular weight polymer strand. Water
removal by application of a vacuum or by azeotropic distillation is crucial to favor polycondensation
over transesterification. Molecular weights of 130 kDa can be obtained this way. Even higher
molecular weights can be attained by carefully crystallizing the crude polymer from the melt.
Carboxylic acid and alcohol end groups are thus concentrated in the amorphous region of the solid
polymer, and so they can react. Molecular weights of 128152 kDa are obtainable thus.[5]
Polymerization of a racemic mixture of L- and D-lactides usually leads to the synthesis of poly-
DL-lactide (PDLLA), which is amorphous. Use of stereospecific catalysts can lead
to heterotactic PLA which has been found to show crystallinity. The degree of crystallinity, and
hence many important properties, is largely controlled by the ratio of D to L enantiomers used,
and to a lesser extent on the type of catalyst used. Apart from lactic acid and lactide, lactic
acid O-carboxyanhydride ("lac-OCA"), a five-membered cyclic compound has been used
academically as well. This compound is more reactive than lactide, because its polymerization is
driven by the loss of one equivalent of carbon dioxide per equivalent of lactic acid. Water is not a
co-product.[6]
The direct biosynthesis of PLA similar to the poly(hydroxyalkanoate)s has been reported as
well.[7]
Another method devised is by contacting lactic acid with a zeolite. This condensation reaction is
a one-step process, and runs about 100C lower in temperature.[8][9]
Manufacturers[edit]
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As of June 2010, NatureWorks was the primary producer of PLA (bioplastic) in the United
States. The second biggest producer of PLA in the world is the weforyou Group with an annual
capacity of pure PLA and compounds of 50,000t. Other companies involved in PLA
manufacturing are Evonik Industries (Germany), Corbion PURAC Biomaterials (The
Netherlands) who have announced a new 75,000 ton PLA plant in Thailand by 2018, and
several[which?] Chinese manufacturers. The primary producer of PDLLA is Evonik Industries and
Corbion PURAC. The Resomer brand of PDLLA is produced in the Health and Nutrition
business segment. Corbion PURAC is a listed company in the Netherlands, and operating plants
worldwide, and the only producer of PDLA, produced from the D-isomer of lactid
acid. Galactic and Total Petrochemicals operate a joint venture, Futerro, which is developing a
second generation polylactic acid product. This project includes the building of a PLA pilot plant
in Belgium capable of producing 1,500 tonnes/year.

Chemical and physical properties[edit]


Due to the chiral nature of lactic acid, several distinct forms of polylactide exist: poly-L-lactide
(PLLA) is the product resulting from polymerization of L,L-lactide (also known as L-lactide). PLLA
has a crystallinity of around 37%, a glass transition temperature 6065 C, a melting
temperature 173178 C and a tensile modulus 2.716 GPa.[10][11] Heat-resistant PLA can
withstand temperatures of 110 C.[12] PLA is soluble in chlorinated solvents,
hot benzene, tetrahydrofuran, and dioxane.[13]
Polylactic acid can be processed like most thermoplastics into fiber (for example, using
conventional melt spinning processes) and film. PLA has similar mechanical properties
to PETE polymer, but has a significantly lower maximum continuous use temperature.[14] The
tensile strength for 3-D printed PLA was previously determined.[15] It was found to range widely
depending on printing conditions, which were obtained using RepRap 3-D printers.[16] Results of
a recent study gave a printed tensile strength of around 50 MPa and show that the act of 3-D
printing PLA affects its propertiesthey showed a strong relationship between tensile
strength and percent crystallinity of a 3-D printed sample and a strong relationship between
percent crystallinity and the extruder temperature.[17]
The melting temperature of PLLA can be increased by 4050 C and its heat deflection
temperature can be increased from approximately 60 C to up to 190 C by physically blending
the polymer with PDLA (poly-D-lactide). PDLA and PLLA form a highly regular stereocomplex
with increased crystallinity. The temperature stability is maximised when a 1:1 blend is used, but
even at lower concentrations of 310% of PDLA, there is still a substantial improvement. In the
latter case, PDLA acts as a nucleating agent, thereby increasing the crystallization rate.
Biodegradation of PDLA is slower than for PLA due to the higher crystallinity of PDLA.
There is also poly(L-lactide-co-D,L-lactide) (PLDLLA) used as PLDLLA/TCP scaffolds for bone
engineering.[18][19]

Applications[edit]

Mulch film made of PLA-blend "bio-flex"

Biodegradable PLA cups in use at a restaurant


Tea bags made of PLA. Peppermint tea is enclosed.

3D printing of a microcoil using a conductive mixture of polylactide and carbon nanotubes.[20]

PLA can be processed by extrusion such as 3d printing, injection molding, film and sheet
casting, and spinning, providing access to a wide range of materials.

3D Printed Human skull with data from Computed Tomography. Transparent PLA.

PLA is used as a feedstock material in desktop fused filament fabrication 3D


printers (e.g. RepRap).[21][22] PLA printed solids can be encased in plaster-like moulding materials,
then burned out in a furnace, so that the resulting void can be filled with molten metal. This is
known as "lost PLA casting", a type of investment casting.
Being able to degrade into innocuous lactic acid, PLA is used as medical implants in the form of
anchors, screws, plates, pins, rods, and as a mesh.[23] Depending on the exact type used, it
breaks down inside the body within 6 months to 2 years. This gradual degradation is desirable
for a support structure, because it gradually transfers the load to the body (e.g. the bone) as that
area heals. The strength characteristics of PLA and PLLA implants are well documented.[24]
PLA can also be used as a decomposable packaging material, either cast, injection-molded, or
spun.[23] Cups and bags have been made from this material. In the form of a film, it shrinks upon
heating, allowing it to be used in shrink tunnels. It is useful for producing loose-fill packaging,
compost bags, food packaging, and disposable tableware. In the form of fibers and nonwoven
fabrics, PLA also has many potential uses, for example as upholstery, disposable
garments, awnings, feminine hygiene products, and diapers.
Racemic and regular PLLA has a low glass transition temperature, which is undesirable. A
stereocomplex of PDLA and PLLA has a higher glass transition temperatures, lending it more
mechanical strength. It has a wide range of applications, such as woven shirts (ironability),
microwavable trays, hot-fill applications and even engineering plastics (in this case, the
stereocomplex is blended with a rubber-like polymer such as ABS). Such blends also have good
form stability and visual transparency, making them useful for low-end packaging applications.
Pure poly-L-lactic acid (PLLA), on the other hand, is the main ingredient in Sculptra, a long-
lasting facial volume enhancer, primarily used for lipoatrophy of cheeks. Progress in
biotechnology has resulted in the development of commercial production of the D enantiomer
form, something that was not possible until recently.[25]

Recycling[edit]

PLA has SPIresin ID code 7

Currently, the SPI resin identification code 7 ("others") is applicable for PLA. In Belgium, Galactic
started the first pilot unit to chemically recycle PLA (Loopla). Unlike mechanical recycling, waste
material can hold various contaminants. Polylactic acid can be recycled to monomer by thermal
depolymerization or hydrolysis. When purified, the monomer can be used for the manufacturing
of virgin PLA with no loss of original properties (cradle-to-cradle recycling).[dubious discuss]

Degradation[edit]
Amycolatopsis and Saccharotrix are able to degrade PLA. A purified protease
from Amycolatopsis sp., PLA depolymerase, can also degrade PLA. Enzymes such
as pronase and most effectively proteinase K from Tritirachium album degrade PLA.[26]
Pure PLLA foams undergo selective hydrolysis when placed in an environment of Dulbeccos
modied Eagle's medium (DMEM) supplemented with fetal bovine serum (FBS) (a solution
mimicking body fluid). After 30 days of submersion in DMEM+FBS, a PLLA scaffold lost about
20% of its weight.[27]
Everything You Need To Know About
Polylactic Acid (PLA)
What is PLA, and what is it used for?

Polylactic Acid (PLA) is different than most thermoplastic polymers in that it is


derived from renewable resources like corn starch or sugar cane. Most
plastics, by contrast, are derived from the distillation and polymerization of
nonrenewable petroleum reserves. Plastics that are derived from biomass
(e.g. PLA) are known as bioplastics.

Polylactic Acid is biodegradable and has characteristics similar


to polypropylene (PP), polyethylene (PE), or polystyrene (PS). It can be
produced from already existing manufacturing equipment (those designed and
originally used for petrochemical industry plastics). This makes it relatively
cost efficient to produce. Accordingly, PLA has the second largest production
volume of any bioplastic (the most common typically cited as thermoplastic
starch).

There are a vast array of applications for Polylactic Acid. Some of the most
common uses include plastic films, bottles, and biodegradable medical
devices (e.g. screws, pins, rods, and plates that are expected to biodegrade
within 6-12 months). For more on medical device prototypes (both
biodegradable and permanent) read here. PLA constricts under heat and is
thereby suitable for use as a shrink wrap material. Additionally, the ease with
which Polylactic Acid melts allows for some interesting applications in 3D
printing (namely lost PLA casting - read more below). On the other hand, its
low glass transition temperature makes many types of PLA (for example,
plastic cups) unsuitable to hold hot liquid.

Here is a look at some different PLA products on the market:


PLA printing filament, photo courtesy Alibaba.com

PLA medical screws, photo courtesy of DSM.com

What Are The Different Types of Polylactic Acid and Why


is it Used so Often?
There are several different types of Polylactic Acid to include Racemic PLLA
(Poly-L-lactic Acid), Regular PLLA (Poly-L-lactic Acid), PDLA (Poly-D-lactic
Acid), and PDLLA (Poly-DL-lactic Acid). They each have slightly different
characteristics but are similar in that they are produced from a renewable
resource (lactic acid: C3H6O3) as opposed to traditional plastics which are
derived from nonrenewable petroleum.

PLA production is a popular idea as it represents the fulfillment of the dream


of cost-efficient, non-petroleum plastic production. The huge benefit of PLA
as a bioplastic is its versatility and the fact that it naturally degrades
when exposed to the environment. For example, a PLA bottle left in the
ocean would typically degrade in six to 24 months. Compared to conventional
plastics (which in the same environment can take several hundred to a
thousand years to degrade) this is truly phenomenal. Accordingly, there is a
high potential for PLA to be very useful in short lifespan applications where
biodegradability is highly beneficial (e.g. as a plastic water bottle or as a
container for fruit and vegetables). Of note, despite its ability to degrade when
exposed to the elements over a long time, PLA is extremely robust in any
normal application (e.g. as a plastic electronics part).

PLA for Prototype Development on CNC Machines and 3D


Printers:
PLA is one of two common plastics used on FDM machines (3D printing)
and is commonly available as a 3D printable filament; the other common 3D
printer plastic is ABS. PLA filament for 3D printing is typically available in a
myriad of colors. Polylactic Acid could be CNC machined but it is typically not
available in sheet stock or rod form. It is, however, typically available as a thin
film for thermoforming or in the form of plastic pellets for injection molding. To
adjust material properties, plastic injection mold pellets are typically produced
and/or blended together.

One of the interesting things you can do with PLA on a 3D printer is


called lost PLA casting. This is a process where PLA is printed in the
shape of an interior cavity and then encased with plaster-like materials. The
PLA is later burned out as it has a lower melting temperature than the
surrounding material. The end result is a void that can be filled (often with
molten metal).

How is PLA made?

Polylactic Acid is principally made through two different processes:


condensation and polymerization. The most common polymerization
technique is known as ring-opening polymerization. This is a process that
utilizes metal catalysts in combination with lactide to create the larger PLA
molecules. The condensation process is similar with the principal difference
being the temperature during the procedure and the by-products
(condensates) that are released as a consequence of the reaction.

What are the Characteristics of Polylactic Acid?

Now that we know what it is used for, lets examine some of the key properties
of Polylactic Acid. PLA is classified as a thermoplastic polyester (as opposed
to thermoset), and the name has to do with the way the plastic responds to
heat. Thermoplastic materials become liquid at their melting point (150-160
degrees Celsius in the case of PLA). A major useful attribute
about thermoplastics is that they can be heated to their melting point, cooled,
and reheated again without significant degradation. Instead of burning,
thermoplastics like Polylactic Acid liquefy, which allows them to be
easily injection molded and then subsequently recycled. By contrast,
thermoset plastics can only be heated once (typically during the injection
molding process). The first heating causes thermoset materials to set (similar
to a 2-part epoxy) resulting in a chemical change that cannot be reversed. If
you tried to heat a thermoset plastic to a high temperature a second time it
would simply burn. This characteristic makes thermoset materials poor
candidates for recycling. PLA falls under the SPI resin identification code of 7
("others").

Is PLA toxic?

In solid form, no. In fact, Polylactic Acid (PLA) is biodegradable. It is often


used in food handling and medical implants that biodegrade within the body
over time. Like most plastics, it has the potential to be toxic if inhaled and/or
absorbed into the skin or eyes as a vapor or liquid (i.e. during manufacturing
processes). Be careful and closely follow handling instructions for molten
polymer in particular.

Recently researchers from the Illinois Institute of Technology published a


paper on Ultrafine Particle (UFP) emissions from commercially available 3D
printers using ABS and PLA feedstock. You can read about the results here.

What are the Disadvantages of Polylactic Acid?

PLA has a relatively low glass transition temperature (typically between 111
and 145 F). This makes it fairly unsuitable for high temperature applications.
Even things like a hot car in the summer could cause parts to soften and
deform.

Polylactic Acid is a little bit more brittle than ABS for 3D prototyping but it has
some advantages as well. For a full comparison of the two plastics as they
relate to 3D printing read here.

What are the properties of PLA?

Here at Biomass, we understand the many problems associated with petroleum-based plastics. We
believe that Compostable Bioplastics, typically made from plant matter like vegetable starch, cane sugar,
cellulose (wood fibers) and lactic acid, are the solution to many of these problems. Polylactic Acid (PLA)
is a bioplastic generally derived from animal-feed corn that can be used for a myriad of different
purposes including cold drink cups, deli and takeout containers, and fresh produce packaging. Sounds
great, right? It is, at least in theory. In practice, however, things are a little more complicated. Today
well be looking at a few of the pros and cons of these corn plastics.

Pros of Polylactic Acid (PLA) or Corn Plastics

PLA is Derived From a Renewable Resource

One of the major problems with petroleum-based plastics is that they are derived from oil which is only
available in finite amounts throughout the world. Eventually, the oil will run out. PLA, however, being
derived from corn, is based on a resource that can be renewed yearly.

PLA Plastics Are Compostable

It is estimated that traditional plastics can take centuries to break down and may never break down into
natural elements. This is especially true when these products end up in landfills where sunlight and air
exposure are drastically curtailed. On the other hand, PLA can break down into natural elements in less
than a month given the right circumstances.

PLA Does Not Produce Toxic Fumes If Incinerated

For decades, weve been warned of the dangerous chemicals that can be released when traditional
plastics are incinerated. Being biologically based, PLA plastics do not produce these toxic fumes if they
end up being incinerated instead of finding their way to a commercial composting facility.

Cons of Polylactic Acid (PLA) or Corn Plastics

PLA Production Depends on Large Fields of Crops

While the corn used to create PLA is a renewable resource, many people point out that the fields use to
grow these crops could be used to create foodstuffs for the worlds growing population. They do have a
point, but it is important to remember that the bioplastics industry is still young. Long term plans in the
industry include determining effective ways to create PLA plastics from agricultural waste like stalks and
stems which could result in bioplastics made from products that are not fit for consumption.

PLA Plastics Are Only Compostable in a Commercial Composting Facility

Unfortunately, most PLA plastic will not break down into natural elements in your backyard composting
pile. Instead, these products need to be sent to a commercial composting facility for processing. At this
time, there are a limited number of such facilities in the United States which means that it can be
difficult to properly dispose of these products. However, as the industry grows, we believe that the
infrastructure for commercial composting will follow.

Improperly Disposed PLA Plastics Can Contaminate Recycling Processes

Whether or not commercial composting facilities are locally available, many PLA products end up getting
mixed in with traditionally recyclable plastics. Because they are derived from very different elements,
this can cause problems in the recycling process if the products are not properly sorted before recycling
begins.

Conclusion
Its not surprising that these pros and cons prove that PLA plastics are not a perfect solution. But as long
as we live in a society that embraces disposable plastic containers, we need to be working toward
finding solutions that are less harmful to the environment than traditional plastics. To that end, we think
that products made from PLA are a positive step toward a world less dependent on oil and more focused
on renewable solutions.

Polylactic acid (PLA), a plastic substitute made from fermented plant starch (usually corn) is quickly
becoming a popular alternative to traditional petroleum-based plastics. As more and more countries and
states follow the lead of China, Ireland, South Africa, Uganda and San Francisco in banning plastic
grocery bags responsible for so much so-called white pollution around the world, PLA is poised to play
a big role as a viable, biodegradable replacement.

PLA HELPS TO REDUCE GREENHOUSE GAS EMISSIONS

Proponents also tout the use of PLAwhich is technically carbon neutral in that it comes from
renewable, carbon-absorbing plantsas yet another way to reduce our emissions of greenhouse
gases in a quickly warming world. PLA also will not emit toxic fumes when incinerated.

PLA BIODEGRADES SLOWLY UNLESS SUBJECTED TO INDUSTRIAL COMPOSTING

But critics say that PLA is far from a panacea for dealing with the worlds plastic waste problem. For one
thing, although PLA does biodegrade, it does so very slowly.

According to Elizabeth Royte, writing in Smithsonian, PLA may well break down into its constituent parts
(carbon dioxide and water) within three months in a controlled composting environment, that is, an
industrial composting facility heated to 140 degrees Fahrenheit and fed a steady diet of digestive
microbes. But it will take far longer in a compost bin, or in a landfill packed so tightly that no light and
little oxygen are available to assist in the process.

Indeed, analysts estimate that a PLA bottle could take anywhere from 100 to 1,000 years to decompose
in a landfill.

RECYCLERS CANT MIX PLA AND OTHER PLASTICS

Another issue with PLA is that, because it is of different origin than regular plastic, it must be kept
separate when recycled, lest it contaminate the recycling stream.

Being plant-based, PLA needs to head to a composting facility, not a recycling facility, when it has out
served its usefulness. And that points to another problem: There are currently a few hundred industrial-
grade composting facilities across the United States.

MOST PLA USES GENETICALLY MODIFIED CORN

Another downside of PLA is that it is typically made from genetically modified corn, at least in the United
States. The largest producer of PLA in the world is NatureWorks, a subsidiary of Cargill, which is the
worlds largest provider of genetically modified corn seed.

With increasing demand for corn to make ethanol fuel, let alone PLA, its no wonder that Cargill and
others have been tampering with genes to produce higher yields. But the future costs of genetic
modification (and the associated pesticides) to the environment and human health are still largely
unknown.

GREEN-MINDED CONSUMERS MAY PREFER ALTERNATIVES TO PLASTICS

While PLA has promise as an alternative to conventional plastic once the means of disposal are worked
out, consumers might be better served by simply switching to reusable containersfrom cloth bags,
baskets and backpacks for grocery shopping (most chains now sell canvas bags for less than a dollar
apiece) to safe, reusable (non-plastic) bottles for beverages.

DESPITE PROBLEMS, PLA HAS MANY USES

As for other types of PLA itemssuch as those plastic clamshells that hold cut fruit (and there is a
whole host of industrial and medical products now made from PLA)there is no reason to pass them by.
But until the kinks are worked out on the disposal and reprocessing end, PLA may not be much better
than the plain old plastic its designed to make obsolete.