Polylactic acid

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Polylactic acid
The skeletal formula of PLA
Identifiers
ChemSpider
  • none
Properties
Density 1.210–1.430 g·cm−3[1]
Melting point 150 to 160 °C (302 to 320 °F; 423 to 433 K)[1]
Insoluble in water[2]
Hazards
NFPA 704
Flammability code 1: Must be pre-heated before ignition can occur. Flash point over 93 °C (200 °F). E.g., canola oilHealth code 0: Exposure under fire conditions would offer no hazard beyond that of ordinary combustible material. E.g., sodium chlorideReactivity code 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g., liquid nitrogenSpecial hazards (white): no codeNFPA 704 four-colored diamond
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

Polylactic acid or polylactide (PLA) is a thermoplastic aliphatic polyester derived from renewable biomass, typically from fermented plant starch such as from corn, cassava, sugarcane or sugar beet pulp. 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]

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. The condensation reaction is reversible and subject to equilibrium, so removal of water is required to generate high molecular weight species. Water removal by application of a vacuum or by azeotropic distillation is required to drive the reaction toward polycondensation. 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 128–152 kDa are obtainable thus.[5]

Two main routes to PLA

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 100 °C lower in temperature.[8][9]

Materials properties[edit]

Chemical 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). PLA is soluble in solvents, hot benzene, tetrahydrofuran, and dioxane.[10]

Physical and mechanical properties[edit]

PLA polymers range from amorphous glassy polymer to semi-crystalline and highly crystalline polymer with a glass transition of 60 °C and melting points of 130-180 °C.[11] PLA has a glass transition temperature 60–65 °C, a melting temperature 173–178 °C and a tensile modulus 2.7–16 GPa.[12][13] Heat-resistant PLA can withstand temperatures of 110 °C.[14] The basic mechanical properties of PLA are between those of polystyrene and PET.[11] The melting temperature of PLLA can be increased by 40–50 °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 3–10% of PDLA, there is still a substantial improvement. In the later case, PDLA acts as a nucleating agent, thereby increasing the crystallization rate[citation needed]. Biodegradation of PDLA is slower than for PLA due to the higher crystallinity of PDLA[citation needed]. The flexural modulus of PLA is higher than polystyrene and PLA has good heat sealability.

Several technologies such as annealing,[15][16][17] adding nucleating agents, forming composites with fibers or nano-particles,[18][19][20] chain extending[21][22] and introducing crosslink structures have been used to enhance the mechanical properties of PLA polymers. 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.[23] With high surface energy, PLA has easy printability which makes it widely used in 3-D printing. The tensile strength for 3-D printed PLA was previously determined.[24]

There is also poly(L-lactide-co-D,L-lactide) (PLDLLA) – used as PLDLLA/TCP scaffolds for bone engineering.[25][26]

Solvent welding[edit]

PlLA can be solvent welded using dichloromethane.[27]

Applications[edit]

PLA is used as a feedstock material in desktop fused filament fabrication 3D printers (e.g. RepRap).[28][29] 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.[30]

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.[31] 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.[32]

PLA can also be used as a decomposable packaging material, either cast, injection-molded, or spun.[31] 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. Thanks to its bio-compatibility and biodegradability, PLA has also found ample interest as a polymeric scaffold for drug delivery purposes.

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.[33]

PLA is also used in the e-tobacco industry. Philip Morris's iQOS heets include PLA to slow the vapour down without absorbing it, giving it time to cool to a more pleasant temperature before inhaling it.[citation needed]

Degradation[edit]

Abiotic PLA degradation is due to 3 mechanisms:[35]

  1. Hydrolysis: The ester groups of the main chain are cleaved, dividing the molecule in two parts, thus reducing molecular weight.
  2. Thermal degradation: A complex phenomenon leading to the appearance of different compounds such as lighter molecules and linear and cyclic oligomers with different Mw, and lactide.
  3. Photodegradation: Sunlight induces degradation due to low-wavelength and high-energy UV radiation. This is a factor mainly where PLA is exposed to sunlight in its applications in plasticulture, packaging containers and films.

The hydrolytic reaction is:

The degradation rate is very slow in ambient temperatures showing no significant advantages against conventional plastics. At 25 °C in seawater, PLA showed no degradation over a year.[36] Plastic pollution would not be improved if PLA was more extensively used, and this is a misconception as PLA is advertised as a biodegradable plastic.

Pure PLA foams undergo selective hydrolysis when placed in an environment of Dulbecco's modified 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.[37]

PLA samples of varying molecular weight were degraded into methyl lactate (a green solvent) by using a metal complex catalyst.[38]

Some bacteria can also degrade PLA, such as Amycolatopsis and Saccharothrix. 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.[39]

End of life[edit]

PLA from different producers (Total Corbion, NatureWorks) has been certified to be compostable in industrial conditions, acording to ASTM D6400. The conditions of industrial composting are 58 °C in presence of humidity and a processing time of 6 months.[40][41]

PLA has SPI resin ID code 7

4 possible end of life scenarios are the most common:

  1. Recycling: which can be either chemical or mechanical. 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 ]
  2. Composting: PLA is biodegradable under industrial composting conditions starting with an hydrolysis process and following with the action of microorganisms to ultimately degrade the PLA.
  3. Incineration: PLA can be incinerated leaving no residue and producing 19.5MJ/kg (8,368 btu/lb) of energy.
  4. Landfill: the less preferable option would be landfilling as PLA degrades very slowly in ambient temperatures.

See also[edit]

References[edit]

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External links[edit]