Search

Home > Knowledge > Content
Polylactic acid
Jul 31, 2018

 

 

Polylactic acid

 


 

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 anybioplastic 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

 

Production Materials properties

Chemical properties

Physical and mechanical properties Solvent welding

Applications Recycling Degradation See also References External links


Polylactic acid


 

 


Production

                                                                                                              

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 distillationis required to drive the reaction toward polycondensation. Molecular weights of 130 kDa can be obtained this w.aEy ven 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 polyme,rand so they can react. Molecular weights of 128–152 Dk a 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 polymerizationis 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 thepoly(hydroxyalkanoate)shas 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

 


Chemical properties

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 chlorinated solvents, hot benzene, tetrahydrofuran, and dioxane.[10]

 

Physical and mechanical properties

PLA polymers range from amorphous glassy polymer to semi-crystalline and highly crystalline polymer with a glass transition of 60oC and melting points of 130-180oC.[11] PLLA has a glass transition temperature 60–65 °C, a melting temperature 173–178 °C and a tensile modulus 2.7–16 MPa.[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. Biodegradationof PDLA is slower than for PLA due to the higher crystallinity of PDLA. 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 intfoiber (for example, using conventionalmelt 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[2. 4]

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

 

 

Solvent welding

PLA can be solvent welded usingdichloromethane.[27]

 

Applications


 

 

 


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

 

 

 


Tea bags made of PLA. Peppermint tea is enclosed.



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.

PLA is used as a feedstock material in desktop fused filament fabrication 3D printers (e.g. RepRap).[29][30] 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.[31]  Depending on



 


Biodegradable PLA cups in use at a restaurant

 

 

 

Play media

3D printing of amicrocoil using a conductive mixture of polylactide and carbon nanotubes.[28]


 

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 documente[d3.2]

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), microwavabletrays, hot-fill applications and even engineering plastics (in this case, the stereocomplexis 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 recentl.y[33]

PLA is also used in e-tobacco industry. Philip Morriss iQOS heets, includes PLA to slow the vapour down without absorbing it, giving it time to cool to a more pleasant temperature before inhaling it.

 

Recycling

 

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 manufacturingof virgin PLA with no loss of original properties c(radle-to-cradle recycling).



Related Industry Knowledge

Copyright © Fancyco All Rights Reserved.