Synthesis of Polylactic acid

Production
Direct condensation of lactic acid single step Ring opening polymerization- Multi step process

Feasible process for the commercial production of PLA by Direct Condensation

Equilibrium between free acid , Water, and polyesters Difficulty in removing the trace amount of water in the late stages of polymerization generally limit the ultimate molecular weight achievable by this approach

To overcome the above

Kinetic control over the reaction Efficient removal of Water : Reletively Suppresion of Depolymerization
high temperatures Reduced pressure Entraining agent such as various solvents

Catalysts employed :
Protonic acids Metals Metal Oxides Metal halides Organic salts of metals

General properties of Polylactic acid O [CH-CO]n CH

3

Transperancy Glass Transition temperature 50-600C Melting Point 130-1800C Crystallinity : 35-40 % Tensile Strength : 4-6 Kg/mm2 Elongation : 3-4 %, brittle Flexural Strength : 9~11 Kg/mm2 Impact Strength :~50 Kg-cm/cm2

Bio-Polymer Production (Cargill-Dow, USA)

Production of Polylactic acid (PLA) polymer from corn sugar replaces petroleum feedstock. PLA can replace PET, polyesters and polystyrene. PLA is compostable. PLA is carbon neutral CO2 is recycled. In the future, PLA will be made from ligno-cellulosic biomass.

Background on P.L.A. Used for 30 years in medicine:

Encapsulation of vaccines Carrier for slow release medication treatment of prostate cancer and infertility

Polylactic Acid (PLA)

A polymer made from cornstarch fermentation, declared a new generic fiber by the US FTC Competitive in price and performance with fossil fuel derived polymers: PE, PS, PP, polyester Can be engineered to be biodegradable Can be used in carpet tiles Cargill Dow's new facility in Blair, Nebraska, will use up to 40,000 bushels of corn each day and can produce more than 300 million pounds of PLA each year

Cargill-Dow LLC Plant. Blair, Nebraska. November, 2001. Completed

August, 2001 August, 2001

September, 2001

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September, 2001

The School of

Packaging

Mechanical, Physical and Barrier Properties of Poly(Lactic Acid)

RAA, 2002

Main Producers
Producer Cargill Dow LLC Mitsui Chemicals Cost U$S / lb
2000 Million lb/yr* 2001 2002 Million lb/yr ** Million lb/yr**

16 1.3 1.5/2.0

300 1.3 1.0

300 1.3 0.5

* Chemical Week V162, 2000 & Plastics Week, Jan17, 2000

Polylactic acid (PLA) for plastics production

Cor n

Starc h

Unrefine d Dextrose

Fermentatio n

Lactic Acid
Monomer Production

Polymer Grades Fiber Film Thermoforming Bottle Woven Non-woven Etc.

Lactide

Polymer Modificati on

PLA

Polymer Production

Polymerization scheme of copolymers from L-lactic acid and D-lactic acid

Recent development of biodegradable sutures

Non-Solvent Process to Prepare PLA

Fermentation Lactic Acid
By heating catalyst.

Prepolymer

Lactide Formation

Dextrose

PLA Polymer

Polymerization
Coordination / Insertion Propagation

Low D Lactide

Corn

Cargill Dow LLC Process. Gruber, et. al. 2000.

Distillation

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Unconverted Polymer

Meso Lactide

Distillation

Biodegradable polymers approved for medical applications

PGA Polyglycolic acid, PLA Polylactic acid, PLGA Copolymer of PLA & PGA

Initial cost of PLA was too high that has limited its packaging applications to high value films, thermoformed containers, and coated papers . PLA has a largest potential market because it is a compostable and biodegradable thermoplastic. Derived from annually renewable agricultural resources . New technologies for mass production of PLA promise to lower its cost and widen its packaging applications, to include food packaging . PLA can be fabricated on a variety of familiar processes . There is a need to better understand its behavior and properties to be fully adapted in packaging applications.

Scheme 1 : Generalized flow sheet for the production of PLA from agricultural waste.

Synthesis of Polylactic acid over Solid acid catalyst

Experimental Section
Lactic acid (LA) is a 85% aqueous solution of the monomer Catalyst Tungastophosphoric acid H3 [ P(W3O10) 4 ] x H2O (HPA) is heated at 1500C for 3 hours. The following products were used without any further treatment Chloroform-d1 with TMS (1%) (deuteration degree not less than 99.5%) from Merck for NMR measurements.

Characterization of Polylactic acid :

IR, TGA, DSC 13C NMR and GPC

Schematic Representation
10 gms of Lactic Acid 40 mg of HPA
H3 [ P(W3O10) 4 ]

Vessel with Dean Stark Trap

Continuous flow of N2

Stirred at 1500C for 3 hrs

Viscous liqiud Poured into 100ml of methanol Precipitate

Filterd & Dried

PLA

Experimental set up for the synthesis of polylactic acid

N 2

Dean stark trap

Water removed through dean stark trap Continuous purging of N2 gas

Infrared Spectral Analysis of PLA

O -C=O
1759 1092

-C-O

13C NMR Analysis of PLA

CDCl 3

13C NMR Analysis of PLA

CDCl 3

13C NMR of PLA ( Solvent CDCl3) 169.5 ( C=O ) 69.0 ( O=C O C H-) 16.6 ( CH3

Thermo Gravimetric Analysis of PLA

3220 C

PLA prepared at 1500C

Differential Scanning Calorimetric Analysis of PLA

Tg = 560 C Tm = 1300C

Thermo Gravimetric Analysis of PLA prepared at 1800C

4000 C

PLA prepared at 1800C

Gel Permeation Chromatography Analysis

Wt Molecular weight 42496

Polymerization of lactic acid by using various catalysts

Comparison with conventional catalyst

Catalyst Temperature (0C)
180 200 220 150

Mw(g/mol) GPC
31000 30600 32600 42496

H2SO4* (Conventional)

HPW#

* reaction duration -12 h # reaction duration -3 h

Table 1 Summary of the catalysts used for polymerization of Lactic acid Condensation polymerization

Catalyst S.No 1 2 3 4 5 6 Tolune sulphonic acid Sulphuric acid Boric acid Phosphoric acid Nafion-H Methyl sulphonic acid

Weight % ofTemp K catalysts 1,2.5 0.1to 1.5,2.5 1 0.1,2.5 2.0 2.5

MW(g/mol)

373-423,4031458 373,403 100000 358-393 31000,65000 453,473, 3800,6500 433 4000 403 20000

Ringopening polymerization
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 ZnCl2 Al(acac) Sn(II)octoate Sb2O3 Ti(IV)butylate Ti(IV)isopropylate Dibutyltin dilaurate (DBTL) Stannous octoate Tetraphenyltin Stannous octoate Mg Al Zn Sn TiO2 ZnO GeO2 ZrO2 SnO SnCl2 SnCl4 Mn(AcO)2 Fe2(LA)3 Co(AcO)2 Ni (AcO)2 Cu (AcO)2 Zn(LA)2 Y(OA)3 Al(iPrO)3 Ti (BuO)4 TiO(acac)2 (Bu)2SnO 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.05 0.01 0.5 0.5 0.5 0.5 0.83 0.62 0.72 0.68 0.57 0.80 1.10 1.57 1.70 1.50 1.51 2.75 1.86 2.92 3.79 3.55 2.74 1.05 353 353 353 353 353 353 353 451 433 433 433 433 433 433 433 433 433 403 403 433 433 433 433 433 433 433 433 403 403 403 4700 3600 8000 10800 15000 9000 6700 37000-76000 14000-100,000 14000-350,000 2100 5400 35000 230000 1600 20000 1300 1500 230000 230000 29000 19000 27000 32000 1400000 1900 20000 20000 1500 8000 7000 13000

Table .2. Typical applications of PLA

Processes Non woven fibres Oriented films Extrusion coatings Flexible film Cast sheet Injection moulding foam End Products Personal hygiene, protective clothing, filtration Container labels, tape Dinnerware, food packaging, mulch film Food wrap, trash bags, shrink wrap Delivery trays Rigid containers, Dairy containers Clam shells, meat trays

Salient features
Developed process utilizes a noncorrosive, environmentally friendly Solid acid catalyst The reaction temperature is decreased from 1800C to 1500C The reaction duration is three hours obtained required Molecular weight The solid acid can be completely recovered and regenerated. The physico-chemical properties of PLA can be widely tunned according to the requirements i.e by changing various solid acid strength