PLA Presentation

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
Click to edit Master subtitle style
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
Click to edit Master subtitle style
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

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What are the main methods for producing Polylactic acid?

What are the main methods for producing Polylactic acid?

What properties are typically analyzed to characterize Polylactic acid?

What properties are typically analyzed to characterize Polylactic acid?

Synthesis of Polylactic acid

Feasible process for the commercial production of PLA by Direct Condensation

To overcome the above

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

Bio-Polymer Production (Cargill-Dow, USA)

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

Polylactic Acid (PLA)

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

Click to edit Master subtitle style

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

300 1.3 1.0

300 1.3 0.5

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

Polylactic acid (PLA) for plastics production

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

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

Recent development of biodegradable sutures

Non-Solvent Process to Prepare PLA

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

Click to edit Master subtitle style

Biodegradable polymers approved for medical applications

Synthesis of Polylactic acid over Solid acid catalyst

Characterization of Polylactic acid :

Vessel with Dean Stark Trap

Stirred at 1500C for 3 hrs

Viscous liqiud Poured into 100ml of methanol Precipitate

Filterd & Dried

Experimental set up for the synthesis of polylactic acid

Dean stark trap

Water removed through dean stark trap Continuous purging of N2 gas

Infrared Spectral Analysis of PLA

13C NMR Analysis of PLA

13C NMR Analysis of PLA

Thermo Gravimetric Analysis of PLA

PLA prepared at 1500C

Differential Scanning Calorimetric Analysis of PLA

Thermo Gravimetric Analysis of PLA prepared at 1800C

PLA prepared at 1800C

Gel Permeation Chromatography Analysis

Wt Molecular weight 42496

Polymerization of lactic acid by using various catalysts

Comparison with conventional catalyst

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

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

Table .2. Typical applications of PLA

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