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Synthesis of Polylactic acid
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Production
Direct condensation of lactic acid single step
Ring opening polymerization- Multi step process
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Feasible process for the commercial production of PLAby Direct Condensation
Kinetic control over the reaction
Efficient removal of Water : Reletively high temperaturesReduced pressureEntraining agent such as various solvents
Suppresion of Depolymerization
Equilibrium between free acid , Water, and polyesters
Difficulty in removing the trace amount of water in thelate stages of polymerization generally limit the ultimatemolecular weight achievable by this approach
To overcome the above
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Catalysts employed :
Protonic acidsMetalsMetal OxidesMetal halidesOrganic salts of metals
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General properties of Polylacticacid
[CH-C-O]n
O
CH3
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
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Production of Polylactic acid (PLA) polymer fromcorn 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-cellulosicbiomass.
Bio-Polymer Production
(Cargill-Dow, USA)
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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
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A polymer made from cornstarch fermentation, declared anew generic fiber by the US FTC
Competitive in price and performance with fossil fuelderived 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 to40,000 bushels of corn each day and can produce morethan 300 million pounds of PLA each year
Polylactic Acid (PLA)
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Cargill-Dow LLC Plant. Blair, Nebraska. November, 2001. Completed
The School ofPackaging
RAA, 2002Mechanical, Physical and BarrierProperties of Poly(Lactic Acid)
August, 2001 August, 2001
September, 2001
September, 2001
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Main Producers
Producer 2000Million lb/yr*
2001Million lb/yr **
2002Million lb/yr**
Cargill Dow LLC 16 300 300
Mitsui Chemicals 1.3 1.3 1.3
Cost U$S / lb 1.5/2.0 1.0 0.5
* Chemical Week V162, 2000 & Plastics Week, Jan17, 2000
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Polylactic acid (PLA) for plastics production
Co rn
S t a r ch
Un r e f i n ed
Dex t r o s e
Po l yme rP roduc t i onPLA
Lactide
Monome rP roduc t i o n
Lactic Acide rmen t a t i on
Polymer Grades
Fiber
Film
Thermoforming
Bottle
Woven
Non-woven
Etc.
PolymerModificati
on
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Polymerization scheme of copolymersfrom L-lactic acid and D-lactic acid
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Recent development of biodegradablesutures
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Non-Solvent Process to Prepare PLA
Dextrose
Lactic
Acid
Fermentation
PrepolymerLactide
Formation
Distillatio
n
Disti
llation
Meso
Lactide
Low D
Lactide
PolymerizationPLA
Polymer
UnconvertedPolymer
Cargill Dow LLC Process. Gruber, et. al. 2000.Corn
Coordination / InsertionPropagation
By heating catalyst.
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Biodegradable polymers approvedfor medical applications
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PGA Polyglycolic acid, PLA Polylactic acid, PLGA Copolymer of PLA & PGA
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Initial cost of PLA was too high that has limited itspackaging applications to high value films, thermoformedcontainers, 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 promiseto 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 andproperties
to be fully adapted in packaging applications.
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Scheme 1 : Generalized flow sheet for the production of PLA from agricultural waste.
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Synthesis of Polylactic acid over
Solid acid catalyst
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Experimental Section
Lactic acid (LA) is a 85% aqueous solution of the monomer
Catalyst Tungastophosphoric acid H3 [ P(W3O10) 4 ] x H2O (HPA) isheated 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%) fromMerckfor NMR measurements.
Characterization of Polylactic acid :
IR, TGA, DSC 13C NMR and GPC
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N
2
Experimental set up for the synthesis of polylactic acid
Water removed through dean stark trap
Continuous purging of N2 gas
Dean starktrap
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Infrared Spectral Analysis of PLA
-C=O
O
1759 1092
-C-O
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CDCl3
13C NMR Analysis of PLA
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13C NMR of PLA ( Solvent CDCl3)
169.5 ( 69.0 ( O=C O C H-)
16.6 (
13C NMR Analysis of PLA
C=O )
CDCl3
CH3
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3220
C
Thermo Gravimetric Analysis of PLA
PLA prepared at1500C
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Thermo Gravimetric Analysis of PLA prepared at 1800C
4000C
PLA prepared at1800C
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Gel Permeation Chromatography Analysis
Wt Molecular weight -42496
Polymerization of lactic acid by using various catalysts
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Polymerization of lactic acid by using various catalysts
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Catalyst Temperature
(0C)
Mw(g/mol)
GPC
H2SO4*(Conventional)
HPW#
180200
220
150
3100030600
32600
42496
Comparison with conventional catalyst
* reaction duration -12h# reaction duration -3 h
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Table 1 Summary of the catalysts used for polymerization of Lactic acidCondensation polymerization
S.No
Catalyst Weight % of catalysts
Temp K MW(g/mol)
123456
Tolune sulphonic acidSulphuric acidBoric acidPhosphoric acidNafion-HMethyl sulphonic acid
1,2.50.1to 1.5,2.510.1,2.52.02.5
373-423,403373,403358-393453,473,433403
145810000031000,650003800,6500400020000
Ringopening polymerization
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Ringopening polymerization
123456
78910111213141516
171819202122232425
26272829303132
ZnCl2Al(acac)Sn(II)octoateSb2O3Ti(IV)butylateTi(IV)isopropylate
Dibutyltin dilaurate (DBTL)Stannous octoateTetraphenyltinStannous octoateMgAlZnSnTiO2ZnO
GeO2ZrO2SnOSnCl2SnCl4Mn(AcO)2Fe2(LA)3Co(AcO)2
Ni (AcO)2
Cu (AcO)2Zn(LA)2Y(OA)3Al(iPrO)3Ti (BuO)4TiO(acac)2(Bu)2SnO
0.10.10.10.10.10.1
0.10.05
0.010.50.50.50.50.830.62
0.720.680.570.801.101.571.701.501.51
2.751.862.923.793.552.741.05
353353353353353353
353
451
433433433433433433
433433433403403433433433433
433433433433403403403
47003600800010800150009000
670037000-7600014000-100,00014000-350,0002100540035000230000160020000
13001500230000230000290001900027000320001400000
1900200002000015008000700013000
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Table .2. Typical applications of PLA
Processes End Products
Non woven fibres Personal hygiene, protective clothing, filtration
Oriented films Container labels, tape
Extrusion coatings Dinnerware, food packaging, mulch film
Flexible film Food wrap, trash bags, shrink wrap
Cast sheet Delivery trays
Injection moulding Rigid containers, Dairy containers
foam Clam shells, meat trays
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Developed process utilizes a noncorrosive, environmentally friendlySolid acid catalyst
The reaction temperature is decreased from 1800C to 1500C
The reaction duration is three hours obtained requiredMolecular weight
The solid acid can be completely recovered and regenerated.
The physico-chemical properties of PLA can be widely tunnedaccordingto the requirements i.e by changing various solid acid strength
Salient features
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