PLA

LICHUNLUANDANTONIOSG.MIKOS

ACRONYMPLA

CLASS

Poly(󰀋-hydroxyesters)

STRUCTURE

Hÿÿ󰂉OÿCjOÿCjjÿÿ󰂊

CHj3

MAJORAPPLICATIONS

deliverytheareaofdevices.tissueD,L-PLAL-PLAisengineering.

isusedusedasmainlysuturesforanddrugdental,delivery.orthopedic,Bothareandofinterestdrug

inPROPERTIESOFSPECIALINTEREST

simpledegradationhydrolysis;PLAofvariousrates,molecularphysical,bioresorbable;Goodweightsmechanical,verybiocompatibility;goodanditsandprocessability;biodegradablecopolymers.

otherpropertiesawidemainlyby

canberangeachievedof

byPREPARATIVETECHNIQUES

synthesizedzinc,byacationicPracticallyringopeningusefulhighmolecularweightPLAcanbe

controllead,agentortinathighascatalysttemperatureandalcoholpolymerizationoflactideusingantimony,andlowasmolecularpressure.weightandreactionrateIRof1%w/vD,L-PLAinchloroform󰂅1󰂆

Structure

Absorptionfrequency(cmÿ1)

OH,Calcoholandcarboxylic3,700±3,450COO󰂈Oacid1,750±1,735Cÿ1,600±1,580CHO1,200±1,000950±700

1

HNMRof10%w/vD,L-PLAindeuteriochloroform󰂅1󰂆

Structure

Chemicalshift(ppm)andpeakmultiplicity

OH

CH7.30,CHÿÿCHCH35.20,s31.55,md

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Poly(lacticacid)

13

CNMRof10%w/vD,L-PLAindeuteriochloroform󰂅1󰂆

Structure

Chemicalshift(ppm)

C󰂈OCÿOCH3169.369.016.7

UnitcelldimensionsofL-PLA

Lattice

Monomersperunitcell

Ê)Celldimension(Aa

b

c(®beraxis)

CellanglesÃ

󰀍(degree)

Chainconformation&nofhelix

Reference

HexagonalOrthorhombic

Pseudo-orthorhombicPseudo-orthorhombicPseudo-orthorhombic

Ã

ÐÐ2020205.910.3110.3410.610.75.918.215.976.16.45Ð9.00Ð28.827.812090909090Ð31103103103(2)(3)(2)(3)(4)

Cellangles󰀋󰂈󰀌󰂈908.

PROPERTYUNITSCONDITIONSVALUEREFERENCE

DegreeofcrystallineXc%

D-PLAL-PLAD,L-PLAP(L-co-DL)LAAmorphousSinglecrystal

L-PLAcompletecrystallineL-PLA®berAsextruded

Afterhot-drawingL-PLAofMv󰂈5,300

Mv󰂈󰂅0X2±6X91󰂆Â105

L-PLAofvariousmolecularweights

L-PLAwithdichloromethaneD,L-PLAofvariousmolecularweights

D,L-PLAwithdichloromethaneD-PLAinjection-molded,Mv󰂈21,000

L-PLAofvariousmolecularweights

Semicrystalline0±37

Amorphous1.2481.2901462.56.40.600.54326±337Ð

323±330Ð444.4418±459

(5)(6)(6)(7)

Density&

gcmÿ3

HeatoffusionÁHf

kJmolÿ1

(8)(9)

HeatcapacityCp

JKÿ1gÿ1

(10)

GlasstransitiontemperatureTg

K

(5,6,8,10,11)(12)(1,5,8)(12)

MeltingpointTmK(13)

(5,6,8,10,11)

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Poly(lacticacid)

PROPERTY

UNITS

CONDITIONS

VALUE

REFERENCE

EquilibriummeltingpointSecondaryrelaxationtemperature

DecompositiontemperatureTd

KKK

L-PLAofMv󰂈550,000L-PLA

󰀌-relaxationat1Hz(95%L-isomer)L-PLAofMw󰂈󰂅0X5±3󰂆Â105

D,L-PLAofMw󰂈󰂅0X21±5X5󰂆Â105

488480228508±528528

(2)(14)(15)(5)

Mark±Houwinkparameters:Kanda

Isoform

Solvent

Temp.(8C)

Conditions

KÂ103(mlgÿ1)

a

Reference

AtacticAtacticAtacticAtacticAtacticAtacticAtacticIsotacticIsotacticIsotacticBenzeneChloroformChloroformChloroformChloroformEthylacetateEthylacetateBenzeneChloroformChloroform30252525302525302530ForForForForForForForForForForMvMnMwMvMvMnMwMvMvMv2.276.606.061.332.211.581.635.722.485.450.750.670.640.790.770.780.730.720.770.73(16)(1)(1)(12)(16)(1)(1)(16)(12)(16)

PROPERTYUNITSCONDITIONSVALUEREFERENCE

Solvents

AcetoneatroomtemperatureBenzeneatT󰂈308C

BromobenzeneatT󰂈858CChloroformatT󰂈258C

m-CresolatroomtemperatureDichloroaceticacid

DichloromethaneatT󰂈258CDioxaneatT󰂈258CDimethylformamide

EthylacetateatT󰂈258CIsoamylalcohol

N-methylpyrrolidoneToluene

Tetrahydrofuran

TrichloromethaneatT󰂈258Cp-XyleneK

L-PLAinp-xylene

399.5

(17)(16)(18)(12)(18)(18)(9)(12)(17)(1)(2)(12)(19)(1)(9)(2)(2)

Equilibriumdissolutiontemperature

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Poly(lacticacid)

PROPERTY

UNITS

CONDITIONS

VALUE

REFERENCE

CloudpointtemperatureInteractionparameter1Swelling

Secondvirialcoef®cientA2Hugginsconstant

SterichindranceparameterCharacteristicratiohr2i0anl2Intrinsicviscosity[󰀑]

KÐ%

molcm3gÿ2ÐÐÐdlgÿ1

D,L-PLAindioxane/watermixtureL-orD,L-PLAindioxaneorchloroformatT󰂈258CL-orD,L-PLAinmethanolorwaterL-PLA®lmin0.2MpH7bufferL-PLAinbromobenzeneat858C,Mw󰂈󰂅0X8±4X9󰂆Â105AtacticorisotacticinbenzeneAtacticinbenzeneorchloroformIsotacticinbenzeneorchloroformL-PLAinbromobenzeneat858CL-PLA

InchloroformatT󰂈258CInchloroformatT󰂈308CInbromobenzeneatT󰂈858CInchloroformIndioxane

InN-methylpyrrolidoneL-orD,L-PLAinmixtureofChloroform/methanolDioxane/water

D,L-PLAinchloroformatT󰂈258CL-PLAcrystallizedfrommeltIsothermalNonisothermal

L-PLAcrystallizedfrommeltL-PLAsinglecrystalsinp-xyleneL-PLAcrystallizedfrommeltIsothermalNonisothermal

L-PLA

InbromobenzeneatT󰂈858CIntetrahydrofuran

Ð0.1±0.3Ð2

3.5±3X2Â10ÿ40.33±0.411.982.692.0

(12)(12)(12)(6)(18)(16)(16)(18)

3.8±8.22.631.384.23.22.3ÐÐ

0.1±1.52X44Â1052X69Â10560X89Â10ÿ375Â10ÿ312X03Â10ÿ313X6Â10ÿ3ÿ0X060.0558

(19)(18)(18)(12)(12)(12)(12)(12)(1)(14)(20)(14)(2)(14)(20)(18)(21)

NucleationconstantKgÐ

Foldsurfaceenergy'eLateralsurfaceenergy'

Jmÿ2Jmÿ2

Refractiveindexincrementdnadc

mlgÿ1

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Poly(lacticacid)

PROPERTY

UNITS

CONDITIONS

VALUE

REFERENCE

Opticalrotation󰂉󰀋󰂊DDegrees

L-PLAatT󰂈258CInchloroform

Inchloroformat!󰂈589nmIndichloromethane

Inchloroform/methanolmixtureIndioxane/watermixture

L-PLAinp-dioxaneat!󰂈365nmInvitro,L-PLAInvitro,D,L-PLAInvivo,D-PLAInvivo,L-PLAInvivo,D,L-PLAMechanism

ÿ151ÿ161ÿ162X8

ÿ158toÿ173ÿ165ÿ443ÐÐÐÐÐÐ

(18)(19)(16)(12)(12)(7)(17,22,23)(17)(13)(13,17)(13,17)(24)

DegradationrateÐ

L-PLA󰂅󰂉󰀑󰂊󰂈16cm3gÿ1inbenzeneatT󰂈308C)under

Atmosphere

Dose(MGy)

60

Coradiation󰂅25󰂆

Cross-linkingGfactor

ChainscissionGfactor

N2N2AirAirLow(`2.5)

Pregelregion(b2.5)Low(`2.5)

Pregelregion(b2.5)26.540.514.523.04.511.00.46.5

PROPERTYUNITSCONDITIONSVALUEREFERENCE

TensilestrengthMPa

L-PLA®lmordisk,Mw󰂈󰂅0X5±3󰂆Â105L-PLAmelt-spun®ber

L-PLAsolution-spun®berfromToluene

Trichloromethane

Chloroform/toluenemixture

D,L-PLA®lmordisk,Mw󰂈󰂅1X07±5X5󰂆Â105L-PLA®lmordisk,Mw󰂈󰂅0X5±3󰂆Â105L-PLAmelt-spun®ber

L-PLAsolution-spun®berfromToluene

Trichloromethane

Chloroform/toluenemixture

D,L-PLA®lmordisk,Mw󰂈󰂅1X07±5X5󰂆Â105

28±50Upto870Upto1000Upto1200Upto230029±351,200±3,000Upto9200Upto10,00012,000±15,000Upto16,0001,900±2,400

(5)(26)(19)(9)(3)(5)(5)(26)(19)(9)(3)(5)

TensilemodulusMPa

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Poly(lacticacid)

PROPERTY

UNITS

CONDITIONS

VALUE

REFERENCE

TensilestoragemodulusEHMPa

L-PLAvarieswithtemperatureMelt-spunmono®lamentat1HzInjection-moldedbarat3HzD,L-PLAvarieswithtemperatureFilmat110HzFilmat11Hz

L-PLAvarieswithtemperatureMelt-spunmono®lamentat1Hz

Filmorinjection-moldedbaratvariousfrequencies

D,L-PLAvarieswithtemperatureFilmat110HzFilmat11Hz

L-PLA®lmordiskMw󰂈󰂅0X5±3󰂆Â105

D,L-PLA®lmordisk,Mw󰂈󰂅1X07±5X5󰂆Â105L-PLApin

L-PLAmelt-spunmono®lamentL-PLApinL-PLApin

L-PLA®lmordisk,Mw󰂈󰂅0X5±3󰂆Â105

D,L-PLA®lmordisk,Mw󰂈󰂅1X07±5X5󰂆Â105L-PLA®lmordisk,Mw󰂈󰂅0X5±3󰂆Â105L-PLA®berspunfromtoluene

L-PLAmelt-spun®ber,Mv󰂈1X8Â105

D,L-PLA®lmordisk,Mw󰂈󰂅1X07±5X5󰂆Â105

ÐÐÐÐÐÐÐÐ

1,400±3,2501,950±2,35054.51,210±1,4301322,8003.7±1.84.0±3.56.0±2.012±26256.0±5.0

(27)(10)(8)(8)(27)(10)(8)(8)(5)(28)(27)(28)(28)(5)(5)(5)(19)(19)(5)

TensilelossmodulusEHH

MPa

FlexuralstoragemodulusShearstrengthShearmodulusBendingstrengthBendingmodulusElongationatyieldElongationatbreak

MPaMPaMPaMPaMPa%%

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