plastics additives and green chemistryadvancinggreenchemistry.org/wp-content/uploads/... · high mw...
TRANSCRIPT
![Page 1: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/1.jpg)
Plas%csAddi%vesandGreenChemistry
EvanBeach
14thAnnualGreenChemistry&EngineeringConference
![Page 2: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/2.jpg)
Addi%ves
1tonne=1000kg
106 ton
nes/yrprodu
ced
About5%(wt.)ofallplas%cisaddi%ves
Plas%cizersaccountfor>50%ofaddi%ves
Flameretardantsaccountforabout25%
![Page 3: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/3.jpg)
Consequences
persistence,bioaccumula1on,toxicity
DOTP(akaDEHP)
PBDEs
![Page 4: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/4.jpg)
Solu%onsandstrategies• Small‐molecule,drop‐inreplacementsforDOTP,PBDEsetc.
• Higher‐MWaddi%vesforreducedmigra%on
• Designingpolymerswithinherentlydesirableproper%es
&
greendesignprinciples
![Page 5: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/5.jpg)
Solu%onsandstrategies• Small‐molecule,drop‐inreplacementsforDOTP,PBDEsetc.
• Higher‐MWaddi%vesforreducedmigra%on
• Designingpolymerswithinherentlydesirableproper%es
&
greendesignprinciples
![Page 6: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/6.jpg)
ImpactsofPVC
PVCaccountsfor80%ofplas%cizeruse;theplas%cizermarketis75‐85%phthalates
0%plas%cizer 85%plas%cizer
![Page 7: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/7.jpg)
PVCconsump1onisnotexpectedtodecreaseintheshortterm
![Page 8: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/8.jpg)
PVCisonlypartofthechallenge
Biopolymersbasedoncellulose,starch,andwheatglutenwillconsumeplas%cizers
Poly(lac%cacid)(Tg=55°C)isbri_lelikePVC(Tg=82°C)andrequiresaddi%vesifitistobeusedasaflexibleplas%c
![Page 9: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/9.jpg)
Smallmoleculealterna%vestoDOTPTheliteratureaboundswithexamples.Manyalterna%vesbelongtothephthalateclass(e.g.DINP).Manyarealsoproblema%c(e.g.mellitateesters).
Certainbio‐basedfeedstocksmightbeexpectedtoresultinlesshazardousproducts.
sorbitolderivedfromglucose tuneproper%esvia
choiceoffa_yacid
C8diestershowsDOTP‐likeperformance
TerVeld,M.G.R.etal.Agric.FoodChem.2006,54,4407‐4416.vanHaveren,J.etal.inFeedstocksfortheFuture.AmericanChemicalSociety:Washington,DC,2006.
Isosorbideestersofalkanoicacidsarefullybiodegradableandpassedtestsforacutetoxicity,sensi%za%on,mutagenicity,&estrogenicity
![Page 10: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/10.jpg)
FlameretardancyisawidespreadneedDemandisexpectedtoincrease5%/yr
M.Chanda,S.K.Roy.IndustrialPolymers,SpecialtyPolymers,andTheirApplica1ons
Limi'ngOxygenIndices(LOI)ofcommonpolymers
Non‐self‐ex%nguishingpolymer
LOI Self‐ex%nguishingpolymer
LOI
polyoxymethylene 16 polycarbonate 27
polyethylene 17 polyarylate 34
polypropylene 18 polyethersulfone 38
polystyrene 18 PEEK 40
PMMA 18 PVC 42
naturalrubber 18 polyamide‐imide 43
ABS 18 poly(phenylenesulfide) 44
Nylon‐6,6 24 polyether‐imide 47
PETE 25 poly(vinylidenechloride) 60
polychloroprene 26 PTFE 95
TheLOIforself‐ex%nguishingisusuallytakenas27,not21(thevolume%ofO2inair)tocorrectforlackofconvec%vehea%nginthetestmethod.
![Page 11: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/11.jpg)
Flameretardants
Source:SRIConsul%ng/h_p://www.flameretardants‐online.com
Goal:compa%blewithplas%cs,effec%veatreasonablelevels,non‐leaching,non‐toxic
![Page 12: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/12.jpg)
Non‐halogenatedflameretardants
• 2007AddConconference:nopapersonhalogenatedchemicals,althoughflameretardantsmadeuponeofthelargestgroupofsubmissions
• Governmentandindustrygroupshaveconductedextensivereviews,e.g.h_p://www.nonhalogenated‐flameretardants.com
• Fewerexamplesfrombio‐organicfeedstocks
• Solu%onsareolenbasedonmechanismsspecifictoapolymer
![Page 13: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/13.jpg)
MolecularHeatEater®• Powderorgelbasedoncarbonateandphosphatesaltsandbenignorganic
acids– citric
– glutaric
– succinic
– oxalic
– formic
– ace%c
– stearic
Someareagriculturalwasteproducts
Sub‐micronpar1clesrequireastrongendothermicreac1ontodecompose
![Page 14: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/14.jpg)
MHEinac%onuntreated treated
![Page 15: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/15.jpg)
Solu%onsandstrategies• Small‐molecule,drop‐inreplacementsforDOTP,PBDEsetc.
• Higher‐MWaddi%vesforreducedmigra%on
• Designingpolymerswithinherentlydesirableproper%es
&
greendesignprinciples
![Page 16: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/16.jpg)
HighMWplas%cizers
• Limitmobilityinpolymermatrix
• Preventtransportacrossbiologicalmembranes
• Degrada%onproductsmustbeconsidered
1,3‐propanediolfromglucoseviaglycerol(engineeredE.coli)
Adipicacidfromglucose(engineeredmicrobes)
MW1500‐2500Da
isabe_erplas%cizerforPLAthan:
MW371
Mar%no,V.P.;Jimenez,A.;Ruseckaite,R.A.J.Appl.Polym.Sci.2009,112,2010‐2018.
![Page 17: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/17.jpg)
Strategiesforhigh‐MWflameretardants• Copolymeriza%onwithspecialmonomers,gralingreac%veaddi%vestobackbone
– Flameretardancyis“permanent”
– Lessdisrup%onofpolymerproper%es
– Effec%veatlowerloadingsthanlow‐MWaddi%ves
Lu,S.‐Y.;Hamerton,I.Prog.Polym.Sci.2002,27,1661‐1712.
![Page 18: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/18.jpg)
Mul%‐wallcarbonnanotubes
max.heatreleaserate~800kW/m2
max.heatreleaserate~500kW/m2
2%nanotubes
• Effec%veinpolycarbonate,polyamide,polyethylene,polypropylene,polystyrene
• Cannotstandalone–butpromising
• Nohalogens,metals,orphosphorus
Schartel,B.etal.Polym.Eng.andSci.2008,48,149‐158.
![Page 19: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/19.jpg)
Solu%onsandstrategies• Small‐molecule,drop‐inreplacementsforDOTP,PBDEsetc.
• Higher‐MWaddi%vesforreducedmigra%on
• Designingpolymerswithinherentlydesirableproper%es
&
greendesignprinciples
![Page 20: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/20.jpg)
Plas%citywithoutaddi%ves:thermoplas%celastomers(TPEs)
• Metallocene‐catalyzedpolyolefins:“thethreattoflexiblePVC”– 1millionlbpolymer/1lbcatalyst/1hr
– JournalofVinylandAddi1veTechnology,1998:poten%altocapture50%oftheflexiblePVCmarket(30‐40%plas%cized)
Wilson,R.B.,Jr.J.VinylAddit.Technol.1998,4,84‐86.
![Page 21: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/21.jpg)
TPEsfromBiobasedMaterials
• Polyethers
• Polyamidesbasedoncanola,castoroil
• Polyurethanesfromvegetableoil
Mizuno’s2009runningshoemodelscontainPebax®Rnew,abio‐basedTPE(upto94%renewablecarbon)
Markarian,J.Plas1csAddi1ves&Compounding2008,10,38‐43.
![Page 22: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/22.jpg)
InherentlyFireRetardantPolymers
Self‐ex'nguishingpolymer
LOI
polycarbonate 27
polyarylate 34
polyethersulfone 38
PEEK 40
PVC 42
polyamide‐imide 43
poly(phenylenesulfide) 44
polyether‐imide 47
poly(vinylidenechloride) 60
PTFE 95
Zhang,H.U.S.DepartmentofTransporta%on,FederalAvia%onAdministra%on,OfficeofAvia%onResearch,2004.
poly(hydroxyamide) poly(benzoxazole)
![Page 23: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/23.jpg)
Challenges• Cost,mechanicalperformance,processingdifficul%es
• Mechanis%cunderstanding– Heteroatoms(N,O,P,S,halogens)
– Aroma%crings
– Heteroatomicrings
– Pro‐crosslinkingorpro‐cycliza%onchemicalgroups
Kevlar®(paralinkages)
Nomex®(metalinkages)
Whysuchasignificantdifferenceinheatrelease?
Zhang,H.U.S.DepartmentofTransporta%on,FederalAvia%onAdministra%on,OfficeofAvia%onResearch,2004.
![Page 24: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/24.jpg)
Inspira%onfromnature:woolWoolfoamsratherthanburns.Igni%ontemperatureis570‐600°C(higherthanrayon,nylon,polyester)
Aneffectofmicrostructure?Chemicalcomposi%on?Both?
Be_erunderstandingofnaturallyflameretardantmaterialswillleadtoinnova%oninfire‐safe,bio‐basedplas%cs
CSIRO,FlameResistanceofWool
![Page 25: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/25.jpg)
Solu%onsandstrategies• Small‐molecule,drop‐inreplacementsforDOTP,PBDEsetc.
• Higher‐MWaddi%vesforreducedmigra%on
• Designingpolymerswithinherentlydesirableproper%es
&
greendesignprinciples
![Page 26: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/26.jpg)
Reducinghazard(atalllifecyclestages)
Useofrenewableresourcesistobeencouraged,butitcannotbetheonlymetric
![Page 27: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/27.jpg)
Conclusions
• Func%onalalterna%vestoDEHPandPBDEsareabundant
• Bio‐basedchemicalplaxormsare(andwillbe)asourceofinnova%on
• Allgreenprinciplesshouldbemetbynewmaterials,toavoidtheproblemsofthepast
![Page 28: Plastics Additives and Green Chemistryadvancinggreenchemistry.org/wp-content/uploads/... · High MW plas%cizers • Limit mobility in polymer matrix • Prevent transport across biological](https://reader035.vdocument.in/reader035/viewer/2022063001/5f1506411cea40376677009b/html5/thumbnails/28.jpg)