ICGCSD BeyondCl2 181204€¦ · 1/3/19 3...
Transcript of ICGCSD BeyondCl2 181204€¦ · 1/3/19 3...
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WORKSHOP(ON(GREEN(AND(SUSTAINABLE(CHEMISTRY:(FOSTERING(CHEMICAL(SAFETY(AND(SECURITY(THROUGH(INNOVATION,(
THE(HAGUE,(THE(NETHERLANDS,(4(– 5(DECEMBER(2018
Chemistry*beyond chlorine:"improving safety"and"security"in"chemical"management
Pietro"TundoIUPAC"Interdivisional"Committee"on"Green"Chemistry"for"Sustainable"
Development
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CHLORINE)IS)A)MAJOR)BUILDING)BLOCK)IN)TODAY’S)CHEMISTRY
! Plastics (polyvinyl chloride, PVC, one of the most widely used plastic materials)
! Solvents for dry cleaning and metal degreasing,
! Textiles
! Agrochemicals and Insecticides (86 % of crop protection chemicals contains chlorine)
!Pharmaceuticals (90 % of pharmaceuticals contain or are manufactured using chlorine)
!Dyestuffs
!Household cleaning products and disinfectants.
!Oxidizing agent (i.e., water disinfectant)
!In Chemistry as leaving group in substitution and elimination reactions.
!As intermediates in the production of a number of important commercial products that do not containchlorine (polycarbonates, polyurethanes,silicones, polytetrafluoroethylene, carboxymethyl cellulose, andpropylene oxide)
Chlorine chemistry
European)chloro-alkali)industry)production)in)2009:)
! 9.1 million tonnes
! 80 plants, mostly (about 95 %) via electrolysis;based techniques (chlor;alkaliindustry);
! 40 000 people in 20 European Union (EU) countries.
! Germany is Europe’s largest chlorine producer, accounting in 2009 for 43.5 %of European production
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Environmental,and,health,concerns
!In 1960s studies about DDT Concerns about the environmental and healthimpact of halocarbons revealed and other halocarbon pesticides.
!Recently (2006) attention raised even about very stable molecules such asperfluorooctanoic acid (PFOA) and Teflon.
!The EU has recently established REACH (Registration, Evaluation,Authorization and Restriction of Chemicals), a single integrated system forthe registration, evaluation, and authorization of chemicals, together with theEuropean Chemicals Agency (ECHA).
!Some international conventions ban or restrict production of specificchemicals i.e., The Stockholm Convention on Persistent Organic Pollutants.
! In 2007, the Intergovernmental Panel on Climate Change (IPCC) stated thatsome halocarbons were a direct cause of global warming, owing to theirnature as GHGs.
Chloroform,)anesthetic)
1,2)Dichloroethane,Solvent.)PVC)manufacture.
PCB,insulator
2,3,7,8>TCDD,)side)product
DDT),)insecticide
Pentachlorophenol,wood)preservative
Dichlorofluoromethane,)refrigerant Hexachlorobenzene,
fungicide
Organochlorine substances (examples), that were regulatedto prevent toxicities, pollution, atmospheric reactivity….
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The$Chlorine industry
Chloro&Alkalimanufacturing
Cement Iron and5Steel AmmoniaProduction
Kg$CO2/Kg 1.5 0.95 1.7 1.3
World$Production$(2008)
Europe,$20MtonsChina$21Mtons
2.3$Btons 1.2$Btons 150$Mtons
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Energy
• Chlorine)industry)is)extremely)energy2intensive,)giving)a)contribution)comparable)to)the)iron)and)steel)industry)in)terms)of)CO2 production/kg)product
• Chlorinated molecules have both a direct (as GHGs) andindirect (CO2 production) impact on climate change at aglobal level
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Can$we$pursue$an$intrinsically$safer,$cleaner,$and$more$
energy6efficient$alternative$to$chlorine6chemistry?
The substitution of compounds where“chlorine is used in the making” meansthat we avoid electrolysis as primaryenergetic source: this however makeschemistry “without chlorine” considerablymore difficult and illustrates why it hasnot been adopted before.
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SPECIAL(TOPIC(ISSUE(ON(CHLORINE/FREE(SYNTHESIS(FOR(GREEN(CHEMISTRY
CONTENTS'OF'SPECIAL'TOPIC'ISSUE
Rationale: to seek useful and industrially relevant examples for alternatives to chlorine insynthesis, so as to facilitate the development of industrially relevant and implementablebreakthrough technologies.
30 Contributions dealing with:
Part@1:@ChlorineBfree@reagents@
Part@2:@ChlorineBfree@catalysts
Part@3:@Carbonate@chemistry
Part@4:@ChlorineBfree@solvents
Part@5:@Benign@chloroBfree@methodologies
Part@6:@Metrics@of@chlorineBfree@syntheses
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© 2016 ISBN 978-3-319-30071-9
Chemistry Beyond ChlorineEditors: Tundo, P., He, L.-N., Lokteva, E., Mota, C.
20.000 downloads
WORKING(PARTY(ON(HAZARD(ASSESSMENT PROJECT:
INTERNATIONAL(BEST(PRACTICES(FOR(IDENTIFICATIONOF((PRIORITIES(FOR(RISKASSESSMENT
Expert(Workshop(on(Approaches(to(SupportAlternativesAssessment(and Substitution
2M3(May,(2018(– Paris, France
Eeva(Leinala,(OECD Secretariat
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Next%Steps%– OECD%%Adhoc%Group%on%%SubstitutionEeva%Leinala,%OECD SecretariatParis,%May%2018
Strategy(to(promote(substitution(to((safer(chemicals(through((innovation
OECD Expert workshop on approaches to support alternatives assessment and substitution
Paris,(2(May 2018
Denis MottetScientific officerRisk(Management(Implementation Unit
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• Goals and approach• Four action areas• More information
Outline
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Substances of low priority under ECHA’s integrated regulatory strategy
European Chemicals Agency
OECD Expert workshop on approaches to support alternatives assessment and substitution
Paris, 3 May 2018
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Content• Integrated Regulatory strategy• Low priority substances under the integrated
regulatory strategy – (de-)prioritisation• Examples
www.brsmeas.org @brsmeas
Identification+and+Documentation++of+Alternatives+4 Learnings+from++
the+Stockholm ConventionKei$Ohno Woodall
Secretariat$of$the$Basel,$Rotterdam$and$StockholmConventionsParis,$May$2018
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Approaches toSupportSubstitutionand11AlternativesAssessment:
Perspectives from theU.S. EPA’sSafer1ChoiceProgram
Paris,1May12, 2018
! AlternativesAssessments! Product Labeling! Safer6Chemical6Ingredients List
Outline
Safer&Choice Program 2
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Identifying*Potential*Candidates for Low4Priority*SubstanceDesignation Under*
the*Toxic*Substances*ControlAct(TSCA)
Lauren'Sweet,'US EPAParis,'May'2018
! Background+on TSCA! Definitions+and+considerations+for+chemical prioritization! Public+Meeting+held+in+December 2017! Relevant+approach:−+Safer+Chemical+Ingredients List
! Summary+of+stakeholder+feedback+and+EPA’s+thinking movingforward
Outline
2Safer&Choice Program
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Safety'and'health'at'work'is'everyone’s'concern.'It’s'good'for'you.'It’s'good'for business.
Training'material'for substitutionOECD'Expert'Workshop'on''Approaches'to'Support Alternative''Assessment'and'Substitution''Paris,'May'2'– 3, 2018
Lothar'Lieck, EUKOSHA
Für$Mensch$&Umwelt
OECD%Expert%Workshop%on%Alternative%Assessment%and Substitution
Activities%of%the%German%Environment%%Agency%in%Sustainable%Chemistry%to%%Stimulate%Substitution
ChristopherBlumGerman$Environment$Agency$$International$Chemicals ManagementParis,$May$2018
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Outline1 SUSTAINABLE+CHEMISTRY+FOR+SUSTAINABLE DEVELOPMENT
2 SUSTAINABLE+CHEMISTRY:+TOOLS+FOR+ALTERNATIVE+ASSESSMENT+AND SUBSTITUTION
a) The&Guide&on&Sustainable&Chemicals&/ SubSelect
b) The&Chemical&Leasing&Checklist&and&SMART 5
3 THE+INTERNATIONAL+SUSTAINABLE+CHEMISTRY+COLLABORATIVE CENTRE
4 SUMMARY
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Activities+of+the+German+Environment+Agency+in+Sustainable+Chemistry+to+Stimulate Substitution
OECD&Expert&Workshop&on&Alternative&Assessment&andSubstitution
2nd&May2018
Presenter'Name'+ Title
A'Look'at'Informed'Substitution'in'Canada’s''Chemicals'Management'Plan'and Beyond
Sarah'Vanden'HovenOECD'Workshop'on'Informed'Substitution
Paris,'May 2, 2018
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• Chemicals+Management+in Canada– Background,+Current+Status+and+Moving Forward
• Looking+at+Informed+Substitution+in Canada– Past,+Current work– Potential+areas+of+future work
Overview
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Reflections+on+the+OECDCross++CountryAnalysis:
1
Insights+from+assessments+of++opportunities+to+advance+alternatives++assessment+and+informedsubstitution++
efforts
Molly+Jacobs++University+ofMassachusetts
Lowell+May+2,2018
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Experience)from)Sharing))Information)on)Alternatives))from)the)OECD SAAToolbox))Case)Studies Section
Paris,'May'2,'2018
Emily'Connor,'AbtAssociates
OECD%SAATToolbox:%%Possible%Additions%andNew%%Functionalities
Paris,'May'2,'2018
Emily'Connor,'AbtAssociates
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Abt$Associates$|"pg 2
OECD%Substitution%and Alternatives%%Assessment Toolbox
! Brings"together"practical""resources"on"chemical""substitution"and alternatives""assessments
! Development"a collaborativeeffort
! Launched"in"February [email protected]
! Updated"on"an"ongoing basis
Approaches to support substitution
RIVMDutch National Institute for Public Health and the Environment
Susanne Waaijers-van der LoopJulia Verhoeven Margaret Wouters
Alternatives Assessments - OECD| 2-3 May 20181
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Instruments)in)the)Netherlands)supporting substitution
● Safe Chemicals Innovation Agenda (see presentation Jochem van
der Waals, Ministry I&W)
● Stakeholder dialogue antifouling
● Website about substitution
● Green Deal plant protection products (sports & recreational fields)
● National Policy Substances of Concern “ZZS” (links to REACH)
– Reduction and prevention of emmissions
● Sustainability methods
● Biobased alternatives this presentation
● REACH restriction and authorisation2 The sharp edges of circular economy | 20 April 2018
Structure
• Project approach• Key concepts• Results• Towards implementation
2 11 May 2018Ministry of Infrastructure and Water Management
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The$Danish$partnership$for$$substitution$and theEco4innovation Programme
OECD%Expert%workshop%on%substitution%%Paris,%
May%3rd, 2018Sidsel%Dyekjær,%Danish EPA
How$DEPA$work$with substitutionMUDP
Development-and-demonstration-programme--for-Environmental Technology
Funding-for-development-of-many-types-of-environmental technology,
Including-funding-for-substitution-of-hazardous-chemicals-in-products-andprocesses
The-Chemicals InitiativesFinance-of-the-DEPA-work-on-hazardous-chemicals-in-general,-including-our-dataDand--information-gathering,-reporting,-preparation-of-proposals-for-new-
legislation,--enforcement,-communication-with-stakeholders etc.
Normally(based(on(political(agreements,(with(all(the(parties(in(“Folketinget”((Danish Parliament).Agreements(have(been(made(for(4Cyear(action(plans(since2006.The(2014(– 2017(plan(included(a(new(Partnership-for substitution
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Chemical)Substitution/)Selection Process– how)do)we)choose)alternative substances
Christine)Lukas)EH&S)Product)Stewardship)and)Fire)Safety ManagerOn)behalf)of)Dow)Performance)Building SolutionsParis,)May)2018Dow.com
OECD EXPERT WORKSHOP ON APPROACHES TO SUPPORT ALTERNATIVES ASSESSMENT
AND SUBSTITUTION
OECD%Conference%Centre,%Paris%%2%3 3%May, 2018
ICGCSDInterdivisional Committee onGreen Chemistry for Sustainable Development
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Dimethyl)Carbonate
(Hard)
(Soft) (Soft)
An Ambiphilic electrophile
Dimethyl carbonate:0Properties
Carboxymethylating and1methylating agents a1
comparison
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Dimethyl)Carbonate)Utilization
Coatings)&)Paints28%
Agrochemicals12%
Electrolyte)Solvent2%
Pharmaceuticals,)Cosmetics)etc
5%
Captive((most(polycarbonate)
53%
Merchant
Dimethyl Carbonate/Reactivity/
NuH$(Hard)BAc2$Mechanism
NuCOOCH3 +$CH3OH
(Hard)
T$=$90$°C
NuH(Soft)$
+$CH3OH$+$CO2$NuCH3
BAl2$Mechanism
(Soft)
T$=$150$°C
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Nucleophilic substitution.occurs.more.easier.if:
i)#A#less#hindered#carbon#is#involved,#as#methyl#shows#the#faster#reaction#rate.#
ii)#Electronic#effects#are#involved#(induction,#conjugation,#etc.)#iii)#A#cyclic#molecule#is#formed#(entropic#effect).#iv)#An#anchimeric assistance#by#neighboring#groups#is#present#(like#mustard#derivatives)
All#such#effects#are#present#in#carbonate#chemistry#and,#over#the#years,#they#have#
led#to#the#unexpected#results.
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Phosgene replacement
1. Polycarbonate production
2. methylisocianate
Alkyl halides replacement
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Dimethyl carbonate:0Reactivity
CH3OCOOH
pKa =)1.7
Methoxycarboxyl anion as leaving group
Methylcarbonic acid
NH2CH2COOH) CH3COOHpKa =)1.99 pKa =)))))))))))))4.76
HSO4E Maleic Acid)
pKa =)1.99))))) pKa1 =)1.99;)pKa2)=)6.58)
Chlorine)based.SN2.chemistry
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DMC$based*SN2*chemistry
Methylation of Phenols, Thiophenolsand Thiols under GL-PTC conditions
ArOH +&DMC catalytic bed(PEGs +&&K2CO3)&
ArOCH3CO2 +&CH3OH
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Monomethylation of methylene-active compounds
ArCH2X''+''DMC ArCH(CH3)X''+''CH3OH''+'CO21802200°C
X Ar Conv.)%
Selectivity)in)Monomethylati
on
Intermediatefor
CN 4;isobuthylphenyl 99 99 Ibuprofen
CN 3;carboxymethylphenyl 100 >99 Ketoprofen
COOCH3 2;(6;methoxynaphtyl) 100 >99 Naproxen
K2CO3
Intramolecular,cyclisations
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Cyclicðers&by&DMC/mediated&intramolecular cyclisation
The$case$if isosorbideand$
dimethyl isosorbide
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Synthesis)of)Cyclic)ethers)via)DMC)chemistry:)industrial)applications
92)%
92)%
IMPROVED)SYNTHETIC)APPROACH
(4.)eq.)mol)
From%renewables%to%green%solvent:%an%improved%synthetic%pathway%to%dimethyl%isosorbide
O
OOH
HO
O
OMeO
OMe
DMIISOSORBIDE
H
H
H
H
DMC, 90°C
base
! The advantage of using solvents derived from renewables is that natural products are present in largeamounts, although only a small fraction (ca 4%) is used
! Dimethyl isosorbide (DMI) is extensively used in cosmetics, primarily as a solvent, but also as a thinningagent. DMI is a potential green solvent with broad applications
!Currently DMI is synthesised by a common methylation reaction which employs toxic and pollutingreagents (i.e. dimethyl sulfate).
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Sulfur&and&Nitrogen&Mustards&
Sulfur&and&Nitrogen&Mustards
From&war&chemistry&to&green&chemistry&
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RS
OH
RS
Cl
RS
OCOOMeDMC
HClmustard-like
innocuous
Sulfur&and&Nitrogen&Mustard&Carbonates:&Reactivity&
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Azacrown from+mustard+carbonate+Analogues
4,15-dimethyl-3,4,5,6,14,15,16,17-octahydrotetranaphtho[2,1-h:1',2'-j:2'',1''-s:1''',2'''-u]-2H-13H-1,7,12,18-tetraoxa-4,15-diazacyclodocosine
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A"POLYMER"FROM"MUSTARD"CARBONATE)ANALOGUES
Tundo p.(and(Arico’(F.(PCT/IB2018/054621(< 22"June"2018
WORKSHOP(ON(GREEN(AND(SUSTAINABLE(CHEMISTRY:(FOSTERING(CHEMICAL(SAFETY(AND(SECURITY(THROUGH(INNOVATION
THE(HAGUE,(THE(NETHERLANDS,(4(– 5(DECEMBER(2018
Chemistry*beyond chlorine:"improving safety"and"security"in"chemical"management
Thank"you"for"your"attention