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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

17

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

2

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

2

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 2015@www.oecdsaatoolbox.org

! 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

42

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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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Cyclic&ethers&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