sustainable solvents products and process ... - Chemspec Events

Thierry Vidal : June 14th, 2012SUSTAINABLE SOLVENTSPRODUCTS AND PROCESS INNOVATIONS

Contents The reasons to develop new solvent based solutions MGN Chain or how reduce NOx release by creating innovative solutions Rhodiasolv® Iris Rhodiasolv® PolarClean OutlookRoyal Society of Chemistry Symposium 2012 – Not Costing the Earth

Aspiring to a Greener WorldThe world is requiring a new chemistry to provide abetter environmental-costcost-efficiency balance.Competitivenessof the new solutionThe rightperformance for theapplicationRenewable Source,Reduction of HSEimpact Green alternatives not competitive so far as costs are driven mostly by oil price Solvent innovation lagging behind evolving legislation to protect environmentand humansRoyal Society of Chemistry Symposium 2012 – Not Costing the Earth

MGN Chain : Rhodiasolv® IRIS based solutionsNew biodegradable and Eco-friendly solvents and formulationsHazardous solvents substitution by responsible solutionsRoyal Society of Chemistry Symposium 2012 – Not Costing the Earth

“Green Solvent” Platform,Roots in the valorisation of Polyamide 6-6 by-productsRawmaterialsCyclohexane Methanol Ammonia Natural gas ButadieneNOxreleaseProduct and intermediaryKA OilAdipic Acid+ DiacidesC4, C5 ,C6linear byproductsalreadyvalorisedRPDEIRISMGNby-productburned untilnow (energyvalorisation)PolarcleanADNHMDASalt NylonMarketsPolyurethaneDiesters & Esteramides familiesNylon 66Textiles, automotive polymersRoyal Society of Chemistry Symposium 2012 – Not Costing the Earth

From a classical synthesis to the Graal (no effluent process)• Traditional process• Use of Acid/Base reactants• Generation of high quantities of salts and effluents (more salts than the product itself)• Non environmentally sustainableSulfuric AcidNH4HSO4EffluentsMGN Diacide IRISMeOH• New catalytical process• Process without salt generation• R&D to develop an extensive chemistry with the use of efficient catalytical systems.• Raw material and energy efficient (high catalytical yield, no reactant, ammoniarecycling on the Nylon chain)Recycled inNylon chainGas phase calatysis Liquid phase catalysisMGNImideIRISNH3 MeOH NH3Royal Society of Chemistry Symposium 2012 – Not Costing the Earth

New process highlights.Step1: MGN Catalytic hydrolysis for the Imide formationStep 2: MGI catalytic esterification to get IrisStep 1 Step 2Process Heterogeneous gas phase Homogeneous liquid phaseT < 250°C 150 - 250 °CP Atm Under pressureCatalyst Ti based catalyst La based catalystPerformancesSelectivity Very High Very HighRoyal Society of Chemistry Symposium 2012 – Not Costing the Earth

One of the lowest carbon footprint of its generationProcess Cost Comparison• New process strength• No salts generation• NH3 valorisation in Nylon chain• No release – all by/co-products may be valorised• Raw material and energy significant savings• Process using intensified technologiesOthersUtilitiesRaw MaterialsInitial processNew ProcessRhodiasolv ® IrisAcetoneDichloromethaneN-MethylpyrrolidoneClimate Change (Kg CO2 Eq.)1.82.23.44Natural Resources (MJ)47694189RiskR11, R36, R66, R67R20, R22, R40R36, R37, R38, R61ClassificationF+, XiXn, CMR3T, Xi, CMR 2Main LabelRoyal Society of Chemistry Symposium 2012 – Not Costing the Earth

Rhodiasolv ® IRIS may replace toxic, carcinogenic or volatilesolvents (NMP, DCM, Acetone)• IRIS has excellent Health, Safetyand Environmental profile:• biodegradable• non toxic• non mutagenic• non flammable• low VOC emission (1999/13/EC)SolventRhodiasolvIRIS DiesterAcetoneDCMNMPFlammability(Flash point)Non flammableFlammableNon flammable86°CEvaporationloseVery lowVery highVery highLowHealth andsafetyNon toxicNon irritantFlammableToxicPot. Carc.S2 2009:Reprotoxic• With good solvency propertiesallowing replacement of existingformulations containing highconcern solvents:• Chlorinated (DCM)• Pyrrolidone (NMP), Butyrolactone• Ketone (Acetone, MEK)• Aromatics (Toluene)• Glycols ethers (MEG), DMSORoyal Society of Chemistry Symposium 2012 – Not Costing the Earth

Rhodiasolv® Iris : Physical PropertiesRhodiasolv IRISCAS number [14035-94-0]OOBranchedCH 3 -O-C- C4 -C-O-CH 3Composition :- dimethyl 2-methylglutarate : 87 - 89 %- dimethyl ethylsuccinate… : 9 -11 %- dimethyl adipate………… : 1 - 2 %Molar masse………………..: 174.2 g/molRefractive index nD at 20°C : 1.4259 ± 0.0003Density at 20 °C…………… : 1.055 ± 0.001 g/cm 3Dynamic viscosity at 20 °C… : 2.85 ± 0.01 mPa.sSurface tension at 23°C……. : 33.0 ± 0.2 mN/mBoiling pt (1013 hPa)……….. : 218 ± 2 °CVapor pressure (20°C)……… : 6.3 PaFreezing point………………. : < - 60 °CKb value ……………………. : 84.5Evaporation rate (at 50°C)…. : 0.040 ± 0.003(n-butyl acetate = 1)Flash point……………….…. : 98 ± 1 °C(Closed cup)Solubility at 23°C – g in 100 g -- of the solvent in water…… : 2.5 ± 0.2 %- of water in the solvent…… : 2.2 ± 0.1 %Hildebrand solubility parameter :δ = 19.4 (J/cm 3 ) ½Hansen solubility parameters :δ D = 16.6 (J/cm 3 ) ½δ P = 8.7 (J/cm 3 ) ½δ H = 5.0 (J/cm 3 ) ½Royal Society of Chemistry Symposium 2012 – Not Costing the Earth

Efficient alternative for Resin Clean-up• Resin clean up• Powerful solution for dissolving resins : Epoxy, Polyester, Alkyd, Polyurethane, Vinyl, etc• Alternative for: NMP (reprotoxic, irritant); DCM (dangerous); Acetone (Flammable, irritant) asdissolution times are in the same range as existing solutions• The low evaporation rate makes it a cost effective solution: limits atmospheric emission, reducesfire risk in industrial installations, and allows recyclability5040302010Unsaturated Polyester Resins Dissolution Time0AcetoneRhodiasolv® IRISRhodiasolv® IRIS (T=40°C)Hand Lay Up/Spray UpResin (visc 200mP a.s)High Quality Coatingand Gelcoats resin(visc 1000 mP a.s)High QualityBM C/ SM C Resin (visc1800 mP a.s)9080706050403020100B ip heno l A b asedresin - D GEB AAcetoneN-Methyl PyrrolidoneRhodiasolv® IRIS (T=40°C)Epoxy Resins Dissolution TimeB ip heno l F b asedresin - D GEB FN o vo lac resin - Pheno lF o r mald ehyd eMethylene ChlorideRhodiasolv® IRISRoyal Society of Chemistry Symposium 2012 – Not Costing the Earth

Efficient alternative for Paint Stripping formulations• Paint stripping• Replacement of: DCM (Dangerous and limited use by European directive 76/769/EEC)• Our offer is a full formulation based on Rhodiasolv ® IRIS that boost performance; customersuse this product to formulate paint-strippers with the correct balance of performance andlabeling for the intended application and user group• Rhodiasolv ® IRIS formulations give similar performance to other DCM free product on thismarket, but• Biodegradable, No “Harmful” and flammable labeling• Non flammable, efficient on a wide range of paint and coatings• On classicalpaint, (alkyds),same efficiencythan best stripperon market afterfew minutesapplication.Royal Society of Chemistry Symposium 2012 – Not Costing the Earth

Rhodiasolv® INFINITY, an efficient subsitution solutionfor cleaning and degreasing• Aqueous formulations and micro-emulsions based on Rhodiasolv ® IRIS for safercleaning and degreasing solutions:• No Hazardous classification allowing a cleaning at neutral pH,• Solutions not VOC and flammable classified ,• Very low odour solutions,• Can substitute aromatic BXTs and flamable solvents, used for example in caustic cleaning. Inrelation with directives 1999/13/EC & EC/1907/2006.• Rhodiasolv ® INFINITY presents a wideapplication range• Cleaning applications (paints, graffiti, resins,textiles, taches murales)• Wide range (ink, pen, food, greases)• Comparable efficiency as aromatics & causticsolutions.Royal Society of Chemistry Symposium 2012 – Not Costing the Earth

Rhodia Agrochemical FormulationsRhodia’s Novel Safe Polar SolventFor Crop Protection FormulationsRhodiasolv® PolarClean

Solvent key role in crop protectionDirect impact of the solvent choice on the ai’s performance.First selection after all other inerts (emulsifier package, adjuvants…) for liquid formulationdevelopmentSolvent play many roles in crop protectionSynthesisChemical reactionand by-productsDiluentsAi’s concentrationAi’s stabilityCarriers enhanceCoverageWetting, sticking, rain fastnessPenetration, translocationRoyal Society of Chemistry Symposium 2012 – Not Costing the Earth

Solvent Benchmark: new solvent recently launched or currentlyused as green or safer solvents in plant protection formulations.ChemistryRaw materialsTox EcotoxLabellingBiodegrad.Boillingpoint °CN, N dimethylocta/decamideFatty acid shortchain from oilXi,R36/R38Readily274N, N dimethyl lactamideLactic acidXi,R36/R38Readily2232 ethyl hexyl lactateLactic acidXi R36/38Skin, eyesReadily246Gamma butyro lactoneGHB, THFXn HarmfulR22/R36Readily205Tetrahydrofurfuryl alcoholFurfuralXi, R36Readily178Glyceryl carbonateGlycerolNoneReadily110 - 115Methyl caprylate caprateFatty acid shortchain from oilNoneReadily200Royal Society of Chemistry Symposium 2012 – Not Costing the Earth

Rhodiasolv ® PolarClean has a goodenvironmental profileToxicological and ecotoxicological dataSTUDY GUIDELINE RESULTAcute Daphnia immobilisation OECD202 CE50 (48H) > 100 mg/lAlgal Growth Test OECD201 CE50 (72H) > 100 mg/lAcute toxicity on Fish OECD203 LC50 (96H) > 100 mg/lBiodegradation (dosed bottle) OECD301F/302B Inherently biodegradableAcute Skin irritation in vivo OECD404 Not irritantAcute eye irritation in vitro (BCOP test) OECD437 Not R41Acute eye irritation in vivo OECD405 Classified as R36Skin sensitization (local lynde node assay) OECD429 Not sensitizingAcute oral toxicity in the rat OECD423 > 2000 mg/kgGene Mutation in bacteria (Ames test) OECD471 Not mutagenicRoyal Society of Chemistry Symposium 2012 – Not Costing the Earth

Rhodiasolv® PolarClean Chemistry Purity: > 98 % Mixture of esteramide and diamide, ratio = 20 : 1Royal Society of Chemistry Symposium 2012 – Not Costing the Earth

Rhodiasolv ® PolarClean iseasy-to-use and to-handlePhysical Properties of Rhodiasolv ® PolarCleanMolar Mass 187.8Refractive Index, nD at 20°C 1.4610 ± 0.0005Density at 20°C 1.043 ± 0.001 g/cm 3Surface tension36.3 ± 0.3 mN/mBoiling Point (1013 hPa) 280 ± 2 °CVapore pressure (20°C)

Rhodiasolv® Polarclean is a powerful solutioncompared to conventional solvents 1/2.Rhodiasolv®PolarcleanApplication Tests on market products0 = not soluble1 = stable 7d @ RT2 = stable 7d @ O°C3 = stable 7d @ 0°C with seedingADMA 8-10Alachlor 48%3Propoxur 20% Chlorpyrifos 40%2Alachlor 48%3Propoxur 20% Chlorpyrifos 40%2Oxyfluorfen 22%alpha-Cypermethrin 10%Oxyfluorfen 22%alpha-Cypermethrin 10%11Difenoconazole 25% 0Phenmedipham 16%Difenoconazole 25% 0Phenmedipham 16%Trifluralin 40%Propanil 36%Trifluralin 40%Propanil 36%Triadimenol 23%Tebuconazole 25%Pendimethalin 33%RhodiaSolv IRISTriadimenol 23%Tebuconazole 25%Pendimethalin 33%Oxyfluorfen 22%P ropoxur 20%Alachlor 48%32Chlorpyrifos 40%alpha-Cypermethrin 10%NN Dimethyl octa/decanamideThe market referencein terms of crystal growth inhibitor1Difenoconazole 25%0Phenmedipham 16%Trifluralin 40%Propanil 36%Triadimeno l 23%Pendimethalin 33%Tebuconazole 25%Solubility of various agricultural actives in Rhodiasolv® PolarClean compared to raw material andother amides commonly used in agrochemicals.Royal Society of Chemistry Symposium 2012 – Not Costing the Earth

Rhodiasolv® Polarclean is a powerful solutioncompared to . conventional solvents 2/2Oxyfluorfen 22%Rhodiasolv®PolarcleanAlachlor 48%3Propoxur 20% Chlorpyrifos 40%21alpha-Cypermethrin 10%Oxyfluorfen 22%Application Tests on market products0 = not soluble1 = stable 7d @ RT2 = stable 7d @ O°C3 = stable 7d @ 0°C with seedingIsophoroneAlachlor 48%3Propoxur 20% Chlorpyrifos 40%21alpha-Cypermethrin 10%Difenoconazole 25% 0Phenmedipham 16%Difenoconazole 25% 0Phenmedipham 16%Trifluralin 40%Propanil 36%NMPTrifluralin 40%Propanil 36%Triadimenol 23%Tebuconazole 25%Pendimethalin 33%Alachlor 48%3Propoxur 20% Chlorpyrifos 40%2Triadimenol 23%Tebuconazole 25%Pendimethalin 33%Oxyfluorfen 22%alpha-Cypermethrin 10%PolarCleanNMPδ D15.818δ P10.712.3δ H9.27.21Difenoconazole 25% 0Phenmedipham 16%The market referenceFor high performance butharmful solventsIsophorone16.68.27.4Trifluralin 40%Propanil 36%ADMA16.56.47.3Triadimenol 23%Solubility of various agricultural actives in Rhodiasolv® PolarClean compared to other harmful butperformant agrochemical solvents.Royal Society of Chemistry Symposium 2012 – Not Costing the EarthTebuconazole 25%Pendimethalin 33%

Suitable solutions for various EC FormulationsEco-friendlysolution blendsCompositionGeneral usesSolutions forMATCH GPolarclean, ADMA*Polar solvents forazole and othersCypermethrin 200Ethofumesate – PMP– DMP (110 – 90 - 70)RhodiasolvMATCH MMATCH 111Polarclean, ADMA*Polarclean, ADMA*,DBE**Polar solventcompositionCyclohexane,isophorone, NMP,NEP substitutionOxyfluorfen 240Tebuconazole 300Fluoxypyr 250Prochloraz 450Amicarbazone 250Uniconazole 50Lufenuron 50MATCH VBPolarclean, ADMA*,estersCyclohexane,isophoronesubstitutionPropanil 360 & 400MATCH UBFPolarclean, DBE**Urease andnitrificationinhibitorsNBPT 250* ADMA = AlkylDiMethylAmide ** DBE = DiBasicEster (dimethylester)Royal Society of Chemistry Symposium 2012 – Not Costing the Earth

Highlights of Rhodiasolv® membersWide range of PolarityFrom water soluble to almost insoluble.Excellent toxicological & ecotoxicologicalprofilesNon-flammable and with very low vapourpressureBased on Rhodia raw material Reducedcarbon foot printChemical structure flexibility to develop thewhole range of solventsProprietary solutions for a wide range ofapplicationsRoyal Society of Chemistry Symposium 2012 – Not Costing the Earth

THANK YOU FOR YOUR KIND ATTENTION