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GREEN & SUSTAINABLE 1K & 2K FOAM SYSTEMS IN AEROSOL CANS OR PRESSURE VESSELS Aster De Schrijver - UTECH 2012 GREENSEAL CHEM “Your better technology partner” YOUR PARTNER WITH THE INTEGRATED TECHNOLOGY APPROACH! Greenseal chem is fully dedicated to GREEN OCF ‘s & TCF ‘s in aerosol cans or pressure vessels. GREENSEAL CHEMICALS NV, B wants to be a leading worldwide mfg/provider of specialty chemicals used in the manufacturing of GREEN OCF’s & TCF’s. GREENSEAL RESEARCH LTD, PT wants to be a leading worldwide active expertise and R&D center on GREEN OCF & TCF CHEMICALS AND FOAM SYSTEMS FOAMING PROCESS The foaming process can be divided in 4 different stages : Liquid mixture inside the can (prepolymer) Froth after dispensing (i) Dispensing of the froth (Initial Expansion) Froth while curing Curing Process (Post Expansion) Cured Foam (f) GREENFOAM MARKET GAP FILLING AND FIXATIONS IN BUILDING APPLICATIONS ACTUAL MARKET FOR ONE COMPONENT PU FOAMS IS ABOUT 380 MILLION OF AEROSOL CANS OF DIFFERENT SIZES. NEW MARKETS SEEN WITH GREENFOAMS PACKAGING FOAMS VOID & CAVITY FILLING SURFACE INSULATION ( Spraying) GREENFOAM TECHNOLOGY (patents pending) A NEW GENERATION OF “LOW MONOMERIC DIISOCYANATE BASED PU FOAMS & ADHESIVES” ENVIRONMENTAL FRIENDLY & HARMLESS TO USE. NOT EVERYBODY TAKES THE NEED FOR HARMLESS & ECOLOGIC & SUSTAINABLE FOAM SYSTEMS SERIOUSLY…. BUT IF YOU DO, WE WANT TO TALK TO YOU!! WHY GREENFOAMS? Reason 1: EUROPEAN GOVERNEMENTAL LEGISLATION IS INSISTING ON SPECIAL LABELLING (R40) FOR HARMFULL PRODUCTS SUCH AS 1 and 2 KPU FOAM SYSTEMS IN AEROSOL CANS OR PRESSURE VESSELS SOLD TO THE CONSUMERS AND CRAFTSMEN. DEATH TREE AND FISH LABELLING FOR CHLORINATED PARAFFINS < C18 COULD BECOME A REALITY. AS A RESULT THE MARKET WILL BE LOOKING FOR LESS HARMFULL FOAMS ALTERNATIVES TODAY ARE RATHER EXPENSIVE ( 3 to 4 times the actual chemical cost of actual PU systems.) WHY GREENFOAMS? Reason 2: ONGOING FURTHER STRATEGIC DEVELOPMENTS…… MARKET IS LOOKING FOR FOAMS CURING INDEPENDENTLY or WITHOUT THE HUMIDITY IN THE AIR (to fill cavities) MARKET IS LOOKING FOR FASTER CURING FOAMS ( to save time) WE ARE SCOUTING FOR NEW PROBLEMS TO BE SOLVED. ( to expand the business) OBJECTIVES • Development of a One Component Foam (OCF) with a free monomeric MDI (fmMDI) content lower than 0,1% on the total chemicals in the aerosol can or pressure vessels GREENFOAM! In December 2010, EU has issued a New Legislation regarding the maximum acceptable % fmMDI % fmMDI 1,0% (on the total chemicals) Price to be competitive than possible alternatives (ex. a – silanes) OCF - Standard Formulation 1. Polyol blend: Greenpol 1-3-01-160;Greenpol 1-2-02-110 (70:30) (GP 1000 + PPG 1000) 2. Greengard 2-09-1-45 and/or Greengard 3-04-3-10 (Cereclor S45+ TCPP) 3. Crude MDI (f=2.7) – up to Index NCO/OH in the range of 4.8 in the active components blend; 4. Reactive chemicals as a whole – 75%; 5. Non-Reacting chemicals (flame retardant, catalyst, Greensil, etc.) – 25%. 6. GAS – up to 60% by volume on total chemicals Series foams with Index NCO/OH 4,8; 4,9; 5,0; 5,1; 5,2: HOW TO LOWER THE % of fmMDI in the backbone and in the total chemicals?? BIG CHALLENGE FOR ALL OF US…..??? Mechanical characteristics of the polymer network Polymer network – most characteristic properties • Crosslink density – MW in between network point (Mc) • Chain flexibility in between network points Determines • Network Tg (brittleness at RT - related to crumbling) • Flexibility of material – mechanical properties REMARKS: • Addition of plasticizer renders combination network properties and plasticity. • Other additives are used to get decent foamed structure / FR (TCPP is plasticiser and FR). One component PUR-foam Prepolymer: comprised of isocyanate end-groups & free isocyanate Network points: within polyol (own choice) Flexibility of chain: combination polyol+urethane bonds (polyol + MDI) Production of CO2: secondary expansion (difficult to hold in hands) HOW TO MAKE GREENFOAMS ? Replace standard Polyether Polyol and add alcohols Replace chlorinated Paraffin Replace standard PMDI By adding green components: GREENGARD 1 -01-155 or GREENGARD 1-010-00 or GREENGARD 1-030-00 GREENPOL 3 -3-03160 GREENCURE 06-008 GREENCURE 06-006 GREENADDUCT 1-001 (a)To (1)substitute the polymeric MDI= COMPONENT B, by Low molecular, Low viscosity NCO-terminated Prepolymers called GREENADDUCT’s and (2) introduce mono and bivalent alcohols called GREENCURE(s) in COMPONENT A (GREENADDUCT 6-001) ----------------------------------------------------------(GREENCURE 06-008) – bivalent (2 OH groups) (GREENCURE 06-006)-monovalent ( 1 OH group) (b) replace chlorinated paraffin’s Three possibilities: - Use non reactive FAME’s (GREENGARD 1-01-0-00) - Use reactive FAME’s ( GREENGARD 1-03-0-00) - Use chlorinated FAME’s (GREENGARD 1-01-1-45) © use sustainable polyols • Replace actual triols by Castor oil (GREENPOL 3-3-03-160) Typical B2 formulation Greenfoam Component A: Polyether: Polyester: Alcohols: Flame retardant: Cell Stabilizer: Catalyst: pbw 13,86 6,86 19,51 13,86 4,04 0,66 Component B: GREENADDUCT GA 13 Component C: Isobutane/DME (70:30) 165,02 52 GREENFOAM PROPERTIES NEEDED 1.Viscosity of the product in aerosol can: similar to the actual OCF systems to assure a good output( min 4,5gr/sec at 5°C/5°C) 2.Cell structure :uniform; no crumbling; no base holes; no cell collapse; 3.Density in mould: less than 30 gr/l 4.Dimensional stability: ±0.1%; 5.Adhesion to different substrates: same values as for standard OCF’s; 6.Shelf life: min 12 months when stored at AT. Shrinkage 0 to 0,1% (mold); Cell structure: Uniform; Adhesion: satisfactory; Base holes and gaps: insignificant, full missing of crumbling; Temperature 23C of staying and spraying; Stability: after 4 weeks under 45C: no visible changes in the quality of the yielded foam; Density: 25 gr/l Final content monomeric MDI on total weight of chemicals: 0,9% (less than 1%) MANUFACTURING STAGES GREENFOAM 1. Component A: Polyol blend: Add mono alcohols into the polyol Blend (component A) together with different polyethers, Polyesters, flame retardants, catalysts, stabilizers... 2. Component B: Greenadduct ( ready supplied by Greenseal chem) a) A prepolymer is made in a 10 ton reactor. The prepo is based on polyether(s),MDI and PMDI. b) Next we do a distillation of the prepolymer in a WFE to reduce the %fmMDI in the Greenadduct (Component B)= concentrate. The distillate is monomeric MDI, which can be reused. COMPONENT B or GREENADDUCT Modification and distillation Wiped Film Evaporator (WFE) (Lab. Pilot plant) Usually used to: - remove contaminants, solvents or unwanted agents imposed by legal determinations. In GREENFOAM is used to: - reduce the level of fmMDI in the Greenadduct (component B). INDUSTRIAL SHORT PATH WIPED FILM EVAPORATOR (WFE) COMPONENT B or GREENADDUCT Modification and distillation Advantages Short Path Wiped Film Evaporator: Low residence time (usually less than 10 seconds) Minimization of formation of allophanates. Can be easily operated continuously. Operated at low pressure, typically 0.1 – 1 mbar ( so that the temperatures in the head of wiped film are usually in the range of 120 – 170 ºC) Optionally a pushing agent can be used to increase effiency (ex. FAME’S- patent pending ). GREENFOAM Preparing the can 1st – prepare the polyol blend (comp. A) and mix 2nd – fill the can with the Greenadduct (comp. B) 3rd – fill the can with the polyol blend (comp. A) 4th – close the can with the Altachem aerosol valve 5th – fill in the gases (comp. C) and shake the can 6th – leave the can for, at least 12hours, before testing. GREENFOAM CHARACTERIZATION 1.Testing the foam - Output - Quick test 2. Evaluation of the foam - Visual evaluation - Density of foam on mould - Shelf-life - Flame propagation (B2,B3) 3. fmMDI content determination on total chemicals!! Please bear in mind, that when you change the Component A and or C, to do a new %fmMDI determination!! TESTING THE FOAM… Output The minimum output, in a full can, at 5ºC should be 4,5g/s, better if it is higher than 10g/s. For this test, both the can and a box are weighted. The foam is sprayed for 10s. The can and the box are weighted again. Quick test The foam should be tested on paper and on mould and left to cure for, at least, 12hours. This test is performed at 23ºC/23°C and 5ºC/5°C EVALUATING THE FOAM… Visual evaluation: - cell structure - base holes - shrinkage - cell collapse Density of the foam on mould should be around 25g/L! If all the properties are considered to be acceptable The tests are repeated after leaving the can in an oven at 45ºC for 4 and 8 weeks to check the shelf life. % fmMDI CONTENT DETERMINATION… The actual European Test method EN 13130-8 has been improved over the last 6 months The improved test method of analysis is based on HPLCMS-MS with triple quadrupole. The work was done by the team of Prof Humberto in the University of Lisboa New EN Norm to be prepared! fmMDI CONTENT DETERMINATION… HPLC-MS-MS Equipment fmMDI CONTENT DETERMINATION… Why Mass Spectrometry (MS)? • Can identify molecules by Molecular Mass (in MS mode) • Generates “finger-print” of each compound (in MS/MS mode) • HPLC-MS/MS is a powerful analytical tool – Chromatographic separation and specific detection – Identifies and Quantify each peak in the same run – EU standard method to measure trace contaminants in food and medicines Improved test method for measuring fmMDI in OCF based on the EN 13130-8 Actual partners involved: a) FEICA b) University of Lisboa c) OCF producers d) CEN (PS. No support was obtained from the big PU raw material manufacturers !) MARKET OPORTUNITIES Greenseal Chemicals NV Belgium Greenseal Research Portugal Lab synthesis of New “Chemical Products Some kinetics & mechanical analyses Formulation foams & testing Greenseal Chem is ready to discuss possible ways to cooperate….