GREEN & SUSTAINABLE 1K & 2K FOAM SYSTEMS IN AEROSOL CANS OR PRESSURE VESSELS Aster De Schrijver -...
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Transcript of GREEN & SUSTAINABLE 1K & 2K FOAM SYSTEMS IN AEROSOL CANS OR PRESSURE VESSELS Aster De Schrijver -...
GREEN & SUSTAINABLE 1K & 2K FOAM SYSTEMS
IN AEROSOL CANS OR PRESSURE VESSELS
Aster De Schrijver - UTECH 2012
GreenSeal Chem GreenSeal Chem
GREENSEAL CHEM“Your better technology
partner”
YOUR PARTNER WITH THE INTEGRATED TECHNOLOGY YOUR PARTNER WITH THE INTEGRATED TECHNOLOGY APPROACH!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
Liquid Liquid mixture mixture inside the inside the cancan((prepolymerprepolymer))
Froth after Froth after dispensingdispensing
((ii))
Cured FoamCured Foam((ff))
Dispensing of Dispensing of the froththe froth(Initial (Initial
Expansion)Expansion)
Froth while Froth while curingcuring
Curing Curing ProcessProcess
(Post (Post Expansion)Expansion)
FOAMING PROCESSFOAMING PROCESS
The foaming process can be divided in 4 different stages :The foaming process can be divided in 4 different stages :
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)
OBJECTIVESOBJECTIVES
• Development of a Development of a OOne ne CComponent omponent FFoam (OCF) with a oam (OCF) with a ffree ree mmonomeric MDI (fmMDI) content onomeric MDI (fmMDI) content lower than 0,1%lower than 0,1% on the on the total chemicals in the aerosol can or pressure vesselstotal chemicals in the aerosol can or pressure vessels
In December 2010, EU has issued a New Legislation regarding the maximum acceptable % fmMDI
% fmMDI 1,0%
(on the total chemicals)
GREENFOAM!
Price to be Price to be competitive than possible competitive than possible
alternatives (ex. alternatives (ex. – silanes) – silanes)
OCF - Standard Formulation OCF - Standard Formulation 1.1.Polyol blend: Greenpol 1-3-01-160;Greenpol 1-2-02-110 (70:30) Polyol blend: Greenpol 1-3-01-160;Greenpol 1-2-02-110 (70:30) (GP 1000 + PPG 1000)(GP 1000 + PPG 1000)
2. Greengard 2-09-1-45 and/or Greengard 3-04-3-102. Greengard 2-09-1-45 and/or Greengard 3-04-3-10(Cereclor S45+ TCPP)(Cereclor S45+ TCPP)
3. Crude MDI (f=2.7) – up to Index NCO/OH in the range of 4.8 in 3. Crude MDI (f=2.7) – up to Index NCO/OH in the range of 4.8 in the active components blend;the active components blend;
4. Reactive chemicals as a whole – 75%;4. Reactive chemicals as a whole – 75%;
5. Non-Reacting chemicals (flame retardant, catalyst, Greensil, 5. Non-Reacting chemicals (flame retardant, catalyst, Greensil, etc.) – 25%.etc.) – 25%.
6. GAS – up to 60% by volume on total chemicals6. 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:Series foams with Index NCO/OH 4,8; 4,9; 5,0; 5,1; 5,2:
HOW TO LOWER THE % of fmMDI in the HOW TO LOWER THE % of fmMDI in the backbone and in the total chemicals?? backbone and in the total chemicals??
BIG CHALLENGE FOR ALL OF US…..???BIG CHALLENGE FOR ALL OF US…..???
Mechanical characteristics Mechanical characteristics of the polymer networkof the polymer network
Polymer network – most characteristic propertiesPolymer network – most characteristic properties• Crosslink density – MW in between network point (MCrosslink density – MW in between network point (Mcc))• Chain flexibility in between network pointsChain flexibility in between network points
DeterminesDetermines• Network Tg (brittleness at RT - related to crumbling)Network Tg (brittleness at RT - related to crumbling)• Flexibility of material – mechanical propertiesFlexibility of material – mechanical properties
REMARKS:REMARKS:• Addition of plasticizer renders combination network properties and Addition of plasticizer renders combination network properties and
plasticity.plasticity.• Other additives are used to get decent foamed structure / FR (TCPP is Other additives are used to get decent foamed structure / FR (TCPP is
plasticiser and FR).plasticiser and FR).
Prepolymer: comprised of isocyanate end-groups & free isocyanatePrepolymer: comprised of isocyanate end-groups & free isocyanate
Network points: within polyol (own choice)Network points: within polyol (own choice)Flexibility of chain: combination polyol+urethane bonds (polyol + MDI)Flexibility of chain: combination polyol+urethane bonds (polyol + MDI)Production of COProduction of CO22: secondary expansion (difficult to hold in hands): secondary expansion (difficult to hold in hands)
One component PUR-foamOne component PUR-foam
after spraying
inside can - prepolymer cured froth - network formation
H2O CO2
HOW TO MAKE GREENFOAMS ?HOW TO MAKE GREENFOAMS ?
Replace chlorinatedReplace chlorinatedParaffinParaffin
Replace standard Replace standard Polyether Polyol and add Polyether Polyol and add
alcoholsalcohols
Replace standard PMDI Replace standard PMDI
By adding green components:By adding green components:
GREENGARD 1 -01-1-GREENGARD 1 -01-1-5555or GREENGARD 1-01-or GREENGARD 1-01-0-000-00or GREENGARD 1-03-or GREENGARD 1-03-0-000-00
GREENPOL 3 -3-03-GREENPOL 3 -3-03-160160GREENPOL 3 -3-03-GREENPOL 3 -3-03-160160
GREENADDUCT 1-001GREENADDUCT 1-001GREENADDUCT 1-001GREENADDUCT 1-001
GREENCURE 06-008GREENCURE 06-008GREENCURE 06-006GREENCURE 06-006
(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:Component A: pbw pbwPolyether:Polyether: 13,8613,86Polyester:Polyester: 6,86 6,86Alcohols:Alcohols: 19,5119,51Flame retardant:Flame retardant: 13,8613,86Cell Stabilizer:Cell Stabilizer: 4,04 4,04Catalyst:Catalyst: 0,66 0,66
Component B: GREENADDUCT GA 13 165,02Component B: GREENADDUCT GA 13 165,02
Component C:Component C: Isobutane/DME (70:30)Isobutane/DME (70:30) 5252
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/l4.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 MANUFACTURING STAGES
1.1. Component A: Polyol blend:Component A: Polyol blend:
Add mono alcohols into the polyol Blend (component A) Add mono alcohols into the polyol Blend (component A) together with different polyethers, Polyesters, flame together with different polyethers, Polyesters, flame retardants, catalysts, stabilizers...retardants, catalysts, stabilizers...
2. Component B:2. Component B: Greenadduct Greenadduct ( ready supplied by Greenseal chem)( ready supplied by Greenseal chem)
a) A prepolymer is made in a 10 ton reactor. The prepo is based a) A prepolymer is made in a 10 ton reactor. The prepo is based on polyether(s),MDI and PMDI.on polyether(s),MDI and PMDI.
b) Next we do a distillation of the prepolymer in a WFE to b) Next we do a distillation of the prepolymer in a WFE to reduce the %fmMDI in the reduce the %fmMDI in the GreenadductGreenadduct (Component B)= (Component B)= concentrate. The distillate is monomeric MDI, which can be concentrate. The distillate is monomeric MDI, which can be reused. reused.
GREENFOAMGREENFOAM
COMPONENT B or GREENADDUCTCOMPONENT B or GREENADDUCT
Modification and distillationModification and distillation
Wiped Film Evaporator (WFE) (Lab. Pilot plant)
In GREENFOAM is used to:
- reduce the level of fmMDI in the Greenadduct (component B).
Usually used to:
- - remove contaminants, solvents or unwanted agents imposed by legal determinations.
INDUSTRIAL INDUSTRIAL
SHORT PATH WIPED FILM SHORT PATH WIPED FILM EVAPORATOREVAPORATOR
(WFE)(WFE)
COMPONENT B or GREENADDUCTCOMPONENT B or GREENADDUCT
Modification and distillationModification and distillation
Advantages Short PathAdvantages 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 ).
GREENFOAMGREENFOAM 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 GREENFOAM CHARACTERIZATIONCHARACTERIZATION
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…TESTING THE FOAM…
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
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.
Output
Quick test
Density of the foam on mould should be around 25g/L!
Visual evaluation: - cell structure - base holes
- shrinkage - cell collapse
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.
EVALUATING THE FOAM…EVALUATING THE FOAM…
% % fmMDI CONTENT fmMDI CONTENT DETERMINATION…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 HPLC-MS-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 fmMDI CONTENT
DETERMINATION…DETERMINATION…
HPLC-MS-MS EquipmentHPLC-MS-MS Equipment
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
fmMDI CONTENT fmMDI CONTENT
DETERMINATION…DETERMINATION…
Improved test method for measuring fmMDI in OCF based on the
EN 13130-8Actual 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 !)
MARKETMARKET OPORTUNITIES OPORTUNITIES
Greenseal Chemicals NV Belgium
Greenseal Research - Greenseal Research - PortugalPortugal
Lab synthesis of New Lab synthesis of New “Chemical Products“Chemical Products
Some kinetics & Some kinetics & mechanical analysesmechanical analyses
Formulation foams & Formulation foams & testingtesting
Greenseal Chem is ready to discuss possible ways to
cooperate….