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….