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POLYETHER POLYOLSPOLYETHER POLYOLS

Production Process

and

Applications

Lisboa, 24 de Maio de 2012

Ciência e Tecnologia de Polímeros

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POLYOLSPOLYOLS

TYPES: APPLICATIONS:

2) Polyester Polyols Rigid foams and

high performance applications

3) Polymeric Polyols High Resilience flexible foams

4) Polyols from vegetal oils Rigid foams(e.g:.mamona oil)




POLYOLSPOLYOLSDEFINITION:Polyols are hydroxyl functional polymers.

TYPES: APPLICATIONS:

1) Polyether Polyols

- Polypropylene gycols (PPG’s)

- Poly(oxide of tetrametylene) glycol (PTMEG) Elastomers

Fibers of PU

- Mannich polyols Foams in spray at low temperatures

Elastomers

PU flexible foams PU rigid foams




POLYETHER POLYOLS POLYETHER POLYOLS

The Polyether Polyols contains ether groups in the backbone and are the largest group of polyol used in Polyurethanes (PU’s).

PROPERTIES: Resistant to alkali medium (base)

Low viscosity

Low temperature flexibility

APPLICATIONS:

They are strongly dependent on the:- Functionality (f) - Molecular weight (MW)




PRODUCTION PROCESSPRODUCTION PROCESSThe polyether polyols results from the reaction of an organic oxide and a iniciator (or starting polyol), which have one or more active hidrogen atoms. In the presence of a basic catalyst, the active hidrogen starts to open the ring of the added oxide. This reaction is extended to reach the desired MW.

Organic Oxide

Epicloridrine

1,2 – Butilene oxide (BO)

Propylene Oxide (PO)

Ethylene Oxide (EO)StructureOxide




PRODUCTION PROCESSPRODUCTION PROCESS

Substances added

Liquid effluents

Gas emissions

Substances added

Liquid effluents

Gas emissions

Substances added

Liquid effluents

Gas emissions

Substances added

Liquid effluents

Gas emissions

Substances added

Liquid effluents

Gas emissions

Substances added

Liquid effluents

Gas emissions

Substances added

Liquid effluents

Gas emissions

Antioxidants

Initiator (Glycerine, DPG, etc.)Catalyst (aq. solution of KOH or NaOH)

Sodium acid pyrophosphate(Puron)

Puron dissolved in water

Water steam

COV (OE and/or OP)OE and/or OP

H2O

N2

Water steamN2

Blender

Reactor

T=115ºC

BlenderT=ºCP=atm

Niagara Filter

Vessel T=ºCP=atm

Weighing Tank

Storage Tank

Bulk Drums IBC’s

Dissolution of Puron in Polyol

NEUTRALIZATION

PACKAGING

FILTRATION

REACTION

INITIATOR PREPARATION

STORAGE

DRYING





1. INITIATOR (or STARTING POLYOL) PREPARATION

A strong base dissolved in water (0.2 - 1.0wt% of final polyol) reacts with the the initiator, forming an anion.

Polyether polyols are formed based on an Anionic mechanism!

Strong Base:- KOH (potash hydroxide)

- NAOH (sodium hydroxide)

- ...





2. REACTIONThe initiator is tranferred to the reactor at T115ºC under N2, where the oxide is gradually added, by spraying. The high ring stress and polar character allow cleavelage easily and the chain extension occurssubsequently. This reaction is a strong exothermic polymerization.

REACTION MECHANISM

⊝





3. NEUTRALIZATIONTo neutralize the poliol, is added Puron (sodium acid pyrophosphate) and water.

4. FILTRATIONThe already neutralized polyol passes through a Niaga filter to remove the Puron.

5. DRYINGAfter passes through a Niaga filter, the polyol is then transferred to the weightening tank, where is dried by vacuum the antioxidant compounds (usually 2 types of Irganox) are added.





5. STORAGEAfter the quality control the polyol is tranferred for the storage tank.

6. PACKAGINGThe polyether polyol can be send to the market in bulk, drums or IBC’s (Intermediate Bulk Container)




POLYETHER POLYOLS CHARACTERIZATIONPOLYETHER POLYOLS CHARACTERIZATION

DURING THE PRODUCTION:

Hidroxyl value (VOH)

Acid value (VA)

Water content

Water content should be

< 0,1%




POLYETHER POLYOLS CHARACTERIZATIONPOLYETHER POLYOLS CHARACTERIZATION

by Titration

FINAL CHARACTERIZATION:

Hidroxyl value (VOH)

Acid value (VA)

Insaturation

Water content

Color

Viscosity

pH

Density

Karl-Fisher Equipment

Brookfield viscosimeter

Colorimeter (APHA)

pH equipment

Picnometer





Ethylene Oxide (EO) vs Propylene Oxide (PO)

Reactivity

Hazard risks• EO and PO are extremely inflammable and should be storaged in refrigerated tasks because they can polymerize at high temperatures.

• EO can not be transported by road, only by boat in maritime containers.

EO and PO are the oxides more used in the polyether polyols production !

PO Polyether Polyols secundary OH groups slower reactive

EO Polyether Polyols primary OH groups more reactive3





Polyether Polyol (Diol)

Ethylene Glicol + 2n PO Diol (linear polyether polyol with f=2)-

KOH

Polyether Polyol (Triol)

Glycerin + 3n PO Triol (star polyether polyol with f=3)-

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1.11.031.021.001.011.00 Density at 25oC (g/cm)

6.5 – 8.06.0 – 7.56.5 – 8.08.6 – 9.66.5 – 8.06.5 – 8.0pH

11000 - 15000600 - 700750 – 900580 – 720450 – 550250 – 350Viscosity at 25oC(mPa.s)

< 0.005< 0.005< 0.05< 0.040.4< 0.04Insaturation (meq/g)5.83.03.04.03.02.0Average functionality 6.96.80,61.11.01.0OH content (meq/g)

380 ± 25380 ± 2535 ± 260 ± 356 ± 356 ± 3VOH (mg KOH/g)860 ± 60440 ± 354800 ± 3003750 ± 2003000 ± 2002000 ± 100Mw

Sacarose + PO

Trimethylol propane + PO

Trimethylolpropane + PO and

OE

Amine + PO and

EO

Glycerin + EO and PO

Propylene glycol + PO

CompositionHRCONVENTIONAL

RIGID FOAMSFLEXIBLE FOAMS CASEAPPLICATION

TYPICAL PROPERTIES TYPICAL PROPERTIES vs vs APPLICATIONAPPLICATION

CASE – Coatings, Adhesives, Sealants and ElastomersHR – High ResilienceAverage fuctionality = Mw OH content (meq/g) / 1000




APPLICATIONSAPPLICATIONS

Polyurethane (PU) Synthesis




1,2-propane diol

Ethylene glycol

Water

Starting polyol

HOCH2CH(CH3)OH

HOCH2CH2OH 265-56400-20002HOH

VOH (mgKOH/g)Mw(g/mol)

f

PPROPERTIES PPROPERTIES vsvs APPLICATIONS APPLICATIONS

PU Elastomers




Triethanol amine

Trimethylol propane

Glycerine

Starting polyol

56-283000-60003

VOH (mgKOH/g)Mw (g/mol)f

PPROPERTIES PPROPERTIES vsvs APPLICATIONS APPLICATIONS

N-(-CH2-CH2OH)3

PU Flexible Foams




6Sorbitol

Saccharose

Dietilenotriamina

4’.4’-diamine diphenylmetane

2,4 toluene diamine (or 2,6)

Etylene diaminePentaeritritol

Starting polyol

H2NCH2CH2NH2

300-800<1000

4

C-(-CH2OH)4

H2NCH2CH2NHCH2CH2NH2

8

5

VOH (mgKOH/g)

Mw (g/mol)

f

PROPERTIES PROPERTIES vsvs APPLICATIONS APPLICATIONS

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FLEXIBLE FOAMSFLEXIBLE FOAMS

Open Cells! Open Cells! (>95%)(>95%)

Opening Cell Mechanisms:

• Bursting after hardning (Delay the Blowing Reaction)

Opercular

No opercular

• Quasi - colapse (No excess of stabilizing silicone)

Measuring Open Cells: Helium or Air picnometers




RIGID FOAMSRIGID FOAMS

OH

OH

HO

HO

+Polyisocyanate

f ~ 2.7 up to 2.9Highly crosslinked

Foam with Low Density

Polyols with high Functionality




THANK YOU VERY MUCH THANK YOU VERY MUCH

FOR FOR

YOUR ATTENTION!YOUR ATTENTION!




polyether polyols production process applications · polyether polyols production process and...

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