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POLYETHER POLYOLS

Production Process
and
Applications

Ciência e Tecnologia de Polímeros

Lisboa, 24 de Maio de 2012

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POLYOLS

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)

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POLYOLS
DEFINITION:
Polyols are hydroxyl functional polymers.

TYPES: APPLICATIONS:
1) Polyether Polyols

Elastomers
- Polypropylene gycols (PPG’s)
PU flexible foams
PU rigid foams

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


Fibers of PU

- Mannich polyols Foams in spray


at low temperatures

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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)

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PRODUCTION PROCESS
The 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.

Oxide Structure
Ethylene Oxide (EO)

Organic Oxide
Propylene Oxide (PO)

1,2 – Butilene oxide (BO)

Epicloridrine

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PRODUCTION PROCESS
Initiator (Glycerine, DPG, etc.)
Catalyst (aq. solution of KOH or NaOH) INITIATOR
Blender
PREPARATION
N2 Water steam

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


N2 T=115ºC

H2O
Sodium acid Vessel Blender NEUTRALIZATION
pyrophosphate(Puron) T=ºC T=ºC
P=atm P=atm
Dissolution of
Puron in Polyol
Water steam FILTRATION
Niagara
Filter Puron dissolved in water
Substances added
Antioxidants
Weighing Tank DRYING
Liquid effluents

Gas emissions Storage Tank STORAGE

PACKAGING
Bulk Drums IBC’s

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PRODUCTION PROCESS

Polyether polyols are formed based on an Anionic mechanism!

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.

Strong Base:
- KOH (potash hydroxide)
- NAOH (sodium hydroxide)
- ...

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PRODUCTION PROCESS

2. REACTION
The initiator is tranferred to the reactor at T115ºC under N2, where the
oxide is gradually added, by spraying. The high ring stress and polar
character allow cleavelage easily and the chain extension occurs
subsequently. This reaction is a strong exothermic polymerization.

REACTION MECHANISM

⊝



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PRODUCTION PROCESS

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

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

5. DRYING
After 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.

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PRODUCTION PROCESS

5. STORAGE
After the quality control the polyol is tranferred for the storage tank.

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

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POLYETHER POLYOLS CHARACTERIZATION

DURING THE PRODUCTION:


 Hidroxyl value (VOH)
 Acid value (VA)
 Water content

Water content
should be
< 0,1%

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POLYETHER POLYOLS CHARACTERIZATION

FINAL CHARACTERIZATION:

 Hidroxyl value (VOH)

 Acid value (VA) by Titration

 Insaturation

 Water content Karl-Fisher Equipment

 Color Colorimeter (APHA)


 Viscosity Brookfield viscosimeter
 pH pH equipment

 Density Picnometer

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PRODUCTION PROCESS

Ethylene Oxide (EO) vs Propylene Oxide (PO)

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

Reactivity
PO Polyether Polyols secundary OH groups slower reactive
3
EO Polyether Polyols primary OH groups more reactive

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.
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PRODUCTION PROCESS

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)
KOH
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TYPICAL PROPERTIES vs APPLICATION
APPLICATION CASE FLEXIBLE FOAMS RIGID FOAMS
CONVENTIONAL HR
Composition Propylene Glycerin + Amine + Trimethylolprop Trimethylol Sacarose +
glycol + PO EO and PO PO and ane + PO and propane + PO PO
EO OE
Mw 2000 ± 100 3000 ± 200 3750 ± 200 4800 ± 300 440 ± 35 860 ± 60
VOH (mg KOH/g) 56 ± 3 56 ± 3 60 ± 3 35 ± 2 380 ± 25 380 ± 25
OH content (meq/g) 1.0 1.0 1.1 0,6 6.8 6.9
Average functionality 2.0 3.0 4.0 3.0 3.0 5.8
Insaturation (meq/g) < 0.04 0.4 < 0.04 < 0.05 < 0.005 < 0.005
Viscosity at 25oC 250 – 350 450 – 550 580 – 720 750 – 900 600 - 700 11000 - 15000
(mPa.s)
pH 6.5 – 8.0 6.5 – 8.0 8.6 – 9.6 6.5 – 8.0 6.0 – 7.5 6.5 – 8.0
Density at 25oC 1.00 1.01 1.00 1.02 1.03 1.1
(g/cm)

CASE – Coatings, Adhesives, Sealants and Elastomers


HR – High Resilience
Average fuctionality = Mw  OH content (meq/g) / 1000
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APPLICATIONS
Polyurethane (PU) Synthesis

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PPROPERTIES vs APPLICATIONS
Starting polyol f Mw VOH (mgKOH/g)
(g/mol)

Water HOH
Ethylene glycol HOCH2CH2OH 2 400-2000 265-56

1,2-propane diol HOCH2CH(CH3)OH

PU Elastomers

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PPROPERTIES vs APPLICATIONS
Starting polyol f Mw (g/mol) VOH (mgKOH/g)

Glycerine

Trimethylol 3 3000-6000 56-28


propane

Triethanol amine N-(-CH2-CH2OH)3

PU Flexible Foams

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PROPERTIES vs APPLICATIONS
Starting polyol f Mw VOH
(g/mol) (mgKOH/g)
Pentaeritritol C-(-CH2OH)4
Etylene diamine H2NCH2CH2NH2
2,4 toluene
diamine (or 2,6) 4

4’.4’-diamine
diphenylmetane
<1000 300-800
Dietilenotriamina H2NCH2CH2NHCH2CH2NH2 5
Sorbitol
6
Saccharose
8

PU Rigid Foams
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FLEXIBLE FOAMS

Open Cells! (>95%)

Opening Cell Mechanisms:

• Bursting after hardning (Delay the Blowing Reaction)

Opercular

• Quasi - colapse (No excess of stabilizing silicone)

Measuring Open Cells: Helium or Air picnometers No opercular

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RIGID FOAMS

OH

HO
Polyisocyanate Highly crosslinked
+
f ~ 2.7 up to 2.9 Foam with Low
HO Density
OH

Polyols with high


Functionality

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THANK YOU VERY MUCH

FOR

YOUR ATTENTION!

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