polyether polyols production process applications · polyether polyols production process and...
TRANSCRIPT
POLYETHER POLYOLSPOLYETHER POLYOLS
Production Process
and
Applications
Lisboa, 24 de Maio de 2012
Ciência e Tecnologia de Polímeros
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
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)
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
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
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
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)
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
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
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
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
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
PRODUCTION PROCESSPRODUCTION PROCESS
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)
- ...
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
PRODUCTION PROCESSPRODUCTION PROCESS
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
⊝
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
PRODUCTION PROCESSPRODUCTION PROCESS
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.
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
PRODUCTION PROCESSPRODUCTION PROCESS
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)
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
POLYETHER POLYOLS CHARACTERIZATIONPOLYETHER POLYOLS CHARACTERIZATION
DURING THE PRODUCTION:
Hidroxyl value (VOH)
Acid value (VA)
Water content
Water content should be
< 0,1%
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
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
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
PRODUCTION PROCESSPRODUCTION PROCESS
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
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
PRODUCTION PROCESSPRODUCTION 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)-
KOHCreate PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
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
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
APPLICATIONSAPPLICATIONS
Polyurethane (PU) Synthesis
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
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
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
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
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
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
PU Rigid FoamsCreate PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
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
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
RIGID FOAMSRIGID FOAMS
OH
OH
HO
HO
+Polyisocyanate
f ~ 2.7 up to 2.9Highly crosslinked
Foam with Low Density
Polyols with high Functionality
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)
THANK YOU VERY MUCH THANK YOU VERY MUCH
FOR FOR
YOUR ATTENTION!YOUR ATTENTION!
Create PDF files without this message by purchasing novaPDF printer (http://www.novapdf.com)