Isocyanate S

Understanding Polyurethanes
Isocyanate Overview
q q q q q q
TDI Polymeric MDI Pure MDI Aliphatic Isocyanates Isocyanate prepolymers & adducts Other Isocyanates
SynUthane International Inc.
Aromatic Isocyanate Products Isocyanate Raw Materials Manufacturing Processes Isocyanate Prepolymers Pure MDI and Polymeric MDI products
Aliphatic Isocyanate Products Aliphatic Isocyanate Adducts Other Isocyanates
Understanding polyurethanes
Aromatic Diisocyanates
Toluene Diisocyanate Diphenylmethane Diisocyanate Polymeric MDI Naphthalene Diisocyanate p- Phenylene Diisocyanate Tolidene Diisocyanate Tetramethylenexylylene Diisocyanate TDI MDI PMDI NDI PPDI TODI
Aliphatic Diisocyanates
Hexamethylene Diisocyanate HDI Adducts Trimer Biuret Dimer Allophonate Isophorone Diisocyanate Hydrogenated MDI Cyclohexane Diisocyanate TMXDI
HDI
IPDI H12MDI CHDI
Isocyanate Production Processes

Phosgenation
q q q q q
Cold / hot process Low pressure Hot process High pressure Vapor phase process Arco process Urea process
Non phosgene processes

q q
Comment on Phosgenation processes
q q q q
q q q q
Amines are blended with solvent or fed directly Phosgene is made in minimum quantity on demand The phosgenation reaction is carried out in solvent Solvents are ODCB (dichlorobenzene) or MCB (momochlorobenzene) Amine concentration varies 15 to 25% Phosgene ratio varies 10 to 20 moles / mole of amine After reaction HCL and phosgene are separated recycled Isocyanate is then separated from solvent and purified
Isocyanate Monomer production
Cold / Hot process phosgenation
q
Amine is reacted with Phosgene in solvent at reduced temperature followed by further reaction at high tempereture This process is usually carried out at atmospheric pressure or low pressure less than 50 psi Here the reactants are preheated and intensely mixed at high pressure over 250 psi Some amines require processing above 1000 psi to generate good yields Processes have also been developed for Vapor phase reaction
Hot process at elevated pressure

q
High pressure process

q
Vapor phase
q
Isocyanate Production (Phosgene Process)

solvent amine COCl2 COCl2 distillation column distillation column distillation column distillation column pdt RNH2 + COCl2 HCl RNCO + HCl solvent lights
reactor
residue
Manufacturing Process Concerns Phosgene Containment Water Contamination Isocyanate Heat Sensitivity Product Freezing Raw Material Purity
Manufacturing Process Concerns Phosgene Containment

1. 2. 3. 4. 5. 6. 7. Critical equipment made of high-nickel alloys Blowout-proof valves for pressure services Emergency power Continuous area monitoring for toxic gases Emergency shutdown and sectionalizing Emergency scrubbing systems Secondary containment
Manufacturing Process Concerns Water Contamination

Product deterioration can occur due to reaction of isocyanates with atmospheric moisture
Isocyanate-containing vessels are blanketed with dry nitrogen Product drums are purged with dry nitrogen before filling
Phosgenation Processing Concerns Isocyanate Heat Sensitivity

Isocyanate molecules react with each other at elevated temperatures to form carbodiimides and CO2, as well as triisocyanurates. The organic materials can cause plugging of equipment. In extreme cases, enough CO2 is generated to overpressure equipment.
Distillation must be done under vacuum conditions to keep column bottom temperature below 350 degrees F Pressure-relief system designs must consider CO2-relief cases, including concerns about two-phase flow as foam
Manufacturing Process Concerns Raw Material Purity

Raw material specifications must be established and adhered to, as seemingly small amounts of contaminants can compromise process safety and product quality.
Carbon monoxide must contain less than 0.4 volume % of hydrogen and less then 0.1 volume % of methane. Higher levels cause overheating of piping and equipment due to heat generated by reaction with chlorine. Continuous monitoring of contaminant levels and process temperatures, as well as associated alarm and shutdown systems, are required. Phosgene must contain less then 300 volume ppm of chlorine for the isocyanate product to achieve specifications for chlorine-containing contaminants.
Non Phosgene processes for Isocyanates
Two nonphosgene commercial production processes
q q q
Both processes based on urea/ ammonia BASF make HDI monomer Creanova make IPDI
Amine is reacted with urea and recycle butanol to generate the dicarbamate and by-product ammonia The dicarbamate is then cracked to give the isocyanate and butanol which is then recycled This process has only been successful for aliphatic Isocyanates
Schematic for IPDI by Amine Alcohol Urea Process

NH3 IPDA Urea IPDI Reactor WFE Condensers WFE Reactor BuOH Distillation Column Residue Butyl Carbonate & DiButyl Carbonate BuOH
Dicarbamate
Reactor
Final Distillation SynUthane International Inc.
Toluene Diisocyanate Major Raw Materials Toluene Nitric Acid Fuel (Natural Gas) Chlorine
Synthesis of 80/20 Toluene Diisocyanate (TDI)
CH3
HNO3 H2SO4
CH3 NO2 O2N
CH3 NO2
NO2 H2 Raney Ni CH3 NH2 H2N CH3 NH2
NH2 COCl2 CH3 NCO OCN CH3 NCO
NCO 80% 20%
Toluene 63% ortho-nitrotoluene 33% para-nitrotoluene 4% meta-nitrotoluene
100% p-nitrotoluene
66% o-nitrotoluene 34% p-nitrotoluene 80% 2,4-DNT 20% 2,6-DNT TDA 80
100%o-nitrotoluene
100% 2,4-DNT
65% 2,4-DNT 35% 2,6-DNT TDA 65
TDA 100
Toluene Diisocyanate Manufacturing Processes Nitration Reforming Reduction Phosgene Production Phosgenation
Toluene Diisocyanate Nitration Toluene + Nitric acid = Dinitrotoluene + Water

1. 2. 3. 4. Performed in the presence of concentrated sulfuric acid Two steps of nitration Diluted sulfuric acid is concentrated and re-used (SAC unit) Product is neutralized and water-washed to remove residual acidity
Toluene Diisocyanate Reduction Dinitrotoluene + Hydrogen = Toluene diamine + Water

1. Requires solid catalyst dispersed in solution 2. One step of reduction 3. Water, toluidine and ortho isomer of TDA are removed by distillation
Toluene Diisocyanate Reforming Natural gas + Oxygen = Carbon monoxide + Hydrogen

1. Performed over solid catalyst at high temperature 2. Water-shift reaction used to adjust relative amounts of CO and H2 3. CO and H2 are separated and purified by cryogenic distillation
Toluene Diisocyanate Phosgene Production Carbon monoxide + Chlorine = Phosgene

1. Reactants are fed in gas phase through carbon catalyst bed 2. Excess CO is used to minimize free chlorine in product
Toluene Diisocyanate Phosgenation Toluene diamine + Phosgene = Toluene diisocyanate + Hydrochloric acid
1. 2. 3. 4. 5. Reaction is performed in a solvent such as monochlorobenzene Phosgene is used in excess to minimize organic byproduct formation Excess phosgene is separated from reaction products and recycled Solvent is removed and purified by distillation TDI is separated from organic byproducts by distillation
TDI (toluene diisocyanate)

Company name Enichem Polimeri Lyondell Petrochemical Co BASF AG/Elastogran BASF AG/Elastogran BASF AG/Elastogran Bayer AG Bayer AG Bayer AG Bayer AG Bayer Shell Isocyanates Bayer Corp Bayer Corp Sumitomo Bayer Urethane Co. Cydsa Bayer Dow Chemical Dow Chemical EniChem Polimeri Region Europe Americas Americas Asia-Pacific Europe Europe Europe Europe Europe Europe Americas Americas Asia-Pacific Americas Americas Americas Europe Qatar Lake Charles, LA Geismar, Louisiana Caojing, PR China Schwarzheide, Germany Brunnsbttel, Germany Dormagen, Germany Leverkusen, Germany Tarragona, Spain Antwerp, Belgium Baytown, Texas New Martinsville, WV Shin Nanyo, Japan Coatzacoalcos, Mexico Freeport, Texas Camari, Brazil Porto Marghera, Italy Location Material TDI TDI TDI TDI TDI TDI TDI TDI TDI TDI TDI TDI TDI TDI TDI TDI TDI Capacity kt 100 113 120 100 40 55 45 36 18 30 60 45 13 16 60 60 110 Acquired from Pronor 50/50 JV By 2001 JV with Chinese firms 40 by end 1997 Expansions planned; kt
TDI (toluene diisocyanate)

Gujurat/Chematur Hindustan Organic Huntsman Polyurethanes Korea Fine Chem Mitsui Toatsu Mitsui Toatsu Nippon Polyurethane Industries Co Ltd Nippon Polyurethane Industries Co Ltd Olin Corp Oriental Chemical Industries Petrochemical Rio Tercero Rhodia Rhodia Sodaso Takeda Chemical Ind Wusong Chemical Asia-Pacific Asia-Pacific Americas Asia-Pacific Asia-Pacific Asia-Pacific Asia-Pacific Asia-Pacific Americas Asia-Pacific Americas Europe Europe Europe Asia-Pacific Asia-Pacific Bharuch, India Raigad, India Geismar, Louisiana Kunsan, Korea Omuta, Japan Omuta, Japan Tokuyama, Japan Omuta, Japan Lake Charles, Louisiana Kunsan, Korea Cordoba, Argentina Pont de Claix, France Lille, France Tuzla, Bosnia Niihama, Japan Shanghai, China TDI TDI TDI TDI TDI TDI TDI TDI TDI TDI TDI TDI TDI TDI TDI TDI 10 10 25 45 93 35 7 15 100 32 21 70 50 40 30 10 Products marketed by Lyondell Petrochemical Co. Products marketed by Lyondell Petrochemical Co. Shutdown
Polymeric MDI major raw materials and process steps - Benzene

Nitration and Reduction - Aniline Hydrochloric acid - Aniline Hydrochloride Reaction with Formaldehyde - Polymeric MDA Phosgene - Polymeric MDI
Methylene Diisocyanate Polymeric Amine Production Aniline + Formaldehyde = Polymeric amine + Water
Performed in aqueous solution using HCl as homogeneous catalyst Excess aniline is used Content of 2-ring oligomer (MDA) is determined primarily by aniline/formaldehyde ratio Isomer distribution of MDA is determined primarily by HCl/aniline ratio Acidic reaction product is neutralized with sodium hydroxide and is water-washed to minimize salt contamination Aniline is removed from amine solution and brine and is recycled
Synthesis of MDA
NH2 NHCH2OH -H2O + CH2O NH2 N=CH2 H+ NHCH2+
H2N
CH2NH + CH2NH NH2
H2N
CH2 4,4-MDA
NH2
NH2
CH2 CH2 NH2 2,4-MDA Polymeric MDA NH2 H2N CH2 NH2
CH2 NH2 H2N
2,2-MDA
Synthesis of MDI
NH2
H2N
CH2 4,4-MDA
NH2
CH2 CH2 NH2 2,4-MDA Polymeric MDA NH2 H2N CH2 NH2
CH2 NH2 H2N COCl2
2,2-MDA
OCN
CH2 4,4-MDI
NCO
NCO
CH2 CH2 NCO 2,4-MDI Polymeric MDI NCO OCN CH2 NCO
CH2 NCO OCN
2,2-MDI
MDA Chemistry
Variables which control the MDA/ Polymeric MDA composition
Aniline to Formaldehyde ratio
Increasing aniline / formaldehyde ratio, with HCL constant q Increases MDA to Oligomer ratio q Decreases the amount of 4,4 isomer
Increasing the acidity, with aniline / Formaldehyde ratio constant

q q q q q
Increases the reaction rate Increases the amount of 4,4 isomer Decreases the MDA / oligomer ratio Increases caustic for neutralization Increases the product cost N methyl 4,4 MDA
Increasing the rate of formaldehyde addition increases impurities

q
Understanding Polyurethanes Polymeric MDI Process

Formaldehyde Aniline Stripper
Aniline Aniline.HCl
Acid Polyamine Neut.& Strip
Caustic Brine Strip Waste
Polyamine MCB MCB Recovery facility MDI Precut Pure MDI Plant Polymeric MDI Phosgene
Storage
HCl
HCl Sales
Polymeric MDI Sales Polymeric MDI from Pure Plant
Liquid Adducts
Pure MDI
Liquid MDI Pre-Polymers

Polymeric MDI and Pure MDI
Polymeric MDI
q
Adjusting the aniline / formaldehyde ratio allows the ratio of MDA ( two Benzene Rings) to polymeric MDA oligomers(three up to five and more benzene rings) The structure of the material is set at the amine stage and then the amine groups are converted to isocyanate during the phosgenation reaction Thus the polymeric MDI has different MDI content depending on the precursor processing conditions When it is desirable to make more pure MDI the ratio is adjusted to generate a higher MDI content in the polymeric This feed stock is then processed to separate the pure MDI and the remaining polymeric MDI is blended with other material to a desired viscosity for sale
Pure MDI
Pure MDI processing
q
q q
Pure MDI is separated by distillation or fractional crystallization The isomer distribution is adjusted by fractionation and for elastomer applications the material is > 97%p,p while for spandex fibers >98% p,p is required Pure MDI is a solid at room temperature mp = 38 0C Pure MDI, at room temperature or as a molten liquid rapidly forms the dimer of MDI, this dimer is very insoluble and rapidly forms a white precipitate which leads to very difficult handling and further processing. The MDI is stored as a frozen solid ( at 10 0F) or shipped as freshly distilled product to the customer for immediate use
Pure MDI products
Prepolymers and carbodiimides( liquid pure MDI products)
q
To reduce the dimer problem, pure MDI is converted to downstream liquid products, which greatly reduce the rate of dimer formation Prepolymers are made by reaction of pure MDI with polyether or polyester polyols MDI is reacted with more MDI and catalyst to generate some carbodiimide with the elimination of by-product CO2 The carbodiimide now forms an adduct with another NCO group and this adduct depresses the freezing point to generate a liquid product The effect of achieving a liquid product is enhanced using a pure MDI with a higher o,p content, high o,p has a lower mp The eutectic mixture of o,p to p,p - 48%o,p is a liquid
MDI (methylene diphenyl diisocyanate)

Company name Afino Fine Chemicals Co. Ltd. (Dahin Group) BASF AG/Elastogran BASF AG/Elastogran BASF AG/Elastogran BASF AG/Elastogran BASF AG/Elastogran Region Location Material Capacity kt Expansions planned; kt
Asia-Pacific Americas Asia-Pacific Asia-Pacific Europe Europe Americas Americas Europe Europe Europe Europe Americas Europe Europe Europe Asia-Pacific Americas Asia-Pacific Europe Asia-Pacific Asia-Pacific
Taipei, Taiwan RoC Geismar, LA Caojing, PR China Yeochun, Korea Antwerp, Belgium Schwarzheide, Germany Baytown, Texas New Martinsville, WV Brunsbttel, Germany Tarragona, Spain Antwerp, Belgium Kazinbarcika, Hungary Laporte, Texas Stade, Germany Estarreja, Portugal Brindisi, Italy Ulsan, Korea Geismar, LA Kuan Yin, Taiwan Rozenburg, NL Omuta, Japan Tokuyama, Japan
MDI distillation MDI MDI MDI MDI MDI MDI MDI MDI MDI MDI MDI MDI MDI MDI MDI MDI MDI Polyether polyols/MDI systems MDI MDI MDI
30 80 100 50 160 36 150 50 60 50 38 32.5 190 130 75 120 40 136 50 by 1996; 80 by 1998 50/50 JV 40 by Aug. 1998 90 by 1996; 120 by 1997 By 2001 JV with Chinese firms 80 by end 1997 200 by 1997
Bayer AG Bayer AG Bayer AG Bayer AG

Bayer Shell Isocyanates Borsodchem Dow Chemical Dow Chemical Dow Chemical
EniChem Polimeri Hanwha-BASF

Huntsman Polyurethanes Huntsman Polyurethanes Huntsman Polyurethanes Mitsui Toatsu NPU (Nippon Polyurethane Industry Co Ltd)
250 55 100
Isocyanate Adducts / Prepolymers Major Raw Materials Diisocyanate Polyol(s)
TDI Adducts
CH3 NCO
Similarly with TDI for Coatings Applications
NCO
CH2OH HOH2C C C2H5 CH2OH Catalyst
CH3 NCO CH3 NCO HNCO O HNCO OH2C H2C C C2H5 HNCO CH2O H3C CH3 NCO
OCN O N O N N O
NCO CH3
NCO CH3
TDI/TMP Adduct
TDI Trimer
Isocyanate Adducts / Prepolymers Reaction Diisocyanate + Polyol = Prepolymer

Typically performed in batch reactor at about 180 degrees F Polyol is added slowly to diisocyanate Diisocyanate remains in excess
Generic Adducts Process

Recycle Monomer Monomer Catalyst Linking Agent Reactor Crude Adduct Finished Adduct Critical Properties NCO Viscosity Monomer Content Acidity Color SynUthane International Inc. Evaporator
Aliphatic Isocyanates Monomers
q q q
Hexamethylene Diisocyanate Isophorone Diisocyanate Hydrogenated MDI
Adducts
q
HDI - Biuret - Trimer - Dimer - Allophonate
IPDI - Trimer - Urea
Isocyanate Chemistry
H2N NH2 Hexamethylene Diamine (HDA) NH2 HCl H3C H3C Isophorone Diamine (IPDA) CH3 NH2 H3C H3C CH3 NCO NCO OCN NCO Hexamethylene Diisocyanate (HDI)
Isophorone Diisocyanate (IPDI)
H2N
NH2
Phosgenation Process
OCN
NCO
Methylene Dicyclohexylamine (H12MDA) CH3 NH2
Methylene Dicyclohexylisocyanate (H12MDI) CH3 NCO
NH2 Toluene Diamine (TDA) COCl2
NCO Toluene Diisocyanate (TDI)
H2N
NH2
OCN
NCO
Methylene Diphenylamine (MDA)
Methylene Diphenylisocyanate (MDI)
IPDI Manufacture
H3 C H3C C H3C CH3 acetone isophorone H3C CN isophorone nitrile NH3/H2 O H3 C O HCN H3C H3C O
H3 C H3C
NCO
H3 C COCl2 H3 C
NH2
H3C CH2NCO isophorone diisocyanate
H3C CH2NH2 isophorone diamine
Hydrogenated MDI
q q q
q q q q
Hydrogenated MDI is the third most important aliphatic Bayer is the only supplier The most important steps are low cost MDA and an economic hydrogenation process H12MDI is growing rapidly in coating applications Waterborne PU systems for leather finishing Thermoplastic urethane polymers- light stable H12MDI based on high trans/trans isomer give TPU elastomers with exceptionally good properties
Polymeric MDA
Pure MDA
H12MDA
H12MDI
Benzene Aniline Polymeric MDA Formaldehyde Pure MDA Hydrogen H12 MDA H12 MDI
Polymeric MDI
Pure MDI
Phosgene
HYDROGENATION OF METHYLENEDIANILINE
H2N NH2
H2N
cis,cis
3H2
H2 N NH2
cis
NH2
3H2
H2N
NH2
cis,trans
H 2N
trans
NH2
H 2N
NH2
trans,trans
MDA
Methylenedianiline
H6MDA
4-(4-aminobenzyl)cyclohexylamine
H12MDA
4,4'-Methylenedi(cyclohexylamine)
Hydrogenated MDI Products

The hydrogenation conditions set Isomer ratio Equilibrium product is a solid 48% Trans / Trans Liquid product is 20% Trans / Trans Solid development products 70% & 100% T,T
Aliphatic Isocyanate Adducts

Aiphatic isocyanate monomers can be reacted to form a range of new higher MW products or adducts Co- reactants such as-q q q q q
Water More isocyanate Hydroxy compounds Ureas Urethane groups
BASIC POLYURETHANE CHEMISTRY
R-NCO RNHCOOR'
N
O O
URETHANE
RNHCONHR' UREA
N
R-NCO DIMER R'-OH R-NCO R'NH2
R-NCO RNCOOR' RNHCO ALLOPHANATE 2R-NCO (RNHCOOH) R'OH RNHCOOR' URETHANE H2O R'NH2 R'OH
R-NCO
OCN-R-N=C=N-R-NCO CARBODIIMIDE
R-NCO
O
RNHCONHR' UREA O
N N N
R-NCO RNH2 + CO2
R-NCO O TRIMER
R-NCO R-NCO
RNCONHR'
RNHCO RNHCONHR UREA BIURET
Adducts Process
Ist 1.2 ft2 WFE 90 gal Feed Tank
1st WFE
Vacuum pump
2nd 1.2 ft2 WFE

2nd WFE
Blower
Feed Tank
Overhead Tank 300 gal Blending Tank
Feed Pump
Three polyisocyanates are made from Hexamethylene Diisocyanate

O OCN N N O N NCO NCO
Biuret
+ H2O
NCO
OCN
Catalyst
NCO
O OCN N
N N O
O NCO
Trimer
Hexamethylene Diisocyanate
Ca taly st
O OCN N O N NCO
Dimer
HDI Adduct / Functionality Comparison

Adduct Viscosity cps @ 25oC Average Isocyanate Functionality
3.5-6.5
Biuret
3,000-9,000
Trimer
2,000-3,000
3.4-3.7
Dimer
70-300
2.2-2.5
Allophanate
300-1,100
2.3-3.5
NCO
CH3 H3 C NCO H3 C CH3 N O CH3 N H3C H3C H3C CH3 NCO OCN catalyst O H3 C N O NCO
H3 C
CH3
IPDI monomer
IPDI Trimer
Similarly for IPDI

NCO
NCO H3 C H3C CH3 NCO catalyst CH3 N
H3 C H3C
N H3C O
CH3 CH3
NCO
IPDI monomer
IPDI Urtidione (dimer)
What is an Allophonate?
An allophanate is the reaction product of an isocyanate with a urethane. The products besides containing the allophanate moiety, may contain mixtures of uretidiones, isocyanurates, urethanes and hybrid combinations of all the above. The products are generally of lower viscosity than conventional adducts such as trimer and biuret but higher than dimer, and may have a functionality below 3. Depending on the alcohol used, the modified structure may be more solvent and additive compatible than conventional adducts.
Allophonate Chemistry
Co-Reactant O R'OH R'O N R RNCO H
R = -(CH 2 )6 NCO Name
O R'O N R RNCO
O N R O R'O N R H H Allophanate
O R'O N R
O N R
O N R R'O H O N H
O (CH2 )6 N H N R
O N R
O OR'
Blocked Isocyanates
Caprolactam: O NH O N O R N H
R-N=C=O
Ketoximes: NOH R-N=C=O + R' R'' R' R'' N O
H N O
OTHER DIISOCYANATES
P-phenylene Diisocyanate T- cyclohexane Diisocyanate Napthalene Diisocyanate Toluidene Diisocyanate M- Xylylene Diisocyanate Tetramethylenexylylene Diisocyanate Isopropenyl dimethylbenzene Isocyanate PPDI CHDI NDI TODI XDI TMXDI TMI
NonPhosgene Route to TMXDI
diisopropenyl benzene
(HNCO)
NCO H3C CH3 H3C
NCO CH3
H3C
CH3 NCO
tetramethylenexylylene diisocyanate (TMXD)I
isopropenyl dimethylbenzene isocyanate (TMI)
Other Commercial Diisocyanates
NCO H3C CH3 NCO CH2
H2C H3C CH3 NCO tetramethylenexylylene diisocyanate (TMXD)I
NCO
m-xylylene diisocyanate (XDI)
NCO
H3C H2 C OCN
CH3
NCO
NCO p-phenylene diisocyanate (PPDI) NCO NCO tolidene diisocyanate (TODI)
NCO napthalenediisocyanate (NDI)
OCN t-cyclohexane diisocyanate (CHDI)

Isocyanate S

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Understanding Polyurethanes

Aliphatic Isocyanate Products Aliphatic Isocyanate Adducts Other Isocyanates

SynUthane International Inc.

IPDI H12MDI CHDI

SynUthane International Inc.

Isocyanate Production Processes

Non phosgene processes

SynUthane International Inc.

SynUthane International Inc.

Hot process at elevated pressure

High pressure process

SynUthane International Inc.

Isocyanate Production (Phosgene Process)

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SynUthane International Inc.

Manufacturing Process Concerns Phosgene Containment

SynUthane International Inc.

Manufacturing Process Concerns Water Contamination

SynUthane International Inc.

Phosgenation Processing Concerns Isocyanate Heat Sensitivity

SynUthane International Inc.

Manufacturing Process Concerns Raw Material Purity

SynUthane International Inc.

Schematic for IPDI by Amine Alcohol Urea Process

Final Distillation SynUthane International Inc.

SynUthane International Inc.

CH3 NO2 O2N

NO2 H2 Raney Ni CH3 NH2 H2N CH3 NH2

NH2 COCl2 CH3 NCO OCN CH3 NCO

NCO 80% 20%

SynUthane International Inc.

Toluene 63% ortho-nitrotoluene 33% para-nitrotoluene 4% meta-nitrotoluene

66% o-nitrotoluene 34% p-nitrotoluene 80% 2,4-DNT 20% 2,6-DNT TDA 80

65% 2,4-DNT 35% 2,6-DNT TDA 65

SynUthane International Inc.

SynUthane International Inc.

Toluene Diisocyanate Nitration Toluene + Nitric acid = Dinitrotoluene + Water

SynUthane International Inc.

Toluene Diisocyanate Reduction Dinitrotoluene + Hydrogen = Toluene diamine + Water

SynUthane International Inc.

Toluene Diisocyanate Reforming Natural gas + Oxygen = Carbon monoxide + Hydrogen

SynUthane International Inc.

Toluene Diisocyanate Phosgene Production Carbon monoxide + Chlorine = Phosgene

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TDI (toluene diisocyanate)

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TDI (toluene diisocyanate)

SynUthane International Inc.

Polymeric MDI major raw materials and process steps - Benzene

CH2NH + CH2NH NH2

CH2 NH2 H2N

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SynUthane International Inc.

CH2 NH2 H2N COCl2

CH2 NCO OCN

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Increasing the acidity, with aniline / Formaldehyde ratio constant

Increasing the rate of formaldehyde addition increases impurities

SynUthane International Inc.

Understanding Polyurethanes Polymeric MDI Process

Acid Polyamine Neut.& Strip

Caustic Brine Strip Waste