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Toluene diisocyanate

Toluene diisocyanate (TDI), with the chemical formula C₉H₆N₂O₂, is an organic compound consisting primarily of the 2,4- and 2,6-isomers in an 80:20 ratio, serving as a key reactive intermediate in the synthesis of polyurethanes.^[1]^[2] It appears as a clear, colorless to pale yellow liquid with a sharp, pungent odor detectable at low concentrations, and it is denser than water with vapors heavier than air.^[3] TDI is highly reactive due to its two isocyanate (-NCO) groups, which readily react with water to form inert polyureas and carbon dioxide, limiting its environmental persistence.^[2]^[4] Produced globally at approximately 2.5 million metric tons per year as of 2025, TDI is manufactured through the phosgenation of toluene diamine (TDA), derived from the nitration of toluene followed by hydrogenation.^[5]^[4]^[6] Approximately 90% of TDI is used in the production of flexible polyurethane foams for applications such as mattresses, furniture cushions, and automotive seating, while the remainder supports rigid foams, coatings, elastomers, adhesives, and sealants.^[2]^[4] These polyurethanes are integral to industries including furniture, automotive, construction, and consumer goods, contributing to lightweight, durable, and insulating materials.^[7] Despite its industrial importance, TDI poses significant health risks, acting as a potent respiratory sensitizer that can cause asthma-like symptoms and decreased lung function upon inhalation at concentrations as low as 0.036 mg/m³.^[2] It is also a severe irritant to the skin, eyes, and respiratory tract, with acute exposure potentially leading to pulmonary edema, and it is classified as reasonably anticipated to be a human carcinogen based on animal studies showing increased tumor incidence.^[7]^[8] Production and handling occur in closed systems with stringent controls to minimize emissions, which are typically less than 0.000005% of output, and spills are neutralized rapidly to prevent widespread exposure.^[4]

Chemical Structure and Properties

Molecular Structure and Isomers

Toluene diisocyanate (TDI) has the molecular formula C₉H₆N₂O₂ and a molecular weight of 174.16 g/mol.^[9]^[10] The molecule features a benzene ring with a methyl group attached at position 1 and two isocyanate functional groups (-N=C=O) substituted on the ring. The two primary isomers are 2,4-toluene diisocyanate (2,4-TDI), where the isocyanate groups are positioned at carbons 2 and 4 relative to the methyl group, and 2,6-toluene diisocyanate (2,6-TDI), with the groups at positions 2 and 6.^[9]^[10] In 2,4-TDI, one isocyanate is ortho to the methyl while the other is para, whereas in 2,6-TDI both are ortho, leading to distinct spatial arrangements. Commercial TDI is predominantly supplied as an 80:20 mixture of the 2,4- and 2,6-isomers, respectively, though pure forms or other ratios like 65:35 are also available.^[11]^[12] The structural symmetry in 2,6-TDI results in identical isocyanate environments, unlike the asymmetric 2,4-TDI. The isomers exhibit subtle differences in physical properties, such as boiling points; for instance, commercial 80:20 TDI boils at approximately 251 °C at atmospheric pressure.^[9]^[13] The 2,6-isomer shows higher volatility at reduced pressures (129–133 °C at 18 mmHg).^[14] More notably, reactivity varies due to steric hindrance: the 2,6-isomer's isocyanate groups are less reactive than those in 2,4-TDI because both are positioned ortho to the methyl group, increasing spatial crowding and reducing accessibility for nucleophilic attack.^[15]^[16] This steric effect in 2,6-TDI lowers its overall reaction rate by factors of up to several times compared to 2,4-TDI at ambient temperatures.^[15]

Physical and Thermodynamic Properties

Toluene diisocyanate (TDI) appears as a colorless to pale yellow liquid at room temperature, often exhibiting a sharp, pungent odor.^[9] This physical form is typical for the commercially predominant 80:20 mixture of its 2,4- and 2,6-isomers, which remains liquid under ambient conditions due to the depressed freezing point of the blend.^[14] Key physical properties include a density of 1.22 g/cm³ at 20°C and a refractive index ranging from 1.5660 to 1.5700.^[17] The boiling point is 251°C at standard pressure, while the melting point varies by isomer: approximately 21°C for the 2,4-isomer and about 10.5°C for the 2,6-isomer in pure forms, resulting in a lower effective melting point for mixtures around 6–10°C.^[13]^[14] Vapor pressure is notably low at 0.03 hPa (0.0225 mmHg) at 20°C, contributing to its limited volatility under normal handling conditions.^[17] Thermodynamically, TDI exhibits a heat of vaporization of approximately 40.6 kJ/mol, reflecting the energy required for phase transition in its liquid state.^[18] Solubility characteristics show TDI as insoluble in water—where it instead undergoes slow hydrolytic reaction—but highly soluble in common organic solvents such as acetone, benzene, kerosene, and nitrobenzene.^[9]^[19] Commercial grades of TDI typically achieve purities exceeding 99%, with the isomeric composition standardized at 80% 2,4-TDI and 20% 2,6-TDI to optimize handling and performance.^[8] Impurities, such as residual toluene or hydrolysis products, can slightly alter physical properties like density and viscosity, potentially reducing the material's stability during storage or transport if purity falls below these standards.^[14]

Synthesis

Industrial Production Methods

Toluene diisocyanate (TDI) is primarily produced industrially through a multi-step process starting from toluene, involving nitration to dinitrotoluene (DNT), hydrogenation to toluenediamine (TDA), and finally phosgenation of TDA to yield TDI.^[20] The nitration step reacts toluene with a mixture of nitric and sulfuric acids at controlled temperatures (typically 50–80°C) to produce a mixture of 2,4- and 2,6-DNT isomers in an approximately 80:20 ratio, with sulfuric acid serving as both solvent and catalyst.^[21] This is followed by hydrogenation of DNT to TDA using catalysts such as Raney nickel or palladium under hydrogen pressure (around 20–50 bar) at 80–120°C, often in aqueous or alcoholic media to facilitate the reduction.^[20] The key phosgenation step converts TDA to TDI by reacting the diamine with phosgene (COCl₂) in an inert organic solvent, such as chlorobenzene or o-dichlorobenzene, at temperatures ranging from 40–150°C to ensure efficient conversion while minimizing side reactions.^[22] The reaction proceeds as follows, where R represents the tolyl group:

$2 \mathrm{RNH_2} + 2 \mathrm{COCl_2} \rightarrow 2 \mathrm{RNCO} + 4 \mathrm{HCl}

^[23] Tertiary amines, such as triethylamine or pyridine, are commonly employed as catalysts to neutralize the evolving HCl and promote the reaction, with the process often conducted in a jet reactor for rapid mixing and heat transfer.^[24] The crude TDI is then purified by distillation to separate the product from solvent, excess phosgene, and byproducts, yielding a commercial mixture of 80% 2,4-TDI and 20% 2,6-TDI isomers.^[25] Global production capacity of TDI reached approximately 3.7 million metric tons annually as of 2024, driven by demand in polyurethane applications, with major capacity concentrated in Asia (particularly China), Europe, and North America.^[26]^[27] Leading producers include Covestro, which operates the largest European facility in Dormagen, Germany (300,000 metric tons per year, modernized in 2025 for enhanced sustainability), and Wanhua Chemical in China (1.44 million metric tons per year as of August 2025 following recent expansions), alongside facilities in the U.S. such as Covestro's site in Baytown, Texas.^[28]^[29]^[30] The process is energy-intensive, requiring significant inputs for nitration (exothermic, cooled by heat exchangers) and phosgenation (endothermic, heated via steam or hot oil), with overall energy consumption estimated at approximately 46 GJ per tonne of TDI.^[31]

Laboratory and Alternative Syntheses

Laboratory and alternative syntheses of toluene diisocyanate (TDI) focus on phosgene-free routes that prioritize safety and sustainability, often explored in research settings to avoid the toxicity associated with the standard industrial phosgenation of toluene-2,4-diamine (TDA).^[32] These methods typically involve multi-step processes starting from TDA or related precursors, yielding dicarbamate intermediates that thermally decompose to TDI, though they generally achieve lower overall efficiencies (70-80%) compared to commercial processes exceeding 95%.^[32] Research on such routes intensified in the 1990s, driven by environmental concerns, with early developments like EniChem's dimethyl carbonate (DMC)-based approach marking a shift toward greener carbonyl sources. One established laboratory method is the Curtius rearrangement, which converts toluene dicarboxylic acid derivatives into TDI via acyl azides. The process begins with the formation of diacyl azides from the corresponding dicarboxylic acid or its derivatives, followed by thermal decomposition to generate the diisocyanate. This rearrangement proceeds through a nitrene intermediate and is typically conducted under mild conditions (e.g., heating in inert solvents like toluene at 80-110°C) to minimize side reactions. While effective for small-scale synthesis of aromatic diisocyanates like TDI, it remains non-industrial due to handling challenges with azides and lower scalability.^[33] Non-phosgene routes often employ carbonylation of TDA using carbon monoxide (CO) as the carbonyl source, either reductively or oxidatively. In oxidative carbonylation, TDA reacts with CO and an oxidant (typically O₂) in the presence of catalysts to form toluene dicarbamate (TDC), which is then pyrolyzed to TDI. For instance, palladium-based catalysts like Pd/CeO₂ enable the reaction at 140°C and pressures up to 100 bar, achieving TDC yields of around 50% with minimal byproducts. Cobalt salen complexes supported on silica, promoted by NaI, facilitate similar conversions at 120-180°C and 5-100 bar, with overall TDI yields optimized to 64-97% in simulated continuous processes. The general reaction is represented as:

\text{RNH}_2 + \text{CO} + \frac{1}{2}\text{O}_2 \rightarrow \text{RNCO} + \text{H}_2\text{O}

where R denotes the toluene-2,4-diyl group, often requiring Pd or Co catalysts at 150-200°C for aromatic substrates.^[34]^[35] These methods, pioneered in the 1990s, face challenges like catalyst deactivation and byproduct separation, limiting yields to 70-80%.^[32] Alternative oxidative approaches utilize urea or DMC as phosgene substitutes to generate carbamate intermediates. The urea method involves reacting TDA with urea and an alcohol to form TDC, followed by thermal decomposition at 190-240°C using zinc oxide or Bi₂O₃/Fe₃O₄ catalysts, yielding up to 91% TDI while producing benign byproducts like NH₃ and alcohol. This "zero-emission" process, researched since the 1990s, emphasizes sustainability but requires efficient ammonia removal.^[32] Similarly, the DMC route, developed by EniChem in the late 1990s, couples TDA with DMC at 160-250°C over Zn(OAc)₂/α-Al₂O₃ or Zr-MOF catalysts to produce TDC (yields ~90-95%), which decomposes at 250-270°C with uranyl zinc acetate to afford TDI at 92.6% yield. These routes highlight innovation in using renewable carbonyl equivalents, though high temperatures and catalyst optimization remain hurdles for broader adoption.^[32]^[36]

Chemical Reactivity

Reactions of the Isocyanate Group

The isocyanate group (-N=C=O) in toluene diisocyanate (TDI) exhibits high reactivity through nucleophilic addition, where nucleophiles attack the electrophilic carbon atom of the C=N double bond, leading to the formation of urethane or urea linkages after proton transfer. This mechanism is facilitated by the cumulative double bonds in the -N=C=O moiety, making the carbon highly susceptible to nucleophilic species such as those containing O-, N-, or S-centered functional groups.^[37] A key reaction involves alcohols, producing urethanes via the addition-elimination pathway:

\text{RNCO} + \text{R'OH} \rightarrow \text{RNH-COOR'}

This process is central to the formation of polyurethane prepolymers and proceeds under mild conditions, with reactivity enhanced in aromatic isocyanates like TDI compared to aliphatic ones.^[37] Reaction with primary or secondary amines yields ureas:

\text{RNCO} + \text{R'NH}_2 \rightarrow \text{RNH-CO-NHR'}

Amines react approximately 10^4 to 10^5 times faster than water, making this one of the most rapid transformations of the isocyanate group.^[37] Exposure to water results in amine and carbon dioxide formation through an unstable carbamic acid intermediate:

\text{RNCO} + \text{H}_2\text{O} \rightarrow \text{RNH}_2 + \text{CO}_2

The initial addition forms RNH-COOH, which decomposes rapidly, and this reaction is slower than those with amines but comparable to that with alcohols due to similar nucleophilicity.^[37] The reactivity of TDI's isocyanate groups varies between isomers due to steric effects from the methyl substituent. In 2,4-TDI, the para-positioned isocyanate group is 5–10 times more reactive than the ortho-positioned one, as the latter experiences greater steric hindrance from the adjacent methyl group.^[38] Overall, 2,4-TDI is more reactive than 2,6-TDI, where both isocyanate groups are ortho to the methyl, leading to approximately half the reactivity observed for 2,4-TDI in model additions, primarily attributable to enhanced steric crowding.

Polymerization and Copolymerization Behaviors

Toluene diisocyanate (TDI) undergoes step-growth polymerization with polyols, primarily through the nucleophilic addition of hydroxyl groups to the isocyanate functionalities, forming polyurethane chains linked by urethane (carbamate) groups. This reaction proceeds through the nucleophilic addition of the hydroxyl oxygen to the electrophilic carbon of the isocyanate group, followed by intramolecular proton transfer from the nitrogen to the oxygen and subsequent tautomerization to the stable urethane linkage, enabling the growth of linear or branched polymer chains depending on the functionality of the reactants.^[39] In copolymerization processes, TDI reacts with diols to yield linear polyurethanes, while incorporation of multifunctional alcohols (e.g., triols or higher) leads to crosslinked networks through branching at multiple sites. Additionally, the reaction of TDI with water generates urea linkages and carbon dioxide, which can contribute to volume expansion in polymer systems. These copolymerizations follow similar step-growth mechanisms, with network density controlled by the stoichiometric ratio of isocyanate to hydroxyl groups.^[40] The kinetics of TDI-polyol polymerization are characterized by second-order dependence on the concentrations of isocyanate and hydroxyl groups, with relatively slow uncatalyzed reactions having rate constants on the order of 10^{-3} L/mol·s at 25°C for TDI with primary alcohols, decreasing with increasing polyol molecular weight due to steric hindrance.^[41] For network formation, gelation occurs when the extent of reaction reaches the percolation threshold predicted by Flory-Stockmayer theory, where the branching coefficient \alpha satisfies \alpha = 1/(f-1) for average functionality f > 2, leading to infinite molecular weight networks.^[40] Catalysts such as organotin compounds, notably dibutyltin dilaurate (DBTDL), greatly accelerate the reaction, increasing rate constants by factors of 10^3 or more to values around 10^2 L/mol·s at 30°C depending on concentration and conditions, while also narrowing the molecular weight distribution by promoting more uniform chain extension and reducing side reactions. This catalytic influence allows precise control over polymerization speed and final polymer architecture in crosslinked systems.^[42]

Applications

Polyurethane Foam Manufacturing

Toluene diisocyanate (TDI) functions as the key isocyanate component in polyurethane foam production, reacting with polyether or polyester polyols to form urethane linkages that define the foam's structure and properties. In flexible foams, TDI's high reactivity promotes rapid polymerization, yielding soft, resilient materials ideal for cushioning applications. For rigid foams, TDI contributes to a more cross-linked network, enhancing structural integrity while maintaining low density.^[43]^[44] The primary manufacturing approach is the one-shot method, where TDI is blended with polyols, catalysts, surfactants, and blowing agents in a continuous or batch mixer to simultaneously initiate gelling and blowing reactions. The NCO:OH index, which measures the molar ratio of isocyanate (NCO) groups to hydroxyl (OH) groups, is typically set at 100-110 to balance foam expansion, cell structure, and mechanical strength; indices around 105, for instance, support consistent rise times of 10-15 seconds. Blowing agents include chemical options like water, which reacts with TDI to produce carbon dioxide gas for cell formation, or physical agents such as hydrofluorocarbons (HFCs) like HFC-245fa (now phased out in many regions in favor of low-GWP alternatives like hydrofluoroolefins (HFOs)), which vaporize to create closed cells in rigid variants; curing occurs at ambient temperatures, often completing within minutes. Recent regulations, effective 2025, have phased out high-GWP HFCs in many regions, promoting alternatives like HFOs to reduce environmental impact.^[45]^[46]^[47]^[48] Flexible slabstock foams, produced via continuous pouring onto conveyor lines, serve in mattresses and furniture, achieving densities of 20-40 kg/m³ through controlled formulation for optimal comfort and durability. Rigid foams, often molded or sprayed, provide insulation with thermal conductivity values around 0.02 W/m·K, owing to their closed-cell structure that traps low-conductivity gases. TDI accounts for approximately 85% of its global production used in the flexible foam segment as of 2024, driven by its cost-effectiveness and performance in high-volume production.^[6]^[49]

Coatings, Adhesives, and Elastomers

Toluene diisocyanate (TDI) plays a key role in producing non-foam polyurethane products, particularly in coatings, adhesives, and elastomers, where it reacts with polyols to form durable materials valued for their mechanical properties. These applications leverage TDI's reactivity to create two-component systems that cure into tough, flexible polymers suitable for industrial and consumer uses. Approximately 15% of global TDI consumption (as of 2024) is directed toward these sectors, including coatings, adhesives, sealants, and elastomers.^[50] In coatings, TDI-based polyurethanes are widely employed in two-component formulations for automotive and wood finishes, offering superior abrasion resistance and flexibility essential for high-wear surfaces. These coatings are prepared by mixing TDI prepolymers with polyols, resulting in films that exhibit excellent toughness and chemical resistance, making them ideal for protecting metal and wooden substrates in demanding environments. For instance, TDI-derived polyurethane coatings on wood provide enhanced durability against scratches and environmental exposure while maintaining aesthetic flexibility.^[51]^[52]^[53] For adhesives, TDI is a primary component in reactive hot-melt polyurethane systems, where it is combined with polyols to form bonds for wood, metal, and other substrates, achieving lap shear strengths exceeding 10 MPa after curing. These adhesives solidify upon cooling and further react with moisture to develop high-strength, durable joints suitable for furniture assembly and structural applications. The use of TDI in such formulations ensures rapid setting times and resistance to environmental stresses, with shear strengths reaching up to 11.2 MPa in advanced crosslinked variants.^[54]^[55] TDI-based elastomers are produced as castable polyurethanes from prepolymers, finding applications in tires, seals, and wheels where high mechanical performance is required, such as in forklift tires and industrial seals. These materials typically exhibit tensile strengths of 20-50 MPa and elongations of 300-600%, providing a balance of elasticity and load-bearing capacity for dynamic uses. Hot-cast TDI prepolymers enable the molding of these elastomers, which demonstrate tear resistance and rebound properties critical for seals and rollers.^[56]^[57]^[58] Formulations for these products often incorporate chain extenders like 1,4-butanediol to control molecular weight and enhance phase separation, leading to improved hardness and elasticity in the final polyurethane. This diol reacts with TDI to form hard segments that contribute to the overall strength, as seen in elastomers and coatings requiring precise property tuning. The polymerization chemistry, involving isocyanate-polyol additions detailed in related sections, underpins these tailored performances.^[59]

Health and Safety

Acute and Chronic Toxicity Effects

Toluene diisocyanate (TDI) primarily exerts acute toxic effects through inhalation, causing severe respiratory irritation due to its high reactivity as a low-molecular-weight chemical. Exposure to TDI vapors leads to symptoms such as coughing, chest tightness, dyspnea, rhinitis, and throat irritation, even at low concentrations; for instance, asthmatics and sensitized individuals may experience these effects at 0.01–0.02 ppm, while healthy subjects reported mild coughing after 2 hours at 0.02 ppm.^[60]^[61] In animal studies, acute inhalation toxicity is evident with 4-hour LC50 values around 10 ppm, such as 9.7 ppm in mice and 13.9 ppm in rats, resulting in epithelial damage, necrosis, and inflammation in the respiratory tract.^[60] Higher acute exposures can progress to pulmonary edema and potentially fatal outcomes, as observed in human case reports involving unquantified high-level inhalations.^[62] Chronic exposure to TDI, particularly via inhalation in occupational settings, induces respiratory sensitization, leading to occupational asthma characterized by wheezing, bronchoconstriction, and persistent airway hyperresponsiveness. The prevalence of TDI-induced occupational asthma has historically ranged from 5–10% among exposed workers, with annual incidence rates of 5–6% before the 1970s at higher exposure levels, though it has declined to less than 1% in recent decades due to improved controls maintaining levels at or below 0.005 ppm.^[62] Long-term exposure is also associated with declines in lung function, such as reduced forced expiratory volume in 1 second (FEV1), and chronic inflammation including rhinitis and pneumonitis in animal models at concentrations as low as 0.05 ppm over 2 years.^[62] Regarding carcinogenicity, the International Agency for Research on Cancer (IARC) classifies TDI as possibly carcinogenic to humans (Group 2B), based on limited evidence from human epidemiological studies suggesting increased lung cancer risk in polyurethane workers and sufficient evidence in experimental animals, though some rodent studies showed no significant tumor increases at exposures up to 0.15 ppm.^[63]^[62] The primary mechanism of TDI toxicity involves its isocyanate groups reacting covalently with nucleophilic sites on lung epithelial and surfactant proteins, forming hapten-protein conjugates that trigger immunological sensitization. This process promotes Type I (IgE-mediated) and Type IV (cell-mediated) hypersensitivity responses, leading to airway inflammation, mast cell degranulation, and eosinophil recruitment upon re-exposure; specific IgE antibodies to TDI-human serum albumin conjugates are detectable in 16–57% of sensitized workers.^[62] Non-immunological irritation may also contribute through direct epithelial damage and altered airway permeability. Dermal exposure to TDI causes primary irritation leading to contact dermatitis, with workers reporting conditions like eczema and rash at a prevalence rate ratio of 2.66 compared to non-exposed groups, though systemic absorption is limited and primarily localizes effects to the skin; these effects are attributed to irritation rather than allergy.^[62] To mitigate health risks, regulatory exposure limits for TDI emphasize stringent controls, with the Occupational Safety and Health Administration (OSHA) permissible exposure limit (PEL) set at a ceiling of 0.02 ppm (0.14 mg/m³) and a skin notation indicating potential dermal absorption; the California Division of Occupational Safety and Health (Cal/OSHA) further specifies a time-weighted average (TWA) of 0.005 ppm alongside the 0.02 ppm ceiling.^[64] These limits reflect the compound's potency, as symptoms can manifest below 0.02 ppm in sensitive populations, underscoring the need for monitoring to prevent sensitization.^[61]

Exposure Controls and Regulations

Engineering controls are essential for minimizing occupational exposure to toluene diisocyanate (TDI), with closed process systems preferred to prevent releases during handling, transfer, and use. Local exhaust ventilation systems should capture vapors at the source, maintaining a face velocity of approximately 100 feet per minute (fpm) to effectively control airborne concentrations below permissible exposure limits (PELs). General dilution ventilation may supplement but cannot replace local exhaust in high-risk areas like mixing or spraying operations.^[65]^[66] Personal protective equipment (PPE) serves as a secondary barrier when engineering controls are insufficient. Workers handling TDI must use NIOSH-approved respirators, such as air-purifying respirators with organic vapor cartridges and particulate filters for low-exposure tasks or supplied-air respirators for higher concentrations or emergencies, in compliance with OSHA's respiratory protection standard (29 CFR 1910.134). Chemical-resistant gloves made from materials like butyl rubber, nitrile, or neoprene (at least 0.4 mm thick for extended protection) and full-body suits of impermeable fabrics such as laminated polyethylene/ethylene vinyl alcohol are required to prevent dermal contact, along with chemical splash goggles or face shields.^[65]^[67] Regulatory frameworks worldwide impose strict limits on TDI to protect workers and consumers. In the European Union, under REACH Annex XVII, diisocyanates including TDI are restricted in mixtures above 0.1% by weight, requiring mandatory training on safe use, labeling, and exposure prevention before professional application. In the United States, TDI is listed under the Toxic Substances Control Act (TSCA) with an EPA action plan addressing consumer exposures, and a proposed Significant New Use Rule (SNUR) to notify the agency of new uses; OSHA enforces a PEL of 0.02 ppm as a 10-minute ceiling. Emergency response guidelines include the NFPA 704 rating for TDI: Health 3 (serious hazard from short exposure), Flammability 1 (low risk), and Reactivity 2 (elevated temperature hazard).^[68]^[69]^[64] Notable incidents have underscored the need for rigorous controls, such as the 2004 explosion of a railcar containing TDI waste during unloading at a U.S. hazardous waste facility, which released toxic vapors and prompted investigations leading to improved monitoring, spill response protocols, and regulatory emphasis on waste handling under the Resource Conservation and Recovery Act (RCRA). These events have driven industry-wide adoption of enhanced engineering safeguards and training to prevent recurrence.^[70]

Environmental Considerations

Production Emissions and Pollution

The production of toluene diisocyanate (TDI) primarily occurs through the phosgenation of toluene diamine (TDA), a process that generates significant emissions of hazardous substances, including phosgene, hydrogen chloride (HCl), and unreacted TDI. Phosgene, a highly toxic intermediate, can escape as fugitive emissions from reactors, distillation columns, and equipment leaks during the reaction and purification stages, with up to 0.0033% (33 lb per million lb) of the phosgene input in uncontrolled scenarios for a plant producing 200 million pounds of phosgene annually.^[71]^[72]^[72] HCl is produced stoichiometrically as a byproduct of the phosgenation reaction and may be released via process vents or neutralization steps if not captured. Residual TDI contributes to fugitive emissions through leaks from pumps, valves, flanges, and storage systems, posing risks due to its volatility and reactivity.^[71]^[72]^[72] These emissions contribute substantially to air pollution, with TDI classified as a hazardous air pollutant (HAP) under the U.S. Clean Air Act due to its potential for respiratory sensitization and environmental persistence in vapor form. As a volatile organic compound (VOC), TDI and associated solvents from TDI production vents and fugitives participate in photochemical reactions, forming ground-level ozone and contributing to smog formation in urban-industrial areas. In the United States, TRI data from 2016 reported approximately 19,050 pounds of TDI air emissions from 134 facilities, highlighting the scale of VOC releases from ongoing production activities. Globally, pre-2020 production was driven by an installed capacity exceeding 2 million tons of TDI per year before widespread adoption of advanced controls, with emissions significantly reduced thereafter. As of 2024, global TDI production capacity has grown to approximately 2.75 million metric tons annually.^[62]^[73]^[62]^[13]^[27] Water pollution arises from wastewater generated during TDA neutralization and phosgene quenching, which contains residual amines (such as TDA), chloride salts, and organic byproducts, leading to high chemical oxygen demand (COD) levels often exceeding 500 mg/L in untreated effluents. For instance, TDI production wastewater can exhibit COD concentrations up to 2,746 mg/L due to dissolved organics and hydrolysis products, necessitating pretreatment to prevent oxygen depletion in receiving waters. These discharges, if unmanaged, elevate salinity and toxicity in aquatic systems, though rapid hydrolysis of TDI limits direct persistence. In 2016 U.S. TRI reports, water releases of TDI isomers totaled around 255 pounds across facilities, underscoring the need for on-site treatment.^[62]^[74]^[75] Mitigation efforts have focused on emission control technologies, particularly scrubbers, which have reduced HCl releases by up to 99% in modern facilities through caustic or water absorption systems integrated into vent streams. Caustic scrubbers in phosgene handling units capture residual phosgene and HCl, converting them to less harmful salts, while leak detection and repair programs limit TDI fugitives to below 0.1 mg/Nm³ in regulated plants. These advancements, implemented widely since the 2010s, have curtailed global emissions significantly, with post-mitigation levels dropping by 70-90% in compliant operations compared to pre-2020 baselines.^[31]^[71]^[72]

Biodegradation and Waste Management

Toluene diisocyanate (TDI) exhibits low biodegradability in environmental media due to its rapid chemical reactivity rather than biological breakdown. In moist soils, sediments, and water, TDI undergoes rapid hydrolysis, with conversion to inert polyureas occurring within hours to days depending on conditions, forming inert polyureas that limit further microbial degradation.^[76] In aerobic conditions, any resulting toluene diamine (TDA) intermediates can be biodegraded by soil microorganisms to carbon dioxide and ammonia. Dry soil environments may extend persistence slightly, with 50% conversion to polyureas occurring in 1–7 hours depending on soil type and moisture.^[4] Polyurethanes derived from TDI, such as flexible foams, demonstrate even slower biodegradation, primarily through gradual microbial hydrolysis of ester linkages in polyester-based variants. Aromatic polyurethanes like those from TDI are more resistant to microbial attack compared to aliphatic counterparts, with degradation rates influenced by polymer structure and environmental conditions.^[77] Under aerobic soil or wastewater conditions, microbial consortia can convert polyurethane carbon to CO2 at rates that vary with hydrolysis stabilizers, but complete breakdown often requires months to years.^[78] Key degradation pathways for TDI and its polyurethane products involve hydrolysis, yielding polyureas, amines like TDA, and ultimately CO2 under biological conditions. In the presence of water, TDI hydrolyzes stepwise to form urea intermediates and solid polyureas, with TDA as a minor byproduct (yield <0.4%).^[4] Photodegradation plays a lesser role for the monomer but contributes to polyurethane breakdown under UV exposure, leading to chain scission and loss of physical integrity without a dominant quantitative rate established for environmental contexts.^[79] Waste management of TDI-based polyurethanes emphasizes recycling and energy recovery to minimize environmental release. Chemical recycling via glycolysis depolymerizes polyurethane foams using glycols and catalysts, recovering 80–90% of polyols for reuse in new formulations, with aromatic amines as byproducts.^[80] Incineration with energy recovery is widely practiced, providing a calorific value of approximately 7,000 kcal/kg while reducing volume by 99%, though it generates nitrogen oxides (NOx) that require flue gas treatment.^[81] Landfilling is discouraged due to the non-biodegradable nature of polyurea residues. In the European Union, polyurethane waste management is governed by directives promoting circularity and restricting disposal. The Waste Electrical and Electronic Equipment (WEEE) Directive (2012/19/EU) mandates separate collection and recycling of polyurethane components in electronics, targeting high reuse rates for such materials.^[82] The Landfill Directive (1999/31/EC), as amended, imposes progressive bans on landfilling waste suitable for recycling or recovery, including polyurethanes, with restrictions tightening to limit such disposals to 10% of municipal waste by 2035.^[83] These measures encourage glycolysis and incineration over landfilling to address non-biodegradable residues.^[84]

References

[1]
[PDF] 2,4-Toluene diisocyanate
... Uses. 2,4-Toluene diisocyanate is used as a chemical intermediate in the production of polyurethane products such as foams, coatings, and elastomers. (3).
[2]
Toluene diisocyanates (EHC 75, 1987) - INCHEM
2.2. Physical and Chemical Properties Toluene diisocyanates are colourless liquids or crystals, turning pale yellow on standing, and having a characteristic ...
[3]
TOLUENE DIISOCYANATE - CAMEO Chemicals - NOAA
A clear colorless to pale yellow liquid with a pungent odor. Denser than water. Burns, but may be difficult to ignite. Vapors are heavier than air.
[4]
[PDF] TDI in the Environment - American Chemistry Council
What is TDI? Toluene diisocyanate (TDI) is a reactive chemical intermediate used primarily in the manufacture of polyurethanes.
[5]
PRODUCTION, IMPORT/EXPORT, USE, AND DISPOSAL - NCBI
PRODUCTION. TDI is manufactured via the dinitration of toluene with mixed acid to produce a mixture of 2,4- and 2,6-dinitro isomers in a 80:20 ratio.
[6]
Medical Management Guidelines for Toluene Diisocyanate - CDC
Toluene diisocyanate is commonly used as a chemical intermediate in the production of polyurethane foams, elastomers, and coatings; paints; varnishes; wire ...Missing: structure | Show results with:structure
[7]
Toluene Diisocyanates - 15th Report on Carcinogens - NCBI
Dec 21, 2021 · Toluene diisocyanates are reasonably anticipated to be human carcinogens based on sufficient evidence of carcinogenicity from studies in ...
[8]
Toluene 2,4-Diisocyanate | C9H6N2O2 | CID 11443 - PubChem
Toluene diisocyanate exists in two isomeric forms (2,4-toluene diisocyanate and 2,6-toluene diisocyanate) which have similar properties and effects.
[9]
Toluene 2,6-Diisocyanate | C9H6N2O2 | CID 7040 - PubChem
4 Boiling Point. 264 to 271 °F at 18 mmHg (EPA, 1998). U.S. Environmental ... Subjects exposed to 2,4-TDI and 2,6-TDI in a test chamber (5.5 ppb for 7.5 ...
[10]
[PDF] Toxicological Profile for Toluene Diisocyanate and ...
4.1 CHEMICAL IDENTITY Commercial-grade TDI is made up of an 80:20 mixture of isomers 2,4- and 2,6-TDI and represents >95% of TDI industrial use (NIOSH 1989). ...
[11]
Toluene 2,6-diisocyanate - an overview | ScienceDirect Topics
Toluene diisocyanate has two common isomers; the 2,4- and 2,6-TDI. The most commonly supplied TDI is a combination of 80% 2,4- and 20% 2,6-TDI. A 65/35 ratio ...
[12]
[PDF] TDI Physical/Chemical Properties - American Chemistry Council
Dec 1, 2001 · Boiling Point oC. (Atmosphere Pressure). 252-254. 249 (DSC)**. 247-249 ... * 80:20 TDI consists of 80% 2,4-TDI and 20% 2,6-TDI. 65:35 TDI ...
[13]
[PDF] MDI and TDI: Safety, Health and the Environment.
The 2,4-isomer is more reactive than the 2,6-isomer, due to steric factors ... This effect can be attributed to the lower reactivity of 2,6-TDI. In such an ...
[14]
Sustainable cycloaliphatic polyurethanes: from synthesis to ...
Dec 15, 2022 · Aromatic isocyanates are efficient given that they have higher reactivity due to the negative charge delocalization on their aromatic ring. The ...
[15]
Toluene diisocyanate CAS#: 26471-62-5 - ChemicalBook
Melting point, 19.5~21.5℃. Boiling point, 247℃. Density, 1.22. vapor pressure, 0.03 hPa ( 20 °C). refractive index, 1.5660 to 1.5700. Flash point, 137 °C.
[16]
Toluene-2,4-diisocyanate (TDI) (PIM 534) - Inchem.org
3 Description Boiling point: 251 °C Melting point: 19.5 to 2l.5 °C Autoignition temperature: 620 °C Flash point: open cup 135 °C closed cup 127 °C (WHO, 1987).
[17]
Toluene 2,4-diisocyanate
Heat of vaporization, 40.61 kJ/mol. Heat of combustion, -4126 kJ/mol. Hazards and Protection. Storage, Store in a cool, dry, well-ventilated area away from ...
[18]
Table 4-2, Physical and Chemical Properties of Toluene ... - NCBI
Table 4-2Physical and Chemical Properties of Toluene Diisocyanate and Methylenediphenyl Diisocyanate ; Melting point, 37°C · 11–14°C ; Boiling point, 196°C (at 5 ...Missing: thermodynamic heat vaporization
[19]
How Toluene Diisocyanate (TDI) is made: A Quick Dive into Process ...
Jul 11, 2025 · Toluene Diisocyanate (TDI) is produced through a multi-step chemical process involving nitration, hydrogenation, and phosgenation.
[20]
[PDF] Toluene Diisocyanate from Toluene (Gas-Phase Phosgenation)
Industrial TDI manufacture is primarily based on toluene raw material. The most common method of preparing TDI on a commercial scale involves the nitration of ...
[21]
A Theoretical Study on the Phosgenation of 2,4-Toluenediamine (2 ...
Industrially relevant phosgenation mechanisms of 2,4-toluenediamine (2,4-TDA) were investigated using G3MP2B3 model chemistry.
[22]
System and process for production of toluene diisocyanate
A method for producing toluene diisocyanate is disclosed which comprises forming a dispersion comprising phosgene gas bubbles dispersed in toluene diamine ...
[23]
A Method to Predict Phosgenation Reaction Performance To ...
May 20, 2013 · Phosgenation reaction is the most important operation in the process of producing TDI, which is commonly performed in a jet reactor.Missing: process | Show results with:process
[24]
Production of Toluene diisocyanate (TDI) - Chempedia - LookChem
Phosgene is reacted with the hydrochlorides at elevated temperatures and with strong agitation to give the diisocyanates. The HCl which evolves is removed with ...<|separator|>
[25]
Toluene DiIsocyanate Market By Size, Share and Forecast 2035
The global Toluene Diisocyanate market stood at approximately 2748 thousand tonnes in 2024 and is anticipated to grow at a CAGR of 4.17% during the forecast ...
[26]
Our six sites | Covestro Germany
Our 6 production sites: Leverkusen, Dormagen, Krefeld-Uerdingen, Brunsbüttel, Bomlitz, and Meppen.``starthilfe'' Makes Young... · A Broad Portfolio Of... · Covestro Management In...Missing: major BASF
[27]
Covestro – Sites in the United States
Baytown, TX: Largest production site in North America · Channelview, TX: Production site · Deerfield, MA: Production site · Elgin, IL: Main office and R&D; Pilot ...
[28]
https://www.covestro.com/press/covestro-successfully-completes-modernization-of-its-dormagen-tdi-plant/
[29]
US9950996B2 - Bio-based aromatic diisocyanates for preparation of ...
... toluene diisocyanate (TDI) using dibutyltin dilaurate (DBTDL) catalyst. ... (e) converting the aromatic diacyl azide by thermal Curtius rearrangement to obtain ...
[30]
https://www.covestro.com/en/company/covestro-worldwide/united-states/covestro-in-the-united-states/about-covestro-llc/sites
[31]
[PDF] PHOSGENEâ•'FREE ROUTE TO TOLUENE DIISOCYANATE - CORE
Oct 10, 2005 · Bayer has developed a gas-phase phosgenation (GPP) process for the production of TDI ... catalysts, solvents and promoters of similar roles as ...
[32]
https://doi.org/10.1021/acsomega.3c10069
[33]
A brief overview of properties and reactions of diisocyanates
May 8, 2022 · Diisocyanates are monomers used to make polyurethane (PU) polymers and are characterized by having two NCO groups as their key reactive sites.Missing: thermodynamic vaporization<|separator|>
[34]
https://doi.org/10.1039/D0GC02412K
[35]
Network formation of polyurethanes due to side reactions
Network formation in polyurethanes due to allophanate and biuret formation: Gel fraction and equilibrium modulus.
[36]
The Kinetics of the Polymerization Reaction of Toluene Diisocyanate ...
In the uncatalyzed and diethylcyclohexylamine-catalyzed reactions, the rate constants were found to decrease with increasing molecular weight of the polyols, ...Missing: growth | Show results with:growth
[37]
Diisocyanates Explained - American Chemistry Council
Diisocyanates are chemical building blocks used to make polyurethane products. They are divided into aromatic and aliphatic types, including TDI and MDI.
[38]
Toluene Diisocyanate is Revolutionising the Automotive Industry
Aug 21, 2024 · Toluene Diisocyanate (TDI) is an organic compound commonly used in the production of flexible and rigid polyurethane foams. It is a vital ...
[39]
Effect of Natural Oil Based Polyols on the Properties of Flexible ...
... polyurethane foam by one shot method. The NCO index (NCO equivalent/OH equivalent) was fixed at 1.00. The characteristic times such as cream time, gel time ...
[40]
WO2010100421A2 - Polyurethane foam - Google Patents
A method of making a polyurethane foam from a mixture of isocyanate modified ... In Examples ZJ and ZK, the TDI index was reduced to a less extreme level of 105.
[41]
Blowing Agent - an overview | ScienceDirect Topics
In flexible urethane foams, the major blowing agent is water and, at the same time, auxiliary blowing agents. An example of a PUR foam mix is the polyol, ...
[42]
[PDF] Eco-profile of Flexible Polyurethane (PU) Foam EUROPUR ...
Feb 10, 2025 · This Eco-profile considers four representative flexible PU foam grades: • TDI-based PU foam without FR, high density 35 to 40 kg/m³. • TDI-based ...
[43]
Advances in Low-Density Flexible Polyurethane Foams by ... - NIH
May 26, 2021 · The flexible polyurethane (PU) foams are used in various applications, such as bedding, furniture, automotive and industrials. The conversion ...
[44]
https://www.palvifze.com/Blog/detail/toluene-diisocyanate-is-revolutionising-the-automotive-industry
[45]
Performance Evaluation of Toluene Diisocyanate TDI-65 ... - BDMAEE
Aug 30, 2025 · ~60% of global TDI production goes into flexible foams (mattresses, car seats). ~15% is used in coatings, adhesives, sealants, and elastomers ( ...
[46]
Synthesis, characterization of poly(urethane amide) resins from ...
As polyurethanes exhibit better abrasion resistance, toughness, chemical resistance ... coatings for the automotive appliance and wood industries [19]. So authors ...
[47]
Preparation of two-component polyurethane coatings from bleached ...
Apr 20, 2015 · Because of their excellent properties (abrasion resistance, toughness, flexibility ... TDI) prepolymer and characterised for use as wood coatings.
[48]
Evaluation of Mesua ferrea L. seed oil modified polyurethane paints
They possess excellent corrosion resistance, abrasion resistance, scratch resistance, flexibility and chemical resistance. Polyurethanes have particularly found ...
[49]
[PDF] Specialties for adhesives & sealants - Perstorp
For the chemical synthesis of polyurethane pre-polymers, we offer Scuranate™ TDI grades with different mixtures of 2,4 and. 2,6 isomers and the two main types ...
[50]
Solvent-free synthesis of pendant crosslinked polyurethane hot melt ...
DAPU exhibited a higher bonding performance (11.2 MPa) than the commercial reactive polyurethane hot melt adhesive (PUR-Ausbond 3550) and can reach 10.2 MPa ...
[51]
Castable Elastomer Systems | Urethane Prepolymers | Hot Cast
Polycoat Products now offers Pre-Pol®, our new line of hot cast TDI based urethane prepolymers for all types of elastomeric applications.
[52]
POLYESTER TDI Hot Cast PU Elastomer
Tensile Strength (kgf/cm2), 350, 250-400. Elongation (%), 625, 400-500. Tear Strength (kgf/cm), 78, 120-160. Compression Set (%), 30, 30. Notice: These values ...Missing: tires | Show results with:tires
[53]
Lyndhurst, NJ - PREPOLYMERS - Polyurethane Specialties Company
Feb 3, 2019 · POLYETHER / TDI ELASTOMERS ; Tensile Strength, psi, 5500 ; Elongation, %, 450 ; Tear Strength, DIE C, pli, 560 ; Tear Strength, D-470, pli, 80.Missing: tires seals
[54]
1,4 Butanediol Chain Extender | Polyurethane Elastomers - Tri-iso
1,4 Butanediol is an aliphatic diol. MW: 90.12 g/mol, OH Value: 1245 mg KOH/g. Used extensively as chain extenders in the manufacture of polyurethanes.Missing: TDI | Show results with:TDI
[55]
Toluene 2,4- and 2,6-Diisocyanate:Acute Exposure Guideline Levels
TDI is among a group of chemicals, the isocyanates, that are highly reactive compounds containing an −NCO group. TDI exists as both 2,4- and 2,6-isomers, which ...Missing: steric | Show results with:steric
[56]
HEALTH EFFECTS - Toxicological Profile for Toluene Diisocyanate ...
Although the exact mechanism of toxicity of TDI and MDI has not been elucidated, there is some indication that occupational asthma observed in some workers ...GENOTOXICITY · TOXICOKINETICS · MECHANISMS OF ACTION
[57]
[PDF] ATSDR TDI and MDI (Toluene Diisocyanate and Methylenediphenyl ...
the corresponding diamines, which are then treated with phosgene to yield TDI, made up of an. 80:20 mixture of isomers 2,4- and 2,6-TDI (HSDB 2012). MDI is ...
[58]
Toluene Diisocyanates (IARC Summary & Evaluation, Volume 71 ...
Apr 13, 1999 · Toluene diisocyanates are possibly carcinogenic to humans (Group 2B). For definition of the italicized terms, see Preamble Evaluation. Synonyms.
[59]
2,4-TOLUENE-DIISOCYANATE | Occupational Safety and Health Administration
### Summary for 2,4-Toluene Diisocyanate (CAS #584-84-9)
[60]
[PDF] CPL_03-00-017.pdf - OSHA
Engineering controls such as closed systems and ventilation should be the principal method for minimizing isocyanate exposure in the workplace. Other controls, ...
[61]
[PDF] Designing a Local Exhaust Ventilation System to Control Toluene ...
Dec 27, 2017 · The suction hood (in most cases, the capture velocity is about 0.5 meters per second) cannot control exhausted pollutants of painting gun ( ...
[62]
[PDF] Guidance for Selection of Personal Protective Equipment for TDI Users
Engineering controls (e.g., local exhaust ventilation) and sound workplace practices may be the first line of defense against potential exposure to TDI, and ...
[63]
Training requirements for users of diisocyanates - Tyosuojelu.fi
Nov 28, 2024 · The training requirement in REACH concerns diisocyanates with a concentration of over 0.1% by weight. Below are examples of diisocyanates subject to REACH ...
[64]
Toluene Diisocyanates (TDI) Action Plan | US EPA
Apr 14, 2025 · This Action Plan addresses the use of toluene diisocyanate (TDI) and related compounds in products that may result in consumer and general population exposures.
[65]
Explosion of a railcar containing toluene diisocyanate waste
Nov 17, 2004 · A railcar containing toluene diisocyanate (TDI) waste exploded during the unloading process at a hazardous waste-treatment and disposal ...Missing: notable | Show results with:notable
[66]
[PDF] Locating and Estimating Air Emission from Sources of Phosgene
Emission source kg/h. Marketable phosgene Phosgene production. 0.38 producer. Toluene diisocyanate Phosgene production. 0.38 producer. TDI production. 0.15.
[67]
[PDF] development of national emission standards for petrochemical plants
• Fugitive emission from valves, pumps, compressors etc. • TDA vacuum distillation vent. • TDI flash distillation. Phosgene, TDI, HCl. 18.0 PTA. • Off gases ...
[68]
National Emission Standards for Hazardous Air Pollutants | US EPA
The primary HAP that will be controlled with this action include hydrochloric acid (HCl), 2,4-toluene diisocyanate (TDI), and hydrogen cyanide (HCN). This ...
[69]
Beneficial effects of micro-electrolysis process in the treatment of TDI ...
Jul 23, 2025 · This study systematically analyzed the physicochemical characteristics of TDI production wastewater, and discussed its treatment difficulties ...
[70]
Application of electro oxidation process for treating wastewater from ...
Jan 19, 2024 · Under suitable operating conditions, COD of petrochemical wastewater was reduced from 2746 to 200 mg/l within 5 h with energy consumption of ...
[71]
[PDF] Cradle-to-Gate-Life-Cycle-Analysis-of-Toluene-Diisocyanate-Resin ...
May 18, 2023 · Toluene diisocyanate is manufactured by first producing intermediate products; diamines (TDA) and phosgene. Diamines are produced from the ...
[72]
[PDF] Toluene Diisocyanate - Regulations.gov
In media where water is present (e.g., water, moist soils, sediment), TDI is considered transient, with a half-life of under a minute (Yakabe et al. 1999). The ...
[73]
the fungal and bacterial biodegradability of polyurethanes - PMC - NIH
Mar 17, 2023 · This review will focus on polyurethanes and their biodegradation, outlining the difficulty of degrading different versions of the same material.
[74]
Effect of Polymer Properties on the Biodegradation of Polyurethane ...
Nov 17, 2022 · We found that the presence of a hydrolysis stabilizer reduced (T)PU fragmentation while not affecting the conversion of (T)PU carbon into CO2.
[75]
[PDF] The Effect of Flexibility on the Photodegradation of Aromatic ... - DTIC
However, in instances where exposure to UV radiation from sun light is required, they are found to rapidly degrade with loss of physical integrity and.
[76]
Recovery of Polyol and Aromatic Amines from Rigid Polyurethane ...
Jul 9, 2025 · Using our standard liquid–liquid extraction method, the pMDA and polyol could be further fractionated, achieving yields of 84 and 80%, and ...
[77]
A systematic review of methodologies and solutions for recycling ...
Dec 15, 2024 · 3.2. Incineration works as a method for heat recovery. Burning 1 kg of PU yields a calorific value of approximately 7000 kcal/kg, which ...
[78]
Waste from Electrical and Electronic Equipment (WEEE) - Environment
Read about EU policy and law on waste electrical and electronic equipment (WEEE or e-waste), such as computers and smartphones.
[79]
Landfill waste - Environment - European Commission
Oct 16, 2025 · Introduces restrictions on the landfilling of all waste that is suitable for recycling or energy recovery from 2030 onwards · Limits the share of ...
[80]
[PDF] Pu euRoPe - Excellence in Insulation
It concludes that the optimum waste management of PU consists of a good mix of recycling, recovery and high efficiency waste- to-energy options. Given long-term ...