Using dibutyltin dilaurate catalyst to accelerate polyurethane foaming reaction

Dibutyltin Dilaurate Catalysis in Polyurethane Foaming: Mechanism, Performance, and Application

Abstract: Polyurethane (PU) foams are widely used in diverse applications due to their versatility and tunable properties. The formation of PU foam involves complex chemical reactions between isocyanates, polyols, and blowing agents, which are typically catalyzed to achieve desired reaction rates and foam morphologies. Dibutyltin dilaurate (DBTDL) is a widely used organotin catalyst in PU foam production, known for its effectiveness in accelerating both the urethane (polyol-isocyanate) and urea (isocyanate-water) reactions. This article provides a comprehensive review of DBTDL’s role in PU foaming, covering its catalytic mechanism, influence on foam properties, impact of reaction parameters, and application in various PU foam formulations. We will also explore the challenges associated with DBTDL usage, including environmental concerns and potential health risks, and discuss emerging alternatives.

Keywords: Polyurethane foam, Dibutyltin dilaurate, Catalyst, Foaming, Reaction kinetics, Foam properties, Organotin catalyst, Environmental impact, Alternatives

1. Introduction

Polyurethane (PU) foams are ubiquitous materials found in insulation, cushioning, packaging, and automotive components. The production of PU foams relies on the simultaneous reactions of isocyanates with polyols to form urethane linkages (polymerization), and with water to generate carbon dioxide (blowing), which creates the cellular structure. These reactions must be carefully controlled to achieve optimal foam properties, such as density, cell size, and mechanical strength. Catalysts play a crucial role in regulating the kinetics of these reactions, ensuring a balanced and efficient foaming process.

Dibutyltin dilaurate (DBTDL) is a widely recognized and extensively used organotin catalyst in the PU foam industry. Its effectiveness stems from its ability to accelerate both the urethane (polyol-isocyanate) and urea (isocyanate-water) reactions. However, due to increasing environmental concerns and potential health hazards associated with organotin compounds, research is ongoing to develop alternative catalysts. This review aims to provide a detailed overview of DBTDL’s role in PU foaming, including its catalytic mechanism, influence on foam properties, factors affecting its performance, and a discussion of potential alternatives.

2. Chemical Properties and Product Parameters of Dibutyltin Dilaurate (DBTDL)

Dibutyltin dilaurate (DBTDL) is an organotin compound with the chemical formula (C₄H₉)₂Sn(OOC(CH₂)₁₀CH₃)₂. It is a colorless or pale yellow liquid at room temperature and is soluble in most organic solvents. Key product parameters are outlined in Table 1.

Table 1: Typical Product Parameters of DBTDL

Parameter	Value	Unit	Test Method
Appearance	Colorless to Pale Yellow Liquid	–	Visual
Tin Content (Sn)	18.0 – 19.0	% by weight	Titration
Specific Gravity (25°C)	1.04 – 1.07	g/cm3	ASTM D4052
Viscosity (25°C)	40 – 60	cPs	ASTM D2196
Acid Value	< 1.0	mg KOH/g	ASTM D465
Water Content	< 0.1	% by weight	Karl Fischer

3. Catalytic Mechanism of DBTDL in Polyurethane Foaming

DBTDL catalyzes both the urethane (polyol-isocyanate) and urea (isocyanate-water) reactions. The generally accepted mechanism involves the coordination of DBTDL to the reactants, facilitating the nucleophilic attack of the polyol hydroxyl group or water molecule on the isocyanate group.

• Urethane Reaction: DBTDL initially coordinates with the polyol hydroxyl group, increasing its nucleophilicity. Simultaneously, it can also coordinate with the isocyanate group, activating it for nucleophilic attack. This dual activation lowers the activation energy of the reaction, accelerating urethane bond formation (Oertel, 1994). The simplified catalytic cycle can be represented as follows:

  1. DBTDL + R-OH ⇌ DBTDL…R-OH (Complex Formation)
  2. DBTDL…R-OH + R’-NCO ⇌ DBTDL…R-OH…R’-NCO (Transition State)
  3. DBTDL…R-OH…R’-NCO → R-O-CO-NH-R’ + DBTDL (Urethane Formation & Catalyst Regeneration)

• Urea Reaction: DBTDL facilitates the reaction between isocyanate and water, leading to the formation of carbamic acid, which subsequently decomposes to form an amine and carbon dioxide. The amine then reacts with another isocyanate molecule to form urea (Rand, 1997). The catalytic mechanism is similar to the urethane reaction, with DBTDL coordinating with both water and isocyanate.

  1. DBTDL + H₂O ⇌ DBTDL…H₂O (Complex Formation)
  2. DBTDL…H₂O + R-NCO ⇌ DBTDL…H₂O…R-NCO (Transition State)
  3. DBTDL…H₂O…R-NCO → R-NHCOOH + DBTDL (Carbamic Acid Formation & Catalyst Regeneration)
  4. R-NHCOOH → R-NH₂ + CO₂ (Decomposition of Carbamic Acid)
  5. R-NH₂ + R-NCO → R-NH-CO-NH-R (Urea Formation)

The relative rates of the urethane and urea reactions are crucial for controlling the foam morphology. DBTDL’s ability to catalyze both reactions makes it a versatile catalyst for PU foam production.

4. Influence of DBTDL on Polyurethane Foam Properties

The concentration of DBTDL significantly impacts the properties of the resulting PU foam. Higher concentrations typically lead to faster reaction rates, shorter cream times, and increased blowing efficiency. This, in turn, can influence cell size, foam density, and mechanical properties.

• Reaction Rate and Cream Time: DBTDL accelerates both the gelation (urethane) and blowing (urea) reactions. Increased DBTDL concentration generally results in a shorter cream time, which is the time it takes for the mixture to start foaming. This is due to the faster generation of carbon dioxide and the increased rate of polymerization.

• Cell Size and Foam Density: The balance between the gelation and blowing reactions is critical for controlling cell size and foam density. An excess of blowing reaction relative to gelation can lead to larger cell sizes and lower density foams. Conversely, an excess of gelation can result in closed-cell foams with higher densities. The optimal DBTDL concentration is dependent on the specific formulation and desired foam properties. Generally, increasing DBTDL concentration promotes a finer cell structure, but excessive amounts can lead to foam collapse due to the rapid release of CO₂ before the polymer network has sufficient strength.

• Mechanical Properties: The mechanical properties of PU foams, such as tensile strength, compressive strength, and elongation at break, are influenced by the cell structure and polymer network. Optimized DBTDL concentration can contribute to a more uniform and robust cell structure, leading to improved mechanical properties. Over-catalyzed systems may result in brittle foams with reduced mechanical strength due to incomplete reactions or uneven cell distribution.

Table 2: Effect of DBTDL Concentration on PU Foam Properties (Illustrative)

DBTDL Concentration (phr)	Cream Time (s)	Rise Time (s)	Cell Size (mm)	Density (kg/m3)	Compressive Strength (kPa)
0.1	60	180	1.5	35	100
0.5	30	120	1.0	30	120
1.0	15	90	0.8	28	130
1.5	10	75	0.6	25	140

Note: phr = parts per hundred parts of polyol. This table is illustrative and actual values will vary based on the specific formulation and reaction conditions.

5. Factors Affecting DBTDL Performance in PU Foaming

Several factors can influence the activity and effectiveness of DBTDL in PU foaming systems. These include temperature, moisture content, and the presence of other additives.

• Temperature: Reaction rate increases with temperature, and DBTDL’s catalytic activity is also temperature-dependent. Higher temperatures generally lead to faster reaction rates and shorter cream times. However, excessively high temperatures can cause premature blowing and foam collapse. Therefore, temperature control is crucial for optimizing the foaming process.

• Moisture Content: Moisture content in the raw materials, particularly polyols, can significantly impact the urea reaction and the overall foaming process. Excess moisture can lead to uncontrolled blowing and poor foam quality. DBTDL can interact with moisture, potentially affecting its catalytic activity. Careful control of moisture content is essential for consistent results.

• Presence of Other Additives: PU foam formulations typically contain a variety of additives, such as surfactants, stabilizers, and flame retardants. These additives can interact with DBTDL, either enhancing or inhibiting its catalytic activity. Surfactants, for example, can influence cell nucleation and stabilization, which can indirectly affect the performance of DBTDL. Flame retardants may contain acidic or basic components that can neutralize or enhance the catalytic activity of DBTDL.

• Polyol Type: The type of polyol used significantly influences the reaction kinetics and the effectiveness of DBTDL. Polyols with higher hydroxyl numbers (more OH groups per molecule) generally react faster with isocyanates. The steric hindrance around the hydroxyl groups can also affect the reaction rate.

6. Applications of DBTDL in Various PU Foam Formulations

DBTDL is used in a wide range of PU foam applications, including:

• Flexible Foams: DBTDL is commonly used in the production of flexible PU foams for cushioning, mattresses, and automotive seating. It helps to achieve the desired cell structure and softness in these applications.

• Rigid Foams: DBTDL is also used in rigid PU foams for insulation in buildings, refrigerators, and other appliances. In rigid foams, it contributes to the formation of a fine cell structure, which enhances the insulation properties.

• Spray Foams: DBTDL is used in spray foam applications for insulation and sealing. The rapid reaction rate catalyzed by DBTDL is important for achieving quick adhesion and expansion in these applications.

• Microcellular Foams: DBTDL can be used in the production of microcellular PU foams for shoe soles, automotive parts, and other applications requiring high strength and durability.

Table 3: Applications of DBTDL in Different PU Foam Types

Foam Type	Application Examples	Role of DBTDL
Flexible Foam	Mattresses, Cushions, Automotive Seating	Contributes to desired cell structure, softness, and resilience.
Rigid Foam	Building Insulation, Refrigerators, Freezers	Promotes fine cell structure for enhanced insulation properties.
Spray Foam	Insulation, Sealing, Roofing	Accelerates reaction for quick adhesion and expansion.
Microcellular Foam	Shoe Soles, Automotive Parts, Seals	Helps achieve high strength, durability, and a fine, uniform cell structure.
Integral Skin Foam	Steering Wheels, Automotive Interior Parts	Facilitates the formation of a dense skin and a foamed core.

7. Environmental and Health Concerns Associated with DBTDL

Despite its effectiveness as a catalyst, DBTDL has raised environmental and health concerns due to the potential toxicity of organotin compounds.

• Environmental Impact: Organotin compounds can persist in the environment and bioaccumulate in aquatic organisms. They can have detrimental effects on marine ecosystems, including endocrine disruption and reproductive impairment in marine life (Champ, 2003).

• Health Risks: DBTDL can be absorbed through the skin and respiratory system. Exposure to DBTDL has been linked to skin irritation, eye irritation, and respiratory problems. Some studies have also suggested potential neurotoxic effects (WHO, 2005).

Due to these concerns, regulatory bodies in many countries have imposed restrictions on the use of DBTDL in certain applications, particularly those that come into direct contact with humans, such as toys and food packaging.

8. Alternatives to DBTDL in Polyurethane Foaming

The environmental and health concerns associated with DBTDL have driven the development of alternative catalysts for PU foam production. These alternatives include:

• Bismuth Carboxylates: Bismuth carboxylates, such as bismuth neodecanoate, are less toxic alternatives to organotin catalysts. They are effective in catalyzing the urethane reaction but generally less effective in catalyzing the urea reaction. Therefore, they are often used in combination with amine catalysts to balance the gelation and blowing reactions (Kanner, 1999).

• Zinc Carboxylates: Zinc carboxylates, such as zinc octoate, are another class of less toxic alternatives. They are generally less active than DBTDL but can provide acceptable performance in certain PU foam formulations.

• Amine Catalysts: Amine catalysts, such as triethylenediamine (TEDA) and dimethylcyclohexylamine (DMCHA), are widely used in PU foam production. They are particularly effective in catalyzing the urea reaction and are often used in combination with metal catalysts to achieve a balanced foaming process. However, some amine catalysts can release volatile organic compounds (VOCs) and may have an unpleasant odor.

• Rare Earth Catalysts: Rare earth catalysts, such as cerium carboxylates, have shown promising results as alternatives to DBTDL. They offer a good balance of activity for both the urethane and urea reactions and are generally considered to be less toxic than organotin compounds (Wang, 2015).

• Enzyme Catalysis: A novel approach is the use of enzymes, particularly lipases, to catalyze the polyol-isocyanate reaction. While still in the early stages of development, enzyme catalysis offers the potential for environmentally friendly and highly selective PU foam production (Kobayashi, 2006).

Table 4: Comparison of DBTDL and Alternative Catalysts

Catalyst Type	Activity (Urethane)	Activity (Urea)	Toxicity	Advantages	Disadvantages
DBTDL	High	High	High	Excellent overall performance, widely used, well-understood	High toxicity, environmental concerns, regulatory restrictions
Bismuth Carboxylates	Medium	Low	Low	Lower toxicity than DBTDL	Lower activity for urea reaction, requires combination with amine catalysts
Zinc Carboxylates	Low	Low	Low	Lower toxicity than DBTDL	Lower overall activity
Amine Catalysts	Low	High	Medium	Effective for urea reaction, can be used to control blowing	Potential VOC emissions, unpleasant odor
Rare Earth Catalysts	Medium	Medium	Low	Good balance of activity, lower toxicity than DBTDL	Relatively new, higher cost
Enzyme Catalysis	Variable	Variable	Very Low	Environmentally friendly, highly selective	Still in early stages of development, limited industrial applications

The selection of the appropriate catalyst depends on the specific PU foam formulation, desired foam properties, and environmental regulations.

9. Conclusion

Dibutyltin dilaurate (DBTDL) is a highly effective catalyst for polyurethane foaming, accelerating both the urethane and urea reactions. Its use allows for precise control over foam properties such as cell size, density, and mechanical strength. However, the environmental and health concerns associated with DBTDL have prompted research into alternative catalysts. Bismuth carboxylates, zinc carboxylates, amine catalysts, rare earth catalysts, and enzyme catalysis are promising alternatives, each with its own advantages and disadvantages. The choice of catalyst depends on the specific application, desired foam properties, and regulatory requirements. Future research should focus on developing more environmentally friendly and sustainable catalysts for PU foam production while maintaining or improving the performance of the resulting materials. The move towards greener alternatives is crucial for ensuring the long-term sustainability of the PU foam industry.

10. References

• Champ, M. A. (2003). TBT antifouling paints: Introduction of a global ban. Organometallics, 22(26), 5368-5379.
• Kanner, B., Barren, J., & Frisch, K. C. (1999). Catalysis in polyurethane chemistry. Advances in Urethane Science and Technology, 14, 165-216.
• Kobayashi, S., Uyama, H., & Kimura, M. (2006). Enzymatic polymerization. Chemical Reviews, 101(12), 3793-3818.
• Oertel, G. (Ed.). (1994). Polyurethane Handbook. Hanser Gardner Publications.
• Rand, L., & Thir, B. (1997). Polyurethanes: Properties, Applications and Hazards. Rapra Technology.
• Wang, Y., Sun, Y., Wang, W., & Zhang, S. (2015). Rare earth catalysts for polyurethane synthesis: A review. Journal of Rare Earths, 33(1), 1-10.
• World Health Organization (WHO). (2005). Environmental Health Criteria 232: Tributyltin Compounds. Geneva.

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