What are the summary and influencing factors of polyurethane foam formulation?

1. Basic Reactions

The formation of polyurethane foam involves two basic reactions: foaming reaction and polymerization reaction (also called gel reaction).

Foaming reaction: Isocyanate reacts with water to produce a reaction of di-substituted urea and carbon dioxide. The reaction equation is as follows:

2R-N=C=O + HOH → R-NH-CO-NH-R + CO2↑

The released carbon dioxide acts as the bubble core, causing the reaction mixture to expand, resulting in foam with an open-cell structure.

Polymerization reaction: The hydroxyl group in the polyether undergoes a stepwise polymerization reaction with isocyanate to form an aminoformate. The reaction equation is as follows:

R=N=C=O + R′-OH → R-NH-COO—R′

2. Polyols

Domestic block foam production uses 3-functionality, molecular weight 3000 (hydroxyl value 56) or 3500 (hydroxyl value 48, less commonly used) soft foam polyethers.

3. Polyisocyanates

The main polyisocyanate used is toluene diisocyanate (TDI). There are three main types of TDI industrial products: pure 2,4-TDI (or TDI100), TDI80/20, and TDI65/35. TDI80/20 has the lowest production cost and is the most widely used variety in industrial applications.

The molecular weight of TDI is 174, with two isocyanate groups (-N=C=O) having a molecular weight of 84. Therefore, the isocyanate content in TDI is 48.28%.

The amount of TDI used has a significant impact on foam properties. In foam formulations, the excess of TDI is expressed as the isocyanate index, which is the ratio of actual usage to theoretical calculated amount. When producing soft foam, the index is generally 105-115 (100 is equal to the theoretical calculated amount). Within this range, as the TDI index increases, the foam hardness increases, tear strength decreases, tensile strength decreases, and elongation at break decreases. If the TDI index is too high, it can lead to large and closed cells, long maturation times, and foam burning; if the TDI index is too low, it may lead to cracking, poor rebound, low strength, and significant compression permanent deformation.

4. Blowing Agents

Water reacting with TDI to produce carbon dioxide is the main blowing agent used in soft foam foaming. Increasing the amount of water in the formulation will increase the urea content, increase foam hardness, decrease foam density, and reduce foam load-bearing capacity. However, TDI reacts with water to produce a large amount of heat. If the water content is too high, it can cause the foam to burn or ignite.

Methylene chloride is a physical blowing agent with a boiling point of 39.8°C. It is a non-flammable gas that can vaporize during foaming, reducing foam density and hardness. The amount of methylene chloride added should prevent the foam from burning while ensuring that too much does not remove too much heat, affecting foam curing. The amount of methylene chloride used is limited.

5. Catalysts

The main role of catalysts is to adjust the speed of foaming and gel reactions to achieve a good balance.

Triethylenediamine (A33, a 33% solution of diisopropyl ether or dipropylene glycol) is the most important tertiary amine catalyst in soft foam production. It is 60% effective in promoting the reaction between isocyanate and water, i.e., foaming reaction, and 40% effective in promoting the reaction between hydroxyl and isocyanate, i.e., gel reaction.

Dibutyltin dilaurate (A-1) is a general-purpose tertiary amine catalyst for soft foam. It is 80% effective in promoting foaming reaction and 20% effective in promoting gel reaction. It is often used in combination with triethylenediamine.

Improper use of amine catalysts can have a significant impact on the product. Too much amine can cause:

(1) Short reaction time, rapid increase in initial viscosity, and excessive smoking during foaming.

(2) Foam cracking. Too little amine will result in slow initiation speed, affecting foam height.

Dibutyltin dilaurate is the most commonly used organic tin catalyst, which is very easy to hydrolyze and oxidize in the presence of water and tertiary amine catalysts in polyether mixtures.

The lower the foam density, the narrower the adjustable range of dibutyltin dilaurate. The effect of tin dosage on foam is as follows:

Too little dosage: Foam cracking.

Too much dosage: Rapid increase in viscosity, foam forming closed cells and shrinking, forming skins on the top and sides.

6. Foam Stabilizers (also called Silicone Oils)

Foam stabilizers reduce the surface tension of the foam system mixture, thereby stabilizing the bubbles, preventing foam collapse, and controlling the size and uniformity of voids.

Increasing the amount of silicone oil from the minimum amount to an appropriate level can produce well-opened foam plastics. When the amount is too high, the closed-cell rate of the foam increases.

7. Other Influencing Factors

In addition to the formulation, process parameters, and environment also have a certain impact on foam properties.

Raw material temperature: Under relatively normal ambient temperatures (20-28°C), the raw material temperature is controlled at 25±3°C, preferably within a range of ±1°C. It can also be controlled within the range of 28-30°C.

The effect of temperature increase or decrease on the speed of foaming and gel reactions varies. An increase in temperature results in a much greater increase in polymerization reaction compared to foaming reaction. Catalysts need to be adjusted for temperature changes.

For the same formulation, using the same amount of blowing agent, foam density is also related to altitude. In high-altitude areas, foam density noticeably decreases.