Polyether Polyol: Hydroxyl Value 36, Primary Hydroxyl > 65%, 60%.

Polymeric Polyol: Hydroxyl Value 28, Copolymer 20%, 40%.

Water: 3%.

80TDI and Polymeric MDI (Viscosity 300mpa): 80:20.

T12: 0.025%.

A33: 0.4%.

HR-3 Silicone Oil: 1%.

HA-1 Crosslinker: 6%.

Di(b-dimethylaminoethyl) Ether: 0.15%.

Phase One: Gas Nucleation Process

The raw materials react in the liquid phase or rely on the generation of gas substances and gas volatilization during the reaction. As the reaction progresses and a large amount of heat is generated, the amount of gas substance generated and volatilized continuously increases. When the gas concentration exceeds the saturation concentration, fine gas bubbles begin to form in the solution phase and rise. As the reaction nears its end, a milky phenomenon appears in the liquid polyurethane material, known as the "milky time."

Phase Two: Self-nucleation Process

In this stage, the gas concentration continues to increase and reaches a certain level. After that, the gas concentration gradually decreases, and new bubbles no longer form. The gas in the solution gradually reaches an equilibrium saturation concentration. During this stage, the viscosity of the liquid material gradually increases, and the gas continuously merges and expands in the gradually viscous liquid phase. The volume of the bubbles continues to expand. The viscous liquid phase forming the outer wall of the bubbles gradually thins. Due to the surface tension relationship between the gas and liquid interfaces, the bubble volume increases from small to large, gradually transforming from a spherical shape into a three-dimensional geometric shape composed of polymer thin films, finally forming an open network structure of three-dimensional micropores. In the synthesis process of polyurethane foam, this stage exhibits polymer volume expansion and foam rising.

Phase Three:

After the gas concentration drops to a certain level, bubbles no longer form. With the permeation of the gas, the concentration continues to decrease, reaching the final saturated equilibrium in the process of the polymeric foam wall transitioning from a viscous liquid state to a non-flowing solid state.

Testing Conditions:

1. Fast foaming is taken from the center of the foam, while molded foam samples are taken from the central part or for whole sample testing.

2. Newly made foam should be matured for 72 hours in its natural state before sampling. Samples should be placed in a constant temperature and humidity environment (as per GB/T2918: 23±2℃, relative humidity 50±5%).

Density: Density = Mass (kg) / Volume (m3)

Hardness: Indentation Load Deflection (ILD), Compression Load Deflection (CLD)

The main difference between these two test methods is the loading area of the foam plastic. In the ILD test, the sample is subjected to a compressed area of 323 cm2, while in CLD the entire sample is compressed. Here, we will only discuss the ILD test method.

In the ILD test, the sample size is 38*38*50mm, with a test head diameter of 200mm (with a round corner of R=10 on the bottom edge), and a support plate with 6mm holes spaced 20mm apart. The test head loading speed is (100±20) mm/min. Initially, a pressure of 5N is applied as the zero point, then the sample is compressed to 70% of its thickness at the zero point, and unloaded at the same speed. This loading and unloading is repeated three times as pre-loading, then immediately compressed at the same speed. The compression thicknesses are 25±1% and 65±1%. After reaching the deformation, hold for 30±1s and record the relative indentation value. The recorded value is the indentation hardness at that compression level.

Additionally, 65% ILD / 25% ILD = Compression Ratio, which is a measure of foam comfort.

Tensile Strength, Elongation at Break: Refers to the maximum tensile stress applied during the tensile test until fracture, and the percentage elongation of the sample at fracture.

Tensile Strength = Load at Fracture / Original Cross-sectional Area of Sample

Elongation at Break = (Fracture Distance - Original Distance) / Original Distance * 100%

Tear Strength: Measures the material's resistance to tearing by applying specified tearing force on a sample of defined shape.

Sample size: 150*25*25mm (GB/T 10808), with the sample thickness direction as the foam rise direction. A 40mm long incision is made along the thickness direction (foam rise direction) at the center of one end of the sample. Measure the thickness along the sample thickness direction, then open the sample and clamp it in the test machine fixture. Apply load at a speed of 50-20mm/min, using a blade to cut the sample, keeping the blade at the center position. Record the maximum value when the sample breaks or tears at 50mm.

Tear Strength = Maximum Force Value (N) / Average Thickness of Sample (cm)

Usually, three samples are tested, and the arithmetic mean is taken.

Resilience: Measures the foam's rebound performance by allowing a given diameter, weight steel ball to freely fall onto the surface of the foam plastic sample from a specified height. The ratio of the rebound height to the steel ball's drop height indicates the foam's resilience.

Test Requirements: Sample size 100*100*50mm, the ball drop direction should be consistent with the foam usage direction. The steel ball size is ∮164mm, weight 16.3g, and it drops from a height of 460mm.

Resilience Rate = Steel Ball Rebound Height / Steel Ball Drop Height * 100%

Note: Samples should be horizontal, steel ball should be fixed before dropping (static), each sample is tested three times with 20s intervals, and the maximum value is recorded.

Compression Permanent Deformation: In a constant environment, the foam material sample is maintained under constant deformation for a certain period, then allowed to recover for a period of time, observing the effect of the deformation on the sample's thickness. The ratio of the difference between the initial thickness and final thickness of the sample to the initial thickness represents the foam plastic's permanent compression deformation.

Compression Permanent Deformation = (Initial Thickness of Sample - Final Thickness of Sample) / Initial Thickness of Sample * 100

Fire Resistance

VOC (Volatile Organic Compounds)

1. Reaction Principles

Polyester-based polyurethane is obtained by the reaction of polyester and isocyanate. The polyester is synthesized by a condensation reaction of polyfunctional acids (such as adipic acid, phthalic acid, succinic acid, etc.) and polyols (such as ethylene glycol, propylene glycol, trimethylolpropane, etc.). Polyester can be divided into hydroxyl polyester and carboxyl polyester. The polyurethane foam is made using hydroxyl polyester with an excess of polyols.

Hydroxyl polyester (excess polyol): 2OH-R-OH + HOOC-R'-COOH → HO-R-OCO-R'-COO-R-OH

Carboxyl polyester (excess polyacid): OH-R-OH + 2HOOC-R'-COOH → HOOC-R'-COO-R-OCO-R'-COOH

Polyether-based polyurethane is obtained by the reaction of polyether polyols and isocyanate. The polyether polyols are obtained by ring-opening polymerization of oxirane compounds (such as ethylene oxide, propylene oxide) using initiators containing active hydrogen (such as alcohols, amines).

Polyether polyols: R-OH + nPO → R-(-O-CH-CH3-CH2-O)n-H

Both types of polyurethanes are finally formed by the reaction of hydroxyl groups with isocyanates to produce urethane groups:

R-NCO + R'-OH → RNHCOOR'

So, the major difference in the reaction mechanism between the two types of polyurethane lies in whether the soft segment molecular chain mainly contains ester bonds (-COO-) or ether bonds (-C-O-C-).

2. Reaction Results

Polyester-based polyurethane has high mechanical strength, good oil resistance, and heat resistance. Therefore, it is mainly used in microporous foam shoe soles, elastomers, coatings, and synthetic leather. However, due to the presence of ester bonds (unsaturated double bonds), polyester-based polyurethane is not as stable in terms of hydrolysis resistance, low-temperature resistance, oxidation resistance, acid resistance, and alkali resistance as polyether-based polyurethane.

3. Development Trends

Due to the high viscosity of polyester polyols, poor compatibility with other components, and difficulty in construction, coupled with high raw material costs, its application in the field of polyurethanes is limited. On the other hand, polyether-based polyurethane has a wide range of applications, mainly in synthetic foam plastics.

In recent years, to improve the processability of polyester polyols, oxirane compounds (such as PO/EO) have been introduced into the polyester polyol molecules. This results in soft segment molecular chains that contain both ester bonds (-COO-) and ether bonds (-C-O-C-). Polyurethanes made from these new polyols have characteristics of both polyester-based and polyether-based polyurethanes.

The production of block-shaped soft foam typically utilizes the batch foam machine foaming process, a gap-type production method. This method evolved from manual foaming in laboratories. The process involves immediately pouring the mixed reaction materials into an open mold resembling a wooden or metal box, hence the name "boxed foam." The molds (boxes) for boxed foam can be rectangular or cylindrical. To prevent the foam block from forming a domed top, a floating cover plate can be placed on the top of the foam during foaming. The cover plate stays closely attached to the top of the foam and gradually moves upward as the foam rises.

The main equipment for boxed foam production includes: 1) Electric-mechanical stirrer, mixing barrel; 2) Mold box; 3) Weighing tools such as scales, platform scales, measuring cups, glass syringes, and other measuring devices; 4) Stopwatch for controlling mixing time. A small amount of mold release agent is applied to the inner walls of the box to facilitate easy removal of the foam.

The advantages of producing soft foam using the boxed foam method include: low equipment investment, small footprint, simple equipment structure, easy and convenient operation and maintenance, and flexible production. Some small and underfunded domestic and township enterprises use this method to produce polyurethane soft foam. Boxed foam molding is a non-continuous production method for soft foam, so the production efficiency is lower than continuous methods, and the equipment is mostly manually operated, resulting in higher labor intensity. Production capacity is limited, and there is a greater loss in cutting foam plastics. The process parameters for boxed foam should be controlled within a certain range because even with the same formula, the foam properties may not be the same when different process parameters are used. The raw material temperature should be controlled at (25±3) degrees Celsius, mixing speed at 900 to 1000r/min, and mixing time at 5 to 12 seconds. The mixing time of the polyether and additives mixture before adding TDI can be flexibly adjusted depending on the situation, and after adding TDI, a mixing time of 3 to 5 seconds is sufficient, with the key being thorough mixing after TDI addition.

During boxed foam molding, attention should be paid to the following aspects:

1) Prepare before production, including material temperature and machine equipment inspection;

2) Measure as accurately as possible;

3) Control the mixing time appropriately;

4) Pour the mixed material liquid quickly and steadily, avoiding excessive force;

5) Ensure the box is placed steadily, with the bottom paper flat, to avoid uneven material flow during pouring;

6) When the foam rises, gently press the cover to ensure the foam rises smoothly;

7) Additives should be used as specified, and pre-mixed materials should not be left for too long.

Three types of foam equipment have emerged in boxed foam molding. Initially, various raw materials were weighed into a container according to the formula, mixed with a high-speed mixer, and poured into the box mold for foaming and shaping. This method often resulted in residue in the mixing container. An improved method used a metering pump to transport the raw materials to the mixing barrel for uniform mixing. A mechanical device automatically closed the bottom of the barrel, and compressed air was used to press the material into the foaming box for shaping. Both of these methods could create eddies due to the rapid influx of materials into the box, which might cause defects or depressions in the foam products. The most reasonable boxed foam device is to place a bottomless mixing barrel directly in the center of the foaming box. A metering pump delivers the various raw materials needed for foaming into the mixing barrel. After mixing for a few seconds, the lifting device raises the mixing barrel out of the foaming box, allowing the foaming material to flow smoothly over the entire box bottom. This prevents foam cracking due to material eddies, and ensures relatively uniform height throughout the foam.

A pressure device can be added to the expanding foam material to produce flat-topped foam, reducing waste during cutting. This device is suitable for the production of polyether-type polyurethane soft foam and high rebound soft block foam. For polyvinyl acetate polyurethane blocks, this method cannot be used due to the high viscosity of the material, and continuous methods are generally employed.