Lab Report No Name Group No Matriculation No

1 Muhammad Farooq 8 764316

Synthesis of Polyurethane Foams

1.4. POLYADDITION
SYNTHESIS OF POLYURETHANE FOAMS Introduction
Since the rise of plastics our lives have been totally altered in terms of living , one cant imagine living without polymers even he realize or not. Plastics are everywhere from clothing to cell phones, from cars to catering and from computers to construction, or we can say from dawn to bed we are having a totally plastic living. Polyurethane was the plastic developed during the time of war by Otto Bayer in 1930s. From its first appearance to till 21st century polyurethane have become a plastic used by everyone without any doubt. If we classify polyurethane foam we will come to know its a thermosetting polymer which cannot go under melting and it will decompose, there are few methods present to recycle polyurethane foam but in most of the cases polyurethane foam is crushed in small pieces like chips and then it is added to the mixture of polyol and isocyanate. Polyurethane is a cellular plastic which can have different chemistry. Major applications of polyurethane foams are Insulation (building construction / refrigerators/ cold rooms) Car seating cushioning Furniture (sofas, mattress) Adhesive (footwear, wood binder ) Coating (flooring)

Major deciding factor in polyurethane foam for its application is the density of polyurethane foams. Higher the density more rigid the foam structure closed cell formation better insulation Lower the density flexible foam open cell formation poor insulation

Test to determine the density of polyurethane foam is ASTM D 1622. Its a water displacement test in which we measure the weight of the polyurethane sample and then divide it with the free volume present in the foam structure by soaking (completely) the sample in water and we get the density of polyurethane foam. Rigid foam density often used for insulation ranges from 30 kg/m3 to 40 kg/m3, it can be more. Flexible foam density for matters and cousins ranges from 10 kg/ m3 to 30 kg/ m3 Upper ranges are purely based on common applications. Density can be increased and decreased just by the change in formulation. A very simple thumb rule is that more the isocyanate higher the density, but this rule also apply to certain criteria as we will see during my experiment very high percentage of isocyanate resulted in very poor cell growth and foam rise.

CHEMISTRY OF POLYURETHANE FOAMS

Polyurethane foams are produced by reacting Polyols and isocyanate. Major classes of polyol and isocyanate are below mentioned

Polyols
Polyether Polyols Polyester Polyols Most commonly used Earlier Used Specialty polyol for particular application Specialty polyol for particular application

Polycarbonate Polyols Polybutadiene Polyols

Isocyanates
Toluene di-isocyanate (TDI) highly toxic (no more in practice) most widely used Specialty isocyanate for particular application

Methylene diphenyl isocyanate (MDI) Hexamethylene di-isocyanate (HDI)

Reaction scheme
Reaction takes places between bi functional isocyanate and polyol which leads to the formation of urethane linkages. These urethane linkages are responsible for the properties of polyurethanes. Isocyanates are multifunctional which can undergo different types of reaction below is the example of addition polymerization reaction.

Monomer A Di-isocyanate

Monomer B Di-ol

Polyurethane

Experiment
During our experiment we investigated 4 different formulation, two groups were involved in this part of experiment. Following are the formulations. Formulation No 1 2 3 4 Polyol (grams) 10 12 16 4 Isocyanate (grams) 10 8 4 16 Polyol : Iso Ratio 1:1 3:2 4:1 1:4 Total weight of polyol & Iso(grams) 20 20 20 20

*Iso = stands for isocyanate

Procedure
Polystyrene cups were used to keep the polyol and isocyanate. Quantities were measure on electrical weighing balance as per the above formulations.

Isocyanate

Polyol

Mixing
Fig 1. Preparation of polyurethane foam

Foam rise

Cell formation and stabilization

Observations
The major visible difference in different formulations resulted in different foam rise. As we can see from the picture that the formulation having ratio 1: 1 and 3:2 had the maximum foam rise which indicates that if polyol / iso ratio is around one foam rise is higher , more will be the foam rise and more will be the degree of crosslinking.
Fig 2. Foam rise of different formations

It also shows us that higher the degree of crosslinking will result in more density of the foam and rigidity. In polyurethane foams density is directly influenced by the cell structure, if the cells are open they foam will be flexible foam where as in rigid foam which have higher degree of crosslinking forms close cell structure.

Since isocyanate forms the hard segments of the foam so sufficient quantity of isocyanate leads toward crosslinking which traps the co2 gas and cellular structure leads towards close cell structure. In flexible foams deficiency of isocyanate causes the co2 to escape through the polyurethane resulting foam hence cells are open and foam results in low density and have open cells.
Fig 3. Foam rise of different formations

If we take porosity into account the rigid foam are less porous than flexible foams. If we analyze the formulation no 3 in which we used 16 grams of polyol and 4 grams of isocyanate, we saw that foam rise was not as in the previous cases, reaction also took longer time and curing was also delayed. Resulting foam was flexible in nature. In formulation no 4 these was hardly any cell growth since it was having very high percentage of isocyanate, Isocyanates are multi functionalities so it must react with polyol to create a crosslink structure.

Observations in a glance
Formulation. No 1 Polyol : Iso Ratio 1:1 Properties Most rigid structure ,High density ,Integral skin formation, High foam rise Uniform cell structure, Few air traps (cross sectional visualization) Most rigid structure(less than the above formulation),High density 2 3:2 Integral skin formation , Highest foam rise, Uniform cell structure Fewer air traps (cross sectional visualization) 3 4:1 Flexible structure, Low density, No Integral skin formation, Low foam rise Non uniform cell structure Longer cure time No cell growth, Isocyanate residues which indicates the incomplete reaction High foam rise, No foam rise, air traps

1:4

Polyols used in the production of polyurethane foams are low molecular weight polymer or we can call them oligomers with hydroxyl groups at the terminals. OH content plays vital role during the addition reaction. One other important feature of polyol oligomers is the functionality which tells us the reactivity of polyol with its corresponding isocyanate. Polyol which we used was having functionality of 2 since its a diol. And the molecular weight ranges from 110000 to 120000. Polyols are responsible for the chain extension and formation of soft segments in polyurethane foams. Isocyanates are compounds containing NCO functional groups. Isocyanates are multifunctional. The average functionality is in the range of 2.5 to 3.0.Isocyantes are responsible for the rigidity in polyurethane foam structure. Isocyanates are highly toxic compounds so while handling the isocyanate one must observe safety precautions.

In response to the question no two in the lab manual the reason behind using polymers for example polyol and isocyanate in the formation of polyurethane foam is the functionality of these compounds. Since Polyols are mostly bi-functional and Isocyanates are also multifunctional and can undergo various reactions. When we use these high molecular weight multifunctional compounds the result is the crosslink in the polyurethane product. Crosslinking also promotes network structure.

Polyurethane foam is composed of two major components as we used Polyols and isocyanate. A foam blowing agent is also necessary like water to produce carbon di oxide which is responsible of foam rise. Other blowing agents like R 11, R 134a, and Cyclopentane are used commercially. Other auxiliary components are physical blowing agents, catalyst, surfactants, and cross-linking agents.

References
Polyurethane and Related Foams: Chemistry and Technology by Kaneyoshi Ashida Chemistry and Technology of Polyols for Polyurethanes by Mihail Ionescu