Manufacturing of PU foams

1. INTRODUCTION

The term “cellular plastics” encompasses a range of materials with widely

varying properties and fields of application. Virtually most polymers, thermoplastic or
thermoset can be made into a cellular or foamed form with resulting products having wide
range of densities.
Foams can be rigid, semi rigid or flexible. In general, cellular plastics can
be produced in the form of slabs, blocks, boards, sheets, molded shapes and sprayed
coatings.
Today it is possible to arrange the cells so that a product may have an
essentially solid skin surface and a cellular core.
There are various techniques for the production of cellular materials. A
range of polymers can be processed either by physical or chemical expansion system in the
production of cellular plastics. Foams are used because
1. They have increased strength to weight ratio than conventional injection molded solids.
2. They are used because reduction of sinkmarks in areas opposite to thick sections.
3. Reduction in manufacturing costs due to lower injection pressure encountered.
4. Can be used and thrown for ex. EPS
5. They can offer cushioning effect.

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2. BLOWING AGENTS
Over the years many methods have been devised for producing cellular
plastics of which most important are
1. Incorporation of a chemical compound which decomposes at processing temp to yield
volatile reaction products.
2. In corporation of Low boiling liquids which volatilise during processing temp.
3. Diffusion of Gases into the polymer under pressure with subsequent expansion of
composition all elevated temp.
4. Incorporation of powdered solid CO2 which volatilises at Elevated Temp.
5. Water produced in exothermic chemical reaction is volatilised within the mass by the
heat of Reaction.
6. Chemical reactions of polymer intermediates during polymerization. This is important
with polyurethanes.
7. Mechanical whipping of polymers in liquid form and subsequent ‘setting’ in whipped
state.
8. Incorporation of hollow or expandable spheres of resin or of glass.

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CURRENT EXAMPLES OF THE BLOWING AGENTS

Blowing Agent Volatiles Decomposition Comments
produced range (oC)
1. Azocarbonamide N2 , CO, CO2 190-230 Used for PVC & polyolefins

2. Dinitrosopenta- N2 , NO, H2O, 160-200 Used in Natural & synthetic

methylenetetramine CH3NH2 Rubbers and some use in
polyolefins.
3. Benzenesulphono- N2 , H2O 150 This powder is affected by
hydrazide phthalate and phosphate
plasticisers.
4. 4, 4'-oxybis N2 , H2O 150 Faster decomposition rate than
(benzenesulphono- azodicarbonamide
hydrazide)
5. N2 , 95-98 Decomposition products are
Azoisobutyronitrile toxic.
6. NaHCO3 (Sodium CO2 100-130 Low cost and used for Rubber
bi-carbonate) and for most plastics.
7. Terephthalazide N2 , 85-112
8. N2 , NH3 275 Due to its high Decomposition
Trihydrazinotriazine temp, it can be used
successfully for Nylons,
Polycarbonate, & most
thermoplastics.
9. Chloroflurocarban Use For PU foam.
CFCl3 & CHFCl2 &
CF2Cl2

3. SELECTION CRITERIA

Requirements for blowing agents

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1. The Gases should be evolved within narrow but clearly defined temp range & in
controlled manner.
2. The Decomposition temp range for a blowing agent should not be above the maximum
processing temp if significant degradation is not to occur.
3. Gases should not corrode the processing equipment/mould plates, mixing equipment.
4. Low cost.
5. Ease of Availability.
6. Should not be toxic.

4. PU FOAMS
Chemistry and Manufacture

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For Polyurethanes only a few Isocyanates are used commercially and they are
1) 80: 20 TDI
i.e. 80:20 mixtures of 2, 4 – tolylene diisocyanate with 2, 6 – tolylene diisocyanate.

CH3 CH3
| |
NCO OCN NCO

|
NCO

2,4 isomer 2,6 isomer

2) 65:35 mixtures of the above.

3) Diphenylmethane diisocyanales (M D I)
4) Naphthylene diisocynate
NCO
|

|
NCO

1,5 Naphthylene diisocynate

5) Hexametheylene diisocyanate and its Derivatives.

Chemistry
Polyurethane foams are prepared by reacting hydroxyl-terminated
compounds called polyols (usually of polyster or polyether Family) with a polyisocyanate.

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In production of urethane foam two reactions occur. The first is a reaction

of polyisocyanate, which is present in excess with the hydroxyl groups of polyol

NCO + HO - NHCO
(Diisocyanate) + (Polyol) O
A urethane

Ex.
O = C = N – R – N = C = O + *HO-R ...... R-OH*
O = C = N – R - N = C = O + *HO-R...... R-OH*
(Polyisocyanate) + polyol
O
||
OCN – R – N – C – OR ...... +
|
H

O O
|| ||
R – O – C – N – R – N – C – OR ....... R – OH*
| |
H* H*
( Polyurethane )
The IInd Reaction which generates the blowing Gas & produces the Expanded foam
structure.
For Low Density flexible foam,
The blowing agent is CO2 produced during the reaction of excess
Isolyanate and water.

NCO NH
|
+ H2O C=O + CO2
NCO |
( Excess icocyanate ) NH

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The Density of product depends on amount of CO 2 evolved and can be

reduced by increasing the isocyanate content of the reaction mixture and by
corrospondingly increasing H2O to react with excess isocyanate.
As a rule of Thumb, high molecular weight, low functionality polyols
produce molecules with a low amount of cross-linking and consequently form a flexible
foam. Conversely low molecular weight polyols of high functionality produce a structure
with a high degree of cross linking and therefore the rigid foam.

5. MODIFIERS AND ADDITIVES

Certain other ingredients are

1. Catalysts primarily tertiary amines are added to accelerate the rate of Reaction.
2. Surfactants
for Ex – Silicone copolymers are used to develop a fine and uniform cell structure.
3. flame Retardants
for Ex halogenated and Phosphorous compounds to reduce combustibility.
4. Dyes and pigments to colour the PU foam.
5. Filler = strength is increased. Mechanical and physical properties are increased & cost
is reduced, Ex barytes, CaCO3 , talc & Kaolin.

6. FLEXIBLE FOAMS

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Polyurethane foams may be rigid, semirigid or flexible. They may be made

from polyesters, polyethers or Natural polyols. This section deals with only flexible foams
1. One shot polyesters.
2. Polyether prepolymers
3. One shot polyethers.
1. One shot polyester foams
Foams can be made from polyester resins by addition of 65:35 TDI, water,
a catalyst, an Emulsifier, a structure modifier and paraffin oil which helps to control pore
size and prevents splitting of the foams.
Among the catalysts described in literature include Dimethylbenzamine,
Dimethyl cyclohexylamine, Diethylaminoethanol & Adipic acid ester of N-diethyl amino
ethanol. Emulsifiers includes sulphonated caster oil and structure modifiers such as
Ammonium oleate and silicone oils.
The bulk of flexible foam is produced in block (Slab stock) form using
machines of the Henecke type or some simple modification of it. In this machine polyester
and isocyanate are fed to a mixing head which oscillates in a horizontal plane. The other
ingredients known as the ‘Activator Mixture’ are then injected or bled into the isocyanate
polyester blend & the whole of mixture is vigoursly stirred and forced out of the base of
mixing head. The Emergent Reacting mixture runs into a trough which is moving
backwards at right angles to the direction of traverse of reciprocating Head. In this way
whole of the trough is evenly covered with the reacting mass which has frequently foamed
within a minute or so of issuing from the mixing head. The principle of Henecke Machine
is illustrated in fig.
Because of the Drag Effect of the side walls of the trough on the expanding
and cross linking foam, the process gives a domed block. ( i.e. Dome shaped block ).
Hence when the block is sliced up into sheet & slab, there is an undesirable level of scrap.
To some extent, the fraction of scrap is reduced by increasing the block size. Over the
years block sizes have been increased and widths of 2.20 m & heights of 1.2 m are
produced although this is more common with polyether rather than polyester foams.
2. Polyether prepolymers

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In this process polyether is reacted with an excess of isocyanate to give an

isocyanate terminated prepolymer which is reasonabaly stable if kept in sealed tins in dry
conditions. If water, catalysts & other ingredients are added to the product a foam will
result. Where linear polyethers are used, it is found that this foam has rather poor load
bearing & cushioning properties and where this is important, a low molecular weight triol
such as glycerol or trihydroxymethylpropane, is added to the polyether before reaction
with isocyanate. This will then provide a site for chain branching. Alternatively a small
amount of water could be added to the system. This would react with terminal isocyanate
groups which link up to produce a urea link. This urea group is more reactive than a
urethane link and reacts with isocyanates to give a biuret link as a site for chain branching.
It is important that CO2 evolved in water- isocyanate reaction be allowed to escape & also
that the reaction is kept down so that premature foaming does not occur.
Advantages : Because there is exotherm, large blocks of foams can be produced. There is
often a flexibility an Design of compounds, the reduced amount of free isocynate reduces
handling hazards & foams will have better cushioning properties.

3. Polyether One-shot foams :

The one-shot polyethers form the bulk of flexible polyurethane foam now
being manufactured. This is a result of favorable economics of polyethers & because

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polyethers generally produce foams of better cushioning characteristics. A typical

formulation for producing a one shot polyether foams will comprise polyol, isocyanate,
catalysts, surfactants & blowing agent.
A variety of polyethers have been used & may be enumerated in their order of
development
1. Polymers of tetrahydrofuran
2. Polymers of Ethylene oxide, cheaper than the tetrahydrofroan polymers, too hydrophilic
to use.
3. Propylene oxide polymers which are less hydrophilic.
4. Block copolymers of Ethylene oxide and propylene oxide.
5. To produce flexible foams of high resiliance, the so called polymer polyols can be used.
6. An alternative approach is to use a polyether containing a reactive organic filler such as
(a) polyurea.
(b) Isocyanate
The second largest component of foam formation is the isocyanate, 80:20 TDI is found to
be the most suitable of various isocyanates available & is most exclusively used.
(c) Catalysts : one shot polyether processes became feasible with the advent of sufficiently
powerful catalysts. For many years tertiary amines were used with both polyesters and the
newer polyethers. Examples include alkyl morpholines & triethylamine. More recent
catalyst such as triethylenediamine is more powerful. Other examples include stannous
Octoate. It was found that by the use of varying combinations of a tin catalyst with a
tertiary amine, it was possible to produce highly active systems in which foaming and
cross linking reactions can be properly balanced.
(d) Surface Active Agents :
They are important components of foam formulation. They decrease the
surface tension of the system & facilitate the dispersion of water in the hydrophobic resin.
They can stabilize the foam and control cell structure. A wide range of such agents both
ionic & non-ionic has been used at various times.
The water present reacts with isocyanate to produce CO2 & urea bridges.
The more the water present, the more the gas evolved & the more the number of active

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urea points for cross linking. Thus the foams of lower density do not necessarily have
inferior load bearing characteristics. When soft foams are required a volatile liquid such as
fluorotrichloromethane may be used. This will volatile during exothermic reaction & will
increase the total gas present but not increase the degree of cross linking.
A typical formulation for the process is as follows –
Contents Parts by weight
Polyether triol = 100
80 : 20 TDI = 40
Water = 3
Triethylene diamine (catalyst) = 0.5
stannous Octoate (catalyst) = 0.3
silicone block copolymer = 1.0
Additives : Commercial formulations may also include other additives. Prominant
amongst these are antiaging additives, fillers, colourants , cell regulators. Flame Retardants
have become increasingly important.
Process : Most foam is produced an machines based in Henecke process, but in many
cases it is necessary to have at least four streams to the mixing head; e.g. polyol,
isocyanate, water, amine, silicone and tin catalyst. Reaction is carried out with slightly
warmed components & foaming is generally complete within a minute of the mixture
emerging from the head. Although slab stock flexible foam remains the largest single
outlet for polyurethane materials, directly moulded foam now claims 30% of the market.
Such direct moulding can be carried out for following reasons.
1. Where it is required to use metal or other inserts for fastening of upholstery elements or
coverings.
2. Where shape of product is complex & it is difficult to cut this readily from slab stock.
3. Where it is uneconomic, because of scrap, to cut from slab stock, for ex , car industry
where moulded foam is used for chair bucks, chair seats, kneestrips & head restraints.
The foam components, mixed in a mixer are laid down onto a conveyer belt usually lined
with sulphate paper or PE foil at the bottom and both sides. The conveyor belt is titled
downward at an angle of 10 to prevent the growing foam from creeping back.

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Petzetakis – Draka process

Another continuous method is the maxiform process in which the mixture
is fed from bottom upward to overflow over a threshhold and on a belt lined with paper on
which it is transported by a conveyer. As expansion proceeds the bottom foam layer is
lowered so a to keep the top surface of foam as flat as possible. Then the expanded PUR
foam passes through a heating tunnel where curing takes place at a temp not exceeding
1600C.

4) Rigid Polyurethane foam :

They are obtained from polyfunctional oligomerols of high hydroxyl
number (450-550). Polymeric isocyanates include crude TDI or MDI (Diphenylmethane
diisocyanate) Blowing agent CFC-11, pentane and CO2.

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In pour technique, a liquid urethane chemical mixture is metered into

cavity. The reactive liquid flows to the bottom of the cavity and starts to expand. Rigid
PU foam has glass transition temp about 200C and their % elongation does not exceed
10%. They vary in density from 10 to 600 kg/m3
Laminates with rigid PUR foam are produced in a continuous process. The
foaming mixture of PUR reactants are applied with a mixing of head onto the surface of
one laminate board laced and belt conveyor. Another laminate board is placed on the
expanded PUR layer before gelation is complete and the sandwich is passed through a
conveyor press. The laminate linings are made from steel sheet, paper, Al foil, or glass
fabrics. The PUR is cured for a few minutes by allowing it to pass through a furnace
(tunnel).
The use of lining has following advantages
1. Increased rigidity compared with PUR foam alone.
2. Barriers to gases & vapours.
3. Thermal barrier preventing ignition.

5. Spray Coating :
Rigid fast curing foams are obtained from oligoetheramines, oligoetherols and MDI (Di-
phenyl methane diisocyanate) blown with water and physical blowing agents.
Ex = CF2 Cl2

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If physical blowing agent of boiling point below 00C ( for Ex = CF2 Cl2) is
used, foaming of mixture undergoes expansion immediately on being released from the
mixing head nozzle & a ready foam can be applied to a substrate. Such foams are reffered
to as froths. They are used to apply to a vertical surface. The above system cure within 2
seconds at room temp. They can be applied by sprayings onto both horizontal and vertical
surfaces & on to ceilings. The sprayings of PUR foam is used to make seamless joints in
insulations.
Portable mobile PURF spraying equipment comprises
1. Drums containing the PUR components.
2. A cylinder of dry N2 to keep the PUR components in an inert atmosphere.
3. A metering device made of pumps of 2 to 14 kg/min delivery & heating elements.
4. A set of hoses 60 to 120 m long to which PUR has low adhesion and a compressor that
allows cleaning of the hoses by flushing with compressed air/solvent.
5. A spray gun.
6. A compressor for metering pumps and spraying equipment.
The portable PUR foam spraying device is illustrated in fig The surface to
be coated should be cleaned beforehand. Before spraying, the surface should be primed to
ensure satisfactory adhesion of the foam-coat to the substrate. The foam coat is applied
perpendicular to the surface not exceeding 10 to 20 mm in are operation. By repeated
operations, insulating layer of foam 20 cm or more thick can be obtained. The adhesion
between successive coats is excellent.
Advantages : This insulating technique is good for the internal and external surfaces of
concrete, metal, wood, paper, textiles etc.

6. Moulded PU foam :

1. Hot moulded Polyurethane foams :

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Moulded PUR foams are expanded in a closed mould under the slight self pressure of the
foam.
Composition :
1. Copolyoxypropylene – ethylene triols
2. TDI = 80
3. Catalyst ( Ex Organotin & Amines )
4. Surface Active Agents
5. Physical blowing Agents
6. Water.
Steel and Al molds are commonly used. As the mould is filled it is closed.
The reactant mixture is foamed and fills the mould. After some time mould is opened and
article is removed. Curing time is upto 40 min and extra heating is required for 1 hour at
120°C.
The Effect of water content v/s hardness and density of hot molded flexible
PUR foam is illustrated.

7. Integral – skin PU foam (Cold molding) :

Integral skin PUR foams have cellular foamed structure of the core integral
with the solid top skin. The principle of the method of manufacturing such foams is the

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use of halocarbons as blowing agents ( with no water) and moulding in cooled (chilled)
wall metal moulds which make blowing agent condense on the cool walls at the molding
pressure (0.1 to 0.4 Mpa) and the polymer to form a solid top skin, whereas bulk of the
product remains hot and cures to a foam. A cross section of flexible integral skin PUR
foam is shown in fig .
Starting materials :
1. Oligomerols of RMM 3000-6500
2. MDI (Diphenylmethane diisocyanate) and Polymeric Isocyanates
3. halocarbon ( a blowing agent) [no water]
4. Catalyst (Amines)
5. Surface active agents
Properties of Integral skin PUR foam v/s Isocyanate functionality (foam density 0.108
g/cm3)
Property MDI functionality 2.8 2.2 2
1. Tensile strength /105 Nm-2 1.1 1.1 2.1
2. Elongation at break / % 80 150 250
3. 40% compression strength/105 Nm-2 2.5 1.2 1.0

HOT MOLDED FOAMS AND COLD MOLDED FOAMS

Hot Molded foams Cold Molded foams
Advantages Advantages
1. Higher load bearing capacity upto 30% 1.Less power consumption in production
2. Higher hardness and hardness to density 2. Less manufacturing space required (as
ratio is higher. no external heating arrangement is made).
3. Lower raw material cost per kg of foam. 3. Lower capital cost.
4. Higher moisture resistence. 4. Less scrape.
5. Lower ignitability.
7. PROPERTIES
PROPERTIES OF MELAMINE MODIFIED FLEXIBLE PUR FOAM
Density (Kg/m3) 42 – 64
Tensile strength (Kpa) 48 – 76

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Elongation at break (%) 80 – 110

Abrasion Resistance (N/m) 158 – 228
Resiliance (%) 55 – 60

Properties of a fast cure high resiliance polyurethane foam.

Sr.No Property Absolute values
1 Core Density / kgm-3 47 – 51
2. Tensile strength/Mpa 0.130 – 0.155
3. Elongation at break / % 135 – 165
4. Abrasion Resistance Nm-1 265 – 325
5. Hardness / N (200 mm)-1 205 – 264

Selected properties of semi-rigid foam.

Property One shot free foaming method.
-3
1. Density/Kgm 55 – 65
2. Tensile strength/Kpa 130 – 170
3. Elongation at break % 50 – 60
4. Stress on 40 % compression/Kpa 14 – 18

Effect of Manufacturing parameters on properties of flexible PUR foam slabstock

1) The apparent density of PURF depends on the quantity of blowing agent. With
increasing water conent and Isocyanate in reaction mixture, more CO2 is produced and
therefore density decreases as well as tensile strength also decreases.

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2) Cell size and cell uniformity are mainly affected by mixing efficiency. If reaction
mixture is mixed uniformly, cells of uniform structure are formed and hence tensile
strength increases.
3) The hardness of flexible PU foam increases
(1) with apparent density and with the degree of cross linking and
(2) with increasing functionality of polyol.
(3) With the presence of fillers.

Properties of oligooxyalkylene – styrene-acrylonitrile PUR foam.

I NCO/OH Density Property

65% compre- Tensile Elongation at
Kgm-3
sion strength Strength break %
Kpa Kpa
1.00 34 4.32 123 150
1.00 28 8.06 128 137
1.10 29 3.56 154 73
1.10 24 2.86 164 100
1.15 22 4.86 265 117

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Effect of amount of water blowing agent on properties of polyurethane foam block

1. Density 2. Tensile strength 3. Elongation at break.

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Load bearing capacity of flexible PUR foam of varying density

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Hardness of PUR foam of density 20 kg/m3 v/s Polyol content at constant isocyanate
index

4) Stress v/s strain curves for rigid PUR foams of varying density

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1) Low density rigid PUR foam 2) High density PUR foam

For same strain, the load beared by high density foam is more. High density PURFs
provide better comfort for users and have a longer service life.

5) Stress Strain Behaviour

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Behaviour of PU foam of density 35 kg/m3 – 1) For polyesterurethane foam 2)

Polyether hot foam 3) High resiliance polyetherurethane cold foam.

A higher degree of cross linking increases the load bearing capacity of PUR foam.
Inert inorganic fillers confer a higher strength and makes their stress v/s Elongation
behaviour more linear. Common fillers are barytes, calcium carbonate, talc and kaolin.

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Stress v/s Strain relation on compression of 41kg/m3 density rigid

foam
1) For free foaming stock
2) For moulding stock

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Relation between compression strength and density for rigid PUR foam

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Hydrolytic stability of polyether type of PUR. Immersion in water at various

temperature.

8. APPLICATIONS OF PU FOAM
1. Flexible PU Foams :
1.Measure interest of flexible PU foam is cushioning and other upholstery materials.
2. In addition to upholstery applications polyester foams are useful as foam backs, i.e.
foambacking in order to stiffen or shape some softer fabrics, examples include car –door,
roof-trim, quilting, shoulder pads and coat interlinings.
3. paint rollers, sponges and packaging for delicate equipments.

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4. Automobile Industry
Widely used in Automobile industry for making chair backs, chair seats, head restraints
etc. The market for cushioning materials is dominated by PU flexible foam.
2. Rigid PU foams
1. Semirigid and high molecular foams are useful in the manufacture of car-crash pads and
in packaging equipments.
2. Construction : When sandwiched between metal, paper, plastic, wood, PU Rigid foam
plays an important role in construction Industry. Such composites can replace
conventional structure of bricks, cement, wood and metal.
3. Thermal Insulation :
Rigid foam offer advantages in thermal insulation of building, refrigerators and domestic
appliances and for heat exchanger- insulation, condensor- insulation.
4. Shoe manufacturing :
Polyurethane coatings are used to improve the appearance and wear resistance of shoe
uppers made from real leather and PVC leathercloth.

9. CONCLUSION
The technique for PU foam manufacturing in the form of sheet, slab, board,
moldings and sprayed coatings with varying level of flexibility offers various grades of
foams with widely varying properties. More than 35 grades of PU foam are important and
they are produced commercially.

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The low cost and Interesting properties of cellular PU make them a

significant group of material for wide range of products ranging from packaging to
insulation and structural foam sections, further improvements will widen its uses.
The PU foams has opened the new area in plastic packaging and other
works and have tremendous scope in future.

10. BIBLIOGRAPHY
1. Chemistry for thrmosets –
J. B. Foreman, 1993. Page no. 310-319.
2. Polymer materials

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J. A. Braidson, Page no.709-720

3. P U Chemistry, Technology & Applications
By Zygmunt Wirpssa – Page no. 220 – 267.
4. S P I Hand Book.
Page no. 540-580
5. www.google.com.

CONTENTS

1. Introduction 1
2. Foaming agents 2

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3. Selection criteria of foaming agents 4

4. Chemistry of forming of PU foams 6
5. Additives 7
6. Manufacturing of PU foams 8
i) One shot polyester foams.
ii) Polyether prepolymers
iii) Polyether one-shot foams
iv) Rigid PU foams
v) Sprayed coatings
vi) Moulded PU foams
vii) Integral skin PU foam
7. Properties of PU foams 17
8. Applications of PU foams 27
9. Conclusion 28
10. Bibliography 29

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Maxifoam system for continuous production of PUR foam blocks

1. Mixing head 2.Trough 3. Bottom paper feed 4. Conveyor belt 5. PURF

Petzetakis – Draka continuous system producing PUR foam blocks

1. Traversing mixing head 2. slide paper (or PE foil ) liner 3. Bottom paper feed 4.
Conveyor belt 5. PURF

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Spray gun for application of PUR foam

( portable metering device in the background).

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Principle of the Henecke machine

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The effect of water content v/s hardness and density of hot molded flexible
PUR foam
1. Density
2. Hardness

Manufacturing of hot molded PUR foam

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Manufacturing of Rigid PUR foam blocks by a batch process

1. Reaction mixture 2. Floating cover 3. Limiters

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Manufacturing of rigid PUR foam laminated boards laminated on both sides with a
lining.
1. Sheet Metal roll 2. Shaping 3. Annealing 4. Mixing head 5. Belt press 6. Cutter
7. Laminating board

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