Chapter 2 Process selection and description

PROCESS SELECTION AND

DESCRIPTION

2.1: PROCESS SELECTION

In this section we will discuss different methods to produce Polyurethane flexible
foam and will select the most suitable process for its production. There are
mainly three methods to produce polyurethane flexible foams
1: Prepolymer process
2: Semi or Quasi prepolymers process
3: One shot process
2.1.1: PREPOLYMER PROCESS
It involves reaction of polyether or polyesters with a diisocyanate prior to
foaming. Here an excess of isocyanate is employed to yield an isocyanate
terminated polymer called as Prepolymer. Foaming occurs by reaction of
Prepolymer with water, with formation of urea linkage and evaluation of carbon
dioxide, which acts as blowing agent. Catalysts and surfactants are employed to
regulate the foaming rate and cell size, respectively.
2.1.2: SEMI OR QUASI PREPOLYMER METHOD
It involves reaction of diisocyanate with a portion of polyether or polyester
resulting in relatively low viscosity, low molecular weight polymer dissolved in
large excess of diisocyanate termed as semi or quasi Prepolymer. Foaming is
brought about by reacting a semi Prepolymer with remainder of polyols and water
in the presence of catalyst and surfactants.

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Chapter 2 Process selection and description

Advantages:
 Mostly used for semi-rigid and rigid foams.
 Less expensive process as compared to Prepolymer process.
 Free NCO content of the quasi-Prepolymer is much high.
Disadvantages
 Low molecular weight foams are formed.
 Low viscosity foams are formed.
 Not used for flexible foam production.
 High cost and difficult to handle

2.1.3: ONE SHOT PROCESS

In this process various foam components are mixed simultaneously. It is mainly
used in the preparation of polyester based foams.
In the one shot process all the reactants are added at the time of foaming and
after a certain time product is taken out of reactor.
Advantages:
 Used for the production of the flexible polyurethane foams.
 Very low density foams are produced.
 Versatility in reactant choice.
. Disadvantages:

 Great sensitivity to operating conditions.

 Greater need for the metering accuracy in foaming machinery.
 A great isocyanate hazard

2.1.4: REASONS OF SELECTING PREPOLYMER PROCESS

 Very easy and simple process and equipment.
 Less sensitive to any other method.
 Complete reactions of low reactivity of polyether diols in the absence of
catalyst.

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Chapter 2 Process selection and description

 Molar ratios of the components can be varied, which provides

intermediated with the desired end groups and defined average molecular
weight distribution.
 Less isocyanate hazard as compared to the one shot process.
 It is possible to make very low density foams.
 Controlled and high viscosity foams as compared to any other method.
 Very much effective for basics development in Pakistan.
 Less hazards due to isocyanate usage.
 High reactivity of ingrediants used in prepolymer production.
Disadvantages of Prepolymer process
 Large curing times.

 Less stability because these react with moisture .

2.2: FLOW SHEET

Fig: 2.1 (block flow diagram)

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Chapter 2 Process selection and description

Fig:2.2 (process flow diagram)

Table 2.1 EQUIPMENT DESIGNATIONS FOR PFD

Equipment No. Equipment Name

R-200 Reactor
R-201 1st votator
R-202 2nd votator
M-300 Mixer
H-101 TDI heater
H-102 PPG heater

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Chapter 2 Process selection and description

Table 2.1
2.2.1: DISCRIPTION
The equipment flow diagram showed the layout of the plant. The principal pieces
of equipments are two scraped surface mixing heat exchangers, called votators.
One of these units is used for heating and other for cooling. Another important
piece of equipment is the jacketed, agitated reactor. The glycol and TDI are
received in tank trucks and stored outside in heated 12,00 gallon tanks at a
temperature of 90 oF. the glycol is unloaded by pumping and the TDI by blowing
over with dry air. The former is stored under an atmosphere of dry nitrogen to
prevent oxidation and the latter under dry air to eliminate moisture contamination.
The glycol is heated to control the viscosity for ease of pumping, and the TDI is
heated to prevent freezing (F.P. 57 oF ). The contents of the storage tanks are
constantly circulated into the compounding building and back to minimize the
effects of temperature. In order to temperature condition the glycol and TDI, the
materials are circulated through tubular heat exchangers to raise the temperature
to 100 oF. The glycol is metered by proportionating pump through a rotameter
into a blender where it is premixed with the water. The mixture is introduced into
the first votator along with the 1st portion of TDI. The TDI and water are pumped
through rotameters for visual control. Pressures are controlled on the suction and
the discharge sides of the pumps to assure uniform deliveries. Tachometers are
provided on each pump for purpose of calibration and monitoring. The glycol
water blend and TDI are thoroughly mixed and heated to 350 oF in the 1st votator.
The temperature is automatically recorded and controlled from a thermocouple in
the outlet stream, which actuates a diaphragm valve in the inlet steam line. Next
the material passes through the jacketed reactor equipped with agitator. Due to
o
exotherm of the reaction, the temperature at outlet reaches 365 F. The
temperature recorder-controller is set at 365 oF. From the hold-up unit the
material flows into a second Votator which is identical to the 1 st but used for
mixing and cooling. The 2nd portion of the TDI is introduced into the process
stream before it enters the votator. It is metered with a proportionating pump,
under controlled temperature and pressure, with a rotameter in the line for visual

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Chapter 2 Process selection and description

checking. The TDI is blended in with the rotor turning and the prepolymer is
cooled to 120 oF using tap water in the jacket. A thermocouple in the outlet
stream actuates a diaphragm valve in the water line through a temperature
recorder-controller. A rotameter is used in the water line to note any fluctuation in
flow.
All of the prepolymer passes from the cooling unit through a recording Brookfield
viscometer into storage tank. Because of the water in the compound, some
carbon dioxide is present in the prepolymer. This is removed by applying vacuum
under gentle agitation to the storage tank while cooling the prepolymer to the
normal foaming temperature of 90 oF. After removal of carbon dioxide, the silicon
and R-II are weighed into the batch.
2.3: SELECTION OF RAW MATERIALS
2.3.1: ISOCYANATES
Isocyanates are used as the source of the NCO groups which react with the
hydroxyl group from the polyol and the water in the formulation.
Various aliphatic and aromatic Isocyanates can be used as raw material.
Aromatic Isocyanates are used due to high reactivity. The reactivity of NCO
group increases due to electron with drawing substitution on ortho or para
position.
Aromatic diisocyanates used are of many forms:
i. Toluene diisocyanate (TDI)
ii. Diphenyl methane diisocyanate (MDI)
iii. Polyphenylene polymethylene polyisocyanates (PMDI)
iv. Hexane diisocyanate (HDI)
2.3.1.1: TOLUENE DIISOCYANATES
Toluene diisocyanates are used for the manufacturing of the flexible
polyurethane foams:
 Reactivity of TDI is more than the others Isocyanates
 Position of NCO group
 Electron with drawing substitution group
 Steric hindrance

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Chapter 2 Process selection and description

Toluene Diisocyanate is produced as 2 isomers:

2, 4- toluene Diisocyanate (2, 4-TDI)
2, 6-tolueneDiisocyanate (2, 6-TDI)
TDI most commonly used in North America, where as MDI has a greater market
demand in European countries.
2, 4-TDI and 2,6-TDI both are used in foam production. The two isomers differ
mainly in way that the relative reaction rates of the different isocyanate groups on
each molecule differ.
They are commercially available in 3 isomer ratios:
 99.5% 2,4-TDI
 80% 2,4-TDI: 20% 2,6-TDI, which is the most common and referred
to in this document as 80:20 mixture
 65% 2, 4-TDI: 35% 2, 6-TDI.

Of these mixtures, the 80:20 blends is, by volume, the most important. Modifying
the isocyanate used can modify foam properties to a certain extent. 80/20
mixture of TDI has great reactivity with the polyols due to NCO position at para.

2.3.1.2: PROPERTIES OF TOLUENE DIISOCYANATE

Chemical structure
TDI's are synthetic organic chemicals with a molecular formula of C 9H6N2O2 and
the following chemical structure (R = -N=C=O).

Physical state

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Chapter 2 Process selection and description

At room temperature liquid or crystals.

Color
Colorless to pale yellow.
Odor
Distinct pungent, sweet, fruity, odor detectable around 0.7mg/m3.
Solubility in water and organic solvents
Soluble in acetone, alcohol, benzene, ethyl acetate, ether, Carbon tetrachloride,
chlorobenzene, kerosene, and various oils.TDI reacts with water, releasing
carbon dioxide.
Auto ignition temperature
620°C
Major products of combustion/ pyrolysis
When heated to decomposition TDI emits toxic fumes of oxides of Nitrogen (Sax
and Lewis, 1989).
Explosion limits
For 2,4 TDI
Concentration (% v/ v)
Lower 0.9%
Upper 9.5%
Boiling point
At 760mmHg 251° C
At 10mmHg 120° C for 2,4-TDI
121° C for commercial mixture
Density (g/cm3)
2,4-TDI 1.22g/mL 25/15
Commercial mixture (2, 4-, 2,6-isomers)
1.22g/mL 25/15 (both mixes)
Vapor pressure
1.3 Pa at 20° C
Relative vapor density
6.0 Kg/m3

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Chapter 2 Process selection and description

2.3.2: POLYOLS
The polyol is the source of the hydroxyl groups. The functionality (number of
reactive group) of the polyol determines the character and the degree of cross
linking or branching. The equivalent weight of the polyol helps to determine the
physical properties of the foam.
There are 2 types of polyols used for the production of flexible polyurethane
foams;
Polyester polyols
Polyether polyol

2.3.2.1: POLYESTERS
Polyester are the high molecular substances which contain the ester group –o-
co- as the repeat unit in the chain obtained through the polycondensation of
multifunctional carboxylic acid and hydroxyl compounds.
The polyester based foams have following properties;
Excellent mechanical properties
Resistance to oxidative aging, oils, solvents
Disadvantages
These are not used for cushioning due to poor humidity aging.
Polyester foams have high modulus at high deflection and low resilience and
high cost.
2.3.2.2: POLYETHER
Polyether polyols are polyhydroxyl compounds made by the reaction of
propylene oxide and/or ethylene oxide with initiator compounds to give polyols of
predetermined average molecular weight with terminal reactive hydroxyl (-OH)
groups.
These compounds are characterized by the repetitive occurrence of the
oxyalkalene structure. The number of reactive sites of the polyether polyols
range from 2 to 8 depending upon the initiator.

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Chapter 2 Process selection and description

The polyether based foams have following properties;

 Softer foams
 More resilient foams
 Better hydrolysis resistance
 Increasing degree of branching
 Increases load bearing properties
 Higher elongation
 Higher glass transition temperature
 More uniform polymer structure
 Cost less than polyesters

2.3.2.2.1: Selection of polypropylene glycol

 Enhance the load bearing properties
 Enhance the resilience properties
 Enhance the foaming properties
 Low cost
2.3.2.2.2: Physical properties of polypropylene glycol

Average mol. wt 2000±100

appearance Clear, color less to slightly

colored
Viscosity at 25°c 250 to 350 MPa.sec

Density at 20°c 1.00 gm/cm³

Average specific heat 0.48 cal/gm/K

Thermal conductivity 0.13 K cal/m/ h/K

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Chapter 2 Process selection and description

Table 2.2
2.3.4: BLOWING AGENT
These are the basic need for the foaming process, used to increase the polymer
viscosity by chain extension hence used to reduce density of foam
CO2 is used as blowing agent which is generated by reaction of water and TDI..
Secondary blowing agents are also used to complete the foaming process which
include CCl3F, CCl2F2 , CHCl2F,CH2Cl2
Important properties of CCl3F are

Blowing Boiling Solidification Critical Density Vapor

agent point point temperature at 20pressure
(°c) (°c) (°c) (°c) inat 30 (°c)
g/cm³ in bar

CCl3F 23.7 -111 198 1.49 1.261

Table 2.3

2.3.5: SURFACTANTS
Surfactants are used to stabilize the cell structure by changing the surface
tension during the foaming reaction. These act as an emulsifier and to assist in
mixing. Silicone surfactants are mostly used in the production of polyurethane
flexible foams.
2.4: REFERENCES
1: Kirk-othmer encyclopedia of chemical technology 2 nd edition volume 9
2: Encyclopedia of chemical processing and design” by John J.Mcketta
3: Polyurethane chemistry and technology
4: Polyurethane foams formulation and manufacture
5: Handbook of Polymer science and technology
6: Mark, J.E. “Encyclopedia of Polymer Science And Technology”, Vol. 1, 3 rd
Edition

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Chapter 2 Process selection and description

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