POLYURETHANE ELASTOMER

POLYURETHANE
 Polyurethanes are the most well known polymers
used to make foams.

 Polyurethanes can be Elastomers, and they can be

paints. They can be fibers, and they can be adhesives.

 polyurethanes are called polyurethanes because in

their backbones they have a urethane linkage.
Note the urethane(carbamate) groups -NH-(C=O)-O- linking the units of the product.
 The reaction of an isocyanate and an alcohol results in the formation
of a urethane.
 R.NCO + HOR----+ R*NH*COOR
 Isocyanates are highly reactive materials and enter into a number of
reactions with groups containing active hydrogen.
The first essential component of a polyurethane polymer is
the isocyanate. Isocyanates can be classed as aromatic,

such as diphenylmethanediisocyanate(MDI) or

toluene diisocyanate (TDI);

or aliphatic, such as

hexamethylenediisocyanate (HDI) or

 isophoronediisocyanate (IPDI) 4,4′-methylene bis(cyclohexyl

isocyanate

Isocyanates can be further modified by partially reacting

them with a polyol to form aprepolymer.
A quasi-prepolymer is formed when the stoichiometric ratio
of isocyanate to hydroxyl groups is greater than 2:1.
A true prepolymer is formed when the stoichiometric ratio is
equal to 2:1.
The second essential component of a polyurethane polymer is the polyol.
In practice, polyols are distinguished from short chain or low-molecular
weight glycol chain extenders and cross linkers such as
ethylene glycol (EG),
1,4-butanediol (BDO),
diethylene glycol (DEG),
glycerine
Polyols are polymers in their own right. They are formed by base-catalyzed
addition of propylene oxide (PO), ethylene oxide (EO) onto a hydroxyl or
amine containing initiator, or by polyesterification of a di-acid, such
as adipic acid, with glycols, such as ethylene glycol or dipropylene
glycol (DPG).
Polyols extended with PO or EO are polyether polyols. Polyols formed by
polyesterificationare polyester polyols.
Others ingredients

Chain Extenders

Catalysts
POLYURETHANE RUBBERS

 Today three types of solid polyurethane rubber may be

recognized, namely:
 (1) Cast polyurethane rubbers.

 ( 2 ) Millable gums.

 ( 3 ) Thermoplastic polyurethane rubbers.

CAST POLYURETHANE
RUBBERS

These material may be subdivided into four groups:

 (1) Unstable prepolymer systems.

 (2) Stable prepolymer systems.

 (3) Quasi-prepolymer systems.

 (4) One-shot systems.

UNSTABLE PREPOLYMER SYSTEMS
(VULKOLLAN SYSTEM)

 Polyester prepared by reacting a glycol such as ethylene or

propylene glycol with adipic acid.
 This is then reacted with an excess of a bulky di-isocyanate
such as l,5 naphthylene di-isoyanate.
*Excellent load-bearing ,excellent heat-resisting
characteristics.
 The molar excess of di-isocyanate is about 30%
 The resulting unit has isocyanate end groups.

 The resulting ‘prepolymer’ can then be chain extended with

glycols or amines by linking cross terminal isocyanate groups
 These reactions cause chain extension and by the formation of
urea and urethane linkages they provide sites for cross-linking.
PROPERTIES
 ‘Bulky’ aromatic isocyanates such as1,5naphthylene di-
isocyanate gave products of much higher tear strength
and tensile strength.
STABLE PREPOLYMER SYSTEMS
 Vulkollan system prepolymer is to be used almost immediately
after manufacture.
 Polyol was polyether polytetramethylene glycol with toulene
diisocyanate as the isocyanate, the latter ingredient providing
the key to the storage stability.
 Inferior products were obtained by using glycols as extenders,

 Both polyethers and polyesters are used, with glycols being the
usual chain extenders.
 Used in Harder grades of printer's rollers

 Wear-resisting applications such as Pipes, pumps and impellers

used in the mining industries.
QUASI-PREPOLYMER SYSTEMS

 Prepolymer is prepared with an excess of isocyanate to

give an isocyanate-terminated molecule.
 This is then reacted with unreacted glycol and other
ingredients.

 Used mainly for the manufacture of microcellular

products.
ONE-SHOT SYSTEMS

 With solid materials the systems are used for the

manufacture of soft rollers for the printing industry.
 Cold-curing systems of this type are also used for such
diverse applications as cable jointing and potting
compounds, and moulds for precast concrete.
MILLABLE GUMS
 (Urepan 600)The isocyanate is reacted with a slight
excess of polyester so that terminal hydroxyl groups are
produced in the prepolymer.
 The prepolymers are rubber-like gums which may be
compounded on two-roll mills with other ingredients.
 They may be cured by addition of a di-isocyanate
 Another type(Adiprene C) is a urethane-type polymer
with unsaturated groups in the polymer.
 Because of the unsaturation the polymer may be
vulcanised with sulphur.
 Has poor tensile strength when unfilled, the use of
carbon black leads to appreciable reinforcement.
PROPERTIES AND APPLICATIONS OF CROSS-
LINKED POLYURETHANE RUBBERS
 They can have higher tensile strengths
 have excellent tear and abrasion resistance.

 They tend to have a high hardness and a low resilience

 Shows outstanding resistance to ozone and oxygen

 Hydrolytic decomposition occurs with acids, alkalis and the

prolonged action of water and steam.
 Urethane rubbers have found steadily increasing use for oil
seals, shoe soles and heels, fork-lift truck tyres, diaphragms, a
variety of mechanical applications.
 Fabric coatings resistant to dry cleaning
 The millable gums are today of limited importance for two
reasons:
 ( 1 ) Their properties are not generally as good as the cast
rubbers.
 (2) It is generally more convenient to use the thermoplastic
polyurethane rubbers
THERMOPLASTIC POLYURETHANE
RUBBERS AND SPANDEX FIBRES
 When an amine is used instead of a glycol as chain
extender:
 In these polymers ‘hard’ blocks with Tg well above
normal ambient temperature are separated by ‘soft’
blocks which in the mass are rubbery in nature.
 Prepolymer is first produced by reacting a linear
polyester with terminal hydroxyl groups, or a similar
polyether with molecular weights in the range 800-2500,
with an excess of di-isocyanate to give an isocyanate-
terminated polyol prepolymer plus free (unchanged)
isocyanate.
 This blend is then reacted with a chain extender, usually
a glycol such as I,4-butane glycol, to give a polymer
with hard polyurethane segments.
 When amines have been used as chain extenders urea
groups are produced.
 Their main uses are for seals, bushes, convoluted
bellows and bearings.
 One particular form of thermoplastic polyurethane
elastomers is the elastic fibre known as spandex fibre.
 Materials consist of hard and soft segments but the
polymer used should contain at least 85% of
segmented polyurethane.
 Both polyethers and polyesters may be used as
polyols with terminal hydroxyl groups.
FLEXIBLE FOAMS
 The gas for flexible foam is usually carbon dioxide
produced during reaction of the polyol, isocyanate and
other additives.
 Polyurethane foams may be rigid, semi-rigid or flexible.
 They may be made from polyesters, polyethers or natural
polyols such as castor oil.
ONE-SHOT POLYESTER FOAMS

The polyesters commonly have a molecular

weight of about 2000 and are commonly
produced from adipic acid and a glycol such as
diethylene glycol together with a small
proportion of a trifunctional ingredient such as
trimethylol propane.
 Foams may be produced from these resins by addition of TDI,
water, a catalyst, an emulsifier, a structure modifier and
paraffin oil which helps to control pore size and prevents
splitting of the foams.
 Catalysts used are dimethylbenzylamine,
dimethlylcyclohexylamine, Emulsifiers include sulphonated
castor oil, structure modifiers such as silicone oils.
 Flexible foam is produced using Henecke type machines
 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 into the isocyanate-polyester blend and the whole
mixture is vigorously stirred and forced out of the base of the
mixing head.
POLYETHER PREPOLYMERS
 linear polyethers give foams with rather poor load-bearing and
cushioning properties
 For better cushioning properties glycerol is added.
 Prepolymer process advantages:
 Less exotherm large blocks of foam can often be produced,
 Greater flexibility in design of compounds,
 The reduced amount of free isocyanate reduces handling
hazards
 Better cushioning properties.
QUASI-PREPOLYMER POLYETHER
FOAMS
 Used when prepolymers are too viscous,
 Polyol is reacted with a large excess of isocyanate so that the
prepolymer formed is of low molecular weight and there are a
large number of free isocyanate groups.
 At the time of foaming with additional hydroxyl compound,
water and catalyst are added to produce the foam.
 Hydroxyl compound may be a polyol such as ethylene glycol
or glycerol
 Advantage of flexibility and of having low-viscosity
components,
 Based on both polyesters, and polyethers, are of interest in
shoe soling;
POLYETHER ONE-SHOT FOAMS

 The one-shot polyethers now form the bulk of the

flexible polyurethane foams.
 Polyethers generally produce foams of better cushioning
characteristics.
 Composed of polyol, isocyanate, catalyst, surfactant and
blowing agent.
PROPERTIES AND APPLICATIONS
OF FLEXIBLE FOAMS

open-cell structures.
 Compared with foams from natural rubber and SBR
latex they are less inflammable and have better
resistance to oxidation and aging.
 Mostly used for cushioning and other upholstery
materials
 Polyether foam with a density of less than half that of
rubber latex foam is widely used as a cushioning
material.
 Polyester foams,are expensive but are used when
initial high modulus is desirable.
 Polyester foams are useful as 'foam back', that is a foam backing
in order to stiffen or shape some softer fabric.
 Examples include car door and roof trim,
 quilting, shoulder pads and coat interlinings.
 Other uses are :paint rollers, sponges, draught excluders and
packaging for delicate equipment.
 One disadvantage is they burn with copious evolution of smoke
and toxic by-products,
TYPICAL APPLICATIONS OF PU
 In situ packaging
 2. Flower arrangements
 1. In situ insulation of
 (a) refrigerators (e) chemical plant
 (b) deep freezers (f) houses
 (c) cold stores (g) building panels
 (d) ships
 2. Buoyancy goods
 3. Chair shells
 1. Moulded insulation using self-skinning properties,
 e.g. refrigerators
 2. Decorative mouldings, e.g. wood beams
 (a) imitation wood
 (b) picture frames
 1. Decorative applications
 (a) furniture of all kinds
 (b) car body parts
 (c) TV, radio and loudspeaker cabinets
 (d) brush handles and gun stocks
 I. Structural plastics mouldings