CHAPTER 8

Coagulation of Polyurethanes

The polymer most often used for the coagulation process is polyurethane.
Nearly all leather substitutes sold in the world consist partially or totally of poly-
urethanes. Therefore a whole chapter is dedicated to the coagulation of poly-
urethanes.
In 1951 a coagulation process for a polyurethane was published for the first
time [1]. Since 1954 [36] additional process steps have been developed to produce
microporous polyurethanes [32].
The structure of the soft segments of the polyurethanes influences the coagu-
lation of the polyurethanes remarkably. Soft segments with a higher hydrophilic
property result in polyurethanes with a better coagulation behavior. The struc-
ture of the hard segments is of minor importance [33].
Only linear polymers have good solubility in organic solvents. Crosslinked
polymers are normally insoluble in solvents; due to a certain decomposition
crosslinked polyurethanes can be dissolved in heated DMF because hot DMF
is able to split branched polymer chains which results in a linearity of the poly-
mer-chains. The NCO/OH ratio determines the linearity of the polyurethane
chain. A ratio NCO/OH < 1 results in easily soluble OH-terminated polyure-
thanes [35], NCO/OH > 1 results in crosslinked, poorly soluble ones (details see
Chap. 25.1).
The following principally different process types are known:

Microporous films may be produced by applying a polymer solution onto a

stainless steel band or a glass fiber fabric coated with a fluorine polymer
(TEFLON by DuPont) dipped in water, stripped off the band or fabric, wash-
ed and dried.
The polymer solution may be applied in a direct coating process onto a fabric
or a nonwoven and coagulating in a bath of water as a nonsolvent [20, 23, 24,
30]. After washing and drying the coated substrate is ready to sell or only
needs an additional finishing step (see Chap. 22). This method is especially
suited if the substrate is treated with the coagulation solution too. Sometimes
it is difficult to get a smooth surface. Air bubbles may show as open pores on
the surface. This may be a disadvantage of the direct coating process.
The indirect process involves a releasing fabric which is, usually, coated with a
thin polyurethane layer, then with a second top layer or finish. After a short
drying of the first layer, the polyurethane solution in DMF is applied and a
textile laminated into the wet solution layer. After coagulation, washing
CHAPTER 21

Nonwovens

According to a Japanese publication, the production of nonwovens has an annual

growth rate of more than 10 % in Japan. The growth rate for nonwovens based on
polyester and polypropylene are responsible for this high growth rate, that for
polyamide is stagnant. Polypropylene is cheap, resistant to chemicals and may be
used in the medical and hygiene fields [97].
Nonwovens are also important substrates for water vapor permeable pro-
ducts.Very often their manufacturing process is linked closely to the production
process of vapor permeable top coats or impregnations. In their manufacturing
process typical reactions are often used as for the production of water vapor
permeable foils or coatings.
A general overview of the most important production processes for non-
wovens is given. For more detailed information it is necessary to look into
surveys [1 7, 13].
Nonwovens can be produced principally in five different ways:
mechanically by carding of staple fibers,
like paper from a fiber slurry treated in paper making,
pneumatically by means of an air stream,
by spinning fibers, or
by a melt blown process [97].
The production of knitted or woven fabrics needs thread. Nearly all nonwovens
are produced with staple fibers. Besides the spinning process all the other pro-
cesses are carried out with more or less short staple fibers.

Carding Process. Cards are machines which have been used for a long time in
the processing of wool fibers. For nonwovens staple fibers are unified on a card,
possibly mixed with other fibers and orientated in the running direction of the
card (Fig. 21-1).
The orientated fibers are then laid by a cross lapper (Fig. 21-2) onto a running
belt and situated at 90 C at the running direction of the card. The cross lapper
moves back and forth over the belt and produces different layers of fibers whose
orientations are no longer in the running direction but in angles. The aim of
this is to finally get a textile substrate which is anisotropic (see Fig. 21-5) in its
physical behavior.
The resulting material is needled, shrunk, bonded, split and buffed. These
operations will be discussed later.
226 23 Modification of Physical Properties by Chemical Methods

23.2
Modification of Physical Properties by Physical Methods
Directly after production the surface of man-made leathers often needs a physi-
cal treatment: Embossing and plating (see Chap. 22) are the usual operations
with calenders or embossed rollers. As previously mentioned, this operation
reduces the porosity of the material. A presupposition for a good embossing or
plating effect is a thermoplasticity of the polymer. By heating thermoplastic,
microporous layers lose part of their water vapor permeability. For instance a
microporous polyurethane foil with a water vapor permeability of 10 mg/hcm2
after lamination to the substrate will have a decrease in water vapor permeabil-
ity to 46 mg/hcm2, after embossing to 24 mg/hcm2, and at the end of the finish-
ing to 12 mg/hcm2 comparable to finished genuine heather.
Increasing water vapor permeability reduces the tensile strength of the film
(see Fig. 23-1). The same effect occurs with the tear propagation strength. The
pore structure also has an influence on the water and air permeability of micro-
porous sheets [6].
To improve the physical properties of microporous sheets a treatment with
high frequency [8] or IR rays at 120 150 C has been discussed. The IR treatment
causes a superficial melting of pores which decreases water vapor permeability
and eliminates stress in the polymer [5].

Tensite strength and Tear strength

water vapor permeability and water vapor permeability
Tensite strength (kp/cm2) Tear strength (kp/cm)

Water vapor permeability (mg/hcm2) Water vapor permeability (mg/hcm2)

Fig. 23-1. The tensile strength and the tear strength of different microporous films with the same
composition decreases with increasing water vapor permeability
270 27 Other Industrial Applications

Modified Lyocell fibers can be used as wound dressings especially for

chronically ill persons. These fibers absorb more water than alginate, which is
usually used [87]. The material is sold under the name of Hydrocel.
Collagen layers are suitable as wound dressings [78] or several layers of
collagen fixed on each other [20].
A self-adhesive wound dressing is produced by applying a hydrogel layer to a
vapor permeable bacterial barrier [96].
Porosity and compliance of microporous polyurethane based microarterial
vessel has an effect on neoarterial wall regeneration [95].
Porous polyurethane films are coated with a layer of a water-absorbing material
an epoxide crosslinked hyaluronate foam and a polyurethane top layer. The result-
ing wound dressing material is soft, resistant to bacteria and is biocompatible [36].
Gels of hydrophilic polyurethanes are also used as wound dressings [47].
Implants produced from aromatic isocyanates should be avoided because
under reductive conditions carcinogenic aromatic amines may be formed which
can be determined by chemical analysis. According to the authors meaning there
is no miracle if, by using polymers based on aromatic isocyanate, carcinogenic
aromatic amines are found [38].
Microporous membranes can be used to protect against noise, heat (11.1 [23])
and chemicals [35]. A publication is available which summarizes all types of
protective clothing for the medical field [55]. All protection includes measures to
avoid penetration by viruses and a good water vapor permeability. This publica-
tion also discusses the advantages and disadvantages of one-time use or dispos-
able clothing, e. g. those of Kimberley-Clark and DuPont, as against reusable
clothing e. g. of Gore.
Clothing and other uses of textile substrates in rooms for surgical operations
are examined in a publication in regard to their cleanability and their ability to
be sterilized by means of ethylene oxide, autoclave, heat etc. [75].
Incontinence and anti-decubitus articles can be produced with Lyocell fibers
and an optional coating [70].
Disposable diapers containing hydrophilic surface layers (12 [39, 40]) are
claimed to have a good feel to human skin [81].
Cosmetic buffs may be produced with a coagulated polyurethane with pores
of a size of 5 100 m [101].

Veterinary Use. Flea collars for dogs protection are produced from a poly-
urethane with a density of 0.3 0.45 g/cm3. The polyurethane is impregnated
with an insecticide and laminated onto a textile substrate. As insecticides, pyre-
throid, carbamates, organophosphorus compounds etc. are used [52].

Food. Hydrophilic foils can be used in food packaging (18.1 [32], [43]).

Other Industrial Applications. Microporous and mesoporous zeolites are used

in chemical processes, in catalysis, in DielsAlder reactions, oxidations etc.
These products are usually inorganic and of a crystalline structure. They differ
from membranes, usually polymeric and elastic, which are the subject of this
book [104].
CHAPTER 28

Ecology

As we have previously seen leather substitutes in most cases consist of a textile

substrate with a polymer coating and or impregnations. Therefore, the ecologi-
cal behavior of the textiles is as important as the polymeric materials used. There
are several environmental influences:
(1) The impact of the chemicals used in processing during and after the produc-
tion of the textile and the substitute.
(2) The chemicals needed to protect the article during usage, and
(3) The disposal of the article when no longer needed.
The following figures demonstrate the quantity of products involved: As an
example, the textile industry in Germany uses 250,000 tons of water annually
which is mainly recycled. 960,000 tons of used clothing are produced of
which 300,000 tons are reused. 560,000 tons of used household textiles are
disposed [26].
Besides the textiles, dyestuffs of textile substrates are a point of ecological
discussion. Since certain dyestuffs are known to contain carcinogenic amines as
components, all azo dyes are often regarded as dangerous. Only some dyestuffs
contain carcinogenic components. The dyestuffs themselves do not need to be
hazardous. Some years ago it was found that such dyestuffs in the human meta-
bolism may resplit by azoreductase in the amines (see Fig. 28-1). Therefore,
dyestuffs containing carcinogenic amines should not be used any longer. In most
countries today their use is forbidden.
All major chemical suppliers test the products they are marketing for toxi-
cological behavior. The safety data sheets [19, 23] which are delivered with the
product include information about safe applications of the product so that
hazards may be avoided for the workers and the environment [18].

Fig. 28-1. Resplitting of an

azo dyestuff
http://www.springer.com/978-3-540-64946-5