Life Cycle of Synthetic Leather and Raw Materials:

In the production of synthetic leather, the raw materials acquired from the earth are
heavily processed to make polyvinyl chloride or polyurethane and excess chemicals
during processing are recycled. While currently manufacturers are feeding excess
chemicals back into the life cycle to produce more synthetic leather, it doesnt seem
efficient. Product durability seems to be a good solution for waste management by
inhibiting the speed of the product life cycle with better raw materials (Blackburn,
2009). However, lowering the product consumption is the best solution. Instead of
creating more product life cycles with recycled material, it would be ideal to have a
lower demand for the product and thus a lower amount of extracted resources, used
energy, and harmful emissions. If people didnt have a constant demand for newer,
more stylish synthetic leather products there would be less resources we must tap
into in order to make polyvinyl chloride or polyurethane for synthetic leather.

Polyvinyl Chloride (PVC) Raw Materials and Production:

Polyvinyl Chloride, or PVC, is a type of plastic coating used on fabric to make
synthetic leather.
PVC is a thermoplastic polymer based on chlorinated
hydrocarbons (Baitz, 2004). Polyvinyl chloride requires additives to prolong its life
cycle because it is a brittle material in its pure form and susceptible to deterioration
under light and heat (Baitz, 2004). Additives include plasticisers, stabilisers, and
fillers. For flexible PVC used in synthetic leather, the weight proportions are 53%
PVC polymer, 40% plasticiser, 1% stabiliser, 5% filler, and 1% other (Baitz, 2004).
PVC can be reduced to its most basic raw materials ethylene and chlorine. These
primary materials go through a thermal decomposition that results in ethylene
dichloride (EDC) and is then converted to Vinyl Chloride (VCM). Polymerisation
takes place creating polyvinyl chloride which is then compounded with additives
and processed for the final product.

Ethylene is produced when petroleum is refined to naphtha, cracked with steam

power, and then chemically reacted to form ethylene (Baitz, 2004). Petroleum
occupies 43% of the polymer weight (Baitz, 2004). Chlorine is taken from rock salt
through an electrolytic process that results in chlorine, sodium, and hydrogen (Baitz,
2004). These resulting elements must be kept separately or else they will produce
undesirable by products (Baitz, 2004). Rock salt contributes 57% of the polymer
weight (Baitz, 2004). When ethylene and chlorine are combined, they chemically
react to form ethylene dichloride or EDC (Baitz, 2004). EDC is then subjected to
heat and cracking which forms a vinyl chloride monomer and hydrochloric acid
(Baitz, 2004). Hydrochloric acid is recycled back into the process by reacting with
ethylene to make EDC again (Baitz, 2004). Alternatively, EDC can be produced from
the natural gas liquids ethane, butane, and propane (Baitz, 2004). EDC acts as a

solvent during an oxychlorination reaction with ethylene, hydrogen chloride, and

oxygen that is catalyzed by copper chloride under high pressure and heat (Baitz,
2004). The resulting EDC is cleansed with water and caustic soda which is later
evaporated to remove contaminants (Baitz, 2004). EDC is converted to VCM
through pyrolysis, a decomposing process initiated with high temperatures (Baitz,
2004). Chlorinated and non chlorinated by products are recycled by combing with
the un reacted EDC which yields HCI (Baitz, 2004). The resulting HCI is re used in
the oxychlorination process (Baitz, 2004). The by products of this process are less
than 2.5% of the final products mass (Baitz, 2004).

PVC polymerisation is the process that gives the coating its transparent and glossy
qualities. Polymerisation requires light, a liquid monomer, and heat or small
amounts of initiators (Baitz, 2004). There are a couple types of polymerisation, but I
am going to assume that the most common type, suspension polymerisation,
applies to the production of synthetic leather. During suspension polymerisation an
impellor agitator is used to distribute a monomer throughout water (Baitz, 2004).
This results in large particles that can absorb an ample amount of plasticiser (Baitz,
2004). Plasticisers are typically made from carboxlyic acid and an alcohol (Baitz,
2004). They separate polymer chains, increasing their movement and the elasticity
of the product (Baitz, 2004). Plasticisers used in flexible PVC for synthetic leather
make up 40% of the product and can reach up to 60% in other soft products
(Baitz, 2004). After the addition of the plasticiser, the polymer is separated from
the water using centripetal force generated by a centrifuge (Baitz, 2004). The
centrifuge spins the polymer until the denser material falls towards the middle and
the lighter material, or in this case the water moves to the outside. The water is
also evaporated with hot air. The VCM is rationed out to a reactor with a
suspension stabiliser, a pH buffer, an anti foam agent, and an initiator like organic
peroxides (Baitz, 2004). The stabiliser is a significant additive because it protects
the final product from damaging heat or UV light. It also protects from thermal
degradation and hydrogen chloride evolution during processing (Baitz, 2004). When
the VCM reaction is 80% to 90% complete, an inhibitor is added to stop the
polymerisation (Baitz, 2004). The suspension is then filtered of the unconverted
VCM with water that is later sent to a treatment plant to be stripped (Baitz, 2004).
The suspension is processed into dry PVC powder using the same centrifuge and
evaporation techniques as earlier (Baitz, 2004). At some point in production,
pigments are added to color the final product. One of the most widely used
pigments is titanium dioxide because it serves as a base for many colors (Baitz,
2004). Chloride and sulphate processes are used to obtain titanium dioxide from
limonite (Baitz, 2004). Titanium dioxide has toxicity potential, requires high energy
consumption, and yields chemical waste (Baitz, 2004). Pigments may also have a
connection to lead in products because lead makes bright colors last longer (Young,
2012).

After polymerisation takes place, some form of heat is required to bind the
PVC particles together and incorporate the additives (Baitz, 2004). The material is
then cooled, and left to recrystallize to form a structure process called gelation or
fusion (Baitz, 2004).

Polyvinyl Chloride and recycling/waste management:

Industry professionals are trying to increase the amount of recycled PVC

entering new life cycles by recycling the raw materials. Only the raw materials that
require extraction, intermediate production, and polymerisation substitutes recycled
material back into a new life cycle (Baitz, 2004). My first finding was that used
hydrochloric acid is recycled to form more EDC in the beginning stages of PVC
production (Baitz, 2004). Also, any unreacted EDC and by products are put back
into the beginning of a new process (Baitz, 2004). Environmental impacts of EDC
and VCM production are fairly low (Baitz, 2004). In the destruction of dioxin
containing solid waste, the by product HCI can be re used in PVC production or refined to a new commercial product (Baitz, 2004). Moving further along the PVC
production process, VCM poses the highest environmental impact. This is because
VCM is heavily involved in PVC production and is made up of ethylene which
requires intensive energy for production (Baitz, 2004). When VCM is filtered out
during the polymerisation process, VCM can be recovered from gas flows using a
condenser (Baitz, 2004). When producers are ready to start a new batch of PVC,
they rinse the reactor with water to remove any residue from the previous process.
With intensive degassing processes throughout polymerisation, they can reduce the
amount of wasted residual monomer (Baitz, 2004). This idea of closed loop
recycling, or putting the by products or unreacted material back into a new life
cycle could lower environmental impacts (Baitz, 2004). This recycling process is
efficient as long as the amount of recycled material is below its demand (Baitz,
2004). On the other hand, problems are predicted with the continuing
enhancement of stabilisers used in PVC manufacturing. New and improved
stabiliser systems may not be compatible with the older stabilisers that remain in
the recycled material; however, this is not currently a problem as we have not
reached this transition in technology (Baitz, 2004). It is hypothesized that recycled
material with an outer layer of the enhanced material could fix this possible
compatibility issue in the future (Baitz, 2004).

Polyurethane Raw Materials and Production:

Another form of plastic coating attached to a fabric base for synthetic

leather is called polyurethane. Polyurethane is composed of isocyanates, polyester
polyols, and additives. The isocyanates are methylene diphenyl diisocyanate (MDI)
and toluene diisocyanates (TDI) (Lee, 2002). In 2000, 4.4 million tons of MDI and
TDI were produced (Lee, 2002). Polyols react with isocyanates and produce
polyurethane polymers powered by hydroxyl groups (Lee, 2002). In 2000, there
were 850,000 tons of polyester polyols produced with a growing demand of 4-5%
per year (Lee, 2002). Polyol blends include additives like catalysts, fire retardents,
blowing agents, coloring agents, and fillers.

MDI isocyanate is derived from benzene (Lee, 2002). Concentrated nitric

and sulphuric acids and benzene are blended to yield nitrobenzene (Lee, 2002).
Nitrobenzene is hydrogenated to aniline by dissolving iron in hydrochloric acid with
nitrobenzene (Lee, 2002). The aniline is purified, then reacted with formaldehyde to
generate a polyamine mixture called methylene dianiline (MDA) (Lee, 2002). Excess
aniline is removed and recycled. The amine groups in MDA must be phosgenated to
convert to isocyanates (Lee, 2002). A phosgene molecule reacts with the amine
group and emits hydrogen chloride gas that must be boiled off and used as a raw
material for other processes (Lee, 2002). Isocyanates are the worlds largest
suppliers of hydrogen chloride gas (Lee, 2002). The excess phosgene and solvent
are removed and recycled (Lee, 2002). The crude diisocyanate stream and residue
is divided into pure MDI and a mixed isomer stream (Lee, 2002).

Toluene is converted into the isocyanate TDI and is processed much like MDI.
Toluene is nitrated into dinitrotoluene which produces an isomer mix (Lee, 2002).
The isomers are hydrogenated to crude toluene diamine (TDA) (Lee, 2002). TDA is
purified by distillation to remove mixed isomers that are disproportional, meaning
they have the wrong level of hydrolysable chlorine and acids that would influence
rates of chemical reactions (Lee, 2002). Purified TDA is phosgenated similarly to the
process in MDI, and excess phosgene is recycled. The isocyanate mixture is distilled
to generate a liquid TDI product and a residue (Lee, 2002).

Polyester polyol raw materials include dibasic acids like adipic acid and AGS
mixed acids, glycols like ethylene glycol, propylene glycol, 1,4-butane diol, and 1,6hexane diol, and branching agents like glycerol and pentaerythritol (Lee, 2002).
The closer together the ratio of glycols to adipic acid in a polyol results in an
extended polymerisation that is desireable for flexible foams (Lee, 2002). I am
assuming flexible or elastomer foams are used in synthetic leather due to its more
flexible qualities as a plastic. Triols such as glycerol or trimethylolpropane increase
functionality of a polyester polyol, which leads to branching of the polyester
backbone (Lee, 2002). In the production of polyester polyols, the raw materials are
first heated under pressure. Water is distilled off, which wastes some acid groups
and slows the rate of polymerisation (Lee, 2002). Azeotropic distillation can be
applied to decrease this loss by using a vacumm and or adding nitrogen to improve
the polymerisation reaction (Lee, 2002). Pigment additives can be organic or
inorganic. Inorganic pigments include titanium dioxide, chromium oxide, carbon
black, and iron oxide (Lee, 2002). Fillers are added to they polyol blend to reduce
cost, increase stiffness, and increase temperature stability. Glass fibre is most
commonly used, although carbon fibre is becoming more popular as its price is
dropping (Lee, 2002). Stabilisers are added to prevent microbial attack by
enzymatic hydrolysis (Lee, 2002). They are usually composed of metal organics
relating to antimony, copper, or arsenic (Lee, 2002). A blend of stabilisers are used
for UV resistance. Benzophenone, benzotriazoles, and amines all work as UV
absorbers (Lee, 2002). Fire retardants like solid melamine, graphite or aluminium
trihydrate and other low viscosity liquid compounds are added to polyols (Lee,
2002). It is typical for fire retardants to contain bromine, chlorine, or phosphorous
(Lee, 2002).

Polyurethane Recycling/waste management:

The nitration of benzene to make MDI is a high yield reaction that leaves 10% of the
materials weight to be recycled (Lee, 2002). The nitric sulphuric acids mixed with
benzene yield water, a process called hydrogenation. The mixture is left to
naturally separate and 20% of the benzene will remain unreacted (Lee, 2002). Once
the water is distilled it is stripped of the remaining benzene for recycling (Lee,
2002). The nitration process works the same for TDI so the isomer mix and
sulphuric acid can be recycled using the same techniques. Also, sulphuric acid can
be recycled and excess reaction heat can be recovered as steam (Lee, 2002). In
production of both isocyanates, excess phosgene the most important chemical for
conversion, is recycled. Renewable materials like sucrose and starch have been

used in beginning stages of production of polyurethane (Lee, 2002). Un wanted

polyester based polyurethane is recycled using transesterification, a process that
shortens the chain extender and breaks down the polyol blend so the material can
be re used (Lee, 2002). Using recycled ground flexible foam as a filler mixed into
the polyol stream is another way to re use raw materials (Lee, 2002).

Overview of Synthetic leather Production:

To conclude the extensive list of raw materials used and the complex
processing, the U.S patent for synthetic leather production gives us an idea of how
the raw materials in polyvinyl chloride and polyurethane will serve the final product.
The processed raw materials form a polymeric sheet that is fused with a fabric base
and all the layers are foamed (Fine, 1982). The initial polymeric layer is attached to
an embossed release paper that is heated to a tacky state (Fine, 1982). The fabric
base is then added along with another polymeric layer, and soon after that a foam
layer (Fine, 1982). The foam layer should have a thin urethane coat that is
mechanically embossed to simulate a leather like surface (Fine, 1982).

Bibliography

Baitz, Martin, Dr., Johannes KreiBig, and Eloise Byrne. "Life Cycle Assessment of PVC
and of Principal Competing Materials." European Commission, July 2004. Web. 20
Feb. 2013. <http://ec.europa.eu/enterprise/sectors/chemicals/files/sustdev/pvcfinal_report_lca_en.pdf>.

Blackburn, R.S., ed. Sustainable Textiles. N.p.: Woodhead, 2009. Print.

Fine, Jerome, and Gene N. Harrington. Production of Synthetic Leather. Cleveland

Plastics of Tennessee, Inc., assignee. Patent 4,349,597. 14 Sept. 1982. Print.