GENERALITIES

The use of plastic-based products is now commonplace. Some properties

like lightness, weather resistance, reduced flammability, high elasticity as well
that shock resistance (resilience) and resistance to aggressive chemicals are the basis for the wide use of
plastic materials. They can replace many materials. About a quarter of the
plastic materials produced are used in the construction sector. Essential items (by
example of packaging materials for food products), household items (for
Example of toys) as well as medical products are of particular importance to the consumer.
amateur.
Technological innovation is rapid and constant.
There is very strict European legislation on food plastics as part of protection.
of the consumer.

THE INDUSTRIAL CONTEXT

Two contexts must be distinguished:

The production of plastics

It is part of the chemical industry. It concerns the synthesis of polymers from small
simple molecules of small molecular weights mostly derived from petrochemicals: monomers
Chemical reactions are distinguished by three types of reactions:
- polymerization
- polycondensation
- polyaddition

Among the macromolecules obtained, we can distinguish the homopolymers (repetition of a single monomer)
) of copolymers composed of two or more polymers.
These polymers are classified into three main categories:

- synthetic polymers: thermoplastics and thermosetting

- natural polymers: rubber, gum, cellulose
- artificial polymers: derivatives of natural rubber and cellulosics

It is the spatial molecular arrangement of synthetic polymers that will determine their characteristics.
fundamental (reaction to heat).
Thermoplastics are presented in linear or slightly branched chains.
Thermosetting materials present a three-dimensional network. This is the cross-linking that is obtained.
by the action of a catalyst known as a 'hardener', potentially supplemented by heat and/or
pressure

The production of polymers is divided into two stages:

- the actual production of the polymer or resin
- the formulation and compounding through manipulation and the addition of additives

Plastics processing

This is a set of techniques for implementing plastic materials. Two can be distinguished.
categories according to the materials used: thermoplastics and various industries for the
thermosetting

The formatting differs according to the type of material used.

Thermosetting resins, before transformation, are in a state of partial polycondensation.

it is called prepolymer
The starting product is available as a molding powder, a resin in solution in the solvents, or
a liquid resin containing a catalyst or a hardener, it becomes solid, insoluble, under the action of the
heat and/or pressure and/or catalysts or hardeners.
The formatting is therefore done before the start of the chemical reaction, using relatively techniques.
simple or sometimes more complex:
Example: casting, compression, injection, layering between heated plates.
The object, once removed from the mold, cannot undergo any further heating, nor can it be recycled.

An example: use of unsaturated polyesters reinforced with fiberglass in shipbuilding.

Thermoplastics are malleable through thermal means (thermoplasticity).

The product is already polymerized and appears as a more or less viscous resin.
powder or granules, heat and pressure are the main agents of transformation.

In this case, the plastic material is melted by heating.

The main techniques used are:

Injection
Extrusion
Calendaring
induction
Powder coating
Thermoforming
Casting, rotation, soaking, sintering

Product classes

Thermoplastics

CHEMICAL CLASS Standard abbreviation

Acetals or polyacetals POM
Polyacrylics and polymethacrylics PMMA PAN
Polyamides PA
Polycarbonates PC
linear polyesters PEBT PBTP PTMT
fluorinated polymers (polyfluoroethenes) PTFE PCTFE PVDF
polyolefins PE EVA PP
polystyrenic PS SAN ABS MBS SBS SIS
polyvinyls PVC PVAL PVAC PVDC PVB
cellulosic CN
polysulfones
Phenylene polysulfide

Thermosetting

CHEMICAL CLASS Standardized abbreviation

Aminoplasts (melamine-formaldehyde or melamine-formol) MF
Aminoplasts (urea-formaldehyde or urea-formol) UF
Phenoplasts (phenol-formaldehyde or phenol-formol) PF
Polyepoxides EP
Unsaturated polyesters (cross-linked) UP
Polyimides
Polyorganosiloxanes YES
Polyurethanes PUR
Alkyd resins modified with oleoglycero-phallic oils
Auxiliary components

They are essential for imparting special characteristics to finished products with specific purposes.
ranging from technical specifications to commercial ones.
The products used are as varied as the raw materials.
We can distinguish among these products:
- the adjuvants: small quantity without fundamental modification
- additives: larger quantity and modification of the final product

Plasticizers
Charges and reinforcements
Pigments and dyes
Solvents
Catalysts and accelerators
Hardeners
Stabilizers and antioxidants
Flame retardants and fire inhibitors
Foaming agents

COMPONENTS OF PLASTIC MATERIALS

THE AUXILIARY AGENTS

the catalysts and accelerators

They cause or accelerate reactions
It mainly concerns organic peroxides such as methyl ethyl ketone peroxide.

MEKP, MEK peroxide, 2-butanone peroxide...) used as a hardener for unsaturated polyesters.
It is an extremely explosive organic peroxide.

There are new generations: metallocenes

foaming or swelling agents

The derivatives of hydrazine

hydrochlorofluorocarbons for polystyrene.
Azo compounds such as azodicarbonamide: N-CONH2 which is a powdery product.

the hardeners

They intervene directly as crosslinking agents.

Amines hardeners

They consist of the following amines:

Tertiary aliphatic amines: TEA, DMEA...

Alicyclic amines: N methylmorpholine

Cycloaliphatic amines

Aromatic amines: MDA: methylene dianiline or DDM: diaminodiphenyl methane

acid hardeners

Here we find acid anhydrides. There are many products that come in powder form.
Let's mention the specific case of trimethyl anhydride, a catalyst for epoxy resins.
stabilizers

Thermostabilizers will prevent the thermal degradation of the polymer during its processing.

Let's quote:
Metallic salts of fatty acids: aluminum stearate, zinc, lead, sodium, cadmium, magnesium,
calcium, or barium.

Lead-derived stabilizers are used to protect PVC against degradation by heat.

and UV (cable insulation..)
the laureates of barium, cadmium, and tin

epoxidized soybean or castor oils

antioxidants
They avoid radical polymerization reactions by the oxygen in the air.
Various chemical families can be found: aromatic amines, phenols, organic phosphites.

Let's take butylated hydroxytoluene or BHT as an example.

The risks mainly arise during the incorporation.

protective agents against UV

This involves, for example, aliphatic amine compounds or nickel compounds, OH-benzophenone and
of the OH-phenylbenzotriazole.

plasticizers

Esters of phthalic acid or adipic acid as well as phosphates are used as

plasticizers.
Phthalates represent the most important class (90%), and they include numerous molecules. They
are remarkable plasticizers for PVC and are used for this purpose 90% of the time.
They are the subject of environmental concerns due to their industrial use.
From a toxicological standpoint, they represent major concerns regarding reproductive risks.

Let’s mention Di-(2-ethylhexyl)phthalate (DEHP)

Adipates, including Di-(2-ethylhexyl)adipate (DEHA), also known by the initials DOA or

dioctyl adipate. It is a component of plastic packaging materials, particularly seals or films.
flexible.
The DEHA would be a safer alternative to phthalates as it is less harmful.

So far, it is only in rodents, after prolonged exposure to DEHA.

or DEHP, a carcinogenic effect has been observed.
Phosphates are plasticizers and flame retardants. Let's mention tricresyl and triphenyl phosphates.
for the most dangerous.

Chlorinated organic derivatives: chlorinated naphthalenes

lubricants

Lubricants facilitate the subsequent processing of polymers during demolding. Paraffins are mainly used.
non-toxic if they are not contaminated) as well as alcohols (cetyl alcohol), stearates
metallic and fatty acid esters (low toxicity).

flame retardants or combustion inhibitors

Phosphorus compounds
halogenated compounds
phosphorus halogenated compounds
compounds of antimony
compounds of boron
aluminum hydrates
Reactive flame retardants: atom of chlorine, bromine or phosphorus.

Let us evoke some of these agents:

Phosphors are dangerous to handle.

Antimony trioxide (SbO3) is widely used. It carries the general risk of antimony derivatives.

Decabromodiphenyl oxide

Bromostyrene

THE CHARGES

They allow improvements in mechanical, physical, thermal, and electrical properties.

These are very varied products: inert dust, metal oxides (lead), silica, talc, and kaolin.

The fibers

Fibers are found in composite materials, FRP: fiber-reinforced polymers.

We can mention two types:

Unsaturated polyesters / fiberglass (skin irritants)

Epoxy resins / carbon fibers (obtained from polyacrylonitrile: PAN)

PIGMENTS AND DYES

Dyes (soluble and organic) leave plastics transparent or translucent.

We particularly find mono or diazo compounds.

Pigments (insoluble) color and opacify. Carbon black, metallic oxides and salts are used.
titanium, lead, iron ...), coupled organics (carbon black), or mixed.
They are often in small quantities, but many are harmful.
the solvents

They are the most dangerous products along with the monomers. We will not detail them as they are to be studied.
in the context of solvents.

Let's mention 1,2 DICHLOROETHANE (betweenothers: PMMA glue) and DIMETHYLFORMAMIDE

(DMF) which is widely used.

Carbon disulfide is very toxic.

EPOXY RESINS

Epichlorohydrin + bisphenol-A = diglycidyl ether of Bisphenol A (DGEBA)

The persistent monomer in resin.
Bisphenol A is an industrial and environmental contaminant.

Tetraglycidylmethylenedianiline (TGMDA)

Triglycidylparaaminophenol (TGPAP)

THE MONOMERS

Vinyl chloride monomer

The best-documented occupational carcinogen. It only concerns a small number of workers.
Prevention based on low concentration in the workplace

Isocyanates

They involve a large number of employees and represent the second cause of occupational asthma.
Exposures are found during polymerization or thermal degradation operations.

Isocyanates are obtained by combining polyisocyanates with compounds containing

several alcohol functions (OH). They contain amine agents.
They are used for lacquers, synthetic fibers, foams, synthetic rubbers, adhesives...

The diisocyanates: MDI and TDI (toluene diisocyanate: DESMODUR) are produced by the action of phosgene.
on ethylene diamine.

Styrene

There are two main uses:

monomer of polystyrene, ABS...
reactive solvent of unsaturated polyesters

Acrylates and Methacrylates

It is about the esters of the corresponding acids.

They are found in dental activities (composite resin-based amalgams, systems
adhesives for filling materials, dental prostheses, sealing cements for prostheses or appliances
orthodontic)

Their irritative potential is variable.

strong for diacrylates
moderate for monoacrylates
weak for monomethacrylates and dimethacrylates

The most common sensitizations among dentists are found with the following products:
2-HEMA, EGDMA, TREGDMA, MMA, EMA and bis-PMA

Acrylamides

Uses:
Soil waterproofing
Flocculant in water treatment
Pulp binder
Electrophoresis gels

THERMAL DEGRADATION PRODUCTS

Without degradation, the toxicity of plastic materials is related to the presence of monomers, oligomers, and
prepolymers (especially for thermosetting) as well as auxiliaries.
These products will behave as airborne contaminants with cutaneous and mucous irritations and
respiratory awareness.
The toxicity of plastics therefore mainly comes from their thermal degradation and will vary depending on
the intensity of this one.
We will distinguish two fundamental situations:

Work situations (implementation) in the strict sense:

overheating during the implementation of thermoplastics

machining: traditional cutting or laser cutting
thermowelding

At the processing temperatures (100 to 400 °C), there is a release of residual monomers and/or
of adjuvants. New manufacturing techniques aim to limit them as much as possible.
Everything must therefore be done to avoid overheating and implement preventive measures.
collectives.

Crisis situations: the fire

Release of very varied pyrolysis products.

At higher temperatures (from pyrolysis to combustion), one must beware of soot and certain others.
pyrolysis products:
Carbon monoxide and carbon dioxide
Ammonia, nitrogen oxides, nitriles, and cyanide (HCN and nitriles)
Chlorinated and fluorinated compounds
Hydrocarbons
Sulfur products
Fires involving plastics are characterized by the significant production of smoke.
Let us remind ourselves of the importance of implementing emergency plans (and for the occupational physician,
the ability to perform first aid on asphyxiated and intoxicated individuals.
REFERENCES

INRS ED 638 PLASTICS & additives 3rd edition September 1993

DIU Toxicology Course Faculty Dijon
DIU Toxicology Course PR CONSO
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