Transcript REACH ASPECTOS CLAVE DEL PRE

Substance
producers
N
S
S
NH
NH
CH3
NH
CH3
Importer,
distributor
Compounders
Moulders
The book
Document that provides:
•technical background about the
methods to identify and classify the
polymers,
•to identify the components inside a
polymer,
•and also a description of the tests
required by the REACH testing annex
•It gives also Use and Exposure related
information
Definition according to ISO standards 472 (Plastics Vocabulary),
2.1. Monomers
A compound consisting of molecules each of which can provide one
or more constitutional units.
2.2. Polymers
A substance composed of molecules characterised by the multiple
repetition of one or more species of atoms (constitutional units),
linked to each others in amounts sufficient to provide a set of
properties that do not vary markedly with the addition or removal
of one or a few of the constitutional units.
3.1 General Chemistry
3.1.1 Chemical Bonds
3.1.2 Valence and Chemical Reactions
3.1.3 Definition of Plastic Materials
3.1.4 Classification of Polymers
3.1.4.1 Thermoplastic Material
3.1.4.2 Thermoset Material
3.1.4. Elastomers
3.2 Methods for Obtaining Polymers
3.2.1 Polymerisation
3.2.2 Polycondensation
3.2.3 Polyaddition
3.3 Properties of Polymers
3.3.1 Average Molecular Weight
3.3.2 Molecular Weight Distribution
3.3.3 Monodisperse and Polydisperse Systems
3.4 Methods for Characterisation
3.4.1 Mechanical Properties
3.4.1.1 Mechanical Tests
3.4.1.2 Tensile Tests
3.4.1.3 Flexural Tests
3.4.1.4 Dynamic Mechanical or
Thermomechanical Tests
3.4.1.5 Impact Tests
3.4.1.6 Compression Tests
3.4.1.7 Creep Tests
3.4.2 Thermal Properties
3.4.2.1 Heat Distortion Tests
3.4.2.2 Vicat Softening
3.4.2.3 Differential Scanning Calorimetry
3.4.2.4 Thermogravimetric Analysis
3.4.2.5 Thermomechanical Analysis
3.4.3 Rheological Properties
3.4.3.1 Melt Index Test
3.4.3.2 Capillary Rheometry
3.5 Applications: Markets for Polymers
3.5.1 Packaging
3.5.2 Building and Construction Market
3.5.3 Electric and Electronic Market
3.5.4 Automotive Market
3.5.5 Leisure and Sport
3.5.6 Agriculture
The 2010, Europa consumed around
57 milion tons (21,5% of the worldwide
production)
Taking into account the potentially
large number of polymer registrations
and the fact that the polymers pose
limited risk because of their nature,
polymers have been exempted from
registration and evaluation. But they
are still subject to authorisation and
restriction.
Many plastic processing companies
have the impression that they are not
concerned by the REACH regulations,
,
The REACH for
Polymers project aims
to clarify the situation
and to inform people in
the polymer sector about
the influence of the
REACH regulations on
their activities.
4. Methods to Determine Whether a Material Falls Under
REACH
Definition of a Polymer
Section 2.2 of the European Chemicals Agency (ECHA)
‘Guidance on the implementation of REACH’ or Article 3(5) of the
regulations:
•Material to be constituted more than 50% of polymer molecules
and to have no more than 50% all the same molecular weight
(MW).
•Polymer molecules identified as having at least three monomer
units attached to another monomer unit or other reactant.
•Other definitions but essentially two key rules for determining a
substance as a polymer:
•The ‘3M+1’ Rule’: More than 50% of the substance
must have a molecular equal to or greater than the MW
corresponding to three monomer units attached to another
monomer unit or other reactant
•The ‘< 50% Rule’: Less than 50% of the substance should
be any specific MW
4.3 Analytical Techniques
The ECHA ‘Guidance on the implementation of REACH’
GPC (Gel Permeation Chromatography)
This document on the determination of the number-average
MW and MW distribution using GPC are available in the Organisation
for Economic Co-operation and Development (OECD) Test Guidelines
(TG) 118 (1996) and also notes that if there are practical difficulties
with GPC that the OECD TG 118 document alternative analytical
methods.
4.3 Analytical Techniques
GPC (Gel Permeation Chromatography)
Partition of solute(s) between two phases
Stationary Phase -- column packing materia
Mobile Phase -- fluid which passes through
4.3.1.1.6 Concentration Detectors
•Differential refractive index (DRI) detect
•Evaporative light scattering detector
(ELSD)
•Calibration
•Solubility probelms
4.3.2 Other Analytical Techniques
The ECHA Guidelines note that when there are practical difficulties
in using GPC, that OECD TG 118 identifies alternative methods for
measuring the number-average molecular weight (Mn).
4.3.2.1 Colligative Properties
•Vapour phase osmometry (VPO) and membrane osmometry (MO)
•applicable for MW less than 20,000 (above this level but precision
will decrease)
4.3.2.2 End-group Analysis
•For some polymers, the nature of the end-groups gives easy
access to various wet chemical approaches to measure the
concentration of endgroups and this can give a measure of the Mn,
•spectroscopic techniques such as nuclear magnetic resonance
RMN
4.4 Low Molecular Weight Polymers
Materials are low MW and close to the rules defining a polymer.
If materials are of such low MW that compliance with the ‘3M+1’ rule
maybe in doubt, it will be necessary to carry out GPC in a manner
that fractionates the polymer into its individual oligomers. It is then
necessary to identify which peak is which oligomer. Assuming this
to be possible, it then needs quantification of the individual peaks
to see whether the ‘3M+1’ rule is satisfied.
The table below shows some example quantifications. For these
examples, it is assumed that different numbers of monomer units
(N) are combined with another component (P) but the other
component could be another monomer unit:
‘Example A’ only contains 40% of
material that is above the ‘3M+1’ rule and
clearly fails to satisfy that rule. ‘Example B’
also fails to satisfy the rule but only
marginally. ‘Example C’ very clearly does
satisfy the ‘3M+1’ rule. ‘Example D’
satisfies the ‘3M+1’ rule but as one
oligomer constitutes more than
50% of the material, it fails to be classified
as a polymer due to the
‘< 50%’ rule.
5 Identification of Components in a Polymer System
Except for stabilisers and impurities, which are considered as part
of the substance (polymer), the other constituents need to be
registered for quantity higher than1 ton per year.
5.2 Definition of Components in a Polymer System and REACH
Guidelines
5.2.1 Stabilisers
•Additives necessary to preserve the stability of the polymer.
•Do not have to be registered
•Heat and antioxidant, Light stabiliser
•Concentrations normally range from 0.05% to 2%, with
some applications up to 5%
•5.2.2 Non-stabiliser
•5.2.2.1 Pigments
•5.2.2.2 Lubricants
•5.2.2.3 Antistatic agent
•5.2.2.4 Mineral Fillers
•5.2.2.5 Nucleating agents
•5.2.2.6 Flame Retardants
5 Identification of Components in a Polymer System
5.2.3 Impurities
•catalyst residues or unreacted monomer.
•do not have to be registered
5.2.4 Reinforcements
5.3 Analytical methods
5.3.1 Separation methods
5.3.1.1 Solid-liquid Extraction
5.3.1.2 Dissolution and precipitation
5.3.1.3 Filtration and centrifuging
5.3.1.4 Separation of additive mixture
into components
5.3.2 UV-visible spectroscopy
5.3.3 Infrared spectroscopy
5.3.4 Mass Spectroscopy
5.3.5 X-ray diffraction and fluorescence
5.3.6 Nuclear magnetic resonance
6 REACH Annex Testing
6.1 Compulsory Tests
Four different categories:
•Physicochemical properties, like solubility or vapour
pressure (necessary in every registry request)
•Environmental properties, like partition coefficient or
biodegradability
•Toxicological data, like the acute toxicity, irritation or
genotoxicity
•Ecotoxicological data, for example toxicity in sea-life or
terrestrial
The information required in the register dossiers increases
proportionally according to the danger and potential exposure risk.
Properties that must be covered by tests are summarised in four
Annexes.
6 REACH Annex Testing
6.1 Compulsory Tests
The following table shows the relationship between volume
production and number of test of each type:
6 REACH Annex Testing
6.2 AlternativeTests
6.2.1 In vitro Methods
Saving vith REACH
¿Is it posible?
In vivo
In vitro
In silico
•QSARs
•Agrupaciones
•Read-across
6.2.1 Validated and prevalidated invitro methods
Use of in-vitro methods
5.3.1.2 Dissolution and precipitation
5.3.1.3 Filtration and centrifuging
5.3.1.4 Separation of additive mixture
into components
5.3.2 UV-visible spectroscopy
5.3.3 Infrared spectroscopy
5.3.4 Mass Spectroscopy
5.3.5 X-ray diffraction and fluorescence
5.3.6 Nuclear magnetic resonance
6 REACH Annex Testing
6.2 AlternativeTests
Article13.1:
“…Information will be obtained if posible by in
vitro methods avoiding the testing with
vertebrate animals
or
models that link structure –activity relationship
quantitative or qualitative QSAR
or
through information of similar substances with
connected structures (agrupation or
extrapolation).”
6 REACH Annex Testing
6.2 AlternativeTests
6.2.2 Quantitative Structure-activity Relationship QSAR
Chemistry,
structure
Mecanism
functional
6 REACH Annex Testing
6.2 AlternativeTests
6.2.2 Quantitative Structure-activity Relationship QSAR
(QSAR) approach seeks to predict the intrinsic
properties of chemicals by using various databases and theoretical
models, instead of conducting tests.
6.2 AlternativeTests
QSAR are computer-based models which are designed to
predict the physico-chemical properties, potential human
health and environmental effects of a substance from
knowledge of its chemical structure. In principle, the results
from validated QSAR could be used to fulfil one or more
of the REACH information requirements or help build
chemical categories without the need to use animal tests
Chemicals strategically selected and tested;
Results extrapolated to prioritize target inventory
Adverse Outcome Pathway
ER-mediated Reproductive Impairment in Fish
MOLECULAR
TARGET
Initiates the
Pathway
Receptor
Binding
Parent
Chemical
(Metabolites/
Speciation)
CELLULAR
RESPONSE
TISSUE/ORGAN
Altered
Protein
Expression
ER Binding
-Effect
-Marker
e.g.,
Vitellogenin
Toxicity Pathway
Liver ;
Gonad
Altered
proteins;
Altered
hormones;
Ova-testis
INDIVIDUAL
Sex
reversal;
Altered
behavior;
Repro.
POPULATION
Skewed
Sex Ratios;
Yr Class
1. What does the Toolbox do?
The Toolbox is a software application intended to be used by
governments, chemical industry and other stakeholders in filling
gaps in (eco)toxicity data needed for assessing the hazards of
chemicals. The Toolbox incorporates information and tools from
various sources into a logical workflow. Crucial to this workflow
is grouping chemicals into chemical categories.
The seminal features of the Toolbox are:
1. Identification of relevant structural characteristics and potential
mechanism or mode of action of a target chemical.
2. Identification of other chemicals that have the same structural
characteristics and/or mechanism or mode of action.
3. Use of existing experimental data to fill the data gap(s).
http://www.oecd.org/document/54/0,3746,en_2649_3437
9_42923638_1_1_1_1,00.html
7 Use and Exposure-related Information
Set of conditions under which the risks associated with the identified
use(s) of a substance can be controlled. Includes:
Operational conditions and risk management measures (e.g., local
exhaust ventilation or a certain type of glove, etc.
The use means any processing, formulation, consumption, storage,
keeping, treatment, filling into containers, transfer from one
container to another, mixing, production of an article or any other
utilisation…
If a manufacturer or importer fails to describe relevant and realistic
measures that control risks for a substance in a certain use he
cannot cover this use in his exposure scenario, and/or he has to
explicitly advise against that use in the safety data sheet [1].
Sustancias candidatas actualmente
http://echa.europa.eu/chem_data/authorisation_process/candidate_list_table_en.asp