Transcript Slide 1

The Current Plasticiser Situation in Europe
David Cadogan, ECPI
Phthalates and new plasticisers for PVC Conference
Copenhagen, Denmark
20 September 2007
Outline
ECPI
Is there a move away from phthalates – Why?
Are phthalates a threat to human health?
Legislation
The plasticisers of yesterday and today
The plasticisers of today and tomorrow - Alternatives to phthalates
Summary
2
ECPI
European Council for Plasticisers and Intermediates
A Sector Group of CEFIC – the European Chemical Industry Council
European producers of plasticisers, alcohols and acids
Sponsorship of scientific studies by independent experts
Provide users, legislators and other interested bodies with information
on safety, health and the environment
Close liaison with equivalent organisations in USA and Japan
3
PVC plus DEHP
Cl
Cl
Cl
Cl
O
Cl
Cl
Cl
Cl
Cl
O
Cl
Cl
CI
O
O
Cl
Cl
Cl
Cl
Cl
Cl
CI
Cl
4
93% of Plasticisers are Phthalates
Phthalates have :
Optimum balance of polar / non-polar groups
Best all round performance / price ratio
DEHP
Performance can be fine tuned by using appropriate alcohol
C4 - C7 alcohol
C8 – C10 alcohols
C11-C13 alcohols
>80% linear
: Lower viscosity, faster processing
: General purpose
: High temperature performance
: Better low / high temperature performance
5
Is there a move away from phthalates?..... Why?
Yes
There is move away from some phthalates
New plasticisers are being developed
Why?
Concern that some phthalates may be a threat to human health
Increasing legislation limiting the use of some phthalates
Need Speciality Plasticisers to meet changing performance requirements
6
Are phthalates a threat to human health?
7
Potential Health Impact - Carcinogenicity
1982 – Liver tumours in rodents caused IARC to classify DEHP as
“possibly carcinogenic to humans”
18 years of research showed :
Phthalates, drugs used to lower cholesterol levels and some other
chemicals cause tumours in rodents by peroxisome proliferation (PP)
No effects in monkeys fed DEHP and DINP
No liver damage in humans taking cholesterol lowering drugs
2000 - IARC Reclassified DEHP - Liver cancer caused by phthalates
in rats and mice is not relevant to humans
8
Potential Health Impact - Reproductive Effects
High levels of some phthalates produce adverse effects in rodents
Little, if any, effects seen with DMP, DEP, DINP and DIDP
Levels can be defined at which no effects occur (NOAEL)
In general NOAELs are orders of magnitude higher than levels of
exposure. Therefore no risk
Studies ongoing to identify the mechanism underlying the
reproductive effects in rodents – are they relevant to humans?
9
Potential Health Impact - Structure / Activity
Phthalate toxicity to rodents depends on number of carbon atoms
in the alcohol backbone
1-3 C
4-6 C
>7C
(DMP, DEP)
(DBP, DEHP)
(DINP, DIDP)
Minimal
Maximum
Minimal
10
Do Phthalates have Adverse Effects on Humans?
No evidence of any phthalate having an adverse effect on human health
20 year follow-up study on 242 low birth weight individuals (high DEHP
exposure in intensive care) showed no effects on male fertility
Adolescents exposed to DEHP via ECMO as neonates show no adverse
effects on growth or sexual maturity
Adverse effects are only seen in rodent studies – not in non-human
primates
The only studies claiming to see effects in humans are considered
by independent epidemiologists and statisticians:
• To be poorly designed
• To use questionable statistical treatment of data and
interpretation of results.
11
Legislative Actions and Expert Opinions
Classification and labelling of substances
Existing substances legislation – Risk assessment and management
Indoor Air
Norwegian proposed ban
Toys and childcare articles
Food contact materials
Medical devices
12
Classification and Labelling
13
Hazard - Classification and Labelling
Category 1
Substances known to cause effects in humans. Based on epidemiological
data.
Category 2
Substances to be regarded as if they cause effects in humans. Based on
clear evidence in animal studies.
Category 3
Substances causing concern for humans. Based on less convincing
evidence in animal studies.
Classification and labelling does not apply to flexible PVC articles
Aim – To ensure safe handling and use in the workplace
14
Classification and Labelling
DMP
DEP
DPrP
DIBP SCL = 25%
DBP
DPP
BBP
DIHP
DEHP
711P (Branched)
DINP
DIDP
79P (Linear)
911P (Linear)
Backbone
1
2
3
3
4
4-5
4-7
5-6
6
5-9
7-8
8-9
7-9
9 - 11
Fertility
None
None
None
Cat 3
Cat 3
Cat 2
Cat 3
None
Cat 2
Cat 3
None
None
None
None
Developmental
None
None
None
Cat 2
Cat 2
Cat 2
Cat 2
Cat 2
Cat 2
Cat 2
None
None
None
None
Existing substances legislation
Risk assessment and management
16
DINP & DIDP Risk Assessments / Risk Reduction
Risk Assessments published in Official Journal on 13 April 2006
Two versatile high volume phthalates
Finally perceived as being “Risk Free” following revision of legislation for
use in toys
For both health and environmental effects
Can be used in all applications except toys and childcare articles “which
can be put in the mouth”
Not hazardous - not classified CMR or Dangerous to the Environment
Driving a large shift in consumption to DINP and DIDP
17
DEHP Risk Assessment / Risk Reduction
Anticipate publication in Q4, 2007
Human Health
• Workers inhalation exposure – Waiting for OEL to be identified. It
will be enforced across the EU
• Children via toys – New legislation in place
• Haemodialysis in adults and long term transfusion in children /
neonates – Awaiting opinion of expert Committee (SCENIHR)
• Theoretical risk to children living near some processing plants –
Marketing and Use Directive to control DEHP emissions
18
DEHP Risk Assessment / Risk Reduction
Environment
• Emissions to water. No risk to aquatic organisms. Only possible risk is
a theoretical one to predators eating fish.
• DEHP is a “Priority Substance” under the Water Framework Directive
and so must meet certain Environmental Quality Standards - These
EQS stipulate the level allowed in water to manage these
theoretical risks.
19
Phthalates in indoor air - Expert opinion
20
SCHER Opinion on Phthalates in Indoor Air
Opinion adopted by the Scientific Committee on Health and
Environmental Risks (SCHER) on May 29th 2007
“Based on the lack of mechanistic support and taking into account the low
exposure level of phthalates by inhalation, SCHER does not find
consistent scientific evidence which indicate that phthalates should be
high concern chemicals in indoor air.
The RA report on DEHP (European Union Risk Assessment report, 2007)
suggests that the MOSs from exposure in indoor air to reproductive
effects, which are the basis for risk characterisation, remain large (over
200 for children, over 1000 for adults).”
21
Proposed Norwegian ban on 19 substances
22
Proposed Norwegian ban on DEHP in consumer
products
Norway is proposing to ban a range of hazardous substances
(including DEHP) in consumer products
• “to limit the harmful effects on human health and the
environment from consumer products, as well as to limit
the content of hazardous substances in waste”.
It would be prohibited to produce, import, export or sell
consumer products that contain more than 0.1% DEHP
• Excludes construction materials for outdoor use
23
Response by EFTA and EU Commission
The EFTA Surveillance Authority reminds the Norwegian
Government that under the Marketing and Use Directive the
MS seeking to limit the use of a substance must :
• Provide all the relevant health and environmental impact
data on the substance and alternatives
• Conduct an adequate risk assessment
The Commission points out that there is no need to exceed the
measures defined by the DEHP RAR and being developed in
the risk reduction strategy. Norway is invited to fully participate
in the discussions
24
Legislative Actions - Toys and childcare articles
25
Toys and Childcare Articles
Permanent measures published in the Official Journal on 27 December 2005
DBP, BBP and DEHP restricted (0.1 wt%) in all toys and childcare articles
DINP, DIDP and DNOP restricted (0.1 wt%) in toys and childcare articles
which can be put in the mouth
National legislation was enacted from 16 January 2007
Entirely political decision ignoring science based risk assessments
Toys and childcare articles which can be put in the mouth are being
produced with alternative plasticisers – citrates, DINCH, etc.
26
Food contact materials
27
Food Contact Materials
Published in the Official Journal on 31st March 2007:
The amendment of Directive 2002/72 (Plastics materials intended to
come into contact with food) and Directive 85/572 (Simulants to be used
for migration testing).
Published in the Official Journal on 3rd April 2007:
Commission Regulation laying down transitional migration limits for
plasticisers in lid gaskets.
28
Food Contact Materials
In practical terms the amendment of Directive 2002/72 will mean:
Repeat Use Applications (tubes, conveyor belts, etc)
BBP, DINP and DIDP – all food types – meet SMLs based on full TDIs
DEHP – only aqueous foods – SML based on 50% TDI
DBP - only aqueous foods – SML based on 50% new TDI - too low
Single Use Applications (cap seals, etc)
BBP, DINP and DIDP – aqueous only – SML based on full TDI
DBP and DEHP may not be used
29
Food Contact Materials
Timetable
Manufacturers and importers have 14 months from adoption of the
Directive before having to meet the requirements
Therefore DEHP can continue to be used in bottle caps for aqueous
foods until April 2008
Additives other than phthalates have until February 2009 to meet the
requirements
Transitional migration limits for plasticisers in lid gaskets – Higher
migration limits allowed for ESBO, citrates, polymerics, etc for 14 months
to allow new formulations to be developed
30
Food Contact Materials
Non-phthalates
DINCH included with no SML or application restrictions.
DEHA and polymerics already included
Simulants to represent milk products
Distilled water to be replaced by 50% ethanol. Most likely excludes
phthalates from milk tubing, etc.
Conclusions
Biggest impact is on DEHP in bottle caps
Lower impact on other phthalates because already used mainly for nonfatty foods. Increased use of speciality plasticisers in lid gaskets.
31
Why use flexible PVC in medical devices?
32
Flexible PVC in Medical Applications - Benefits
Used successfully for more than 40 years
Flexible PVC containing DEHP is approved by European Pharmacopoeia
for medical containers and tubes
Excellent biocompatibility and ease of processing
Wide variety of applications with significant benefits
• Steam sterilisation
• Low temperature storage
• Gas permeability
• Withstands centrifugation forces. No kinking
33
DEHP in Medical Applications - Risk Assessment
RAR states – Risk / benefit analysis is not taken into account
Conservative NOAEL = 4.8 mg/kg bw/day (oral)
Should use NOAEL based on IV studies
Risks to patients (MOS < 100) associated with exposure to DEHP via :
• Long term haemodialysis (adults)
• Transfusions (neonates)
• Long term blood transfusion (children) (Lowest MOS via IV = 800)
There are no risks associated with :
• Lifetime exposure to DEHP during infusions
• Long term blood transfusion (adults)
34
Expert opinions on medical devices
35
SCMPMD, SCENIHR and UK MHRA Opinions
EU Scientific Committee on Medicinal Products and Medical Devices
(SCMPMD) September 2002
• Opinion - Risk / benefit analysis is needed and no specific
recommendations can be made to limit the use of DEHP or PVC
EU Scientific Committee on Emerging and Newly Identified Health Risks
(SCENIHR)
• July 2007 – Opinion expected on whether alternatives to PVC and
DEHP should be used in certain applications.
UK Medicines and Healthcare Products Regulatory Agency (MHRA)
conclude that no phase out or substitution of DEHP in medical devices
should be considered until the SCENIHR has delivered its opinion.
36
Legislative position on medical devices
37
Legislative position
EU Parliament, Council and Commission came to a first reading
agreement on 27 February 2007 (Did not wait for SCENIHR Opinion)
DEHP is not banned in medical devices
“Phthalate containing” label must be placed on device or packaging for all
medical devices in contact with bodily fluids or medicines, where
phthalates classified as CMR are used
Label to be defined by CEN
Medical device manufacturers to justify use of CMR phthalates in
applications for children or pregnant women.
Increasing quantities of speciality plasticisers becoming available
for certain medical applications
38
Plasticiser consumption trends
39
Source: ECPI, 2007
2006
2005
2004
2003
2002
2001
2000
1999
1998
1997
1996
1995
1994
1993
1992
1991
1990
1989
1988
1987
1986
1985
1984
1983
1982
1981
1980
1979
Western Europe Plasticiser Consumption
(‘000s of tons)
1200
1000
800
600
400
200
0
40
Plasticiser Consumption
Total plasticiser consumption relatively stable
A marked trend to less hazardous phthalates
• DEHP replaced by DINP and DIDP
• DBP being replaced by DIBP and others
• BBP consumption diminishing and being replaced by benzoates
ECPI statistics not very sensitive to changes in non-phthalates usage
41
European Plasticiser Consumption - Trends
Other
Plasticisers
8%
Other
Phthalates
15%
1999
DINP/DIDP
35%
DEHP
42%
2006
Other
Phthalates
12%
Other
Plasticisers
7%
DEHP
20%
Source: ECPI, 2007
DINP/DIDP
61%
42
Alternatives to phthalates
43
Adipates
Confer good flexibility at low temperatures
Low plastisol viscosity
Approved for use in food contact applications
Relatively volatile
Limited compatibility with PVC
Rapid migration
Higher adipates usually regarded as 'secondary' plasticisers
44
Polyesters (Polymeric plasticisers)
Most commonly based on propyleneglycol and adipic acid
Used only where high resistance to migration (into oils, solvents,
adhesives etc.) is a requirement. Hence used in some medical
applications
Approved for use in materials in contact with food
Polyesters have very high viscosity which can make processing difficult
Confer poor low temperature flexibility
45
Trimellitates
O
O
O
O
O
O
Low volatility in high temperature cable compounds
Non-fogging automotive interior trim
Generally good balance of properties
Low migration hence some use in medical applications
Limited supply of trimellitic anhydride and its precursor pseudocumene
46
Citrates
Low tonnage products
The most important is acetyl tributyl citrate, ATBC
Has a variety of food contact approvals and is used in PVdC film
Process costs for citrate manufacture are relatively high
Used in limited medical applications but some adverse human reactions
47
Benzoates
Main commercial product is dipropyleneglycol dibenzoate
Competes with butyl benzyl phthalate
Speciality fast fusing stain-resistant plasticiser in vinyl flooring
Poor flexibility at low temperatures and relatively high volatility prevent
general purpose use
48
Alkyl sulphonate esters
Used in some applications where their chemical stability (resistance to
hydrolysis) is beneficial
Generally good all-round technical performance
Good PVC fusion characteristics
Single source
Large scale expansion in production likely to be feedstock constrained
49
Di-2-ethylhexyl terephthalate (DEHT)
Based on terephthalic acid (para) rather than phthalic anhydride (ortho)
Metabolised differently in rats
2-generation reproduction study in rats – much lower potency than
DEHP. Similar to higher phthalates, eg DINP
Plasticising performance similar to DEHP
50
Epoxidised oils and esters
Produced by epoxidising unsaturation in soya bean and linseed oils
(esters of glycerol with C18 acids)
Also based on esters of synthetic alcohols and C18 acids
Have a dual function as co-stabilisers and plasticisers
Low compatibility with PVC hence only suitable as secondary plasticisers
Good toxicological profile – used at low levels in food contact materials
Stabilising action is to bind HCL by opening the oxirane ring.
Unfortunately this leads to formation of epichlorohydrin
51
Acetylated glycerol ester
O
O
O
H C
O
C
O
C
HC
O
C
O
CH
H C
O
C
CH
2
2
10
H
20
C
CH
CH
C H
6
3
13
3
3
Danisco – Grinsted Soft-n-Safe. Capacity increased from 5 to 10 ktpa
Acetylated castor oil
Plasticiser performance similar to DEHP
No adverse efects in tests conducted to date. Reproductive effects ?
52
DINCH
Di-IsoNonylCycloHexanedicarboxylate
Comprehensive toxicological studies
No adverse health or environmental effects have been found
Performance similar to phthalates
Undergoing trials in medical and other applications
BASF capacity - 25 ktpa since 2002. Increased to 100 ktpa in May 2007
53
Diesters of isosorbide
OH
O
OH
OH
HO
OH
OH
+ 2
HO
O
O
R
R
catalyst
O
R
O
O
+ 4 H2O
O
Hydrolyse starch to glucose. Hydrogenate glucose to sorbitol
Isosorbide prepared by dehydration of sorbitol
Raw materials cheap and abundant but slow process and variable colour
Linear esters of isosorbide - similar plasticising performance to phthalates
Similar substances used in food and pharmaceuticals but this does not
guarantee lack of toxicity
54
Plasticisers – The Way Forward
Classification, labelling and risk assessments are resulting in a move to
DINP and DIDP and a decrease in DEHP, DBP and BBP consumption
Health effects are not seen in primates - only in rodent studies
It is unlikely that phthalates really are a threat to human health.
Legislative changes and concerns regarding toys, food contact and
medical devices will cause a move to speciality plasticisers that are lower
migrating or have lower animal toxicity.
The shift to less hazardous phthalates and the development of new
speciality plasticisers means that there is still a very strong future for
flexible PVC
55