The Current Plasticiser Situation in Europe David Cadogan, ECPI Phthalates and new plasticisers for...

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The Current Plasticiser Situation in Europe

David Cadogan, ECPI

Phthalates and new plasticisers for PVC ConferenceCopenhagen, Denmark

20 September 2007

Outline

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

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

Cl CI ClOO

Cl CI Cl

PVC plus DEHP

93% of Plasticisers are Phthalates

Phthalates have :Optimum balance of polar / non-polar groupsBest all round performance / price ratio

C4 - C7 alcohol : Lower viscosity, faster processingC8 – C10 alcohols : General purpose C11-C13 alcohols : High temperature performance>80% linear : Better low / high temperature performance

Performance can be fine tuned by using appropriate alcohol

Is there a move away from phthalates?..... Why?

There is move away from some phthalates

New plasticisers are being developed

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

Are phthalates a threat to human health?

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

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?

Potential Health Impact - Structure / Activity

Phthalate toxicity to rodents depends on number of carbon atoms in the alcohol backbone

1-3 C (DMP, DEP) Minimal4-6 C (DBP, DEHP) Maximum> 7 C (DINP, DIDP) Minimal

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.

Do Phthalates have Adverse Effects on Humans?

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

Classification and Labelling

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

Backbone Fertility

Developmental

DMP 1 None None

DEP 2 None None

DPrP 3 None None

DIBP SCL = 25% 3 Cat 3 Cat 2

DBP 4 Cat 3 Cat 2

DPP 4 - 5 Cat 2 Cat 2BBP 4 - 7 Cat 3 Cat 2DIHP 5 - 6 None Cat 2

DEHP 6 Cat 2 Cat 2

711P (Branched) 5 - 9 Cat 3 Cat 2

DINP 7 - 8 None None

DIDP 8 - 9 None None

79P (Linear) 7 - 9 None None

911P (Linear) 9 - 11 None None

Classification and Labelling

Existing substances legislationRisk assessment and management

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

DINP & DIDP Risk Assessments / 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

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.

DEHP Risk Assessment / Risk Reduction

Phthalates in indoor air - Expert opinion

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).”

Proposed Norwegian ban on 19 substances

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

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

Legislative Actions - 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.

Toys and Childcare Articles

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.

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

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

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 non-fatty foods. Increased use of speciality plasticisers in lid gaskets.

Why use flexible PVC in medical devices?

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

Flexible PVC in Medical Applications - Benefits

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 studiesRisks 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)

DEHP in Medical Applications - Risk Assessment

Expert opinions on medical devices

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.

SCMPMD, SCENIHR and UK MHRA Opinions

Legislative position on medical devices

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

Legislative position

Plasticiser consumption trends

Western Europe Plasticiser Consumption

(‘000s of tons)

Source: ECPI, 2007

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

European Plasticiser Consumption - Trends

DEHP20%

Other Phthalates

Other Plasticisers

DINP/DIDP61%

DEHP42%Other

Phthalates15%

Other Plasticisers

DINP/DIDP35%

Source: ECPI, 2007

Alternatives to phthalates

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

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

Trimellitates

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

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

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

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

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

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

Acetylated glycerol ester

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 ?

O CH2C C

O C CH3

CH C6H

O C CH3

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

Diesters of isosorbide

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

+ 4 H2O+ 2 HO

catalyst

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

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