Green polymer additives based on renewable resources

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Green polymer additives based on renewable
resources
Polymers, Composites and Additives ATO B.V.
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Polymer Additives
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Major thermoplastic materials
Total 30.251.000 tonnes in 1997
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Trends and driving forces within polymer additive
industry

• Processing of materials at higher temperatures
• Plastics having a natural look
• Lightweight fillers
• Decreased migration
• Recycling of plastics
• Stronger growth numbers of polyolefines compared
  to PVC
• One pack formulations
• Urge to comply with future legislative regulations

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Polymer additives being perceived as green
Future legislative regulations are a strong
driving force towards innovation - As a result of
continuing controversy, heavy metal based heat
stabilisers, pigments and flame retardants, as
well as phthalate based plasticisers currently
remain under pressure -More environmentally
sound, non-toxic, green additives are
desirable - If a good price/performance ratio
can be obtained, additives based on renewable
resources, offer the ideal green additive
...
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Additives and renewables

• Present Polymer additives are overwhelmingly
  based on petrochemical resources
• Examples of commercially available additives
  already partly based on renewables
• Lubricants
• Antistatic agents
• Anti fogging agents
• (Specialty) plasticisers
• Clarifying agents

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Projects aimed at developing renewable additives

• Development of heavy metal free heat stabilisers
  for PVC
• Mechanistic study on structure-activity
  relations of polyols as heat stabiliser for PVC
• Plasticisers based on renewable materials
• (Natural) Colorants for use in thermoplastic
  materials
• Development of heavy metal free and halogen free
  flame retardants
• Agro-fibres as reinforcing fillers

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Technology offers existing and in development

• Natural antioxidants for use in thermoplastics
• Plasticisers for non-PVC applications
• UV stabilisers based on natural resources
• Methods for controlled delivery of additives
• External and internal lubricants
• Fillers based on renewable materials
• Biopolymers with permanently antistatic
  behavior
• Biopolymer-clay based nanocomposites

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Sugar polyols (potential) applications

• European sugar polyol production is currently
  approximately 260.000 tonnes
• Examples sorbitol, mannitol, maltitol,
  lactitol, xylitol, erythritol
• Sorbitol is being produced in largest quantities
• Applications areas for sorbitol
• Food
• Pharmaceuticals
• Personal care
• Non -food
• Surface active agents
• Alkyd paints
• Polyurethanes
• Heat stabilisers?
• Plasticisers?

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Development of heavy metal free heat stabilisers

• Environmental concerns are currently changing
  the PVC heat stabiliser market
• Particularly in Europe PVC processors intend to
  replace lead containing heat stabilisers for PVC
• The European PVC industry has offered a
  voluntarily commitment to the European Commission
  of a 100 replacement of lead stabilisers by
  suitable alternatives in 2015
• In heavy metal free systems role of organic
  components acting as (co)-stabilisers will be
  more pronounced

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Development of heavy metal free heat stabilisers

• Different stabilising mechanisms

C interruption of conjugation
P early substitution of labile chlorine atoms
blocking of polyene formation
colour reduction/ correction
S absorption of HCl
suppression of auto catalytic dehydrochlorination
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Development of heavy metal free heat stabilisers
Fundamental project to increase applicability of
polyols as heat stabiliser

• reduction of negative impact on early colour and
  plate out
• rational design polyols
• make usage of polyols in zinc free formulation

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Development of heavy metal free heat stabilisers
Dehydrochlorination curves for various different
polyols
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Development of heavy metal free heat stabilisers
Sorbitol 20 mmol
Glycerol 20 mmol
TMP (13 mmol)
Blank
0 min at 200 ºC
30 min at 200 ºC
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Development of heavy metal free heat stabilisers
Experiments with glycerol and Cereclor as a model
compound indicate that polyols work by covalent
reaction of HCl with OH-groups

• Stabilising efficiency is highest when primary
  hydroxy group in combination with secundary OH is
  present

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Development of heavy metal free heat stabilisers
Effect of different polyols on rheology
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Development of heavy metal free heat stabilisers
Effect on rheology of combining sorbitol with
other stabilising additives
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Development of heavy metal free heat stabilisers
Static heat stability results obtained in zinc
free rigid S-PVC formulation
2.4 phr of stabiliser components based on 100 phr
PVC
Combination of sorbitol and dihydropyridine
results in synergistic effect
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PVC plasticisers from renewable resources
Plasticiser production volumes
1) Source BRG Townsend 2) Source ECPI
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PVC plasticisers from renewable resources

• Plasticisers for poly (vinyl chloride)
• Phthalates 80-90 of all plasticisers
• DEHP (DOP) BBP
• Phthalates are under environmental pressure
• need for non-toxic, environmentally benign and
  commercially viable alternatives.

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PVC plasticisers from renewable resources

• Essential properties of alternatives to
  phthalates
• non-toxic (human- and eco toxicity)
• comparable performance (e.g. primary plasticiser)
• competitive price
• Commercially available alternatives
• adipates expensive, secondary plasticisers
• benzoates mixtures
• citrates expensive
• specialties (ESO, polyesters) expensive,
  secondary plasticisers

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PVC plasticisers from renewable resources

• New Plasticisers based on isosorbide
• Example IsDEH structural DEHP
  analogue
• Passed primary toxicity tests
• Performances are good to excellent
• Raw materials
• sorbitol, prepared by reduction of starch cheap
  and abundant
• alkanoic acids, from petrochemical or renewable
  source

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PVC plasticisers from renewable resources

• Synthesis of isosorbide diesters simple
  esterification procedure
• Starting from isosorbide ( 1,4-3,6-dianhydrosorbi
  tol)
• Or simply starting from sorbitol

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PVC plasticisers from renewable resources

• Shore A hardness values (45 phr)

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PVC plasticisers from renewable resources

• E-modulus (MPa) values for 45 phr PVC compounds

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PVC plasticisers from renewable resources

• Compatibility Fogging results (45 phr)
• (DIN 75201/b)

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PVC plasticisers from renewable resources

• Optical properties (45 phr)
• 454514 mm sample

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PVC plasticisers from renewable resources

• Other properties
• Heat stability
• comparable to phthalates
• comparable to DOA
• superior to BBP and benzoates
• Bio-degradability (aqueous, aerobic)
• readily biodegradable
• Migration/extractability
• again comparable to phthalates
• Plastisol viscosity and stability are also good
• Fusion characteristics are also excellent

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PVC plasticisers from renewable resources

• Plasticiser development is continued, starting
  december 2001, by a
• consortium consisting of ATO, PVC producers,
  PVC processors and
• sorbitol producer Cerestar
• Scope and application possibilities will be
  further explored
• (also outside PVC)
• Particular emphasis will be on enhancing the
  efficiency of the production
• process and registration issues

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Natural antioxidants for polyolefines

• Additives that suppress oxidation are essential
  to virtually all polymers
• Hindered phenols are widely used to prevent
  oxidative thermal degradation during processing
  or long term usage
• Traditional antioxidants might have drawbacks
  with respect to surface
• blooming, yellowing, volatilization,
  toxicity, leaching and migration in
• contact with solvents/chemicals
• Regulations concerning indirect food contact
  generate a growing
• requirement for high performance stabilisers
  with optimal health,
• environment and safety aspects

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Natural antioxidants for polyolefines
Formation of carbonyl compounds as a result of
oxidative thermal degradation
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Natural antioxidants for polyolefines
Effect on MFI after thermal ageing
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General conclusions
Cheap, abundantly available, renewable raw
materials have the potential to serve as
(starting) materials for the production of
environmentally friendly additives for
thermoplastics resins In combination with other
environmentally friendly additives they can make
a valuable contribution to the development of a
sustainable polymer (additives) industry
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Acknowledgements
People working on the various polymer additive
projects R. Blaauw M. v.d. Oever R. C.
Bezemer E. Scott C. Boeriu J.
Steenwijk D. S. van Es S. de Spirt G.
Frissen J. Stoutjesdijk J. v. Heemst M.
Snijder J. Jansen I. de Keijzer H. Luitjes R.
Langerock K. Molenveld
The Dutch Ministry of Economic Affairs, the
Ministry of Education, Culture and Science and
the Ministry of Agriculture, Nature Management
and Fisheries, for partly financing the
developments
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Acknowledgements
People working on the various polymer additive
projects R. Blaauw M. v.d. Oever R. C.
Bezemer E. Scott C. Boeriu J.
Steenwijk D. S. van Es S. de Spirt G.
Frissen J. Stoutjesdijk J. v. Heemst M.
Snijder J. Jansen I. de Keijzer H. Luitjes R.
Langerock K. Molenveld
The Dutch Ministry of Economic Affairs, the
Ministry of Education, Culture and Science and
the Ministry of Agriculture, Nature Management
and Fisheries, for partly financing the
developments