phthalate plasticizers ce 435 introduction to polymers brian amato sarah karl carla ng
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Phthalate PlasticizersPhthalate Plasticizers
CE 435 Introduction to CE 435 Introduction to PolymersPolymers
Brian AmatoBrian Amato
Sarah KarlSarah Karl
Carla NgCarla Ng
Timeline (history)Timeline (history)
FirstPlasticizer
1860 1930
Phthalates Introduced
1980’s
DEHP Declared Carcinogenic
2001
IARC Re-classifies DEHP as non-carcinogenic
1998
European Parliament calls for alternatives to phthalates
OutlineOutline
IntroductionIntroduction A Plasticizer A Plasticizer
TimelineTimeline TheoryTheory What are What are
Phthalate Phthalate PlasticizersPlasticizers(and why do we care)?(and why do we care)?
The Plasticizer The Plasticizer MarketMarket
Health Health ConcernsConcernsScience and Science and Industry Industry ResponseResponseGovernment Government PositionsPositionsHealth or Health or Hype?Hype?Conclusions.Conclusions.
IntroductionIntroduction
What is a plasticizer?What is a plasticizer? Where are they commonly found?Where are they commonly found?
General DefinitionGeneral Definition
A Plasticizer is a polymer A Plasticizer is a polymer additiveadditive.. Effect on polymer properties: an Effect on polymer properties: an
important distinction from other important distinction from other additives.additives.
Increases polymer flexibility, Increases polymer flexibility, elongation or workability.elongation or workability.
Types of Plasticizer (I)Types of Plasticizer (I)
Internal vs. ExternalInternal vs. External Internal plasticization occurs via Internal plasticization occurs via
chemicalchemical interactions. interactions. Copolymerization is one type of Copolymerization is one type of
internal plasticization.internal plasticization. External plasticization occurs via External plasticization occurs via
physicalphysical interactions. interactions. External is the most common: cost, External is the most common: cost,
ease of processing.ease of processing.
Types of Plasticizer (II)Types of Plasticizer (II)
Primary vs. SecondaryPrimary vs. Secondary Primary Plasticizer affects resin Primary Plasticizer affects resin
properties.properties. Secondary is a “Plasticizer-Secondary is a “Plasticizer-
plasticizer”: used to increase the plasticizer”: used to increase the effectiveness of the primary effectiveness of the primary plasticizer.plasticizer.
Plasticizers In PVCPlasticizers In PVC
Cling-film for food Cling-film for food packaging.packaging.
Medical devices: Medical devices: blood bags, IV blood bags, IV bags, tubing.bags, tubing.
Vinyl floors.Vinyl floors. Synthetic leather.Synthetic leather. Electrical Cables.Electrical Cables.
Toys: teethers for Toys: teethers for infants and infants and Ernie’s favorite Ernie’s favorite bath-time bath-time companion.companion.
Plasticizers All Around UsPlasticizers All Around Us
Non-PVC UsesNon-PVC Uses Liquid plasticizers used in Liquid plasticizers used in
coating to protect car chassis.coating to protect car chassis. Paints.Paints. Printing Inks.Printing Inks. Adhesives.Adhesives.
Plasticizer TheoryPlasticizer Theory
Three Mechanisms:Three Mechanisms:
• Lubricity TheoryLubricity Theory• Gel TheoryGel Theory• Free-Volume TheoryFree-Volume Theory
Lubricity TheoryLubricity Theory
Assumes the rigidity of the resin Assumes the rigidity of the resin (pure polymer) arises from (pure polymer) arises from “intermolecular friction.”“intermolecular friction.”
Plasticizer molecules are Plasticizer molecules are introduced on heating.introduced on heating.
At room temperature, these At room temperature, these molecules act as lubricants for the molecules act as lubricants for the polymer chains.polymer chains.
Gel TheoryGel Theory
Resin-resin interactions occur at Resin-resin interactions occur at “centers of attachment.”“centers of attachment.”
Plasticizer molecules break these Plasticizer molecules break these interactions and masks the centers interactions and masks the centers from each other, preventing re-from each other, preventing re-formation.formation.
This theory is not sufficient to This theory is not sufficient to describe interaction– should be describe interaction– should be combined with Lubricity Theory.combined with Lubricity Theory.
Free-Volume TheoryFree-Volume Theory
Free volume: “internal space” Free volume: “internal space” available in the polymer for the available in the polymer for the chains to move.chains to move.
This volume increases sharply at the This volume increases sharply at the glass transition temperature, Tg.glass transition temperature, Tg.
Plasticizer is meant to decrease the Plasticizer is meant to decrease the glass transition temperature, glass transition temperature, imparting increased flexibility to imparting increased flexibility to polymer at room temperature.polymer at room temperature.
Choosing Your PlasticizerChoosing Your Plasticizer
Effectiveness ConsiderationsEffectiveness Considerations How Much Plasticizer NecessaryHow Much Plasticizer Necessary Interaction Parameters: Our Friends Interaction Parameters: Our Friends
Flory and Huggins.Flory and Huggins. Application ConsiderationsApplication Considerations::
Temperature RangeTemperature Range Degree of Flexibility DesiredDegree of Flexibility Desired
Phthalates: the #1 Choice for Phthalates: the #1 Choice for PVCPVC
Plasticizer MarketPlasticizer Market
Yearly Plasticizer ProductionYearly Plasticizer Production Plasticizers are the largest class of polymer Plasticizers are the largest class of polymer
additives produced.additives produced. Global volume of 10 billion lbs in 1999Global volume of 10 billion lbs in 1999 $5 billion value with 2-3% yearly market $5 billion value with 2-3% yearly market
growth.growth. <1% of Phthalates produced are used in <1% of Phthalates produced are used in
children’s toys.children’s toys. 10% are used in medical applications.10% are used in medical applications.
Phthalate PlasiticizersPhthalate Plasiticizers
What are they Chemically What are they Chemically Speaking?Speaking? A Phthalate ester derived from A Phthalate ester derived from
phthalic acid by an esterification phthalic acid by an esterification reaction.reaction.
Mechanism: Mechanism: phthalic acid to phthalate phthalic acid to phthalate esterester
H
Phthalate PlasiticizersPhthalate Plasiticizers
PropertiesProperties ColorlessColorless Oily liquid ( like vegetable oil)Oily liquid ( like vegetable oil) Ester odorEster odor High boiling pointHigh boiling point Inert, and very stable over long Inert, and very stable over long
periodsperiods
Phthalate PlasiticizersPhthalate Plasiticizers
Types:Types: DEHP (Di(2-ethylhexyl) phthalate)DEHP (Di(2-ethylhexyl) phthalate)
StructureStructure
Phthalate PlasiticizersPhthalate Plasiticizers
Properties of DEHPProperties of DEHP Insoluble in HInsoluble in H22oo Soluble in mineral oil, hexane, most Soluble in mineral oil, hexane, most
organic solventsorganic solvents Easily dissolved in bodily fluids, such as Easily dissolved in bodily fluids, such as
saliva and plasma.saliva and plasma. Boiling point: 386.9Boiling point: 386.9oocc Density: 0.9732 g/LDensity: 0.9732 g/L Molecular weight: 390.5618 g/molMolecular weight: 390.5618 g/mol
Phthalate PlasiticizersPhthalate Plasiticizers Uses of DEHP:Uses of DEHP:
Used in medical devicesUsed in medical devices ToysToys PacifiersPacifiers Vinyl UpholsteryVinyl Upholstery Food containersFood containers Table clothsTable cloths Shower curtainsShower curtains Raincoats ( and the list goes on……..)Raincoats ( and the list goes on……..)
Phthalate PlasiticizersPhthalate Plasiticizers
DINP (Diisononyl Phthalate)DINP (Diisononyl Phthalate) StructureStructure
Phthalate PlasiticizersPhthalate Plasiticizers
Properties of DINPProperties of DINP Insoluble in HInsoluble in H22OO Soluble in most organic solventsSoluble in most organic solvents Boiling point: not availableBoiling point: not available Density: not availableDensity: not available Molecular weight: 418.6 g/molMolecular weight: 418.6 g/mol
Phthalate PlasiticizersPhthalate Plasiticizers
Uses of DINP:Uses of DINP: Replaced DEHP in toys when initially Replaced DEHP in toys when initially
determined to be carcinogenic.determined to be carcinogenic.
Uses of DEHP in Medical Uses of DEHP in Medical DevicesDevices
Phthalates (DEHP) in Medical Devices:Phthalates (DEHP) in Medical Devices: Blood Storage BagsBlood Storage Bags IV BagsIV Bags CathetersCatheters Dialysis tubingDialysis tubing
Benefits:Benefits: Why is DEHP used?Why is DEHP used?
Cost efficiencyCost efficiency SafetySafety Resists kinkingResists kinking
Uses of DEHP in Medical Uses of DEHP in Medical DevicesDevices
Long shelf lifeLong shelf life Transparent Transparent Withstands high pressures without leakingWithstands high pressures without leaking Withstands both freezing and steam Withstands both freezing and steam
sterilizationsterilization Collapse when empty, therefore they do Collapse when empty, therefore they do
not have to be injected with sterile air to not have to be injected with sterile air to replace the blood or fluid being withdrawn.replace the blood or fluid being withdrawn.
Uses of DEHP in Medical Uses of DEHP in Medical DevicesDevices
Other convincing reasonsOther convincing reasons DEHP contributes to the extended DEHP contributes to the extended
storage of red blood cells.storage of red blood cells. Doubles shelf life compared to other Doubles shelf life compared to other
plasitcizers.plasitcizers. 5-7 billion patient days of exposure 5-7 billion patient days of exposure
without any reported adverse health without any reported adverse health effectseffects
Health ConcernsHealth Concerns
DEHP is a Carcinogen?DEHP is a Carcinogen?
Studies in the early 1980’s on the effects of Studies in the early 1980’s on the effects of DEHP on rodents by U.S National Toxicology DEHP on rodents by U.S National Toxicology Program and International Agency for Program and International Agency for Research show carcinogenic effect. Research show carcinogenic effect.
Scientific papers give rise to concerns of Scientific papers give rise to concerns of reduced sperm counts from phthalates, due reduced sperm counts from phthalates, due to the endocrine disruption theory. to the endocrine disruption theory.
Health ConcernsHealth Concerns
Concerns Abated:Concerns Abated:
The International Agency for Research The International Agency for Research on Cancer changes reverses its on Cancer changes reverses its position on DEHPs Carcinogenic position on DEHPs Carcinogenic effects.effects.
Endocrine disruption theory in Endocrine disruption theory in regards to DEHP disproved.regards to DEHP disproved.
Health ConcernsHealth Concerns
Research with laboratory rats Research with laboratory rats suggests sexual developmental suggests sexual developmental issues by reducing fetal issues by reducing fetal testosterone levelstestosterone levels
Testosterone levels were reduced Testosterone levels were reduced to female levels to female levels
How does this relate to Humans? How does this relate to Humans? Or does it?Or does it?
Health ConcernsHealth Concerns
Tests were performed on Monkeys Tests were performed on Monkeys who are primates like humanswho are primates like humans
DEHP & DINP were both used and DEHP & DINP were both used and yielded no noticeable biological or yielded no noticeable biological or physical responses to treatmentphysical responses to treatment
Species specificity? Species specificity?
Health ConcernsHealth Concerns
Should this give manufacturers of Should this give manufacturers of Phthalates a clear conscience? Not Phthalates a clear conscience? Not NecessarilyNecessarily
Researchers in Puerto Rico claim that Researchers in Puerto Rico claim that premature breast development of premature breast development of young girls, thelarche, may be the young girls, thelarche, may be the result of Phthalate exposure result of Phthalate exposure
8 out of every 1000 girls suffer from this 8 out of every 1000 girls suffer from this conditioncondition
Other Health Concerns Other Health Concerns Aside From MedicalAside From Medical
Plasticizers and Infants:Plasticizers and Infants: Toys and TeethersToys and Teethers
Plasticizers in Food:Plasticizers in Food: Packaging FilmPackaging Film
Industry/Science ResponseIndustry/Science Response In response to concerns about the safety of In response to concerns about the safety of
plasticizers, industry and science worked plasticizers, industry and science worked together to study the effects and disseminate together to study the effects and disseminate information.information. Toy manufacturers voluntarily replaced Toy manufacturers voluntarily replaced
phthalates and, in some cases, PVC.phthalates and, in some cases, PVC. European Chemical Industry Council (CEFIC) European Chemical Industry Council (CEFIC)
forms EMSG, ECPI.forms EMSG, ECPI. ECPI conducts joint research with Chemical ECPI conducts joint research with Chemical
Manufacturer’s Association (CMA) in the U.S.Manufacturer’s Association (CMA) in the U.S. The EPA, the Vinyl Institute and NIH provide The EPA, the Vinyl Institute and NIH provide
information to consumers about their rights and information to consumers about their rights and the safety of phthalate-containing products.the safety of phthalate-containing products.
Government DecisionsGovernment Decisions
EuropeEurope Several European nations banned the use of Several European nations banned the use of
phthalates in toys.phthalates in toys. International Agency for Research on Cancer International Agency for Research on Cancer
classifies DEHP as carcinogenic, then classifies DEHP as carcinogenic, then reverses their decision in February of 2000.reverses their decision in February of 2000.
As late as April of this year, the European As late as April of this year, the European Parliament calls for the use of substitution Parliament calls for the use of substitution products. Seek to eliminate environmental products. Seek to eliminate environmental effects of phthalates.effects of phthalates.
Government DecisionsGovernment Decisions United StatesUnited States
The EPA regulates the amount of DEHP and DINP The EPA regulates the amount of DEHP and DINP in the environment. They are listed as toxic in the environment. They are listed as toxic chemicals subject to reporting requirements chemicals subject to reporting requirements under the Pollution Prevention Act (PPA).under the Pollution Prevention Act (PPA).
The FDA has issued no warnings on phthalate The FDA has issued no warnings on phthalate plasticizers, and does not consider them to be plasticizers, and does not consider them to be carcinogenic. No action has been taken by the carcinogenic. No action has been taken by the US government in issues outside of the US government in issues outside of the environmental aspect of phthalates. Any environmental aspect of phthalates. Any consumer product industry response has been consumer product industry response has been voluntary.voluntary.
Health or Hype? Health or Hype? Evaluating the Positions of the Major Evaluating the Positions of the Major PlayersPlayers
GreenpeaceGreenpeace Have come out against the Vinyl Have come out against the Vinyl
industry in general, due to their belief in industry in general, due to their belief in the toxicity of chlorine.the toxicity of chlorine.
The Vinyl InstituteThe Vinyl Institute Seeks to disseminate information about Seeks to disseminate information about
the importance of vinyl products in our the importance of vinyl products in our life and the evidence that they are not life and the evidence that they are not harmful to humans.harmful to humans.
Alternatives to PlasicizersAlternatives to Plasicizers
Benzoates Citrates DINA EPZ (Edible Plasticizer) TXIB Plasticizer (hard oil) 168 Plasticizer DEHP is still used in medical devices although
alternatives are being explored
ConclusionConclusion
Michael Fumento of the Hudson Institute: Michael Fumento of the Hudson Institute: “If your child eats toys, phthalates are the “If your child eats toys, phthalates are the least of your worries!”least of your worries!”
Conflicting evidence about the effects of Conflicting evidence about the effects of phthalates in humans and the environment.phthalates in humans and the environment.
Possible consequences for the food chain.Possible consequences for the food chain. In the end, it is up to consumers to educate In the end, it is up to consumers to educate
themselves and make informed decisions. themselves and make informed decisions.
ReferencesReferences
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Diethylhexyl Phthalate Induces Diethylhexyl Phthalate Induces Malformations by Decreasing Fetal Malformations by Decreasing Fetal
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