phthalate plasticizers ce 435 introduction to polymers brian amato sarah karl carla ng

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


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


Types:Types: DEHP (Di(2-ethylhexyl) phthalate)DEHP (Di(2-ethylhexyl) phthalate)

StructureStructure


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……..)


DINP (Diisononyl Phthalate)DINP (Diisononyl Phthalate) StructureStructure


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


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


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.


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.


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.


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?


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?


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

1.1.

http://www.fda.gov/cher/minutes/plast101089http://www.fda.gov/cher/minutes/plast1010899.html9.html

2.2.http://www.pirg.org/masspirg/enviro/sw/pvchttp://www.pirg.org/masspirg/enviro/sw/pvc3.Abbott, Barbara D. (2000). “The Plasticizer 3.Abbott, Barbara D. (2000). “The Plasticizer

Diethylhexyl Phthalate Induces Diethylhexyl Phthalate Induces Malformations by Decreasing Fetal Malformations by Decreasing Fetal

Testosterone Synthesis during SexualTestosterone Synthesis during Sexual Differentiation in the Male Rat.” Differentiation in the Male Rat.” Toxicological Toxicological

SciencesSciences 58, 339-349 58, 339-349

4.4.Ackley, David C. (2000). “Effects of Di-isononyl Ackley, David C. (2000). “Effects of Di-isononyl Phthalate, Di-2-ethylhexylPhthalate, Di-2-ethylhexyl

Phthalate, and Clofibrate in Cynomologus Phthalate, and Clofibrate in Cynomologus Monkeys.” Monkeys.” Toxicological SciencesToxicological Sciences 56, 56,

181-188181-1885.Carraher, Charles E. 5.Carraher, Charles E. Polymer Chemistry: an Polymer Chemistry: an

IntroductionIntroduction 4 4thth Ed. (1996) Marcel Dekker, Inc. NY, Ed. (1996) Marcel Dekker, Inc. NY, New York 424-426New York 424-426

6.Durodie, Bill “Poisonous Propaganda, Global Echoes of 6.Durodie, Bill “Poisonous Propaganda, Global Echoes of an Anti-Vinyl Agenda.” Competitive Enterprise an Anti-Vinyl Agenda.” Competitive Enterprise Institute, July 2000Institute, July 2000

7.7.http://www.cei.orghttp://www.cei.org

8.Christensen, Jackie Hunt. Toxic Toy Story. 8.Christensen, Jackie Hunt. Toxic Toy Story. MotheringMothering. Sept. 1998 p38 (1). Sept. 1998 p38 (1)9.O’Mara, Peggy. Winning the Fight Against 9.O’Mara, Peggy. Winning the Fight Against PVC. PVC. MotheringMothering. March 1999 p35 (1). March 1999 p35 (1)10.Raloff, J. Girls May Face Risks from 10.Raloff, J. Girls May Face Risks from Phthalates. Phthalates. Science NewsScience News. Sept 9, 2000 . Sept 9, 2000 v158 ill p165v158 ill p16511.Ullman’s Encyclopedia of Industrial 11.Ullman’s Encyclopedia of Industrial Chemistry, Vol A20 pp439-451, VCH Chemistry, Vol A20 pp439-451, VCH Publishers, Inc, 1992Publishers, Inc, 1992

12.Woodyatt, K.G. Lambe, K.A. Myers, J.D. 12.Woodyatt, K.G. Lambe, K.A. Myers, J.D. Tugwood and R.A. Roberts, “The Tugwood and R.A. Roberts, “The Peroxisome Proliferator (PP) response Peroxisome Proliferator (PP) response element upstream of the human CoA element upstream of the human CoA oxidase gene is inactive among a sample oxidase gene is inactive among a sample human population: significance for human population: significance for species differences in response to PPs.” species differences in response to PPs.” CarcinogenesisCarcinogenesis, vol.20 no.3 pp.369-371, , vol.20 no.3 pp.369-371, 19991999

13.Zacharewski, T.R., M.D. Meek, J.H. 13.Zacharewski, T.R., M.D. Meek, J.H. Clemons, Z.F. Wu, M.R. Fielden and Clemons, Z.F. Wu, M.R. Fielden and J.B. Matthews, “Examination of the in J.B. Matthews, “Examination of the in vitro and in vivo estrogenic activities vitro and in vivo estrogenic activities of eight commercial phthalate of eight commercial phthalate esters.” esters.” Toxicological SciencesToxicological Sciences, Vol. , Vol. 46, pp.282-293, 199846, pp.282-293, 1998

phthalate plasticizers ce 435 introduction to polymers brian amato sarah karl carla ng

Documents

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plasticizer theory

types of plasticizer

plasticizer molecules

secondary primary plasticizer

polymer properties

external plasticization

polymer flexibility